Sample records for near-edge structure xanes

  1. Microanalysis of iron oxidation state in iron oxides using X Ray Absorption Near Edge Structure (XANES)

    NASA Technical Reports Server (NTRS)

    Sutton, S. R.; Delaney, J.; Bajt, S.; Rivers, M. L.; Smith, J. V.

    1993-01-01

    An exploratory application of x ray absorption near edge structure (XANES) analysis using the synchrotron x ray microprobe was undertaken to obtain Fe XANES spectra on individual sub-millimeter grains in conventional polished sections. The experiments concentrated on determinations of Fe valence in a suite of iron oxide minerals for which independent estimates of the iron speciation could be made by electron microprobe analysis and x ray diffraction.

  2. Interaction of Nanostructured Calcium Silicate Hydrate with Ibuprofen Drug Molecules: X-ray Absorption Near Edge Structure (XANES) Study at the Ca, Si and O K-edge

    NASA Astrophysics Data System (ADS)

    Guo, X. X.; Sham, T. K.; Zhu, Y. J.; Hu, Y. F.

    2013-04-01

    Mesoporous calcium silicate hydrate (CSH) nanostructure has been proven to be bioactive and biocompatible, and has a bright future in the application of bone treatment among other applications. X-ray absorption near edge structure (XANES) is a powerful tool for the study of the interactions of calcium silicate hydrates with drug molecules because it is element specific and it probes the unoccupied electronic states. Herein, we report the use of the calcium, silicon and oxygen K-edge XANES spectroscopy to identify how drug molecules interact with different groups in calcium silicate hydrate mesoporous nano-carriers with different morphologies. Significant changes are observed in XANES spectra after drug loading into the calcium silicate hydrate system, especially at the Si and O K-edge. The implications of these findings are discussed.

  3. Reduced chromium in olivine grains from lunar basalt 15555 - X-ray Absorption Near Edge Structure (XANES)

    NASA Technical Reports Server (NTRS)

    Sutton, S. R.; Jones, K. W.; Gordon, B.; Rivers, M. L.; Bajt, S.; Smith, J. V.

    1993-01-01

    The oxidation state of Cr in 200-micron regions within individual lunar olivine and pyroxene grains from lunar basalt 15555 was inferred using X-ray Absorption Near Edge Structure (XANES). Reference materials had previously been studied by optical absorption spectroscopy and included Cr-bearing borosilicate glasses synthesized under controlled oxygen fugacity and Cr-doped olivines. The energy dependence of XANES spectral features defined by these reference materials indicated that Cr is predominantly divalent in the lunar olivine and trivalent in the pyroxene. These results, coupled with the apparent f(02)-independence of partitioning coefficients for Cr into olivine, imply that the source magma was dominated by divalent Cr at the time of olivine crystallization.

  4. X-ray absorption spectroscopy: EXAFS (Extended X-ray Absorption Fine Structure) and XANES (X-ray Absorption Near Edge Structure)

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

    Alp, E.E.; Mini, S.M.; Ramanathan, M.

    1990-04-01

    The x-ray absorption spectroscopy (XAS) had been an essential tool to gather spectroscopic information about atomic energy level structure in the early decades of this century. It has also played an important role in the discovery and systematization of rare-earth elements. The discovery of synchrotron radiation in 1952, and later the availability of broadly tunable synchrotron based x-ray sources have revitalized this technique since the 1970's. The correct interpretation of the oscillatory structure in the x-ray absorption cross-section above the absorption edge by Sayers et. al. has transformed XAS from a spectroscopic tool to a structural technique. EXAFS (Extended X-raymore » Absorption Fine Structure) yields information about the interatomic distances, near neighbor coordination numbers, and lattice dynamics. An excellent description of the principles and data analysis techniques of EXAFS is given by Teo. XANES (X-ray Absorption Near Edge Structure), on the other hand, gives information about the valence state, energy bandwidth and bond angles. Today, there are about 50 experimental stations in various synchrotrons around the world dedicated to collecting x-ray absorption data from the bulk and surfaces of solids and liquids. In this chapter, we will give the basic principles of XAS, explain the information content of essentially two different aspects of the absorption process leading to EXAFS and XANES, and discuss the source and samples limitations.« less

  5. Local structure in LaMnO3 and CaMnO3 perovskites: A quantitative structural refinement of Mn K -edge XANES data

    NASA Astrophysics Data System (ADS)

    Monesi, C.; Meneghini, C.; Bardelli, F.; Benfatto, M.; Mobilio, S.; Manju, U.; Sarma, D. D.

    2005-11-01

    Hole-doped perovskites such as La1-xCaxMnO3 present special magnetic and magnetotransport properties, and it is commonly accepted that the local atomic structure around Mn ions plays a crucial role in determining these peculiar features. Therefore experimental techniques directly probing the local atomic structure, like x-ray absorption spectroscopy (XAS), have been widely exploited to deeply understand the physics of these compounds. Quantitative XAS analysis usually concerns the extended region [extended x-ray absorption fine structure (EXAFS)] of the absorption spectra. The near-edge region [x-ray absorption near-edge spectroscopy (XANES)] of XAS spectra can provide detailed complementary information on the electronic structure and local atomic topology around the absorber. However, the complexity of the XANES analysis usually prevents a quantitative understanding of the data. This work exploits the recently developed MXAN code to achieve a quantitative structural refinement of the Mn K -edge XANES of LaMnO3 and CaMnO3 compounds; they are the end compounds of the doped manganite series LaxCa1-xMnO3 . The results derived from the EXAFS and XANES analyses are in good agreement, demonstrating that a quantitative picture of the local structure can be obtained from XANES in these crystalline compounds. Moreover, the quantitative XANES analysis provides topological information not directly achievable from EXAFS data analysis. This work demonstrates that combining the analysis of extended and near-edge regions of Mn K -edge XAS spectra could provide a complete and accurate description of Mn local atomic environment in these compounds.

  6. Solid energy calibration standards for P K-edge XANES: electronic structure analysis of PPh4Br.

    PubMed

    Blake, Anastasia V; Wei, Haochuan; Donahue, Courtney M; Lee, Kyounghoon; Keith, Jason M; Daly, Scott R

    2018-03-01

    P K-edge X-ray absorption near-edge structure (XANES) spectroscopy is a powerful method for analyzing the electronic structure of organic and inorganic phosphorus compounds. Like all XANES experiments, P K-edge XANES requires well defined and readily accessible calibration standards for energy referencing so that spectra collected at different beamlines or under different conditions can be compared. This is especially true for ligand K-edge X-ray absorption spectroscopy, which has well established energy calibration standards for Cl (Cs 2 CuCl 4 ) and S (Na 2 S 2 O 3 ·5H 2 O), but not neighboring P. This paper presents a review of common P K-edge XANES energy calibration standards and analysis of PPh 4 Br as a potential alternative. The P K-edge XANES region of commercially available PPh 4 Br revealed a single, highly resolved pre-edge feature with a maximum at 2146.96 eV. PPh 4 Br also showed no evidence of photodecomposition when repeatedly scanned over the course of several days. In contrast, we found that PPh 3 rapidly decomposes under identical conditions. Density functional theory calculations performed on PPh 3 and PPh 4 + revealed large differences in the molecular orbital energies that were ascribed to differences in the phosphorus oxidation state (III versus V) and molecular charge (neutral versus +1). Time-dependent density functional theory calculations corroborated the experimental data and allowed the spectral features to be assigned. The first pre-edge feature in the P K-edge XANES spectrum of PPh 4 Br was assigned to P 1s → P-C π* transitions, whereas those at higher energy were P 1s → P-C σ*. Overall, the analysis suggests that PPh 4 Br is an excellent alternative to other solid energy calibration standards commonly used in P K-edge XANES experiments.

  7. 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

  8. Magnesium K-edge XANES spectroscopy of geological standards.

    PubMed

    Yoshimura, Toshihiro; Tamenori, Yusuke; Iwasaki, Nozomu; Hasegawa, Hiroshi; Suzuki, Atsushi; Kawahata, Hodaka

    2013-09-01

    Magnesium K-edge X-ray absorption near-edge structure (XANES) spectra have been investigated to develop a systematic understanding of a suite of Mg-bearing geological materials such as silicate and carbonate minerals, sediments, rocks and chemical reagents. For the model compounds the Mg XANES was found to vary widely between compounds and to provide a fingerprint for the form of Mg involved in geologic materials. The energy positions and resonance features obtained from these spectra can be used to specify the dominant molecular host site of Mg, thus shedding light on Mg partitioning and isotope fractionation in geologic materials and providing a valuable complement to existing knowledge of Mg geochemistry.

  9. X-ray absorption near edge structure/electron energy loss near edge structure calculation using the supercell orthogonalized linear combination of atomic orbitals method

    NASA Astrophysics Data System (ADS)

    Ching, Wai-Yim; Rulis, Paul

    2009-03-01

    Over the last eight years, a large number of x-ray absorption near edge structure (XANES) and/or electron energy loss near edge structure (ELNES) spectroscopic calculations for complex oxides and nitrides have been performed using the supercell-OLCAO (orthogonalized linear combination of atomic orbitals) method, obtaining results in very good agreement with experiments. The method takes into account the core-hole effect and includes the dipole matrix elements calculated from ab initio wavefunctions. In this paper, we describe the method in considerable detail, emphasizing the special advantages of this method for large complex systems. Selected results are reviewed and several hitherto unpublished results are also presented. These include the Y K edge of Y ions segregated to the core of a Σ31 grain boundary in alumina, O K edges of water molecules, C K edges in different types of single walled carbon nanotubes, and the Co K edge in the cyanocobalamin (vitamin B12) molecule. On the basis of these results, it is argued that the interpretation of specific features of the calculated XANES/ELNES edges is not simple for complex material systems because of the delocalized nature of the conduction band states. The long-standing notion of the 'fingerprinting' technique for spectral interpretation of experimental data is not tenable. A better approach is to fully characterize the structure under study, using either crystalline data or accurate ab initio modeling. Comparison between calculated XANES/ELNES spectra and available measurements enables us to ascertain the validity of the modeled structure. For complex crystals or structures, it is necessary to use the weighted sum of the spectra from structurally nonequivalent sites for comparison with the measured data. Future application of the supercell-OLCAO method to complex biomolecular systems is also discussed.

  10. Speciation of sulfur in humic and fulvic acids using X-ray absorption near-edge structure (XANES) spectroscopy

    NASA Astrophysics Data System (ADS)

    Morra, Matthew J.; Fendorf, Scott E.; Brown, Paul D.

    1997-02-01

    Sulfur species in soils and sediments have previously been determined indirectly using destructive techniques. A direct and more accurate method for S speciation would improve our understanding of S biogeochemistry. X-ray absorption near edge structure (XANES) spectroscopy was performed on purified humic and fulvic acids from terrestrial and aquatic environments. This methodology allows direct determination of S species using the relationship that exists with the energy required for core electron transitions and in some cases, correlation with additional spectral features. Soil, peat, and aquatic humic acids were dominated by sulfonates with an oxidation state of +5, but also contained ester-bonded sulfates with an oxidation state of +6. Leonardite humic acid contained ester-bonded sulfate and an unidentified S compound with an oxidation state of +4.0. In contrast, high-valent S in soil, peat, and aquatic fulvic acids was exclusively in the form of sulfonic acids. Reduced S species were also present in both humic and fulvic acids. XANES is a valuable method for the speciation of S in humic materials and of potential use in S speciation of unfractionated soils.

  11. First-Principles Fe L 2,3 -Edge and O K-Edge XANES and XMCD Spectra for Iron Oxides

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

    Sassi, Michel; Pearce, Carolyn I.; Bagus, Paul S.

    X-ray absorption near-edge structure (XANES) and X-ray magnetic circular dichroism (XMCD) spectroscopies are tools in widespread use for providing detailed local atomic structure, oxidation state, and magnetic structure information for materials and organometallic complexes. The analysis of these spectra for transition-metal L-edges is routinely performed on the basis of ligand-field multiplet theory because one- and two-particle mean-field ab initio methods typically cannot describe the multiplet structure. Here we show that multireference configuration interaction (MRCI) calculations can satisfactorily reproduce measured XANES spectra for a range of complex iron oxide materials including hematite and magnetite. MRCI Fe L2,3-edge XANES and XMCD spectramore » of Fe(II)O6, Fe(III)O6, and Fe(III)O4 in magnetite are found to be in very good qualitative agreement with experiment and multiplet calculations. Point-charge embedding and small distortions of the first-shell oxygen ligands have only small effects. Oxygen K-edge XANES/XMCD spectra for magnetite investigated by a real-space Green’s function approach complete the very good qualitative agreement with experiment. Material-specific differences in local coordination and site symmetry are well reproduced, making the approach useful for assigning spectral features to specific oxidation states and coordination environments.« less

  12. Direct determination of oxidation state of gold deposits in metal-reducing bacterium Shewanella algae using X-ray absorption near-edge structure spectroscopy (XANES).

    PubMed

    Konishi, Yasuhiro; Tsukiyama, Takeshi; Saitoh, Norizoh; Nomura, Toshiyuki; Nagamine, Shinsuke; Takahashi, Yoshio; Uruga, Tomoya

    2007-06-01

    X-ray absorption near-edge structure spectroscopy (XANES) was successfully employed to determine the gold valence in the metal-reducing bacterium Shewanella algae after exposure to a 1 mM aqueous HAuCl4 solution for 10-120 min. XANES spectra revealed the oxidation state of gold in the bacterial cells to be Au(0) without any contribution from Au(III), demonstrating that S. algae cells can reduce AuCl4- ions to elemental gold. Transmission electron microscopy (TEM) and energy dispersive X-ray (EDX) analysis confirmed that gold nanoparticles 5-15 nm in size were deposited in the periplasmic space of the bacterial cells; a preferable, cell surface location for the easy recovery of biogenic nanoparticles.

  13. The origin of luminescence from di[4-(4-diphenylaminophenyl)phenyl]sulfone (DAPSF), a blue light emitter: an X-ray excited optical luminescence (XEOL) and X-ray absorption near edge structure (XANES) study.

    PubMed

    Zhang, Duo; Zhang, Hui; Zhang, Xiaohong; Sham, Tsun-Kong; Hu, Yongfeng; Sun, Xuhui

    2016-03-07

    The electronic structure and optical properties of di[4-(4-diphenylaminophenyl)phenyl]sulfone (denoted as DAPSF), a highly efficient fluorophor, have been investigated using X-ray excited optical luminescence (XEOL) and X-ray absorption near edge structure (XANES) spectroscopy at excitation energies across the C, N, O K-edges and the sulfur K-edge. The results indicate that the blue luminescence is mainly related to the sulfur functional group.

  14. Nitrogen K-edge x-ray absorption near edge structure of pyrimidine-containing nucleotides in aqueous solution

    NASA Astrophysics Data System (ADS)

    Shimada, Hiroyuki; Minami, Hirotake; Okuizumi, Naoto; Sakuma, Ichiro; Ukai, Masatoshi; Fujii, Kentaro; Yokoya, Akinari; Fukuda, Yoshihiro; Saitoh, Yuji

    2015-05-01

    X-ray absorption near edge structure (XANES) was measured at energies around the N K-edge of the pyrimidine-containing nucleotides, cytidine 5'-monophosphate (CMP), 2'-deoxythymidine 5'-monophosphate (dTMP), and uridine 5'-monophosphate (UMP), in aqueous solutions and in dried films under various pH conditions. The features of resonant excitations below the N K-edge in the XANES spectra for CMP, dTMP, and UMP changed depending on the pH of the solutions. The spectral change thus observed is systematically explained by the chemical shift of the core-levels of N atoms in the nucleobase moieties caused by structural changes due to protonation or deprotonation at different proton concentrations. This interpretation is supported by the results of theoretical calculations using density functional theory for the corresponding nucleobases in the neutral and protonated or deprotonated forms.

  15. Nitrogen K-edge x-ray absorption near edge structure of pyrimidine-containing nucleotides in aqueous solution

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

    Shimada, Hiroyuki, E-mail: hshimada@cc.tuat.ac.jp; Minami, Hirotake; Okuizumi, Naoto

    2015-05-07

    X-ray absorption near edge structure (XANES) was measured at energies around the N K-edge of the pyrimidine-containing nucleotides, cytidine 5′-monophosphate (CMP), 2′-deoxythymidine 5′-monophosphate (dTMP), and uridine 5′-monophosphate (UMP), in aqueous solutions and in dried films under various pH conditions. The features of resonant excitations below the N K-edge in the XANES spectra for CMP, dTMP, and UMP changed depending on the pH of the solutions. The spectral change thus observed is systematically explained by the chemical shift of the core-levels of N atoms in the nucleobase moieties caused by structural changes due to protonation or deprotonation at different proton concentrations.more » This interpretation is supported by the results of theoretical calculations using density functional theory for the corresponding nucleobases in the neutral and protonated or deprotonated forms.« less

  16. 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.

  17. 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.

  18. Identification of F impurities in F-doped ZnO by synchrotron X-ray absorption near edge structures

    NASA Astrophysics Data System (ADS)

    Na-Phattalung, Sutassana; Limpijumnong, Sukit; Min, Chul-Hee; Cho, Deok-Yong; Lee, Seung-Ran; Char, Kookrin; Yu, Jaejun

    2018-04-01

    Synchrotron X-ray absorption near edge structure (XANES) measurements of F K-edge in conjunction with first-principles calculations are used to identify the local structure of the fluorine (F) atom in F-doped ZnO. The ZnO film was grown by pulsed laser deposition with an Nd:YAG laser, and an oxyfluoridation method was used to introduce F ions into the ZnO films. The measured XANES spectrum of the sample was compared against the first-principles XANES calculations based on various models for local atomic structures surrounding F atoms. The observed spectral features are attributed to ZnF2 and FO defects in wurtzite bulk ZnO.

  19. Silicon K-edge XANES spectra of silicate minerals

    NASA Astrophysics Data System (ADS)

    Li, Dien; Bancroft, G. M.; Fleet, M. E.; Feng, X. H.

    1995-03-01

    Silicon K-edge x-ray absorption near-edge structure (XANES) spectra of a selection of silicate and aluminosilicate minerals have been measured using synchrotron radiation (SR). The spectra are qualitatively interpreted based on MO calculation of the tetrahedral SiO{4/4-}cluster. The Si K-edge generally shifts to higher energy with increased polymerization of silicates by about 1.3 eV, but with considerable overlap for silicates of different polymerization types. The substitution of Al for Si shifts the Si K-edge to lower energy. The chemical shift of Si K-edge is also sensitive to cations in more distant atom shells; for example, the Si K-edge shifts to lower energy with the substitution of Al for Mg in octahedral sites. The shifts of the Si K-edge show weak correlation with average Si-O bond distance (dSi-O), Si-O bond valence (sSi-O) and distortion of SiO4 tetrahedra, due to the crystal structure complexity of silicate minerals and multiple factors effecting the x-ray absorption processes.

  20. The interaction of copper ions with Staphylococcus aureus, Pseudomonas aeruginosa, and Escherichia coli: an X-ray absorption near-edge structure (XANES) spectroscopy study.

    PubMed

    Zanzen, Ulrike; Bovenkamp-Langlois, Lisa; Klysubun, Wantana; Hormes, Josef; Prange, Alexander

    2018-04-01

    The antimicrobial properties of copper ions have been known for a long time. However, the exact mechanism of action of the transition metal on microorganisms has long been unclear. X-ray absorption near-edge structure (XANES) spectroscopy at the Cu K edge allows the determination of copper speciation in Staphylococcus aureus, Escherichia coli, and Pseudomonas aeruginosa that have been treated with Cu(II) and Cu(I) solutions. The death/inactivation of the bacteria was observed using plate counting and light microscopy. The Cu K-XANES spectra of the two Gram-negative bacteria are different than those of the Gram-positive strain. The results clearly show that the Cu + -S bond contributes to the antibacterial activity of copper, as in the case of silver. The detailed evaluation of the differentiated absorption spectra shows that Cu + (not Cu 2+ ) is the dominant ion that binds to the bacteria. Because Cu + is not the most common copper ion, copper is not as effective an antibacterial agent as silver, whose common valency is actually + 1. Any reaction of copper with phosphorus from the bacteria can be excluded after the evaluation of the absorption spectra.

  1. X-Ray Absorption Near-Edge Structure (XANES) Spectroscopy Study of the Interaction of Silver Ions with Staphylococcus aureus, Listeria monocytogenes, and Escherichia coli

    PubMed Central

    Zanzen, Ulrike; Krishna, Katla Sai; Hormes, Josef

    2013-01-01

    Silver ions are widely used as antibacterial agents, but the basic molecular mechanism of this effect is still poorly understood. X-ray absorption near-edge structure (XANES) spectroscopy at the Ag LIII, S K, and P K edges reveals the chemical forms of silver in Staphylococcus aureus and Escherichia coli (Ag+ treated). The Ag LIII-edge XANES spectra of the bacteria are all slightly different and very different from the spectra of silver ions (silver nitrate and silver acetate), which confirms that a reaction occurs. Death or inactivation of bacteria was observed by plate counting and light microscopy. Silver bonding to sulfhydryl groups (Ag-S) in cysteine and Ag-N or Ag-O bonding in histidine, alanine, and dl-aspartic acid was detected by using synthesized silver-amino acids. Significantly lower silver-cysteine content, coupled with higher silver-histidine content, in Gram-positive S. aureus and Listeria monocytogenes cells indicates that the peptidoglycan multilayer could be buffering the biocidal effect of silver on Gram-positive bacteria, at least in part. Bonding of silver to phosphate groups was not detected. Interaction with DNA or proteins can occur through Ag-N bonding. The formation of silver-cysteine can be confirmed for both bacterial cell types, which supports the hypothesis that enzyme-catalyzed reactions and the electron transport chain within the cell are disrupted. PMID:23934494

  2. Use of X-ray absorption near edge structure (XANES) to identify physisorption and chemisorption of phosphate onto ferrihydrite-modified diatomite.

    PubMed

    Xiong, Wenhui; Peng, Jian; Hu, Yongfeng

    2012-02-15

    This paper presents a novel technique integrating bulk-sensitive and surface-sensitive XANES methods to distinguish between physisorption and chemisorption for phosphate adsorption onto ferrihydrite-modified diatomite (FHMD). XANES P K-edge, L-edge, and Fe M-edge spectra were obtained for reference samples (K(2)HPO(4) and FePO(4)·2H(2)O) and test samples (phosphate adsorbed onto FHMD (FHMD-Ps) and Si-containing ferrihydrite (FHYD-Ps)). A resolvable pre-edge peak in the P K-edge spectra of FHMD-Ps and FHYD-Ps provided direct evidence for the formation of P-O-Fe(III) coordination and the occurrence of chemisorption. The resemblance between the P L-edge spectra of K(2)HPO(4) and FHMD-Ps and the marked difference between the spectra of FHMD-Ps and FePO(4)·2H(2)O indicated the intact existence of the adsorbate and the adsorbent. The similarity between Fe M-edge spectra of FHMD and FHMD-Ps and the difference between the spectra of FHMD-Ps and FePO(4)·2H(2)O confirmed the findings from P L-edge analyses. Therefore, chemisorption and physisorption coexisted during phosphate adsorption onto FHMD. Phosphate chemisorption occurred in the deeper zone of FHMD (from 50 nm to 5 μm); whereas physisorption occurred in the zone of FHMD shallower than 50 nm since the probing depth of XANES P K-edge method is 5 μm and that of P L-edge and Fe M-edge methods is 50 nm. Copyright © 2011 Elsevier Inc. All rights reserved.

  3. Characterization of extracellular polymeric substances in the biofilms of typical bacteria by the sulfur K-edge XANES spectroscopy.

    PubMed

    Lin, Huirong; Ye, Chengsong; Lv, Lu; Zheng, Clark Renjun; Zhang, Shenghua; Zheng, Lei; Zhao, Yidong; Yu, Xin

    2014-08-01

    A combined approach of physicochemical extraction and sulfur K-edge X-ray absorption near-edge structure (XANES) spectroscopy was applied to characterize the extracellular polymeric substances (EPS) of typical bacterial biofilms in this study. Physicochemical analysis showed variation of the contents of DNA, polysaccharide and protein in different fractions of EPS in different mediums. The sulfur K-edge XANES analysis yielded a variety of spectra. Spectral fitting of the XANES spectra utilizing a large set of model compounds showed that there was more reduced sulfur in both LB-EPS (loosely bound EPS) and TB-EPS (tightly bound EPS) of all the biofilms in LB medium than in R2A medium. More oxidized sulfur was identified in LB-EPS than that in TB-EPS, suggesting different niches and physiological heterogeneity in the biofilms. Our results suggested that the sulfur K-edge XANES can be a useful tool to analyze the sulfur speciation in EPS of biofilms. Copyright © 2014. Published by Elsevier B.V.

  4. Near-edge X-ray absorption spectra for metallic Cu and Mn

    NASA Astrophysics Data System (ADS)

    Greaves, G. N.; Durham, P. J.; Diakun, G.; Quinn, P.

    1981-11-01

    The measurement of X-ray absorption fine structure of metals- both in the extended region (EXAFS) as well as in the near edge region (XANES)-has been widely discussed (see refs 1-6 for Cu and refs 7-9 for Mn). The recent availability of intense X-ray fluxes from storage rings has usually been exploited for EXAFS leaving the XANES often with poorer resolution than earlier work performed on conventional sources (for example, compare the near edge structure for copper in ref. 1 with refs 3 or 6). In addition, whilst the theory and analysis of EXAFS is relatively well-established2,10, a theory for the strong scattering regime near to the absorption edge has only recently been developed11. We report here the first high resolution XANES spectra for Cu and Mn which were performed at the SRS storage ring at Daresbury. Although both metals have close-packed structures consisting of atoms of similar size their local atomic structure is different in detail. Significant differences are found in their respective XANES reflecting the senstivity of this region of the X-ray absorption fine structure to the local atomic structure. Spectra for the two metals have been analysed using the new multiple scattering formalism. This is a real space calculation and unlike a conventional band structure approach it does not require structural periodicity but works from the local arrangement of atoms.

  5. Studies on absorption coefficient near edge of multi elements

    NASA Astrophysics Data System (ADS)

    Eisa, M. H.; Shen, H.; Yao, H. Y.; Mi, Y.; Zhou, Z. Y.; Hu, T. D.; Xie, Y. N.

    2005-12-01

    X-ray absorption near edge structure (XANES) was used to study the near edge mass-absorption coefficients of seven elements, such as, Ti, V, Fe, Co, Ni, Cu and Zn. It is well known that, on the near edge absorption of element, when incident X-ray a few eV change can make the absorption coefficient an order magnitude alteration. So that, there are only a few points mass-absorption coefficient at the near edge absorption and that always average value in published table. Our results showed a wide range of data, the total measured data of mass-absorption coefficient of the seven elements was about 505. The investigation confirmed that XANES is useful technique for multi-element absorption coefficient measurement. Details of experimental methods and results are given and discussed. The experimental work has been performed at Beijing Synchrotron Radiation Facility. The measured values were compared with the published data. Good agreement between experimental results and published data is obtained.

  6. Influence of point defects on the near edge structure of hexagonal boron nitride

    NASA Astrophysics Data System (ADS)

    McDougall, Nicholas L.; Partridge, Jim G.; Nicholls, Rebecca J.; Russo, Salvy P.; McCulloch, Dougal G.

    2017-10-01

    Hexagonal boron nitride (hBN) is a wide-band-gap semiconductor with applications including gate insulation layers in graphene transistors, far-ultraviolet light emitting devices and as hydrogen storage media. Due to its complex microstructure, defects in hBN are challenging to identify. Here, we combine x-ray absorption near edge structure (XANES) spectroscopy with ab initio theoretical modeling to identify energetically favorable defects. Following annealing of hBN samples in vacuum and oxygen, the B and N K edges exhibited angular-dependent peak modifications consistent with in-plane defects. Theoretical calculations showed that the energetically favorable defects all produce signature features in XANES. Comparing these calculations with experiments, the principle defects were attributed to substitutional oxygen at the nitrogen site, substitutional carbon at the boron site, and hydrogen passivated boron vacancies. Hydrogen passivation of defects was found to significantly affect the formation energies, electronic states, and XANES. In the B K edge, multiple peaks above the major 1 s to π* peak occur as a result of these defects and the hydrogen passivated boron vacancy produces the frequently observed doublet in the 1 s to σ* transition. While the N K edge is less sensitive to defects, features attributable to substitutional C at the B site were observed. This defect was also calculated to have mid-gap states in its band structure that may be responsible for the 4.1-eV ultraviolet emission frequently observed from this material.

  7. Aluminium X-ray absorption Near Edge Structure in model compounds and Earth's surface minerals

    NASA Astrophysics Data System (ADS)

    Ildefonse, P.; Cabaret, D.; Sainctavit, P.; Calas, G.; Flank, A.-M.; Lagarde, P.

    Aluminium K-edge X-ray absorption near edge spectra (XANES) of a suite of silicate and oxides minerals consist of electronic excitations occurring in the edge region, and multiple scattering resonances at higher energies. The main XANES feature for four-fold Al is at around 2 eV lower energy than the main XANES feature for six-fold Al. This provides a useful probe for coordination numbers in clay minerals, gels, glasses or material with unknown Al-coordination number. Six-fold aluminium yields a large variety of XANES features which can be correlated with octahedral point symmetry, number of aluminium sites and distribution of Al-O distances. These three parameters may act together, and the quantitative interpretation of XANES spectra is difficult. For a low point symmetry (1), variations are mainly related to the number of Al sites and distribution of Al-O distances: pyrophyllite, one Al site, is clearly distinguished from kaolinite and gibbsite presenting two Al sites. For a given number of Al-site (1), variations are controlled by changes in point symmetry, the number of XANES features being increased as point symmetry decreases. For a given point symmetry (1) and a given number of Al site (1), variations are related to second nearest neighbours (gibbsite versus kaolinite). The amplitude of the XANES feature at about 1566 eV is a useful probe for the assessment of AlIV/Altotal ratios in 2/1 phyllosilicates. Al-K XANES has been performed on synthetic Al-bearing goethites which cannot be studied by 27Al NMR. At low Al content, Al-K XANES is very different from that of α-AlOOH but at the highest level, XANES spectrum tends to that of diaspore. Al-K XAS is thus a promising tool for the structural study of poorly ordered materials such as clay minerals and natural alumino-silicate gels together with Al-subsituted Fe-oxyhydroxides.

  8. Borosilicate glass structure: An investigation of high resolution B K-edge XANES

    NASA Astrophysics Data System (ADS)

    Dong, S.; Henderson, G. S.; Galoisy, L.; Calas, G.

    2009-05-01

    The Alkali-borosilicate glasses in the systems Na2O-B2O3-SiO2 and K2O- B2O3-SiO2 have been prepared by melting/quenching in air and studied using synchrotron radiation B K-edge XANES to estimate the evolution of boron coordination as a function of composition. The ratio of alkali/B2O3 (R) and SiO2/B2O3 (K) in the glasses are respectively between 0.5 to 2.0 and 0.5 to 7.0. The edge features of trigonal B ([3]B) and tetrahedral B ([4]B) in B K-edge XANES spectra have been interpreted carefully from B standards such as (B2O3 and BPO4), as well as, a wide range of borate minerals. We find that the proportion of tetrahedral B in glass is increasing as a function of both R and K, similar to previous studies. Contributions of the [3]B and [4]B features to the B K-edge XANES is complex with 6-7 individual transitions contributing to the overall spectral envelope. Many of these transitions are common to both B coordination states making extraction of quantitative [4]B numbers difficult. However, we can calculate the proportion of tetrahedral B accurately by appropriate curve- fitting.

  9. Analysis of the detailed configuration of hydrated lanthanoid(III) ions in aqueous solution and crystalline salts by using K- and L(3)-edge XANES spectroscopy.

    PubMed

    D'Angelo, Paola; Zitolo, Andrea; Migliorati, Valentina; Persson, Ingmar

    2010-01-11

    The structural properties of the hydrated lanthanoid(III) ions in aqueous solution and in the isostructural trifluoromethanesulfonate salts have been investigated by a quantitative analysis of the X-ray absorption near-edge structure (XANES) spectra at the K- and L(3)-edges. The XANES analysis has provided a clear description of the variation of lanthanoid(III) hydration properties across the series. It was found that all of the lanthanoid(III) hydration complexes retain a tricapped trigonal prism (TTP) geometry, and along the series two of the capping water molecules become less and less strongly bound, before finally, on average, one of them leaves the hydration cluster. This gives rise to an eight-coordinated distorted bicapped trigonal prism with two different Ln--O capping distances for the smallest lanthanoid(III) ions. This systematic study has shown that for lanthanoid compounds more accurate structural information is obtained from the analysis of the L(3)-edge than from K-edge XANES data. Moreover, whereas the second hydration shells provide a detectable contribution to the L(3)-edge XANES spectra of the lighter lanthanoid ions, the K-edge spectra are insensitive to the more distant coordination spheres.

  10. Structural evolution of fluorinated graphene upon molten-alkali treatment probed by X-ray absorption near-edge structure spectroscopy

    NASA Astrophysics Data System (ADS)

    Liang, Xianqing; Pan, Deyou; Lao, Ming; Liang, Shuiying; Huang, Dan; Zhou, Wenzheng; Guo, Jin

    2017-05-01

    The structural evolution of fluorinated graphene (FG) nanosheets upon molten-alkali treatment has been systematically investigated utilizing X-ray absorption near-edge structure (XANES) spectroscopy. It is found that the hydroxyl groups can progressively displace fluorine atoms to form covalent bonds to the graphene sheets under designed molten-alkali condition. The XANES spectra also reveal the formation of epoxide groups through intramolecular dehydration of neighbouring hydroxyl groups after substitution reaction. At high alkali-FG weight ratio, the restoration of the π-conjugated structure in graphene sheets can be observed due to the gradual decomposition of epoxide groups. Our experimental results indicate that the surface chemistry and electronic structure of hydroxyl-functionalized FG (HFG) can be readily tuned by varying the ratio of reactants.

  11. Application toward Confocal Full-Field Microscopic X-ray Absorption Near Edge Structure Spectroscopy.

    PubMed

    Tack, Pieter; Vekemans, Bart; Laforce, Brecht; Rudloff-Grund, Jennifer; Hernández, Willinton Y; Garrevoet, Jan; Falkenberg, Gerald; Brenker, Frank; Van Der Voort, Pascal; Vincze, Laszlo

    2017-02-07

    Using X-ray absorption near edge structure (XANES) spectroscopy, information on the local chemical structure and oxidation state of an element of interest can be acquired. Conventionally, this information can be obtained in a spatially resolved manner by scanning a sample through a focused X-ray beam. Recently, full-field methods have been developed to obtain direct 2D chemical state information by imaging a large sample area. These methods are usually in transmission mode, thus restricting the use to thin and transmitting samples. Here, a fluorescence method is displayed using an energy-dispersive pnCCD detector, the SLcam, characterized by measurement times far superior to what is generally applicable. Additionally, this method operates in confocal mode, thus providing direct 3D spatially resolved chemical state information from a selected subvolume of a sample, without the need of rotating a sample. The method is applied to two samples: a gold-supported magnesia catalyst (Au/MgO) and a natural diamond containing Fe-rich inclusions. Both samples provide XANES spectra that can be overlapped with reference XANES spectra, allowing this method to be used for fingerprinting and linear combination analysis of known XANES reference compounds.

  12. Effect of aluminum on the local structure of silicon in zeolites as studied by Si K edge X-ray absorption near-edge fine structure: spectra simulation with a non-muffin tin atomic background.

    PubMed

    Bugaev, Lusegen A; Bokhoven, Jeroen A van; Khrapko, Valerii V

    2009-04-09

    Experimental Si K edge X-ray absorption near-edge fine structure (XANES) of zeolite faujasite, mordenite, and beta are interpreted by means of the FEFF8 code, replacing the theoretical atomic background mu(0) by a background that was extracted from an experimental spectrum. To some extent, this diminished the effect of the inaccuracy introduced by the MT potential and accounted for the intrinsic loss of photoelectrons. The agreement of the theoretical and experimental spectra at energies above the white lines enabled us to identify structural distortion around silicon, which occurs with increasing aluminum content. The Si K edge XANES spectra are very sensitive to slight distortions in the silicon coordination. Placing an aluminum atom on a nearest neighboring T site causes a distortion in the silicon tetrahedron, shortening one of the silicon-oxygen bonds relative to the other three.

  13. Chemical forms of sulfur in geological and archeological asphaltenes from Middle East, France, and Spain determined by sulfur K- and L-edge X-ray absorption near-edge structure spectroscopy

    NASA Astrophysics Data System (ADS)

    Sarret, Géraldine; Connan, Jacques; Kasrai, Masoud; Bancroft, G. Michael; Charrié-Duhaut, Armelle; Lemoine, Sylvie; Adam, Pierre; Albrecht, Pierre; Eybert-Bérard, Laurent

    1999-11-01

    Asphaltene samples extracted from archeological and geological bitumens from the Middle East, France, and Spain were studied by sulfur K- and L-edge X-ray absorption near-edge structure (XANES) spectroscopy in combination with isotopic analyses (δ 13C and δD). Within each series, the samples were genetically related by their δ 13C values. The gross and elemental composition and the δD values were used to characterize the weathering state of the samples. Sulfur K- and L-edge XANES results show that in all the samples, dibenzothiophenes are the dominant forms of sulfur. In the least oxidized asphaltenes, minor species include disulfides, alkyl and aryl sulfides, and sulfoxides. With increasing alteration the proportion of oxidized sulfur (sulfoxides, sulfones, sulfonates and sulfates) increases, whereas the disulfide and sulfide content decreases. This evolution is observed in all the series, regardless of the origin of the asphaltenes. This work illustrates the advantages of XANES spectroscopy as a selective probe for determining sulfur speciation in natural samples. It also shows that S K- and L-edge XANES spectroscopy are complementary for identifying the oxidized and reduced forms of sulfur, respectively.

  14. Polarized XANES Monitors Femtosecond Structural Evolution of Photoexcited Vitamin B 12

    DOE PAGES

    Miller, Nicholas A.; Deb, Aniruddha; Alonso-Mori, Roberto; ...

    2017-01-30

    Ultrafast, polarization-selective time-resolved X-ray absorption near-edge structure (XANES) was used to characterize the photochemistry of vitamin B 12, cyanocobalamin (CNCbl), in solution. Cobalamins are important biological cofactors involved in methyl transfer, radical rearrangement, and light-activated gene regulation, while also holding promise as light-activated agents for spatiotemporal controlled delivery of therapeutics. We introduce polarized femtosecond XANES, combined with UV–visible spectroscopy, to reveal sequential structural evolution of CNCbl in the excited electronic state. Femtosecond polarized XANES provides the crucial structural dynamics link between computed potential energy surfaces and optical transient absorption spectroscopy. Polarization selectivity can be used to uniquely identify electronic contributionsmore » and structural changes, even in isotropic samples when well-defined electronic transitions are excited. Our XANES measurements reveal that the structural changes upon photoexcitation occur mainly in the axial direction, where elongation of the axial Co–CN bond and Co–N Im bond on a 110 fs time scale is followed by corrin ring relaxation on a 260 fs time scale. In conclusion, these observations expose features of the potential energy surfaces controlling cobalamin reactivity and deactivation.« less

  15. Polarized XANES Monitors Femtosecond Structural Evolution of Photoexcited Vitamin B 12

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

    Miller, Nicholas A.; Deb, Aniruddha; Alonso-Mori, Roberto

    Ultrafast, polarization-selective time-resolved X-ray absorption near-edge structure (XANES) was used to characterize the photochemistry of vitamin B 12, cyanocobalamin (CNCbl), in solution. Cobalamins are important biological cofactors involved in methyl transfer, radical rearrangement, and light-activated gene regulation, while also holding promise as light-activated agents for spatiotemporal controlled delivery of therapeutics. We introduce polarized femtosecond XANES, combined with UV–visible spectroscopy, to reveal sequential structural evolution of CNCbl in the excited electronic state. Femtosecond polarized XANES provides the crucial structural dynamics link between computed potential energy surfaces and optical transient absorption spectroscopy. Polarization selectivity can be used to uniquely identify electronic contributionsmore » and structural changes, even in isotropic samples when well-defined electronic transitions are excited. Our XANES measurements reveal that the structural changes upon photoexcitation occur mainly in the axial direction, where elongation of the axial Co–CN bond and Co–N Im bond on a 110 fs time scale is followed by corrin ring relaxation on a 260 fs time scale. In conclusion, these observations expose features of the potential energy surfaces controlling cobalamin reactivity and deactivation.« less

  16. Full-Field Calcium K-Edge X-ray Absorption Near-Edge Structure Spectroscopy on Cortical Bone at the Micron-Scale: Polarization Effects Reveal Mineral Orientation.

    PubMed

    Hesse, Bernhard; Salome, Murielle; Castillo-Michel, Hiram; Cotte, Marine; Fayard, Barbara; Sahle, Christoph J; De Nolf, Wout; Hradilova, Jana; Masic, Admir; Kanngießer, Birgit; Bohner, Marc; Varga, Peter; Raum, Kay; Schrof, Susanne

    2016-04-05

    Here, we show results on X-ray absorption near edge structure spectroscopy in both transmission and X-ray fluorescence full-field mode (FF-XANES) at the calcium K-edge on human bone tissue in healthy and diseased conditions and for different tissue maturation stages. We observe that the dominating spectral differences originating from different tissue regions, which are well pronounced in the white line and postedge structures are associated with polarization effects. These polarization effects dominate the spectral variance and must be well understood and modeled before analyzing the very subtle spectral variations related to the bone tissue variations itself. However, these modulations in the fine structure of the spectra can potentially be of high interest to quantify orientations of the apatite crystals in highly structured tissue matrices such as bone. Due to the extremely short wavelengths of X-rays, FF-XANES overcomes the limited spatial resolution of other optical and spectroscopic techniques exploiting visible light. Since the field of view in FF-XANES is rather large the acquisition times for analyzing the same region are short compared to, for example, X-ray diffraction techniques. Our results on the angular absorption dependence were verified by both site-matched polarized Raman spectroscopy, which has been shown to be sensitive to the orientation of bone building blocks and by mathematical simulations of the angular absorbance dependence. As an outlook we further demonstrate the polarization based assessment of calcium-containing crystal orientation and specification of calcium in a beta-tricalcium phosphate (β-Ca3(PO4)2 scaffold implanted into ovine bone. Regarding the use of XANES to assess chemical properties of Ca in human bone tissue our data suggest that neither the anatomical site (tibia vs jaw) nor pathology (healthy vs necrotic jaw bone tissue) affected the averaged spectral shape of the XANES spectra.

  17. Study on Coloration Mechanism of Chinese Ancient Ceramics by X-ray Absorption Near-edge Structure

    NASA Astrophysics Data System (ADS)

    Peng, Y. H.; Xie, Z.; He, J. F.; Liu, Q. H.; Pan, Z. Y.; Cheng, W. R.; Wei, S. Q.

    2013-04-01

    The Fe K-edge X-ray absorption near-edge structure (XANES) spectra of a series of ceramic shards were measured by fluorescence mode to reveal the color-generating techniques of Chinese porcelain. The analysis disclosed relationships among the chemical form of the iron, the firing conditions and the colors of the ceramics. The results indicate that the coloration for different ceramics depend on the valence states of iron as the main color element in glaze and the proportion of Fe2+ and Fe3+ was attributed to the baking technology. The findings provide important information for archaeologist on the coloration researches.

  18. Dynamic study of sub-micro sized LiFePO4 cathodes by in-situ tender X-ray absorption near edge structure

    NASA Astrophysics Data System (ADS)

    Wang, Dongniu; Wang, Huixin; Yang, Jinli; Zhou, Jigang; Hu, Yongfeng; Xiao, Qunfeng; Fang, Haitao; Sham, Tsun-Kong

    2016-01-01

    Olivine-type phosphates (LiMPO4, M = Fe, Mn, Co) are promising cathode materials for lithium-ion batteries that are generally accepted to follow first order equilibrium phase transformations. Herein, the phase transformation dynamics of sub-micro sized LiFePO4 particles with limited rate capability at a low current density of 0.14 C was investigated. An in-situ X-ray Absorption Near Edge Structure (XANES) measurement was conducted at the Fe and P K-edge for the dynamic studies upon lithiation and delithiation. Fe K-edge XANES spectra demonstrate that not only lithium-rich intermediate phase LixFePO4 (x = 0.6-0.75), but also lithium-poor intermediate phase LiyFePO4 (y = 0.1-0.25) exist during the charge and discharge, respectively. Furthermore, during charge and discharge, a fluctuation of the FePO4 and LiFePO4 fractions obtained by liner combination fitting around the imaginary phase fractions followed Faraday's law and the equilibrium first-order two-phase transformation versus reaction time is present, respectively. The charging and discharging process has a reversible phase transformation dynamics with symmetric structural evolution routes. P K-edge XANES spectra reveal an enrichment of PF6-1 anions at the surface of the electrode during charging.

  19. Solving local structure around dopants in metal nanoparticles with ab initio modeling of X-ray absorption near edge structure

    DOE PAGES

    Timoshenko, J.; Shivhare, A.; Scott, R. W.; ...

    2016-06-30

    We adopted ab-initio X-ray Absorption Near Edge Structure (XANES) modelling for structural refinement of local environments around metal impurities in a large variety of materials. Our method enables both direct modelling, where the candidate structures are known, and the inverse modelling, where the unknown structural motifs are deciphered from the experimental spectra. We present also estimates of systematic errors, and their influence on the stability and accuracy of the obtained results. We illustrate our approach by following the evolution of local environment of palladium atoms in palladium-doped gold thiolate clusters upon chemical and thermal treatments.

  20. Near-edge study of gold-substituted YBa2Cu3O(7-delta)

    NASA Technical Reports Server (NTRS)

    Ruckman, Mark W.; Hepp, Aloysius F.

    1991-01-01

    The valence of Cu and Au in YBa2Au0.3Cu2.7O7-delta was investigated using X-ray absorption near edge structure (XANES). X-ray and neutron diffraction studies indicate that Au goes on the Cu(1) site and Cu K-edge XANES shows that this has little effect on the oxidation state of the remaining copper. The Au L3 edge develops a white line feature whose position lies between that of trivalent gold oxide and monovalent potassium gold cyanide, and whose height relative to the edge step is smaller than in the two reference compounds. The appearance of the Au L3 edge suggests that fewer Au 3d states are involved in forming the Au-O bond in YBa2Au0.3Cu2.7O7-delta than in trivalent gold oxide.

  1. Near-edge study of gold-substituted YBa2Cu3O(7-delta)

    NASA Technical Reports Server (NTRS)

    Ruckman, Mark W.; Hepp, Aloysius F.

    1991-01-01

    The valence of Cu and Au in YBa2Au0.3Cu2.7O7-delta was investigated using x-ray absorption near edge structure (XANES). X-ray and neutron diffraction studies indicate that Au goes on the Cu(1) site and Cu K-edge XANES shows that this has little effect on the oxidation state of the remaining copper. The Au L3 edge develops a white line feature whose position lies between that of trivalent gold oxide and monovalent potassium gold cyanide, and whose height relative to the edge step is smaller than in the two reference compounds. The appearance of the Au L3 edge suggests that fewer Au 3d states are involved in forming the Au-O bond in YBa2Au0.3Cu2.7O7-delta than in trivalent gold oxide.

  2. Electronic structure of Cr doped Fe3O4 thin films by X-ray absorption near-edge structure spectroscopy

    NASA Astrophysics Data System (ADS)

    Chen, Chi-Liang; Dong, Chung-Li; Asokan, Kandasami; Chern, G.; Chang, C. L.

    2018-04-01

    Present study reports the electronic structures of Cr doped Fe3O4 (Fe3-xCrxO4 (0 ≤ x ≤ 3) grown on MgO (100) substrates in the form of thin films fabricated by a plasma-oxygen assisted Molecular Beam Epitaxy (MBE). X-ray absorption near-edge structure (XANES) spectra at Cr & Fe L-, and O K-edges were used to understand the electronic structure: changes in the bonding nature, valence states, and site occupancies. Cr doping in Fe3O4 results in the change of charge transfer, crystal structure, and selective occupation of ions in octahedral and tetrahedral sites. Such change modifies the electrical and magnetic properties due to the covalency of Cr ions. The physical and chemical properties of ferrites are strongly dependent on the lattice site, ion size of dopant, and magnetic nature present at different structural symmetry of the spinel structure.

  3. Iron K-edge X-ray absorption near-edge structure spectroscopy of aerodynamically levitated silicate melts and glasses

    DOE PAGES

    Alderman, O. L. G.; Wilding, M. C.; Tamalonis, A.; ...

    2017-01-26

    Here, the local structure about Fe(II) and Fe(III) in silicate melts was investigated in-situ using iron K-edge X-ray absorption near-edge structure (XANES) spectroscopy. An aerodynamic levitation and laser heating system was used to allow access to high temperatures without contamination, and was combined with a chamber and gas mixing system to allow the iron oxidation state, Fe 3+/ΣFe, to be varied by systematic control of the atmospheric oxygen fugacity. Eleven alkali-free, mostly iron-rich and depolymerized base compositions were chosen for the experiments, including pure oxide FeO, olivines (Fe,Mg) 2SiO 4, pyroxenes (Fe,Mg)SiO 3, calcic FeO-CaSiO 3, and a calcium aluminosilicatemore » composition, where total iron content is denoted by FeO for convenience. Melt temperatures varied between 1410 and 2160 K and oxygen fugacities between FMQ – 2.3(3) to FMQ + 9.1(3) log units (uncertainties in parentheses) relative to the fayalite-magnetite-β-quartz (FMQ) buffer.« less

  4. Experimental and theoretical XANES of CdSxSe1-x nanostructures

    NASA Astrophysics Data System (ADS)

    Yiu, Y. M.; Murphy, M. W.; Liu, L.; Hu, Y.; Sham, T. K.

    2014-03-01

    The morphology and electronic properties of the CdSxSe1-x nanostructures with varying alloy compositions have been acquired experimentally by X-ray Absorption Near-Edge Structures (XANES) at the Cd, Se and S K-edge and L3,2-edges. The theoretical XANES spectra have been calculated using the density functional approach. It is found that the optical band-gap emission of these CdSxSe1-x nano-ribbons can be tuned to the range between that of pure CdS (2.43 eV) and CdSe (1.74 eV) by changing the S and Se ratio. This gradual shift in (optical and structural) properties from CdS character to CdSe character is also seen in the electronic structures. The densities of states and band structures show that with the addition of Se replacing S in CdS, the band gap shrinks. The K and L3,2 edges of Cd, Se, and S of the XANES structures of both the CdS and CdSe in B4 (wurtzite) and B3 (cubic zinc-blende) structures have been calculated and compared.

  5. Effects of strain relaxation in Pr 0.67Sr 0.33MnO 3 films probed by polarization dependent X-ray absorption near edge structure

    DOE PAGES

    zhang, Bangmin; Chen, Jingsheng; Venkatesan, T.; ...

    2016-01-28

    In this study, the Mn K edge X-ray absorption near edge structure (XANES) of Pr 0.67Sr 0.33MnO 3 films with different thicknesses on (001) LaAlO 3 substrate were measured, and the effects of strain relaxation on film properties were investigated. The films experienced in-plane compressive strain and out-of-plane tensile strain. Strain relaxation evolved with the film thickness. In the polarization dependent XANES measurements, the in-plane (parallel) and out-of-plane (perpendicular) XANES spectrocopies were anisotropic with different absorption energy E r. The resonance energy Er along two directions shifted towards each other with increasing film thickness. Based on the X-ray diffraction results,more » it was suggested that the strain relaxation weakened the difference of the local environment and probability of electronic charge transfer (between Mn 3d and O 2p orbitals) along the in-plane and out-of-plane directions, which was responsible for the change of E r. XANES is a useful tool to probe the electronic structures, of which the effects on magnetic properties with the strain relaxation was also been studied.« less

  6. Identification of Second Shell Coordination in Transition Metal Species Using Theoretical XANES: Example of Ti–O–(C, Si, Ge) Complexes

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

    Spanjers, Charles S.; Guillo, Pascal; Tilley, T. Don

    X-ray absorption near-edge structure (XANES) is a common technique for elucidating oxidation state and first shell coordination geometry in transition metal complexes, among many other materials. However, the structural information obtained from XANES is often limited to the first coordination sphere. In this study, we show how XANES can be used to differentiate between C, Si, and Ge in the second coordination shell of Ti–O–(C, Si, Ge) molecular complexes based on differences in their Ti K-edge XANES spectra. Experimental spectra were compared with theoretical spectra calculated using density functional theory structural optimization and ab initio XANES calculations. The unique featuresmore » for second shell C, Si, and Ge present in the Ti K pre-edge XANES are attributed to the interaction between the Ti center and the O–X (X = C, Si, or Ge) antibonding orbitals.« less

  7. A New Look at the Structural and Magnetic Properties of Potassium Neptunate K2NpO4 Combining XRD, XANES Spectroscopy, and Low-Temperature Heat Capacity.

    PubMed

    Smith, Anna L; Colineau, Eric; Griveau, Jean-Christophe; Popa, Karin; Kauric, Guilhem; Martin, Philippe; Scheinost, Andreas C; Cheetham, Anthony K; Konings, Rudy J M

    2017-05-15

    The physicochemical properties of the potassium neptunate K 2 NpO 4 have been investigated in this work using X-ray diffraction, X-ray absorption near edge structure (XANES) spectroscopy at the Np-L 3 edge, and low-temperature heat capacity measurements. A Rietveld refinement of the crystal structure is reported for the first time. The Np(VI) valence state has been confirmed by the XANES data, and the absorption edge threshold of the XANES spectrum has been correlated to the Mössbauer isomer shift value reported in the literature. The standard entropy and heat capacity of K 2 NpO 4 have been derived at 298.15 K from the low-temperature heat capacity data. The latter suggest the existence of a magnetic ordering transition around 25.9 K, most probably of the ferromagnetic type.

  8. X-ray absorption near-edge structure micro-spectroscopy study of vanadium speciation in Phycomyces blakesleeanus mycelium.

    PubMed

    Žižić, Milan; Dučić, Tanja; Grolimund, Daniel; Bajuk-Bogdanović, Danica; Nikolic, Miroslav; Stanić, Marina; Križak, Strahinja; Zakrzewska, Joanna

    2015-09-01

    Vanadium speciation in the fungus Phycomyces blakesleeanus was examined by X-ray absorption near-edge structure (XANES) spectroscopy, enabling assessment of oxidation states and related molecular symmetries of this transition element in the fungus. The exposure of P. blakesleeanus to two physiologically important vanadium species (V(5+) and V(4+)) resulted in the accumulation of this metal in central compartments of 24 h old mycelia, most probably in vacuoles. Tetrahedral V(5+), octahedral V(4+), and proposed intracellular complexes of V(5+) were detected simultaneously after addition of a physiologically relevant concentration of V(5+) to the mycelium. A substantial fraction of the externally added V(4+) remained mostly in its original form. However, observable variations in the pre-edge-peak intensities in the XANES spectra indicated intracellular complexation and corresponding changes in the molecular coordination symmetry. Vanadate complexation was confirmed by (51)V NMR and Raman spectroscopy, and potential binding compounds including cell-wall constituents (chitosan and/or chitin), (poly)phosphates, DNA, and proteins are proposed. The evidenced vanadate complexation and reduction could also explain the resistance of P. blakesleeanus to high extracellular concentrations of vanadium.

  9. In Situ X-ray Absorption Near-Edge Structure Spectroscopy of ZnO Nanowire Growth During Chemical Bath Deposition

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

    McPeak, Kevin M.; Becker, Matthew A.; Britton, Nathan G.

    2010-12-03

    Chemical bath deposition (CBD) offers a simple and inexpensive route to deposit semiconductor nanostructures, but lack of fundamental understanding and control of the underlying chemistry has limited its versatility. Here we report the first use of in situ X-ray absorption spectroscopy during CBD, enabling detailed investigation of both reaction mechanisms and kinetics of ZnO nanowire growth from zinc nitrate and hexamethylenetetramine (HMTA) precursors. Time-resolved X-ray absorption near-edge structure (XANES) spectra were used to quantify Zn(II) speciation in both solution and solid phases. ZnO crystallizes directly from [Zn(H{sub 2}O){sub 6}]{sup 2+} without long-lived intermediates. Using ZnO nanowire deposition as an example,more » this study establishes in situ XANES spectroscopy as an excellent quantitative tool to understand CBD of nanomaterials.« less

  10. XANES study of hydrogen incorporation in a Pd-capped Nb thin film

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

    Ruckman, M.W.; Reisfeld, G.; Jisrawi, N.M.

    X-ray absorption near-edge structure (XANES) measurements were used to probe the H-charging-induced electronic structure changes of a 2400 {Angstrom} Nb film capped with Pd. These results are discussed in terms of {ital ab initio} linear augmented plane-wave (LAPW) band-structure calculations for this material. The Pd-L{sub 3}-edge XANES clearly manifested the spectral (Pd-d state related) changes expected for Pd-hydride formation, a white line feature degradation, and the appearance of a Pd-H antibonding feature at 6 eV above the threshold. The Nb-L{sub 2,3} edge changes with H charging show a distinct enhancement of the white line strength; a feature 6 eV abovemore » the edges, associated with Nb-H antibonding states in analogy with the Pd results; the suppression of a threshold-onset feature of Nb metal; and a shift of the centrum of the white line feature towards the threshold. Comparison of the Nb sphere projection of the d{sub 3/2} component of the LAPW density of states (DOS) to the Nb-L{sub 2}-edge spectra yields good basic agreement with the observed spectral changes. In particular, the substantial theoretical reduction in the DOS at, and just above, the Fermi energy (E{sub f}) is directly related to the near threshold Nb-L{sub 2,3} spectral changes. The more modest white line enhancement in the theoretical DOS is noted and discussed. Nb-K-edge XANES are also discussed in terms of the Nb-site p-state projected LAPW DOS. This last comparison indicates a p-state reduction near E{sub f} upon H charging of the Nb. {copyright} {ital 1998} {ital The American Physical Society}« less

  11. The speciation of soluble sulphur compounds in bacterial culture fluids by X-ray absorption near edge structure spectroscopy.

    PubMed

    Franz, Bettina; Lichtenberg, Henning; Hormes, Josef; Dahl, Christiane; Prange, Alexander

    2009-11-01

    Over the last decade X-ray absorption near edge structure (XANES) spectroscopy has been used in an increasing number of microbiological studies. In addition to other applications it has served as a valuable tool for the investigation of the sulphur globules deposited intra- or extracellularly by certain photo- and chemotrophic sulphur-oxidizing (Sox) bacteria. For XANES measurements, these deposits can easily be concentrated by filtration or sedimentation through centrifugation. However, during oxidative metabolism of reduced sulphur compounds, such as sulphide or thiosulphate, sulphur deposits are not the only intermediates formed. Soluble intermediates such as sulphite may also be produced and released into the medium. In this study, we explored the potential of XANES spectroscopy for the detection and speciation of sulphur compounds in culture supernatants of the phototrophic purple sulphur bacterium Allochromatium vinosum. More specifically, we investigated A. vinosum DeltasoxY, a strain with an in frame deletion of the soxY gene. This gene encodes an essential component of the thiosulphate-oxidizing Sox enzyme complex. Improved sample preparation techniques developed for the DeltasoxY strain allowed for the first time not only the qualitative but also the quantitative analysis of bacterial culture supernatants by XANES spectroscopy. The results thus obtained verified and supplemented conventional HPLC analysis of soluble sulphur compounds. Sulphite and also oxidized organic sulphur compounds were shown by XANES spectroscopy to be present, some of which were not seen when standard HPLC protocols were used.

  12. Temperature dependence of pre-edge features in Ti K-edge XANES spectra for ATiO₃ (A = Ca and Sr), A₂TiO₄ (A = Mg and Fe), TiO₂ rutile and TiO₂ anatase.

    PubMed

    Hiratoko, Tatsuya; Yoshiasa, Akira; Nakatani, Tomotaka; Okube, Maki; Nakatsuka, Akihiko; Sugiyama, Kazumasa

    2013-07-01

    XANES (X-ray absorption near-edge structure) spectra of the Ti K-edges of ATiO3 (A = Ca and Sr), A2TiO4 (A = Mg and Fe), TiO2 rutile and TiO2 anatase were measured in the temperature range 20-900 K. Ti atoms for all samples were located in TiO6 octahedral sites. The absorption intensity invariant point (AIIP) was found to be between the pre-edge and post-edge. After the AIIP, amplitudes damped due to Debye-Waller factor effects with temperature. Amplitudes in the pre-edge region increased with temperature normally by thermal vibration. Use of the AIIP peak intensity as a standard point enables a quantitative comparison of the intensity of the pre-edge peaks in various titanium compounds over a wide temperature range.

  13. XANES analysis of dried and calcined bones.

    PubMed

    Rajendran, Jayapradhi; Gialanella, Stefano; Aswath, Pranesh B

    2013-10-01

    The structure of dried and calcined bones from chicken, bovine, deer, pig, sheep and chamois was examined using X-ray Absorption Near Edge Structure (XANES) spectroscopy. The oxygen K-edge absorption edge indicates that the surface of dried bone has a larger proportion of carbonate than the interior that is made up of phosphates. The phosphorus L and K edge clearly indicate that pyrophosphates, α-tricalcium phosphate (α-TCP) and hydrogen phosphates of Ca do not exist in either the dried bone or calcined bone and phosphorus exists as either β-tricalcium phosphate (β-TCP) or hydroxyapatite, both in the dried and calcined conditions. The Ca K-edge analysis indicates that β-TCP is the likely form of phosphate in both the dried and calcined conditions. Copyright © 2013 Elsevier B.V. All rights reserved.

  14. Fe K-Edge X-ray absorption near-edge spectroscopy (XANES) and X-ray diffraction (XRD) analyses of LiFePO4 and its base materials

    NASA Astrophysics Data System (ADS)

    Latif, C.; Negara, V. S. I.; Wongtepa, W.; Thamatkeng, P.; Zainuri, M.; Pratapa, S.

    2018-03-01

    XANES analysis has been performed with the aim of knowing the Fe oxidation state in a synthesized LiFePO4 and its base materials. XANES measurements were performed at SLRI on energy around Fe K-edge. An XRD analysis has also been performed with the aim of knowing the phase composition, lattice parameters and crystallite size of the LiFePO4 as well as the base materials. From the XRD analysis, it was found that the dominating phase in the iron sand sample was Fe3O4 and the only phase found after calcination was LiFePO4. The latter phase exhibited crystallite size of 100 nm and lattice parameters a = 10.169916 Å, b = 5.919674 Å, c = 4.627893 Å. Qualitative analysis of XANES data revealed that the oxidation number of Fe in the sample before calcination was greater than that after calcination and Fe in the natural iron sand, indicated by the E0 values of 7129.2 eV, 7120.6 eV and 7124.4 eV respectively.

  15. Local Environment Sensitivity of the Cu K-Edge XANES Features in Cu-SSZ-13: Analysis from First-Principles.

    PubMed

    Zhang, Renqin; McEwen, Jean-Sabin

    2018-05-22

    Cu K-edge X-ray absorption near-edge spectra (XANES) have been widely used to study the properties of Cu-SSZ-13. In this Letter, the sensitivity of the XANES features to the local environment for a Cu + cation with a linear configuration and a Cu 2+ cation with a square-linear configuration in Cu-SSZ-13 is reported. When a Cu + cation is bonded to H 2 O or NH 3 in a linear configuration, the XANES has a strong peak at around 8983 eV. The intensity of this peak decreases as the linear configuration is broken. As for the Cu 2+ cations in a square-planar configuration with a coordination number of 4, two peaks at around 8986 and 8993 eV are found. An intensity decrease for both peaks at around 8986 and 8993 eV is found in an NH 3 _4_Z 2 Cu model as the N-Cu-N angle changes from 180 to 100°. We correlate these features to the variation of the 4p state by PDOS analysis. In addition, the feature peaks for both the Cu + cation and Cu 2+ cation do not show a dependence on the Cu-N bond length. We further show that the feature peaks also change when the coordination number of the Cu cation is varied, while these feature peaks are independent of the zeolite topology. These findings help elucidate the experimental XANES features at an atomic and an electronic level.

  16. The P K-near edge absorption spectra of phosphates

    NASA Astrophysics Data System (ADS)

    Franke, R.; Hormes, J.

    1995-12-01

    The X-ray absorption near edge structure (XANES) at the P K-edge in several orthophosphates with various cations, in condensed, and in substituted sodium phosphates have been measured using synchrotron radiation from the ELSA storage ring at the University of Bonn. The measured spectra demonstrate that chemical changes beyond the PO 4- tetrahedra are reflected by energy shifts of the pre-edge and continuum resonances, by the presence of characteristic shoulders and new peaks and by differences in the intensity of the white line. We discuss the energy differences between the white line positions and the corresponding P ls binding energies as a measure of half of the energy gap. The corresponding values correlate with the valence of the cations and the intensity of the white lines. The energy positions of the continuum resonances are discussed on the basis of an empirical bond-length correlation supporting a 1/ r2 - dependence.

  17. Monitoring morphology and hydrogen coverage of nanometric Pt/γ-Al2 O3 particles by in situ HERFD-XANES and quantum simulations.

    PubMed

    Gorczyca, Agnes; Moizan, Virginie; Chizallet, Celine; Proux, Olivier; Del Net, William; Lahera, Eric; Hazemann, Jean-Louis; Raybaud, Pascal; Joly, Yves

    2014-11-10

    Platinum nanoclusters highly dispersed on γ-alumina are widely used as heterogeneous catalysts. To understand the chemical interplay between the Pt nanoparticles, the support, and the reductive atmosphere, we performed X-ray absorption near edge structure (XANES) in situ experiments recorded in high energy resolution fluorescence detection (HERFD) mode. Spectra are assigned by comparison with simulated XANES spectra on models obtained by molecular dynamics (DFT-MD). We propose platinum cluster morphologies and quantify the hydrogen coverages compatible with XANES spectra recorded at variable hydrogen pressures and temperatures. Using cutting-edge methodologies to assign XANES spectra, this work gives unequalled atomic insights into the characterization of supported nanoclusters. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. XANES and EXAFS study of Au-substituted YBa2Cu3O(7-delta)

    NASA Technical Reports Server (NTRS)

    Ruckman, Mark W.; Hepp, Aloysius F.

    1990-01-01

    The near-edge structure (XANES) of the Au L3 and Cu K edges of YBa2Au(0.3)Cu(2.7)O(7-delta) was studied. X ray diffraction suggests that Au goes on the Cu(1) site and XANES shows that this has little effect on the oxidation state of the remaining copper. The gold L3 edge develops a white line feature whose position lies between that of trivalent gold oxide (Au2O3) and monovalent potassium gold cyanide (KAu(CN)2) and whose intensity relative to the edge step is smaller than in the two reference compounds. The L3 EXAFS for Au in the superconductor resembles that of Au2O3. However, differences in the envelope of the Fourier filtered component for the first shell suggest that the local structure of the Au in the superconductor is not equivalent to Au2O3.

  19. Inherent size effects on XANES of nanometer metal clusters: Size-selected platinum clusters on silica

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

    Dai, Yang; Gorey, Timothy J.; Anderson, Scott L.

    2016-12-12

    X-ray absorption near-edge structure (XANES) is commonly used to probe the oxidation state of metal-containing nanomaterials, however, as the particle size in the material drops below a few nanometers, it becomes important to consider inherent size effects on the electronic structure of the materials. In this paper, we analyze a series of size-selected Pt n/SiO 2 samples, using X-ray photoelectron spectroscopy (XPS), low energy ion scattering, grazing-incidence small angle X-ray scattering, and XANES. The oxidation state and morphology are characterized both as-deposited in UHV, and after air/O 2 exposure and annealing in H 2. Here, the clusters are found tomore » be stable during deposition and upon air exposure, but sinter if heated above ~150 °C. XANES shows shifts in the Pt L 3 edge, relative to bulk Pt, that increase with decreasing cluster size, and the cluster samples show high white line intensity. Reference to bulk standards would suggest that the clusters are oxidized, however, XPS shows that they are not. Instead, the XANES effects are attributable to development of a band gap and localization of empty state wavefunctions in small clusters.« less

  20. XANES study of Fe-implanted strontium titanate

    NASA Astrophysics Data System (ADS)

    Lobacheva, O.; Goncharova, L. V.; Chavarha, M.; Sham, T. K.

    2014-03-01

    Properties of strontium titanate SrTiO3 (STO) depend to a great extent on the substitutional dopants and defects of crystal structure. The ion beam implantation method was used for doping STO (001) crystals with Fe at different doses. Implanted samples were then annealed at 350°C in oxygen to induce recrystallization and remove oxygen vacancies produced during ion implantation process. The effect of Fe doping and post-implantation annealing was studied by X-ray Absorption Near Edge Spectroscopy (XANES) method and Superconducting Quantum Interference Device (SQUID). XANES allowed to monitor the change in structure of STO crystals and in the local environment of Fe following the implantation and annealing steps. SQUID measurements revealed correlation between magnetic moment and Fe implantation dose. Ferromagnetic hysteresis was observed on selected Fe-implanted STO at 5 K. The observed magnetic properties can be correlated with the several Fe oxide phases in addition to the presence of O/Ti vacancies.

  1. Mn K-Edge XANES and Kβ XES Studies of Two Mn–Oxo Binuclear Complexes: Investigation of Three Different Oxidation States Relevant to the Oxygen-Evolving Complex of Photosystem II

    PubMed Central

    Visser, Hendrik; Anxolabéhère-Mallart, Elodie; Bergmann, Uwe; Glatzel, Pieter; Robblee, John H.; Cramer, Stephen P.; Girerd, Jean-Jacques; Sauer, Kenneth; Klein, Melvin P.; Yachandra, Vittal K.

    2014-01-01

    Two structurally homologous Mn compounds in different oxidation states were studied to investigate the relative influence of oxidation state and ligand environment on Mn K-edge X-ray absorption near-edge structure (XANES) and Mn Kβ X-ray emission spectroscopy (Kβ XES). The two manganese compounds are the di-μ-oxo compound [L′2MnIIIO2MnIVL′2](ClO4)3, where L′ is 1,10-phenanthroline (Cooper, S. R.; Calvin, M. J. Am. Chem. Soc. 1977, 99, 6623–6630) and the linear mono-μ-oxo compound [LMnIIIOMnIIIL](ClO4)2, where L− is the monoanionic N,N-bis(2-pyridylmethyl)-N′-salicylidene-1,2-diaminoethane ligand (Horner, O.; Anxolabéhère-Mallart, E.; Charlot, M. F.; Tchertanov, L.; Guilhem, J.; Mattioli, T. A.; Boussac, A.; Girerd, J.-J. Inorg. Chem. 1999, 38, 1222–1232). Preparative bulk electrolysis in acetonitrile was used to obtain higher oxidation states of the compounds: the MnIVMnIV species for the di-μ-oxo compound and the MnIIIMnIV and MnIVMnIV species for the mono-μ-oxo compound. IR, UV/vis, EPR, and EXAFS spectra were used to determine the purity and integrity of the various sample solutions. The Mn K-edge XANES spectra shift to higher energy upon oxidation when the ligand environment remains similar. However, shifts in energy are also observed when only the ligand environment is altered. This is achieved by comparing the di-μ-oxo and linear mono-μ-oxo Mn–Mn moieties in equivalent oxidation states, which represent major structural changes. The magnitude of an energy shift due to major changes in ligand environment can be as large as that of an oxidation-state change. Therefore, care must be exercised when correlating the Mn K-edge energies to manganese oxidation states without taking into account the nature of the ligand environment and the overall structure of the compound. In contrast to Mn K-edge XANES, Kβ XES spectra show less dependence on ligand environment. The Kβ1,3 peak energies are comparable for the di-μ-oxo and mono

  2. Ab-initio Calculation of the XANES of Lithium Phosphates and LiFePO4

    NASA Astrophysics Data System (ADS)

    Yiu, Y. M.; Yang, Songlan; Wang, Dongniu; Sun, Xueliang; Sham, T. K.

    2013-04-01

    Lithium iron phosphate has been regarded as a promising cathode material for the next generation lithium ion batteries due to its high specific capacity, superior thermal and cyclic stability [1]. In this study, the XANES (X-ray Absorption Near Edge Structure) spectra of lithium iron phosphate and lithium phosphates of various compositions at the Li K, P L3,2, Fe M3,2 and O K-edges have been simulated self-consistently using ab-initio calculations based on multiple scattering theory (the FEFF9 code) and DFT (Density Functional Theory, the Wien2k code). The lithium phosphates under investigation include LiFePO4, γ-Li3PO4, Li4P2O7 and LiPO3. The calculated spectra are compared to the experimental XANES recorded in total electron yield (TEY) and fluorescence yield (FLY). This work was carried out to assess the XANES of possible phases presented in LiFePO4 based Li ion battery applications [2].

  3. XPS and Ag L3-edge XANES characterization of silver and silver-gold sulfoselenides

    NASA Astrophysics Data System (ADS)

    Mikhlin, Yuri L.; Pal'yanova, Galina A.; Tomashevich, Yevgeny V.; Vishnyakova, Elena A.; Vorobyev, Sergey A.; Kokh, Konstantin A.

    2018-05-01

    Gold and silver sulfoselenides are of interest as materials with high ionic conductivity and promising magnetoresistive, thermoelectric, optical, and other physico-chemical properties, which are strongly dependent on composition and structure. Here, we applied X-ray photoelectron spectroscopy and Ag L3 X-ray absorption near-edge structure (XANES) to study the electronic structures of low-temperature compounds and solid solutions Ag2SxSe1-x (0 < x < 1), AgAuS, and Ag3AuSxSe2-x (x = 0, 1, 2). Upon substitution of Se with S, a steady increase in the positive charge at Ag(I) sites and only minor changes in the local charge at chalcogen atoms were found from the photoelectron Ag 3d, S 2p, Se 3d, and Ag M4,5VV Auger spectra. The intensity of the Ag L3-edge peak, which is known to correlate with hole counts in the Ag 4d shell having a formal d10 configuration, was enhanced by 20-25% from Ag2Se to Ag2S and from Ag3AuSe2 to Ag3AuS2. The effect of gold is more pronounced, and the number of Ag d holes and the negative charge of S and Se notably decreased for Au-containing compounds; in particular, the Ag L3-edge peak is about 35% lower for AgAuS relative to Ag2S. At the same time, the Au 4f binding energy and, therefore, charge at Au(I) sites increase with increasing S content due to the transfer of electron density from Au to Ag atoms. It was concluded that the effects mainly originate from shortening of the metal-chalcogen and especially the Ausbnd Ag interatomic distances in substances having similar coordination geometry.

  4. [Effect of Long-Term Fertilization on Organic Nitrogen Functional Groups in Black Soil as Revealed by Synchrotron-Based X-Ray Absorption Near-Edge Structure Spectroscopy].

    PubMed

    Li, Hui; Gao, Qiang; Wang, Shuai; Zhu, Ping; Zhang, Jin-jing; Zhao, Yi-dong

    2015-07-01

    Nitrogen (N) is a common limiting nutrient in crop production. The N content of soil has been used as an important soil fertility index. Organic N is the major form of N in soil. In most agricultural surface soils, more than 90% of total N occurs in organic forms. Therefore, understanding the compositional characteristics of soil organic N functional groups can provide the scientific basis for formulating the reasonable farmland management strategies. Synchrotron radiation soft X-ray absorption near-edge structure (N K-edge XANES) spectroscopy is the most powerful tool to characterize in situ organic N functional groups compositions in soil. However, to our most knowledge, no studies have been conducted to examine the organic N functional groups compositions of soil using N K-edge XANES spectroscopy under long-term fertilization practices. Based on a long-term field experiment (started in 1990) in a black soil (Gongzhuling, Northeast China), we investigated the differences in organic N functional groups compositions in bulk soil and clay-size soil fraction among fertilization patterns using synchrotron-based N K- edge XANES spectroscopy. Composite soil samples (0-20 cm) were collected in 2008. The present study included six treatments: farmland fallow (FALL), no-fertilization control (CK), chemical nitrogen, phosphorus, and potassium fertilization (NPK), NPK in combination with organic manure (NPKM), 1.5 times of NPKM (1.5 NPKM), and NPK in combination with maize straw (NPKS). The results showed that N K-edge XANES spectra of all the treatments under study exhibited characteristic absorption peaks in the ranges of 401.2-401.6 and 402.7-403.1 eV, which were assigned as amides/amine-N and pyrrole-N, respectively. These characteristic absorption peaks were more obvious in clay-size soil fraction than in bulk soil. The results obtained from the semi-quantitative analysis of N K-edge XANES spectra indicated that the relative proportion of amides/amine-N was the highest

  5. 4d Electronic structure analysis of ruthenium in the perovskite oxides by Ru K- and L-edge XAS.

    PubMed

    Kim, J Y; Hwang, S H; Kim, S J; Demazeau, G; Choy, J H; Shimada, H

    2001-03-01

    The 4d electronic structure of ruthenium in the perovskite oxides, La2MRuIVO6 (M = Zn, Mg, and Li) and Ba2YRuVO6, has been investigated by the Ru K-and L-edge XANES and EXAFS analyses. Such X-ray absorption spectroscopic results clarify that the RuIV (d4) and RuV (d3) ions are stabilized in nearly regular Oh site. Comparing the Ru L-edge XANES spectra of perovskites containing isovalent ruthenium, it has been found that the t2g state is mainly influenced by A site cation, whereas the eg is mainly affected by neighboring B site cation. The experimental EXAFS spectra in the range of R < or = approximately 4.5 A are well reproduced by ab-initio calculation based on crystallographic data, which supports the long-range structure presented by Rietveld refinement.

  6. Electronic structure of nickel silicide in subhalf-micron lines and blanket films: An x-ray absorption fine structures study at the Ni and Si L3,2 edge

    NASA Astrophysics Data System (ADS)

    Naftel, S. J.; Coulthard, I.; Sham, T. K.; Xu, D.-X.; Erickson, L.; Das, S. R.

    1999-05-01

    We report a Ni and Si L3,2-edge x-ray absorption near edge structures (XANES) study of nickel-silicon interaction in submicron (0.15 and 0.2 μm) lines on a n-Si(100) wafer as well as a series of well characterized Ni-Si blanket films. XANES measurements recorded in both total electron yield and soft x-ray fluorescence yield indicate that under the selected silicidation conditions, the more desirable low resistivity phase, NiSi, is indeed the dominant phase in the subhalf-micron lines although the formation of this phase is less complete as the line becomes narrower and this is accompanied by a Ni rich surface.

  7. Speciation of sulfur from filamentous microbial mats from sulfidic cave springs using X-ray absorption near-edge spectroscopy.

    PubMed

    Engel, Annette Summers; Lichtenberg, Henning; Prange, Alexander; Hormes, Josef

    2007-04-01

    Most transformations within the sulfur cycle are controlled by the biosphere, and deciphering the abiotic and biotic nature and turnover of sulfur is critical to understand the geochemical and ecological changes that have occurred throughout the Earth's history. Here, synchrotron radiation-based sulfur K-edge X-ray absorption near-edge structure (XANES) spectroscopy is used to examine sulfur speciation in natural microbial mats from two aphotic (cave) settings. Habitat geochemistry, microbial community compositions, and sulfur isotope systematics were also evaluated. Microorganisms associated with sulfur metabolism dominated the mats, including members of the Epsilonproteobacteria and Gammaproteobacteria. These groups have not been examined previously by sulfur K-edge XANES. All of the mats consisted of elemental sulfur, with greater contributions of cyclo-octasulfur (S8) compared with polymeric sulfur (Smicro). While this could be a biological fingerprint for some bacteria, the signature may also indicate preferential oxidation of Smicro and S8 accumulation. Higher sulfate content correlated to less S8 in the presence of Epsilonproteobacteria. Sulfur isotope compositions confirmed that sulfur content and sulfur speciation may not correlate to microbial metabolic processes in natural samples, thereby complicating the interpretation of modern and ancient sulfur records.

  8. Sulfur K-edge XANES and acid volatile sulfide analyses of changes in chemical speciation of S and Fe during sequential extraction of trace metals in anoxic sludge from biogas reactors.

    PubMed

    Shakeri Yekta, Sepehr; Gustavsson, Jenny; Svensson, Bo H; Skyllberg, Ulf

    2012-01-30

    The effect of sequential extraction of trace metals on sulfur (S) speciation in anoxic sludge samples from two lab-scale biogas reactors augmented with Fe was investigated. Analyses of sulfur K-edge X-ray absorption near edge structure (S XANES) spectroscopy and acid volatile sulfide (AVS) were conducted on the residues from each step of the sequential extraction. The S speciation in sludge samples after AVS analysis was also determined by S XANES. Sulfur was mainly present as FeS (≈ 60% of total S) and reduced organic S (≈ 30% of total S), such as organic sulfide and thiol groups, in the anoxic solid phase. Sulfur XANES and AVS analyses showed that during first step of the extraction procedure (the removal of exchangeable cations), a part of the FeS fraction corresponding to 20% of total S was transformed to zero-valent S, whereas Fe was not released into the solution during this transformation. After the last extraction step (organic/sulfide fraction) a secondary Fe phase was formed. The change in chemical speciation of S and Fe occurring during sequential extraction procedure suggests indirect effects on trace metals associated to the FeS fraction that may lead to incorrect results. Furthermore, by S XANES it was verified that the AVS analysis effectively removed the FeS fraction. The present results identified critical limitations for the application of sequential extraction for trace metal speciation analysis outside the framework for which the methods were developed. Copyright © 2011 Elsevier B.V. All rights reserved.

  9. Experimental and theoretical studies of dipole and quadrupole contributions to the vanadium K-edge XANES for VOPO4.2H2O xerogel

    NASA Astrophysics Data System (ADS)

    Poumellec, B.; Kraizman, V.; Aifa, Y.; Cortès, R.; Novakovich, A.; Vedrinskii, R.

    1998-09-01

    Angular dependence of the vanadium K-edge x-ray appearance near-edge structure (XANES) for the VOPO4.2H2O xerogel is thoroughly studied both experimentally and theoretically. The main attention is paid to the pre-edge fine structure (PEFS) of the spectra which was shown earlier to be a useful tool for the atomic short order investigations. Good quantitative agreement between theory and experiment obtained for both dipole and quadrupole contributions to the spectra proves validity of the calculation method developed and enables us to ascertain the nature of all the features in the PEFS's. The p-d mixture effect due to distortion of the central coordination octahedron and the quadrupole transitions are proved to be the only mechanisms responsible for the PEFS formation in the case considered. We show that in order to achieve quantitative agreement between experimental and theoretical spectra, it is necessary to include the effect of atomic vibrations, which makes the forbidden transitions to molecular orbitals of the central octahedron (MOCO's) dipole allowed, and to take into account deviation of the crystal layers from the substrate plane, which is not a single crystal but a texture.

  10. Existence of Fe{sup 4+} ions in Co{sub 2.25}Fe{sub 0.75}O{sub 4} spinel ferrite confirmed from SXRD and XANES spectroscopy

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

    Panda, Manas Ranjan, E-mail: manasranjan056@gmail.com; Bhowmik, R. N.; Sinha, A. K.

    2015-06-24

    The Co{sub 2.25}Fe{sub 0.75}O{sub 4} ferrite composition has been prepared by chemical co-precipitation route. The as-prepared sample after annealing at 900°C in air formed single phase cubic spinel structure. Synchrotron X-ray diffraction and X-ray absorption near edge structure (XANES) measurements were used to study charge states of the cations in octahedral and tetrahedral sites of the cubic spinel structure. Raman spectra indicated normal cubic spinel structure. XANES data suggested the existence of Fe{sup 4+} ions in the spinel structure.

  11. Fe K-edge XANES of Maya blue pigment

    NASA Astrophysics Data System (ADS)

    Río, M. Sánchez del; Sodo, A.; Eeckhout, S. G.; Neisius, T.; Martinetto, P.; Dooryhée, E.; Reyes-Valerio, C.

    2005-08-01

    The utilization of techniques used in Materials Science for the characterization of artefacts of interest for cultural heritage is getting more and more attention nowadays. One of the products of the ancient Maya chemistry is the "Maya blue" pigment, made with natural indigo and palygorskite. This pigment is different from any other pigment used in other parts of the world. It is durable and acid-resistant, and still keeps many secrets to scientists even though it has been studied for more than 50 years. Although the pigment is basically made of palygorskite Si8(Mg2Al2)O20(OH)2(OH2)4.4H2O and an organic colourant (indigo: C16H10N2O2), a number of other compounds have been found in previous studies on archaeological samples, like other clays and minerals, iron nanoparticles, iron oxides, impurities of transition metals (Cr, Mn, Ti, V), etc. We measured at the ESRF ID26 beamline the Fe K-edge XANES spectra of the blue pigment in ancient samples. They are compared to XANES spectra of Maya blue samples synthesized under controlled conditions, and iron oxides usually employed as pigments (hematite and goethite). Our results show that the iron found in ancient Maya blue pigment is related to the Fe exchanged in the palygorskite clay. We did not find iron in metallic form or goethite in archaeological Maya blue.

  12. XANES Identification of Plutonium Speciation in RFETS Samples

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

    LoPresti, V.; Conradson, S.D.; Clark, D.L.

    2009-06-03

    Using primarily X-ray absorption near edge spectroscopy (XANES) with standards run in tandem with samples, probable plutonium speciation was determined for 13 samples from contaminated soil, acid-splash or fire-deposition building interior surfaces, or asphalt pads from the Rocky Flats Environmental Technology Site (RFETS). Save for extreme oxidizing situations, all other samples were found to be of Pu(IV) speciation, supporting the supposition that such contamination is less likely to show mobility off site. EXAFS analysis conducted on two of the 13 samples supported the validity of the XANES features employed as determinants of the plutonium valence.

  13. Solid-phase cadmium speciation in soil using L3-edge XANES spectroscopy with partial least-squares regression.

    PubMed

    Siebers, Nina; Kruse, Jens; Eckhardt, Kai-Uwe; Hu, Yongfeng; Leinweber, Peter

    2012-07-01

    Cadmium (Cd) has a high toxicity and resolving its speciation in soil is challenging but essential for estimating the environmental risk. In this study partial least-square (PLS) regression was tested for its capability to deconvolute Cd L(3)-edge X-ray absorption near-edge structure (XANES) spectra of multi-compound mixtures. For this, a library of Cd reference compound spectra and a spectrum of a soil sample were acquired. A good coefficient of determination (R(2)) of Cd compounds in mixtures was obtained for the PLS model using binary and ternary mixtures of various Cd reference compounds proving the validity of this approach. In order to describe complex systems like soil, multi-compound mixtures of a variety of Cd compounds must be included in the PLS model. The obtained PLS regression model was then applied to a highly Cd-contaminated soil revealing Cd(3)(PO(4))(2) (36.1%), Cd(NO(3))(2)·4H(2)O (24.5%), Cd(OH)(2) (21.7%), CdCO(3) (17.1%) and CdCl(2) (0.4%). These preliminary results proved that PLS regression is a promising approach for a direct determination of Cd speciation in the solid phase of a soil sample.

  14. Speciation of Soil Phosphorus Assessed by XANES Spectroscopy at Different Spatial Scales

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

    Hesterberg, Dean; McNulty, Ian; Thieme, Juergen

    Precise management of soil phosphorus (P) to meet competing demands of agriculture and environmental protection can benefit from more comprehensive characterization of P speciation in soils. Our objectives were to provide spatial context for spectroscopic analyses of soil P speciation in relation to molecular-scale species and landscape-scale management of P, and to compare soil P-species diversity from spectroscopic measurements at submicron and millimeter scales. The spatial range of ~26 orders of magnitude between atomic and field scales presents a challenge to upscaling and downscaling information from spectroscopic analyses of soils. Scanning fluorescence X-ray microscopy images of a 50-mm ´ 45-mmmore » area of an organic soil sample showed heterogeneous distributions of P, Al, and Si. Microscale X-ray absorption near edge structure (μ-XANES) spectra collected at the P K-edge from 12 spots on the soil sample exhibited diverse features that indicated variations in highly localized P speciation. Linear combination fitting analysis of the μ-XANES spectra included various proportions of three standards that appeared in fits for most spots and five standards that appeared in fits for one spot each. The fit to a bulk-soil spectrum was dominated by two of the common standards in the μ-XANES fits, and a fit to the sum of m-XANES spectra included four of the standards. Lastly, these results illustrate a gain in P species sensitivity from spatially resolved XANES analysis. Integrating spectroscopic analyses from multiple scales determines soil P species diversity and will ultimately help connect speciation to the chemical reactivity and mobility of P in soils.« less

  15. Speciation of Soil Phosphorus Assessed by XANES Spectroscopy at Different Spatial Scales

    DOE PAGES

    Hesterberg, Dean; McNulty, Ian; Thieme, Juergen

    2017-07-27

    Precise management of soil phosphorus (P) to meet competing demands of agriculture and environmental protection can benefit from more comprehensive characterization of P speciation in soils. Our objectives were to provide spatial context for spectroscopic analyses of soil P speciation in relation to molecular-scale species and landscape-scale management of P, and to compare soil P-species diversity from spectroscopic measurements at submicron and millimeter scales. The spatial range of ~26 orders of magnitude between atomic and field scales presents a challenge to upscaling and downscaling information from spectroscopic analyses of soils. Scanning fluorescence X-ray microscopy images of a 50-mm ´ 45-mmmore » area of an organic soil sample showed heterogeneous distributions of P, Al, and Si. Microscale X-ray absorption near edge structure (μ-XANES) spectra collected at the P K-edge from 12 spots on the soil sample exhibited diverse features that indicated variations in highly localized P speciation. Linear combination fitting analysis of the μ-XANES spectra included various proportions of three standards that appeared in fits for most spots and five standards that appeared in fits for one spot each. The fit to a bulk-soil spectrum was dominated by two of the common standards in the μ-XANES fits, and a fit to the sum of m-XANES spectra included four of the standards. Lastly, these results illustrate a gain in P species sensitivity from spatially resolved XANES analysis. Integrating spectroscopic analyses from multiple scales determines soil P species diversity and will ultimately help connect speciation to the chemical reactivity and mobility of P in soils.« less

  16. X-Ray Absorption Near Edge Structure And Extended X-Ray Absorption Fine Structure Analysis of Standards And Biological Samples Containing Mixed Oxidation States of Chromium(III) And Chromium(VI)

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

    Parsons, J.G.; Dokken, K.; Peralta-Videa, J.R.

    For the first time a method has been developed for the extended X-ray absorption fine structure (EXAFS) data analyses of biological samples containing multiple oxidation states of chromium. In this study, the first shell coordination and interatomic distances based on the data analysis of known standards of potassium chromate (Cr(VI)) and chromium nitrate hexahydrate (Cr(III)) were investigated. The standards examined were mixtures of the following molar ratios of Cr(VI):Cr(III), 0:1, 0.25:0.75, 0.5:0.5, 0.75:0.25, and 1:0. It was determined from the calibration data that the fitting error associated with linear combination X-ray absorption near edge structure (LC-XANES) fittings was approximately {+-}10%more » of the total fitting. The peak height of the Cr(VI) pre-edge feature after normalization of the X-ray absorption (XAS) spectra was used to prepare a calibration curve. The EXAFS fittings of the standards were also investigated and fittings to lechuguilla biomass samples laden with different ratios of Cr(III) and Cr(VI) were performed as well. An excellent agreement between the XANES data and the data presented in the EXAFS spectra was observed. The EXFAS data also presented mean coordination numbers directly related to the ratios of the different chromium oxidation states in the sample. The chromium oxygen interactions had two different bond lengths at approximately 1.68 and 1.98 {angstrom} for the Cr(VI) and Cr(III) in the sample, respectively.« less

  17. µ-XANES AND µ-XRF INVESTIGATIONS OF METAL BINDING MECHANISMS IN BIOSOLIDS

    EPA Science Inventory

    Micro-X-ray fluorescence (µ-XRF) microprobe analysis and micro-X-ray absorption near edge spectroscopy (µ-XANES) were employed to identify Fe and Mn phases and their association with selected toxic elements in two biosolids (limed composted and Nu-Earth) containing low ...

  18. Diamond xenolith and matrix organic matter in the Sutter's Mill meteorite measured by C-XANES

    NASA Astrophysics Data System (ADS)

    Kebukawa, Yoko; Zolensky, Michael E.; Kilcoyne, A. L. David; Rahman, Zia; Jenniskens, Peter; Cody, George D.

    2014-11-01

    The Sutter's Mill (SM) meteorite fell in El Dorado County, California, on April 22, 2012. This meteorite is a regolith breccia composed of CM chondrite material and at least one xenolithic phase: oldhamite. The meteorite studied here, SM2 (subsample 5), was one of three meteorites collected before it rained extensively on the debris site, thus preserving the original asteroid regolith mineralogy. Two relatively large (10 μm sized) possible diamond grains were observed in SM2-5 surrounded by fine-grained matrix. In the present work, we analyzed a focused ion beam (FIB) milled thin section that transected a region containing these two potential diamond grains as well as the surrounding fine-grained matrix employing carbon and nitrogen X-ray absorption near-edge structure (C-XANES and N-XANES) spectroscopy using a scanning transmission X-ray microscope (STXM) (Beamline 5.3.2 at the Advanced Light Source, Lawrence Berkeley National Laboratory). The STXM analysis revealed that the matrix of SM2-5 contains C-rich grains, possibly organic nanoglobules. A single carbonate grain was also detected. The C-XANES spectrum of the matrix is similar to that of insoluble organic matter (IOM) found in other CM chondrites. However, no significant nitrogen-bearing functional groups were observed with N-XANES. One of the possible diamond grains contains a Ca-bearing inclusion that is not carbonate. C-XANES features of the diamond-edges suggest that the diamond might have formed by the CVD process, or in a high-temperature and -pressure environment in the interior of a much larger parent body.

  19. Correlated XANES, TEM, and NanoSIMS of presolar graphite grains

    NASA Astrophysics Data System (ADS)

    Groopman, Evan E.; Nittler, Larry R.

    2018-01-01

    We report correlated XANES, TEM, and NanoSIMS measurements of twelve presolar graphite grains extracted from primitive meteorites and for which isotopic data indicate predominantly Type-II supernovae origins. We find continued evidence for isotopic heterogeneities in presolar graphite grains, including the first observation of a radial gradient in the inferred initial 26Al/27Al within a presolar graphite grain. The XANES spectra of these samples show a variety of minor absorbances near the C K-edge, attributable to vinyl-keto, aliphatic, carboxyl, and carbonate molecules, as well as possible damage during sample preparation. Each sample exhibits homogeneous C K-edge XANES spectra within the graphite, however, showing no correlation with isotopic heterogeneities. Gradients in the isotope ratios of C, N, O, and Al could be due to both processes during condensation, e.g., mixing in stellar ejecta and granular transport, and post-condensation effects, such as isotope dilution and exchange with isotopically normal material in the early Solar System or laboratory, the latter of which is a significant issue for high-density presolar graphite grains. It remains unknown whether the mechanisms behind isotope exchange would also affect the local chemistry and therefore the XANES spectra. Ti L-edge XANES from most Ti-rich subgrains match standard spectra for TiC and potentially TiCN. A rare rutile (TiO2) subgrain has been identified, though it lacks the lowest energy L3 peak typically seen in standard spectra. Ca has also been identified by EDXS in TiC subgrains, likely due to the decay of live 44Ti at the time of formation. Future NanoSIMS measurements will determine the variability of initial 44Ti in TiC subgrains, an important constraint on mixing in the ejecta of the grains' parent supernovae.

  20. XANES mapping of organic sulfate in three scleractinian coral skeletons

    NASA Astrophysics Data System (ADS)

    Cuif, Jean-Pierre; Dauphin, Yannicke; Doucet, Jean; Salome, Murielle; Susini, Jean

    2003-01-01

    The presence and localization of organic sulfate within coral skeletons are studied by using X-ray absorption near edge structure spectroscopy (XANES) fluorescence. XANES spectra are recorded from four reference sulfur-bearing organic molecules: three amino acids (H-S-C bonds in cysteine; C-S-C bonds in methionine; one disulfide bond C-S-S-C bonds in cystine) and a sulfated sugar (C-SO 4 bonds in chondroitin sulfate). Spectral responses of three coral skeletons show that the sulfated form is extremely dominant in coral aragonite, and practically exclusive within both centres of calcification and the surrounding fibrous tissues of coral septa. Mapping of S-sulfate concentrations in centres and fibres gives us direct evidence of high concentration of organic sulfate in centres of calcification. Additionally, a banding pattern of S-sulfate is visible in fibrous part of the coral septa, evidencing a biochemical zonation that corresponds to the step-by-step growth of fibres.

  1. Surface modification study of borate materials from B K-edge X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Kasrai, Masoud; Fleet, Michael E.; Muthupari, Swaminathan; Li, D.; Bancroft, G. M.

    The B K-edge X-ray absorption near-edge structure (XANES) spectra of two borates with tetrahedrally-coordinated B [[4]B; natural danburite (CaB2Si2O8) and synthetic boron phosphate (BPO4)] have been recorded in total electron yield (TEY) and fluorescence yield (FY) modes to investigate the surface and bulk structure of these materials. The TEY XANES measurement shows that danburite is susceptible to surface damage involving conversion of [4]B sites to [3]B sites by reaction with moisture and/or mechanical abrasion (grinding, polishing, etc.). The bulk of the mineral is essentially unaffected. Commercial boron phosphate powder exhibits more extensive surface and bulk damage, which increases with air exposure but is recovered on heating at 650°C. In contrast to ELNES, the XANES technique is not affected by beam damage and when collected in the FY mode is capable of yielding meaningful information on the coordination and intermediate-range structure of B in borate and borosilicate materials.

  2. Low Z elements (Mg, Al, and Si) K-edge X-ray absorption spectroscopy in minerals and disordered systems

    NASA Astrophysics Data System (ADS)

    Ildefonse, Ph.; Calas, G.; Flank, A. M.; Lagarde, P.

    1995-05-01

    Soft X-ray absorption near edge spectroscopy (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy have been performed at the Mg-, Al- and Si-K edges in order to establish the ability of this spectroscopy to derive structural information in disordered solids such as glasses and gels. Mg- and Al-K XANES are good structural probes to determine the coordination state of these elements in important minerals, glasses and gels. In a CaOsbnd MgOsbnd 2SiO2 glass Mg XANES spectra differ from that found in the crystalline equivalent, with a significant shift of the edge maxima to lower energy, consistent with a CN lower than 6. Mg-EXAFS on the same sample are in agreement and indicate the presence of 5-coordinated Mg with Mgsbnd O distances of 2.01Å. In aluminosilicate gels, Alsbnd K XANES has been used to investigate the [4]Al/Altotal ratios. These ratios increase as the Al/Si ratios decrease. Aluminosilicate and ferric-silicate gels were studied by using Sisbnd K edge XANES. XANES spectra differ significantly among the samples studied. Aluminosilicate gels with Al/Si= 1 present a different Al and Si local environment from that known in clay minerals with the same Al/Si ratio. The gel-to-mineral transformation thus implies a dissolution-recrystallization mechanism. On the contrary, ferric-silicate gel presents a Si local environment close to that found in nontronite which may be formed by a long range ordering of the initial gels.

  3. 279 - Xanes Studies on UV-Irradiated Interstellar Ice Analogs: A Comparison to STARDUST Samples

    NASA Technical Reports Server (NTRS)

    Milam, Stefanie N.; Cody, George D.; Kilcoyne, A. L. David; Nuevo, Michel; Sandford, Scott A.; Stroud, Rhonda M.; DeGregorio, Bradley T.

    2010-01-01

    We present C-, N-, and O-XANES (X-ray Absorption Near-Edge Spectroscopy) results of organic residues produced in the laboratory from the UV irradiation of astrophysical ice analogs containing H20, CO, CH30H, NH31 in order to mimic processes that may occur in cold icy bodies of the outer Solar System, particularly in comets, Such analyses showed that laboratory-formed organic residues mainly consist of a solid phase and an oily phase. C-XANES analysis of the solid phase suggests a rich distribution of organic functionalities, among which carbonyl groups, C=C bonds, and alcohols are present. Results from N-XANES indicate the possible presence of amide, amine, and nitrile groups, The O-XANES spectra confirmed the a-bearing groups, These results are compared with the XANES spectra obtained from STARDUST cometary samples,

  4. Organometallic model complexes elucidate the active gallium species in alkane dehydrogenation catalysts based on ligand effects in Ga K-edge XANES

    DOE PAGES

    Getsoian, Andrew "Bean"; Das, Ujjal; Camacho-Bunquin, Jeffrey; ...

    2016-06-13

    Gallium-modified zeolites are known catalysts for the dehydrogenation of alkanes, reactivity that finds industrial application in the aromatization of light alkanes by Ga-ZSM5. While the role of gallium cations in alkane activation is well known, the oxidation state and coordination environment of gallium under reaction conditions has been the subject of debate. Edge shifts in Ga K-edge XANES spectra acquired under reaction conditions have long been interpreted as evidence for reduction of Ga(III) to Ga(I). However, a change in oxidation state is not the only factor that can give rise to a change in the XANES spectrum. In order tomore » better understand the XANES spectra of working catalysts, we have synthesized a series of molecular model compounds and grafted surface organometallic Ga species and compared their XANES spectra to those of gallium-based catalysts acquired under reducing conditions. We demonstrate that changes in the identity and number of gallium nearest neighbors can give rise to changes in XANES spectra similar to those attributed in literature to changes in oxidation state. Specifically, spectral features previously attributed to Ga(I) may be equally well interpreted as evidence for low-coordinate Ga(III) alkyl or hydride species. Furthermore, these findings apply both to gallium-impregnated zeolite catalysts and to silica-supported single site gallium catalysts, the latter of which is found to be active and selective for dehydrogenation of propane and hydrogenation of propylene.« less

  5. Analysis of sulfidic linkages formed in natural rubber latex medical gloves by using X-ray absorption near edge structure

    NASA Astrophysics Data System (ADS)

    Chankrachang, M.; Limphirat, W.; Yongyingsakthavorn, P.; Nontakaew, U.; Tohsan, A.

    2017-09-01

    A study of sulfidic linkages formed in natural rubber (NR) latex medical gloves by using X-ray Absorption Near Edge Structure (XANES) is presented in this paper. The NR latex compound was prepared by using prevulcanization method, that is, it was prevulcanized at room temperature for 24 hrs before utilization. After the 24 hrs of prevulcanization, the latex film samples were obtained by dipping process. The dipped films were subjected to vulcanize at 110°C for 5 to 25 min. It was observed that after the compound was prevulcanized for 24 hrs, polysulfidic linkages were mainly formed in the sample. It was however found that after curing at 110°C for 5-25 min, the polysulfidic linkages are tended to change into disulfide linkages. Especially, in the case of 25 minutes cured sample, disulfide linkages are found to be the main linkages. In term of tensile strength, it was observed that when cure time increased from 5 - 10 min, tensile strengths were also increased. But when the cure time of the film is 25 minutes, tensile strength was slightly dropped. The dropped of tensile strength when cure time is longer than 10 minutes can be ascribed to a degradation of polysulfidic and disulfidic linkages during curing. Therefore, by using XANES analysis, it was found to be very useful to understand the cure characteristic, thus it can be very helpful to optimize cure time and tensile properties of the product.

  6. Ca 3d unoccupied states in Bi2Sr2CaCu2O8 investigated by Ca L2,3 x-ray-absorption near-edge structure

    NASA Astrophysics Data System (ADS)

    Borg, A.; King, P. L.; Pianetta, P.; Lindau, I.; Mitzi, D. B.; Kapitulnik, A.; Soldatov, A. V.; della Longa, S.; Bianconi, A.

    1992-10-01

    The high-resolution Ca L2,3 x-ray-absorption near-edge-structure (XANES) spectrum of a Bi2Sr2CaCu2O8 single crystal has been measured by use of a magnetic-projection x-ray microscope probing a surface area of 200×200 μm2. The Ca L2,3 XANES spectrum is analyzed by performing a multiple-scattering XANES calculation in real space and comparing the results with the spectrum of CaF2. Good agreement between the calculated and experimental crystal-field splitting Δf of the Ca 3d final states is found and the splitting is shown to be smaller by 0.5 eV than in the initial state. The Ca 3d partial density of states is found to be close to the Fermi level in the initial state. The Ca-O(in plane) distance is shown to be a critical parameter associated with the shift of the Ca 3d states relative to the Fermi level; in particular, we have studied the effect of the out-of-plane dimpling mode of the in-plane oxygen atoms O(in plane) that will move the Ca 3d states on or off the Fermi level. This mode can therefore play a role in modulating the charge transfer between the two CuO2 planes separated by the Ca ions.

  7. Sulfur species in source rock bitumen before and after hydrous pyrolysis determined by X-ray absorption near-edge structure

    USGS Publications Warehouse

    Bolin, Trudy B.; Birdwell, Justin E.; Lewan, Michael; Hill, Ronald J.; Grayson, Michael B.; Mitra-Kirtley, Sudipa; Bake, Kyle D.; Craddock, Paul R.; Abdallah, Wael; Pomerantz, Andrew E.

    2016-01-01

    The sulfur speciation of source rock bitumen (chloroform-extractable organic matter in sedimentary rocks) was examined using sulfur K-edge X-ray absorption near-edge structure (XANES) spectroscopy for a suite of 11 source rocks from around the world. Sulfur speciation was determined for both the native bitumen in thermally immature rocks and the bitumen produced by thermal maturation of kerogen via hydrous pyrolysis (360 °C for 72 h) and retained within the rock matrix. In this study, the immature bitumens had higher sulfur concentrations than those extracted from samples after hydrous pyrolysis. In addition, dramatic and systematic evolution of the bitumen sulfur moiety distributions following artificial thermal maturation was observed consistently for all samples. Specifically, sulfoxide sulfur (sulfur double bonded to oxygen) is abundant in all immature bitumen samples but decreases substantially following hydrous pyrolysis. The loss in sulfoxide sulfur is associated with a relative increase in the fraction of thiophene sulfur (sulfur bonded to aromatic carbon) to the extent that thiophene is the dominant sulfur form in all post-pyrolysis bitumen samples. This suggests that sulfur moiety distributions might be used for estimating thermal maturity in source rocks based on the character of the extractable organic matter.

  8. Ce(III) and Ce(IV) (re)distribution and fractionation in a laterite profile from Madagascar: Insights from in situ XANES spectroscopy at the Ce LIII-edge

    NASA Astrophysics Data System (ADS)

    Janots, Emilie; Bernier, Felix; Brunet, Fabrice; Muñoz, Manuel; Trcera, Nicolas; Berger, Alfons; Lanson, Martine

    2015-03-01

    The distribution of trivalent and tetravalent cerium, Ce(III) and Ce(IV) respectively, in a lateritic profile from Madagascar, has been characterized by X-ray-absorption near-edge structure (XANES) spectroscopy at the Ce LIII-edge on the LUCIA beamline (SOLEIL synchrotron, France). XANES spectra were acquired on bulk-rock samples as well as on specific lateritic minerals or polymineral zones (in-situ measurements) of the tonalite bedrock and the three overlying weathered horizons (C-, B- and A-horizons). Geochemically, the bedrock, and the A- and C-horizons show similar rare earth element content (REE = 363-405 mg/kg). They also display the same positive Ce-anomaly (CeCN/Ce∗ = 1.12-1.45), which is therefore likely to be inherited from the bedrock. In the B-horizon, the higher REE content (REE = 2194 mg/kg) and the larger Ce-anomaly (CeCN/Ce∗ = 4.26) are consistent with an accumulation zone caused by the evaporation of groundwater during the dry season. There is a good agreement between the Ce(III)/Cetotal ratio (XCe(III)) deduced from the positive Ce-anomaly (bulk-rock geochemical data) and that derived from XANES spectroscopy on the same bulk-rock samples (BR-XCe(III)-XANES) in the bedrock, and the C- and B-horizons. In the A-horizon, XANES measurements on bulk rock and minerals revealed a higher BR-XCe(III)-XANES (up to 100%) compared to the XCe(III) deduced from geochemical data (XCe(III) = 79%). The preservation of a positive Ce-anomaly in the A-horizon suggests that the Ce mobilization and redistribution during weathering occurred with no significant Ce fractionation from other trivalent REE. Remarkably, the only investigated sample where cerianite is observed belongs to the B-horizon. Within this horizon, Ce oxidation state varies depending on the microstructural position (porosity, cracks, clay-rich groundmass). The highest Ce(IV) concentrations are measured in cerianite (and aluminophosphates) localized in pores at the vicinity of Mn-rich domains (XCe(III)-XANES

  9. Indium local geometry in In-Sb-Te thin films using XANES and DFT calculations

    NASA Astrophysics Data System (ADS)

    Bilovol, V.; Gil Rebaza, A. V.; Mudarra Navarro, A. M.; Errico, L.; Fontana, M.; Arcondo, B.

    2017-12-01

    In-Sb-Te when is a thin film presents a huge difference in its electrical resistivity when transform from the amorphous (insulating) to the crystalline (conducting) phase. This property made this system one of the main phase-change materials used in the data storage industry. The change in the electrical conductivity is probably associated to a change in the bonding geometry of some of its constituents. To explore this point, we present in this work an study of the bonding geometry of In atoms in In-Sb-Te films by means of In K-edge X-ray absorption near edge structure (XANES) spectroscopy using synchrotron radiation in both as deposited (amorphous) and crystalline thin films obtained as a result of resistance (R) vs temperature (T) measurements. Comparison of the XANES spectra obtained for ternary amorphous films and binary crystalline reference films suggests that in amorphous films the bonding geometry of In atoms is tetrahedral-like. After the thermal annealing has been carried out the differences in the XANES spectra of the as deposited and the annealed films indicate that the bonding geometry of In atoms changes. Based on X-ray diffraction results and ab initio calculations in the framework of the Density Functional Theory (DFT) we show that the new coordination geometry is associated with a tendency of In atoms towards octahedral-like.

  10. Reference spectra of important adsorbed organic and inorganic phosphate binding forms for soil P speciation using synchrotron-based K-edge XANES spectroscopy.

    PubMed

    Prietzel, Jörg; Harrington, Gertraud; Häusler, Werner; Heister, Katja; Werner, Florian; Klysubun, Wantana

    2016-03-01

    Direct speciation of soil phosphorus (P) by linear combination fitting (LCF) of P K-edge XANES spectra requires a standard set of spectra representing all major P species supposed to be present in the investigated soil. Here, available spectra of free- and cation-bound inositol hexakisphosphate (IHP), representing organic P, and of Fe, Al and Ca phosphate minerals are supplemented with spectra of adsorbed P binding forms. First, various soil constituents assumed to be potentially relevant for P sorption were compared with respect to their retention efficiency for orthophosphate and IHP at P levels typical for soils. Then, P K-edge XANES spectra for orthophosphate and IHP retained by the most relevant constituents were acquired. The spectra were compared with each other as well as with spectra of Ca, Al or Fe orthophosphate and IHP precipitates. Orthophosphate and IHP were retained particularly efficiently by ferrihydrite, boehmite, Al-saturated montmorillonite and Al-saturated soil organic matter (SOM), but far less efficiently by hematite, Ca-saturated montmorillonite and Ca-saturated SOM. P retention by dolomite was negligible. Calcite retained a large portion of the applied IHP, but no orthophosphate. The respective P K-edge XANES spectra of orthophosphate and IHP adsorbed to ferrihydrite, boehmite, Al-saturated montmorillonite and Al-saturated SOM differ from each other. They also are different from the spectra of amorphous FePO4, amorphous or crystalline AlPO4, Ca phosphates and free IHP. Inclusion of reference spectra of orthophosphate as well as IHP adsorbed to P-retaining soil minerals in addition to spectra of free or cation-bound IHP, AlPO4, FePO4 and Ca phosphate minerals in linear combination fitting exercises results in improved fit quality and a more realistic soil P speciation. A standard set of P K-edge XANES spectra of the most relevant adsorbed P binding forms in soils is presented.

  11. Electronic structure of transition metal-cysteine complexes from X-ray absorption spectroscopy.

    PubMed

    Leung, Bonnie O; Jalilehvand, Farideh; Szilagyi, Robert K

    2008-04-17

    The electronic structures of HgII, NiII, CrIII, and MoV complexes with cysteine were investigated by sulfur K-edge X-ray absorption near-edge structure (XANES) spectroscopy and density functional theory. The covalency in the metal-sulfur bond was determined by analyzing the intensities of the electric-dipole allowed pre-edge features appearing in the XANES spectra below the ionization threshold. Because of the well-defined structures of the selected cysteine complexes, the current work provides a reference set for further sulfur K-edge XAS studies of bioinorganic active sites with transition metal-sulfur bonds from cysteine residues as well as more complex coordination compounds with thiolate ligands.

  12. X-ray absorption near-edge spectroscopy in bioinorganic chemistry: Application to M–O2 systems

    PubMed Central

    Sarangi, Ritimukta

    2012-01-01

    Metal K-edge X-ray absorption spectroscopy (XAS) has been extensively applied to bioinorganic chemistry to obtain geometric structure information on metalloprotein and biomimetic model complex active sites by analyzing the higher energy extended X-ray absorption fine structure (EXAFS) region of the spectrum. In recent years, focus has been on developing methodologies to interpret the lower energy K-pre-edge and rising-edge regions (XANES) and using it for electronic structure determination in complex bioinorganic systems. In this review, the evolution and progress of 3d-transition metal K-pre-edge and rising-edge methodology development is presented with particular focus on applications to bioinorganic systems. Applications to biomimetic transition metal–O2 intermediates (M = Fe, Co, Ni and Cu) are reviewed, which demonstrate the power of the method as an electronic structure determination technique and its impact in understanding the role of supporting ligands in tuning the electronic configuration of transition metal–O2 systems. PMID:23525635

  13. X-Ray Absorption near Edge Structure Spectroscopy of Nanodiamonds from the Allende Meteorite

    NASA Technical Reports Server (NTRS)

    Flynn, G. J.; Keller, L. P.; Hill, H.; Jacobsen, C.; Wirick, S.

    2000-01-01

    Carbon X-ray Absorption Near Edge Structure Spectroscopy shows Allende DM nanodiamonds have two pre-edge peaks, consistent with other small diamonds, but fail to show a diamond exciton which is seen in 3.6 nm diamond thin films.

  14. Diversity in C-Xanes Spectra Obtained from Carbonaceous Solid Inclusions from Monahans Halite

    NASA Technical Reports Server (NTRS)

    Kebukawa, Y.; Zolensky, M. E.; Fries, M.; Kilcoyne, A. L. D.; Rahman, Z.; Cody, G. D.

    2014-01-01

    Monahans meteorite (H5) contains fluid inclusion- bearing halite (NaCl) crystals [1]. Microthermometry and Raman spectroscopy showed that the fluid in the inclusions is an aqueous brine and they were trapped near 25degC [1]. Their continued presence in the halite grains requires that their incorporation into the H chondrite asteroid was post metamorphism [2]. Abundant solid inclusions are also present in the halites. The solid inclusions include abundant and widely variable organics [2]. Analyses by Raman microprobe, SEM/EDX, synchrotron X-ray diffraction and TEM reveal that these grains include macromolecular carbon similar in structure to CV3 chondrite matrix carbon, aliphatic carbon compounds, olivine (Fo99-59), high- and low-Ca pyroxene, feldspars, magnetite, sulfides, lepidocrocite, carbonates, diamond, apatite and possibly the zeolite phillipsite [3]. Here we report organic analyses of these carbonaceous residues in Monahans halite using C-, N-, and O- X-ray absorption near edge structure (XANES). Samples and Methods: Approximately 100 nm-thick sections were extracted with a focused ion beam (FIB) at JSC from solid inclusions from Monahans halite. The sections were analyzed using the scanning transmission X-ray microscope (STXM) on beamline 5.3.2.2 at the Advanced Light Source, Lawrence Berkeley National Laboratory for XANES spectroscopy. Results and Discussion: C-XANES spectra of the solid inclusions show micrometer-scale heterogeneity, indicating that the macromolecular carbon in the inclusions have complex chemical variations. C-XANES features include 284.7 eV assigned to aromatic C=C, 288.4-288.8 eV assigned to carboxyl, and 290.6 eV assigned to carbonate. The carbonyl features obtained by CXANES might have been caused by the FIB used in sample preparation. No specific N-XANES features are observed. The CXANES spectra obtained from several areas in the FIB sections include type 1&2 chondritic IOM like, type 3 chondritic IOM like, and none of the above

  15. Oxidation of shallow conduit magma: Insight from μ-XANES analysis on volcanic ash particle

    NASA Astrophysics Data System (ADS)

    Miwa, T.; Ishibashi, H.; Iguchi, M.

    2014-12-01

    Redox state of magma is important to understand dynamics of volcanic eruptions because magma properties such as composition of degassed volatiles, stability field of minerals, and rheology of magma depend on redox state. To evaluate redox state of magma, Fe3+/ΣFe ratio [= Fe3+/( Fe3++ Fe2+)] of volcanic glass has been measured non-destructively by Fe-K edge μ-XANES (micro X-ray Absorption Near Edge Structure) spectroscopy (e.g., Cottrell and Kelly, 2011). We performed textural, compositional, and Fe-K edge μ-XANES analyses on volcanic ash to infer oxidation process of magma at shallow conduit during eruption at Bromo Volcano, Indonesia. The volcanic ash particles were collected in 24th March 2011 by real-time sampling from ongoing activity. The activity was characterized by strombolian eruption showing magma head ascended to near the ground surface. The ash sample contains two type of volcanic glasses named as Brown and Black glasses (BrG and BlG), based on their color. Textual analysis shows microlite crystallinities are same in the two type of glasses, ranging from 0 to 3 vol.%. EPMA analyses show that all of the glasses have almost identical andesitic composition with SiO2 = 60 wt.%. In contrast, Fe-K edge μ-XANES spectra with the analytical method by Ishibashi et al. (in prep) demonstrate that BrG (Fe3+/ΣFe = 0.20-0.26) is more oxidized than BlG (Fe3+/ΣFe = 0.32-0.60). From combination of the glass composition, the measured Fe3+/ΣFe ratio and 1060 degree C of temperature (Kress and Carmichael, 1991), the oxygen fugacities are estimated to be NNO and NNO+4 for BrG and BlG, respectively. The volcanic glasses preserve syn-eruptive physicochemical conditions by rapid quenching due to their small size ranging from 125 to 250 μm. Our results demonstrate that BrG and BlG magmas are textually and chemically identical but their redox conditions are different at the eruption. The oxidation of magma can be caused by following two processes; 1) diffusive transport

  16. Combining µXANES and µXRD mapping to analyse the heterogeneity in calcium carbonate granules excreted by the earthworm Lumbricus terrestris

    PubMed Central

    Brinza, Loredana; Schofield, Paul F.; Hodson, Mark E.; Weller, Sophie; Ignatyev, Konstantin; Geraki, Kalotina; Quinn, Paul D.; Mosselmans, J. Frederick W.

    2014-01-01

    The use of fluorescence full spectral micro-X-ray absorption near-edge structureXANES) mapping is becoming more widespread in the hard energy regime. This experimental method using the Ca K-edge combined with micro-X-ray diffraction (µXRD) mapping of the same sample has been enabled on beamline I18 at Diamond Light Source. This combined approach has been used to probe both long- and short-range order in calcium carbonate granules produced by the earthworm Lumbricus terrestris. In granules produced by earthworms cultured in a control artificial soil, calcite and vaterite are observed in the granules. However, granules produced by earthworms cultivated in the same artificial soil amended with 500 p.p.m. Mg also contain an aragonite. The two techniques, µXRD and µXANES, probe different sample volumes but there is good agreement in the phase maps produced. PMID:24365942

  17. XANES Analysis of Organic Residues Produced from the UV Irradiation of Astrophysical Ice Analogs

    NASA Technical Reports Server (NTRS)

    Nuevo, M.; Milam, S N.; Sandford, S A.; De Gregorio, B T.; Cody, G D.; Kilcoyne, A L.

    2011-01-01

    Organic residues formed in the laboratory from the ultraviolet (UV) photo-irradiation or ion bombardment of astrophysical ice analogs have been extensively studied for the last 15 years with a broad suite of techniques, including infrared (IR) and UV spectroscopies, as well as mass spectrometry. Analyses of these materials show that they consist of complex mixtures of organic compounds stable at room temperature, mostly soluble, that have not been fully characterized. However, the hydrolysis products of these residues have been partly identified using chromatography techniques, which indicate that they contain molecular precursors of prebiotic interest such as amino acids, nitrile-bearing compounds, and amphiphilic compounds. In this study, we present the first X-ray absorption near-edge structure (XANES) spectroscopy measurements of three organic residues made from the UV irradiation of ices having different starting compositions. XANES spectra confirm the presence of different chemical functions in these residues, and indicate that they are rich in nitrogenand oxygen-bearing species. These data can be compared with XANES measurements of extraterrestrial materials. Finally, this study also shows how soft X rays can alter the chemical composition of samples.

  18. Characterization of local atomic structure in Co/Zn based ZIFs by XAFS

    NASA Astrophysics Data System (ADS)

    Podkovyrina, Yulia; Butova, Vera; Bulanova, Elena; Budnyk, Andriy; Kremennaya, Maria; Soldatov, Alexander; Lamberti, Carlo

    2018-03-01

    The local atomic structure in bimetallic Co/Zn zeolitic imidazolate frameworks (ZIFs) was studied using X-ray Absorption Fine Structure (XAFS) spectroscopy and theoretical calculations. The experimental Co K-edge and Zn K-edge XANES (X-ray Absorption Near Edge Structure) spectra of Zn1-xCoxC8H10N4 samples (x = 0.05, 0.25, 0.75) synthesized by microwave synthesis were compared with the data for the ZIF-67 (x=1) and ZIF-8 (x=0). Theoretical XANES spectra for the bimetallic ZIFs were calculated. It was shown that in bimetallic ZIFs the Co and Zn atoms have the similar local environment.

  19. Synchrotron WAXS and XANES studies of silica (SiO2) powders synthesized from Indonesian natural sands

    NASA Astrophysics Data System (ADS)

    Muchlis, Khairanissa; Aini Fauziyah, Nur; Soontaranon, Siriwat; Limpirat, Wanwisa; Pratapa, Suminar

    2017-01-01

    In this study, we have investigated polymorphic silica (SiO2) powders using, Wide Angle X-ray Scattering (WAXS) and X-Ray Absorption Near Edge Spectroscopy (XANES), laboratory X-Ray Diffraction (XRD) instruments. The WAXS and XANES spectra were collected using synchrotron radiation at Synchrotron Light Research Institute (SLRI), Nakhon Ratchasima, Thailand. The silica powders were obtained by processing silica sand from Tanah Laut, South Kalimantan, Indonesia. Purification process of silica sand was done by magnetic separation and immersion with HCl. The purification step was needed to reduce impurity or undesirable non Si elements. Three polymorphs of silica were produced, i.e. amorphous phase (A), quartz (B), and cristobalite (C). WAXS profile for each phase was presented in terms of intensity vs. 2θ prior to analyses. Both XRD (λCuKα=1.54056 Å) and WAXS (λ=1.09 Å) patttern show that (1) A sample contains no crystallites, (2) B sample is monophasic, contains only quartz, and (3) C sample contains cristobalite and trydimite. XRD quantitative analysis using Rietica gave 98,8 wt% cristobalite, while the associated WAXS data provided 98.7 wt% cristobalite. Si K-edge XANES spectra were measured at energy range 1840 to 1920 eV. Qualitatively, the pre-edge and edge features for all phases are similar, but their main peaks in the post-edge region are different.

  20. Alternative difference analysis scheme combining R-space EXAFS fit with global optimization XANES fit for X-ray transient absorption spectroscopy.

    PubMed

    Zhan, Fei; Tao, Ye; Zhao, Haifeng

    2017-07-01

    Time-resolved X-ray absorption spectroscopy (TR-XAS), based on the laser-pump/X-ray-probe method, is powerful in capturing the change of the geometrical and electronic structure of the absorbing atom upon excitation. TR-XAS data analysis is generally performed on the laser-on minus laser-off difference spectrum. Here, a new analysis scheme is presented for the TR-XAS difference fitting in both the extended X-ray absorption fine-structure (EXAFS) and the X-ray absorption near-edge structure (XANES) regions. R-space EXAFS difference fitting could quickly provide the main quantitative structure change of the first shell. The XANES fitting part introduces a global non-derivative optimization algorithm and optimizes the local structure change in a flexible way where both the core XAS calculation package and the search method in the fitting shell are changeable. The scheme was applied to the TR-XAS difference analysis of Fe(phen) 3 spin crossover complex and yielded reliable distance change and excitation population.

  1. Minerals discovered in paleolithic black pigments by transmission electron microscopy and micro-X-ray absorption near-edge structure

    NASA Astrophysics Data System (ADS)

    Chalmin, E.; Vignaud, C.; Salomon, H.; Farges, F.; Susini, J.; Menu, M.

    2006-05-01

    Analysis of archeological materials aims to rediscover the know-how of prehistoric men by determining the nature of the painting matter, its preparation mode, and the geographic origin of its raw materials. The preparation mode of the painting matter of the paleolithic rock art apparently consisted of mixing, grinding, and also heat-treatment. In this study, we focus on black pigments and more particularly manganese oxides. Using the combined approach of transmission electron microscopy (TEM) and Mn K-edge X-ray absorption near-edge structure (XANES) spectroscopy, we analyzed a variety of archeological black painted samples. The studied pigments arise from the caves of Ekain (Basque country, Spain), Labastide and Gargas (Hautes-Pyrénées, France). In addition, a black “crayon” (i.e., a “pen”) from the cave of Combe Saunière (Dordogne, France) was also investigated. From the analysis of these painting matters, several unusual minerals have been identified as black pigment, such as manganite, groutite, todorokite and birnessite. These conclusions enable us to estimate the technical level of paleolithic artists: they didn’t use heat-treatment to prepare black painting matter. Consequently, the unusual mineralogy found in some of these pigments suggests that some of the manganese ores are coming from geological settings that are sometimes relatively far away from the Dordogne and Basque region such as in Ariège (central-oriental Pyrénées).

  2. Electrosynthesis of ZnO nanorods and nanotowers: Morphology and X-ray Absorption Near Edge Spectroscopy studies

    NASA Astrophysics Data System (ADS)

    Sigircik, Gokmen; Erken, Ozge; Tuken, Tunc; Gumus, Cebrail; Ozkendir, Osman M.; Ufuktepe, Yuksel

    2015-06-01

    Deposition mechanism of nano-structured ZnO films has been investigated in the absence and presence of chloride ions from aqueous solution. The resulting opto-electronic properties were interpreted extensively, using X-ray diffraction (XRD), X-ray Absorption Near Edge Spectroscopy (XANES), field emission scanning electron microscopy (FE-SEM), UV-Visible spectroscopy and four probe techniques. The ZnO deposition is mass transport controlled process and the interaction of chloride ions with the surface has great influence on diffusion kinetics, considering the substantial species (Zn2+ and OH-) involved in the construction of ZnO film. This effect does not change major lattice parameters, as shown with detailed analysis of XRD data. However, the texture coefficient (Tc) (0 0 2) value is higher in presence of chloride ions containing synthesis solution which gave vertically aligned, well defined and uniformly dispersed nanorods structure. The calculated Eg values are in the range 3.28-3.41 eV and 3.22-3.31 eV for ZnO nanorods and nanotowers synthesized at different deposition periods, respectively. Furthermore, the charge mobility values regarding the deposition periods were measured to be in the ranges from 130.4 to 449.2 cm2 V-1 s-1 and 126.2 to 204.7 cm2 V-1 s-1 for nanorods and nanotowers, respectively. From XANES results, it was shown that the Zn K-edge spectrum is dominated by the transition of Zn 1s core electrons into the unoccupied Zn 4p states of the conduction band. Comparing the rod and tower nano-structured ZnO thin films, the excitation behavior of valence band electrons is different. Moreover, the density states of Zn 4p are higher for ZnO nanorods.

  3. Bone char effects on soil: sequential fractionations and XANES spectroscopy

    NASA Astrophysics Data System (ADS)

    Morshedizad, Mohsen; Panten, Kerstin; Klysubun, Wantana; Leinweber, Peter

    2018-01-01

    The acceptability of novel bone char fertilizers depends on their P release, but reactions at bone char surfaces and impacts on soil P speciation are insufficiently known. By using sequential fractionation and synchrotron-based X-ray absorption near-edge structure (XANES) spectroscopy we investigated whether and how the chemical composition of bone char particles has been altered in soil and has consequently affected the P speciation of amended soils. Therefore, two different kinds of bone char particles (BC produced by the pyrolysis of degreased animal bone chips at 800 °C and BCplus, a BC enriched with reduced sulfur compounds) were manually separated from the soil at the end of two different experiments: incubation leaching and ryegrass cultivation. Sequential P fractionation of amended soils showed P enrichment in all fractions compared to the control. The most P increase between all treatments significantly occurred in the NaOH-P and resin-P fractions in response to BCplus application in both incubation-leaching and ryegrass cultivation experiments. This increase in the readily available P fraction in BCplus-treated soils was confirmed by linear combination fitting (LCF) analysis on P K-edge XANES spectra of BC particles and amended soils. The proportion of Ca hydroxyapatite decreased, whereas the proportion of CaHPO4 increased in BCplus particles after amended soils had been incubated and leached and cropped by ryegrass. Based on P XANES speciation as determined by LCF analysis, the proportion of inorganic Ca(H2PO4)2 increased in amended soils after BCplus application. These results indicate that soil amendment with BCplus particles leads to elevated P concentration and maintains more soluble P species than BC particles even after 230 days of ryegrass cultivation.

  4. Surface complexation and precipitate geometry for aqueous Zn(II) sorption on ferrihydrite: II. XANES analysis and simulation

    USGS Publications Warehouse

    Waychunas, G.A.; Fuller, C.C.; Davis, J.A.; Rehr, J.J.

    2003-01-01

    X-ray absorption near-edge spectroscopy (XANES) analysis of sorption complexes has the advantages of high sensitivity (10- to 20-fold greater than extended X-ray absorption fine structure [EXAFS] analysis) and relative ease and speed of data collection (because of the short k-space range). It is thus a potentially powerful tool for characterization of environmentally significant surface complexes and precipitates at very low surface coverages. However, quantitative analysis has been limited largely to "fingerprint" comparison with model spectra because of the difficulty of obtaining accurate multiple-scattering amplitudes for small clusters with high confidence. In the present work, calculations of the XANES for 50- to 200-atom clusters of structure from Zn model compounds using the full multiple-scattering code Feff 8.0 accurately replicate experimental spectra and display features characteristic of specific first-neighbor anion coordination geometry and second-neighbor cation geometry and number. Analogous calculations of the XANES for small molecular clusters indicative of precipitation and sorption geometries for aqueous Zn on ferrihydrite, and suggested by EXAFS analysis, are in good agreement with observed spectral trends with sample composition, with Zn-oxygen coordination and with changes in second-neighbor cation coordination as a function of sorption coverage. Empirical analysis of experimental XANES features further verifies the validity of the calculations. The findings agree well with a complete EXAFS analysis previously reported for the same sample set, namely, that octahedrally coordinated aqueous Zn2+ species sorb as a tetrahedral complex on ferrihydrite with varying local geometry depending on sorption density. At significantly higher densities but below those at which Zn hydroxide is expected to precipitate, a mainly octahedral coordinated Zn2+ precipitate is observed. An analysis of the multiple scattering paths contributing to the XANES

  5. Experimental evidence of six-fold oxygen coordination for phosphorus and XANES calculations

    NASA Astrophysics Data System (ADS)

    Flank, A.-M.; Trcera, N.; Brunet, F.; Itié, J.-P.; Irifune, T.; Lagarde, P.

    2009-11-01

    Phosphorus, a group V element, has always been found so far in minerals, biological systems and synthetic compounds with an oxygen coordination number of four (i.e, PO4 groups). We demonstrate here using phosphorus K-edge XANES spectroscopy that this element can also adopt a six-fold oxygen coordination (i.e, PO6 groups). This new coordination was achieved in AlPO4 doped SiO2 stishovite synthesized at 18 GPa and 1873 K and quenched down to ambient conditions. The well-crystallized P-bearing stishovite grains (up to 100μm diameter) were embedded in the back-transformation products of high pressure form of AlPO4 matrix. They were identified by elemental mapping (μ-XRF). μ-XANES spectra collected at the Si and P K edges in the Si rich region with a very low concentration of P present striking resemblance, Si itself being characteristic of pure stishovite. We can therefore infer that phosphorus in the corresponding stishovite crystal is involved in an octahedral coordination made of six oxygen atoms. First principle XANES calculations using a plane-wave density functional formalism with core-hole effects treated in a supercell approach at the P K edge for a P atom substituting an Si one in the stishovite structure confirm this assertion. This result shows that in the lower-mantle where all silicon is six-fold coordinated, phosphorus has the crystal-chemical ability to remain incorporated into silicate structures.

  6. Alternative difference analysis scheme combining R -space EXAFS fit with global optimization XANES fit for X-ray transient absorption spectroscopy

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

    Zhan, Fei; Tao, Ye; Zhao, Haifeng

    Time-resolved X-ray absorption spectroscopy (TR-XAS), based on the laser-pump/X-ray-probe method, is powerful in capturing the change of the geometrical and electronic structure of the absorbing atom upon excitation. TR-XAS data analysis is generally performed on the laser-on minus laser-off difference spectrum. Here, a new analysis scheme is presented for the TR-XAS difference fitting in both the extended X-ray absorption fine-structure (EXAFS) and the X-ray absorption near-edge structure (XANES) regions.R-space EXAFS difference fitting could quickly provide the main quantitative structure change of the first shell. The XANES fitting part introduces a global non-derivative optimization algorithm and optimizes the local structure changemore » in a flexible way where both the core XAS calculation package and the search method in the fitting shell are changeable. The scheme was applied to the TR-XAS difference analysis of Fe(phen) 3spin crossover complex and yielded reliable distance change and excitation population.« less

  7. EXAFS and XANES investigation of the ETS-10 microporous titanosilicate.

    PubMed

    Prestipino, C; Solari, P L; Lamberti, C

    2005-07-14

    In this work, we report state-of-the-art analysis of both Ti K-edge high-resolution XANES and EXAFS data collected on the ETS-10 molecular sieve at the GILDA BM8 beamline of the ESRF facility. The interatomic distances and the angles obtained in our EXAFS study are in fair agreement with the single-crystal XRD data of Wang and Jacobson (Chem. Commun. 1999, 973) and with the recent ab initio periodic study of Damin et al. (J. Phys. Chem. B 2004, 108, 1328) Differently from previous EXAFS work (J. Phys. Chem. 1996, 100, 449), our study supports a model of ETS-10 where the Ti atoms are bonded with two equivalent axial oxygen atoms. This model is also able to reproduce the edge and the post-edge region of the XANES spectrum. Conversely, the weak but well-defined pre-edge peak at 4971.3 eV can be explained only by assuming that a fraction of Ti atoms are in a local geometry similar to that of the pentacoordinated Ti sites in the ETS-4 structure. These Ti atoms in ETS-10 should be the terminal of the -Ti-O-Ti-O-Ti- chains, of which the actual number is strongly increased by the high crystal defectivity (Ti vacancies).

  8. Electronic Structures and Optical Properties of α-Al2O3Nanowires

    NASA Astrophysics Data System (ADS)

    Wang, Zhiqiang; Li, Chunlei; Liu, Lijia; Sham, Tsun-Kong

    2013-04-01

    The electronic structure and optical properties of α-Al2O3 nanowires (NWs) have been investigated using X-ray absorption near-edge structures (XANES) and X-ray excited optical luminescence (XEOL). The XANES were recorded in total electron yield (TEY) and total fluorescence yield (TFY) across the K- and L3,2-edges of aluminium and the K-edge of oxygen. The results indicate that the NWs are of a core/shell structure with a single-crystalline core and an amorphous shell. The XEOL spectra of the NWs show an intense peak at 404 nm, which comes from the F centre located in the amorphous shell of the NWs. The implication of these findings and the sensitivity of XEOL for defect detection are discussed.

  9. Optimized Finite Difference Method for the Full-Potential XANES Simulations: Application to Molecular Adsorption Geometries in MOFs and Metal-Ligand Intersystem Crossing Transients.

    PubMed

    Guda, Sergey A; Guda, Alexander A; Soldatov, Mikhail A; Lomachenko, Kirill A; Bugaev, Aram L; Lamberti, Carlo; Gawelda, Wojciech; Bressler, Christian; Smolentsev, Grigory; Soldatov, Alexander V; Joly, Yves

    2015-09-08

    Accurate modeling of the X-ray absorption near-edge spectra (XANES) is required to unravel the local structure of metal sites in complex systems and their structural changes upon chemical or light stimuli. Two relevant examples are reported here concerning the following: (i) the effect of molecular adsorption on 3d metals hosted inside metal-organic frameworks and (ii) light induced dynamics of spin crossover in metal-organic complexes. In both cases, the amount of structural models for simulation can reach a hundred, depending on the number of structural parameters. Thus, the choice of an accurate but computationally demanding finite difference method for the ab initio X-ray absorption simulations severely restricts the range of molecular systems that can be analyzed by personal computers. Employing the FDMNES code [Phys. Rev. B, 2001, 63, 125120] we show that this problem can be handled if a proper diagonalization scheme is applied. Due to the use of dedicated solvers for sparse matrices, the calculation time was reduced by more than 1 order of magnitude compared to the standard Gaussian method, while the amount of required RAM was halved. Ni K-edge XANES simulations performed by the accelerated version of the code allowed analyzing the coordination geometry of CO and NO on the Ni active sites in CPO-27-Ni MOF. The Ni-CO configuration was found to be linear, while Ni-NO was bent by almost 90°. Modeling of the Fe K-edge XANES of photoexcited aqueous [Fe(bpy)3](2+) with a 100 ps delay we identified the Fe-N distance elongation and bipyridine rotation upon transition from the initial low-spin to the final high-spin state. Subsequently, the X-ray absorption spectrum for the intermediate triplet state with expected 100 fs lifetime was theoretically predicted.

  10. Tetrahedrally Coordinated Fe3+ in Silicate Glasses: A Mossbauer, Iron K-edge XANES and Raman Spectroscopies Study

    NASA Astrophysics Data System (ADS)

    Cochain, B.; Neuville, D. R.; McCammon, C.; Henderson, G. S.; de Ligny, D.; Pinet, O.; Richet, P.

    2009-05-01

    In natural or industrial glasses, iron is the most abundant transition metal. A good knowledge of its redox equilibrium is important to better understand the chemical and structural evolution of magmas (crystallization, viscosity), and also to optimize vitrification processes and properties of iron-bearing glasses. To study the role of iron in silicate glasses and melts, we have used in a consistent manner the Mössbauer, iron K-edge XANES and Raman spectroscopies to investigate several series of silicate glasses as a function of redox state. The samples were selected to cover a wide composition range and to investigate the interactions of iron with two network forming cations, namely, Al3+ and B3+. The glasses investigated were synthesized at high temperature under various conditions of oxygen fugacity to achieve different redox ratios for each composition. Therefore, the iron redox state was varied from the most oxidized to the most reduced. Iron redox ratios were first determined by wet chemical analysis and in some cases by room temperature Mossbauer spectroscopy. This experimental method was also used to determine the local structure of iron of some of the investigated glasses. These results where compared to iron K-edge XANES/EXAFS spectroscopy results, which lead to the iron redox state and indicate that Fe2+ is in octahedral coordination whereas Fe3+ is in tetrahedral coordination. In addition, Raman spectroscopy gave us information on the network polymerization of glasses. Clearly changes in Raman spectra are visible with the evolution of iron redox ratio. For a given composition, we observed systematically, in the 800-1200 cm-1 envelope, which is sensitive to the environment of tetrahedrally coordinated cations, the growth of a band with the iron content and the oxidation state of the sample. The peak area of this band, which we attribute to vibrational modes involving tetrahedrally coordinated Fe3+, increases with the oxidation of the sample. This

  11. Ti K-edge EXAFS and XANES study on tektites from different strewnfields

    NASA Astrophysics Data System (ADS)

    Wang, L.; Furuta, T.; Okube, M.; Yoshiasa, A.

    2011-12-01

    The concentration and local structure of each element may have various kinds of information about the asteroid impact and mass extinction. Farges and Brown have discussed about the Ti local structure by XANES, and concluded that Ti in tektite occupies 4-coordinated site. EXAFS can be analyzed to give precise information about the distance from Ti to near neighbors. The XAFS measurement of Ti local structure was preformed at the beamline 9C of the Photon Factory in KEK, Tsukuba, Japan. The specimens of tektites are from different strewnfields, they are: indochinite, bediasite, hainanite, philippinite, australite and moldavite. Sample for comparison are Libya desert glass and suevite. The k3χ(k) function was transformed into the radial structure function (RSF) for Ti K-edge of six tektites. The RSF for the Ti atom in indochinite and bediasite are similar; hainanite, australite and philippinite are similar; and moldavite is discriminated from others. It indicates that they have the same local atomic environmental around the Ti atoms and extended structure respectively. Coordination numbers and radial structure function are determined by EXAFS analyses (Table 1). We classified the tektites in three types: in indochinite and bediasite, Ti occupies 4-coordinated tetrahedral site and Ti-O distances are 1.84-1.81 Å; in hainanite, australite and philippinite, Ti occupies 5-coordinated trigonal bi-pyramidal or tetragonal pyramidal site and Ti-O distances are 1.92-1.87 Å; in moldavite, Ti occupies the 6-coordinated octahedral site and Ti-O distance is 2.00-1.96 Å. Formation of tektites is related to the impact process. It is generally recognized that tektites were formed under higher temperature and high pressure. But through this study, local structures of Ti are differing in three strewnfields and even different locations of the same strewnfield. What caused the various local structures will be another topic of tektite studies. Local structure of Ti may be changed in

  12. In Situ XANES of U and Th in Silicate Liquids at High Pressure and Temperature

    NASA Astrophysics Data System (ADS)

    Mallmann, G.; Wykes, J.; Berry, A.; O'Neill, H. S.; Cline, C. J., II; Turner, S.; Rushmer, T. A.

    2016-12-01

    Although the chemical environments of elements in silicate melts at specific conditions of temperature, pressure and oxygen fugacity (fO2) are often inferred from measurements after quenching the melts to glasses, it is widely recognized that changes may occur during the quenching process, making measurements in situ at high pressure and temperature highly desirable. A case of importance in geochemistry is the speciation of uranium in silicate melts as a function of pressure. Evidence from mineral-melt partitioning and XANES (X-ray Absorption Near-Edge Structure) spectroscopy of glasses suggests that U5+ may be stable at low pressures in the Earth's crust (along with U4+ or U6+, depending on fO2) where basaltic liquids crystallize, but not in the Earth's upper mantle where peridotite partially melts to produce such liquids. To test these observations we recorded in situ transmission U and Th L3-edge XANES spectra of U and Th-doped silicate liquids at 1.6 GPa and 1350°C using the D-DIA apparatus at the X-ray Absorption Spectroscopy Beamline of the Australian Synchrotron. Data for thorium, which occurs exclusively as a tetravalent cation under terrestrial fO2 conditions, were collected as a `control' to monitor for changes in coordination. The cell assembly consisted of a boron-epoxy cube as pressure medium, alumina sleeve and cylindrical graphite heater. The starting mix, a powdered synthetic average MORB silicate glass doped with 2 wt.% of U and Th, was loaded into San Carlos olivine capsules along with solid oxygen buffers (either Re-ReO2 or Ru-RuO2) in a sandwich arrangement. The capsule was then placed inside the graphite heater and insulated with crushable MgO powder. Temperature was monitored using a type D thermocouple. U and Th L3-edge XANES spectra were recorded throughout the heating/compression cycle and then after quenching. Our preliminary assessment indicates that the U-XANES spectra recorded for the liquid in situ at high pressure and temperature and

  13. XANES: observation of quantum confinement in the conduction band of colloidal PbS quantum dots

    NASA Astrophysics Data System (ADS)

    Demchenko, I. N.; Chernyshova, M.; He, X.; Minikayev, R.; Syryanyy, Y.; Derkachova, A.; Derkachov, G.; Stolte, W. C.; Piskorska-Hommel, E.; Reszka, A.; Liang, H.

    2013-04-01

    The presented investigations aimed at development of inexpensive method for synthesized materials suitable for utilization of solar energy. This important issue was addressed by focusing, mainly, on electronic local structure studies with supporting x-ray diffraction (XRD) and transmission electron microscopy (TEM) analysis of colloidal galena nano-particles (NPs) and quantum dots (QDs) synthesized using wet chemistry under microwave irradiation. Performed x-ray absorption near edge structure (XANES) analysis revealed an evidence of quantum confinement for the sample with QDs, where the bottom of the conduction band was shifted to higher energy. The QDs were found to be passivated with oxides at the surface. Existence of sulfate/sulfite and thiosulfate species in pure PbS and QDs, respectively, was identified.

  14. How water molecules affect the catalytic activity of hydrolases--a XANES study of the local structures of peptide deformylase.

    PubMed

    Cui, Peixin; Wang, Yu; Chu, Wangsheng; Guo, Xiaoyun; Yang, Feifei; Yu, Meijuan; Zhao, Haifeng; Dong, Yuhui; Xie, Yaning; Gong, Weimin; Wu, Ziyu

    2014-12-12

    Peptide deformylase (PDF) is a prokaryotic enzyme that catalyzes the deformylation of nascent peptides generated during protein synthesis and water molecules play a key role in these hydrolases. Using X-ray absorption near edge spectroscopy (XANES) and ab initio calculations we accurately probe the local atomic environment of the metal ion binding in the active site of PDF at different pH values and with different metal ions. This new approach is an effective way to monitor existing correlations among functions and structural changes. We show for the first time that the enzymatic activity depends on pH values and metal ions via the bond length of the nearest coordinating water (Wat1) to the metal ion. Combining experimental and theoretical data we may claim that PDF exhibits an enhanced enzymatic activity only when the distance of the Wat1 molecule with the metal ion falls in the limited range from 2.15 to 2.55 Å.

  15. EXAFS and XANES analysis of oxides at the nanoscale.

    PubMed

    Kuzmin, Alexei; Chaboy, Jesús

    2014-11-01

    Worldwide research activity at the nanoscale is triggering the appearance of new, and frequently surprising, materials properties in which the increasing importance of surface and interface effects plays a fundamental role. This opens further possibilities in the development of new multifunctional materials with tuned physical properties that do not arise together at the bulk scale. Unfortunately, the standard methods currently available for solving the atomic structure of bulk crystals fail for nanomaterials due to nanoscale effects (very small crystallite sizes, large surface-to-volume ratio, near-surface relaxation, local lattice distortions etc.). As a consequence, a critical reexamination of the available local-structure characterization methods is needed. This work discusses the real possibilities and limits of X-ray absorption spectroscopy (XAS) analysis at the nanoscale. To this end, the present state of the art for the interpretation of extended X-ray absorption fine structure (EXAFS) is described, including an advanced approach based on the use of classical molecular dynamics and its application to nickel oxide nanoparticles. The limits and possibilities of X-ray absorption near-edge spectroscopy (XANES) to determine several effects associated with the nanocrystalline nature of materials are discussed in connection with the development of ZnO-based dilute magnetic semiconductors (DMSs) and iron oxide nanoparticles.

  16. Characterization of Unsteady Flow Structures Near Leading-Edge Slat. Part 1; PIV Measurements

    NASA Technical Reports Server (NTRS)

    Jenkins, Luther N.; Khorrami, Mehdi R.; Choudhari, Meelan

    2004-01-01

    A comprehensive computational and experimental study has been performed at the NASA Langley Research Center as part of the Quiet Aircraft Technology (QAT) Program to investigate the unsteady flow near a leading-edge slat of a two-dimensional, high-lift system. This paper focuses on the experimental effort conducted in the NASA Langley Basic Aerodynamics Research Tunnel (BART) where Particle Image Velocimetry (PIV) data was acquired in the slat cove and at the slat trailing edge of a three-element, high-lift model at 4, 6, and 8 degrees angle of attack and a freestream Mach Number of 0.17. Instantaneous velocities obtained from PIV images are used to obtain mean and fluctuating components of velocity and vorticity. The data show the recirculation in the cove, reattachment of the shear layer on the slat lower surface, and discrete vortical structures within the shear layer emanating from the slat cusp and slat trailing edge. Detailed measurements are used to examine the shear layer formation at the slat cusp, vortex shedding at the slat trailing edge, and convection of vortical structures through the slat gap. Selected results are discussed and compared with unsteady, Reynolds-Averaged Navier-Stokes (URANS) computations for the same configuration in a companion paper by Khorrami, Choudhari, and Jenkins (2004). The experimental dataset provides essential flow-field information for the validation of near-field inputs to noise prediction tools.

  17. The effect of site geometry, Ti content and Ti oxidation state on the Ti K-edge XANES spectrum of synthetic hibonite

    NASA Astrophysics Data System (ADS)

    Doyle, P. M.; Berry, A. J.; Schofield, P. F.; Mosselmans, J. F. W.

    2016-08-01

    The Al-rich oxide hibonite (CaAl12O19) is modeled to be the second mineral to condense from a gas of solar composition and is found within calcium-aluminum-rich inclusions and the matrix of chondritic meteorites. Both Ti3+ and Ti4+ are reported in meteoritic hibonite, so hibonite has been proposed as a single mineral oxybarometer that could be used to elucidate conditions within the first 0.2 Myrs of the Solar System. Synthetic hibonites with Ti3+/(Ti3+ + Ti4+) (hereafter Ti3+/ΣTi) ranging between 0 and 1 were prepared as matrix-matched standards for meteoritic hibonite. The largest yield of both Ti-free and Ti-bearing hibonite at ∼1300 and ∼1400 °C was obtained by a single sinter under reducing conditions. In situ micro-beam Ti K-edge X-ray absorption near edge structure (XANES) spectra were recorded from the synthetic hibonites, as well as from terrestrial hibonite. Spectral features in the post-crest region were shown to correlate with the Ti4+ content. Furthermore, Ti4+ on the M2 trigonal bipyramidal and the adjoining M4 octahedral sites appears to cause variability in the post-crest region as a function of orientation. For this suite of synthetic hibonites it was observed that the pre-edge peak region is not influenced by orientation, but is controlled by Ti3+/ΣTi, site geometry and/or Ti concentration. In particular, the pre-edge peak intensities reflect Ti coordination environment and distortion of the M4 octahedral site. Therefore, although pre-edge peak intensities have previously been used to determine Ti3+/ΣTi in meteoritic minerals, we excluded use of the pre-edge peak intensities for quantifying Ti valence states in hibonite. The energy of the absorption edge at a normalized intensity of 0.8 (E0.8) and the energy of the minimum between the pre-edge region and the absorption edge (Em1) were found to vary systematically with Ti3+/ΣTi. Ti3+/ΣTi in hibonite as a function of Em1 was modeled by a quadratic function that may be used to quantify Ti3

  18. Experimental and theoretical study of the structural environment of magnesium in minerals and silicate glasses using X-ray absorption near-edge structure

    NASA Astrophysics Data System (ADS)

    Trcera, Nicolas; Cabaret, Delphine; Rossano, Stéphanie; Farges, François; Flank, Anne-Marie; Lagarde, Pierre

    2009-05-01

    X-ray absorption spectroscopy at the Mg K-edge is used to obtain information on magnesium environment in minerals, silicate and alumino-silicate glasses. First-principles XANES calculations are performed for minerals using a plane-wave density functional formalism with core-hole effects treated in a supercell approach. The good agreement obtained between experimental and theoretical spectra provides useful information to interpret the spectral features. With the help of calculation, the position of the first peak of XANES spectra is related to both coordination and polyhedron distortion changes. In alumino-silicate glasses, magnesium is found to be mainly 5-fold coordinated to oxygen whatever the aluminum saturation index value. In silicate glasses, magnesium coordination increases from 4 in Cs-, Rb- and K-bearing glasses to 5 in Na- and Li-bearing glasses but remains equal as the polymerization degree of the glass varies. The variation of the C feature (position and intensity) is strongly related to the alkali type providing information on the medium range order.

  19. Micro-XANES Determination Fe Speciation in Natural Basalts at Mantle-Relevant fO2

    NASA Astrophysics Data System (ADS)

    Fischer, R.; Cottrell, E.; Lanzirotti, A.; Kelley, K. A.

    2007-12-01

    We demonstrate that the oxidation state of iron (Fe3+/ΣFe) can be determined with a precision of ±0.02 (10% relative) on natural basalt glasses at mantle-relevant fO2 using Fe K-edge X-ray absorption near edge structure (XANES) spectroscopy. This is equivalent to ±0.25 log unit resolution relative to the QFM buffer. Precise determination of the oxidation state over this narrow range (Fe3+/ΣFe=0.06-0.30) and at low fO2 (down to QFM-2) relies on appropriate standards, high spectral resolution, and highly reproducible methods for extracting the pre-edge centroid position. We equilibrated natural tholeiite powder in a CO/CO2 gas mixing furnace at 1350°C from QFM-3 to QFM+2 to create six glasses of known Fe3+/ΣFe, independently determined by Mössbauer spectroscopy. XANES spectra were collected at station X26A at NSLS, Brookhaven Natl. Lab, in fluorescence mode (9 element Ge array detector) using both Si(111) and Si(311) monochromators. Generally, the energy position of the 1s→3d (pre-edge) transition centroid is the most sensitive monitor of Fe oxidation state using XANES. For the mixture of Fe oxidation states in these glasses and the resulting coordination geometries, the pre-edge spectra are best defined by two multiple 3d crystal field transitions. The Si(311) monochromator, with higher energy resolution, substantially improved spectral resolution for the 1s→3d transition. Dwell times of 5s at 0.1eV intervals across the pre-edge region yielded spectra with the 1s→3d transition peaks clearly resolved. The pre-edge centroid position is highly sensitive to the background subtraction and peak fitting procedures. Differences in fitting models result in small but significant differences in the calculated peak area of each pre-edge multiplet, and the relative contribution of each peak to the calculated centroid. We assessed several schemes and obtained robust centroid positions by simultaneously fitting the background with a damped harmonic oscillator (DHO

  20. Supervised Machine-Learning-Based Determination of Three-Dimensional Structure of Metallic Nanoparticles

    DOE PAGES

    Timoshenko, Janis; Lu, Deyu; Lin, Yuewei; ...

    2017-09-29

    Tracking the structure of heterogeneous catalysts under operando conditions remains a challenge due to the paucity of experimental techniques that can provide atomic-level information for catalytic metal species. Here we report on the use of X-ray absorption near edge structure (XANES) spectroscopy and supervised machine learning (SML) for refining the three-dimensional geometry of metal catalysts. SML is used to unravel the hidden relationship between the XANES features and catalyst geometry. To train our SML method, we rely on ab-initio XANES simulations. Our approach allows one to solve the structure of a metal catalyst from its experimental XANES, as demonstrated heremore » by reconstructing the average size, shape and morphology of well-defined platinum nanoparticles. This method is applicable to the determination of the nanoparticle structure in operando studies and can be generalized to other nanoscale systems. In conclusion, it also allows on-the-fly XANES analysis, and is a promising approach for high-throughput and time-dependent studies.« less

  1. Supervised Machine-Learning-Based Determination of Three-Dimensional Structure of Metallic Nanoparticles

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

    Timoshenko, Janis; Lu, Deyu; Lin, Yuewei

    Tracking the structure of heterogeneous catalysts under operando conditions remains a challenge due to the paucity of experimental techniques that can provide atomic-level information for catalytic metal species. Here we report on the use of X-ray absorption near edge structure (XANES) spectroscopy and supervised machine learning (SML) for refining the three-dimensional geometry of metal catalysts. SML is used to unravel the hidden relationship between the XANES features and catalyst geometry. To train our SML method, we rely on ab-initio XANES simulations. Our approach allows one to solve the structure of a metal catalyst from its experimental XANES, as demonstrated heremore » by reconstructing the average size, shape and morphology of well-defined platinum nanoparticles. This method is applicable to the determination of the nanoparticle structure in operando studies and can be generalized to other nanoscale systems. In conclusion, it also allows on-the-fly XANES analysis, and is a promising approach for high-throughput and time-dependent studies.« less

  2. Polarized XANES and EXAFS spectroscopic investigation into copper(II) complexes on vermiculite

    NASA Astrophysics Data System (ADS)

    Furnare, Luca J.; Vailionis, Arturas; Strawn, Daniel G.

    2005-11-01

    Interaction of heavy metals with clay minerals can dominate solid-solution reactions in soil, controlling the fate of the metals in the environment. In this study we used powdered and polarized extended X-ray absorption fine structure (EXAFS) spectroscopy and X-ray absorption near edge spectroscopy (XANES) to investigate Cu sorbed on Llano vermiculite and compare the results to reported Cu sorption mechanism on Wyoming (WY) smectite and reduced South African (SA) vermiculite. Analysis of the Cu K-edge spectra revealed that Cu sorbed on Llano vermiculite at high ionic strength ( I) has the greatest degree of covalent bond character, followed by Cu sorbed on montmorillonite at high I, and Cu sorbed on reduced SA vermiculite at high I. Cu sorbed on clay minerals at low I has the least covalent character. EXAFS data from Cu sorbed Ca- and K-equilibrated Llano vermiculites showed the presence of a second-shell Al, Si, or Mg backscatterer at 3.02 Å. This distance is consistent with Cu sorbing via a corner-sharing monodentate or bidentate bond. Polarized XANES and EXAFS results revealed that the angle between the Cu atom and the mineral sorption sites is 68° with respect to the [001] direction. From the bond angle and the persistence of the second-shell backscatterer when the interlayer is collapsed (K-equilibration), we conclude that Cu adsorption on the Llano vermiculite is not occurring in the interlayer but rather Cu is adsorbing onto the edges of the vermiculite. Results from this research provide evidence that Cu forms inner-sphere and outer-sphere complexes on clay minerals, and does not form the vast multinuclear surface precipitates that have been observed for Co, Zn, and Ni.

  3. PROCEEDINGS ON SYNCHROTRON RADIATION: Transfer characterization of sulfur from coal-burning emission to plant leaves by PIXE and XANES

    NASA Astrophysics Data System (ADS)

    Bao, Liang-Man; Zhang, Gui-Lin; Zhang, Yuan-Xim; Li, Yan; Lin, Jun; Liu, Wei; Cao, Qing-Chen; Zhao, Yi-Dong; Ma, Chen-Yan; Han, Yong

    2009-11-01

    The impact of coal-burning emission on sulfur in camphor leaves was investigated using Proton Induced X-ray Emission (PIXE) and synchrotron radiation technique X-ray Absorption Near-Edge Structure (XANES) spectroscopy. The PIXE results show that the sulfur concentrations in the leaves collected at the polluted site are significantly higher than those in controls. The Sulfur XANES spectra show the presence of organic (disulfides, thiols, thioethers, sulfonates and sulfoxides) and inorganic sulfur (sulfates) in the leaves. The inorganic sulfur in the leaves of camphor tree polluted by coal combustion is 15% more than that of the control site. The results suggest that the long-term coal-burning pollution resulted in an enhanced content of the total sulfur and sulfate in the leaves, and the uptake of sulfur by leaves had exceeded the metabolic requirement of plants and the excess of sulfur was stored as SO2-4. It can monitor the sulfur pollution in atmosphere.

  4. A high pressure La K-edge X-ray absorption fine structure spectroscopy investigation of La1/3NbO3

    NASA Astrophysics Data System (ADS)

    Marini, C.; Joseph, B.; Noked, O.; Shuker, R.; Kennedy, B. J.; Mathon, O.; Pascarelli, S.; Sterer, E.

    2018-01-01

    La K-edge X-ray absorption spectroscopy has been used to elucidate the changes in the local electronic and lattice structure that occur in the A-site deficient double perovskite La?NbO? up to 6 GPa. The pressure evolution of the oxygen dodecahedrum around the A-site has been examined. XANES (X-ray absorption near edge structure) data show modifications ascribed to the increase of bands overlapping as a consequence of the bond distance contraction, which has been directly probed by EXAFS (extended x-ray absorption fine structure) spectra. The La-O Debye Waller factors (DWFs) tend to increase whereas the La-Nb bond DWFs show only a tendency to decrease indicating the robustness of the crystal lattice structure, even in presence of the oxygen disordering. This permits the system to reverse back to its original conditions in this pressure range as evident from the measurements upon pressure release. The present results have been interpreted in the light of charge transfer related to the two-step reduction mechanism acting at the Nb site (with niobium ions passing from Nb? to Nb?) which also results in the elongation of the Nb-O bond distances in the octahedra, in agreement with the Nb K-edge results reported earlier.

  5. A pre-edge analysis of Mn K-edge XANES spectra to help determine the speciation of manganese in minerals and glasses

    NASA Astrophysics Data System (ADS)

    Chalmin, E.; Farges, F.; Brown, G. E.

    2009-01-01

    High-resolution manganese K-edge X-ray absorption near edge structure spectra were collected on a set of 40 Mn-bearing minerals. The pre-edge feature information (position, area) was investigated to extract as much as possible quantitative valence and symmetry information for manganese in various “test” and “unknown” minerals and glasses. The samples present a range of manganese symmetry environments (tetrahedral, square planar, octahedral, and cubic) and valences (II to VII). The extraction of the pre-edge information is based on a previous multiple scattering and multiplet calculations for model compounds. Using the method described in this study, a robust estimation of the manganese valence could be obtained from the pre-edge region at 5% accuracy level. This method applied to 20 “test” compounds (such as hausmannite and rancieite) and to 15 “unknown” compounds (such as axinite and birnessite) provides a quantitative estimate of the average valence of manganese in complex minerals and silicate glasses.

  6. Chemical species of sulfur in prostate cancer cells studied by XANES spectroscopy

    NASA Astrophysics Data System (ADS)

    Czapla, Joanna; Kwiatek, Wojciech M.; Lekki, Janusz; Dulińska-Litewka, Joanna; Steininger, Ralph; Göttlicher, Jörg

    2013-12-01

    The role of sulfur in prostate cancer progression may be significant for understanding the process of carcinogenesis. This work, based on X-ray Absorption Near Edge Structure (XANES) spectroscopy, is focused on determination of sulfur chemical species occurring in prostate cancer cell lines. The experimental material consisted of four commercially available cell lines: three from metastasized prostate cancer (PC3, LNCaP, and DU145) and one, used as a control, from the non-tumourigenic peripheral zone of the prostate (PZ-HPV-7). The experiment was performed at the SUL-X beamline of the synchrotron radiation source ANKA, Karlsruhe (Germany). The K-edge XANES spectra of sulfur were analyzed by deconvolution in order to establish sulfur species that occur in prostate cancer cells and to find out whether there are any differences in their content between various cell lines. Experimental spectra were fitted in two ways: with two Gaussian peaks and one arctangent step function, and additionally by a Linear Combination Fit with spectra of reference compounds in order to obtain quantitative chemical information. All fitting procedures were performed with the Athena code (Ravel and Newville, 2005) and the results of deconvolution were used to determine the fraction of each sulfur form. The results of data analysis showed that cell lines from different metastasis had different ratio of reduced to oxidized sulfur species. The LCF analysis demonstrated that the highest content of GSH, one of the most important sulfur-bearing compounds in cells, was observed in DU145 cells. These findings may confirm the hypothesis of changes in redox balance in case of cancer initiation and progression.

  7. 2D XANES-XEOL mapping: observation of enhanced band gap emission from ZnO nanowire arrays

    NASA Astrophysics Data System (ADS)

    Wang, Zhiqiang; Guo, Xiaoxuan; Sham, Tsun-Kong

    2014-05-01

    Using 2D XANES-XEOL spectroscopy, it is found that the band gap emission of ZnO nanowire arrays is substantially enhanced i.e. that the intensity ratio between the band gap and defect emissions increases by more than an order of magnitude when the excitation energy is scanned across the O K-edge. Possible mechanisms are discussed.Using 2D XANES-XEOL spectroscopy, it is found that the band gap emission of ZnO nanowire arrays is substantially enhanced i.e. that the intensity ratio between the band gap and defect emissions increases by more than an order of magnitude when the excitation energy is scanned across the O K-edge. Possible mechanisms are discussed. Electronic supplementary information (ESI) available: XEOL spectra with different excitation energies. X-ray attenuation length vs. photon energy. Details of surface defects in ZnO NWs. The second O K-edge and Zn L-edge 2D XANES-XEOL maps. Comparison of the first and second TEY at O K-edge and Zn L-edge scans, respectively. Raman spectra of the ZnO NWs with different IBGE/IDE ratios. See DOI: 10.1039/c4nr01049c

  8. Structural investigations of Pu{sup III} phosphate by X-ray diffraction, MAS-NMR and XANES spectroscopy

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

    Popa, Karin; Raison, Philippe E., E-mail: philippe.raison@ec.europa.eu; Martel, Laura

    2015-10-15

    PuPO{sub 4} was prepared by a solid state reaction method and its crystal structure at room temperature was solved by powder X-ray diffraction combined with Rietveld refinement. High resolution XANES measurements confirm the +III valence state of plutonium, in agreement with valence bond derivation. The presence of the americium (as β{sup −} decay product of plutonium) in the +III oxidation state was determined based on XANES spectroscopy. High resolution solid state {sup 31}P NMR agrees with the XANES results and the presence of a solid-solution. - Graphical abstract: A full structural analysis of PuPO{sub 4} based on Rietveld analysis ofmore » room temperature X-ray diffraction data, XANES and MAS NMR measurements was performed. - Highlights: • The crystal structure of PuPO{sub 4} monazite is solved. • In PuPO{sub 4} plutonium is strictly trivalent. • The presence of a minute amount of Am{sup III} is highlighted. • We propose PuPO{sub 4} as a potential reference material for spectroscopic and microscopic studies.« less

  9. Effect of Fe-substitution on the structure and magnetism of single crystals Mn2-xFexBO4

    NASA Astrophysics Data System (ADS)

    Platunov, M. S.; Kazak, N. V.; Knyazev, Yu. V.; Bezmaternykh, L. N.; Moshkina, E. M.; Trigub, A. L.; Veligzhanin, A. A.; Zubavichus, Y. V.; Solovyov, L. A.; Velikanov, D. A.; Ovchinnikov, S. G.

    2017-10-01

    Single crystalline Mn2-xFexBO4 with x = 0.3, 0.5, 0.7 grown by the flux method have been studied by means of X-ray diffraction and X-ray absorption spectroscopy at both Mn and Fe K edges. The compounds were found to crystallize in an orthorhombic warwickite structure (sp. gr. Pnam). The lattice parameters change linearly with x thus obeying the Vegard's law. The Fe3+ substitution for Mn3+ has been deduced from the X-ray absorption near-edge structure (XANES) spectra. Two energy positions of the absorption edges have been observed in Mn K-edge XANES spectra indicating the presence of manganese in two different oxidation states. Extended X-ray absorption fine structure (EXAFS) analysis has shown the reduction of local structural distortions upon Fe substitution. The magnetization data have revealed a spin-glass transition at TSG = 11, 14 and 18 K for x = 0.3, 0.5 and 0.7, respectively.

  10. Fischer-Tropsch Synthesis: XANES Investigation of Hydrogen Chloride Poisoned Iron and Cobalt-Based Catalysts at the K-Edges of Cl, Fe, and Co

    DOE PAGES

    Pendyala, Venkat Ramana Rao; Jacobs, Gary; Ma, Wenping; ...

    2016-07-23

    The effect of co-fed hydrogen chloride (HCl) in syngas on the performance of iron and cobalt-based Fischer-Tropsch (FT) catalysts was investigated in our earlier studies [ACS Catal. 5 (2015) 3124-3136 and DOE final report 2011; Catal. Lett. 144 (2014) 1127-1133]. For an iron catalyst, lower HCl concentrations (< 2.0 ppmw of HCl)) in syngas did not significantly affect the activity, whereas rapid deactivation occurred at higher concentrations (~20 ppmw). With cobalt catalysts, even low concentrations of HCl (100 ppbw) caused catalyst deactivation, and the deactivation rate increased with increasing HCl concentration in the syngas. The deactivation of the catalysts ismore » explained by the chloride being adsorbed on the catalyst surface to (1) block the active sites and/or (2) electronically modify the sites. In this study, XANES spectroscopy was employed to investigate HCl poisoning mechanism on the iron and cobalt catalysts. Cl K-edge normalized XANES results indicate that Cl is indeed present on the catalyst following HCl poisoning and exhibits a structure similar to the family of compounds MCl; two main peaks are formed, with the second peak consisting of a main peak and a higher energy shoulder. At the Co K and Fe K edges, the white line was observed to be slightly increased relative to the same catalyst under clean conditions. There is then the additional possibility that Cl adsorption may act in part to intercept electron density from the FT metallic function (e.g.,cobalt or iron carbide). If so, this would result in less back-donation and therefore hinder the scission of molecules such as CO.« less

  11. XANES study on Fe, U and Th in hydrous melts at high temperature and pressure

    NASA Astrophysics Data System (ADS)

    Wilke, M.; Schmidt, C.; Farges, F.; Borchert, M.; Simionovici, A.; Hahn, M.

    2005-12-01

    Insight to the structural units of melts is an important key to model properties of magmas. The effect of water and pressure on the local structure around minor to trace elements in silicate melts was investigated at in-situ conditions. The study was performed using XANES spectroscopy and a diamond anvil-cell. This was done to characterize spurious effects observed on glasses that are potentially invoked by quenching [1] and to understand better the processes occurring during the quench. We present results of in-situ XANES measurements on iron, uranium and thorium in hydrous silicate melt up to 1 GPa and 700° C. In-situ XANES spectra were recorded at the ESRF (Grenoble, France), beamline ID 22, using a hydrothermal diamond anvil cell with a design optimized for such measurements [2], i.e. recesses on the front and the back-side of one of the diamond anvils that provide the possibility to collect spectra at relatively low energies (down to 7 keV) and relatively low concentrations (0.1-1 wt%). In-situ Fe K-edge XANES spectra of Fe(II) in hydrous haplogranitic melt at 700° C and 500 MPa suggests that the local structure around Fe in hydrous glass observed previously is probably due to ordering during the quench. Additionally, the XANES is very similar to in-situ spectra taken on Fe(II) in anhydrous haplogranitic melt at 1150° C and ambient pressure. This indicates that the combined effect of water and pressure (0-500 MPa range) does not influence drastically the local structure of Fe in this type of melt composition. In-situ LIII-edge XANES of U in hydrous haplogranitic melt (1 wt% U) at 700° C and 620 MPa show that, upon reduction, U precipitated as uraninite. This suggests a low amount of NBO's (to which tetravalent actinides preferentially bond [3]) in this water-saturated melt. In contrast, U-bearing (1000 ppm) hydrous sodium-tri-silicate melt shows the presence of U(IV) dissolved in the melt as 6-7 coordinated species, as in dry glasses [3]. Similar

  12. Correlation between bonding structure and microstructure in fullerenelike carbon nitride thin films

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

    Gago, R.; Abendroth, B.; Moeller, W.

    2005-03-15

    The bonding structure of highly ordered fullerenelike (FL) carbon nitride (CN{sub x}) thin films has been assessed by x-ray absorption near-edge spectroscopy (XANES). Samples with different degrees of FL character have been analyzed to discern spectral signatures related to the FL microstructure. The XANES spectra of FL-CN{sub x} films resemble that of graphitic CN{sub x}, evidencing the sp{sup 2} hybridization of both C and N atoms. The FL structure is achieved with the promotion of N in threefold positions over pyridinelike and cyanidelike bonding environments. In addition, the relative {pi}{sup *}/{sigma}* XANES intensity ratio at the C(1s) edge is independentmore » of the FL character, while it decreases {approx}40% at the N(1s) edge with the formation of FL arrangements. This result indicates that there is no appreciable introduction of C-sp{sup 3} hybrids with the development of FL structures and, additionally, that a different spatial localization of {pi} electrons at C and N sites takes place in curved graphitic structures. The latter has implications for the elastic properties of graphene sheets and could, as such, explain the outstanding elastic properties of FL-CN{sub x}.« less

  13. Interface structure in nanoscale multilayers near continuous-to-discontinuous regime

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

    Pradhan, P. C.; Majhi, A.; Nayak, M., E-mail: mnayak@rrcat.gov.in

    2016-07-28

    Interfacial atomic diffusion, reaction, and formation of microstructure in nanoscale level are investigated in W/B{sub 4}C multilayer (ML) system as functions of thickness in ultrathin limit. Hard x-ray reflectivity (XRR) and x-ray diffuse scattering in conjunction with x-ray absorption near edge spectroscopy (XANES) in soft x-ray and hard x-ray regimes and depth profiling x-ray photoelectron spectroscopy (XPS) have been used to precisely evaluate detailed interfacial structure by systematically varying the individual layer thickness from continuous-to-discontinuous regime. It is observed that the interfacial morphology undergoes an unexpected significant modification as the layer thickness varies from continuous-to-discontinuous regime. The interfacial atomic diffusionmore » increases, the physical density of W layer decreases and that of B{sub 4}C layer increases, and further more interestingly the in-plane correlation length decreases substantially as the layer thickness varies from continuous-to-discontinuous regime. This is corroborated using combined XRR and x-ray diffused scattering analysis. XANES and XPS results show formation of more and more tungsten compounds at the interfaces as the layer thickness decreases below the percolation threshold due to increase in the contact area between the elements. The formation of compound enhances to minimize certain degree of disorder at the interfaces in the discontinuous region that enables to maintain the periodic structure in ML. The degree of interfacial atomic diffusion, interlayer interaction, and microstructure is correlated as a function of layer thickness during early stage of film growth.« less

  14. Nanoindentation near the edge

    Treesearch

    J.E. Jakes; C.R. Frihart; J.F. Beecher; R.J. Moon; P.J. Resto; Z.H. Melgarejo; O.M. Saurez; H. Baumgart; A.A. Elmustafa; D.S. Stone

    2009-01-01

    Whenever a nanoindent is placed near an edge, such as the free edge of the specimen or heterophase interface intersecting the surface, the elastic discontinuity associated with the edge produces artifacts in the load-depth data. Unless properly handled in the data analysis, the artifacts can produce spurious results that obscure any real trends in properties as...

  15. PREFACE: Proceedings of the First International Workshop on the Theoretical Calculation of ELNES and XANES (TEX2008) (Nagoya, Japan, 2-4 July 2008) Proceedings of the First International Workshop on the Theoretical Calculation of ELNES and XANES (TEX2008) (Nagoya, Japan, 2-4 July 2008)

    NASA Astrophysics Data System (ADS)

    Tanaka, Isao; Mizoguchi, Teruyasu; Yamamoto, Tomoyuki

    2009-03-01

    Both electron energy loss near edge structure (ELNES) spectroscopy and x-ray absorption near edge structure (XANES) spectroscopy provide information on the local structural and chemical environments of selected elements of interest. Recent technological progress in scanning transmission electron microscopy has enabled ELNES measurements with atomic column spatial resolution. Very dilute concentrations (nanograms per milliliter or ppb level) of dopants can be observed using third-generation synchrotron facilities when x-ray fluorescence is measured with highly efficient detectors. With such technical developments, ELNES and XANES have become established as essential tools in a large number of fields of natural science, including condensed matter physics, chemistry, mineralogy and materials science. In addition to these developments in experimental methodology, notable progress in reproducing spectra using theoretical methods has recently been made. Using first-principles methods, one can analyze and interpret spectra without reference to experiment. This is quite important since we are often interested in the analysis of exotic materials or specific atoms located at lattice discontinuities such as surfaces and interfaces, where appropriate experimental data are difficult to obtain. Using the structures predicted by reliable first-principles calculations, one can calculate theoretical ELNES and XANES spectra without too much difficulty even in such cases. Despite the fact that ELNES and XANES probe the same phenomenon—essentially the electric dipole transition from a core orbital to an unoccupied band—there have not been many opportunities for researchers in the two areas to meet and discuss. Theoretical calculations of ELNES spectra have been mainly confined to the electron microscopy community. On the other hand, the theory of XANES has been developed principally by researchers in the x-ray community. Publications describing the methods have been written more

  16. [Distribution and speciation of Pb in Arabidopsis thaliana shoot and rhizosphere soil by in situ synchrotron radiation micro X-ray fluorescence and X-ray absorption near edge structure].

    PubMed

    Shen, Ya-Ting

    2014-03-01

    In order to investigate plant reacting mechanism with heavy metal stress in organ and tissue level, synchrotron radiation micro X-ray fluorescence (micro-SRXRF) was used to determine element distribution characteristics of K, Ca, Mn, Fe, Cu, Zn, Pb in an Arabidopsis thaliana seedling grown in tailing dam soil taken from a lead-zinc mine exploration area. The results showed a regular distribution characters of K, Ca, Fe, Cu and Zn, while Pb appeared not only in root, but also in a leaf bud which was beyond previously understanding that Pb mainly appeared in plant root. Pb competed with Mn in the distribution of the whole seedling. Pb may cause the increase of oxidative stress in root and leaf bud, and restrict Mn absorption and utilization which explained the phenomenon of seedling death in this tailing damp soil. Speciation of Pb in Arabidopsis thaliana and tailing damp rhizosphere soil were also presented after using PbL3 micro X-ray absorption near edge structure (micro-XANES). By comparison of PbL3 XANES peak shape and peak position between standard samples and rhizosphere soil sample, it was demonstrated that the tailing damp soil was mainly formed by amorphous forms like PbO (64.2%), Pb (OH)2 (28.8%) and Pb3O4 (6.3%) rather than mineral or organic Pb speciations. The low plant bioavailability of Pb demonstrated a further research focusing on Pb absorption and speciation conversion is needed, especially the role of dissolve organic matter in soil which may enhance Pb bioavailability.

  17. Antimony leaching and chemical species analyses in an industrial solid waste: Surface and bulk speciation using ToF-SIMS and XANES.

    PubMed

    Kappen, P; Ferrando-Miguel, G; Reichman, S M; Innes, L; Welter, E; Pigram, P J

    2017-05-05

    The surface chemistry and bulk chemical speciation of solid industrial wastes containing 8wt-% antimony (Sb) were investigated using synchrotron X-ray Absorption Near Edge Structure (XANES) and Time-of-Flight Ion Secondary Mass Spectrometry (ToF-SIMS). Leaching experiments were conducted in order to better understand the behavior of Sb in waste streams and to inform regulatory management of antimony-containing wastes. The experiments also demonstrate how a combination of XANES and ToF-SIMS adds value to the field of waste investigations. Leaching treatments (acid and base) were performed at a synchrotron over 24h time periods. Surface analyses of the wastes before leaching showed the presence of Sb associated with S and O. Bulk analyses revealed Sb to be present, primarily, as trivalent sulfide species. Both acid and base leaching did not change the antimony speciation on the solid. Leaching transferred about 1% of the total Sb into solution where Sb was found to be present as Sb(V). XANES data showed similarities between leachate and FeSbO 4 . During base leaching, the Sb content in solution gradually increased over time, and potential desorption mechanisms are discussed. Copyright © 2017 Elsevier B.V. All rights reserved.

  18. Reduced As Components in Highly Oxidized Environments: Evidence from Full Spectral XANES Imaging using the Maia Massively Parallel Detector

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

    Etschmann, B.; Ryan, C; Brugger, J

    2010-01-01

    Synchrotron X-ray fluorescence (SXRF) and X-ray absorption spectroscopy (XAS) have become standard tools to measure element concentration, distribution at micrometer- to nanometer-scale, and speciation (e.g., nature of host phase; oxidation state) in inhomogeneous geomaterials. The new Maia X-ray detector system provides a quantum leap for the method in terms of data acquisition rate. It is now possible to rapidly collect fully quantitative maps of the distribution of major and trace elements at micrometer spatial resolution over areas as large as 1 x 5 cm{sup 2}. Fast data acquisition rates also open the way to X-ray absorption near-edge structure (XANES) imaging,more » in which spectroscopic information is available at each pixel in the map. These capabilities are critical for studying inhomogeneous Earth materials. Using a 96-element prototype Maia detector, we imaged thin sections of an oxidized pisolitic regolith (2 x 4.5 mm{sup 2} at 2.5 x 2.5 {micro}m{sup 2} pixel size) and a metamorphosed, sedimentary exhalative Mn-Fe ore (3.3 x 4 mm{sup 2} at 1.25 x 5 {micro}m{sup 2}). In both cases, As K-edge XANES imaging reveals localized occurrence of reduced As in parts of these oxidized samples, which would have been difficult to recognize using traditional approaches.« less

  19. Single shot near edge x-ray absorption fine structure spectroscopy in the laboratory

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

    Mantouvalou, I., E-mail: ioanna.mantouvalou@tu-berlin.de; Witte, K.; Martyanov, W.

    With the help of adapted off-axis reflection zone plates, near edge X-ray absorption fine structure spectra at the C and N K-absorption edge have been recorded using a single 1.2 ns long soft X-ray pulse. The transmission experiments were performed with a laser-produced plasma source in the laboratory rendering time resolved measurements feasible independent on large scale facilities. A resolving power of E/ΔE ∼ 950 at the respective edges could be demonstrated. A comparison of single shot spectra with those collected with longer measuring time proves that all features of the used reference samples (silicon nitrate and polyimide) can be resolved in 1.2 ns.more » Hence, investigations of radiation sensitive biological specimen become possible due to the high efficiency of the optical elements enabling low dose experiments.« less

  20. The Effect of Thermal Reduction on the Photoluminescence and Electronic Structures of Graphene Oxides

    PubMed Central

    Chuang, C.-H.; Wang, Y.-F.; Shao, Y.-C.; Yeh, Y.-C.; Wang, D.-Y.; Chen, C.-W.; Chiou, J. W.; Ray, Sekhar C.; Pong, W. F.; Zhang, L.; Zhu, J. F.; Guo, J. H.

    2014-01-01

    Electronic structures of graphene oxide (GO) and hydro-thermally reduced graphene oxides (rGOs) processed at low temperatures (120–180°C) were studied using X-ray absorption near-edge structure (XANES), X-ray emission spectroscopy (XES) and resonant inelastic X-ray scattering (RIXS). C K-edge XANES spectra of rGOs reveal that thermal reduction restores C = C sp2 bonds and removes some of the oxygen and hydroxyl groups of GO, which initiates the evolution of carbonaceous species. The combination of C K-edge XANES and Kα XES spectra shows that the overlapping π and π* orbitals in rGOs and GO are similar to that of highly ordered pyrolytic graphite (HOPG), which has no band-gap. C Kα RIXS spectra provide evidence that thermal reduction changes the density of states (DOSs) that is generated in the π-region and/or in the gap between the π and π* levels of the GO and rGOs. Two-dimensional C Kα RIXS mapping of the heavy reduction of rGOs further confirms that the residual oxygen and/or oxygen-containing functional groups modify the π and σ features, which are dispersed by the photon excitation energy. The dispersion behavior near the K point is approximately linear and differs from the parabolic-like dispersion observed in HOPG. PMID:24717290

  1. The effect of thermal reduction on the photoluminescence and electronic structures of graphene oxides.

    PubMed

    Chuang, C-H; Wang, Y-F; Shao, Y-C; Yeh, Y-C; Wang, D-Y; Chen, C-W; Chiou, J W; Ray, Sekhar C; Pong, W F; Zhang, L; Zhu, J F; Guo, J H

    2014-04-10

    Electronic structures of graphene oxide (GO) and hydro-thermally reduced graphene oxides (rGOs) processed at low temperatures (120-180°C) were studied using X-ray absorption near-edge structure (XANES), X-ray emission spectroscopy (XES) and resonant inelastic X-ray scattering (RIXS). C K-edge XANES spectra of rGOs reveal that thermal reduction restores C = C sp(2) bonds and removes some of the oxygen and hydroxyl groups of GO, which initiates the evolution of carbonaceous species. The combination of C K-edge XANES and Kα XES spectra shows that the overlapping π and π* orbitals in rGOs and GO are similar to that of highly ordered pyrolytic graphite (HOPG), which has no band-gap. C Kα RIXS spectra provide evidence that thermal reduction changes the density of states (DOSs) that is generated in the π-region and/or in the gap between the π and π* levels of the GO and rGOs. Two-dimensional C Kα RIXS mapping of the heavy reduction of rGOs further confirms that the residual oxygen and/or oxygen-containing functional groups modify the π and σ features, which are dispersed by the photon excitation energy. The dispersion behavior near the K point is approximately linear and differs from the parabolic-like dispersion observed in HOPG.

  2. Distribution and oxidation state of copper in the cell walls of treated wood examined by synchrotron based XANES and XFM

    Treesearch

    Samuel L. Zelinka; Grant T. Kirker; Joseph E. Jakes; Leandro Passarini; Barry Lai

    2016-01-01

    Recently, synchrotron based X-ray fluorescence microscopy (XFM) and X-ray absorption near edge spectroscopy (XANES) were used to examine the metal fastener corrosion in copper-treated wood. XFM is able to map the copper concentration in the wood with a spatial resolution of 0.5 µm and is able to quantify the copper concentration to within 0.05 µg cm-3...

  3. Simulation studies of structure and edge tension of lipid bilayer edges: effects of tail structure and force-field.

    PubMed

    West, Ana; Ma, Kevin; Chung, Jonathan L; Kindt, James T

    2013-08-15

    Molecular dynamics simulations of lipid bilayer ribbons have been performed to investigate the structures and line tensions associated with free bilayer edges. Simulations carried out for dioleoyl phosphatidylcholine with three different force-field parameter sets yielded edge line tensions of 45 ± 2 pN, over 50% greater than the most recently reported experimentally determined value for this lipid. Edge tensions obtained from simulations of a series of phosphatidylcholine lipid bilayer ribbons with saturated acyl tails of length 12-16 carbons and with monounsaturated acyl tails of length 14-18 carbons could be correlated with the excess area associated with forming the edge, through a two-parameter fit. Saturated-tail lipids underwent local thickening near the edge, producing denser packing that correlated with lower line tensions, while unsaturated-tail lipids showed little or no local thickening. In a dipalmitoyl phosphatidylcholine ribbon initiated in a tilted gel-phase structure, lipid headgroups tended to tilt toward the nearer edge producing a herringbone pattern, an accommodation that may account for the reported edge-induced stabilization of an ordered structure at temperatures near a lipid gel-fluid phase transition.

  4. Correlated NanoSIMS, TEM, and XANES Studies of Presolar Grains

    NASA Astrophysics Data System (ADS)

    Groopman, Evan Edward

    The objective of this thesis is to describe the correlated study of individual presolar grains via Nano-scale Secondary Ion Mass Spectrometry (NanoSIMS), Transmission Electron Microscopy (TEM), and Scanning Transmission X-ray Microscopy (STXM) utilizing X-ray Absorption Near Edge Structure (XANES), with a focus on connecting these correlated laboratory studies to astrophysical phenomena. The correlated isotopic, chemical, and microstructural studies of individual presolar grains provide the most detailed description of their formation environments, and help to inform astrophysical models and observations of stellar objects. As a part of this thesis I have developed and improved upon laboratory techniques for micromanipulating presolar grains and embedding them in resin for ultramicrotomy after NanoSIMS analyses and prior to TEM characterization. The new methods have yielded a 100% success rate and allow for the specific correlation of microstructural and isotopic properties of individual grains. Knowing these properties allows for inferences to be made regarding the condensation sequences and the origins of the stellar material that condensed to form these grains. NanoSIMS studies of ultramicrotomed sections of presolar graphite grains have revealed complex isotopic heterogeneities that appear to be primary products of the grains' formation environments and not secondary processing during the grains' lifetimes. Correlated excesses in 15N and 18O were identified as being carried by TiC subgrains within presolar graphite grains from supernovae (SNe). These spatially-correlated isotopic anomalies pinpoint the origin of the material that formed these grains: the inner He/C zone. Complex microstructures and isotopic heterogeneities also provide evidence for mixing in globular SN ejecta, which is corroborated by models and telescopic observations. In addition to these significant isotopic discoveries, I have also observed the first reported nanocrystalline core

  5. A X-Ray Absorption Study of Transition Metal Oxides

    NASA Astrophysics Data System (ADS)

    Bunker, Grant Byrd

    This work is an experimental and theoretical study of the x-ray absorption near-edge structure of selected 3d transition metal compounds. The goal is to understand the physical mechanisms of XANES, using the competing multiple scattering (MS) and single scattering formalisms of Durham et al, and of Muller and Schaich, respectively. Careful experimental measurements of the K edge absorption of Mn oxides and KMnO(,4) at 300(DEGREES)K, 140(DEGREES)K and 80(DEGREES)K were made. These materials were chosen because they exhibit a variety of structures and oxidation states. Computer simulations of the XANES using the formalisms above were also performed. The experimental results show that atoms beyond the first coordination shell significantly affect the XANES near and above the edge; in particular the temperature dependent XANES and the "white line" in MnO establish this. We conclude that XANES, like EXAFS, is primarily sensitive to geometrical structure, except within about 1 Rydberg of the Fermi level. Two types of MS are distinguished: type 1 (forward scattering) is important in both XANES and EXAFS regions; type 2 (large angle scattering) is important only at and below the edge. MS of the photoelectron among the first shell Oxygen atoms in KMnO(,4) is observed experimentally, and found to become negligible above (DBLTURN) 1 Rydberg past the edge. The sharp features in XANES are primarily due to scattering from distant atoms, rather than localized states, except below the edge. This is supported by the observation that (alpha)-Mn(,2)O(,3) and Mn(,3)O(,4) spectra are nearly identical; their structures are the same, but the average oxidation states are different. We find the bond length strongly affects the edge position and the intensity of the 3d absorption in tetrahedrally coordinated transition metals. Other new results are the first shell EXAFS amplitude in MnO shows an anomalous energy dependence, which apparently cannot be explained by current theory. A new

  6. Integrated experimental and theoretical approach for the structural characterization of Hg2+ aqueous solutions

    NASA Astrophysics Data System (ADS)

    D'Angelo, Paola; Migliorati, Valentina; Mancini, Giordano; Barone, Vincenzo; Chillemi, Giovanni

    2008-02-01

    The structural and dynamic properties of the solvated Hg2+ ion in aqueous solution have been investigated by a combined experimental-theoretical approach employing x-ray absorption spectroscopy and molecular dynamics (MD) simulations. This method allows one to perform a quantitative analysis of the x-ray absorption near-edge structure (XANES) spectra of ionic solutions using a proper description of the thermal and structural fluctuations. XANES spectra have been computed starting from the MD trajectory, without carrying out any minimization in the structural parameter space. The XANES experimental data are accurately reproduced by a first-shell heptacoordinated cluster only if the second hydration shell is included in the calculations. These results confirm at the same time the existence of a sevenfold first hydration shell for the Hg2+ ion in aqueous solution and the reliability of the potentials used in the MD simulations. The combination of MD and XANES is found to be very helpful to get important new insights into the quantitative estimation of structural properties of disordered systems.

  7. Coordination chemistry of titanium (IV) in silicate glasses and melts: IV. XANES studies of synthetic and natural volcanic glasses and tektites at ambient temperature and pressure

    NASA Astrophysics Data System (ADS)

    Farges, François; Brown, Gordon E.

    1997-05-01

    The coordination environment of Ti(IV) in seven natural and synthetic glasses of basaltic, trachytic, rhyolitic composition as well as four tektites has been studied using high-resolution Ti K-edge x-ray absorption near edge structure (XANES) spectroscopy at ambient temperature and pressure. Pre-edge features of Ti K-edge XANES spectra for these glasses suggest that [5]Ti is the dominant Ti coordination in all volcanic glasses. However, in the less polymerized glasses studied (basaltic and trachytic), [6]Ti is also important (30-50% of the total Ti) but [4]Ti was not detected. In contrast, [4]Ti is important in the most polymerized glasses (rhyolites and tektites) (from 30 to 60% of the total Ti depending on NBO/T) with [6]Ti below the detection level (≈10 at%). The local structure around Ti in the natural volcanic glasses is similar to that observed in compositionally similar synthetic silicate glasses and also in Ti-bearing silicate glass and melts with simpler compositions. The presence of F, Cl, and H 2O does not appear to affect the coordination of Ti, based on Ti K-edge XANES measurements of natural glasses bearing these volatile components. In contrast, the presence of nonbridging oxygens (produced by network modifiers) favors [5]Ti in these glass/melts. In parallel, [4]Ti is important when nonbridging oxygens are at small concentrations (NBO/T < 0.1). [6]Ti is detected (i.e., when present >10% of the total Ti) when alkaline-earths are dominant over alkalis, in agreement with bond-valence predictions for Ti-bearing silicate glass/melts below TiO 2 saturation. The abundance of [5]Ti in these silicate glasses (and presumably their melts) is in sharp contrast with the rarity of this Ti coordination state in common rock-forming minerals. Titanium cannot readily enter the structure of most rock-forming minerals, because it is present dominantly as titanyl-bearing ( [5]TiO) units in most natural magmas. In contrast, [6]Ti and [4]Ti (present, respectively, in

  8. Structure, Bonding, and Stability of Mercury Complexes with Thiolate and Thioether Ligands from High-Resolution XANES Spectroscopy and First-Principles Calculations.

    PubMed

    Manceau, Alain; Lemouchi, Cyprien; Rovezzi, Mauro; Lanson, Martine; Glatzel, Pieter; Nagy, Kathryn L; Gautier-Luneau, Isabelle; Joly, Yves; Enescu, Mironel

    2015-12-21

    We present results obtained from high energy-resolution L3-edge XANES spectroscopy and first-principles calculations for the structure, bonding, and stability of mercury(II) complexes with thiolate and thioether ligands in crystalline compounds, aqueous solution, and macromolecular natural organic matter (NOM). Core-to-valence XANES features that vary in intensity differentiate with unprecedented sensitivity the number and identity of Hg ligands and the geometry of the ligand environment. Post-Hartree-Fock XANES calculations, coupled with natural population analysis, performed on MP2-optimized Hg[(SR)2···(RSR)n] complexes show that the shape, position, and number of electronic transitions observed at high energy-resolution are directly correlated to the Hg and S (l,m)-projected empty densities of states and occupations of the hybridized Hg 6s and 5d valence orbitals. Linear two-coordination, the most common coordination geometry in mercury chemistry, yields a sharp 2p to 6s + 5d electronic transition. This transition varies in intensity for Hg bonded to thiol groups in macromolecular NOM. The intensity variation is explained by contributions from next-nearest, low-charge, thioether-type RSR ligands at 3.0-3.3 Å from Hg. Thus, Hg in NOM has two strong bonds to thiol S and k additional weak Hg···S contacts, or 2 + k coordination. The calculated stabilization energy is -5 kcal/mol per RSR ligand. Detection of distant ligands beyond the first coordination shell requires precise measurement of, and comparison to, spectra of reference compounds as well as accurate calculation of spectra for representative molecular models. The combined experimental and theoretical approaches described here for Hg can be applied to other closed-shell atoms, such as Ag(I) and Au(I). To facilitate further calculation of XANES spectra, experimental data, a new crystallographic structure of a key mercury thioether complex, Cartesian coordinates of the computed models, and examples of

  9. Unraveling the atomic structure of biogenic silica: evidence of the structural association of Al and Si in diatom frustules

    NASA Astrophysics Data System (ADS)

    Gehlen, M.; Beck, L.; Calas, G.; Flank, A.-M.; Van Bennekom, A. J.; Van Beusekom, J. E. E.

    2002-05-01

    We used X-ray absorption spectroscopy at the Al K-edge to investigate the atomic structure of biogenic silica and to assess the effect of Al on its crystal chemistry. Our study provides the first direct evidence for a structural association of Al and Si in biogenic silica. In samples of cultured diatoms, Al is present exclusively in fourfold coordination. The location and relative intensity of X-ray absorption near-edge structure (XANES) features suggests the structural insertion of tetrahedral Al inside the silica framework synthesized by the organism. In diatom samples collected in the marine environment, Al is present in mixed six- and fourfold coordination. The relative intensity of XANES structures indicates the coexistence of structural Al with a clay component, which most likely reflects sample contamination by adhering mineral particles. Extended X-ray absorption fine structure spectroscopy has been used to get Al-O distances in biogenic silica of cultured diatoms, confirming a tetrahedral coordination. Because of its effect on solubility and reaction kinetics of biogenic silica, the structural association between Al and biogenic silica at the stage of biosynthesis has consequences for the use of sedimentary biogenic silica as an indicator of past environmental conditions.

  10. Sulfur K-edge XANES analysis of natural and synthetic basaltic glasses: Implications for S speciation and S content as function of oxygen fugacity

    NASA Astrophysics Data System (ADS)

    Jugo, Pedro J.; Wilke, Max; Botcharnikov, Roman E.

    2010-05-01

    XANES analyses at the sulfur K-edge were used to determine the oxidation state of S in natural and synthetic basaltic glasses and to constrain the fO2 conditions for the transition from sulfide (S2-) to sulfate (S6+) in silicate melts. XANES spectra of basaltic samples from the Galapagos spreading center, the Juan de Fuca ridge and the Lau Basin showed a dominant broad peak at 2476.8 eV, similar to the spectra obtained from synthetic sulfide-saturated basalts and pyrrhotite. An additional sharp peak at 2469.8 eV, similar to that of crystalline sulfides, was present in synthetic glasses quenched from hydrous melts but absent in anhydrous glasses and may indicate differences in sulfide species with hydration or presence of minute sulfide inclusions exsolved during quenching. The XANES spectra of a basalt from the 1991 eruption of Mount Pinatubo, Philippines, and absarokitic basalts from the Cascades Range, Oregon, U.S.A., showed a sharp peak at 2482.8 eV, characteristic of synthetic sulfate-saturated basaltic glasses and crystalline sulfate-bearing minerals such as haüyne. Basaltic samples from the Lamont Seamount, the early submarine phase of Kilauea volcano and the Loihi Seamount showed unequivocal evidence of the coexistence of S2- and S6+ species, emphasizing the relevance of S6+ to these systems. XANES spectra of basaltic glasses synthesized in internally-heated pressure vessels and equilibrated at fO2 ranging from FMQ-1.7 to FMQ+2.7 showed systematic changes in the features related to S2- and S6+ with changes in fO2. No significant features related to sulfite (S4+) species were observed. These results were used to construct a function that allows estimates of S6+/ΣS from XANES data. Theoretical considerations and comparison of compiled S6+/ΣS data obtained by SKα shifts estimated with electron probe microanalysis (EPMA) and S6+/ΣS obtained from XANES spectra show that data obtained from EPMA measurements underestimate S6+/ΣS in samples that are sulfate

  11. Sulfur K-edge XANES analysis of natural and synthetic basaltic glasses: Implications for S speciation and S content as function of oxygen fugacity

    NASA Astrophysics Data System (ADS)

    Jugo, Pedro J.; Wilke, Max; Botcharnikov, Roman E.

    2010-10-01

    XANES analyses at the sulfur K-edge were used to determine the oxidation state of S species in natural and synthetic basaltic glasses and to constrain the fO 2 conditions for the transition from sulfide (S 2-) to sulfate (S 6+) in silicate melts. XANES spectra of basaltic samples from the Galapagos spreading center, the Juan de Fuca ridge and the Lau Basin showed a dominant broad peak at 2476.8 eV, similar to the spectra obtained from synthetic sulfide-saturated basalts and pyrrhotite. An additional sharp peak at 2469.8 eV, similar to that of crystalline sulfides, was present in synthetic glasses quenched from hydrous melts but absent in anhydrous glasses and may indicate differences in sulfide species with hydration or presence of minute sulfide inclusions exsolved during quenching. The XANES spectra of a basalt from the 1991 eruption of Mount Pinatubo, Philippines, and absarokitic basalts from the Cascades Range, Oregon, USA, showed a sharp peak at 2482.8 eV, characteristic of synthetic sulfate-saturated basaltic glasses and crystalline sulfate-bearing minerals such as hauyne. Basaltic samples from the Lamont Seamount, the early submarine phase of Kilauea volcano and the Loihi Seamount showed unequivocal evidence of the coexistence of S 2- and S 6+ species, emphasizing the relevance of S 6+ to these systems. XANES spectra of basaltic glasses synthesized in internally-heated pressure vessels and equilibrated at fO 2 ranging from FMQ - 1.4 to FMQ + 2.7 showed systematic changes in the features related to S 2- and S 6+ with changes in fO 2. No significant features related to sulfite (S 4+) species were observed. These results were used to construct a function that allows estimates of S 6+/ΣS from XANES data. Comparison of S 6+/ΣS data obtained by S Kα shifts measured with electron probe microanalysis (EPMA), S 6+/ΣS obtained from XANES spectra, and theoretical considerations show that data obtained from EPMA measurements underestimate S 6+/ΣS in samples that

  12. Comparison of Nickel XANES Spectra and Elemental Maps from a Ureilite, a LL3.8 Ordinary Chondrite, Two Carbonaceous Chondrites and Two Large Cluster IDPs

    NASA Technical Reports Server (NTRS)

    Wirick, S.; Flynn, G. J.; Sutton, S.; Zolensky, M. E.

    2014-01-01

    Nickel in the extraterrestrial world is commonly found in both Fe-Ni sulfide and Fe-Ni met-al forms [1] and in the pure metal state in the interior of iron meteorites where it is not easily oxidized. Ni is also found in olivine, pyroxene and glasses and in some melts the partitioning of Ni between the olivines and glass is controlled by the amount of S in the melt [2]. Its most common valence state is Ni(2+) but Ni also occurs as Ni(0), Ni(+), and Ni(3+) and rarely as Ni(2-), Ni(1-) and Ni(4+) [3]. It's valence state in olivines is Ni(2+) in octa-hedral coordination on the M1 site and rarely on the M2 site.[4]. The chemical sensitivity of X-ray absorp-tion near-edge structure (XANES) spectroscopy is well established and can be used to determine not only va-lence states but also coordination sites [5]. We report here Ni XANES spectroscopy and elemental maps collected from 2 carbonaceous chondrites, 2 large clus-ter IDPs, 1 ureilite and 1 LL3 orginary chondrite.Using XANES it may be possible to find a common trait in the large cluster IDPs that will also be found in mete-orite samples.

  13. Theory and X-ray Absorption Spectroscopy for Aluminum Coordination Complexes – Al K-Edge Studies of Charge and Bonding in (BDI)Al, (BDI)AlR2, and (BDI)AlX2 Complexes.

    PubMed

    Altman, Alison B; Pemmaraju, C D; Camp, Clément; Arnold, John; Minasian, Stefan G; Prendergast, David; Shuh, David K; Tyliszczak, Tolek

    2015-08-19

    Polarized aluminum K-edge X-ray absorption near edge structure (XANES) spectroscopy and first-principles calculations were used to probe electronic structure in a series of (BDI)Al, (BDI)AlX2, and (BDI)AlR2 coordination compounds (X = F, Cl, I; R = H, Me; BDI = 2,6-diisopropylphenyl-β-diketiminate). Spectral interpretations were guided by examination of the calculated transition energies and polarization-dependent oscillator strengths, which agreed well with the XANES spectroscopy measurements. Pre-edge features were assigned to transitions associated with the Al 3p orbitals involved in metal-ligand bonding. Qualitative trends in Al 1s core energy and valence orbital occupation were established through a systematic comparison of excited states derived from Al 3p orbitals with similar symmetries in a molecular orbital framework. These trends suggested that the higher transition energies observed for (BDI)AlX2 systems with more electronegative X(1-) ligands could be ascribed to a decrease in electron density around the aluminum atom, which causes an increase in the attractive potential of the Al nucleus and concomitant increase in the binding energy of the Al 1s core orbitals. For (BDI)Al and (BDI)AlH2 the experimental Al K-edge XANES spectra and spectra calculated using the eXcited electron and Core-Hole (XCH) approach had nearly identical energies for transitions to final state orbitals of similar composition and symmetry. These results implied that the charge distributions about the aluminum atoms in (BDI)Al and (BDI)AlH2 are similar relative to the (BDI)AlX2 and (BDI)AlMe2 compounds, despite having different formal oxidation states of +1 and +3, respectively. However, (BDI)Al was unique in that it exhibited a low-energy feature that was attributed to transitions into a low-lying p-orbital of b1 symmetry that is localized on Al and orthogonal to the (BDI)Al plane. The presence of this low-energy unoccupied molecular orbital on electron-rich (BDI)Al distinguishes

  14. Combined Mössbauer spectroscopic, multi-edge X-ray absorption spectroscopic, and density functional theoretical study of the radical SAM enzyme spore photoproduct lyase.

    PubMed

    Silver, Sunshine C; Gardenghi, David J; Naik, Sunil G; Shepard, Eric M; Huynh, Boi Hanh; Szilagyi, Robert K; Broderick, Joan B

    2014-03-01

    Spore photoproduct lyase (SPL), a member of the radical S-adenosyl-L-methionine (SAM) superfamily, catalyzes the direct reversal of the spore photoproduct, a thymine dimer specific to bacterial spores, to two thymines. SPL requires SAM and a redox-active [4Fe-4S] cluster for catalysis. Mössbauer analysis of anaerobically purified SPL indicates the presence of a mixture of cluster states with the majority (40 %) as [2Fe-2S](2+) clusters and a smaller amount (15 %) as [4Fe-4S](2+) clusters. On reduction, the cluster content changes to primarily (60 %) [4Fe-4S](+). The speciation information from Mössbauer data allowed us to deconvolute iron and sulfur K-edge X-ray absorption spectra to uncover electronic (X-ray absorption near-edge structure, XANES) and geometric (extended X-ray absorption fine structure, EXAFS) structural features of the Fe-S clusters, and their interactions with SAM. The iron K-edge EXAFS data provide evidence for elongation of a [2Fe-2S] rhomb of the [4Fe-4S] cluster on binding SAM on the basis of an Fe···Fe scatterer at 3.0 Å. The XANES spectra of reduced SPL in the absence and presence of SAM overlay one another, indicating that SAM is not undergoing reductive cleavage. The X-ray absorption spectroscopy data for SPL samples and data for model complexes from the literature allowed the deconvolution of contributions from [2Fe-2S] and [4Fe-4S] clusters to the sulfur K-edge XANES spectra. The analysis of pre-edge features revealed electronic changes in the Fe-S clusters as a function of the presence of SAM. The spectroscopic findings were further corroborated by density functional theory calculations that provided insights into structural and electronic perturbations that can be correlated by considering the role of SAM as a catalyst or substrate.

  15. Crystal structure and electronic states of Co and Gd ions in a Gd0.4Sr0.6CoO2.85 single crystal

    NASA Astrophysics Data System (ADS)

    Platunov, M. S.; Dudnikov, V. A.; Orlov, Yu. S.; Kazak, N. V.; Solovyov, L. A.; Zubavichus, Ya. V.; Veligzhanin, A. A.; Dorovatovskii, P. V.; Vereshchagin, S. N.; Shaykhutdinov, K. A.; Ovchinnikov, S. G.

    2016-02-01

    X-ray diffraction and X-ray absorption near edge structure (XANES) spectra have been measured at the Co K-edge and Gd L 3-edge in GdCoO3 and Gd0.4Sr0.6CoO2.85 cobaltites. The effect of Sr substitution on the crystal structure and electronic and magnetic states of Co3+ ions in a Gd0.4Sr0.6CoO2.85 single crystal has been analyzed. The XANES measurements at the Co K-edge have not showed a noticeable shift of the absorption edge with an increase in the concentration of Sr. This indicates that the effective valence of cobalt does not change. An increase in the intensity of absorption at the Gd L 3-edge is due to an increase in the degree of hybridization of the Gd(5 d) and O(2 p) states. The effect of hole doping on the magnetic properties results in the appearance of the ferromagnetic component and in a significant increase in the magnetic moment.

  16. [XANES study of lead speciation in duckweed].

    PubMed

    Chu, Bin-Bin; Luo, Li-Qiang; Xu, Tao; Yuan, Jing; Sun, Jian-Ling; Zeng, Yuan; Ma, Yan-Hong; Yi, Shan

    2012-07-01

    Qixiashan lead-zinc mine of Nanjing was one of the largest lead zinc deposits in East China Its exploitation has been over 50 years, and the environmental pollution has also been increasing. The lead concentration in the local environment was high, but lead migration and toxic mechanism has not been clear. Therefore, biogeochemistry research of the lead zinc mine was carried out. Using ICP-MS and Pb-L III edge XANES, lead concentration and speciation were analyzed respectively, and duckweed which can tolerate and enriched heavy metals was found in the pollution area. The results showed that the lead concentration of duckweed was 39.4 mg x kg(-1). XANES analysis and linear combination fit indicated that lead stearate and lead sulfide accounted for 65% and 36.9% respectively in the lead speciation of duckweed, suggesting that the main lead speciation of duckweed was sulfur-containing lead-organic acid.

  17. Olivine-melt relationships and syneruptive redox variations in the 1959 eruption of K$$\\bar{i}$$lauea Volcano as revealed by XANES

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

    Helz, R. T.; Cottrell, E.; Brounce, M. N.

    The 1959 summit eruption of Kmore » $$\\bar{i}$$lauea Volcano exhibited high lava fountains of gas-rich, primitive magma, containing olivine + chromian spinel in highly vesicular brown glass. Microprobe analysis of these samples shows that euhedral rims on olivine phenocrysts, in direct contact with glass, vary significantly in forsterite (Fo) content, at constant major-element melt composition, as do unzoned groundmass olivine crystals. Ferric/total iron (Fe+ 3/FeT)ratios for matrix and interstitial glasses, plus olivine-hosted glass inclusions in eight 1959 scoria samples have been determined by micro X-ray absorption near-edge structure spectroscopy (μ-XANES). These data show that much of the variation in Fo content reflects variation in oxidation state of iron in the melt, which varies with sulfur concentration in the glass and (locally) with proximity to scoria edges in contact with air. Data for 24 olivine-melt pairs in the better-equilibrated samples from later in the eruption show KD averaging 0.280 ± 0.03 for the exchange of Fe and Mg between olivine and melt, somewhat displaced from the value of 0.30 ± 0.03 given by Roeder and Emslie (1970). This may reflect the low SiO2 content of the 1959 magmas, which is lower than that in most K$$\\bar{i}$$lauea tholeiites. More broadly, we show the potential of μ-XANES and electron microprobe to revisit and refine the value of KD in natural systems.« less

  18. Roles of Pt and BaO in the Sulfation of Pt/BaO/Al2O3 Lean NOx Trap Materials: Sulfur K-edge XANES and Pt LIII XAFS Studies

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

    Kim, Do Heui; Kwak, Ja Hun; Szanyi, Janos

    2008-02-28

    The roles of barium oxide and platinum during the sulfation of Pt-BaO/Al2O3 lean NOx trap catalysts were investigated by S K edge XANES (X-ray absorption near-edge spectroscopy) and Pt LIII XAFS (X-ray absorption fine structure). All of the samples studied (Al2O3, BaO/Al2O3, Pt/Al2O3 and Pt-BaO/Al2O3) were pre-sulfated prior to the X-ray absorption measurements. It was found that barium oxide itself has the ability to directly form barium sulfate even in the absence of Pt and gas phase oxygen. In the platinum-containing samples, the presence of Pt-O species plays an important role in the formation of sulfate species. Even if bariummore » and aluminum sites are available for SO2 to form sulfate, for the case of the BaO(8)/Al2O3 sample, where the barium coverage is about 0.26 ML, S XANES spectroscopy results show that barium sulfates are preferentially produced over aluminum sulfates . When oxygen is absent from the gas phase, the sulfation route that involves Pt-O is eliminated after the initially present Pt-O species are completely consumed. In this case, formation of sulfates is suppressed unless barium oxide is also present. Pt LIII XAFS results show that the first coordination sphere around the Pt atoms in the Pt particles is dependent upon the redox nature of the gas mixture used during the sulfation process. Sulfation under reducing environments (e.g. SO2+H2) leads to formation of Pt-S bonds, while oxidizing conditions (e.g. SO2+O2) continue to show the presence of Pt-O bonds. In addition, the former condition was found to give rise to a higher degree of Pt sintering than the latter one. This result explains why samples sulfated under reducing conditions had lower NOx uptakes than those sulfated under oxidizing conditions. Therefore, our results provide needed information for the development of optimum practical operation conditions (e.g. sulfation or desulfation) for lean NOx trap catalysts that minimize deactivation by sulfur.« less

  19. Roles of Pt and BaO in the Sulfation of Pt/BaO/Al2O3 Lean NOx Trap Materials: Sulfur K-edge XANES and Pt Llll XAFS Studies

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

    Kim,D.; Kwak, J.; Szanyi, J.

    2008-01-01

    The roles of barium oxide and platinum during the sulfation of Pt-BaO/Al2O3 lean NOx trap catalysts were investigated by S K edge XANES (X-ray absorption near-edge spectroscopy) and Pt LIII XAFS (X-ray absorption fine structure). All of the samples studied [Al2O3, BaO(x; x = 8 or 20 wt %)/Al2O3, Pt(2.5 wt %)/Al2O3, and Pt(2 wt %)-BaO(x; x = 8 or 20 wt %)/Al2O3] were pre-sulfated prior to the X-ray absorption measurements. It was found that barium oxide itself has the ability to directly form barium sulfate even in the absence of Pt and gas-phase oxygen. In the platinum-containing samples, themore » presence of Pt-O species plays an important role in the formation of sulfate species. For the case of the BaO(8)/Al2O3 sample, where the barium coverage is about 0.26 ML, both baria and alumina phases are available for sulfation. S XANES results show that barium sulfates are formed preferentially over aluminum sulfates. When oxygen is absent from the gas phase, the sulfation route that involves Pt-O is eliminated after the initially present Pt-O species are completely consumed. In this case, formation of sulfates is suppressed unless barium oxide is also present. Pt LIII XAFS results show that the first coordination sphere around the Pt atoms in the Pt particles is dependent upon the gas mixture used during the sulfation process. Sulfation under reducing environments (e.g., SO2/H2) leads to formation of Pt-S bonds, while oxidizing conditions (e.g., SO2/O2) continue to show the presence of Pt-O bonds. In addition, a reducing environment was found to cause Pt sintering in greater extent than an oxidizing one. This result explains why samples sulfated under reducing conditions had lower NOx uptakes than those sulfated under oxidizing conditions. Therefore, our results provide needed information for the development of optimum practical operation conditions (e.g., sulfation or desulfation) for lean NOx trap catalysts that minimize deactivation by sulfur.« less

  20. EXAFS and XANES investigation of (Li, Ni) codoped ZnO thin films grown by pulsed laser deposition.

    PubMed

    Mino, Lorenzo; Gianolio, Diego; Bardelli, Fabrizio; Prestipino, Carmelo; Senthil Kumar, E; Bellarmine, F; Ramanjaneyulu, M; Lamberti, Carlo; Ramachandra Rao, M S

    2013-09-25

    Ni doped, Li doped and (Li, Ni) codoped ZnO thin films were successfully grown using a pulsed laser deposition technique. Undoped and doped ZnO thin films were investigated using extended x-ray absorption fine structure (EXAFS) and x-ray absorption near edge spectroscopy (XANES). Preliminary investigations on the Zn K-edge of the undoped and doped ZnO thin films revealed that doping has not influenced the average Zn-Zn bond length and Debye-Waller factor. This shows that both Ni and Li doping do not appreciably affect the average local environment of Zn. All the doped ZnO thin films exhibited more than 50% of substitutional Ni, with a maximum of 77% for 2% Ni and 2% Li doped ZnO thin film. The contribution of Ni metal to the EXAFS signal clearly reveals the presence of Ni clusters. The Ni-Ni distance in the Ni(0) nanoclusters, which are formed in the film, is shorter with respect to the reference Ni metal foil and the Debye-Waller factor is higher. Both facts perfectly reflect what is expected for metal nanoparticles. At the highest doping concentration (5%), the presence of Li favors the growth of a secondary NiO phase. Indeed, 2% Ni and 5% Li doped ZnO thin film shows %Nisub = 75 ± 11, %Nimet = 10 ± 8, %NiO = 15 ± 8. XANES studies further confirm that the substitutional Ni is more than 50% in all the samples. These results explain the observed magnetic properties.

  1. SORPTION OF ARSENATE AND ARSENITE ON RUO2 X H2O: ANALYSIS OF SORBED PHASE OXIDATION STATE BY XANES IN ADVANCED PHOTON SOURCE ACTIVITY REPORT 2002

    EPA Science Inventory

    The sorption reactions of arsenate (As(V)) and arsenite (As(III)) on RuO2 x H2O were examined by X-ray Absorption Near Edge Spectroscopy (XANES) to elucidate the solid state speciation of sorbed As. At all pH values studied (pH 4-8), RuO2 x H

  2. Development of XAFS Into a Structure Determination Technique

    NASA Astrophysics Data System (ADS)

    Stern, E. A.

    After the detection of diffraction of x-rays by M. Laue in 1912, the technique was soon applied to structure determination by Bragg within a year. On the other hand, although the edge steps in X-Ray absorption were discovered even earlier by Barkla and both the near edge (XANES) and extended X-Ray fine structure (EXAFS) past the edge were detected by 1929, it still took over 40 years to realize the structure information contained in this X-Ray absorption fine structure (XAFS). To understand this delay a brief historical review of the development of the scientific ideas that transformed XAFS into the premiere technique for local structure determination is given. The development includes both advances in theoretical understanding and calculational capabilities, and in experimental facilities, especially synchrotron radiation sources. The present state of the XAFS technique and its capabilities are summarized.

  3. Specific features of the atomic structure of metallic layers of multilayered (CoFeZr/SiO2)32 and (CoFeZr/ a-Si)40 nanostructures with different interlayers

    NASA Astrophysics Data System (ADS)

    Domashevskaya, E. P.; Guda, A. A.; Chernyshev, A. V.; Sitnikov, V. G.

    2017-02-01

    Multilayered nanostructures (MN) were prepared by ion-beam successive sputtering from two targets, one of which was a metallic Co45Fe45Zr10 alloy plate and another target was a quartz (SiO2) or silicon plate on the surface of a rotating glass-ceramic substrate in an argon atmosphere. The Co and Fe K edges X-ray absorption fine structure of XANES in the (CoFeZr/SiO2)32 sample with oxide interlayers was similar to XANES of metallic Fe foil. This indicated the existence in metallic layers of multilayered CoFeZr nanocrystals with a local environment similar to the atomic environment in solid solutions on the base of bcc Fe structure, which is also confirmed by XRD data. XANES near the Co and Fe K edges absorption in another multilayered nanostructure with silicon interlayers (CoFeZr/ a-Si)40 differs from XANES of MN with dielectric SiO2 interlayer, which demonstrates a dominant influence of the Fe-Si and Co-Si bonds in the local environment of 3 d Co and Fe metals when they form CoFeSi-type silicide phases in thinner bilayers of this MN.

  4. In situ XANES and EXAFS Analysis of Redox Active Fe Center Ionic Liquids

    DOE PAGES

    Apblett, Christopher A.; Stewart, David M.; Fryer, Robert T.; ...

    2015-10-23

    We apply in situ X-Ray Absorption Near Edge Spectroscopy (XANES) and Extended X-Ray Absorption Fine Structure (EXAFS) techniques to a metal center ionic liquid undergoing oxidation and reduction in a three electrode spectroscopic cell. Furthermore, the determination of the extent of reduction under negative bias on the working electrode and the extent of oxidation are determined after pulse voltammetry to quiescence. While the ionic liquid undergoes full oxidation, it undergoes only partial reduction, likely due to transport issues on the timescale of the experiment. Nearest neighbor Fe-O distances in the fully oxidized state match well to expected values for similarlymore » coordinated solids, but reduction does not result in an extension of the Fe-O bond length, as would be expected from comparisons to the solid phase. Instead, little change in bond length is observed. Finally, we suggest that this may be due to a more complex interaction between the monodentate ligands of the metal center anion and the surrounding charge cloud, rather than straightforward electrostatics between the metal center and the nearest neighbor grouping.« less

  5. Relating electronic and geometric structure of atomic layer deposited BaTiO 3 to its electrical properties

    DOE PAGES

    Torgersen, Jan; Acharya, Shinjita; Dadlani, Anup Lal; ...

    2016-03-24

    Atomic layer deposition allows the fabrication of BaTiO 3 (BTO) ultrathin films with tunable dielectric properties, which is a promising material for electronic and optical technology. Industrial applicability necessitates a better understanding of their atomic structure and corresponding properties. Through the use of element-specific X-ray absorption near edge structure (XANES) analysis, O K-edge of BTO as a function of cation composition and underlying substrate (RuO 2 and SiO 2) is revealed. By employing density functional theory and multiple scattering simulations, we analyze the distortions in BTO’s bonding environment captured by the XANES spectra. The spectral weight shifts to lower energymore » with increasing Ti content and provides an atomic scale (microscopic) explanation for the increase in leakage current density. Differences in film morphologies in the first few layers near substrate–film interfaces reveal BTO’s homogeneous growth on RuO 2 and its distorted growth on SiO 2. As a result, this work links structural changes to BTO thin-film properties and provides insight necessary for optimizing future BTO and other ternary metal oxide-based thin-film devices.« less

  6. Local structural variation with oxygen fugacity in Fe 2SiO 4+x fayalitic iron silicate melts

    DOE PAGES

    Alderman, O.L.G.; Lazareva, L.; Wilding, M. C.; ...

    2017-01-07

    Here, the structure of molten Fe 2SiO 4+x has been studied using both high-energy X-ray diffraction and Fe K-edge X-ray absorption near-edge structure (XANES) spectroscopy, combined with aerodynamic levitation and laser beam heating. A wide range of Fe 3+ contents were accessed by varying the levitation and atmospheric gas composition. Diffraction measurements were made in the temperature ( T) and oxygen partial pressure ranges 1624(21) < T < 2183(94) K (uncertainties in parentheses) and –5.6(3) < ΔFMQ < +2.8(5) log units (relative to the Fayalite-Magnetite-Quartz buffer). Iron K-edge XANES measurements covered the ranges 1557(33) < T < 1994(36) K andmore » –2.1(3) < ΔFMQ < +4.4(3) log units. Fe 3+ contents, x = Fe 3+/ΣFe, estimated directly from the pre-edge peaks of the XANES spectra varied between 0.15(1) and 0.40(2). While these agree in some cases with semi-empirical models, notable discrepancies are discussed in the context of the redox kinetics and the limitations in both the models and in the calibrations used to derive oxidation state from XANES spectra. XANES pre-edge peak areas imply average Fe–O coordination numbers, n FeO, close to 5 for all Fe 3+/ΣFe. Diffraction measurements yielded values of 4.4(2) < n FeO < 4.7(1). There is limited evidence for a linear trend n FeO(x) = 4.46(3) + 0.4(1)x. Asymmetric Fe–O bond length distributions peak at around 1.96 Å and have a shoulder arising from longer interatomic distances. Mean r FeO lie close to 2.06 Å, consistent with n FeO close to 5. These observations suggest that Fe 2+ is less efficient at stabilizing tetrahedral Fe 3+ compared to large monovalent alkali cations. Comparison of in-situ XANES estimates of Fe 3+/ΣFe in the melts to those of the quenched solids obtained from XANES as well as Mössbauer spectroscopy indicate rapid oxidation during cooling, enabled by stirring of the melt by the levitation gas flow. As such, the oxidation state of hot komatiitic and other highly fluid melts

  7. Local structural variation with oxygen fugacity in Fe2SiO4+x fayalitic iron silicate melts

    NASA Astrophysics Data System (ADS)

    Alderman, O. L. G.; Lazareva, L.; Wilding, M. C.; Benmore, C. J.; Heald, S. M.; Johnson, C. E.; Johnson, J. A.; Hah, H.-Y.; Sendelbach, S.; Tamalonis, A.; Skinner, L. B.; Parise, J. B.; Weber, J. K. R.

    2017-04-01

    The structure of molten Fe2SiO4+x has been studied using both high-energy X-ray diffraction and Fe K-edge X-ray absorption near-edge structure (XANES) spectroscopy, combined with aerodynamic levitation and laser beam heating. A wide range of Fe3+ contents were accessed by varying the levitation and atmospheric gas composition. Diffraction measurements were made in the temperature (T) and oxygen partial pressure ranges 1624(21) < T < 2183(94) K (uncertainties in parentheses) and -5.6(3) < ΔFMQ < +2.8(5) log units (relative to the Fayalite-Magnetite-Quartz buffer). Iron K-edge XANES measurements covered the ranges 1557(33) < T < 1994(36) K and -2.1(3) < ΔFMQ < +4.4(3) log units. Fe3+ contents, x = Fe3+/ΣFe, estimated directly from the pre-edge peaks of the XANES spectra varied between 0.15(1) and 0.40(2). While these agree in some cases with semi-empirical models, notable discrepancies are discussed in the context of the redox kinetics and the limitations in both the models and in the calibrations used to derive oxidation state from XANES spectra. XANES pre-edge peak areas imply average Fe-O coordination numbers, nFeO, close to 5 for all Fe3+/ΣFe. Diffraction measurements yielded values of 4.4(2) < nFeO < 4.7(1). There is limited evidence for a linear trend nFeO(x) = 4.46(3) + 0.4(1)x. Asymmetric Fe-O bond length distributions peak at around 1.96 Å and have a shoulder arising from longer interatomic distances. Mean rFeO lie close to 2.06 Å, consistent with nFeO close to 5. These observations suggest that Fe2+ is less efficient at stabilizing tetrahedral Fe3+ compared to large monovalent alkali cations. Comparison of in-situ XANES estimates of Fe3+/ΣFe in the melts to those of the quenched solids obtained from XANES as well as Mössbauer spectroscopy indicate rapid oxidation during cooling, enabled by stirring of the melt by the levitation gas flow. As such, the oxidation state of hot komatiitic and other highly fluid melts may not be retained, even during

  8. Fischer–Tropsch Synthesis: XANES Spectra of Potassium in Promoted Precipitated Iron Catalysts as a Function of Time On-stream

    DOE PAGES

    Jacobs, Gary; Pendyala, Venkat Ramana Rao; Martinelli, Michela; ...

    2017-06-06

    XANES K-edge spectra of potassium promoter in precipitated Fe catalysts were acquired following activation by carburization in CO and as a function of time on-stream during the course of a Fischer–Tropsch synthesis run for a 100Fe:2K catalyst by withdrawing catalysts, sealed in wax product, for analysis. CO-activated and end-of-run spectra of the catalyst were also obtained for a 100Fe:5K catalyst. Peaks representing electronic transitions and multiple scattering were observed and resembled reference spectra for potassium carbonate or potassium formate. The shift in the multiple scattering peak to higher energy was consistent with sintering of potassium promoter during the course ofmore » the reaction test. The catalyst, however, retained its carbidic state, as demonstrated by XANES and EXAFS spectra at the iron K-edge, suggesting that sintering of potassium did not adversely affect the carburization rate, which is important for preventing iron carbides from oxidizing. This method serves as a starting point for developing better understanding of the chemical state and changes in structure occurring with alkali promoter.« less

  9. Combination of first-principles molecular dynamics and XANES simulations for LiCoO2-electrolyte interfacial reactions in a lithium-ion battery

    NASA Astrophysics Data System (ADS)

    Tamura, Tomoyuki; Kohyama, Masanori; Ogata, Shuji

    2017-07-01

    We performed a first-principles molecular dynamics (FPMD) simulation of the interfacial reactions between a LiCoO2 electrode and a liquid ethylene carbonate (EC) electrolyte. For configurations during the FPMD simulation, we also performed first-principles Co K-edge x-ray absorption near-edge structure (XANES) simulations, which can properly reproduce the bulk and surface spectra of LiCoO2. We observed strong absorption of an EC molecule on the LiCoO2 {110} surface, involving ring opening of the molecule, bond formation between oxygen atoms in the molecule and surface Co ions, and emission of one surface Li ion, while all the surface Co ions remain Co3 +. The surface Co ions having the bond with an oxygen atom in the molecule showed remarkable changes in simulated K-edge spectra which are similar to those of the in situ observation under electrolyte soaking [D. Takamatsu et al., Angew. Chem., Int. Ed. 51, 11597 (2012), 10.1002/anie.201203910]. Thus, the local environmental changes of surface Co ions due to the reactions with an EC molecule can explain the experimental spectrum changes.

  10. Solvation structure of the halides from x-ray absorption spectroscopy

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

    Antalek, Matthew; Hedman, Britt; Sarangi, Ritimukta, E-mail: ritis@slac.stanford.edu

    2016-07-28

    Three-dimensional models for the aqueous solvation structures of chloride, bromide, and iodide are reported. K-edge extended X-ray absorption fine structure (EXAFS) and Minuit X-ray absorption near edge (MXAN) analyses found well-defined single shell solvation spheres for bromide and iodide. However, dissolved chloride proved structurally distinct, with two solvation shells needed to explain its strikingly different X-ray absorption near edge structure (XANES) spectrum. Final solvation models were as follows: iodide, 8 water molecules at 3.60 ± 0.13 Å and bromide, 8 water molecules at 3.40 ± 0.14 Å, while chloride solvation included 7 water molecules at 3.15 ± 0.10 Å, andmore » a second shell of 7 water molecules at 4.14 ± 0.30 Å. Each of the three derived solvation shells is approximately uniformly disposed about the halides, with no global asymmetry. Time-dependent density functional theory calculations simulating the chloride XANES spectra following from alternative solvation spheres revealed surprising sensitivity of the electronic state to 6-, 7-, or 8-coordination, implying a strongly bounded phase space for the correct structure during an MXAN fit. MXAN analysis further showed that the asymmetric solvation predicted from molecular dynamics simulations using halide polarization can play no significant part in bulk solvation. Classical molecular dynamics used to explore chloride solvation found a 7-water solvation shell at 3.12 (−0.04/+0.3) Å, supporting the experimental result. These experiments provide the first fully three-dimensional structures presenting to atomic resolution the aqueous solvation spheres of the larger halide ions.« less

  11. EXAFS/XANES studies of plutonium-loaded sodalite/glass waste forms

    NASA Astrophysics Data System (ADS)

    Richmann, Michael K.; Reed, Donald T.; Kropf, A. Jeremy; Aase, Scott B.; Lewis, Michele A.

    2001-09-01

    A sodalite/glass ceramic waste form is being developed to immobilize highly radioactive nuclear wastes in chloride form, as part of an electrochemical cleanup process. Two types of simulated waste forms were studied: where the plutonium was alone in an LiCl/KCl matrix and where simulated fission-product elements were added representative of the electrometallurgical treatment process used to recover uranium from spent nuclear fuel also containing plutonium and a variety of fission products. Extended X-ray absorption fine structure spectroscopy (EXAFS) and X-ray absorption near-edge spectroscopy (XANES) studies were performed to determine the location, oxidation state, and particle size of the plutonium within these waste form samples. Plutonium was found to segregate as plutonium(IV) oxide with a crystallite size of at least 4.8 nm in the non-fission-element case and 1.3 nm with fission elements present. No plutonium was observed within the sodalite in the waste form made from the plutonium-loaded LiCl/KCl eutectic salt. Up to 35% of the plutonium in the waste form made from the plutonium-loaded simulated fission-product salt may be segregated with a heavy-element nearest neighbor other than plutonium or occluded internally within the sodalite lattice.

  12. In situ TPR XANES study of the partial oxidation of methane using a Ni-substituted hexaaluminate catalyst

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

    Kugler, E.L.; Gardner, T.H.; Campos, Andrew

    2008-04-01

    Metallic Ni formation near the mirror cation site, Ba in this study, is believed to cause the partial oxidation activity observed in Ni-substituted hexaaluminate catalysts. The BaNi1.0Al11.6O19-d catalyst was prepared by coprecipitation with nitrate salt precursors; following the coprecipitation procedure, the catalyst was calcined at 1400°C to create the hexaaluminate structure. TPR XANES in fluorescence was used to probe the local structure of the BaNi1.0Al11.6O19-d catalyst to determine whether metallic nickel forms at different temperatures: 825°C, 875°C, 925°C. The XANES results indicate that the Ni in the hexaaluminate catalyst only reduces if the temperature is maintained at 925°C. Once themore » metallic state is formed, the oxidation state is stable; even in the POX environment. Future work using a theoretical approach to the XANES data using FEFF 8.4 gives information on the interactions between Ni and Ba, which will be used to further optimize the catalyst.« less

  13. The Valence of Iron in CM Chondrite Serpentine as Measured by Synchrotron Xanes

    NASA Technical Reports Server (NTRS)

    Mikouchi, T.; Zolensky, Michael E.; Satake, W.; Le, L.

    2012-01-01

    Fe-bearing phyllosilicates are the dominant product of aqueous alteration in carbonaceous chondrites, and serpentine is the most abundant phyllosilicate in CM2 chondrites that are the most abundant carbonaceous chondrite. Browning et al. predicted that Fe(3+)/(sum of Fe) ratios of serpentine in CM chondrites should change with progressive alteration. They proposed that progressive CM alteration is best monitored by evaluating the progress of Si and Fe3+ substitutions that necessarily attend the transition from end-member cronstedtite to serpentine. Their proposed Mineralogic Alteration Index, 2-(Fe(3+)/(2-Si)), was intended to highlight and utilize the relevant ex-change information in the stoichiometric phyllosilicate formulas based upon the coupled substitution of 2(Fe(3+), Al) = Si + (Mg, Fe(2+)...) in serpentine. The value of this ratio increases as alteration proceeds. We always wanted to directly test Browning s pre-diction through actual measurements of the Fe3+ con-tent of serpentine at the micron scale appropriate to EPMA analyses (Zega et al. have measured it at much finer scale), and this test can now be made using Synchrotron Radiation X-ray Absorption Near-Edge Structure (SR-XANES). Thus, we have recently begun investigation with CMs that span a large portion of the range of observed aqueous alteration, and we first analyzed Murray, Nogoya, and ALH84029 by SR-XANES. However, we did not find clear correlation between Fe3+/(sum of Fe) ratios of serpentine and their alteration degrees. We thus analyzed serpentine in three more CMs and here report their Fe3+/(sum of Fe) ratios in comparison with our previous results.

  14. Electrochemically-Induced Redox Reactions in Basalt at High Pressure and Temperature: An Iron and Vanadium K-edge XANES Study

    NASA Astrophysics Data System (ADS)

    Kavner, A.; Walker, D.; Newville, M.; Sutton, S. R.

    2005-12-01

    An applied electric field across a silicate sample at high pressures and temperatures in a piston cylinder apparatus can generate a wide range of oxidation states of polyvalent cations within a single experiment. If two or more polyvalent cations are included, this technique can be used to cross-calibrate oxybarometers within a single experiment. The redox state of Fe and V within a partially melted basaltic silicate was manipulated in situ in a piston-cylinder experiment with a DC power supply providing a source and sink of electrons to the sample. A 1V electrical potential differential was applied across vanadium-doped and Fe-bearing synthetic basalt samples for 24 hrs. at 20 kbar and 1400°C in a specially-designed piston cylinder sample assembly. Three experiments were performed: a control sample with no applied voltage, one with bottom cathode and top anode, and a third with top cathode and bottom anode. Synchrotron-based x-ray absorption near edge structure (XANES) spectroscopy was used to provide spot analysis of iron and vanadium oxidation states with 5μm x 5μm spatial resolution throughout the recovered samples. Systematic spatial changes of increasing oxidation states of V and Fe were observed approaching the anode. The differences in oxidation states were mapped to a corresponding local effective oxygen fugacity by comparison and extension of a calibration of vanadium oxidation states as a function of controlled oxygen fugacity from a previous study (Sutton et al., 2005, GCA, vol. 69, pp. 2333-2348). The vanadium mapping indicates that a 1V potential drop across the sample induces effective oxygen fugacity perturbations in excess of ten orders of magnitude. The presence of both Fe and V within the same sample provides a wide range of oxygen fugacity cross-calibration in these recovered samples. A relationship between oxygen fugacity and electrochemical driving force is derived. The experimental results are in good agreement with the derived

  15. The use of C-near edge X-ray absorption fine structure spectroscopy for the elaboration of chemistry in lignocellulosics

    Treesearch

    Lucian A. Lucia; Hiroki Nanko; Alan W. Rudie; Doug G. Mancosky; Sue Wirick

    2006-01-01

    The research presented elucidates the oxidation chemistry occurring in hydrogen peroxide bleached kraft pulp fibers by employing carbon near edge x-ray absorption fine structure spectroscopy (C-NEXAFS). C-NEXAFS is a soft x-ray technique that selectively interrogates atomic moieties using photoelectrons (Xrays) of variable energies. The X1A beam line at the National...

  16. Novel visualization studies of lignocellulosic oxidation chemistry by application of C-near edge X-ray absorption fine structure spectroscopy

    Treesearch

    Douglas G. Mancosky; Lucian A. Lucia; Hiroki Nanko; Sue Wirick; Alan W. Rudie; Robert Braun

    2005-01-01

    The research presented herein is the first attempt to probe the chemical nature of lignocellulosic samples by the application of carbon near edge X-ray absorption fine structure spectroscopy (C-NEXAFS). C-NEXAFS is a soft X-ray technique that principally provides selective interrogation of discrete atomic moieties using photoelectrons of variable energies. The X1A beam...

  17. Retention Mechanisms of Citric Acid in Ternary Kaolinite-Fe(III)-Citrate Acid Systems Using Fe K-edge EXAFS and L3,2-edge XANES Spectroscopy

    PubMed Central

    Yang, Jianjun; Wang, Jian; Pan, Weinan; Regier, Tom; Hu, Yongfeng; Rumpel, Cornelia; Bolan, Nanthi; Sparks, Donald

    2016-01-01

    Organic carbon (OC) stability in tropical soils is strongly interlinked with multivalent cation interaction and mineral association. Low molecular weight organic acids (LMWOAs) represent the readily biodegradable OC. Therefore, investigating retention mechanisms of LMWOAs in mineral-cation-LMWOAs systems is critical to understanding soil C cycling. Given the general acidic conditions and dominance of kaolinite in tropical soils, we investigated the retention mechanisms of citric acid (CA) in kaolinite-Fe(III)-CA systems with various Fe/CA molar ratios at pH ~3.5 using Fe K-edge EXAFS and L3,2-edge XANES techniques. With Fe/CA molar ratios >2, the formed ferrihydrite mainly contributed to CA retention through adsorption and/or coprecipitation. With Fe/CA molar ratios from 2 to 0.5, ternary complexation of CA to kaolinite via a five-coordinated Fe(III) bridge retained higher CA than ferrihydrite-induced adsorption and/or coprecipitation. With Fe/CA molar ratios ≤0.5, kaolinite-Fe(III)-citrate complexation preferentially occurred, but less CA was retained than via outer-sphere kaolinite-CA complexation. This study highlighted the significant impact of varied Fe/CA molar ratios on CA retention mechanisms in kaolinite-Fe(III)-CA systems under acidic conditions, and clearly showed the important contribution of Fe-bridged ternary complexation on CA retention. These findings will enhance our understanding of the dynamics of CA and other LMWOAs in tropical soils. PMID:27212680

  18. Retention mechanisms of citric acid in ternary kaolinite-Fe(III)-citrate acid systems using Fe K-edge EXAFS and L 3,2-edge XANES spectroscopy

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

    Yang, Jianjun; Wang, Jian; Pan, Weinan

    Organic carbon (OC) stability in tropical soils is strongly interlinked with multivalent cation interaction and mineral association. Low molecular weight organic acids (LMWOAs) represent the readily biodegradable OC. Therefore, investigating retention mechanisms of LMWOAs in mineral-cation-LMWOAs systems is critical to understanding soil C cycling. Given the general acidic conditions and dominance of kaolinite in tropical soils, we investigated the retention mechanisms of citric acid (CA) in kaolinite-Fe(III)-CA systems with various Fe/CA molar ratios at pH ~3.5 using Fe K-edge EXAFS and L- 3,2-edge XANES techniques. With Fe/CA molar ratios >2, the formed ferrihydrite mainly contributed to CA retention through adsorptionmore » and/or coprecipitation. With Fe/CA molar ratios from 2 to 0.5, ternary complexation of CA to kaolinite via a five-coordinated Fe(III) bridge retained higher CA than ferrihydrite-induced adsorption and/or coprecipitation. With Fe/CA molar ratios ≤ 0.5, kaolinite-Fe(III)-citrate complexation preferentially occurred, but less CA was retained than via outer-sphere kaolinite-CA complexation. This study highlighted the significant impact of varied Fe/CA molar ratios on CA retention mechanisms in kaolinite-Fe(III)-CA systems under acidic conditions, and clearly showed the important contribution of Fe-bridged ternary complexation on CA retention. In conclusion, these findings will enhance our understanding of the dynamics of CA and other LMWOAs in tropical soils.« less

  19. Retention mechanisms of citric acid in ternary kaolinite-Fe(III)-citrate acid systems using Fe K-edge EXAFS and L 3,2-edge XANES spectroscopy

    DOE PAGES

    Yang, Jianjun; Wang, Jian; Pan, Weinan; ...

    2016-05-23

    Organic carbon (OC) stability in tropical soils is strongly interlinked with multivalent cation interaction and mineral association. Low molecular weight organic acids (LMWOAs) represent the readily biodegradable OC. Therefore, investigating retention mechanisms of LMWOAs in mineral-cation-LMWOAs systems is critical to understanding soil C cycling. Given the general acidic conditions and dominance of kaolinite in tropical soils, we investigated the retention mechanisms of citric acid (CA) in kaolinite-Fe(III)-CA systems with various Fe/CA molar ratios at pH ~3.5 using Fe K-edge EXAFS and L- 3,2-edge XANES techniques. With Fe/CA molar ratios >2, the formed ferrihydrite mainly contributed to CA retention through adsorptionmore » and/or coprecipitation. With Fe/CA molar ratios from 2 to 0.5, ternary complexation of CA to kaolinite via a five-coordinated Fe(III) bridge retained higher CA than ferrihydrite-induced adsorption and/or coprecipitation. With Fe/CA molar ratios ≤ 0.5, kaolinite-Fe(III)-citrate complexation preferentially occurred, but less CA was retained than via outer-sphere kaolinite-CA complexation. This study highlighted the significant impact of varied Fe/CA molar ratios on CA retention mechanisms in kaolinite-Fe(III)-CA systems under acidic conditions, and clearly showed the important contribution of Fe-bridged ternary complexation on CA retention. In conclusion, these findings will enhance our understanding of the dynamics of CA and other LMWOAs in tropical soils.« less

  20. First-Principles Predictions of Near-Edge X-ray Absorption Fine Structure Spectra of Semiconducting Polymers

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

    Su, Gregory M.; Patel, Shrayesh N.; Pemmaraju, C. D.

    The electronic structure and molecular orientation of semiconducting polymers in thin films determine their ability to transport charge. Methods based on near-edge X-ray absorption fine structure (NEXAFS) spectroscopy can be used to probe both the electronic structure and microstructure of semiconducting polymers in both crystalline and amorphous films. However, it can be challenging to interpret NEXAFS spectra on the basis of experimental data alone, and accurate, predictive calculations are needed to complement experiments. Here, we show that first-principles density functional theory (DFT) can be used to model NEXAFS spectra of semiconducting polymers and to identify the nature of transitions inmore » complicated NEXAFS spectra. Core-level X-ray absorption spectra of a set of semiconducting polymers were calculated using the excited electron and core-hole (XCH) approach based on constrained-occupancy DFT. A comparison of calculations on model oligomers and periodic structures with experimental data revealed the requirements for accurate prediction of NEXAFS spectra of both conjugated homopolymers and donor–acceptor polymers. The NEXAFS spectra predicted by the XCH approach were applied to study molecular orientation in donor–acceptor polymers using experimental spectra and revealed the complexity of using carbon edge spectra in systems with large monomeric units. The XCH approach has sufficient accuracy in predicting experimental NEXAFS spectra of polymers that it should be considered for design and analysis of measurements using soft X-ray techniques, such as resonant soft X-ray scattering and scanning transmission X-ray microscopy.« less

  1. Effects of Edge Directions on the Structural Controllability of Complex Networks.

    PubMed

    Xiao, Yandong; Lao, Songyang; Hou, Lvlin; Small, Michael; Bai, Liang

    2015-01-01

    Recent advances indicate that assigning or reversing edge direction can significantly improve the structural controllability of complex networks. For directed networks, approaching the optimal structural controllability can be achieved by detecting and reversing certain "inappropriate" edge directions. However, the existence of multiple sets of "inappropriate" edge directions suggests that different edges have different effects on optimal controllability-that is, different combinations of edges can be reversed to achieve the same structural controllability. Therefore, we classify edges into three categories based on their direction: critical, redundant and intermittent. We then investigate the effects of changing these edge directions on network controllability, and demonstrate that the existence of more critical edge directions implies not only a lower cost of modifying inappropriate edges but also better controllability. Motivated by this finding, we present a simple edge orientation method aimed at producing more critical edge directions-utilizing only local information-which achieves near optimal controllability. Furthermore, we explore the effects of edge direction on the controllability of several real networks.

  2. Delocalization and occupancy effects of 5f orbitals in plutonium intermetallics using L3-edge resonant X-ray emission spectroscopy

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

    Booth, C. H.; Medling, S. A.; Jiang, Yu

    2014-06-24

    Although actinide (An) L3 -edge X-ray absorption near-edge structure (XANES) spectroscopy has been very effective in determining An oxidation states in insulating, ionically bonded materials, such as in certain coordination compounds and mineral systems, the technique fails in systems featuring more delocalized 5f orbitals, especially in metals. Recently, actinide L3-edge resonant X-ray emission spec- troscopy (RXES) has been shown to be an effective alternative. This technique is further demonstrated here using a parameterized partial unoccupied density of states method to quantify both occupancy and delocalization of the 5f orbital in ?-Pu, ?-Pu, PuCoGa5 , PuCoIn5 , and PuSb2. These newmore » results, supported by FEFF calculations, highlight the effects of strong correlations on RXES spectra and the technique?s ability to differentiate between f-orbital occupation and delocalization.« less

  3. Strength evaluation of butt joint by stress intensity factor of small edge crack near interface edge

    NASA Astrophysics Data System (ADS)

    Sato, T.; Oda, K.; Tsutsumi, N.

    2018-06-01

    Failure of the bonded dissimilar materials generally initiates near the interface, or just from the interface edge due to the stress singularity at the interface edge. In this study, the stress intensity factor of an edge crack close to the interface between the dissimilar materials is analyzed. The small edge crack is strongly dominated by the singular stress field near the interface edge. The analysis of stress intensity factor of small edge crack near the interface in bi-material and butt joint plates is carried out by changing the length and the location of the crack and the region dominated by the interface edge is examined. It is found that the dimensionless stress intensity factor of small crack, normalized by the singular stress at the crack tip point in the bonded plate without the crack, is equal to 1.12, independent of the material combination and adhesive layer thickness, when the relative crack length with respect to the crack location is less than 0.01. The adhesive strength of the bonded plate with various adhesive layer thicknesses can be expressed as the constant critical stress intensity factor of the small edge crack.

  4. First principles pseudopotential calculation of electron energy loss near edge structures of lattice imperfections.

    PubMed

    Mizoguchi, Teruyasu; Matsunaga, Katsuyuki; Tochigi, Eita; Ikuhara, Yuichi

    2012-01-01

    Theoretical calculations of electron energy loss near edge structures (ELNES) of lattice imperfections, particularly a Ni(111)/ZrO₂(111) heterointerface and an Al₂O₃ stacking fault on the {1100} plane, are performed using a first principles pseudopotential method. The present calculation can qualitatively reproduce spectral features as well as chemical shifts in experiment by employing a special pseudopotential designed for the excited atom with a core-hole. From the calculation, spectral changes observed in O-K ELNES from a Ni/ZrO₂ interface can be attributable to interfacial oxygen-Ni interactions. In the O-K ELNES of Al₂O₃ stacking faults, theoretical calculation suggests that the spectral feature reflects coordination environment and chemical bonding. Powerful combinations of ELNES with a pseudopotential method used to investigate the atomic and electronic structures of lattice imperfections are demonstrated. Copyright © 2011 Elsevier Ltd. All rights reserved.

  5. XPS and XANES studies of biomimetic composites based on B-type nano-hydroxyapatite

    NASA Astrophysics Data System (ADS)

    Goloshchapov, D. L.; Gushchin, M. S.; Kashkarov, V. M.; Seredin, P. V.; Ippolitov, Y. A.; Khmelevsky, N. O.; Aksenenko, A. Yu.

    2018-06-01

    The paper presents an investigation of the local atomic structure of nanocrystalline carbonate-substituted hydroxyapatite (CHAP) contained in biomimetic composites - analogues of intact human tooth tissues. Using the XPS technique, the presence of impurity Mg and F atoms and structurally bound carbon in CHAP, at the concentrations typical of apatite enamel and dentine was determined. The XANES method was used to study the changes occurring in P L2,3 spectra of biocomposites with CHAP, depending on the percentage of the amino acid matrix. The appearance of maxima in the spectra of XANES P L2,3 near 135.7 eV for the samples with the composition of amino acid complex/hydroxyapatite - 5/95, 25/75 and the splitting of a broad peak of 146.9 eV in the spectrum of a biocomposite with a composition of 40/60 indicates at the interaction of molecular complex of amino acids with atomic environment of phosphorus. This fact can be used in the fundamental medicine for synthesizing of new biomaterials in dentistry.

  6. Speciation and distribution of copper in a mining soil using multiple synchrotron-based bulk and microscopic techniques.

    PubMed

    Yang, Jianjun; Liu, Jin; Dynes, James J; Peak, Derek; Regier, Tom; Wang, Jian; Zhu, Shenhai; Shi, Jiyan; Tse, John S

    2014-02-01

    Molecular-level understanding of soil Cu speciation and distribution assists in management of Cu contamination in mining sites. In this study, one soil sample, collected from a mining site contaminated since 1950s, was characterized complementarily by multiple synchrotron-based bulk and spatially resolved techniques for the speciation and distribution of Cu as well as other related elements (Fe, Ca, Mn, K, Al, and Si). Bulk X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy revealed that soil Cu was predominantly associated with Fe oxides instead of soil organic matter. This agreed with the closest association of Cu to Fe by microscopic X-ray fluorescence (U-XRF) and scanning transmission X-ray microscopy (STXM) nanoanalysis, along with the non-occurrence of photoreduction of soil Cu(II) by quick Cu L3,2-edge XANES spectroscopy (Q-XANES) which often occurs when Cu organic complexes are present. Furthermore, bulk-EXAFS and STXM-coupled Fe L3,2-edge nano-XANES analysis revealed soil Cu adsorbed primarily to Fe(III) oxides by inner-sphere complexation. Additionally, Cu K-edge μ-XANES, L3,2-edge bulk-XANES, and successive Q-XANES results identified the presence of Cu2S rather than radiation-damage artifacts dominant in certain microsites of the mining soil. This study demonstrates the great benefits in use of multiple combined synchrotron-based techniques for comprehensive understanding of Cu speciation in heterogeneous soil matrix, which facilitates our prediction of Cu reactivity and environmental fate in the mining site.

  7. Near-Edge X-ray Absorption Fine Structure Studies of Electrospun Poly(dimethylsiloxane)/Poly (methyl methacrylate)/Multiwall Carbon Nanotube Composites

    PubMed Central

    Winter, A. Douglas; Larios, Eduardo; Alamgir, Faisal M.; Jaye, Cherno; Fischer, Daniel; Campo, Eva M.

    2014-01-01

    This work describes the near conduction band edge structure of electrospun mats of MWCNT-PDMS-PMMA by near edge X-Ray absorption fine structure (NEXAFS) spectroscopy. Effects of adding nanofillers of different sizes were addressed. Despite observed morphological variations and inhomogeneous carbon nanotube distribution, spun mats appeared homogeneous under NEXAFS analysis. Spectra revealed differences in emissions from glancing and normal spectra; which may evidence phase separation within the bulk of the micron-size fibers. Further, dichroic ratios show polymer chains did not align, even in the presence of nanofillers. Addition of nanofillers affected emissions in the C-H, C=O and C-C regimes, suggesting their involvement in interfacial matrix-carbon nanotube bonding. Spectral differences at glancing angles between pristine and composite mats suggest that geometric conformational configurations are taking place between polymeric chains and carbon nanotubes. These differences appear to be carbon nanotube-dimension dependent, and are promoted upon room temperature mixing and shear flow during electrospinning. CH-π bonding between polymer chains and graphitic walls, as well as H-bonds between impurities in the as-grown CNTs and polymer pendant groups are proposed bonding mechanisms promoting matrix conformation. PMID:24308286

  8. Analysis of electronic structure of amorphous InGaZnO/SiO{sub 2} interface by angle-resolved X-ray photoelectron spectroscopy

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

    Ueoka, Y.; Ishikawa, Y.; Maejima, N.

    2013-10-28

    The electronic structures of amorphous indium gallium zinc oxide (a-IGZO) on a SiO{sub 2} layers before and after annealing were observed by constant final state X-ray photoelectron spectroscopy (CFS-XPS) and X-ray adsorption near-edge structure spectroscopy (XANES). From the results of angle-resolved CFS-XPS, the change in the electronic state was clearly observed in the a-IGZO bulk rather than in the a-IGZO/SiO{sub 2} interface. This suggests that the electronic structures of the a-IGZO bulk strongly affected the thin-film transistor characteristics. The results of XANES indicated an increase in the number of tail states upon atmospheric annealing (AT). We consider that the increasemore » in the number of tail states decreased the channel mobility of AT samples.« less

  9. 2D Radiative Processes Near Cloud Edges

    NASA Technical Reports Server (NTRS)

    Varnai, T.

    2012-01-01

    Because of the importance and complexity of dynamical, microphysical, and radiative processes taking place near cloud edges, the transition zone between clouds and cloud free air has been the subject of intense research both in the ASR program and in the wider community. One challenge in this research is that the one-dimensional (1D) radiative models widely used in both remote sensing and dynamical simulations become less accurate near cloud edges: The large horizontal gradients in particle concentrations imply that accurate radiative calculations need to consider multi-dimensional radiative interactions among areas that have widely different optical properties. This study examines the way the importance of multidimensional shortwave radiative interactions changes as we approach cloud edges. For this, the study relies on radiative simulations performed for a multiyear dataset of clouds observed over the NSA, SGP, and TWP sites. This dataset is based on Microbase cloud profiles as well as wind measurements and ARM cloud classification products. The study analyzes the way the difference between 1D and 2D simulation results increases near cloud edges. It considers both monochromatic radiances and broadband radiative heating, and it also examines the influence of factors such as cloud type and height, and solar elevation. The results provide insights into the workings of radiative processes and may help better interpret radiance measurements and better estimate the radiative impacts of this critical region.

  10. Effects of Edge Directions on the Structural Controllability of Complex Networks

    PubMed Central

    Xiao, Yandong; Lao, Songyang; Hou, Lvlin; Small, Michael; Bai, Liang

    2015-01-01

    Recent advances indicate that assigning or reversing edge direction can significantly improve the structural controllability of complex networks. For directed networks, approaching the optimal structural controllability can be achieved by detecting and reversing certain “inappropriate” edge directions. However, the existence of multiple sets of “inappropriate” edge directions suggests that different edges have different effects on optimal controllability—that is, different combinations of edges can be reversed to achieve the same structural controllability. Therefore, we classify edges into three categories based on their direction: critical, redundant and intermittent. We then investigate the effects of changing these edge directions on network controllability, and demonstrate that the existence of more critical edge directions implies not only a lower cost of modifying inappropriate edges but also better controllability. Motivated by this finding, we present a simple edge orientation method aimed at producing more critical edge directions—utilizing only local information—which achieves near optimal controllability. Furthermore, we explore the effects of edge direction on the controllability of several real networks. PMID:26281042

  11. STXM-XANES Analysis of Organic Matter in Dark Clasts and Halite Crystals in Zag and Monahans Meteorites

    NASA Technical Reports Server (NTRS)

    Kebukawa, Y.; Zolensky, M. E.; Fries, M.; Nakato, A.; Kilcoyne, A. L. D.; Takeichi, Y.; Suga, H.; Miyamoto, C.; Rahman, Z.; Kobayashi, K.; hide

    2016-01-01

    Zag and Monahans meteorites (H5) contains xenolithic dark clasts and halite (NaCl) crystals [e.g., 1]. The proposed source of the H chondrites is asteroid 6 Hebe [2]. The modern orbits of 1 Ceres and 6 Hebe essentially cross, with aphelion/perihelion of Ceres and Hebe of 2.99/2.55 and 2.91/1.94 AU (Astronomical Units), respectively. Therefore, Ceres might be the source of the clasts and halite in Zag and Monahans meteorites. Recent results from NASA's Dawn mission shows that bright spots in Ceres's crater may be hydrated magnesium sulfate with some water ice, and an average global surface contains ammoniated phyllosilicates that is likely of outer Solar System origin. One dark clast and all halite crystals in Zag and Monahans meteorites contain carbon-rich particles. We report organic analyses of these carbon-rich particles using carbon, nitrogen, and oxygen X-ray absorption near edge structure (C-, N-, and O-XANES), in order to constrain the origin of the clast and halite crystals.

  12. Comparative investigation of N donor ligand-lanthanide complexes from the metal and ligand point of view

    NASA Astrophysics Data System (ADS)

    Prüßmann, T.; Denecke, M. A.; Geist, A.; Rothe, J.; Lindqvist-Reis, P.; Löble, M.; Breher, F.; Batchelor, D. R.; Apostolidis, C.; Walter, O.; Caliebe, W.; Kvashnina, K.; Jorissen, K.; Kas, J. J.; Rehr, J. J.; Vitova, T.

    2013-04-01

    N-donor ligands such as n-Pr-BTP (2,6-bis(5,6-dipropyl-1,2,4-triazin-3-yl)pyridine) studied here preferentially bind An(III) over Ln(III) in liquid-liquid separation of trivalent ac-tinides from spent nuclear fuel. The chemical and physical processes responsible for this selectivity are not yet well understood. We present systematic comparative near-edge X-ray absorption structure (XANES) spectroscopy investigations at the Gd L3 edge of [GdBTP3](NO3)3, [Gd(BTP)3](OTf)3, Gd(NO3)3, Gd(OTf)3 and N K edge of [Gd(BTP)3](NO3)3, Gd(NO3)3 complexes. The pre-edge absorption resonance in Gd L3 edge high-energy resolution X-ray absorption near edge structure spectra (HR-XANES) is explained as arising from 2p3/2 → 4f/5d electronic transitions by calculations with the FEFF9.5 code. Experimental evidence is found for higher electronic density on Gd in [Gd(BTP)3](NO3)3 and [Gd(BTP)3](OTf)3 compared to Gd in Gd(NO3)3 and Gd(OTf)3, and on N in [Gd(BTP)3](NO3)3 compared to n-Pr-BTP. The origin of the pre-edge structure in the N K edge XANES is explained by density functional theory (DFT) with the ORCA code. Results at the N K edge suggest a change in ligand orbital occupancies and mixing upon complexation but further work is necessary to interpret observed spectral variations.

  13. Specimen charging in X-ray absorption spectroscopy: correction of total electron yield data from stabilized zirconia in the energy range 250-915 eV.

    PubMed

    Vlachos, Dimitrios; Craven, Alan J; McComb, David W

    2005-03-01

    The effects of specimen charging on X-ray absorption spectroscopy using total electron yield have been investigated using powder samples of zirconia stabilized by a range of oxides. The stabilized zirconia powder was mixed with graphite to minimize the charging but significant modifications of the intensities of features in the X-ray absorption near-edge fine structure (XANES) still occurred. The time dependence of the charging was measured experimentally using a time scan, and an algorithm was developed to use this measured time dependence to correct the effects of the charging. The algorithm assumes that the system approaches the equilibrium state by an exponential decay. The corrected XANES show improved agreement with the electron energy-loss near-edge fine structure obtained from the same samples.

  14. California gull chicks raised near colony edges have elevated stress levels

    USGS Publications Warehouse

    Herring, Garth; Ackerman, Joshua T.

    2011-01-01

    Coloniality in nesting birds represents an important life history strategy for maximizing reproductive success. Birds nesting near the edge of colonies tend to have lower reproductive success than individuals nesting near colony centers, and offspring of edge-nesting parents may be impaired relative to those of central-nesting parents. We used fecal corticosterone metabolites in California gull chicks (Larus californicus) to examine whether colony size or location within the colony influenced a chick's physiological condition. We found that chicks being raised near colony edges had higher fecal corticosterone metabolite concentrations than chicks raised near colony centers, but that colony size (ranging from 150 to 11,554 nests) had no influence on fecal corticosterone levels. Fecal corticosterone metabolite concentrations also increased with chick age. Our results suggest that similarly aged California gull chicks raised near colony edges may be more physiologically stressed, as indicated by corticosterone metabolites, than chicks raised near colony centers.

  15. Local atomic and electronic structures of epitaxial strained LaCoO3 thin films

    NASA Astrophysics Data System (ADS)

    Sterbinsky, G. E.; Ryan, P. J.; Kim, J.-W.; Karapetrova, E.; Ma, J. X.; Shi, J.; Woicik, J. C.

    2012-01-01

    We have examined the atomic and electronic structures of perovskite lanthanum cobaltite (LaCoO3) thin films using Co K-edge x-ray absorption fine structure (XAFS) spectroscopy. Extended XAFS (EXAFS) demonstrates that a large difference between in-plane and out-of-plane Co-O bond lengths results from tetragonal distortion in highly strained films. The structural distortions are strongly coupled to the hybridization between atomic orbitals of the Co and O atoms, as shown by x-ray absorption near edge spectroscopy (XANES). Our results indicate that increased hybridization is not the cause of ferromagnetism in strained LaCoO3 films. Instead, we suggest that the strain-induced distortions of the oxygen octahedra increase the population of eg electrons and concurrently depopulate t2g electrons beyond a stabilization threshold for ferromagnetic order.

  16. Study of distorted octahedral structure in 3d transition metal complexes using XAFS

    NASA Astrophysics Data System (ADS)

    Gaur, A.; Nitin Nair, N.; Shrivastava, B. D.; Das, B. K.; Chakrabortty, Monideepa; Jha, S. N.; Bhattacharyya, D.

    2018-01-01

    Distortion in octahedral structure of 3d transition metal complexes (Mn, Fe, Co, Ni, Cu, Zn) has been studied using XAFS showing divergent nature of Cu complex. EXAFS analysis showed elongated metal-oxygen bonds for Cu complex leading to more distorted structure. Derivative XANES spectrum at Cu K-edge exhibits splitting of main edge which is correlated to elongated Cu-O bond length. Using these coordination geometry around metal centers, theoretical XANES spectra have been generated and features observed have been correlated to the corresponding metals p-DOS. It has been shown that distorted octahedral field in Cu complex is responsible for splitting of p-DOS.

  17. Electronic structure and electric polarity of edge-functionalized graphene nanoribbons

    NASA Astrophysics Data System (ADS)

    Taira, Remi; Yamanaka, Ayaka; Okada, Susumu

    2017-08-01

    On the basis of the density functional theory combined with the effective screening medium method, we studied the electronic structure of graphene nanoribbons with zigzag edges, which are terminated by functional groups. The work function of the nanoribbons is sensitive to the functional groups. The edge state inherent in the zigzag edges is robust against edge functionalization. OH termination causes the injection of electrons into the nearly free electron states situated alongside the nanoribbons, resulting in the formation of free electron channels outside the nanoribbons. We also demonstrated that the polarity of zigzag graphene nanoribbons is controllable by the asymmetrical functionalization of their edges.

  18. Reactions of SO 2 on hydrated cement particle system for atmospheric pollution reduction: A DRIFTS and XANES study

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

    Ramakrishnan, Girish; Wu, Qiyuan; Moon, Juhyuk

    An investigation of the adsorptive property of hydrated cement particle system for sulfur dioxide (SO2) removal was conducted. In situ and ex situ experiments using Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) and X-ray Absorption Near Edge Spectroscopy (XANES) characterization techniques were employed to identify surface species formed during the exposure to SO2. Oxidation of SO2 to sulfate and sulfite species observed during these experiments indicated dominant reaction pathways for SO2 reaction with concrete constituents, such as calcium hydroxide, which were also moderated by adsorption on porous surfaces of crushed aggregates. The impact of variable composition of concrete on itsmore » adsorption capacity and reaction mechanisms was also proposed in this work.« less

  19. New insights into the role of Mn and Fe in coloring origin of blue decorations of blue-and-white porcelains by XANES spectroscopy

    NASA Astrophysics Data System (ADS)

    Zhu, Jian; Luo, Wugan; Chen, Dongliang; Xu, Wei; Ming, Chaofang; Wang, Changsui; Wang, Lihua

    2013-04-01

    Blue and white porcelain is one of the most valuable ancient ceramics varieties in ancient China. It is well known for its beautiful blue decorations. However, the origin of its blue color has not been very clear till now. In this research, two blue and white porcelains from Jingdezhen, Jiangxi province were selected and Mn and Fe K-edge XANES spectra were recorded from blue decorations with or without transparent glaze. Results showed that Mn K-edge XANES features were almost identical between different samples while that of iron changed. The above findings indicated the positive role of iron in the variation of blue decorations. As for manganese, although more system researches were need, its negative role on the variations of the tone of blue decorations was obtained. On the other hand, the paper also revealed the XAFS results will be affect by the glaze layer above the pigment. These findings provided us more information to understand the coloring origin of blue decorations of blue-and-white porcelain by means of XANES spectroscopy.

  20. Collision mechanics and the structure of planetary ring edges

    NASA Technical Reports Server (NTRS)

    Spaute, Dominique; Greenberg, Richard

    1987-01-01

    The present numerical simulation of collisional evolution, in the case of a hypothetical ring whose parameters are modeled after those of Saturn's rings, gives attention to changes in radial structure near the ring edges and notes that when random motion is in equilibrium, the rings tend to spread in order to conserve angular momentum while energy is dissipated in collisions. As long as random motion is damped, ring edges may contract rather than spread, producing a concentration of material at the ring edges. For isotropic scattering, damping dominates for a coefficient of restitution of velocity value of up to 0.83.

  1. Structure formation in organic thin films observed in real time by energy dispersive near-edge x-ray absorption fine-structure spectroscopy

    NASA Astrophysics Data System (ADS)

    Scholz, M.; Sauer, C.; Wiessner, M.; Nguyen, N.; Schöll, A.; Reinert, F.

    2013-08-01

    We study the structure formation of 1,4,5,8-naphthalene-tetracarboxylicacid-dianhydride (NTCDA) multilayer films on Ag(111) surfaces by energy dispersive near-edge x-ray absorption fine-structure spectroscopy (NEXAFS) and photoelectron spectroscopy. The time resolution of seconds of the method allows us to identify several sub-processes, which occur during the post-growth three-dimensional structural ordering, as well as their characteristic time scales. After deposition at low temperature the NTCDA molecules are preferentially flat lying and the films exhibit no long-range order. Upon annealing the molecules flip into an upright orientation followed by an aggregation in a transient phase which exists for several minutes. Finally, three-dimensional islands are established with bulk-crystalline structure involving substantial mass transport on the surface and morphological roughening. By applying the Kolmogorov-Johnson-Mehl-Avrami model the activation energies of the temperature-driven sub-processes can be derived from the time evolution of the NEXAFS signal.

  2. Edge-functionalization of armchair graphene nanoribbons with pentagonal-hexagonal edge structures.

    PubMed

    Ryou, Junga; Park, Jinwoo; Kim, Gunn; Hong, Suklyun

    2017-06-21

    Using density functional theory calculations, we have studied the edge-functionalization of armchair graphene nanoribbons (AGNRs) with pentagonal-hexagonal edge structures. While the AGNRs with pentagonal-hexagonal edge structures (labeled (5,6)-AGNRs) are metallic, the edge-functionalized (5,6)-AGNRs with substitutional atoms opens a band gap. We find that the band structures of edge-functionalized (5,6)-N-AGNRs by substitution resemble those of defect-free (N-1)-AGNR at the Γ point, whereas those at the X point show the original ones of the defect-free N-AGNR. The overall electronic structures of edge-functionalized (5,6)-AGNRs depend on the number of electrons, supplied by substitutional atoms, at the edges of functionalized (5,6)-AGNRs.

  3. Pressure induced coordination change of Al in silicate melts from Al K edge XANES of high pressure NaAlSi2O6-NaAlSi3O8 glasses

    NASA Astrophysics Data System (ADS)

    Li, Dien; Secco, R. A.; Bancroft, G. M.; Fleet, M. E.

    Aluminum K-edge XANES spectra of high pressure and high temperature (4.4 GPa and 1575°C) glasses along the NaAlSi2O6 (Jd)-NaAlSi3O8 (Ab) join are reported using synchrotron radiation, and shown to provide direct experimental evidence for the pressure-induced coordination change of Al. Five- and six-fold coordinated Al (5Al and 6Al), characterized by Al K-edge positions at 1567.8 and 1568.7 eV, respectively, first appear in glass of composition Jd60Ab40 and increase in proportion progressively with increasing Jd content. The end-member jadeite glass contains about 6% of each of 5Al and 6Al. The present direct measurements confirm literature suggestions for the important role of Al in controlling viscosity and diffusion in mantle melts.

  4. XANES evidence for sulphur speciation in Mn-, Ni- and W-bearing silicate melts

    NASA Astrophysics Data System (ADS)

    Evans, K. A.; O'Neill, H. St. C.; Mavrogenes, J. A.; Keller, N. S.; Jang, L.-Y.; Lee, J.-F.

    2009-11-01

    S K-edge XANES and Mn-, W- and Ni-XANES and EXAFS spectra of silicate glasses synthesised at 1400 °C and 1 bar with compositions in the CaO-MgO-Al 2O 3-SiO 2-S plus MnO, NiO, or WO 3 systems were used to investigate sulphur speciation in silicate glasses. S K-edge spectra comprised a composite peak with an edge between 2470 and 2471.4 eV, which was attributed to S 2-, and a peak of variable height with an edge at 2480.2-2480.8 eV, which is consistent with the presence of S 6+. The latter peak was attributed to sample oxidation during sample storage. W-rich samples produced an additional lower energy peak at 2469.8 eV that is tentatively attributed to the existence of S 3p orbitals hybridised with the W 5d states. Deconvolution of the composite peak reveals that the composite peak for Mn-bearing samples fits well to a model that combines three Lorentzians at 2473.1, 2474.9 and 2476.2 eV with an arctan edge step. The composite peak for W-bearing samples fits well to the same combination plus an additional Lorentzian at 2469.8 eV. The ratio of the proportions of the signal accounted for by peaks at 2473.1 and 2476.2 eV correlates with Mn:Ca molar ratios, but not with W:Ca ratios. Spectra from Ni-bearing samples were qualitatively similar but S levels were too low to allow robust quantification of peak components. Some part of the signal accounted for by the 2473.1 eV peak was therefore taken to record the formation of Mn-S melt species, while the 2469.8 peak is interpreted to record the formation of W-S melt species. The 2474.9 and 2476.2 eV peaks were taken to be dominated by Ca-S and Mg-S interactions. However, a 1:1 relationship between peak components and specific energy transitions is not proposed. This interpretation is consistent with known features of the lower parts of the conduction band in monosulphide minerals and indicates a similarity between sulphur species in the melts and the monosulphides. S-XANES spectra cannot be reproduced by a combination of the

  5. From lapis lazuli to ultramarine blue: investigating Cennino Cennini’s recipe using sulfur K-edge XANES

    DOE PAGES

    Ganio, Monica; Pouyet, Emeline S.; Webb, Samuel M.; ...

    2017-09-22

    As one of the most desired and expensive artists’ materials throughout history, there has long been interest in studying natural lapis lazuli. The traditional method of extracting the blue component, lazurite, from lapis lazuli, as outlined in Cennini’s Il Libro dell’Arte, involves a lengthy purification process: (1) finely grind the rock; (2) mix with pine rosin, gum mastic, and beeswax; (3) massage in water to collect the lazurite. Repeating the process produces several grades of the pigment, typically referred to as ultramarine blue. Here, we investigate the sulfur environment within the aluminosilicate framework of lazurite during its extraction from lapismore » lazuli. The sulfur XANES fingerprint from samples taken at the different stages in Cennini’s extraction method were examined. All spectra contain a strong absorption peak at 2483 eV, attributable to sulfate present in the lazurite structure. However, intensity variations appear in the broad envelope of peaks between 2470 and 2475 eV and the pre-peak at 2469.1 eV, indicating a variation in the content of trisulfur (S 3 –˙) radicals. By studying the effect of each step of Cennini’s process, this study elucidates the changes occurring during the extraction and the variability within different grades of the precious coloring material. The increasing application of XANES to the study of artist’s materials and works of art motivated extending the research to assess the possibility of X-ray induced damage. Direct comparison of micro-focused and unfocused beam experiments suggests an increase of the S 3 –˙ radicals with prolonged exposure. Furthermore, analysis indicates that induced damage follows first-order kinetics, providing a first assessment on the acceptable amount of radiation exposure to define the optimal acquisition parameters to allow safe analyses of lapis lazuli and ultramarine pigments.« less

  6. From lapis lazuli to ultramarine blue: investigating Cennino Cennini’s recipe using sulfur K-edge XANES

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

    Ganio, Monica; Pouyet, Emeline S.; Webb, Samuel M.

    As one of the most desired and expensive artists’ materials throughout history, there has long been interest in studying natural lapis lazuli. The traditional method of extracting the blue component, lazurite, from lapis lazuli, as outlined in Cennini’s Il Libro dell’Arte, involves a lengthy purification process: (1) finely grind the rock; (2) mix with pine rosin, gum mastic, and beeswax; (3) massage in water to collect the lazurite. Repeating the process produces several grades of the pigment, typically referred to as ultramarine blue. Here, we investigate the sulfur environment within the aluminosilicate framework of lazurite during its extraction from lapismore » lazuli. The sulfur XANES fingerprint from samples taken at the different stages in Cennini’s extraction method were examined. All spectra contain a strong absorption peak at 2483 eV, attributable to sulfate present in the lazurite structure. However, intensity variations appear in the broad envelope of peaks between 2470 and 2475 eV and the pre-peak at 2469.1 eV, indicating a variation in the content of trisulfur (S 3 –˙) radicals. By studying the effect of each step of Cennini’s process, this study elucidates the changes occurring during the extraction and the variability within different grades of the precious coloring material. The increasing application of XANES to the study of artist’s materials and works of art motivated extending the research to assess the possibility of X-ray induced damage. Direct comparison of micro-focused and unfocused beam experiments suggests an increase of the S 3 –˙ radicals with prolonged exposure. Furthermore, analysis indicates that induced damage follows first-order kinetics, providing a first assessment on the acceptable amount of radiation exposure to define the optimal acquisition parameters to allow safe analyses of lapis lazuli and ultramarine pigments.« less

  7. Solid state synthesis of layered sodium manganese oxide for sodium-ion battery by in-situ high energy X-ray diffraction and X-ray absorption near edge spectroscopy [Solid state synthesis of layered sodium manganese oxide for sodium-ion battery by in-situ HEXRD and XANES

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

    Ma, Tianyuan; Xu, Gui -Liang; Zeng, Xiaoqiao

    In situ high energy X-ray diffraction (HEXRD) and in situ X-ray absorption near edge spectroscopy (XANES) were carried out to understand the soild state synthesis of Na xMnO 2, with particular interest on the synthesis of P2 type Na 2/3MnO 2. It was found that there were multi intermediate phases formed before NaMnO 2 appeared at about 600 °C. And the final product after cooling process is a combination of O'3 NaMnO 2 with P2 Na 2/3MnO 2. A P2 type Na 2/3MnO 2 was synthesized at reduced temperature (600 °C). The influence of Na 2CO 3 impurity on themore » electrochemical performance of P2 Na 2/3MnO 2 was thoroughly investigated in our work. It was found that the content of Na 2CO 3 can be reduced by optimizing Na 2CO 3/MnCO 3 ratio during the solid state reaction or other post treatment such as washing with water. Lastly, we expected our results could provide a good guide for future development of high performance cathode materials for sodium-ion batteries.« less

  8. Solid state synthesis of layered sodium manganese oxide for sodium-ion battery by in-situ high energy X-ray diffraction and X-ray absorption near edge spectroscopy [Solid state synthesis of layered sodium manganese oxide for sodium-ion battery by in-situ HEXRD and XANES

    DOE PAGES

    Ma, Tianyuan; Xu, Gui -Liang; Zeng, Xiaoqiao; ...

    2016-12-07

    In situ high energy X-ray diffraction (HEXRD) and in situ X-ray absorption near edge spectroscopy (XANES) were carried out to understand the soild state synthesis of Na xMnO 2, with particular interest on the synthesis of P2 type Na 2/3MnO 2. It was found that there were multi intermediate phases formed before NaMnO 2 appeared at about 600 °C. And the final product after cooling process is a combination of O'3 NaMnO 2 with P2 Na 2/3MnO 2. A P2 type Na 2/3MnO 2 was synthesized at reduced temperature (600 °C). The influence of Na 2CO 3 impurity on themore » electrochemical performance of P2 Na 2/3MnO 2 was thoroughly investigated in our work. It was found that the content of Na 2CO 3 can be reduced by optimizing Na 2CO 3/MnCO 3 ratio during the solid state reaction or other post treatment such as washing with water. Lastly, we expected our results could provide a good guide for future development of high performance cathode materials for sodium-ion batteries.« less

  9. First Ti-XANES analyses of refractory inclusions from Murchison

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

    Simon, S.B.; Sutton, S.R.; Grossman, L.

    2009-03-23

    Ti valence in refractory phases is an important recorder of redox conditions in the early solar nebula. We report the valence of Ti in pyroxene, spinel and hibonite in spinel-hibonite and spinel-pyroxene inclusions and in a coarse hibonite grain. A system of solar composition is so reducing that Ti{sup 3+} and Ti{sup 4+} can coexist, making the valence of Ti a valuable indicator of f{sub O2} conditions during formation of nebular materials. The Ti{sup 3+}/Ti{sup 4+} ratios observed in the Ti-rich phases fassaite and rhoenite in coarse-grained refractory inclusions from CV3 chondrites have been shown to be quantitatively consistent withmore » formation in a gas of solar composition (log f{sub O2} = IW-6.8), but these are the only objects in chondrites for which this is the case. Here, we report the valence of Ti in various phases in refractory inclusions from the Murchison CM2 chondrite. The second-highest temperature, major-element-bearing phase predicted to condense from a gas of solar composition, hibonite (ideally CaAl{sub 12}O{sub 19}), can contain significant amounts of Ti, but the hibonite structure can have oxygen vacancies, so calculation of Ti valence from stoichiometry of electron probe analyses is not recommended for hibonite. To date, the only reported measurement of Ti valence in meteoritic hibonite was done by electron spin resonance, on coarse crystals from a Murchison hibonite-perovskite-melilite inclusion. Spinel and most of the pyroxene in CM inclusions contain too little Ti for derivation of Ti{sup 3+}/Ti{sup 4+} ratios from electron probe analyses. X-ray absorption near edge spectroscopy (XANES), however, allows determination of Ti valence in relatively Ti-poor phases. In the present work, we apply synchrotron microXANES to a large hibonite grain from Murchison and to spinel-hibonite (sp-hib) and spinel-pyroxene (sp-pyx) inclusions from Murchison, refractory materials whose Ti{sup 3+}/Ti{sup 4+} ratios have not been previously measured

  10. Structural and Dynamical Properties of 2:1 Phyllosilicates Edges and Nanoparticles

    NASA Astrophysics Data System (ADS)

    Newton, A. G.; Sposito, G.

    2012-12-01

    and dynamical properties of the phyllosilicate edge interface differ from those of the 2:1 phyllosilicate basal surface. The non-planar surface structure and abundant oxygen atoms and hydroxyl groups at the edge order the water layers such that a steep gradient in the water self-diffusion coefficient exists near the surface. Isolated phyllosilicate nanoparticles maintain the original crystal habit; disordered edge structures emerge upon stacking of the particles. These simulations validate CLAYFF as a general forcefield for 2:1 phyllosilicate edges and nanoparticles and demonstrate a powerful method for future investigations of geologic media at the mesoscale.

  11. Simulation of Near-Edge X-ray Absorption Fine Structure with Time-Dependent Equation-of-Motion Coupled-Cluster Theory.

    PubMed

    Nascimento, Daniel R; DePrince, A Eugene

    2017-07-06

    An explicitly time-dependent (TD) approach to equation-of-motion (EOM) coupled-cluster theory with single and double excitations (CCSD) is implemented for simulating near-edge X-ray absorption fine structure in molecular systems. The TD-EOM-CCSD absorption line shape function is given by the Fourier transform of the CCSD dipole autocorrelation function. We represent this transform by its Padé approximant, which provides converged spectra in much shorter simulation times than are required by the Fourier form. The result is a powerful framework for the blackbox simulation of broadband absorption spectra. K-edge X-ray absorption spectra for carbon, nitrogen, and oxygen in several small molecules are obtained from the real part of the absorption line shape function and are compared with experiment. The computed and experimentally obtained spectra are in good agreement; the mean unsigned error in the predicted peak positions is only 1.2 eV. We also explore the spectral signatures of protonation in these molecules.

  12. Application of x-ray absorption fine structure (XAFS) to local-order analysis in Fe-Cr maghemite-like materials

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

    Montero-Cabrera, M. E., E-mail: elena.montero@cimav.edu.mx; Fuentes-Cobas, L. E.; Macías-Ríos, E.

    2015-07-23

    The maghemite-like oxide system γ-Fe{sub 2-x}Cr{sub x}O{sub 3} (x=0.75, 1 and 1.25) was studied by X-ray absorption fine structure (XAFS) and by synchrotron radiation X-ray diffraction (XRD). Measurements were performed at the Stanford Synchrotron Radiation Lightsource at room temperature, at beamlines 2-1, 2-3 and 4-3. High-resolution XRD patterns were processed by means of the Rietveld method. In cases of atoms being neighbors in the Periodic Table, the order/disorder degree of the considered solutions is indiscernible by “normal” (absence of “anomalous scattering”) diffraction experiments. Thus, maghemite-like materials were investigated by XAFS in both Fe and Cr K-edges to clarify, via short-rangemore » structure characterization, the local ordering of the investigated system. Athena and Artemis graphic user interfaces for IFEFFIT and FEFF8.4 codes were employed for XAFS spectra interpretation. Pre-edge decomposition and theoretical modeling of X-ray absorption near edge structure (XANES) transitions were performed. By analysis of the Cr K-edge XANES, it has been confirmed that Cr is located in an octahedral environment. Fitting of the extended X-ray absorption fine structure (EXAFS) spectra was performed under the consideration that the central atom of Fe is allowed to occupy octa- and tetrahedral positions, while Cr occupies only octahedral ones. Coordination number of neighboring atoms, interatomic distances and their quadratic deviation average were determined for x=1, by fitting simultaneously the EXAFS spectra of both Fe and Cr K-edges. The results of fitting the experimental spectra with theoretical standards showed that the cation vacancies tend to follow a regular pattern within the structure of the iron-chromium maghemite (FeCrO{sub 3})« less

  13. Electronic structure and optical properties of CdSxSe1-x solid solution nanostructures from X-ray absorption near edge structure, X-ray excited optical luminescence, and density functional theory investigations

    NASA Astrophysics Data System (ADS)

    Murphy, M. W.; Yiu, Y. M.; Ward, M. J.; Liu, L.; Hu, Y.; Zapien, J. A.; Liu, Yingkai; Sham, T. K.

    2014-11-01

    The electronic structure and optical properties of a series of iso-electronic and iso-structural CdSxSe1-x solid solution nanostructures have been investigated using X-ray absorption near edge structure, extended X-ray absorption fine structure, and X-ray excited optical luminescence at various absorption edges of Cd, S, and Se. It is found that the system exhibits compositions, with variable local structure in-between that of CdS and CdSe accompanied by tunable optical band gap between that of CdS and CdSe. Theoretical calculation using density functional theory has been carried out to elucidate the observations. It is also found that luminescence induced by X-ray excitation shows new optical channels not observed previously with laser excitation. The implications of these observations are discussed.

  14. Near Field Trailing Edge Tone Noise Computation

    NASA Technical Reports Server (NTRS)

    Loh, Ching Y.

    2002-01-01

    Blunt trailing edges in a flow often generate tone noise due to wall-jet shear layer and vortex shedding. In this paper, the space-time conservation element (CE/SE) method is employed to numerically study the near-field noise of blunt trailing edges. Two typical cases, namely, flow past a circular cylinder (aeolian noise problem) and flow past a flat plate of finite thickness are considered. The computed frequencies compare well with experimental data. For the aeolian noise problem, comparisons with the results of other numerical approaches are also presented.

  15. An x-ray absorption spectroscopy study of Ni-Mn-Ga shape memory alloys.

    PubMed

    Sathe, V G; Dubey, Aditi; Banik, Soma; Barman, S R; Olivi, L

    2013-01-30

    The austenite to martensite phase transition in Ni-Mn-Ga ferromagnetic shape memory alloys was studied by extended x-ray absorption fine structure (EXAFS) and x-ray absorption near-edge structure (XANES) spectroscopy. The spectra at all the three elements', namely, Mn, Ga and Ni, K-edges in several Ni-Mn-Ga samples (with both Ni and Mn excess) were analyzed at room temperature and low temperatures. The EXAFS analysis suggested a displacement of Mn and Ga atoms in opposite direction with respect to the Ni atoms when the compound transforms from the austenite phase to the martensite phase. The first coordination distances around the Mn and Ga atoms remained undisturbed on transition, while the second and subsequent shells showed dramatic changes indicating the presence of a modulated structure. The Mn rich compounds showed the presence of antisite disorder of Mn and Ga. The XANES results showed remarkable changes in the unoccupied partial density of states corresponding to Mn and Ni, while the electronic structure of Ga remained unperturbed across the martensite transition. The post-edge features in the Mn K-edge XANES spectra changed from a double peak like structure to a flat peak like structure upon phase transition. The study establishes strong correlation between the crystal structure and the unoccupied electronic structure in these shape memory alloys.

  16. The local structure and ferromagnetism in Fe-implanted SrTiO3 single crystals

    NASA Astrophysics Data System (ADS)

    Lobacheva, O.; Chavarha, M.; Yiu, Y. M.; Sham, T. K.; Goncharova, L. V.

    2014-07-01

    We report a connection between the local structure of low-level Fe impurities and vacancies as the cause of ferromagnetic behavior observed in strontium titanate single crystals (STO), which were implanted with Fe and Si ions at different doses then annealed in oxygen. The effects of Fe doping and post-implantation annealing of STO were studied by X-ray Absorption Near Edge Structure (XANES) spectroscopy and Superconducting Quantum Interference Device magnetometry. XANES spectra for Fe and Ti K- and L-edge reveal the changes in the local environment of Fe and Ti following the implantation and annealing steps. The annealing in oxygen atmosphere partially healed implantation damages and changed the oxidation state of the implanted iron from metallic Fe0 to Fe2+/Fe3+ oxide. The STO single crystals were weak ferromagnets prior to implantation. The maximum saturation moment was obtained after our highest implantation dose of 2 × 1016 Fe atom/cm2, which could be correlated with the metallic Fe0 phases in addition to the presence of O/Ti vacancies. After recrystallization annealing, the ferromagnetic response disappears. Iron oxide phases with Fe2+ and Fe3+ corresponding to this regime were identified and confirmed by calculations using Real Space Multiple Scattering program (FEFF9).

  17. Electrostatic potential barrier for electron emission at graphene edges induced by the nearly free electron states

    NASA Astrophysics Data System (ADS)

    Gao, Yanlin; Okada, Susumu

    2017-05-01

    Using the density functional theory, we studied the electronic structures of zigzag graphene nanoribbons with hydroxyl, H, ketone, aldehyde, or carboxyl terminations under a lateral electric field. The critical electric field for electron emission is proportional to the work function of the functionalized edges except the hydroxylated edge, which leads to the anomalous electric field outside the edge, owing to the electrons in the nearly free electron (NFE) state in the vacuum region. The strong electric field also causes a potential barrier for the electron emission from the H-terminated edge owing to the downward shift of the NFE state.

  18. Assignment of polarization-dependent peaks in carbon K-edge spectra from biogenic and geologic aragonite.

    PubMed

    Zhou, Dong; Metzler, Rebecca A; Tyliszczak, Tolek; Guo, Jinghua; Abrecht, Mike; Coppersmith, Susan N; Gilbert, P U P A

    2008-10-16

    Many biominerals, including mollusk and echinoderm shells, avian eggshells, modern and fossil bacterial sediments, planktonic coccolithophores, and foraminifera, contain carbonates in the form of biogenic aragonite or calcite. Here we analyze biogenic and geologic aragonite using different kinds of surface- and bulk-sensitive X-ray absorption near-edge structure (XANES) spectroscopy at the carbon K-edge, as well as high-resolution scanning transmission X-ray microscopy (STXM). Besides the well-known main pi* and sigma* carbonate peaks, we observed and fully characterized four minor peaks, at energies between the main pi* and sigma* peaks. As expected, the main peaks are similar in geologic and biogenic aragonite, while the minor peaks differ in relative intensity. In this and previous work, the minor peaks appear to be the ones most affected in biomineralization processes, hence the interest in characterizing them. Peak assignment was achieved by correlation of polarization-dependent behavior of the minor peaks with that of the main pi* and sigma* peaks. The present characterization provides the background for future studies of aragonitic biominerals.

  19. Effects of sulfation level on the desulfation behavior of pre-sulfated Pt BaO/Al2O3 lean NOx trap catalysts: a combined H2 Temperature-Programmed Reaction, in-situ sulfur K-edge X-ray Absorption Near-Edge Spectroscopy, X-ray Photoelectron Spectroscopy, and Time-Resolved X-ray Diffraction Study

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

    Kim, Do Heui; Szanyi, Janos; Kwak, Ja Hun

    2009-04-03

    Desulfation by hydrogen of pre-sulfated Pt(2wt%) BaO(20wt%)/Al2O3 with various sulfur loading (S/Ba = 0.12, 0.31 and 0.62) were investigated by combining H2 temperature programmed reaction (TPRX), x-ray photoelectron spectroscopy (XPS), in-situ sulfur K-edge x-ray absorption near-edge spectroscopy (XANES), and synchrotron time-resolved x-ray diffraction (TR-XRD) techniques. We find that the amount of H2S desorbed during the desulfation in the H2 TPRX experiments is not proportional to the amount of initial sulfur loading. The results of both in-situ sulfur K-edge XANES and TR-XRD show that at low sulfur loadings, sulfates were transformed to a BaS phase and remained in the catalyst, rathermore » than being removed as H2S. On the other hand, when the deposited sulfur level exceeded a certain threshold (at least S/Ba = 0.31) sulfates were reduced to form H2S, and the relative amount of the residual sulfide species in the catalyst was much less than at low sulfur loading. Unlike samples with high sulfur loading (e.g., S/Ba = 0.62), H2O did not promote the desulfation for the sample with S/Ba of 0.12, implying that the formed BaS species originating from the reduction of sulfates at low sulfur loading are more stable to hydrolysis. The results of this combined spectroscopy investigation provide clear evidence to show that sulfates at low sulfur loadings are less likely to be removed as H2S and have a greater tendency to be transformed to BaS on the material, leading to the conclusion that desulfation behavior of Pt BaO/Al2O3 lean NOx trap catalysts is markedly dependent on the sulfation levels.« less

  20. Near-edge x-ray absorption fine structure spectroscopy at atmospheric pressure with a table-top laser-induced soft x-ray source

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

    Kühl, Frank-Christian, E-mail: Frank-christian.kuehl@mail.de; Müller, Matthias, E-mail: matthias.mueller@llg-ev.de; Schellhorn, Meike

    2016-07-15

    The authors present a table-top soft x-ray absorption spectrometer, accomplishing investigations of the near-edge x-ray absorption fine structure (NEXAFS) in a laboratory environment. The system is based on a low debris plasma ignited by a picosecond laser in a pulsed krypton gas jet, emitting soft x-ray radiation in the range from 1 to 5 nm. For absorption spectroscopy in and around the “water window” (2.3–4.4 nm), a compact helium purged sample compartment for experiments at atmospheric pressure has been constructed and tested. NEXAFS measurements on CaCl{sub 2} and KMnO{sub 4} samples were conducted at the calcium and manganese L-edges, as well asmore » at the oxygen K-edge in air, atmospheric helium, and under vacuum, respectively. The results indicate the importance of atmospheric conditions for an investigation of sample hydration processes.« less

  1. Degradation in carbon stocks near tropical forest edges.

    PubMed

    Chaplin-Kramer, Rebecca; Ramler, Ivan; Sharp, Richard; Haddad, Nick M; Gerber, James S; West, Paul C; Mandle, Lisa; Engstrom, Peder; Baccini, Alessandro; Sim, Sarah; Mueller, Carina; King, Henry

    2015-12-18

    Carbon stock estimates based on land cover type are critical for informing climate change assessment and landscape management, but field and theoretical evidence indicates that forest fragmentation reduces the amount of carbon stored at forest edges. Here, using remotely sensed pantropical biomass and land cover data sets, we estimate that biomass within the first 500 m of the forest edge is on average 25% lower than in forest interiors and that reductions of 10% extend to 1.5 km from the forest edge. These findings suggest that IPCC Tier 1 methods overestimate carbon stocks in tropical forests by nearly 10%. Proper accounting for degradation at forest edges will inform better landscape and forest management and policies, as well as the assessment of carbon stocks at landscape and national levels.

  2. Degradation in carbon stocks near tropical forest edges

    PubMed Central

    Chaplin-Kramer, Rebecca; Ramler, Ivan; Sharp, Richard; Haddad, Nick M.; Gerber, James S.; West, Paul C.; Mandle, Lisa; Engstrom, Peder; Baccini, Alessandro; Sim, Sarah; Mueller, Carina; King, Henry

    2015-01-01

    Carbon stock estimates based on land cover type are critical for informing climate change assessment and landscape management, but field and theoretical evidence indicates that forest fragmentation reduces the amount of carbon stored at forest edges. Here, using remotely sensed pantropical biomass and land cover data sets, we estimate that biomass within the first 500 m of the forest edge is on average 25% lower than in forest interiors and that reductions of 10% extend to 1.5 km from the forest edge. These findings suggest that IPCC Tier 1 methods overestimate carbon stocks in tropical forests by nearly 10%. Proper accounting for degradation at forest edges will inform better landscape and forest management and policies, as well as the assessment of carbon stocks at landscape and national levels. PMID:26679749

  3. Drift paths of ions composing multiple-nose spectral structures near the inner edge of the plasma sheet

    NASA Astrophysics Data System (ADS)

    Ferradas, C. P.; Zhang, J.-C.; Spence, H. E.; Kistler, L. M.; Larsen, B. A.; Reeves, G.; Skoug, R.; Funsten, H.

    2016-11-01

    We present a case study of the H+, He+, and O+ multiple-nose structures observed by the Helium, Oxygen, Proton, and Electron instrument on board Van Allen Probe A over one complete orbit on 28 September 2013. Nose structures are observed near the inner edge of the plasma sheet and constitute the signatures of ion drift in the highly dynamic environment of the inner magnetosphere. We find that the multiple noses are intrinsically associated with variations in the solar wind. Backward ion drift path tracings show new details of the drift trajectories of these ions; i.e., multiple noses are formed by ions with a short drift time from the assumed source location to the inner region and whose trajectories (1) encircle the Earth different number of times or (2) encircle the Earth equal number of times but with different drift time, before reaching the observation site.

  4. Manganese speciation in Diplodon chilensis patagonicus shells: a XANES study

    NASA Astrophysics Data System (ADS)

    Soldati, A. L.; Vicente-Vilas, V.; Goettlicher, J.; Jacob, D. E.

    2009-04-01

    century, resolving the environmental signal annually and even seasonally (Soldati et al., 2008b). High resolution trace elemental analysis by LA-ICPMS and EPMA in the shells show that elements like Mg and Mn are related to the seasonal pattern and can be enriched along the organic-rich annual shell growth lines. Thus, these elements could possibly be bound organically instead of occupying a defined site in the crystal lattice of the calcium carbonate phase. LA-ICP-MS results show that Mn concentrations in these Diplodon shells range between 1000-300 g/g and 100-10 g/g and that the areas of enrichment are in the micrometer range. Raman and XRD measurements at high spatial resolution failed in recognizing whether the Mn is in carbonate solid solution or not. Therefore, speciation techniques like X-ray absorption fine structure (XAFS) spectroscopy with a high lateral resolution are required to address this question. Prior to XAFS spectroscopy the samples were mapped with the intensity of the Mn Kα fluorescence emission line in order to locate the Mn rich areas of interest. Because of the Mn concentrations in the sub % range the XAFS spectra at the positions of interest have been recorded in fluorescence mode using a 7 element Si(Li) detector. This study focuses on the near edge (XANES: X-ray absorption near edge structure) part of the spectra. For data evaluation, XANES spectra of reference substances were additionally measured in order to get first hints to Mn valence and bonding. As standards were used Mn and Mn rich carbonates, Mn oxides with Mn in different oxidation states, and Mn in organic compounds (Mn-porphyrin and Mn-acetate). The XAFS measurements have been carried out at the SUL-X beamline of the synchrotron radiation source ANKA of the Forschungszentrum Karlsruhe. Data evaluation is ongoing. References MEIBOM, A., CUIF, J.P., HOULBREQUE, F., MOSTEFAOUI, S., DAUPHIN, Y., MEIBOM; K.L. & DUNBAR, R. (2008). Compositional variations at ultra-structure length scales

  5. XANES, EXAFS and Kbeta spectroscopic studies of the oxygen-evolving complex in Photosystem II

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

    Robblee, John Henry

    A key question for the understanding of photosynthetic water oxidation is whether the four oxidizing equivalents necessary to oxidize water to dioxygen are accumulated on the four Mn ions of the oxygen evolving complex (OEC), or whether some ligand-centered oxidations take place before the formation and release of dioxygen during the S 3 → [S 4] → S 0 transition. Progress in instrumentation and flash sample preparation allowed us to apply Mn Kβ X-ray emission spectroscopy (Kb XES) to this problem for the first time. The Kβ XES results, in combination with Mn X-ray absorption near-edge structure (XANES) and electronmore » paramagnetic resonance (EPR) data obtained from the same set of samples, show that the S 2 → S 3 transition, in contrast to the S 0 → S 1 and S 1 → S 2 transitions, does not involve a Mn-centered oxidation. This is rationalized by manganese μ-oxo bridge radical formation during the S 2 → S 3 transition. Using extended X-ray absorption fine structure (EXAFS) spectroscopy, the local environment of the Mn atoms in the S 0 state has been structurally characterized. These results show that the Mn-Mn distance in one of the di-μ-oxo-bridged Mn-Mn moieties increases from 2.7 Å in the S 1} state to 2.85 Å in the S 0 state. Furthermore, evidence is presented that shows three di-μ-oxo binuclear Mn 2 clusters may be present in the OEC, which is contrary to the widely held theory that two such clusters are present in the OEC. The EPR properties of the S 0 state have been investigated and a characteristic ''multiline'' signal in the S 0 state has been discovered in the presence of methanol. This provides the first direct confirmation that the native S 0 state is paramagnetic. In addition, this signal was simulated using parameters derived from three possible oxidation states of Mn in the S 0 state. The dichroic nature of X-rays from synchrotron radiation and single-crystal Mn complexes have been exploited to selectively probe Mn-ligand bonds

  6. Si K EDGE STRUCTURE AND VARIABILITY IN GALACTIC X-RAY BINARIES

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

    Schulz, Norbert S.; Corrales, Lia; Canizares, Claude R.

    2016-08-10

    We survey the Si K edge structure in various absorbed Galactic low-mass X-ray binaries (LMXBs) to study states of silicon in the inter- and circum-stellar medium. The bulk of these LMXBs lie toward the Galactic bulge region and all have column densities above 10{sup 22} cm{sup −2}. The observations were performed using the Chandra High Energy Transmission Grating Spectrometer. The Si K edge in all sources appears at an energy value of 1844 ± 0.001 eV. The edge exhibits significant substructure that can be described by a near edge absorption feature at 1849 ± 0.002 eV and a far edgemore » absorption feature at 1865 ± 0.002 eV. Both of these absorption features appear variable with equivalent widths up to several mÅ. We can describe the edge structure using several components: multiple edge functions, near edge absorption excesses from silicates in dust form, signatures from X-ray scattering optical depths, and a variable warm absorber from ionized atomic silicon. The measured optical depths of the edges indicate much higher values than expected from atomic silicon cross sections and interstellar medium abundances, and they appear consistent with predictions from silicate X-ray absorption and scattering. A comparison with models also indicates a preference for larger dust grain sizes. In many cases, we identify Si xiii resonance absorption and determine ionization parameters between log ξ = 1.8 and 2.8 and turbulent velocities between 300 and 1000 km s{sup −1}. This places the warm absorber in close vicinity of the X-ray binaries. In some data, we observe a weak edge at 1.840 keV, potentially from a lesser contribution of neutral atomic silicon.« less

  7. Structural transformations in high-capacity Li 2Cu 0.5Ni 0.5O 2 cathodes

    DOE PAGES

    Ruther, Rose E.; Pandian, Amaresh Samuthira; Yan, Pengfei; ...

    2017-03-09

    Cathode materials that can cycle >1 Li + per transition metal are of substantial interest for increasing the overall energy density of lithium-ion batteries. Li 2Cu 0.5Ni 0.5O 2 has a very high theoretical capacity of ~500 mAh/g assuming both Li+ ions are cycled reversibly. The Cu 2+/3+ and Ni 2+/3+/4+ redox couples are also at high voltage, which could further boost the energy density of this system. Despite such promise, Li 2Cu 0.5Ni 0.5O 2 undergoes irreversible phase changes during charge (delithiation) that result in large first-cycle irreversible loss and poor long-term cycling stability. Oxygen evolves before the Cumore » 2+/3+ or Ni 3+/4+ transitions are accessed. In this contribution, X-ray diffraction, transmission electron microscopy (TEM), and transmission X-ray microscopy combined with X-ray absorption near edge structure (TXM–XANES) are used to follow the chemical and structural changes that occur in Li 2Cu 0.5Ni 0.5O 2 during electrochemical cycling. Li 2Cu 0.5Ni 0.5O 2 is a solid solution of orthorhombic Li2CuO2 and Li2NiO2, but the structural changes more closely mimic the changes that the Li 2NiO 2 endmember undergoes. Li 2Cu 0.5Ni 0.5O 2 loses long-range order during charge, but TEM analysis provides clear evidence of particle exfoliation and the transformation from orthorhombic to a partially layered structure. Linear combination fitting and principal component analysis of TXM–XANES are used to map the different phases that emerge during cycling ex situ and in situ. Lastly, significant changes in the XANES at the Cu and Ni K-edges correlate with the onset of oxygen evolution.« less

  8. Study of the Warm Dense Matter with XANES spectroscopy - Applications to planetary interiors

    NASA Astrophysics Data System (ADS)

    Denoeud, Adrien

    With the recent discovery of many exoplanets, modelling the interior of these celestial bodies is becoming a fascinating scientific challenge. In this context, it is crucial to accurately know the equations of state and the macroscopic and microscopic physical properties of their constituent materials in the Warm Dense Matter regime (WDM). Moreover, planetary models rely almost exclusively on physical properties obtained using first principles simulations based on density functional theory (DFT) predictions. It is thus of paramount importance to validate the basic underlying mechanisms occurring for key planetary constituents (metallization, dissociation, structural modifications, phase transitions, etc....) as pressure and temperature both increase. In this work, we were interested in two materials that can be mainly found in the Earth-like planets: silica, or SiO2, as a model compound of the silicates that constitute the major part of their mantles, and iron, which is found in abundance in their cores. These two materials were compressed and brought to the WDM regime by using strong shock created by laser pulses during various experiments performed on the LULI2000 (Palaiseau, France) and the JLF (Livermore, US) laser facilities and on the LCLS XFEL (Stanford, US). In order to penetrate this dense matter and to have access to its both ionic and electronic structures, we have probed silica and iron with time-resolved X-ray Absorption Near Edge Structure (XANES). In parallel with these experiments, we performed quantum molecular dynamics simulations based on DFT at conditions representative of the region investigated experimentally so as to extract the interesting physical processes and comprehend the limits of the implemented models. In particular, these works allowed us to highlight the metallization processes of silica in temperature and the structural changes of its liquid in density, as well as to more constrain the melting curve of iron at very high pressures.

  9. Structure and magnetic properties of Fe-doped ZnO prepared by the sol-gel method.

    PubMed

    Liu, Huilian; Yang, Jinghai; Zhang, Yongjun; Yang, Lili; Wei, Maobin; Ding, Xue

    2009-04-08

    Zn(0.97)Fe(0.03)O nanoparticles were synthesized by the sol-gel method. X-ray diffraction (XRD) and transmission electron microscope (TEM) analysis revealed that the samples had pure ZnO wurtzite structure and Fe ions were well incorporated into the ZnO crystal lattice. X-ray photoelectron spectroscopy (XPS) showed that both Fe(2+) and Fe(3+) existed in Zn(0.97)Fe(0.03)O. The result of x-ray absorption near-edge structure (XANES) further testified that Fe ions took the place of Zn sites in our samples. Magnetic measurements indicated that Zn(0.97)Fe(0.03)O was ferromagnetic at room temperature.

  10. Atomistic nucleation sites of Pt nanoparticles on N-doped carbon nanotubes.

    PubMed

    Sun, Chia-Liang; Pao, Chih-Wen; Tsai, Huang-Ming; Chiou, Jau-Wern; Ray, Sekhar C; Wang, Houng-Wei; Hayashi, Michitoshi; Chen, Li-Chyong; Lin, Hong-Ji; Lee, Jyh-Fu; Chang, Li; Tsai, Min-Hsiung; Chen, Kuei-Hsien; Pong, Way-Faung

    2013-08-07

    The atomistic nucleation sites of Pt nanoparticles (Pt NPs) on N-doped carbon nanotubes (N-CNTs) were investigated using C and N K-edge and Pt L3-edge X-ray absorption near-edge structure (XANES)/extended X-ray absorption fine structure (EXAFS) spectroscopy. Transmission electron microscopy and XANES/EXAFS results revealed that the self-organized Pt NPs on N-CNTs are uniformly distributed because of the relatively high binding energies of the adsorbed Pt atoms at the imperfect sites. During the atomistic nucleation process of Pt NPs on N-CNTs, stable Pt-C and Pt-N bonds are presumably formed, and charge transfer occurs at the surface/interface of the N-CNTs. The findings in this study were consistent with density functional theory calculations performed using cluster models for the undoped, substitutional-N-doped and pyridine-like-N-doped CNTs.

  11. Drift paths of ions composing multiple-nose spectral structures near the inner edge of the plasma sheet

    DOE PAGES

    Ferradas, C. P.; Zhang, J. -C.; Spence, H. E.; ...

    2016-11-05

    Here in this paper, we present a case study of the H +, He +, and O + multiple-nose structures observed by the Helium, Oxygen, Proton, and Electron instrument on board Van Allen Probe A over one complete orbit on 28 September 2013. Nose structures are observed near the inner edge of the plasma sheet and constitute the signatures of ion drift in the highly dynamic environment of the inner magnetosphere. We find that the multiple noses are intrinsically associated with variations in the solar wind. Backward ion drift path tracings show new details of the drift trajectories of thesemore » ions; i.e., multiple noses are formed by ions with a short drift time from the assumed source location to the inner region and whose trajectories (1) encircle the Earth different number of times or (2) encircle the Earth equal number of times but with different drift time, before reaching the observation site.« less

  12. Drift paths of ions composing multiple-nose spectral structures near the inner edge of the plasma sheet

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

    Ferradas, C. P.; Zhang, J. -C.; Spence, H. E.

    Here in this paper, we present a case study of the H +, He +, and O + multiple-nose structures observed by the Helium, Oxygen, Proton, and Electron instrument on board Van Allen Probe A over one complete orbit on 28 September 2013. Nose structures are observed near the inner edge of the plasma sheet and constitute the signatures of ion drift in the highly dynamic environment of the inner magnetosphere. We find that the multiple noses are intrinsically associated with variations in the solar wind. Backward ion drift path tracings show new details of the drift trajectories of thesemore » ions; i.e., multiple noses are formed by ions with a short drift time from the assumed source location to the inner region and whose trajectories (1) encircle the Earth different number of times or (2) encircle the Earth equal number of times but with different drift time, before reaching the observation site.« less

  13. Depth distribution of secondary phases in kesterite Cu 2ZnSnS 4 by angle-resolved X-ray absorption spectroscopy

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

    Just, J.; Lützenkirchen-Hecht, D.; Müller, O.

    The depth distribution of secondary phases in the solar cell absorber material Cu 2ZnSnS 4 (CZTS) is quantitatively investigated using X-ray Absorption Near Edge Structure (XANES) analysis at the K-edge of sulfur at varying incidence angles. Varying information depths from several nanometers up to the full thickness is achieved. A quantitative profile of the phase distribution is obtained by a self-consistent fit of a multilayer model to the XANES spectra for different angles. Single step co-evaporated CZTS thin-films are found to exhibit zinc and copper sulfide secondary phases preferentially at the front or back interfaces of the film.

  14. Depth distribution of secondary phases in kesterite Cu 2ZnSnS 4 by angle-resolved X-ray absorption spectroscopy

    DOE PAGES

    Just, J.; Lützenkirchen-Hecht, D.; Müller, O.; ...

    2017-12-12

    The depth distribution of secondary phases in the solar cell absorber material Cu 2ZnSnS 4 (CZTS) is quantitatively investigated using X-ray Absorption Near Edge Structure (XANES) analysis at the K-edge of sulfur at varying incidence angles. Varying information depths from several nanometers up to the full thickness is achieved. A quantitative profile of the phase distribution is obtained by a self-consistent fit of a multilayer model to the XANES spectra for different angles. Single step co-evaporated CZTS thin-films are found to exhibit zinc and copper sulfide secondary phases preferentially at the front or back interfaces of the film.

  15. Near Edge X-Ray Absorption and X-Ray Photoelectron Diffraction Studies of the Structural Environment of Ge-Si Systems

    NASA Astrophysics Data System (ADS)

    Castrucci, P.; Gunnella, R.; Pinto, N.; Bernardini, R.; de Crescenzi, M.; Sacchi, M.

    Near edge X-ray absorption spectroscopy (XAS), X-ray photoelectron diffraction (XPD) and Auger electron diffraction (AED) are powerful techniques for the qualitative study of the structural and electronic properties of several systems. The recent development of a multiple scattering approach to simulating experimental spectra opened a friendly way to the study of structural environments of solids and surfaces. This article reviews recent X-ray absorption experiments using synchrotron radiation which were performed at Ge L edges and core level electron diffraction measurements obtained using a traditional X-ray source from Ge core levels for ultrathin Ge films deposited on silicon substrates. Thermodynamics and surface reconstruction have been found to play a crucial role in the first stages of Ge growth on Si(001) and Si(111) surfaces. Both techniques show the occurrence of intermixing processes even for room-temperature-grown Ge/Si(001) samples and give a straightforward measurement of the overlayer tetragonal distortion. The effects of Sb as a surfactant on the Ge/Si(001) interface have also been investigated. In this case, evidence of layer-by-layer growth of the fully strained Ge overlayer with a reduced intermixing is obtained when one monolayer of Sb is predeposited on the surface.

  16. Sequestration of Tellurium From Seawater by Ferromanganese Crusts: A XANES/EXAFS Perspective

    NASA Astrophysics Data System (ADS)

    Hein, J. R.; Bargar, J.; Koschinsky, A.; Dunham, R.; Halliday, A. N.

    2007-12-01

    Marine iron-oxyhydroxide/manganese-oxide crusts (Fe-Mn crusts) provide the richest known source of tellurium (Te). Te averages about 50 ppm in Fe-Mn crusts distributed globally, with concentrations locally up to 210 ppm. The sorption of Te onto Fe-Mn crusts likely controls the dominant redox species and concentration of Te in the global ocean (Hein et al., 2003). However, little is known about the mechanisms by which Te is sequestered by Fe-Mn crusts and Fe-Mn colloids in the water column, and then stabilized in the Fe/Mn oxyhydroxide/oxide framework. Two primary hypotheses are being tested: (a) Te(IV) is initially the predominant adsorbed species, which is subsequently oxidized on the Fe-oxyhydroxide and/or Mn oxide phases in natural systems and in sorption experiments. (b) Once oxidized, Te(VI) remains tightly bound to the Fe phase in Fe-Mn crusts as adsorbed surface complexes. These hypotheses are being examined by using the Stanford Synchrotron Radiation Laboratory's (SSRL) synchrotron-based XANES (x-ray absorption near-edge structure) spectroscopy to assess Te oxidation state in natural samples and samples in which Te(IV) and Te(VI) were sorbed onto synthetic and natural FeOOH and Mn oxides. EXAFS (extended x-ray absorption fine structure) spectroscopy is being used to resolve the local molecular-scale structure around Te in these same samples. Data have thus far been obtained for six Fe-Mn crusts from a variety of geographic locations and water depths of occurrence, with differing chemical compositions; and two model compounds, Te(IV) sorbed on FeOOH and Te(IV) sorbed on MnO2. XANES data show that for all six Fe-Mn crust samples, 85 to 100 percent of the Te occurs as Te(VI). For the model compounds, about 65 percent of the Te(IV) sorbed onto the MnO2 had oxidized to Te(VI) by the time (one week) the sample was analyzed, whereas Te sorbed onto FeOOH remained at about 100 percent Te(IV). The most striking result from the EXAFS data is that all spectra for the

  17. Optimal perturbations of a finite-width mixing layer near the trailing edge

    NASA Astrophysics Data System (ADS)

    Gumbart, James C.; Rabchuk, James

    2002-03-01

    The trailing edge of a surface separating two fluid flows can act as an efficient receptor for acoustic or other disturbances. The incident wave energy is converted by a linear mechanism into incipient flow instabilities which lead further downstream to the transition to turbulence. Understanding this process is essential for analyzing feedback loops and other resonances which can cause unwanted structural vibrations in the surface material or directed acoustic emissions from the mixing region. Previously, the modes of instability in a finite-width mixing layer near the trailing edge were studied as a function of frequency by assuming that vorticity was continually being introduced into the flow at the trailing edge by the forcing field. It was found that the initial amplitude of the growing instability mode was a sharply decreasing function of forcing frequency, and that the initial amplitude was a minimum for the frequency at which the rate of instability growth was a maximum^1. This result has led to a study of the adjoint equation for the perturbation stream function, whose eigensolutions are known to be associated with the optimal perturbation field for the frequency of forcing leading to the greatest instability growth downstream. We have obtained these solutions for a piecewise linear velocity profile near the trailing edge using group-theoretic techniques and have shown that they are indeed optimal. We have also analyzed the nature of the physical forcing field that might produce these optimal perturbations. ^1 Rabchuk, J.A., July 2000, Physics of Fluids.

  18. Olivine-melt relationships and syneruptive redox variations in the 1959 eruption of Kīlauea Volcano as revealed by XANES

    NASA Astrophysics Data System (ADS)

    Helz, R. T.; Cottrell, E.; Brounce, M. N.; Kelley, K. A.

    2017-03-01

    The 1959 summit eruption of Kīlauea Volcano exhibited high lava fountains of gas-rich, primitive magma, containing olivine + chromian spinel in highly vesicular brown glass. Microprobe analysis of these samples shows that euhedral rims on olivine phenocrysts, in direct contact with glass, vary significantly in forsterite (Fo) content, at constant major-element melt composition, as do unzoned groundmass olivine crystals. Ferric/total iron (Fe+ 3/FeT)ratios for matrix and interstitial glasses, plus olivine-hosted glass inclusions in eight 1959 scoria samples have been determined by micro X-ray absorption near-edge structure spectroscopy (μ-XANES). These data show that much of the variation in Fo content reflects variation in oxidation state of iron in the melt, which varies with sulfur concentration in the glass and (locally) with proximity to scoria edges in contact with air. Data for 24 olivine-melt pairs in the better-equilibrated samples from later in the eruption show KD averaging 0.280 ± 0.03 for the exchange of Fe and Mg between olivine and melt, somewhat displaced from the value of 0.30 ± 0.03 given by Roeder and Emslie (1970). This may reflect the low SiO2 content of the 1959 magmas, which is lower than that in most Kīlauea tholeiites. More broadly, we show the potential of μ-XANES and electron microprobe to revisit and refine the value of KD in natural systems. The observed variations of Fe+ 3/FeT ratios in the glasses reflect two distinct processes. The main process, sulfur degassing, produces steady decrease of the Fe+ 3/FeT ratio. Melt inclusions in olivine are high in sulfur (1060-1500 ppm S), with Fe+ 3/FeT = 0.160-0.175. Matrix glasses are degassed (mostly S < 200 ppm) with generally lower Fe+ 3/FeT (0.114-0.135). Interstitial glasses within clumps of olivine crystals locally show intermediate levels of sulfur and Fe+ 3/FeT ratio. The correlation suggests that (1) the 1959 magma was significantly reduced by sulfur degassing during the eruption

  19. Near band edge photoluminescence of ZnO nanowires: Optimization via surface engineering

    NASA Astrophysics Data System (ADS)

    Yan, Danhua; Zhang, Wenrui; Cen, Jiajie; Stavitski, Eli; Sadowski, Jerzy T.; Vescovo, Elio; Walter, Andrew; Attenkofer, Klaus; Stacchiola, Darío J.; Liu, Mingzhao

    2017-12-01

    Zinc oxide (ZnO) nanowire arrays have potential applications for various devices such as ultra-violet light emitting diodes and lasers, where photoluminescence of intense near band edge emission without defect emissions is usually desired. Here, we demonstrate, counter-intuitively, that the near band edge emission may become dominant by introducing certain surface defects to ZnO nanowires via surface engineering. Specifically, near band edge emission (NBE) is effectively enhanced after a low pressure O2 plasma treatment that sputters off surface oxygen species to produce a reduced and oxygen vacancy-rich surface. The effect is attributed to the lowered surface valence band maximum of the reduced ZnO surface that creates an accumulative band bending, which screens the photo-generated minority carriers (holes) from reaching or being trapped by the surface defects.

  20. Changes in the near edge X-ray absorption fine structure of hybrid organic-inorganic resists upon exposure.

    PubMed

    Fallica, Roberto; Watts, Benjamin; Roesner, Benedikt; Della Giustina, Gioia; Brigo, Laura; Brusatin, Giovanna; Ekinci, Yasin

    2018-06-14

    We report on the near edge X-ray absorption fine structure (NEXAFS) spectroscopy of hybrid organic-inorganic resists. These materials are nonchemically amplified systems based on Si, Zr, and Ti oxides, synthesized from organically modified precursors and transition metal alkoxides by a sol-gel route and designed for ultraviolet, extreme ultraviolet and electron beam lithography. The experiments were conducted using a scanning transmission X-ray microscope (STXM) which combines high spatial-resolution microscopy and NEXAFS spectroscopy. The absorption spectra were collected in the proximity of the carbon edge (~ 290 eV) before and after in situ exposure, enabling the measurement of a significant photo-induced degradation of the organic group (phenyl or methyl methacrylate, respectively), the degree of which depends on the configuration of the ligand. Photo-induced degradation was more efficient in the resist synthesized with pendant phenyl substituents than it was in the case of systems based on bridging phenyl groups. The degradation of the methyl methacrylate group was relatively efficient, with about half of the initial ligands dissociated upon exposure. Our data reveal that the such dissociation can produce different outcomes, depending on the structural configuration. While all the organic groups were expected to detach and desorb from the resist in their entirety, a sizeable amount of them remain and form undesired byproducts such as alkene chains. In the framework of the materials synthesis and engineering through specific building blocks, these results provide a deeper insight into the photochemistry of resists, in particular for extreme ultraviolet lithography. © 2018 IOP Publishing Ltd.

  1. A structural study of bone changes in knee osteoarthritis by synchrotron-based X-ray fluorescence and X-ray absorption spectroscopy techniques

    NASA Astrophysics Data System (ADS)

    Sindhupakorn, Bura; Thienpratharn, Suwittaya; Kidkhunthod, Pinit

    2017-10-01

    Osteoarthritis (OA) is characterized by degeneration of articular cartilage and thickening of subchondral bone. The present study investigated the changing of biochemical components of cartilage and bone compared between normal and OA people. Using Synchrotron-based X-ray fluorescence (SR-XRF) and X-ray absorption spectroscopy (XAS) techniquesincluding X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) were employed for the bone changes in kneeosteoarthritisstudies. The bone samples were collected from various osteoarthritis patients with both male and female in the ages range between 20 and 74 years old. SR-XRF results excited at 4240 eV for Ca elements show a majority three main groups, based on their XRF intensities, 20-36 years, 40-60 years and over 70 years, respectively. By employing XAS techniques, XANES features can be used to clearly explain in term of electronic transitions occurring in bone samples which are affected from osteoarthritis symptoms. Moreover, a structural change around Ca ions in bone samples is obviously obtained by EXAFS results indicating an increase of Ca-amorphous phase when the ages increase.

  2. Synchrotron applications in wood preservation and deterioration

    Treesearch

    Barbara L. Illman

    2003-01-01

    Several non-intrusive synchrotron techniques are being used to detect and study wood decay. The techniques use high intensity synchrotron-generated X-rays to determine the atomic structure of materials with imaging, diffraction, and absorption. Some of the techniques are X-ray absorption near edge structure (XANES), X-ray fluorescence spectroscopy (XFS), X-ray...

  3. Multi-edge X-ray absorption spectroscopy study of road dust samples from a traffic area of Venice using stoichiometric and environmental references

    NASA Astrophysics Data System (ADS)

    Valotto, Gabrio; Cattaruzza, Elti; Bardelli, Fabrizio

    2017-02-01

    The appropriate selection of representative pure compounds to be used as reference is a crucial step for successful analysis of X-ray absorption near edge spectroscopy (XANES) data, and it is often not a trivial task. This is particularly true when complex environmental matrices are investigated, being their elemental speciation a priori unknown. In this paper, an investigation on the speciation of Cu, Zn, and Sb based on the use of conventional (stoichiometric compounds) and non-conventional (environmental samples or relevant certified materials) references is explored. This method can be useful in when the effectiveness of XANES analysis is limited because of the difficulty in obtaining a set of references sufficiently representative of the investigated samples. Road dust samples collected along the bridge connecting Venice to the mainland were used to show the potentialities and the limits of this approach.

  4. Near band edge photoluminescence of ZnO nanowires: Optimization via surface engineering

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

    Yan, Danhua; Zhang, Wenrui; Cen, Jiajie

    Zinc oxide (ZnO) nanowire arrays have potential applications for various devices including ultra-violet light emitting diodes and lasers, where photoluminescence of intense near band edge emission without defect emissions is usually desired. Here, we demonstrate, counter-intuitively, that the near band edge emission may become dominant by introducing certain surface defects to ZnO nanowires via surface engineering. Specifically, near band edge emission (NBE) is effectively enhanced after a low pressure O 2 plasma treatment that sputters off surface oxygen species to produce a reduced and oxygen vacancy-rich surface. The effect is attributed to the lowered surface valence band maximum of themore » reduced ZnO surface that creates an accumulative band bending, which screens the photo-generated minority carriers (holes) from reaching or being trapped by the surface defects.« less

  5. Near band edge photoluminescence of ZnO nanowires: Optimization via surface engineering

    DOE PAGES

    Yan, Danhua; Zhang, Wenrui; Cen, Jiajie; ...

    2017-12-04

    Zinc oxide (ZnO) nanowire arrays have potential applications for various devices including ultra-violet light emitting diodes and lasers, where photoluminescence of intense near band edge emission without defect emissions is usually desired. Here, we demonstrate, counter-intuitively, that the near band edge emission may become dominant by introducing certain surface defects to ZnO nanowires via surface engineering. Specifically, near band edge emission (NBE) is effectively enhanced after a low pressure O 2 plasma treatment that sputters off surface oxygen species to produce a reduced and oxygen vacancy-rich surface. The effect is attributed to the lowered surface valence band maximum of themore » reduced ZnO surface that creates an accumulative band bending, which screens the photo-generated minority carriers (holes) from reaching or being trapped by the surface defects.« less

  6. Tracking the Chemical Transformations at the Brønsted Acid Site upon Water-Induced Deprotonation in a Zeolite Pore

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

    Vjunov, Aleksei; Wang, Meng; Govind, Niranjan

    We report the structural changes induced by Brønsted acidic site deprotonation in a zeolite with MFI structure as a function of temperature up to 430°C using in situ Al K-edge X-ray absorption fine structure spectroscopy (XAFS). At ambient conditions, the protons are present as hydrated hydronium ions (H3O+(H2O)n) that are ion-paired to the anionic, Al tetrahedral (T) site. At elevated temperatures, loss of water molecules hydrating the hydronium ions leads to an unstable free hydronium ion that disso-ciates to form the hydroxylated T-site. The formation of this (-O3)-Al-(OH-) species leads to the elongation of one of the four Al-O bondsmore » and causes significant distortion of the tetrahedral symmetry about the Al atom. This distortion leads to the appearance of new pre-edge features in the Al K-edge X-ray absorption near edge structure (XANES) spectra. The pre-edge peak assignment is confirmed by time-dependent density functional theory calculation of the XANES spectrum. The XANES spectra are also sensitive to solutes or solvent that are in proximity to the T-site. A second structural transition occurs at about the same temperature, namely the conversion of a minor fraction of extra-framework octahedral Al present in the sample at ambient conditions to a tetrahedral species through the de-coordination of H2O-ligands. Both IR spectroscopy and thermogravimetric analysis (TGA) are further used to confirm the overall chemical transformation of the T-site.« less

  7. Effects of Sulfation Level on the Desulfation Behavior of Presulfated Pt-BaO/Al2O3 Lean NOx Trap Catalysts: A Combined H2 Temperature-Programmed Reaction, in Situ Sulfur K-Edge X-ray Absorption Near-Edge Spectroscopy, X-ray Photoelectron Spectroscopy, and Time-Resolved X-ray Diffraction Study

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

    Kim, D.H.; Hanson, J.; Szanyi, J.

    2009-04-30

    Desulfation by hydrogen of presulfated Pt (2 wt %)-BaO(20 wt %)/Al{sub 2}O{sub 3} with various sulfur loading (S/Ba = 0.12, 0.31, and 0.62) were investigated by combining H{sub 2} temperature programmed reaction (TPRX), X-ray photoelectron spectroscopy (XPS), in situ sulfur K-edge X-ray absorption near-edge spectroscopy (XANES), and synchrotron time-resolved X-ray diffraction (TR-XRD) techniques. We find that the amount of H{sub 2}S desorbed during the desulfation in the H{sub 2} TPRX experiments is not proportional to the amount of initial sulfur loading. The results of both in situ sulfur K-edge XANES and TR-XRD show that at low sulfur loadings, sulfates weremore » transformed to a BaS phase and remained in the catalyst rather than being removed as H{sub 2}S. On the other hand, when the deposited sulfur level exceeded a certain threshold (at least S/Ba = 0.31) sulfates were reduced to form H{sub 2}S, and the relative amount of the residual sulfide species in the catalyst was much less than at low sulfur loading. Unlike samples with high sulfur loading (e.g., S/Ba = 0.62), H{sub 2}O did not promote the desulfation for the sample with S/Ba of 0.12, implying that the formed BaS species originating from the reduction of sulfates at low sulfur loading are more stable to hydrolysis. The results of this combined spectroscopy investigation provide clear evidence to show that sulfates at low sulfur loadings are less likely to be removed as H{sub 2}S and have a greater tendency to be transformed to BaS on the material, leading to the conclusion that desulfation behavior of Pt-BaO/Al{sub 2}O{sub 3} lean NO{sub x} trap catalysts is markedly dependent on the sulfation levels.« less

  8. Fate and lability of silver in soils: Effect of ageing

    EPA Science Inventory

    The fate and lability of added soluble Ag in soils over time was examined by measurement of labile metal (E-value) by isotopic dilution using the 110mAg radioactive isotope and the solid-phase speciation of Ag by X-ray absorption near edge structure (XANES) spectrosco...

  9. On the aeroacoustic and flow structures developed on a flat plate with a serrated sawtooth trailing edge

    NASA Astrophysics Data System (ADS)

    Chong, Tze Pei; Vathylakis, Alexandros

    2015-10-01

    Results of an experimental study on turbulent flow over a flat plate with a serrated sawtooth trailing edge are presented in this paper. After tripping the boundary layer to become turbulent, the broadband noise sources at the sawtooth serrated trailing edge is studied by several experimental techniques. Broadband noise reduction by the serrated sawtooth trailing edge can be realistically achieved in the flat plate configuration. The variations of wall pressure power spectral density and the spanwise coherence (which relates to the spanwise correlation length) in a sawtooth trailing edge play a minor role in the mechanisms underpinning the reduction of self noise radiation. Conditional-averaging technique was applied in the boundary layer data where a pair of pressure-driven oblique vortical structures near the sawtooth side edges is identified. In the current flat plate configuration, the interaction between the vortical structures and the local turbulent boundary layer results in a redistribution of the momentum transport and turbulent shear stress near the sawtooth side edges as well as the sawtooth tip, thus affecting the efficiency of self noise radiation.

  10. Investigation of the Structural Stability of Ion-Implanted Gd 2Ti 2-xSn xO 7 Pyrochlore-Type Oxides by Glancing Angle X-ray Absorption Spectroscopy

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

    Aluri, Esther Rani; Hayes, John R.; Walker, James D.S.

    2016-03-24

    Rare-earth titanate and stannate pyrochlore-type oxides have been investigated in the past for the sequestration of nuclear waste elements because of their resistance to radiation-induced structural damage. In order to enhance this property, it is necessary to understand the effect of radioactive decay of the incorporated actinide elements on the local chemical environment. In this study, Gd 2Ti 2–xSn xO 7 materials have been implanted with Au– ions to simulate radiation-induced structural damage. Glancing angle X-ray absorption near-edge spectroscopy (GA-XANES), glancing angle X-ray absorption fine structure (GA-EXAFS) analysis, and powder X-ray diffraction have been used to investigate changes in themore » local coordination environment of the metal atoms in the damaged surface layer. Examination of GA-XANES/EXAFS spectra from the implanted Gd 2Ti 2–xSn xO 7 materials collected at various glancing angles allowed for an investigation of how the local coordination environment around the absorbing atoms changed at different depths in the damaged surface layer. This study has shown the usefulness of GA-XANES to the examination of ion-implanted materials and has suggested that Gd 2Ti 2–xSn xO 7 becomes more susceptible to ion-beam-induced structural damage with increasing Sn concentration.« less

  11. The influence of coordination geometry and valency on the K-edge absorption near edge spectra of selected chromium compounds

    NASA Astrophysics Data System (ADS)

    Pantelouris, A.; Modrow, H.; Pantelouris, M.; Hormes, J.; Reinen, D.

    2004-05-01

    X-ray absorption spectra at the chromium K-edge are reported for a number of selected chromium compounds of known chemical structure. The spectra were obtained with use of synchrotron radiation available at the ELectron Stretcher Accelerator ELSA in Bonn. The compounds studied include the tetrahedrally coordinated compounds Ca 2Ge 0.8Cr 0.2O 4, Ba 2Ge 0.1Cr 0.9O 4, Sr 2CrO 4, Ca 2(PO 4) x(CrO 4) 1- xCl ( x=0.25,0.5), Ca 5(CrO 4) 3Cl, CrO 3, the octahedrally coordinated compounds Cr(II)-acetate, CrCl 3, CrF 3, Cr 2O 3, KCr(SO 4) 2 · 12H 2O, CrO 2 and cubic coordinated metallic chromium. In these compounds chromium exhibits a wide range of formal oxidation states (0 to VI). The absorption features in the near edge region are shown to be characteristic of the spatial environment of the absorbing atom. The occurrence of a single pre-edge line easily allows one to distinguish between tetrahedral and octahedral coordination geometry, whereas the energy position of the absorption edge is found to be very sensitive to the valency of the excited chromium atom. Calculations of the ionisation potential of Cr in different oxidation states using the non-relativistic Hartree-Fock method (Froese-Fischer) confirm that the ionisation limit shifts to higher energy with increasing Cr valency. More detailed information on the electronic structure of the different compounds is gained by real-space full multiple scattering calculations using the FEFF8 code.

  12. Speciation and Elemental Mapping of Metal Containing Aerosols

    NASA Astrophysics Data System (ADS)

    Fraund, M. W.; Moffet, R.; Harder, T.; Williams, G.; Chen-Wiegart, Y. C. K.; Laskin, A.; Gilles, M. K.; Schoonen, M. A.; Thieme, J.

    2017-12-01

    Transition metals play a key roles in biogeochemical processes and health effects of aerosols. The Submicron Resolution X-ray (SRX) beamline at the second National Synchrotron Light Source (NSLS-II) can be used to obtain spatially resolved elemental composition using X-ray fluorescence (XRF) as well as element specific molecular information through X-ray absorption near edge structure (XANES) spectroscopy. Here, XANES spectroscopy was used to identify the oxidation state of iron-rich particles collected from the Cape Hedo Observatory on the island of Okinawa, Japan which is subject to aerosols from both biogenic (Gobi desert) and anthropogenic sources (e.g. Beijing and Shanghai). This data was compared with standards to help classify the minerology and source of these aerosol particles with regards to their potential solubility and bioavailability. In another application of the XRF/XANES measurements from NSLS-II, Pb rich particles from Mexico City were probed for distribution and speciation of Pb. Prior study has indicated that elevated concentrations of Pb occur in an industrialized section of northern Mexico City. It has been established that Pb and Zn are internally mixed in atmospheric aerosol and that Zn primarily exists as ZnCl2 and Zn(NO3)2. Based on these observations, it is hypothesized that Pb also exists as PbCl2 and Pb(NO3)­2. In this study it is shown that X-ray absorption near edge structure (XANES) spectroscopy at the Pb L-edge supports Pb being present as PbCl2 and Pb(NO3)2. Submicron resolution X-ray fluorescence mapping is also used to provide complimentary information on the collocation of other high-Z elements.

  13. CNNEDGEPOT: CNN based edge detection of 2D near surface potential field data

    NASA Astrophysics Data System (ADS)

    Aydogan, D.

    2012-09-01

    All anomalies are important in the interpretation of gravity and magnetic data because they indicate some important structural features. One of the advantages of using gravity or magnetic data for searching contacts is to be detected buried structures whose signs could not be seen on the surface. In this paper, a general view of the cellular neural network (CNN) method with a large scale nonlinear circuit is presented focusing on its image processing applications. The proposed CNN model is used consecutively in order to extract body and body edges. The algorithm is a stochastic image processing method based on close neighborhood relationship of the cells and optimization of A, B and I matrices entitled as cloning template operators. Setting up a CNN (continues time cellular neural network (CTCNN) or discrete time cellular neural network (DTCNN)) for a particular task needs a proper selection of cloning templates which determine the dynamics of the method. The proposed algorithm is used for image enhancement and edge detection. The proposed method is applied on synthetic and field data generated for edge detection of near-surface geological bodies that mask each other in various depths and dimensions. The program named as CNNEDGEPOT is a set of functions written in MATLAB software. The GUI helps the user to easily change all the required CNN model parameters. A visual evaluation of the outputs due to DTCNN and CTCNN are carried out and the results are compared with each other. These examples demonstrate that in detecting the geological features the CNN model can be used for visual interpretation of near surface gravity or magnetic anomaly maps.

  14. Near-field tsunami edge waves and complex earthquake rupture

    USGS Publications Warehouse

    Geist, Eric L.

    2013-01-01

    The effect of distributed coseismic slip on progressive, near-field edge waves is examined for continental shelf tsunamis. Detailed observations of edge waves are difficult to separate from the other tsunami phases that are observed on tide gauge records. In this study, analytic methods are used to compute tsunami edge waves distributed over a finite number of modes and for uniformly sloping bathymetry. Coseismic displacements from static elastic theory are introduced as initial conditions in calculating the evolution of progressive edge-waves. Both simple crack representations (constant stress drop) and stochastic slip models (heterogeneous stress drop) are tested on a fault with geometry similar to that of the M w = 8.8 2010 Chile earthquake. Crack-like ruptures that are beneath or that span the shoreline result in similar longshore patterns of maximum edge-wave amplitude. Ruptures located farther offshore result in reduced edge-wave excitation, consistent with previous studies. Introduction of stress-drop heterogeneity by way of stochastic slip models results in significantly more variability in longshore edge-wave patterns compared to crack-like ruptures for the same offshore source position. In some cases, regions of high slip that are spatially distinct will yield sub-events, in terms of tsunami generation. Constructive interference of both non-trapped and trapped waves can yield significantly larger tsunamis than those that produced by simple earthquake characterizations.

  15. Changes in local surface structure and Sr depletion in Fe-implanted SrTiO3 (001)

    NASA Astrophysics Data System (ADS)

    Lobacheva, O.; Yiu, Y. M.; Chen, N.; Sham, T. K.; Goncharova, L. V.

    2017-01-01

    Local surface structure of single crystal strontium titanate SrTiO3 (001) samples implanted with Fe in the range of concentrations between 2 × 1014 to 2 × 1016 Fe/cm2 at 30 keV has been investigated. In order to facilitate Fe substitution (doping), implanted samples were annealed in oxygen at 350 °C. Sr depletion was observed from the near-surface layers impacted by the ion-implantation process, as revealed by Rutherford Backscattering Spectrometry (RBS), X-ray photoelectron spectroscopy (XPS), X-ray Absorption Near Edge Spectroscopy (XANES), and Atomic Force Microscopy (AFM). Hydrocarbon contaminations on the surface may contribute to the mechanisms of Sr depletion, which have important implications for Sr(Ti1-xFex)O3-δ materials in gas sensing applications.

  16. Investigation of arsenic species in tailings and windblown dust from a gold mining area.

    PubMed

    Ono, F B; Tappero, R; Sparks, D; Guilherme, L R G

    2016-01-01

    Research has shown the presence of high levels of arsenic (up to 2666 mg As kg(-1)) in tailings from a gold mining area of Brazil. This is an important point of attention, generating concerns about impacts on human health. Yet, a recent study showed that As bioaccessibility in the same area was very low (<4.4%). Thus, determination of the direct solid-phase speciation of As in the mine tailings and windblown dust is needed to explain this low bioaccessibility. Mine samples were collected from four subareas and windblown dust from eight sites. Synchrotron-based bulk-X-ray absorption near-edge structure (bulk-XANES) spectroscopy, micro-X-ray absorption near-edge structure (μ-XANES), and μ-X-ray fluorescence (μ-SXRF) spectroscopy were applied to determine As speciation. Bulk-XANES spectra indicated that As occurs as the As(V) oxidation state. Micro-XANES and μ-SXRF analyses revealed that As was also present as arsenopyrite (FeAsS) and its weathering products, but mostly it was As(V) as poorly crystalline ferric arsenate. This supports the findings of low bioaccessible As and highlights the importance of Fe oxides in immobilizing As in the terrestrial environment. All air particulate samples exhibited As-rich particles (up to 313 mg As kg(-1)). The air particulates exhibited solid-phase As species very similar to those found in the mine samples, which indicates that As in the windblown dust is not easily available.

  17. Analysis of buried interfaces in multilayer mirrors using grazing incidence extreme ultraviolet reflectometry near resonance edges.

    PubMed

    Sertsu, M G; Nardello, M; Giglia, A; Corso, A J; Maurizio, C; Juschkin, L; Nicolosi, P

    2015-12-10

    Accurate measurements of optical properties of multilayer (ML) mirrors and chemical compositions of interdiffusion layers are particularly challenging to date. In this work, an innovative and nondestructive experimental characterization method for multilayers is discussed. The method is based on extreme ultraviolet (EUV) reflectivity measurements performed on a wide grazing incidence angular range at an energy near the absorption resonance edge of low-Z elements in the ML components. This experimental method combined with the underlying physical phenomenon of abrupt changes of optical constants near EUV resonance edges enables us to characterize optical and structural properties of multilayers with high sensitivity. A major advantage of the method is to perform detailed quantitative analysis of buried interfaces of multilayer structures in a nondestructive and nonimaging setup. Coatings of Si/Mo multilayers on a Si substrate with period d=16.4  nm, number of bilayers N=25, and different capping structures are investigated. Stoichiometric compositions of Si-on-Mo and Mo-on-Si interface diffusion layers are derived. Effects of surface oxidation reactions and carbon contaminations on the optical constants of capping layers and the impact of neighboring atoms' interactions on optical responses of Si and Mo layers are discussed.

  18. Systematic oxidation of polystyrene by ultraviolet-ozone, characterized by near-edge X-ray absorption fine structure and contact angle.

    PubMed

    Klein, Robert J; Fischer, Daniel A; Lenhart, Joseph L

    2008-08-05

    The process of implanting oxygen in polystyrene (PS) via exposure to ultraviolet-ozone (UV-O) was systematically investigated using the characterization technique of near-edge X-ray absorption fine structure (NEXAFS). Samples of PS exposed to UV-O for 10-300 s and washed with isopropanol were analyzed using the carbon and oxygen K-edge NEXAFS partial electron yields, using various retarding bias voltages to depth-profile the oxygen penetration into the surface. Evaluation of reference polymers provided a scale to quantify the oxygen concentration implanted by UV-O treatment. We find that ozone initially reacts with the double bonds on the phenyl rings, forming carbonyl groups, but within 1 min of exposure, the ratio of double to single oxygen bonds stabilizes at a lower value. Oxygen penetrates the film with relative ease, creating a fairly uniform distribution of oxygen within at least the first 4 nm (the effective depth probed by NEXAFS here). Before oxygen accumulates in large concentrations, however, it preferentially degrades the uppermost layer of the film by removing oxygenated low-molecular-weight oligomers. The failure to accumulate high concentrations of oxygen is seen in the nearly constant carbon edge jump, the low concentration of oxygen even at 5 min exposure (58% of that in poly(4-acetoxystyrene), the polymer with the most similarities to UV-O-treated PS), and the relatively high contact angles. At 5 min exposure the oxygen concentration contains ca. 7 atomic % oxygen. The oxygen species that are implanted consist predominantly of single O-C bonds and double O=C bonds but also include a small fraction of O-H. UV-O treatment leads a plateau after 2 min exposure in the water contact angle hysteresis, at a value of 67 +/- 2 degrees , due primarily to chemical heterogeneity. Annealing above T(g) allows oxygenated species to move short distances away from the surface but not diffuse further than 1-2 nm.

  19. Stoichiometry of mercury-thiol complexes on bacterial cell envelopes

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

    Mishra, Bhoopesh; Shoenfelt, Elizabeth; Yu, Qiang

    We have examined the speciation of Hg(II) complexed with intact cell suspensions (1013 cells L- 1) of Bacillus subtilis, a common gram-positive soil bacterium, Shewanella oneidensis MR-1, a facultative gram-negative aquatic organism, and Geobacter sulfurreducens, a gram-negative anaerobic bacterium capable of Hg-methylation at Hg(II) loadings spanning four orders of magnitude (120 nM to 350 μM) at pH 5.5 (± 0.2). The coordination environments of Hg on bacterial cells were analyzed using synchrotron based X-ray Absorption Near Edge Structure (XANES) and Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy at the Hg LIII edge. The abundance of thiols on intact cells wasmore » determined by a fluorescence-spectroscopy based method using a soluble bromobimane, monobromo(trimethylammonio)bimane (qBBr) to block thiol sites, and potentiometric titrations of biomass with and without qBBr treatment. The chemical forms of S on intact bacterial cells were determined using S k-edge XANES spectroscopy.« less

  20. Multi-edge X-ray absorption spectroscopy study of road dust samples from a traffic area of Venice using stoichiometric and environmental references.

    PubMed

    Valotto, Gabrio; Cattaruzza, Elti; Bardelli, Fabrizio

    2017-02-15

    The appropriate selection of representative pure compounds to be used as reference is a crucial step for successful analysis of X-ray absorption near edge spectroscopy (XANES) data, and it is often not a trivial task. This is particularly true when complex environmental matrices are investigated, being their elemental speciation a priori unknown. In this paper, an investigation on the speciation of Cu, Zn, and Sb based on the use of conventional (stoichiometric compounds) and non-conventional (environmental samples or relevant certified materials) references is explored. This method can be useful in when the effectiveness of XANES analysis is limited because of the difficulty in obtaining a set of references sufficiently representative of the investigated samples. Road dust samples collected along the bridge connecting Venice to the mainland were used to show the potentialities and the limits of this approach. Copyright © 2016 Elsevier B.V. All rights reserved.

  1. Forensic analysis of tire rubbers based on their sulfur chemical states.

    PubMed

    Funatsuki, Atsushi; Shiota, Kenji; Takaoka, Masaki; Tamenori, Yusuke

    2015-05-01

    The chemical states of sulfur in 11 tires were analyzed using X-ray absorption near-edge structure (XANES) in order to discriminate between various tire rubbers. All tires had peaks around 2471.5 and 2480.5eV, and the shapes and heights of these peaks differed among tires, suggesting that the sulfur chemical state could be used for discrimination between tire rubbers. Based on t-tests on the results of XANES, 43 of 55 combinations were different at a significance level of 5%. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

  2. HgL(3) XANES Study of Mercury Methylation in Shredded Eichhornia Crassipes

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

    Rajan, M.; Darrow, J.; Hua, M.

    2009-05-21

    Eichhornia crassipes (water hyacinth) is a non-native plant found in abundance in the Sacramento-San Joaquin River Delta (hereafter called Delta). This species has become a problem, clogging waterways and wetlands. Water hyacinth are also known to accumulate mercury. Recent attempts to curb its proliferation have included shredding with specialized boats. The purpose of this research is to better understand the ability of water hyacinth to phytoremediate mercury and to determine the effect of shredding and anoxic conditions on mercury speciation in plant tissue. In the field assessment, total mercury levels in sediment from the Dow Wetlands in the Delta weremore » found to be 0.273 {+-} 0.070 ppm Hg, and levels in hyacinth roots and shoots from this site were 1.17 {+-} 0.08 ppm and 1.03 {+-} 0.52 ppm, respectively, indicating bioaccumulation of mercury. Plant samples collected at this site were also grown in nutrient solution with 1 ppm HgCl{sub 2} under (1) aerobic conditions, (2) anaerobic conditions, and (3) with shredded plant material only. The greatest accumulation was found in the roots of whole plants. Plants grown in these conditions were also analyzed at Stanford Synchrotron Radiation Laboratory using Hg L{sub 3} X-ray Absorption Near Edge Spectroscopy (XANES), a method to examine speciation that is element-specific and noninvasive. Least-squares fitting of the XANES data to methylated and inorganic mercury(II) model compounds revealed that in plants grown live and aerobically, 5 {+-} 3% of the mercury was in the form of methylmercury, in a form similar to methylmercury cysteine. This percentage increased to 16 {+-} 4% in live plants grown anaerobically and to 22 {+-} 6% in shredded anaerobic plants. We conclude that shredding of the hyacinth plants and, in fact, subjection of plants to anaerobic conditions (e.g., as in normal decay, or in crowded growth conditions) increases mercury methylation. Mechanical removal of the entire plant is significantly

  3. Edge-closed laminated structures for thin-film heads

    NASA Astrophysics Data System (ADS)

    Herman, D. A.; Argyle, B. E.; Lee, H.-P.; Trouilloud, P. O.; Petek, B.

    1991-04-01

    Magnetic film laminations containing nonmagnetic spacers have been explored with the hope of eliminating domain walls to diminish Barkhausen instabilities. Such laminates have limitations however, which originate in their ``edge-curling walls'' (ECWs).1 We have developed a new structure, free of ECWs, in which flux closure at opposing edges occurs via edge-shorting material added to circulate the easy-axis flux of the flat layers. We show experimentally with Kerr-effect imaging that (1) this edge-closed laminated (ECL) structure can support an (ECW-free) ``easy-axis'' (EA) magnetic state under conditions as modeled recently by Slonczewski,2 and (2) that this EA state is quite robust in the face of imperfect structure fabrication. This is, if the imperfections are not too severe, the resultant states depart minimally from the pure EA state and conduct hard-axis-driven flux nearly as well. Flat-film ECL elements in diamond, stripe, and recording-head-yoke shapes, plus experimental heads with ECL top yokes, were fabricated. Our domain images verify some key predictions from Slonczewski's static equilibrium modeling; additional results taken in applied magnetic fields extend the micromagnetic understanding. The sketch shows a typical domain pattem for a yoke-shaped element. The most stable state in the open portion of the yoke is the single domain shown. This remanent pattern was stable in the face of (slowly varying) external fields up to the 150 Oe that could be applied. The pole tip region contained a few 180° walls as indicated. On close inspection, these walls were seen to end in vestigial, nontouching, closure domains as predicted by the model when only partial flux closure occurs via the edge shorting material. The wall spacing in the tip varied somewhat following saturation-demagnetization cycles. The dynamic stability of this EA state was investigated in the experimental heads having ECL top yokes. The pseudodynamic LAMOM technique3 was applied using ``write

  4. Olivine-melt relationships and syneruptive redox variations in the 1959 eruption of Kīlauea Volcano as revealed by XANES

    USGS Publications Warehouse

    Helz, Rosalind L.; Cottrell, Elizabeth; Brounce, Maryjo N.; Kelley, Katherine A.

    2017-01-01

    The 1959 summit eruption of Kīlauea Volcano exhibited high lava fountains of gas-rich, primitive magma, containing olivine + chromian spinel in highly vesicular brown glass. Microprobe analysis of these samples shows that euhedral rims on olivine phenocrysts, in direct contact with glass, vary significantly in forsterite (Fo) content, at constant major-element melt composition, as do unzoned groundmass olivine crystals. Ferric/total iron (Fe+ 3/FeT)ratios for matrix and interstitial glasses, plus olivine-hosted glass inclusions in eight 1959 scoria samples have been determined by micro X-ray absorption near-edge structure spectroscopy (μ-XANES). These data show that much of the variation in Fo content reflects variation in oxidation state of iron in the melt, which varies with sulfur concentration in the glass and (locally) with proximity to scoria edges in contact with air. Data for 24 olivine-melt pairs in the better-equilibrated samples from later in the eruption show KD averaging 0.280 ± 0.03 for the exchange of Fe and Mg between olivine and melt, somewhat displaced from the value of 0.30 ± 0.03 given by Roeder and Emslie (1970). This may reflect the low SiO2 content of the 1959 magmas, which is lower than that in most Kīlauea tholeiites. More broadly, we show the potential of μ-XANES and electron microprobe to revisit and refine the value of KD in natural systems.The observed variations of Fe+ 3/FeT ratios in the glasses reflect two distinct processes. The main process, sulfur degassing, produces steady decrease of the Fe+ 3/FeT ratio. Melt inclusions in olivine are high in sulfur (1060–1500 ppm S), with Fe+ 3/FeT = 0.160–0.175. Matrix glasses are degassed (mostly S < 200 ppm) with generally lower Fe+ 3/FeT(0.114–0.135). Interstitial glasses within clumps of olivine crystals locally show intermediate levels of sulfur and Fe+ 3/FeT ratio. The correlation suggests that (1) the 1959 magma was significantly reduced by sulfur

  5. Complete wetting near an edge of a rectangular-shaped substrate

    NASA Astrophysics Data System (ADS)

    Malijevský, Alexandr

    2014-08-01

    We consider fluid adsorption near a rectangular edge of a solid substrate that interacts with the fluid atoms via long range (dispersion) forces. The curved geometry of the liquid-vapour interface dictates that the local height of the interface above the edge ℓE must remain finite at any subcritical temperature, even when a macroscopically thick film is formed far from the edge. Using an interfacial Hamiltonian theory and a more microscopic fundamental measure density functional theory (DFT), we study the complete wetting near a single edge and show that {{\\ell}_{\\text{E}}}\\left(0\\right)-{{\\ell}_{\\text{E}}}\\left(\\delta \\mu \\right)\\sim \\delta {{\\mu}^{\\beta _{\\text{E}}^{\\text{co}}}} , as the chemical potential departure from the bulk coexistence δμ = μs(T) - μ tends to zero. The exponent \\beta _{\\text{E}}^{\\text{co}} depends on the range of the molecular forces and in particular \\beta _{\\text{E}}^{\\text{co}}=2/3 for three-dimensional systems with van der Waals forces. We further show that for a substrate model that is characterised by a finite linear dimension L, the height of the interface deviates from the one at the infinite substrate as δℓE(L) ˜ L-1 in the limit of large L. Both predictions are supported by numerical solutions of the DFT.

  6. X-ray absorption studies of gamma irradiated Nd doped phosphate glass

    NASA Astrophysics Data System (ADS)

    Rai, V. N.; Rajput, Parasmani; Jha, S. N.; Bhattacharyya, D.

    2015-06-01

    This paper presents the X-ray absorption near edge structure (XANES) studies of Nd doped phosphate glasses before and after gamma irradiation. The intensity and location of LIII edge white line peak of Nd changes depending on its concentration as well as on the ratio of O/Nd in the glass matrix. The decrease in the peak intensity of white line after gamma irradiation indicates towards reduction of Nd3+ to Nd2+ in the glass matrix, which increases with an increase in the doses of gamma irradiation. Similarity in the XANES spectra of Nd doped phosphate glasses and Nd2O3 suggests that coordination geometry around Nd3+ in glass samples may be identical to that of Nd2O3.

  7. XANES Spectroscopic Analysis of Phosphorus Speciation in Alum-Amended Poultry Litter

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

    Seiter,J.; Staats-Borda, K.; Ginder-Vogel, M.

    2008-01-01

    Aluminum sulfate (alum; Al2(SO4)3{center_dot}14H2O) is used as a chemical treatment of poultry litter to reduce the solubility and release of phosphate, thereby minimizing the impacts on adjacent aquatic ecosystems when poultry litter is land applied as a crop fertilizer. The objective of this study was to determine, through the use of X-ray absorption near edge structure (XANES) spectroscopy and sequential extraction, how alum amendments alter P distribution and solid-state speciation within the poultry litter system. Our results indicate that traditional sequential fractionation procedures may not account for variability in P speciation in heterogeneous animal manures. Analysis shows that NaOH-extracted Pmore » in alum amended litters is predominantly organic ({approx}80%), whereas in the control samples, >60% of NaOH-extracted P was inorganic P. Linear least squares fitting (LLSF) analysis of spectra collected of sequentially extracted litters showed that the P is present in inorganic (P sorbed on Al oxides, calcium phosphates) and organic forms (phytic acid, polyphosphates, and monoesters) in alum- and non-alum-amended poultry litter. When determining land application rates of poultry litter, all of these compounds must be considered, especially organic P. Results of the sequential extractions in conjunction with LLSF suggest that no P species is completely removed by a single extractant. Rather, there is a continuum of removal as extractant strength increases. Overall, alum-amended litters exhibited higher proportions of Al-bound P species and phytic acid, whereas untreated samples contained Ca-P minerals and organic P compounds. This study provides in situ information about P speciation in the poultry litter solid and about P availability in alum- and non-alum-treated poultry litter that will dictate P losses to ground and surface water systems.« less

  8. Fe-doping effects on the structural, vibrational, magnetic, and electronic properties of ceria nanoparticles

    NASA Astrophysics Data System (ADS)

    Aragón, Fermin F. H.; Aquino, Juan C. R.; Ramos, Jesus E.; Coaquira, José A. H.; Gonzalez, Ismael; Macedo, Waldemar A. A.; da Silva, Sebastião W.; Morais, Paulo C.

    2017-11-01

    In this work, we report on a single-pot synthesis route based on a polymeric precursor method used for successfully producing undoped and iron-doped CeO2 nanoparticles with iron contents up to 10.0 mol. %. The formation of high-crystalline nanoparticles with a cubic fluorite structure is determined for all the studied samples. Meanwhile, the magnetic measurements of the undoped ceria nanoparticles revealed the occurrence of ferromagnetism of bound magnetic polarons of a fraction of Ce3+ at room temperature, and only a paramagnetic behavior of Fe3+ ions was determined for Fe-doped ceria nanoparticles. A monotonous reduction of the effective magnetic moment of the Fe3+ ions was determined. It suggests a change from a high-spin to low-spin state of Fe ions as the Fe content is increased. The 3+ valence state of the iron ions has been confirmed by the Fe K-edge X-ray absorption near-edge structure (XANES) and Mössbauer spectroscopy measurements. X-ray photoelectron spectroscopy data analysis evidenced a coexistence of Ce3+ and Ce4+ ions and a decreasing tendency of the relative fraction of Ce3+ ions in the surface region of the particles as the iron content is increased. Although the coexistence of Ce3+ and Ce4+ is confirmed by results obtained via Ce L3-edge XANES measurements, any clear dependence of the relative relation of Ce3+ ions on the iron content is determined, suggesting a homogeneous distribution of Ce3+ and Ce4+-ions in the whole volume of the particles. Ce L3-edge extended X-ray absorption fine structure revealed that the Ce-O bond distance shows a monotonous decrease as the Fe content is increased, which is in good agreement with the shrinking of the unit cell volume with the iron content determined from XRD data analysis, reinforcing the substitutional solution of Ce and Fe ions in the CeO2 matrix.

  9. Origin of luminescence from ZnO/CdS core/shell nanowire arrays

    NASA Astrophysics Data System (ADS)

    Wang, Zhiqiang; Wang, Jian; Sham, Tsun-Kong; Yang, Shaoguang

    2014-07-01

    Chemical imaging, electronic structure and optical properties of ZnO/CdS nano-composites have been investigated using scanning transmission X-ray microscopy (STXM), X-ray absorption near-edge structure (XANES) and X-ray excited optical luminescence (XEOL) spectroscopy. STXM and XANES results confirm that the as-prepared product is ZnO/CdS core/shell nanowires (NWs), and further indicate that ZnS was formed on the surface of ZnO NWs as the interface between ZnO and CdS. The XEOL from ZnO/CdS NW arrays exhibits one weak ultraviolet (UV) emission at 375 nm, one strong green emission at 512 nm, and two broad infrared (IR) emissions at 750 and 900 nm. Combining XANES and XEOL, it is concluded that the UV luminescence is the near band gap emission (BGE) of ZnO; the green luminescence comes from both the BGE of CdS and defect emission (DE, zinc vacancies) of ZnO; the IR luminescence is attributed to the DE (bulk defect related to the S site) of CdS; ZnS contributes little to the luminescence of the ZnO/CdS NW arrays. Interestingly, the BGE and DE from oxygen vacancies of ZnO in the ZnO/CdS nano-composites are almost entirely quenched, while DE from zinc vacancies changes little.Chemical imaging, electronic structure and optical properties of ZnO/CdS nano-composites have been investigated using scanning transmission X-ray microscopy (STXM), X-ray absorption near-edge structure (XANES) and X-ray excited optical luminescence (XEOL) spectroscopy. STXM and XANES results confirm that the as-prepared product is ZnO/CdS core/shell nanowires (NWs), and further indicate that ZnS was formed on the surface of ZnO NWs as the interface between ZnO and CdS. The XEOL from ZnO/CdS NW arrays exhibits one weak ultraviolet (UV) emission at 375 nm, one strong green emission at 512 nm, and two broad infrared (IR) emissions at 750 and 900 nm. Combining XANES and XEOL, it is concluded that the UV luminescence is the near band gap emission (BGE) of ZnO; the green luminescence comes from both the

  10. A XANES Study of Sulfur Speciation and Reactivity in Cokes for Anodes Used in Aluminum Production

    NASA Astrophysics Data System (ADS)

    Jahrsengene, Gøril; Wells, Hannah C.; Rørvik, Stein; Ratvik, Arne Petter; Haverkamp, Richard G.; Svensson, Ann Mari

    2018-03-01

    Availability of anode raw materials in the growing aluminum industry results in a wider range of petroleum cokes being used to produce carbon anodes. The boundary between anode grade cokes and what previously was considered non-anode grades are no longer as distinct as before, leading to introduction of cokes with higher sulfur and higher trace metal impurity content in anode manufacturing. In this work, the chemical nature of sulfur in five industrial cokes, ranging from 1.42 to 5.54 wt pct S, was investigated with K-edge XANES, while the reactivity of the cokes towards CO2 was measured by a standard mass loss test. XANES identified most of the sulfur as organic sulfur compounds. In addition, a significant amount is identified (16 to 53 pct) as S-S bound sulfur. A strong inverse correlation is observed between CO2-reactivity and S-S bound sulfur in the cokes, indicating that the reduction in reactivity is more dependent on the amount of this type of sulfur compound rather than the total amount of sulfur or the amount of organic sulfur.

  11. A XANES Study of Sulfur Speciation and Reactivity in Cokes for Anodes Used in Aluminum Production

    NASA Astrophysics Data System (ADS)

    Jahrsengene, Gøril; Wells, Hannah C.; Rørvik, Stein; Ratvik, Arne Petter; Haverkamp, Richard G.; Svensson, Ann Mari

    2018-06-01

    Availability of anode raw materials in the growing aluminum industry results in a wider range of petroleum cokes being used to produce carbon anodes. The boundary between anode grade cokes and what previously was considered non-anode grades are no longer as distinct as before, leading to introduction of cokes with higher sulfur and higher trace metal impurity content in anode manufacturing. In this work, the chemical nature of sulfur in five industrial cokes, ranging from 1.42 to 5.54 wt pct S, was investigated with K-edge XANES, while the reactivity of the cokes towards CO2 was measured by a standard mass loss test. XANES identified most of the sulfur as organic sulfur compounds. In addition, a significant amount is identified (16 to 53 pct) as S-S bound sulfur. A strong inverse correlation is observed between CO2-reactivity and S-S bound sulfur in the cokes, indicating that the reduction in reactivity is more dependent on the amount of this type of sulfur compound rather than the total amount of sulfur or the amount of organic sulfur.

  12. The effect of nitrogen incorporation on the bonding structure of hydrogenated carbon nitride films

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

    Camero, M.; Buijnsters, J. G.; Gomez-Aleixandre, C.

    2007-03-15

    This work describes the composition and bonding structure of hydrogenated carbon nitride (a-CN{sub x}:H) films synthesized by electron cyclotron resonance chemical vapor deposition using as precursor gases argon, methane, and nitrogen. The composition of the films was derived from Rutherford backscattering and elastic recoil detection analysis and the bonding structure was examined by infrared (IR) spectroscopy and x-ray absorption near edge spectroscopy (XANES). By varying the nitrogen to methane ratio in the applied gas mixture, polymeric a-CN{sub x}:H films with N/C contents varying from 0.06 to 0.49 were obtained. Remarkably, the H content of the films ({approx}40 at. %) wasmore » rather unaffected by the nitrogenation process. The different bonding states as detected in the measured XANES C(1s) and N(1s) spectra have been correlated with those of a large number of reference samples. The XANES and IR spectroscopy results indicate that N atoms are efficiently incorporated into the amorphous carbon network and can be found in different bonding environments, such as pyridinelike, graphitelike, nitrilelike, and amino groups. The nitrogenation of the films results in the formation of N-H bonding environments at the cost of C-H structures. Also, the insertion of N induces a higher fraction of double bonds in the structure at the expense of the linear polymerlike chains, hence resulting in a more cross-linked solid. The formation of double bonds takes place through complex C=N structures and not by formation of graphitic aromatic rings. Also, the mechanical and tribological properties (hardness, friction, and wear) of the films have been studied as a function of the nitrogen content. Despite the major modifications in the bonding structure with nitrogen uptake, no significant changes in these properties are observed.« less

  13. X-ray absorption studies of chlorine valence and local environments in borosilicate waste glasses

    NASA Astrophysics Data System (ADS)

    McKeown, David A.; Gan, Hao; Pegg, Ian L.; Stolte, W. C.; Demchenko, I. N.

    2011-01-01

    Chlorine (Cl) is a constituent of certain types of nuclear wastes and its presence can affect the physical and chemical properties of silicate melts and glasses developed for the immobilization of such wastes. Cl K-edge X-ray absorption spectra (XAS) were collected and analyzed to characterize the unknown Cl environments in borosilicate waste glass formulations, ranging in Cl-content from 0.23 to 0.94 wt.%. Both X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) data for the glasses show trends dependent on calcium (Ca) content. Near-edge data for the Ca-rich glasses are most similar to the Cl XANES of CaCl 2, where Cl - is coordinated to three Ca atoms, while the XANES for the Ca-poor glasses are more similar to the mineral davyne, where Cl is most commonly coordinated to two Ca in one site, as well as Cl and oxygen nearest-neighbors in other sites. With increasing Ca content in the glass, Cl XANES for the glasses approach that for CaCl 2, indicating more Ca nearest-neighbors around Cl. Reliable structural information obtained from the EXAFS data for the glasses is limited, however, to Cl sbnd Cl, Cl sbnd O, and Cl sbnd Na distances; Cl sbnd Ca contributions could not be fit to the glass data, due to the narrow k-space range available for analysis. Structural models that best fit the glass EXAFS data include Cl sbnd Cl, Cl sbnd O, and Cl sbnd Na correlations, where Cl sbnd O and Cl sbnd Na distances decrease by approximately 0.16 Å as glass Ca content increases. XAS for the glasses indicates Cl - is found in multiple sites where most Cl-sites have Ca neighbors, with oxygen, and possibly, Na second-nearest neighbors. EXAFS analyses suggest that Cl sbnd Cl environments may also exist in the glasses in minor amounts. These results are generally consistent with earlier findings for silicate glasses, where Cl - was associated with Ca 2+ and Na + in network modifier sites.

  14. Synchrotron-based XAS on structure investigation of La0.99-xSrx(Na, K, Ba)0.01MnO3 nanoparticles: Evidence of magnetic properties

    NASA Astrophysics Data System (ADS)

    Daengsakul, Sujittra; Saengplot, Saowalak; Kidkhunthod, Pinit; Pimsawat, Adulphan; Maensiri, Santi

    2018-04-01

    This work presents the structural study of La0.99-xSrx(Na, K, Ba)0.01MnO3 or LSAM nanoparticles synthesized using thermal-hydro decomposition method where A denotes Na, K, Sr and Ba, respectively. The effect of ionic radii size of A dopants or rA from the substitution of A for La and Sr on the MnO6 octrahedral structure, where the average size of the cations occupying in A-site or 〈rA〉 is fixed at ∼ 1.24 Å, is focused. The LSAM nanoparticles are carefully studied using X-ray diffraction (XRD) including Rietveld refinement and X-ray Absorption Spectroscopy (XAS) including X-ray Absorption Near edge Structure (XANES) and X-ray Absorption Fine Structure (EXAFS). The Rietveld refinement shows all nano-powder samples have rhombohedral structure. By XANES technique we found that the effect of A substitutions at A-site causes a slight change of mean oxidation state of Mn between 3.54 and 3.60. Furthermore, the structural distortion of MnO6 octrahedral in samples is analysed and obtained from EXAFS. The observed trend of ferromagnetism for all LSAM samples can be clearly explained by evidences of A-site doping, structural distortion around Mn atoms and mixing Mn3+/Mn4+ valence states.

  15. Orientational behavior of thin films of poly(3-methylthiophene) on platinium: A FTIR and near edge x-ray absorption fine structure (NEXAFS) study

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

    Yang, X.Q.; Chen, J.; Hale, P.D.

    1988-01-01

    Near edge x-ray absorption fine structure (NEXAFS) and infrared reflection-absorption spectroscopy (IRRAS) have been used to study the orientational behavior of thin films of poly(3-methylthiophene) electrochemically polymerized on a platinum surface. Clear orientational effects, with the thiophene rings predominantly oriented parallel to the platinum surface, were observed when the thickness of the polymer films were within a few hundred /angstrom/A. It was found that more highly ordered films were produced at lower polymerization potential (1.4V vs SCE) than at higher potential (1.8V vs SCE). 5 refs., 4 figs., 2 tabs.

  16. XANES and Mg isotopic analyses of spinels in Ca-Al-rich inclusions: Evidence for formation under oxidizing conditions

    NASA Astrophysics Data System (ADS)

    Paque, J. M.; Sutton, S. R.; Simon, S. B.; Beckett, J. R.; Burnett, D. S.; Grossman, L.; Yurimoto, H.; Itoh, S.; Connolly, H. C.

    2013-10-01

    Ti valence measurements in MgAl2O4 spinel from calcium-aluminum-rich inclusions (CAIs) by X-ray absorption near-edge structure (XANES) spectroscopy show that many spinels have predominantly tetravalent Ti, regardless of host phases. The average spinel in Allende type B1 inclusion TS34 has 87% Ti+4. Most spinels in fluffy type A (FTA) inclusions also have high Ti valence. In contrast, the rims of some spinels in TS34 and spinel grain cores in two Vigarano type B inclusions have larger amounts of trivalent titanium. Spinels from TS34 have approximately equal amounts of divalent and trivalent vanadium. Based on experiments conducted on CAI-like compositions over a range of redox conditions, both clinopyroxene and spinel should be Ti+3-rich if they equilibrated with CAI liquids under near-solar oxygen fugacities. In igneous inclusions, the seeming paradox of high-valence spinels coexisting with low-valence clinopyroxene can be explained either by transient oxidizing conditions accompanying low-pressure evaporation or by equilibration of spinel with relict Ti+4-rich phases (e.g., perovskite) prior to or during melting. Ion probe analyses of large spinel grains in TS34 show that they are enriched in heavy Mg, with an average Δ25Mg of 4.25 ± 0.028‰, consistent with formation of the spinel from an evaporating liquid. Δ25Mg shows small, but significant, variation, both within individual spinels and between spinel and adjacent melilite hosts. The Δ25Mg data are most simply explained by the low-pressure evaporation model, but this model has difficulty explaining the high Ti+4 concentrations in spinel.

  17. Activation of an intense near band edge emission from ZnTe/ZnMgTe core/shell nanowires grown on silicon.

    PubMed

    Wojnar, P; Szymura, M; Zaleszczyk, W; Kłopotowski, L; Janik, E; Wiater, M; Baczewski, L T; Kret, S; Karczewski, G; Kossut, J; Wojtowicz, T

    2013-09-13

    The absence of luminescence in the near band edge energy region of Te-anion based semiconductor nanowires grown by gold catalyst assisted molecular beam epitaxy has strongly limited their applications in the field of photonics. In this paper, an enhancement of the near band edge emission intensity from ZnTe/ZnMgTe core/shell nanowires grown on Si substrates is reported. A special role of the use of Si substrates instead of GaAs substrates is emphasized, which results in an increase of the near band edge emission intensity by at least one order of magnitude accompanied by a simultaneous reduction of the defect related luminescence. A possible explanation of this effect relies on the presence of Ga-related deep level defects in structures grown on GaAs substrates, which are absent when Si substrates are used. Monochromatic mapping of the cathodoluminescence clearly confirms that the observed emission originates, indeed, from the ZnTe/ZnMgTe core/shell nanowires, whereas individual objects are studied by means of microphotoluminescence.

  18. Strain-Dependent Edge Structures in MoS2 Layers.

    PubMed

    Tinoco, Miguel; Maduro, Luigi; Masaki, Mukai; Okunishi, Eiji; Conesa-Boj, Sonia

    2017-11-08

    Edge structures are low-dimensional defects unavoidable in layered materials of the transition metal dichalcogenides (TMD) family. Among the various types of such structures, the armchair (AC) and zigzag (ZZ) edge types are the most common. It has been predicted that the presence of intrinsic strain localized along these edges structures can have direct implications for the customization of their electronic properties. However, pinning down the relation between local structure and electronic properties at these edges is challenging. Here, we quantify the local strain field that arises at the edges of MoS 2 flakes by combining aberration-corrected transmission electron microscopy (TEM) with the geometrical-phase analysis (GPA) method. We also provide further insight on the possible effects of such edge strain on the resulting electronic behavior by means of electron energy loss spectroscopy (EELS) measurements. Our results reveal that the two-dominant edge structures, ZZ and AC, induce the formation of different amounts of localized strain fields. We also show that by varying the free edge curvature from concave to convex, compressive strain turns into tensile strain. These results pave the way toward the customization of edge structures in MoS 2 , which can be used to engineer the properties of layered materials and thus contribute to the optimization of the next generation of atomic-scale electronic devices built upon them.

  19. In situ X-ray near-edge absorption spectroscopy investigation of the state of charge of all-vanadium redox flow batteries.

    PubMed

    Jia, Chuankun; Liu, Qi; Sun, Cheng-Jun; Yang, Fan; Ren, Yang; Heald, Steve M; Liu, Yadong; Li, Zhe-Fei; Lu, Wenquan; Xie, Jian

    2014-10-22

    Synchrotron-based in situ X-ray near-edge absorption spectroscopy (XANES) has been used to study the valence state evolution of the vanadium ion for both the catholyte and anolyte in all-vanadium redox flow batteries (VRB) under realistic cycling conditions. The results indicate that, when using the widely used charge-discharge profile during the first charge process (charging the VRB cell to 1.65 V under a constant current mode), the vanadium ion valence did not reach V(V) in the catholyte and did not reach V(II) in the anolyte. Consequently, the state of charge (SOC) for the VRB cell was only 82%, far below the desired 100% SOC. Thus, such incompletely charged mix electrolytes results in not only wasting the electrolytes but also decreasing the cell performance in the following cycles. On the basis of our study, we proposed a new charge-discharge profile (first charged at a constant current mode up to 1.65 V and then continuously charged at a constant voltage mode until the capacity was close to the theoretical value) for the first charge process that achieved 100% SOC after the initial charge process. Utilizing this new charge-discharge profile, the theoretical charge capacity and the full utilization of electrolytes has been achieved, thus having a significant impact on the cost reduction of the electrolytes in VRB.

  20. Local Structure Determination of Carbon/Nickel Ferrite Composite Nanofibers Probed by X-ray Absorption Spectroscopy.

    PubMed

    Nilmoung, Sukunya; Kidkhunthod, Pinit; Maensiri, Santi

    2015-11-01

    Carbon/NiFe2O4 composite nanofibers have been successfully prepared by electrospinning method using a various concentration solution of Ni and Fe nitrates dispersed into polyacrylonitride (PAN) solution in N,N' dimethylformamide. The phase and mophology of PAN/NiFe2O4 composite samples were characterized and investigated by X-ray diffraction and scanning electron microscopy. The magnetic properties of the prepared samples were measured at ambient temperature by a vibrating sample magnetometer. It is found that all composite samples exhibit ferromagnetism. This could be local-structurally explained by the existed oxidation states of Ni2+ and Fe3+ in the samples. Moreover, local environments around Ni and Fe ions could be revealed by X-ray absorption spectroscopy (XAS) measurement including X-ray absorption near edge structure (XANES) and Extended X-ray absorption fine structure (EXAFS).

  1. Nb K-edge x-ray absorption investigation of the pressure induced amorphization in A-site deficient double perovskite La1/3NbO3.

    PubMed

    Marini, C; Noked, O; Kantor, I; Joseph, B; Mathon, O; Shuker, R; Kennedy, B J; Pascarelli, S; Sterer, E

    2016-02-03

    Nb K-edge x-ray absorption spectroscopy is utilized to investigate the changes in the local structure of the A-site deficient double perovskite La1/3NbO3 which undergoes a pressure induced irreversible amorphization. EXAFS results show that with increasing pressure up to 7.5 GPa, the average Nb-O bond distance decreases in agreement with the expected compression and tilting of the NbO6 octahedra. On the contrary, above 7.5 GPa, the average Nb-O bond distance show a tendency to increase. Significant changes in the Nb K-edge XANES spectrum with evident low energy shift of the pre-peak and the absorption edge is found to happen in La1/3NbO3 above 6.3 GPa. These changes evidence a gradual reduction of the Nb cations from Nb(5+) towards Nb(4+) above 6.3 GPa. Such a valence change accompanied by the elongation of the average Nb-O bond distances in the octahedra, introduces repulsion forces between non-bonding adjacent oxygen anions in the unoccupied A-sites. Above a critical pressure, the Nb reduction mechanism can no longer be sustained by the changing local structure and amorphization occurs, apparently due to the build-up of local strain. EXAFS and XANES results indicate two distinct pressure regimes having different local and electronic response in the La1/3NbO3 system before the occurence of the pressure induced amorphization at  ∼14.5 GPa.

  2. Investigation of Pb species in soils, celery and duckweed by synchrotron radiation X-ray absorption near-edge structure spectrometry

    NASA Astrophysics Data System (ADS)

    Luo, Liqiang; Shen, Yating; Liu, Jian; Zeng, Yuan

    2016-08-01

    The Pb species play a key role in its translocation in biogeochemical cycles. Soils, sediments and plants were collected from farmlands around Pb mines, and the Pb species in them was identified by X-ray absorption near-edge structure spectrometry. In soils, Pb5(PO4)3Cl and Pb3(PO4)2 were detected, and in sediments, Pb-fulvic acids (FAs) complex was identified. A Pb complex with FA fragments was also detected in celery samples. We found that (1) different Pb species were present in soils and sediments; (2) the Pb species in celery, which was grown in sediments, was different from the species present in duckweed, which grew in water; and (3) a Pb-FA-like compound was present in celery roots. The newly identified Pb species, the Pb-FA-like compound, may play a key role in Pb tolerance and translocation within plants.

  3. Linear instabilities near the DIII-D edge simulated in fluid models

    NASA Astrophysics Data System (ADS)

    Bass, Eric; Holland, Christopher

    2017-10-01

    The linear instability spectrum is reported near the DIII-D edge (within the separatrix) for L-mode and H-mode shots using the new eigenvalue solver FluTES (Fluid Toroidal Eigenvalue Solver). FluTES circumvents difficulties with convergence to clean linear eigenmodes (required for diagnosis of nonlinear simulations in codes such as BOUT++) often encountered with fluid initial-value solvers. FluTES is well-verified in analytic cases and against a BOUT++/ELITE benchmark toroidal case. We report results for both a 3-field, one-fluid model (the well-known ``elm-pb'' model) and a 5-field, two-fluid model. For the peeling-ballooning-dominated H-mode, the two solutions are qualitatively the same. In the driftwave-dominated L-mode edge, only the two-fluid solution gives robust instabilities which occur primarily at n > 50 . FluTES is optimized for this regime (near-flutelike limit, toroidally spectral). Cross-separatrix, coupled fluid and drift instabilities may play a role in explaining the gyrokinetic L-mode edge transport shortfall. Extension of FluTES into the open-field-line region is underway. Prepared by UCSD under Contract Number DE-FG02-06ER54871.

  4. The coordination of sulfur in synthetic and biogenic Mg calcites: The red coral case

    NASA Astrophysics Data System (ADS)

    Perrin, J.; Rivard, C.; Vielzeuf, D.; Laporte, D.; Fonquernie, C.; Ricolleau, A.; Cotte, M.; Floquet, N.

    2017-01-01

    Sulfur has been recognized in biogenic calcites for a long time. However, its structural position is matter of debate. For some authors, sulfur is a marker of the organic matrix while it is part of the calcite structure itself for others. To better understand the place of sulfur in calcite, sulfated magnesian calcites (S-MgCalcite) have been synthetized at high pressure and temperature and studied by μ-XANES spectroscopy. S-MgCalcite XANES spectra show two different types of sulfur: sulfate (SO42-) as a predominant species and a small contribution of sulfite (SO32-), both substituting for carbonate ions in the calcite structure. To address the question of the position of sulfur in biogenic calcites, the oxidation states of sulfur in the skeleton and organic tissues of Corallium rubrum have been investigated by micro X-ray fluorescence (μ-XRF) and sulfur K-edge micro X-ray absorption near edge structure (μ-XANES) spectroscopy at the European Synchrotron Radiation Facility (ESRF, Grenoble, France) on beamline ID21. In the skeleton, sulfur is mainly present as oxidized sulfur SO42- (+VI), plus a weak sulfite contribution. XANES spectra indicate that sulfur is inorganically incorporated as sulfur structurally substituted to carbonate ions (SSS). Although an organic matrix is present in the red coral skeleton, reduced organic sulfur could not be detected by μ-XANES spectroscopy in the skeleton probably due to low organic/inorganic sulfur ratio. In the organic tissues surrounding the skeleton, several sulfur oxidation states have been detected including disulfide (S-S), thioether (R-S-CH3), sulfoxide (SO2), sulfonate (SO2O-) and sulfate (SO42-). The unexpected occurrence of inorganic sulfate within the organic tissues suggests the presence of pre-organized organic/inorganic complexes in the circulatory system of the red coral, precursors to biomineralization ahead of the growth front.

  5. X-ray Absorption Near Edge Structure Spectroscopy to Resolve the in Vivo Chemistry of the Redox-Active Indazolium trans-[Tetrachlorobis(1H-indazole)ruthenate(III)] (KP1019)

    PubMed Central

    2013-01-01

    Indazolium trans-[tetrachlorobis(1H-indazole)ruthenate(III)] (1, KP1019) and its analogue sodium trans-[tetrachlorobis(1H-indazole)ruthenate(III)] (2, KP1339) are promising redox-active anticancer drug candidates that were investigated with X-ray absorption near edge structure spectroscopy. The analysis was based on the concept of the coordination charge and ruthenium model compounds representing possible coordinations and oxidation states in vivo. 1 was investigated in citrate saline buffer (pH 3.5) and in carbonate buffer (pH 7.4) at 37 °C for different time intervals. Interaction studies on 1 with glutathione in saline buffer and apo-transferrin in carbonate buffer were undertaken, and the coordination of 1 and 2 in tumor tissues was studied too. The most likely coordinations and oxidation states of the compound under the above mentioned conditions were assigned. Microprobe X-ray fluorescence of tumor thin sections showed the strong penetration of ruthenium into the tumor tissue, with the highest concentrations near blood vessels and in the edge regions of the tissue samples. PMID:23282017

  6. XRF and XANES Data for Kaplan U Paper

    EPA Pesticide Factsheets

    The dataset contains two XRF images of iron and uranium distribution on plant roots and a database of XANES data used to produce XANES spectra figure for Figure 7 in the published paper.This dataset is associated with the following publication:Kaplan, D., R. Kukkadapu, J. Seaman, B. Arey, A. Dohnalkova, S. Buettner, D. Li, T. Varga, K. Scheckel, and P. Jaffe. Iron Mineralogy and Uranium-Binding Environment in the Rhizosphere of a Wetland Soil. D. Barcelo SCIENCE OF THE TOTAL ENVIRONMENT. Elsevier BV, AMSTERDAM, NETHERLANDS, 569: 53-64, (2016).

  7. Determination of Arsenic Poisoning and Metabolism in Hair by Synchrotron Radiation: The Case of Phar Lap

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

    Kempson, Ivan M.; Henry, Dermot A.; U. South Australia)

    2010-08-26

    Fresh physical evidence about the demise of the racehorse Phar Lap (see photograph) has been gathered from the study of mane hair samples by synchrotron radiation analysis with high resolution X-ray fluorescence (XRF) and X-ray absorption near edge structure (XANES) analyses. The results are indicative of arsenic ingestion and metabolism, and show that the racing champion died from arsenic poisoning.

  8. Self-Supported Copper Oxide Electrocatalyst for Water Oxidation at Low Overpotential and Confirmation of Its Robustness by Cu K-edge X-ray Absorption Spectroscopy

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

    Liu, Xiang; Cui, Shengsheng; Sun, Zijun

    Developing efficient water oxidation catalysts made of earth-abundant elements is a demanding challenge that should be met to fulfill the promise of water splitting for clean energy. Herein we report an annealing approach to synthesize binder-free, self-supported heterogeneous copper oxide (CuO) on conductive electrodes for oxygen evolution reaction (OER), producing electrodes with excellent electrocatalytic properties such as high efficiency, low overpotential, and good stability. The catalysts were grown in situ on fluorine-doped tin oxide (FTO) by electrodeposition from a simple Cu(II) salt solution, followed by annealing at a high temperature. Under optimal conditions, the CuO-based OER catalyst shows an onsetmore » potential of <0.58 V (vs Ag/AgCl) in 1.0 M KOH at pH 13.6. From the Tafel plot, the required overpotentials for current densities of 0.1 and 1.0 mA/cm2 are only 360 and 430 mV, respectively. The structure and the presence of a CuO motif in the catalyst have been identified by high-energy X-ray diffraction (HE-XRD), Cu K-edge X-ray absorption (XAS) spectra including X-ray absorption near-edge structure (XANES), and extended X-ray absorption fine structure (EXAFS). To the best of our knowledge, this represents the best catalytic activity for CuO-based OER catalysts to date.« less

  9. Local Structure and Surface Properties of CoxZn1-xO Thin Films for Ozone Gas Sensing.

    PubMed

    Catto, Ariadne C; Silva, Luís F da; Bernardi, Maria Inês B; Bernardini, Sandrine; Aguir, Khalifa; Longo, Elson; Mastelaro, Valmor R

    2016-10-05

    A detailed study of the structural, surface, and gas-sensing properties of nanostructured Co x Zn 1-x O films is presented. X-ray diffraction (XRD) analysis revealed a decrease in the crystallization degree with increasing Co content. The X-ray absorption near-edge structure (XANES) and X-ray photoelectron spectroscopies (XPS) revealed that the Co 2+ ions preferentially occupied the Zn 2+ sites and that the oxygen vacancy concentration increased as the amount of cobalt increased. Electrical measurements showed that the Co dopants not only enhanced the sensor response at low ozone levels (ca. 42 ppb) but also led to a decrease in the operating temperature and improved selectivity. The enhancement in the gas-sensing properties was attributed to the presence of oxygen vacancies, which facilitated ozone adsorption.

  10. Photo-oxidative doping in π-conjugated zig-zag chain of carbon atoms with sulfur-functional group

    NASA Astrophysics Data System (ADS)

    Ikeura-Sekiguchi, Hiromi; Sekiguchi, Tetsuhiro

    2017-12-01

    Photo-oxidative doping processes were studied for the trans-polyacetylene backbone with the -SCH3 side group as a chemically representative of the precisely controlled S-functionalized zig-zag graphene nanoribbon edge. Sulfur K-edge X-ray absorption near edge structure (XANES) spectroscopy indicates that photochemical reaction of S-CH3 with atmospheric O2 forms selectively oxidized products such as -S(O)CH3 and -SO3- bound to the polyacetylene (PA) backbone. Using the correlation between the oxidation states of sulfur and the XANES peak positions, the partial charge distribution of CH3Sδ+-PAδ- has been estimated. Such positively charged sulfur atoms can attract higher electronegative oxygen atoms and expect to enhance the photooxidization capabilities. The formation of the -SO3- side group is evidently responsible for hole doping into the PA backbone. The results can provide some strategy for area-selective and controllable doping processes of atomic-scale molecular systems with the assistance of UV light.

  11. Magnetic properties of Gd T2Zn20 (T =Fe , Co) investigated by x-ray diffraction and spectroscopy

    NASA Astrophysics Data System (ADS)

    Mardegan, J. R. L.; Francoual, S.; Fabbris, G.; Veiga, L. S. I.; Strempfer, J.; Haskel, D.; Ribeiro, R. A.; Avila, M. A.; Giles, C.

    2016-01-01

    We investigate the magnetic and electronic properties of the Gd T2Zn20 (T =Fe and Co) compounds using x-ray resonant magnetic scattering (XRMS), x-ray absorption near-edge structure (XANES), and x-ray magnetic circular dichroism (XMCD). The XRMS measurements reveal that GdCo2Zn20 has a commensurate antiferromagnetic spin structure with a magnetic propagation vector τ ⃗=(1/2 ,1/2 ,1/2 ) below the Néel temperature (TN˜ 5.7 K). Only the Gd ions carry a magnetic moment forming an antiferromagnetic structure with magnetic representation Γ6. For the ferromagnetic GdFe2Zn20 compound, an extensive investigation was performed at low temperature and under magnetic field using XANES and XMCD. A strong XMCD signal of about 12.5 % and 9.7 % is observed below the Curie temperature (TC˜85 K ) at the Gd L2 and L3 edges, respectively. In addition, a small magnetic signal of about 0.06 % of the jump is recorded at the Zn K edge, suggesting that the Zn 4 p states are spin polarized by the Gd 5 d extended orbitals.

  12. Magnetic properties of GdT 2Zn 20 (T = Fe, Co) investigated by x-ray diffraction and spectroscopy

    DOE PAGES

    J. R. L. Mardegan; Fabbris, G.; Francoual, S.; ...

    2016-01-26

    In this study, we investigate the magnetic and electronic properties of the GdT 2Zn 20 (T=Fe and Co) compounds using x-ray resonant magnetic scattering (XRMS), x-ray absorption near-edge structure (XANES), and x-ray magnetic circular dichroism (XMCD). The XRMS measurements reveal that GdCo 2Zn 20 has a commensurate antiferromagnetic spin structure with a magnetic propagation vector →/ τ = (12,12,12) below the Néel temperature (T N ~ 5.7 K). Only the Gd ions carry a magnetic moment forming an antiferromagnetic structure with magnetic representation Γ 6. For the ferromagnetic GdFe 2Zn 20 compound, an extensive investigation was performed at low temperaturemore » and under magnetic field using XANES and XMCD. A strong XMCD signal of about 12.5% and 9.7% is observed below the Curie temperature (T C ~ 85K) at the Gd L 2 and L 3 edges, respectively. In addition, a small magnetic signal of about 0.06% of the jump is recorded at the Zn K edge, suggesting that the Zn 4p states are spin polarized by the Gd 5d extended orbitals.« less

  13. Extended x-ray absorption fine structure spectroscopy and x-ray absorption near edge spectroscopy study of aliovalent doped ceria to correlate local structural changes with oxygen vacancies clustering

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

    Shirbhate, S. C.; Acharya, S. A., E-mail: saha275@yahoo.com; Yadav, A. K.

    2016-04-04

    This study provides atomic scale insight to understand the role of aliovalent dopants on oxygen vacancies clustering and dissociation mechanism in ceria system in order to enhance the performance of oxy-ion conductor. Dopants induced microscale changes in ceria are probed by extended X-ray absorption fine structure spectroscopy, X-ray absorption near edge spectra, and Raman spectroscopy. The results are explored to establish a correlation between atomic level structural changes (coordination number, interatomic spacing) → formation of dimer and trimer type cation-oxygen vacancies defect complex (intrinsic and extrinsic) → dissociation of oxygen vacancies from defect cluster → ionic conductivity temperature. It ismore » a strategic approach to understand key physics of ionic conductivity mechanism in order to reduce operating temperature of electrolytes for intermediate temperature (300–450 °C) electrochemical devices for the first time.« less

  14. Retention and chemical speciation of uranium in an oxidized wetland sediment from the Savannah River Site.

    PubMed

    Li, Dien; Seaman, John C; Chang, Hyun-Shik; Jaffe, Peter R; Koster van Groos, Paul; Jiang, De-Tong; Chen, Ning; Lin, Jinru; Arthur, Zachary; Pan, Yuanming; Scheckel, Kirk G; Newville, Matthew; Lanzirotti, Antonio; Kaplan, Daniel I

    2014-05-01

    Uranium speciation and retention mechanisms onto Savannah River Site (SRS) wetland sediments was studied using batch (ad)sorption experiments, sequential extraction, U L3-edge X-ray absorption near-edge structure (XANES) spectroscopy, fluorescence mapping and μ-XANES. Under oxidized conditions, U was highly retained by the SRS wetland sediments. In contrast to other similar but much lower natural organic matter (NOM) sediments, significant sorption of U onto the SRS sediments was observed at pH < 4 and pH > 8. Sequential extraction indicated that the U species were primarily associated with the acid soluble fraction (weak acetic acid extractable) and organic fraction (Na-pyrophosphate extractable). Uranium L3-edge XANES spectra of the U-bound sediments were nearly identical to that of uranyl acetate. Based on fluorescence mapping, U and Fe distributions in the sediment were poorly correlated, U was distributed throughout the sample and did not appear as isolated U mineral phases. The primary oxidation state of U in these oxidized sediments was U(VI), and there was little evidence that the high sorptive capacity of the sediments could be ascribed to abiotic or biotic reduction to the less soluble U(IV) species or to secondary mineral formation. Collectively, this study suggests that U may be strongly bound to wetland sediments, not only under reducing conditions by reductive precipitation, but also under oxidizing conditions through NOM-uranium bonding. Published by Elsevier Ltd.

  15. Nanoparticulate mackinawite formation; a stopped and continuous flow XANES and EXAFS investigation

    NASA Astrophysics Data System (ADS)

    Butler, I. B.; Bell, A. M.; Charnock, J. M.; Rickard, D.; Vaughan, D. J.; Oldroyd, A.

    2009-12-01

    The sequestration of sulfur and iron within sedimentary iron sulfides, and ultimately as pyrite, is a major sink in global biogeochemical cycles of those elements and has impacts on global carbon and oxygen cycles. The formation of the metastable black iron (II) monosulfide mackinawite is a key process because mackinawite forms in aqueous solutions where the Fe(II) and S(-II) IAP exceeds mackinawite’s Ksp. Mackinawite is the first formed iron sulfide phase, a consequence of Ostwald’s step rule and is a reactant phase during the formation of thermodynamically stable sedimentary iron sulfide minerals such as pyrite. The reaction of dissolved Fe(II) and sulfide is extremely fast and reactions in the environmentally significant near-neutral pH range tend to completion in <1 second. We have combined stopped and continuous flow techniques with X-ray absorption spectroscopy to evaluate the products of the fast precipitation kinetics of mackinawite over millisecond timescales. EXAFS spectra and data collected during flow experiments were compared with those from a well characterised freeze-dried nanoparticulate mackinawite standard and with published data. Published work has used Rietveld crystal structure refinement to determine bond distances of 2.2558 and 2.5976Å for Fe-S and Fe-Fe respectively. In our experiments Fe K edge XANES is consistent with tetrahedrally coordinated Fe in the precipitated sulfide phase. EXAFS data show that local Fe-S and Fe-Fe coordination and interatomic distances (Fe-S = 2.24Å; Fe-Fe = 2.57Å) are consistent with those determined for the standard mackinawite and published data. The coordination and spacing are developed in the precipitated phase after <10ms reaction at pH5, and considerably faster in experiments at near neutral to alkaline pH. No evidence for phases structurally intermediate between hexaqua Fe(II) and precipitated mackinawite was observed. Aqueous FeS° cluster complexes previously identified as intermediates during

  16. Structural reconstruction of the catalytic center of LiPDF through multiple scattering calculation with MXAN

    NASA Astrophysics Data System (ADS)

    Guo, Xiaoyun; Chu, Wangsheng; Ma, Sixuan; Gong, Weimin; Benfatto, Maurizio; Hu, Tiandou; Xie, Yaning; Wu, ZiYu

    2006-11-01

    Peptide deformylase (PDF, EC 3.5.1.27) is essential for the normal growth of eubacterium but not for mammalians. Recently, PDF has been studied as a target for new antibiotics. In this paper, X-ray absorption spectroscopy was employed to determine the local structure around the zinc ion of PDF from Leptospira Interrogans in dry powder, because it is very difficult to obtain the crystallized sample of LiPDF. We performed X-ray absorption near edge structure (XANES) calculation and reconstructed successfully the local geometry of the active center, and the results from calculations show that a water molecule (Wat1) has moved towards the zinc ion and lies in the distance range to coordinate with the zinc ion weakly. In addition, the sensitivity of theoretical spectra to the different ligand bodies was evaluated in terms of goodness-of-fit.

  17. Low-temperature adsorption of H2S on Ni(001) studied by near-edge- and surface-extended-x-ray-absorption fine structure

    NASA Astrophysics Data System (ADS)

    McGrath, R.; MacDowell, A. A.; Hashizume, T.; Sette, F.; Citrin, P. H.

    1989-11-01

    The adsorption of H2S on Ni(001) has been studied with surface-extended x-ray-absorption fine structure and near-edge x-ray-absorption fine structure (NEXAFS) using the AT&T Bell Laboratories X15B beamline at the National Synchrotron Light Source. At 95 K and full saturation coverage, ~0.45 monolayer (ML) of S atoms in fourfold-hollow sites are produced, characteristic of room-temperature adsorption, accompanied by ~0.05 ML of oriented molecular H2S. Both these atomic and molecular chemisorbed species are buried under ~0.9 ML of disordered physisorbed H2S. No evidence for HS is found. Above 190 K the two molecular H2S phases desorb, leaving only dissociated S. These findings differ from previously reported interpretations of data obtained with high-resolution electron-energy-loss spectroscopy. They also exemplify the utility of NEXAFS for identifying and quantifying atomic and molecular surface species even when their difference involves only H and the two species coexist.

  18. Observation of high-spin mixed oxidation state of cobalt in ceramic Co3TeO6

    NASA Astrophysics Data System (ADS)

    Singh, Harishchandra; Ghosh, Haranath; Chandrasekhar Rao, T. V.; Sinha, A. K.; Rajput, Parasmani

    2014-12-01

    We report coexistence of high spin Co3+ and Co2+ in ceramic Co3TeO6 using X-ray Absorption Near Edge Structure (XANES), DC magnetization, and first principles ab-initio calculations. The main absorption line of cobalt Co K-edge XANES spectra, along with a linear combination fit, led us to estimate relative concentration of Co2+ and Co3+as 60:40. The pre edge feature of XANES spectrum shows crystal field splitting of ˜1.26 eV between eg and t2g states, suggesting a mixture of high spin states of both Co2+ and Co3+. Temperature dependent high field DC magnetization measurements reveal dominant antiferromagnetic order with two Neel temperatures (TN1 ˜ 29 K and TN2 ˜ 18 K), consistent with single crystal study. A larger effective magnetic moment is observed in comparison to that reported for single crystal (which contains only Co2+), supports our inference that Co3+ exists in high spin state. Furthermore, we show that both Co2+ and Co3+ being in high spin states constitute a favorable ground state through first principles ab-initio calculations, where Rietveld refined synchrotron X-ray diffraction data are used as input.

  19. Communication: X-ray excited optical luminescence from TbCl3 at the giant resonance of terbium

    NASA Astrophysics Data System (ADS)

    Heigl, F.; Jürgensen, A.; Zhou, X.-T.; Hu, Y.-F.; Zuin, L.; Sham, T. K.

    2013-02-01

    We have studied the optical recombination channels of TbCl3 using x-ray excited optical luminescence at the N4,5 absorption edge of Tb (giant resonance) in both the energy and time domain. The luminescence exhibits a relatively fast 5D3, and a slow 5D4 decay channel in the blue and green, respectively. The rather short lifetime of the 5D3 state indicates that the decay is mainly driven by Tb-Tb ion interaction via non-radiative energy transfer (cross-relaxation). At the giant resonance the X-ray Absorption Near Edge Structure (XANES) recorded using partial photoluminescence yield is inverted. In the pre-edge region the contrast of the spectral feature is significantly better in optical XANES than in total electron yield. Changes in the intensity of 5D3-7F5 (544 nm) and 5D4-7F6 (382 nm) optical transitions as the excitation energy is tuned across the giant resonance are also noted. The results provide detailed insight into the dynamics of the optical recombination channels and an alternative method to obtain high sensitivity, high energy resolution XANES at the giant resonance of light emitting rare-earth materials.

  20. Ba3Fe1.56Ir1.44O9: A Polar Semiconducting Triple Perovskite with Near Room Temperature Magnetic Ordering.

    PubMed

    Ferreira, Timothy; Carone, Darren; Huon, Amanda; Herklotz, Andreas; Stoian, Sebastian A; Heald, Steve M; Morrison, Gregory; Smith, Mark D; Loye, Hans-Conrad Zur

    2018-05-29

    The crystal chemistry and magnetic properties for two triple perovskites, Ba 3 Fe 1.56 Ir 1.44 O 9 and Ba 3 NiIr 2 O 9 , grown as large, highly faceted single crystals from a molten strontium carbonate flux, are reported. Unlike the idealized A 3 MM 2 'O 9 hexagonal symmetry characteristic of most triple perovskites, including Ba 3 NiIr 2 O 9, Ba 3 Fe 1.56 Ir 1.44 O 9 possesses significant site-disorder, resulting in a noncentrosymmetric polar structure with trigonal symmetry. The valence of iron and iridium in the heavily distorted Fe/Ir sites was determined to be Fe(III) and Ir(V) by X-ray absorption near edge spectroscopy (XANES). Density functional theory calculations were conducted to understand the effect of the trigonal distortion on the local Fe(III)O 6 electronic structure, and the spin state of iron was determined to be S = 5/2 by Mössbauer spectroscopy. Conductivity measurements indicate thermally activated semiconducting behavior in the trigonal perovskite. Magnetic properties were measured and near room temperature magnetic ordering (T N = 270 K) was observed for Ba 3 Fe 1.56 Ir 1.44 O 9 .

  1. 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

  2. Dehydration of the Uranyl Peroxide Studtite, [UO 2(η 2-O 2)(H 2O) 2]·2H 2O, Affords a Drastic Change in the Electronic Structure: A Combined X-ray Spectroscopic and Theoretical Analysis

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

    Vitova, Tonya; Pidchenko, Ivan; Biswas, Saptarshi

    The dehydration of studtite, [UO 2(2-O 2)(H 2O)2]·2H 2O, to metastudtite, [UO 2(2-O 2)(H 2O) 2], uranyl peroxide minerals that are major oxidative alteration phases of UO2 under conditions of geological storage, has been studied using X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy. XPS of the U 4f region shows small but significant differences between studtite and metastudtite, with the 4f binding energy of studtite the highest reported for a uranyl mineral studied by this technique. Further information on the changes in the electronic structure was elucidated using U M4-edge High Energy Resolution XANES (HR-XANES) spectroscopy, which directly probesmore » f-orbital states. The transition from the 3d to the 5f* orbital is sensitive to variations of the U=Oaxial bond length and to changes in the bond covalency. We report evidences that the covalence in the uranyl fragment decreases upon dehydration. Photoluminescence spectroscopy at near liquid helium temperatures reveals significant spectral differences between the two materials, correlating with the X-ray spectroscopy results. A theoretical investigation has been conducted on the structures of both studtite and metastudtite and benchmarked to the HR-XANES spectra. These illustrate the sensitivity of the 3d to the 5f * transition towards U=Oaxial bond variation.« less

  3. Identification of B-K near edge x-ray absorption fine structure peaks of boron nitride thin films prepared by sputtering deposition

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

    Niibe, Masahito; Miyamoto, Kazuyoshi; Mitamura, Tohru

    2010-09-15

    Four {pi}{sup *} resonance peaks were observed in the B-K near edge x-ray absorption fine structure spectra of boron nitride thin films prepared by magnetron sputtering. In the past, these peaks have been explained as the K-absorption of boron atoms, which are present in environment containing nitrogen vacancies, the number of which is 1-3 corresponding to the three peaks at higher photon energy. However, the authors found that there was a strong correlation between the intensities of these three peaks and that of O-K absorption after wide range scanning and simultaneous measurement of nitrogen and oxygen K-absorptions of the BNmore » films. Therefore, the authors conclude that these three peaks at the higher energy side correspond to boron atoms bound to one-to-three oxygen atoms instead of three nitrogen atoms surrounding the boron atom in the h-BN structure. The result of the first-principles calculation with a simple cluster model supported the validity of this explanation.« less

  4. Near band edge emission characteristics of sputtered nano-crystalline ZnO films

    NASA Astrophysics Data System (ADS)

    Kunj, Saurabh; Sreenivas, K.

    2016-05-01

    Sputtered zinc oxide (ZnO) thin films deposited on unheated glass substrate under different sputtering gas mixtures (Ar+O2) have been investigated using X-ray diffraction and photo luminescence spectroscopy. Earlier reported studies on ZnO films prepared by different techniques exhibit either a sharp/broad near band edge (NBE) emission peak depending on the crystalline quality of the film. In the present study zinc oxide films, grown on unheated substrates, are seen to possess a preferred (002) orientation with a microstructure consisting of clustered nano-sized crystallites. The splitting in the near band edge emission (NBE) into three characteristic peaks is attributed to quantum confinement effect, and is observed specifically under an excitation of 270 nm. Deep level emission (DLE) in the range 400 to 700 nm is not observed indicating absence of deep level radiative defects.

  5. Magnetite Crisis in Miniature: Vanadium, Sulfur, and Iron Valence State Measurements in Melt Inclusions from Nyamuragira Volcano (D.R. Congo, Africa)

    NASA Astrophysics Data System (ADS)

    Head, E.; Lanzirotti, A.; Sutton, S.; Newville, M.

    2017-12-01

    Sulfur (S), vanadium (V), and iron (Fe) K-edge micro-X-ray absorption near edge structure (micro-XANES) spectroscopy of melt inclusions (MI) from Nyamuragira volcano (D.R. Congo, Africa) shows that diffusive loss of H from olivine-hosted melt inclusions may lead to crystallization of submicron magnetite and sulfide crystallites that are imperceptible petrographically or via electron microscopy. Micro-XANES was used to constrain the evolution of oxygen fugacity (fO2) and sulfur speciation for MI preserved in Nyamuragira tephra (1986 and 2006) and lava (1938 and 1948). The S, V, and Fe valence state oxybarometry for 1938, 1948, and 2006 MI are all consistent with equilibration at FMQ-1, and sulfur in MI from these three eruptions are sulfide-dominated (< 9% sulfate). However, Fe and V micro-XANES data for 1986 MI appear to be more reduced by 1-2 log units, while S micro-XANES data indicate more variable sulfate content. The 1986 results are best explained by diffusive loss of H from the entrapped melt. Submicron magnetite forms as Fe oxidizes in the melt in response to the loss of H, and V strongly partitions into these magnetite nanolites due to its compatibility. The nanolites are consistently analyzed within the beam volume and, thus, the measured V XANES appears more ordered. Magnetite crystallization from the melt also triggers precipitation of crystalline FeS phases within the inclusion, leading to a more ordered S XANES spectra as well. This may suggest a different magma storage history for the 1986 eruption compared to the others. Results demonstrate that coupled S, V, and Fe micro-XANES analysis of alkalic MI can provide accurate measures of the fO2 of entrapped melts, and that S and V micro-XANES spectroscopy are potentially highly sensitive tools for identifying diffusive water loss in olivine-hosted MIs.

  6. Determination of interstitial oxygen atom position in U2N3+xOy by near edge structure study

    NASA Astrophysics Data System (ADS)

    Jiang, A. K.; Zhao, Y. W.; Long, Z.; Hu, Y.; Wang, X. F.; Yang, R. L.; Bao, H. L.; Zeng, R. G.; Liu, K. Z.

    2018-06-01

    The determination of interstitial oxygen atom site in U2N3+xOy film could facilitate the understanding of the oxidation mechanism of α-U2N3 and the effect of U2N3+xOy on anti-oxidation. By comparing the similarities and variances between N K edge and O K edge electron energy loss spectra (EELS) for oxidized α-U2N3 and UO2, the present work looks at the local structure of nitrogen and oxygen atoms in U2N3+xOy film, identifying the most possible position of interstitial O atom.

  7. Atomistic simulation and XAS investigation of Mn induced defects in Bi{sub 12}TiO{sub 20}

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

    Rezende, Marcos V dos S.; Santos, Denise J.; Jackson, Robert A.

    2016-06-15

    This work reports an investigation of the valence and site occupancy of Mn dopants in Bi{sub 12}TiO{sub 20} (BTO: Mn) host using X-ray Absorption (XAS) and atomistic simulation techniques based on energy minimisation. X-ray Absorption Near Edge Structure (XANES) at the Mn K-edges gave typical results for Mn ions with mixed valences of 3+ and 4+. Extended X-ray Absorption Fine Structure (EXAFS) results indicated that Mn ions are probably substituted at Ti sites. Atomistic simulation was performed assuming the incorporation of Mn{sup 2+}, Mn{sup 3+} and Mn{sup 4+} ions at either Bi{sup 3+} or Ti{sup 4+} sites, and the resultsmore » were compared to XANES and EXAFS measurements. Electrical conductivity for pure and doped samples was used to evaluate the consistency of the proposed model. - Graphical abstract: The structure of Bi{sub 12}TiO{sub 20} (BTO). Display Omitted - Highlights: • Pure and Mn-doped Bi{sub 12}TiO{sub 20} samples were studied by experimental techniques combined with atomistic simulation. • Good agreement between experimental and simulation results was obtained. • XANES results suggest a mixture of 3+ and 4+ valences for Mn, occupying the Ti4+ site in both cases. • Charge compensation by holes is most energetically favoured, explaining the enhancement observed in AC dark conductivity.« less

  8. The characterization of Cr secondary oxide phases in ZnO films studied by X-ray spectroscopy and photoemission spectroscopy

    NASA Astrophysics Data System (ADS)

    Chiou, J. W.; Chang, S. Y.; Huang, W. H.; Chen, Y. T.; Hsu, C. W.; Hu, Y. M.; Chen, J. M.; Chen, C.-H.; Kumar, K.; Guo, J.-H.

    2011-03-01

    X-ray absorption near-edge structure (XANES), X-ray emission spectroscopy (XES), and X-ray photoemission spectroscopy (XPS) were used to characterize the Cr secondary oxide phases in ZnO films that had been prepared using a co-sputtering method. Analysis of the Cr L3,2-edge XANES spectra reveals that the intensity of white-line features decreases subtly as the sputtering power increases, indicating that the occupation of Cr 3 d orbitals increases with Cr concentration in (Zn, Cr)O films. The O K-edge spectra show that the intensity of XANES features of (Zn, Cr)O films is lower than those of ZnO film, suggesting enhanced occupation of O 2 p-derived states through O 2 p-Cr 3 d hybridization. The XES and XPS spectra indicate that the line shapes in the valence band of (Zn, Cr)O films are quite different from those of ZnO and that the Cr 2O 3 phase dominates the spinel structure of (Zn, Cr)O films increasingly as the Cr sputtering power is increased. Over all results suggest that the non-ferromagnetic behavior of (Zn, Cr)O films can be attributed to the dominant presence of Cr 2O 3, whereas the bulk comprise phase segregations of Cr 2O 3 and/or ZnCr 2O 4, which results them the most stable TM-doped ZnO material against etching.

  9. Polarization dependent formation of femtosecond laser-induced periodic surface structures near stepped features

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

    Murphy, Ryan D.; Torralva, Ben; Adams, David P.

    2014-06-09

    Laser-induced periodic surface structures (LIPSS) are formed near 110 nm-tall Au microstructured edges on Si substrates after single-pulse femtosecond irradiation with a 150 fs pulse centered near a 780 nm wavelength. We investigate the contributions of Fresnel diffraction from step-edges and surface plasmon polariton (SPP) excitation to LIPSS formation on Au and Si surfaces. For certain laser polarization vector orientations, LIPSS formation is dominated by SPP excitation; however, when SPP excitation is minimized, Fresnel diffraction dominates. The LIPSS orientation and period distributions are shown to depend on which mechanism is activated. These results support previous observations of the laser polarization vectormore » influencing LIPSS formation on bulk surfaces.« less

  10. Ionic gold in calcrete revealed by LA-ICP-MS, SXRF and XANES

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

    Lintern, Melvyn J.; Hough, Robert M.; Ryan, Chris G.

    2009-04-02

    Highly anomalous Au concentrations in calcrete were discovered in 1987 at the Bounty Gold Deposit, Western Australia. A strong correlation was noted between the Ca, Mg, Sr and Au in soil profiles which have not only attracted the interest of mineral explorers but also chemists, soil scientists, metallurgists and climatologists. Gold has been considered an inert element and so its strong association with the alkaline earth group of relatively mobile elements is both remarkable and intriguing. Despite widespread interest, there have been few published papers on the Au-calcrete phenomenon. Here, we present work conducted on calcareous soil samples from abovemore » the Bounty mineralization in Western Australia, prior to mining. Using SXRF (synchrotron X-ray fluorescence) and XANES (micro-X-ray absorption near-edge structure), we have shown for the first time the distribution of Au in calcrete and that it occurs in both particulate and ionic form. Much of the ionic Au associated with Br is found in a root tubule. The observations are consistent with an evapotranspiration model for the formation of Au in the calcrete; Au has been mobilized then precipitated as vadose water has been removed from the soil by trees and shrubs. While the association between Au and Ca is very strong in bulk sample analyses down the soil profile, other detailed analyses on sub-samples using wet chemical, LA-ICP-MS (laser ablation inductively coupled mass spectrometry) and SXRF techniques show that it is not apparent at the sub-millimeter scale. This suggests that the Au and Ca are behaving similarly but independently and they do not (at the {micro}m scale) co-precipitate with carbonate minerals. These results corroborate other studies that suggest biotic influences can affect the mobilization and distribution of Au in surficial materials. Water-extractable Au in calcrete has been reported previously and the ionic Au described in this study likely represents that soluble component. The

  11. Solution XAS Analysis for Exploring the Active Species in Homogeneous Vanadium Complex Catalysis

    NASA Astrophysics Data System (ADS)

    Nomura, Kotohiro; Mitsudome, Takato; Tsutsumi, Ken; Yamazoe, Seiji

    2018-06-01

    Selected examples in V K-edge X-ray Absorption Near Edge Structure (XANES) analysis of a series of vanadium complexes containing imido ligands (possessing metal-nitrogen double bond) in toluene solution have been introduced, and their pre-edge and the edge were affected by their structures and nature of ligands. Selected results in exploring the oxidation states of the active species in ethylene dimerization/polymerization using homogeneous vanadium catalysts [consisting of (imido)vanadium(V) complexes and Al cocatalysts] by X-ray absorption spectroscopy (XAS) analyses have been introduced. It has been demonstrated that the method should provide more clear information concerning the active species in situ, especially by combination with the other methods (NMR and ESR spectra, X-ray crystallographic analysis, and reaction chemistry), and should be powerful tool for study of catalysis mechanism as well as for the structural analysis in solution.

  12. Time-dependent mean-field theory for x-ray near-edge spectroscopy

    NASA Astrophysics Data System (ADS)

    Bertsch, G. F.; Lee, A. J.

    2014-02-01

    We derive equations of motion for calculating the near-edge x-ray absorption spectrum in molecules and condensed matter, based on a two-determinant approximation and Dirac's variational principle. The theory provides an exact solution for the linear response when the Hamiltonian or energy functional has only diagonal interactions in some basis. We numerically solve the equations to compare with the Mahan-Nozières-De Dominicis theory of the edge singularity in metallic conductors. Our extracted power-law exponents are similar to those of the analytic theory, but are not in quantitative agreement. The calculational method can be readily generalized to treat Kohn-Sham Hamiltonians with electron-electron interactions derived from correlation-exchange potentials.

  13. XANES study of elemental mercury oxidation over RuO 2/TiO 2 and selective catalytic reduction catalysts for mercury emissions control

    DOE PAGES

    Liu, Zhouyang; Li, Can; Sriram, Vishnu; ...

    2016-07-25

    Linear combination fitting of the X-ray Absorption Near Edge Spectroscopy (XANES) was used to quantify oxidized mercury species over RuO 2/TiO 2 and Selective Catalytic Reduction (SCR) catalysts under different simulated flue gas conditions. Halogen gases play a major role in mercury oxidation. In the absence of halogen gas, elemental mercury can react with sulfur that is contained in both the RuO2/TiO2 and SCR catalysts to form HgS and HgSO 4. In the presence of HCl or HBr gas, HgCl 2 or HgBr 2 is the main oxidized mercury species. When both HCl and HBr gases are present, HgBr2 ismore » the preferred oxidation product and no HgCl 2 can be found. The formation of HgO and HgS cannot be neglected with or without halogen gas. Other simulated flue gas components such as NO, NH 3, SO 2 and CO 2 do not have significant effect on oxidized mercury speciation when halogen gas is present.« less

  14. Nonlinear reconnecting edge localized modes in current-carrying plasmas

    DOE PAGES

    Ebrahimi, F.

    2017-05-22

    Nonlinear edge localized modes in a tokamak are examined using global three-dimensional resistive magnetohydrodynamics simulations. Coherent current-carrying filament (ribbon-like) structures wrapped around the torus are nonlinearly formed due to nonaxisymmetric reconnecting current sheet instabilities, the so-called peeling-like edge localized modes. These fast growing modes saturate by breaking axisymmetric current layers isolated near the plasma edge and go through repetitive relaxation cycles by expelling current radially outward and relaxing it back. The local bidirectional fluctuation-induced electromotive force (emf) from the edge localized modes, the dynamo action, relaxes the axisymmetric current density and forms current holes near the edge. Furthermore, the three-dimensionalmore » coherent current-carrying filament structures (sometimes referred to as 3-D plasmoids) observed here should also have strong implications for solar and astrophysical reconnection.« less

  15. Direct Determination of the Intracellular Oxidation State of Plutonium

    PubMed Central

    Gorman-Lewis, Drew; Aryal, Baikuntha P.; Paunesku, Tatjana; Vogt, Stefan; Lai, Barry; Woloschak, Gayle E.; Jensen, Mark P.

    2013-01-01

    Microprobe X-ray absorption near edge structure (μ-XANES) measurements were used to determine directly, for the first time, the oxidation state of intracellular plutonium in individual 0.1 μm2 areas within single rat pheochromocytoma cells (PC12). The living cells were incubated in vitro for 3 hours in the presence of Pu added to the media in different oxidation states (Pu(III), Pu(IV), and Pu(VI)) and in different chemical forms. Regardless of the initial oxidation state or chemical form of Pu presented to the cells, the XANES spectra of the intracellular Pu deposits was always consistent with tetravalent Pu even though the intracellular milieu is generally reducing. PMID:21755934

  16. Optically Unraveling the Edge Chirality-Dependent Band Structure and Plasmon Damping in Graphene Edges.

    PubMed

    Duan, Jiahua; Chen, Runkun; Cheng, Yuan; Yang, Tianzhong; Zhai, Feng; Dai, Qing; Chen, Jianing

    2018-05-01

    The nontrivial topological origin and pseudospinorial character of electron wavefunctions make edge states possess unusual electronic properties. Twenty years ago, the tight-binding model calculation predicted that zigzag termination of 2D sheets of carbon atoms have peculiar edge states, which show potential application in spintronics and modern information technologies. Although scanning probe microscopy is employed to capture this phenomenon, the experimental demonstration of its optical response remains challenging. Here, the propagating graphene plasmon provides an edge-selective polaritonic probe to directly detect and control the electronic edge state at ambient condition. Compared with armchair, the edge-band structure in the bandgap gives rise to additional optical absorption and strongly absorbed rim at zigzag edge. Furthermore, the optical conductivity is reconstructed and the anisotropic plasmon damping in graphene systems is revealed. The reported approach paves the way for detecting edge-specific phenomena in other van der Waals materials and topological insulators. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Progressive Oxidation of Pyrite in Five Bituminous Coal Samples: An As XANES and 57Fe Mossbauer Spectroscopic Study

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

    Kolker,A.; Huggins, F.

    2007-01-01

    Naturally occurring pyrite commonly contains minor substituted metals and metalloids (As, Se, Hg, Cu, Ni, etc.) that can be released to the environment as a result of its weathering. Arsenic, often the most abundant minor constituent in pyrite, is a sensitive monitor of progressive pyrite oxidation in coal. To test the effect of pyrite composition and environmental parameters on the rate and extent of pyrite oxidation in coal, splits of five bituminous coal samples having differing amounts of pyrite and extents of As substitution in the pyrite, were exposed to a range of simulated weathering conditions over a period ofmore » 17 months. Samples investigated include a Springfield coal from Indiana (whole coal pyritic S = 2.13 wt.%; As in pyrite = detection limit (d.l.) to 0.06 wt.%), two Pittsburgh coal samples from West Virginia (pyritic S = 1.32-1.58 wt.%; As in pyrite = d.l. to 0.34 wt.%), and two samples from the Warrior Basin, Alabama (pyritic S = 0.26-0.27 wt.%; As in pyrite = d.l. to 2.72 wt.%). Samples were collected from active mine faces, and expected differences in the concentration of As in pyrite were confirmed by electron microprobe analysis. Experimental weathering conditions in test chambers were maintained as follows: (1) dry Ar atmosphere; (2) dry O{sub 2} atmosphere; (3) room atmosphere (relative humidity {approx}20-60%); and (4) room atmosphere with samples wetted periodically with double-distilled water. Sample splits were removed after one month, nine months, and 17 months to monitor the extent of As and Fe oxidation using As X-ray absorption near-edge structure (XANES) spectroscopy and {sup 57}Fe Mossbauer spectroscopy, respectively. Arsenic XANES spectroscopy shows progressive oxidation of pyritic As to arsenate, with wetted samples showing the most rapid oxidation. {sup 57}Fe Mossbauer spectroscopy also shows a much greater proportion of Fe{sup 3+} forms (jarosite, Fe{sup 3+} sulfate, FeOOH) for samples stored under wet conditions, but much

  18. Edge detection based on computational ghost imaging with structured illuminations

    NASA Astrophysics Data System (ADS)

    Yuan, Sheng; Xiang, Dong; Liu, Xuemei; Zhou, Xin; Bing, Pibin

    2018-03-01

    Edge detection is one of the most important tools to recognize the features of an object. In this paper, we propose an optical edge detection method based on computational ghost imaging (CGI) with structured illuminations which are generated by an interference system. The structured intensity patterns are designed to make the edge of an object be directly imaged from detected data in CGI. This edge detection method can extract the boundaries for both binary and grayscale objects in any direction at one time. We also numerically test the influence of distance deviations in the interference system on edge extraction, i.e., the tolerance of the optical edge detection system to distance deviation. Hopefully, it may provide a guideline for scholars to build an experimental system.

  19. Predictions of the near edge transport shortfall in DIII-D L-mode plasmas using the trapped gyro-Landau-fluid model [Predictions of the near edge transport shortfall in DIII-D L-mode plasmas using the TGLF model

    DOE PAGES

    Kinsey, Jon E.; Staebler, Gary M.; Candy, Jefferey M.; ...

    2015-01-14

    Previous studies of DIII-D L-mode plasmas have shown that a transport shortfall exists in that our current models of turbulent transport can significantly underestimate the energy transport in the near edge region. In this paper, the Trapped Gyro-Landau-Fluid (TGLF) drift wave transport model is used to simulate the near edge transport in a DIII-D L-mode experiment designed to explore the impact of varying the safety factor on the shortfall. We find that the shortfall systematically increases with increasing safety factor and is more pronounced for the electrons than for the ions. Within the shortfall dataset, a single high current casemore » has been found where no transport shortfall is predicted. Reduced neutral beam injection power has been identified as the key parameter separating this discharge from other discharges exhibiting a shortfall. Further analysis shows that the energy transport in the L-mode near edge region is not stiff according to TGLF. Unlike the H-mode core region, the predicted temperature profiles are relatively more responsive to changes in auxiliary heating power. In testing the fidelity of TGLF for the near edge region, we find that a recalibration of the collision model is warranted. A recalibration improves agreement between TGLF and nonlinear gyrokinetic simulations performed using the GYRO code with electron-ion collisions. As a result, the recalibration only slightly impacts the predicted shortfall.« less

  20. STM/STS investigation of edge structure in epitaxial graphene

    NASA Astrophysics Data System (ADS)

    Ridene, M.; Girard, J. C.; Travers, L.; David, C.; Ouerghi, A.

    2012-08-01

    In this paper, we have used low temperature scanning tunneling microscopy and spectroscopy (LT-STM/STS) to study zigzag or armchair edges of epitaxial graphene on 6H-SiC (0001). The monolayer carbon structures exhibit occasionally one-dimensional ridge (1D) in close vicinity to step edge. This ridge exhibits different edges orientations in armchair-zigzag transition which give rise to different local density of states (LDOS) along this 1D structure. This ridge formation is likely explained by residual compressive in-plane stresses.

  1. Time dependent density functional theory study of the near-edge x-ray absorption fine structure of benzene in gas phase and on metal surfaces.

    PubMed

    Asmuruf, Frans A; Besley, Nicholas A

    2008-08-14

    The near-edge x-ray absorption fine structure of benzene in the gas phase and adsorbed on the Au(111) and Pt(111) surfaces is studied with time dependent density functional theory. Excitation energies computed with hybrid exchange-correlation functionals are too low compared to experiment. However, after applying a constant shift the spectra are in good agreement with experiment. For benzene on the Au(111) surface, two bands arising from excitation to the e(2u)(pi(*)) and b(2g)(pi(*)) orbitals of benzene are observed for photon incidence parallel to the surface. On Pt(111) surface, a broader band arises from excitation to benzene orbitals that are mixed with the surface and have both sigma(*)(Pt-C) and pi(*) characters.

  2. Temperature dependence of Ti 1s near-edge spectra in Ti-based perovskites: theory and experiment

    NASA Astrophysics Data System (ADS)

    Shirley, Eric; Cockayne, Eric; Ravel, Bruce; Woicik, Joseph

    Ti 1s near-edge spectra (around 4970 eV) in SrTiO3 and PbTiO3 reveal electric-dipole and quadrupole transitions to Ti 3d, 4p and mixed 3d-4p states. Crystal field-split pre-edge features attributed to 1s ->3d transitions are small compared to the main edge jump at the onset of the Ti 4s/4p continuum. Pre-edge and subsequent near-edge features are predicted to be weaker than what is observed, unless one accounts for ferroelectric polarization in PbTiO3 and thermal motion in both compounds. Using density-functional theory molecular dynamics simulations at various temperatures (including sampling two phases of PbTiO3), we capture the statistically averaged root-mean-square deviations of Ti4+ ions from the centers of their oxygen cages. By sampling appropriate snapshots of atomic configurations and averaging Ti 1s absorption spectra computed within a Bethe-Salpeter Equation framework, we obtain absorption spectra that agree well with experiment, including details related to ferroelectric polarization, phase transitions, and fluctuations of atomic coordinates.

  3. In situ XAFS and micro-XAFS studies on LiNi 0.8Co 0.15Al 0.05O 2 cathode material for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Nonaka, T.; Okuda, C.; Seno, Y.; Nakano, H.; Koumoto, K.; Ukyo, Y.

    We have applied in situ X-ray absorption fine structure (XAFS) and in situ micro-XAFS techniques to study LiNi 0.8Co 0.15Al 0.05O 2 cathode materials in Li-ion coin cells that show various levels of capacity fading: fresh cell, cycle tested cell and aging tested cell. The change in the oxidation state and local structure of Ni and Co during charge has been investigated. Ni and Co K-edge X-ray absorption near edge structure (XANES) show that the Ni oxidation state is converted from Ni 3+ to Ni 4+ upon charging, whereas the Co oxidation state hardly changes. Ni K-edge extended X-ray absorption fine structure (EXAFS) reveals that the Jahn-Teller distorted NiO 6 octahedron turns into the symmetric octahedron upon charging, which is consistent with the change in the Ni oxidation state. Ni K-edge micro-XANES show that the oxidation of Ni proceeds homogeneously in a grain of LiNi 0.8Co 0.15Al 0.05O 2 within the special resolution of ∼2 μm, and proceeds independently of the grain size. All the behaviors of Ni and Co observed in these experiments for the fresh cell remain unchanged after the capacity fade is induced by cycle tests or aging tests, which demonstrates the considerable stability of the LiNi 0.8Co 0.15Al 0.05O 2 cathode material.

  4. Papers from U.S. Department of Energy Science Undergraduate Laboratory Internship Program (SULI) 2010

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

    Not Available

    2011-06-22

    The solvation sphere of halides in water has been investigated using a combination of extended x-ray absorption fine structure (EXAFS) and x-ray absorption near-edge structure (XANES) analysis techniques. The results have indicated that I{sup -} and Br{sup -} both have an asymmetric, 8 water molecule primary solvation spheres. These spheres are identical, with the Br{sup -} sphere about .3 {angstrom} smaller than the I{sup -} sphere. This study utilized near-edge analysis to supplement EXAFS analysis which suffers from signal dampening/broadening due to thermal noise. This paper has reported on the solvation first sphere of I{sup -} and Br{sup -} inmore » water. Using EXAFS and XANES analysis, strong models which describe the geometric configuration of water molecules coordinated to a central anion have been developed. The combination of these techniques has provided us with a more substantiated argument than relying solely on one or the other. An important finding of this study is that the size of the anion plays a smaller role than previously assumed in determining the number of coordinating water molecules. Further experimental and theoretical investigation is required to understand why the size of the anion plays a minor role in determining the number of water molecules bound.« less

  5. Determining the Oxygen Fugacity of Lunar Pyroclastic Glasses Using Vanadium Valence - An Update

    NASA Technical Reports Server (NTRS)

    Karner, J. M.; Sutton, S. R.; Papike, J. J.; Shearer, C. K.; Jones, J. H.; Newville, M.

    2004-01-01

    We have been developing an oxygen barometer based on the valence state of V (V(2+), V(3+), V(4+), and V(5+)) in solar system basaltic glasses. The V valence is determined by synchrotron micro x-ray absorption near edge structure (XANES), which uses x-ray absorption associated with core-electronic transitions (absorption edges) to reveal a pre-edge peak whose intensity is directly proportional to the valence state of an element. XANES has advantages over other techniques that determine elemental valence because measurements can be made non-destructively in air and in situ on conventional thin sections at a micrometer spatial resolution with elemental sensitivities of approx. 100 ppm. Recent results show that fO2 values derived from the V valence technique are consistent with fO2 estimates determined by other techniques for materials that crystallized above the IW buffer. The fO2's determined by V valence (IW-3.8 to IW-2) for the lunar pyroclastic glasses, however, are on the order of 1 to 2.8 log units below previous estimates. Furthermore, the calculated fO2's decrease with increasing TiO2 contents from the A17 VLT to the A17 Orange glasses. In order to investigate these results further, we have synthesized lunar green and orange glasses and examined them by XANES.

  6. Investigation of the nanoscale two-component ZnS-ZnO heterostructures by means of HR-TEM and X-ray based analysis

    NASA Astrophysics Data System (ADS)

    Pankin, I. A.; Polozhentsev, O. E.; Soldatov, M. A.; Bugaev, A. L.; Tsaturyan, A.; Lomachenko, K. A.; Guda, A. A.; Budnyk, A. P.; Lamberti, C.; Soldatov, A. V.

    2018-06-01

    This article is devoted to the spectroscopic characterization of ZnS-ZnO nanoscale heterostructures synthesized by the microwave-assisted solvothermal method. The synthesized samples were investigated by means of X-ray powder diffraction (XRPD), high energy resolution fluorescence detected X-ray absorption near-edge-structure (HERFD-XANES) spectroscopy, valence-to-core X-ray emission spectroscopy (VtC-XES) and high resolution transmission electron microscopy (HR-TEM) as well as energy dispersive X-ray spectroscopy (EDX). The average crystallite size estimated by the broadening of XRPD peaks increases from 2.7 nm to 3.7 nm in the temperature range from 100 °C to 150 °C. HR-TEM images show that nanoparticles are arranged in aggregates with the 60-200 nm size. Theoretical estimation shows that the systems synthesized at higher temperatures more prone to the agglomeration. The full profile Reitveld analysis of XRPD data reveals the formation of hexagonal zinc sulfide structure, whereas electron diffraction data reveal also the formation of cubic zinc sulfide and claim the polymorphous character of the system. High energy resolution Zn K-edge XANES data unambiguously demonstrate the presence of a certain amount of the zinc oxide which is likely to have an amorphous structure and could not be detected by XRPD. Qualitative analysis of XANES data allows deriving ZnS/ZnO ratio as a function of synthesis temperature. EDX analysis depicts homogeneous distribution of ZnS and amorphous ZnO phases across the conglomerates. A complementary element-selective valence to core X-ray emission spectroscopy evidences formation of two-component system and confirms estimations of ZnS/ZnO fractions obtained by linear combination fit of XANES data.

  7. Electronic structure of Rh and Ru doped Sr2IrO4

    NASA Astrophysics Data System (ADS)

    Chikara, Shalinee; Fabbris, Gilberto; Terzic, Jasminka; Qi, Tongfei; Butrouna, Kamal; Veiga, Larissa; Souza Neto, Narcizo; Cao, Gang; Haskel, Daniel

    2014-03-01

    Sr2IrO4 is a spin-orbit interaction(SOI) assisted insulator. It has been proposed that the weaker SOI in the 4 d -substituted Sr2Ir1-x(Ru, Rh)xO4 closes the insulating gap, rendering it a paramagnetic metal. Rh(4d5) is isoelectronic to Ir(5d5) whereas Ru(4d4) has one less electron in the 4 d -band. The AFM-I/PM-M transition takes place at lower x for Ru than Rh, presumably due to the effect of hole doping. X-ray absorption near edge structure (XANES) and x-ray magnetic circular dichroism (XMCD) measurements at the Ir L2 , 3 edges show that < L . S > is non-zero and independent of x. This is indicative of a strong local 5 d spin orbit interaction that is rather insensitive to the 4 d doping. In contrast, measurements at the L2 , 3 edges of Ru and Rh show < L . S > ~ 0 for all x. The results point to the importance of local 4 d / 5 d - 2 p hybridization as opposed to 4 d - 5 d band formation in the Rh and Ru doped Sr2IrO4.

  8. Local structure investigation of Ga and Yb dopants in Co 4 Sb 12 skutterudites

    DOE PAGES

    Hu, Yanyun; Chen, Ning; Clancy, J. P.; ...

    2017-12-29

    We report our x-ray absorption spectroscopy studies at both Ga K-edge and Yb L 2-edge to elucidate the local structure of Ga and Yb dopants in Yb xGa yCo 4Sb 12. Our extended x-ray absorption fine structure (EXAFS) data confirm that Ga atoms occupy two crystallographic sites: one is the 24g site replacing Sb, and the other is the 2a site in the off-center void position. We find that the occupancy ratio of these two sites varies significantly as a function of the filling fraction of additional Yb, which exclusively occupies the 2a on-center site. At low concentrations of Yb,more » Ga 24g and Ga 2a dopants coexist and they form a charge-compensated compound defect proposed by Qiu et al. [Adv. Mater. 23, 3194 (2013)]. The Ga 24g occupancy increases gradually with increasing Yb concentration, and almost all Ga occupies the 24g site for the highest Yb concentration (x = 0.4). In addition to the local crystal structure evidence provided by our EXAFS data, we also present x-ray absorption near-edge structure (XANES) spectra, which show a small Ga K-edge energy shift as a function of Yb concentration consistent with the change from predominantly Ga 2a to Ga 24g states. Our result suggests that the increased solubility of Yb in Yb-Ga co-doped Co 4Sb 12 skutterudites is due to the increased Ga 24g electron acceptor, and thus provides an important strategy to optimize the carrier concentration in partially filled skutterudites.« less

  9. Local structure investigation of Ga and Yb dopants in Co4Sb12 skutterudites

    NASA Astrophysics Data System (ADS)

    Hu, Yanyun; Chen, Ning; Clancy, J. P.; Salvador, James R.; Kim, Chang-Yong; Shi, Xiaoya; Li, Qiang; Kim, Young-June

    2017-12-01

    We report comprehensive x-ray absorption spectroscopy studies at both the Ga K edge and Yb L2 edge to elucidate the local structure of Ga and Yb dopants in YbxGayCo4Sb12 . Our extended x-ray absorption fine structure (EXAFS) data confirm that Ga atoms occupy two crystallographic sites: one is the 24 g site replacing Sb, and the other is the 2 a site in the off-center void position. We find that the occupancy ratio of these two sites varies significantly as a function of the filling fraction of additional Yb, which exclusively occupies the 2 a on-center site. At low concentrations of Yb, Ga24 g and Ga2 a dopants coexist and they form a charge-compensated compound defect proposed by Qiu et al. [Adv. Funct. Mater. 23, 3194 (2013), 10.1002/adfm.201202571]. The Ga24 g occupancy increases gradually with increasing Yb concentration, and almost all Ga occupies the 24 g site for the highest Yb concentration studied (x =0.4 ). In addition to the local structural evidence provided by our EXAFS data, we also present x-ray absorption near-edge structure (XANES) spectra, which show a small Ga K -edge energy shift as a function of Yb concentration consistent with the change from predominantly Ga2 a to Ga24 g states. Our result suggests that the increased solubility of Yb in Yb-Ga co-doped Co4Sb12 skutterudites is due to the increased Ga24 g electron acceptor, and thus provides an important strategy to optimize the carrier concentration in partially filled skutterudites.

  10. Local structure investigation of Ga and Yb dopants in Co 4 Sb 12 skutterudites

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

    Hu, Yanyun; Chen, Ning; Clancy, J. P.

    We report our x-ray absorption spectroscopy studies at both Ga K-edge and Yb L 2-edge to elucidate the local structure of Ga and Yb dopants in Yb xGa yCo 4Sb 12. Our extended x-ray absorption fine structure (EXAFS) data confirm that Ga atoms occupy two crystallographic sites: one is the 24g site replacing Sb, and the other is the 2a site in the off-center void position. We find that the occupancy ratio of these two sites varies significantly as a function of the filling fraction of additional Yb, which exclusively occupies the 2a on-center site. At low concentrations of Yb,more » Ga 24g and Ga 2a dopants coexist and they form a charge-compensated compound defect proposed by Qiu et al. [Adv. Mater. 23, 3194 (2013)]. The Ga 24g occupancy increases gradually with increasing Yb concentration, and almost all Ga occupies the 24g site for the highest Yb concentration (x = 0.4). In addition to the local crystal structure evidence provided by our EXAFS data, we also present x-ray absorption near-edge structure (XANES) spectra, which show a small Ga K-edge energy shift as a function of Yb concentration consistent with the change from predominantly Ga 2a to Ga 24g states. Our result suggests that the increased solubility of Yb in Yb-Ga co-doped Co 4Sb 12 skutterudites is due to the increased Ga 24g electron acceptor, and thus provides an important strategy to optimize the carrier concentration in partially filled skutterudites.« less

  11. ECCENTRICITY TRAP: TRAPPING OF RESONANTLY INTERACTING PLANETS NEAR THE DISK INNER EDGE

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

    Ogihara, Masahiro; Ida, Shigeru; Duncan, Martin J., E-mail: ogihara@geo.titech.ac.j, E-mail: ida@geo.titech.ac.j, E-mail: duncan@astro.queensu.c

    2010-10-01

    Using orbital integration and analytical arguments, we have found a new mechanism (an 'eccentricity trap') to halt type I migration of planets near the inner edge of a protoplanetary disk. Because asymmetric eccentricity damping due to disk-planet interaction on the innermost planet at the disk edge plays a crucial role in the trap, this mechanism requires continuous eccentricity excitation and hence works for a resonantly interacting convoy of planets. This trap is so strong that the edge torque exerted on the innermost planet can completely halt type I migrations of many outer planets through mutual resonant perturbations. Consequently, the convoymore » stays outside the disk edge, as a whole. We have derived a semi-analytical formula for the condition for the eccentricity trap and predict how many planets are likely to be trapped. We found that several planets or more should be trapped by this mechanism in protoplanetary disks that have cavities. It can be responsible for the formation of non-resonant, multiple, close-in super-Earth systems extending beyond 0.1 AU. Such systems are being revealed by radial velocity observations to be quite common around solar-type stars.« less

  12. Improving the opto-microwave performance of SiGe/Si phototransistor through edge-illuminated structure

    NASA Astrophysics Data System (ADS)

    Tegegne, Z. G.; Viana, C.; Polleux, J. L.; Grzeskowiak, M.; Richalot, E.

    2016-03-01

    This paper demonstrates the experimental study of edge and top illuminated SiGe phototransistors (HPT) implemented using the existing industrial SiGe2RF Telefunken GmbH BiCMOS technology for opto-microwave (OM) applications using 850nm Multi-Mode Fibers (MMF). Its technology and structure are described. Two different optical window size HPTs with top illumination (5x5μm2, 10x10μm2) and an edge illuminated HPTs having 5μm x5μm size are presented and compared. A two-step post fabrication process was used to create an optical access on the edge of the HPT for lateral illumination with a lensed MMF through simple polishing and dicing techniques. We perform Opto-microwave Scanning Near-field Optical Microscopy (OM-SNOM) analysis on edge and top illuminated HPTs in order to observe the fastest and the highest sensitive regions of the HPTs. This analysis also allows understanding the parasitic effect from the substrate, and thus draws a conclusion on the design aspect of SiGe/Si HPT. A low frequency OM responsivity of 0.45A/W and a cutoff frequency, f-3dB, of 890MHz were measured for edge illuminated HPT. Compared to the top illuminated HPT of the same size, the edge illuminated HPT improves the f-3dB by a factor of more than two and also improves the low frequency responsivity by a factor of more than four. These results demonstrate that a simple etched HPT is still enough to achieve performance improvements compared to the top illuminated HPT without requiring a complex coupling structure. Indeed, it also proves the potential of edge coupled SiGe HPT in the ultra-low-cost silicon based optoelectronics circuits with a new approach of the optical packaging and system integration to 850nm MMF.

  13. Arsenic speciation in biological samples using XAS and mixed oxidation state calibration standards of inorganic arsenic.

    PubMed

    Parsons, J G; Lopez, M L; Castillo-Michel, H; Peralta-Videa, J R; Gardea-Torresdey, J L

    2009-08-01

    The speciation of elements without pre-edge features preformed with X-ray absorption near edge structure (XANES) can lead to problems when the energy difference between two species is small. The speciation of arsenic (As) in plant samples was investigated using the mixtures As2S3/As2O5, As2S3/As2O3, or As2O3/As2O5. The data showed that the energy separation (eV) between As2O5 and As2S3 was 5.8, between As2O3 and As2O5 was 3.6, and between As2S3 and As2O3 was 2.1. From the intensity of the white-line feature and the concentration of As species, calibration curves showing a limit of detection of approximately 10% were generated. In addition, an error of +/-10% was determined for the linear combination-XANES (LC-XANES) fitting technique. The difference between the LC-XANES fittings and calculations from the calibration curves was <10%. The data also showed that the speciation of As in a sample can be determined using EXAFS (extended X-ray absorption fine structure). Finally, it was also shown that both EXAFS and XANES of the sample should be examined to determine the true speciation of an element. Even though there is a difference of 2 eV between As(III) bound to O and As(III) bound to S, in the EXAFS region the As(III)-S and As(III)-O ligands are clearly visible. However, distinction between the As(III)-O and As(V)-O ligands in the EXAFS spectra was not clearly visible in this study.

  14. Effects of phonon broadening on x-ray near-edge spectra in molecular crystals

    NASA Astrophysics Data System (ADS)

    Vinson, John; Jach, Terrence; Elam, Tim; Denlinger, Jonathon

    2014-03-01

    Calculations of near-edge x-ray spectra are often carried out using the average atomic coordinates from x-ray or neutron scattering experiments or from density functional theory (DFT) energy minimization. This neglects disorder from thermal and zero-point vibrations. Here we look at the nitrogen K-edge of ammonium chloride and ammonium nitrate, comparing Bethe-Salpeter calculations of absorption and fluorescence to experiment. We find that intra-molecular vibrational effects lead to significant, non-uniform broadening of the spectra, and that for some features zero-point motion is the primary source of the observed shape.

  15. On the Structure of the Iron K-Edge

    NASA Technical Reports Server (NTRS)

    Palmeri, P.; Mendoza, C.; Kallman, T. R.; Bautista, M. A.; White, Nicholas E. (Technical Monitor)

    2002-01-01

    It is shown that the commonly held view of a sharp Fe K edge must be modified if the decay pathways of the series of resonances converging to the K thresholds are adequately taken into account. These resonances display damped Lorentzian profiles of nearly constant widths that are smeared to impose continuity across the threshold. By modeling the effects of K damping on opacities, it is found that the broadening of the K edge grows with the ionization level of the plasma, and the appearance at high ionization of a localized absorption feature at 7.2 keV is identified as the Kbeta unresolved transition array.

  16. Uranium association with iron-bearing phases in mill tailings from Gunnar, Canada.

    PubMed

    Othmane, Guillaume; Allard, Thierry; Morin, Guillaume; Sélo, Madeleine; Brest, Jessica; Llorens, Isabelle; Chen, Ning; Bargar, John R; Fayek, Mostafa; Calas, Georges

    2013-11-19

    The speciation of uranium was studied in the mill tailings of the Gunnar uranium mine (Saskatchewan, Canada), which operated in the 1950s and 1960s. The nature, quantification, and spatial distribution of uranium-bearing phases were investigated by chemical and mineralogical analyses, fission track mapping, electron microscopy, and X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopies at the U LIII-edge and Fe K-edge. In addition to uranium-containing phases from the ore, uranium is mostly associated with iron-bearing minerals in all tailing sites. XANES and EXAFS data and transmission electron microscopy analyses of the samples with the highest uranium concentrations (∼400-700 mg kg(-1) of U) demonstrate that uranium primarily occurs as monomeric uranyl ions (UO2(2+)), forming inner-sphere surface complexes bound to ferrihydrite (50-70% of the total U) and to a lesser extent to chlorite (30-40% of the total U). Thus, the stability and mobility of uranium at the Gunnar site are mainly influenced by sorption/desorption processes. In this context, acidic pH or alkaline pH with the presence of UO2(2+)- and/or Fe(3+)-complexing agents (e.g., carbonate) could potentially solubilize U in the tailings pore waters.

  17. Characterization of yellow and colorless decorative glasses from the Temple of the Emerald Buddha, Bangkok, Thailand

    NASA Astrophysics Data System (ADS)

    Klysubun, Wantana; Ravel, Bruce; Klysubun, Prapong; Sombunchoo, Panidtha; Deenan, Weeraya

    2013-06-01

    Yellow and colorless ancient glasses, which were once used to decorate the Temple of the Emerald Buddha, Bangkok, Thailand, around 150 years ago, are studied to unravel the long-lost glass-making recipes and manufacturing techniques. Analyses of chemical compositions, using synchrotron x-ray fluorescence (SRXRF), indicate that the Thai ancient glasses are soda lime silica glasses (60 % SiO2; 10 % Na2O; 10 % CaO) bearing lead oxide between 2-16 %. Iron (1.5-9.4 % Fe2O3) and manganese (1.7 % MnO) are present in larger abundance than the other 3 d transition metals detected (0.04-0.2 %). K-edge x-ray absorption near edge spectroscopy (XANES) and extended x-ray absorption fine structure spectroscopy (EXAFS) provide conclusive evidence on the oxidation states of Fe being 3+ and Mn being 2+ and on short-length tetrahedral structures around the cations. This suggests that iron is used as a yellow colorant with manganese as a decolorant. L 3-edge XANES results reveal the oxidation states of lead as 2+. The results from this work provide information crucial for replicating these decorative glasses for the future restoration of the Temple of the Emerald Buddha.

  18. Ag XANES data of biosolids

    EPA Pesticide Factsheets

    The dataset contains energy and absorption data for XANES spectra indicated in Figure 1 of the manuscript.This dataset is associated with the following publication:Donner, E., K. Scheckel , R. Sekine, R. Popelka-Filcoff, J. Bennett, G. Brunetti, R. Naidu, S. McGrath, and E. Lombi. Non-labile silver species in biosolids remain stable throughout 50 years of weathering and ageing.. D.O. Carpenter, and E.Y. Zeng ENVIRONMENTAL POLLUTION. Elsevier Science Ltd, New York, NY, USA, 205: 78-86, (2015).

  19. The effect of crystal structure of TiO2 nanotubes on the formation of calcium phosphate coatings during biomimetic deposition

    NASA Astrophysics Data System (ADS)

    Liu, Yi; Kim, Sun; McLeod, John A.; Li, Jun; Guo, Xiaoxuan; Sham, Tsun-Kong; Liu, Lijia

    2017-02-01

    The crystallization process of bioactive calcium phosphate (CaP) species via biomimetic deposition onto anodic TiO2 nanotubes is investigated. The porous surface of nanostructured TiO2 provides an ideal substrate for CaP crystallization. The compositions of CaP coatings are studied using X-ray absorption near-edge structures (XANES) at the Ca K-edge. Using detection modes with different probing depths, both the surface of the CaP coating and the CaP-TiO2 interface are simultaneously analyzed. Calcium phosphate (CaP) species, such as hydroxyapatite (HAp), octacalcium phosphate (Ca8(HPO4)2(PO4)4·5H2O, OCP), brushite (CaHPO4·2H2O, DCPD), and amorphous calcium phosphate (ACP), are found in the CaP coatings. TiO2 nanotubes of amorphous and anatase phases are comparatively studied to determine their effect on the efficiency of CaP formation and the phase transformation among CaP species in prolonged deposition time. It is found the composition of CaP coating has a strong dependency on the crystal structure of TiO2 substrate and the kinetics (deposition time).

  20. Characterization of pentavalent and hexavalent americium complexes in nitric acid using X-ray absorption fine structure spectroscopy and first-principles modeling

    DOE PAGES

    Riddle, Catherine; Czerwinski, Kenneth; Kim, Eunja; ...

    2016-01-18

    We studied the speciation of pentavalent and hexavalent americium (Am) complexes in nitric acidicby X-ray absorption fine structure spectroscopy (XAFS), UV-visible spectroscopy, and density functional theory (DFT). Extended x-ray absorption fine structure (EXAFS) and x-ray absorption near edge structure (XANES) results were consistent with the presence of a mixture of AmO 2 + and AmO 2 2+ with only a small amount AmO 2 present. The resulting average bond distances we found were 1.71 Å for Am=O and 2.44 Å for Am-O. All-electron scalar relativistic calculations were also carried out using DFT to predict the equilibrium geometries and properties ofmore » the AmO 2 + and AmO 2 2+ aquo complexes. Calculated bond distances for the Am(VI) complex are in reasonable agreement with EXAFS data and the computed energy gaps between frontier molecular orbitals suggest a slightly higher kinetic stability and chemical hardness of Am(VI) compared to Am(V).« less

  1. Vanadium, sulfur, and iron valences in melt inclusions as a window into magmatic processes: A case study at Nyamuragira volcano, Africa

    NASA Astrophysics Data System (ADS)

    Head, Elisabet; Lanzirotti, Antonio; Newville, Matthew; Sutton, Stephen

    2018-04-01

    This study describes microscale sulfur (S), vanadium (V), and iron (Fe) K-edge X-ray absorption near edge structure (μ-XANES) spectroscopy measurements on olivine-hosted melt inclusions (MI) preserved in tephras (1986 and 2006) and lavas (1938 and 1948) erupted from Nyamuragira volcano (D.R. Congo, Africa). The S, V, and Fe spectroscopic data are used to constrain the evolution of oxygen fugacity (fO2) and sulfur speciation for the entrapped melts. Melt inclusions from lavas show evidence of post-entrapment crystallization and were thus reheated prior to μ-XANES analysis. The MI from tephra show no evidence of post-entrapment crystallization and were, therefore, not reheated. Sulfur, V, and Fe μ-XANES results from 1938, 1948, and 2006 eruptive materials are all similar within analytical uncertainty and provide similar average calculated melt fO2's based on XANES oxybarometry. However, olivine-hosted MI from the 1986 tephras yield significantly different S, V, and Fe XANES spectra when compared to MI from the other eruptions, with disagreement between calculated fO2's from the three valence state oxybarometers beyond the uncertainty of the calibration models. Their V μ-XANES spectra are also significantly more ordered and yield more reduced average V valence. The S μ-XANES spectra display a significantly more intense low-energy spectral resonance, which indicates differences in Fe-S bonding character, and greater variability in their measured sulfate content. These V and S spectroscopic features are best explained by crystallization of sub-micrometer magnetite and sulfide crystallites within the 1986 inclusions. The sensitivity of XANES spectroscopy to short-range order allows these crystallites to be recognized even though they are not easily detected by imaging analysis. This shows that V and S μ-XANES are potentially highly sensitive tools for identifying the presence of volumetrically minor amounts of spinel and sulfide within inclusions extracted from

  2. Noninvasive Synchrotron-Based X-ray Raman Scattering Discriminates Carbonaceous Compounds in Ancient and Historical Materials [ In situ synchrotron-based X-Ray Raman scattering discriminates carbonaceous compounds in ancient and historical materials

    DOE PAGES

    Gueriau, Pierre; Rueff, Jean -Pascal; Bernard, Sylvain; ...

    2017-09-13

    Carbon compounds are ubiquitous and occur in a diversity of chemical forms in many systems including ancient and historic materials ranging from cultural heritage to paleontology. Determining their speciation cannot only provide unique information on their origin but may also elucidate degradation processes. Synchrotron-based X-ray absorption near-edge structure (XANES) spectroscopy at the carbon K-edge (280–350 eV) is a very powerful method to probe carbon speciation. However, the short penetration depth of soft X-rays imposes stringent constraints on sample type, preparation, and analytical environment. A hard X-ray probe such as X-ray Raman scattering (XRS) can overcome many of these difficulties. Heremore » we report the use of XRS at ~6 keV incident energy to collect carbon K-edge XANES data and probe the speciation of organic carbon in several specimens relevant to cultural heritage and natural history. This methodology enables the measurement to be done in a nondestructive way, in air, and provides information that is not compromised by surface contamination by ensuring that the dominant signal contribution is from the bulk of the probed material. Using the backscattering geometry at large photon momentum transfer maximizes the XRS signal at the given X-ray energy and enhances nondipole contributions compared to conventional XANES, thereby augmenting the speciation sensitivity. The capabilities and limitations of the technique are discussed. As a result, we show that despite its small cross section, for a range of systems the XRS method can provide satisfactory signals at realistic experimental conditions. XRS constitutes a powerful complement to FT-IR, Raman, and conventional XANES spectroscopy, overcoming some of the limitations of these techniques.« less

  3. MoS2 edges and heterophase interfaces: energy, structure and phase engineering

    NASA Astrophysics Data System (ADS)

    Zhou, Songsong; Han, Jian; Sun, Jianwei; Srolovitz, David J.

    2017-06-01

    The transition metal dichalcogenides exhibit polymorphism; i.e. both 2H and 1T‧ crystal structures, each with unique electronic properties. These two phases can coexist within the same monolayer microstructure, producing 2H/1T‧ interfaces. Here we report a systematic investigation of the energetics of the experimentally most important MoS2 heterophase interfaces and edges. The stable interface and edge structures change with chemical potential (these edges/interfaces are usually non-stoichiometric). Stable edges tend to be those of highest atomic density and the stable interfaces correspond to those with local atomic structure very similar to the 2H crystal. The interfacial energies are lower than those of the edges, and the 1T‧ edges have lower energy than the 2H edges. Because the 1T‧ edges have much lower energy than the 2H edges, a sufficiently narrow 1T‧ ribbon will be more stable than the corresponding 2H ribbon (this critical width is much larger in MoTe2 than in MoS2). Similarly, a large 2H flake have an equilibrium strip of 1T‧ along its edge (again this effect is much larger in MoTe2 than in MoS2). Application of tensile strains can increase the width of the stable 1T‧ strip or the critical thickness below which a ribbon favors the 1T‧ structure. These effects provide a means to phase engineer transition metal dichalcogenide microstructures.

  4. X-ray absorption Studies of Zinc species in Centella asiatica

    NASA Astrophysics Data System (ADS)

    Dehipawala, Sunil; Cheung, Tak; Hogan, Clayton; Agoudavi, Yao; Dehipawala, Sumudu

    2013-03-01

    Zinc is a very important mineral present in a variety of vegetables. It is an essential element in cellular metabolism and several bodily functions. We used X-ray fluorescence, and X-ray Absorption near Edge structure(XANES) to study the amount of zinc present in several leafy vegetables as well as its chemical environment within the plant. Main absorption edge position of XANES is sensitive to the oxidation state of zinc and is useful when comparing the type of zinc present in different vegetables to the standard zinc present in supplements. Normalized main edge height is proportional to the amount of zinc present in the sample. Several leafy greens were used in this study, such as Spinacia oleracea, Basella alba, Brassica oleracea, Cardiospermum halicacabumand Centella asiatica. All of these plant leaves contained approximately the same amount of zinc in the leaf portion of the plant and a slightly lower amount in the stems, except Centella asiatica. Both leaves and stems of the plant Centella asiatica contained nearly two times the zinc compared to other plants. Further investigation of zinc's chemical environment within Centella asiatica could lead to a much more efficient dietary consumption of zinc. Use of the National Synchrotron Light Source, Brookhaven National Laboratory, was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-98CH10886

  5. XANES analyses of silicon crystalline irradiated by nitrogen/oxygen ions.

    PubMed

    Yoshida, T; Hara, T; Li, T; Yoshida, H; Tanabe, T

    2001-03-01

    X-ray absorption techniques have been applied to the characterization of 5 keV nitrogen / oxygen ions implanted silicon samples. The depth selective measurement of XANES by recording in PEY mode and the quantitative analysis by superposition of XANES spectra were carried out to elucidate the depth profile of implanted ions. It has been revealed that the silicon nitride phase were formed in silicon after prolonged N+ irradiation and it extended over the deep part of the damaged region from the surface. On the other hand, for the O+ irradiation, silicon dioxide phase were produced only in the shallow part of the damaged region, i.e., the silicon dioxide phase likely broke off during the irradiation.

  6. Speciation Mapping of Environmental Samples Using XANES Imaging

    EPA Science Inventory

    Fast X-ray detectors with large solid angles and high dynamic ranges open the door to XANES imaging, in which millions of spectra are collected to image the speciation of metals at micrometre resolution, over areas up to several square centimetres. This paper explores how such mu...

  7. Defect induced structural inhomogeneity, ultraviolet light emission and near-band-edge photoluminescence broadening in degenerate In2O3 nanowires

    NASA Astrophysics Data System (ADS)

    Mukherjee, Souvik; Sarkar, Ketaki; Wiederrecht, Gary P.; Schaller, Richard D.; Gosztola, David J.; Stroscio, Michael A.; Dutta, Mitra

    2018-04-01

    We demonstrate here defect induced changes on the morphology and surface properties of indium oxide (In2O3) nanowires and further study their effects on the near-band-edge (NBE) emission, thereby showing the significant influence of surface states on In2O3 nanostructure based device characteristics for potential optoelectronic applications. In2O3 nanowires with cubic crystal structure (c-In2O3) were synthesized via carbothermal reduction technique using a gold-catalyst-assisted vapor-liquid-solid method. Onset of strong optical absorption could be observed at energies greater than 3.5 eV consistent with highly n-type characteristics due to unintentional doping from oxygen vacancy ({V}{{O}}) defects as confirmed using Raman spectroscopy. A combination of high resolution transmission electron microscopy, x-ray photoelectron spectroscopy and valence band analysis on the nanowire morphology and stoichiometry reveals presence of high-density of {V}{{O}} defects on the surface of the nanowires. As a result, chemisorbed oxygen species can be observed leading to upward band bending at the surface which corresponds to a smaller valence band offset of 2.15 eV. Temperature dependent photoluminescence (PL) spectroscopy was used to study the nature of the defect states and the influence of the surface states on the electronic band structure and NBE emission has been discussed. Our data reveals significant broadening of the NBE PL peak consistent with impurity band broadening leading to band-tailing effect from heavy doping.

  8. Defect induced structural inhomogeneity, ultraviolet light emission and near-band-edge photoluminescence broadening in degenerate In 2 O 3 nanowires

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

    Mukherjee, Souvik; Sarkar, Ketaki; Wiederrecht, Gary P.

    We demonstrate here defect induced changes on the morphology and surface properties of indium oxide (In2O3) nanowires and further study their effects on the near-band-edge (NBE) emission, thereby showing the significant influence of surface states on In2O3 nanostructure based device characteristics for potential optoelectronic applications. In2O3 nanowires with cubic crystal structure (c-In2O3) were synthesized via carbothermal reduction technique using a gold-catalyst-assisted vapor–liquid–solid method. Onset of strong optical absorption could be observed at energies greater than 3.5 eV consistent with highly n-type characteristics due to unintentional doping from oxygen vacancy (VO) defects as confirmed using Raman spectroscopy. A combination of highmore » resolution transmission electron microscopy, x-ray photoelectron spectroscopy and valence band analysis on the nanowire morphology and stoichiometry reveals presence of high-density of VO defects on the surface of the nanowires. As a result, chemisorbed oxygen species can be observed leading to upward band bending at the surface which corresponds to a smaller valence band offset of 2.15 eV. Temperature dependent photoluminescence (PL) spectroscopy was used to study the nature of the defect states and the influence of the surface states on the electronic band structure and NBE emission has been discussed. Our data reveals significant broadening of the NBE PL peak consistent with impurity band broadening leading to band-tailing effect from heavy doping.« less

  9. Defect induced structural inhomogeneity, ultraviolet light emission and near-band-edge photoluminescence broadening in degenerate In2O3 nanowires.

    PubMed

    Mukherjee, Souvik; Sarkar, Ketaki; Wiederrecht, Gary P; Schaller, Richard D; Gosztola, David J; Stroscio, Michael A; Dutta, Mitra

    2018-04-27

    We demonstrate here defect induced changes on the morphology and surface properties of indium oxide (In 2 O 3 ) nanowires and further study their effects on the near-band-edge (NBE) emission, thereby showing the significant influence of surface states on In 2 O 3 nanostructure based device characteristics for potential optoelectronic applications. In 2 O 3 nanowires with cubic crystal structure (c-In 2 O 3 ) were synthesized via carbothermal reduction technique using a gold-catalyst-assisted vapor-liquid-solid method. Onset of strong optical absorption could be observed at energies greater than 3.5 eV consistent with highly n-type characteristics due to unintentional doping from oxygen vacancy [Formula: see text] defects as confirmed using Raman spectroscopy. A combination of high resolution transmission electron microscopy, x-ray photoelectron spectroscopy and valence band analysis on the nanowire morphology and stoichiometry reveals presence of high-density of [Formula: see text] defects on the surface of the nanowires. As a result, chemisorbed oxygen species can be observed leading to upward band bending at the surface which corresponds to a smaller valence band offset of 2.15 eV. Temperature dependent photoluminescence (PL) spectroscopy was used to study the nature of the defect states and the influence of the surface states on the electronic band structure and NBE emission has been discussed. Our data reveals significant broadening of the NBE PL peak consistent with impurity band broadening leading to band-tailing effect from heavy doping.

  10. Structural design of morphing trailing edge actuated by SMA

    NASA Astrophysics Data System (ADS)

    Wang, Qi; Xu, Zhiwei; Zhu, Qian

    2013-09-01

    In this paper, the morphing trailing edge is designed to achieve the up and down deflection under the aerodynamic load. After a detailed and accurate computational analysis to determine the SMA specifications and layout programs, a solid model is created in CATIA and the structures of the morphing wing trailing edge are produced by CNC machining. A set of DSP measurement and control system is designed to accomplish the controlling experiment of the morphing wing trailing edge. At last, via the force analysis, the trailing edge is fabricated with four sections of aluminum alloy, and the arrangement scheme of SMA wires is determined. Experiment of precise control integral has been performed to survey the control effect. The experiment consists of deflection angle tests of the third joint and the integral structure. Primarily, the ultimate deflection angle is tested in these two experiments. Therefore, the controlling experiment of different angles could be performed within this range. The results show that the deflection error is less than 4%and response time is less than 6.7 s, the precise controlling of the morphing trailing edge is preliminary realized.

  11. Effect of iron oxide reductive dissolution on the transformation and immobilization of arsenic in soils: New insights from X-ray photoelectron and X-ray absorption spectroscopy.

    PubMed

    Fan, Jian-Xin; Wang, Yu-Jun; Liu, Cun; Wang, Li-Hua; Yang, Ke; Zhou, Dong-Mei; Li, Wei; Sparks, Donald L

    2014-08-30

    The geochemical behavior and speciation of arsenic (As) in paddy soils is strongly controlled by soil redox conditions and the sequestration by soil iron oxyhydroxides. Hence, the effects of iron oxide reductive dissolution on the adsorption, transformation and precipitation of As(III) and As(V) in soils were investigated using batch experiments and synchrotron based techniques to gain a deeper understanding at both macroscopic and microscopic scales. The results of batch sorption experiments revealed that the sorption capacity of As(V) on anoxic soil was much higher than that on control soil. Synchrotron based X-ray fluorescence (μ-XRF) mapping studies indicated that As was heterogeneously distributed and was mainly associated with iron in the soil. X-ray absorption near edge structure (XANES), micro-X-ray absorption near edge structure (μ-XANES) and X-ray photoelectron spectroscopy (XPS) analyses revealed that the primary speciation of As in the soil is As(V). These results further suggested that, when As(V) was introduced into the anoxic soil, the rapid coprecipitation of As(V) with ferric/ferrous ion prevented its reduction to As(III), and was the main mechanism controlling the immobilization of As. This research could improve the current understanding of soil As chemistry in paddy and wetland soils. Copyright © 2014 Elsevier B.V. All rights reserved.

  12. Composition analysis of a polymer electrolyte membrane fuel cell microporous layer using scanning transmission X-ray microscopy and near edge X-ray absorption fine structure analysis

    NASA Astrophysics Data System (ADS)

    George, Michael G.; Wang, Jian; Banerjee, Rupak; Bazylak, Aimy

    2016-03-01

    The novel application of scanning transmission X-ray microscopy (STXM) to the microporous layer (MPL) of a polymer electrolyte membrane fuel cell is investigated. A spatially resolved chemical component distribution map is obtained for the MPL of a commercially available SGL 25 BC sample. This is achieved with near edge X-ray absorption fine structure spectroscopic analysis. Prior to analysis the sample is embedded in non-reactive epoxy and ultra-microtomed to a thickness of 100 nm. Polytetrafluoroethylene (PTFE), carbon particle agglomerates, and supporting epoxy resin distributions are identified and reconstructed for a scanning area of 6 μm × 6 μm. It is observed that the spatial distribution of PTFE is strongly correlated to the carbon particle agglomerations. Additionally, agglomerate structures of PTFE are identified, possibly indicating the presence of a unique mesostructure in the MPL. STXM analysis is presented as a useful technique for the investigation of chemical species distributions in the MPL.

  13. PKP Waveform Complexity and Its Implications to Fine Structure Near the Edge of African Large Low Shear Velocity Province

    NASA Astrophysics Data System (ADS)

    Song, Teh-Ru Alex; Tanaka, Satoru; Takeuchi, Nozomu

    2010-05-01

    and receiver-side structure do not play a predominant role in generating these anomalous PKPab waveforms. We then look into structural anomaly near the core-mantle-boundary (CMB) since PKPab grazes the CMB at a very shallow angle and it can effectively interact with it and possibly produce anomalous PKPab waveforms. We first explore 1-D model space by introducing velocity anomaly directly above the CMB, with a velocity perturbation up to a few tens of percents in S wave velocity and P wave velocity. We calculate synthetics up to 2 Hz by Direct Solution Method (DSM) and Reflectivity Method to examine waveform anomaly at long period band (0.01-0.2 Hz) as well as short-period band (0.5-2 Hz). Our preliminary result indicates that the model with a thin (~ 15 km) ultra-low velocity zone (ULVZ, 30% reduction in P wave and S wave velocity) is capable of reproducing characteristics of these anomalous PKPab waveforms at both frequency bands. The pierce points of PKPab in the source side at CMB are near the southeast Indian Ocean where S wave velocity is only slightly faster than PREM. On the other hand, the pierce points in the receiver side are at the eastern edge of the African Large Low Shear Velocity Province (LLSVP). One interesting feature of our ULVZ model is that dlnVs/dlnVp is about 1, which is different from most ULVZ models where dlnVs/dlnVp is about 3.

  14. Correlation of the oxidation state of cerium in sol-gel glasses as a function of thermal treatment via optical spectroscopy and XANES studies.

    PubMed

    Assefa, Zerihun; Haire, R G; Caulder, D L; Shuh, D K

    2004-07-01

    Sol-gel glass matrices containing lanthanides have numerous technological applications and their formation involves several chemical facets. In the case of cerium, its ability to exist in two different oxidation states or in mixed valence state provides additional complexities for the sol-gel process. The oxidation state of cerium present during different facets of preparation of sol-gel glasses, and also as a function of the starting oxidation state of cerium added, were studied both by optical spectroscopy and X-ray absorption near-edge structures (XANES). The findings acquired by each approach were compared. The primary focus was on the redox chemistries associated with sample preparation, gelation, and thermal treatment. When Ce3+ is introduced into the starting sols, the trivalent state normally prevails in the wet and room temperature-dried gels. Heating in air at >100 degrees C can generate a light yellow coloration with partial oxidation to the tetravalent state. Above 200 degrees C and up to approximately 1000 degrees C, cerium is oxidized to its tetravalent state. In contrast, when tetravalent cerium is introduced into the sol, both the wet and room temperature-dried gels lose the yellow-brown color of the initial ceric ammonium nitrate solution. When the sol-gel is heated to 110 degrees C it turns yellowish as the cerium tends to be re-oxidized. The yellow color is believed to represent the effect of oxidation and oligomerization of the cerium-silanol units in the matrix. The luminescence properties are also affected by these changes, the details of which are reported herein.

  15. A Study of Ziegler–Natta Propylene Polymerization Catalysts by Spectroscopic Methods

    PubMed Central

    Tkachenko, Olga P.; Kucherov, Alexey V.; Kustov, Leonid M.; Virkkunen, Ville; Leinonen, Timo; Denifl, Peter

    2017-01-01

    Ziegler–Natta polymerization catalysts were characterized by a complex of surface- and bulk-sensitive methods (DRIFTS, XPS, ESR, and XAS = XANES + EXAFS). A diffuse-reflectance Fourier-transform IR spectroscopy (DRIFTS) study showed the presence of strong Lewis acid sites in different concentrations and absence of strong basic sites in the polymerization catalysts. X-ray photoelectron spectroscopy (XPS), electron-spin resonance (ESR), and (X-ray absorption near-edge structure (XANES) analysis revealed the presence of Ti4+, Ti3+, Ti2+, and Ti1+ species in the surface layers and in the bulk of catalysts. The samples under study differ drastically in terms of the number of ESR-visible paramagnetic sites. The EXAFS study shows the presence of a Cl atom as a nearest neighbor of the absorbing Ti atom. PMID:28772850

  16. Tuning the Selectivity of Single-Site Supported Metal Catalysts with Ionic Liquids

    DOE PAGES

    Babucci, Melike; Fang, Chia -Yu; Hoffman, Adam S.; ...

    2017-09-11

    1,3-Dialkylimidazolium ionic liquid coatings act as electron donors, increasing the selectivity for partial hydrogenation of 1,3-butadiene catalyzed by iridium complexes supported on high-surface-area γ-Al 2O 3. High-energy-resolution fluorescence detection X-ray absorption near-edge structure (HERFD XANES) measurements quantify the electron donation and are correlated with the catalytic activity and selectivity. Furthermore, the results demonstrate broad opportunities to tune electronic environments and catalytic properties of atomically dispersed supported metal catalysts.

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

    Babucci, Melike; Fang, Chia -Yu; Hoffman, Adam S.

    1,3-Dialkylimidazolium ionic liquid coatings act as electron donors, increasing the selectivity for partial hydrogenation of 1,3-butadiene catalyzed by iridium complexes supported on high-surface-area γ-Al 2O 3. High-energy-resolution fluorescence detection X-ray absorption near-edge structure (HERFD XANES) measurements quantify the electron donation and are correlated with the catalytic activity and selectivity. Furthermore, the results demonstrate broad opportunities to tune electronic environments and catalytic properties of atomically dispersed supported metal catalysts.

  18. Wrinkling reduction of membrane structure by trimming edges

    NASA Astrophysics Data System (ADS)

    Liu, Mingjun; Huang, Jin; Liu, Mingyue

    2017-05-01

    Thin membranes have negligible bending stiffness, compressive stresses inevitably lead to wrinkling. Therefore, it is important to keep the surface of membrane structures flat in order to guarantee high precision. Edge-trimming is an effective method to passively diminish wrinkles, however a key difficulty in this process is the determination of the optimal trimming level. In this paper, regular polygonal membrane structures subjected to equal radial forces were analyzed, and a new stress field distribution model for arc-edge square membrane structure was proposed to predict the optimal trimming level. This model is simple and applicable to any polygonal membrane structures. Comparison among the results of the finite element analysis, and the experimental and analytical results showed that the proposed model accurately described the stress field distribution and guaranteed that there are no wrinkles appear inside the effective inscribed circle region for the optimal trimming level.

  19. Ab initio X-ray absorption modeling of Cu-SAPO-34: Characterization of Cu exchange sites under different conditions

    DOE PAGES

    Zhang, Renqin; Helling, Kathy; McEwen, Jean-Sabin

    2016-03-29

    Copper-exchanged SAPO-34 (Cu-SAPO-34) provides excellent catalytic activity and hydrothermal sta-bility in the selective catalytic reduction (SCR) of NOxby using NH3as a reductant. Here, we find that the6-membered ring (6MR) site is the most energetically favorable for a Cu+ion while the 8-memberedring (8MR) sites are less favorable by about 0.5 eV with respect to the 6MR site in Cu-SAPO-34. Uponadsorption of molecular species (H2O, O, OH, O2), the energy differences between Cu in the 8MR and 6MRsites decreases and almost disappears. Further, a thermodynamic phase diagram study shows that a Cu+ion bound to a single H2O molecule is the most stablemore » species at low oxygen potential values while aCu2+ion bound to 2 OH species is more stable when the oxygen chemical potential is sufficiently high. Bycomparing Cu K-edge XANES between Cu-SSZ-13 and Cu-SAPO-34 with Cu in different oxidation states,we conclude that it is difficult to differentiate the simulated XANES of Cu in these structures at a givenoxidation state. By studying the Cu K-edge XANES of several favorable structures in Cu-SAPO-34 in thepresence of adspecies, the simulated XANES results capture the real trend of the edge shift with oxidationstate and gives new insights into the experimentally determined XANES of Cu-SAPO-34 obtained understandard SCR conditions.« less

  20. The competitive growth of cubic domains in Ti(1-x)AlxN films studied by diffraction anomalous near-edge structure spectroscopy.

    PubMed

    Pinot, Y; Tuilier, M-H; Pac, M-J; Rousselot, C; Thiaudière, D

    2015-11-01

    Titanium and aluminium nitride films deposited by magnetron sputtering generally grow as columnar domains made of oriented nanocrystallites with cubic or hexagonal symmetry depending on Al content, which are embedded in more disordered grain boundaries. The substitution of Al atoms for Ti in the cubic lattice of the films improves their resistance to wear and oxidation, allowing their use as protective coatings. Ti K-edge X-ray absorption spectroscopy, which probes both crystallized and more disordered grain boundaries, and X-ray diffraction anomalous fine structure, which is sensitive to short- and long-range order within a given crystallized domain, are carried out on a set of Ti(1-x)AlxN films deposited by magnetron sputtering on Si substrates. Attention is paid to the shape of the pre-edge region, which is sensitive to the symmetry of the site occupied by Ti atoms, either octahedral in face-centred-cubic Ti-rich (TiN, Ti0.54Al0.46N) samples or tetrahedral in hexagonal-close-packed Al-rich (Ti0.32Al0.68N) films. In order to obain information on the titanium environment in the well crystallized areas, subtraction of the smooth part of the energy-dependent structure factor for the Bragg reflections is applied to the pre-edge region of the diffraction anomalous data in order to restore their spectroscopic appearance. A flat pre-edge is related to the typical octahedral environment of Ti atoms for cubic reflections. The difference observed between pre-edge spectra associated with face-centred-cubic 200 and 111 Bragg reflections of Ti0.54Al0.46N is assigned to Ti enrichment of 111 large well ordered domains compared with the more disordered 200 ones. The sharp peak observed in the spectrum recorded from the hexagonal 002 peak of Ti0.32Al0.68N can be regarded as a standard for the pure tetrahedral Ti environment in hexagonal-close-packed nitride.

  1. Near-edge X-ray refraction fine structure microscopy

    DOE PAGES

    Farmand, Maryam; Celestre, Richard; Denes, Peter; ...

    2017-02-06

    We demonstrate a method for obtaining increased spatial resolution and specificity in nanoscale chemical composition maps through the use of full refractive reference spectra in soft x-ray spectro-microscopy. Using soft x-ray ptychography, we measure both the absorption and refraction of x-rays through pristine reference materials as a function of photon energy and use these reference spectra as the basis for decomposing spatially resolved spectra from a heterogeneous sample, thereby quantifying the composition at high resolution. While conventional instruments are limited to absorption contrast, our novel refraction based method takes advantage of the strongly energy dependent scattering cross-section and can seemore » nearly five-fold improved spatial resolution on resonance.« less

  2. Structure of assemblies of metal nanowires in mesoporous alumina membranes studied by EXAFS, XANES, X-ray diffraction and SAXS.

    PubMed

    Benfield, Robert E; Grandjean, Didier; Dore, John C; Esfahanian, Hamid; Wu, Zhonghua; Kröll, Michael; Geerkens, Marcus; Schmid, Günter

    2004-01-01

    Mesoporous alumina membranes ("anodic aluminium oxide", or "AAO") are made by anodic oxidation of aluminium metal. These membranes contain hexagonal arrays of parallel non-intersecting cylindrical pores perpendicular to the membrane surface. By varying the anodisation voltage, the pore diameters are controllable within the range 5-250 nm. We have used AAO membranes as templates for the electrochemical deposition of metals within the pores to produce nanowires. These represent assemblies of one-dimensional quantum wires with prospective applications in electronic, optoelectronic and magnetic devices. Detailed characterisation of the structures of these nanowire assemblies on a variety of length scales is essential to understand their physical properties and evaluate their possible applications. We have used EXAFS, XANES, WAXS, high energy X-ray diffraction and SAXS to study their structure and bonding. In this paper we report the results of our studies of four different nanowire systems supported in AAO membranes. These are the ferromagnetic metals iron and cobalt, the superconducting metal tin, and the semiconductor gallium nitride. Iron nanowires in pores of diameter over the range 12 nm-72 nm are structurally very similar to bcc bulk iron. They have a strong preferred orientation within the alumina pores. Their XANES shows significant differences from that of bulk iron, showing that the electronic structure of the iron nanowires depends systematically on their diameter. Cobalt nanowires are composed of a mixture of hcp and fcc phases, but the ratio of the two phases does not depend in a simple way on the pore diameter or preparation conditions. In bulk cobalt, the fcc beta-phase is normally stable only at high temperatures. Strong preferred orientation of the c-axis in the pores was found. Tin nanowires in alumina membranes with pores diameters between 12 nm and 72 nm have a tetragonal beta-structure at ambient temperature and also at 80 K. Magnetic

  3. Gyrokinetic simulations of DIII-D near-edge L-mode plasmas

    NASA Astrophysics Data System (ADS)

    Neiser, Tom; Jenko, Frank; Carter, Troy; Schmitz, Lothar; Merlo, Gabriele; Told, Daniel; Banon Navarro, Alejandro; McKee, George; Yan, Zheng

    2017-10-01

    In order to understand the L-H transition, a good understanding of the L-mode edge region is necessary. We perform nonlinear gyrokinetic simulations of a DIII-D L-mode discharge with the GENE code in the near-edge, which we define as ρtor >= 0.8 . At ρ = 0.9 , ion-scale simulations reproduce experimental heat fluxes within the uncertainty of the experiment. At ρ = 0 . 8 , electron-scale simulations reproduce the experimental electron heat flux while ion-scale simulations do not reproduce the respective ion heat flux due to a strong poloidal zonal flow. However, we reproduce both electron and ion heat fluxes by increasing the local ion temperature gradient by 80 % . Local fitting to the CER data in the domain 0.7 <= ρ <= 0.9 is compatible with such an increase in ion temperature gradient within the error bars. Ongoing multi-scale simulations are investigating whether radial electron streamers could dampen the poloidal zonal flows at ρ = 0.8 and increase the radial ion-scale flux. Supported by U.S. DOE under Contract Numbers DE-FG02-08ER54984, DE-FC02-04ER54698, and DE-AC02-05CH11231.

  4. THE DISTRIBUTION, SOLID-PHASE SPECIATION, AND DESORPTION/DISSOLUTION OF AS IN IRON-BASED DRINKING WATER TREATMENT MEDIA 1

    EPA Science Inventory

    Arsenic concentrations (Total Recoverable As by EPA Method 3051, soluble, Toxicity Characteristic Leaching Procedure extractable) and solid-phase speciation (by X-ray Absorption Near-Edge Spectroscopy-XANES) were assessed as a function of depth through Fe-media beds for two comme...

  5. THE DISTRIBUTION, SOLID-PHASE SPECIATION, AND DESORPTION/DISSOLUTION OF AS IN IRON-BASED DRINKING WATER TREATMENT MEDIA - JOURNAL

    EPA Science Inventory

    Arsenic concentrations (Total Recoverable As by EPA Method 3051, soluble, Toxicity Characteristic Leaching Procedure extractable) and solid-phase speciation (by X-ray Absorption Near-Edge Spectroscopy-XANES) were assessed as a function of depth through Fe-media beds for two comme...

  6. Evolution of Eu valence and superconductivity in layered Eu0.5La0.5FBiS2 -xSex system

    NASA Astrophysics Data System (ADS)

    Mizuguchi, Y.; Paris, E.; Wakita, T.; Jinno, G.; Puri, A.; Terashima, K.; Joseph, B.; Miura, O.; Yokoya, T.; Saini, N. L.

    2017-02-01

    We have studied the effect of Se substitution on Eu valence in a layered Eu0.5La0.5FBiS2 -xSex superconductor using a combined analysis of x-ray absorption near-edge structure (XANES) and x-ray photoelectron spectroscopy (XPS) measurements. Eu L3-edge XANES spectra reveal that Eu is in the mixed valence state with coexisting Eu2 + and Eu3 +. The average Eu valence decreases sharply from ˜2.3 for x =0.0 to ˜2.1 for x =0.4 . Consistently, Eu 3 d XPS shows a clear decrease in the average valence by Se substitution. Bi 4 f XPS indicates that effective charge carriers in the BiCh2 (Ch = S, Se) layers are slightly increased by Se substitution. On the basis of the present results it has been discussed that the metallic character induced by Se substitution in Eu0.5La0.5FBiS2 -xSex is likely to be due to increased in-plane orbital overlap driven by reduced in-plane disorder that affects the carrier mobility.

  7. Ground-state wave function of plutonium in PuSb as determined via x-ray magnetic circular dichroism

    DOE PAGES

    Janoschek, M.; Haskel, D.; Fernandez-Rodriguez, J.; ...

    2015-01-14

    Measurements of x-ray magnetic circular dichroism (XMCD) and x-ray absorption near-edge structure (XANES) spectroscopy at the Pu M₄,₅ edges of the ferromagnet PuSb are reported. Using bulk magnetization measurements and a sum rule analysis of the XMCD spectra, we determine the individual orbital [μ L = 2.8(1)μ B/Pu] and spin moments [μ S = –2.0(1)μ B/Pu] of the Pu 5f electrons for the first time. Atomic multiplet calculations of the XMCD and XANES spectra reproduce well the experimental data and are consistent with the experimental value of the spin moment. These measurements of L z and S z are inmore » excellent agreement with the values that have been extracted from neutron magnetic form factor measurements, and confirm the local character of the 5f electrons in PuSb. We demonstrate that a split M₅ as well as a narrow M₄ XMCD signal may serve as a signature of 5f electron localization in actinide compounds.« less

  8. Electronic Structures of Silicene Nanoribbons: Two-Edge-Chemistry Modification and First-Principles Study.

    PubMed

    Yao, Yin; Liu, Anping; Bai, Jianhui; Zhang, Xuanmei; Wang, Rui

    2016-12-01

    In this paper, we investigate the structural and electronic properties of zigzag silicene nanoribbons (ZSiNRs) with edge-chemistry modified by H, F, OH, and O, using the ab initio density functional theory method and local spin-density approximation. Three kinds of spin polarized configurations are considered: nonspin polarization (NM), ferromagnetic spin coupling for all electrons (FM), ferromagnetic ordering along each edge, and antiparallel spin orientation between the two edges (AFM). The H, F, and OH groups modified 8-ZSiNRs have the AFM ground state. The directly edge oxidized (O1) ZSiNRs yield the same energy and band structure for NM, FM, and AFM configurations, owning to the same s p (2) hybridization. And replacing the Si atoms on the two edges with O atoms (O2) yields FM ground state. The edge-chemistry-modified ZSiNRs all exhibit metallic band structures. And the modifications introduce special edge state strongly localized at the Si atoms in the edge, except for the O1 form. The modification of the zigzag edges of silicene nanoribbons is a key issue to apply the silicene into the field effect transistors (FETs) and gives more necessity to better understand the experimental findings.

  9. Sulfur Speciation in Biochars by Very High Resolution Benchtop Kα X-ray Emission Spectroscopy.

    PubMed

    Holden, William M; Seidler, Gerald T; Cheah, Singfoong

    2018-05-30

    The analytical chemistry of sulfur-containing materials poses substantial technical challenges, especially due to the limitations of 33 S NMR and the time-intensive preparations required for wet-chemistry analyses. A number of prior studies have found that synchrotron-based X-ray absorption near edge structure (XANES) measurements can give detailed speciation of sulfur chemistry in such cases. However, due to the obvious access limitations, synchrotron XANES of sulfur cannot be part of routine analytical practice across the chemical sciences community. Here, in a study of the sulfur chemistry in biochars, we compare and contrast the chemical inferences available from synchrotron XANES with that given by benchtop, extremely high resolution wavelength-dispersive X-ray fluorescence (WD-XRF) spectroscopy, also often called X-ray emission spectroscopy (XES). While the XANES spectra have higher total information content, often giving differentiation between different moieties having the same oxidation state, the lower sensitivity of the S Kα XES to coordination and local structure provides pragmatic benefit for the more limited goal of quantifying the S oxidation state distribution. Within that constrained metric, we find good agreement between the two methods. As the sulfur concentrations were as low as 150 ppm, these measurements provide proof-of-principle for characterization of the sulfur chemistry of biochars and potential applications to other areas such as soils, batteries, catalysts, and fossil fuels and their combustion products.

  10. Fluid-structure interaction analysis and lifetime estimation of a natural gas pipeline centrifugal compressor under near-choke and near-surge conditions

    NASA Astrophysics Data System (ADS)

    Ju, Yaping; Liu, Hui; Yao, Ziyun; Xing, Peng; Zhang, Chuhua

    2015-11-01

    Up to present, there have been no studies concerning the application of fluid-structure interaction (FSI) analysis to the lifetime estimation of multi-stage centrifugal compressors under dangerous unsteady aerodynamic excitations. In this paper, computational fluid dynamics (CFD) simulations of a three-stage natural gas pipeline centrifugal compressor are performed under near-choke and near-surge conditions, and the unsteady aerodynamic pressure acting on impeller blades are obtained. Then computational structural dynamics (CSD) analysis is conducted through a one-way coupling FSI model to predict alternating stresses in impeller blades. Finally, the compressor lifetime is estimated using the nominal stress approach. The FSI results show that the impellers of latter stages suffer larger fluctuation stresses but smaller mean stresses than those at preceding stages under near-choke and near-surge conditions. The most dangerous position in the compressor is found to be located near the leading edge of the last-stage impeller blade. Compressor lifetime estimation shows that the investigated compressor can run up to 102.7 h under the near-choke condition and 200.2 h under the near-surge condition. This study is expected to provide a scientific guidance for the operation safety of natural gas pipeline centrifugal compressors.

  11. Combining state-of-the-art experiment and ab initio calculations for a better understanding of the interplay between valence, magnetism and structure in Eu compounds at high pressure

    DOE PAGES

    Souza-Neto, N. M.; Haskel, D.; dos Reis, R. D.; ...

    2016-07-26

    Here, we describe how first principle calculations can play a key role in the interpretation of X-ray absorption near-edge structure (XANES) and X-ray magnetic circular dichroism (XMCD) spectra for a better understanding of emergent phenomena in condensed matter physics at high applied pressure. Eu compounds are used as case study to illustrate the advantages of this methodology, ranging from studies of electronic charge transfer probed by quadrupolar and dipolar contributions, to accurately determining electronic valence, and to inform about the influence of pressure on RKKY interactions and magnetism. This description should help advance studies where the pressure dependence of XANESmore » and XMCD data must be tackled with the support of theoretical calculations for a proper understanding of the electronic properties of materials.« less

  12. Electronic Structure of Manganese Corroles Revisited: X-ray Structures, Optical and X-ray Absorption Spectroscopies, and Electrochemistry as Probes of Ligand Noninnocence

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

    Ganguly, Sumit; MCormick, Laura J.; Conradie, Jeanet

    Presented herein is a detailed multitechnique investigation of ligand noninnocence in S = 3/2 manganese corrole derivatives at the formal Mn IV oxidation state. The Soret maxima of Mn[T pXPC]Cl (T pXPC = meso-tris( p-X-phenyl)corrole, where X = CF 3, H, Me, and OMe) were found to red-shift over a range of 37 nm with increasing electron-donating character of X. For Mn[T pXPC]Ph, in contrast, the complex Soret envelopes were found to be largely independent of X. These observations suggested a noninnocent corrole •2–-like ligand for the MnCl complexes and an innocent corrole 3– ligand for the MnPh complexes. Single-crystalmore » X-ray structures of three Mn[T pXPC]Cl complexes revealed skeletal bond-length alternations indicative of a noninnocent corrole, while no such alternation was observed for Mn[T pOMePC]Ph. B3LYP density functional theory (DFT) calculations on Mn[TPC]Cl yielded strong spatial separation of the α and β spin densities, consistent with an antiferromagnetically coupled Mn III-corrole •2– description. By comparison, relatively little spatial separation of the α and β spin densities was found for Mn[TPC]Ph, consistent with an essentially Mn IV-corrole 3– description. X-ray absorption of near-edge spectroscopy (XANES) revealed a moderate blue shift of 0.6 eV for the Mn K-pre-edge of Mn[T pCF 3PC]Ph and a striking enhancement of the pre-edge intensity, relative to Mn[T pCF 3PC]Cl, consistent with a more oxidized, i.e., Mn IV, center in Mn[T pCF 3PC]Ph. Time-dependent DFT calculations indicated that the enhanced intensity of the Mn K-pre-edge of Mn[T pCF 3PC]Ph results from the extra 3d z2 hole, which mixes strongly with the Mn 4p z orbital. Combined with similar results on Fe[TPC]Cl and Fe[TPC]Ph, the present study underscores the considerable potential of metal K-edge XANES in probing ligand noninnocence in first-row transition-metal corroles. As a result, cyclic voltammetry measurements revealed highly negative first reduction

  13. Electronic Structure of Manganese Corroles Revisited: X-ray Structures, Optical and X-ray Absorption Spectroscopies, and Electrochemistry as Probes of Ligand Noninnocence

    DOE PAGES

    Ganguly, Sumit; MCormick, Laura J.; Conradie, Jeanet; ...

    2018-06-06

    Presented herein is a detailed multitechnique investigation of ligand noninnocence in S = 3/2 manganese corrole derivatives at the formal Mn IV oxidation state. The Soret maxima of Mn[T pXPC]Cl (T pXPC = meso-tris( p-X-phenyl)corrole, where X = CF 3, H, Me, and OMe) were found to red-shift over a range of 37 nm with increasing electron-donating character of X. For Mn[T pXPC]Ph, in contrast, the complex Soret envelopes were found to be largely independent of X. These observations suggested a noninnocent corrole •2–-like ligand for the MnCl complexes and an innocent corrole 3– ligand for the MnPh complexes. Single-crystalmore » X-ray structures of three Mn[T pXPC]Cl complexes revealed skeletal bond-length alternations indicative of a noninnocent corrole, while no such alternation was observed for Mn[T pOMePC]Ph. B3LYP density functional theory (DFT) calculations on Mn[TPC]Cl yielded strong spatial separation of the α and β spin densities, consistent with an antiferromagnetically coupled Mn III-corrole •2– description. By comparison, relatively little spatial separation of the α and β spin densities was found for Mn[TPC]Ph, consistent with an essentially Mn IV-corrole 3– description. X-ray absorption of near-edge spectroscopy (XANES) revealed a moderate blue shift of 0.6 eV for the Mn K-pre-edge of Mn[T pCF 3PC]Ph and a striking enhancement of the pre-edge intensity, relative to Mn[T pCF 3PC]Cl, consistent with a more oxidized, i.e., Mn IV, center in Mn[T pCF 3PC]Ph. Time-dependent DFT calculations indicated that the enhanced intensity of the Mn K-pre-edge of Mn[T pCF 3PC]Ph results from the extra 3d z2 hole, which mixes strongly with the Mn 4p z orbital. Combined with similar results on Fe[TPC]Cl and Fe[TPC]Ph, the present study underscores the considerable potential of metal K-edge XANES in probing ligand noninnocence in first-row transition-metal corroles. As a result, cyclic voltammetry measurements revealed highly negative first reduction

  14. Soft edges--organizational structure in dental education.

    PubMed

    Chambers, D W

    1995-03-01

    There is no one best organizational structure for dental schools or for their major subunits. The classical alternatives of functional and divisional organization are discussed in light of the rule that follows function, and the advantages and disadvantages of each are presented. Newer models--decentralization, matrix, and heterarchy--show how features of functional and divisional structure can be blended. Virtual organizations, systems theory, and networks are also considered as new expressions of classical structures. The principle of suboptimization (soft edges) is presented.

  15. High Confinement Mode and Edge Localized Mode Characteristics in a Near-Unity Aspect Ratio Tokamak.

    PubMed

    Thome, K E; Bongard, M W; Barr, J L; Bodner, G M; Burke, M G; Fonck, R J; Kriete, D M; Perry, J M; Schlossberg, D J

    2016-04-29

    Tokamak experiments at near-unity aspect ratio A≲1.2 offer new insights into the self-organized H-mode plasma confinement regime. In contrast to conventional A∼3 plasmas, the L-H power threshold P_{LH} is ∼15× higher than scaling predictions, and it is insensitive to magnetic topology, consistent with modeling. Edge localized mode (ELM) instabilities shift to lower toroidal mode numbers as A decreases. These ultralow-A operations enable heretofore inaccessible J_{edge}(R,t) measurements through an ELM that show a complex multimodal collapse and the ejection of a current-carrying filament.

  16. High confinement mode and edge localized mode characteristics in a near-unity aspect ratio tokamak

    DOE PAGES

    Thome, Kathreen E.; Bongard, Michael W.; Barr, Jayson L.; ...

    2016-04-27

    Tokamak experiments at near-unity aspect ratio A ≲ 1.2 offer new insights into the self-organized H-mode plasma confinement regime. In contrast to conventional A ~ 3 plasmas, the L–H power threshold P LH is ~15× higher than scaling predictions, and it is insensitive to magnetic topology, consistent with modeling. Edge localized mode (ELM) instabilities shift to lower toroidal mode numbers as A decreases. Furthermore, these ultralow-A operations enable heretofore inaccessible J edge(R,t) measurements through an ELM that show a complex multimodal collapse and the ejection of a current-carrying filament.

  17. Sulfonates: A novel class of organic sulfur compounds in marine sediments

    NASA Astrophysics Data System (ADS)

    Vairavamurthy, Appathurai; Zhou, Weiqing; Eglinton, Timothy; Manowitz, Bernard

    1994-11-01

    X-ray absorption near-edge structure spectroscopy (XANES) used to measure sulfur speciation in a variety of organic-rich marine sediments has established sulfonates as a novel and major component of sedimentary organic sulfur. The origins of sulfonates in sediments are not clear, although both biological and geochemical mechanisms are possible. The accumulation of oxidized sulfonate sulfur in reducing marine sediments was not known previously; hence, a new perspective in sulfur geochemistry is established. The biogeochemical implications of the presence of sulfonates in marine sediments are discussed.

  18. Forests on the edge: Microenvironmental drivers of carbon cycle response to edge effects

    NASA Astrophysics Data System (ADS)

    Reinmann, A.; Hutyra, L.; Smith, I. A.; Thompson, J.

    2017-12-01

    Twenty percent of the world's forest is within 100 m of a forest edge, but much of our understanding of forest carbon (C) cycling comes from large, intact ecosystems, which creates an important mismatch between the landscapes we study and those we aim to characterize. The temperate broadleaf forest is the most heavily fragmented forest biome in the world and its growth and carbon storage responses to forest edge effects appear to be the opposite of those in the tropical and boreal regions. We used field measurements to quantify the drivers of temperate forest C cycling response to edge effects, characterizing vegetative growth, respiration, and forest structure. We find large gradients in air and soil temperature from the forest interior to edge (up to 4 and 10° C, respectively) and the magnitude of this gradient is inversely correlated to the size of the forest edge growth enhancement. Further, leaf area index increases with proximity to the forest edge. While we also find increases in soil respiration between the forest interior and edge, this flux is small relative to aboveground growth enhancement near the edge. These findings represent an important advancement in our understanding of forest C cycle response to edge effects and will greatly improve our capacity to constrain biogenic C fluxes in fragmented and heterogeneous landscapes.

  19. XAS Studies of Arsenic in the Environment

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

    Charnock, J. M.; School of Earth, Atmospheric and Environmental Sciences, University of Manchester, Oxford Road, Manchester, M13 9PL; Polya, D. A.

    2007-02-02

    Arsenic is present in low concentrations in much of the Earth's crust and changes in its speciation are vital to understanding its transport and toxicity in the environment. We have used X-ray absorption spectroscopy to investigate the coordination sites of arsenic in a wide variety of samples, including soil and earthworm tissues from arsenic-contaminated land, and human hair and nail samples from people exposed to arsenic in Cambodia. Our results confirm the effectiveness of using X-ray absorption near edge structure (XANES) and X-ray absorption fine structure (EXAFS) spectroscopy to determine speciation changes in environmental samples.

  20. Probing the Electronic Structure of - and Electron-Doped High-Temperature Superconductors with Photoemission and X-Ray Absorption Spectroscopies

    NASA Astrophysics Data System (ADS)

    Lederman, Eli R.

    1990-01-01

    The electronic structures of hole- and electron -doped high temperature superconductors have been probed using x-ray absorption near-edge spectroscopy (XANES) and photoelectron emission spectroscopy (PES). These measurements have been performed on RBa_2Cu _3O_{rm 7-y} , La_{rm 2-x}Sr _{rm x}CuO _4 and Ln_{rm 2 -x}Ce_{rm x} CuO_{rm 4} for R = Y, Eu and Ln = Nd, Pr and Sm. The parameters x and y have been varied to include a range of hole and electron carrier densities and the undoped parent compounds. Previous XANES and PES results have indicated that unoccupied states of O 2p character can be associated with the carriers in the materials RBa_2 Cu_3O_{ rm 7-y} and La_{ rm 2-x}Sr_{rm x}CuO_4 and that the density of holes increases with O and Sr content, respectively. Conduction was hole-based in all known high-T_{ rm c} cuprates until the recent discovery of superconductivity in Ln_{rm 2-x}Ce_{rm x} CuO_4. Hall coefficient measurements have suggested that the carriers in this system are electrons added with Ce doping. It has been anticipated that these electron-doped materials will provide an important test for models of high temperature superconductivity. PES measurements are presented that show significant Cu 3d character in the valence band of these electron-based materials, but that the Cu^{2+} /Cu^{1+} ratio is unchanged by the level of Ce doping, indicating that doped electrons are itinerant rather than highly correlated. Resonant photoemission from the valence band indicates the presence of unoccupied O 2p states, but these holes are less abundant than in the hole-doped materials. Measurements of XANES at the O 1s edge suggest that unoccupied states of O 2p character in the electron -doped materials are not related to conduction in a simple way. The density of these holes is shown to decrease upon Ce doping and the process of reduction, despite the fact that both are necessary of superconductivity. Furthermore, whereas the O 2p holes are at E_{rm F} in the

  1. High spin state driven magnetism and thermoelectricity in Mn doped topological insulator Bi2Se3

    NASA Astrophysics Data System (ADS)

    Maurya, V. K.; Dong, C. L.; Chen, C. L.; Asokan, K.; Patnaik, S.

    2018-06-01

    We report on the synthesis, and structural - magnetic characterizations of Mn doped Bi2Se3 towards achieving a magnetically doped topological insulator. High quality single crystals of MnxBi2-xSe3 (x = 0, 0.03, 0.05, 0.1) are grown and analysed by X-ray diffraction (XRD), Low Energy Electron Diffraction (LEED), Scanning electron microscopy (SEM), and X-ray absorption near-edge structure spectroscopy (XANES). Magnetic properties of these samples under ZFC-FC protocol and isothermal magnetization confirm ferromagnetic correlation above x = 0.03 value. XANES measurements confirm that the dopant Mn is in Mn2+ state. This is further reconfirmed to be in high spin state by fitting magnetic data with Brillouin function for J = 5/2. Both Hall and Seebeck measurements indicate a sign change of charge carriers above x = 0.03 value of Mn doping. We propose Mn doped Bi2Se3 to be a potential candidate for electromagnetic and thermoelectric device applications involving topological surface states.

  2. Strong excitonic interactions in the oxygen K-edge of perovskite oxides.

    PubMed

    Tomita, Kota; Miyata, Tomohiro; Olovsson, Weine; Mizoguchi, Teruyasu

    2017-07-01

    Excitonic interactions of the oxygen K-edge electron energy-loss near-edge structure (ELNES) of perovskite oxides, CaTiO 3 , SrTiO 3 , and BaTiO 3 , together with reference oxides, MgO, CaO, SrO, BaO, and TiO 2 , were investigated using a first-principles Bethe-Salpeter equation calculation. Although the transition energy of oxygen K-edge is high, strong excitonic interactions were present in the oxygen K-edge ELNES of the perovskite oxides, whereas the excitonic interactions were negligible in the oxygen K-edge ELNES of the reference compounds. Detailed investigation of the electronic structure suggests that the strong excitonic interaction in the oxygen K-edge ELNES of the perovskite oxides is caused by the directionally confined, low-dimensional electronic structure at the Ti-O-Ti bonds. Copyright © 2016 Elsevier B.V. All rights reserved.

  3. A Theory of Oscillating Edge Flames

    NASA Technical Reports Server (NTRS)

    Buckmaster, J.; Zhang, Yi

    1999-01-01

    It has been known for some years that when a near-limit flame spreads over a liquid pool of fuel, the edge of the flame can oscillate relative to a frame moving with the mean speed. Each period of oscillation is characterized by long intervals of modest motion during which the edge gases radiate like those of a diffusion flame, punctuated by bursts of rapid advance during which the edge gases radiate like those in a deflagration. Substantial resources have been brought to bear on this issue within the microgravity program, both experimental and numerical. It is also known that when a near-asphyxiated candle-flame burns at zero gravity, the edge of the (hemispherical) flame can oscillate violently prior to extinction. Thus a web-surfer, turning to the NASA web-site at http://microgravity.msfc.nasa.gov, and following the trail combustion science/experiments/experimental results/candle flame, will find photographs and a description of candle burning experiments carried out on board both the Space-shuttle and the Russian space station Mir. A brief report can also be found in the proceedings of the Fourth Workshop. And recently, in a third microgravity program, the leading edge of the flame supported by injection of ethane through the porous surface of a plate over which air is blown has been found to oscillate when conditions are close to blow-off. A number of important points can be made with respect to these observations: It is the edge itself which oscillates, advancing and retreating, not the diffusion flame that trails behind the edge; oscillations only occur under near limit conditions; in each case the Lewis number of the fuel is significantly larger than 1; and because of the edge curvature, the heat losses from the reacting edge structure are larger than those from the trailing diffusion flame. We propose a general theory for these oscillations, invoking Occam's 'Law of Parsimony' in an expanded form, to wit: The same mechanism is responsible for the

  4. Revealing mechanism responsible for structural reversibility of single-crystal VO 2 nanorods upon lithiation/delithiation

    DOE PAGES

    Liu, Qi; Tan, Guoqiang; Wang, Peng; ...

    2017-04-17

    A pure phase of VO 2(B) nanorods have been synthesized through an energy-efficient microwave hydrothermal reaction and used as cathode materials of lithium ion batteries, which exhibit promising specific capacity (e.g., 130 mA h g -1 even after 100 charge/discharge cycles) and rate capacity (e.g., ~130 mA h g -1 at a high current of 400 mA g -1). The excellent cyclability originates from the structural reversibility of VO 2(B) upon lithiation/delithiation that is confirmed by the in situ high-energy synchrotron X-ray diffraction (HEXRD) and in situ x-ray adsorption near-edge spectroscopy (XANES) of the VO 2 nanorods in operating batterymore » cells. As a result, the real-time results reveal that discharge forces lithium ions to insert firstly into the tunnels with the largest size along b direction followed by the second largest tunnels along c direction, which is completely reversible in the charge process.« less

  5. Revealing mechanism responsible for structural reversibility of single-crystal VO 2 nanorods upon lithiation/delithiation

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

    Liu, Qi; Tan, Guoqiang; Wang, Peng

    A pure phase of VO 2(B) nanorods have been synthesized through an energy-efficient microwave hydrothermal reaction and used as cathode materials of lithium ion batteries, which exhibit promising specific capacity (e.g., 130 mA h g -1 even after 100 charge/discharge cycles) and rate capacity (e.g., ~130 mA h g -1 at a high current of 400 mA g -1). The excellent cyclability originates from the structural reversibility of VO 2(B) upon lithiation/delithiation that is confirmed by the in situ high-energy synchrotron X-ray diffraction (HEXRD) and in situ x-ray adsorption near-edge spectroscopy (XANES) of the VO 2 nanorods in operating batterymore » cells. As a result, the real-time results reveal that discharge forces lithium ions to insert firstly into the tunnels with the largest size along b direction followed by the second largest tunnels along c direction, which is completely reversible in the charge process.« less

  6. InAs Band-Edge Exciton Fine Structure

    DTIC Science & Technology

    2015-07-29

    Chapter 1 InAs Band-Edge Exciton Fine Structure 1.1 Contributions This work was carried out in collaboration with Oscar Sandoval, a summer student at...diffusion,1,2 charg- ing,2,3 and excitonic fine structure.1,3–9 While spectral diffusion and charging are most likely photoinduced effects and thus can be...unavoidable. A complete understanding of the excitonic 1 Distribution A: Public Release energy landscape enables us to determine dephasing rates

  7. Beyond edge effects: landscape controls on forest structure in the southeastern US

    NASA Astrophysics Data System (ADS)

    Fagan, M. E.; Morton, D. C.; Cook, B.; Masek, J. G.; Zhao, F. A.; Nelson, R.; Huang, C.

    2016-12-01

    The structure of forest canopies (i.e., their height and complexity) is known to be influenced by a variety of factors, including forest age, species composition, disturbance, edaphic and topographical conditions, and exposure to edge environments. The combined impact of each of these factors on canopy structure is not well characterized for most forest ecosystems, however, which limits our ability to predict the regional impacts of forest fragmentation. The objective of this study was to elucidate the main biophysical drivers of canopy structure across two dominant ecosystems in the southeastern U.S: natural mixed deciduous forests, and industrial conifer plantations. We analyzed spatial changes in canopy structure along aerial transects of LiDAR data ( 3,000 km in all). High-resolution (1 m) LiDAR data from Goddard's LiDAR, Hyperspectral, and Thermal Airborne Imager (G-LiHT) were combined with time series of Landsat imagery to quantify forest type, age, composition, and fragmentation. Forest structural metrics (height, gap fraction, and canopy roughness) were examined across forest types, ages, topography, and decreasing edge exposure. We hypothesized that 1) structural edge effects would be weak in both natural and plantation forest types, and 2) age, composition, and topography would be the dominant influences on natural forest structure. We analyzed all large (>4 ha) fragments from the 8562 distinct forests measured during G-LiHT data collections in 2011 across the southeastern U.S. In general, the relationship between forest structural metrics and edge exposure was highly variable in both natural forests and plantations. However, variability in all structural metrics decreased with distance from an edge. Forest age and topography were strong predictors of canopy structure in natural forests. However plantations tended to be located in sites with limited topographical variation, and thinning disturbances of conifer plantations decreased the strength of the age-structure

  8. Selenium Accumulation, Distribution, and Speciation in Spineless Prickly Pear Cactus: A Drought- and Salt-Tolerant, Selenium-Enriched Nutraceutical Fruit Crop for Biofortified Foods1[OA

    PubMed Central

    Bañuelos, Gary S.; Fakra, Sirine C.; Walse, Spencer S.; Marcus, Matthew A.; Yang, Soo In; Pickering, Ingrid J.; Pilon-Smits, Elizabeth A.H.; Freeman, John L.

    2011-01-01

    The organ-specific accumulation, spatial distribution, and chemical speciation of selenium (Se) were previously unknown for any species of cactus. We investigated Se in Opuntia ficus-indica using inductively coupled plasma mass spectrometry, microfocused x-ray fluorescence elemental and chemical mapping (μXRF), Se K-edge x-ray absorption near-edge structure (XANES) spectroscopy, and liquid chromatography-mass spectrometry (LC-MS). μXRF showed Se concentrated inside small conic, vestigial leaves (cladode tips), the cladode vasculature, and the seed embryos. Se K-edge XANES demonstrated that approximately 96% of total Se in cladode, fruit juice, fruit pulp, and seed is carbon-Se-carbon (C-Se-C). Micro and bulk XANES analysis showed that cladode tips contained both selenate and C-Se-C forms. Inductively coupled plasma mass spectrometry quantification of Se in high-performance liquid chromatography fractions followed by LC-MS structural identification showed selenocystathionine-to-selenomethionine (SeMet) ratios of 75:25, 71:29, and 32:68, respectively in cladode, fruit, and seed. Enzymatic digestions and subsequent analysis confirmed that Se was mainly present in a “free” nonproteinaceous form inside cladode and fruit, while in the seed, Se was incorporated into proteins associated with lipids. μXRF chemical mapping illuminated the specific location of Se reduction and assimilation from selenate accumulated in the cladode tips into the two LC-MS-identified C-Se-C forms before they were transported into the cladode mesophyll. We conclude that Opuntia is a secondary Se-accumulating plant whose fruit and cladode contain mostly free selenocystathionine and SeMet, while seeds contain mainly SeMet in protein. When eaten, the organic Se forms in Opuntia fruit, cladode, and seed may improve health, increase Se mineral nutrition, and help prevent multiple human cancers. PMID:21059825

  9. Selenium Accumulation, Distribution, and Speciation in Spineless Prickly Pear Cactus: A Drought- and Salt-Tolerant, Selenium-Enriched Nutraceutical Fruit Crop for Biofortified Foods

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

    Banuelos, Gary S.; Fakra, Sirine C.; Walse, Spencer S.

    The organ-specific accumulation, spatial distribution, and chemical speciation of selenium (Se) were previously unknown for any species of cactus. We investigated Se in Opuntia ficus-indica using inductively coupled plasma mass spectrometry, microfocused x-ray fluorescence elemental and chemical mapping ({micro}XRF), Se K-edge x-ray absorption near-edge structure (XANES) spectroscopy, and liquid chromatography-mass spectrometry (LC-MS). {micro}XRF showed Se concentrated inside small conic, vestigial leaves (cladode tips), the cladode vasculature, and the seed embryos. Se K-edge XANES demonstrated that approximately 96% of total Se in cladode, fruit juice, fruit pulp, and seed is carbon-Se-carbon (C-Se-C). Micro and bulk XANES analysis showed that cladode tipsmore » contained both selenate and C-Se-C forms. Inductively coupled plasma mass spectrometry quantification of Se in high-performance liquid chromatography fractions followed by LC-MS structural identification showed selenocystathionine-to-selenomethionine (SeMet) ratios of 75:25, 71:29, and 32:68, respectively in cladode, fruit, and seed. Enzymatic digestions and subsequent analysis confirmed that Se was mainly present in a 'free' nonproteinaceous form inside cladode and fruit, while in the seed, Se was incorporated into proteins associated with lipids. {micro}XRF chemical mapping illuminated the specific location of Se reduction and assimilation from selenate accumulated in the cladode tips into the two LC-MS-identified C-Se-C forms before they were transported into the cladode mesophyll. We conclude that Opuntia is a secondary Se-accumulating plant whose fruit and cladode contain mostly free selenocystathionine and SeMet, while seeds contain mainly SeMet in protein. When eaten, the organic Se forms in Opuntia fruit, cladode, and seed may improve health, increase Se mineral nutrition, and help prevent multiple human cancers.« less

  10. Mullite and Mullite Ceramics

    DTIC Science & Technology

    1994-01-01

    possible. The here reported measurements were carried out with synchrotron radiation from the electron storage ring ELSA of the Bonn University. All...Physikalisches Institut der Universitdt Bonn , Bonn , Germany Measurements of X-ray absorption spectra near the absorption edge of a selected element (XANES

  11. THE DISTRIBUTION, SOLID-PHASE SPECIATION, AND DESORPTION/DISSOLUTION OF AS IN IRON-BASED TREATMENT MEDIA

    EPA Science Inventory

    Arsenic concentrations (Total Recoverable As by EPA Method 3051) and solid-phase speciation (by X-ray Absorption Near-Edge Spectroscopy-XANES) were assessed as a function of depth through Fe-media beds for two commercially available products from pilot-scale field tests. These re...

  12. THE DISTRIBUTION AND SOLID-PHASE SPECIATION OF AS IN IRON-BASED TREATMENT MEDIA

    EPA Science Inventory

    Arsenic concentrations (Total Recoverable As by EPA Method 3051) and solid-phase speciation (by X-ray Absorption Near-Edge Spectroscopy-XANES) were assessed as a function of depth through Fe-media beds for two commercially available products from pilot-scale field tests. These r...

  13. Living on the edge: roads and edge effects on small mammal populations.

    PubMed

    Fuentes-Montemayor, Elisa; Cuarón, Alfredo D; Vázquez-Domínguez, Ella; Benítez-Malvido, Julieta; Valenzuela-Galván, David; Andresen, Ellen

    2009-07-01

    1. Roads may affect wildlife populations through habitat loss and disturbances, as they create an abrupt linear edge, increasing the proportion of edge exposed to a different habitat. Three types of edge effects have been recognized: abiotic, direct biotic, and indirect biotic. 2. We explored the direct biotic edge effects of 3- to 4-m wide roads, and also a previously unrecognized type of edge effect: social. We live-trapped two threatened endemic rodents from Cozumel Island (Oryzomys couesi cozumelae and Reithrodontomys spectabilis) in 16 plots delimited by roads on two sides, to compare edge effects between two adjacent edges (corners), single-edge and interior forest, on life history and social variables. 3. No significant edge effects were observed on the life-history variables, with the exception of differences in body condition between males and females of O. c. cozumelae near edges. Both species showed significant and contrasting effects on their social variables. 4. O. c. cozumelae was distributed according to its age and sex: the proportion of adults and males was higher in interior than near edges, while juveniles and females were more abundant near edges. More nonreproductive females were present in corners than in single-edge and interior, while the opposite distribution was observed for nonreproductive males. 5. The distribution of R. spectabilis was related to its age and reproductive condition, but not to its sex. The proportion of adults was significantly higher in corners, while juveniles were only caught in single-edge and interior quadrants. The proportion of reproductive individuals was higher in edge than interior quadrants, while reproductive females were only present in edge quadrants. 6. We found significant differences between the quadrants with the greatest edge exposure in comparison with other quadrants. The social edge effects we identified complement the typology of edge effects recognized in ecological literature. Our study provides

  14. Electron-beam induced amorphization of stishovite: Silicon-coordination change observed using Si K-edge extended electron energy-loss fine structure

    NASA Astrophysics Data System (ADS)

    van Aken, P. A.; Sharp, T. G.; Seifert, F.

    The analysis of the extended energy-loss fine structure (EXELFS) of the Si K-edge for sixfold-coordinated Si in synthetic stishovite and fourfold-coordinated Si in natural α-quartz is reported by using electron energy-loss spectroscopy (EELS) in combination with transmission electron microscopy (TEM). The stishovite Si K-edge EXELFS spectra were measured as a time-dependent series to document irradiation-induced amorphization. The amorphization was also investigated through the change in Si K- and O K-edge energy-loss near edge structure (ELNES). For α-quartz, in contrast to stishovite, electron irradiation-induced vitrification, verified by selected area electron diffraction (SAED), produced no detectable changes of the EXELFS. The Si K-edge EXELFS were analysed with the classical extended X-ray absorption fine structure (EXAFS) treatment and compared to ab initio curve-waved multiple-scattering (MS) calculations of EXAFS spectra for stishovite and α-quartz. Highly accurate information on the local atomic environment of the silicon atoms during the irradiation-induced amorphization of stishovite is obtained from the EXELFS structure parameters (Si-O bond distances, coordination numbers and Debye-Waller factors). The mean Si-O bond distance R and mean Si coordination number N changes from R=0.1775 nm and N=6 for stishovite through a disordered intermediate state (R 0.172 nm and N 5) to R 0.167 nm and N 4.5 for a nearly amorphous state similar to α-quartz (R=0.1609 nm and N=4). During the amorphization process, the Debye-Waller factor (DWF) passes through a maximum value of as it changes from for sixfold to for fourfold coordination of Si. This increase in Debye-Waller factor indicates an increase in mean-square relative displacement (MSRD) between the central silicon atom and its oxygen neighbours that is consistent with the presence of an intermediate structural state with fivefold coordination of Si. The distribution of coordination states can be estimated by

  15. Biosorption of Cr(VI) by coconut coir: spectroscopic investigation on the reaction mechanism of Cr(VI) with lignocellulosic material.

    PubMed

    Shen, Ying-Shuian; Wang, Shan-Li; Huang, Shiuh-Tsuen; Tzou, Yu-Min; Huang, Jang-Hung

    2010-07-15

    In this study, the removal mechanism of Cr(VI) from water by coconut coir (CC) was investigated using X-ray photoelectron spectroscopy (XPS), Cr K-edge X-ray absorption near edge structure (XANES) and FTIR spectroscopy. The results showed that, upon reaction with CC at pH 3, Cr(VI) was reduced to Cr(III), which was either bound to CC or released back into solution. As revealed by the FTIR spectra of CC before and after reacting with Cr(VI), the phenolic methoxyl and hydroxyl groups of lignin in CC are the dominant drivers of Cr(VI) reduction, giving rise to carbonyl and carboxyl groups on CC. These functional groups can subsequently provide binding sites for Cr(III) resulting from Cr(VI) reduction. In conjunction with forming complexes with carbonyl and carboxyl groups, the formation of Cr(III) hydroxide precipitate could also readily occur as revealed by the linear combination fitting of the Cr K-edge XANES spectrum using a set of reference compounds. The phenolic groups in lignin are responsible for initiating Cr(VI) reduction, so lignocellulosic materials containing a higher amount of phenolic groups are expected to be more effective scavengers for removal of Cr(VI) from the environment. 2010 Elsevier B.V. All rights reserved.

  16. 3D local structure around copper site of rabbit prion-related protein: Quantitative determination by XANES spectroscopy combined with multiple-scattering calculations

    NASA Astrophysics Data System (ADS)

    Cui, P. X.; Lian, F. L.; Wang, Y.; Wen, Yi; Chu, W. S.; Zhao, H. F.; Zhang, S.; Li, J.; Lin, D. H.; Wu, Z. Y.

    2014-02-01

    Prion-related protein (PrP), a cell-surface copper-binding glycoprotein, is considered to be responsible for a number of transmissible spongiform encephalopathies (TSEs). The structural conversion of PrP from the normal cellular isoform (PrPC) to the post-translationally modified form (PrPSc) is thought to be relevant to Cu2+ binding to histidine residues. Rabbits are one of the few mammalian species that appear to be resistant to TSEs, because of the structural characteristics of the rabbit prion protein (RaPrPC) itself. Here we determined the three-dimensional local structure around the C-terminal high-affinity copper-binding sites using X-ray absorption near-edge structure combined with ab initio calculations in the framework of the multiple-scattering (MS) theory. Result shows that two amino acid resides, Gln97 and Met108, and two histidine residues, His95 and His110, are involved in binding this copper(II) ion. It might help us understand the roles of copper in prion conformation conversions, and the molecular mechanisms of prion-involved diseases.

  17. XAFS study of copper(II) complexes with square planar and square pyramidal coordination geometries

    NASA Astrophysics Data System (ADS)

    Gaur, A.; Klysubun, W.; Nitin Nair, N.; Shrivastava, B. D.; Prasad, J.; Srivastava, K.

    2016-08-01

    X-ray absorption fine structure of six Cu(II) complexes, Cu2(Clna)4 2H2O (1), Cu2(ac)4 2H2O (2), Cu2(phac)4 (pyz) (3), Cu2(bpy)2(na)2 H2O (ClO4) (4), Cu2(teen)4(OH)2(ClO4)2 (5) and Cu2(tmen)4(OH)2(ClO4)2 (6) (where ac, phac, pyz, bpy, na, teen, tmen = acetate, phenyl acetate, pyrazole, bipyridine, nicotinic acid, tetraethyethylenediamine, tetramethylethylenediamine, respectively), which were supposed to have square pyramidal and square planar coordination geometries have been investigated. The differences observed in the X-ray absorption near edge structure (XANES) features of the standard compounds having four, five and six coordination geometry points towards presence of square planar and square pyramidal geometry around Cu centre in the studied complexes. The presence of intense pre-edge feature in the spectra of four complexes, 1-4, indicates square pyramidal coordination. Another important XANES feature, present in complexes 5 and 6, is prominent shoulder in the rising part of edge whose intensity decreases in the presence of axial ligands and thus indicates four coordination in these complexes. Ab initio calculations were carried out for square planar and square pyramidal Cu centres to observe the variation of 4p density of states in the presence and absence of axial ligands. To determine the number and distance of scattering atoms around Cu centre in the complexes, EXAFS analysis has been done using the paths obtained from Cu(II) oxide model and an axial Cu-O path from model of a square pyramidal complex. The results obtained from EXAFS analysis have been reported which confirmed the inference drawn from XANES features. Thus, it has been shown that these paths from model of a standard compound can be used to determine the structural parameters for complexes having unknown structure.

  18. Bifurcations of edge states—topologically protected and non-protected—in continuous 2D honeycomb structures

    NASA Astrophysics Data System (ADS)

    Fefferman, C. L.; Lee-Thorp, J. P.; Weinstein, M. I.

    2016-03-01

    Edge states are time-harmonic solutions to energy-conserving wave equations, which are propagating parallel to a line-defect or ‘edge’ and are localized transverse to it. This paper summarizes and extends the authors’ work on the bifurcation of topologically protected edge states in continuous two-dimensional (2D) honeycomb structures. We consider a family of Schrödinger Hamiltonians consisting of a bulk honeycomb potential and a perturbing edge potential. The edge potential interpolates between two different periodic structures via a domain wall. We begin by reviewing our recent bifurcation theory of edge states for continuous 2D honeycomb structures (http://arxiv.org/abs/1506.06111). The topologically protected edge state bifurcation is seeded by the zero-energy eigenstate of a one-dimensional Dirac operator. We contrast these protected bifurcations with (more common) non-protected bifurcations from spectral band edges, which are induced by bound states of an effective Schrödinger operator. Numerical simulations for honeycomb structures of varying contrasts and ‘rational edges’ (zigzag, armchair and others), support the following scenario: (a) for low contrast, under a sign condition on a distinguished Fourier coefficient of the bulk honeycomb potential, there exist topologically protected edge states localized transverse to zigzag edges. Otherwise, and for general edges, we expect long lived edge quasi-modes which slowly leak energy into the bulk. (b) For an arbitrary rational edge, there is a threshold in the medium-contrast (depending on the choice of edge) above which there exist topologically protected edge states. In the special case of the armchair edge, there are two families of protected edge states; for each parallel quasimomentum (the quantum number associated with translation invariance) there are edge states which propagate in opposite directions along the armchair edge.

  19. Electronic structure, bonding, charge distribution, and x-ray absorption spectra of the (001) surfaces of fluorapatite and hydroxyapatite from first principles

    NASA Astrophysics Data System (ADS)

    Rulis, Paul; Yao, Hongzhi; Ouyang, Lizhi; Ching, W. Y.

    2007-12-01

    Fluorapatite (FAP) and hydroxyapatite (HAP) are two very important bioceramic crystals. The (001) surfaces of FAP and HAP crystals are studied by ab initio density functional calculations using a supercell slab geometry. It is shown that in both crystals, the O-terminated (001) surface is more stable with calculated surface energies of 0.865 and 0.871J/m2 for FAP and HAP, respectively. In FAP, the two surfaces are symmetric. In HAP, the orientation of the OH group along the c axis reduces the symmetry such that the top and bottom surfaces are no longer symmetric. It is revealed that the atoms near the surface and subsurface are significantly relaxed especially in the case of HAP. The largest relaxations occurred via the lateral movements of the O ions at the subsurface level. The electronic structures of the surface models in the form of layer-by-layer resolved partial density of states for all the atoms show systematic variation from the surface region toward the bulk region. The calculated Mulliken effective charge on each type of atom and the bond order values between cations (Ca, P) and anions (O, F) show different charge transfers and bond strength variations from the bulk crystal values. Electron charge density calculations show that the surfaces of both FAP and HAP crystals are mostly positively charged due to the presence of Ca ions at the surface. The positively charged surfaces have implications for the absorption on apatite surfaces of water and other organic molecules in an aqueous environment which are an important part of its bioactivity. The x-ray absorption near-edge structure (XANES) spectra ( Ca-K , O-K , F-K , P-K , and P-L3 edges) of both the surface models and the bulk crystals are calculated and compared. The calculations use a supercell approach which takes into account the electron-core-hole interaction. It is shown that the site-specific XANES spectra show significant differences between atoms near the surface and in the bulk and are very

  20. Advanced leading edge thermal-structure concept. Direct bond reusable surface insulation to a composite structure

    NASA Technical Reports Server (NTRS)

    Riccitiello, S. R.; Figueroa, H.; Coe, C. F.; Kuo, C. P.

    1984-01-01

    An advanced leading-edge concept was analyzed using the space shuttle leading edge system as a reference model. The comparison indicates that a direct-bond system utilizing a high temperature (2700 F) fibrous refractory composite insulation tile bonded to a high temperature (PI/graphite) composite structure can result in a weight savings of up to 800 lb. The concern that tile damage or loss during ascent would result in adverse entry aerodynamics if a leading edge tile system were used is addressed. It was found from experiment that missing tiles (as many as 22) on the leading edge would not significantly affect the basic force-and-moment aerodynamic coefficients. Additionally, this concept affords a degree of redundancy to a thermal protection system in that the base structure (being a composite material) ablates and neither melts nor burns through when subjected to entry heating in the event tiles are actually lost or damaged during ascent.

  1. Spontaneous emission near the edge of a photonic band gap

    NASA Astrophysics Data System (ADS)

    John, Sajeev; Quang, Tran

    1994-08-01

    The spectral and dynamical features of spontaneous emission from two and three-level atoms in which one transition frequency lay near the edge of a photonic band gap (PBG) were derived. These features included temporal oscillations, fractionalized steady-state atomic population on the excited state, spectral splitting and subnatural bandwidth. The effect of N-1 unexcited atoms were also taken into account. The direct consequences of photon localization as embodied in the photon-atom bound state were observed. One feasible experimental accomplishment of these effects may ensue from laser-cooled atoms in the void regions of a PBG medium. Another option is the application of an organic impurity molecule such as pentacene. Such molecules were known to show extremely narrow linewidths when placed in fitting solid hosts.

  2. Structural Health Monitoring Analysis for the Orbiter Wing Leading Edge

    NASA Technical Reports Server (NTRS)

    Yap, Keng C.

    2010-01-01

    This viewgraph presentation reviews Structural Health Monitoring Analysis for the Orbiter Wing Leading Edge. The Wing Leading Edge Impact Detection System (WLE IDS) and the Impact Analysis Process are also described to monitor WLE debris threats. The contents include: 1) Risk Management via SHM; 2) Hardware Overview; 3) Instrumentation; 4) Sensor Configuration; 5) Debris Hazard Monitoring; 6) Ascent Response Summary; 7) Response Signal; 8) Distribution of Flight Indications; 9) Probabilistic Risk Analysis (PRA); 10) Model Correlation; 11) Impact Tests; 12) Wing Leading Edge Modeling; 13) Ascent Debris PRA Results; and 14) MM/OD PRA Results.

  3. Near- and Extended-Edge X-Ray-Absorption Fine-Structure Spectroscopy Using Ultrafast Coherent High-Order Harmonic Supercontinua

    NASA Astrophysics Data System (ADS)

    Popmintchev, Dimitar; Galloway, Benjamin R.; Chen, Ming-Chang; Dollar, Franklin; Mancuso, Christopher A.; Hankla, Amelia; Miaja-Avila, Luis; O'Neil, Galen; Shaw, Justin M.; Fan, Guangyu; Ališauskas, Skirmantas; Andriukaitis, Giedrius; Balčiunas, Tadas; Mücke, Oliver D.; Pugzlys, Audrius; Baltuška, Andrius; Kapteyn, Henry C.; Popmintchev, Tenio; Murnane, Margaret M.

    2018-03-01

    Recent advances in high-order harmonic generation have made it possible to use a tabletop-scale setup to produce spatially and temporally coherent beams of light with bandwidth spanning 12 octaves, from the ultraviolet up to x-ray photon energies >1.6 keV . Here we demonstrate the use of this light for x-ray-absorption spectroscopy at the K - and L -absorption edges of solids at photon energies near 1 keV. We also report x-ray-absorption spectroscopy in the water window spectral region (284-543 eV) using a high flux high-order harmonic generation x-ray supercontinuum with 109 photons/s in 1% bandwidth, 3 orders of magnitude larger than has previously been possible using tabletop sources. Since this x-ray radiation emerges as a single attosecond-to-femtosecond pulse with peak brightness exceeding 1026 photons/s /mrad2/mm2/1 % bandwidth, these novel coherent x-ray sources are ideal for probing the fastest molecular and materials processes on femtosecond-to-attosecond time scales and picometer length scales.

  4. Revealing the halide effect on the kinetics of the aerobic oxidation of Cu(I) to Cu(II)

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

    Deng, Yi; Zhang, Guanghui; Qi, Xiaotian

    2015-01-01

    In situ infrared (IR) and X-ray absorption near-edge structure (XANES) spectroscopic investigations reveal that different halide ligands have distinct effects on the aerobic oxidation of Cu(I) to Cu(II) in the presence of TMEDA (tetramethylethylenediamine). The iodide ligand gives the lowest rate and thus leads to the lowest catalytic reaction rate of aerobic oxidation of hydroquinone to benzoquinone. Further DFT calculations suggest that oxidation of CuI–TMEDA involves a side-on transition state, while oxidation of CuCl–TMEDA involves an end-on transition state which has a lower activation energy.

  5. An experimental study of the local electronic structure of B-site gallium doped bismuth ferrite powders

    NASA Astrophysics Data System (ADS)

    Gholam, Turghunjan; Ablat, Abduleziz; Mamat, Mamatrishat; Wu, Rong; Aimidula, Aimierding; Bake, Muhammad Ali; Zheng, Lirong; Wang, Jiaou; Qian, Haijie; Wu, Rui; Ibrahim, Kurash

    2017-08-01

    The un-doped and gallium (Ga) doped multiferroic bismuth ferrite (BiFeO3) compounds were successfully synthesized by the hydrothermal technique. This is then followed by a series of detailed investigations into the influence of Ga doping on the structural, morphological, optical and magnetic properties of BiFe1 - xGaxO3 (0 ≤ x ≤ 0.15). X-ray diffraction (XRD) analyses reveal that B-site doping of Ga may lead to the transformation of its crystal structure from a rhombohedral with a space group of R3c to an orthorhombic with a space group of Pbnm phase. The scanning electron microscope (SEM) images show that doping with Ga causes a significant reduction in particle size, when compared to un-doped BiFeO3. X-ray absorption near-edge structure (XANES) spectra have also shown that as the substitution of Ga increases, the Fe K and Bi LIII-edge absorption spectra shift towards higher energy site. It also implies that doping of Ga affects the local structures of both Bi and Fe atoms. Distinct transmission band fluctuations, as shown by Fourier transform infrared (FT-IR) spectra, can provide significant evidence for a transformation in crystal structure, following the increase of Ga concentration. The magnetization hysteresis measurements show that the magnetization decreases when Ga content is x ≥ 0.05. Such a phenomenon mainly stems from the substitution of Fe for an excessive amount of Ga, resulting in reduction of both valence fluctuations and the magnetization in the BiFe1 - xGaxO3 system.

  6. Sulfur Speciation in Biochars by Very High Resolution Benchtop Ka X-Ray Emission Spectroscopy

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

    Cheah, Singfoong; Holden, William M.; Seidler, Gerald T.

    The analytical chemistry of sulfur-containing materials poses substantial technical challenges, especially due to the limitations of 33S NMR and the time-intensive preparations required for wet-chemistry analyses. A number of prior studies have found that synchrotron-based X-ray absorption near edge structure (XANES) measurements can give detailed speciation of sulfur chemistry in such cases. However, due to the obvious access limitations, synchrotron XANES of sulfur cannot be part of routine analytical practice across the chemical sciences community. Here, in a study of the sulfur chemistry in biochars, we compare and contrast the chemical inferences available from synchrotron XANES with that given bymore » benchtop, extremely high resolution wavelength-dispersive X-ray fluorescence (WD-XRF) spectroscopy, also often called X-ray emission spectroscopy (XES). While the XANES spectra have higher total information content, often giving differentiation between different moieties having the same oxidation state, the lower sensitivity of the S Ka XES to coordination and local structure provides pragmatic benefit for the more limited goal of quantifying the S oxidation state distribution. Within that constrained metric, we find good agreement between the two methods. As the sulfur concentrations were as low as 150 ppm, these measurements provide proof-of-principle for characterization of the sulfur chemistry of biochars and potential applications to other areas such as soils, batteries, catalysts, and fossil fuels and their combustion products.« less

  7. Magneto-electronic properties of graphene nanoribbons with various edge structures passivated by phosphorus and hydrogen atoms.

    PubMed

    Yu, Z L; Wang, D; Zhu, Z; Zhang, Z H

    2015-10-07

    The electronic and magnetic structures of graphene nanoribbons (GNRs) with various edge structures passivated by P atoms are investigated systematically, and compared with H passivation as well. GNRs with the entire reconstructed Klein edge or armchair edge are found to be nonmagnetic regardless of P or H passivation. However, if the edge of GNRs is a mixture of zigzag edge and reconstructed Klein edge, they are nonmagnetic for H passivation but significantly magnetic for P passivation, which could be attributed to the "charge transfer doping" effect. And the corresponding magnetic device shows a noticeable negative differential resistance phenomenon and an excellent spin filtering effect under AP configuration, which originate from the special energy band structure. The GNRs with zigzag edge, reconstructed Klein edge, or mixed edge shapes are all metals in the nonmagnetic state regardless of the H or P atoms involved. The relationship between the energy gap and the width in armchair-edged GNRs by P passivation with a dimer structure also satisfies the 3p periodicity, but different in detail from the case of H passivation. The calculated edge formation energy indicates that P-passivated GNRs are energetically more favorable, suggesting that they can stably exist in the experiment.

  8. Edge-localized mode avoidance and pedestal structure in I-mode plasmasa)

    NASA Astrophysics Data System (ADS)

    Walk, J. R.; Hughes, J. W.; Hubbard, A. E.; Terry, J. L.; Whyte, D. G.; White, A. E.; Baek, S. G.; Reinke, M. L.; Theiler, C.; Churchill, R. M.; Rice, J. E.; Snyder, P. B.; Osborne, T.; Dominguez, A.; Cziegler, I.

    2014-05-01

    I-mode is a high-performance tokamak regime characterized by the formation of a temperature pedestal and enhanced energy confinement, without an accompanying density pedestal or drop in particle and impurity transport. I-mode operation appears to have naturally occurring suppression of large Edge-Localized Modes (ELMs) in addition to its highly favorable scalings of pedestal structure and overall performance. Extensive study of the ELMy H-mode has led to the development of the EPED model, which utilizes calculations of coupled peeling-ballooning MHD modes and kinetic-ballooning mode (KBM) stability limits to predict the pedestal structure preceding an ELM crash. We apply similar tools to the structure and ELM stability of I-mode pedestals. Analysis of I-mode discharges prepared with high-resolution pedestal data from the most recent C-Mod campaign reveals favorable pedestal scalings for extrapolation to large machines—pedestal temperature scales strongly with power per particle Pnet/n ¯e, and likewise pedestal pressure scales as the net heating power (consistent with weak degradation of confinement with heating power). Matched discharges in current, field, and shaping demonstrate the decoupling of energy and particle transport in I-mode, increasing fueling to span nearly a factor of two in density while maintaining matched temperature pedestals with consistent levels of Pnet/n ¯e. This is consistent with targets for increased performance in I-mode, elevating pedestal βp and global performance with matched increases in density and heating power. MHD calculations using the ELITE code indicate that I-mode pedestals are strongly stable to edge peeling-ballooning instabilities. Likewise, numerical modeling of the KBM turbulence onset, as well as scalings of the pedestal width with poloidal beta, indicates that I-mode pedestals are not limited by KBM turbulence—both features identified with the trigger for large ELMs, consistent with the observed suppression of

  9. Electronic and chemical state of aluminum from the single- (K) and double-electron excitation (KL II&III, KL I) x-ray absorption near-edge spectra of α-alumina, sodium aluminate, aqueous Al³⁺•(H₂O)₆, and aqueous Al(OH)₄⁻

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

    Fulton, John L.; Govind, Niranjan; Huthwelker, Thomas

    2015-07-02

    We probe, at high energy resolution, the double electron excitation (KL II&II) x-ray absorption region that lies approximately 115 eV above the main Al K-edge (1566 eV) of α-alumina and sodium aluminate. The two solid standards, α-alumina (octahedral) and sodium aluminate (tetrahedral) are compared to aqueous species that have the same Al coordination symmetries, Al³⁺•6H₂O (octahedral) and Al(OH)₄⁻ (tetrahedral). For the octahedral species, the edge height of the KL II&III-edge is approximately 10% of the main K-edge however the edge height is much weaker (3% of K-edge height) for Al species with tetrahedral symmetry. For the α-alumina and aqueous Al³⁺•6H₂Omore » the KL II&III spectra contain white line features and extended absorption fine structure (EXAFS) that mimics the K-edge spectra. The KL II&III-edge feature interferes with an important region of the extended-XAFS region of the spectra for the K-edge of the crystalline and aqueous standards. The K-edge spectra and K-edge positions are predicted using time-dependent density functional theory (TDDFT). The TDDFT calculations for the K-edge XANES spectra reproduce the observed transitions in the experimental spectra of the four Al species. The KL II&III and KL I onsets and their corresponding chemical shifts for the four standards are estimated using the delta self-consistent field (ΔSCF) method. Research by JLF, NG, EJB, AV, TDS was supported by U.S. Department of Energy’s (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. NG thanks Amity Andersen for help with the α-Al₂O₃ and tetrahedral sodium aluminate (NaAlO₂) clusters. All the calculations were performed using the Molecular Science Computing Capability at EMSL, a national scientific user facility sponsored by the U.S. Department of Energy’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL

  10. Coexistence of strongly and weakly confined energy levels in (Cd,Zn)Se quantum dots: Tailoring the near-band-edge and defect-levels for white light emission

    NASA Astrophysics Data System (ADS)

    Das, Tapan Kumar; Ilaiyaraja, P.; Sudakar, C.

    2017-05-01

    We demonstrate white light emission (WLE) from (Cd,Zn)Se system, which is a composite of Zn alloyed CdSe quantum dot and ZnSe-amorphous (ZnSe-a) phase. Detailed structural and photoluminescence emission studies on pure CdSe and (Cd,Zn)Se show cubic zinc blende structure in the size range of 2.5 to 5 nm. (Cd,Zn)Se quantum dots (QDs) also have a significant fraction of ZnSe-a phase. The near-band-edge green-emission in crystalline CdSe and (Cd,Zn)Se is tunable between 500 to 600 nm. The (Cd,Zn)Se system also exhibits a broad, deep defect level (DL) red-emission in the range 600 to 750 nm and a sharp ZnSe near-band-edge blue-emission (ZS-NBE) between 445 to 465 nm. While DL and CdSe near-band-edge (CS-NBE) emissions significantly shift with the size of QD due to strong confinement effect, the ZS-NBE show minimal change in peak position indicating a weak confinement effect. The intensities of ZS-NBE and DL emissions also exhibit a strong dependence on the QD size. A gamut of emission colors is obtained by combining the CS-NBE with the ZS-NBE emission and broad DL emission in (Cd,Zn)Se system. Interestingly, we find the convergence of Commission Internationale de l'Eclairage (CIE) coordinates towards the white light with increasing Zn concentration in CdSe. We demonstrate by combining these three emissions in a proper weight ratio WLE can be achieved. Cd1-yZnySe (y = 0. 5; QD size ˜4.9 nm) alloy with a maximum quantum yield of 57% exhibits CIE coordinates of (0.39, 0.4), color rendering index (CRI) of 82, correlated color temperature (CCT) of 3922 K, and Duv of 0.0078 which is very promising for white light applications.

  11. Evaluating the electronic structure of formal Ln II ions in Ln II(C 5H 4SiMe 3) 3 1– using XANES spectroscopy and DFT calculations

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

    Fieser, Megan E.; Ferrier, Maryline Ghislaine; Su, Jing

    Here, the isolation of [K(2.2.2-cryptand)][Ln(C 5H 4SiMe 3) 3], formally containing LnII, for all lanthanides (excluding Pm) was surprising given that +2 oxidation states are typically regarded as inaccessible for most 4f-elements. Herein, X-ray absorption near-edge spectroscopy (XANES), ground-state density functional theory (DFT), and transition dipole moment calculations are used to investigate the possibility that Ln(C 5H 4SiMe 3) 3 1– (Ln = Pr, Nd, Sm, Gd, Tb, Dy, Y, Ho, Er, Tm, Yb and Lu) compounds represented molecular Ln II complexes. Results from the ground-state DFT calculations were supported by additional calculations that utilized complete-active-space multi-configuration approach with second-ordermore » perturbation theoretical correction (CASPT2). Through comparisons with standards, Ln(C 5H 4SiMe 3) 3 1– (Ln = Sm, Tm, Yb, Lu, Y) are determined to contain 4f 6 5d 0 (Sm II), 4f 13 5d 0 (Tm II), 4f 14 5d 0 (Yb II), 4f 14 5d 1 (Lu II), and 4d 1 (Y II) electronic configurations. Additionally, our results suggest that Ln(C 5H 4SiMe 3) 3 1– (Ln = Pr, Nd, Gd, Tb, Dy, Ho, and Er) also contain Ln II ions, but with 4f n 5d 1 configurations (not 4f n +1 5d 0). In these 4f n 5d 1 complexes, the C 3h-symmetric ligand environment provides a highly shielded 5d-orbital of a' symmetry that made the 4f n 5d 1 electronic configurations lower in energy than the more typical 4f n+1 5d 0 configuration.« less

  12. Evaluating the electronic structure of formal Ln II ions in Ln II(C 5H 4SiMe 3) 3 1– using XANES spectroscopy and DFT calculations

    DOE PAGES

    Fieser, Megan E.; Ferrier, Maryline Ghislaine; Su, Jing; ...

    2017-06-30

    Here, the isolation of [K(2.2.2-cryptand)][Ln(C 5H 4SiMe 3) 3], formally containing LnII, for all lanthanides (excluding Pm) was surprising given that +2 oxidation states are typically regarded as inaccessible for most 4f-elements. Herein, X-ray absorption near-edge spectroscopy (XANES), ground-state density functional theory (DFT), and transition dipole moment calculations are used to investigate the possibility that Ln(C 5H 4SiMe 3) 3 1– (Ln = Pr, Nd, Sm, Gd, Tb, Dy, Y, Ho, Er, Tm, Yb and Lu) compounds represented molecular Ln II complexes. Results from the ground-state DFT calculations were supported by additional calculations that utilized complete-active-space multi-configuration approach with second-ordermore » perturbation theoretical correction (CASPT2). Through comparisons with standards, Ln(C 5H 4SiMe 3) 3 1– (Ln = Sm, Tm, Yb, Lu, Y) are determined to contain 4f 6 5d 0 (Sm II), 4f 13 5d 0 (Tm II), 4f 14 5d 0 (Yb II), 4f 14 5d 1 (Lu II), and 4d 1 (Y II) electronic configurations. Additionally, our results suggest that Ln(C 5H 4SiMe 3) 3 1– (Ln = Pr, Nd, Gd, Tb, Dy, Ho, and Er) also contain Ln II ions, but with 4f n 5d 1 configurations (not 4f n +1 5d 0). In these 4f n 5d 1 complexes, the C 3h-symmetric ligand environment provides a highly shielded 5d-orbital of a' symmetry that made the 4f n 5d 1 electronic configurations lower in energy than the more typical 4f n+1 5d 0 configuration.« less

  13. Phosphorus transformations in plant-based and bio-waste materials induced by pyrolysis.

    PubMed

    Robinson, James Stephen; Baumann, Karen; Hu, Yongfeng; Hagemann, Philipp; Kebelmann, Lutz; Leinweber, Peter

    2018-01-01

    Strategies are needed to increase the sustainability of phosphorus (P) fertiliser management in agriculture. This paper reports on the potential of pyrolysis treatment to recycle P from renewable materials previously regarded as wastes. The study used K-edge X-ray absorption near-edge structure (XANES) spectroscopy to examine chemical forms of P in the waste feedstock materials and corresponding biochars (pyrolysis at 480-500 °C) of four ligno-cellulosic, plant-based residues and five relatively P-rich livestock and water-treatment by-products, to acquire information on changes in potential P fertiliser value. Pyrolysis enriched P in the biochars by factors of 1.3-4.3, thus offering wide-ranging P fertiliser potential. XANES spectroscopy revealed hydroxyapatite (HAP) as one of the dominant chemical P compounds in the feedstocks, ranging from 14% (rice husks) to 98% (animal bone) of total P. For most materials, pyrolysis increased the proportion of HAP, and pyrophosphates were generated in several cases. These alterations possibly lead to diversity in the P solubility characteristics of the biochars if used as soil amendments; this is an important property of environmentally sound P fertilisers.

  14. Phase transitions in biogenic amorphous calcium carbonate.

    PubMed

    Gong, Yutao U T; Killian, Christopher E; Olson, Ian C; Appathurai, Narayana P; Amasino, Audra L; Martin, Michael C; Holt, Liam J; Wilt, Fred H; Gilbert, P U P A

    2012-04-17

    Crystalline biominerals do not resemble faceted crystals. Current explanations for this property involve formation via amorphous phases. Using X-ray absorption near-edge structure (XANES) spectroscopy and photoelectron emission microscopy (PEEM), here we examine forming spicules in embryos of Strongylocentrotus purpuratus sea urchins, and observe a sequence of three mineral phases: hydrated amorphous calcium carbonate (ACC · H(2)O) → dehydrated amorphous calcium carbonate (ACC) → calcite. Unexpectedly, we find ACC · H(2)O-rich nanoparticles that persist after the surrounding mineral has dehydrated and crystallized. Protein matrix components occluded within the mineral must inhibit ACC · H(2)O dehydration. We devised an in vitro, also using XANES-PEEM, assay to identify spicule proteins that may play a role in stabilizing various mineral phases, and found that the most abundant occluded matrix protein in the sea urchin spicules, SM50, stabilizes ACC · H(2)O in vitro.

  15. Genetic structure of tree and shrubby species among anthropogenic edges, natural edges, and interior of an atlantic forest fragment.

    PubMed

    Ramos, Flavio Nunes; de Lima, Paula Feliciano; Zucchi, Maria Imaculada; Colombo, Carlos Augusto; Solferini, Vera Nisaka

    2010-04-01

    Two species, Psychotria tenuinervis (shrub, Rubiaceae) and Guarea guidonia (tree, Meliaceae), were used as models to compare the genetic structure of tree and shrubby species among natural edges, anthropogenic edges, and a fragment interior. There were significant differences between two genetic markers. For isozymes, P. tenuinervis presented greater heterozygosity (expected and observed) and a higher percentage of polymorphic loci and median number of alleles than G. guidonia. For microsatellites, there was no difference in genetic variability between the species. Only P. tenuinervis, for isozymes, showed differences in genetic variability among the three habitats. There was no genetic structure (F (ST) < 0.05) among habitats in both plant species for both genetic markers. Isozymes showed great endogamy for both plant species, but not microsatellites. The forest fragmentation may have negative effects on both spatial (among edges and interior) and temporal genetic variability.

  16. Near sulfur L-edge X-ray absorption spectra of methanethiol in isolation and adsorbed on a Au(111) surface: a theoretical study using the four-component static exchange approximation.

    PubMed

    Villaume, Sebastien; Ekström, Ulf; Ottosson, Henrik; Norman, Patrick

    2010-06-07

    The relativistic four-component static exchange approach for calculation of near-edge X-ray absorption spectra has been reviewed. Application of the method is made to the Au(111) interface and the adsorption of methanethiol by a study of the near sulfur L-edge spectrum. The binding energies of the sulfur 2p(1/2) and 2p(3/2) sublevels in methanethiol are determined to be split by 1.2 eV due to spin-orbit coupling, and the binding energy of the 2p(3/2) shell is lowered from 169.2 eV for the isolated system to 167.4 and 166.7-166.8 eV for methanethiol in mono- and di-coordinated adsorption sites, respectively (with reference to vacuum). In the near L-edge X-ray absorption fine structure spectrum only the sigma*(S-C) peak at 166 eV remains intact by surface adsorption, whereas transitions of predominantly Rydberg character are largely quenched in the surface spectra. The sigma*(S-H) peak of methanethiol is replaced by low-lying, isolated, sigma*(S-Au) peak(s), where the number of peaks in the latter category and their splittings are characteristic of the local bonding situation of the sulfur.

  17. Molybdenum X-Ray Absorption Edges from 200 – 20,000 eV, The Benefits of Soft X-Ray Spectroscopy for Chemical Speciation

    PubMed Central

    George, Simon J.; Drury, Owen B.; Fu, Juxia; Friedrich, Stephan; Doonan, Christian J.; George, Graham N.; White, Jonathan M.; Young, Charles G.; Cramer, Stephen P.

    2009-01-01

    We have surveyed the chemical utility of the near-edge structure of molybdenum x-ray absorption edges from the hard x-ray K-edge at 20,000 eV down to the soft x-ray M4,5-edges at ~230 eV. We compared, for each edge, the spectra of two tetrahedral anions, MoO4 and MoS42-. We used three criteria for assessing near-edge structure of each edge: (i) the ratio of the observed chemical shift between MoO42- and MoS42- and the linewidth, (ii) the chemical information from analysis of the near-edge structure and (iii) the ease of measurement using fluorescence detection. Not surprisingly, the K-edge was by far the easiest to measure, but it contained the least information. The L2,3-edges, although harder to measure, had benefits with regard to selection rules and chemical speciation in that they had both a greater chemical shift as well as detailed lineshapes which could be theoretically analyzed in terms of Mo ligand field, symmetry, and covalency. The soft x-ray M2,3-edges were perhaps the least useful, in that they were difficult to measure using fluorescence detection and had very similar information content to the corresponding L2,3-edges. Interestingly, the soft x-ray, low energy (~230 eV) M4,5-edges had greatest potential chemical sensitivity and using our high resolution superconducting tunnel junction (STJ) fluorescence detector they appear to be straightforward to measure. The spectra were amenable to analysis using both the TT-multiplet approach and FEFF. The results using FEFF indicate that the sharp near-edge peaks arise from 3d → 5p transitions, while the broad edge structure has predominately 3d → 4f character. A proper understanding of the dependence of these soft x-ray spectra on ligand field and site geometry is necessary before a complete assessment of the utility of the Mo M4,5-edges can be made. This work includes crystallographic characterization of sodium tetrathiomolybdate. PMID:19041140

  18. Flow Phenomena in the Very Near Wake of a Flat Plate with a Circular Trailing Edge

    NASA Technical Reports Server (NTRS)

    Rai, Man Mohan

    2014-01-01

    The very near wake of a flat plate with a circular trailing edge, exhibiting pronounced shedding of wake vortices, is investigated with data from a direct numerical simulation. The separating boundary layers are turbulent and statistically identical thus resulting in a wake that is symmetric in the mean. The focus here is on the instability of the detached shear layers, the evolution of rib-vortex induced localized regions of reverse flow that detach from the main body of reverse flow in the trailing edge region and convect downstream, and phaseaveraged velocity statistics in the very near wake. The detached shear layers are found to exhibit unstable behavior intermittently, including the development of shear layer vortices as in earlier cylinder flow investigations with laminar separating boundary layers. Only a small fraction of the separated turbulent boundary layers undergo this instability, and form the initial shed vortices. Pressure spectra within the shear layers show a broadband peak at a multiple of shedding frequency. Phase-averaged intensity and shear stress distributions of the randomly fluctuating component of velocity are compared with those obtained in the near wake. The distributions of the production terms in the transport equations for the turbulent stresses are also provided.

  19. Visualization of the separation and subsequent transition near the leading edge of airfoils

    NASA Technical Reports Server (NTRS)

    Arena, A. V.; Mueller, T. J.

    1978-01-01

    A visual study was performed using the low speed smoke wind tunnels with the objective of obtaining a better understanding of the structure of leading edge separation bubbles on airfoils. The location of separation, transition and reattachment for a cylindrical nose constant-thickness airfoil model were obtained from smoke photographs and surface oil flow techniques. These data, together with static pressure distributions along the leading edge and upper surface of the model, produced the influence of Reynolds number, angle of attack, and trailing edge flap angle on the size and characteristics of the bubble. Additional visual insight into the unsteady nature of the separation bubble was provided by high speed 16 mm movies. The 8 mm color movies taken of the surface oil flow supported the findings of the high speed movies and clearly showed the formation of a scalloped spanwise separation line at the higher Reynolds number.

  20. Structure of short-range-ordered iron(III)-precipitates formed by iron(II) oxidation in water containing phosphate, silicate, and calcium

    NASA Astrophysics Data System (ADS)

    Voegelin, A.; Frommer, J.; Vantelon, D.; Kaegi, R.; Hug, S. J.

    2009-04-01

    The oxidation of Fe(II) in water leads to the formation of Fe(III)-precipitates that strongly affect the fate of nutrients and contaminants in natural and engineered systems. Examples include the cycling of As in rice fields irrigated with As-rich groundwater or the treatment of drinking water for As removal. Knowledge of the types of Fe(III)-precipitates forming in such systems is essential for the quantitative modeling of nutrient and contaminant dynamics and for the optimization of water purification techniques on the basis of a mechanistic understanding of the relevant biogeochemical processes. In this study, we investigated the local coordination of Fe, P, and Ca in Fe(III)-precipitates formed by aeration of synthetic Fe(II)-containing groundwater with variable composition (pH 7, 2-30 mg/L Fe(II), 2-20 mg/L phosphate-P, 2-20 mg/L silicate-Si, 8 mM Na-bicarbonate or 2.5 mM Ca-&1.5 mM Mg-bicarbonate). After 4 hours of oxidation, Fe(III)-precipitates were collected on 0.2 µm nylon filters and dried. The precipitates were analyzed by Fe K-edge EXAFS (XAS beamline, ANKA, Germany) and by P and Ca K-edge XANES spectroscopy (LUCIA beamline, SLS, Switzerland). The Fe K-edge EXAFS spectra indicated that local Fe coordination in the precipitates systematically shifted with water composition. As long as water contained P, mainly short-range-ordered Fe(III)-phosphate formed (with molar P/Fe ~0.5). In the absence of P, Fe(III) precipitated as hydrous ferric oxide at high Si/Fe>0.5, as ferrihydrite at intermediate Si/Fe, and mainly as lepidocrocite at Si/Fe<0.2. Analysis of the EXAFS by shell-fitting indicated that Fe(III)-phosphates mainly contained mono- or oligomeric (edge- or corner-sharing) Fe and that the linkage between neighboring Fe(III)-octahedra changed from predominantly edge-sharing in Si-rich hydrous ferric oxide to edge- and corner-sharing in ferrihydrite. Electron microscopic data showed that changes in local precipitate structure were systematically

  1. Investigating the Geochemical Model for Molybdenum Mineralization in the JEB Tailings Management Facility at McClean Lake, Saskatchewan: An X-ray Absorption Spectroscopy Study.

    PubMed

    Blanchard, Peter E R; Hayes, John R; Grosvenor, Andrew P; Rowson, John; Hughes, Kebbi; Brown, Caitlin

    2015-06-02

    The geochemical model for Mo mineralization in the JEB Tailings Management Facility (JEB TMF), operated by AREVA Resources Canada at McClean Lake, Saskatchewan, was investigated using X-ray Absorption Near-Edge Spectroscopy (XANES), an elemental-specific technique that is sensitive to low elemental concentrations. Twenty five samples collected during the 2013 sampling campaign from various locations and depths in the TMF were analyzed by XANES. Mo K-edge XANES analysis indicated that the tailings consisted primarily of Mo(6+) species: powellite (CaMoO4), ferrimolybdite (Fe2(MoO4)3·8H2O), and molybdate adsorbed on ferrihydrite (Fe(OH)3 - MoO4). A minor concentration of a Mo(4+) species in the form of molybdenite (MoS2) was also present. Changes in the Mo mineralization over time were inferred by comparing the relative amounts of the Mo species in the tailings to the independently measured aqueous Mo pore water concentration. It was found that ferrimolybdite and molybdate adsorbed on ferrihydrite initially dissolves in the TMF and precipitates as powellite.

  2. The Positive Environmental Contribution of Jarosite by Retaining Lead in Acid Mine Drainage Areas

    PubMed Central

    Figueiredo, Maria-Ondina; da Silva, Teresa Pereira

    2011-01-01

    Jarosite, KFe3(SO4)2(OH)6, is a secondary iron sulphate often found in acid mine drainage (AMD) environments, particularly in mining wastes from polymetallic sulphide ore deposits. Despite the negative environmental connotation usually ascribed to secondary sulphate minerals due to the release of hazardous elements to aquifers and soils, jarosite acts as an efficient remover and immobilizer of such metals, particularly lead. The mineral chemistry of jarosite is reviewed and the results of a Fe K-edge XANES (X-Ray Absorption Near-Edge Structure) study of K-, Na- and Pb-jarosite are described and discussed within the context of the abandoned old mines of São Domingos and Aljustrel located in southern Portugal, in the Iberian Pyrite Belt (IPB). PMID:21655138

  3. Approximating the near-edge mass absorption coefficients for Ni using an ultra-thin bimetal foil

    DOE PAGES

    Alkire, Randall W.

    2016-11-01

    In an effort to improve the characteristics of a fluorescing metal-foil-based beam position monitor, a new bimetal ultra-thin (0.98/0.67 µm) Ti–Ni foil was introduced to replace an existing single-element ultra-thin 0.5 µm thick Cr foil. During characterization it was determined that absorption measurements on the bimetal foil could be used to fit the Ni mass absorption coefficients accurately in the vicinity of the NiKedge. Comparison with experimental results from the literature demonstrated that the fitting procedure produced coefficients with uncertainties of the order of ±1%. Once determined, these fit coefficients allowed the thickness of an independently mounted 8 µm thickmore » Ni foil to be computed from absorption measurements instead of relying on a tool-based measurement of the foil thickness. Using the 8 µm thick foil, a continuous map of Ni mass absorption coefficients was produced at 1 eV resolution throughout the near-edge region. Lastly, this high-resolution map marks a significant improvement over the existing NIST XCOM or FFAST database mass absorption coefficients, which have estimated errors of 10–20% for the near-edge region.« less

  4. Asymptotic theory of two-dimensional trailing-edge flows

    NASA Technical Reports Server (NTRS)

    Melnik, R. E.; Chow, R.

    1975-01-01

    Problems of laminar and turbulent viscous interaction near trailing edges of streamlined bodies are considered. Asymptotic expansions of the Navier-Stokes equations in the limit of large Reynolds numbers are used to describe the local solution near the trailing edge of cusped or nearly cusped airfoils at small angles of attack in compressible flow. A complicated inverse iterative procedure, involving finite-difference solutions of the triple-deck equations coupled with asymptotic solutions of the boundary values, is used to accurately solve the viscous interaction problem. Results are given for the correction to the boundary-layer solution for drag of a finite flat plate at zero angle of attack and for the viscous correction to the lift of an airfoil at incidence. A rational asymptotic theory is developed for treating turbulent interactions near trailing edges and is shown to lead to a multilayer structure of turbulent boundary layers. The flow over most of the boundary layer is described by a Lighthill model of inviscid rotational flow. The main features of the model are discussed and a sample solution for the skin friction is obtained and compared with the data of Schubauer and Klebanoff for a turbulent flow in a moderately large adverse pressure gradient.

  5. Probabilistic Structural Health Monitoring of the Orbiter Wing Leading Edge

    NASA Technical Reports Server (NTRS)

    Yap, Keng C.; Macias, Jesus; Kaouk, Mohamed; Gafka, Tammy L.; Kerr, Justin H.

    2011-01-01

    A structural health monitoring (SHM) system can contribute to the risk management of a structure operating under hazardous conditions. An example is the Wing Leading Edge Impact Detection System (WLEIDS) that monitors the debris hazards to the Space Shuttle Orbiter s Reinforced Carbon-Carbon (RCC) panels. Since Return-to-Flight (RTF) after the Columbia accident, WLEIDS was developed and subsequently deployed on board the Orbiter to detect ascent and on-orbit debris impacts, so as to support the assessment of wing leading edge structural integrity prior to Orbiter re-entry. As SHM is inherently an inverse problem, the analyses involved, including those performed for WLEIDS, tend to be associated with significant uncertainty. The use of probabilistic approaches to handle the uncertainty has resulted in the successful implementation of many development and application milestones.

  6. The Dynamics of Turbulent Scalar Mixing near the Edge of a Shear Layer

    NASA Astrophysics Data System (ADS)

    Taveira, R. M. R.; da Silva, C. B.; Pereira, J. C. F.

    2011-12-01

    In free shear flows a sharp and convoluted turbulent/nonturbulent (T/NT) interface separates the outer fluid region, where the flow is essentially irrotational, from the shear layer turbulent region. It was found recently that the entrainment mechanism is mainly caused by small scale ("nibbling") motions (Westerweel et al. (2005)). The dynamics of this interface is crucial to understand important exchanges of enstrophy and scalars that can be conceived as a three-stage process of entrainment, dispersion and diffusion (Dimotakis (2005)). A thorough understanding of scalar mixing and transport is of indisputable relevance to control turbulent combustion, propulsion and contaminant dispersion (Stanley et al. (2002)). The present work uses several DNS of turbulent jets at Reynolds number ranging from Reλ = 120 to Reλ = 160 (da Silva & Taveira (2010)) and a Schmidt number Sc = 0.7 to analyze the "scalar interface" and turbulent mixing of a passive scalar. Specifically, we employ conditional statistics, denoted by langlerangleI, in order to eliminate the intermittency that affects statistics close to the jet edge. The physical mechanisms behind scalar mixing near the T/NT interfaces, their scales and topology are investigated detail. Analysis of the instantaneous fields showed intense scalar gradient sheet-like structures along regions of persistent strain, in particular at the T/NT interface. The scalar gradient transport equation, at the jet edge, showed that almost all mixing mechanisms are taking place in a confined region, beyond which they become reduced to an almost in perfect balance between production and dissipation of scalar variance. At the T/NT interface transport mechanisms are the ones responsible for the growth in the scalar fluctuations to the entrained fluid, where convection plays a dominant role, smoothing scalar gradients inside the interface and boosting them as far as

  7. Discriminating the Drivers of Edge Effects on Nest Predation: Forest Edges Reduce Capture Rates of Ship Rats (Rattus rattus), a Globally Invasive Nest Predator, by Altering Vegetation Structure

    PubMed Central

    Ruffell, Jay; Didham, Raphael K.; Barrett, Paul; Gorman, Nic; Pike, Rhonda; Hickey-Elliott, Andrée; Sievwright, Karin; Armstrong, Doug P.

    2014-01-01

    Forest edges can strongly affect avian nest success by altering nest predation rates, but this relationship is inconsistent and context dependent. There is a need for researchers to improve the predictability of edge effects on nest predation rates by examining the mechanisms driving their occurrence and variability. In this study, we examined how the capture rates of ship rats, an invasive nest predator responsible for avian declines globally, varied with distance from the forest edge within forest fragments in a pastoral landscape in New Zealand. We hypothesised that forest edges would affect capture rates by altering vegetation structure within fragments, and that the strength of edge effects would depend on whether fragments were grazed by livestock. We measured vegetation structure and rat capture rates at 488 locations ranging from 0–212 m from the forest edge in 15 forest fragments, seven of which were grazed. Contrary to the vast majority of previous studies of edge effects on nest predation, ship rat capture rates increased with increasing distance from the forest edge. For grazed fragments, capture rates were estimated to be 78% lower at the forest edge than 118 m into the forest interior (the farthest distance for grazed fragments). This relationship was similar for ungrazed fragments, with capture rates estimated to be 51% lower at the forest edge than 118 m into the forest interior. A subsequent path analysis suggested that these ‘reverse’ edge effects were largely or entirely mediated by changes in vegetation structure, implying that edge effects on ship rats can be predicted from the response of vegetation structure to forest edges. We suggest the occurrence, strength, and direction of edge effects on nest predation rates may depend on edge-driven changes in local habitat when the dominant predator is primarily restricted to forest patches. PMID:25412340

  8. Discriminating the drivers of edge effects on nest predation: forest edges reduce capture rates of ship rats (Rattus rattus), a globally invasive nest predator, by altering vegetation structure.

    PubMed

    Ruffell, Jay; Didham, Raphael K; Barrett, Paul; Gorman, Nic; Pike, Rhonda; Hickey-Elliott, Andrée; Sievwright, Karin; Armstrong, Doug P

    2014-01-01

    Forest edges can strongly affect avian nest success by altering nest predation rates, but this relationship is inconsistent and context dependent. There is a need for researchers to improve the predictability of edge effects on nest predation rates by examining the mechanisms driving their occurrence and variability. In this study, we examined how the capture rates of ship rats, an invasive nest predator responsible for avian declines globally, varied with distance from the forest edge within forest fragments in a pastoral landscape in New Zealand. We hypothesised that forest edges would affect capture rates by altering vegetation structure within fragments, and that the strength of edge effects would depend on whether fragments were grazed by livestock. We measured vegetation structure and rat capture rates at 488 locations ranging from 0-212 m from the forest edge in 15 forest fragments, seven of which were grazed. Contrary to the vast majority of previous studies of edge effects on nest predation, ship rat capture rates increased with increasing distance from the forest edge. For grazed fragments, capture rates were estimated to be 78% lower at the forest edge than 118 m into the forest interior (the farthest distance for grazed fragments). This relationship was similar for ungrazed fragments, with capture rates estimated to be 51% lower at the forest edge than 118 m into the forest interior. A subsequent path analysis suggested that these 'reverse' edge effects were largely or entirely mediated by changes in vegetation structure, implying that edge effects on ship rats can be predicted from the response of vegetation structure to forest edges. We suggest the occurrence, strength, and direction of edge effects on nest predation rates may depend on edge-driven changes in local habitat when the dominant predator is primarily restricted to forest patches.

  9. Homoclinic tangle on the edge of shear turbulence.

    PubMed

    van Veen, Lennaert; Kawahara, Genta

    2011-09-09

    Experiments and simulations lend mounting evidence for the edge state hypothesis on subcritical transition to turbulence, which asserts that simple states of fluid motion mediate between laminar and turbulent shear flow as their stable manifolds separate the two in state space. In this Letter we describe flows homoclinic to a time-periodic edge state that display the essential properties of turbulent bursting. During a burst, vortical structures and the associated energy dissipation are highly localized near the wall, in contrast with the familiar regeneration cycle.

  10. Thermo-Active Behavior of Ethylene-Vinyl Acetate | Multiwall Carbon Nanotube Composites Examined by in Situ near-Edge X-ray Absorption Fine-Structure Spectroscopy

    PubMed Central

    2015-01-01

    NEXAFS spectroscopy was used to investigate the temperature dependence of thermally active ethylene-vinyl acetate | multiwall carbon nanotube (EVA|MWCNT) films. The data shows systematic variations of intensities with increasing temperature. Molecular orbital assignment of interplaying intensities identified the 1s → π*C=C and 1s → π*C=O transitions as the main actors during temperature variation. Furthermore, enhanced near-edge interplay was observed in prestrained composites. Because macroscopic observations confirmed enhanced thermal-mechanical actuation in prestrained composites, our findings suggest that the interplay of C=C and C=O π orbitals may be instrumental to actuation. PMID:24803975

  11. Imaging of drug loading distributions in individual microspheres of calcium silicate hydrate - an X-ray spectromicroscopy study

    NASA Astrophysics Data System (ADS)

    Guo, Xiaoxuan; Wang, Zhiqiang; Wu, Jin; Wang, Jian; Zhu, Ying-Jie; Sham, Tsun-Kong

    2015-04-01

    Imaging is one of the most direct and ideal ways to track drug loading distributions in drug carriers on the molecular level, which will facilitate the optimization of drug carriers and drug loading capacities. Herein, we report the mapping of an individual mesoporous calcium silicate hydrate (CSH) microsphere before and after the loading of ibuprofen (IBU) and the interactions between drug carriers and drug molecules simultaneously by scanning transmission X-ray microscopy (STXM). Nanoscaled X-ray absorption near edge structure (XANES) spectroscopy clearly indicates that IBU is bonded to calcium and silicate sites via carboxylic acid groups. More importantly, STXM has been successfully used to determine the absolute thickness of IBU, revealing its distribution in the CSH microsphere.Imaging is one of the most direct and ideal ways to track drug loading distributions in drug carriers on the molecular level, which will facilitate the optimization of drug carriers and drug loading capacities. Herein, we report the mapping of an individual mesoporous calcium silicate hydrate (CSH) microsphere before and after the loading of ibuprofen (IBU) and the interactions between drug carriers and drug molecules simultaneously by scanning transmission X-ray microscopy (STXM). Nanoscaled X-ray absorption near edge structure (XANES) spectroscopy clearly indicates that IBU is bonded to calcium and silicate sites via carboxylic acid groups. More importantly, STXM has been successfully used to determine the absolute thickness of IBU, revealing its distribution in the CSH microsphere. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr07471h

  12. The origins of near band-edge transitions in hexagonal boron nitride epilayers

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

    Du, X. Z.; Li, J.; Lin, J. Y.

    2016-02-01

    Photoluminescence spectroscopy has been employed to probe the near band-edge transitions in hexagonal BN (h-BN) epilayers synthesized under varying ammonia flow rates. The results suggest that the quasi-donor-acceptor pair emission line at 5.3 eV is due to the transition between the nitrogen vacancy and a deep acceptor, whereas the 5.5 eV emission line is due to the recombination of an exciton bound to a deep acceptor formed by carbon impurity occupying the nitrogen site. By growing h-BN under high ammonia flow rates, nitrogen vacancy related peaks can be eliminated and epilayers exhibiting pure free exciton emission have been obtained.

  13. Excitation-Power Dependence of the Near Band-Edge PL Spectra of CdMnTe with High Mn Concentrations

    NASA Astrophysics Data System (ADS)

    Hwang, Younghun; Um, Youngho; Park, Hyoyeol

    2011-12-01

    Temperature and excitation power dependences of photoluminescence (PL) measurements were studied for the CdMnTe crystal grown by the vertical Bridgman method. The near band-edge and intra-Mn2+ emissions were investigated as a function of temperature. The observed band-edge peak of the PL spectrum showed a clear blue-shift with decreasing temperature. However, the peak energy of the intra-Mn2+ transition did not decrease monotonically with changing temperature, as can be seen above 70 K. With increasing the excitation power, the intensity of the emission peak was increased.

  14. Dimensionless, Scale Invariant, Edge Weight Metric for the Study of Complex Structural Networks

    PubMed Central

    Colon-Perez, Luis M.; Spindler, Caitlin; Goicochea, Shelby; Triplett, William; Parekh, Mansi; Montie, Eric; Carney, Paul R.; Price, Catherine; Mareci, Thomas H.

    2015-01-01

    High spatial and angular resolution diffusion weighted imaging (DWI) with network analysis provides a unique framework for the study of brain structure in vivo. DWI-derived brain connectivity patterns are best characterized with graph theory using an edge weight to quantify the strength of white matter connections between gray matter nodes. Here a dimensionless, scale-invariant edge weight is introduced to measure node connectivity. This edge weight metric provides reasonable and consistent values over any size scale (e.g. rodents to humans) used to quantify the strength of connection. Firstly, simulations were used to assess the effects of tractography seed point density and random errors in the estimated fiber orientations; with sufficient signal-to-noise ratio (SNR), edge weight estimates improve as the seed density increases. Secondly to evaluate the application of the edge weight in the human brain, ten repeated measures of DWI in the same healthy human subject were analyzed. Mean edge weight values within the cingulum and corpus callosum were consistent and showed low variability. Thirdly, using excised rat brains to study the effects of spatial resolution, the weight of edges connecting major structures in the temporal lobe were used to characterize connectivity in this local network. The results indicate that with adequate resolution and SNR, connections between network nodes are characterized well by this edge weight metric. Therefore this new dimensionless, scale-invariant edge weight metric provides a robust measure of network connectivity that can be applied in any size regime. PMID:26173147

  15. Dimensionless, Scale Invariant, Edge Weight Metric for the Study of Complex Structural Networks.

    PubMed

    Colon-Perez, Luis M; Spindler, Caitlin; Goicochea, Shelby; Triplett, William; Parekh, Mansi; Montie, Eric; Carney, Paul R; Price, Catherine; Mareci, Thomas H

    2015-01-01

    High spatial and angular resolution diffusion weighted imaging (DWI) with network analysis provides a unique framework for the study of brain structure in vivo. DWI-derived brain connectivity patterns are best characterized with graph theory using an edge weight to quantify the strength of white matter connections between gray matter nodes. Here a dimensionless, scale-invariant edge weight is introduced to measure node connectivity. This edge weight metric provides reasonable and consistent values over any size scale (e.g. rodents to humans) used to quantify the strength of connection. Firstly, simulations were used to assess the effects of tractography seed point density and random errors in the estimated fiber orientations; with sufficient signal-to-noise ratio (SNR), edge weight estimates improve as the seed density increases. Secondly to evaluate the application of the edge weight in the human brain, ten repeated measures of DWI in the same healthy human subject were analyzed. Mean edge weight values within the cingulum and corpus callosum were consistent and showed low variability. Thirdly, using excised rat brains to study the effects of spatial resolution, the weight of edges connecting major structures in the temporal lobe were used to characterize connectivity in this local network. The results indicate that with adequate resolution and SNR, connections between network nodes are characterized well by this edge weight metric. Therefore this new dimensionless, scale-invariant edge weight metric provides a robust measure of network connectivity that can be applied in any size regime.

  16. Mechanism study of sulfur fertilization mediating copper translocation and biotransformation in rice (Oryza sativa L.) plants.

    PubMed

    Sun, Lijuan; Yang, Jianjun; Fang, Huaxiang; Xu, Chen; Peng, Cheng; Huang, Haomin; Lu, Lingli; Duan, Dechao; Zhang, Xiangzhi; Shi, Jiyan

    2017-07-01

    Metabolism of sulfur (S) is suggested to be an important factor for the homeostasis and detoxification of Cu in plants. We investigated the effects of S fertilizers (S 0 , Na 2 SO 4 ) on Cu translocation and biotransformation in rice plants by using multiple synchrotron-based techniques. Fertilization of S increased the biomass and yield of rice plants, as well as the translocation factor of Cu from root to shoot and shoot to grain, resulting in enhanced Cu in grain. Sulfur K-edge X-ray near edge structure (XANES) analysis showed that fertilization of S increased the concentration of glutathione in different rice tissues, especially in rice stem and leaf. Copper K-edge XANES results indicated that a much higher proportion of Cu (I) species existed in rice grain than husk and leaf, which was further confirmed by soft X-ray scanning transmission microscopy results. Sulfur increased the proportion of Cu (I) species in rice grain, husk and leaf, suggesting the inducing of Cu (II) reduction in rice tissues by S fertilization. These results suggested that fertilization of S in paddy soils increased the accumulation of Cu in rice grain, possibly due to the reduction of Cu (II) to Cu (I) by enhancing glutathione synthesis and increasing the translocation of Cu from shoot to grain. Copyright © 2017 Elsevier Ltd. All rights reserved.

  17. Elastically Deformable Side-Edge Link for Trailing-Edge Flap Aeroacoustic Noise Reduction

    NASA Technical Reports Server (NTRS)

    Khorrami, Mehdi R. (Inventor); Lockard, David P. (Inventor); Moore, James B. (Inventor); Su, Ji (Inventor); Turner, Travis L. (Inventor); Lin, John C. (Inventor); Taminger, Karen M. (Inventor); Kahng, Seun K. (Inventor); Verden, Scott A. (Inventor)

    2014-01-01

    A system is provided for reducing aeroacoustic noise generated by an aircraft having wings equipped with trailing-edge flaps. The system includes a plurality of elastically deformable structures. Each structure is coupled to and along one of the side edges of one of the trailing-edge flaps, and is coupled to a portion of one of the wings that is adjacent to the one of the side edges. The structures elastically deform when the trailing-edge flaps are deployed away from the wings.

  18. Observation of the origin of d0 magnetism in ZnO nanostructures using X-ray-based microscopic and spectroscopic techniques

    NASA Astrophysics Data System (ADS)

    Singh, Shashi B.; Wang, Yu-Fu; Shao, Yu-Cheng; Lai, Hsuan-Yu; Hsieh, Shang-Hsien; Limaye, Mukta V.; Chuang, Chen-Hao; Hsueh, Hung-Chung; Wang, Hsaiotsu; Chiou, Jau-Wern; Tsai, Hung-Ming; Pao, Chih-Wen; Chen, Chia-Hao; Lin, Hong-Ji; Lee, Jyh-Fu; Wu, Chun-Te; Wu, Jih-Jen; Pong, Way-Faung; Ohigashi, Takuji; Kosugi, Nobuhiro; Wang, Jian; Zhou, Jigang; Regier, Tom; Sham, Tsun-Kong

    2014-07-01

    Efforts have been made to elucidate the origin of d0 magnetism in ZnO nanocactuses (NCs) and nanowires (NWs) using X-ray-based microscopic and spectroscopic techniques. The photoluminescence and O K-edge and Zn L3,2-edge X-ray-excited optical luminescence spectra showed that ZnO NCs contain more defects than NWs do and that in ZnO NCs, more defects are present at the O sites than at the Zn sites. Specifically, the results of O K-edge scanning transmission X-ray microscopy (STXM) and the corresponding X-ray-absorption near-edge structure (XANES) spectroscopy demonstrated that the impurity (non-stoichiometric) region in ZnO NCs contains a greater defect population than the thick region. The intensity of O K-edge STXM-XANES in the impurity region is more predominant in ZnO NCs than in NWs. The increase in the unoccupied (occupied) density of states at/above (at/below) the conduction-band minimum (valence-band maximum) or the Fermi level is related to the population of defects at the O sites, as revealed by comparing the ZnO NCs to the NWs. The results of O K-edge and Zn L3,2-edge X-ray magnetic circular dichroism demonstrated that the origin of magnetization is attributable to the O 2p orbitals rather than the Zn d orbitals. Further, the local density approximation (LDA) + U verified that vacancies in the form of dangling or unpaired 2p states (due to Zn vacancies) induced a significant local spin moment in the nearest-neighboring O atoms to the defect center, which was determined from the uneven local spin density by analyzing the partial density of states of O 2p in ZnO.Efforts have been made to elucidate the origin of d0 magnetism in ZnO nanocactuses (NCs) and nanowires (NWs) using X-ray-based microscopic and spectroscopic techniques. The photoluminescence and O K-edge and Zn L3,2-edge X-ray-excited optical luminescence spectra showed that ZnO NCs contain more defects than NWs do and that in ZnO NCs, more defects are present at the O sites than at the Zn sites

  19. Public Data Set: High Confinement Mode and Edge Localized Mode Characteristics in a Near-Unity Aspect Ratio Tokamak

    DOE Data Explorer

    Thome, Kathreen E. [University of Wisconsin-Madison] (ORCID:0000000248013922); Bongard, Michael W. [University of Wisconsin-Madison] (ORCID:0000000231609746); Barr, Jayson L. [University of Wisconsin-Madison] (ORCID:0000000177685931); Bodner, Grant M. [University of Wisconsin-Madison] (ORCID:0000000324979172); Burke, Marcus G. [University of Wisconsin-Madison] (ORCID:0000000176193724); Fonck, Raymond J. [University of Wisconsin-Madison] (ORCID:0000000294386762); Kriete, David M. [University of Wisconsin-Madison] (ORCID:0000000236572911); Perry, Justin M. [University of Wisconsin-Madison] (ORCID:0000000171228609); Schlossberg, David J. [University of Wisconsin-Madison] (ORCID:0000000287139448)

    2016-04-27

    This data set contains openly-documented, machine readable digital research data corresponding to figures published in K.E. Thome et al., 'High Confinement Mode and Edge Localized Mode Characteristics in a Near-Unity Aspect Ratio Tokamak,' Phys. Rev. Lett. 116, 175001 (2016).

  20. Chemical and structural characterization of copper adsorbed on mosses (Bryophyta).

    PubMed

    González, Aridane G; Jimenez-Villacorta, Felix; Beike, Anna K; Reski, Ralf; Adamo, Paola; Pokrovsky, Oleg S

    2016-05-05

    The adsorption of copper on passive biomonitors (devitalized mosses Hypnum sp., Sphagnum denticulatum, Pseudoscleropodium purum and Brachythecium rutabulum) was studied under different experimental conditions such as a function of pH and Cu concentration in solution. Cu assimilation by living Physcomitrella patents was also investigated. Molecular structure of surface adsorbed and incorporated Cu was studied by X-ray Absorption Spectroscopy (XAS). Devitalized mosses exhibited the universal adsorption pattern of Cu as a function of pH, with a total binding sites number 0.05-0.06 mmolg(dry)(-1) and a maximal adsorption capacity of 0.93-1.25 mmolg(dry)(-1) for these devitalized species. The Extended X-ray Absorption Fine Structure (EXAFS) fit of the first neighbor demonstrated that for all studied mosses there are ∼4.5 O/N atoms around Cu at ∼1.95 Å likely in a pseudo-square geometry. The X-ray Absorption Near Edge Structure (XANES) analysis demonstrated that Cu(II)-cellulose (representing carboxylate groups) and Cu(II)-phosphate are the main moss surface binding moieties, and the percentage of these sites varies as a function of solution pH. P. patens exposed during one month to Cu(2+) yielded ∼20% of Cu(I) in the form of Cu-S(CN) complexes, suggesting metabolically-controlled reduction of adsorbed and assimilated Cu(2+). Copyright © 2016 Elsevier B.V. All rights reserved.

  1. Spatial and Temporal Extent of Ion Spectral Structures at the Inner Edge of the Plasma Sheet

    NASA Astrophysics Data System (ADS)

    Ferradas, C.; Reeves, G. D.; Zhang, J.; Spence, H. E.; Kistler, L. M.; Larsen, B.; Skoug, R. M.; Funsten, H. O.

    2017-12-01

    Several ion spectral structures are observed near the inner edge of the plasma sheet and constitute the signatures of ion drift and loss in the highly dynamic environment of the inner magnetosphere. Their study helps us understand ion access and losses in this region. Several studies have found that these structures vary with geomagnetic activity, local time, and ion species, but their spatial and temporal extent remain undetermined. We use data from the Helium, Oxygen, Proton, and Electron (HOPE) mass spectrometers onboard the Van Allen Probes to analyze the spectral structures in the energy range of 1- 50 keV. HOPE measurements on both Van Allen Probes spacecraft enable us to resolve the extent of these ion structures in space and time. As the structures respond to changes in the convection electric field on a variety of time scales, the lapping of the two spacecraft on time scales of minutes to hours helps determine their spatial and temporal evolution.

  2. Studies by Near Edge X-ray Absorption Spectroscopies of Bonding Dynamics at the Graphene/Guanine Interface - A Proposal for High Mobility, Organic Graphene Field Effect Transistors

    DTIC Science & Technology

    2015-07-01

    AFRL-AFOSR-UK-TR-2015-0034 Studies by Near Edge X-ray Absorption Spectroscopies of Bonding Dynamics at the Graphene /Guanine...Interface – A Proposal for High Mobility, Organic Graphene Field Effect Transistors Eva Campo BANGOR UNIVERSITY COLLEGE ROAD BANGOR...April 2015 4. TITLE AND SUBTITLE Studies by Near Edge X-ray Absorption Spectroscopies of Bonding Dynamics at the Graphene /Guanine Interface - A

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

    Smith, Euan; Kempson, Ivan; Juhasz, Albert L.

    The consumption of arsenic (As) contaminated rice is an important exposure route for humans in countries where rice cultivation employs As contaminated irrigation water. Arsenic toxicity and mobility are a function of its chemical-speciation. The distribution and identification of As in the rice plant are hence necessary to determine the uptake, transformation and potential risk posed by As contaminated rice. In this study we report on the distribution and chemical-speciation of As in rice (Oryza sativa Quest) by X-ray fluorescence (XRF) and X-ray absorption near edge structure (XANES) measurements of rice plants grown in As contaminated paddy water. Investigations ofmore » {mu}XRF images from rice tissues found that As was present in all rice tissues, and its presence correlated with the presence of iron at the root surface and copper in the rice leaf. X-ray absorption near edge structure analysis of rice tissues identified that inorganic As was the predominant form of As in all rice tissues studied, and that arsenite became increasingly dominant in the aerial portion of the rice plant.« less

  4. A high-voltage rechargeable magnesium-sodium hybrid battery

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

    Li, Yifei; An, Qinyou; Cheng, Yingwen

    2017-04-01

    Growing global demand of safe and low-cost energy storage technology triggers strong interests in novel battery concepts beyond state-of-art Li-ion batteries. Here we report a high-voltage rechargeable Mg–Na hybrid battery featuring dendrite-free deposition of Mg anode and Na-intercalation cathode as a low-cost and safe alternative to Li-ion batteries for large-scale energy storage. A prototype device using a Na3V2(PO4)3 cathode, a Mg anode, and a Mg–Na dual salt electrolyte exhibits the highest voltage (2.60 V vs. Mg) and best rate performance (86% capacity retention at 10C rate) among reported hybrid batteries. Synchrotron radiation-based X-ray absorption near edge structure (XANES), atomic-pair distributionmore » function (PDF), and high-resolution X-ray diffraction (HRXRD) studies reveal the chemical environment and structural change of Na3V2(PO4)3 cathode during the Na ion insertion/deinsertion process. XANES study shows a clear reversible shift of vanadium K-edge and HRXRD and PDF studies reveal a reversible two-phase transformation and V–O bond length change during cycling. The energy density of the hybrid cell could be further improved by developing electrolytes with a higher salt concentration and wider electrochemical window. This work represents a significant step forward for practical safe and low-cost hybrid batteries.« less

  5. Phase transitions in biogenic amorphous calcium carbonate

    PubMed Central

    Gong, Yutao U. T.; Killian, Christopher E.; Olson, Ian C.; Appathurai, Narayana P.; Amasino, Audra L.; Martin, Michael C.; Holt, Liam J.; Wilt, Fred H.; Gilbert, P. U. P. A.

    2012-01-01

    Crystalline biominerals do not resemble faceted crystals. Current explanations for this property involve formation via amorphous phases. Using X-ray absorption near-edge structure (XANES) spectroscopy and photoelectron emission microscopy (PEEM), here we examine forming spicules in embryos of Strongylocentrotus purpuratus sea urchins, and observe a sequence of three mineral phases: hydrated amorphous calcium carbonate (ACC·H2O) → dehydrated amorphous calcium carbonate (ACC) → calcite. Unexpectedly, we find ACC·H2O-rich nanoparticles that persist after the surrounding mineral has dehydrated and crystallized. Protein matrix components occluded within the mineral must inhibit ACC·H2O dehydration. We devised an in vitro, also using XANES-PEEM, assay to identify spicule proteins that may play a role in stabilizing various mineral phases, and found that the most abundant occluded matrix protein in the sea urchin spicules, SM50, stabilizes ACC·H2O in vitro. PMID:22492931

  6. Speciation of copper diffused in a bi-porous molecular sieve

    NASA Astrophysics Data System (ADS)

    Huang, C.-H.; Paul Wang, H.; Wei, Y.-L.; Chang, J.-E.

    2010-07-01

    To better understand diffusion of copper in the micro- and mesopores, speciation of copper in a bi-porous molecular sieve (BPMS) possessing inter-connecting 3-D micropores (0.50-0.55 nm) and 2-D mesopores (4.1 nm) has been studied by X-ray absorption near edge structure (XANES) spectroscopy. It is found that about 77% (16% of CuO nanoparticles and 61% of CuO clusters) and 23% (CuO ads) of copper can be diffused into the meso- and micropores, respectively, in the BPMS. At least two diffusion steps in the BPMS may be involved: (i) free diffusion of copper in the mesopores and (ii) diffusion-controlled copper migrating into the micropores of the BPMS. The XANES data also indicate that diffusion rate of copper in the BPMS (4.68×10 -5 g/s) is greater than that in the ZSM-5 (1.11×10 -6 g/s) or MCM-41 (1.17×10 -5 g/s).

  7. Edge-localized mode avoidance and pedestal structure in I-mode plasmas

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

    Walk, J. R., E-mail: jrwalk@psfc.mit.edu; Hughes, J. W.; Hubbard, A. E.

    I-mode is a high-performance tokamak regime characterized by the formation of a temperature pedestal and enhanced energy confinement, without an accompanying density pedestal or drop in particle and impurity transport. I-mode operation appears to have naturally occurring suppression of large Edge-Localized Modes (ELMs) in addition to its highly favorable scalings of pedestal structure and overall performance. Extensive study of the ELMy H-mode has led to the development of the EPED model, which utilizes calculations of coupled peeling-ballooning MHD modes and kinetic-ballooning mode (KBM) stability limits to predict the pedestal structure preceding an ELM crash. We apply similar tools to themore » structure and ELM stability of I-mode pedestals. Analysis of I-mode discharges prepared with high-resolution pedestal data from the most recent C-Mod campaign reveals favorable pedestal scalings for extrapolation to large machines—pedestal temperature scales strongly with power per particle P{sub net}/n{sup ¯}{sub e}, and likewise pedestal pressure scales as the net heating power (consistent with weak degradation of confinement with heating power). Matched discharges in current, field, and shaping demonstrate the decoupling of energy and particle transport in I-mode, increasing fueling to span nearly a factor of two in density while maintaining matched temperature pedestals with consistent levels of P{sub net}/n{sup ¯}{sub e}. This is consistent with targets for increased performance in I-mode, elevating pedestal β{sub p} and global performance with matched increases in density and heating power. MHD calculations using the ELITE code indicate that I-mode pedestals are strongly stable to edge peeling-ballooning instabilities. Likewise, numerical modeling of the KBM turbulence onset, as well as scalings of the pedestal width with poloidal beta, indicates that I-mode pedestals are not limited by KBM turbulence—both features identified with the trigger for large ELMs

  8. Tuning the band structure of graphene nanoribbons through defect-interaction-driven edge patterning

    NASA Astrophysics Data System (ADS)

    Du, Lin; Nguyen, Tam N.; Gilman, Ari; Muniz, André R.; Maroudas, Dimitrios

    2017-12-01

    We report a systematic analysis of pore-edge interactions in graphene nanoribbons (GNRs) and their outcomes based on first-principles calculations and classical molecular-dynamics simulations. We find a strong attractive interaction between nanopores and GNR edges that drives the pores to migrate toward and coalesce with the GNR edges, which can be exploited to form GNR edge patterns that impact the GNR electronic band structure and tune the GNR band gap. Our analysis introduces a viable physical processing strategy for modifying GNR properties by combining defect engineering and thermal annealing.

  9. Direct deconvolution of two-state pump-probe X-ray absorption spectra and the structural changes in a 100 ps transient of Ni(II)-tetramesitylporphyrin.

    PubMed

    Della-Longa, S; Chen, L X; Frank, P; Hayakawa, K; Hatada, K; Benfatto, M

    2009-05-04

    Full multiple scattering (FMS) Minuit XANES (MXAN) has been combined with laser pump-probe K-edge X-ray absorption spectroscopy (XAS) to determine the structure of photoexcited Ni(II)tetramesitylporphyrin, Ni(II)TMP, in dilute toluene solution. It is shown that an excellent simulation of the XANES spectrum is obtained, excluding the lowest-energy bound-state transitions. In ground-state Ni(II)TMP, the first-shell and second-shell distances are, respectively, d(Ni-N) = (1.93 +/- 0.02) A and d(Ni-C) = (2.94 +/- 0.03) A, in agreement with a previous EXAFS result. The time-resolved XANES difference spectrum was obtained (1) from the spectra of Ni(II)TMP in its photoexcited T(1) state and its ground state, S(0). The XANES difference spectrum has been analyzed to obtain both the structure and the fraction of the T(1) state. If the T(1) fraction is kept fixed at the value (0.37 +/- 0.10) determined by optical transient spectroscopy, a 0.07 A elongation of the Ni-N and Ni-C distances [d(Ni-N) and d(Ni-C)] is found, in agreement with the EXAFS result. However, an evaluation of both the distance elongation and the T(1) fraction can also be obtained using XANES data only. According to experimental evidence, and MXAN simulations, the T(1) fraction is (0.60 +/- 0.15) with d(Ni-N) = (1.98 +/- 0.03) A (0.05 A elongation). The overall uncertainty of these results depends on the statistical correlation between the distances and T(1) fraction, and the chemical shift of the ionization energy because of subtle changes of metal charge between the T(1) and S(0) states. The T(1) excited-state structure results, independently obtained without the excited-state fraction from optical transient spectroscopy, are still in agreement with previous EXAFS investigations. Thus, full multiple scattering theory applied through the MXAN formalism can be used to provide structural information, not only on the ground-state molecules but also on very short-lived excited states through differential

  10. Initial Edge Stability Observations in the PEGASUS Toroidal Experiment

    NASA Astrophysics Data System (ADS)

    Bongard, M. W.; Battaglia, D. J.; Garstka, G. D.; Sontag, A. C.; Unterberg, E. A.

    2007-11-01

    Edge stability is an important consideration for design of fusion experiments, as transient heat loads generated by edge instabilities may damage the first wall. Such instabilities are now believed to include peeling (current driven) and ballooning (pressure driven) components. Peeling instability may be expected for high values of edge j||/B and low edge pressure gradient. This matches the operating space of Pegasus, with typical ˜100 kA/m^2, |B|˜ 0.01 T, and an L-mode edge. A new camera system has observed filamentary structures in the edge of nearly all ohmically-heated discharges. Ideal stability analysis of these discharges with DCON indicates marginal stability to resistive interchange for ψN>= 0.95. Modification of triangularity during startup is observed to delay instability onset. A plasma control system based on that used on DIII-D will allow study of the influence of plasma shaping on mode stability characteristics. An array of magnetic probes capable of insertion into the scrape-off layer and plasma edge is being developed to provide a local constraint on the edge current profile.

  11. Studies on effective atomic numbers, electron densities from mass attenuation coefficients near the K edge in some samarium compounds.

    PubMed

    Akman, F; Durak, R; Turhan, M F; Kaçal, M R

    2015-07-01

    The effective atomic numbers and electron densities of some samarium compounds were determined using the experimental total mass attenuation coefficient values near the K edge in the X-ray energy range from 36.847 up to 57.142 keV. The measurements, in the region from 36.847 to 57.142 keV, were done in a transmission geometry utilizing the Kα2, Kα1, Kβ1 and Kβ2 X-rays from different secondary source targets excited by the 59.54 keV gamma-photons from an Am-241 annular source. This paper presents the first measurement of the effective atomic numbers and electron densities for some samarium compounds near the K edge. The results of the study showed that the measured values were in good agreement with the theoretically calculated ones. Copyright © 2015 Elsevier Ltd. All rights reserved.

  12. Shortcomings with Tree-Structured Edge Encodings for Neural Networks

    NASA Technical Reports Server (NTRS)

    Hornby, Gregory S.

    2004-01-01

    In evolutionary algorithms a common method for encoding neural networks is to use a tree structured assembly procedure for constructing them. Since node operators have difficulties in specifying edge weights and these operators are execution-order dependent, an alternative is to use edge operators. Here we identify three problems with edge operators: in the initialization phase most randomly created genotypes produce an incorrect number of inputs and outputs; variation operators can easily change the number of input/output (I/O) units; and units have a connectivity bias based on their order of creation. Instead of creating I/O nodes as part of the construction process we propose using parameterized operators to connect to preexisting I/O units. Results from experiments show that these parameterized operators greatly improve the probability of creating and maintaining networks with the correct number of I/O units, remove the connectivity bias with I/O units and produce better controllers for a goal-scoring task.

  13. Detailed investigation of Na2.24FePO4CO3 as a cathode material for Na-ion batteries

    PubMed Central

    Huang, Weifeng; Zhou, Jing; Li, Biao; Ma, Jin; Tao, Shi; Xia, Dingguo; Chu, Wangsheng; Wu, Ziyu

    2014-01-01

    Na-ion batteries are gaining an increased recognition as the next generation low cost energy storage devices. Here, we present a characterization of Na3FePO4CO3 nanoplates as a novel cathode material for sodium ion batteries. First-principles calculations reveal that there are two paths for Na ion migration along b and c axis. In-situ and ex-situ Fe K-edge X-ray absorption near edge structure (XANES) point out that in Na3FePO4CO3 both Fe2+/Fe3+ and Fe3+/Fe4+ redox couples are electrochemically active, suggesting also the existence of a two-electron intercalation reaction. Ex-situ X-ray powder diffraction data demonstrates that the crystalline structure of Na3FePO4CO3 remains stable during the charging/discharging process within the range 2.0–4.55 V. PMID:24595232

  14. Sulfur and iron accumulation in three marine-archaeological shipwrecks in the Baltic Sea: The Ghost, the Crown and the Sword

    NASA Astrophysics Data System (ADS)

    Fors, Yvonne; Grudd, Håkan; Rindby, Anders; Jalilehvand, Farideh; Sandström, Magnus; Cato, Ingemar; Bornmalm, Lennart

    2014-02-01

    Sulfur and iron concentrations in wood from three 17th century shipwrecks in the Baltic Sea, the Ghost wreck, the Crown and the Sword, were obtained by X-ray fluorescence (XRF) scanning. In near anaerobic environments symbiotic microorganisms degrade waterlogged wood, reduce sulfate and promote accumulation of low-valent sulfur compounds, as previously found for the famous wrecks of the Vasa and Mary Rose. Sulfur K-edge X-ray absorption near-edge structure (XANES) analyses of Ghost wreck wood show that organic thiols and disulfides dominate, together with elemental sulfur probably generated by sulfur-oxidizing Beggiatoa bacteria. Iron sulfides were not detected, consistent with the relatively low iron concentration in the wood. In a museum climate with high atmospheric humidity oxidation processes, especially of iron sulfides formed in the presence of corroding iron, may induce post-conservation wood degradation. Subject to more general confirmation by further analyses no severe conservation concerns are expected for the Ghost wreck wood.

  15. Fate of zinc in an electroplating sludge during electrokinetic treatments.

    PubMed

    Liu, Shou-Heng; Wang, H Paul

    2008-08-01

    Chemical structure of zinc in the electrokinetic treatments of an electroplating sludge has been studied by in situ extended X-ray absorption fine structural (EXAFS) and X-ray absorption near edge structural (XANES) spectroscopies in the present work. The least-square fitted XANES spectra indicate that the main zinc compounds in the sludge were ZnCO(3) (75%), ZnOSiO(2) (17%) and Zn(OH)(2) (7%). Zinc in the sludge possessed a Zn-O bond distance of 2.07 A with a coordination number (CN) of 5. In the second shells, the bond distance of Zn-(O)-Si was 3.05 A (CN=2). An increase of Zn-(O)-Si (0.05 A) with a decrease of its CN (from 5 to <1) was found in the early stage of the electrokinetic treatment. Prolong the electrokinetic treatment time to 180 min, about 34% of Zn(II) was dissolved into the aqueous phase and about 68% of Zn(II) in the sludge (or 23% of total zinc) was migrated to the cathode under the electric field (5 V cm(-1)). The dissolution and electromigration rates of Zn(II) in the sludge were 1.0 and 0.6 mmol h(-1)g(-1) sludge, respectively during the electrokinetic treatment. This work also exemplifies the utilization of in situ EXAFS and XANES for revealing speciation and possible reaction pathways during the course of zinc recycling from the sludge by electrokinetic treatments.

  16. Transmission X-ray microscopy for full-field nano-imaging of biomaterials

    PubMed Central

    ANDREWS, JOY C; MEIRER, FLORIAN; LIU, YIJIN; MESTER, ZOLTAN; PIANETTA, PIERO

    2010-01-01

    Imaging of cellular structure and extended tissue in biological materials requires nanometer resolution and good sample penetration, which can be provided by current full-field transmission X-ray microscopic techniques in the soft and hard X-ray regions. The various capabilities of full-field transmission X-ray microscopy (TXM) include 3D tomography, Zernike phase contrast, quantification of absorption, and chemical identification via X-ray fluorescence and X-ray absorption near edge structure (XANES) imaging. These techniques are discussed and compared in light of results from imaging of biological materials including microorganisms, bone and mineralized tissue and plants, with a focus on hard X-ray TXM at ≤ 40 nm resolution. PMID:20734414

  17. Structure and stability of pyrophyllite edge surfaces: Effect of temperature and water chemical potential

    NASA Astrophysics Data System (ADS)

    Kwon, Kideok D.; Newton, Aric G.

    2016-10-01

    The surfaces of clay minerals, which are abundant in atmospheric mineral dust, serve as an important medium to catalyze ice nucleation. The lateral edge surface of 2:1 clay minerals is postulated to be a potential site for ice nucleation. However, experimental investigations of the edge surface structure itself have been limited compared to the basal planes of clay minerals. Density functional theory (DFT) computational studies have provided insights into the pyrophyllite edge surface. Pyrophyllite is an ideal surrogate mineral for the edge surfaces of 2:1 clay minerals as it possesses no or little structural charge. Of the two most-common hydrated edge surfaces, the AC edge, (1 1 0) surface in the monoclinic polytype notation, is predicted to be more stable than the B edge, (0 1 0) surface. These stabilities, however, were determined based on the total energies calculated at 0 K and did not consider environmental effects such as temperature and humidity. In this study, atomistic thermodynamics based on periodic DFT electronic calculations was applied to examine the effects of environmental variables on the structure and thermodynamic stability of the common edge surfaces in equilibrium with bulk pyrophyllite and water vapor. We demonstrate that the temperature-dependent vibrational energy of sorbed water molecules at the edge surface is a significant component of the surface free energy and cannot be neglected when determining the surface stability of pyrophyllite. The surface free energies were calculated as a function of temperature from 240 to 600 K and water chemical potential corresponding to conditions from ultrahigh vacuum to the saturation vapor pressure of water. We show that at lower water chemical potentials (dry conditions), the AC and B edge surfaces possessed similar stabilities; at higher chemical potentials (humid conditions) the AC edge surface was more stable than the B edge surface. At high temperatures, both surfaces showed similar stabilities

  18. Structural Changes Correlated with Magnetic Spin State Isomorphism in the S2 State of the Mn4CaO5 Cluster in the Oxygen-Evolving Complex of Photosystem II

    PubMed Central

    Chatterjee, Ruchira; Han, Guangye; Kern, Jan; Gul, Sheraz; Fuller, Franklin D.; Garachtchenko, Anna; Young, Iris; Weng, Tsu-Chien; Nordlund, Dennis; Alonso-Mori, Roberto; Bergmann, Uwe; Sokaras, Dimosthenis; Hatakeyama, Makoto; Yachandra, Vittal K.; Yano, Junko

    2016-01-01

    The Mn4CaO5 cluster in Photosystem II catalyzes the four-electron redox reaction of water oxidation in natural photosynthesis. This catalytic reaction cycles through four intermediate states (Si, i = 0 to 4), involving changes in the redox state of the four Mn atoms in the cluster. Recent studies suggest the presence and importance of isomorphous structures within the same redox/intermediate S-state. It is highly likely that geometric and electronic structural flexibility play a role in the catalytic mechanism. Among the catalytic intermediates that have been identified experimentally thus far, there is clear evidence of such isomorphism in the S2 state, with a high-spin (5/2) (HS) and a low spin (1/2) (LS) form, identified and characterized by their distinct electron paramagnetic resonance (EPR spectroscopy) signals. We studied these two S2 isomers with Mn extended X-ray absorption fine structure (EXAFS) and absorption and emission spectroscopy (XANES/XES) to characterize the structural and electronic structural properties. The geometric and electronic structure of the HS and LS S2 states are different as determined using Mn EXAFS and XANES/XES, respectively. The Mn K-edge XANES and XES for the HS form are different from the LS and indicate a slightly lower positive charge on the Mn atoms compared to the LS form. Based on the EXAFS results which are clearly different, we propose possible structural differences between the two spin states. Such structural and magnetic redox-isomers if present at room temperature, will likely play a role in the mechanism for water-exchange/oxidation in photosynthesis. PMID:28044099

  19. Structural changes correlated with magnetic spin state isomorphism in the S 2 state of the Mn 4CaO 5 cluster in the oxygen-evolving complex of photosystem II

    DOE PAGES

    Chatterjee, Ruchira; Han, Guangye; Kern, Jan; ...

    2016-05-09

    The Mn 4CaO 5 cluster in photosystem II catalyzes the four-electron redox reaction of water oxidation in natural photosynthesis. This catalytic reaction cycles through four intermediate states (S i, i = 0 to 4), involving changes in the redox state of the four Mn atoms in the cluster. Recent studies suggest the presence and importance of isomorphous structures within the same redox/intermediate S-state. It is highly likely that geometric and electronic structural flexibility play a role in the catalytic mechanism. Among the catalytic intermediates that have been identified experimentally thus far, there is clear evidence of such isomorphism in themore » S2 state, with a high-spin (5/2) (HS) and a low spin (1/2) (LS) form, identified and characterized by their distinct electron paramagnetic resonance (EPR spectroscopy) signals. We studied these two S2 isomers with Mn extended X-ray absorption fine structure (EXAFS) and absorption and emission spectroscopy (XANES/XES) to characterize the structural and electronic structural properties. The geometric and electronic structure of the HS and LS S2 states are different as determined using Mn EXAFS and XANES/XES, respectively. The Mn K-edge XANES and XES for the HS form are different from the LS and indicate a slightly lower positive charge on the Mn atoms compared to the LS form. Based on the EXAFS results which are clearly different, we propose possible structural differences between the two spin states. As a result, such structural and magnetic redox-isomers if present at room temperature, will likely play a role in the mechanism for water-exchange/oxidation in photosynthesis.« less

  20. Chromium-removal processes during groundwater remediation by a zerovalent iron permeable reactive barrier.

    PubMed

    Wilkin, Richard T; Su, Chunming; Ford, Robert G; Paul, Cynthia J

    2005-06-15

    Solid-phase associations of chromium were examined in core materials collected from a full-scale, zerovalent iron permeable reactive barrier (PRB) at the U.S. Coast Guard Support Center located near Elizabeth City, NC. The PRB was installed in 1996 to treat groundwater contaminated with hexavalent chromium. After eight years of operation, the PRB remains effective at reducing concentrations of Cr from average values >1500 microg L(-1) in groundwater hydraulically upgradient of the PRB to values <1 microg L(-1) in groundwater within and hydraulically downgradient of the PRB. Chromium removal from groundwater occurs at the leading edge of the PRB and also within the aquifer immediately upgradient of the PRB. These regions also witness the greatest amount of secondary mineral formation due to steep geochemical gradients that result from the corrosion of zerovalent iron. X-ray absorption near-edge structure (XANES) spectroscopy indicated that chromium is predominantly in the trivalent oxidation state, confirming that reductive processes are responsible for Cr sequestration. XANES spectra and microscopy results suggest that Cr is, in part, associated with iron sulfide grains formed as a consequence of microbially mediated sulfate reduction in and around the PRB. Results of this study provide evidence that secondary iron-bearing mineral products may enhance the capacity of zerovalent iron systems to remediate Cr in groundwater, either through redox reactions at the mineral-water interface or by the release of Fe(II) to solution via mineral dissolution and/or metal corrosion.

  1. Sulfur and iron speciation in gas-rich impact-melt glasses from basaltic shergottites determined by microXANES

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

    Sutton, S.R.; Rao, M.N.; Nyquist, L.E.

    2008-04-28

    Sulfur and iron K XANES measurements were made on GRIM glasses from EET 79001. Iron is in the ferrous state. Sulfur speciation is predominately sulfide coordination but is Fe coordinated in Lith B and, most likely, Ca coordinated in Lith A. Sulfur is abundantly present as sulfate near Martian surface based on chemical and mineralogical investigations on soils and rocks in Viking, Pathfinder and MER missions. Jarosite is identified by Moessbauer studies on rocks at Meridian and Gusev, whereas MgSO{sub 4} is deduced from MgO-SO{sub 3} correlations in Pathfinder MER and Viking soils. Other sulfate minerals such as gypsum andmore » alunogen/S-rich aluminosilicates and halides are detected only in martian meteorites such as shergottites and nakhlites using SEM/FE-SEM and EMPA techniques. Because sulfur has the capacity to occur in multiple valence states, determination of sulfur speciation (sulfide/sulfate) in secondary mineral assemblages in soils and rocks near Mars surface may help us understand whether the fluid-rock interactions occurred under oxidizing or reducing conditions. On Earth, volcanic rocks contain measurable quantities of sulfur present as both sulfide and sulfate. Carroll and Rutherford showed that oxidized forms of sulfur may comprise a significant fraction of total dissolved sulfur, if the oxidation state is higher than {approx}2 log fO{sub 2} units relative to the QFM buffer. Terrestrial samples containing sulfates up to {approx}25% in fresh basalts from the Galapagos Rift on one hand and high sulfide contents present in oceanic basalts on the other indicate that the relative abundance of sulfide and sulfate varies depending on the oxygen fugacity of the system. Basaltic shergottites (bulk) such as Shergotty, EET79001 and Zagami usually contain small amounts of sulfur ({approx}0.5%) as pyrrhotite. But, in isolated glass pockets containing secondary salts (known as GRIM glasses) in these meteorites, sulfur is present in high abundance ({approx}1

  2. Method of Preparation AZP4330 PR Pattern with Edge Slope 40°

    NASA Astrophysics Data System (ADS)

    Wu, Jie; Zhao, Hongyuan; Yu, Yuanwei; Zhu, Jian

    2018-03-01

    When the edge which is under the multi-film is more steep or angular, the stress in the multilayer film near the edge is concentrated, this situation will greatly reduce the reliability of electronic components. And sometimes, we need some special structure such as a slope with a specific angle in the MEMS, so that the metal line can take the signal to the output pad through the slope instead of deep step. To cover these problems, the lithography method of preparing the structure with edge slope is studied. In this paper, based on the Kirchhoff scalar diffraction theory we try to change the contact exposure gap and the post-baking time at the specific temperature to find out the effect about the edge angle of the photoresist. After test by SEM, the results were presented by using AZP4330 photoresist, we can get the PR Pattern with edge slope 40° of the process and the specific process parameters.

  3. Arsenic speciation in sinter mineralization from a hydrothermal channel of El Tatio geothermal field, Chile

    NASA Astrophysics Data System (ADS)

    Alsina, Marco A.; Zanella, Luciana; Hoel, Cathleen; Pizarro, Gonzalo E.; Gaillard, Jean-François; Pasten, Pablo A.

    2014-10-01

    El Tatio geothermal field is the principal natural source of arsenic for the Loa River, the main surface water resource in the hyper-arid Atacama Desert (Antofagasta Region, Northern Chile). Prior investigations by bulk X-ray absorption spectroscopy have identified hydrous ferric oxides as the principal arsenic-containing phase in sinter material from El Tatio, suggesting sorption as the main mechanism for arsenic scavenging by the solid phases of these hot spring environments. Here we examine siliceous sinter material sampled from a hydrothermal channel using synchrotron based X-ray micro-probe techniques, including As and Fe Kα X-ray fluorescence (μ-XRF), As K-edge X-ray absorption near edge structure (μ-XANES), and X-ray diffraction (μ-XRD). Least-squares linear fitting of μ-XANES spectra shows that arsenic is predominantly present as arsenate sorbed on hydrous ferric oxides (63% molar proportion), but we also identify nodular arsenide micro-mineralizations (37% molar proportion) similar to loellingite (FeAs2), not previously detected during bulk-scale analysis of the sinter material. Presence of arsenide mineralizations indicates development of anoxic environments on the surface of the siliceous sinter, and suggests a more complex biogeochemistry for arsenic than previously observed for circum-neutral pH brine hot spring environments.

  4. Radiation damages during synchrotron X-ray micro-analyses of Prussian blue and zinc white historic paintings: detection, mitigation and integration

    NASA Astrophysics Data System (ADS)

    Gervais, Claire; Thoury, Mathieu; Réguer, Solenn; Gueriau, Pierre; Mass, Jennifer

    2015-11-01

    High-flux synchrotron techniques allow microspectroscopic analyses of artworks that were not feasible even a few years ago, allowing for a more detailed characterization of their constituent materials and a better understanding of their chemistry. However, interaction between high-flux photons and matter at the sub-microscale can generate damages which are not visually detectable. We show here different methodologies allowing to evidence the damages induced by microscopic X-ray absorption near-edge structure spectroscopy analysis (μXANES) at the Fe and Zn K-edges of a painting dating from the turn of the twentieth century containing Prussian blue and zinc white. No significant degradation of the pigments was noticed, in agreement with the excellent condition of the painting. However, synchrotron radiation damages occurred at several levels, from chemical changes of the binder, modification of crystal defects in zinc oxide, to Prussian blue photoreduction. They could be identified by using both the μXANES signal during analysis and with photoluminescence imaging in the deep ultraviolet and visible ranges after analysis. We show that recording accurately damaged areas is a key step to prevent misinterpretation of results during future re-examination of the sample. We conclude by proposing good practices that could help in integrating radiation damage avoidance into the analytical pathway.

  5. KRISTINA: Kinematic rib-based structural system for innovative adaptive trailing edge

    NASA Astrophysics Data System (ADS)

    Pecora, R.; Amoroso, F.; Magnifico, M.; Dimino, I.; Concilio, A.

    2016-04-01

    Nature teaches that the flight of the birds succeeds perfectly since they are able to change the shape of their wings in a continuous manner. The careful observation of this phenomenon has re-introduced in the recent research topics the study of "metamorphic" wing structures; these innovative architectures allow for the controlled wing shape adaptation to different flight conditions with the ultimate goal of getting desirable improvements such as the increase of aerodynamic efficiency or load control effectiveness. In this framework, the European research project SARISTU aimed at combining morphing and smart ideas to the leading edge, the trailing edge and the winglet of a large commercial airplane (EASA CS25 category) while assessing integrated technologies validation through high-speed wind tunnel test on a true scale outer wing segment. The design process of the adaptive trailing edge (ATED) addressed by SARISTU is here outlined, from the conceptual definition of the camber-morphing architecture up to the assessment of the device executive layout. Rational design criteria were implemented in order to preliminarily define ATED structural layout and the general configuration of the embedded mechanisms enabling morphing under the action of aerodynamic loads. Advanced FE analyses were then carried out and the robustness of adopted structural arrangements was proven in compliance with applicable airworthiness requirements.

  6. Crystal structure and properties of tetragonal EuAg{sub 4}In{sub 8} grown by metal flux technique

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

    Subbarao, Udumula; Sarkar, Sumanta; Peter, Sebastian C., E-mail: sebastiancp@jncasr.ac.in

    The compound EuAg{sub 4}In{sub 8} has been obtained as single crystals in high yield from reactions run in liquid indium. X-ray diffraction on single crystals suggests that EuAg{sub 4}In{sub 8} crystallizes in the CeMn{sub 4}Al{sub 8} structure type, tetragonal space group I4/mmm with lattice constants a=b=9.7937(2) Å and c=5.7492(2) Å. Crystal structure of EuAg{sub 4}In{sub 8} is composed of pseudo Frank–Kasper cages occupied by one europium atom in each ring, which are shared through the corner along the ab plane resulting in a three dimensional network. The magnetic susceptibility of EuAg{sub 4}In{sub 8} was measured in the temperature range 2–300more » K, which obeyed Curie–Weiss law above 50 K. Magnetic moment value calculated from the fitting indicates the presence of divalent europium, which was confirmed by X-ray absorption near edge spectroscopy. Electrical resistivity measurements suggest that EuAg{sub 4}In{sub 8} is metallic in nature with a probable Fermi liquid behavior at low temperature. - Graphical abstract: The tetragonal EuAg{sub 4}In{sub 8} has been grown as single crystals from reactions run in liquid indium. Magnetic and XANES measurements suggest divalent nature of Eu and resistivity measurements suggest metallic nature. - Highlights: • EuAg{sub 4}In{sub 8} phase having tetragonal phase is grown by metal flux technique. • Magnetic and XANES measurements exhibit divalent nature of Eu in EuAg{sub 4}In{sub 8}. • Resistivity measurement suggests metallic nature and probable Fermi liquid behavior.« less

  7. Pressure-induced amorphization and collapse of magnetic order in the type-I clathrate Eu8Ga16Ge30

    NASA Astrophysics Data System (ADS)

    Mardegan, J. R. L.; Fabbris, G.; Veiga, L. S. I.; Adriano, C.; Avila, M. A.; Haskel, D.; Giles, C.

    2013-10-01

    We investigate the low temperature structural and electronic properties of the type-I clathrate Eu8Ga16Ge30 under pressure using x-ray powder diffraction (XRD), x-ray absorption near-edge structure (XANES), and x-ray magnetic circular dichroism (XMCD) techniques. The XRD measurements reveal a transition to an amorphous phase above 18 GPa. Unlike previous reports on other clathrate compounds, no volume collapse is observed prior to the crystalline-amorphous phase transition which takes place when the unit cell volume is reduced to 81% of its ambient pressure value. Fits of the pressure-dependent relative volume to a Murnaghan equation of state yield a bulk modulus B0=65±3 GPa and a pressure derivative B0'=3.3±0.5. The Eu L2-edge XMCD data shows quenching of the magnetic order at a pressure coincident with the crystalline-amorphous phase transition. This information along with the persistence of an Eu2+ valence state observed in the XANES spectra up to the highest pressure point (22 GPa) indicates that the suppression of XMCD intensity is due to the loss of long range magnetic order. When compared with other clathrates, the results point to the importance of guest ion-cage interactions in determining the mechanical stability of the framework structure and the critical pressure for amorphization. Finally, the crystalline structure is not found to recover after pressure release, resulting in an amorphous material that is at least metastable at ambient pressure and temperature.

  8. Plans to Observe the 2017 Total Solar Eclipse from near the Path Edges

    NASA Astrophysics Data System (ADS)

    Waring Dunham, David; Nugent, Richard; Guhl, Konrad; Bode, Hans-Joachim

    2015-08-01

    The August 21st, 2017 solar eclipse provides a good opportunity, to time the totality contacts, other Baily’s bead phenomena, and observe other dynamic edge phenomena, from locations near the edges of the path of totality. A good network of roads and generally favorable weather prospects means that more observers will likely be able to deploy more equipment than during most previous eclipses. The value of contact and Baily’s bead timings of total solar eclipses, for determining solar diameter and intensity variations, was described in an earlier presentation in Focus Meeting 13. This presentation will concentrate on how observations of different types that have been used during past eclipses can be made by different observers, to obtain better information about the accuracy of the different types of observations for determining the mean solar diameter, and the systematic differences between them. A problem has been that the few observers who have attempted recording Baily’s beads from path edge locations have wanted to use the latest technology, to try to record the observations better, rather than try to make the observations in the same ways that were used for many past eclipses. Several observers trying different techniques at the same location, and doing that at several locations at different places along the path, is needed. Past techniques that we would like to compare include direct visual observation (but keeping eye safety in mind); visual observation of telescopically projected images; direct filtered video telescopic observations; and recording the flash spectrum. There are several towns that straddle the path edges. The International Occultation Timing Association would like to mobilize people in those towns to observe the eclipse from many places, to say whether or not the eclipse happened, and if it did, time it. A suitable cell phone app could be designed to report observations, including the observer’s location, as was attempted for an

  9. Thermodynamics, Kinetics and Structural Evolution of ε-LiVOPO 4 over Multiple Lithium Intercalation

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

    Lin, Yuh-Chieh; Wen, Bohua; Wiaderek, Kamila M.

    In this work, we demonstrate the stable cycling of more than one Li in solid-state-synthesized ε-LiVOPO4 over more than 20 cycles for the first time. Using a combination of density functional theory (DFT) calculations, X-ray pair distribution function (PDF) analysis and X-ray absorption near edge structure (XANES) measurements, we present a comprehensive analysis of the thermodynamics, kinetics, and structural evolution of ε-LixVOPO4 over the entire lithiation range. We identify two intermediate phases at x = 1.5 and 1.75 in the low-voltage regime using DFT calculations, and the computed and electrochemical voltage profiles are in excellent agreement. Operando PDF and EXAFSmore » techniques show a reversible hysteretic change in the short (<2 Å) V—O bond lengths coupled with an irreversible extension of the long V—O bond (>2.4 Å) during low-voltage cycling. Hydrogen intercalation from electrolyte decomposition is a possible explanation for the ~2.4 Å V—O bond and its irreversible extension. Finally, we show that ε-LixVOPO4 is likely a pseudo-1D ionic diffuser with low electronic conductivity using DFT calculations, which suggests that nanosizing and carbon coating is necessary to achieve good electrochemical performance in this material.« less

  10. Development of a cyber physical apparatus for investigating fluid structure interaction on leading edge vortex evolution

    NASA Astrophysics Data System (ADS)

    Raghu Gowda, Belagumba Venkatachalaiah

    This dissertation examines how simple structural compliance impacts a specific transient vortex phenomenon that occurs on high angle of attack lifting surfaces termed dynamic stall. In many Fluid structure interaction (FSI) research efforts, a purely physical or purely computational approach is taken. In this work a low cost cyber-physical (CPFD) system is designed and developed for representing the FSI in the leading edge vortex (LEV) development problem. The leading edge compliance appears to be favorable in a specific spring constant range for a given wing. When the leading edge compliance prescribed via CPFD system is too low compared with the moment due to dynamic pressure or fluid unsteady effect, the LEV behavior is similar to that of a rigid wing system. When the leading edge compliance is too high, excessive compliance is introduced into the wing system and the leading edge vortex evolution is affected by the large change in wing angle. At moderate leading edge compliance, a balance appears to be achieved in which the leading edge vorticity shedding rate supports the long term evolution of the leading edge vortex. Further investigation is required to determine specific parameters governing these leading edge compliance ranges.

  11. Using X-ray absorption to probe sulfur oxidation states in complex molecules

    NASA Astrophysics Data System (ADS)

    Vairavamurthy, A.

    1998-10-01

    X-ray absorption near-edge structure (XANES) spectroscopy offers an important non-destructive tool for determining oxidation states and for characterizing chemical speciation. The technique was used to experimentally verify the oxidation states of sulfur in different types of complex molecules because there are irregularities and uncertainties in assigning the values traditionally. The usual practice of determining oxidation states involves using a set of conventional rules. The oxidation state is an important control in the chemical speciation of sulfur, ranging from -2 to +6 in its different compounds. Experimental oxidation-state values for various types of sulfur compounds, using their XANES peak-energy positions, were assigned from a scale in which elemental sulfur and sulfate are designated as 0 and +6, respectively. Because these XANES-based values differed considerably from conventionally determined oxidation states for most sulfur compounds, a new term 'oxidation index' was coined to describe them. The experimental values were closer to those conventional values obtained by assigning shared electrons to the more electronegative atoms than to those based on other customary rules for assigning them. Because the oxidation index is distinct and characteristic for each different type of sulfur functionality, it becomes an important parameter for characterizing sulfur species, and for experimentally verifying uncertain oxidation states.

  12. Bio-Inspired Control of Roughness and Trailing Edge Noise

    NASA Astrophysics Data System (ADS)

    Clark, Ian Andrew

    Noise from fluid flow over rough surfaces is an important consideration in the design and performance of certain vehicles with high surface-area-to-perimeter ratios. A new method of noise control based on the anatomy of owls is developed and consists of fabric or fibrous canopies suspended above the surface. The method is tested experimentally and is found to reduce the total far-field noise emitted by the surface. The treatment also is found to reduce the magnitude of pressure fluctuations felt by the underlying surface by up to three orders of magnitude. Experimental investigations into the effects of geometric parameters of the canopies lead to an optimized design which maximizes noise reduction. The results obtained during the canopy experiment inspired a separate new device for the reduction of trailing edge noise. This type of noise is generated by flow past the wing of an aircraft or the blades of a wind turbine, and is a source of annoyance for those in surrounding communities. The newly developed treatment consists of small fins, or "finlets," placed near the trailing edge of an airfoil. The treatment is tested experimentally at near-full-scale conditions and is found to reduce the magnitude of far-field noise by up to 10 dB. Geometric parameters of the finlets are tested to determine the optimal size and spacing of the finlets to maximize noise reduction. Follow-up computational and experimental studies reveal the fluid mechanics behind the noise reduction by showing that the finlets produce a velocity deficit in the flow near the trailing edge and limit the magnitude and spanwise correlation lengthscale of turbulence near the trailing edge, factors which determine the magnitude of far-field noise. In a final experiment, the finlets are applied to a marine propeller and are found to reduce not only trailing edge noise, but also noise caused by the bluntness of the trailing edge. The results of this experiment show the potential usefulness of finlets to

  13. Influence of oxygen on growth of carbon thin films

    NASA Astrophysics Data System (ADS)

    Kumar, Prabhat; Gupta, Mukul; Phase, D. M.; Stahn, Jochen

    2018-04-01

    In this work we studied the influence of oxygen gas on growth of carbon thin films in a magnetron sputtering process. X-ray absorption spectroscopy (XAS), x-ray and neutron reflectivity techniques were used to probe carbon thin films deposited with and without oxygen at room temperature. XAS in particularly x-ray absorption near edge spectroscopy (XANES) is powerful technique to identify the nature of hybridization of carbon atoms with other elements. In a XANES pattern, presence of C=O and C-O bonds is generally observed in spite of the fact that oxygen has not been deliberately included in the growth process. In order to confirm the presence of such features, we introduced a small amount of oxygen at 1% during the growth of carbon thin films. Though such additions do not affect the number density as observed by x-ray and neutron reflectivity, they severally affect the C K-edge spectra as evidenced by an enhancement in carbon-oxygen hybridization. Observed results are helpful in analyzing the C K-edge spectra more confidently.

  14. The aquatic hyphomycete Heliscus lugdunensis protects its hyphae tip cells from cadmium: A micro X-ray fluorescence and X-ray absorption near edge structure spectroscopy study

    NASA Astrophysics Data System (ADS)

    Isaure, Marie-Pierre; Leyh, Benjamin; Salomé, Murielle; Krauss, Gerd-Joachim; Schaumlöffel, Dirk; Dobritzsch, Dirk

    2017-11-01

    Aquatic fungi can be used to evaluate the functioning of natural ecosystems. Heliscus lugdunensis is an early colonizer of allochthone leafs. Since this aquatic hyphomycete is able to develop in metal contaminated habitats and tolerates cadmium, it appears to be a good candidate to investigate adaptation to metal pollution. This study aimed at examining the sequestration of Cd in the hyphae of H. lugdunensis, and particularly the role of the tip cells. For that, H. lugdunensis growth was evaluated under various Cd concentrations, and a combination of synchrotron micro X-ray fluorescence and X-ray absorption near edge structure spectroscopy was carried out to determine the compartments of Cd accumulation and the Cd chemical species, respectively. Results showed that the hyphal tip cells were depleted in Cd, and that the metal was stored in older cells. Cd was mainly associated with sulfur ligands and to a lesser extent bound to phosphates and carboxyl/hydroxyl groups from cell wall and/or organic acids. Finally, the aquatic fungus was able to maintain the tip cell as a functional system, thus allowing the colonization of contaminated environments.

  15. Detection of uranium and chemical state analysis of individual radioactive microparticles emitted from the Fukushima nuclear accident using multiple synchrotron radiation X-ray analyses.

    PubMed

    Abe, Yoshinari; Iizawa, Yushin; Terada, Yasuko; Adachi, Kouji; Igarashi, Yasuhito; Nakai, Izumi

    2014-09-02

    Synchrotron radiation (SR) X-ray microbeam analyses revealed the detailed chemical nature of radioactive aerosol microparticles emitted during the Fukushima Daiichi Nuclear Power Plant (FDNPP) accident, resulting in better understanding of what occurred in the plant during the early stages of the accident. Three spherical microparticles (∼2 μm, diameter) containing radioactive Cs were found in aerosol samples collected on March 14th and 15th, 2011, in Tsukuba, 172 km southwest of the FDNPP. SR-μ-X-ray fluorescence analysis detected the following 10 heavy elements in all three particles: Fe, Zn, Rb, Zr, Mo, Sn, Sb, Te, Cs, and Ba. In addition, U was found for the first time in two of the particles, further confirmed by U L-edge X-ray absorption near-edge structure (XANES) spectra, implying that U fuel and its fission products were contained in these particles along with radioactive Cs. These results strongly suggest that the FDNPP was damaged sufficiently to emit U fuel and fission products outside the containment vessel as aerosol particles. SR-μ-XANES spectra of Fe, Zn, Mo, and Sn K-edges for the individual particles revealed that they were present at high oxidation states, i.e., Fe(3+), Zn(2+), Mo(6+), and Sn(4+) in the glass matrix, confirmed by SR-μ-X-ray diffraction analysis. These radioactive materials in a glassy state may remain in the environment longer than those emitted as water-soluble radioactive Cs aerosol particles.

  16. Structural Transformations in High-Capacity Li 2 Cu 0.5 Ni 0.5 O 2 Cathodes

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

    Ruther, Rose E.; Samuthira Pandian, Amaresh; Yan, Pengfei

    2017-03-21

    Cathode materials that can cycle > 1 Li+ per transition metal are of substantial interest to increase the overall energy density of lithium-ion batteries. Li2Cu0.5Ni0.5O2 has a very high theoretical capacity of ~ 500 mAh/g assuming both Li+ are cycled reversibly. The Cu2+/3+ and Ni2+/3+/4+ redox couples are also at high voltage, which could further boost the energy density of this system. Despite such promise, Li2Cu0.5Ni0.5O2 undergoes irreversible phase changes during charge (delithiation) that result in large first-cycle irreversible loss and poor long-term cycling stability. Oxygen is evolved before the Cu2+/3+ or Ni3+/4+ transitions are accessed. In this contribution, XRD,more » TEM, and TXM-XANES are used to follow the chemical and structural changes that occur in Li2Cu0.5Ni0.5O2 during electrochemical cycling. Li2Cu0.5Ni0.5O2 is a solid solution of orthorhombic Li2CuO2 and Li2NiO2, but the structural changes more closely mimic the Li2NiO2 endmember. Li2Cu0.5Ni0.5O2 loses long-range order during charge, but TEM analysis provides clear evidence for particle exfoliation and the transformation from orthorhombic to a partially layered structure. Linear combination fitting and principal component analysis of TXM-XANES are used to map the different phases that emerge during cycling ex situ and in situ. Significant changes in the XANES at the Cu and Ni K-edges correlate with the onset of oxygen evolution.« less

  17. Investigation on porous MnO microsphere anode for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Zhong, Kaifu; Zhang, Bin; Luo, Shihai; Wen, Wen; Li, Hong; Huang, Xuejie; Chen, Liquan

    MnO microspheres with and without carbon coating are prepared as anode materials for lithium ion batteries. The MnO microsphere material shows a reversible capacity of 800 mAh g -1 and an initial efficiency of 71%. It can deliver 600 mAh g -1 at a rate of 400 mA g -1. Results of Mn K-edge X-ray absorption near-edge structure (XANES) spectra and extended X-ray absorption fine structure (EXAFS) confirm further the conversion reaction mechanism, indicate that pristine MnO is reduced to Mn 0 after discharging to 0 V and part of reduced Mn 0 is not oxidized to Mn 2+ after charging to 3 V. This explains the origin of the initial irreversible capacity loss partially. The quasi open circuit voltage and the relationship between the current density and the overpotential are investigated. Both indicate that there is a significant voltage difference between the charging and discharging profiles even when the current density decreases to zero.

  18. Effects of X-ray irradiation on the Eu3+ → Eu2+ conversion in CaAl2O4 phosphors

    NASA Astrophysics Data System (ADS)

    Gomes, Manassés A.; Carvalho, Jéssica C.; Andrade, Adriano B.; Rezende, Marcos V.; Macedo, Zélia S.; Valerio, Mário E. G.

    2018-01-01

    This paper reports structural and luminescence properties of Eu-doped CaAl2O4 produced by an alternative sol-gel method using coconut water. Results of differential thermal analysis (DTA), thermogravimetric analysis (TGA), and X-ray diffraction (XRD) allowed us to identify the best synthesis conditions for sample preparation. Simultaneous measurements of X-ray absorption spectroscopy (XAS) and X-ray excited optical luminescence (XEOL) were also performed in the X-ray energy range of the Eu LIII edge. Results from photoluminescence (PL) showed only the characteristic Eu3+ emission. However, radioluminescence emission spectra from Eu-doped CaAl2O4 shows a process of conversion of Eu3+ to Eu2+, which is induced by X-ray irradiation and is dependent on the radiation dose energy. X-ray absorption near edge structure (XANES) measurements corroborate Eu reduction due to irradiation, showing that only the Eu3+ ion is present in stable form in the CaAl2O4.

  19. Observation of Eye Pattern on Super-Resolution Near-Field Structure Disk with Write-Strategy Technique

    NASA Astrophysics Data System (ADS)

    Fuji, Hiroshi; Kikukawa, Takashi; Tominaga, Junji

    2004-07-01

    Pit-edge recording at a density of 150 nm pits and spaces is carried out on a super-resolution near-field structure (super-RENS) disk with a platinum oxide layer. Pits are recorded and read using a 635-nm-wavelength laser and an objective lens with a 0.6 numerical aperture. We arrange laser pulses to correctly record the pits on the disk by a write-strategy technique. The laser-pulse figure includes a unit time of 0.25 T and intensities of Pw1, Pw2 and Pw3. After recording pits of various lengths, the observation of an eye pattern is achieved despite a pit smaller than the resolution limit. Furthermore, the eye pattern maintains its shape even though other pits fill the adjacent tracks at a track density of 600 nm. The disk can be used as a pit-edge recording system through a write-strategy technique.

  20. Chromium in urban sediment particulates: an integrated micro-chemical and XANES study

    NASA Astrophysics Data System (ADS)

    Taylor, Kevin; Byrne, Patrick; Hudson-Edwards, Karen

    2015-04-01

    Chromium is generally common within the urban sediment cascade as a result of abundant industrial and transport-related sources. The risks that Cr-bearing particles pose to ecosystems and humans depend on the solid phase chemical speciation of Cr in the particles. In this study, we use bulk chemical digests, sequential chemical extraction analysis, electron microscopy, electron microprobe and microfocus XANES analysis to describe the solid-phase speciation of Cr in urban particulate matter from both aquatic sediment and road dust sediment (RDS) in Manchester, UK. Cr-bearing grains within RDS are predominantly iron oxide grains, commonly of goethite or haematite mineralogy, but Cr-bearing silicate glass grains are also present. Iron oxide glass grains most likely have sorbed Cr, and derive from the rusting of Cr-steel particles from vehicles. Electron microprobe analysis indicates concentrations of Cr up to 3200 μg/g in these grains, and XANES analysis indicates that Cr(III) is the dominant oxidation state, with some trace amounts of Cr(VI). Cr-bearing grains within aquatic sediments are dominated by alumino-silicate glass grains derived from industrial waste. These grains contain Cr-rich areas with up to 19% Cr2O3 and XANES analysis indicates that Cr is present as Cr(III). The dominance of Cr(III) in these urban particulate grains suggests limited bioavailability or toxicity. However, the presence within two markedly different grain types (iron oxides and silicate glasses) indicates that the long-term geochemical behaviour and environmental risk of RDS and the aquatic sediments studied are likely to be quite different. These findings highlight the importance of understanding sources of metal contaminants in urban environments and the geochemical processes that affect their transfer through the urban sediment cascade and the wider river basin.

  1. Edge-based image restoration.

    PubMed

    Rareş, Andrei; Reinders, Marcel J T; Biemond, Jan

    2005-10-01

    In this paper, we propose a new image inpainting algorithm that relies on explicit edge information. The edge information is used both for the reconstruction of a skeleton image structure in the missing areas, as well as for guiding the interpolation that follows. The structure reconstruction part exploits different properties of the edges, such as the colors of the objects they separate, an estimate of how well one edge continues into another one, and the spatial order of the edges with respect to each other. In order to preserve both sharp and smooth edges, the areas delimited by the recovered structure are interpolated independently, and the process is guided by the direction of the nearby edges. The novelty of our approach lies primarily in exploiting explicitly the constraint enforced by the numerical interpretation of the sequential order of edges, as well as in the pixel filling method which takes into account the proximity and direction of edges. Extensive experiments are carried out in order to validate and compare the algorithm both quantitatively and qualitatively. They show the advantages of our algorithm and its readily application to real world cases.

  2. Complex polarization propagator approach in the restricted open-shell, self-consistent field approximation: the near K-edge X-ray absorption fine structure spectra of allyl and copper phthalocyanine.

    PubMed

    Linares, Mathieu; Stafström, Sven; Rinkevicius, Zilvinas; Ågren, Hans; Norman, Patrick

    2011-05-12

    A presentation of the complex polarization propagator in the restricted open-shell self-consistent field approximation is given. It rests on a formulation of a resonant-convergent, first-order polarization propagator approach that makes it possible to directly calculate the X-ray absorption cross section at a particular frequency without explicitly addressing the excited states. The quality of the predicted X-ray spectra relates only to the type of density functional applied without any separate treatment of dynamical relaxation effects. The method is applied to the calculation of the near K-edge X-ray absorption fine structure spectra of allyl and copper phthalocyanine. Comparison is made between the spectra of the radicals and those of the corresponding cations and anions to assess the effect of the increase of electron charge in the frontier orbital. The method offers the possibility for unique assignment of symmetry-independent atoms. The overall excellent spectral agreement motivates the application of the method as a routine precise tool for analyzing X-ray absorption of large systems of technological interest.

  3. Effect of edge defects on band structure of zigzag graphene nanoribbons

    NASA Astrophysics Data System (ADS)

    Wadhwa, Payal; Kumar, Shailesh; Dhilip Kumar, T. J.; Shukla, Alok; Kumar, Rakesh

    2018-04-01

    In this article, we report band structure studies of zigzag graphene nanoribbons (ZGNRs) on introducing defects (sp3 hybridized carbon atoms) in different concentrations at edges by varying the ratio of sp3 to sp2 hybridized carbon atoms. On the basis of theoretical analyses, bandgap values of ZGNRs are found to be strongly dependent on the relative arrangement of sp3 to sp2 hybridized carbon atoms at the edges for a defect concentration; so the findings would greatly help in understanding the bandgap of nanoribbons for their electronic applications.

  4. Understanding of sub-band gap absorption of femtosecond-laser sulfur hyperdoped silicon using synchrotron-based techniques

    PubMed Central

    Limaye, Mukta V.; Chen, S. C.; Lee, C. Y.; Chen, L. Y.; Singh, Shashi B.; Shao, Y. C.; Wang, Y. F.; Hsieh, S. H.; Hsueh, H. C.; Chiou, J. W.; Chen, C. H.; Jang, L. Y.; Cheng, C. L.; Pong, W. F.; Hu, Y. F.

    2015-01-01

    The correlation between sub-band gap absorption and the chemical states and electronic and atomic structures of S-hyperdoped Si have been extensively studied, using synchrotron-based x-ray photoelectron spectroscopy (XPS), x-ray absorption near-edge spectroscopy (XANES), extended x-ray absorption fine structure (EXAFS), valence-band photoemission spectroscopy (VB-PES) and first-principles calculation. S 2p XPS spectra reveal that the S-hyperdoped Si with the greatest (~87%) sub-band gap absorption contains the highest concentration of S2− (monosulfide) species. Annealing S-hyperdoped Si reduces the sub-band gap absorptance and the concentration of S2− species, but significantly increases the concentration of larger S clusters [polysulfides (Sn2−, n > 2)]. The Si K-edge XANES spectra show that S hyperdoping in Si increases (decreased) the occupied (unoccupied) electronic density of states at/above the conduction-band-minimum. VB-PES spectra evidently reveal that the S-dopants not only form an impurity band deep within the band gap, giving rise to the sub-band gap absorption, but also cause the insulator-to-metal transition in S-hyperdoped Si samples. Based on the experimental results and the calculations by density functional theory, the chemical state of the S species and the formation of the S-dopant states in the band gap of Si are critical in determining the sub-band gap absorptance of hyperdoped Si samples. PMID:26098075

  5. A high-voltage rechargeable magnesium-sodium hybrid battery

    DOE PAGES

    Li, Yifei; An, Qinyou; Cheng, Yingwen; ...

    2017-02-13

    There is a growing global demand for safe and low-cost energy storage technology which triggers strong interests in novel battery concepts beyond state-of-art Li-ion batteries. We report a high-voltage rechargeable Mg–Na hybrid battery featuring dendrite-free deposition of Mg anode and Na-intercalation cathode as a low-cost and safe alternative to Li-ion batteries for large-scale energy storage. A prototype device using a Na 3V 2(PO 4) 3 cathode, a Mg anode, and a Mg–Na dual salt electrolyte exhibits the highest voltage (2.60 V vs. Mg) and best rate performance (86% capacity retention at 10 C rate) among reported hybrid batteries. Synchrotron radiation-basedmore » X-ray absorption near edge structure (XANES), atomic-pair distribution function (PDF), and high-resolution X-ray diffraction (HRXRD) studies reveal the chemical environment and structural change of Na 3V 2(PO 4) 3 cathode during the Na ion insertion/deinsertion process. XANES study shows a clear reversible shift of vanadium K-edge and HRXRD and PDF studies reveal a reversible two-phase transformation and V–O bond length change during cycling. The energy density of the hybrid cell could be further improved by developing electrolytes with a higher salt concentration and wider electrochemical window. Our work represents a significant step forward for practical safe and low-cost hybrid batteries.« less

  6. Damage and annealing recovery of boron-implanted ultra-shallow junction: The correlation between beam current and surface configuration

    NASA Astrophysics Data System (ADS)

    Chang, Feng-Ming; Wu, Zong-Zhe; Lin, Yen-Fu; Kao, Li-Chi; Wu, Cheng-Ta; JangJian, Shiu-Ko; Chen, Yuan-Nian; Lo, Kuang Yao

    2018-03-01

    The condition of the beam current in the implantation process is a key issue in the damage rate and structural evolution in the sequent annealing process, especially for ultra-shallow layers. In this work, we develop a compensative optical method combined with UV Raman, X-ray photoelectron spectroscopy (XPS), and X-ray absorption near edge spectroscopy (XANES) to inspect the influence of the beam current in the implantation process. The optima condition of the beam current in the implantation process is determined by higher effective Si-B bond portion in UV Raman spectra and less the peak of B-B bond in XPS spectra which is caused by B cluster defects. Results of XANES indicate that the B oxide layer is formed on the surface of the ultra-shallow junction. The defects in the ultra-shallow junction after annealing are analyzed by novel optical analyses, which cannot be inspected by a traditional thermal wave and resistance measurement. This work exhibits the structural variation of the ultra-shallow junction via a variant beam current and provides a valuable metrology in examining the chemical states and the effective activation in the implantation technology.

  7. In situ spectroscopic and solution analyses of the reductive dissolution of Mn02 by Fe(II)

    USGS Publications Warehouse

    Villinski, John E.; O'Day, Peggy A.; Corley, Timothy L.; Conklin, Martha H.

    2001-01-01

    The reductive dissolution of MnO2 by Fe(II) under conditions simulating acid mine drainage (pH 3, 100 mM SO42-) was investigated by utilizing a flow-through reaction cell and synchrotron X-ray absorption spectroscopy. This configuration allows collection of in situ, real-time X-ray absorption near-edge structure (XANES) spectra and bulk solution samples. Analysis of the solution chemistry suggests that the reaction mechanism changed (decreased reaction rate) as MnO2 was reduced and Fe(III) precipitated, primarily as ferrihydrite. Simultaneously, we observed an additional phase, with the local structure of jacobsite (MnFe2O4), in the Mn XANES spectra of reactants and products. The X-ray absorbance of this intermediate phase increased during the experiment, implying an increase in concentration. The presence of this phase, which probably formed as a surface coating, helps to explain the reduced rate of dissolution of manganese(IV) oxide. In natural environments affected by acid mine drainage, the formation of complex intermediate solid phases on mineral surfaces undergoing reductive dissolution may likewise influence the rate of release of metals to solution.

  8. Chlorine levels and species in fine and size resolved atmospheric particles by X-ray absorption near-edge structure spectroscopy analysis in Beijing, China.

    PubMed

    Ouyang, Jie; Yang, Guo-Sheng; Ma, Ling-Ling; Luo, Min; Zheng, Lei; Huo, Qing; Zhao, Yi-Dong; Hu, Tian-Dou; Cai, Zhen-Feng; Xu, Dian-Dou

    2018-04-01

    An understanding of the species of chlorine is crucial in the metropolis-Beijing, which is suffering serious haze pollution with high frequency. Particulate Matters (PMs) with five different sizes were collected in Beijing from July 2009 to March 2016, and characterized non-destructively by X-ray absorption near edge structure spectroscopy. PM <0.2 , PM 0.2-0.5 and PM >2.5 contributed for the major PMs mass in spring and summer, PM 0.5-1.0 and PM 1.0-2.5 contributed for the major PMs mass in autumn and winter. The concentrations of the three chlorine species were in the order of inorganic chlorine (Cl inorg ) > aliphatic chlorine (Cl ali ) > aromatic chlorine (Cl aro ), indicating that Cl inorg constituted the primary chlorine fraction and less toxic Cl ali constituted the primary total organic chlorine (Cl ali  + Cl aro , abbreviated as Cl org ) in the PMs in Beijing. In addition, these three chlorine species exhibited identical seasonal variation in PM 2.5 : winter > autumn > spring > summer. Wet precipitation is an important factor to result in the lower mass concentrations of these three chlorine species in summer. The temporal variations of both size resolved PM mass concentrations and chlorine species concentrations suggested that the air pollution prevention and control in Beijing has just won initial success. Copyright © 2017 Elsevier Ltd. All rights reserved.

  9. Structural Evolution of Reversible Mg Insertion into a Bilayer Structure of V 2 O 5 · n H 2 O Xerogel Material

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

    Sa, Niya; Kinnibrugh, Tiffany L.; Wang, Hao

    Functional multivalent intercalation cathodes represent one of the largest hurdles in the development of Mg batteries. While there are many reports of Mg cathodes, many times the evidence of intercalation chemistry is only circumstantial. In this work, direct evidence of Mg intercalation into a bilayer structure of V2O5·nH2O xerogel is confirmed, and the nature of the Mg intercalated species is reported. The interlayer spacing of V2O5·nH2O contracts upon Mg intercalation and expands for Mg deintercalation due to the strong electrostatic interaction between the divalent cation and the cathode. A combination of NMR, pair distribution function (PDF) analysis, and X-ray absorptionmore » near edge spectroscopy (XANES) confirmed reversible Mg insertion into the V2O5·nH2O material, and structural evolution of Mg intercalation leads to the formation of multiple new phases. Structures of V2O5·nH2O with Mg intercalation were further supported by the first principle simulations. A solvent cointercalated Mg in V2O5·nH2O is observed for the first time, and the 25Mg magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy was used to elucidate the structure obtained upon electrochemical cycling. Specifically, existence of a well-defined Mg–O environment is revealed for the Mg intercalated structures. Information reported here reveals the fundamental Mg ion intercalation mechanism in a bilayer structure of V2O5·nH2O material and provides insightful design metrics for future Mg cathodes.« less

  10. Automated generation and ensemble-learned matching of X-ray absorption spectra

    NASA Astrophysics Data System (ADS)

    Zheng, Chen; Mathew, Kiran; Chen, Chi; Chen, Yiming; Tang, Hanmei; Dozier, Alan; Kas, Joshua J.; Vila, Fernando D.; Rehr, John J.; Piper, Louis F. J.; Persson, Kristin A.; Ong, Shyue Ping

    2018-12-01

    X-ray absorption spectroscopy (XAS) is a widely used materials characterization technique to determine oxidation states, coordination environment, and other local atomic structure information. Analysis of XAS relies on comparison of measured spectra to reliable reference spectra. However, existing databases of XAS spectra are highly limited both in terms of the number of reference spectra available as well as the breadth of chemistry coverage. In this work, we report the development of XASdb, a large database of computed reference XAS, and an Ensemble-Learned Spectra IdEntification (ELSIE) algorithm for the matching of spectra. XASdb currently hosts more than 800,000 K-edge X-ray absorption near-edge spectra (XANES) for over 40,000 materials from the open-science Materials Project database. We discuss a high-throughput automation framework for FEFF calculations, built on robust, rigorously benchmarked parameters. FEFF is a computer program uses a real-space Green's function approach to calculate X-ray absorption spectra. We will demonstrate that the ELSIE algorithm, which combines 33 weak "learners" comprising a set of preprocessing steps and a similarity metric, can achieve up to 84.2% accuracy in identifying the correct oxidation state and coordination environment of a test set of 19 K-edge XANES spectra encompassing a diverse range of chemistries and crystal structures. The XASdb with the ELSIE algorithm has been integrated into a web application in the Materials Project, providing an important new public resource for the analysis of XAS to all materials researchers. Finally, the ELSIE algorithm itself has been made available as part of veidt, an open source machine-learning library for materials science.

  11. XAS Characterization of the Zn Site of Non-structural Protein 3 (NS3) from Hepatitis C Virus

    NASA Astrophysics Data System (ADS)

    Ascone, I.; Nobili, G.; Benfatto, M.; Congiu-Castellano, A.

    2007-02-01

    XANES spectra of non structural protein 3 (NS3) have been calculated using 4 Zn coordination models from three crystallographic structures in the Protein Data Base (PDB): 1DY9, subunit B, 1CU1 subunit A and B, and 1JXP subunit B. Results indicate that XANES is an appropriate tool to distinguish among them. Experimental XANES spectra have been simulated refining crystallographic data. The model obtained by XAS is compared with the PDB models.

  12. Characterization of Sulfur Compounds in Coffee Beans by Sulfur K-XANES Spectroscopy

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

    Lichtenberg, H.; Hormes, J.; Institute of Physics, University of Bonn, Nussallee 12, 53115 Bonn

    2007-02-02

    In this 'feasibility study' the influence of roasting on the sulfur speciation in Mexican coffee beans was investigated by sulfur K-XANES Spectroscopy. Spectra of green and slightly roasted beans could be fitted to a linear combination of 'standard' reference spectra for biological samples, whereas longer roasting obviously involves formation of additional sulfur compounds in considerable amounts.

  13. Boundaries in ground beetle (Coleoptera: Carabidae) and environmental variables at the edges of forest patches with residential developments

    PubMed Central

    Davis, Doreen E.

    2018-01-01

    Background Few studies of edge effects on wildlife objectively identify habitat edges or explore non-linear responses. In this paper, we build on ground beetle (Coleoptera: Carabidae) research that has begun to address these domains by using triangulation wombling to identify boundaries in beetle community structure and composition at the edges of forest patches with residential developments. We hypothesized that edges are characterized by boundaries in environmental variables that correspond to marked discontinuities in vegetation structure between maintained yards and forest. We expected environmental boundaries to be associated with beetle boundaries. Methods We collected beetles and measured environmental variables in 200 m by 200 m sampling grids centered at the edges of three forest patches, each with a rural, suburban, or urban context, in Charlotte, North Carolina, USA. We identified boundaries within each grid at two spatial scales and tested their significance and overlap using boundary statistics and overlap statistics, respectively. We complemented boundary delineation with k-means clustering. Results Boundaries in environmental variables, such as temperature, grass cover, and leaf litter depth, occurred at or near the edges of all three sites, in many cases at both scales. The beetle variables that exhibited the most pronounced boundary structure in relation to edges were total species evenness, generalist abundance, generalist richness, generalist evenness, and Agonum punctiforme abundance. Environmental and beetle boundaries also occurred within forest patches and residential developments, indicating substantial localized spatial variation on either side of edges. Boundaries in beetle and environmental variables that displayed boundary structure at edges significantly overlapped, as did boundaries on either side of edges. The comparison of boundaries and clusters revealed that boundaries formed parts of the borders of patches of similar beetle or

  14. Boundaries in ground beetle (Coleoptera: Carabidae) and environmental variables at the edges of forest patches with residential developments.

    PubMed

    Davis, Doreen E; Gagné, Sara A

    2018-01-01

    Few studies of edge effects on wildlife objectively identify habitat edges or explore non-linear responses. In this paper, we build on ground beetle (Coleoptera: Carabidae) research that has begun to address these domains by using triangulation wombling to identify boundaries in beetle community structure and composition at the edges of forest patches with residential developments. We hypothesized that edges are characterized by boundaries in environmental variables that correspond to marked discontinuities in vegetation structure between maintained yards and forest. We expected environmental boundaries to be associated with beetle boundaries. We collected beetles and measured environmental variables in 200 m by 200 m sampling grids centered at the edges of three forest patches, each with a rural, suburban, or urban context, in Charlotte, North Carolina, USA. We identified boundaries within each grid at two spatial scales and tested their significance and overlap using boundary statistics and overlap statistics, respectively. We complemented boundary delineation with k -means clustering. Boundaries in environmental variables, such as temperature, grass cover, and leaf litter depth, occurred at or near the edges of all three sites, in many cases at both scales. The beetle variables that exhibited the most pronounced boundary structure in relation to edges were total species evenness, generalist abundance, generalist richness, generalist evenness, and Agonum punctiforme abundance. Environmental and beetle boundaries also occurred within forest patches and residential developments, indicating substantial localized spatial variation on either side of edges. Boundaries in beetle and environmental variables that displayed boundary structure at edges significantly overlapped, as did boundaries on either side of edges. The comparison of boundaries and clusters revealed that boundaries formed parts of the borders of patches of similar beetle or environmental condition. We

  15. Electronic-Reconstruction-Enhanced Tunneling Conductance at Terrace Edges of Ultrathin Oxide Films.

    PubMed

    Wang, Lingfei; Kim, Rokyeon; Kim, Yoonkoo; Kim, Choong H; Hwang, Sangwoon; Cho, Myung Rae; Shin, Yeong Jae; Das, Saikat; Kim, Jeong Rae; Kalinin, Sergei V; Kim, Miyoung; Yang, Sang Mo; Noh, Tae Won

    2017-11-01

    Quantum mechanical tunneling of electrons across ultrathin insulating oxide barriers has been studied extensively for decades due to its great potential in electronic-device applications. In the few-nanometers-thick epitaxial oxide films, atomic-scale structural imperfections, such as the ubiquitously existed one-unit-cell-high terrace edges, can dramatically affect the tunneling probability and device performance. However, the underlying physics has not been investigated adequately. Here, taking ultrathin BaTiO 3 films as a model system, an intrinsic tunneling-conductance enhancement is reported near the terrace edges. Scanning-probe-microscopy results demonstrate the existence of highly conductive regions (tens of nanometers wide) near the terrace edges. First-principles calculations suggest that the terrace-edge geometry can trigger an electronic reconstruction, which reduces the effective tunneling barrier width locally. Furthermore, such tunneling-conductance enhancement can be discovered in other transition metal oxides and controlled by surface-termination engineering. The controllable electronic reconstruction can facilitate the implementation of oxide electronic devices and discovery of exotic low-dimensional quantum phases. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Discovery of Super-Thin Disks in Nearby Edge-on Spiral Galaxies

    NASA Astrophysics Data System (ADS)

    Schechtman-Rook, A.; Bershady, M. A.

    2014-03-01

    We report the identification of a super-thin disk (hz˜ 60 pc) in the edge-on spiral galaxy NGC 891. This component is only apparent after we perform a physically motivated attenuation correction, based on detailed radiation transfer models, to our sub-arcsecond resolution near-infrared imaging. In addition to the super-thin disk, we also find several structural features near the center of NGC 891, including an inner disk truncation at ˜3 kpc. Inner disk truncations may be commonplace among massive spiral galaxies, possibly due to the effects of instabilities, such as bars. Having successfully demonstrated our methods, we are poised to apply them to a small sample of nearby edge-on galaxies, consisting both of massive and low-mass spirals.

  17. Elucidating the Nature of the Excited State of a Heteroleptic Copper Photosensitizer by using Time-Resolved X-ray Absorption Spectroscopy.

    PubMed

    Moonshiram, Dooshaye; Garrido-Barros, Pablo; Gimbert-Suriñach, Carolina; Picón, Antonio; Liu, Cunming; Zhang, Xiaoyi; Karnahl, Michael; Llobet, Antoni

    2018-04-25

    We report the light-induced electronic and geometric changes taking place within a heteroleptic Cu I photosensitizer, namely [(xant)Cu(Me 2 phenPh 2 )]PF 6 (xant=xantphos, Me 2 phenPh 2 =bathocuproine), by time-resolved X-ray absorption spectroscopy in the ps-μs time regime. Time-resolved X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) analysis enabled the elucidation of the electronic and structural configuration of the copper center in the excited state as well as its decay dynamics in different solvent conditions with and without triethylamine acting as a sacrificial electron donor. A three-fold decrease in the decay lifetime of the excited state is observed in the presence of triethylamine, showing the feasibility of the reductive quenching pathway in the latter case. A prominent pre-edge feature is observed in the XANES spectrum of the excited state upon metal to charge ligand transfer transition, showing an increased hybridization of the 3d states with the ligand p orbitals in the tetrahedron around the Cu center. EXAFS and density functional theory illustrate a significant shortening of the Cu-N and an elongation of the Cu-P bonds together with a decrease in the torsional angle between the xantphos and bathocuproine ligand. This study provides mechanistic time-resolved understanding for the development of improved heteroleptic Cu I photosensitizers, which can be used for the light-driven production of hydrogen from water. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Edge effect on a vacancy state in semi-infinite graphene

    NASA Astrophysics Data System (ADS)

    Deng, Hai-Yao; Wakabayashi, Katsunori

    2014-09-01

    The edge effect on a single vacancy state of semi-infinite graphene (SIG) has been studied using Green's function method within the tight-binding model. In the case of infinite graphene, it is known that a vacancy induces a zero-energy resonance state, whose wave function decays inversely with distance (R) from the vacancy and is not normalizable. However, for SIG with an armchair edge, we find that the corresponding wave function decays as R-2 and hence becomes normalizable owing to the intervalley interference caused by the armchair edge. For SIG with a zigzag edge, the vacancy state depends on the sublattice of the vacancy. When the vacancy and the edge belong to different sublattices, the vacancy has no effect on the zero-energy vacancy state. In contrast, when the vacancy is located on the same sublattice as the edge, the resonance state disappears but the wave function at zero energy is strongly distorted near the vacancy. Our results reveal that the presence of edges crucially changes the vacancy state in graphene, and thus such a state can be used to probe the edge structure.

  19. Numerical Investigations of the Influence of Unsteady Vane Trailing Edge Shock Wave on Film Cooling Effectiveness of Rotor Blade Leading Edge

    NASA Astrophysics Data System (ADS)

    Wang, Yufeng; Cai, Le; Wang, Songtao; Zhou, Xun

    2018-04-01

    Unsteady numerical simulations of a high-load transonic turbine stage have been carried out to study the influences of vane trailing edge outer-extending shockwave on rotor blade leading edge film cooling performance. The turbine stage used in this paper is composed of a vane section and a rotor one which are both near the root section of a transonic high-load turbine stage. The Mach number is 0.94 at vane outlet, and the relative Mach number is above 1.10 at rotor outlet. Various positions and oblique angles of film cooling holes were investigated in this research. Results show that the cooling efficiency on the blade surface of rotor near leading edge is significantly affected by vane trailing edge outer-extending shockwave in some cases. In the cases that film holes are close to leading edge, cooling performance suffers more from the sweeping vane trailing edge outer-extending shockwave. In addition, coolant flow ejected from oblique film holes is harder to separate from the blade surface of rotor, and can cover more blade area even under the effects of sweeping vane trailing edge shockwave. As a result, oblique film holes can provide better film cooling performance than vertical film holes do near the leading edge on turbine blade which is swept by shockwaves.

  20. Effect of edge pruning on structural controllability and observability of complex networks

    PubMed Central

    Mengiste, Simachew Abebe; Aertsen, Ad; Kumar, Arvind

    2015-01-01

    Controllability and observability of complex systems are vital concepts in many fields of science. The network structure of the system plays a crucial role in determining its controllability and observability. Because most naturally occurring complex systems show dynamic changes in their network connectivity, it is important to understand how perturbations in the connectivity affect the controllability of the system. To this end, we studied the control structure of different types of artificial, social and biological neuronal networks (BNN) as their connections were progressively pruned using four different pruning strategies. We show that the BNNs are more similar to scale-free networks than to small-world networks, when comparing the robustness of their control structure to structural perturbations. We introduce a new graph descriptor, ‘the cardinality curve’, to quantify the robustness of the control structure of a network to progressive edge pruning. Knowing the susceptibility of control structures to different pruning methods could help design strategies to destroy the control structures of dangerous networks such as epidemic networks. On the other hand, it could help make useful networks more resistant to edge attacks. PMID:26674854