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Sample records for techniques xanes exafs

  1. XANES and EXAFS study of the TiN Thin films grown by the pulsed DC sputtering technique assisted by balanced magnetron

    Energy Technology Data Exchange (ETDEWEB)

    Duarte M, A.; Esparza P, H.; Gonzalez V, C. [Centro de Investigacion en Materiales Avanzados, S. C., Miguel de Cervantes 120, Complejo Industrial Chihuahua Chihuahua, Chih. 31109 (Mexico); Yocupicio, I. [Universidad de Sonora, Unidad Regional Sur Lazaro Cardenas No. 100 Col. Fco. Villa, Navojoa, Sonora (Mexico)

    2007-07-01

    A series of different Ti{sub x}N{sub y} thin films were grown by the DC-sputtering technique. The purpose for this work was to study through XAS interpretation, how the different amounts of N{sub 2} during growing thin TiN thin films, affects the stoichiometry of the TiN deposited. Also the results obtained determinate how to interpret the spectra to see the different valences of Ti in TiN, are working. The results were supported with the EXAFS and XANES analysis. This work concludes the adequate conditions for this experiment to obtain TiN as thin film by the DC sputtering assisted by pulsed balanced magnetron at room temperature and concludes which XANES spectra are the finger print for valences of Ti. (Author)

  2. EXAFS and XANES analysis of oxides at the nanoscale

    Directory of Open Access Journals (Sweden)

    Alexei Kuzmin

    2014-11-01

    Full Text Available 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.

  3. XANES, EXAFS and photoluminescence investigations on the amorphous Eu:HfO2.

    Science.gov (United States)

    Sharma, Aditya; Varshney, Mayora; Shin, Hyun-Joon; Chae, KeunHwa; Won, Sung Ok

    2017-02-15

    We report detailed investigations on the local electronic/atomic structure and photoluminescence properties of chemically synthesized Eu:HfO2 powders. X-ray diffraction (XRD), X-ray absorption near edge structure (XANES), extended X-ray absorption fine structure (EXAFS) and photoluminescence (PL) measurements were performed to analyze the crystal structure, local atomic/electronic structure and luminescence properties of the samples. No crystalline phases were detected with Cu Kα (λ=1.5418Å) based XRD; however, local monoclinic structure was confirmed by the Hf L-edge XANES and EXAFS. O K-edge XANES spectral features could be deconvoluted with doublets and triplets in eg and t2g orbitals, respectively, which ascribed to the local monoclinic structure for all of the samples. Eu M5,4-edge XANES confirmed the pre-dominancy of Eu(3+) ions in the HfO2 samples with a fractional amount of Eu(2+) ions. PL spectra revealed the electric dipole allowed ((5)D0-(7)F0,2,4) emission properties of Eu:HfO2 samples. The orange-red emission is ascribed to the Eu interstitial/surface segregation induced defects. Copyright © 2016. Published by Elsevier B.V.

  4. XANES, EXAFS and photoluminescence investigations on the amorphous Eu:HfO2

    Science.gov (United States)

    Sharma, Aditya; Varshney, Mayora; Shin, Hyun-Joon; Chae, KeunHwa; Won, Sung Ok

    2017-02-01

    We report detailed investigations on the local electronic/atomic structure and photoluminescence properties of chemically synthesized Eu:HfO2 powders. X-ray diffraction (XRD), X-ray absorption near edge structure (XANES), extended X-ray absorption fine structure (EXAFS) and photoluminescence (PL) measurements were performed to analyze the crystal structure, local atomic/electronic structure and luminescence properties of the samples. No crystalline phases were detected with Cu Kα (λ = 1.5418 Å) based XRD; however, local monoclinic structure was confirmed by the Hf L-edge XANES and EXAFS. O K-edge XANES spectral features could be deconvoluted with doublets and triplets in eg and t2g orbitals, respectively, which ascribed to the local monoclinic structure for all of the samples. Eu M5,4-edge XANES confirmed the pre-dominancy of Eu3 + ions in the HfO2 samples with a fractional amount of Eu2 + ions. PL spectra revealed the electric dipole allowed (5D0-7F0,2,4) emission properties of Eu:HfO2 samples. The orange-red emission is ascribed to the Eu interstitial/surface segregation induced defects.

  5. An EXAFS and XANES study of MBE grown Cu-doped ZnO

    CERN Document Server

    Fons, P; Iwata, K; Matsubara, K; Niki, S; Nakahara, K; Takasu, H

    2003-01-01

    The wide bandgap semiconductor, ZnO, is intrinsically n-type and one of the remaining hurdles to be overcome before it can be used for optoelectronic applications is achieving p-type doping. A potential candidate for a p-type dopant is Cu. Towards this end, X-ray near-edge absorption (XANES) has been used to determine changes in valency of Cu in molecular beam epitaxial grown ZnO as a function of growth parameters. Growth parameters varied include the Cu flux which was varied over roughly three orders of magnitude T sub C sub u =800-1000 deg. C and two substrate temperatures: 300 and 600 deg. C. XANES measurements confirmed that Cu was in the +1 valence state for all as-grown samples. Preliminary EXAFS measurements also demonstrated that Cu incorporated into a Zn-atom position substitutionally. X-ray diffraction also indicated significant phase separation with the presence of both metallic Cu and CuO indicated for Cu concentrations >3x10 sup 2 sup 1 cm sup - sup 3.

  6. EXAFS, XANES, and DFT study of the mixed-valence compound YMn2O5 : Site-selective substitution of Fe for Mn

    Science.gov (United States)

    Wunderlich, F.; Leisegang, T.; Weißbach, T.; Zschornak, M.; Stöcker, H.; Dshemuchadse, J.; Lubk, A.; Führlich, T.; Welter, E.; Souptel, D.; Gemming, S.; Seifert, G.; Meyer, D. C.

    2010-07-01

    In YMn2O5 , the Mn atoms occupy two nonequivalent Wyckoff sites within the unit cell exhibiting different oxygen coordinations, i.e., the system can be characterized as a mixed-valence compound. For the formation of the orthorhombic crystal structure, Jahn-Teller distortions are assumed to play an important role. In this study, we aimed at the investigation of the crystal structure changes upon the substitution of Mn by the non-Jahn-Teller cation Fe3+ . Therefore, we synthesized a series of YMn2-xFexO5 powder samples with x=0 , 0.5, and 1 by a citrate technique. We utilized extended x-ray absorption fine structure (EXAFS) and x-ray absorption near-edge structure (XANES) analysis as well as density-functional theory (DFT) to investigate the two nonequivalent Wyckoff sites within the orthorhombic crystal structure (confirmed for all compositions) occupied by transition-metal atoms. For quantitative determination of structural short-range order, all plausible options of substitution of Fe for Mn are discussed. On the basis of these evaluations, the EXAFS and XANES behavior is analyzed and appropriate crystallographic weights are assigned to the subset of structural models in accordance with the experimental data. From EXAFS analysis, using multiple-scattering theory, we conclude only the 4h Wyckoff site to be occupied by Fe [occupancy refined is (100±3)% in case of x=1 ]. Furthermore, taking the XANES spectra into account, we are able to verify the EXAFS results and additionally explain the differences in the MnK XANES spectra in dependence on x to be caused by changes in the dipole transitions to 4p final states. From quantitative pre-edge analysis an oxidation number of +4 for the Mn atom for x=1 is determined whereas the Fe valence is shown to be unchanged. Since the substitution process only involves one Wyckoff site, the experimentally observed limit to a maximum amount of x=1 is explained. Additionally, a possible disorder, discussed in the literature, is not

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

    Science.gov (United States)

    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

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

    Energy Technology Data Exchange (ETDEWEB)

    Robblee, John Henry [Univ. of California, Berkeley, CA (United States)

    2000-12-01

    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 S3 → [S4] → S0 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 electron paramagnetic resonance (EPR) data obtained from the same set of samples, show that the S2 → S3 transition, in contrast to the S0 → S1 and S1 → S2 transitions, does not involve a Mn-centered oxidation. This is rationalized by manganese μ-oxo bridge radical formation during the S2 → S3 transition. Using extended X-ray absorption fine structure (EXAFS) spectroscopy, the local environment of the Mn atoms in the S0 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 S1} state to 2.85 Å in the S0 state. Furthermore, evidence is presented that shows three di-μ-oxo binuclear Mn2 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 S0 state have been investigated and a characteristic ''multiline'' signal in the S0 state has been discovered in the presence of methanol. This provides the first direct confirmation that the native S0 state is paramagnetic. In addition, this signal was simulated using parameters derived from three

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

    Energy Technology Data Exchange (ETDEWEB)

    Robblee, John H.

    2000-12-01

    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{sub 3} {r_arrow} [S{sub 4}] {r_arrow} S{sub 0} transition. Progress in instrumentation and flash sample preparation allowed us to apply Mn K{beta} X-ray emission spectroscopy (Kb XES) to this problem for the first time. The K{beta} XES results, in combination with Mn X-ray absorption near-edge structure (XANES) and electron paramagnetic resonance (EPR) data obtained from the same set of samples, show that the S{sub 2} {r_arrow} S{sub 3} transition, in contrast to the S{sub 0} {r_arrow} S{sub 1} and S{sub 1} {r_arrow} S{sub 2} transitions, does not involve a Mn-centered oxidation. This is rationalized by manganese {mu}-oxo bridge radical formation during the S{sub 2} {r_arrow} S{sub 3} transition. Using extended X-ray absorption fine structure (EXAFS) spectroscopy, the local environment of the Mn atoms in the S{sub 0} state has been structurally characterized. These results show that the Mn-Mn distance in one of the di-{mu}-oxo-bridged Mn-Mn moieties increases from 2.7 {angstrom} in the S{sub 1} state to 2.85 {angstrom} in the S{sub 0} state. Furthermore, evidence is presented that shows three di-{mu}-oxo binuclear Mn{sub 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{sub 0} state have been investigated and a characteristic ''multiline'' signal in the S{sub 0} state has been discovered in the presence of methanol. This provides the first direct confirmation that the native S{sub 0} state is paramagnetic. In addition, this signal was simulated using parameters derived from three possible oxidation states of

  10. Reduction and re-oxidation of Cu/Al{sub 2}O{sub 3} catalysts investigated with quick-scanning XANES and EXAFS

    Energy Technology Data Exchange (ETDEWEB)

    Stoetzel, J; Luetzenkirchen-Hecht, D; Frahm, R [Department of Physics, University of Wuppertal, Gaussstr. 20, D-42097 Wuppertal (Germany); Kimmerle, B; Baiker, A [Department of Chemistry and Applied Biosciences, ETH Zuerich, CH-8093 Zuerich (Switzerland); Nachtegaal, M [Paul Scherrer Institut, CH-5232 Villigen (Switzerland); Beier, M J; Grunwaldt, J-D, E-mail: j.stoetzel@uni-wuppertal.d, E-mail: jdg@kt.dtu.d [Department of Chemical and Biochemical Engineering, Technical University of Denmark, Building 229, DK-2800 Kgs. Lyngby (Denmark)

    2009-11-15

    In the present study the structure of copper catalysts on alumina support were investigated in situ and time resolved during reduction and re-oxidation at different temperatures with the quick-scanning EXAFS (QEXAFS) technique. Different impregnation times (2 min and 90 min) were chosen for the preparation which resulted in different copper species that show a strong variation in the reduction/re-oxidation behaviour. These dynamic changes as well as possible intermediate phases during the gas atmospheres changes were followed with up to 20 EXAFS spectra per second at the copper K-edge covering an energy range of 450 eV. The high time resolution provided new insights into the dynamics of the catalysts e.g. revealing Cu(I) as intermediate state during re-oxidation. Latest advances in the data acquisition hardware are leading to an improved data quality of spectra collected at the SuperXAS beamline. Thus, not only accurate analysis of the catalysts via XANES but also by EXAFS was possible. This is also due to the recent upgrade to monitor the Bragg angle directly with an encoder during the experiments.

  11. Shape resonances and EXAFS scattering in the $Pt L_{2,3}$ XANES from a Pt electrode

    CERN Document Server

    O'Grady, W E

    1999-01-01

    Atomic hydrogen and oxygen adsorption on a platinum electrode in H /sub 2/SO/sub 4/ and HClO/sub 4/ electrolytes were studied by Pt L /sub 23/ XANES. The Pt electrode was formed of highly dispersed 1.5-3.0 nm particles supported on $9 carbon. A difference procedure utilizing the L/sub 2/ and L/sub 3/ spectra at various applied voltages was used to isolate the electronic and geometric effects in the XANES spectra. At 0.54 V (relative to RHE) the Pt electrode in $9 HClO/sub 4/ is assumed to be "clean". By taking the difference between the spectra at 0.0 and 0.54 V, the Pt-H antibonding state (electronic effect) is isolated and found to have a Fano-resonance line shape. In addition, a $9 significant Pt-H EXAFS scattering (geometric effect) was found for photon energies 0 to 20 eV above the edge. The difference between the spectra at 1.14 and 0.54 V allows isolation of the Pt-O antibonding state and the Pt-O EXAFS $9 scattering. (7 refs).

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  14. Reinvestigation of the EXAFS and xanes spectra of ferrocene and nickelocene in the framework of the multiple scattering theory

    Science.gov (United States)

    Ruiz-Lopez, M. F.; Loos, M.; Goulon, J.; Benfatto, M.; Natoli, C. R.

    1988-04-01

    This paper produces direct evidences that even non-collinear scattering paths can give rise to well-detectable and interpretable signatures in EXAFS spectra. Ferrocene or nickelocene are most favourable examples to study these rather small signals because the shortest intermolecular distances are too large to interfer with them and add no significant contribution to the EXAFS spectrum. For the first time, we have been able to resolve in the R-space individual contributions of specific double and triple scattering paths and also to reproduce their relative amplitudes and phases using full ab initio simulations carried out in the general regime of spherical wave propagation of the ejected/scattered photoelectron. Due to considerable rotational disorder of the cyclopentadienyl (C p) rings, especially at room temperature, all multiple scattering paths involving carbon atoms located on different rings were found to vanish. Full multiple scattering XANES calculations have also been performed on the same systems and were shown to be identical in the staggered (D 5d) or eclipsed (D 5h) conformations of the C p rings. The experimental XANES spectra exhibit a shoulder which is better resolved in the case of ferrocene: our simulations have established the origin of this shoulder and that its resolution was sensitive to small variations of the metal…C bond lengths. The weak pre-edge structure can be explained either by a quadrupolar allowed transition to an antibonding (3d-like) excited state of symmetry 5e 1g if the rings have D 5d group symmetry, or by a disorder-allowed dipolar transition to the corresponding state if the group symmetry is reduced to D 5. In the case of ferrocene, there is also an additional "bump" at ≈ 12 eV past the main absorption peak, which is not reproduced by our single-electron calculations: a possible interpretation which, however, is not yet firmly established, is to assign this feature to a multielectron shakeup satellite.

  15. Mechanistic insights on the electronic properties and electronic/atomic structure aspects in orthorhombic SrVO3 thin films: XANES-EXAFS study.

    Science.gov (United States)

    Sharma, Aditya; Varshney, Mayora; Cheol Lim, Weon; Shin, Hyun-Joon; Pal Singh, Jitendra; Ok Won, Sung; Hwa Chae, Keun

    2017-03-01

    Correlations among the B-O6 octahedra distortions, existing polymorphous phases, band structures and electronic conductivities of ABO3 perovskites are matters for debate and require a deep understanding of their local atomic/electronic structures and diverse assets. In this study, to illustrate the distortion in V-O6 octahedra and its implication on the band structure and electronic properties, spectroscopic investigations on the RF-sputtering grown insulating SrVO3 thin films were employed using X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS). V K-edge and V L3,2-edge XANES, along with atomic multiplet calculations, have confirmed the 4+ oxidation state of V ions in the pristine and annealed SrVO3 thin films. Lower t2g/eg peak intensity ratio and smaller energy separation between t2g and eg peaks in the O K-edge XANES spectra, compared to the VO2 reference sample, have confirmed a larger V-O6 distortion in the orthorhombic SrVO3 thin films. Moreover, from the EXAFS data analysis, the local orthorhombic structure has been identified in the pristine and annealed SrVO3 thin films, compelling significant distortion in the V-O6 octahedra. Dimerization in the vanadium chains and V-V twisting, caused by V-O6 octahedra distortion, manifests a miscellaneous ligand field interaction between O 2p and V 3d orbitals and facilitates (i) a larger separation between the bonding and antibonding d‖ orbitals and (ii) an upward shift of the π* band in the band structure, leading to larger band gaps in the insulating SrVO3 thin films. Our spectroscopy results may open up new avenues for the mechanism of insulating/conducting character in other complicated perovskite materials using XANES-EXAFS.

  16. The status of strontium in biological apatites: an XANES/EXAFS investigation.

    Science.gov (United States)

    Bazin, Dominique; Dessombz, Arnaud; Nguyen, Christelle; Ea, Hang Korng; Lioté, Frédéric; Rehr, John; Chappard, Christine; Rouzière, Stephan; Thiaudière, Dominique; Reguer, Solen; Daudon, Michel

    2014-01-01

    Osteoporosis represents a major public health problem through its association with fragility fractures. The public health burden of osteoporotic fractures will rise in future generations, due in part to an increase in life expectancy. Strontium-based drugs have been shown to increase bone mass in postmenopausal osteoporosis patients and to reduce fracture risk but the molecular mechanisms of the action of these Sr-based drugs are not totally elucidated. The local environment of Sr(2+) cations in biological apatites present in pathological and physiological calcifications in patients without such Sr-based drugs has been assessed. In this investigation, X-ray absorption spectra have been collected for 17 pathological and physiological calcifications. These experimental data have been combined with a set of numerical simulations using the ab initio FEFF9 X-ray spectroscopy program which takes into account possible distortion and Ca/Sr substitution in the environment of the Sr(2+) cations. For selected samples, Fourier transforms of the EXAFS modulations have been performed. The complete set of experimental data collected on 17 samples indicates that there is no relationship between the nature of the calcification (physiological and pathological) and the adsorption mode of Sr(2+) cations (simple adsorption or insertion). Such structural considerations have medical implications. Pathological and physiological calcifications correspond to two very different preparation procedures but are associated with the same localization of Sr(2+) versus apatite crystals. Based on this study, it seems that for supplementation of Sr at low concentration, Sr(2+) cations will be localized into the apatite network.

  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

    Science.gov (United States)

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

    2016-05-01

    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.

  18. Combined sulfur K-edge XANES-EXAFS study of the effect of protonation on the sulfate tetrahedron in solids and solutions.

    Science.gov (United States)

    Pin, S; Huthwelker, T; Brown, M A; Vogel, F

    2013-09-01

    Sulfur K-edge X-ray absorption spectroscopy (XAS) has been used to distinguish between aqueous and solid sulfates and to investigate changes in their speciation. Data have been collected for tetrahedrally coordinated S in K2SO4 and KHSO4 solids and aqueous solutions. With a first qualitative analysis of the X-ray absorption near-edge structure (XANES) spectra, it has been observed that those for solids are much more structured and distinguishable from those of aqueous solutions. The protonation state has a strong effect on the white line of sulfates and has been assigned to the different charge delocalization in the samples, the effect of the solvating water molecules and multiple scattering effects. In the extended X-ray absorption fine structure (EXAFS) spectra, the backscattering from the first O shell dominated the EXAFS fine structure function, χ(k), but the nonlinear multiple scattering contributions occurring in the first coordination shell are significant and must be considered in the EXAFS analysis. The intensity of these contributions strongly depend on the symmetry of the system. For a distorted tetrahedron, the intensity of the multiple scattering contributions is less than that found in a regular tetrahedron. The FEFF code has been used to model the contributions of the multiple-scattering processes. The observed experimental evidence in the XAS data can be used to distinguish between sulfates in solids and liquids. This is applicable to many chemical, geochemical, and biological systems.

  19. Mechanical investigation of U(VI) on pyrrhotite by batch, EXAFS and modeling techniques.

    Science.gov (United States)

    Liu, Haibo; Zhu, Yuke; Xu, Bin; Li, Ping; Sun, Yubing; Chen, Tianhu

    2017-01-15

    The interaction mechanism of U(VI) on pyrrhotite was demonstrated by batch, spectroscopic and modeling techniques. Pyrite was selected as control group in this study. The removal of U(VI) on pyrite and pyrrhotite significantly decreased with increasing ionic strength from 0.001 to 0.1mol/L at pH 2.0-6.0, whereas the no effect of ionic strength was observed at pH >6.0. The maximum removal capacity of U(VI) on pyrite and pyrrhotite calculated from Langmuir model was 10.20 and 21.34mgg(-1) at pH 4.0 and 333K, respectively. The XPS analysis indicated the U(VI) was primarily adsorbed on pyrrhotite and pyrite and then approximately 15.5 and 9.8% of U(VI) were reduced to U(IV) by pyrrhotite and pyrite after 20 days, respectively. Based on the XANES analysis, the adsorption edge of uranium-containing pyrrhotite located between U(IV)O2(s) and U(VI)O2(2+) spectra. The EXAFS analysis demonstrated the inner-sphere surface complexation of U(VI) on pyrrhotite due to the occurrence of U-S shell, whereas the U-U shell revealed the reductive co-precipitates of U(VI) on pyrrhotite/pyrite with increasing reaction times. The surface complexation modeling showed that outer- and inner-surface complexation dominated the U(VI) removal at pH5.0, respectively. The findings presented herein play a crucial role in the removal of radionuclides on iron sulfide in environmental cleanup applications.

  20. Effect of Fe(II)/Ce(III) dosage ratio on the structure and anion adsorptive removal of hydrothermally precipitated composites: Insights from EXAFS/XANES, XRD and FTIR.

    Science.gov (United States)

    Chubar, Natalia; Gerda, Vasyl; Banerjee, Dipanjan; Yablokova, Ganna

    2017-02-01

    In this work, we present material chemistry in the hydrothermal synthesis of new complex structure materials based on various dosage ratios of Fe and Ce (1:0, 2:1, 1:1, 1:2, 0:1), characterize them by the relevant methods that allow characterization of both crystalline and amorphous phases and correlate their structure/surface properties with the adsorptive performance of the five toxic anions. The applied synthesis conditions resulted in the formation of different compounds of Fe and Ce components. The Fe-component was dominated by various phases of Fe hydrous oxides, whereas the Ce-component was composed of various phases of Ce carbonates. The presence of two metal salts in raw materials resulted in the formation of a mesoporous structure and averaged the surface area compared to one metal-based material. The surface of all Fe-Ce composites was abundant in Fe component phases. Two-metal systems showed stronger anion removal performance than one-metal materials. The best adsorption was demonstrated by Fe-Ce based materials that had low crystallinity, that were rich in phases and that exhibited surfaces were abundant in greater number of surface functional groups. Notably, Fe extended fine structures simulated by EXAFS in these better adsorbents were rich from oscillations from both heavy and light atoms. This work provides new insights on the structure of composite inorganic materials useful to develop their applications in adsorption and catalysis. It also presents new inorganic anion exchangers with very high removal potential to fluoride and arsenate. Copyright © 2016 Elsevier Inc. All rights reserved.

  1. Effect of Fe(II)/Ce(III) dosage ratio on the structure and anion adsorptive removal of hydrothermally precipitated composites: Insights from EXAFS/XANES, XRD and FTIR

    KAUST Repository

    Chubar, Natalia

    2016-10-24

    In this work, we present material chemistry in the hydrothermal synthesis of new complex structure materials based on various dosage ratios of Fe and Ce (1:0, 2:1, 1:1, 1:2, 0:1), characterize them by the relevant methods that allow characterization of both crystalline and amorphous phases and correlate their structure/surface properties with the adsorptive performance of the five toxic anions. The applied synthesis conditions resulted in the formation of different compounds of Fe and Ce components. The Fe-component was dominated by various phases of Fe hydrous oxides, whereas the Ce-component was composed of various phases of Ce carbonates. The presence of two metal salts in raw materials resulted in the formation of a mesoporous structure and averaged the surface area compared to one metal-based material. The surface of all Fe-Ce composites was abundant in Fe component phases. Two-metal systems showed stronger anion removal performance than one-metal materials. The best adsorption was demonstrated by Fe-Ce based materials that had low crystallinity, that were rich in phases and that exhibited surfaces were abundant in greater number of surface functional groups. Notably, Fe extended fine structures simulated by EXAFS in these better adsorbents were rich from oscillations from both heavy and light atoms. This work provides new insights on the structure of composite inorganic materials useful to develop their applications in adsorption and catalysis. It also presents new inorganic anion exchangers with very high removal potential to fluoride and arsenate.

  2. Can we trust mass spectrometry for determination of arsenic peptides in plants: comparison of LC-ICP-MS and LC-ES-MS/ICP-MS with XANES/EXAFS in analysis of Thunbergia alata.

    Science.gov (United States)

    Bluemlein, Katharina; Raab, Andrea; Meharg, Andrew A; Charnock, John M; Feldmann, Jörg

    2008-04-01

    The weakest step in the analytical procedure for speciation analysis is extraction from a biological material into an aqueous solution which undergoes HPLC separation and then simultaneous online detection by elemental and molecular mass spectrometry (ICP-MS/ES-MS). This paper describes a study to determine the speciation of arsenic and, in particular, the arsenite phytochelatin complexes in the root from an ornamental garden plant Thunbergia alata exposed to 1 mg As L(-1) as arsenate. The approach of formic acid extraction followed by HPLC-ES-MS/ICP-MS identified different As(III)-PC complexes in the extract of this plant and made their quantification via sulfur (m/z 32) and arsenic (m/z 75) possible. Although sulfur sensitivity could be significantly increased when xenon was used as collision gas in ICP-qMS, or when HR-ICP-MS was used in medium resolution, the As:S ratio gave misleading results in the identification of As(III)-PC complexes due to the relatively low resolution of the chromatography system in relation to the variety of As-peptides in plants. Hence only the parallel use of ES-MS/ICP-MS was able to prove the occurrence of such arsenite phytochelatin complexes. Between 55 and 64% of the arsenic was bound to the sulfur of peptides mainly as As(III)(PC(2))(2), As(III)(PC(3)) and As(III)(PC(4)). XANES (X-ray absorption near-edge spectroscopy) measurement, using the freshly exposed plant root directly, confirmed that most of the arsenic is trivalent and binds to S of peptides (53% As-S) while 38% occurred as arsenite and only 9% unchanged as arsenate. EXAFS data confirmed that As-S and As-O bonds occur in the plants. This study confirms, for the first time, that As-peptides can be extracted by formic acid and chromatographically separated on a reversed-phase column without significant decomposition or de-novo synthesis during the extraction step.

  3. EXAFS studies of crystalline materials

    Energy Technology Data Exchange (ETDEWEB)

    Knapp, G.S.; Georgopoulos, P.

    1982-01-01

    The application of extended x-ray absorption fine structure (EXAFS) technique to the study of crystalline materials is discussed, and previously published work on the subject is reviewed with 46 references being cited. The theory of EXAFS, methods of data analysis, and the experimental techniques, including those based on synchrotron and laboratory facilities are all discussed. Absorption and fluorescence methods of detecting EXAFS also receive attention. (BLM)

  4. Polydispersity and EXAFS simulations

    Energy Technology Data Exchange (ETDEWEB)

    Cammelli, S; Degueldre, C; Bertsch, J [Laboratory for Nuclear Material, NES, Paul Scherrer Institute, 5232 Villigen PSI (Switzerland); Luetzenkirchen-Hecht, D; Frahm, R, E-mail: sebastiano.cammelli@psi.c [Fachbereich C - Physik, Bergische Universitaet Wuppertal, Gauss-Str. 20, 42097 Wuppertal (Germany)

    2009-11-15

    EXAFS is an important experimental technique for determining the local atomic structure of nanoclusters embedded in a bulk material. In practical cases, nanocluster samples do not contain homogeneous clusters of just one size, and the average cluster size is strongly influenced by the specific distribution of cluster sizes. Combinations of different cluster sizes might provide very similar results; this issue is called polydispersity. The goal of this study is to understand if there are any principal limitations for EXAFS studies related to polydispersity. Here a new approach based on EXAFS simulations followed by linear combination (LC) on EXAFS spectra is presented. The simulations were performed on pure Cu and binary Cu-Fe clusters. The main result of this study concerns the proof that polydispersity does not affect XAFS studies on nano-clusters within a size of up to 140 atoms.

  5. Adsorption of U(VI) on sericite in the presence of Bacillus subtilis: A combined batch, EXAFS and modeling techniques

    Science.gov (United States)

    Sun, Yubing; Zhang, Rui; Ding, Congcong; Wang, Xiangxue; Cheng, Wencai; Chen, Changlun; Wang, Xiangke

    2016-05-01

    The effect of Bacillus subtilis (B. subtilis) on the adsorption of U(VI) onto sericite was investigated using batch, EXAFS and modeling techniques. The batch adsorption indicated that the increased adsorption of U(VI) on sericite + B. subtilis systems at pH 6.0 due to the combination of deprotonated carboxyl groups of B. subtilis with the hydroxyl of sericite. The slightly enhanced adsorption of U(VI) on sericite + B. subtilis with increasing CO2 contents at pH 7.0 owing to electrostatic repulsion between negatively charged sericite + B. subtilis and negatively charged U(VI) species such as UO2(OH)3- or UO2(CO3)22- species. According to EXAFS analysis, the increased adsorption mechanism of U(VI) on sericite + B. subtilis at pH 4.0 was attributed to the formation of U-P shell, whereas the bidentate inner-sphere surface complexes was also observed at pH 7.0 due to the formation of U-C shell (2.92 Å) and/or U-Si/Al (3.18 Å) shell. Under the range of allowable error, the pH-dependent and isothermal adsorption of U(VI) on sericite + B. subtilis can be fitted by surface complexation modeling using ion exchange and surface complexation reaction by using equilibrium parameters obtained from each binary systems. These findings are important to understand the fate and transport of U(VI) on the mineral-bacteria ternary systems in the near-surface environment.

  6. Influence of 300°C thermal conversion of Fe-Ce hydrous oxides prepared by hydrothermal precipitation on the adsorptive performance of five anions: Insights from EXAFS/XANES, XRD and FTIR (companion paper).

    Science.gov (United States)

    Chubar, Natalia; Gerda, Vasyl; Banerjee, Dipanjan

    2017-04-01

    In this work, we report atomic-scale reconstruction processes in Fe-Ce oxide-based composites (hydrothermally precipitated at Fe-to-Ce dosage ratios of 1:0, 2:1, 1:1, 1:2, and 0:1), upon treatment at 300°C. The structural changes are correlated with the adsorptive removal of arsenate, phosphate, fluoride, bromide, and bromate. The presence of the carbonate-based Ce-component and surface sulfate in precursor samples creates favorable conditions for phase transformation, resulting in the formation of novel (unknown) layered compounds of Fe and Ce. These compounds are of the layered double hydroxide type, with sulfate in the interlayer space. In spite of general awareness of the importance of surface area in adsorptive removal, the increase in surface area upon thermal treatment did not increase adsorption of the studied anions. However, EXAFS simulations and the adsorption tests provided evidence of regularities between local structures of Fe in composites obtained at 80 and 300°C and adsorption performance of most studied anions. The best adsorption of tetrahedral anions was demonstrated by samples whose simulated outer Fe shells resulted from oscillations from both O and Fe atoms. In contrast, the loss of extended x-ray absorption fine structure was correlated with the decrease of adsorptive removal. Both Fe K-edge and Ce L3 -edge EXAFS suggested the formation of solid solutions. For the first time, the utilization of extended x-ray absorption fine structure is suggested as a methodological approach (first expressed in the companion paper) to estimate the surface reactivity of inorganic materials intended for use as anion exchange adsorbents. Copyright © 2016 Elsevier Inc. All rights reserved.

  7. Influence of 300°C thermal conversion of Fe-Ce hydrous oxides prepared by hydrothermal precipitation on the adsorptive performance of five anions: Insights from EXAFS/XANES, XRD and FTIR (companion paper)

    KAUST Repository

    Chubar, Natalia

    2016-12-07

    In this work, we report atomic-scale reconstruction processes in Fe-Ce oxide-based composites (hydrothermally precipitated at Fe-to-Ce dosage ratios of 1:0, 2:1, 1:1, 1:2, and 0:1), upon treatment at 300 °C. The structural changes are correlated with the adsorptive removal of arsenate, phosphate, fluoride, bromide, and bromate. The presence of the carbonate-based Ce-component and surface sulfate in precursor samples creates favorable conditions for phase transformation, resulting in the formation of novel (unknown) layered compounds of Fe and Ce. These compounds are of the layered double hydroxide type, with sulfate in the interlayer space. In spite of general awareness of the importance of surface area in adsorptive removal, the increase in surface area upon thermal treatment did not increase adsorption of the studied anions. However, EXAFS simulations and the adsorption tests provided evidence of regularities between local structures of Fe in composites obtained at 80 and 300 °C and adsorption performance of most studied anions. The best adsorption of tetrahedral anions was demonstrated by samples whose simulated outer Fe shells resulted from oscillations from both O and Fe atoms. In contrast, the loss of extended x-ray absorption fine structure was correlated with the decrease of adsorptive removal. Both Fe K-edge and Ce L3 -edge EXAFS suggested the formation of solid solutions. For the first time, the utilization of extended x-ray absorption fine structure is suggested as a methodological approach (first expressed in the companion paper) to estimate the surface reactivity of inorganic materials intended for use as anion exchange adsorbents.

  8. Macroscopic and microscopic investigation of Ni(II) sequestration on diatomite by batch, XPS, and EXAFS techniques.

    Science.gov (United States)

    Sheng, Guodong; Yang, Shitong; Sheng, Jiang; Hu, Jun; Tan, Xiaoli; Wang, Xiangke

    2011-09-15

    Sequestration of Ni(II) on diatomite as a function of time, pH, and temperature was investigated by batch, XPS, and EXAFS techniques. The ionic strength-dependent sorption at pH diatomite/water interface: (1) outer-sphere and/or inner-sphere complexation; (2) dissolution of Si which is the rate limiting step during Ni uptake; and (3) extensive growth of surface (co)precipitates. Under acidic conditions, outer-sphere complexation is the main mechanism controlling Ni uptake, which is in good agreement with the macroscopic results. At contact time of 1 h or 1 day or pH = 7.0-8.0, surface coprecipitates occur concurrently with inner-sphere complexes on diatomite surface, whereas at contact time of 1 month or pH = 10.0, surface (co)precipitates dominate Ni uptake. Furthermore, surface loading increases with temperature increasing, and surface coprecipitates become the dominant mechanism at elevated temperature. The results are important to understand Ni interaction with minerals at the solid-water interface, which is helpful to evaluate the mobility of Ni(II) in the natural environment.

  9. Investigation of impact materials from the Barringer Meteor Crater by micro-XANES and micro-PIXE techniques

    Energy Technology Data Exchange (ETDEWEB)

    Szikszai, Z. [Institute of Nuclear Research of the Hungarian Academy of Sciences, MTA ATOMKI, H-4001 Debrecen, P.O. Box 51 (Hungary)], E-mail: szikszai@atomki.hu; Uzonyi, I.; Kiss, A.Z.; Sziki, G.A. [Institute of Nuclear Research of the Hungarian Academy of Sciences, MTA ATOMKI, H-4001 Debrecen, P.O. Box 51 (Hungary); Vantelon, D. [Synchrotron SOLEIL, L' Orme des Merisiers, St. Aubin-BP 48, F-91192 Gif sur Yvette Cedex (France); Rozsa, P. [Department of Mineralogy and Geology, University of Debrecen, H-4010 Debrecen, Egyetem ter 1 (Hungary)

    2009-06-15

    Impact materials from the Barringer Meteor Crater were examined by combined micro-X-ray absorption near edge structure (micro-XANES) and micro-particle induced X-ray emission (micro-PIXE) methods. Efforts were focussed on the complex characterization of their iron-rich inclusions. The lateral distribution of elements as well as the oxidation state of iron was determined. The study demonstrates the capabilities of chemical speciation screening based on energy selective micro-XRF maps in geology. With the help of this method zero-valent (metallic) and three-valent iron were excluded in the studied specimens without performing XANES in every pixel.

  10. Quantitative structural refinement of Mn K edge XANES in LaMnO{sub 3} and CaMnO{sub 3} perovskites

    Energy Technology Data Exchange (ETDEWEB)

    Monesi, C. [Dipartimento di Fisica, Universita di ' Roma Tre' , Via Della Vasca Navale, 84, I-00146 Rome (Italy); Meneghini, C. [Dipartimento di Fisica, Universita di ' Roma Tre' , Via Della Vasca Navale, 84, I-00146 Rome (Italy) and INFM-GILDA, c/o ESRF, Grenoble (France)]. E-mail: meneghini@fis.uniroma3.it; Bardelli, F. [Dipartimento di Fisica, Universita di ' Roma Tre' , Via Della Vasca Navale, 84, I-00146 Rome (Italy); INFM-GILDA, c/o ESRF, Grenoble (France); Benfatto, M. [INFN Laboratori Nazionali di Frascati, Via E. Fermi 40, I-00044 Frascati (Italy); Mobilio, S. [Dipartimento di Fisica, Universita di ' Roma Tre' , Via Della Vasca Navale, 84, I-00146 Rome (Italy); INFM-GILDA, c/o ESRF, Grenoble (France); INFN Laboratori Nazionali di Frascati, Via E. Fermi 40, I-00044 Frascati (Italy); Manju, U. [Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560 012 (India); Sarma, D.D. [Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560 012 (India)

    2006-05-15

    The special magnetotransport properties of hole doped manganese perovskites originate from a complex interplay among structural, magnetic and electronic degree of freedom. In this picture the local atomic structure around Mn ions plays a special role and this is the reason why short range order techniques like X-ray absorption spectroscopy (XAS) have been deeply exploited for studying these compounds. The analysis of near edge region features (XANES) of XAS spectra can provide very fine details of the local structure around Mn, complementary to the EXAFS, so contributing to the full understanding of the peculiar physical properties of these materials. Nevertheless the XANES analysis is complicated by the large amount of structural and electronic details involved making difficult the quantitative interpretation. This work exploits the recently developed MXAN code to achieve a full structural refinement of the Mn K edge XANES of LaMnO{sub 3} and CaMnO{sub 3} compounds; they are the end compounds of the doped manganite series La {sub x}Ca{sub 1-x}MnO{sub 3}, in which the Mn ions are present only in one charge state as Mn{sup 3+} and Mn{sup 4+} respectively. The good agreement between the results derived from the analysis of near edge and extended region of the XAS spectra demonstrates that a quantitative picture of the local structure can be obtained from structural refinement of Mn K edge XANES data in these crystalline compounds. The XANES analysis offers, in addition, the possibility to directly achieve information on the topology of local atomic structure around the absorber not directly achievable from EXAFS.

  11. Amyloid-β peptide active site: theoretical Cu K-edge XANES study

    Science.gov (United States)

    Chaynikov, A. P.; Soldatov, M. A.; Streltsov, V.; Soldatov, A. V.

    2013-04-01

    This article is dedicated to the local atomic structure analysis of the copper binding site in amyloid-β peptide. Here we considered two possible structural models that were previously obtained by means of EXAFS analysis and density functional theory simulations. We present the calculations of Cu K-edge XANES spectra for both models and make comparison of these spectra with experiment.

  12. Investigation of Eu(III) immobilization on γ-Al2O3 surfaces by combining batch technique and EXAFS analyses: Role of contact time and humic acid

    Science.gov (United States)

    Yang, Shitong; Sheng, Guodong; Montavon, Gilles; Guo, Zhiqiang; Tan, Xiaoli; Grambow, Bernd; Wang, Xiangke

    2013-11-01

    Aluminum (hydr)oxides play an important role in the regulation of the composition of soil/water, sediment/water and other natural water systems. In this study, the interactions among Eu(III), humic acid (HA) and γ-Al2O3 were investigated using a combination of batch and extended X-ray absorption fine structure (EXAFS) techniques. Experiments were performed with varying contact times (2, 15, 60 and 180 d) at a pH of 6.5 for both the binary γ-Al2O3/Eu(III) and the ternary γ-Al2O3/HA/Eu(III) systems. In addition, two representative pH values (pH 6.5 for a near-neutral condition and pH 8.5 for an alkalescence condition) were selected to determine the sequestration mechanisms of Eu(III) in the ternary γ-Al2O3/HA/Eu(III) systems. To verify the specific binding modes and corresponding chemical species, a coordination geometry calculation and a quantitative comparison between the HA binding site concentration and the initial Eu(III) concentration were conducted along with EXAFS data analysis. The microstructure and thermodynamic stability of the formed Eu(III) species were dependent on various environmental parameters. For the binary γ-Al2O3/Eu(III) systems, quantitative analysis results of EXAFS spectra suggested the presence of two Eu(III) species within a contact time of 15 d. Using a coordination geometry calculation, the REu-Al values at ∼3.28 Å and ∼3.99 Å corresponded to the formation of edge-shared and corner-shared surface complexes, respectively. For samples reacted longer than 15 d, the appearance of an additional Eu-Eu shell at ∼3.50 Å was indicative of a structural rearrangement process, leading to the formation of thermodynamically stable surface polynuclear complexes. For the ternary γ-Al2O3/HA/Eu(III) systems, the EXAFS-derived structural parameters indicated the formation of 1:1 type B ternary complexes and binary corner-shared complexes at pH 6.5 after 2 d. In contrast, the Eu(III) sequestration mechanisms at pH 8.5 were mainly attributed

  13. XRD and XANES study of some Cu-doped MnBi materials

    Science.gov (United States)

    Mishra, Ashutosh; Patil, Harsha

    2016-10-01

    High purity MnBi low temperature phase has been prepared and analyzed using X- ray diffraction (XRD) and X-ray absorption near edge structure (XANES) measurements. The X-ray diffraction measurements were carried out using Bruker D8 Advance X-ray diffractometer. The X-rays were produced using a sealed tube and the wavelength of X-ray was 154 nm (Cu K-alpha). and X-rays were detected using a fast counting detector based on Silicon strip technology (Bruker LynxEye detector)[1]. and the X-ray absorption spectra has emerged as a powerful technique for local structure determination, which can be applied to any type of material. The X-ray absorption measurements of two Cu-doped MnBi alloys have been performed at the recently developed BL-8 Dispersive EXAFS beam line at 2.5 GeV Indus-2 synchrotron at RRCAT, Indore, India[2]. The X-ray absorption near edge structure (XANES) data obtained has been processed using data analysis program Athena. The energies of the K absorption edge, chemical shifts, edge-widths, shifts of the principal absorption maximum in the alloys have been determined.

  14. Validation of EXAFS Analysis of Iridium Compounds

    Science.gov (United States)

    Feiters, M. C.; Longo, A.; Banerjee, D.; van der Ham, C. J. M.; Hetterscheid, D. G. H.

    2016-05-01

    Results of iridium L3 edge EXAFS measurements of compounds relevant for water oxidation catalysis are compared to those of other structural techniques. The structural results from EXAFS for the Ir compounds investigated here compare well to those of other structural techniques. Multiple scattering contributions are important in the coordinated Cp* and NHC ligands as well as in the IrCl6 unit and the IrO2 rutile structure. NHC is relatively weak compared to Ir, Cl, and even Cp* and O, and often out of phase with the other contributions.

  15. EXAFS as a tool for catalyst characterization: a review of the data analysis methods

    Directory of Open Access Journals (Sweden)

    NORONHA F. B.

    1999-01-01

    Full Text Available A review of the EXAFS data analysis methods is presented. A detailed description of the EXAFS signal extraction and the Fourier transform of the data are discussed. The procedure for determining interatomic distances, coordination numbers and disorder effects from EXAFS data is described. This paper also discusses the data analysis statistics. Finally, one example of catalyst characterization by the EXAFS technique is reported.

  16. EXAFS studies of actinide ions in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Karim, D P; Georgopoulos, P; Knapp, G S

    1979-01-01

    The applicability of the EXAFS technique in the study of actinide systems is discussed. Uranium L/sub III/-edge spectra obtained on an in-lab rotating anode EXAFS facility are presented and analyzed for crystalline UO/sub 2/F/sub 2/ and aqueous solutions containing hexavalent uranium ions. Methods for the extension of the technique to more dilute systems are discussed.

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

    Science.gov (United States)

    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.

  18. X-ray absorption spectroscopy of Mn doped ZnO thin films prepared by rf sputtering technique

    Energy Technology Data Exchange (ETDEWEB)

    Yadav, Ashok Kumar; Jha, S. N.; Bhattacharyya, D., E-mail: dibyendu@barc.gov.in [Atomic & Molecular Physics Division, Bhabha Atomic Research Centre, Mumbai – 400 085 (India); Haque, Sk Maidul [Atomic & Molecular Physics Division, Bhabha Atomic Research Centre, VIZAG Centre, Visakhapatnam-530012 (India); Shukla, Dinesh; Choudhary, Ram Janay [UGC DAE Consortium for Scientific Research, Indore-452001 (India)

    2015-11-15

    A set of r.f. sputter deposited ZnO thin films prepared with different Mn doping concentrations have been characterised by Extended X-ray Absorption Fine Structure (EXAFS) and X-ray Absorption Near Edge Spectroscopy (XANES) measurements at Zn, Mn and O K edges and at Mn L{sub 2,3} edges apart from long range structural characterisation by Grazing Incident X-ray Diffraction (GIXRD) technique. Magnetic measurements show room temperature ferromagnetism in samples with lower Mn doping which is however, gets destroyed at higher Mn doping concentration. The results of the magnetic measurements have been explained using the local structure information obtained from EXAFS and XANES measurements.

  19. EXAFS spectra using synchrotron radiation of Cu (II) complexes

    Science.gov (United States)

    Ninama, Samrath; Mishra, A.

    2016-10-01

    EXAFS analysis of Cu (II) complex as a ligand of 2-methyl-3-[(bis-aniline(R) phenyl]- 3H-1, 5 benzodiazepine. Extended X-ray absorption fine structure (EXAFS) spectra have been recorded at the K-edge of Cu (II) using the energy dispersive EXAFS beam line at 2.5GeV Indus - 2 synchrotron source at RRCAT, Indore, India. A theoretical EXAFS data analysis is also carried out by Fourier analysis of experimental EXAFS data of the copper (II) complexes. This analysis includes details of the Fourier transform of the data and the extraction of metal-ligand bond length. Bond lengths determined from data analysis methods are compared with the bond lengths obtained from several other known techniques, namely, Levy's, Lytle's and Lytle, Sayers and Stern's (LSS) methods. These data have also been calibrated by derivative method and bond lengths have also been obtained from Fourier transformation method and the results have been compared with the each other. The EXAFS data have been analyzed using the computer software Athena.

  20. 3rd International EXAFS Conference

    CERN Document Server

    Hedman, Britt; Penner-Hahn, James

    1984-01-01

    This volume contains the Proceedings of the Third International EXAFS Conference, hosted by Stanford University and the Stanford Synchrotron Radiation Laboratory on July 16-20, 1984. The meeting, co-chaired by Professors Arthur Bienenstock and Keith Hodgson, was attended by over 200 scientists representing a wide range of scientific disciplines. The format of the meeting consisted of 51 invited presenta­ tions and four days of poster sessions. This Proceedings is a compilation of 139 contributions from both invited speakers and authors of contributed posters. The last ten years has seen the rapid maturation of x-ray absorption spectrosco­ pyas a scientific discipline. The vitality of the field is reflected in the diver­ sity of applications found in the Proceedings. Recent work continues to probe the limits of x-ray spectroscopy, with proven techniques being extended to, for examp­ le, very low or high energy studies, to very dilute systems, and to studies of surface structure. In fact, the title of the c...

  1. Moessbauer and EXAFS spectroscopy investigation of iron and arsenic adsorption to lettuce leaves

    Energy Technology Data Exchange (ETDEWEB)

    Vasconcelos, Igor F., E-mail: ifvasco@ufc.br [Universidade Federal do Ceara, Dep. Eng. Metalurgica e de Materiais (Brazil); Silva, Gabriela C.; Carvalho, Regina P.; Dantas, Maria Sylvia S.; Ciminelli, Virginia S. T. [Universidade Federal de Minas Gerais, Dep. Eng. Metalurgica e de Materiais (Brazil)

    2010-01-15

    The accumulation of iron and arsenic from aqueous solution by lettuce leaves biomass was investigated using Moessbauer and EXAFS spectroscopic techniques. Moessbauer spectroscopy results show that iron is oxidized during sorption while EXAFS results indicate that iron is coordinated by approximately 6 oxygen and 2 carbon atoms while arsenic is coordinated by approximately 4 oxygen atoms with iron as a second neighbor.

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

    Science.gov (United States)

    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

  3. General considerations for a laboratory EXAFS facility

    Energy Technology Data Exchange (ETDEWEB)

    Knapp, G.S.; Georgopoulos, P.

    1980-12-01

    In this paper a complete laboratory system capable of making high quality EXAFS meaurements will be described. A discussion will be given of the design of an EXAFS spectrometer, how to achieve an optimum combination of intensity and resolution, the range of energies which are practical to take EXAFS patterns, the elimination of errors caused by characteristic lines, detector systems, and the computer requirements to obtain and analyze the data. (AIP)

  4. Magnetic properties and EXAFS study of nanocrystalline Fe{sub 2}Mn{sub 0.5}Cu{sub 0.5}Al synthesized using mechanical alloying technique

    Energy Technology Data Exchange (ETDEWEB)

    Nanto, Dwi [Department of Physics, Chungbuk National University, Cheongju 361-763 (Korea, Republic of); Physics Education, Syarif Hidayatullah State Islamic University, Jakarta 15412 (Indonesia); Yang, Dong-Seok [Physics Division, School of Science Education, Chungbuk National University, Cheongju 361-763 (Korea, Republic of); Yu, Seong-Cho, E-mail: scyu@chungbuk.ac.kr [Department of Physics, Chungbuk National University, Cheongju 361-763 (Korea, Republic of)

    2014-02-15

    Nanocrystalline Fe{sub 2}Mn{sub 0.5}Cu{sub 0.5}Al has been synthesized by the mechanical alloying technique and studied as a function of milling time. Alloy nature of Fe{sub 2}Mn{sub 0.5}Cu{sub 0.5}Al was observed in a sample milled for 96 h. The magnetic saturation is 4.0 μ{sub B}/f.u., which coincidently follows Slater–Pauling rule at 5 K. Nanocrystalline Fe{sub 2}Mn{sub 0.5}Cu{sub 0.5}Al has enhanced saturate magnetization compared to any other fabrication of Fe{sub 2}MnAl reported. Cu element plays an important role in site competes with other elements and may result in the enhancement of saturate magnetization. In accordance to the magnetic results and EXAFS pattern, it was revealed that the dynamics of magnetic properties were confirmed as structural changes of nanocrystalline Fe{sub 2}Mn{sub 0.5}Cu{sub 0.5}Al.

  5. Luminescence, vibrational and XANES studies of AlN nanomaterials

    Energy Technology Data Exchange (ETDEWEB)

    Bellucci, S. [INFN-Laboratori Nazionali di Frascati, Via E. Fermi 40, 00044 Frascati (Italy); Popov, A.I. [Institut Laue-Langevin, 6 rue Jules Horowitz, 38042 Grenoble (France); Institute for Solid State Physics, University of Latvia, Kengaraga 8, LV-1063 Riga (Latvia); Balasubramanian, C. [INFN-Laboratori Nazionali di Frascati, Via E. Fermi 40, 00044 Frascati (Italy); Department of Environmental, Occupational and Social Medicine, University of Rome Tor Vergata, 00133 Rome (Italy); Cinque, G.; Marcelli, A. [INFN-Laboratori Nazionali di Frascati, Via E. Fermi 40, 00044 Frascati (Italy); Karbovnyk, I. [Ivan Franko National University of Lviv, Faculty of Electronics, 107 Tarnavskogo str., 79017 Lviv (Ukraine)], E-mail: ivan_karbovnyck@yahoo.com; Savchyn, V.; Krutyak, N. [Ivan Franko National University of Lviv, Faculty of Electronics, 107 Tarnavskogo str., 79017 Lviv (Ukraine)

    2007-04-15

    The paper reports comparative studies on synthesized aluminium nitride nanotubes, nanoparticles and commercially available micron-sized AlN powder using different spectroscopic techniques: cathodoluminescence measurements (CL), X-ray absorption near edge spectroscopy (XANES) and Fourier-transform infrared spectroscopy (FTIR). Crucial distinctions in CL spectra are observed for nano- and microsized aluminium nitride powders; systematic shift of the IR absorption maximum has been detected for nanostructured aluminium nitride as compared to commercial samples. Through XANES experiments on Al K-edge structural differences between nano- and bulk AlN are revealed, intensity of features in absorption spectra has been found to be a function of wurtzite and zincblend phases amount in nanostructured samples.

  6. Amorphous semiconductor sample preparation for transmission EXAFS measurements

    Energy Technology Data Exchange (ETDEWEB)

    Ridgway, M.C.; Glover, C.J.; Tan, H.H. [Australian National Univ., Canberra (Australia). Dept. of Electronic Materials Engineering] [and others

    1998-12-31

    A novel methodology has been developed for the preparation of amorphous semiconductor samples for use in transmission extended x-ray absorption fine structure (EXAFS) measurements. Epitaxial heterostructures were fabricated by metal organic chemical vapor deposition (group III-Vs) or molecular beam epitaxy (group IVs). An epitaxial layer of {approximately} 2 {micro}m thickness was separated from the underlying substrate by selective chemical etching of an intermediate sacrificial layer. Ion implantation was utilized to amorphize the epitaxial layer either before or after selective chemical etching. The resulting samples were both stoichiometric and homogeneous in contrast to those produced by conventional techniques. The fabrication of amorphous GaAs, InP, In{sub 0.53}Ga{sub 0.47}As and Si{sub x}Ge{sub 1{minus}x} samples is described. Furthermore, EXAFS measurements comparing both fluorescence and transmission detection, and crystalline and amorphized GaAs, are shown.

  7. Temperature-dependent magnetic EXAFS investigation of Gd

    CERN Document Server

    Wende, H; Poulopoulos, P N; Rogalev, A; Goulon, J; Schlagel, D L; Lograsso, T A; Baberschke, K

    2001-01-01

    Magnetic EXAFS (MEXAFS) is the helicity-dependent counterpart of the well-established EXAFS technique. By means of MEXAFS it is possible not only to analyze the local magnetic structure but also to learn about magnetic fluctuations. Here we present the MEXAFS of a Gd single crystal at the L sub 3 sub , sub 2 -edges in the temperature range of 10-250 K. For the first time MEXAFS was probed over a large range in reduced temperature of 0.04<=T/T sub C<=0.85 with T sub C =293 K. We show that the vibrational damping described by means of a Debye temperature of theta sub D =160 K must be taken into account for the spin-dependent MEXAFS before analyzing magnetic fluctuations. For a detailed analysis of the MEXAFS and the EXAFS, the experimental data are compared to ab initio calculations. This enables us to separate the individual single- from the multiple-scattering contributions. The MEXAFS data have been recorded at the ID 12A beamline of the European Synchrotron Radiation Facility (ESRF). To ensure that th...

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

    Science.gov (United States)

    Spanjers, Charles S; Guillo, Pascal; Tilley, T Don; Janik, Michael J; Rioux, Robert M

    2017-01-12

    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 features 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.

  9. A new technique to measure the differential XAFS spectrum

    Science.gov (United States)

    Wu, Min; Zheng, Li-Rong; Chu, Sheng-Qi; Zhou, Ai-Yu; Zhang, Jing; Hu, Tian-Dou

    2016-04-01

    A new technique has been developed for direct measurement of the differential X-ray absorption fine structure (XAFS) spectrum by the energy-modulation method. To acquire the energy-oscillating incident X-ray beam, a piezoelectric actuator is used to control the double-crystal monochromator. A logarithmic converter circuit and a lock-in amplifier are used to extract the modulated signals. The normal and differential XAFS spectra of the Mn K-edge of Li2MnO3 have been collected. The X-ray-absorption near-edge-structure (XANES) spectra verify that the signal-to-noise ratio has been greatly improved by the new technique, and the extended X-ray absorption fine structure (EXAFS) spectra demonstrate that this new technique can efficiently enhance the signals of the backscattering atoms. Supported by NSFC (11175202)

  10. High resolution x-ray fluorescence spectroscopy - a new technique for site- and spin-selectivity

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xin [Univ. of California, Davis, CA (United States). Dept. of Applied Science

    1996-12-01

    X-ray spectroscopy has long been used to elucidate electronic and structural information of molecules. One of the weaknesses of x-ray absorption is its sensitivity to all of the atoms of a particular element in a sample. Through out this thesis, a new technique for enhancing the site- and spin-selectivity of the x-ray absorption has been developed. By high resolution fluorescence detection, the chemical sensitivity of K emission spectra can be used to identify oxidation and spin states; it can also be used to facilitate site-selective X-ray Absorption Near Edge Structure (XANES) and site-selective Extended X-ray Absorption Fine Structure (EXAFS). The spin polarization in K fluorescence could be used to generate spin selective XANES or spin-polarized EXAFS, which provides a new measure of the spin density, or the nature of magnetic neighboring atoms. Finally, dramatic line-sharpening effects by the combination of absorption and emission processes allow observation of structure that is normally unobservable. All these unique characters can enormously simplify a complex x-ray spectrum. Applications of this novel technique have generated information from various transition-metal model compounds to metalloproteins. The absorption and emission spectra by high resolution fluorescence detection are interdependent. The ligand field multiplet model has been used for the analysis of K{alpha} and K{beta} emission spectra. First demonstration on different chemical states of Fe compounds has shown the applicability of site selectivity and spin polarization. Different interatomic distances of the same element in different chemical forms have been detected using site-selective EXAFS.

  11. XANES spectra of metal phytate compounds

    Science.gov (United States)

    Metal speciation of phosphate and metal-phosphate interactions can be investigated by molecular-scale X-ray absorption near edge structure (XANES) spectroscopic analysis. Much of the effort, however, has been focused on inorganic P speciation (i. e. metal-orthophosphate interactions). Phytate (inosi...

  12. XANES spectra of transition metal compounds

    NARCIS (Netherlands)

    de Groot, F.M.F.|info:eu-repo/dai/nl/08747610X

    2009-01-01

    An overview is given of the interactions that determine the XANES spectral shapes of transition metal compounds. The interactions are divided into ground state effects, final state effects and transition effects. The metal L edges, metal K edges and ligand K edges are analysed with respect to these

  13. Hemeproteins: Recent Advances in Quantitative XANES Analysis

    Science.gov (United States)

    Arcovito, Alessandro; Benfatto, Maurizio; D'Angelo, Paola; Della Longa, Stefano

    2007-02-01

    Recently, we have shown that multiple scattering (MS) theory, via the MXAN package, is able to reproduce the experimental X-ray absorption near edge structure (XANES) data of biological samples, in particular hemeproteins, from the rising edge up to ˜150-200 eV above the edge. In the present work, we illustrate how XANES can be used either as an independent tool to provide bond-lengths and bond-angles for a metalloprotein active site in solution, or in combination with X-ray Diffraction for structural determinations of ligand binding geometry of the same diffracting protein crystal, providing atomic precision even for crystallographic structures solved at > 1.2 Å resolution. At low temperature, XANES can be applied to provide the Fe-heme structure of trapped intermediate conformations of light triggered processes, and some aspects of the ligand binding dynamics. Very recently, XANES difference spectra have been analyzed to provide the Fe-heme structure of multiple intermediates of carbonmonoxy-myoglobin, obtained under different photolysis protocols in solution state.

  14. Surface EXAFS of Sulphur on Nickel.

    Science.gov (United States)

    Brennan, Sean Micheal

    The structural determination of adsorption geometries on surfaces has been limited to low-energy electron diffraction (LEED), photoelectron diffraction (PD), ion scattering, and surface extended x-ray absorption fine structure (SEXAFS). SEXAFS has the advantage that it can be analyzed without depending on calculated phase shifts, and does not require long range order on the surface. However, in the past SEXAFS measurements have often suffered from signal-to-noise problems which have limited the inherent high accuracy of the technique for structure determinations. Here are presented SEXAFS results on the low-Z adsorbate sulphur on Ni(100) which exhibit bulklike signal-to-noise ratios and allow the precise determination of the chemisorption site and adsorbate near -neighbor distances. The c(2x2) S on Ni(100) system was chosen because it has been studied extensively by other techniques and the relative merits of SEXAFS could be best demonstrated. The S-Ni first-nearest-neighbor distance was found to be 2.23 (+OR-) 0.02A, the accuracy being limited only by the EXAFS technique itself. For normal x-ray incidence the second-nearest-neighbor distance to Ni atoms in the (100) surface plane is clearly observed, and its distance of 4.15 (+OR-) 0.10A determines the adsorption site to be the fourfold hollow. This site is independently confirmed from analysis of the polarization-dependent nearest-neighbor SEXAFS amplitudes (relative amplitude ratios) and thirdly from determination of the absolute S coordination number on the surface by comparison with a bulk NiS standard. This variety of site-determination techniques will become even more important for the study of disordered surfaces, where the choice of adsorption sites is not restricted by the long range symmetry of the surface. When compared to the results obtained by the other available surface structural techniques it becomes clear that SEXAFS is the technique of choice for the determination of adsorbates on surfaces.

  15. Molecular characterization of brominated persistent pollutants using extended X-ray absorption fine structure (EXAFS) spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Bergknut, Magnus; Skyllberg, Ulf [Swedish University of Agricultural Sciences (SLU), Department of Forest Ecology and Management, Umeaa (Sweden); Persson, Per [Umeaa University, Department of Chemistry, Umeaa (Sweden)

    2008-02-15

    X-ray absorption fine structure (EXAFS) spectroscopy spectra were collected for three brominated persistent pollutants: 6-bromo-2,4,5-trichlorophenol (BrTriClP), pentabromophenol (PentaBrP) and 3,3',5,5'-tetrabromobisphenol A (TBBA). The substances were selected to be symmetrical (BrTriClP and TBBA) or asymmetrical (PentaBrP) with respect to the atomic Br positions and to differ in the number of bromine and other halide atoms, as well as their relative positions. The asymmetrical PentaBrP was modelled with special detail as not all bromine atoms have identical coordination environments. The studied substances displayed unique EXAFS spectra, which could be used to determine the molecular structure in fair detail. We conclude that EXAFS spectroscopy is a suitable technique for molecular characterization of the comparatively complex molecules within the class of compounds of brominated organic persistent pollutants. A detailed understanding of the EXAFS spectra of the pure compounds opens up possibilities to study the interactions with soil and sediment matrices by means of EXAFS spectroscopy. (orig.)

  16. Development of ReflEXAFS data analysis for deeper surface structure studies

    Science.gov (United States)

    López-Flores, Víctor; Ansell, Stuart; Ramos, Silvia; Bowron, Daniel T.; Díaz-Moreno, Sofía; Muñoz-Páez, Adela

    2009-11-01

    An analytical approach to the analysis of ReflEXAFS data collected from complex multilayer samples, at a range of angles above and below the critical angle is presented. The aim of the technique is to generate a structural model of the investigated system that is consistent with the variable depth sensitivity of the experimental data. The procedure follows three main steps (i) the determination of the free atom reflectivity background for the multilayer system, (ii) the estimation of the depth dependent EXAFS signals and (iii) the calculation of the corresponding ReflEXAFS components. By iterating between steps (ii) and (iii), and varying the estimates of the EXAFS signals, a consistent set of structural parameters is extracted that reflects the bulk structure of the multilayer system through the basic reflectivity signals, and the depth dependent local atomic structure through the estimated EXAFS components. An example of the depth dependent structure of copper in a copper-chromium multilayer stack is presented to illustrate the capabilities of the method.

  17. EXAFS investigation and luminescent properties of nanosized Tb: Lu2O3 phosphors

    Institute of Scientific and Technical Information of China (English)

    REN

    2010-01-01

    Nanosized terbium doped Lu2O3 phosphors were synthesized via a modified co-precipitation processing.The as-prepared Tb:Lu2O3 phosphors was consisted of well crystallized nanosized sphere particles with a diameter of about 30 nnx Local structure of Tb ions in Lu2O3 lattice was investigated by an analytical approach based on Fourier transformation of the extended X-ray absorption fine structure(EXAFS) data.X-ray near edge structure (XANES) spectra suggested that all Tb ions doped were tervalonce.EXAFS results indicated that Tb ions have entered the Lu2O3 cubic lattice by means of solid solution.The coordination number and first shell Tb-O distance dropped with the increasing of Tb concentration.Emission spectra of the phosphors was shown to be typical for Tb3+ with main components at 542,550 and 490 nm,derived from irradiative relaxation of 5D4 level.The emission intensity decreased severely with the increasing of Tb concentration from 1 mol.% to 15 tool.%,suggesting a significant concentration quenching above 1 mol.% Tb.The reduction of emission intensity was interpreted by higher distortion derived relaxation among the surface state resident Tb3+ ions.

  18. Probing Local Lattice Fluctautions in Cuprates and Manganites by High k-Resolution EXAFS

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    X-ray absorption fine structure has been exploited as a tool tostudy local lattice distortions in the perovskite cuperates and manganites, showing novel phenomena as high temperature superconductivity and colossal magneto-resistance. Temperature dependent Cu K-edge and Mn K-edge EXAFS have been used to investigate the local lattice distortions associated with the doped charge at metallic densities in these materials. Temperature dependent correlated Debye-Waller factors of the Cu-O in the cuprates shows an upturn at the stripe formation temperature Tso. Capabilities of the EXAFS technique have been further demonstrated for the case of the manganites, revealing key information on their metal-insulator transition. The EXAFS has been shown to be capable of providing quantitative local distortions that are closely associated with the characteristic properties of these complex materials.

  19. Towards advanced structural analysis of iron oxide clusters on the surface of γ-Al2O3 using EXAFS

    Science.gov (United States)

    Boubnov, Alexey; Roppertz, Andreas; Kundrat, Matthew D.; Mangold, Stefan; Reznik, Boris; Jacob, Christoph R.; Kureti, Sven; Grunwaldt, Jan-Dierk

    2016-11-01

    Iron oxide centres are structurally investigated in 0.1% Fe/γ-Al2O3, which is known as highly active catalyst, for instance in the oxidation of CO. The sample was characterised by using X-ray absorption spectroscopy (XAS) in terms of X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS), Mössbauer spectroscopy, X-ray diffraction (XRD) and transmission electron microscopy (TEM). These analyses evidenced high dispersion of the iron oxide entities without significant presence of bulk-like aggregates associated with the low Fe content of the catalyst. A library of structural models of Al2O3-supported surface Fe was created as input for EXAFS fitting. Additionally, several model structures of Fe substituting Al ions in bulk γ-Al2O3 were created with optimised geometry based on density-functional theory (DFT) calculations. From EXAFS refinement of the best 8 out of 24 models, it was found that the trivalent Fe ions are coordinated by 4-5 oxygen atoms and are located on octahedral lattice sites of the exposed surfaces of γ-Al2O3. These iron oxide species exist mainly as a mixture of monomeric and binuclear species and due to the low concentration represent suitable model systems as alternative to single crystal systems for structure-function relationships.

  20. Characterization of Phosphorus Species in Biosolids and Manures Using XANES Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Shober,A.; Hesterberg, D.; Sims, J.; Gardner, S.

    2006-01-01

    Received for publication March 10, 2006. Identification of the chemical P species in biosolids or manures will improve our understanding of the long-term potential for P loss when these materials are land applied. The objectives of this study were to determine the P species in dairy manures, poultry litters, and biosolids using X-ray absorption near-edge structure (XANES) spectroscopy and to determine if chemical fractionation techniques can provide useful information when interpreted based on the results of more definitive P speciation studies. Our XANES fitting results indicated that the predominant forms of P in organic P sources included hydroxylapatite, PO{sub 4} sorbed to Al hydroxides, and phytic acid in lime-stabilized biosolids and manures; hydroxylapatite, PO{sub 4} sorbed on ferrihydrite, and phytic acid in lime- and Fe-treated biosolids; and PO{sub 4} sorbed on ferrihydrite, hydroxylapatite, {beta}-tricalcium phosphate ({beta}-TCP), and often PO{sub 4} sorbed to Al hydroxides in Fe-treated and digested biosolids. Strong relationships existed between the proportions of XANES PO{sub 4} sorbed to Al hydroxides and NH{sub 4}Cl- + NH{sub 4}F-extractable P, XANES PO{sub 4} sorbed to ferrihydrite + phytic acid and NaOH-extractable P, and XANES hydroxylapatite + {beta}-TCP and dithionite-citrate-bicarbonate (DCB)- + H{sub 2}SO{sub 4}-extractable P ({gamma}{sup 2} = 0.67 [P = 0.01], 0.78 [P = 0.01], and 0.89 [P = 0.001], respectively). Our XANES fitting results can be used to make predictions about long-term solubility of P when biosolids and manures are land applied. Fractionation techniques indicate that there are differences in the forms of P in these materials but should be interpreted based on P speciation data obtained using more advanced analytical tools.

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

    Science.gov (United States)

    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

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

    Science.gov (United States)

    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.

  3. EXAFS: New tool for study of battery and fuel cell materials

    Science.gov (United States)

    Mcbreen, James; Ogrady, William E.; Pandya, Kaumudi I.

    1987-01-01

    Extended X ray absorption fine structure (EXAFS) is a powerful technique for probing the local atomic structure of battery and fuel cell materials. The major advantages of EXAFS are that both the probe and the signal are X rays and the technique is element selective and applicable to all states of matter. This permits in situ studies of electrodes and determination of the structure of single components in composite electrodes, or even complete cells. EXAFS specifically probes short range order and yields coordination numbers, bond distances, and chemical identity of nearest neighbors. Thus, it is ideal for structural studies of ions in solution and the poorly crystallized materials that are often the active materials or catalysts in batteries and fuel cells. Studies on typical battery and fuel cell components are used to describe the technique and the capability of EXAFS as a structural tool in these applications. Typical experimental and data analysis procedures are outlined. The advantages and limitations of the technique are also briefly discussed.

  4. Platinum states in citrate sols by EXAFS.

    Science.gov (United States)

    Lin, Chia-Shiang; Khan, Maksudur R; Lin, Shawn D

    2005-07-01

    Platinum sols have been prepared by citrate reduction in the temperature range of 343-363 K. The Pt state in the solution was examined by EXAFS (extended X-ray absorption fine-structure spectroscopy). It did not show any PtPt bonding, a characteristic for reduced Pt sols. EXAFS model fitting further proved the presence of PtO with 4 oxygen neighbors, which suggests a tetraplanar coordination configuration. The possibility of neighboring Pt sharing oxygen ligand or the formation of PtO(x) is rejected by EXAFS model fitting. Citrate was found to be the most likely ligand to orient its oxygen end toward a charged Pt center. Thus we have revealed that the citrate treatment at this temperature range was clearly insufficient to reduce H2PtCl(6(aq)). Neither an extended period of reaction time nor an excess citrate reduced the Pt precursor. It is therefore highly recommended that the citrate sols should be carefully prepared and used.

  5. Chemical state analysis of conversion coatings by SR-XPS and TEY-XANES

    CERN Document Server

    Noro, H; Nagoshi, M

    2002-01-01

    Chromate coatings on galvanized steel have been studied by Synchrotron Radiation (SR) based techniques that include X-ray Photoelectron Spectroscopy (XPS) and Total-Electron-Yield X-ray Absorption Near Edge Structure (TEY-XANES). Non-destructive depth profiling of the coatings by SR-XPS reveals the enhancement of Cr sup 6 sup + in the outer surface. TEY-XANES spectroscopy based on simple specimen current measurement is demonstrated as an effective technique for analyzing chemical states of conversion coatings on general bulk substrates. The sampling depth of this technique, which exceeds several tens of nanometer, is determined by the penetration length of Auger electrons excited by X-ray and the inelastic mean free path of secondary electrons excited by inelastically scattered Auger electrons. The chemical states of phosphoric acid added chromate coatings are studied using this technique. The phosphoric acid is taken into the chromate coatings as partially changed into zinc and chromium phosphates, and the r...

  6. Observation of Ultrafast Bond-length Expansion at the Initial Stage of Laser Ablation by Picosecond Time-resolved EXAFS

    Science.gov (United States)

    Oguri, Katsuya; Okano, Yasuaki; Nishikawa, Tadashi; Nakano, Hidetoshi

    We have demonstrated a time-resolved extended X-ray absorption fine structure (EXAFS) technique by using a femtosecond laser produced plasma soft X-ray source. By applying this technique to the measurement of the initial stage of the laser ablation in Si foil, we were able to observe a slight shortening of the EXAFS oscillation period. This result suggests that the Si-Si atomic bond length expands as a result of the solid-liquid phase transition in Si. The realization of this technique is the first step toward understanding atomic structural dynamics during a chemical reaction.

  7. Predetermining acceptable noise limits in EXAFS spectra in the limit of stochastic noise

    Energy Technology Data Exchange (ETDEWEB)

    Hu, Yung-Jin; Booth, Corwin H

    2009-12-14

    EXAFS measurements are used to probe a variety of experimental systems, but excel at elucidating local structure in samples which have slight disorder or no long-range crystalline order. Of special interest to the authors is the use of EXAFS in understanding the molecular-level binding structure and characteristics of actinides on the surface of environmental minerals and model mineral analogs. In environmental systems the element of interest can be on the order of 10-7% by weight of the total sample. Obviously such samples would be impossible to measure using EXAFS techniques. It is therefore essential to increase the concentration of the element of interest while still preserving a sample's ability to represent environmental conditions. Under such low concentration limits it is expected that the collected data is countrate, or stochastically limited. This condition occurs as we approach the signal-to-noise (S/N) limit of the technique where the random noise of the measurement process dominates over possible systematic errors. When stochastic error is expected to dominate systematic error, it is possible to predict, with the use of simulations, the ability of model fits to tolerate a certain level of stochastic noise. Elsewhere in these proceedings, we discuss how to tell when systematic errors dominate in measured EXAFS spectrum. Here, we outline a technique for determining the number of EXAFS scans necessary to test the relevance of a given structural model. Appropriate stochastic noise levels are determined for each point in r-space by collecting data on a real system. These noise levels are then applied to EXAFS simulations using a test model. In this way, all significant systematic error sources are eliminated in the simulated data. The structural model is then fit to the simulated data, decreasing the noise and increasing the k-range of the fit until the veracity of the model passes an F-test. This paper outlines a method of testing model systems in

  8. XANES analysis of dried and calcined bones

    Energy Technology Data Exchange (ETDEWEB)

    Rajendran, Jayapradhi [Materials Science and Engineering Department, University of Texas at Arlington (United States); Gialanella, Stefano [Materials Science and Industrial Technology Department, University of Trento (Italy); Aswath, Pranesh B., E-mail: aswath@uta.edu [Materials Science and Engineering Department, University of Texas at Arlington (United States)

    2013-10-15

    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. - Highlights: • For the first time bones of five different species of vertebrates have been compared in both the dried and calcined states. • O, P and Ca edges detail the local coordination of these atoms in dried and calcined bone. • O K-edge shows that the surface of bone has more CO{sub 3} while the interior has more PO{sub 4}. • P and Ca edges eliminate the presence of pyrophosphates and confirmed the presence of HA and β-TCP. • The stability of these phosphates on calcination has been examined using XANES.

  9. EXAFS analysis of a human Cu,Zn SOD isoform focused using non-denaturing gel electrophoresis

    Energy Technology Data Exchange (ETDEWEB)

    Chevreux, Sylviane; Roudeau, Stephane; Deves, Guillaume; Ortega, Richard [Laboratoire de Chimie Nucleaire Analytique et Bioenvironnementale, CNRS UMR5084, Universite Bordeaux 1, Chemin du Solarium, F-33175 Gradignan cedex (France); Solari, Pier Lorenzo [Synchrotron SOLEIL, L' Orme des Merisiers, BP 48, F-91192 Gif-sur-Yvette cedex, Saint-Aubin (France); Alliot, Isabelle; Testemale, Denis; Hazemann, Jean Louis, E-mail: ortega@cenbg.in2p3.f [FAME, ESRF, 6 rue Jules Horowitz, BP220, F-38043 Grenoble cedex (France)

    2009-11-15

    Isoelectric point isoforms of a metalloprotein, copper-zinc superoxide dismutase (CuZnSOD), separated on electrophoresis gels were analyzed using X-ray Absorption Spectroscopy. Mutations of this protein are involved in familial cases of amyotrophic lateral sclerosis. The toxicity of mutants could be relied to defects in the metallation state. Our purpose is to establish analytical protocols to study metallation state of protein isoforms such as those from CuZnSOD. We previously highlighted differences in the copper oxidation state between CuZnSOD isoforms using XANES. Here, we present the first results for EXAFS analyses performed at Cu and Zn K-edge on the majoritary expressed isoform of human CuZnSOD separated on electrophoresis gels.

  10. EXAFS analysis of a human Cu,Zn SOD isoform focused using non-denaturing gel electrophoresis

    Science.gov (United States)

    Chevreux, Sylviane; Solari, Pier Lorenzo; Roudeau, Stéphane; Deves, Guillaume; Alliot, Isabelle; Testemale, Denis; Hazemann, Jean Louis; Ortega, Richard

    2009-11-01

    Isoelectric point isoforms of a metalloprotein, copper-zinc superoxide dismutase (CuZnSOD), separated on electrophoresis gels were analyzed using X-ray Absorption Spectroscopy. Mutations of this protein are involved in familial cases of amyotrophic lateral sclerosis. The toxicity of mutants could be relied to defects in the metallation state. Our purpose is to establish analytical protocols to study metallation state of protein isoforms such as those from CuZnSOD. We previously highlighted differences in the copper oxidation state between CuZnSOD isoforms using XANES. Here, we present the first results for EXAFS analyses performed at Cu and Zn K-edge on the majoritary expressed isoform of human CuZnSOD separated on electrophoresis gels.

  11. Fe K-edge XANES of Maya blue pigment

    Energy Technology Data Exchange (ETDEWEB)

    Rio, M. Sanchez del [ESRF, Experiments Division, B.P. 220, F-38043, Grenoble Cedex (France)]. E-mail: srio@esrf.fr; Sodo, A. [ESRF, Experiments Division, B.P. 220, F-38043, Grenoble Cedex (France); Eeckhout, S.G. [ESRF, Experiments Division, B.P. 220, F-38043, Grenoble Cedex (France); Neisius, T. [ESRF, Experiments Division, B.P. 220, F-38043, Grenoble Cedex (France); Martinetto, P. [Laboratoire de Cristallographie, CNRS, Grenoble B.P. 166, F-38042, Grenoble Cedex 09 (France); Dooryhee, E. [Laboratoire de Cristallographie, CNRS, Grenoble B.P. 166, F-38042, Grenoble Cedex 09 (France); Reyes-Valerio, C. [INAH, Mexico DF (Mexico)

    2005-08-15

    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 Si{sub 8}(Mg{sub 2}Al{sub 2})O{sub 20}(OH){sub 2}(OH{sub 2}){sub 4}.4H{sub 2}O and an organic colourant (indigo: C{sub 16}H{sub 10}N{sub 2}O{sub 2}), 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. K-edge EXAFS and XANES studies of Cu in CdTe thin-film solar cells

    Science.gov (United States)

    Liu, Xiangxin; Gupta, Akhlesh; Compaan, Alvin D.; Leyarovska, Nadia; Terry, Jeff

    2002-03-01

    Copper has been identified as a very important dopant element in CdTe thin-film solar cells. Cu is a deep acceptor in CdTe and is commonly used to obtain a heavily doped, low resistance back contact to polycrystalline CdTe. Cu also helps to increase the open circuit voltage of the cell. However, Cu is also a fast diffuser in CdTe, especially along grain boundaries, and can accumulate at the CdS/CdTe junction. It is suspected of leading to cell performance degradation in some cases. The present study is designed to help identify the lattice location of the Cu in CdTe. Cu K-edge, x-ray absorption (XAS) measurements were conducted on Cu in thin films of CdTe. Experiments were performed at the MR-CAT beamline at the Advanced Photon Source. The 3 mm CdTe layers were magnetron sputtered onto fused silica substrates. Some films were diffused with Cu from a 200 Å layer of evaporated Cu. XAS spectra were collected in fluorescence geometry with a 13 elements Ge detector. Quantitative fluorescence spectroscopy measurements were also performed. Details of the Cu environment and possible changes with time will be reported.

  13. Synchrotron EXAFS and XANES spectroscopy studies of transition aluminas doped with La and Cr for catalytic applications

    Science.gov (United States)

    Glazoff, Michael V.

    2016-04-01

    Transition aluminas doped with Cr find widespread application in the dehydrogenation catalysis industry, while La-stabilized transition aluminas are used extensively for high-temperature application as catalytic supports (Wefers and Misra in Oxides and hydroxides of aluminum, Alcoa Laboratories, Pittsburgh, 1987). In this work, detailed synchrotron XAFS spectroscopy studies were conducted to shed light upon the atomic mechanisms of surface and subsurface reconstructions and/or catalytic support stabilization of doped aluminas. It was demonstrated that in four transition aluminas doped with Cr, it is the atoms which are mostly in the state of oxidation Cr3+ and enter nanoparticles of Cr-bearing phases (Cr2O3 in the case of gamma- and chi-alumina). In the transition series aluminas: "gamma- chi- theta- eta-alumina," the change of properties (in particular, the dramatic increase in dehydrogenation catalytic activity and catalyst longevity and the coloration of samples) takes place because of the reduction in the average size of Cr clusters and their appearance on the Al2O3 surface, probably responsible for change in catalytic activity. It was demonstrated that in the samples of gamma-alumina doped with La any substantial change in the local coordination of the La atoms takes place only upon heating up to 1400 °C. This makes the La-stabilized gamma-alumina a perfect catalytic support for the numerous applications, e.g., catalytic three-way conversion of automobile exhaust gases. This change manifested itself in the form of increased La-O bond lengths and the La coordination number (from 8 to 12). Furthermore, it was demonstrated that the local environment of La in this new La-bearing phase cannot be explained in terms of the LaAlO3 formation. The absence of the La atoms in the second coordination sphere favors monoatomic distribution of La atoms on grain boundaries, proving that only very small amount of this rare earth material is required to achieve full stabilization. It is inferred that the tendency of La atoms to get surrounded by oxygen atoms, and also the impossibility of going into the alumina bulk, could be a major reason of the increased thermal stability of gamma-alumina doped with lanthanum.

  14. A multi-technique approach to assess chemical speciation of phosphate in soils

    Science.gov (United States)

    Belchior Abdala, Dalton; Rodrigues, Marcos; Herrera, Wilfrand; Pavinato, Paulo Sergio

    2017-04-01

    different P pools considered in the fractionation protocol, (ii) two synchrotron-based X-ray absorption spectroscopic techniques, XANES and EXAFS, for chemical characterization of the P forms and mineralogy of Fe-(hydr)oxides present in a sample, and (iii) Scanning Electron Microscopy and Energy-Dispersive spectroscopy, SEM/EDS, to provide complimentary information to corroborate and aid in the interpretation of our P XANES data. It was shown that the combination of techniques can assist us not only in the determination of the P chemical species present in a given material, but also to better understand the complex and dynamic processes to which P is subjected in soils. The association of spectroscopy (XANES and EXAFS) and microscopy (SEM/EDS) with wet chemistry data in this study was key to shift our understanding of the relationship between P and other soil mineral components from a macroscopic into a microscopic one. This represents a strong driving force to integrate the results of multi-analytical techniques into a more complete understanding of the systems under study. In addition, we provide a library of reference spectra for P K-edge XANES containing P sorbed to single and binary mixtures of mineral analogues intended to assist in the identification of P sorbed species commonly found in soils and sediments. Key-words: P K-edge XANES, Fe K-edge EXAFS, sequential chemical fractionation, soil phosphorus

  15. In situ sulfiding of Ni-W hydrocracking catalysts : differentiation of different preparation procedures using EXAFS and HRTEM.

    Energy Technology Data Exchange (ETDEWEB)

    Kelly, S. D.; Yang, N.; Mickelson, G. E.; Greenlay, N.; Karapetrova, E.; Sinkler, W.; Bare, S. R.; UOP LLC; EXAFS Analysis

    2009-01-01

    The detailed structural characterization of the metal function of two fully formulated Ni-W hydrocracking catalysts was investigated by time resolved in situ X-ray absorption spectroscopy (EXAFS and XANES) at both the Ni K-edge and W L{sub 3}-edge, and by high resolution transmission electron microscopy. These two hydrocracking catalysts (designated as HCA and HCB) contained the same wt% of Ni and W, the same wt% of the other constituents ({gamma}-Al{sub 2}O{sub 3}/silico-aluminate), and were calcined at the same temperature, but were prepared by different methods in order to highlight the sensitivity of the characterization techniques to the structural differences. The morphology of the WS{sub 2} particles in the sulfided catalyst is substantially different between the two catalysts: in the HCA catalyst there are many more particles with multiple WS{sub 2} layers whereas in HCB there are more single layers. The average diameter of the WS{sub 2} plates is similar in both. The catalysts show a difference in the amount of W sulfidation after the 410 C sulfidation treatment in 10% H{sub 2}S/H{sub 2}. The W of HCA catalyst was completely sulfided whereas 16% W of HCB catalyst was unsulfided. Similarly there is a difference in the amount of sulfided Ni: 16% Ni in HCA and 60% Ni in HCB remain unsulfided. In the sulfided form of both catalysts the Ni exists in three different morphologies: oxidized Ni (six-fold coordinate as a nickel aluminate), nanoparticulate Ni{sub 3}S{sub 2}, and Ni decorating the edge sites of the WS{sub 2}. In both the Ni{sub 3}S{sub 2}, and Ni decorating the edge sites of the WS{sub 2}, the Ni is in a tetrahedral coordination with sulfur. In both catalysts the sulfidation of the Ni and W occurs essentially simultaneously over most of the temperature range and the sulfidation of the W proceeds through the same tungsten oxysulfide in both samples. The characterization methodology presented here is a powerful one for elucidating the structural

  16. The use of synchrotron radiation techniques in the characterization of strained semiconductor heterostructures and thin films [review article

    Science.gov (United States)

    Lamberti, C.

    2004-05-01

    In the last couple of decades, high-performance electronic and optoelectronic devices based on semiconductor heterostructures have been required to obtain increasingly strict and well-defined performances, needing a detailed control, at the atomic level, of the structural composition of the buried interfaces. This goal has been achieved by an improvement of the epitaxial growth techniques and by the parallel use of increasingly sophisticated characterization techniques. Among them, a leading role has been certainly played by those exploiting synchrotron radiation (SR) sources. In fact synchrotron radiation has distinct advantages as a photon source, notably high brilliance and continuous energy spectrum; by using the latter characteristic atomic selectivity can be obtained and this is of fundamental help to investigate the structural environment of atoms present only in a few angstrom (Å) thick interface layers of heterostructures. The third generation synchrotron radiation sources have allowed to reach the limit of measuring a monolayer of material, corresponding to about 10 14 atoms/cm 2. Since, in the last decade, the use of intentionally strained heterostructures has greatly enhanced the performance of electrical and electro-optical semiconductor, a particular attention will be devoted to intentionally strained superlattices. First the effect of strain on the band lineups alignments in strained heterostructures will be discussed deeply. Then the attention will be focused on to review the most important results obtained by several groups in the characterization of semiconductor heterostructures using the following structural SR techniques: (i) X-ray absorption-based techniques such as EXAFS, polarization-dependent EXAFS, surface EXAFS and NEXAFS (or XANES); (ii) X-ray diffraction-based techniques such as high-resolution XRD, grazing incidence XRD, XRD reciprocal space maps, X-ray standing waves and diffraction anomalous fine structure (DAFS); (iii

  17. Towards advanced structural analysis of iron oxide clusters on the surface of γ-Al{sub 2}O{sub 3} using EXAFS

    Energy Technology Data Exchange (ETDEWEB)

    Boubnov, Alexey [Institute for Chemical Technology and Polymer Chemistry, Karlsruhe Institute of Technology, Kaiserstr. 12, D-76131 Karlsruhe (Germany); Institute of Catalysis Research and Technology, Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, D-76344 Eggenstein-Leopoldshafen (Germany); Roppertz, Andreas [Institute of Energy Process Engineering and Chemical Engineering, Chair of Reaction Engineering, Technical University of Freiberg, Fuchsmuehlenweg 9, D-09599 Freiberg (Germany); Kundrat, Matthew D. [Center for Functional Nanostructures and Institute of Physical Chemistry, Karlsruhe Institute of Technology, Kaiserstr. 12, D-76131 Karlsruhe (Germany); Mangold, Stefan [Institut für Beschleunigerphysik und Technologie (IBPT), Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, D-76344 Eggenstein-Leopoldshafen (Germany); Reznik, Boris [Institute of Applied Geosciences, Karlsruhe Institute of Technology, Kaiserstr. 12, D-76131 Karlsruhe (Germany); Jacob, Christoph R. [Center for Functional Nanostructures and Institute of Physical Chemistry, Karlsruhe Institute of Technology, Kaiserstr. 12, D-76131 Karlsruhe (Germany); Institute of Physical and Theoretical Chemistry, TU Braunschweig, Hans-Sommer-Str. 10, D-38106 Braunschweig (Germany); Kureti, Sven [Institute of Energy Process Engineering and Chemical Engineering, Chair of Reaction Engineering, Technical University of Freiberg, Fuchsmuehlenweg 9, D-09599 Freiberg (Germany); Grunwaldt, Jan-Dierk, E-mail: grunwaldt@kit.edu [Institute for Chemical Technology and Polymer Chemistry, Karlsruhe Institute of Technology, Kaiserstr. 12, D-76131 Karlsruhe (Germany); Institute of Catalysis Research and Technology, Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, D-76344 Eggenstein-Leopoldshafen (Germany)

    2016-11-15

    Highlights: • Analysis of isolated and oligomeric FeOx (x = 4, 5) on Al{sub 2}O{sub 3} by XANES and EXAFS. • Iron is trivalent and is mainly located at octahedral lattice sites of Al{sub 2}O{sub 3}. • Low Fe loading (0.1%) guarantees high dispersion of catalytically active iron sites. • Surface Fe-cluster on Al{sub 2}O{sub 3} and DFT-optimised Fe-doped Al{sub 2}O{sub 3} as input models for EXAFS. • Interactions of iron with support are well-accounted for using realistic models. - Abstract: Iron oxide centres are structurally investigated in 0.1% Fe/γ-Al{sub 2}O{sub 3}, which is known as highly active catalyst, for instance in the oxidation of CO. The sample was characterised by using X-ray absorption spectroscopy (XAS) in terms of X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS), Mössbauer spectroscopy, X-ray diffraction (XRD) and transmission electron microscopy (TEM). These analyses evidenced high dispersion of the iron oxide entities without significant presence of bulk-like aggregates associated with the low Fe content of the catalyst. A library of structural models of Al{sub 2}O{sub 3}-supported surface Fe was created as input for EXAFS fitting. Additionally, several model structures of Fe substituting Al ions in bulk γ-Al{sub 2}O{sub 3} were created with optimised geometry based on density-functional theory (DFT) calculations. From EXAFS refinement of the best 8 out of 24 models, it was found that the trivalent Fe ions are coordinated by 4–5 oxygen atoms and are located on octahedral lattice sites of the exposed surfaces of γ-Al{sub 2}O{sub 3}. These iron oxide species exist mainly as a mixture of monomeric and binuclear species and due to the low concentration represent suitable model systems as alternative to single crystal systems for structure-function relationships.

  18. Merging Structural Information from X-ray Crystallography, Quantum Chemistry, and EXAFS Spectra: The Oxygen-Evolving Complex in PSII.

    Science.gov (United States)

    Chernev, Petko; Zaharieva, Ivelina; Rossini, Emanuele; Galstyan, Artur; Dau, Holger; Knapp, Ernst-Walter

    2016-10-12

    Structural data of the oxygen-evolving complex (OEC) in photosystem II (PSII) determined by X-ray crystallography, quantum chemistry (QC), and extended X-ray absorption fine structure (EXAFS) analyses are presently inconsistent. Therefore, a detailed study of what information can be gained about the OEC through a comparison of QC and crystallographic structure information combined with the information from range-extended EXAFS spectra was undertaken. An analysis for determining the precision of the atomic coordinates of the OEC by QC is carried out. OEC model structures based on crystallographic data that are obtained by QC from different research groups are compared with one another and with structures obtained by high-resolution crystallography. The theory of EXAFS spectra is summarized, and the application of EXAFS spectra to the experimental determination of the structure of the OEC is detailed. We discriminate three types of parameters entering the formula for the EXAFS spectrum: (1) model-independent, predefined, and fixed; (2) model-dependent that can be computed or adjusted; and (3) model-dependent that must be adjusted. The information content of EXAFS spectra is estimated and is related to the precision of atomic coordinates and resolution power to discriminate different atom-pair distances of the OEC. It is demonstrated how a precise adjustment of atomic coordinates can yield a nearly perfect representation of the experimental OEC EXAFS spectrum, but at the expense of overfitting and losing the knowledge of the initial OEC model structure. Introducing a novel type of penalty function, it is shown that moderate adjustment of atomic coordinates to the EXAFS spectrum limited by constraints avoids overfitting and can be used to validate different OEC model structures. This technique is used to identify the OEC model structures whose computed OEC EXAFS spectra agree best with the measured spectrum. In this way, the most likely S-state and protonation pattern

  19. An X-ray Raman spectrometer for EXAFS studies on minerals: bent Laue spectrometer with 20 keV X-rays.

    Science.gov (United States)

    Hiraoka, N; Fukui, H; Tanida, H; Toyokawa, H; Cai, Y Q; Tsuei, K D

    2013-03-01

    An X-ray Raman spectrometer for studies of local structures in minerals is discussed. Contrary to widely adopted back-scattering spectrometers using ≤10 keV X-rays, a spectrometer utilizing ~20 keV X-rays and a bent Laue analyzer is proposed. The 20 keV photons penetrate mineral samples much more deeply than 10 keV photons, so that high intensity is obtained owing to an enhancement of the scattering volume. Furthermore, a bent Laue analyzer provides a wide band-pass and a high reflectivity, leading to a much enhanced integrated intensity. A prototype spectrometer has been constructed and performance tests carried out. The oxygen K-edge in SiO(2) glass and crystal (α-quartz) has been measured with energy resolutions of 4 eV (EXAFS mode) and 1.3 eV (XANES mode). Unlike methods previously adopted, it is proposed to determine the pre-edge curve based on a theoretical Compton profile and a Monte Carlo multiple-scattering simulation before extracting EXAFS features. It is shown that the obtained EXAFS features are reproduced fairly well by a cluster model with a minimal set of fitting parameters. The spectrometer and the data processing proposed here are readily applicable to high-pressure studies.

  20. EXAFS characterization of amorphous GaAs

    Energy Technology Data Exchange (ETDEWEB)

    Ridgway, M.C.; Glover, C.J. [Australia National Univ., Canberra (Australia); Foran, G.J. [Australian Nuclear Science and Technology Organization, Menai (Australia); Yu, K.M. [Lawrence Berkeley National Lab., CA (United States). Materials Sciences Div.

    1998-12-31

    The structural parameters of stoichiometric, amorphous GaAs have been determined with extended x-ray absorption fine structure (EXAFS) measurements performed in transmission mode at 10 K. Amorphous GaAs samples were fabricated with a combination of epitaxial growth, ion implantation and selective chemical etching. Relative to a crystalline sample, the nearest-neighbor bond length and Debye-Waller factor both increased for amorphous material. In contrast, the coordination numbers about both Ga and As atoms in the amorphous phase decreased to {approximately} 3.85 atoms from the crystalline value of four. All structural parameters were independent of implantation conditions and as a consequence, were considered representative of intrinsic, amorphous GaAs as opposed to an implantation-induced extrinsic structure.

  1. Investigation of gamma radiation induced changes in local structure of borosilicate glass by TDPAC and EXAFS

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, Ashwani, E-mail: kashwani@barc.gov.in [Bhabha Atomic Research Centre, Radioanalytical Chemistry Division (India); Nayak, C.; Rajput, P. [Bhabha Atomic Research Centre, Atomic and Molecular Physics Division (India); Mishra, R. K. [Bhabha Atomic Research Centre, Waste Management Division (India); Bhattacharyya, D. [Bhabha Atomic Research Centre, Atomic and Molecular Physics Division (India); Kaushik, C. P. [Bhabha Atomic Research Centre, Waste Management Division (India); Tomar, B. S. [Bhabha Atomic Research Centre, Radioanalytical Chemistry Division (India)

    2016-12-15

    Gamma radiation induced changes in local structure around the probe atom (Hafnium) were investigated in sodium barium borosilicate (NBS) glass, used for immobilization of high level liquid waste generated from the reprocessing plant at Trombay, Mumbai. The (NBS) glass was doped with {sup 181}Hf as a probe for time differential perturbed angular correlation (TDPAC) spectroscopy studies, while for studies using extended X-ray absorption fine structure (EXAFS) spectroscopy, the same was doped with 0.5 and 2 % (mole %) hafnium oxide. The irradiated as well as un-irradiated glass samples were studied by TDPAC and EXAFS techniques to obtain information about the changes (if any) around the probe atom due to gamma irradiation. TDPAC spectra of unirradiated and irradiated glasses were similar and reminescent of amorphous materials, indicating negligible effect of gamma radiation on the microstructure around Hafnium probe atom, though the quaqdrupole interaction frequency (ω{sub Q}) and asymmetry parameter (η) did show a marginal decrease in the irradiated glass compared to that in the unirradiated glass. EXAFS measurements showed a slight decrease in the Hf-O bond distance upon gamma irradiation of Hf doped NBS glass indicating densification of the glass matrix, while the cordination number around hafnium remains unchanged.

  2. Investigation of gamma radiation induced changes in local structure of borosilicate glass by TDPAC and EXAFS

    Science.gov (United States)

    Kumar, Ashwani; Nayak, C.; Rajput, P.; Mishra, R. K.; Bhattacharyya, D.; Kaushik, C. P.; Tomar, B. S.

    2016-12-01

    Gamma radiation induced changes in local structure around the probe atom (Hafnium) were investigated in sodium barium borosilicate (NBS) glass, used for immobilization of high level liquid waste generated from the reprocessing plant at Trombay, Mumbai. The (NBS) glass was doped with 181Hf as a probe for time differential perturbed angular correlation (TDPAC) spectroscopy studies, while for studies using extended X-ray absorption fine structure (EXAFS) spectroscopy, the same was doped with 0.5 and 2 % (mole %) hafnium oxide. The irradiated as well as un-irradiated glass samples were studied by TDPAC and EXAFS techniques to obtain information about the changes (if any) around the probe atom due to gamma irradiation. TDPAC spectra of unirradiated and irradiated glasses were similar and reminescent of amorphous materials, indicating negligible effect of gamma radiation on the microstructure around Hafnium probe atom, though the quaqdrupole interaction frequency ( ω Q) and asymmetry parameter ( η) did show a marginal decrease in the irradiated glass compared to that in the unirradiated glass. EXAFS measurements showed a slight decrease in the Hf-O bond distance upon gamma irradiation of Hf doped NBS glass indicating densification of the glass matrix, while the cordination number around hafnium remains unchanged.

  3. Development of synchrotron x-ray micro-spectroscopic techniques and application to problems in low temperature geochemistry. Progress report

    Energy Technology Data Exchange (ETDEWEB)

    1993-10-01

    The focus of the technical development effort has been the development of apparatus and techniques for the utilization of X-ray Fluorescence (XRF), Extended X-ray Absorption Fine Structure (EXAFS) and X-ray Absorption Near Edge Structure (XANES) spectroscopies in a microprobe mode. The present XRM uses white synchrotron radiation (3 to 30 keV) from a bending magnet for trace element analyses using the x-ray fluorescence technique Two significant improvements to this device have been recently implemented. Focusing Mirror: An 8:1 ellipsoidal mirror was installed in the X26A beamline to focus the incident synchrotron radiation and thereby increase the flux on the sample by about a factor of 30. Incident Beam Monochromator: The monochromator has been successfully installed and commissioned in the X26A beamline upstream of the mirror to permit analyses with focused monochromatic radiation. The monochromator consists of a channel-cut silicon (111) crystal driven by a Klinger stepping motor translator. We have demonstrated the operating range of this instrument is 4 and 20 keV with 0.01 eV steps and produces a beam with a {approximately}10{sup {minus}4} energy bandwidth. The primary purpose of the monochromator is for x-ray absorption spectroscopy (XAS) measurements but it is also used for selective excitation in trace element microanalysis. To date, we have conducted XANES studies on Ti, Cr, Fe, Ce and U, spanning the entire accessible energy range and including both K and L edge spectra. Practical detection limits for microXANES are 10--100 ppM for 100 {mu}m spots.

  4. Adsorption of Eu( Ⅲ) on titanate nanotubes studied by a combination of batch and EXAFS technique%静态法和EXAFS技术研究Eu(Ⅲ)在钛酸纳米管上的吸附行为和微观机制

    Institute of Scientific and Technical Information of China (English)

    盛国栋; 杨世通; 赵东林; 盛江; 王祥科

    2012-01-01

    The effects of pH, contact time and natural organic ligands on radionuclide Eu(III) adsorption and mechanism on titanate nanotubes (TNTs) are studied by a combination of batch and extended X-ray absorption fine structure (EXAF S) techniques. Macroscopic measurements show that the adsorption is ionic strength dependent at pH 6.0. The presence of humic acid (HA)/fulvic acid (FA) increases Eu(III) adsorption on TNTs at low pH, but reduces Eu(III) adsorption at high pH. The results of EXAFS analysis indicate that Eu(III) adsorption on TNTs is dominated by outer-sphere surface complexation at pH 6.0. At pH < 6.0, Eu(III) consists of ~ 9 O atoms at RFu-o ≈ 2.40 A in the first coordination sphere, and a decrease in NEuo with increasing pH indicates the introduction of more asymmetry in the first sphere of adsorbed Eu(III). At long contact time or high pH values, the Eu(III) consists of ~2 Eu at Reu ~ 3.60 A and ~ 1 Ti at REu-Ti ~ 4.40 (A), indicating the formation of inner-sphere surface complexation, surface precipitation or surface polymers. Surface adsorbed HA/FA on TNTs modifies the species of adsorbed Eu(III) as well as the local atomic structures of adsorbed Eu(lll) on HA/FA-TNT hybrids. Adsorbed Eu(III) on HA/FA-TNT hybrids forms both ligand-bridging ternary surface complexes (Eu-HA/FA-TNTs) as well as surface complexes in which Eu(III) remains directly bound to TNT surface hydroxyl groups (i.e., binary Eu-TNTs or Eu-bridging ternary surface complexes (HA/FA-Eu-TNTs)). The findings in this work are important to describe Eu(III) interaction with nanomaterials at molecular level and will help to improve the understanding of Eu(III) physicochemical behavior in the natural environment.%结合静态实验和X射线吸收精细结构谱学(EXAFS)技术研究了pH、时间、有机配体等环境因素对放射性核素Eu(Ⅲ)在钛酸纳米管上的吸附行为和微观机制的影响.宏观实验结果表明:Eu(Ⅲ)在钛酸纳米管上的吸附在pH<6.0条件下

  5. Pd nanoparticles formation inside porous polymeric scaffolds followed by in situ XANES/SAXS

    Science.gov (United States)

    Longo, A.; Lamberti, C.; Agostini, G.; Borfecchia, E.; Lazzarini, A.; Liu, W.; Giannici, F.; Portale, G.; Groppo, E.

    2016-05-01

    Simultaneous time-resolved SAXS and XANES techniques were employed to follow in situ the formation of Pd nanoparticles from palladium acetate precursor in two porous polymeric supports: polystyrene (PS) and poly(4-vinyl-pyridine) (P4VP). In this study we have investigated the effect of the use of different reducing agents (H2 and CO) from the gas phase. These results, in conjunction with data obtained by diffuse reflectance IR (DRIFT) spectroscopy and TEM measurements, allowed us to unravel the different roles played by gaseous H2 and CO in the formation of the Pd nanoparticles for both PS and P4VP hosting scaffolds.

  6. EXAFS determination of cation local order in layered perovskites

    Energy Technology Data Exchange (ETDEWEB)

    Montero C, M. E.; Fuentes M, L.; Duarte M, J. A.; Fuentes C, L. [Centro de Investigacion en Materiales Avanzados S. C., Miguel de Cervantes Saavedra 120, Complejo Industrial Chihuahua, 31109 Chihuahua (Mexico); Garcia G, M. [Instituto de Fisica, UNAM, Ciudad Universitaria, 04510 Mexico D. F. (Mexico); Mehta, A.; Webb, S. [Stanford Synchrotron Radiation Laboratory, CA (United States)

    2008-02-15

    EXAFS analysis of Bi{sub 6}Ti{sub 3}Fe{sub 2}O{sub 18} Aurivillius ceramic was performed to elucidate the local environment of Fe cations. Experiments were performed at Stanford Synchrotron Radiation Laboratory, at T = 10, 30, 50, 75, 100 and 298 K, in fluorescence regime. EXAFS spectra were processed using the ab initio multiple scattering program FEFF6. Distances among representative atomic pairs were refined. As a basic result, the previous hypothesis suggested by X-ray diffraction experiments, regarding a preference of iron atoms for the centered perovskite layer of the unit cell, was confirmed. (Author)

  7. Automating an EXAFS facility: hardware and software considerations

    Energy Technology Data Exchange (ETDEWEB)

    Georgopoulos, P; Sayers, D E; Bunker, B; Elam, T; Grote, W A

    1981-01-01

    The basic design considerations for computer hardware and software, applicable not only to laboratory EXAFS facilities, but also to synchrotron installations, are reviewed. Uniformity and standardization of both hardware configurations and program packages for data collection and analysis are heavily emphasized. Specific recommendations are made with respect to choice of computers, peripherals, and interfaces, and guidelines for the development of software packages are set forth. A description of two working computer-interfaced EXAFS facilities is presented which can serve as prototypes for future developments. 3 figures.

  8. EXAFS studies of lanthanide coordination in crystalline phosphates and amorphous phytates

    Energy Technology Data Exchange (ETDEWEB)

    Morss, L.R.; Schmidt, M.A.J.; Nash, K.L. [and others

    1995-12-31

    As part of the DOE Efficient Separations and Processing Integrated Program, techniques are being developed to stabilize radioactive and hazardous contaminants to prevent their migration from buried wastes. This report is part of a study to immobilize actinide ions in the near-surface environment by reacting them with organophosphorus complexants that decompose to phosphates. Nd and Gd ions were used as models for Pu, Am, and Cm ions; phytic acid was used as the complexant. Solid Nd and Gd phytates were prepared and the coordination characterized by EXAFS.

  9. Study of XANES near Ta-L edges in LiTaO{sub 3} through thermal wave, fluorescence and first principles

    Energy Technology Data Exchange (ETDEWEB)

    Kane, S.R.; Singh, Ajit Kumar [Raja Ramanna Centre for Advanced Technology, Indus Synchrotrons Utilisation Division, Indore (India); Kumar, Shailendra; Ghosh, Haranath; Tiwari, M.K. [Raja Ramanna Centre for Advanced Technology, Indus Synchrotrons Utilisation Division, Indore (India); BARC, Homi Bhabha National Institute, Mumbai (India)

    2016-01-15

    X-ray absorption near-edge spectra (XANES) of Ta-L{sub 2} and L{sub 3} edges in LiTaO{sub 3} (LTO) crystals are measured by measuring amplitude and phase of thermal waves generated within the LTO crystal, using pyroelectric property of LTO. Thus, LTO crystal is used both as a sample as well as sensor material. XANES of Ta-L edges in LTO are also measured by fluorescence. XANES spectra from fluorescence and first-principles simulations agree excellently well. The onset of the pre-edge region of XANES, measured by both techniques, extends below the edge by about 50 eV. This pre-edge onset of absorption is explained in terms of the core-hole lifetime effect on near-edge absorption using density functional theory. However, detailed nature of XANES peaks near Ta-L{sub 3} and Ta-L{sub 2} absorption edges, measured by thermal waves and fluorescence, differ. Possible origins of these differences are discussed. (orig.)

  10. Local Structure of La1-xSrxCoO3 determined from EXAFS and neutron PDF studies

    Energy Technology Data Exchange (ETDEWEB)

    Sundaram, N.; Jiang, Y.; Anderson, I. E.; Belanger, D. P.; Booth, C. H.; Bridges, F.; Mitchell, J. F.; Proffen, Th.; Zheng, H.

    2009-01-26

    The combined local structure techniques, extended x-ray absorption fine structure (EXAFS) and neutron pair distribution function analysis, have been used for temperatures 4<= T<= 330 K to rule out a large Jahn-Teller (JT) distortion of the Co-O bond in La1?xSrxCoO3 for a significant fraction of Co sites (x<= 0.35), indicating few, if any, JT-active, singly occupied eg Co sites exist.

  11. Pressure effects in Debye-Waller factors and in EXAFS

    Energy Technology Data Exchange (ETDEWEB)

    Nguyen Van Hung, E-mail: hungnv@vnu.edu.v [University of Science, VNU Hanoi, 334 Nguyen Trai, Thanh Xuan, Hanoi (Viet Nam); Vu Van Hung [Hanoi National University of Education, 136 Xuan Thuy, Cau Giay, Hanoi (Viet Nam); Ho Khac Hieu [University of Science, VNU Hanoi, 334 Nguyen Trai, Thanh Xuan, Hanoi (Viet Nam); National University of Civil Engineering, 55 Giai Phong, Hai Ba Trung, Hanoi (Viet Nam); Frahm, Ronald R. [Bergische Universitaet-Gesamthochschule Wuppertal, FB: 8-Physik, Gauss Strasse 20, 42097 Wuppertal (Germany)

    2011-02-01

    Anharmonic correlated Einstein model (ACEM) and statistical moment method (SMM) have been developed to derive analytical expressions for pressure dependence of the lattice bond length, effective spring constant, correlated Einstein frequency and temperature, Debye-Waller factors (DWF) or second cumulant, first and third cumulants in Extended X-ray Absorption Fine Structure (EXAFS) at a given temperature. Numerical results for pressure-dependent DWF of Kr and Cu agree well with experiment and other theoretical values. Simulated EXAFS of Cu and its Fourier transform magnitude using our calculated pressure-induced change in the 1st shell are found to be in a reasonable agreement with those using X-ray diffraction (XRD) experimental results. -- Research Highlights: {yields} We have developed anharmonic correlated Einstein model and statistical moment method. {yields} The pressure effects in cumulants including DWF and in EXAFS has been investigated. {yields} Calculated pressure-dependent DWF for Kr, Cu agree with experiment and other results. {yields} Simulated EXAFS and Fourier transform magnitude of Cu agree with those using XRD data.

  12. Aqueous U(VI) interaction with magnetite nanoparticles in a mixed flow reactor system: HR-XANES study

    Science.gov (United States)

    Pidchenko, I.; Heberling, F.; Kvashnina, KO; Finck, N.; Schild, D.; Bohnert, E.; Schäfer, T.; Rothe, J.; Geckeis, H.; Vitova, T.

    2016-05-01

    The redox variations and changes in local atomic environment of uranium (U) interacted with the magnetite nanoparticles were studied in a proof of principle experiment by the U L3 and M4 edges high energy resolution X-ray absorption near edge structure (HR-XANES) technique. We designed and applied a mixed flow reactor (MFR) set-up to maintain dynamic flow conditions during U-magnetite interactions. Formation of hydrolyzed, bi- and poly-nuclear U species were excluded by slow continuous injection of U(VI) (10-6 M) and pH control integrated in the MFR set-up. The applied U HR-XANES technique is more sensitive to minor changes in the U redox states and bonding compared to the conventional XANES method. Major U(VI) contribution in uranyl type of bonding is found in the magnetite nanoparticles after three days operation time of the MFR. Indications for shortening of the U-Oaxial bond length for the magnetite compared to the maghemite system are present too.

  13. EXAFS STUDY OF THE SHORT RANGE STRUCTURE OF NANOCRYSTALLINE BCC-Fe80Cu20 SOLID SOLUTION

    Institute of Scientific and Technical Information of China (English)

    Y.Z. Yang; X.J. Bai; T.C. Kuang; G.M. Wang; S. Q. Wei

    2002-01-01

    The structure of bcc-Fe80 Cu2o solid solution produced by mechanical alloying of theelemental bcc-Fe and fcc-Cu powders has been studied using X-ray diffraction and theextended X-ray absorption fine structure (EXAFS) techniques. The disappearance ofelemental Fe and Cu X-ray diffraction (XRD) peaks and the presence of bcc structuralXRD peaks illustrate the formation of a nanocrystalline single-phase bcc-Fe80 Gu20solid solution. From the EXAFS results, the clear observation of Cu atoms taking onbcc coordination in the solid solution and Fe atoms remaining bcc structure furtherverifies the reality of atomic alloying between Fe and Cu atoms and the lattice changeof Cu from fcc to bcc. However, the supersaturated bcc solid solution is not chemicallyuniform, i.e., some regions are rich in Fe atoms and other regions rich in Cu atoms.

  14. A XANES study of chromophores in archaeological glass

    Energy Technology Data Exchange (ETDEWEB)

    Arletti, Rossella [Universita di Torino, Dipartimento di Scienze della Terra, Torino (Italy); Quartieri, Simona [Universita di Messina, Dipartimento di Fisica e Scienze della Terra, Messina S' Agata (Italy); Freestone, Ian C. [Institute of Archaeology, London (United Kingdom)

    2013-04-15

    We applied X-ray absorption near edge spectroscopy (XANES) to obtain information on the origin of glass colour of several archaeological samples and on the oxidation conditions employed during their production. We studied a series of selected glass fragments - mainly from excavated primary and secondary production centres and dated to the first millennium AD - containing iron and manganese in a wide compositional range. In most of the studied samples iron is rather oxidised, while Mn K-edge XANES data show that, in all the studied glasses, Mn is mainly present in its reduced form (predominantly 2+), with the possible subordinate presence of Mn{sup 3+}. The most oxidised samples are the HIMT (high iron manganese titanium) glasses, while the less oxidised ones belong to the primary natron glass series from the early Islamic tank furnaces at Bet Eliezer (Israel), and to the series coming from a Roman glass workshop excavated in Basinghall Street, London. In these glasses, iron is approximately equally distributed over the 2+ and 3+ oxidation states. The XANES analyses of two glasses which had been deliberately decolourized using Sb- and Mn-based decolourizers demonstrate that Sb is more effective than Mn as oxidant. (orig.)

  15. The blue of iron in mineral pigments: a Fe K-edge XANES study of vivianite

    Science.gov (United States)

    Figueiredo, M. O.; Silva, T. P.; Veiga, J. P.

    2010-05-01

    Iron is a powerful chromophore element whose pigmenting properties were the first to be recognized among transition metals. The interest in blue iron minerals as pigments for painting was enhanced with the use of vivianite—a natural hydrated ferrous phosphate, Fe3(PO4)2ṡ8H2O—which in medieval Europe became an alternative to the expensive lapis lazuli, (Na, Ca)4(AlSiO4)3(SO4, Cl, S), a member of the ultramarines whose appreciated blue tone is due to the presence of sulfur polyanions. Conversely, vivianite coloring is attributed to the intervalence charge transfer (IVCT) Fe2+-Fe3+ that in later decades was studied by optical techniques and Mössbauer spectroscopy. However, the aging of blue vivianite pigments in old paintings has become a serious concern for conservators, but the aging process still awaits a satisfactory explanation. As an input to this problem, an X-ray absorption near-edge structure (XANES) study at the Fe K-edge of vivianite with different colors and origins was undertaken at the European Synchrotron Radiation Facility using the instrumental facilities of beamline ID-21. The analysis of pre-edge features corroborates previous data on the origin of vivianite color and emphasizes the need for a precautious assessment of iron speciation on the exclusive basis of XANES data. Actual results are discussed and further work is outlined.

  16. MULTIPLE SCATTERING IN THE EXAFS OF CALCIUM PHOSPHATES

    OpenAIRE

    1986-01-01

    Analysis of the EXAFS spectra of hydroxyapatite, brushite and monetite, recorded above the calcium K edge, requires the inclusion of multiple scattering by phosphorus atoms at 0.37 nm, from calcium. If multiple scattering is not included, some variable parameters acquire physically unreasonable values. Atomic radii never had to be varied by more than 0.01 nm from their values in the accepted crystal structures.

  17. EXAFS investigation of nanoparticles produced in a thermal plasma process

    Energy Technology Data Exchange (ETDEWEB)

    Luetzenkirchen-Hecht, D.; Frahm, R. [Heinrich-Heine-Univ. Duesseldorf, Inst. fuer Angewandte Physik (Germany); Buchner, P. [Heinrich-Heine-Univ. Duesseldorf, Inst. fuer Laser- und Plasmaphysik (Germany); Strehblow, H.H. [Heinrich-Heine-Univ., Inst. fuer Physikalische Chemie (Germany)

    1999-11-01

    Nanosized ceramic powders (Cu/SiC, Y{sub 2}O{sub 3}-stabilized cubic ZrO{sub 2}) were produced by evaporation of coarsely grained powders of the respective materials in an inductively coupled thermal plasma process and rapid quenching of the vapor. The atomic short range order of these nanoparticles with an average diameter of about 10 nm was investigated ex situ with EXAFS. The results are compared to crystalline reference materials. (au) 10 refs.

  18. EXAFS investigations of Cu-Mg-O compound

    CERN Document Server

    Sidorenko, A F; Babanov, Y A; Naumov, S V; Samokhvalov, A A

    2001-01-01

    The interest to systems containing copper oxide is connected with the problem of high-temperature superconductivity because of the closeness of its basic physical properties and properties of superconductor mother Cu-compounds. In this work, EXAFS study of the Cu sub 0 sub . sub 2 Mg sub 0 sub . sub 8 O compound is presented. A new iterative algorithm of the solution of ill-posed problem on determining three partial pair correlation functions from one EXAFS-data set near the Cu K-edge is described. The results of X-ray scattering study of a given sample show a presence of a single phase with the MgO structure and a lattice parameter of 4.219 A instead of 4.208 A for pure MgO. From the EXAFS investigations, we find the local distortion of the lattice. We revealed that the short range order differs both from a hypothetical alloy with the MgO structure and from copper oxide.

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

    Science.gov (United States)

    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

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

    Energy Technology Data Exchange (ETDEWEB)

    Brinza, Loredana [Diamond Light Source, Harwell Campus, Didcot, Oxon OX11 0DE (United Kingdom); Schofield, Paul F. [Natural History Museum, Cromwell Road, London SW7 5BD (United Kingdom); Hodson, Mark E. [University of York, York YO10 5DD (United Kingdom); Weller, Sophie [University of Oxford, South Parks Road, Oxford OX1 3QR (United Kingdom); Ignatyev, Konstantin; Geraki, Kalotina; Quinn, Paul D.; Mosselmans, J. Frederick W., E-mail: fred.mosselmans@diamond.ac.uk [Diamond Light Source, Harwell Campus, Didcot, Oxon OX11 0DE (United Kingdom)

    2014-01-01

    A new experimental set-up enabling microfocus fluorescence XANES mapping and microfocus XRD mapping on the same sample at beamline I18 at Diamond Light Source is described. To demonstrate this set-up the heterogeneous mineralogy in calcium carbonate granules excreted by the earthworm Lumbricus terrestris has been analysed. Data analysis methods have been developed which enable µXRD and µXANES two-dimensional maps to be compared. The use of fluorescence full spectral micro-X-ray absorption near-edge structure (µXANES) 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.

  1. XANES study of Fe-implanted strontium titanate

    Science.gov (United States)

    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.

  2. A reinvestigation of EXAFS and EPR spectroscopic measurements of chromium(VI) reduction by coir pith

    Energy Technology Data Exchange (ETDEWEB)

    Suksabye, Parinda [Department of Environmental Science, Faculty of Science and Technology, Suan Dusit Rajabhat University, 10300 (Thailand); Worasith, Niramon; Thiravetyan, Paitip [Division of Biotechnology, School of Bioresources and Technology King Mongkut' s University of Technology, Thonburi, Bangkhuntien, Bangkok (Thailand); Nakajima, Akira [Division of Chemistry, Department of Medical Science, Faculty of Medicine, University of Miyazaki, Kiyotake, Miyazaki 8891692 (Japan); Goodman, Bernard A., E-mail: bernard_a_goodman@yahoo.com [Health and Environment Department, Unit of Environmental Resources and Technologies, Austrian Institute of Technology, Seibersdorf A-2444 (Austria)

    2010-08-15

    New measurements using extended X-ray absorption fine structure (EXAFS) and electron paramagnetic resonance (EPR) techniques are consistent with Cr in the Cr(III) oxidation state as the main product from the adsorption of Cr(VI) on coir pith. These confirm the previous X-ray measurements, but differ from the results of previous EPR studies, which indicated that Cr(V) was the main form of Cr. The reason for this discrepancy is the presence of a broad signal from Cr(III) in an unsymmetrical environment that was missed previously; the Cr(V) component is in fact only a minor reaction product. As a result of this problem with spectral acquisition and interpretation, some simple recommendations are presented for conducting EPR investigations on natural systems.

  3. A reinvestigation of EXAFS and EPR spectroscopic measurements of chromium(VI) reduction by coir pith.

    Science.gov (United States)

    Suksabye, Parinda; Worasith, Niramon; Thiravetyan, Paitip; Nakajima, Akira; Goodman, Bernard A

    2010-08-15

    New measurements using extended X-ray absorption fine structure (EXAFS) and electron paramagnetic resonance (EPR) techniques are consistent with Cr in the Cr(III) oxidation state as the main product from the adsorption of Cr(VI) on coir pith. These confirm the previous X-ray measurements, but differ from the results of previous EPR studies, which indicated that Cr(V) was the main form of Cr. The reason for this discrepancy is the presence of a broad signal from Cr(III) in an unsymmetrical environment that was missed previously; the Cr(V) component is in fact only a minor reaction product. As a result of this problem with spectral acquisition and interpretation, some simple recommendations are presented for conducting EPR investigations on natural systems.

  4. EXAFS investigation of low temperature nitrided stainless steel

    DEFF Research Database (Denmark)

    Oddershede, Jette; Christiansen, Thomas; Ståhl, Kenny

    2008-01-01

    Low temperature nitrided stainless steel AISI 316 flakes were investigated with EXAFS and X-ray diffraction analysis. The stainless steel flakes were transformed into a mixture of nitrogen expanded austenite and nitride phases. Two treatments were carried out yielding different overall nitrogen...... contents: (1) nitriding in pure NH3 and (2)nitriding in pure NH3 followed by reduction in H2. The majority of the Cr atoms in the stainless steel after treatment 1 and 2 was associated with a nitrogen–chromium bond distance comparable to that of the chemical compound CrN. The possibility of the occurrence...

  5. ROCK: the new Quick-EXAFS beamline at SOLEIL

    Science.gov (United States)

    Briois, V.; La Fontaine, C.; Belin, S.; Barthe, L.; Moreno, Th; Pinty, V.; Carcy, A.; Girardot, R.; Fonda, E.

    2016-05-01

    ROCK is a new beamline at SOLEIL dedicated to Quick-EXAFS measurements. The optical layout has been optimized to get full advantage of the monochromators, which were designed at SOLEIL and successfully used at SAMBA from 2009 to 2014. ROCK has started user operations since March 2015. It is mainly employed to monitor fast kinetic processes in materials used in catalysis and energy sciences. A review of the ROCK performances and capabilities is presented. The high automation achieved for fast change of monochromators, optimization of mirrors for harmonic rejection and detectors allows the simultaneous operando characterization of different chemical elements present in a material during the same reaction.

  6. Redox-dependent changes in manganese speciation in Baltic Sea sediments from the Holocene Thermal Maximum: An EXAFS, XANES and LA-ICP-MS study

    NARCIS (Netherlands)

    Lenz, C.; Behrends, T.|info:eu-repo/dai/nl/30484358X; Jilbert, T.|info:eu-repo/dai/nl/304835714; Silveira, M.; Slomp, C.P.|info:eu-repo/dai/nl/159424003

    2014-01-01

    Manganese (Mn) enrichments in sediments of the deep basins of the Baltic Sea are believed to consist of Ca-Mn-carbonates that form from Mn oxides following periodic inflows of oxygen-rich North Sea waters. However, a range of Mn-bearing mineral phases, that besides Mn-carbonates (e.g.

  7. Following the crystallisation of Bi2Mo2O9 catalyst by combined XRD/QuEXAFS

    Indian Academy of Sciences (India)

    Andrew M Beale; Gopinathan Sankar

    2003-10-01

    The formation of -phase Bi2Mo2O9 catalyst from a precursor precipitate has been studied using the in situ combined XRD/QuEXAFS technique and DSC during calcination. Accordingly the precursor was observed to undergo a number of changes in both the molybdenum (VI) coordination and long-range ordering during this heating. Initially the two other forms of bismuth molybdate (-and -phases) were observed to form from the poorly crystalline precursor at about 230°C, however, the -phase eventually crystallised after prolonged heating at 560°C.

  8. Combined mineralogical and EXAFS characterization of polluted sediments for the definition of technological variables and constraints

    Science.gov (United States)

    Brigatti, M. F.; Elmi, C.; Laurora, A.; Malferrari, D.; Medici, L.

    2009-04-01

    An extremely severe aspect, both from environmental and economic viewpoint, is the management of polluted sediments removed from drainage and irrigation canals. Canals, in order to retain their functionality over the time, need to have their beds, periodically cleaned from sediments there accumulating. The management of removed sediments is extremely demanding, also from an economical perspective, if these latter needs to be treated as dangerous waste materials, as stated in numerous international standards. Furthermore the disposal of such a large amount of material may introduce a significant environmental impact as well. An appealing alternative is the recovery or reuse of these materials, for example in brick and tile industry, after obviously the application of appropriate techniques and protocols that could render these latter no longer a threat for human health. The assessment of the effective potential danger for human health and ecosystem of sediments before and after treatment obviously requires both a careful chemical and mineralogical characterization and, even if not always considered in the international standards, the definition of the coordination shell of heavy metals dangerous for human health, as a function of their oxidation state and coordination (e.g. Cr and Pb), and introducing technological constraints or affecting the features of the end products. Fe is a good representative for this second category, as the features of the end product, such as color, strongly depend not only from Fe concentration but also from its oxidation state, speciation and coordination. This work will first of all provide mineralogical characterization of sediments from various sampling points of irrigation and drainage canals of Po river region in the north-eastern of Italy. Samples were investigated with various approaches including X-ray powder diffraction under non-ambient conditions, thermal analysis and EXAFS spectroscopy. Obtained results, and in particular

  9. A XANES characterization of structural defects in single-walled carbon nanotubes

    Energy Technology Data Exchange (ETDEWEB)

    Zhong Jun [Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China); Song Li [Institute of Physics, Chinese Academy of Sciences, Beijing 100080 (China); Yan Dongwei [Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080 (China); Wu Ziyu [Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China) and National Center for NanoScience and Technology, Beijing 100080 (China)]. E-mail: wuzy@mail.ihep.ac.cn; Wang Chunru [Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080 (China); Xie Sishen [Institute of Physics, Chinese Academy of Sciences, Beijing 100080 (China); Qian Haijie [Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China)

    2006-11-15

    Structural defects play an important role in the physics of carbon nanototube. However, very few investigations of the structural changes induced by purifying process and other treatments have been performed by means of X-ray absorption near-edge structure (XANES) spectroscopy. We used XANES spectroscopy to detect the presence of defects induced in single-walled carbon nanotubes (SWNTs) by nitric acid treated processes and by an Ar{sup +} ion bombardment. The relationship between the features in XANES spectrum and the structural defects has been discussed systematically. Data also addresses evidence of oxygen effect induced by aging on nanotubes.

  10. EXAFS simulations in Zn-doped LiNbO3 based on defect calculations

    Science.gov (United States)

    Valerio, Mário E. G.; Jackson, Robert A.; Bridges, Frank G.

    2017-02-01

    Lithium niobate, LiNbO3, is an important technological material with good electro-optic, acousto-optic, elasto-optic, piezoelectric and nonlinear properties. EXAFS on Zn-doped LiNbO3 found strong evidences that Zn substitutes primarily at the Li site on highly doped samples. In this work the EXAFS results were revisited using a different approach where the models for simulating the EXAFS results were obtained from the output of defect calculations. The strategy uses the relaxed positions of the ions surrounding the dopants to generate a cluster from where the EXAFS oscillations can be calculated. The defect involves not only the Zn possible substitution at either Li or Nb sites but also the charge compensating defects, when needed. From previous defect modelling, a subset of defects was selected based on the energetics of the defect production in the LiNbO3 lattice. From them, all possible clusters were generated and the simulated EXAFS were computed. The simulated EXAFS were them compared to available EXAFS results in the literature. Based on this comparison different models could be proposed to explain the behaviour of Zn in the LiNbO3 matrix.

  11. MULTI ELEMENT SI SENSOR WITH READOUT ASIC FOR EXAFS SPECTROSCOPY.

    Energy Technology Data Exchange (ETDEWEB)

    DE GERONIMO,G.; O CONNOR,P.; BEUTTENMULLER,R.H.; LI,Z.; KUCZEWSKI,A.J.; SIDDONS,D.P.

    2002-09-09

    Extended X-ray Absorption Fine Structure (EXAFS) experiments impose stringent requirements on a detection system, due to the need for processing ionizing events at a high rate, typically above of 10Mcps/cm{sup 2}, and with a high resolution, typically better than 300eV. The detection system here presented is being developed targeting these stringent requirements. It is the result of a cooperation between the Instrumentation Division and the National Synchrotron Light Source (NSLS) of the Brookhaven National Laboratory (BNL). The system is composed of a multi-element Si sensor with dedicated per pixel electronics. The combination of high rate, high resolution and moderate complexity makes this system attractive when compared to other multi-element solutions. In sections 2, 3 and 4 the sensor, the interconnect and the electronics are briefly described. Section 5 reports on the first experimental results.

  12. EXAFS study of ion beam mixed Fe/Al multilayers

    CERN Document Server

    Arcon, I; Zalar, A; Kodre, A; Jagielski, J

    2003-01-01

    Composition and structure of Fe/Al multilayer coatings after ion beam mixing at different temperatures are studied. Samples were prepared by consecutive sputter deposition of Fe and Al on well-polished silicon substrate. The samples were ion beam mixed with 330 keV Ar ions at the dose of 3x10 sup 1 sup 5 ions/cm sup 2 in the temperature range between room temperature and 400 deg. C. AES depth profiles showed that mixing between Fe and Al layers started at 100 deg. C and was complete at 400 deg. C. Fe K-edge EXAFS, however, reveals that Fe bcc metallic phase is still present at all temperatures. The amount of an additional Fe-Al phase is about 20% up to 300 deg. C, increasing to 50% at 400 deg. C.

  13. EXAFS study on arsenic species and transformation in arsenic hyperaccumulator

    Institute of Scientific and Technical Information of China (English)

    HUANG Zechun; CHEN Tongbin; LEI Mei; HU Tiandou; HUANG Qifei

    2004-01-01

    Synchrotron radiation extended X-ray absorption fine structure (SR EXAFS) was employed to study the transformation of coordination environment and the redox speciation of arsenic in a newly discovered arsenic hyperaccumulator, Cretan brake (Pteris cretica L. var nervosa Thunb). It showed that the arsenic in the plant mainly coordinated with oxygen, except that some arsenic coordinated with S as As-GSH in root. The complexation of arsenic with GSH might not be the predominant detoxification mechanism in Cretan brake. Although some arsenic in root presented as As(V) in Na2HAsO4 treatments, most of arsenic in plant presented as As(III)-O in both treatments, indicating that As(V) tended to be reduced to As(III) after it was taken up into the root, and arsenic was kept as As(III) when it was transported to the above-ground tissues. The reduction of As(V) primarily proceeded in the root.

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

    Science.gov (United States)

    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 structure (µXANES) 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.

  15. Elucidation of structure and nature of the PdO-Pd transformation using in situ PDF and XAS techniques.

    Science.gov (United States)

    Keating, Jonathan; Sankar, Gopinathan; Hyde, Timothy I; Kohara, Shinji; Ohara, Koji

    2013-06-14

    The PdO-Pd phase transformation in a 4 wt% Pd/Al2O3 catalyst has been investigated using in situ X-ray absorption spectroscopy (XAS) and in situ X-ray total scattering (also known as high-energy X-ray diffraction) techniques. Both the partial and total pair distribution functions (PDF) from these respective techniques have been analysed in depth. New information from PDF analysis of total scattering data has been garnered using the differential PDF (d-PDF) approach where only correlations orginating from PdO and metallic Pd are extracted. This method circumvents problems encountered in characerising the catalytically active components due to the diffuse scattering from the disordered γ-Al2O3 support phase. Quantitative analysis of the palladium components within the catalyst allowed for the phase composition to be established at various temperatures. Above 850 °C it was found that PdO had converted to metallic Pd, however, the extent of reduction was of the order ca. 70% Pd metal and 30% PdO. Complementary in situ XANES and EXAFS were performed, with heating to high temperature and subsequent cooling in air, and the results of the analyses support the observations, that residual PdO is detected at elevated temperatures. Hysteresis in the transformation upon cooling is confirmed from XAS studies where reoxidation occurs below 680 °C.

  16. Short Range Order Signature in Crystalline and Amorphous GeSbTe Xanes Spectra

    Science.gov (United States)

    Raty, Jean-Yves; Otjacques, C. Éline; Pekoz, Rengin; Bichara, Christophe; Lordi, Vince

    2011-03-01

    A new implementation of XANES spectra calculations within DFT and PAW potentials is used to compute the XANES spectra of various amorphous and crystalline GeSbTe structures. A clear correlation between the local order, either tetrahedral or distorted octahedral, and the shape of the XANES signal is observed. These calculations provide a new interpretation of past XANES measurements, relating essentially the phase change mechanism to a moderate modification of the local environment of the Ge atoms. This work performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344. This work was supported by the Belgian PAI 3/42 program and the FNRS-FRFC.

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

    Energy Technology Data Exchange (ETDEWEB)

    Simon, S.B.; Sutton, S.R.; Grossman, L. (UC)

    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 with 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. Analysis of

  18. Solution Structures of Highly Active Molecular Ir Water-Oxidation Catalysts from Density Functional Theory Combined with High-Energy X-ray Scattering and EXAFS Spectroscopy.

    Science.gov (United States)

    Yang, Ke R; Matula, Adam J; Kwon, Gihan; Hong, Jiyun; Sheehan, Stafford W; Thomsen, Julianne M; Brudvig, Gary W; Crabtree, Robert H; Tiede, David M; Chen, Lin X; Batista, Victor S

    2016-05-04

    The solution structures of highly active Ir water-oxidation catalysts are elucidated by combining density functional theory, high-energy X-ray scattering (HEXS), and extended X-ray absorption fine structure (EXAFS) spectroscopy. We find that the catalysts are Ir dimers with mono-μ-O cores and terminal anionic ligands, generated in situ through partial oxidation of a common catalyst precursor. The proposed structures are supported by (1)H and (17)O NMR, EPR, resonance Raman and UV-vis spectra, electrophoresis, etc. Our findings are particularly valuable to understand the mechanism of water oxidation by highly reactive Ir catalysts. Importantly, our DFT-EXAFS-HEXS methodology provides a new in situ technique for characterization of active species in catalytic systems.

  19. φXANES: In vivo imaging of metal-protein coordination environments

    Science.gov (United States)

    James, Simon A.; Hare, Dominic J.; Jenkins, Nicole L.; de Jonge, Martin D.; Bush, Ashley I.; McColl, Gawain

    2016-02-01

    We have developed an X-ray absorption near edge structure spectroscopy method using fluorescence detection for visualizing in vivo coordination environments of metals in biological specimens. This approach, which we term fluorescence imaging XANESXANES), allows us to spatially depict metal-protein associations in a native, hydrated state whilst avoiding intrinsic chemical damage from radiation. This method was validated using iron-challenged Caenorhabditis elegans to observe marked alterations in redox environment.

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

    Science.gov (United States)

    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

  1. XANES Reveals the Flexible Nature of Hydrated Strontium in Aqueous Solution.

    Science.gov (United States)

    D'Angelo, Paola; Migliorati, Valentina; Sessa, Francesco; Mancini, Giordano; Persson, Ingmar

    2016-05-05

    X-ray absorption near-edge structure (XANES) spectroscopy has been used to determine the structure of the hydrated strontium in aqueous solution. The XANES analysis has been carried out using solid [Sr(H2O)8](OH)2 as reference model. Classical and Car-Parrinello molecular dynamics (MD) simulations have been carried out and in the former case two different sets of Lennard-Jones parameters have been used for the Sr(2+) ion. The best performing theoretical approach has been chosen on the basis of the experimental results. XANES spectra have been calculated starting from MD trajectories, without carrying out any minimization of the structural parameters. This procedure allowed us to properly account for thermal and structural fluctuations occurring in the aqueous solution in the analysis of the experimental spectrum. A deconvolution procedure has been applied to the raw absorption data thus increasing the sensitivity of XANES spectroscopy. One of the classical MD simulations has been found to provide a XANES theoretical spectrum in better agreement with the experimental data. An 8-fold hydration complex with a Sr-O distance of 2.60 Å has been found to be compatible with the XANES data, in agreement with previous findings. However, the hydration shells of the strontium ions have been found to have a flexible nature with a fast ligand exchange rate between the first and second hydration shell occurring in the picosecond time scale.

  2. Characterization and EXAFS Studies of Cobalt Synthesized by sol-gel auto Combustion Method

    Science.gov (United States)

    Mishra, Ashutosh; Singh, Priya; Ninama, Samrath

    2016-10-01

    The Co-Ni ferrites with general formula NiXCo1-XFe2O4 (where X=0.0, 0.1, 0.15, 2, 0.4) were prepared by Sol-gel auto combustion method. X-ray, FTIR and EXAFS measurement were carried out. Extended X ray Absorption Fine Structure (EXAFS) spectra have been recorded at the K-edge of Fe using the Dispersive EXAFS (DEXAFS) beam line-8 Indus-2 synchrotron radiation source RRCAT, Indore, India. The EXAFS data have been analysed using the computer softer Athena. These have been used to determine the Bond length in these ferrites with help of four different methods, namely, Levy's, Lytle's and Lytle, Sayers and stern's (LSS).

  3. An EXAFS study of the luminescent Bi3+ center in LaPO4---Bi

    NARCIS (Netherlands)

    Zon, F.B.M. van; Koningsberger, D.C.; Oomen, E.W.J.L.; Blasse, G.

    1987-01-01

    In order to determine the oxygen coordination of the Bi3+ ion in LaPO4---Bi, extended X-ray absorption fine structure (EXAFS) spectra were measured of BiPO4 and LaPO4---Bi. Analysis of the EXAFS data shows that the Bi3+ ion in LaPO4---Bi occupies the La3+ site, but that the oxygen coordination of th

  4. High-Resolution Mn EXAFS of the Oxygen-Evolving Complex inPhotosystem II: Structural Implications for the Mn4Ca Cluster

    Energy Technology Data Exchange (ETDEWEB)

    Yano, Junko; Pushkar, Yulia; Glatzel, Pieter; Lewis, Azul; Sauer,Kenneth; Messinger, Johannes; Bergmann, Uwe; Yachandra, Vittal

    2005-09-06

    The biological generation of oxygen by the oxygen-evolving complex in photosystem II (PS II) is one of natures most important reactions. The recent X-ray crystal structures, while limited by resolutions of 3.2 to 3.5 A, have located the electron density associated with the Mn4Ca complex within the multi-protein PS II complex. Detailed structures critically depend on input from spectroscopic techniques such as EXAFS and EPR/ENDOR, as the XRD resolution does not allow for accurate determination of the position of Mn/Ca or the bridging and terminal ligand atoms. The number and distances of Mn-Mn/Ca/ligand interactions determined from EXAFS provide important constraints for the structure of the Mn cluster. Here we present data from a high-resolution EXAFS method using a novel multi-crystal monochromator that show three short Mn-Mn distances between 2.7 and 2.8 A and hence the presence of three di-mu-oxobridged units in the Mn4Ca cluster. This result imposes clear limitations on the proposed structures based on spectroscopic and diffraction data and provides input for refining such structures.

  5. Structure of UC{sub 2} and U{sub 2}C{sub 3}:XRD, {sup 13}C NMR and EXAFS study

    Energy Technology Data Exchange (ETDEWEB)

    Carvajal Nuñez, U. [European Commission, Joint Research Centre, Institute for Transuranium Elements, P.O. Box 2340, D-76125 Karlsruhe (Germany); Eloirdi, R., E-mail: rachel.eloirdi@ec.europa.eu [European Commission, Joint Research Centre, Institute for Transuranium Elements, P.O. Box 2340, D-76125 Karlsruhe (Germany); Prieur, D.; Martel, L. [European Commission, Joint Research Centre, Institute for Transuranium Elements, P.O. Box 2340, D-76125 Karlsruhe (Germany); López Honorato, E. [Centro de Investigatión y de Estudios Avanzados del IPN (CINVESTAV), Unidad Saltillo, Av. Industria Metalúrgica 1062, Ramos Arizpe, Coahuila 25900 (Mexico); Farnan, I. [University of Cambridge, Cambridge CB2 1TN (United Kingdom); Vitova, T. [Institut für Nukleare Entsorgung (INE), P.O. Box 3640, D- 76021 Karlsruhe (Germany); Somers, J. [European Commission, Joint Research Centre, Institute for Transuranium Elements, P.O. Box 2340, D-76125 Karlsruhe (Germany)

    2014-03-15

    Highlights: • A structural investigation of UC{sub 2} and U{sub 2}C{sub 3} phases was made with XRD, NMR and EXAFS. • Heat treatment of a pulverised UC{sub 2} ingot, repressed into a pellet yields a U{sub 2}C{sub 3} phase coexisting with UC{sub 2−z}. • Heat treatment of UC{sub 2} as cast ingots results in a partial decomposition to UC. • EXAFS data confirmed the CaC{sub 2} and Pu{sub 2}C{sub 3} type structure for UC{sub 2} and U{sub 2}C{sub 3} respectively. • {sup 13}C MAS NMR identified a contribution of a well and less ordered phases in UC{sub 2}. -- Abstract: In this study, uranium dicarbide (UC{sub 2}) has been prepared by arc melting and heat treated under vacuum to form uranium sequicarbide (U{sub 2}C{sub 3}) in the presence of a second phase UC{sub 2−z}. Both samples, as cast and heat treated, have been characterised by chemical analyses, X-ray diffraction (XRD), {sup 13}C magic angle spinning nuclear magnetic resonance (MAS-NMR) and by extended X-ray absorption fine structure (EXAFS). The composition, the purity, the various environments of both U and C atoms as well as the bonds length with the coordination number have been determined. By combining a long-range order method (XRD) and short-range order spectroscopy techniques (EXAFS and NMR), a unique view on the microstructure of UC{sub 2}, before and after heat treatment, and of U{sub 2}C{sub 3} phase has been achieved.

  6. XANES evidence of arsenate removal from water with magnetic ferrite.

    Science.gov (United States)

    Tu, Yao-Jen; You, Chen-Feng; Chang, Chien-Kuei; Wang, Shan-Li

    2013-05-15

    Arsenic (As) in groundwater and surface water is a worldwide problem possessing a serious threat to public health. In this study, a magnetic ferrite, was synthesized and investigated for its As(V) removal efficiency. The adsorption of As(V) by magnetic ferrite exhibited an L-shaped nonlinear isotherm, suggesting limiting binding sites on the adsorbent surface. The As K-edge X-Ray Absorption Near-Edge Structure (XANES) revealed that the adsorbed As(V) on ferrite was not reduced to more toxic As(III) by Fe(2+) in the ferrite structure. The maximum As adsorption capacity of ferrite was 14 mg/g at pH 3 and decreased with increasing pH due to enhanced electrostatic repulsion between As(V) and the adsorbent surface. Desorption of As(V) using six different acid and salt solutions showed that the desorption rate decreased in an order of H3PO4 > Na3PO4 > H2SO4 > Na2SO4 > HCl > HNO3. These results suggest that magnetic ferrite without surface modification is an effective adsorbent for removing As(V) from water, which was confirmed by the effective removal of As(V) from contaminated groundwater using this material. The used material can then be recovered using a magnet because of its paramagnetism; the adsorbed As(V) on the material can be recovered using H3PO4 or Na3PO4 solutions.

  7. Localization an speciation of Zn in mycorrhized roots by μSXRF and μEXAFS

    Science.gov (United States)

    Sarret, G.; Schroeder, W. H.; Marcus, M. A.; Geoffroy, N.; Manceau, A.

    2003-05-01

    Mycorrhizae are symbiotic associations between soil fungi and plant mots, which enhance mineral nutrition for the plant, and might play an important role in metals acquisition and accumulation. The processes allowing metals mobilizaiion in the soil, absorption by the root and/or the fungus, transfert or bioaccumulation we still poorly understood. However, the properties of mycorrhizal fungi could be used for phytoremediation, a soft technique using plants for the clean-up of metal polluted soils. In this work, mycorrhized roots of tomato plants grown in a Zn-contaminated sail were investigated. The distribution of metals and the speciation of Zn were studied at the micron scale using micro synchrotron-based X-ray fluorescence (μSXRF) and micro X-ray absorption spectroscopy (μEXAFS). Zn associated to the root was Zn malate and/or Zn citrate, and Zn associated to the fungus was Zn phyllosilicate. This study illustrates the great potential of X-ray microbeams for the study of biological samples containing various amounts of metals.

  8. Characterisation of Reticon and Hamamatsu photodiode array and the subsequent development of high performance VME-based detector systems optimised for energy dispersive EXAFS

    Energy Technology Data Exchange (ETDEWEB)

    Bogg, D.; Dent, A.J.; Derbyshire, G.E.; Farrow, R.C.; Ramsdale, C.A.; Salvini, G. [Daresbury Lab., Warrington (United Kingdom). CCLRC

    1997-06-21

    Energy dispersive EXAFS is an established and successful technique employed at Daresbury Laboratory for the study of dynamic experiments. At the heart of this technique is an in house developed high-performance VME-based detector system using a photodiode array. This system originally used a Reticon RL1024S array but extensive investigation of three other photodiode arrays namely the Reticon 512T, 512SB and the Hamamatsu S3904 has enabled their characterisation and the subsequent development of optimised drive and signal processing electronics. This has provided two further systems which exhibit improved signal to noise, excellent linearity and increased operational speed. (orig.).

  9. Coordination geometry around copper in a Schiff-base trinuclear copper complex using EXAFS spectroscopy

    Science.gov (United States)

    Gaur, Abhijeet; Shrivastava, B. D.; Gaur, D. C.; Prasad, J.; Srivastava, K.; Jha, S. N.; Bhattacharyya, D.; Poswal, A.

    2012-05-01

    In the present investigation, we have studied extended X-ray absorption fine structure (EXAFS) spectra of a trinuclear Schiff-base copper complex tetraaqua-di-μ3-(N-salicylidene-DL-glutamato)-tricopper(II)heptahydrate, [Cu3(C12H10NO5)2 (H2O)4]. 7H2O, in which three metal sites are present. One metal site is square-pyramidal (4+1) and other two similar metal sites are tetragonally distorted octahedral (4+2). EXAFS has been recorded at the K-edge of copper in the complex at the dispersive EXAFS beamline at 2 GeV Indus-2 synchrotron source at RRCAT, Indore, India. The analysis of EXAFS spectra of multinuclear metal complexes pose some problems due to the presence of many absorbing atoms, even when the absorbing atoms may be of the same element. Hence, using the available crystal structure of the complex, theoretical models have been generated for the different copper sites separately, which are then fitted to the experimental EXAFS data. The two coordination geometries around the copper sites have been determined. The contributions of the different copper sites to the experimental spectrum have been estimated. The structural parameters, which include bond-lengths, coordination numbers and thermal disorders, for the two types of copper sites have been reported. Further, copper has been found to be in +2 oxidation state at these metal sites.

  10. 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)

    Science.gov (United States)

    Tanaka, Isao; Mizoguchi, Teruyasu; Yamamoto, Tomoyuki

    2009-03-01

    -or-less independently by the two communities. The three-day workshop on the Theoretical Calculation of ELNES and XANES (TEX2008) was planned to help remedy this situation. It aimed to demonstrate capability of state-of-the-art theoretical techniques to explain and predict ELNES and XANES spectra, and to allow deep discussion between scientists in the two communities. It also provided an excellent opportunity to introduce experimentalists to the computational techniques available. Invited talks and poster presentations by leading scientists were given on the first day, which was followed by tutorial sessions for five computer programs on the second and third days. Excellent lectures were given by Peter Blaha (Vienna, Austria) on the WIEN2k code, Chris J Pickard (St Andrews, UK) on the CASTEP code, John J Rehr (Seattle, USA) on the FEFF8 code, Frank de Groot (Utrecht, The Netherlands) on the CTM4XAS code, and Hidekazu Ikeno (Kyoto, Japan) on the first-principles CI-multiplet code. Thanks to the enthusiastic participation of more than 100 scientists from around the world, the workshop was a complete success. The aim of this special issue in Journal of Physics: Condensed Matter is to share with the readers the most up-to-date knowledge presented at the workshop. We believe this will prove useful as a reference for researchers in many different fields, as well as an overview of the current status and future directions of theoretical calculations for ELNES and XANES. TEX2008 was a satellite meeting of the First International Symposium on Advanced Microscopy and Theoretical Calculations (AMTC1) (Nagoya, Japan, 29-30 June 2008), which was held in commemoration of the establishment of the Nanostuctures Research Laboratory (NSRL) at the Japan Fine Ceramics Center (JFCC) and as a daughter event of EXPO 2005, Aichi, Japan. A Grant-in-Aid for Scientific Research on Priority Areas 'Nano Materials Science for Atomic-Scale Modification' from the Ministry of Education, Culture, Sports and Technology

  11. Preparation, spectroscopy, EXAFS, electrochemistry and pharmacology of new ruthenium(II) carbonyl complexes containing ferrocenylthiosemicarbazone and triphenylphosphine/arsine

    Science.gov (United States)

    Prabhakaran, R.; Anantharaman, S.; Thilagavathi, M.; Kaveri, M. V.; Kalaivani, P.; Karvembu, R.; Dharmaraj, N.; Bertagnolli, H.; Dallemer, F.; Natarajan, K.

    2011-02-01

    A new series of new hetero-bimetallic complexes containing iron and ruthenium of the general formula [RuCl(CO)(B)(EPh 3)(L)] (where E = P or As; B = PPh 3, AsPh 3, py or pip; L = ferrocene derived monobasic bidentate thiosemicarbazone ligand) have been synthesized by the reaction between ferrocene-derived thiosemicarbazones and ruthenium(II) complexes of the type [RuHCl(CO)(B)(EPh 3) 2] (where E = P or As; B = PPh 3, AsPh 3, py or pip). The new complexes have been characterized by elemental analyses, IR, electronic, NMR ( 1H, 13C and 31P), EXAFS (extended X-ray absorption fine structure spectroscopy) and cyclic voltammetric techniques. Antibacterial activity of the new complexes has been screened against Escherichia coli, Vibrio cholerae, and Pseudomonas aeruginosa species.

  12. In-situ reflection-XANES study of ZDDP and MoDTC lubricant films formed on steel and diamond like carbon (DLC) surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Morina, Ardian, E-mail: A.Morina@leeds.ac.uk [Institute of Engineering Thermofluids, Surfaces and Interfaces, School of Mechanical Engineering, University of Leeds, Leeds (United Kingdom); Zhao, Hongyuan [Institute of Engineering Thermofluids, Surfaces and Interfaces, School of Mechanical Engineering, University of Leeds, Leeds (United Kingdom); Mosselmans, J. Fred W. [Diamond Light Source Ltd., Diamond House, Harwell Science and Innovation Campus, Didcot, Oxfordshire OX11 0DE (United Kingdom)

    2014-04-01

    Highlights: • S, P, Zn and Mo species formed in lubricant films can be characterised in-situ and in-lubro by using the reflection mode XAS technique. • Heating the lubricated steel and DLC samples affects the chemical reaction between the adsorbed species and the surface, resulting in different chemical composition of the ZDDP + MoDTC thermal film formed on steel or DLC. • There is a greater effect of temperature on S species than P species formed on ZDDP thermal films. - Abstract: Chemical characterisation of boundary lubricated interfaces is essential for developing mechanistic models that describe lubricant additive interactions with the surface and their effect on tribological performance. In this study the potential for using the synchrotron-based reflection mode X-ray absorption spectroscopy (XAS) technique for in-situ chemical characterisation of lubricant films has been studied. Thermal films formed from zinc dialkyl dithio phosphate (ZDDP) and molybdenum dialkyl dithio carbamate (MoDTC) lubricant additives have been formed and analysed in-situ using the X-ray absorption near edge structure (XANES) spectroscopy technique. The surface sensitivity of this approach was improved by doing the analysis in reflection mode, enabling analysis of only top layer (up to around 10 nm) of the solid surface. In addition, in-lubro analysis of pre-formed tribofilms from the same additives was done using non-vacuum conditions. The results are discussed in conjunction with XANES and X-ray photoelectron spectroscopy (XPS) analysis of similar additives published in the literature. The results obtained are consistent with the existing ZDDP and MoDTC literature and provide some new insight into intermediate species not reported before. The advantages and disadvantages of the developed XANES methodology for in-situ surface chemical analysis of lubricated conditions are discussed.

  13. The pH dependence of Am(III) complexation with acetate: an EXAFS study.

    Science.gov (United States)

    Fröhlich, Daniel R; Skerencak-Frech, Andrej; Bauer, Nicole; Rossberg, André; Panak, Petra J

    2015-01-01

    The complexation of acetate with Am(III) is studied as a function of the pH (1-6) by extended X-ray absorption fine-structure (EXAFS) spectroscopy. The molecular structure of the Am(III)-acetate complexes (coordination numbers, oxygen and carbon distances) is determined from the raw k(3)-weighted Am LIII-edge EXAFS spectra. The results show a continuous shift of Am(III) speciation with increasing pH value towards the complexed species. Furthermore, it is verified that acetate coordinates in a bidentate coordination mode to Am(III) (Am-C distance: 2.82 ± 0.03 Å). The EXAFS data are analyzed by iterative transformation factor analysis to further verify the chemical speciation, which is calculated on the basis of thermodynamic constants, and the used structural model. The experimental results are in very good agreement with the thermodynamic modelling.

  14. HIGH-TEMPERATURE EXAFS EXPERIMENTS ON LIQUID KPB ALLOYS ANALYZED WITH THE REVERSE MONTE-CARLO METHOD

    NARCIS (Netherlands)

    BRAS, W; XU, R; WICKS, JD; VANDERHORST, F; OVERSLUIZEN, M; MCGREEVY, RL; VANDERLUGT, W

    1994-01-01

    A new sample chamber has been designed which allows high temperature Extended X-ray Absorption Fine Structure (EXAFS) experiments on metallic melts which offer a number of special experimental problems: they are highly corrosive, have high vapour pressures and strongly absorb X-rays. The EXAFS spect

  15. Influence of Preparation Method on the Metal Cluster Size of Platinum/ZSM-5 Catalysts as studied with EXAFS.

    NARCIS (Netherlands)

    Koningsberger, D.C.; Kampers, F.W.H.; Engelen, C.W.R.; Hooff, J.H.C. van

    1990-01-01

    The size of Pt particles introduced into the channels of ZSM-5 zeolite by two different preparation methods has been studied with EXAFS. ZSM-5 was loaded with 2 wt 5% Pt by ion exchange and by impregnation. By careful calcination of the catalysts the dispersion was maintained. The EXAFS measurements

  16. HIGH-TEMPERATURE EXAFS EXPERIMENTS ON LIQUID KPB ALLOYS ANALYZED WITH THE REVERSE MONTE-CARLO METHOD

    NARCIS (Netherlands)

    BRAS, W; XU, R; WICKS, JD; VANDERHORST, F; OVERSLUIZEN, M; MCGREEVY, RL; VANDERLUGT, W

    1994-01-01

    A new sample chamber has been designed which allows high temperature Extended X-ray Absorption Fine Structure (EXAFS) experiments on metallic melts which offer a number of special experimental problems: they are highly corrosive, have high vapour pressures and strongly absorb X-rays. The EXAFS

  17. A comparative study of the spectra recorded at RRCAT synchrotron BL-8 dispersive EXAFS beamline with other beamlines

    Indian Academy of Sciences (India)

    Abhijeet Gaur; B D Shrivastava; S N Jha; D Bhattacharyya; A Poswal

    2013-01-01

    The aim of the present work is to make a comparative study of the EXAFS spectra recorded at the BL-8 dispersive EXAFS beamline at 2 GeV Indus-2 synchrotron source at RRCAT, Indore (India) with those recorded at other synchrotron EXAFS beamlines, viz., X-19A at NSLS, BNL (USA), EXAFS wiggler beamline 4-1 at the SSRL (USA) and beamline 11.1 at ELETTRA (Italy). For this purpose, EXAFS spectra at Cu K-edge in copper metal have been recorded at these four beamlines. Further, EXAFS spectra at Cu K-edge in a copper complex have also been recorded at BL-8 beamline and beamline 11.1 at ELETTRA (Italy). The obtained experimental () data have been background-subtracted and then normalized. The normalized data have been then converted to () data, which have been Fourier-transformed and then fitted with the theoretical model, thereby yielding different structural parameters. It has been shown that the results obtained from the EXAFS spectra recorded at the BL-8 beamline are comparable with those obtained from other synchrotron EXAFS beamlines and also with the crystallographic results reported by earlier workers. The reliability, usefulness and data quality of the BL-8 beamline have been discussed.

  18. EXAFS of Poly [μ-hexakis(2-methylimidazolato-N,N')triiron( II)]: Implications for Metalloprotein Studies

    NARCIS (Netherlands)

    Vliegenthart, J.F.G.; Feiters, M.C.; Navaratnam, S.; Al-Hakim, M.; Allen, J.C.; Spek, A.L.; Veldink, G.A.

    1988-01-01

    EXAFS data at the Fe K-edge of the coordination compound poly[mu-hexakis(2-methylimidazolato-N,N3triiron(II)] are presented. Single-scattering analysis of the EXAFS gives good agreement with the crystallographic data for the first two shells of atoms around the iron, but beyond that, multiple-scatte

  19. Fischer-Tropsch synthesis: study of the promotion of Pt on the reduction property of Co/Al2O3 catalysts by in situ EXAFS of Co K and Pt LIII edges and XPS.

    Science.gov (United States)

    Jacobs, Gary; Chaney, John A; Patterson, Patricia M; Das, Tapan K; Maillot, Julie C; Davis, Burtron H

    2004-09-01

    The addition of platinum metal to cobalt/alumina-based Fischer-Tropsch synthesis (FTS) catalysts increases both the reduction rate and, consequently, the density of active cobalt sites. Platinum also lowers the temperature of the two-step conversion of cobalt oxide to cobalt metal observed in temperature programmed reduction (TPR) as Co3O4 to CoO and CoO to Co0. The interaction of the alumina support with cobalt oxide ultimately determines the active site density of the catalyst surface. This interaction can be controlled by varying the cobalt loading and dispersion, selecting supports with differing surface areas or pore sizes, or changing the noble metal promoter. However, the active site density is observed to depend primarily on the cluster size and extent of reduction, and there is a direct relationship between site density and FTS rate. In this work, in situ extended X-ray absorption fine structure (EXAFS) at the LIII edge of Pt was used to show that isolated Pt atoms interact with supported cobalt clusters without forming observable Pt--Pt bonds. K-edge EXAFS was also used to verify that the cobalt cluster size increases slightly for those systems with Pt promotion. X-ray absorption near-edge spectroscopy (XANES) was used to examine the remaining cobalt clusters after the first stage of TPR, and it revealed that the species were almost entirely cobalt (II) oxide. After the second stage of TPR to form cobalt metal, a residual oxide persists in the sample, and this oxide has been identified as cobalt (II) aluminate using X-ray photoelectron spectroscopy (XPS). Sequential in situ reduction of promoted and unpromoted systems was also monitored through XPS, and Pt was seen to increase the extent of cobalt reduction by a factor of two.

  20. Co (II) Complexes with Schiff Base Ligands: Synthesis and EXAFS Study

    Science.gov (United States)

    Mishra, Ashutosh; Mansuri, Amantulla; Ninama, Samrath; Trivedi, Apurva; Patidar, Sushma; Jamod, Mahesh; Awate, Ruchita

    2016-10-01

    Thesynthesis of transition metal Schiff base complexes of Co(II) are prepared by chemical root method. Obtained by the condensation of O-phenylenediamine, salicylaldehyde and isatin / 2-hydroxy- 1 Naphthaldehyde is presented. The complexes were characterized by Co- K- edge EXAFS measurements using the dispersive beam line at 2.5GeV energy of Indus-2 synchrotron radiation source RRCAT Indore. The recorded EXAFS data were analyzed using the computer software Athena for determine the nearest neighboring distances (bond lengths) of these complexes with conventional methods and were compared with Fourier transform (FT) analysis.

  1. A Variation of the F-Test for Determining Statistical Relevance ofParticular Parameters in EXAFS Fits

    Energy Technology Data Exchange (ETDEWEB)

    Downward, L.; Booth, C.H.; Lukens, W.W.; Bridges, F.

    2006-07-25

    A general problem when fitting EXAFS data is determining whether particular parameters are statistically significant. The F-test is an excellent way of determining relevancy in EXAFS because it only relies on the ratio of the fit residual of two possible models, and therefore the data errors approximately cancel. Although this test is widely used in crystallography (there, it is often called a 'Hamilton test') and has been properly applied to EXAFS data in the past, it is very rarely applied in EXAFS analysis. We have implemented a variation of the F-test adapted for EXAFS data analysis in the RSXAP analysis package, and demonstrate its applicability with a few examples, including determining whether a particular scattering shell is warranted, and differentiating between two possible species or two possible structures in a given shell.

  2. On the method of calibration of the energy dispersive EXAFS beamline at Indus-2 and fitting theoretical model to the EXAFS spectrum

    Indian Academy of Sciences (India)

    Abhijeet Gaur; Ajita Johari; B D Shrivastava; D C Gaur; S N Jha; D Bhattacharyya; A Poswal; S K Deb

    2011-06-01

    A procedure for calibration of the recently developed energy dispersive EXAFS beamline at the Indus-2 synchrotron source at RRCAT, Indore, India has been described. The procedure involves recording of absorption spectra of two standard samples, whose absorption edge energies are well-established. Two methods have been considered for calibration. In the first method, the position of the first maximum of the derivative of absorption curve is taken as the position of the edge energy. In the second method, the position of the point at half edge step in the absorption curve is taken as the position of the edge energy. It has been shown that only the first method gives same values of dispersion even when the beam current is varied and should be used for calibrating the experimental spectra. Further, it is recommended that the performance of the beamline for a particular setting should be checked by recording and analysing EXAFS of a standard. Hence, the procedure for analysis and extracting information about the various parameters that can be determined by fitting the EXAFS data with a theoretical model has also been described, by taking the example of -absorption spectra of copper metal foil recorded on this beamline.

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

    Science.gov (United States)

    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.

  4. Study on the local atomic structure of germanium in organic germanium compounds by EXAFS

    Institute of Scientific and Technical Information of China (English)

    1999-01-01

    Organic germanium compounds have been extensively applied in medicine as tonics,In this paper,the local structures of two organic germanium compounds,carboxyethylgermanium sesquioxide and polymeric germanium glutamate,were determined by EXAFS.The structure parameters including coordination numbers and bond lengths were reported,and possible structure patterns were discussed.

  5. Structural characterization of Am(III) formate complexes. Combining EXAFS spectroscopy with DFT and thermodynamical calculations

    Energy Technology Data Exchange (ETDEWEB)

    Rossberg, Andre [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Molecular Structures; Froehlich, D.R. [Heidelberg Univ. (Germany). Physikalisch-Chemisches Inst.

    2017-06-01

    We used iterative transformation factor analysis (ITFA) in order to isolate the EXAFS spectral contributions of the complexing ligand from a Am(III)/formate pH-series. Thermodynamic calculations were used as constraint for ITFA and for density functional theory (DFT) calculations to identify the coordination mode within the formed complexes.

  6. EXAFS as a tool to interrogate the size and shape of mono and bimetallic catalyst nanoparticles

    NARCIS (Netherlands)

    Beale, A.M.|info:eu-repo/dai/nl/325802068; Weckhuysen, B.M.|info:eu-repo/dai/nl/285484397

    2013-01-01

    The influence of atom packing and the geometric arrangement of atoms on the coordination number(s) and resultant simulated EXAFS spectra for face centrered cubic (fcc), hexagonal close packed (hcp) and body centered cubic (bcc) monometallic structures and fcc bimetallic structures, has been examined

  7. EXAFS as a tool to interrogate the size and shape of mono and bimetallic catalyst nanoparticles

    NARCIS (Netherlands)

    Beale, A.M.; Weckhuysen, B.M.

    2013-01-01

    The influence of atom packing and the geometric arrangement of atoms on the coordination number(s) and resultant simulated EXAFS spectra for face centrered cubic (fcc), hexagonal close packed (hcp) and body centered cubic (bcc) monometallic structures and fcc bimetallic structures, has been examined

  8. EXAFS studies of the martensitic transformation in Fe-Ni alloys

    Energy Technology Data Exchange (ETDEWEB)

    Rutsky, K.J.; Georgopoulos, P.

    1986-03-01

    Unlike Mossbauer and Debye-Waller factor measurements, EXAFS provides information about vibrational amplitudes along various crystallographic directions separately. In addition, the quantity measured is the mean-square amplitude of relative displacements, i.e. the uncertainty in interatomic distance, rather than atomic positions. As such, it is more sensitive to short wavelength vibrational modes.

  9. TRANSFERABILITY OF SCATTERING AMPLITUDES AND PHASES IN EXAFS BETWEEN NEIGHBORING ELEMENTS IN THE PERIODIC TABLE

    OpenAIRE

    Lengeler, B.

    1986-01-01

    Model compounds can be used for EXAFS data analysis when the absorber and backscatterer are neighboring elements in the periodic table to the absorber and backscatterers of the system to be analysed. The errors Ɗr1 in the interatomic distances are small and linear in the difference ƊZ in the atomic numbers.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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

  12. Spectral Analysis by XANES Reveals that GPNMB Influences the Chemical Composition of Intact Melanosomes

    Energy Technology Data Exchange (ETDEWEB)

    T Haraszti; C Trantow; A Hedberg-Buenz; M Grunze; M Anderson

    2011-12-31

    GPNMB is a unique melanosomal protein. Unlike many melanosomal proteins, GPNMB has not been associated with any forms of albinism, and it is unclear whether GPNMB has any direct influence on melanosomes. Here, melanosomes from congenic strains of C57BL/6J mice mutant for Gpnmb are compared to strain-matched controls using standard transmission electron microscopy and synchrotron-based X-ray absorption near-edge structure analysis (XANES). Whereas electron microscopy did not detect any ultrastructural changes in melanosomes lacking functional GPNMB, XANES uncovered multiple spectral phenotypes. These results directly demonstrate that GPNMB influences the chemical composition of melanosomes and more broadly illustrate the potential for using genetic approaches in combination with nano-imaging technologies to study organelle biology.

  13. Mn K-edge XANES spectra of manganites measured by Kbeta emission.

    Science.gov (United States)

    García, J; Sánchez, M C; Subías, G; Blasco, J; Proietti, M G

    2001-03-01

    The electronic state of Mn atoms in mixed valence manganites has been studied by means of X-ray absorption spectroscopy at the Mn K-edge. Higher resolution than in conventional measurements has been achieved by measuring the Mn Kbeta fluorescence line. We have found a unique resonance at the edge in the XANES spectra of intermediate composition RE1-xCa(x)MnO3 samples. The features of these XANES spectra do not depend on small changes in the local structure around the Mn atom. However, the spectra of the intermediate composition samples can not be reproduced by a linear combination of REMnO3 and CaMnO3 spectra. Accordingly, the electronic state of Mn atoms in these compounds can not be considered as a mixture of Mn3+ and Mn4+ pure states.

  14. Phosphorus Speciation of Forest-soil Organic Surface Layers using P K-edge XANES Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    J Prietzel; J Thieme; D Paterson

    2011-12-31

    The phosphorus (P) speciation of organic surface layers from two adjacent German forest soils with different degree of water-logging (Stagnosol, Rheic Histosol) was analyzed by P K-edge XANES and subsequent Linear Combination Fitting. In both soils, {approx}70% of the P was inorganic phosphate and {approx}30% organic phosphate; reduced P forms such as phosphonate were absent. The increased degree of water-logging in the Histosol compared to the Stagnosol did not affect P speciation.

  15. A Mexican kaolin deposit: XANES characterization, mineralogical phase analysis and applications

    OpenAIRE

    Martínez, A.; Garza, L. L.; L. M. Torres; Vázquez, F.; López, W.

    2009-01-01

    A kaolin obtained from Villa de Reyes, a region near to San Luis Potosí (México) was characterized by means of X-ray powder diffraction (XRD, optical microscopy (OM), scanning electron microscopy (SEM), X-ray fluorescence (XRF), X-Ray Absorption Near Edge Spectroscopy (XANES), thermal analysis (DTA/TGA), dilatometry (DIL), and chemical analysis. Mineralogical and morphological characteristics of the mineral are presented. The kaolin sample was formed mainly by kaolinite, but other minor phase...

  16. Microstructure of organic–inorganic composite coatings studied by TEM and XANES

    Directory of Open Access Journals (Sweden)

    Etsuo Hamada, Masayasu Nagoshi, Kaoru Sato, Akira Matsuzaki, Takafumi Yamaji and Kotaro Kuroda

    2003-01-01

    Full Text Available Chromate coatings on Zn or Zn alloy coated steel sheets often include silica for the aim to improve corrosion resistance. In the case of dry-in-place chromate coatings containing acrylic resin (hereafter referred to as an organic–inorganic composite coating, an addition of silica, however, did not show an improvement in corrosion resistance. The microstructures of the organic–inorganic composite coatings were observed by transmission electron microscopy (TEM and the chemical states of Cr were investigated by the total electron yield X-ray absorption near edge structure (TEY-XANES method. TEM samples were successfully prepared by dry ultramicrotomy preventing water-soluble components in the coatings from dissolving out. TEY-XANES revealed the chemical states of components even in the organic matrix. Using these methods, it was found that the addition of silica changed just the morphology of the chromium compound in the organic–inorganic composite coating but not the chemical state of Cr. This is a reason for the addition of silica being not effective at improving corrosion resistance. The combination of dry ultramicrotomy-TEM and TEY-XANES spectroscopy was proven to be a powerful tool for characterizing organic–inorganic composite coatings.

  17. Standard Protocol and Quality Assessment of Soil Phosphorus Speciation by P K-Edge XANES Spectroscopy.

    Science.gov (United States)

    Werner, Florian; Prietzel, Jörg

    2015-09-01

    Phosphorus (P) in soils is most often bound as phosphate to one or more of the following four elements or compounds: calcium, aluminum, iron, and soil organic matter. A promising method for direct P speciation in soils is synchrotron-based X-ray absorption near edge structure (XANES) spectroscopy at the K-edge of P. However, the quality of this method is debated controversially, partly because a standard protocol for reproducible spectrum deconvolution is lacking and minor modifications of the applied deconvolution procedure can lead to considerable changes in the P speciation results. On the basis of the observation that appropriate baseline correction and edge-step normalization are crucial for correct linear combination (LC) fitting results, we established a standard protocol for the deconvolution and LC fitting of P K-edge XANES spectra. We evaluated the quality of LC fits obtained according to this standard protocol with 16 defined dilute (2 mg P g(-1)) ternary mixtures of aluminum phosphate, iron phosphate, hydroxyapatite, and phytic acid in a quartz matrix. The LC fitting results were compared with the contribution of the different P compounds to total P in the various mixtures. Compared to using a traditional LC fitting procedure, our standard protocol reduced the fitting error by 6% (absolute). However, P portions smaller than 5% should be confirmed with other methods or excluded from the P speciation results. A publicly available database of P K-edge XANES reference spectra was initiated.

  18. Zinc distribution and speciation within rocket plants (Eruca vesicaria L. Cavalieri) grown on a polluted soil amended with compost as determined by XRF microtomography and micro-XANES.

    Science.gov (United States)

    Terzano, Roberto; Al Chami, Ziad; Vekemans, Bart; Janssens, Koen; Miano, Teodoro; Ruggiero, Pacifico

    2008-05-14

    Zinc distribution and speciation within different organs (root, petiole, and leaf) of the edible plant Eruca vesicaria L. Cavalieri were determined using synchrotron microbeam X-ray techniques (XRF microtomography and mu-XANES) for plants grown in polluted soil with or without compost amendment. Data on soil derived from different extraction procedures and using mu-XANES analyses on rhizospheric soil indicated that compost amendment did not significantly influence the Zn speciation and availability in soil. However, major differences were observed within the plants. Plants grown in the presence of compost were able to partly block zinc immediately outside the root endodermis in the form of zinc-phytate, while a smaller Zn fraction was allowed to xylem transport as zinc-citrate. In the leaves, zinc was largely excluded from leaf cells, and about approximately 50% was in the form of phosphate precipitates, and the other 50% was complexed by cysteine and histidine residues. The reported data provide new information concerning the mechanisms of zinc tolerance in E. vesicaria L. Cavalieri, a very common edible plant in Mediterranean regions, and on the role of compost in influencing the molecular strategies involved in zinc uptake and detoxification.

  19. ZnS Semiconductive Powder Doped with Transition Metal Ions via Mechanochemical Synthesis Technique

    Institute of Scientific and Technical Information of China (English)

    R.F. Louh; C.K. Lin; Oscar Lin; G.S. Chen; C.C. Chan

    2004-01-01

    The solid state synthesis can be carried out by using the initial pure metal zinc and inorganic sulfur powder mixtures by means of the mechanochemical synthesis route. The completion of solid state reaction between pure zinc and sulfur powder to produce c-ZnS and h-ZnS phases via such a route was rather fast, as compared to other non-sulfide systems by the similar method. The study was aimed to investigate the microstructure development and phase formation through the solid state reaction by controlling the processing parameters involved in this process including grinding media to powder weight ratio, solid state reaction duration, reaction atmosphere, stoichiometric ratio of zinc and sulfur elements, grinding media and choice of minor additives such as teflon-based polymeric lubricants and transition metal dopants (Mn, Cu). Both as-synthesized powders and heat-treated ZnS materials with various stoichiometric ratios were characterized by XRD, EXAFS and XANES analysis. The interesting results from X-ray absorption spectroscopy (XAS) would provide us some strong evidence whether stoichiometric and non-stoichiometric ZnS material can be successfully formed. The minor amount (0.5wt%)of Mn+2 or Cu+2 ion dopants added to the powder batch with the Zn/S stoichiometric ratio between1.00 to 1.05 was found to favor the reaction rate in the mechanochemical synthesis. Moreover, the obtained results of ZnS phase development under reaction conditions and different transition metal dopants in this study would imply that synthesis of other kind of sulfide compounds can be achieved using the demonstrated technique.

  20. Extended X-ray absorption fine structure (EXAFS) investigations of Ti bonding environment in sputter-deposited nanocomposite TiBC/a-C thin films

    Energy Technology Data Exchange (ETDEWEB)

    Endrino, J L; Gago, R; Jimenez, I [Instituto de Ciencias de Materiales de Madrid, Consejo Superior de Investigaciones Cientificas, Campus de Cantoblanco, E-28049 Madrid (Spain); Abad, M D; Sanchez-Lopez, J C [Instituto de Ciencia de Materiales de Sevilla, CSIC-Universidad de Sevilla, Avda. Americo Vespucio 49, 41092 Sevilla (Spain); Horwat, D, E-mail: jlendrino@icmm.csic.es [Institut Jean Lamour, Departement CP2S, Nancy Universite, Ecole des Mines, CS14234 Parc de Saurupt, 54042 Nancy Cedex (France)

    2010-06-15

    In this study, we have successfully used the extended X-ray absorption fine structure (EXAFS) technique at the Ti-K edge to extract the local structure in a set of nanocomposite TiBC/a-C coatings deposited by a combined d.c.-pulsed and r.f.-magnetron sputtering deposition process. The sequence of Fourier transform spectra in the deposited films shows that there is an increase in the number of Ti-C bonds in the films of higher carbon content in parallel with the increment of the total carbon content. In addition, Ti-K EXAFS spectra indicate that in all the deposited TiBC/a-C films, first-shell neighbours are in a nearer structural arrangement than the one expected for a bulk hexagonal TiB2, which could be due to the formation of mixed Ti-B-C compound in a structural unit similar to the one found in h-TiB{sub 2}.

  1. Exceptional adsorption-induced cluster and network deformation in the flexible metal-organic framework DUT-8(Ni) observed by in situ X-ray diffraction and EXAFS.

    Science.gov (United States)

    Bon, Volodymyr; Klein, Nicole; Senkovska, Irena; Heerwig, Andreas; Getzschmann, Jürgen; Wallacher, Dirk; Zizak, Ivo; Brzhezinskaya, Maria; Mueller, Uwe; Kaskel, Stefan

    2015-07-14

    The "gate opening" mechanism in the highly flexible MOF Ni2(2,6-ndc)2dabco (DUT-8(Ni), DUT = Dresden University of Technology) with unprecedented unit cell volume change was elucidated in detail using combined single crystal X-ray diffraction, in situ XRD and EXAFS techniques. The analysis of the crystal structures of closed pore (cp) and large pore (lp) phases reveals a drastic and unique unit cell volume expansion of up to 254%, caused by adsorption of gases, surpassing other gas-pressure switchable MOFs significantly. To a certain extent, the structural deformation is specific for the guest molecule triggering the transformation due to subtle differences in adsorption enthalpy, shape, and kinetic diameter of the guest. Combined adsorption and powder diffraction experiments using nitrogen (77 K), carbon dioxide (195 K), and n-butane (272.5 K) as a probe molecules reveal a one-step structural transformation from cp to lp. In contrast, adsorption of ethane (185 K) or ethylene (169 K) results in a two-step transformation with the formation of intermediate phases. In situ EXAFS during nitrogen adsorption was used for the first time to monitor the local coordination geometry of the metal atoms during the structural transformation in flexible MOFs revealing a unique local deformation of the nickel-based paddle-wheel node.

  2. Commissioning and first results of scanning type EXAFS beamline (BL-09) at INDUS-2 synchrotron source

    Energy Technology Data Exchange (ETDEWEB)

    Poswal, A. K., E-mail: poswalashwini@gmail.com; Agrawal, A., E-mail: poswalashwini@gmail.com; Yadav, A. K., E-mail: poswalashwini@gmail.com; Nayak, C., E-mail: poswalashwini@gmail.com; Basu, S., E-mail: poswalashwini@gmail.com; Bhattachryya, D.; Jha, S. N.; Sahoo, N. K. [Atomic and Molecular Physics Division, Bhabha Atomic Research Centre, Mumbai -400085 (India); Kane, S. R.; Garg, C. K. [Indus Synchrotrons Utilization Division, Raja Ramanna Centre for Advanced Technology, Indore- 452013 (India)

    2014-04-24

    An Energy Scanning X-ray Absorption Fine Structure spectroscopy beamline has recently been installed and commissioned at BL-09 bending magnet port of INDUS-2 synchrotron source, Indore. The beamline uses an UHV compatible fixed exit double crystal monochromator (DCM) with two Si (111) crystals. Two grazing incidence cylindrical mirrors are also used in this beamline; the pre-mirror is used as a collimating mirror while the post mirror is used for vertical focusing and higher harmonic rejection. In this beamline it is possible to carry out EXAFS measurements both in transmission and fluorescence mode on various types of samples, using Ionization chamber detectors and solid state drift detector respectively. In this paper, results from first experiments of the Energy Scanning EXAFS beamline are presented.

  3. Structural evolution of Ga-Ge-Te glasses by combined EXAFS and XPS analysis

    Energy Technology Data Exchange (ETDEWEB)

    Golovchak, R. [Department of Physics and Astronomy, Austin Peay State University, Clarksville, Tennessee 37044 (United States); Materials Science and Engineering Department, Lehigh University, 5 East Packer Avenue, Bethlehem, Pennsylvania 18015 (United States); Calvez, L.; Bureau, B. [Laboratoire des Verres et Ceramiques, Institut des Sciences Chimiques de Rennes, UMR-CNRS6226, University of Rennes 1 (France); Jain, H. [Materials Science and Engineering Department, Lehigh University, 5 East Packer Avenue, Bethlehem, Pennsylvania 18015 (United States)

    2013-08-07

    The structural evolution of Ga{sub x}Ge{sub y}Te{sub 100−x−y} glasses in the vicinity of GeTe{sub 4}-GaTe{sub 3} pseudo-binary tie-line is determined with high-resolution X-ray photoelectron (XPS) and extended X-ray absorption fine structure (EXAFS) spectroscopies. The analysis of XPS data is complicated by similar electronegativity values for the constituent chemical elements, but then the interpretation is facilitated by information from complementary EXAFS analysis of the structure around each element independently. The results show 4/4/2 coordination for Ga/Ge/Te atoms and absence of Ga(Ge)-Ge(Ga) bonds or extended Te clusters in significant concentrations within the whole range of studied composition. The observed structural features correlate well with the measured basic physical properties of Ga-containing germanium telluride glasses.

  4. X-ray source development for EXAFS measurements on the National Ignition Facility

    Science.gov (United States)

    Coppari, F.; Thorn, D. B.; Kemp, G. E.; Craxton, R. S.; Garcia, E. M.; Ping, Y.; Eggert, J. H.; Schneider, M. B.

    2017-08-01

    Extended X-ray absorption Fine Structure (EXAFS) measurements require a bright, spectrally smooth, and broad-band x-ray source. In a laser facility, such an x-ray source can be generated by a laser-driven capsule implosion. In order to optimize the x-ray emission, different capsule types and laser irradiations have been tested at the National Ignition Facility (NIF). A crystal spectrometer is used to disperse the x-rays and high efficiency image plate detectors are used to measure the absorption spectra in transmission geometry. EXAFS measurements at the K-edge of iron at ambient conditions have been obtained for the first time on the NIF laser, and the requirements for optimization have been established.

  5. X-ray source development for EXAFS measurements on the National Ignition Facility.

    Science.gov (United States)

    Coppari, F; Thorn, D B; Kemp, G E; Craxton, R S; Garcia, E M; Ping, Y; Eggert, J H; Schneider, M B

    2017-08-01

    Extended X-ray absorption Fine Structure (EXAFS) measurements require a bright, spectrally smooth, and broad-band x-ray source. In a laser facility, such an x-ray source can be generated by a laser-driven capsule implosion. In order to optimize the x-ray emission, different capsule types and laser irradiations have been tested at the National Ignition Facility (NIF). A crystal spectrometer is used to disperse the x-rays and high efficiency image plate detectors are used to measure the absorption spectra in transmission geometry. EXAFS measurements at the K-edge of iron at ambient conditions have been obtained for the first time on the NIF laser, and the requirements for optimization have been established.

  6. EXAFS structural study of platinum-based anticancer drugs degradation in presence of sulfur nucleophilic species.

    Science.gov (United States)

    Provost, Karine; Bouvet-Muller, Diane; Crauste-Manciet, Sylvie; Moscovici, Jacques; Olivi, Luca; Vlaic, Gilberto; Michalowicz, Alain

    2009-10-01

    Three platinum complexes, cisplatin, carboplatin and oxaliplatin are currently used worldwide. Investigation of their main structural modifications in presence of sulfur nucleophiles is of particular interest because of the implication of thiol and thioether groups in biochemical mechanism of action, resistance mechanism and in vivo or in vitro detoxification. We present the main structural results we have obtained concerning the reaction of these drugs with diverse sulfur nucleophiles (cysteine, glutathione, methionine, thiosulfate and thiocyanate), monitored in solution or as precipitates by EXAFS spectroscopy. The reactivities of the carboxylate and amine ligands of both carboplatin and oxaliplatin are compared, on the basis of first-coordination sphere modeling. Among the new results of this EXAFS study, we present the first observation of oxaliplatin diaminocyclohexane ligand displacement by sulfur nucleophiles.

  7. A gas microstrip X-ray detector for soft energy fluorescence EXAFS

    CERN Document Server

    Smith, A D; Derbyshire, G E; Duxbury, D M; Lipp, J; Spill, E J; Stephenson, R

    2001-01-01

    Gas microstrip detectors have been previously developed by the particle physics community, where their robustness, compactness and high counting speed have been recognised. These features are particularly attractive to synchrotron radiation use. In this paper, we describe a gas microstrip detector employing multi-element readout and specifically developed for high count rate fluorescence EXAFS at soft X-ray energies below 4 keV.

  8. Femtometer accuracy EXAFS measurements: Isotopic effect in the first, second and third coordination shells of germanium

    Energy Technology Data Exchange (ETDEWEB)

    Purans, J; Timoshenko, J; Kuzmin, A [Institute of Solid State Physics, University of Latvia, Kengaraga 8, LV-1063 Riga (Latvia); Dalba, G; Fornasini, P; Grisenti, R; Afify, N D [Dip. di Fisica dell' Universita di Trento, Via Sommarive 14, I-38050 Povo, Trento (Italy); Rocca, F [Istituto di Fotonica e Nanotecnologie del CNR, Sezione ' FBK-CeFSA' di Trento, Povo, Trento (Italy); De Panfilis, S [Research Center Soft INFM-CNR, c/o Universita di Roma La Sapienza, I-00185 Roma (Italy); Ozhogin, I [Institute of Molecular Physics, Russian Research Centre ' Kurchatov Institute' , 123182 Moscow (Russian Federation); Tiutiunnikov, S I, E-mail: purans@cfi.lu.l [Joint Institute for Nuclear Research, 141980 Dubna, Moscow Region (Russian Federation)

    2009-11-15

    The analysis of the EXAFS signals from {sup 70}Ge and {sup 76}Ge has evidenced the low-temperature effect of isotopic mass difference on the amplitude of relative atomic vibrations. This effect is reflected in the difference of the Debye-Waller factors of the first three coordination shells, and on the difference of nearest-neighbour average interatomic distances, evaluated with femtometer accuracy. The experimental results are in agreement with theoretical expectations.

  9. Structure of Amorphous Ferric Arsenate from EXAFS Spectroscopy and Total X-ray Scattering

    Science.gov (United States)

    Mikutta, Christian; Michel, Frederick Marc; Mandaliev, Petar; Kretzschmar, Ruben

    2013-04-01

    Short-range ordered ferric arsenate (FeAsO4 ×nH2O) is a secondary As mineral frequently encountered in acid mine-waste environments. Its structure has been proposed to resemble that of scorodite (FeAsO4×2H2O) in which isolated FeO6 octahedra share corners with four adjacent arsenate (AsO4) tetrahedra in a three-dimensional network (scorodite model). Conversely, short-range ordered ferric arsenate was postulated to consist of single chains of corner-sharing FeO6 octahedra being bridged by arsenate bound in a monodentate binuclear 2C complex (butlerite/fibroferrite model). In order to test the accuracy of both structural models, we synthesized ferric arsenates and analyzed their structure by As and Fe K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy and total X-ray scattering. We found that both As and Fe K-edge EXAFS spectra were most compatible with isolated FeO6 octahedra being bridged by AsO4 tetrahedra (RFe-As= 3.33 ± 0.01 Å). EXAFS shell-fits and reduced pair distribution functions, G(r), indicated a lack of evidence for single corner-sharing FeO6 linkages in ferric arsenate. Wavelet-transform analyses of the Fe K-edge EXAFS spectra of ferric arsenates complemented by shell fitting confirmed Fe atoms at an average distance of 5.3 Å, consistent with crystallographic data of scorodite and in disagreement with the butlerite/fibroferrite model. A scorodite-type local structure of short-range ordered ferric arsenates provides a plausible explanation for their rapid transformation into scorodite in acid mining environments.

  10. EXAFS study of molybdenum oxide on the structure Al2O3

    Institute of Scientific and Technical Information of China (English)

    Weipingshi; XiaohaiCai; JiyingWei; Junma; TiandouHu; NianzuWu; Youch

    2001-01-01

    In this paper,MoO3 dispersed on an alumina support was studied.The dispersion threshold was determined by x-ray diffraction and the Mo-O coordination structure was detected by extended x-ray absorption fine structure(EXAFS),which shows that the preferred dispersion phase is madu up of [MoO4] polyhedrons.Copyright 2001 John Wiley and sons,Lad.

  11. The structure of nickel and indium oxide thin films from EXAFS data

    Science.gov (United States)

    Bets, V.; Zamozdiks, T.; Lusis, A.; Purans, J.; Bausk, N.; Sheromov, M.

    1987-11-01

    The structure of nickel oxide and indium oxide doped by tin films prepared by reactive magnetron sputtering has been studied by the EXAFS method. It has been found that the nickel oxide thin film has a microcrystalline structure with significant disorder proved by the increase of the Debye-Waller factor and the sharp decrease of peak amplitudes. The indium oxide thin film has a noticeable structural disorder due to 8% tin dopping.

  12. EXAFS study of Co - SiO{sub 2} granular solid

    Energy Technology Data Exchange (ETDEWEB)

    Cezar, Julio C.; Tolentino, Helio C.N. [National Synchrotron Light Laboratory (LNLS), Campinas, SP (Brazil); Denardin, Juliano; Knobel, Marcelo [Universidade Estadual de Campinas (IFGW/UNICAMP), SP (Brazil). Inst. de Fisica Gleb Wataghin. Lab. de Materiais e Baixas Temperaturas

    2002-07-01

    Full text: Here we show preliminary results obtained from Exafs measurements on granular solids composed by cobalt dispersed in a silica matrix. This system is very interesting from the magnetic point of view, once that it displays the Giant Magnetoresistance (G MR) property. Furthermore, the electronic transport in this system is basically determined by the tunneling of electrons between metallic clusters dispersed in the non-conducting matrix. This kind of system has been studied as a promising material for magneto electronics applications. The samples have the composition Co{sub x}(SiO{sub 2}){sub (1-x)}, with x = 0.36, 0.41, 0.44, 0.50 , and were deposited over kapton by sputtering. The absorption measurements were taken in transmission mode at the XAS beamline of LNLS. Simple inspection in the Fourier transform of the EXAFS spectra shows a distortion in the coordination shell of Cobalt. This is an indication of oxidation of cobalt, revealing an interaction between the matrix and the particle. This interaction could give raise to different magnetic anisotropy for the particle surface. On the other hand, we hope that the quantitative analysis of the EXAFS data allows us to estimate the cluster size. This procedure already had been used in similar systems [1]. This information could then be compared with the diameters obtained from TEM measurements and one could relate the structural properties of the magnetic clusters with the magnetic properties of these samples [2]. (author) [1] Arcon, I., et al. EXAFS determination of the size of Co clusters on silica, J. Synchr. Rad. (2001), 8, 575-577. [2] Denardin, J. C., et al., Ordinary and extraordinary giant Hall effects in Co-SiO2 granular films, J. Mag. Mag. Mater., 226-230 (2001) 680-682. ; Denardin, J. C., et al., Thermo remanence and ZFC-FC susceptibility study of Co-SiO2 granular films, to be published

  13. Characterizing Ni(II) hydration in aqueous solution using DFT and EXAFS.

    Science.gov (United States)

    Liu, H Y; Fang, C H; Fang, Y; Zhou, Y Q; Ge, H W; Zhu, F Y; Sun, P C; Miao, J T

    2016-01-01

    In the present work, a detailed investigation of Ni(II) hydration in water solutions was carried out using density functional theory (DFT) and extended X-ray absorption fine structure (EXAFS) spectroscopy. The hydrated characteristics of [Ni(H2O)n](2+) clusters, such as energy parameters, atomic charge distributions, and bond parameters, were explored using DFT with Becke's three-parameter exchange potential and the Lee-Yang-Parr correlation functional (B3LYP). DFT calculations indicated that the preferred structure of the first hydration shell of Ni(II) generally has a coordination number of six and is almost unaffected by the water molecules in the outer solvation shell, whereas the structure of the second solvation shell varies as the hydration proceeds. EXAFS measurements are reported for aqueous NiSO4 and Ni(NO3)2 solutions and the Ni(NO3)2·6H2O crystal. Analysis of the EXAFS spectra of these three systems using a multiparameter fitting procedure showed that, in each case, the first coordination shell consists of six water molecules with a Ni-O coordination distance of 2.04 Å, and that there is no Ni-S or Ni-N coordination in the first shell. There was no evidence of outer-shell SO4(2-) or NO3(-) ions substituting inner-sphere water molecules in NiSO4 and Ni(NO3)2. The characteristics of Ni(II) hydration obtained from DFT calculations agreed well with those obtained experimentally using EXAFS.

  14. Local atomic structure of solid solutions with overlapping shells by EXAFS: The regularization method

    Energy Technology Data Exchange (ETDEWEB)

    Babanov, Yu.A., E-mail: babanov@imp.uran.ru [M.N. Miheev Institute of Metal Physics, Ural Branch, Russian Academy of Sciences, Ekaterinburg 620990 (Russian Federation); Ponomarev, D.A.; Ustinov, V.V. [M.N. Miheev Institute of Metal Physics, Ural Branch, Russian Academy of Sciences, Ekaterinburg 620990 (Russian Federation); Baranov, A.N. [M.V. Lomonosov Moscow State University, Moscow 119991 (Russian Federation); Zubavichus, Ya.V. [Russian Research Centre “Kurchatov Institute”, 123182 Moscow (Russian Federation)

    2016-08-15

    Highlights: • A method for determining bond lengths from combined EXAFS spectra for solid oxide solutions is proposed. • We have demonstrated a high resolution in r-space of close spacing atoms in the Periodical Table. • These results were obtained without any assumptions concerning interatomic distances for multi-component systems. • Coordinates ions for the solid solution with rock salt structure are determined. - Abstract: The regularization method of solving ill-posed problem is used to determine five partial interatomic distances on the basis of combined two EXAFS spectra. Mathematical algorithm and experimental results of the EXAFS analysis for Ni{sub c}Zn{sub 1−c}O (c = 0.0, 0.3, 0.5, 0.7, 1.0) solid solutions with the rock salt (rs) crystal structure are discussed. Samples were synthesized from the binary oxide powders at pressure of 7.7 GPa and temperatures 1450–1650 K. The measurements were performed using synchrotron facilities (Russian Research Centre “Kurchatov Institute”, Moscow). The Ni and Zn K absorption spectra were recorded in transmission mode under room temperature. It is shown, the ideal rock salt lattice is distorted and long-range order exists only in the average (Vegard law). In order to determine coordinates ions for the solid solution with rock salt structure, we used the Pauling model. The simulation is performed for 343,000 cluster of oxide ions. The distribution functions for ions (Ni−O, Ni−Ni, Ni−Zn, Zn−Zn, Zn−O, O−O) depending on the distance are obtained. The width of the Gaussian distribution function is determined by the difference of the radii of the metal ions. The results are consistent with the data both X-ray diffraction and the EXAFS spectroscopy.

  15. HERFD-XANES and XES as complementary operando tools for monitoring the structure of Cu-based zeolite catalysts during NOx-removal by ammonia SCR

    Science.gov (United States)

    Günter, T.; Doronkin, D. E.; Carvalho, H. W. P.; Casapu, M.; Grunwaldt, J.-D.

    2016-05-01

    In this article, we demonstrate the potential of hard X-ray techniques to characterize catalysts under working conditions. Operando high energy resolution fluorescence detected (HERFD) XANES and valence to core (vtc) X-ray emission spectroscopy (XES) have been used in a spatially-resolved manner to study Cu-zeolite catalysts during the standard-SCR reaction and related model conditions. The results show a gradient in Cu oxidation state and coordination along the catalyst bed as the reactants are consumed. Vtc-XES gives complementary information on the direct adsorption of ammonia at the Cu sites. The structural information on the catalyst shows the suitability of X-ray techniques to understand catalytic reactions and to facilitate catalyst optimization.

  16. Temperature-driven oxidation behavior on pure iron surface investigated by time-resolved EXAFS measurements

    Energy Technology Data Exchange (ETDEWEB)

    Doh, S.J.; Lee, J.M.; Je, J.H. [POSTECH, Pohang (Korea, Republic of); Noh, D.Y. [K-JIST, Kwangju (Korea, Republic of). Dept. of Materials Science and Engineering

    1998-12-31

    The surface-front oxidation mechanism of iron was investigated by time-resolved, glancing-angle Fe K-edge fluorescence EXAFS measurements at various oxidation temperatures of 200--700 C. The glancing angle was chosen according to the depth of the oxide layer, roughly 1,500--2,000 {angstrom}. The oxidation behavior under rapid heating (up to 600 C within 10 minutes) was compared with the slowly heated oxidation process using the Quick-EXAFS measurements. In the slowly heated process, Fe{sub 3}O{sub 4} was the dominating phase at a relatively low temperature (300--400 C) initially. However, at a relatively high temperature (above 600 C), the Fe{sub 2}O{sub 3} and FeO crystalline phases are gradually enriched as the successive oxidation process involving intrusive oxygen proceeded. Remarkably under a prolonged heat treatment above 600 C, the stable FeO phase that exists in a deep-lying interface structure and Fe{sub 2}O{sub 3} phase eventually dominates the thick front-surface structure. In a quickly heated process, however, Fe{sub 3}O{sub 4} phase is less dominating, which is contradictory to the commonly accepted oxidation models. The EXAFS results are discussed in conjunction with the x-ray diffraction features under the same heat treatment conditions.

  17. Interaction of NH3 with Cu-SSZ-13 Catalyst: A Complementary FTIR, XANES, and XES Study.

    Science.gov (United States)

    Giordanino, Filippo; Borfecchia, Elisa; Lomachenko, Kirill A; Lazzarini, Andrea; Agostini, Giovanni; Gallo, Erik; Soldatov, Alexander V; Beato, Pablo; Bordiga, Silvia; Lamberti, Carlo

    2014-05-01

    In the typical NH3-SCR temperature range (100-500 °C), ammonia is one of the main adsorbed species on acidic sites of Cu-SSZ-13 catalyst. Therefore, the study of adsorbed ammonia at high temperature is a key step for the understanding of its role in the NH3-SCR catalytic cycle. We employed different spectroscopic techniques to investigate the nature of the different complexes occurring upon NH3 interaction. In particular, FTIR spectroscopy revealed the formation of different NH3 species, that is, (i) NH3 bonded to copper centers, (ii) NH3 bonded to Brønsted sites, and (iii) NH4(+)·nNH3 associations. XANES and XES spectroscopy allowed us to get an insight into the geometry and electronic structure of Cu centers upon NH3 adsorption, revealing for the first time in Cu-SSZ-13 the presence of linear Cu(+) species in Ofw-Cu-NH3 or H3N-Cu-NH3 configuration.

  18. The Use of Differential EXAFS Analysis for the determination of Small Structural Differences between two closely-related Ruthenium Complexes

    Science.gov (United States)

    Gianolio, D.; Borfecchia, E.; Garino, C.; Ruiu, T.; Lamberti, C.; Salassa, L.

    2013-04-01

    X-ray Absorption Spectroscopy (XAS) is a sensitive and powerful technique in revealing the structure of a material, providing as well high accuracy on interatomic distances. Nevertheless, when dealing with systems that differ only by small structural features, a standard data analysis might be unable of discriminating between such differences. A differential approach was proposed by Bressler, Chergui, and co-workers [2003, Phys. Rev. Lett. 90, 047403][2006, J. Phys. Chem B, 110, 14035][2009 Angew. Chem., Int. Ed. 48 2711] to solve this problem and differentiate between excited and unexcited state structures during pump-and-probe transient XAS experiments. In this contribution, we apply the differential data analysis procedure to the study of two closely-related molecular complexes, namely cis-[Ru(bpy)2(py)2]2+ and cis-[Ru(bpy)2(py)(H2O)]2+, characterized under static conditions. It is herein demonstrated that the method, based on a direct fit of differential curves, is able to reveal the small differences present between the two structures which, conversely, could not be resolved by standard EXAFS fitting of full spectra.

  19. K-edge XANES investigation of octakis(DMSO)lanthanoid(III) complexes in DMSO solution and solid iodides.

    Science.gov (United States)

    D'Angelo, Paola; Migliorati, Valentina; Spezia, Riccardo; De Panfilis, Simone; Persson, Ingmar; Zitolo, Andrea

    2013-06-14

    The potential of high energy XANES (X-ray absorption near edge structure) as a tool for the structural analysis of lanthanoid-containing systems has been explored. The K-edge XANES spectra of La(3+), Gd(3+), and Lu(3+) ions both in DMSO solution and solid octakis(DMSO)lanthanoid(III) iodides have been analysed. Although the K-edges of lanthanoids cover the energy range of 38 (La) to 65 (Lu) keV, the large widths of the core hole states do not appreciably reduce the potential structural information of the XANES data. We show that, for lanthanoid compounds, accurate structural parameters are obtained from the analysis of K-edge XANES signals if a deconvolution procedure is carried out. We found that in solid octakis(DMSO)lanthanoid(III) iodides the Ln(3+) ions are coordinated by eight DMSO ligands arranged in a quite symmetric fashion. In DMSO solution the Ln(3+) ions retain a regular eight-coordination structure and the coordination number does not change along the series. In contrast to when in water the second coordination shell has been found to provide a negligible contribution to the XANES spectra of Ln(3+) ions in DMSO solution.

  20. Total electron yield XANES of zinc-blende MnTe

    Science.gov (United States)

    Iwanowski, R. J.; Welter, E.; Janik, E.

    2008-09-01

    The electronic structure and chemical bond of zinc-blende (zb) MnTe have been studied by using total-electron-yield (TEY) X-ray absorption near-edge structure (XANES) spectroscopy. Close resemblances of the shape of Mn K-edge XANES in zb-MnTe and in Zn 1- xMn xTe [A. Titov, X. Biquard, D. Halley, S. Kuroda, E. Bellet-Amalric, H. Mariette, J. Cibert, A.E. Merad, G. Merad, M.B. Kanoun, E. Kulatov, Yu.A. Uspenskii, Phys. Rev. B 72 (2005) 115209] indicated predominant influence of the 1st coordination shell. In particular, identical single-peak pre-edge structure for both cases was mainly ascribed to the Mn 1s-3d/4p weakly allowed dipole transitions. The quantitative analysis of XANES in zb-MnTe concerned the observed chemical shift of Mn K-edge threshold energy and a magnitude of the relevant cation-anion charge transfer (or effective cation charge), q(Mn-Te) [calculated after M. Kitamura, H. Chen, J. Phys. Chem. Solids 52 (1991) 731]. It also provided a comparison with our earlier X-ray absorption studies of Zn 1- xMn xB alloys (B = S, Se). The estimated charge transfer within the chemical bond of zb-MnTe enabled us to complete the q(Mn-B) versus chalcogen ligand (B = S, Se, Te) dependence and to interpret it in terms of p-d hybridization and a contribution of Mn 3d electrons to the overall charge transfer.

  1. Chromium in urban sediment particulates: an integrated micro-chemical and XANES study

    Science.gov (United States)

    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.

  2. Assessing sulfur redox state and distribution in abyssal serpentinites using XANES spectroscopy

    Science.gov (United States)

    Debret, Baptiste; Andreani, Muriel; Delacour, Adélie; Rouméjon, Stéphane; Trcera, Nicolas; Williams, Helen

    2017-05-01

    Sulfur is one of the main redox sensitive and volatile elements involved in chemical transfers between earth surface and the deep mantle. At mid-oceanic ridges, sulfur cycle is highly influenced by serpentinite formation which acts as a sink of sulfur under various oxidation states (S2-, S-, S0 and S6+). Sulfur sequestration in serpentinites is usually attributed to the crystallization of secondary minerals, such as sulfides (e.g. pyrite, pyrrhotite) or sulfates (e.g. anhydrite). However, the role of serpentine minerals as potential sulfur carriers is not constrained. We investigate the distribution and redox state of sulfur at micro-scale combining in situ spectroscopic (X-ray absorption near-edge structure: XANES) and geochemical (SIMS) measurements in abyssal serpentinites from the SWIR (South West Indian Ridge), the Rainbow and the MARK (Mid-Atlantic Ridge, Kane Fracture Zone) areas. These serpentinites are formed in different tectono-metamorphic settings and provide a meaningful database to understand the fate of sulfur during seafloor serpentinization. XANES spectra of serpentinite powders show that the sulfur budget of the studied samples is dominated by oxidized sulfur (S6+ / ∑ S = 0.6- 1) although sulfate micro-phases, such as barite and anhydrite, are absent. Indeed, μ-XANES analyses of mesh, bastite and antigorite veins in thin sections and of serpentine grains rather suggest the presence of S6+ ions incorporated into serpentine minerals. The structural incorporation of S in serpentine minerals is also supported by X-ray fluorescence mapping revealing large areas (1600 μm2) of serpentinite where S is homogeneously distributed. Our observations show that serpentine minerals can incorporate high S concentrations, from 140 to 1350 ppm, and that this can account for 60 to 100% of the sulfur budget of abyssal serpentinites. Serpentine minerals thus play an important role in S exchanges between the hydrosphere and the mantle at mid-oceanic ridges and may

  3. The status of strontium in biological apatites: an XANES investigation.

    Science.gov (United States)

    Bazin, D; Daudon, M; Chappard, Ch; Rehr, J J; Thiaudière, D; Reguer, S

    2011-11-01

    Osteoporosis represents a major public health problem and increases patient morbidity through its association with fragility fractures. Among the different treatments proposed, strontium-based drugs have been shown to increase bone mass in postmenopausal osteoporosis patients and to reduce fracture risk. While the localization of Sr(2+) cations in the bone matrix has been extensively studied, little is known regarding the status of Sr(2+) cations in natural biological apatite. In this investigation the local environment of Sr(2+) cations has been investigated through XANES (X-ray absorption near-edge structure) spectroscopy in a set of pathological and physiological apatites. To assess the localization of Sr(2+) cations in these biological apatites, numerical simulations using the ab initio FEFF9 X-ray spectroscopy program have been performed. The complete set of data show that the XANES part of the absorption spectra may be used as a fingerprint to determine the localization of Sr(2+) cations versus the mineral part of calcifications. More precisely, it appears that a relationship exists between some features present in the XANES part and a Sr(2+)/Ca(2+) substitution process in site (I) of crystal apatite. Regarding the data, further experiments are needed to confirm a possible link between the relationship between the preparation mode of the calcification (cellular activity for physiological calcification and precipitation for the pathological one) and the adsorption mode of Sr(2+) cations (simple adsorption or insertion). Is it possible to draw a line between life and chemistry through the localization of Sr in apatite? The question is open for discussion. A better structural description of these physiological and pathological calcifications will help to develop specific therapies targeting the demineralization process in the case of osteoporosis.

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

    Science.gov (United States)

    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

  5. Combined application of XANES and XPS to study oxygen species adsorbed on Ag foil

    CERN Document Server

    Bukhtiyarov, V I; Kaichev, V V; Knop-Gericke, A; Mayer, R W; Schloegl, R

    2001-01-01

    Adsorbed oxygen species realized in the course of ethylene epoxidation over polycrystalline silver have been characterized by X-ray absorption near the edge structure and X-ray photoelectron spectroscopy. Namely, the combined application of XANES and XPS in similar UHV conditions using the same sample allowed us to assign an XAS feature to the nucleophilic and electrophilic oxygen. This is of great significance, since these species are suggested to be included into the active center for ethylene epoxidation. The differences in the oxygen-silver bonding of these oxygen species are discussed.

  6. In situ XANES study on TiO2-SiO2 aerogels and flame made materials

    DEFF Research Database (Denmark)

    Grunwaldt, J.D.; Beck, C.; Stark, W.;

    2002-01-01

    The structures of TiO2-SiO2 based aerogels and flame made particles, used as epoxidation catalysts, are compared by X-ray absorption near edge structure (XANES) spectroscopy and in situ XANES during dehydration of the calcined catalyst samples. The results are interpreted in terms of the titanium...... species present in the catalyst and the catalytic performance in the test reaction, the epoxidation of 2-cyclohexene-1-ol by tert butylhydroperoxide ( THBP) at 90degreesC. XANES shows that tetrahedral titanium sites are the favoured sites at low TiO2 concentrations (1-3.2 wt. % in this study......). The catalytic performance (turnover frequency, selectivity) of such aerogels or flame made materials with low TiO2 content is much better than that of corresponding samples with high TiO2 content. In aerogels, regardless of the TiO2 content, the amount of titanium with tetrahedral coordination increases...

  7. XANES studies of titanium dioxide nanoparticles synthesized by using Peltophorum pterocarpum plant extract

    Energy Technology Data Exchange (ETDEWEB)

    Saravanan, S. [Centre for Photonics and Nanotechnology, Sona College of Technology, Salem 636005, Tamilnadu (India); Balamurugan, M., E-mail: chem.muruga@gmail.com [Centre for Photonics and Nanotechnology, Sona College of Technology, Salem 636005, Tamilnadu (India); Lippitz, A. [Bundesanstalt für Materialforschung und -prüfung, 6.8 Oberflächenanalytik und Grenzflächenchemie Unter den Eichen 44 – 46, 12203, Berlin (Germany); Fonda, E.; Swaraj, S. [Synchrotron SOLEIL, L’ormes des merisiers, Saint Aubin BP-48, 91192, Gif-Sur-Yvette Cedex (France)

    2016-12-15

    The preparation and characterization of a Titanium dioxide (TiO{sub 2}) by a simple, cost effective, facile and eco-friendly green synthesis method using Peltophorum pterocarpum plant extract is presented. The green synthesized nanoparticles were characterized using X-ray diffraction (XRD), Raman spectroscopy, High-resolution transmission electron microscopy (HR-TEM) and X-ray absorption near edge spectroscopy (XANES). XRD results show that the prepared TiO{sub 2} NPs were significantly crystalline with various percentages of anatase and rutile phases. The nanoparticles were found to have different diameters ranging from 20 to 80 nm. No evidence of any intermediate or different TiO{sub 2} phases were found in XANES measurements performed at the Ti K- and L-edge. It is shown that the TiO{sub 2} NPs with high uniformity, high surface area and minimum aggregation can be prepared with relative ease and the desired anatase: rutile phase ratio can be obtained by controlling the experimental conditions.

  8. Valence determination of rare earth elements in lanthanide silicates by L 3-XANES spectroscopy

    Science.gov (United States)

    Kravtsova, Antonina N.; Guda, Alexander A.; Goettlicher, Joerg; Soldatov, Alexander V.; Taroev, Vladimir K.; Kashaev, Anvar A.; Suvorova, Lyudmila F.; Tauson, Vladimir L.

    2016-05-01

    Lanthanide silicates have been hydrothermally synthesized using Cu and Ni containers. Chemical formulae of the synthesized compounds correspond to K3Eu[Si6O15] 2H2O, HK6Eu[Si10O25], K7Sm3[Si12O32], K2Sm[AlSi4O12] 0.375H2O, K4Yb2[Si8O21], K4Ce2[Al2Si8O24]. The oxidation state of lanthanides (Eu, Ce, Tb, Sm, Yb) in these silicates has been determined using XANES spectroscopy at the Eu, Ce, Tb, Sm, Yb, L 3- edges. The experimental XANES spectra were recorded using the synchrotron radiation source ANKA (Karlsruhe Institute of Technology) and the X-ray laboratory spectrometer Rigaku R- XAS. By comparing the absorption edge energies and white line intensities of the silicates with the ones of reference spectra the oxidation state of lanthanides Eu, Ce, Tb, Sm, Yb has been found to be equal to +3 in all investigated silicates except of the Ce-containing silicate from the run in Cu container where the cerium oxidation state ranges from +3 (Ce in silicate apatite and in a KCe silicate with Si12O32 layers) to +4 (starting CeO2 or oxidized Ce2O3).

  9. XANES studies of titanium dioxide nanoparticles synthesized by using Peltophorum pterocarpum plant extract

    Science.gov (United States)

    Saravanan, S.; Balamurugan, M.; Lippitz, A.; Fonda, E.; Swaraj, S.

    2016-12-01

    The preparation and characterization of a Titanium dioxide (TiO2) by a simple, cost effective, facile and eco-friendly green synthesis method using Peltophorum pterocarpum plant extract is presented. The green synthesized nanoparticles were characterized using X-ray diffraction (XRD), Raman spectroscopy, High-resolution transmission electron microscopy (HR-TEM) and X-ray absorption near edge spectroscopy (XANES). XRD results show that the prepared TiO2 NPs were significantly crystalline with various percentages of anatase and rutile phases. The nanoparticles were found to have different diameters ranging from 20 to 80 nm. No evidence of any intermediate or different TiO2 phases were found in XANES measurements performed at the Ti K- and L-edge. It is shown that the TiO2 NPs with high uniformity, high surface area and minimum aggregation can be prepared with relative ease and the desired anatase: rutile phase ratio can be obtained by controlling the experimental conditions.

  10. Sulfur K-edge XANES study of S sorbed onto volcanic ashes

    Energy Technology Data Exchange (ETDEWEB)

    Farges, F; Keppler, H [Bayerische Geoinsitut, Universitaet Bayreuth, Bayreuth (Germany); Flank, A-M; Lagarde, P, E-mail: farges@mnhn.f [CNRS UR1 Synchrotron Soleil, BP 48, 91192 Gif sur Yvette (France)

    2009-11-15

    Powders of four synthetic glasses of volcanic composition, a silica glass and crystalline quartz were equilibrated with SO{sub 2} to study the speciation of S sorbed onto their surface. These samples mimic the aerosols injected into the atmosphere during volcanic eruptions. Volcanic sulfur is known to globally affect the Earth's climate with an opposite effect to CO{sub 2}. However, absorption on ashes may reduce the amount of sulfur entering the stratosphere. S K-edge micro-XANES ({mu}XANES) spectra and {mu}XRF maps were collected at the LUCIA beamline (SOLEIL) at the SLS (Switzerland). When photoreduction is minimized, SO{sub 2} is sorbed mostly as sulfates moieties. The sorption of S is controlled by the surface structure of the powders probed. Presence of defects, non-bridging oxygens and network-modifiers (alkali and alkali-earths) enhance S-sorption as sulfate moieties onto the powders surface. Therefore, the quantity of S released to the atmosphere is highly dependant on the type of ash produced during eruptions that help to better model the climatic impact of volcanic S.

  11. EXAFS study of structural characteristics of nanocrystalline selenium with different grain sizes

    Institute of Scientific and Technical Information of China (English)

    1999-01-01

    Extended x-ray-absorption fine-structure measurements(EXAFS) were performed on nanocrystalline (nc) elemental Se samples with grain sizes ranging from 13 to 60 nm.Accompanied with the previous study,we concluded that,with the refinement in nc.Se.the intrachain structure (the bond length,the coordination number)is unchanged while the interchain spacing is enlarged.The grain boundary in the nc Se is found to be in a low-energy configuration that is different from the disordered gaslike grain boundary structure.

  12. New Graphical User Interface for EXAFS analysis with the GNXAS suite of programs

    Science.gov (United States)

    Hatada, Keisuke; Iesari, Fabio; Properzi, Leonardo; Minicucci, M.; di Cicco, Andrea

    2016-05-01

    GNXAS is a suite of programs based on multiple scattering calculations which performs a structural refinement of EXAFS spectra. It can be used for any system although it has been mainly developed to determine the local structure of disordered substances. We developed a user-friendly graphical user interface (GUI) to facilitate use of the codes by using wxPython. The developed GUI and the codes are multiplatform running on Windows, Macintosh and Linux systems, and are free shareware (http://gnxas.unicam.it). In this work we illustrate features and potentials of this newly developed version of GNXAS (w-GNXAS).

  13. Determination of double decker sanwich structured La—substituted chlorophyll a by EXAFS

    Institute of Scientific and Technical Information of China (English)

    W.Chen; Z.Wei; F.Hong; Y.Tao; G.Zhao; J.Yang; S.lkeda; J.Jiang; T.Hu

    2001-01-01

    As a representative naural porphyrin derivative,it is interesting to know the chemical form of lanthanide in chlorophyll a.We select the natural fern dicranopteris dichotoma,the most lanthanide-concentrated plant known,to isolate the chlorophyll a for our study. It is found by EXAFS that lanthanum substutes in the magnesium position in chorophyll and coordinates with the porphyrin ring.The lanthanum is seen to have a similar coordination structure to a sandwich-type lanthanide complex,with the La surrounded by eight nitrogen atoms from two porphyrin rings with average La-N bond length of 2.65A.

  14. BONDLENGTH ALTERNATION OF NANOPARTICLES Fe2O3 COATED WITH ORGANIC SURFACTANTS PROBED BY EXAFS

    Institute of Scientific and Technical Information of China (English)

    1999-01-01

    The nanoparticles γ-Fe2O3 coated with surfactants.DBS,ST and CTAB.repsectively.were synthesized by microemulsion method.The coated ferric oxides.which show enhanced nonlinear optical properties compared with their bulk counterpart.were probed by EXAFS in solution forms.The x=-ray absorption spectra for Fe K edge were measured at room temperature by help of synchrotron radiation light source.Extended x-ray absorption fine structure analysis shows that the coating layers of organic molecules interact with surface atoms of nanopartices,the Fe-O bond length was extended.

  15. The Mn site in Mn-doped Ga-As nanowires: an EXAFS study

    OpenAIRE

    d'Acapito, F.; Rovezzi, M.; Boscherini, F; Jabeen, F; Bais, G.; Piccin, M.; Rubini, S.; Martelli, F.

    2012-01-01

    We present an EXAFS study of the Mn atomic environment in Mn-doped GaAs nanowires. Mn doping has been obtained either via the diffusion of the Mn used as seed for the nanowire growth or by providing Mn during the growth of Au-induced wires. As a general finding, we observe that Mn forms chemical bonds with As but is not incorporated in a substitutional site. In Mn-induced GaAs wires, Mn is mostly found bonded to As in a rather disordered environment and with a stretched bond length, reminisce...

  16. XAFS data acquisition with 2D-detectors: Transmission mode XAFS and grazing incidence EXAFS spectroscopy

    Science.gov (United States)

    Lützenkirchen-Hecht, D.; Gasse, J.-C.; Bögel, R.; Wagner, R.; Frahm, R.

    2016-05-01

    XAFS-experiments in transmission and reflection modes have been performed using a Pilatus 100K pixel detector. Transmission mode XAFS spectra from a Co metal foil and Co3O4 were recorded to evaluate the data quality offered by this 2D-detector. Furthermore, the pixel detector was also used to measure reflection mode grazing incidence EXAFS data. Using different regions of interest in the collected scattering patterns, we will show that the diffuse scattering can be separated for the different contributing surfaces and interfaces, allowing simultaneous investigations of surfaces and buried interfaces within multi-layered samples.

  17. Direct determination of heavy metal speciation in soils by Exafs spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Manceau, A.; Harge, J.C.; Sarret, G.; Hazemann, J.L. [Universite de Grenoble, 38 (France); Boisset, M.C. [Paris-6 Univ., 75 (France). Laboratoire de Mineralogie, Cristallographie; Mench, M. [Institut National de Recherches Agronomiques (INRA), 33 - Villenave d`Ornon (France). Unite de Recherches en Agronomie; Cambier, Ph.; Prost, R. [Institut National de Recherches Agronomiques (INRA), 78 - Versailles (France). Unite de Science du Sol

    1997-12-31

    The potential of EXAFS spectroscopy to speciate and quantify the form of heavy metals in the solid fraction of soils is examined, taking lead and zinc as case studies. Three soils contaminated by different kinds of lead industrial activities (lead organometallics synthesis, Pb-Zn smelting and recycling lead from acid batteries). Results show the interaction of heavy metals with soil constituents, and direct molecular-level evidences are provided for the strong binding of lead by organic matter and of zinc by Mn oxides in soils. The low solubility and weak bio-degradability of these elements contribute to explain the fairly immobile nature of lead and zinc in these soils

  18. Calcium EXAFS establishes the Mn-Ca cluster in the oxygen-evolving complex of Photosystem II

    Energy Technology Data Exchange (ETDEWEB)

    Cinco, Roehl M.; McFarlane Holman, Karen L.; Robblee, John H.; Yano, Junko; Pizarro, Shelly A.; Bellacchio, Emanuele; Sauer, Kenneth; Yachandra, Vittal K.

    2002-08-02

    The proximity of Ca to the Mn cluster of the photosynthetic water-oxidation complex is demonstrated by X-ray absorption spectroscopy. We have collected EXAFS data at the Ca K-edge using active PS II membrane samples that contain approximately 2 Ca per 4 Mn. These samples are much less perturbed than previously investigated Sr-substituted samples, which were prepared subsequent to Ca depletion. The new Ca EXAFS clearly shows backscattering from Mn at 3.4 angstroms, a distance that agrees with that surmised from previously recorded Mn EXAFS. This result is also consistent with earlier related experiments at the Sr K-edge, using samples that contained functional Sr, that show Mn is {approx}; 3.5 angstroms distant from Sr. The totality of the evidence clearly advances the notion that the catalytic center of oxygen evolution is a Mn-Ca heteronuclear cluster.

  19. Influence of 300 °C thermal conversion of Fe-Ce hydrous oxides prepared by hydrothermal precipitation on the adsorptive performance of five anions : Insights from EXAFS/XANES, XRD and FTIR (companion paper)

    NARCIS (Netherlands)

    Chubar, Natalia; Gerda, Vasyl; Banerjee, Dipanjan

    2017-01-01

    In this work, we report atomic-scale reconstruction processes in Fe-Ce oxide-based composites (hydrothermally precipitated at Fe-to-Ce dosage ratios of 1:0, 2:1, 1:1, 1:2, and 0:1), upon treatment at 300 °C. The structural changes are correlated with the adsorptive removal of arsenate, phosphate,

  20. Incorporation of Eu(III) into hydrotalcite: a TRLFS and EXAFS study.

    Science.gov (United States)

    Stumpf, T; Curtius, H; Walther, C; Dardenne, K; Ufer, K; Fanghänelt, T

    2007-05-01

    The behavior of radionuclides in the environment (geo-, hydro-, and biosphere) is determined by interface reactions like adsorption, ion exchange, and incorporation processes. Presently, operational gross parameters for the distribution between solution and minerals are available. For predictive modeling of the radionuclide mobility in such systems, however, individual reactions and processes need to be localized, characterized, and quantified. A prerequisite for localization and clarification of the concerned processes is the use of modern advanced analytical and speciation methods, especially spectroscopy. In this study, Eu(III) was chosen as an analogue for trivalent actinides to identify the different species that occur by the Ln(III)/hydrotalcite interaction. Therefore, Eu(III) doped Mg-Al-Cl-hydrotalcite was synthesized and investigated by TRLFS, EXAFS, and XRD measurements. Two different Eu/hydrotalcite species were obtained. The minor part of the lanthanide is found to be inner-sphere sorbed onto the mineral surface, while the dominating Eu/hydrotalcite species consists of Eu(III) that is incorporated into the hydrotalcite lattice. Both Eu/hydrotalcite species have been characterized by their fluorescence emission spectra and lifetimes. Structural parameters of the incorporated Eu(III) species determined by EXAFS indicate a coordination number of 6.6 +/- 1.3 and distances of 2.41 +/- 0.02 A for the first Eu-OH shell.

  1. Sorption Speciation of Lanthanides/Actinides on Minerals by TRLFS, EXAFS and DFT Studies: A Review

    Directory of Open Access Journals (Sweden)

    Xiaoli Tan

    2010-11-01

    Full Text Available Lanthanides/actinides sorption speciation on minerals and oxides by means of time resolved laser fluorescence spectroscopy (TRLFS, extended X-ray absorption fine structure spectroscopy (EXAFS and density functional theory (DFT is reviewed in the field of nuclear disposal safety research. The theoretical aspects of the methods are concisely presented. Examples of recent research results of lanthanide/actinide speciation and local atomic structures using TRLFS, EXAFS and DFT are discussed. The interaction of lanthanides/actinides with oxides and minerals as well as their uptake are also of common interest in radionuclide chemistry. Especially the sorption and inclusion of radionuclides into several minerals lead to an improvement in knowledge of minor components in solids. In the solid-liquid interface, the speciation and local atomic structures of Eu(III, Cm(III, U(VI, and Np(IV/VI in several natural and synthetic minerals and oxides are also reviewed and discussed. The review is important to understand the physicochemical behavior of lanthanides/actinides at a molecular level in the natural environment.

  2. Interaction between guest AgI and host zeolite FAU studied by optical spectra and EXAFS

    Science.gov (United States)

    Kodaira, T.; Kubota, T.; Okamoto, Y.; Koshizaki, N.

    2005-07-01

    AgI molecules were dilutely adsorbed into nano-cages of Na{}^+, K{}+ and Cs{}+ type FAU zeolites in order to understand the interaction between host zeolite and guest AgI. This interaction was investigated using optical absorption spectroscopy and extended X-ray absorption fine structure (EXAFS). The optical spectra strongly depend on the type of the alkali cations. Compared with the lowest absorption band of AgI molecules in gas phase, the spectra of AgI molecules adsorbed in the zeolite cages shifts to higher energy in the order of Cs{}^+, K{}^+, and Na{}^+. On the contrary, Ag-I bond lengths of adsorbed AgI molecules obtained from EXAFS were independent of the type of the alkali-cations. The bond length was very close to gas phase AgI molecules. Therefore, the interaction between AgI molecules and the zeolite, whose magnitude is Na{}+ > K{}+ > Cs{}^+, is important in the photo-excited electronic state.

  3. APEX version 2.0: latest version of the cross-platform analysis program for EXAFS.

    Science.gov (United States)

    Dimakis, N; Bunker, G

    2001-03-01

    This report describes recent progress on APEX, a free, open source, cross platform set of EXAFS data analysis software. In a previous report we described APEX 1.0 (Dimakis, N. and Bunker, G., 1999), a free and open source code suite of basic X-Ray Absorption Fine Structure (XAFS) data analysis programs for classical data reduction and single scattering analysis. The first version of APEX was the only cross platform (linux/irix/windows/MacOS) EXAFS analysis program to our knowledge, but it lacked important features like multiple scattering fitting, generic format conversion from ASCII to University of Washington (UW) binary-type files, and user friendly interactive graphics. In the enhanced version described here we have added cross-platform interactive graphics based on the BLT package, which is an extension to TCL/TK. Some of the utilities have been rewritten in native TCL/TK, allowing for faster and more integrated functionality with the main package. The package also has been ported to SunOS. APEX 2.0 in its current form is suitable for routine data analysis and training. Addition of more advanced methods of data analysis are planned.

  4. EXAFS and FTIR studies of selenite and selenate sorption by alkoxide-free sol–gel generated Mg–Al–CO 3 layered double hydroxide with very labile interlayer anions

    KAUST Repository

    Chubar, Natalia

    2014-08-08

    © the Partner Organisations 2014. Current research on Layered Double Hydroxides (LDHs, also known as hydrotalcites, HTs) is predominantly focused on their intercalations, but the industrial application of LDHs for anion exchange adsorption has not yet been achieved. It was recently recognized that, to develop LDH applications, these materials should be produced using methods other than direct co-precipitation. Mg-Al-CO3LDH produced using an alkoxide-free sol-gel synthesis showed exceptional removal properties for aqueous selenium species. Se K-edge EXAFS/XANES and FTIR studies (supporting the data by XRD patterns) were performed to explain the unusual adsorptive performance of Mg-Al LDH by revealing the molecular-level mechanism of HSeO3 -, SeO4 2-and {HSeO3 -+ SeO4 2-} uptake at pH 5, 7 and 8.5. The role of inner-sphere complexation (exhibited by inorganic adsorbents with good performance) in adsorption of both selenium aqueous species was not confirmed. However, Mg-Al LDH fully met the other expectations regarding the involvement of the interlayer anions. The interlayer carbonate (due to its favorable speciation and generous HT hydration) gave a "second breath" to selenite sorption and was the only mechanism that controlled the removal of Se(vi). Because inner sphere complexation was the leading mechanism for selenite removal, ion exchange via surface OH-and interlayer CO3 2-species was the only mechanism for selenate removal; both of these species were easily bound to Mg-Al LDH (on its surface and gently parked into the interlayer forming a multilayer without violation of the structure of Mg-Al-CO3LDH). This work provides the first theoretical explanation of why it is more difficult to sorb selenate than selenite and which material should be used for this purpose. This journal is

  5. Speciation of magnesium in monohydrocalcite: XANES, ab initio and geochemical modeling

    Science.gov (United States)

    Fukushi, Keisuke; Suzuki, Yuma; Kawano, Jun; Ohno, Takeshi; Ogawa, Masahiro; Yaji, Toyonari; Takahashi, Yoshio

    2017-09-01

    Monohydrocalcite (MHC: CaCO3·H2O), a rare carbonate mineral formed under surface conditions, is usually observed in nature as containing a variable amount of Mg, with a 0.007-0.45 Mg/Ca mole ratio. The variable Mg composition in MHC is anticipated as a promising proxy to assess paleo-hydrochemistry especially in saline lakes. Although the roles of Mg on the formation and stability of MHC have been studied intensively, the Mg speciation in MHC has remained unclear and controversial. This study examined Mg speciation in MHC using X-ray absorption near edge structure (XANES), ab initio molecular simulation, and geochemical modeling. Mg-XANES spectra of MHC with different Mg/Ca ratios prepared from mixing solutions of Na2CO3, CaCl2 and MgCl2 revealed that the Mg in MHC is a mixture of amorphous Mg carbonate (AMC) and other Mg containing phase. The contribution of AMC to total Mg is negatively correlated to the crystallinity of MHC. Results show that AMC might play a protective role in the crystallization and the transformation to stable calcium carbonates. Ab initio calculation of Mg2+ substitution into MHC showed that a limited amount of Mg2+ can be incorporated into the MHC structure. Six-fold coordination of Mg2+ is substituted for eight-fold coordination of Ca2+ in the MHC structure. The other type of Mg in MHC revealed from the XANES analyses most likely corresponds to the structural Mg in MHC. The contribution of the structural Mg is almost constant at 0.06 in Mg/Ca, representing the limit of solid solubility of Mg in MHC. The solubility products of the MHC with the limit of solid solubility of Mg and the AMC associated with MHC were estimated from the reacted solution compositions. Prediction of the Mg/Ca ratio as a function of the initial solution conditions using solubility reasonably reproduces the observed apparent Mg/Ca ratios in MHC from the present study and earlier studies. The apparent Mg/Ca ratio of MHC is useful to elucidate water chemistry

  6. Exafs spectrometer

    Energy Technology Data Exchange (ETDEWEB)

    Georgopoulos, P.

    1987-02-10

    An apparatus is described for performing X-ray absorption fine structure measurements on a specimen by using a source X-ray beam and an assembly adapted to carry out a set of predetermined operating conditions, comprising: a monochromator crystal means rotatably positioned at the center of the assembly for diffracting the source X-ray beam to provide a monchromatic X-ray beam for selected angles of incidence of the source X-ray beam with respect to the crystal means. The crystal means provides the monochromatic X-ray beam having a different wavelength upon changing to a different respective associated on of the angles of incidence; deforming means for automatically distorting the monochromator crystal means at the angles of incidence to provide the monochromatic X-ray beam having the different wavelength at the respective associated angles of incidence; detector means for measuring the intensity of the monochromatic X-ray beam before and after passing through the specimen; and stage means for supporting the specimen and the detector means. The stage means is slidingly engaged with a receiving track of the assembly to enable movement on the track to an angular position twice that of the respective associated angle of incidence of the X-ray beam with the crystal means.

  7. EXAFS, ab Initio Molecular Dynamics, and NICIS Spectroscopy Studies on an Organic Dye Model at the Dye-Sensitized Solar Cell Photoelectrode Interface.

    Science.gov (United States)

    Liu, Peng; Johansson, Viktor; Trilaksana, Herri; Rosdahl, Jan; Andersson, Gunther G; Kloo, Lars

    2017-06-14

    The organization of dye molecules in the dye layer adsorbed on the semiconductor substrate in dye-sensitized solar cells has been studied using a combination of theoretical methods and experimental techniques. The model system is based on the simple D-π-A dye L0, which has been chemically modified by substituting the acceptor group CN with Br (L0Br) to offer better X-ray contrast. Experimental EXAFS data based on the Br K-edge backscattering show no obvious difference between dye-sensitized titania powder and titania film samples, thus allowing model systems to be based on powder slurries. Ab initio molecular dynamic (aiMD) calculations have been performed to extract less biased information from the experimental EXASF data. Using the aiMD calculation as input, the EXAFS structural models can be generated a priori that match the experimental data. Our study shows that the L0Br dye adsorbs in the trans-L0Br configuration and that adsorption involves both a proximity to other L0Br dye molecules and the titanium atoms in the TiO2 substrate. These results indicate direct coordination of the dye molecules to the TiO2 surface in contrast to previous results on metal-organic dyes. The molecular coverage of L0Br on mesoporous TiO2 was also estimated using NICIS spectroscopy. The NICISS results emphasized that the L0Br dye on nanoporous titania mainly forms monolayers with a small contribution of multilayer coverage.

  8. First Principles Fe L2,3-Edge and O K-Edge XANES and XMCD Spectra for Iron Oxides.

    Science.gov (United States)

    Sassi, Michel; Pearce, Carolyn I; Bagus, Paul S; Arenholz, Elke; Rosso, Kevin M

    2017-09-21

    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. 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 spectra 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 completes 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.

  9. Measurement of inorganic arsenic species in rice after nitric acid extraction by HPLC-ICPMS: verification using XANES.

    Science.gov (United States)

    Maher, W; Foster, S; Krikowa, F; Donner, E; Lombi, E

    2013-06-04

    The measurement of As species in rice is normally accomplished by extraction followed by HPLC-ICPMS analysis. This method, however, has not been comprehensively validated by comparing these speciation results with XANES, which does not require sample extraction, due to the challenge of conducting XANES analysis at very low As concentrations. In this study As speciation data using nitric acid extraction/HPLC-ICPMS and XANES are compared to verify the efficacy of using 2% v/v nitric acid extraction and HPLC-ICPMS to measure inorganic As, DMA, and MA in reference rice materials and common rice varieties obtainable in Australia. Total As and As species (As(III), As(V), DMA, and MA) concentrations measured in 8 reference materials were in agreement with published values. XANES analysis was performed on 5 samples having total As concentrations ranging from 0.198 to 0.335 μg g(-1). XANES results gave similar proportions of total As(III), As(V), and DMA to HPLC-ICPMS. XANES was able to distinguish two forms of As(III): As(III) and As(III)GSH. Total As concentrations in rice samples varied from 0.006 to 0.45 μg g(-1) As (n = 47) with a mean ± std of 0.127 ± 0.112 μg g(-1) As with most As present as inorganic species (63 ± 26%). DMA was found in nearly all the rice samples with the majority of samples containing concentrations below 0.05 μg g(-1) As while MA concentrations were negligible (<0.003 μg g(-1) As). Six rice varieties produced in Australia, China, and Spain all had elevated DMA concentrations (0.170-0.399 μg g(-1) As) that were correlated with total As concentrations (r(2) = 0.7518). In conclusion, comparison of As speciation by HPLC-ICPMS and XANES showed that similar As species were detected indicating the appropriateness of using 2% v/v nitric acid for extraction of rice prior to speciation. Common rice varieties obtainable in Australia generally have low As concentrations with most As present as inorganic As.

  10. A Mexican kaolin deposit: XANES characterization, mineralogical phase analysis and applications

    Directory of Open Access Journals (Sweden)

    Martínez, A.

    2009-06-01

    Full Text Available A kaolin obtained from Villa de Reyes, a region near to San Luis Potosí (México was characterized by means of X-ray powder diffraction (XRD, optical microscopy (OM, scanning electron microscopy (SEM, X-ray fluorescence (XRF, X-Ray Absorption Near Edge Spectroscopy (XANES, thermal analysis (DTA/TGA, dilatometry (DIL, and chemical analysis. Mineralogical and morphological characteristics of the mineral are presented. The kaolin sample was formed mainly by kaolinite, but other minor phases were also detected such as quartz, cristobalite, tridymite, and dolomite. The high content of volcanic glass detected, by optical microscopy, revealed an incomplete kaolinization process of the raw material. The reddish color of the kaolin was associated with the free iron content in the form of limonite [FeO(OH], which was determined by XANES. The influence of the particle size on the whiteness of kaolin was evaluated. Dilatometric analysis revealed a strong thermal expansion between 110 y 240 °C, which would difficult the use of this material in traditional ceramic applications. On the other hand the presence of glass and high temperature phases of SiO2, such as cristobalite and tridymite will favor its use in the cement industry.El caolín obtenido de Villa de Reyes, una región cercana a San Luis Potosí, México, fue caracterizado por las siguientes técnicas: difracción de rayos-X en polvos (DRX, microscopía óptica (MO, microscopía electrónica de barrido (MEB, fluorescencia de rayos-X (FRX, espectroscopía de absorción de rayos-X (XANES, análisis térmico (DTA/TGA, dilatometría (DIL y análisis químico. Los resultados del análisis mineralógico mediante DRX mostraron un mineral constituido principalmente de caolinita, con una contribución minoritaria de cuarzo, cristobalita, tridimita y dolomita. El análisis por microscopía óptica reveló un alto contenido de material amorfo volcánico, indicando una caolinización incompleta del material v

  11. Time resolved XANES illustrates a substrate-mediated redox process in Prussian blue cultural heritage materials

    Science.gov (United States)

    Gervais, Claire; Lanquille, Marie-Angélique; Moretti, Giulia; Réguer, Solenn

    2016-05-01

    The pigment Prussian blue is studied in heritage science because of its capricious fading behavior under light exposure. We show here that XANES can be used to study the photosensitivity of Prussian blue heritage materials despite X-ray radiation damage. We used an original approach based on X-ray photochemistry to investigate in depth the redox process of Prussian blue when it is associated with a cellulosic substrate, as in cyanotypes and watercolors. By modifying cation and proton contents of the paper substrate, we could tune both rate and extent of Prussian blue reduction. These results demonstrate that the photoreduction and fading of Prussian blue is principally mediated by the substrate and its interaction with the oxygen of the environment.

  12. In Situ XANES/XPS Investigation of Doped Manganese Perovskite Catalysts

    Directory of Open Access Journals (Sweden)

    Daniel Mierwaldt

    2014-04-01

    Full Text Available Studying catalysts in situ is of high interest for understanding their surface structure and electronic states in operation. Herein, we present a study of epitaxial manganite perovskite thin films (Pr1−xCaxMnO3 active for the oxygen evolution reaction (OER from electro-catalytic water splitting. X-ray absorption near-edge spectroscopy (XANES at the Mn L- and O K-edges, as well as X-ray photoemission spectroscopy (XPS of the O 1s and Ca 2p states have been performed in ultra-high vacuum and in water vapor under positive applied bias at room temperature. It is shown that under the oxidizing conditions of the OER a reduced Mn2+ species is generated at the catalyst surface. The Mn valence shift is accompanied by the formation of surface oxygen vacancies. Annealing of the catalysts in O2 atmosphere at 120 °C restores the virgin surfaces.

  13. The study of interaction of HIV-1 surface GP120 protein with CD4 cell receptor by EXAFS spectroscopy

    Science.gov (United States)

    Lukashev, Vitaly Alexeevich; Bausk, Nikolay Vladimirovich; Mazalov, Lev Nikolaevich; Kaurov, Oleg Alexeevich; Kolobov, Alexandr Alexandrovich; Naumochkin, Andrey Nikolaevich; Kulichkov, Vladimir Anatolevich

    1995-02-01

    This work is aimed at the study of the interaction between gp120 protein (HIV-1) and peptides, which are similar to CD4 protein receptors from T4 lymphocytes. The preliminary results demonstrated that peptide structural information could be obtained from fluorescent EXAFS.

  14. Strontium speciation during reaction of kaolinite with simulated tank-waste leachate: bulk and microfocused EXAFS analysis.

    Science.gov (United States)

    Choi, Sunkyung; O'Day, Peggy A; Rivera, Nelson A; Mueller, Karl T; Vairavamurthy, Murthy A; Seraphin, Supapan; Chorover, Jon

    2006-04-15

    Radioactive strontium (90Sr) is an important constituent of the complex wastes from past nuclear weapons production and has been stored in underground tanks at U.S. DOE sites (e.g., Hanford, WA). Using bulk and microfocused EXAFS spectroscopy, we examined temporal changes in solid-phase Sr speciation in kaolinite samples reacted for 1-369 d with high-pH, high ionic strength synthetic tank-waste leachate containing Sr(2+) and Cs(+) at 10(-3) mol kg(-1). Analyses of bulk EXAFS spectra showed that Sr initially forms a precipitate by 7 d with a local structure similar to SrCO(3-) (s). At 33 d, microfocused EXAFS of individual particles in one sample revealed a mixture of hydrated and dehydrated Sr associated with neoformed sodalite-type phases. At aging times of 93 d and longer, bulk EXAFS spectra and supporting characterizations indicated nonexchangeable Sr with a local structure consistent with incorporation into increasingly crystalline aluminosilicate particles, particularly sodalite. These experimental studies suggest that irreversible trapping of radionuclides occurs if they are present during the formation and aging of feldspathoid alteration products of local Si-bearing sediment minerals. This may serve as an effective contaminant sequestration mechanism at sites such as Hanford.

  15. Structural, Optical and EXAFS Studies of Nickel Substituted Copper Ferrites Nano-Particle by Sol-Gel Auto Combustion Method

    Science.gov (United States)

    Mishra, Ashutosh; khan, Mehjabeen; Jarabana, Kanaka M.; Bisen, Supriya

    2016-10-01

    The Cu-Ni ferrites with general formula Cu1-xNixFe2O4 (where x=0.0, 0.1, 0.2, 0.3) were prepared by sol gel method. The Extended X-ray absorption fine structure (EXAFS), X- ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) measurements were carried out. EXAFS spectra have been recorded at the k edge of Iron using the dispersive EXAFS (DEXAFS) beam line at 2.5 GeV at Indus -2 synchrotron radiation source RRCAT, Indore, India. The EXAFS data have been analyzed using the computer software Athena. These have been used to determine the bond lengths in these ferrites with the help of three different methods, namely, Levy's, Lytle's and Lytle, Sayers and Stern's (LSS) methods. The phase uncorrected bond lengths have also been obtained from Fourier transformation method and the results obtained have been compared with the results obtained from LSS method, which also gives phase uncorrected bond lengths. XRD shows the structure is the tetragonal, and FTIR was used to determine the nature of the vibrational modes present in the system.

  16. REDOX state analysis of platinoid elements in simulated high-level radioactive waste glass by synchrotron radiation based EXAFS

    Science.gov (United States)

    Okamoto, Yoshihiro; Shiwaku, Hideaki; Nakada, Masami; Komamine, Satoshi; Ochi, Eiji; Akabori, Mitsuo

    2016-04-01

    Extended X-ray Absorption Fine Structure (EXAFS) analyses were performed to evaluate REDOX (REDuction and OXidation) state of platinoid elements in simulated high-level nuclear waste glass samples prepared under different conditions of temperature and atmosphere. At first, EXAFS functions were compared with those of standard materials such as RuO2. Then structural parameters were obtained from a curve fitting analysis. In addition, a fitting analysis used a linear combination of the two standard EXAFS functions of a given elements metal and oxide was applied to determine ratio of metal/oxide in the simulated glass. The redox state of Ru was successfully evaluated from the linear combination fitting results of EXAFS functions. The ratio of metal increased at more reducing atmosphere and at higher temperatures. Chemical form of rhodium oxide in the simulated glass samples was RhO2 unlike expected Rh2O3. It can be estimated rhodium behaves according with ruthenium when the chemical form is oxide.

  17. X-ray powder diffraction and EXAFS studies on SnAPO-5 and Cu : SnAPO-5

    DEFF Research Database (Denmark)

    Flavell, W. R.; Nicholson, D. G.; Nilsen, M. H.;

    2001-01-01

    SnAPO-5 was synthesised and calcined at 800 degreesC. Copper was introduced into the calcined material by the incipient wetness method. The as-synthesised, calcined and copper-incorporated SnAPO-5 have been studied using X-ray powder diffraction and EXAFS. Rietveld refinements show that the overa...

  18. The time-resolved and extreme conditions XAS (TEXAS) facility at the European Synchrotron Radiation Facility: the general-purpose EXAFS bending-magnet beamline BM23

    Energy Technology Data Exchange (ETDEWEB)

    Mathon, O., E-mail: mathon@esrf.fr; Beteva, A.; Borrel, J.; Bugnazet, D.; Gatla, S.; Hino, R.; Kantor, I.; Mairs, T. [European Synchrotron Radiation Facility, CS 40220, 38043 Grenoble Cedex 9 (France); Munoz, M. [European Synchrotron Radiation Facility, CS 40220, 38043 Grenoble Cedex 9 (France); Université Joseph Fourier, 1381 rue de la Piscine, BP 53, 38041 Grenoble Cedex 9 (France); Pasternak, S.; Perrin, F.; Pascarelli, S. [European Synchrotron Radiation Facility, CS 40220, 38043 Grenoble Cedex 9 (France)

    2015-10-17

    BM23 is the general-purpose EXAFS bending-magnet beamline at the ESRF, replacing the former BM29 beamline in the framework of the ESRF upgrade. Its mission is to serve the whole XAS user community by providing access to a basic service in addition to the many specialized instruments available at the ESRF. BM23 offers high-signal-to-noise ratio EXAFS in a large energy range (5–75 keV), continuous energy scanning for quick-EXAFS on the second timescale and a micro-XAS station delivering a spot size of 4 µm × 4 µm FWHM. BM23 is the general-purpose EXAFS bending-magnet beamline at the ESRF, replacing the former BM29 beamline in the framework of the ESRF upgrade. Its mission is to serve the whole XAS user community by providing access to a basic service in addition to the many specialized instruments available at the ESRF. BM23 offers high signal-to-noise ratio EXAFS in a large energy range (5–75 keV), continuous energy scanning for quick-EXAFS on the second timescale and a micro-XAS station delivering a spot size of 4 µm × 4 µm FWHM. It is a user-friendly facility featuring a high degree of automation, online EXAFS data reduction and a flexible sample environment.

  19. EXAFS and XRD characterization of palladium sorbents for high temperature mercury capture from fuel gas.

    Science.gov (United States)

    Poulston, Stephen; Hyde, Timothy I; Hamilton, Hugh; Mathon, Olivier; Prestipino, Carmelo; Sankar, Gopinathan; Smith, Andrew W J

    2010-01-14

    Removal of pollutants such as mercury at elevated temperatures provides improvements in the overall thermal efficiency during the process of coal gasification. The two high temperature sorbents studied were 5 wt% Pd/Al(2)O(3) and 5 wt% Pd/SiO(2): materials shown to have significantly different Hg adsorption capacities. A combination of XRD and EXAFS has been used to characterize the Pd-Hg alloy formed when these Pd-based sorbents were exposed to fuel gas (CO, CO(2), H(2)) containing Hg vapour at 204 degrees C. Significant differences were found in the nature of the alloy formed on the two sorbents following Hg exposure. The Pd/Al(2)O(3) sorbent produced a single homogeneous solid solution of Pd-Hg whilst the silica-supported Pd produced an alloy of varying composition.

  20. Improving Resolution in k and r Space: A FEFF-based Wavelet for EXAFS Data Analysis

    Science.gov (United States)

    Funke, H.; Chukalina, M.; Voegelin, A.; Scheinost, A. C.

    2007-02-01

    Applying a wavelet analysis based on the Morlet mother function, we previously demonstrated the presence of both Al and Zn atoms in the first metal shell (r ≈ 3 Å from the central Zn atom) of Zn-Al layered double hydroxide (LDH). However, this approach was not suited to resolve the second and third metal shells (r ≈ 5 - 6 Å) in r and k space independently. Therefore, we developed a new FEFF-Morlet wavelet, where the EXAFS function itself, extracted from the FEFF model, is combined with the complex Morlet wavelet. With this method, we were able to distinguish the second metal shell (Zn atoms only) from the third metal shell (Zn and Al atoms), thereby proving a regular, dioctahedral distribution of Zn atoms in the hydroxide layers.

  1. Lattice Instability in High Temperature Superconducting Cuprates and FeAs Systems: Polarons Probed by EXAFS

    Directory of Open Access Journals (Sweden)

    H. Oyanagi

    2010-01-01

    Full Text Available Carrier-induced lattice distortion (signature of polaron in oxypnictide superconductors is found by an instantaneous local probe, extended X-ray absorption fine structure (EXAFS. Polaron formation is detected as two distinct nearest neighbor distances (Fe-As, implying an incoherent local mode that develops coherence at the critical temperature. Comparing the results with the unusual lattice response in cuprate superconductors, intimate correlation between evolution of local lattice mode and superconductivity is revealed. The results suggest that strong electron-lattice interaction is present as a common ingredient in the microscopic mechanism of superconducting transition. The effect of magnetic impurity atoms in cuprates further indicates that magnetic scattering becomes diluted as long as polaron formation is conserved. We argue that polaron coherence dominates electrical conduction and magnetic interaction in oxypnictide and cuprate superconductors.

  2. Characterization of nanocrystalline Pd by x-ray diffraction and EXAFS

    Energy Technology Data Exchange (ETDEWEB)

    Eastman, J.A. (Argonne National Lab., IL (USA)); Fitzsimmons, M.R.; Mueller-Stach, M.; Wallner, G. (Ludwig-Maximilians-Universitaet, Munich (Germany, F.R.)); Elam, W.T. (Naval Research Lab., Washington, DC (USA))

    1990-12-01

    Since the fraction of atoms located within a few atomic distances of one or more internal interfaces increases rapidly with decreasing grain size in the nanometer regime, it is expected that the structure of grain boundaries plays an important role in determining and controlling the properties of nanocrystalline materials. A high resolution electron microscopy study of nanocrystalline Pd found no evidence for extended, disordered boundary regions that would differ from boundaries in coarse-grained materials. Recent results from x-ray diffraction, EXAFS and hydriding studies have yielded clear evidence that the boundaries in nanocrystalline Pd are ordered and/or extremely localized in nature. The present paper will summarize and discuss the principal results of these three studies. 12 refs., 4 figs.

  3. Colloidal diatomite, radionickel, and humic substance interaction: a combined batch, XPS, and EXAFS investigation.

    Science.gov (United States)

    Sheng, Guodong; Shen, Runpu; Dong, Huaping; Li, Yimin

    2013-06-01

    This work determined the influence of humic acid (HA) and fulvic acid (FA) on the interaction mechanism and microstructure of Ni(II) onto diatomite by using batch experiments, X-ray photoelectron spectroscopy (XPS), and extended X-ray absorption fine structure (EXAFS) methods. Macroscopic and spectroscopic experiments have been combined to see the evolution of the interaction mechanism and microstructure of Ni(II) in the presence of HA/FA as compared with that in the absence of HA/FA. The results indicated that the interaction of Ni(II) with diatomite presents the expected solution pH edge at 7.0, which is modified by addition of HA/FA. In the presence of HA/FA, the interaction of Ni(II) with diatomite increased below solution pH 7.0, while Ni(II) interaction decreased above solution pH 7.0. XPS analysis suggested that the enrichment of Ni(II) onto diatomite may be due to the formation of (≡SO)2Ni. EXAFS results showed that binary surface complexes and ternary surface complexes of Ni(II) can be simultaneously formed in the presence of HA/FA, whereas only binary surface complexes of Ni(II) are formed in the absence of HA/FA, which contribute to the enhanced Ni(II) uptake at low pH values. The results observed in this work are important for the evaluation of Ni(II) and related radionuclide physicochemical behavior in the natural soil and water environment.

  4. Molecular dynamics and reverse Monte Carlo modeling of scheelite-type AWO4 (A = Ca, Sr, Ba) W L 3-edge EXAFS spectra

    Science.gov (United States)

    Kalinko, Aleksandr; Bauer, Matthias; Timoshenko, Janis; Kuzmin, Alexei

    2016-11-01

    Classical molecular dynamics (MD) and reverse Monte Carlo methods coupled with ab initio multiple-scattering extended x-ray absorption fine structure (EXAFS) calculations were used for modeling of scheelite-type AWO4 (A = Ca, Sr, Ba) W L 3-edge EXAFS spectra. The two theoretical approaches are complementary and allowed us to perform analysis of full EXAFS spectra. Both methods reproduce well the structure and dynamics of tungstates in the outer coordination shells, however the classical MD simulations underestimate the W-O bond MSRD due to a neglect of quantum zero-point-motion. The thermal vibration amplitudes, correlation effects and anisotropy of the tungstate structure were also estimated.

  5. Synchrotron Micro-XANES Measurements of Vanadium Oxidation State in Glasses as a Function of Oxygen Fugacity: Experimental Calibration of Data Relevant to Partition Coefficient Determination

    Science.gov (United States)

    Delaney, J. S.; Sutton, S. R.; Newville, M.; Jones, J. H.; Hanson, B.; Dyar, M. D.; Schreiber, H.

    2000-01-01

    Oxidation state microanalyses for V in glass have been made by calibrating XANES spectral features with optical spectroscopic measurements. The oxidation state change with fugacity of O2 will strongly influence partitioning results.

  6. A XANES and Raman investigation of sulfur speciation and structural order in Murchison and Allende meteorites

    Science.gov (United States)

    Bose, M.; Root, R. A.; Pizzarello, S.

    2017-03-01

    Insoluble organic matter (IOM) and hydrothermally treated IOM extracted from two carbonaceous chondrites, Murchison and Allende, was studied using sulfur K-edge XANES (X-ray absorption near edge structure) and μ-Raman spectroscopy, with the aim to understand their IOM's sulfur speciation and structural order, and how aqueous alteration or thermal metamorphism may have transformed these materials. We found that the sulfur-functional group chemistry of both the Murchison IOM and hydrothermally treated IOM samples have a large chemical variability ranging from oxidation states of S-2 to S+6, and exhibit a transformation in their oxidation state after the hydrothermal treatment (HT) to produce thiophenes and thiol compounds. Sulfoxide and sulfite peaks are also present in Murchison. Sulfates considered intrinsic to Murchison are most likely preaccretionary in nature, and not a result of reactions with water at high temperatures on the asteroid parent body. We argue that the reduced sulfides may have formed in the CM parent body, while the thiophenes and thiol compounds are a result of the HT. Micro-Raman spectra show the presence of aliphatic and aromatic moieties in Murchison's material as observed previously, which exhibits no change after HT. Because the Murchison IOM was modified, as seen by XANES analysis, absence of a change observed using micro-Raman indicated that although the alkyl carbons of IOM were cleaved, the aromatic network was not largely modified after HT. By contrast, Allende IOM contains primarily disulfide and elemental sulfur, no organic sulfur, and shows no transformation after HT. This nontransformation of Allende IOM after HT would indicate that parent body alteration of sulfide to sulfate is not feasible up to temperatures of 300°C. The reduced sulfur products indicate extreme secondary chemical processing from the precursor compounds in its parent body at temperatures as high as 624°C, as estimated from μ-Raman D band parameters. The

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

    Energy Technology Data Exchange (ETDEWEB)

    Rajan, M.; Darrow, J.; Hua, M.; Barnett, B.; Mendoza, M.; Greenfield, B.K.; Andrews, J.C.

    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 were 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 more

  8. Quantification of chemical sulphur species in bulk soil and organic sulphur fractions by S K-edge Xanes spectroscopy

    DEFF Research Database (Denmark)

    Boye, K; Almkvist, G; Nilsson, S I

    2011-01-01

    A new data treatment method for fitting spectra obtained by sulphur (S) K-edge X-ray absorption near-edge structure (XANES) spectroscopy was used to quantify the chemical S speciation at three experimental sites with arable soils receiving the same long-term field treatments. Two treatments, crop...... the opposite trend was observed. Sulphur XANES spectroscopy of acetylacetone extracts of physically protected and unprotected organic S in two of the soils revealed that physical protection was not related to S speciation; however, intermediate forms of oxidized S species appeared to accumulate in the residual...... enhanced the reliability of quantitative determination of contributing S species in soil samples and soil extracts. The results indicated that long-term FYM application shifted S species composition from highly oxidized towards intermediate oxidization in two of the soils, but in the third soil...

  9. The electronic structure of homogeneous ferromagnetic (Ga, Mn)N epitaxial films

    Energy Technology Data Exchange (ETDEWEB)

    Piskorska-Hommel, E., E-mail: e.piskorska@int.pan.wroc.pl [Institute of Low Temperature and Structure Research, Polish Academy of Sciences, Institute W. Trzebiatowski, Wroclaw (Poland); Institute of Solid State Physics, University of Bremen, Bremen (Germany); Winiarski, M. J. [Institute of Low Temperature and Structure Research, Polish Academy of Sciences, Institute W. Trzebiatowski, Wroclaw (Poland); Kunert, G.; Falta, J. [Institute of Solid State Physics, University of Bremen, Bremen (Germany); Demchenko, I. N. [Institute of Physic, Polish Academy of Sciences, Warsaw (Poland); Roshchupkina, O. D.; Grenzer, J. [Helmholtz-Zentrum Dresden-Rossendorf, Institute of Ion Beam Physics and Materials Research, Bautzner Landstraße 400, 01328 Dresden (Germany); Hommel, D. [Institute of Solid State Physics, University of Bremen, Bremen (Germany); Wrocław Research Center EIT+ Sp. z o.o., Wroclaw (Poland); Experimental Physics, University of Wroclaw, Wroclaw (Poland); Holý, V. [Department of Condensed Matter Physics, Faculty of Mathematics and Physics, Charles University in Prague, Praha (Czech Republic)

    2015-02-14

    X-ray Absorption Fine Structure (XAFS) techniques, namely, X-ray Near Edge Structure (XANES), Extended XAFS (EXAFS), and Anomalous X-ray Diffraction (AXRD) were used to investigate the local atomic and electronic structure of (Ga, Mn)N magnetic layers with Mn concentrations of up to 10% grown by Molecular Beam Epitaxy. The XANES and AXRD analysis prove the Mn incorporation on substitutional GaN lattice sites. EXAFS results indicate the good quality of the structure under examination, although 0.5 nitride atom vacancies were found. The Wien2k code was applied to interpret the XANES spectra quantitatively, i.e., to determine the electronic structure of the Mn atoms. It was shown that accounting for the core-hole effect is necessary to reconstruct effectively the XANES spectra. Conducted charge density analysis based on DFT calculations identified the valency of Mn atom to be of 2.4+.

  10. Sulfur K-edge XANES for methylene blue in photocatalytic reaction over WO{sub 3} nanomaterials

    Energy Technology Data Exchange (ETDEWEB)

    Komori, K. [Graduate School of Engineering, Nagoya University, Nagoya 464-8603 (Japan); Yoshida, T. [EcoTopia Science Institute, Nagoya University, Nagoya 464-8603 (Japan); Nomoto, T. [Aichi Synchrotron Radiation Center, 250-3, Minamiyamaguchi-cho, Seto 489-0965 (Japan); Yamamoto, M.; Tsukada, C. [Graduate School of Engineering, Nagoya University, Nagoya 464-8603 (Japan); Yagi, S. [EcoTopia Science Institute, Nagoya University, Nagoya 464-8603 (Japan); Yajima, M. [Graduate School of Engineering, Nagoya University, Nagoya 464-8603 (Japan); Kajita, S. [EcoTopia Science Institute, Nagoya University, Nagoya 464-8603 (Japan); Ohno, N. [Graduate School of Engineering, Nagoya University, Nagoya 464-8603 (Japan)

    2015-12-15

    We investigated the photocatalysis of dendritic nanostructured WO{sub 3}/W composite materials fabricated by He plasma irradiation to tungsten plates, followed by the surface oxidation. The samples promoted the decolorization reaction of methylene blue (MB) aqueous solution under near infrared (NIR) light irradiation. To verify the MB molecule is actually decomposed by the photocatalysis of the samples, reaction products were analyzed by S K-edge XANES measurements for the MB solution kept with the samples under the light irradiation or in the dark. By the light irradiation, the σ{sup *}(S–C) peak in the XANES spectra reduced and a new peak originated from SO{sub 4}{sup 2−} species was clearly observed, suggesting that S–C bonds in a MB molecule are broken by the NIR light irradiation and finally the sulfur species exists in the solution in the state of SO{sub 4}{sup 2−} ion. After the adsorption reaction in the dark, the XANES spectra of the sample surfaces showed a sharp π{sup *}(S–C) peaks, indicating that MB molecules are adsorbed on the sample surfaces and stacked each other by the π–π interaction. These results demonstrate that the photocatalytic decomposition of MB molecules really proceeds over WO{sub 3}/W composite materials even under NIR light irradiation.

  11. On the origin of the differences in the Cu K-edge XANES of isostructural and isoelectronic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Sipr, O [Institute of Physics, Academy of Sciences of the Czech Republic, Cukrovarnicka 10, CZ-162 53 Prague (Czech Republic); Rocca, F [IFN-CNR, Istituto di Fotonica e Nanotecnologie del Consiglio Nazionale delle Ricerche, Sezione ' FBK-CeFSA' di Trento, Via alla Cascata 56/C, I-38123 Povo (Trento) (Italy); Fornasini, P [Dipartimento di Fisica, Universita di Trento, Via Sommarive 14, I-38123 Povo (Trento) (Italy)], E-mail: sipr@fzu.cz

    2009-06-24

    Cu K-edge x-ray absorption near-edge structure (XANES) spectra of trigonal (3R) CuScO{sub 2} and CuLaO{sub 2} and of hexagonal (2H) CuScO{sub 2} were investigated experimentally and theoretically, in order to study differences between spectra of isostructural and isoelectronic compounds. Significant differences were found in the Cu K-edge XANES of 3R CuScO{sub 2} and 3R CuLaO{sub 2}; these differences can be understood by considering the calculated polarization dependence of the XANES spectra and the differences between the phaseshifts of Sc and La. Spectra of the 3R and 2H polytypes of CuScO{sub 2} differ only weakly and the difference originates from the long-range order. The pre-edge peak around 8980 eV is generated by the same mechanism as the pre-edge peak in Cu{sub 2}O, i.e. involving scattering by the Cu atoms in the plane which is perpendicular to the O-Cu-O axis.

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

    Science.gov (United States)

    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.

  13. On the origin of the differences in the Cu K-edge XANES of isostructural and isoelectronic compounds.

    Science.gov (United States)

    Sipr, O; Rocca, F; Fornasini, P

    2009-06-24

    Cu K-edge x-ray absorption near-edge structure (XANES) spectra of trigonal (3R) CuScO(2) and CuLaO(2) and of hexagonal (2H) CuScO(2) were investigated experimentally and theoretically, in order to study differences between spectra of isostructural and isoelectronic compounds. Significant differences were found in the Cu K-edge XANES of 3R CuScO(2) and 3R CuLaO(2); these differences can be understood by considering the calculated polarization dependence of the XANES spectra and the differences between the phaseshifts of Sc and La. Spectra of the 3R and 2H polytypes of CuScO(2) differ only weakly and the difference originates from the long-range order. The pre-edge peak around 8980 eV is generated by the same mechanism as the pre-edge peak in Cu(2)O, i.e. involving scattering by the Cu atoms in the plane which is perpendicular to the O-Cu-O axis.

  14. XANES analysis of tribochemical and thermal films generating from some organic polysulfides

    Institute of Scientific and Technical Information of China (English)

    YI Hongling; ZENG Xiangqiong; CAO Yan; REN Tianhui; M. Kasrai; G. M. Bancroft

    2006-01-01

    X-ray absorption near edge structure (XANES) spectroscopy has been firstly used to characterize the chemical nature of tribochemical and thermal films generated from alkyl, benzyl and acylcontaining organic polysulfides. It has been found that the thermal films generated from these polysulfides are mainly composed of FeSO4, and alkyl disulfides also exist in the subsurface and bulk of thermal films generated from acyl-containing polysulfides. Under tribochemical conditions, the composition of film is dependent on the molecular structure of the additives.Namely, the tribochemical film generated from alkyl polysulfide is composed of alkyl disulfide in the out surface, a mixture of FeSO4, FeS2 and sulfoxide in the subsurface, and FeSO4 in the bulk; the composition of the tribochemical film for benzyl polysulfide consists of FeSO4 in the out surface, while the composition in subsurface and bulk is the same as the alkyl polysulfide. For acyl-containing polysulfides, the tribochemical films consist of alkyl disulfide in the out surface, and FeS2 in the subsurface and bulk.

  15. Environmental impacts of steel slag reused in road construction: a crystallographic and molecular (XANES) approach.

    Science.gov (United States)

    Chaurand, Perrine; Rose, Jerome; Briois, Valérie; Olivi, Luca; Hazemann, Jean-Louis; Proux, Olivier; Domas, Jérémie; Bottero, Jean-Yves

    2007-01-31

    Basic oxygen furnace (BOF) steel slag is a residue from the basic oxygen converter in steel-making operations, and is partially reused as an aggregate for road constructions. Although BOF slag is an attractive building material, its long-term behaviour and the associated environmental impacts must be taken into account. Indeed BOF slag is mainly composed of calcium, silicon and iron but also contains trace amounts of potential toxic elements, specifically chromium and vanadium, which can be released. The present research focuses (i) on the release of Cr and V during leaching and (ii) on their speciation within the bearing phase. Indeed the mobility and toxicity of heavy metals strongly depend on their speciation. Leaching tests show that only low amounts of Cr, present at relatively high concentration in steel slag, are released while the release of V is significantly high. X-ray absorption near-edge structure (XANES) spectroscopy indicates that Cr is present in the less mobile and less toxic trivalent form and that its speciation does not evolve during leaching. On the contrary, V which is predominantly present in the 4+ oxidation state seems to become oxidized to the pentavalent form (the most toxic form) during leaching.

  16. FORMATION OF CHROMATE CONVERSION COATINGS ON ALUMINUM AND ITS ALLOYS: AN IN SITU XANES STUDY.

    Energy Technology Data Exchange (ETDEWEB)

    SASAKI,K.; ISAACS,H.S.; JAFFCOATE,C.S.; BUCHHAIT,R.; LEGAT,V.; LEE,H.; SRINIVASAMURTHI,V.

    2001-09-02

    We used in situ X-ray adsorption near-edge structure (XANES) to investigate the formation of chromate conversion coatings on pure Al, commercial Al alloys (AA 1100, AA2024, and AA7075), and a series of binary Al-Cu alloys. The method employed a new electrochemical cell that can determine the ratio of hexavalent chromium (Cr(VI)) to total chromium (Cr(total)) speciation in conversion coatings as a function of exposure time to a chromate solution. The spectra showed that the initial Cr(VI)/Cr(total) ratios are greater than later ones for pure Al and AA1100, but not for AA2024 and AA7075. Measurements with Al-Cu alloys demonstrated that the difference observed in AA2024 and AA7075 may not be due to Cu alloying. The proportion of Cr(VI) in the coatings becomes approximately constant after 180 s of exposure for all the specimens examined even though the coatings continue to grow.

  17. Environmental impacts of steel slag reused in road construction: A crystallographic and molecular (XANES) approach

    Energy Technology Data Exchange (ETDEWEB)

    Chaurand, Perrine [CEREGE, UMR 6635 CNRS, University Paul Cezanne, IFR 112 PMSE, Europole Mediterraneen de l' Arbois, BP 80, 13545 Aix en Provence Cedex 04 (France)]. E-mail: chaurand@cerege.fr; Rose, Jerome [CEREGE, UMR 6635 CNRS, University Paul Cezanne, IFR 112 PMSE, Europole Mediterraneen de l' Arbois, BP 80, 13545 Aix en Provence Cedex 04 (France); Briois, Valerie [LURE Laboratoire pour l' Utilisation du Rayonnement Electromagnetique, Universite Paris-Sud, Orsay (France); Olivi, Luca [Sincrotrone Trieste S.C.p.A. S.S., 14 Km 163.5, 34012 Basovizza Trieste (Italy); Hazemann, Jean-Louis [Laboratoire de Cristallographie, BP 166, 38042 Grenoble Cedex 09 (France); Proux, Olivier [Laboratoire de Geophysique Interne et de Tectonophysique, UMR CNRS Universite Joseph Fourier, 1381 rue de la piscine, Domaine Universitaire, 38400 St Martin d' Heres (France); Domas, Jeremie [INERIS, Domaine du petit Arbois, Batiment Laennec, BP 33, 13545 Aix en Provence Cedex 04 (France); Bottero, Jean-Yves [CEREGE, UMR 6635 CNRS, University Paul Cezanne, IFR 112 PMSE, Europole Mediterraneen de l' Arbois, BP 80, 13545 Aix en Provence Cedex 04 (France)

    2007-01-31

    Basic oxygen furnace (BOF) steel slag is a residue from the basic oxygen converter in steel-making operations, and is partially reused as an aggregate for road constructions. Although BOF slag is an attractive building material, its long-term behaviour and the associated environmental impacts must be taken into account. Indeed BOF slag is mainly composed of calcium, silicon and iron but also contains trace amounts of potential toxic elements, specifically chromium and vanadium, which can be released. The present research focuses (i) on the release of Cr and V during leaching and (ii) on their speciation within the bearing phase. Indeed the mobility and toxicity of heavy metals strongly depend on their speciation. Leaching tests show that only low amounts of Cr, present at relatively high concentration in steel slag, are released while the release of V is significantly high. X-ray absorption near-edge structure (XANES) spectroscopy indicates that Cr is present in the less mobile and less toxic trivalent form and that its speciation does not evolve during leaching. On the contrary, V which is predominantly present in the 4+ oxidation state seems to become oxidized to the pentavalent form (the most toxic form) during leaching.

  18. Chemical ordering in Pd$_{81}$Ge$_{19}$ metallic glass studied by reverse Monte-Carlo modelling of XRD, ND and EXAFS experimental data

    CERN Document Server

    Pethes, Ildikó; Stoica, Mihai; Beuneu, Brigitte; Jóvári, Pál

    2016-01-01

    Pd$_{81}$Ge$_{19}$ metallic glass was investigated by neutron diffraction, X-ray diffraction and extended X-ray absorption fine structure spectroscopy (EXAFS) at the Ge K-edge. Large scale structural models were obtained by fitting the three measurements simultaneously in the framework of the reverse Monte Carlo simulation technique. It was found that the experimental data sets can be adequately fitted without Ge-Ge nearest neighbours. Mean Pd-Pd and Pd-Ge distances are 2.80$\\pm$0.02 {\\AA} and 2.50$\\pm$0.02 {\\AA}, respectively. The total average coordination number of Pd is 12.1$\\pm$0.5 while Ge is surrounded by 10.6$\\pm$1.1 Pd atoms. The coordination numbers calculated from partial pair correlation functions were compared to those obtained by Voronoi tessellation method. It was found that the latter technique overestimates the number of nearest neighbours by about 20% due to the significant contribution of distant pairs.

  19. Surface chemistry of ferrihydrite: Part 1. EXAFS studies of the geometry of coprecipitated and adsorbed arsenate

    Science.gov (United States)

    Waychunas, G. A.; Rea, B. A.; Fuller, C. C.; Davis, J. A.

    1993-05-01

    EXAFS spectra were collected on both the As and Fe K-edges from samples of two-line ferrihydrite with adsorbed (ADS) and coprecipitated (CPT) arsenate prepared over a range of conditions and arsenate surface coverages. Spectra also were collected for arsenate adsorbed on the surfaces of three FeOOH crystalline polymorphs, α (goethite), β (akaganeite), and γ (lepidocrocite), and as a free ion in aqueous: solution. Analyses of the As EXAFS show clear evidence for inner sphere bidentate (bridging) arsenate complexes on the ferrihydrite surface and on the surfaces of the crystalline FeOOH polymorphs. The bridging arsenate is attached to adjacent apices of edge-sharing Fe oxyhydroxyl octahedra. The arsenic-iron distance at the interface ( 3.28 ±0.01 Å) is close to that expected for this geometry on the FeOOH polymorph surfaces, but is slightly shorter on the ferrihydrite surfaces ( 3.25 ± 0.02 Å). Mono-dentate arsenate linkages ( 3.60 ± 0.03 Å) also occur on the ferrihydrite, but are not generally observed on the crystalline FeOOH polymorphs. The proportion of monodentate bonds appears largest for adsorption samples with the smallest As/Fe molar ratio. In all cases the arsenate tetrahedral complex is relatively undistorted with As-O bonds of 1.66 ± 0.01 Å. Precipitation of arsenate or scorodite-like phases was not observed for any samples, all of which were prepared at a pH value of 8. The Fe EXAFS results confirm that the Fe-Fe correlations in the ferrihydrite are progressively disrupted in the CPT samples as the As/Fe ratio is increased. Coherent crystallite size is probably no more than 10 Å in diameter and no Fe oxyhydroxyl octahedra corner-sharing linkages (as would be present in FeOOH polymorphs) are observed at the largest As/Fe ratios. Comparison of the number and type of Fe-Fe neighbors with the topological constraints imposed by the arsenate saturation limit in the CPT samples (about 0.7 As/Fe) indicates ferrihydrite units consisting mainly of Fe

  20. EXAFS study on solute precipitation in FeCu alloy induced by energetic electron bombardments and thermal aging

    Energy Technology Data Exchange (ETDEWEB)

    Fujimura, Y., E-mail: su110030@edu.osakafu-u.ac.jp [Department of Materials Science, Osaka Prefecture University, Sakai, Osaka 599-8531 (Japan); Yoshizaki, H.; Nakagawa, Shou [Department of Materials Science, Osaka Prefecture University, Sakai, Osaka 599-8531 (Japan); Okamoto, Y. [Quantum Beam Science Center, Japan Atomic Energy Agency, Tokai, Ibaraki 319-1195 (Japan); Ishikawa, N. [Nuclear Science and Engineering Center, Japan Atomic Energy Agency, Tokai, Ibaraki 319-1195 (Japan); Saitoh, Y. [Takasaki Advanced Radiation Research Institute, Japan Atomic Energy Agency, Takasaki, Gumma 370-1292 (Japan); Hori, F.; Iwase, A. [Department of Materials Science, Osaka Prefecture University, Sakai, Osaka 599-8531 (Japan)

    2015-07-01

    The extended X-ray absorption fine structure (EXAFS) measurement is a useful tool for the observation of local atomic arrangements around selected atoms. We performed EXAFS measurements for the electron-irradiated and the thermally-aged Fe–0.6 wt.% Cu alloy and compared the experimental result with that of the simulation by the FEFF simulation code in order to investigate the local atomic structure around Cu atoms. Cu precipitates which were produced by the thermal aging at 773 K transformed from the bcc structure to the fcc structure as the precipitates grow large enough. However, for electron-irradiated specimens, although the hardness greatly increased, the transformation of Cu precipitates from the bcc to the fcc structure was not clearly confirmed. This result indicates that small sized Cu precipitates which had the bcc structure were produced by the electron irradiation and they could hardly coarsen during the irradiation.

  1. EXAFS study on solute precipitation in FeCu alloy induced by energetic electron bombardments and thermal aging

    Science.gov (United States)

    Fujimura, Y.; Yoshizaki, H.; Nakagawa, Shou; Okamoto, Y.; Ishikawa, N.; Saitoh, Y.; Hori, F.; Iwase, A.

    2015-07-01

    The extended X-ray absorption fine structure (EXAFS) measurement is a useful tool for the observation of local atomic arrangements around selected atoms. We performed EXAFS measurements for the electron-irradiated and the thermally-aged Fe-0.6 wt.% Cu alloy and compared the experimental result with that of the simulation by the FEFF simulation code in order to investigate the local atomic structure around Cu atoms. Cu precipitates which were produced by the thermal aging at 773 K transformed from the bcc structure to the fcc structure as the precipitates grow large enough. However, for electron-irradiated specimens, although the hardness greatly increased, the transformation of Cu precipitates from the bcc to the fcc structure was not clearly confirmed. This result indicates that small sized Cu precipitates which had the bcc structure were produced by the electron irradiation and they could hardly coarsen during the irradiation.

  2. EXAFS studies on Gd-doped ZrO2 thin films deposited by RF magnetron sputtering.

    Science.gov (United States)

    Maidul Haque, S; Tripathi, S; Jha, S N; Bhattacharyya, D; Sahoo, N K

    2016-09-10

    ZrO2 thin films with 0%, 7%, 9%, 11%, and 13% Gd doping have been prepared by RF magnetron sputtering and have been characterized by grazing incidence x-ray diffraction, spectroscopic ellipsometry, and optical transmission measurements to probe their structural and optical properties. Extended x-ray absorption fine structure (EXAFS) measurements have also been carried out on the samples at the Zr K- and Gd L3-edges. It has been observed that Gd goes to Zr sites up to 9%-11% doping concentration, and for Gd doping concentrations beyond 11%, Gd precipitates out as a separate Gd2O3 phase. The local structure information surrounding the Zr and Gd sites obtained from the analysis of the EXAFS studies have also been used to explain the macroscopic optical properties of the samples.

  3. EXAFS Studies of (Pb,Cd) 1212 phase superconductor and (Bi,Cd)1212 phase compound

    Institute of Scientific and Technical Information of China (English)

    YeTao; ShiqiangWei; 等

    1999-01-01

    We synthesized (Pb,Cd)Sr2(Y,Ca)Cu2O7+x,phase superconductor.After substitution of Pb with Bi,the BiCd1212 phase shows no superconductivity.Although previous EXAFS study has shown the local structure environment of the Cu is similar in both compounds,EXAFS results of Bi and Pb here demonstrate that σ2 of Pb-Oin-plane is larger than that of Bi-O inplane,whereas σ2 of Pb-Oapical is smaller than that of Bi-O,wherase σ2 of Pb-O apical is smaller than that of Bi-Oapical.The Sr shell features are also differnet,it appeared that superconductivity needs some disorder .in carrier reservoir layer,which is due to the substitutional defect caused by different ionic radii.

  4. EXAFS and X-ray diffraction study of LaCoO3 across the spin-state transition

    Science.gov (United States)

    Sikolenko, V. V.; Troyanchuk, I. O.; Efimov, V. V.; Efimova, E. A.; Tiutiunnikov, S. I.; Karpinsky, D. V.; Pascarelli, S.; Zaharko, O.; Ignatov, A.; Aquilanti, D.; Selutin, A. G.; Shmakov, A. N.; Prabhakaran, D.

    2016-05-01

    A combined high-resolution Co K-edge extended x-ray absorption fine structure (EXAFS) and high-resolution X-ray powder diffraction (XRD) study has been performed to clarify the detail of anomalous behavior of temperature-dependent magnetic susceptibility curve on the LaCoO3 across the spin-state (∼120 K) transition. According to XRD analysis, the Debye-Waller factor of Co-O bond exhibit rapid growth below 20 K whereas the temperature dependence of the average Co-O bond length shows linear behavior from 10 K to 400 K. The EXAFS data show an anomalous decrease of the Co-O bond lengths with respect to those obtained by XRD. No local distortion of CoO6 octahedral as temperature increases up to 400 K has been detected.

  5. Combined EXAFS Spectroscopic and Quantum Chemical Study on the Complex Formation of Am(III) with Formate.

    Science.gov (United States)

    Fröhlich, Daniel R; Kremleva, Alena; Rossberg, André; Skerencak-Frech, Andrej; Koke, Carsten; Krüger, Sven; Rösch, Notker; Panak, Petra J

    2017-06-19

    The complexation of Am(III) with formate in aqueous solution is studied as a function of the pH value using a combination of extended X-ray absorption fine structure (EXAFS) spectroscopy, iterative transformation factor analysis (ITFA), and quantum chemical calculations. The Am LIII-edge EXAFS spectra are analyzed to determine the molecular structure (coordination numbers; Am-O and Am-C distances) of the formed Am(III)-formate species and to track the shift of the Am(III) speciation with increasing pH. The experimental data are compared to predictions from density functional calculations. The results indicate that formate binds to Am(III) in a monodentate fashion, in agreement with crystal structures of lanthanide formates. Furthermore, the investigations are complemented by thermodynamic speciation calculations to verify further the results obtained.

  6. Th uptake on montmorillonite: a powder and polarized extended X-ray absorption fine structure (EXAFS) study.

    Science.gov (United States)

    Dähn, Rainer; Scheidegger, André M; Manceau, Alain; Curti, Enzo; Baeyens, Bart; Bradbury, Michael H; Chateigner, Daniel

    2002-05-01

    The uptake process of Th(IV) onto montmorillonite was studied using powder and polarized-EXAFS (P-EXAFS) spectroscopy. Sorption samples were prepared in 0.1 M NaClO(4) solutions either undersaturated (pH 2 and 3, [Th](initial): 2.7x10(-6) to 4x10(-4) M) or supersatured (pH 5, [Th](initial): 4.3x10(-5) to 4x10(-4) M) with respect to amorphous ThO(2). Th loading varied between 1-157 micromol/g at pH 3 and 14-166 micromol/g at pH 5 and equaled 41 micromol/g at pH 2. At pH 5 and high surface loading the EXAFS spectrum resembled that of amorphous Th(OH)(4), suggesting the precipitation of a Th hydrous hydroxide. At low and intermediate surface coverage two O coordination shells at approximately 2.24 and approximately 2.48 A, and one Si shell at 3.81-3.88 A, were systematically observed regardless of pH. The formation of Th nucleation products and Th-Si solution complexes and the sorption of Th on a silica precipitate were excluded from the EXAFS spectra analysis and solution chemistry. In these conditions, Th was shown to bond the montmorillonite surface by sharing double corners with Si tetrahedra. This structural interpretation is consistent with surface coverage calculations which showed that the edge sites were saturated in the two highest concentrated samples (34 and 157 micromol/g) at pH 3.

  7. Se EXAFS study of the elevated wurtzite to rock salt structural phase transition in CdSe nanocrystals

    Energy Technology Data Exchange (ETDEWEB)

    Tolbert, S.H.; Alivisatos, A.P. [Lawrence Berkeley Lab., CA (United States)]|[California Univ., Berkeley, CA (United States). Dept. of Chemistry

    1993-09-01

    High pressure Se EXAFS data has been obtained on 2.7 nm radius CdSe semiconductor nanocrystals. This system is observed to undergo a solid-solid phase transition at 6.5 GPa which is approximately twice the reported value for bulk CdSe. In combination with high pressure optical absorption experiments, EXAFS data can be used to identify the high-pressure phase structure as rock salt. EXAFS data can be fit with equations of state to yield pressure volume curves. Resultant values of bulk modulus and its derivative with respect to pressure are B{sub o} = 37 {plus_minus} 5 GPa and B{sub o}{prime} = 11 {plus_minus} 3. A thermodynamic model for the data is presented in which the internal energy in each phase is modified by a surface energy term. Differences in surface energy are used to explain the elevation in phase transition pressure. The model can be used to estimate a value for the surface energy in the rock salt phase; 1.9 {plus_minus} 0.3 N/m is obtained in comparison to 0.9 {plus_minus} 0. 1 N/m for the wurtzite phase.

  8. Characterization of phosphate sequestration by a lanthanum modified bentonite clay: A solid- state NMR, EXAFS and PXRD study

    Energy Technology Data Exchange (ETDEWEB)

    Dithmer, Line; Lipton, Andrew S.; Reitzel, Kasper; Warner, Terence E.; Lundberg, Daniel; Nielsen, Ulla Gro

    2015-04-07

    Phosphate (P) sequestration by a lanthanum (La) exchanged bentonite (a clay mineral), which is extensively used in chemical lake restoration, was investigated on the molecular level using a combination of 31P and 139La solid state NMR spectroscopy (SSNMR), extended X-ray absorption spectroscopy (EX-AFS) and powder X-ray diffraction (PXRD) in combination with sorption studies. 31P SSNMR show that all phosphate is immobilized as rhabdophane, LaPO4·xH2O, which is further supported by 139La SSNMR and EXAFS; whereas PXRD results are ambiguous with respect to rhabdophane and monazite (LaPO4). Adsorption studies show that, at humic acids (HA) concentrations above ca. 250 μM the binding capacity is only 50 % of the theoretical value or even less. No other lanthanum or phosphate phases are detected by SSNMR and EXAFS indicating the effect of HA is kinetic. Moreover, 31P SSNMR shows that rhabdophane formed upon P sequestration is in close proximity to the clay matrix.

  9. Copper, nickel and zinc speciation in a biosolid-amended soil: pH adsorption edge, μ-XRF and μ-XANES investigations.

    Science.gov (United States)

    Mamindy-Pajany, Yannick; Sayen, Stéphanie; Mosselmans, J Frederick W; Guillon, Emmanuel

    2014-07-01

    Metal solid phase speciation plays an important role in the control of the long-term stability of metals in biosolid-amended soils. The present work used pH-adsorption edge experiments and synchrotron-based spectroscopy techniques to understand the solid phase speciation of copper, nickel and zinc in a biosolid-amended soil. Comparison of metal adsorption edges on the biosolid-amended soil and the soil sample showed that Cu, Ni, and Zn can be retained by both soil and biosolid components such as amorphous iron phases, organic matter and clay minerals. These data are combined with microscopic results to obtain structural information about the surface complexes formed. Linear combination fitting of K-edge XANES spectra of metal hot-spots indicated consistent differences in metal speciation between metals. While organic matter plays a dominant role in Ni binding in the biosolid-amended soil, it was of lesser importance for Cu and Zn. This study suggests that even if the metals can be associated with soil components (clay minerals and organic matter), biosolid application will increase metals retention in the biosolid-amended soil by providing reactive organic matter and iron oxide fractions. Among the studied metals, the long-term mobility of Ni could be affected by organic matter degradation while Cu and Zn are strongly associated with iron oxides.

  10. DEVELOPMENT OF A HIGH RATE HIGH RESOLUTION DETECTOR FOR EXAFS EXPERIMENTS.

    Energy Technology Data Exchange (ETDEWEB)

    DE GERONIMO,G.; O CONNOR,P.; BEUTTENMULLER,R.H.; LI,Z.; KUCZEWSKI,A.J.; SIDDONS,D.P.

    2002-11-10

    A new detector for EXAFS experiments is being developed. It is based on a multi-element Si sensor and dedicated readout ASICs. The sensor is composed of 384 pixels, each having 1 mm{sup 2} area, arranged in four quadrants of 12 x 8 elements, and wire-bonded to 32-channel front-end ASICs. Each channel implements low noise preamplification with self-adaptive continuous reset, high order shaper, band-gap referenced baseline stabilizer, one threshold comparator and two DAC adjustable window comparators, each followed by a 24-bit counter. Fabricated in 0.35{micro}m CMOS dissipates about 8mW per channel. First measurements show at room temperature a resolution of 14 rms electrons without the detector and of 40 rms electrons (340eV) with the detector connected and biased. Cooling at -35C a FWHM of 205eV (167eV from electronics) was measured at the Mn-K{alpha} line. A resolution of about 300eV was measured for rates approaching 100kcps/cm{sup 2} per channel, corresponding to an overall rate in excess of 10MHz/cm{sup 2}. A channel-to-channel threshold dispersion after DACs adjustment of 2.5 rms electrons was also measured.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    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 P 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.

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

    Science.gov (United States)

    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.

  13. Comparative study of the electronic structure of natural and synthetic rubies using XAFS and EDAX analyses

    Indian Academy of Sciences (India)

    P Parikh; D M Bhardwaj; R P Gupta; N L Saini; S Fernandes; R K Singhal; D C Jain; K B Garg

    2002-12-01

    We have studied the Cr–K-edge XANES and EXAFS in natural Indian rubies from two sources and a synthetic ruby at ESRF. Weight % of various constituents in them is determined using EDAX measurements. Taking the results from the three techniques together we are able to demonstrate their feasibility in quantitative study of precious stones.

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

    Energy Technology Data Exchange (ETDEWEB)

    Getsoian, Andrew “Bean”; Das, Ujjal; Camacho-Bunquin, Jeffrey; Zhang, Guanghui; Gallagher, James R.; Hu, Bo; Cheah, Singfoong; Schaidle, Joshua A.; Ruddy, Daniel A.; Hensley, Jesse E.; Krause, Theodore R.; Curtiss, Larry A.; Miller, Jeffrey T.; Hock, Adam S.

    2016-01-01

    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 to 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. 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.

  15. Identification of Martian Regolith Sulfur Components in Shergottites Using Sulfur K Xanes and Fe/S Ratios

    Science.gov (United States)

    Sutton, S. R.; Ross, D. K.; Rao, M. N.; Nyquist, L. E.

    2014-01-01

    Based on isotopic anomalies in Kr and Sm, Sr-isotopes, S-isotopes, XANES results on S-speciation, Fe/S ratios in sulfide immiscible melts [5], and major element correlations with S determined in impact glasses in EET79001 Lith A & Lith B and Tissint, we have provided very strong evidence for the occurrence of a Martian regolith component in some impact melt glasses in shergottites. Using REE measurements by LA-ICP-MS in shergottite impact glasses, Barrat and co-workers have recently reported conflicting conclusions about the occurrence of Martian regolith components: (a) Positive evidence was reported for a Tissint impact melt, but (b) Negative evidence for impact melt in EET79001 and another impact melt in Tissint. Here, we address some specific issues related to sulfur speciation and their relevance to identifying Martian regolith components in impact glasses in EET79001 and Tissint using sulfur K XANES and Fe/S ratios in sulfide immiscible melts. XANES and FE-SEM measurements in approx. 5 micron size individual sulfur blebs in EET79001 and Tissint glasses are carried out by us using sub-micron size beams, whereas Barrat and coworkers used approx. 90 micron size laser spots for LA- ICP-MS to determine REE abundances in bulk samples of the impact melt glasses. We contend that Martian regolith components in some shergottite impact glasses are present locally, and that studying impact melts in various shergottites can give evidence both for and against regolith components because of sample heterogeneity.

  16. Complexation of zinc in organic soils--EXAFS evidence for sulfur associations.

    Science.gov (United States)

    Karlsson, Torbjörn; Skyllberg, Ulf

    2007-01-01

    Even if it is generally accepted that associations with natural organic matter (NOM) to a great extent determine the bioavailability and mobility of trace metals in soils and waters, the knowledge about the identity of NOM functional groups involved is still limited. In this study, extended X-ray absorption fine structure (EXAFS) spectroscopy was used to determine the coordination chemistry of zinc (Zn) in two organic soils (500-10,000 microg Zn g(-), pH 5.6-7.3). In both soils Zn was coordinated by a mixture of oxygen/nitrogen (O/N) and sulfur (S) ligands in the first coordination shell. In average, 0.4-0.9 S atoms were located at a distance of 2.29-2.33 angstom, well in agreement with a 4-fold coordination with thiolates (RS-) in proteins. In addition 2.7-3.7 O/N atoms were located at 1.99-2.04 angstrom. The improved merit of fit by inclusion of S atoms was shown to be significant after adjusting for the improvement caused merely by increasing the number of fitting parameters. Two second shell Zn-C distances were used in our model: 3.0-4.2 carbon (C) atoms, associated to first shell O/N, were encountered at an average distance of 2.84 amgstrom, and 0.4-0.9 C atoms, associated to first shell S, were encountered at an average distance of 3.32 angstrom. These Zn-C distances are well in agreement with distances determined in well-defined organic molecules. It is concluded that Zn forms mainly inner-sphere complexes with a mixture of 4-fold coordination with S and O/N ligands and 6-fold coordination with O ligands in organic soils.

  17. New insights into metal interactions with the prion protein: EXAFS analysis and structure calculations of copper binding to a single octarepeat from the prion protein.

    Science.gov (United States)

    McDonald, Alex; Pushie, M Jake; Millhauser, Glenn L; George, Graham N

    2013-11-07

    Copper coordination to the prion protein (PrP) has garnered considerable interest for almost 20 years, due in part to the possibility that this interaction may be part of the normal function of PrP. The most characterized form of copper binding to PrP has been Cu(2+) interaction with the conserved tandem repeats in the N-terminal domain of PrP, termed the octarepeats, with many studies focusing on single and multiple repeats of PHGGGWGQ. Extended X-ray absorption fine structure (EXAFS) spectroscopy has been used in several previous instances to characterize the solution structure of Cu(2+) binding into the peptide backbone in the HGGG portion of the octarepeats. All previous EXAFS studies, however, have benefitted from crystallographic structure information for [Cu(II) (Ac-HGGGW-NH2)(-2H)] but have not conclusively demonstrated that the complex EXAFS spectrum represents the same coordination environment for Cu(2+) bound to the peptide backbone. Density functional structure calculations as well as full multiple scattering EXAFS curve fitting analysis are brought to bear on the predominant coordination mode for Cu(2+) with the Ac-PHGGGWGQ-NH2 peptide at physiological pH, under high Cu(2+) occupancy conditions. In addition to the structure calculations, which provide a thermodynamic link to structural information, methods are also presented for extensive deconvolution of the EXAFS spectrum. We demonstrate how the EXAFS data can be analyzed to extract the maximum structural information and arrive at a structural model that is significantly improved over previous EXAFS characterizations. The EXAFS spectrum for the chemically reduced form of copper binding to the Ac-PHGGGWGQ-NH2 peptide is presented, which is best modeled as a linear two-coordinate species with a single His imidazole ligand and a water molecule. The extent of in situ photoreduction of the copper center during standard data collection is also presented, and EXAFS curve fitting of the photoreduced species

  18. Atomistic simulations of the Fe K-edge EXAFS in FeF3 using molecular dynamics and reverse Monte Carlo methods

    Science.gov (United States)

    Jonane, Inga; Timoshenko, Janis; Kuzmin, Alexei

    2016-10-01

    Atomistic simulations of the experimental Fe K-edge extended x-ray absorption fine structure (EXAFS) of rhombohedral (space group R\\bar{3}c) FeF3 at T = 300 K were performed using classical molecular dynamics and reverse Monte Carlo (RMC) methods. The use of two complementary theoretical approaches allowed us to account accurately for thermal disorder effects in EXAFS and to validate the developed force-field model, which was constructed as a sum of two-body Buckingham-type (Fe-F and F-F), three-body harmonic (Fe-F-Fe) and Coulomb potentials. We found that the shape of the Fe K-edge EXAFS spectrum of FeF3 is a more sensitive probe for the determination of potential parameters than the values of structural parameters (a, c, x(F)) available from diffraction studies. The best overall agreement between the experimental and theoretical EXAFS spectra calculated using ab initio multiple-scattering approach was obtained for the iron effective charge q(Fe) = 1.71. The RMC method coupled with the evolutionary algorithm was used for more elaborate analysis of the EXAFS data. The obtained results suggest that our force-field model slightly underestimates the amplitude of thermal vibrations of fluorine atoms in the direction perpendicular to the Fe-F bonds.

  19. Constraints on the oxidation state of chondrule precursors from titanium XANES analysis of Semarkona Chondrules

    Energy Technology Data Exchange (ETDEWEB)

    Simon, S.B.; Sutton, S.R.; Grossman, L. (UofC)

    2008-04-28

    The valence of Ti is not easily reset during chondrule formation. To investigate the oxidation state of chondrule precursors, we measured the valence of Ti in olivine, pyroxene and mesostasis in a type I and a type II chondrule in Semarkona. Chondrules are very important because they formed in the solar nebula and are a major component of chondrites, the most common type of meteorite. In unequilibrated chondrites, the ferromagnesian silicates in chondrules exhibit wide ranges of fe (Fe/(Mg + Fe)). On this basis, chondrules can be divided into type I (fe < 0.1) and type II (fe > 0.1). Because a metal must be oxidized to enter a silicate, mafic silicates with low fe's are inferred to have formed in environments where little oxidized iron was available, implying reducing conditions. Therefore, type I and type II chondrules record different oxidation states. A fundamental question in the study of chondrules is whether this difference was established during chondrule formation, or if it reflects differences in their precursors. Last year, we reported the presence of trivalent Ti in refractory forsterite found in the dense fraction of the Tagish Lake CM chondrite. In addition, in the corresponding oral presentation, we reported high Ti{sup 3+}/Ti{sup 4+} in refractory forsterite containing 0.4-0.7 wt% FeO, present in a type I chondrule. Even these low FeO contents reflect a much higher fO{sub 2} than that at which pyroxene with equivalent Ti{sup 3+}/Ti{sup 4+} would be stable. This suggests that either: the equilibrium Ti{sup 3+}/Ti{sup 4+} is higher in olivine than in pyroxene for a given fO{sub 2}; or the grains formed under highly reducing conditions and the valence of Ti in chondrule olivine is a robust recorder of the oxidation state of chondrule precursors, not easily reset during chondrule formation. To improve our understanding of the origin of chondrules we have used XANES (X-ray absorption near edge structure) spectroscopy to measure the valence state of

  20. What first principles molecular dynamics can tell us about EXAFS spectroscopy of radioactive heavy metal cations in water

    Energy Technology Data Exchange (ETDEWEB)

    Duvail, M.; Gaigeot, M.P.; Spezia, R. [Lab. Analyse et Modelisation pour la Biologie et l' Environnement, UMR 8587 CNRS, Univ. d' Evry Val d' Essonne, Evry (France); D' Angelo, P. [Dipt. di Chimica, Univ. di Roma La Sapienza (Italy); Vitorge, P. [Lab. Analyse et Modelisation pour la Biologie et l' Environnement, UMR 8587 CNRS, Univ. d' Evry Val d' Essonne, Evry (France); Lab. de Speciation des Radionucleides et Molecules, CEA Saclay, DEN/DPC/SECR, Gif-sur-Yvette (France)

    2009-07-01

    In this paper we show how molecular dynamics simulation can improve comprehension of structure and dynamics of water solvent around heavy cations. In particular, metal-water radial distribution function obtained from molecular dynamics can be used into EXAFS equation to improve the experimental signal fitting. Here we show results on structure and dynamics of Co{sup 2+}, that is a radiocontaminant cation in its isotopic form {sup 60}Co, and lanthanoids(III) that are the chemical analogues of actinides(III) in aqueous solution. (orig.)

  1. Dynamics of Zn in an urban wetland soil-plant system: Coupling isotopic and EXAFS approaches

    Science.gov (United States)

    Aucour, Anne-Marie; Bedell, Jean-Philippe; Queyron, Marine; Magnin, Valérie; Testemale, Denis; Sarret, Géraldine

    2015-07-01

    Plants play a key role in the stabilization of metals in contaminated environments. Studies have been performed on Zn uptake and storage mechanisms, mainly for Zn hyperaccumulating plants, though less is known about Zn stabilization in the rhizosphere of non-accumulating plants. This study was focused on the dynamics of Zn in a whole soil-litter-plant system and the processes controlling Zn mobilization and stabilization. The site studied was an infiltration basin receiving urban stormwater, in which Phalaris arundinacea (reed canary grass) developed spontaneously. A combination of chemical extractions (CaCl2, DTPA), EXAFS spectroscopy and Zn stable isotope measurements was applied for the water inlet, soil, plant organs and decaying biomass. Zn speciation changed from the water inlet to the soil. In the soil, Zn was present as Zn-layered double hydroxide (Zn-LDH), tetrahedral and octahedral sorbed Zn species. The formation of Zn-LDH participates in Zn stabilization. Tetrahedral Zn species, which were partly DTPA exchangeable, were enriched in heavy isotopes, whereas octahedral Zn (Zn-LDH and sorbed species) were enriched in light isotopes. Based on a linear model between δ66Zn and Zn speciation, δ66Zn for pure tetrahedral and octahedral end-members were estimated at ca. 0.33‰ and 0.04‰, respectively. In the plant, a mixture of octahedral Zn (attributed to aqueous Zn-organic acid complexes present in the symplasm), and tetrahedral Zn (attributed to apoplasmic Zn-cell wall complexes) was observed in all organs. Large enrichment in light isotopes from the soil to the plant Δ66Zn (of ca. -0.6‰) was observed. The stem was enriched in light isotopes versus roots and, to a lesser extent, versus leaves. The results suggest that Zn was taken up via a low-affinity transport system and that Zn was sequestrated in the stem symplasm after transit through leaves. Finally, intense Zn exchanges were observed between the decaying biomass and the soil, with the sorption of

  2. Spin Equilibria in Monomeric Manganocenes: Solid State Magnetic and EXAFS Studies

    Energy Technology Data Exchange (ETDEWEB)

    Walter, M. D.; Sofield, C. D.; Booth, C. H.; Andersen, R. A.

    2009-02-09

    Magnetic susceptibility measurements and X-ray data confirm that tert-butyl-substituted manganocenes [(Me{sub 3}C){sub n}C{sub 5}H{sub 5?n}]{sub 2}Mn (n = 1, 2) follow the trend previously observed with the methylated manganocenes; that is, electron-donating groups attached to the Cp ring stabilize the low-spin (LS) electronic ground state relative to Cp{sub 2}Mn and exhibit higher spin-crossover (SCO) temperatures. However, introducing three CMe{sub 3} groups on each ring gives a temperature-invariant high-spin (HS) state manganocene. The origin of the high-spin state in [1,2,4-(Me{sub 3}C){sub 3}C{sub 5}H{sub 2}]{sub 2}Mn is due to the significant bulk of the [1,2,4-(Me{sub 3}C){sub 3}C{sub 5}H{sub 2}]{sup -} ligand, which is sufficient to generate severe inter-ring steric strain that prevents the realization of the low-spin state. Interestingly, the spin transition in [1,3-(Me{sub 3}C){sub 2}C{sub 5}H{sub 3}]{sub 2}Mn is accompanied by a phase transition resulting in a significant irreversible hysteresis ({Delta}T{sub c} = 16 K). This structural transition was also observed by extended X-ray absorption fine-structure (EXAFS) measurements. Magnetic susceptibility studies and X-ray diffraction data on SiMe{sub 3}-substituted manganocenes [(Me{sub 3}Si){sub n}C{sub 5}H{sub 5-n}]{sub 2}Mn (n = 1, 2, 3) show high-spin configurations in these cases. Although tetra- and hexasubstituted manganocenes are high-spin at all accessible temperatures, the disubstituted manganocenes exhibit a small low-spin admixture at low temperature. In this respect it behaves similarly to [(Me{sub 3}C)(Me{sub 3}Si)C{sub 5}H{sub 3}]{sub 2}Mn, which has a constant low-spin admixture up to 90 K and then gradually converts to high-spin. Thermal spin-trapping can be observed for [(Me{sub 3}C)(Me{sub 3}Si)C{sub 5}H{sub 3}]{sub 2}Mn on rapid cooling.

  3. EXAFS speciation and phytoavailability of Pb in a contaminated soil amended with compost and gypsum.

    Science.gov (United States)

    Hashimoto, Yohey; Yamaguchi, Noriko; Takaoka, Masaki; Shiota, Kenji

    2011-02-01

    Due to unregulated uses of lead pellets for hunting purposes in Japan, soils and sediments in some river basins and wetlands have become highly contaminated with Pb. Deterioration of natural vegetation has occurred sporadically in these areas, and therefore revegetation is needed for ecological restoration. The objectives of the present study were to assess the effects of surface applications of compost and gypsum amendments on Pb availability to a watercress plant (Nasturtium officinale W.T. Aiton) and molecular-scale speciation of Pb in soil solid phases. The compost and gypsum amendments significantly decreased dissolved Pb and Sb in pore water. The concentration of Pb in aboveground plant tissues was 190mg kg(-1) in the control soil and was reduced to soils. The concentration of Sb in plants grown in the control soil was 13mg kg(-1), whereas that in the soils receiving compost and gypsum decreased below detectable levels. Redox potential was higher in vegetated soils (ave. 349mV) than in the unvegetated soils (ave. 99mV) due to oxygen introduced by plant roots. Extended X-ray absorption fine structure (EXAFS) spectroscopy illustrated that Pb occurred as Pb sorbed on birnessite and/or ferrihydrite (Pb-Mn/Fe, ~60%) and Pb sorbed on organic matter (Pb-org, ~15%), and galena (PbS, ~10%) in the vegetated and unvegetated control soils. The compost amendment increased the proportion of Pb-org by 2-fold than in the control soils. The amended soils with plant growth decreased the proportion of Pb-Mn/Fe phases by half of that without plant growth. Galena and anglesite (PbSO(4)) were not detected in compost-amended soils and even in gypsum-amended soils since a significant soil reduction to anoxic levels did not occur in the entire soil. The present study indicated that, under flooded conditions, surface applications of compost and gypsum amendments reduced plant Pb uptake from the Pb contaminated soil. Crown Copyright © 2010. Published by Elsevier B.V. All rights

  4. In-Plane Structure of Underpotentially Deposited Copper on Gold (111) Determined by Surface EXAFS (Extended X-Ray Absorption Fine Structure).

    Science.gov (United States)

    1988-01-28

    D-Al 263 INN-PLANE STRUCTURE OF UNDERPOTENTIALLY DEPOSITED COPPER /. ON GOLD (Iii) DET (U) PUERTO RICO UNIV RIO PIEDRAS DEPT OF PHVS I CS 0 R...051-0776 TECHNICAL REPORT #33 In-Plane Structure of Underpotentially Deposited Copper on Gold (111) Determined by Surface EXAFS by O.R. Melroy*, M.G...Strueture of Underpotentially Deposited Copper on Gold ( 11) determincd hv Surface EXAFS 0. R. Melroy*, N1. G. Samant, G. L. Borges. and J. G. Gordon

  5. EXAFS Peaks and TPR Characterizing Bimetallic Interactions: Effects of Impregnation Methods on the Structure of Pt-Ru/C Catalysts

    Directory of Open Access Journals (Sweden)

    Nan-Yu Chen

    2014-01-01

    Full Text Available To investigate bimetallic interactions, Pt-Ru/C catalysts were prepared by coimpregnation (Pt-Ruco/C and successive impregnation (Ru-Ptse/C, while Pt/C, Ru/C, and reduced Pt-Rublack were used as reference. Those samples were characterized by XAS and TPR. When Pt(absorber-Ru(backscatter phase-and-amplitude correction is applied to Fourier transformed (FT EXAFS of Pt-Rublack at Pt edge, the characteristic peak of Pt-Ru interactions appears at 2.70 Å´, whereas, when Pt-Pt correction is applied, the peak appears at about 2.5 Å´. Detailed EXAFS analysis for Pt-Ruco/C and Pt-Ruse/C confirms the nature of the characteristic peak and further indicates that the interactions can semiquantitatively be determined by the relative intensity between Pt-Ru and Pt-Pt characteristic peaks. This simple method in determining bimetallic interaction can be extended to characterize Pt-Pd/γ-Al2O3. However, for Pt-Re/γ-Al2O3, Pt-Re interactions cannot be determined by the method because of the overlap of Pt-Pt and Pt-Re characteristic peaks due to similar phase functions.

  6. XRD and EXAFS studies on the structure of Er{sup 3+}-doped SiO{sub 2}-HfO{sub 2} glass-ceramic waveguides: Er{sup 3+}-activated HfO{sub 2} nanocrystals

    Energy Technology Data Exchange (ETDEWEB)

    Afify, N D; Dalba, G [Dipartimento di Fisica, Universita di Trento, Via Sommarive 14, I-38123 Povo (Trento) (Italy); Rocca, F [IFN-CNR, Istituto di Fotonica e Nanotecnologie del Consiglio Nazionale delle Ricerche, Sezione ' FBK-CeFSA' di Trento, Via alla Cascata 56/C, I-38123 Povo (Trento) (Italy)], E-mail: rocca@science.unitn.it

    2009-06-07

    This paper describes the structure of Er{sup 3+}-doped SiO{sub 2}-HfO{sub 2} waveguides containing nanocrystals of HfO{sub 2}. Pure and 1 mol% Er{sup 3+}-doped 70SiO{sub 2}-30HfO{sub 2} films were deposited by the sol-gel method on amorphous SiO{sub 2} substrates using the dip-coating technique. Each waveguide has experienced a single thermal treatment at temperatures ranging from 900 to 1200 deg. C, for either short (30 min) or long (24 h) durations. Crystallization and microstructure were studied by x-ray diffraction (XRD). The local environments of hafnium and erbium ions were determined, respectively, from Hf and Er L{sub 3}-edges extended x-ray absorption fine structure (EXAFS) experiments. Both XRD and EXAFS results demonstrate the substitution of Hf{sup 4+} by Er{sup 3+} ions in the crystalline structure. XRD shows the nucleation of tetragonal HfO{sub 2} nanocrystals after heat treatment at 1000 deg. C for 30 min in the pure waveguide, and at 900 deg. C for 24 h in the waveguide doped with Er{sup 3+}. In both series, partial transformation from tetragonal to monoclinic HfO{sub 2} nanocrystals starts after heat treatment at 1100 deg. C for 24 h. The average crystallite size and size distribution can be controlled by thermal annealing temperature and duration, respectively, with brief treatment yielding a more homogeneous nanocrystal size.

  7. Influence of Steam Activation on Pore Structure and Acidity of Zeolite Beta: An Al K Edge XANES Study of Aluminum Coordination

    NARCIS (Netherlands)

    Koningsberger, D.C.; Bokhoven, J.A. van; Kunkeler, P.J.; Bekkum, H. van

    2002-01-01

    The effect of steam activation on the aluminum coordination in zeolite NH{4}-beta was investigated by means of quantitative analysis of Al K edge XANES spectra. Framework tetrahedral aluminum is converted to octahedral aluminum after calcination and steaming, a process that, at the same time,

  8. Diurnal Variation and Spatial Distribution Effects on Sulfur Speciation in Aerosol Samples as Assessed by X-Ray Absorption Near-Edge Structure (XANES

    Directory of Open Access Journals (Sweden)

    Siwatt Pongpiachan

    2012-01-01

    Full Text Available This paper focuses on providing new results relating to the impacts of Diurnal variation, Vertical distribution, and Emission source on sulfur K-edge XANES spectrum of aerosol samples. All aerosol samples used in the diurnal variation experiment were preserved using anoxic preservation stainless cylinders (APSCs and pressure-controlled glove boxes (PCGBs, which were specially designed to prevent oxidation of the sulfur states in PM10. Further investigation of sulfur K-edge XANES spectra revealed that PM10 samples were dominated by S(VI, even when preserved in anoxic conditions. The “Emission source effect” on the sulfur oxidation state of PM10 was examined by comparing sulfur K-edge XANES spectra collected from various emission sources in southern Thailand, while “Vertical distribution effects” on the sulfur oxidation state of PM10 were made with samples collected from three different altitudes from rooftops of the highest buildings in three major cities in Thailand. The analytical results have demonstrated that neither “Emission source” nor “Vertical distribution” appreciably contribute to the characteristic fingerprint of sulfur K-edge XANES spectrum in PM10.

  9. Combined XRD and XANES studies of a Re-promoted Co/γ-Al2O3 catalyst at Fischer–Tropsch synthesis conditions

    DEFF Research Database (Denmark)

    Rønning, Magnus; Tsakoumis, Nikolaos E.; Voronov, Alexey

    2010-01-01

    structure (XANES) were used to reveal information on the particle and crystallite size and the oxidation states of the active component. Conditions giving high selectivity towards light hydrocarbons (methanation, 673K, 10bar and high GHSV) were compared to conditions were higher hydrocarbons are the main...

  10. Fe K-edge XANES and pre-edge polarization dependance for the determination of the oxidation state of iron in antigorite and other phyllosilicates

    Science.gov (United States)

    Munoz, M.; Vidal, O.; Marcaillou, C.; Pascarelli, S.; Mathon, O.; Farges, F.

    2012-04-01

    Iron oxidation state in minerals is often a crucial indicator for the understanding of mineralogical reactions related to hydrothermalism, or various natural processes. We investigated here the influence of the linear polarization of the synchrotron X-ray beam on the determination of the iron oxidation state in phyllosilicates. Fe K-edge XANES spectra and pre-peaks of biotite (Bt), chlorite (Chl), talc (Tlc) and antigorite (Atg) crystals have been recorded at different crystal orientations. As a function of the crystal orientation, the experimental results show, 1) important changes both for XANES and pre-peaks, 2) typical changes of spectral signatures for all mineral species, 3) uncorrelated changes between XANES and pre-peaks, 4) important changes of the pre-peak energies, but no significant change of the integrated areas. Ab initio XANES calculations, performed for 6 orientations of the Bt structure are consistent with the experimental measurements. The energy position of the pre-peak centroids changes with crystal orientation by 0.4 eV for Bt and Tlc crystals, and by 0.2 eV for Chl and Atg, which correspond to XFe(apparent)3+ variations (2δ) of 0.22 and 0.15, respectively. Measurements on powdered crystals show that - (2/3)2δ

  11. X-ray fluorescence mapping and micro-XANES spectroscopic characterization of exhaust particulates emitted from auto engines burning MMT-added gasoline.

    Science.gov (United States)

    Mölders, N; Schilling, P J; Wong, J; Roos, J W; Smith, I L

    2001-08-01

    The elemental distribution and compositional homogeneity in auto exhaust particulates emitted from methylcyclopentadienyl manganese tricarbonyl-(MMT-)added gasoline engines have been investigated using a newly installed synchrotron X-ray microprobe. Two representative groups of exhaust particulate matter, as defined in a recent bulk X-ray absorption fine structure (XAFS) spectroscopic study at the Mn K-edge, were studied. The micro-X-ray absorption near-edge structure (XANES) spectra indicate a relatively homogeneous distribution of phases within a given particulate sample, down to a spatial extent of 40 microm (the resolution of microprobe). The micro-XANES also enabled analysis of several areas which displayed compositions different from the bulk sample, supporting the general theory describing manganese species formation in the exhaust. The ability to evaluate small regions also enabled direct verification of manganese sulfate from the S XANES despite the vast excess of sulfur present in other forms. The presence of a chloride compound, introduced through the sample dilution air and engine intake air, was also revealed. The study demonstrates the value of the combined X-ray microfluorescence with excitation by polychromatic radiation for elemental mapping and micro-XANES spectroscopy for chemical speciation in the study of dilute environmental materials containing low-Z constituents such as Cl, S, and P.

  12. The chemical sensitivity of X-ray spectroscopy: high energy resolution XANES versus X-ray emission spectroscopy of substituted ferrocenes.

    Science.gov (United States)

    Atkins, Andrew J; Bauer, Matthias; Jacob, Christoph R

    2013-06-07

    X-ray spectroscopy at the metal K-edge is an important tool for understanding catalytic processes and provides insight into the geometric and electronic structures of transition metal complexes. In particular, X-ray emission-based methods such as high-energy resolution fluorescence detection (HERFD), X-ray absorption near-edge spectroscopy (XANES) and valence-to-core X-ray emission spectroscopy (V2C-XES) hold the promise of providing increased chemical sensitivity compared to conventional X-ray absorption spectroscopy. Here, we explore the ability of HERFD-XANES and V2C-XES spectroscopy to distinguish substitutions beyond the directly coordinated atoms for the example of ferrocene and selected ferrocene derivatives. The experimental spectra are assigned and interpreted through the use of density functional theory (DFT) calculations. We find that while the pre-edge peaks in the HERFD-XANES spectra are affected by substituents at the cyclopentadienyl ring containing π-bonds [A. J. Atkins, Ch. R. Jacob and M. Bauer, Chem.-Eur. J., 2012, 18, 7021], the V2C-XES spectra are virtually unchanged. The pre-edge in HERFD-XANES probes the weak transition to unoccupied metal d-orbitals, while the V2C-XES spectra are determined by dipole-allowed transitions from occupied ligand orbitals to the 1s core hole. The latter turn out to be less sensitive to changes beyond the first coordination shell.

  13. Structural properties of zinc oxide and titanium dioxide nanoparticles prepared by chemical vapor synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Akgul, Guvenc, E-mail: guvencakgul@gmail.com [Bor Vocational School, Nigde University, 51700 Nigde (Turkey); Advanced Photon Source, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, IL 60439 (United States); Akgul, Funda Aksoy [Physics Department, Nigde University, 51240 Nigde (Turkey); Attenkofer, Klaus [Advanced Photon Source, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, IL 60439 (United States); Winterer, Markus [Nanoparticle Process Technology, Department of Engineering Sciences, and Center for NanoIntegration Duisburg-Essen, CeNIDE, University of Duisburg-Essen (Germany)

    2013-03-25

    Highlights: ► Local structure determination of ZnO and TiO{sub 2} nanostructures by XANES and EXAFS. ► Zn K and Ti K absorption edge XANES investigations of nanopowder samples. ► Investigation of pre-edge peak features of TiO{sub 2} nanosamples. ► Obtaining of local structure parameters of nano ZnO and TiO{sub 2} using EXAFS. ► Good agreement of EXAFS results and crystal structure datas. -- Abstract: Transition metal (TM) oxides provide a wide range of functional materials especially when nanostructured. Titanium dioxide (TiO{sub 2}) and wurtzite type zinc oxide (ZnO) nanostructured materials were fabricated by chemical vapor synthesis (CVS). Crystal and local structures of the prepared nanosamples were ascertained using X-ray diffraction (XRD), X-ray absorption near edge structure (XANES), and extended X-ray absorption fine structure (EXAFS) techniques. Based on the XRD data, a second phase(s) was not found in both samples. A single wurtzite and anatase type structures were observed in ZnO and TiO{sub 2} nanosamples, respectively. Ti K pre-edge features of XANES spectrum indicated the presence of sixfold coordinated Ti in TiO{sub 2} nanosamples. The results showed that CVS is quite useful method to produce high crystalline nanoparticles.

  14. Determination of the forms of calcium present in coal chars by Ca K-edge XANES with Synchrotron Radiation

    CERN Document Server

    Liu, Lijuan; Cui, Mingqi; Hu, Yongfeng; Zheng, Lei; Zhao, Yidong; Ma, Chenyan; Xi, Shibo; Yang, Dongliang; Guo, Zhiying; Wang, Jie

    2012-01-01

    This work is concerned with the Ca transformations during the pyrolysis of Ca(OH)2 or CaCO3-added coals. Ca K-edge X-ray absorption near edge structure (XANES) spectroscopy was applied to determine the forms of Ca in chars prepared from the pyrolysis of Ca-added coal. Results showed that Ca(OH)2 and CaSO4 existed in both the Ca(OH)2-added chars and the CaCO3-added chars, while CaS and CaO only existed in the chars prepared from the Ca(OH)2-added coal. Moreover, it was found that carboxyl Ca was formed during pyrolysis for either the Ca(OH)2-added coal or the CaCO3-added coals.

  15. Quantitative measurement of the reduction of platinum(IV) complexes using X-ray absorption near-edge spectroscopy (XANES).

    Science.gov (United States)

    Hall, Matthew D; Daly, Helen L; Zhang, Jenny Z; Zhang, Mei; Alderden, Rebecca A; Pursche, Daniel; Foran, Garry J; Hambley, Trevor W

    2012-06-01

    The platinum(II) drugs cisplatin, carboplatin and oxaliplatin are usefully employed against a range of malignancies, but toxicities and resistance have spurred the search for improved analogs. This has included investigation of the platinum(IV) oxidation state, which provides greater kinetic inertness. It is generally accepted that Pt(IV) complexes must be reduced to Pt(II) for activation. As such, the ability to monitor reduction of Pt(IV) complexes is critical to guiding the design of candidates, and providing mechanistic understanding. Here we report in full that the white line height of X-ray absorption near-edge spectra (XANES) of Pt complexes, normalized to the post-edge minima, can be used to quantitatively determine the proportion of each oxidation state in a mixture. A series of Pt(IV) complexes based on the Pt(II) complexes cisplatin and transplatin were prepared with chlorido, acetato or hydroxido axial ligands, and studies into their reduction potential and cytotoxicity against A2780 human ovarian cancer cells were performed, demonstrating the relationship between reduction potential and cytotoxicity. Analysis of white line height demonstrated a clear and consistent difference between Pt(II) (1.52 ± 0.05) and Pt(IV) (2.43 ± 0.19) complexes. Reduction of Pt(IV) complexes over time in cell growth media and A2780 cells was observed by XANES, and shown to correspond with their reduction potentials and cytotoxicities. We propose that this method is useful for monitoring reduction of metal-based drug candidates in complex biological systems.

  16. Hydration effects on the molecular structure of silica-supported vanadium oxide catalysts: A combined IR, Raman, UV–vis and EXAFS study

    NARCIS (Netherlands)

    Keller, D.E.; Visser, T.; Soulimani, F.; Koningsberger, D.C.; Weckhuysen, B.M.

    2007-01-01

    The effect of hydration on the molecular structure of silica-supported vanadium oxide catalysts with loadings of 1–16 wt.% V has been systematically investigated by infrared, Raman, UV–vis and EXAFS spectroscopy. IR and Raman spectra recorded during hydration revealed the formation of V–OH groups, c

  17. Microsecond time-resolved energy-dispersive EXAFS measurement and its application to film the thermolysis of (NH₄)₂[PtCl₆].

    Science.gov (United States)

    Kong, Qingyu; Baudelet, Francois; Han, Jun; Chagnot, Sebastien; Barthe, Laurent; Headspith, Jon; Goldsbrough, Roger; Picca, Frederic E; Spalla, Olivier

    2012-01-01

    Microsecond (μs) time-resolved extended X-ray absorption fine structure spectroscopy (EXAFS) has been developed using an energy-dispersive EXAFS (EDE) setup equipped with a silicon Quantum Detector ULTRA. The feasibility was investigated with a prototypical thermally driven redox reaction, the thermal decomposition of (NH₄)₂[PtCl₆]. EXAFS data were collected with snapshots every 60 μs during the course of the thermolysis reaction, then averaged for 100 times along the reaction to get better signal to noise ratio which reduces the time resolution to 6 millisecond (ms). Our results provide direct structural evidence of cis-PtCl₂(NH₃)₂ as the intermediate, together with continuous electronic and geometric structure dynamics of the reactant, intermediate and final product during the course of the thermolysis of ((NH₄)₂[PtCl₆]. The thermal effect on EXAFS signals at high temperatures is considered in the data analysis, which is essential to follow the reaction process correctly. This method could also be applied to other reaction dynamics.

  18. Microsecond time-resolved energy-dispersive EXAFS measurement and its application to film the thermolysis of (NH4)2[PtCl6

    Science.gov (United States)

    Kong, Qingyu; Baudelet, Francois; Han, Jun; Chagnot, Sebastien; Barthe, Laurent; Headspith, Jon; Goldsbrough, Roger; Picca, Frederic E.; Spalla, Olivier

    2012-01-01

    Microsecond (μs) time-resolved extended X-ray absorption fine structure spectroscopy (EXAFS) has been developed using an energy-dispersive EXAFS (EDE) setup equipped with a silicon Quantum Detector ULTRA. The feasibility was investigated with a prototypical thermally driven redox reaction, the thermal decomposition of (NH4)2[PtCl6]. EXAFS data were collected with snapshots every 60 μs during the course of the thermolysis reaction, then averaged for 100 times along the reaction to get better signal to noise ratio which reduces the time resolution to 6 millisecond (ms). Our results provide direct structural evidence of cis-PtCl2(NH3)2 as the intermediate, together with continuous electronic and geometric structure dynamics of the reactant, intermediate and final product during the course of the thermolysis of (NH4)2[PtCl6]. The thermal effect on EXAFS signals at high temperatures is considered in the data analysis, which is essential to follow the reaction process correctly. This method could also be applied to other reaction dynamics. PMID:23264880

  19. EXAFS investigation on U(VI) immobilization in hardened cement paste. Influence of experimental conditions on speciation

    Energy Technology Data Exchange (ETDEWEB)

    Mace, N.; Wieland, E.; Daehn, R.; Tits, J. [Paul Scherrer Inst. (PSI), Villigen (Switzerland). Lab. for Waste Management; Scheinost, A.C. [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Inst. of Resource Ecology; Rossendorf Beamline (ROBL), Grenoble (France). ESRF

    2013-08-01

    Extended X-ray absorption fine structure (EXAFS) spectroscopy has been used to investigate the coordination environment of U(VI) in cementitious materials. The EXAFS measurements were carried out on U(VI)-doped samples prepared under varying conditions, such as samples from sorption, hydration and diffusion experiments, and using different cementitious materials, such as crushed hydrated hardened cement paste (HCP) and calcium silicate hydrates (C-S-H). The samples had U(VI) loadings ranging from 1700 {mu}g/g to 45000 {mu}g/g. Applying principal component analysis (PCA) on 13 EXAFS spectra (each spectra corresponding to a minimum of five different scans) of the low loading samples, one single species is obtained indicating a similar U(VI) coordination environment for both HCP and C-S-H samples. This result confirms that C-S-H phases control the uptake of U(VI) in the complex cement matrix. The coordination environment structure of this species is similar to a U(VI) surface complex or to U(VI) in uranyl silicate minerals (two axial O atoms at 1.82 {+-} 0.02 A; four equatorial O atoms at 2.25 {+-} 0.01 A; one Si atom at 3.10 {+-} 0.03 A). At high U(VI) loading, PCA revealed a second U(VI) species, with a coordination environment similar to that of U(VI) in calcium uranate (two axial O atoms at 1.94 {+-} 0.04 A; five equatorial O atoms at 2.26 {+-} 0.01 A; four Ca atoms at 3.69 {+-} 0.05 A and five U atoms at 3.85 {+-} 0.04 A). This study suggest that, at low U(VI) loading, U(VI) is bound to C-S-H phases in HCP while at high U(VI) loading, the immobilization of U(VI) in cementitious materials is mainly controlled by the precipitation of a calcium uranate-type phase. (orig.)

  20. Large negative thermal expansion of the Co subnetwork measured by EXAFS in highly disordered Nd₁-xCox thin films with perpendicular magnetic anisotropy.

    Science.gov (United States)

    Díaz, J; Cid, R; Hierro, A; M Álvarez-Prado, L; Quirós, C; Alameda, J M

    2013-10-23

    We have measured a negative thermal expansion (NTE) of the Co subnetwork in amorphous Nd1-xCox (0.78 < x < 0.84) thin films of the order of 1% in volume using linearly polarized EXAFS spectroscopy at RT and 10 K. The expansion, which is anisotropic, is uncorrelated with the perpendicular magnetic anisotropy (PMA) observed in all the films, but correlated with the method used to deposit them. The atomic environments of the Nd atoms resulted in such a strong disorder that Nd-Nd and Nd-Co environments were invisible to EXAFS, and only Co-Co atomic environments were detected. The information on the Nd subnetwork was obtained through its magnetic moment measured by XMCD. These measurements demonstrate an increasing interaction of neodymium atoms with their particular local crystal field as the temperature decreased, suggesting possible structural modifications at their sites. Since the magnetic moment of the cobalt subnetwork remains essentially constant with the temperature, it is proposed that its detected NTE may be caused by the mechanical response of the amorphous network to structural transformations at the Nd sites. These results support that the PMA in RE-TM alloys is localized at the RE sites. The complete absence of EXAFS oscillations in the Nd L3 EXAFS spectra is remarkable: it means that the coherence length of the photoemitted electrons in disordered matter can be strongly reduced from that expected by atomic calculations to the point of being less than first neighbor distances, which is contrary to the common belief that first neighbors are always visible by EXAFS.

  1. Variation of local atomic structure due to devitrification of Ni-Zr alloy thin films probed by EXAFS measurements

    Science.gov (United States)

    Bhattacharya, Debarati; Tiwari, Nidhi; Bhattacharyya, Dibyendu; Jha, S. N.; Basu, S.

    2016-05-01

    Thin film metallic glasses (TFMGs) exhibit properties superior to their bulk counterparts allowing them to be potentially useful in many practical applications. Apart from their technological interest, when converted to crystallized state (devitrification) TFMGs can also act as precursors for partially crystallized or fully crystallized forms. Such devitrified forms are attractive due to their novel structural and magnetic properties. The amorphous-to-crystalline transformation of co-sputtered Ni-Zr alloy thin films through annealing was studied using EXAFS (Extended X-ray Absorption Fine Structure) measurements. Investigation through an atomic probe gives a better insight into the local environment of the atomic species, rendering a deeper understanding of thermal evolution of such materials.

  2. Variation of local atomic structure due to devitrification of Ni-Zr alloy thin films probed by EXAFS measurements

    Energy Technology Data Exchange (ETDEWEB)

    Bhattacharya, Debarati, E-mail: debarati@barc.gov.in; Basu, S. [Solid State Physics Division, Bhabha Atomic Research Centre, Mumbai 400085 India (India); Tiwari, Nidhi; Bhattacharyya, Dibyendu; Jha, S. N. [Atomic & Molecular Physics Division, Bhabha Atomic Research Centre, Mumbai 400085 India (India)

    2016-05-23

    Thin film metallic glasses (TFMGs) exhibit properties superior to their bulk counterparts allowing them to be potentially useful in many practical applications. Apart from their technological interest, when converted to crystallized state (devitrification) TFMGs can also act as precursors for partially crystallized or fully crystallized forms. Such devitrified forms are attractive due to their novel structural and magnetic properties. The amorphous-to-crystalline transformation of co-sputtered Ni-Zr alloy thin films through annealing was studied using EXAFS (Extended X-ray Absorption Fine Structure) measurements. Investigation through an atomic probe gives a better insight into the local environment of the atomic species, rendering a deeper understanding of thermal evolution of such materials.

  3. EXAFS analysis of the pH dependence of the blue-copper site in amicyanin from Thiobacillus versutus.

    Science.gov (United States)

    Lommen, A; Pandya, K I; Koningsberger, D C; Canters, G W

    1991-02-15

    The room temperature Cu K-edge EXAFS (extended X-ray absorption fine structure) spectrum of reduced and oxidized amicyanin, the blue copper protein from Thiobacillus versutus, was measured at low and high pH. The data interpretation was partly based on independent NMR evidence for the occurrence of a ligand histidine protonation at low pH (pKa = 6.9) in the reduced protein. In the oxidized protein two nitrogen-donors (from two histidines; Cu-N distances 1.95-2.01 A and 1.86-1.89 A) and a sulfur-donor (from a cysteine; Cu-S distance 2.11-2.13 A) were identified and the coordination appears independent of pH. Upon reduction at high pH the Cu-S bond and one of the Cu-N bonds lengthen slightly (from 2.11 to 2.19 A and from 2.01 to 2.18 A, respectively). Upon lowering of the pH one of the N-donors of the Cu in reduced amicyanin disappears from the Cu EXAFS and a second S-donor (from a methionine) becomes visible at 2.41 A from the Cu. The Debye-Waller factors are compatible with a Cu-N vibrational stretch frequency in the range of 150-250 cm-1 and one greater than 285 cm-1, and a Cu-S vibrational stretch frequency of about 150 cm-1 (Cu-Smet; reduced amicyanin at low pH) and one in the range of 230-800 cm-1 (Cu-Scys).

  4. EXAFS study on yttrium oxide thin films deposited by RF plasma enhanced MOCVD under the influence of varying RF self-bias

    Energy Technology Data Exchange (ETDEWEB)

    Chopade, S.S. [Laser and Plasma Technology Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400085 (India); Nayak, C.; Bhattacharyya, D.; Jha, S.N.; Tokas, R.B.; Sahoo, N.K. [Atomic and Molecular Physics Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400085 (India); Patil, D.S., E-mail: dspatil@barc.gov.in [Laser and Plasma Technology Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400085 (India)

    2014-09-30

    Highlights: • Local structure and surface morphology of Y{sub 2}O{sub 3} thin films deposited by RF plasma MOCVD at different RF self-bias level investigated by EXAFS and AFM. • Bond length and oxygen coordination changes with bias. • Films are nanostructured with structural distortion at higher bias. • Surface morphology of films changes with bias. • Changes observed in local structural parameters are correlated with observed properties of films. • EXAFS study on Y{sub 2}O{sub 3} films deposited under different RF self-bias levels is not been reported so far. - Abstract: Extended X-ray absorption fine structure (EXAFS) and atomic force microscopy (AFM) studies are carried out on yttrium oxide (Y{sub 2}O{sub 3}) thin films deposited by radio frequency plasma assisted metalorganic chemical vapor deposition (MOCVD) process at different RF self-bias (−50 V to −175 V with a step of −25 V) on silicon substrates. A (2,2,6,6-tetramethyl-3,5-heptanedionate) yttrium (commonly known as Y(thd){sub 3}) precursor is used in a plasma of argon and oxygen gases at a substrate temperature of 350 °C for deposition. To gain profound understanding about influence of RF self-bias on the properties of the deposited Y{sub 2}O{sub 3} thin films, the films are characterized by EXAFS and AFM measurements. From the EXAFS measurements it is observed that oxygen co-ordination is high for the film deposited at the lowest self bias (−50 V) which is due to presence of higher amount of hydroxyl group in the sample. Oxygen coordination however decrease to lower values for the films deposited at self bias of −75 V. Y-O bond length decreases gradually with increase in self bias indicating reduction in hydroxyl content. However there is reduction in bond length for the film deposited at −100 V as compared to other films resulting from structural changes. The disorder factor obtained from EXAFS measurement increases for films deposited at voltages beyond −125 V due to

  5. Progressive oxidation of pyrite in five bituminous coal samples: An As XANES and 57Fe Mössbauer spectroscopic study

    Science.gov (United States)

    Kolker, Allan; Huggins, Frank E.

    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 of 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 O2 atmosphere; (3) room atmosphere (relative humidity ∼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 57Fe Mössbauer spectroscopy, respectively. Arsenic XANES spectroscopy shows progressive oxidation of pyritic As to arsenate, with wetted samples showing the most rapid oxidation. 57Fe Mössbauer spectroscopy also shows a much greater proportion of Fe3+ forms (jarosite, Fe3+ sulfate, FeOOH) for samples stored under wet conditions, but much less

  6. Change in Localizations of Arsenic in Rice Grains After Cooking with High Arsenic Waters - µXRF and XANES studies

    Science.gov (United States)

    Datta, S.; Ryan, B.; Kumar, N.; Bortz, T.; Bolen, Z. T.

    2016-12-01

    Threats of Arsenic (As) through food uptake, via consumption of rice, is a potential pathway that presents a concern not only for the millions of inhabitants who reside in river valleys and irrigate their soil with contaminated water, but the global rice market as well. This study focuses on high As rice from India and Bangladesh grown in such soils, and the effect of boiling rice with As-contaminated water in preparation for dietary intake. Husked and unhusked rice grains were boiled with >500 µg/L As-bearing water from the field to simulate local cooking methods. The resulting cooked water was analyzed using iCAP low limit detection via ICP-MS to understand the changes in dissolved elemental concentrations before and after cooking, and HPLC was introduced to measure for changes in As speciation in the waters. Using spectroscopic methods such as µXRF mapping associated with µXANES, distribution/localization and speciation changes of As in rice grains were identified. Further, with Linear Combination Fitting (LCF) of XANES spectra utilizing relevant reference compounds (As-S, AsIII, AsV, MMA and DMA), organic and inorganic As species were able to be mapped within rice grains. The results for uncooked/raw grains showed that predominantly As-S combined with AsIII and AsV accounted for 90% of speciation in most samples, localized in areas such as the outer aleurone layer. When analyzing cooked rice grains, the speciation appears to be an unidentified As species while the best LCF shows between 63-93% of As as MMA. Arsenic was found less localized throughout the cooked grains but rather heterogeneously distributed when compared to the uncooked/raw samples. The analyses of boiled/cooked water resulted in a significant decrease in dissolved As post-cooking (90%), but a subsequent increase in elements such as K, La, Li, Mo, Na, Ni, and Zr was observed; As-V was shown to be the main in-As species in the cooked water. The impact that this study portrays is consuming rice

  7. Nitrogen K-edge X-ray absorption near edge structure (XANES) spectra of purine-containing nucleotides in aqueous solution.

    Science.gov (United States)

    Shimada, Hiroyuki; Fukao, Taishi; Minami, Hirotake; Ukai, Masatoshi; Fujii, Kentaro; Yokoya, Akinari; Fukuda, Yoshihiro; Saitoh, Yuji

    2014-08-07

    The N K-edge X-ray absorption near edge structure (XANES) spectra of the purine-containing nucleotide, guanosine 5'-monophosphate (GMP), in aqueous solution are measured under various pH conditions. The spectra show characteristic peaks, which originate from resonant excitations of N 1s electrons to π* orbitals inside the guanine moiety of GMP. The relative intensities of these peaks depend on the pH values of the solution. The pH dependence is explained by the core-level shift of N atoms at specific sites caused by protonation and deprotonation. The experimental spectra are compared with theoretical spectra calculated by using density functional theory for GMP and the other purine-containing nucleotides, adenosine 5'-monophosphate, and adenosine 5'-triphosphate. The N K-edge XANES spectra for all of these nucleotides are classified by the numbers of N atoms with particular chemical bonding characteristics in the purine moiety.

  8. Order-disorder in olivine minerals by synchrotron X-ray absorption near-edge structure (Xane) spectroscopy at the Mg, Fe and Ca K edges

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Z.; Marcelli, A.; Cibin, G. [Istituto Nazionale di Fisica Nucleare, Frascati, RM (Italy). Laboratori Nazionali di Frascati; Mottana, A. [Istituto Nazionale di Fisica Nucleare, Frascati, RM (Italy). Laboratori Nazionali di Frascati; Rome Univ. Roma Tre, Rome (Italy). Dipt. di Scienze Geologiche; Paris, E.; Giuli, G [INFM, Camerino Univ., Camerino, MC (Italy). Dipt. di Scienze della Terra

    1999-07-01

    In this paper, are presented new, high-resolution experimental spectra at the Mg and Fe K edges for the two Fe-Mg end members F o and F a, and for three other olivines. Two are the Ca end members of the family, namely monticellite (Mtc: CaMgSiO4) and kirschsteinite (Krs: CaFeSiO4). The main purpose of this work is to investigate the effects of Mg, Fe, and Ca partition in the Pbnm (or {alpha}) olivine structure on the electronic properties, as well as the relationships that exist between chemical substitutions and features occurring in Xanes spectra. One wants to explore the relationships that intervene between LRO, as determined by XRD, and SRO, as determined by Xanes, on the endmembers and on a well-known intermediate member as well, and deduce from it a model for the behavior of the entire olivine solid-solution system.

  9. Effect of atomic vibrations in XANES: polarization-dependent damping of the fine structure at the Cu K-edge of (creat)2CuCl4.

    Science.gov (United States)

    Šipr, Ondřej; Vackář, Jiří; Kuzmin, Alexei

    2016-11-01

    Polarization-dependent damping of the fine structure in the Cu K-edge spectrum of creatinium tetrachlorocuprate [(creat)2CuCl4] in the X-ray absorption near-edge structure (XANES) region is shown to be due to atomic vibrations. These vibrations can be separated into two groups, depending on whether the respective atoms belong to the same molecular block; individual molecular blocks can be treated as semi-rigid entities while the mutual positions of these blocks are subject to large mean relative displacements. The effect of vibrations can be efficiently included in XANES calculations by using the same formula as for static systems but with a modified free-electron propagator which accounts for fluctuations in interatomic distances.

  10. XANES and IR spectroscopy study of the electronic structure and chemical composition of porous silicon on n- and p-type substrates

    Energy Technology Data Exchange (ETDEWEB)

    Lenshin, A. S., E-mail: lenshinas@phys.vsu.ru; Kashkarov, V. M.; Seredin, P. V. [Voronezh State University (Russian Federation); Spivak, Yu. M.; Moshnikov, V. A. [LETI St. Petersburg State Electrotechnical University (Russian Federation)

    2011-09-15

    The differences in the electronic structure and composition of porous silicon samples obtained under identical conditions of electrochemical etching on the most commonly used n- and p-type substrates with different conductivities are demonstrated by X-ray absorption near-edge spectroscopy (XANES) and Fourier transform IR spectroscopy (FTIR) methods. It is shown that significantly higher oxidation and saturation with hydrogen is observed for the porous layer on n-type substrates.

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

    Science.gov (United States)

    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.

  12. Elemental bioimaging and speciation analysis for the investigation of Wilson's disease using μXRF and XANES.

    Science.gov (United States)

    Hachmöller, Oliver; Buzanich, Ana Guilherme; Aichler, Michaela; Radtke, Martin; Dietrich, Dörthe; Schwamborn, Kristina; Lutz, Lisa; Werner, Martin; Sperling, Michael; Walch, Axel; Karst, Uwe

    2016-07-13

    A liver biopsy specimen from a Wilson's disease (WD) patient was analyzed by means of micro-X-ray fluorescence (μXRF) spectroscopy to determine the elemental distribution. First, bench-top μXRF was utilized for a coarse scan of the sample under laboratory conditions. The resulting distribution maps of copper and iron enabled the determination of a region of interest (ROI) for further analysis. In order to obtain more detailed elemental information, this ROI was analyzed by synchrotron radiation (SR)-based μXRF with a beam size of 4 μm offering a resolution at the cellular level. Distribution maps of additional elements to copper and iron like zinc and manganese were obtained due to a higher sensitivity of SR-μXRF. In addition to this, X-ray absorption near edge structure spectroscopy (XANES) was performed to identify the oxidation states of copper in WD. This speciation analysis indicated a mixture of copper(i) and copper(ii) within the WD liver tissue.

  13. The darkening of zinc yellow: XANES speciation of chromium in artist;s paints after light and chemical exposures

    Energy Technology Data Exchange (ETDEWEB)

    Zanella, Luciana; Casadio, Francesca; Gray, Kimberly A.; Warta, Richard; Ma, Qing; Gaillard, Jean-François

    2012-03-14

    The color darkening of selected brushstrokes of the masterpiece A Sunday on La Grande Jatte - 1884 (by Georges Seurat) has been attributed to the alteration of the chromate pigment zinc yellow. The pigment originally displays a bright greenish-yellow color but may undergo, after aging, darkening to a dull, ocher tone. We used XANES to probe the oxidation state of Cr on paint reconstructions, and show that color changes are associated with the reduction of Cr(VI) to Cr(III). Paint mixtures containing the pigment and linseed oil to mimic mixtures used in La Grande Jatte were subjected to artificial aging in the presence of light, SO{sub 2}, and variable air humidity - 50 and 90% relative humidity. High relative humidity led to the largest degree of Cr(VI) reduction whereas low relative humidity promoted light-induced alterations. These results are corroborated by visible reflectance measurements on the same laboratory samples and contribute to a better understanding of the chemical reactivity of chromate pigments, which are present in many historical works of art.

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

    Science.gov (United States)

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

    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.

  15. Determination of localized Fe 2+/Fe 3+ ratios in inks of historic documents by means of μ-XANES

    Science.gov (United States)

    Proost, K.; Janssens, K.; Wagner, B.; Bulska, E.; Schreiner, M.

    2004-01-01

    An important part of the European cultural heritage is composed of hand-written documents. Many of these documents were drawn up with iron-gall ink. This type of ink present a serious conservation problem, as it slowly oxidizes ('burns') the paper it is written on, thereby gradually disintegrating the historic document. Acid hydrolysis of the cellulose and/or the oxidation of organic compounds promoted by radical intermediates that are formed due to the presence of Fe 2+ ions are considered to be the cause of the disintegration. μ-XANES measurements were performed with a lateral resolution of 30-50 μm in order to determine the local Fe 2+/Fe 3+ ratio in 19th C. documents from the Austrian National Archives and fragments of 16th C documents from the Polish National Library. In the 19th C documents, no significant amount of Fe 2+ was detected. On the other hand, in the 16th C fragments, significant amounts of Fe 2+ and appreciable differences in distribution of Fe 2+ and Fe 3+ within individual letters/ink stains were observed.

  16. Coordination of Cd 2+ ions in the internal pore system of zeolite-X: A combined EXAFS and isotopic exchange study

    Science.gov (United States)

    Ahmed, I. A. M.; Young, S. D.; Mosselmans, J. F. W.; Crout, N. M. J.; Bailey, E. H.

    2009-03-01

    The effect of prolonged contact time (up to 130 days) on the immobilization of Cd by sorption to calcium exchanged zeolite-X (CaX), under environmentally relevant conditions, was studied using both isotopic exchange and extended X-ray absorption fine structure spectroscopy (EXAFS). Sorption and isotopic exchange measurements revealed time-dependent Cd sorption and indicated the movement of Cd 2+ ions into less accessible sites due to ageing. EXAFS suggested progressive fixation of Cd in the double six-ring ( D6R) unit of the CaX structure. Proportional allocation of the apparent Cd-Si bond distance to two 'end-members', across all contact times, indicated that the bond distance for labile Cd was 3.41 Å and for non-labile (or fixed) Cd was 3.47 Å.

  17. Sequestration of Sr(II) by calcium oxalate—A batch uptake study and EXAFS analysis of model compounds and reaction products

    Science.gov (United States)

    Singer, David M.; Johnson, Stephen B.; Catalano, Jeffrey G.; Farges, François; Brown, Gordon E., Jr.

    2008-10-01

    Calcium oxalate monohydrate (CaC 2O 4·H 2O—abbreviated as CaOx) is produced by two-thirds of all plant families, comprising up to 80 wt.% of the plant tissue and found in many surface environments. It is unclear, however, how CaOx in plants and soils interacts with metal ions and possibly sequesters them. This study examines the speciation of Sr(II) aq following its reaction with CaOx. Batch uptake experiments were conducted over the pH range 4-10, with initial Sr solution concentrations, [Sr] aq, ranging from 1 × 10 -4 to 1 × 10 -3 M and ionic strengths ranging of 0.001-0.1 M, using NaCl as the background electrolyte. Experimental results indicate that Sr uptake is independent of pH and ionic strength over these ranges. After exposure of CaOx to Sr aq for two days, the solution Ca concentration, [Ca] aq, increased for all samples relative to the control CaOx suspension (with no Sr added). The amount of Sr aq removed from solution was nearly equal to the total [Ca] aq after exposure of CaOx to Sr. These results suggest that nearly 90% of the Sr is removed from solution to a solid phase as Ca is released into solution. We suggest that the other 10% is sequestered through surface adsorption on a solid phase, although we have no direct evidence for this. Extended X-ray absorption fine structure (EXAFS) spectroscopy was used to determine the molecular-level speciation of Sr in the reaction products. Deconvolutions of the Sr K-edge EXAFS spectra were performed to identify multi-electron excitation (MEE) features. MEE effects were found to give rise to low-frequency peaks in the Fourier transform before the first shell of oxygen atoms and do not affect EXAFS fitting results. Because of potential problems caused by asymmetric distributions of Sr-O distances when fitting Sr K-edge EXAFS data using the standard harmonic model, we also employed a cumulant expansion model and an asymmetric analytical model to account for anharmonic effects in the EXAFS data. For Sr

  18. Aqueous and solid phase speciation of arsenic in a Bengali aquifer using IC-ICP-MS and EXAFS

    Science.gov (United States)

    Gault, A. G.; Davidson, L. E.; Lythgoe, P. R.; Charnock, J. M.; Chatterjee, D.; Abou-Shakra, F. R.; Walker, H. J.; Polya, D. A.

    2003-04-01

    Contamination of groundwater and drinking water supplies with arsenic has been reported in many parts of the world and constitutes a serious public health threat. Nowhere is this more apparent than in West Bengal and Bangladesh where arsenic concentrations exceed both World Health Organisation (WHO) and national limits in drinking water supplies leading to what has been described as the worst mass poisoning of a human population in history. Knowledge of both aqueous and solid phase speciation of arsenic in such hazardous arsenic-rich groundwaters is crucial to understanding the processes controlling arsenic release. We report here preliminary work involving the determination of dissolved arsenic speciation in West Bengali groundwaters and extended X-ray absorption fine structure (EXAFS) analysis of the associated sediment. Groundwater samples collected from Nadia district, West Bengal were analysed for arsenic speciation by ion chromatography-inductively coupled plasma-mass spectrometry (IC-ICP-MS) within 14 days of collection. Total arsenic concentrations exceeding 850 ug/L were determined; inorganic arsenic constituted the bulk of the dissolved arsenic burden with As(III) as the dominant form. Minor amounts of methylated arsenicals were also detected, however, their concentration did not exceed 5 ug/L. The local coordination environment of arsenic in sediment associated with such groundwaters was probed using K-edge As EXAFS. This revealed that arsenic exists predominantly in its oxidised form, As(V), most likely adsorbed as bidentate arsenate tetrahedra on metal (Fe and/or Al) oxide/hydroxide surfaces, although incorporation of arsenic into a metal oxide structure cannot be unequivocally ruled out. Arsenic was found to occur in several different coordination environments and this, together with the low concentration (arsenic in the sediment, prevented the unambiguous assignment of the second coordination sphere. The analysis of the trends of key groundwater

  19. Potential Dependent Structural Changes of Underpotentially Deposited Copper on an Iodine Treated Platinum Surface Determined In Situ by Surface EXAFS and Its Polarization Dependence

    Science.gov (United States)

    1993-08-25

    of Underpotentially Deposited Copper on an Iodine Treated Platinum Surface Determined In Situ by Surface EXAFS and Its Polarization Dependence G.M...fiCAtson) Potential Dependent Structural Changes of Underpotentially Deposited Copper on an Irodine Treated Platinum Surface Determined In Situ by...necessary and identify by block number) An in situ structural investigation of the underpotential deposition of copper on an iodine covered platinum

  20. Lanthanide complexes of macrocyclic polyoxovanadates by VO4 units: synthesis, characterization, and structure elucidation by X-ray crystallography and EXAFS spectroscopy.

    Science.gov (United States)

    Nishio, Masaki; Inami, Shinnosuke; Katayama, Misaki; Ozutsumi, Kazuhiko; Hayashi, Yoshihito

    2012-01-16

    Reactions of a tetravanadate anion, [V(4)O(12)](4-), with a series of lanthanide(III) salts yield three types of lanthanide complexes of macrocyclic polyoxovanadates: (Et(4)N)(6)[Ln(III)V(9)O(27)] [Ln = Nd (1), Sm (2), Eu (3), Gd (4), Tb (5), Dy (6)], (Et(4)N)(5)[(H(2)O)Ho(III)(V(4)O(12))(2)] (7), and (Et(4)N)(7)[Ln(III)V(10)O(30)] [Ln = Er (8), Tm (9), Yb (10), Lu (11)]. Lanthanide complexes 1-11 are isolated and characterized by IR, elemental analysis, single-crystal X-ray diffraction, and extended X-ray absorption fine structure spectroscopy (EXAFS). Lanthanide complexes 1-6 are composed of a square-antiprism eight-coordinated Ln(III) center with a macrocyclic polyoxovanadate that is constructed from nine VO(4) tetrahedra through vertex sharing. The structure of 7 is composed of a seven-coordinated Ho(III) center, which exhibits a capped trigonal-prism coordination environment by the sandwiching of two cyclic tetravanadates with a capping H(2)O ligand. Lanthanide complexes 8-11 have a six-coordinated Ln(III) center with a 10-membered vanadate ligand. The structural trend to adopt a larger coordination number for a larger lanthanide ion among the three types of structures is accompanied by a change in the vanadate ring sizes. These lanthanide complexes are examined by EXAFS spectroscopies on lanthanide L(III) absorption edges, and the EXAFS oscillations of each of the samples in the solid state and in acetonitrile are identical. The Ln-O and Ln···V bond lengths obtained from fits of the EXAFS data are consistent with the data from the single-crystal X-ray studies, reflecting retention of the structures in acetonitrile.

  1. Phosphorus dynamics in Swedish agricultural soils as influenced by fertilization and mineralogical properties: Insights gained from batch experiments and XANES spectroscopy.

    Science.gov (United States)

    Eriksson, Ann Kristin; Hesterberg, Dean; Klysubun, Wantana; Gustafsson, Jon Petter

    2016-10-01

    The soil chemistry of phosphorus (P) is important for understanding the processes governing plant availability as well as the risk of environmental losses of P. The objective of this research was to investigate both the speciation and the pH-dependent solubility patterns of P in clayey agricultural soils in relation to soil mineralogy and fertilization history. The study focused on soil samples from six fields that were subjected to different P fertilization regimes for periods of 45 to 57years. Soil P speciation was analyzed by P K-edge XANES spectroscopy and chemical fractionation, sorption isotherms were constructed, and dissolved P was measured as a function of pH. The XANES fitting results showed that organic P and P adsorbed to Fe and Al (hydr)oxides were common P constituents in all soils. Calcium phosphates were identified in five of six soil samples. The XANES results also indicated an increase in P adsorbed to Al and to a lesser extent Fe (hydr)oxides as a result of fertilization. Moreover, the fluorescence intensity from the P K-edge XANES analysis was most strongly correlated with HCl-digestible P (r=0.81***). Consistent with the XANES analysis, laboratory sorption isotherm models showed that the Freundlich sorption coefficient (KF) was most closely related to oxalate-extractable Al. Greater proportions of Ca phosphate in two of the heavily fertilized soils in combination with enhanced PO4 solubilization upon sample acidification indicated neoformation of Ca-phosphate precipitates. The results for the unfertilized soil samples generally showed a minimum in dissolved PO4 between pH6.5 and 7.5, with increases particularly at lower pH. This behavior can be explained either by the dissolution of Al-hydroxide-type sorbents or Ca phosphates at lower pH. In fertilized soils, there was no consistent trend in pH-dependent solubilization of P, with a complex relationship to solid-phase speciation. To conclude, inorganic P species changed most dynamically in

  2. Simulation of the isotropic EXAFS spectra for the S2 and S3 structures of the oxygen evolving complex in photosystem II.

    Science.gov (United States)

    Li, Xichen; Siegbahn, Per E M; Ryde, Ulf

    2015-03-31

    Most of the main features of water oxidation in photosystem II are now well understood, including the mechanism for O-O bond formation. For the intermediate S2 and S3 structures there is also nearly complete agreement between quantum chemical modeling and experiments. Given the present high degree of consensus for these structures, it is of high interest to go back to previous suggestions concerning what happens in the S2-S3 transition. Analyses of extended X-ray adsorption fine structure (EXAFS) experiments have indicated relatively large structural changes in this transition, with changes of distances sometimes larger than 0.3 Å and a change of topology. In contrast, our previous density functional theory (DFT)(B3LYP) calculations on a cluster model showed very small changes, less than 0.1 Å. It is here found that the DFT structures are also consistent with the EXAFS spectra for the S2 and S3 states within normal errors of DFT. The analysis suggests that there are severe problems in interpreting EXAFS spectra for these complicated systems.

  3. Coupling XRD, EXAFS, and 13C NMR to study the effect of the carbon stoichiometry on the local structure of UC(1±x).

    Science.gov (United States)

    Carvajal Nuñez, U; Martel, L; Prieur, D; Lopez Honorato, E; Eloirdi, R; Farnan, I; Vitova, T; Somers, J

    2013-10-07

    A series of uranium carbide samples, prepared by arc melting with a C/U ratio ranging from 0.96 to 1.04, has been studied by X-ray diffraction (XRD), (13)C nuclear magnetic resonance (NMR), and extended X-ray absorption fine structure (EXAFS). XRD determines phase uniqueness and the increase of the lattice parameter versus the carbon content. In contrast, (13)C NMR detects the different carbon environments in the lattice and in this study, clearly identifies the presence of discrete peaks for carbon in the octahedral lattice site in UC and an additional peak associated with excess carbon in hyperstoichiometric samples. Two peaks associated with different levels of carbon deficiency are detected for all hypostoichiometric compositions. More than one carbon environment is always detected by (13)C NMR. This exemplifies the difficulty in obtaining a perfect stoichiometric uranium monocarbide UC(1.00). The (13)C MAS spectra of uranium carbides exhibit the effects resulting from the carbon content on both the broadening of the peaks and on the Knight shift. An abrupt spectral change occurs between hypo- and hyperstoichiometric samples. The results obtained by EXAFS highlight subtle differences between the different stoichiometries, and in the hyperstoichiometric samples, the EXAFS results are consistent with the excess carbon atoms being in the tetrahedral interstitial position.

  4. Probing Selenium-Ion Distributions and Changes in Redox-State at Biofilm/Mineral Interfaces by Coupling Long-period X-ray Standing Wave and XANES Measurements

    Science.gov (United States)

    Templeton, A. S.; Trainor, T. P.; Spormann, A. M.; Brown, G. E.

    2002-12-01

    Metal sorption and precipitation reactions at biological as well as mineral surfaces are important controls on metal speciation and bioavailability in natural environments. When highly hydrated biofilms form on mineral surfaces, numerous competitive and synergistic effects are predicted to occur. Experimentally, it is challenging to determine where the sorbed metal ions are localized, the relative affinity of the biological vs. mineral surface sites, or to monitor biomineralization reactions or changes in metal speciation that may also occur. A large part of the difficulty is due to the low concentrations of sorbed ions, the small length-scale of the biofilm-mineral interface, and the complex interplay between microbially-catalayzed redox transformations vs. sorption and/or transport processes. Long-period x-ray standing wave (XSW) techniques are well-suited to determining the vertical distribution of metal(oid) species within biofilms overlying mineral surfaces. We will discuss experiments where Se fluorescence yield profiles are used to compare the affinity of Burkholderia cepacia biofilms for binding Se(IV) and Se(VI) species relative to underlying alpha-Al2O3 substrates over three orders of magnitude in [Se]. In addition, we will discuss how coupling the XSW experiments to grazing-incidence, spatially-resolved Se K-edge XANES spectroscopy can be used to differentiate between the oxidation state of the Se complexes localized within the biofilm vs. the mineral surface. This approach is used to monitor changes in the relative distributions of Se(VI), Se(IV) and Se(0) species as a function of time and proximity to the mineral surface. The long-period XSW data show that selenite preferentially binds to the oxide surfaces, particularly at low [Se]. When B. cepacia is metabolically active, B. cepacia rapidly reduces a fraction of the Se(IV) to the red elemental Se form. In contrast, selenate is preferentially partitioned into the B. cepacia biofilms at all [Se] tested

  5. MICROSCANNING XRF, XANES, AND XRD STUDIES OF THEDECORATED SURFACE OF ROMAN TERRA SIGILLATA CERAMICS

    Energy Technology Data Exchange (ETDEWEB)

    Mirguet, C.; Sciau, P.; Goudeau, P.; Mehta, A.; Pianetta, P.; Liu, Z.; Tamura, N.

    2008-10-24

    Different microscanning synchrotron techniques were used to better understand the elaboration process and origins of Terra Sigillata potteries from the Roman period. A mixture Gallic slip sample cross-section showing red and yellow colors was studied. The small (micron) size of the X-ray beam available at Stanford Synchrotron Radiation Laboratory (SSRL) and Advanced Light Source (ALS) synchrotron sources, coupled with the use of a sample scanning stage allowed us to spatially resolve the distribution of the constitutive mineral phases related to the chemical composition. Results show that red color is a result of iron-rich hematite crystals and the yellow part is a result of the presence of Ti-rich rutile-type phase (brookite). Volcanic-type clay is at the origin of these marble Terra Sigillata.

  6. Uranium-bearing francolites present in organic-rich limestones of NW Greece: a preliminary study using synchrotron radiation and fission track techniques

    DEFF Research Database (Denmark)

    Tzifas, I. T.; Glasmacher, U. A.; Misaelides, P.;

    2017-01-01

    Synchrotron radiation techniques (μ-XRF and μ-XANES) were applied to the study of organic-rich phosphatized limestones of NW Greece (Epirus). The results revealed uranium accumulation in areas of the material containing, among others, carbonate apatite (francolite) and organic matter. The UL3-edge...

  7. Design, fabrication and testing of elliptical crystal bender for the EXAFS beam-line at INDUS-II synchrotron source

    Indian Academy of Sciences (India)

    N C Das; S N Jha; D Bhattacharyya; A K Poswal; A K Sinha; V K Mishra

    2004-10-01

    An extended X-ray absorption fine structure (EXAFS) beam-line for X-ray absorption studies using energy dispersive geometry and position sensitive detector is being developed for the INDUS-II synchrotron source. The optical design of the beam-line has been completed based on the working principle that a single crystal bent in the shape of an ellipse by a crystal bender would act as a dispersing as well as focusing element. The heart of the beam-line is the crystal bender which has been designed on the basis of the principle of four-point bending and has been fabricated indigenously. The crystal bender is capable of producing pre-defined elliptical curvature on a crystal surface by applying different couples at the two-ends of the crystal which has variable width along its length. The focusing property of the crystal bender has been tested using a laser source and has been compared with the theoretically simulated results.

  8. EXAFS study of cation reordering in NaYF4:Yb3+,Tb3+up-conversion luminescence materials

    Institute of Scientific and Technical Information of China (English)

    H.F. Brito; J. Hls; T. Laamanen; T. Laihinen; M. Lastusaari; L. Pihlgren; L.C.V. Rodrigues; T. Soukka

    2014-01-01

    The NaYF4:Yb3+,Tb3+(xYb:0.20, xTb:0.04) materials were prepared using the co-precipitation method. The as-prepared material was washed either with or without water in addition to ethanol and thereafter annealed for 5 hat 500 °C. This resulted in materials with moderate or very high up-conversıon luminescence intensity, respectively. The structural study carried out with X-ray powder diffraction revealed microstrains in the rare earth (R) sublattice that were relaxed for the material with very high up-conversion intensity thus decreasing energy losses. The local structural details were investigated with R LII and YK edge ex-tended X-ray absorption fine structure (EXAFS) using synchrotron radiation. Around 10 mol.% of the Yb3+ions were found to occupy the Na site in the material with very high up-conversion intensity. These Yb species formed clusters with the Tb3+ions occupying the regular Na/R sites. Such clustering enhanced the energy transfer between Yb3+ and Tb3+ thus intensifying the up-conversion emission.

  9. HARD REAL TIME QUICK EXAFS DATA ACQUISITION WITH ALL OPEN SOURCE SOFTWARE ON A COMMODITY PERSONAL COMPUTER.

    Energy Technology Data Exchange (ETDEWEB)

    SO,I.; SIDDONS, D.P.; CALIEBE, W.A.; KHALID, S.

    2007-04-25

    We describe here the data acquisition subsystem of the Quick EXAFS (QEXAFS) experiment at the National Synchrotron Light Source of Brookhaven National Laboratory. For ease of future growth and flexibility, almost all software components are open source with very active maintainers. Among them, Linux running on x86 desktop computer, RTAI for real-time response, COMEDI driver for the data acquisition hardware, Qt and PyQt for graphical user interface, PyQwt for plotting, and Python for scripting. The signal (A/D) and energy-reading (IK220 encoder) devices in the PCI computer are also EPICS enabled. The control system scans the monochromator energy through a networked EPICS motor. With the real-time kernel, the system is capable of deterministic data-sampling period of tens of micro-seconds with typical timing-jitter of several micro-seconds. At the same time, Linux is running in other non-real-time processes handling the user-interface. A modern Qt-based controls-front end enhances productivity. The fast plotting and zooming of data in time or energy coordinates let the experimenters verify the quality of the data before detailed analysis. Python scripting is built-in for automation. The typical data-rate for continuous runs are around ten mega-bytes per minute.

  10. The influence of dissolved Si on Ni precipitate formation at the kaolinite water interface: Kinetics, DRS and EXAFS analysis.

    Science.gov (United States)

    Tan, Xiaoli; Liu, Ge; Mei, Huiyang; Fang, Ming; Ren, Xuemei; Chen, Changlun

    2017-04-01

    Unraveling the formation process of Ni precipitates at molecular scale is important for understanding the fate and mobility of Ni species in the real environment. Dissolved Si presents in the natural environment ubiquitously, which can alter Ni sorption as well as incorporation into neoformed precipitates. Batch experiments show that the dissolved Si leads to a rapid increase in the Ni sorption rate and interferes with the formation of Ni precipitates. The results of diffuse reflectance spectroscopy (DRS) and extended X-ray absorption fine structure (EXAFS) spectroscopy analyses suggest that the nucleation of a (Ni,Al) phyllosilicate phase involves a kaolinite-like local structure. Then, the substantial presence of Si affects the initial formation of Ni precipitate nucleation and the resulting crystal growth. Dioctahedral kaolinite may act as a nucleating surface for the heterogeneous formation of trioctahedral (Ni,Al) phyllosilicates under environmentally relevant conditions. This study provides experimental evidence on nucleation and epitaxial growth processes of Ni precipitate on kaolinite and provides insight on the relationship between substrates and precipitation, which is crucial for understanding the physicochemical behavior of Ni on mineral surfaces.

  11. Iron speciation in soft-water lakes and soils as determined by EXAFS spectroscopy and geochemical modelling

    Science.gov (United States)

    Sjöstedt, Carin; Persson, Ingmar; Hesterberg, Dean; Kleja, Dan Berggren; Borg, Hans; Gustafsson, Jon Petter

    2013-03-01

    Complexation of iron by organic matter can potentially compete with toxic metals for binding sites. Iron(III) forms both monomeric and di/trimeric complexes with fulvic and humic acids, but the nature and extent of complexation with natural organic matter samples from soft-water lakes has not been extensively studied. The aim of this study was to determine the coordination of iron in complexes with organic matter in two soft-water lakes and in the surrounding Oe soil horizons. Iron K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy was performed on particles and large colloids (>0.45 μm) collected by in-line pre-filtration, and on smaller colloids isolated both on an AGMP-1 anion-exchange column and by concentration using 1000 Da ultrafiltration. The results showed that iron(III) was mainly present in monomeric complexes with organic matter, both in the lake water smaller colloids and in the soil samples. Evidence for iron(III) (hydr)oxides was found for the lake particles, in the ultrafiltration retentates, and in some of the soils. Overall, the results suggest that complexation of iron(III) to organic matter prevents hydrolysis into polymeric forms. Strong complexation of iron(III) would lead to competition with other metals for organic-matter binding sites.

  12. Effect of Organic Matter on Sorption of Zn on Soil: Elucidation by Wien Effect Measurements and EXAFS Spectroscopy.

    Science.gov (United States)

    Fan, Ting-Ting; Wang, Yu-Jun; Li, Cheng-Bao; He, Jian-Zhou; Gao, Juan; Zhou, Dong-Mei; Friedman, Shmulik P; Sparks, Donald L

    2016-03-15

    Soil organic matter (SOM) is the major factor affecting sequestration of heavy metals in soil. The mean free binding energy and the mean free adsorption energy and speciation of Zn in soil, as affected by SOM, were determined by employing Wien effect measurements. The presence of SOM markedly decreased the Zn binding energy in soils in the following order: Top (5.86 kJ mol(-1)) soil particles by reducing nonspecific adsorption of Zn on their surfaces. The speciation of Zn in soils was elucidated by extended X-ray absorption fine structure spectroscopy and microfocus X-ray fluorescence. The results obtained by linear combination fitting of EXAFS spectra revealed that the main forms of Zn in soil were outer-sphere Zn, Zn-illite, Zn-kaolinite, and HA-Zn. As the SOM content increased, the proportion of HA-Zn among the total immobilized Zn increased, and the proportion of nonspecific adsorbed Zn decreased. The present results implied that SOM is an important controlling factor for the environmental behavior of Zn in soils.

  13. HARD REAL TIME QUICK EXAFS DATA ACQUISITION WITH ALL OPEN SOURCE SOFTWARE ON A COMMODITY PERSONAL COMPUTER.

    Energy Technology Data Exchange (ETDEWEB)

    SO,I.; SIDDONS, D.P.; CALIEBE, W.A.; KHALID, S.

    2007-04-25

    We describe here the data acquisition subsystem of the Quick EXAFS (QEXAFS) experiment at the National Synchrotron Light Source of Brookhaven National Laboratory. For ease of future growth and flexibility, almost all software components are open source with very active maintainers. Among them, Linux running on x86 desktop computer, RTAI for real-time response, COMEDI driver for the data acquisition hardware, Qt and PyQt for graphical user interface, PyQwt for plotting, and Python for scripting. The signal (A/D) and energy-reading (IK220 encoder) devices in the PCI computer are also EPICS enabled. The control system scans the monochromator energy through a networked EPICS motor. With the real-time kernel, the system is capable of deterministic data-sampling period of tens of micro-seconds with typical timing-jitter of several micro-seconds. At the same time, Linux is running in other non-real-time processes handling the user-interface. A modern Qt-based controls-front end enhances productivity. The fast plotting and zooming of data in time or energy coordinates let the experimenters verify the quality of the data before detailed analysis. Python scripting is built-in for automation. The typical data-rate for continuous runs are around ten mega-bytes per minute.

  14. The O2-Evolving Complex of Photosystem II: Recent Insights from Quantum Mechanics/Molecular Mechanics (QM/MM), Extended X-ray Absorption Fine Structure (EXAFS), and Femtosecond X-ray Crystallography Data.

    Science.gov (United States)

    Askerka, Mikhail; Brudvig, Gary W; Batista, Victor S

    2017-01-17

    Efficient photoelectrochemical water oxidation may open a way to produce energy from renewable solar power. In biology, generation of fuel due to water oxidation happens efficiently on an immense scale during the light reactions of photosynthesis. To oxidize water, photosynthetic organisms have evolved a highly conserved protein complex, Photosystem II. Within that complex, water oxidation happens at the CaMn4O5 inorganic catalytic cluster, the so-called oxygen-evolving complex (OEC), which cycles through storage "S" states as it accumulates oxidizing equivalents and produces molecular oxygen. In recent years, there has been significant progress in understanding the OEC as it evolves through the catalytic cycle. Studies have combined conventional and femtosecond X-ray crystallography with extended X-ray absorption fine structure (EXAFS) and quantum mechanics/molecular mechanics (QM/MM) methods and have addressed changes in protonation states of μ-oxo bridges and the coordination of substrate water through the analysis of ammonia binding as a chemical analog of water. These advances are thought to be critical to understanding the catalytic cycle since protonation states regulate the relative stability of different redox states and the geometry of the OEC. Therefore, establishing the mechanism for substrate water binding and the nature of protonation/redox state transitions in the OEC is essential for understanding the catalytic cycle of O2 evolution. The structure of the dark-stable S1 state has been a target for X-ray crystallography for the past 15 years. However, traditional X-ray crystallography has been hampered by radiation-induced reduction of the OEC. Very recently, a revolutionary X-ray free electron laser (XFEL) technique was applied to PSII to reveal atomic positions at 1.95 Å without radiation damage, which brought us closer than ever to establishing the ultimate structure of the OEC in the S1 state. However, the atom positions in this crystal

  15. The local structure of Ca-Na pyroxenes. 2-Xanes studies at the Mg and A1 K edges

    Energy Technology Data Exchange (ETDEWEB)

    Mottana, A. [Rome Univ. Roma Tre, Rome (Italy). Dipt. di Scienze Geologiche; Murata, T. [Kyoto University of Education, Kyoto (Japan). Dept. of Physics; Marcelli, A. [Istituto Nazionale di Fisica Nucleare, Frascati, RM (Italy). Laboratori Nazionali di Frascati; Wu, Z.Y. [Istituto Nazionale di Fisica Nucleare, Frascati, RM (Italy). Laboratori Nazionali di Frascati]|[Laboratoire Piere Suee, Gif-sur Yvette Cedex, (France); Cibin, G. [Istituto Nazionale di Fisica Nucleare, Frascati, RM (Italy). Laboratori Nazionali di Frascati; Paris, E. [Camerino Univ., Camerino, MC (Italy). Dipt. di Scienze della Terra; Giuli, G. [Camerino Univ., Camerino, MC (Italy). Dipt. di Scienze della Terra]|[Florence Univ., Florence (Italy). Dipt. di Scienze della Terra

    1999-07-01

    X-ray absorption spectra at the Mg and A1 K edges have been recorded on synthetic end member diopside (Di) and jadeite (Jd) and on a series of natural Fe-poor Ca-Na clinopyroxenes compositionally straddling the Jd-Di join. The spectra of C2/c members of the series (C-omphacites) are different from having P2/n symmetry (P-omphacites). Differences can be explained by theoretical spectra calculated via the multiple-scattering formalism on atomic clusters with at least 89 atoms, extending to a. 0.62 nm away from the Mg viz. A1 absorber: Xanes detects in these systems medium- rather than short-range order-disorder relationships. Near-edge features of C-omphacites reflect the single-type of octahedral arrangement of the back scattering nearest-neighbours (six O atoms) around the absorber (Mg resp. A1) at the centre of the cluster (site M1). Others arise again from medium-range order. P-omphacites show more complicated spectra than C-omphacites. Their additional features reflect the increased local disorder around the probed atom (Mg resp. A1) induced by the two alternative M1, M11 configurations of the six O atoms forming the first co-ordination spheres. Mg and A1 are confirmed to be preferentially partitioned in the M1 resp. M11 site of the P-omphacite crystal structure, however never exclusively, but in a ratio close to 85:15 (plus or minus 10%) that implies a certain degree of local disorder. Changes in the relative heights of some prominent features are more evident in the A1 than in the Mg K-edge spectra. They are diagnostic to qualitatively distinguish C-from P-omphacites.

  16. Local structure information by EXAFS analysis using two algorithms for Fourier transform calculation

    Energy Technology Data Exchange (ETDEWEB)

    Aldea, N; Pintea, S; Rednic, V [National Institute for Research and Development of Isotopic and Molecular Technologies, 65-103 Donath, 400293 Cluj-Napoca (Romania); Matei, F [University of Agricultural Sciences and Veterinary Medicine, 3-5 Calea Manastur, 400372 Cluj-Napoca (Romania); Hu Tiandou; Xie Yaning, E-mail: nicolae.aldea@itim-cj.r [Beijing Synchrotron Radiation Facilities of Beijing Electron Positron Collider National Laboratory (China)

    2009-08-01

    The present work is a comparison study between different algorithms of Fourier transform for obtaining very accurate local structure results using Extended X-ray Absorption Fine Structure technique. In this paper we focus on the local structural characteristics of supported nickel catalysts and Fe{sub 3}O{sub 4} core-shell nanocomposites. The radial distribution function could be efficiently calculated by the fast Fourier transform when the coordination shells are well separated while the Filon quadrature gave remarkable results for close-shell coordination.

  17. Chromium speciation in hazardous, cement-based waste forms

    Science.gov (United States)

    Lee, J. F.; Bajt, S.; Clark, S. B.; Lamble, G. M.; Langton, C. A.; Oji, L.

    1995-02-01

    XANES and EXAFS techniques were used to determine the oxidation states and local structural environment of Cr in cement-based waste forms. Results show that Cr in untreated Portland cement formulations remains as toxic Cr 6+, while slag additives to the cement reduce Cr 6+ to the less toxic, less mobile Cr 3+ species. EXAFS analysis suggests that the Cr 6+ species is surrounded by four nearest oxygen atoms, while the reduced Cr 3+ sp ecies is surrounded by six oxygen atoms. The fitted CrO bond lengths for Cr 6+ and Cr 3+ species are around 1.66 and 1.98 Å, respectively.

  18. Study of Ga incorporation in glassy arsenic selenides by high-resolution XPS and EXAFS

    Energy Technology Data Exchange (ETDEWEB)

    Golovchak, R., E-mail: holovchakr@apsu.edu [Department of Physics and Astronomy, Austin Peay State University, Clarksville, Tennessee 37044 (United States); Shpotyuk, Ya. [Equipe Verres et Céramiques UMR-CNRS 6226, Université de Rennes 1, 35042 Rennes Cedex (France); Scientific Research Company “Carat”, 202, Stryjska Str., 79031 Lviv (Ukraine); Nazabal, V.; Boussard-Pledel, C.; Bureau, B. [Equipe Verres et Céramiques UMR-CNRS 6226, Université de Rennes 1, 35042 Rennes Cedex (France); Cebulski, J. [Center for Microelectronics and Nanotechnology, University of Rzeszow, 1, Pigonia Str., 35-310 Rzeszow (Poland); Jain, H. [Department of Materials Science and Engineering, Lehigh University, 5 East Packer Avenue, Bethlehem, Pennsylvania 18015-3195 (United States)

    2015-05-14

    Effect of Ga addition on the structure of vitreous As{sub 2}Se{sub 3} is studied using high-resolution X-ray photoelectron spectroscopy and extended X-ray absorption fine structure techniques. The “8-N” rule is shown to be violated for Ga atoms and, possibly, for certain number of As atoms. On the contrary, Se keeps its 2-fold coordination according to “8-N” rule in the amorphous phase throughout all the compositions. Crystalline inclusions appear in the amorphous structure of the investigated glasses at Ga concentrations greater than 3 at. %. These inclusions are presumably associated with Ga{sub 2}Se{sub 3} crystallites and transition phases/defects formed at the boundaries of these crystallites and host amorphous matrix. The existence of Ga–As and Se–Se bonds in the samples with higher Ga content is supported by present studies.

  19. Study of Ga incorporation in glassy arsenic selenides by high-resolution XPS and EXAFS.

    Science.gov (United States)

    Golovchak, R; Shpotyuk, Ya; Nazabal, V; Boussard-Pledel, C; Bureau, B; Cebulski, J; Jain, H

    2015-05-14

    Effect of Ga addition on the structure of vitreous As2Se3 is studied using high-resolution X-ray photoelectron spectroscopy and extended X-ray absorption fine structure techniques. The "8-N" rule is shown to be violated for Ga atoms and, possibly, for certain number of As atoms. On the contrary, Se keeps its 2-fold coordination according to "8-N" rule in the amorphous phase throughout all the compositions. Crystalline inclusions appear in the amorphous structure of the investigated glasses at Ga concentrations greater than 3 at. %. These inclusions are presumably associated with Ga2Se3 crystallites and transition phases/defects formed at the boundaries of these crystallites and host amorphous matrix. The existence of Ga-As and Se-Se bonds in the samples with higher Ga content is supported by present studies.

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

    Science.gov (United States)

    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.

  1. Adsorption of Cu(II) to Bacillus subtilis: A pH-dependent EXAFS and thermodynamic modelling study

    Science.gov (United States)

    Moon, Ellen M.; Peacock, Caroline L.

    2011-11-01

    Bacteria are very efficient sorbents of trace metals, and their abundance in a wide variety of natural aqueous systems means biosorption plays an important role in the biogeochemical cycling of many elements. We measured the adsorption of Cu(II) to Bacillus subtilis as a function of pH and surface loading. Adsorption edge and XAS experiments were performed at high bacteria-to-metal ratio, analogous to Cu uptake in natural geologic and aqueous environments. We report significant Cu adsorption to B. subtilis across the entire pH range studied (pH ˜2-7), with adsorption increasing with pH to a maximum at pH ˜6. We determine directly for the first time that Cu adsorbs to B. subtilis as a (CuO 5H n) n-8 monodentate, inner-sphere surface complex involving carboxyl surface functional groups. This Cu-carboxyl complex is able to account for the observed Cu adsorption across the entire pH range studied. Having determined the molecular adsorption mechanism of Cu to B. subtilis, we have developed a new thermodynamic surface complexation model for Cu adsorption that is informed by and consistent with EXAFS results. We model the surface electrostatics using the 1p K basic Stern approximation. We fit our adsorption data to the formation of a monodentate, inner-sphere tbnd RCOOCu + surface complex. In agreement with previous studies, this work indicates that in order to accurately predict the fate and mobility of Cu in complex biogeochemical systems, we must incorporate the formation of Cu-bacteria surface complexes in reactive transport models. To this end, this work recommends log K tbnd RCOOCu + = 7.13 for geologic and aqueous systems with generally high B. subtilis-to-metal ratio.

  2. XANES at Eu-L3 edge and valence of europium in SrB4O7: Eu and BaB8O13: Eu

    Institute of Scientific and Technical Information of China (English)

    LIANG, Hong- Bin(梁宏斌); HU, Tian-Dou(胡天斗); WANG, Shu-Bin(王淑彬); ZENG, Qing-Hua(曾庆华); PEI, Zhi-Wu(裴治武); SU, Qiang(苏锵)

    2000-01-01

    The luminescent materials SrB4O7: Eu and BaB8O13: Eu were synthesized, and the valence states of europium in the materials were measured by means of XANES at Eu-L3 edge. It is found that the Eu3+ and Eu2+ ions are all present in the materials, and more Eu3+ ions can be reduced in SrB4O7:Eu than in BaB8O13:Eu. The excitation and emission spectra of Eu3+in SrB4O7:Eu and BaB8O13:Eu were determined.

  3. A comparison between powders and thin films of single-walled carbon nanotubes for the adsorption behaviors of phenylalanine and glycine by XANES study

    Institute of Scientific and Technical Information of China (English)

    IBRAHIM; Kurash

    2010-01-01

    We have compared the adsorption behaviors between single-walled carbon nanotube (SWCNT) powders and thin films with amino acids such as phenylalanine and glycine by using the X-ray absorption near edge structure (XANES) spectroscopy. On SWCNT powders very weak adsorption occurs as confirmed also by studies at high solution concentrations. The comparison of the adsorption behaviors with previous reports for thin films of SWCNTs shows that, due to their compact structure, thin films favor the adsorption of amino acids and represent themselves good candidate for a reliable evaluation of the interaction among amino acids and SWCNTs.

  4. Localization and speciation of Zn in mycorrhized roots by {mu}SXRF and{mu}EXAFS

    Energy Technology Data Exchange (ETDEWEB)

    Sarret, G.; Schroeder, W.H.; Marcus, Matthew A.; Geoffroy, N.; Manceau, Alain

    2004-09-23

    Mycorrizae are symbiotic associations between soil fungi and plant roots, which enhance mineral nutrition for the plant, and might play an important role in metals acquisition and accumulation. The processes allowing metal mobilization in the soil, absorption by the root and/or the fungus, transfer or bioaccumulation are still poorly understood. However, the properties of mycorrhizal fungi could be used for phytoremediation, a soft technique using plants for the clean-up of metal-polluted soils. In this work, mycorrhized roots of tomato plants grown in a Zn-contaminated soil were investigated. The distribution of metals and the speciation of Zn were studied on the micron scale using micro synchrotron-based X-ray fluorescence and micro X-ray absorption spectroscopy. Zn associated to the root was Zn malate and/or Zn citrate, and Zn associated to the fungus was Zn phyllosilicate. This study illustrates the great potential of X-ray microbeams for the study of biological samples containing various amounts of metals.

  5. Disorder effects on EXAFS modeling for catalysts working at elevated temperatures

    Science.gov (United States)

    Sun, Xueping; Sun, Fanfei; Sun, Zhihu; Chen, Jing; Du, Xianlong; Wang, Jianqiang; Jiang, Zheng; Huang, Yuying

    2017-08-01

    In-situ X-ray absorption fine structure spectroscopy (XAFS) has been widely used to study the structure around active site of catalysts at elevated pressures and temperatures for decades. However, methods of XAFS data analysis can vary significantly, depending on the disorder degree of the material system investigated. In this work, in-situ XAFS was explored to investigate the structural evolutions of the industry CuO/ZnO/Al2O3 catalyst for methanol synthesis at elevated temperatures in nitrogen (N2) atmosphere. Due to the large Debye-Waller factor, data analysis using the conventional Gaussian mode resulted in erroneously contracted Cu-Cu bond distances which made the conventional Gaussian mode invalid in this system. To account for the deviation from harmonic behavior, the cumulant expansion technique was used to correct the error in the bond contraction, and the frequency pattern could be fully reproduced by considering cumulants up to C3. In order to elucidate the contributions of the structure and thermal components to the Debye-Waller factors, the Einstein method was also used to analyze the data that provides a straightforward proof regarding the effect of the temperature on the in-situ XAFS experiment.

  6. Structural characterization and EXAFS wavelet analysis of Yb doped ZnO by wet chemistry route

    Energy Technology Data Exchange (ETDEWEB)

    Otal, Eugenio H., E-mail: eugenio.otal@citedef.gob.ar [Division of Porous Materials, UNIDEF, CITEDEF, CONICET, S.J.B de la Salle 4397, Villa Martelli (B1603ALO), Buenos Aires (Argentina); Laboratory for Materials Science and Technology, FRSC-UTN, Av. Inmigrantes 555, Río Gallegos 9400 (Argentina); Sileo, Elsa [INQUIMAE, Departamento de Química Inorgánica, Analítica y Química Física, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires (Argentina); Aguirre, Myriam H. [Dept. of Physics Condensed Matter, University of Zaragoza (Spain); Laboratory of Advanced Microscopy (LMA), Institute of Nanoscience of Aragón (INA), University of Zaragoza (Spain); Fabregas, Ismael O. [Division of Porous Materials, UNIDEF, CITEDEF, CONICET, S.J.B de la Salle 4397, Villa Martelli (B1603ALO), Buenos Aires (Argentina); Kim, Manuela [Division of Porous Materials, UNIDEF, CITEDEF, CONICET, S.J.B de la Salle 4397, Villa Martelli (B1603ALO), Buenos Aires (Argentina); Laboratory for Materials Science and Technology, FRSC-UTN, Av. Inmigrantes 555, Río Gallegos 9400 (Argentina)

    2015-02-15

    Highlights: • Optical and electrical properties of ZnO are influenced by lanthanide doping. • Optical and electrical properties of ZnO are influenced by lanthanide positioning. • Yb is incorporated in the O{sub h} sites of the wurtzite structure. • There is not Yb{sub 2}O{sub 3} clustering or segregation for treatments below 800 °C. - Abstract: Lanthanide doped ZnO are interesting materials for optical and electrical applications. The wide band gap of this semiconductor makes it transparent in the visible range (E{sub gap} = 3.2 eV), allowing a sharp emission from intra shell transition from the lanthanides. From the electrical side, ZnO is a widely used material in varistors and its electrical properties can be tailored by the inclusion of lanthanides. Both applications are influenced by the location of the lanthanides, grain boundaries or lattice inclusion. Yb doped ZnO samples obtained by wet chemistry route were annealed at different temperatures and characterized by Transmission Electron Microscopy (TEM), X-ray Diffraction (XRD), Rietveld refinement of XRD data, and X-ray Absorption Fine Structure (XAFS). These techniques allowed to follow the changes occurred in the matrix and the Yb environment. The use of the Cauchy continuous wavelet transform allowed identifying a second coordination shell composed of Zn atoms, supporting the observations from XRD Rietveld refinement and XAFS fittings. The information obtained confirmed the incorporation of Yb in O{sub h} sites of the wurtzite structure without Yb{sub 2}O{sub 3} clustering in the lattice.

  7. Biogéochimie structurale du zinc et du plomb par spectroscopie EXAFS : interactions avec des acides humiques, des parois cellulaires de champignon, et des lichens

    OpenAIRE

    Sarret, Géraldine

    1998-01-01

    Le risque écotoxicologique des métaux présents dans le milieu naturel dépend beaucoup plus de leur statut physico-chimique que de leur concentration totale. Afin de déterminer ce statut, nous avons étudié par spectroscopie EXAFS les interactions au niveau moléculaire du zinc et du plomb avec différents systèmes naturels organiques: des acides humiques (AH), constituants de la matière organique des sols; des parois cellulaires de champignons filamenteux , utilisés comme biosorbants pour le tra...

  8. Coupling XRD, EXAFS and 13C NMR to study the effect of the carbon stoichiometry on the local structure of UC1±x

    OpenAIRE

    CARVAJAL NUNEZ URSULA; MARTEL LAURA; PRIEUR DAMIEN; Eloirdi, Rachel; FARNAN Ian; Vitova, Tonya; Somers, Joseph; LOPEZ HONORATO Eddie

    2012-01-01

    A series of uranium carbide samples, prepared by arc melting with a C/U ratio ranging from 0.96 to 1.04, has been studied by X-Ray Diffraction (XRD), 13C Nuclear Magnetic Resonance (NMR) and by Extended X-ray Absorption Fine Structure (EXAFS). XRD determines phase uniqueness and the increase of the lattice parameter versus the carbon content. In contrast, 13C NMR detects the different carbon environments in the lattice and in this study, clearly identifies the presence of discrete peaks for c...

  9. Simulation of temperature distribution by finite element analysis on different components of the EXAFS beamline at INDUS-II synchrotron source

    Indian Academy of Sciences (India)

    D Bhattacharyya; S N Jha; N C Das; Vishnu Verma; S G Markandeya; A K Ghosh

    2005-12-01

    An extended X-ray absorption fine structure (EXAFS) beamline is being developed for the INDUS-II synchrotron source. Several optical and mechanical components of the beamline are exposed to high intensity synchrotron radiation while in operation. The temperature rise on different components of the beamline on exposure to the synchrotron beam has been simulated by finite element analysis. Design of the cooling mechanism for each of these components has been carried out and estimation of the temperature rise has also been done incorporating the cooling mechanism.

  10. EXAFS investigations on nanocomposites composed of surface-modified zirconium and zirconium/titanium mixed metal oxo-clusters and organic polymers

    CERN Document Server

    Kickelbick, G; Trimmel, G; Schubert, U; Feth, M P; Bertagnolli, H

    2002-01-01

    The surface-modified oxometallate clusters Zr sub 6 (OH) sub 4 O sub 4 (OMc) sub 1 sub 2 , Ti sub 4 Zr sub 4 O sub 6 (OBu) sub 4 (OMc) sub 1 sub 6 , and Ti sub 2 Zr sub 4 O sub 4 (OBu) sub 2 (OMc) sub 1 sub 4 (OMc methacrylate) as well as their nanocomposites with polystyrene, poly(methacrylic acid) and poly(methyl methacrylate) were investigated by EXAFS. Studies on the nanocomposites revealed that the structure of the cluster core is retained in the hybrid materials. (author)

  11. Nitrogen K-edge X-ray absorption near edge structure (XANES) spectra of purine-containing nucleotides in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Shimada, Hiroyuki; Fukao, Taishi; Minami, Hirotake; Ukai, Masatoshi [Department of Applied Physics, Tokyo University of Agriculture and Technology, Koganei-shi, Tokyo 184-8588 (Japan); Fujii, Kentaro; Yokoya, Akinari [Advanced Science Research Center, Japan Atomic Energy Agency, Tokai-mura, Naka-gun, Ibaraki 319-1195 (Japan); Fukuda, Yoshihiro; Saitoh, Yuji [Synchrotron Radiation Research Center, Japan Atomic Energy Agency, Sayo-gun, Hyougo 679-5148 (Japan)

    2014-08-07

    The N K-edge X-ray absorption near edge structure (XANES) spectra of the purine-containing nucleotide, guanosine 5{sup ′}-monophosphate (GMP), in aqueous solution are measured under various pH conditions. The spectra show characteristic peaks, which originate from resonant excitations of N 1s electrons to π* orbitals inside the guanine moiety of GMP. The relative intensities of these peaks depend on the pH values of the solution. The pH dependence is explained by the core-level shift of N atoms at specific sites caused by protonation and deprotonation. The experimental spectra are compared with theoretical spectra calculated by using density functional theory for GMP and the other purine-containing nucleotides, adenosine 5{sup ′}-monophosphate, and adenosine 5{sup ′}-triphosphate. The N K-edge XANES spectra for all of these nucleotides are classified by the numbers of N atoms with particular chemical bonding characteristics in the purine moiety.

  12. In situ XANES studies of TiO{sub 2}/Fe{sub 3}O{sub 4}-C during photocatalytic degradation of trichloroethylene

    Energy Technology Data Exchange (ETDEWEB)

    Hsu, T.-F.; Hsiung, T.-L. [Department of Environmental Engineering, National Cheng Kung University, Tainan 70101, Taiwan (China); Wang, James [Department of Biomedical Engineering, University of Southern California, Los Angeles 90007 (United States); Huang, C.-H. [Department of Environmental Engineering, National Cheng Kung University, Tainan 70101, Taiwan (China); Paul Wang, H., E-mail: wanghp@mail.ncku.edu.t [Department of Environmental Engineering, National Cheng Kung University, Tainan 70101, Taiwan (China); Sustainable Environmental Research Center, National Cheng Kung University, Tainan 70101, Taiwan (China)

    2010-07-21

    Mainly anatase and Fe{sub 3}O{sub 4} in the magnetic photocatalysts (TiO{sub 2} on Fe{sub 3}O{sub 4}-C core-shell nanoparticles (TiO{sub 2}/Fe{sub 3}O{sub 4}-C)) are observed by X-ray powder diffraction (XRD) spectroscopy. The Ti K-edge least-square fitted XANES spectra of the TiO{sub 2}/Fe{sub 3}O{sub 4}-C photocatalyst indicate that the main titanium species are nanosize TiO{sub 2} (9 nm) (77%) and bulky TiO{sub 2} (23%). Speciation of titanium in the TiO{sub 2}/Fe{sub 3}O{sub 4}-C during photocatalytic degradation of 100 ppm of trichloroethylene (TCE) has also been studied by in situ X-ray absorption near-edge structural (XANES) spectroscopy. TiO{sub 2} is not perturbed during the course of photocatalysis. However, it is worth to note that during photocatalytic degradation of TCE, about 33% of FeO and 67% of Fe{sub 3}O{sub 4} are observed in the photocatalyst. It seems that the carbon layer on the TiO{sub 2}/Fe{sub 3}O{sub 4}-C photocatalysts can reduce the possibility for photoexcited electron-hole recombination as usually found on the relatively narrow bandgap of ferric oxide during photocatalysis.

  13. EXAFS study of mercury(II) sorption to Fe- and Al-(hydr)oxides - II. Effects of chloride and sulfate

    Science.gov (United States)

    Kim, C.S.; Rytuba, J.J.; Brown, Gordon E.

    2004-01-01

    Common complexing ligands such as chloride and sulfate can significantly impact the sorption of Hg(II) to particle surfaces in aqueous environmental systems. To examine the effects of these ligands on Hg(II) sorption to mineral sorbents, macroscopic Hg(II) uptake measurements were conducted at pH 6 and [Hg]i=0.5 mM on goethite (??-FeOOH), ??-alumina (??-Al2O3), and bayerite (??-Al(OH)3) in the presence of chloride or sulfate, and the sorption products were characterized by extended X-ray absorption fine structure (EXAFS) spectroscopy. The presence of chloride resulted in reduced uptake of Hg(II) on all three substrates over the Cl- concentration ([Cl-]) range 10-5 to 10-2 M, lowering Hg surface coverages on goethite, ??-alumina, and bayerite from 0.42 to 0.07 ??mol/m2, 0.06 to 0.006 ??mol/m2, and 0.55 to 0.39 ??mol/m2 ([Cl -]=10-5 to 10-3 M only), respectively. This reduction in Hg(II) uptake is primarily a result of the formation of stable, nonsorbing aqueous HgCl2 complexes in solution, limiting the amount of free Hg(II) available to sorb. At higher [Cl-] beam reduction of Hg(II) to Hg(I) was observed, resulting in the possible formation of aqueous Hg2Cl2 species and the precipitation of calomel, Hg 2Cl2(s). The presence of sulfate caused enhanced Hg(II) uptake over the sulfate concentration ([SO42-]) range 10-5 to 0.9 M, increasing Hg surface coverages on goethite, ??-alumina, and bayerite from 0.39 to 0.45 ??mol/m2, 0.11 to 0.38 ??mol/m2, and 0.36 to 3.33 ??mol/m2, respectively. This effect is likely due to the direct sorption or accumulation of sulfate ions at the substrate interface, effectively reducing the positive surface charge that electrostatically inhibits Hg(II) sorption. Spectroscopic evidence for ternary surface complexation was observed in isolated cases, specifically in the Hg-goethite-sulfate system at high [SO42-] and in the Hg-goethite-chloride system. ?? 2003 Elsevier Inc. All rights reserved.

  14. Assessment of uranium and selenium speciation in human and bacterial biological models to probe changes in their structural environment

    Energy Technology Data Exchange (ETDEWEB)

    Avoscan, L.; Milgram, S.; Untereiner, G.; Collins, R.; Khodja, H.; Carriere, M.; Gouget, B. [Lab. Pierre Sue, CEA-CNRS UMR 9956, CEA/Saclay, Gif-sur-Yvette (France); Coves, J. [Inst. de Biologie Structurale - J.-P. Ebel, Lab. des Proteines Membranaires, Grenoble (France); Hazemann, J.L. [Lab. de Geophysique Interne et Tectonopbysique, UMR CNRS/Univ. Joseph Fourier, Saint-Martin-D' Heres (France)

    2009-07-01

    This study illustrates the potential of physicochemical techniques to speciate uranium (U) and selenium (Se) in biological samples. Speciation, defined he0re as the study of structural environment, of both toxic elements, was characterized at several levels in biological media and directly in human cells or bacteria once the metal(loid)s were internalized. External speciation that is extracellular speciation in culture media was predicted by thermodynamic equilibrium computer modelling using the JChess software and validated by spectroscopic measurements (XANES and EXAFS). Internal speciation that is intracellular speciation in eukaryotic and prokaryotic cells was studied in vitro with a soil bacterium Cupriavidus metallidurans CH34 and ROS 17/2.8 osteoblasts, human cells responsible for bone formation. XANES, EXAFS, HPLC-ICP-MS and SDS-PAGE coupled to particle induced X-ray emission (PIXE) permitted the identification and quantification of complexes formed with organic or inorganic molecules and/or larger proteins. (orig.)

  15. FTIR and EXAFS investigations of microstructures of gold solvent extraction:hydrogen bonding between modifier and Au(CN)2—

    Institute of Scientific and Technical Information of China (English)

    GangMa; TiandouHu; 等

    1999-01-01

    The microstructures of loaded organic phases of three quaternary amine solvent extraction systems for gold,which were N263-xylene,N263-tributyl phosphate(TBP)-dodecane and N263-2 -ethylhexanol (isooctanol)-dodecane(N263-trialkylmethylammonium chloride;alkyl=C8-C10),were studied by Fourier transform infrared (FTIR) spectroscopy and extended X-ray abso\\rption fine structure(EXAFS) spectroscopy. According to the EXAFS results,it was found that the gold coordination environment was the same before and after extraction.However,the C≡N stretching vibrations of Au(CN)2-were also found to be different,In order to explain the differences in the IR characteristics of C≡N in the three extraction systems,three microstructure models are proposed.For the N263-xylene system,the model is a simple ion pair.For the other two systems with a modifier(TBP and isooctanol),the models are two supramolecular structues based on hydrogen bonding between the modifier and Au(CN)2-.Some related work such as on the hydration of acetonitrile and the fine structure of C≡N in solid K Au(CN)2 was also performed in order to offer additional supporting evidence for the reliability of the proposed models.

  16. Atomic resolution crystal structures, EXAFS, and quantum chemical studies of rusticyanin and its two mutants provide insight into its unusual properties.

    Science.gov (United States)

    Barrett, Mark L; Harvey, Ian; Sundararajan, Mahesh; Surendran, Rajeev; Hall, John F; Ellis, Mark J; Hough, Michael A; Strange, Richard W; Hillier, Ian H; Hasnain, S Samar

    2006-03-07

    Rusticyanin from the extremophile Thiobacillus ferrooxidans is a blue copper protein with unusually high redox potential and acid stability. We present the crystal structures of native rusticyanin and of its Cu site mutant His143Met at 1.27 and 1.10 A, respectively. The very high resolution of these structures allows a direct comparison with EXAFS data and with quantum chemical models of the oxidized and reduced forms of the proteins, based upon both isolated and embedded clusters and density functional theory (DFT) methods. We further predict the structure of the Cu(II) form of the His143Met mutant which has been experimentally inaccessible due to its very high redox potential. We also present metrical EXAFS data and quantum chemical calculations for the oxidized and reduced states of the Met148Gln mutant, this protein having the lowest redox potential of all currently characterized mutants of rusticyanin. These data offer new insights into the structural factors which affect the redox potential in this important class of proteins. Calculations successfully predict the structure and the order of redox potentials for the three proteins. The calculated redox potential of H143M ( approximately 400 mV greater than native rusticyanin) is consistent with the failure of readily available chemical oxidants to restore a Cu(II) species of this mutant. The structural and energetic effects of mutating the equatorial cysteine to serine, yet to be studied experimentally, are predicted to be considerable by our calculations.

  17. Temperature dependent changes of the Mn 3d and 4p bands near $T_{c}$ in Colossal Magnetoresistance systems : a XANES study of $La_{1-x}Ca_{x}MnO_{3}$

    NARCIS (Netherlands)

    Bridges, F; Booth, C. H.; Kwei, G. H.; Neumeier, J. J.; Sawatzky, G. A.

    2000-01-01

    Abstract: We report high-resolution X-ray Absorption Near Edge Structure (XANES)measurements at the Mn K-edge as a function of temperature, forLa$_{1-x}$Ca$_x$MnO$_3$ samples, with a focus mainly on the pre-edge region.Small peaks labeled A$_1$-A$_3$ are observed which corresponds to

  18. Iron Oxide with Different Crystal Phases (α- and γ-Fe2O3) in Electroanalysis and Ultrasensitive and Selective Detection of Lead(II): An Advancing Approach Using XPS and EXAFS.

    Science.gov (United States)

    Li, Shan-Shan; Li, Wen-Juan; Jiang, Tian-Jia; Liu, Zhong-Gang; Chen, Xing; Cong, Huai-Ping; Liu, Jin-Huai; Huang, Yu-Ying; Li, Li-Na; Huang, Xing-Jiu

    2016-01-01

    Iron oxide with different crystal phases (α- and γ-Fe2O3) has been applied to electrode coatings and been demonstrated to ultrasensitive and selective electrochemical sensing toward heavy metal ions (e.g., Pb(II)). A range of Pb(II) contents in micromoles (0.1 to 1.0 μM) at α-Fe2O3 nanoflowers with a sensitivity of 137.23 μA μM(-1) cm(-2) and nanomoles (from 0.1 to 1.0 nM) at γ-Fe2O3 nanoflowers with a sensitivity of 197.82 μA nM(-1) cm(-2) have been investigated. Furthermore, an extended X-ray absorption fine structure (EXAFS) technique was applied to characterize the difference of local structural environment of the adsorbed Pb(II) on the surface of α- and γ-Fe2O3. The results first showed that α- and γ-Fe2O3 had diverse interaction between Pb(II) and iron (hydro)oxides, which were consistent with the difference of electrochemical performance. Determining the responses of Cu(II) and Hg(II) as the most appropriate choice for comparison, the stripping voltammetric quantification of Pb(II) with high sensitivity and selectivity at γ-Fe2O3 nanoflower has been demonstrated. This work reveals that the stripping performances of a nanomodifier have to be directly connected with its intrinsic surface atom arrangement.

  19. The Perovskite to Post-Perovskite phase transition in Al-bearing (Mg,Fe)SiO3: A XANES in-situ analysis at the Fe K-edge

    Science.gov (United States)

    Andrault, D.; Munoz, M.; Bolfan-Casanova, N.; Guignot, N.; Perrillat, J.; Aquilanti, G.; Pascarelli, S.

    2008-12-01

    Phase transition from perovskite (Pv) to Post-Pv (PPv) phase in MgSiO3 has been studied by many groups since its discovery in 2004 (1,2) and the different studies find similar transition pressures. The effect of Al and Fe on the phase transition remains more controversial. The most recent studies suggest an increase of the transition pressure with increasing Fe-content (3,4), but other experimental work (5) as well as ab-initio calculations (6) show the opposite effect. The effect of Al was reported to increase slightly the pressure transition to the CaIrO3 form (4,7), but its influence on the Fe3+ content in the PPv phase has not been documented yet. By means of in situ study of the Fe K-edge fine structures (XANES), we investigated the phase relations between Pv and PPv phases for three different Al-(Mg,Fe)SiO3 compositions. For this, we synthesized various Pv and PPv mixtures using laser-heated diamond anvil cell (DAC) for pressures between 60 and 170 GPa. The sample's mineralogy, i.e. the Pv and PPv phase fractions, was determined using in-situ X-ray diffraction at the ID27 beamline of the ESRF (8,9). Then, we probed the Fe speciation, i.e. the Fe concentration in each phases, in-situ in the DAC using the µ-XANES mapping technique available at the ID24 beamline (10,11). Both pieces of information were combined to retrieve the Fe partitioning coefficient between the two high-pressure phases. Our results show that Fe partitions strongly into the PPv phase, which implies a very large binary loop of coexistence of the two phases. Thus, at the core-mantle boundary pressure (135 GPa), the Pv and PPv phase always coexist for all geophysically relevant Al-(Mg,Fe)SiO3 compositions, and the Fe-content in the PPv-phase is only a few percent. References: 1. M. Murakami, K. Hirose, K. Kawamura, N. Sata, Y. Ohishi, Science 304, 855 (2004). 2. A. R. Oganov, S. Ono, Nature 430, 445 (2004). 3. S. Tateno, K. Hirose, N. Sata, Y. Ohishi, Phys. Earth Planet. Inter. 160, 319 (2007

  20. Application of XANES profiles to X-ray spectromicroscopy for biomedical specimens: part II. Mapping oxidation state of cysteine in human hair.

    Science.gov (United States)

    Inoue, Takafumi; Takehara, Kouji; Shimizu, Norio; Kitajima, Yoshinori; Shinohara, Kunio; Ito, Atsushi

    2011-01-01

    Human hair fibers are primarily composed of keratin protein, characterized by a very high content of cysteine, a sulfur-containing amino acid, which ordinarily forms cystine via a disulfide bond. It is known that some cystine residues are converted to cysteic acid during permanent waving or hair coloring, although details of their distribution and extent are still unclear. In this study, by using difference in XANES profiles of cystine and cysteic acid at the S-K absorption edge, the formation of cysteic acid was confirmed for homogenized samples of permed or bleached hair. Furthermore chemical mapping of cysteic acid was performed on hair-section samples with X-ray contact microscopy. The peripheral region, cuticle, in bleached hair showed the highest content of cysteic acid compared with the other parts, while permed hair showed relatively uniform distribution. This finding suggests that perming and bleaching damage hair by different mechanisms.

  1. EXAFS Determination of the Change in the Structure of Rhodium in Highly Dispersed Rhodium/gamma-Aluminum Oxide Catalysts after Carbon Monoxide and/or Hydrogen Adsorption at Different Temperatures

    NARCIS (Netherlands)

    Koningsberger, D.C.; Blik, H.F.J. van 't; Zon, J.B.A.D. van; Prins, R.

    1984-01-01

    Extended X-ray absorption spectroscopy (EXAFS) has been applied to study the Rh K-edge of two ultradisperse Rh/Al{2}O{3} catalysts containing 0.47 and 1.04 wt.% rhodium respectively. The structural properties of the Rh crystallites were determined after reduction with H{2}, evacuation at elevated te

  2. Chemical Heterogeneity of a Large Cluster IDP: Clues to its Formation History Using X-ray Fluorescence Mapping and XANES Spectroscopy

    Science.gov (United States)

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

    2013-01-01

    Chondritic porous IDPs may be among the most primitive objects found in our solar system [1]. They consist of many micron to submicron minerals, glasses and carbonaceous matter [2,3,4,5,6,7] with > 10(exp 4) grains in a 10 micron cluster [8]. Speculation on the environment where these fine grained, porous IDPs formed varies with possible sources being presolar dusty plasma clouds, protostellar condensation, solar asteroids or comets [4,6,9]. Also, fine grained dust forms in our solar system today [10,11]. Isotopic anomalies in some particles in IDPs suggest an interstellar source[4,7,12]. IDPs contain relic particles left from the dusty plasma that existed before the protostellar disk formed and other grains in the IDPs formed later after the cold dense nebula cloud collapsed to form our protostar and other grains formed more recently. Fe and CR XANES spectroscopy is used here to investigate the oxygen environment in a large (>50 10 micron or larger sub-units) IDP. Conclusions: Analyzing large (>50 10 micron or larger sub-units) CP IDPs gives one a view on the environments where these fine dust grains formed which is different from that found by only analyzing the small, 10 micron IDPs. As with cluster IDP L2008#5 [3], L2009R2 cluster #13 appears to be an aggregate of grains that sample a diversity of solar and perhaps presolar environments. Sub-micron, grain by grain measurement of trace element contents and elemental oxidation states determined by XANES spectroscopy offers the possibility of understanding the environments in which these grains formed when compared to standard spectra. By comparing thermodynamic modeling of condensates with analytical data an understanding of transport mechanisms operating in the early solar system may be attained.

  3. XANES investigation of Chinese faience excavated from Peng State Cemetery site in Western Zhou Period (BC1046–BC771)

    Energy Technology Data Exchange (ETDEWEB)

    Hao, Wentao; Yang, Yimin [Key Laboratory of Vertebrate Evolution and Human Origins of Chinese Academy of Sciences, Institute of Vertebrate Paleontology and Paleoanthropology, Chinese Academy of Sciences, Beijing 100044 (China); Department of Scientific History and Archaeometry, University of Chinese Academy of Sciences, Beijing 100049 (China); Zhu, Jian, E-mail: jzhu@ucas.ac.cn [Key Laboratory of Vertebrate Evolution and Human Origins of Chinese Academy of Sciences, Institute of Vertebrate Paleontology and Paleoanthropology, Chinese Academy of Sciences, Beijing 100044 (China); Department of Scientific History and Archaeometry, University of Chinese Academy of Sciences, Beijing 100049 (China); Gu, Zhou [Key Laboratory of Vertebrate Evolution and Human Origins of Chinese Academy of Sciences, Institute of Vertebrate Paleontology and Paleoanthropology, Chinese Academy of Sciences, Beijing 100044 (China); Department of Scientific History and Archaeometry, University of Chinese Academy of Sciences, Beijing 100049 (China); Xie, Yaoting [Institute of Archaeology of Shanxi Province, Taiyuan 030001 (China); Zhang, Jing [Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China); Wang, Lihua [Shanghai Synchrotron Radiation Facility, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201204 (China)

    2014-10-15

    Highlights: • We analyzed faience of Peng State archaeological cemetery site in Western Zhou Dynasty (BC1046–BC771). • We investigated the chemical composition and oxidation state by energy dispersive X-ray fluorescence (EDXRF) and X-ray absorption near edge spectroscopy (XANES), respectively. • The coloring element in both beads is copper in +2 valence, and the color divergence of these two beads may originate from different local chemical environments of Cu{sup 2+}. • Chinese faience in this period is the earliest glaze with copper colorant. - Abstract: As a special kind of glazed ceramic, faience has an important role to play in the technological trajectory that eventually leads to the development of ancient glass. In China, faience products first emerged in early Western Zhou Dynasty (1046BC–771BC), and their great significance as well as brilliant colors varying between blue and green attracted a lot of scholars. However, scientific researches on the color source of Chinese faience in view of microstructure characterization are quite few. In the present work, analyses by energy dispersive X-ray fluorescence (EDXRF) and X-ray absorption near edge spectroscopy (XANES) were carried out on two faience beads with relatively blue and green color, respectively, both of which were excavated from Peng State archaeological cemetery site in Western Zhou Dynasty. The results show that the coloring element in both beads is copper with +2 valence, and the color divergence of these two beads may originate from different local chemical environments of Cu{sup 2+}. It is suggested that the faience in this period is the earliest glaze with copper colorant in China.

  4. An EXAFS study on the photo-assisted growth of silver nanoparticles on titanium dioxide thin-films and the identification of their photochromic states.

    Science.gov (United States)

    Kafizas, Andreas; A Parry, Stephen; Chadwick, Alan V; Carmalt, Claire J; Parkin, Ivan P

    2013-06-07

    Anatase TiO2 thin-films were formed on glass by a sol-gel dip-coating method and annealed at 500 °C. Ag nanoparticles were grown on the surface of TiO2 by a photo-assisted process from AgNO3 salt using either UVC - 254 nm or UVA - 365 nm light. The size, shape and coverage of the particles were assessed by scanning electron microscopy. Changes in surface plasmon properties were investigated by UV-visible spectroscopy. A greater level of spherical Ag nanoparticles grew on TiO2 when using UVA light (365 nm); with particles 96 ± 33 nm wide on average and covering 29% of the surface. In the case of UVC light (254 nm), particles were 78 ± 14 nm wide on average and covered 13% of the surface. EXAFS measurements performed in situ of the Ag K-edge showed that the photo-assisted growth was more rapid when UVA light was used, leading to the full conversion of the AgNO3 salt layer in ≈1900 seconds. When UVC light was used, ≈50% of the salt layer was converted in ≈6100 seconds. The inhibited growth under UVC conditions was attributed to the absorption of light by the Ag nanoparticles as they formed (as opposed to the semiconductor beneath). The films also displayed reversible photochromism. The change in phase from the coloured (metallic Ag) to the bleached state (oxidized Ag) was identified using EXAFS spectroscopy. By comparing the EXAFS pattern with simulated model structures, it was shown that the transition from cubic Ag to cubic Ag2O was most likely, with an ≈70% conversion with 12 hours of white light irradiance. We believe that this is the first time the bleached form of silver in photochromic Ag-TiO2 thin-films has been identified by a direct method. In addition, we believe that this is the first case in which the photo-assisted formation of Ag-TiO2 has been monitored in situ under ambient temperature and pressure.

  5. Structure of the local environment of titanium atoms in multicomponent nitride coatings produced by plasma-ion techniques

    Science.gov (United States)

    Krysina, O. V.; Timchenko, N. A.; Koval, N. N.; Zubavichus, Ya V.

    2016-01-01

    An experiment was performed to examine the X-ray Absorption Near-Edge Structure (XANES) and the Extended X-ray Absorption Fine Structure (EXAFS) near the K-edge of titanium in nanocrystalline titanium nitride coatings containing additives of copper, silicon, and aluminum. Using the observation data, the structure parameters of the local environment of titanium atoms have been estimated for the coatings. According to crystallographic data, the Ti-N distance in the bulk phase of titanium nitride is 2.12 Å and the Ti-Ti distance is 3.0 Å. Nearly these values have been obtained for the respective parameters of the coatings. The presence of copper as an additive in a TiN coating increases the Ti-N distance inappreciably compared to that estimated for titanium nitride, whereas addition of silicon decreases the bond distance. It has been revealed that the copper and silicon atoms in Ti-Cu-N and Ti-Si-N coatings do not enter into the crystallographic phase of titanium nitride and do not form bonds with titanium and nitrogen, whereas the aluminum atoms in Ti-Al-N coatings form intermetallic phases with titanium and nitride phases.

  6. Ex-situ and in-situ investigations of thermal anti-oxidation treatments of stainless steels by reflection mode EXAFS

    Science.gov (United States)

    Lützenkirchen-Hecht, D.; Wulff, D.; Wagner, R.; Holländer, U.; Maier, HJ; Frahm, R.

    2016-05-01

    Different thermal treatments were performed for the anti-oxidation of steel surfaces, and the processes were investigated ex-situ and in-situ by surface sensitive reflection mode EXAFS experiments at the Cr and Fe K-edges. While the samples for the ex-situ studies were heat-treated in a conveyor belt furnace at temperatures between 600 and 900 °C in inert carrier gases (N2 or Ar) using different additives such as hydrogen (H2) and monosilane (SiH4), the in- situ anti-oxidation treatments have been performed in a high vacuum environment (p < 10-6 mbar). While the ex-situ experiments suggest that SiH4-additives are needed for the reduction of the steel to a metallic state, the in-vacuum treatments appear successful for temperatures above approx. 900 °C.

  7. Interaction of Cm(III) and Am(III) with human serum transferrin studied by time-resolved laser fluorescence and EXAFS spectroscopy.

    Science.gov (United States)

    Bauer, Nicole; Fröhlich, Daniel R; Panak, Petra J

    2014-05-14

    The complexation of Cm(III) with human serum transferrin was investigated in a pH range from 3.5 to 11.0 using time-resolved laser fluorescence spectroscopy (TRLFS). At pH ≥ 7.4 Cm(III) is incorporated at the Fe(III) binding site of transferrin whereas at lower pH a partially bound Cm(III) transferrin species is formed. At physiological temperature (310 K) at pH 7.4, about 70% of the partially bound and 30% of the incorporated Cm(III) transferrin species are present in solution. The Cm(III) results obtained by TRLFS are in very good agreement with Am(III) EXAFS results, confirming the incorporation of Am(III) at the Fe(III) binding site at pH 8.5.

  8. Low kinetic energy photoelectron diffractions for C 1s and O 1s electrons of free CO molecules in the EXAFS region

    Energy Technology Data Exchange (ETDEWEB)

    Adachi, Jun-ichi; Yamazaki, Masakazu; Kimura, Yasuyuki; Yagishita, Akira [Photon Factory, IMSS, KEK, 1-1 Oho, Tsukuba 305-0801 (Japan); Kazama, Misato; Ohori, Yusuke; Fujikawa, Takashi [Graduate School of Advanced Integration Science, Chiba University, 1-33 Yayoi-cho, Inage 263-8522 (Japan); Teramoto, Takahiro, E-mail: jun-ichi.adachi@kek.j [Graduate School of Science, University of Tokyo, Bunkyo-ku, Tokyo, 113-0033 (Japan)

    2009-11-15

    We have measured molecular-frame photoelectron angular distributions from carbon 1s and oxygen 1s levels of CO molecules up to a photoelectron kinetic energy (KE) of {approx}150 eV. The backward-scattering intensities exhibited a strong modulation as a function of the kinetic energy of the photoelectrons, whereas the intensities for the forward-scattering gradually increased and then became nearly constant over KE {approx}100 eV. Multiple scattering calculations with a muffin-tin potential qualitatively reproduced the experimental results. The present results may be considered as the observation of low-energy photoelectron diffraction patterns for gaseous free CO molecules, which are involved in modulations in extended X-ray absorption fine structure (EXAFS) spectra.

  9. Quick-EXAFS setup at the SuperXAS beamline for in situ X-ray absorption spectroscopy with 10 ms time resolution

    Energy Technology Data Exchange (ETDEWEB)

    Müller, Oliver, E-mail: o.mueller@uni-wuppertal.de [University of Wuppertal, Gaußstraße 20, 42119 Wuppertal (Germany); Nachtegaal, Maarten [Paul Scherrer Institute, 5232 Villigen (Switzerland); Just, Justus [University of Wuppertal, Gaußstraße 20, 42119 Wuppertal (Germany); Helmholtz-Zentrum Berlin für Materialien und Energie, Hahn-Meitner-Platz 1, 14109 Berlin (Germany); Lützenkirchen-Hecht, Dirk; Frahm, Ronald [University of Wuppertal, Gaußstraße 20, 42119 Wuppertal (Germany)

    2016-01-01

    A new quick-scanning EXAFS (QEXAFS) monochromator, ionization chambers and data acquisition system have been developed and installed at the SuperXAS beamline at the Swiss Light Source to reach a temporal resolution of 10 ms. The quick-EXAFS (QEXAFS) method adds time resolution to X-ray absorption spectroscopy (XAS) and allows dynamic structural changes to be followed. A completely new QEXAFS setup consisting of monochromator, detectors and data acquisition system is presented, as installed at the SuperXAS bending-magnet beamline at the Swiss Light Source (Paul Scherrer Institute, Switzerland). The monochromator uses Si(111) and Si(311) channel-cut crystals mounted on one crystal stage, and remote exchange allows an energy range from 4.0 keV to 32 keV to be covered. The spectral scan range can be electronically adjusted up to several keV to cover multiple absorption edges in one scan. The determination of the Bragg angle close to the position of the crystals allows high-accuracy measurements. Absorption spectra can be acquired with fast gridded ionization chambers at oscillation frequencies of up to 50 Hz resulting in a time resolution of 10 ms, using both scan directions of each oscillation period. The carefully developed low-noise detector system yields high-quality absorption data. The unique setup allows both state-of-the-art QEXAFS and stable step-scan operation without the need to exchange whole monochromators. The long-term stability of the Bragg angle was investigated and absorption spectra of reference materials as well as of a fast chemical reaction demonstrate the overall capabilities of the new setup.

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

    Science.gov (United States)

    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 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 and (2) the melts originally had Fe+ 3/FeT ≥ 0.175, consistent with

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

    Science.gov (United States)

    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 units above the fayalite-magnetite-quartz (FMQ) buffer at 1 atm and magmatic temperature of 1200 °C.The second process is interaction between the melts and atmospheric oxygen, which results in higher Fe+ 3/FeT ratios. Detailed μ-XANES traverses show gradients in Fe+ 3

  12. XANES analysis of calcium and sodium phosphates and silicates and hydroxyapatite-Bioglass (registered) 45S5 co-sintered bioceramics

    Energy Technology Data Exchange (ETDEWEB)

    Demirkiran, Hande [Graduate Student, Materials Science and Engineering Department, University of Texas at Arlington, Arlington, TX (United States); Hu Yongfeng; Zuin, Lucia [Beamline Scientist, Canadian Light Source, Saskatoon, SK (Canada); Appathurai, Narayana [Beamline Scientist, Synchrotron Radiation Center, Madison, WI (United States); Aswath, Pranesh B., E-mail: aswath@uta.edu [Materials Science and Engineering Department, University of Texas at Arlington, Arlington, TX (United States)

    2011-03-12

    Bioglass (registered) 45S5 was co-sintered with hydroxyapatite at 1200 deg. C. When small amounts (< 5 wt.%) of Bioglass (registered) 45S5 was added it behaved as a sintering aid and also enhanced the decomposition of hydroxyapatite to {beta}-tricalcium phosphate. However when 10 wt.% and 25 wt.% Bioglass (registered) 45S5 was used it resulted in the formation of Ca{sub 5}(PO{sub 4}){sub 2}SiO{sub 4} and Na{sub 3}Ca{sub 6}(PO{sub 4}){sub 5} in an amorphous silicate matrix respectively. These chemistries show improved bioactivity compared to hydroxyapatite and are the subject of this study. The structure of several crystalline calcium and sodium phosphates and silicates as well as the co-sintered hydroxyapatite-Bioglass (registered) 45S5 bioceramics were examined using XANES spectroscopy. The nature of the crystalline and amorphous phases were studied using silicon (Si) and phosphorus (P) K- and L{sub 2,3}-edge and calcium (Ca) K-edge XANES. Si L{sub 2,3}-edge spectra of sintered bioceramic compositions indicates that the primary silicates present in these compositions are sodium silicates in the amorphous state. From Si K-edge spectra, it is shown that the silicates are in a similar structural environment in all the sintered bioceramic compositions with 4-fold coordination. Using P L{sub 2,3}-edge it is clearly shown that there is no evidence of sodium phosphate present in the sintered bioceramic compositions. In the P K-edge spectra, the post-edge shoulder peak at around 2155 eV indicates that this shoulder to be more defined for calcium phosphate compounds with decreasing solubility and increasing thermodynamic stability. This shoulder peak is more noticeable in hydroxyapatite and {beta}-TCP indicating greater stability of the phosphate phase. The only spectra that does not show a noticeable peak is the composition with Na{sub 3}Ca{sub 6}(PO{sub 4}){sub 5} in a silicate matrix indicating that it is more soluble compared to the other compositions.

  13. XANES Study of Lead Speciation in Duckweed%铅锌矿区浮萍中铅的XANES形态分析

    Institute of Scientific and Technical Information of China (English)

    储彬彬; 罗立强; 许涛; 袁静; 孙建伶; 曾远; 马艳红; 易杉

    2012-01-01

    南京栖霞山铅锌矿是华东地区最大的铅锌矿床之一,已开采50多年,由此引发的环境问题日益突出.当地环境中铅含量较高,但铅的迁移和毒性机理不明.为此在该地区开展了铅锌矿生物地球化学研究,借助ICP-MS铅含量分析和Pb-LⅢ边XANES形态分析技术,在该污染区发现了耐受并富集重金属的浮萍样品,浮萍中铅的含量为39.4 mg·kg 1.XANES分析和形态拟合结果显示其含硬脂酸铅65%和硫化铅36.9%,从而揭示浮萍样品中铅以含硫的有机酸铅形式存在.%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-LⅢ 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·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.

  14. Following the movement of Cu ions in a SSZ-13 zeolite during dehydration, reduction and adsorption: a combined in situ TP-XRD, XANES/DRIFTS study

    Energy Technology Data Exchange (ETDEWEB)

    Kwak, Ja Hun; Varga, Tamas; Peden, Charles HF; Gao, Feng; Hanson, Jonathan C.; Szanyi, Janos

    2014-05-05

    Cu-SSZ-13 has been shown to possess high activity and superior N2 formation selectivity in the selective catalytic reduction of NOx under oxygen rich conditions. Here, a combination of synchrotron-based (XRD and XANES) and vibrational (DRIFTS) spectroscopy tools have been used to follow the changes in the location and coordination environment of copper ions in a Cu-SSZ-13 zeolite during calcinations, reduction with CO, and adsorption of CO and H2O. XANES spectra collected during these procedures provides critical information not only on the variation in the oxidation state of the copper species in the zeolite structure, but also on the changes in the coordination environment around these ions as they interact with the framework, and with different adsorbates (H2O and CO). Time-resolved XRD data indicate the movement of copper ions and the consequent variation of the unit cell parameters during dehydration. DRIFT spectra provide information about the adsorbed species present in the zeolite, as well as the oxidation states of and coordination environment around the copper ions. A careful analysis of the asymmetric T-O-T vibrations of the CHA framework perturbed by copper ions in different coordination environments proved to be especially informative. The results of this study will aid the identification of the location, coordination and oxidation states of copper ions obtained during in operando catalytic studies. Financial support was provided by the US Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy, Vehicle Technologies Program. Part of this work (sample preparation) was performed in the Environmental Molecular Sciences Laboratory (EMSL) at Pacific Northwest National Laboratory (PNNL). The EMSL is a national scientific user facility supported by the US DOE, Office of Biological and Environmental Research. PNNL is a multi-program national laboratory operated for the US DOE by Battelle. All of the spectroscopy work reported here was

  15. XANES measurements probing the local order and electronic structure of Pb{sub 1−x}Ba{sub x}Zr{sub 0.40}Ti{sub 0.60}O{sub 3} ferroelectric materials

    Energy Technology Data Exchange (ETDEWEB)

    Mesquita, A. [Instituto de Geociências e Ciências Exatas, Universidade Estadual Paulista, Rio Claro, SP (Brazil); Institut de Chimie et des Materiaux Paris Est, CNRS and Université Paris-Est, 94320 Thiais (France); Instituto de Física de São Carlos, Universidade de São Paulo, São Carlos, SP (Brazil); Michalowicz, A. [Institut de Chimie et des Materiaux Paris Est, CNRS and Université Paris-Est, 94320 Thiais (France); Mastelaro, V.R. [Instituto de Física de São Carlos, Universidade de São Paulo, São Carlos, SP (Brazil)

    2015-08-15

    Highlights: • Structural characterization of Pb{sub 1−x}Ba{sub x}Zr{sub 0.40}Ti{sub 0.60}O{sub 3} (PBZT) ferroelectric ceramic. • X-ray absorption and spectroscopy was used to probe the structure of PBZT. • O K-edge XANES spectra showed hybridization between the O 2p and Pb 6sp states. • Relaxor behavior are related to weakening of the O 2p and Pb 6sp hybridization. - Abstract: In this study, the electronic and local structures of Pb{sub 1−x}Ba{sub x}Zr{sub 0.40}Ti{sub 0.60}O{sub 3} ferroelectric ceramic samples were characterized using X-ray absorption near-edge structure (XANES) measurements. The analysis of XANES spectra collected at the Ti K- and L-edges showed that the substitution of Pb by Ba leads to a decrease in the local distortion around the Ti atoms in the TiO{sub 6} octahedron. The analysis of O K-edge XANES spectra and density of states ab initio calculations showed that the hybridization between the O 2p and Pb 6sp states is related to the displacement of Ti atoms in the TiO{sub 6} octahedra. Based on these results, it is possible to determine that the degree of ferroelectricity in these samples and the manifestation of relaxor behavior are directly related to the weakening of O 2p and Pb 6sp hybridization.

  16. Binuclear Pt-Tl bonded complex with square pyramidal coordination around Pt: a combined multinuclear NMR, EXAFS, UV-Vis, and DFT/TDDFT study in dimethylsulfoxide solution.

    Science.gov (United States)

    Purgel, Mihály; Maliarik, Mikhail; Glaser, Julius; Platas-Iglesias, Carlos; Persson, Ingmar; Tóth, Imre

    2011-07-04

    The structure and bonding of a new Pt-Tl bonded complex formed in dimethylsulfoxide (dmso), (CN)(4)Pt-Tl(dmso)(5)(+), have been studied by multinuclear NMR and UV-vis spectroscopies, and EXAFS measurements in combination with density functional theory (DFT) and time dependent density functional theory (TDDFT) calculations. This complex is formed following the equilibrium reaction Pt(CN)(4)(2-) + Tl(dmso)(6)(3+) ⇆ (CN)(4)Pt-Tl(dmso)(5)(+) + dmso. The stability constant of the Pt-Tl bonded species, as determined using (13)C NMR spectroscopy, amounts to log K = 2.9 ± 0.2. The (NC)(4)Pt-Tl(dmso)(5)(+) species constitutes the first example of a Pt-Tl bonded cyanide complex in which the sixth coordination position around Pt (in trans with respect to the Tl atom) is not occupied. The spectral parameters confirm the formation of the metal-metal bond, but differ substantially from those measured earlier in aqueous solution for complexes (CN)(5)Pt-Tl(CN)(n)(H(2)O)(x)(n-) (n = 0-3). The (205) Tl NMR chemical shift, δ = 75 ppm, is at extraordinary high field, while spin-spin coupling constant, (1)J(Pt-Tl) = 93 kHz, is the largest measured to date for a Pt-Tl bond in the absence of supporting bridging ligands. The absorption spectrum is dominated by two strong absorption bands in the UV region that are assigned to MMCT (Pt → Tl) and LMCT (dmso → Tl) bands, respectively, on the basis of MO and TDDFT calculations. The solution of the complex has a bright yellow color as a result of a shoulder present on the low energy side of the band at 355 nm. The geometry of the (CN)(4)Pt-Tl core can be elucidated from NMR data, but the particular stoichiometry and structure involving the dmso ligands are established by using Tl and Pt L(III)-edge EXAFS measurements. The Pt-Tl bond distance is 2.67(1) Å, the Tl-O bond distance is 2.282(6) Å, and the Pt-C-N entity is linear with Pt-C and Pt···N distances amounting to 1.969(6) and 3.096(6) Å, respectively. Geometry optimizations on

  17. Synchrotron micro-XRF and micro-XANES confirmation of the uptake and translocation of TiO₂ nanoparticles in cucumber (Cucumis sativus) plants.

    Science.gov (United States)

    Servin, Alia D; Castillo-Michel, Hiram; Hernandez-Viezcas, Jose A; Diaz, Baltazar Corral; Peralta-Videa, Jose R; Gardea-Torresdey, Jorge L

    2012-07-17

    Advances in nanotechnology have raised concerns about possible effects of engineered nanomaterials (ENMs) in the environment, especially in terrestrial plants. In this research, the impacts of TiO(2) nanoparticles (NPs) were evaluated in hydroponically grown cucumber (Cucumis sativus) plants. Seven day old seedlings were treated with TiO(2) NPs at concentrations varying from 0 to 4000 mg L(-1). At harvest, the size of roots and shoots were measured. In addition, micro X- ray fluorescence (micro-XRF) and micro X-ray absorption spectroscopy (micro-XAS), respectively, were used to track the presence and chemical speciation of Ti within plant tissues. Results showed that at all concentrations, TiO(2) significantly increased root length (average >300%). By using micro-XRF it was found that Ti was transported from the roots to the leaf trichomes, suggesting that trichomes are possible sink or excretory system for the Ti. The micro-XANES spectra showed that the absorbed Ti was present as TiO(2) within the cucumber tissues, demonstrating that the TiO(2) NPs were not biotransformed.

  18. MXAN Analysis of the XANES Energy Region of LiPDF%用MXAN拟合钩端螺旋体去甲酰化酶XANES谱

    Institute of Scientific and Technical Information of China (English)

    郭晓云; 储旺盛; 龚为民; 董宇辉; 谢亚宁; 杨飞飞; Maurizio; Benfatto; 吴自玉

    2007-01-01

    钩端螺旋体去甲酰化酶(Leptospira interrogans PDF)是一种重要的含锌金属蛋白酶,对钩端螺旋体这一广泛存在的致病菌的蛋白合成起着关键的催化作用,是一个很好的药物设计靶蛋白.本文测试了LiPDF在pH3.0的溶液状态下的X射线吸收近边结构(XANES:X-Ray Absorption Near-Edge Structure)谱,利用以从头计算(ab.initio)的多重散射(Multiple Scattering)为基础的MXAN方法确定金属蛋白活性中心的精细结构.研究发现结合合适的初始结构模型,可以更好地重现LiPDF蛋白的XANES曲线,从而能够得到更加准确的结构参数.活性中心的精细结构为理解LiPDF的pH依赖的催化活性提供了结构基础.

  19. X-ray absorption near-edge structure (XANES) studies on Sb-doped Bi2UO6 at Bi and U edges

    Science.gov (United States)

    Yadav, A. K.; Misra, N. L.; Dhara, Sangita; Phatak, Rohan; Poswal, A. K.; Jha, S. N.; Bhattacharyya, D.

    2013-02-01

    X-ray absorption spectroscopy (XAS) measurements at Bi and U LIII edges with synchrotron radiation have been carried out on Bi2-xSbxUO6 samples for x= 0.04, 0.08, 0.12, 0.16 and 0.40 which are possible by-products of Bi based coolant and Uranium based fuels in advanced high temperature nuclear reactors. The chemical shift of the Bi absorption edges in the samples have been determined accurately from the XANES region of the X-ray absorption spectra and have been explained in terms of the difference in electronegativity values of Sb and Bi. The chemical shift of absorption edges show systematic variation only upto x = 0.08 (i.e., 4% Sb doping), which shows that the Sb enter in the matrix properly up to 4% doping concentration. The local structure of U is found to remain unchanged on Sb doping indicating clearly that Sb dopants preferably replace Bi atoms.

  20. Quasi-in-situ reflection mode XANES at the Ti K-edge of lithium intercalated TiO{sub 2} rutile and anatase

    Energy Technology Data Exchange (ETDEWEB)

    Wagemaker, M.; Luetzenkirchen-Hecht, D.; Keil, P.; Well, A.A. van; Frahm, R

    2003-08-01

    The near surface structure of Li-intercalated rutile and anatase TiO{sub 2} electrodes was investigated with grazing incidence reflection mode XANES spectroscopy. Though real in situ experiments are not feasible due to the extremely strong parasitic absorption of the electrolyte, a new cell was constructed. It enables the electrochemical processing of samples which are sensitive to oxidation as well as it permits reflection mode X-ray experiments after the controlled emersion of the electrodes from the electrolyte. Our results show that even Li containing electrolytes and Li intercalated electrodes can be processed inside the cell. During the electrochemical Li intercalation in rutile, only a thin surface layer of some few nm thickness was changed by the lithiation. The structure of this layer seems to have a similar structure compared to the Li titanate Li{sub 0.6}TiO{sub 2} (space group imma). The anatase layer could be fully intercalated showing the characteristic Li-titanate structure. In the surface region the Li intercalation results in an edge shift that corresponds to Ti{sup 3+} states in contrast to the Ti{sup 3.4+} states in the bulk.

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

    Science.gov (United States)

    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.

  2. Identification of sources of lead in the atmosphere by chemical speciation using X-ray absorption near-edge structure (XANES) spectroscopy.

    Science.gov (United States)

    Sakata, Kohei; Sakaguchi, Aya; Tanimizu, Masaharu; Takaku, Yuichi; Yokoyama, Yuka; Takahashi, Yoshio

    2014-02-01

    Sources of Pb pollution in the local atmosphere together with Pb species, major ions, and heavy metal concentrations in a size-fractionated aerosol sample from Higashi-Hiroshima (Japan) have been determined by X-ray absorption near-edge structure (XANES) spectroscopy, ion chromatography, and ICP-MS/AES, respectively. About 80% of total Pb was concentrated in fine aerosol particles. Lead species in the coarse aerosol particles were PbC2O4, 2PbCO3 Pb(OH)2, and Pb(NO3)2, whereas Pb species in the fine aerosol particles were PbC2O4, PbSO4, and Pb(NO3)2. Chemical speciation and abundance data suggested that the source of Pb in the fine aerosol particles was different from that of the coarse ones. The dominant sources of Pb in the fine aerosol particles were judged to be fly ash from a municipal solid waste incinerator and heavy oil combustion. For the coarse aerosol particles, road dust was considered to be the main Pb source. In addition to Pb species, elemental concentrations in the aerosols were also determined. The results suggested that Pb species in size-fractionated aerosols can be used to identify the origin of aerosol particles in the atmosphere as an alternative to Pb isotope ratio measurement.

  3. Stability of mineral fibres in contact with human cell cultures. An in situ μXANES, μXRD and XRF iron mapping study.

    Science.gov (United States)

    Pollastri, Simone; Gualtieri, Alessandro F; Vigliaturo, Ruggero; Ignatyev, Konstantin; Strafella, Elisabetta; Pugnaloni, Armanda; Croce, Alessandro

    2016-12-01

    Relevant mineral fibres of social and economic importance (chrysotile UICC, crocidolite UICC and a fibrous erionite from Jersey, Nevada, USA) were put in contact with cultured diploid human non-tumorigenic bronchial epithelial (Beas2B) and pleural transformed mesothelial (MeT5A) cells to test their cytotoxicity. Slides of each sample at different contact times up to 96 h were studied in situ using synchrotron XRF, μ-XRD and μ-XAS (I18 beamline, Diamond Light Source, UK) and TEM investigations. XRF maps of samples treated for 96 h evidenced that iron is still present within the chrysotile and crocidolite fibres and retained at the surface of the erionite fibres, indicating its null to minor mobilization in contact with cell media; this picture was confirmed by the results of XANES pre-edge analyses. μ-XRD and TEM data indicate greater morphological and crystallinity modifications occurring in chrysotile, whereas crocidolite and erionite show to be resistant in the biological environment. The contact of chrysotile with the cell cultures seems to lead to earlier amorphization, interpreted as the first dissolution step of these fibres. The formation of such silica-rich fibre skeleton may prompt the production of HO in synergy with surface iron species and could indicate that chrysotile may be much more reactive and cytotoxic in vitro in the (very) short term whereas the activity of crocidolite and erionite would be much more sluggish but persistent in the long term.

  4. Determination of localized Fe{sup 2+}/Fe{sup 3+} ratios in inks of historic documents by means of {mu}-XANES

    Energy Technology Data Exchange (ETDEWEB)

    Proost, K.; Janssens, K. E-mail: koen.janssens@ua.ac.be; Wagner, B.; Bulska, E.; Schreiner, M

    2004-01-01

    An important part of the European cultural heritage is composed of hand-written documents. Many of these documents were drawn up with iron-gall ink. This type of ink present a serious conservation problem, as it slowly oxidizes ('burns') the paper it is written on, thereby gradually disintegrating the historic document. Acid hydrolysis of the cellulose and/or the oxidation of organic compounds promoted by radical intermediates that are formed due to the presence of Fe{sup 2+} ions are considered to be the cause of the disintegration. {mu}-XANES measurements were performed with a lateral resolution of 30-50 {mu}m in order to determine the local Fe{sup 2+}/Fe{sup 3+} ratio in 19th C. documents from the Austrian National Archives and fragments of 16th C documents from the Polish National Library. In the 19th C documents, no significant amount of Fe{sup 2+} was detected. On the other hand, in the 16th C fragments, significant amounts of Fe{sup 2+} and appreciable differences in distribution of Fe{sup 2+} and Fe{sup 3+} within individual letters/ink stains were observed.

  5. Structure and water exchange dynamics of hydrated oxo halo ions in aqueous solution using QMCF MD simulation, large angle X-ray scattering and EXAFS

    Science.gov (United States)

    Eklund, Lars; Hofer, Tomas S.

    2014-01-01

    Theoretical ab initio quantum mechanical charge field molecular dynamics (QMCF MD) has been applied in conjunction with experimental large angle X-ray scattering (LAXS) and EXAFS measurements to study structure and dynamics of the hydrated oxo chloro anions chlorite, ClO2−, chlorate, ClO3−, and perchlorate, ClO4−. In addition, the structures of the hydrated hypochlorite, ClO−, bromate, BrO3−, iodate, IO3− and metaperiodate, IO4−, ions have been determined in aqueous solution by means of LAXS. The structures of the bromate, metaperiodate, and orthoperiodate, H2IO63−, ions have been determined by EXAFS as solid sodium salts and in aqueous solution as well. The results show clearly that the only form of periodate present in aqueous solution is metaperiodate. The Cl-O bond distances in the hydrated oxo chloro anions as determined by LAXS and obtained in the QMCF MD simulations are in excellent agreement, being 0.01–0.02 Å longer than in solid anhydrous salts due to hydration through hydrogen bonding to water molecules. The oxo halo anions, all with unit negative charge, have low charge density making them typical structure breakers, thus the hydrogen bonds formed to the hydrating water molecules are weaker and more short-lived than those between water molecules in pure water. The water exchange mechanism of the oxo chloro anions resembles those of the oxo sulfur anions with a direct exchange at the oxygen atoms for perchlorate and sulfate. The water exchange rate for the perchlorate ion is significantly faster, τ0.5=1.4 ps, compared to the hydrated sulfate ion and pure water, τ0.5=2.6 and 1.7 ps, respectively. The angular radial distribution functions show that the chlorate and sulfite ions have a more complex water exchange mechanism. As the chlorite and chlorate ions are more weakly hydrated than the sulfite ion the spatial occupancy is less well-defined and it is not possible to follow any well-defined migration pattern as it is difficult to

  6. 不同方法制备的硫化态K-Co-Mo催化剂的EXAFS研究%An EXAFS Study of Sulfided K-Co-Mo CatalystsPrepared by Different Method

    Institute of Scientific and Technical Information of China (English)

    鲍骏; 卞国柱; 伏义路; 刘涛; 谢亚宁; 胡天斗

    2001-01-01

    采用共沉淀法和溶胶-凝胶法制备了同组分的硫化态K-Co-Mo催化剂,并用EXAFS研究了体系中Mo原子和Co原子的局域配位情况.结果表明,硫化态K-Co-Mo样品中Mo原子以类似于MoS2结构的物种存在,而Co原子除了以Co9S8形式存在外,还以一种Co-Mo-S相的形式存在,Co-Mo-S的晶相结构与MoS2类似.结合活性测试结果认为Co-Mo-S的形成促进了样品催化活性的提高.此外,EXAFS结果还表明,不同制备方法对K-Co-Mo样品中Mo物种晶粒尺寸具有较大的影响,而对Co9S8粒子则影响不明显,其中,采用溶胶-凝胶方法制备,并且在氩气中处理过的样品中Mo物种具有最小的晶粒尺寸.%A kind of sulfided K-Co-Mo catalyst, prepared by sol-gel andprecipitation method respectively, was characterized by EXAFS technique. The results indicate that, in the sulfided samples, the Mo atoms exist as MoS2-like species, the Co atoms exist not only as Co9S8, but also as a kind of Co-Mo-S phase, which almost has the same structure as MoS2. Combining the activity results, it is suggested that the formation of Co-Mo-S improves the activity toward alcohol. Additionally, it is found that the sample prepared by sol-gel method and treated in argon atmosphere has the smallest size of MoS2 crystallites, while the Co9S8 shows no notable change.

  7. MAX: Multiplatform Applications for XAFS

    Energy Technology Data Exchange (ETDEWEB)

    Alain, Michalowicz; Jacques, Moscovici; Diane, Muller-Bouvet; Karine, Provost, E-mail: michalov@univ-paris12.f [Institut de Chimie et des Materiaux Paris Est (ICMPE) UMR CNRS and Universite Paris 12, 2 rue H. Dunant, 94320 Thiais (France)

    2009-11-15

    MAX is a new EXAFS and XANES analysis package, replacing our old 'EXAFS pour le Mac' software suite. The major improvement is the ability to work with strictly the same code, compiled at once for Microsoft Windows, Apple MacOSX and LINUX systems, justifying the title 'Multiplatform Applications for XAFS'. It is organized as four modules: ABSORBIX (X-ray absorbance and fluorescence self-absorption calculations), CHEROKEE (EXAFS and XANES data treatment), ROUNDMIDNIGHT (EXAFS modeling and fit) and CRYSTALFFREV (from crystal structures and molecular modeling to FEFF EXAFS and XANES theoretical calculations). Most features developed in 'EXAFS pour le Mac' are still available, but with much improvements in the user's interface, data treatment algorithms and new functionalities.

  8. EXAFS Studies and GAUSSIAN VIEW Energy Calculations of the Complexation of Europium with 1,3,5-trideoxy-1,3,5-tris((2-hydroxybenzyl)amino)-cis-inositol

    Energy Technology Data Exchange (ETDEWEB)

    Taylor,D.; Choppin, G.; Dodge, C.; Francis, A.

    2008-01-01

    Complexation of 1, 3,5-trideoxy-1, 3,5-tris((2-hydroxybenzyl)amino)-cis-inositol (thci) in I = 1.00 M (NaClO4) with Eu(III) and La(III) was studied by EXAFS measurements and gaussian view energy calculations. EXAFS studies indicated that two complexes Eu(thci){sup 2+} and Eu(thci){sub 2}{sup 2+} are formed with thci and Eu(III). At lower pH, Eu(III) is bonded to thci via two hydroxyl groups (cyclohexanetriol or 2-hydroxybenzylamino moieties) and 7 H2O molecules, for a total of 9 Eu-O bonds. However, at higher pH there are two hydroxyl groups (cyclohexanetriol or 2-hydroxybenzylamino moieties), two amino groups, and five water molecules for a total Eu(III) coordination number of 9. gaussian view energy calculations indicate that in the Eu(thci)2+, thci bonds to Eu(III) in a similar manner and is in good correlation with the EXAFS data.

  9. STXMPy: a new software package for automated region of interest selection and statistical analysis of XANES data

    Directory of Open Access Journals (Sweden)

    Grunze Michael

    2010-06-01

    Full Text Available Abstract Background Soft X-ray spectromicroscopy based absorption near-edge structure analysis, is a spectroscopic technique useful for investigating sample composition at a nanoscale of resolution. While the technique holds great promise for analysis of biological samples, current methodologies are challenged by a lack of automatic analysis software e. g. for selection of regions of interest and statistical comparisons of sample variability. Results We have implemented a set of functions and scripts in Python to provide a semiautomatic treatment of data obtained using scanning transmission X-ray microscopy. The toolkit includes a novel line-by-line absorption conversion and data filtering automatically identifying image components with significant absorption. Results are provided to the user by direct graphical output to the screen and by output images and data files, including the average and standard deviation of the X-ray absorption spectrum. Using isolated mouse melanosomes as a sample biological tissue, application of STXMPy in analysis of biological tissues is illustrated. Conclusion The STXMPy package allows both interactive and automated batch processing of scanning transmission X-ray microscopic data. It is open source, cross platform, and offers rapid script development using the interpreted Python language.

  10. The pathogenesis of Randall's plaque: a papilla cartography of Ca compounds through an ex vivo investigation based on XANES spectroscopy.

    Science.gov (United States)

    Carpentier, Xavier; Bazin, Dominique; Jungers, Paul; Reguer, Solenn; Thiaudière, Dominique; Daudon, Michel

    2010-05-01

    At the surface of attached kidney stones, a particular deposit termed Randall's plaque (RP) serves as a nucleus. This structural particularity as well as other major public health problems such as diabetes type-2 may explain the dramatic increase in urolithiasis now affecting up to 20% of the population in the industrialized countries. Regarding the chemical composition, even if other phosphate phases such as whitlockite or brushite can be found as minor components (less than 5%), calcium phosphate apatite as well as amorphous carbonated calcium phosphate (ACCP) are the major components of most RPs. Through X-ray absorption spectroscopy performed at the Ca K-absorption edge, a technique specific to synchrotron radiation, the presence and crystallinity of the Ca phosphate phases present in RP were determined ex vivo. The sensitivity of the technique was used as well as the fact that the measurements can be performed directly on the papilla. The sample was stored in formol. Moreover, a first mapping of the chemical phase from the top of the papilla to the deep medulla is obtained. Direct structural evidence of the presence of ACCP as a major constituent is given for the first time. This set of data, coherent with previous studies, shows that this chemical phase can be considered as one precursor in the genesis of RP.

  11. The double-well oscillating potential of oxygen atoms in perovskite system Ba(K)BiO sub 3 : EXAFS - analysis results

    CERN Document Server

    Menushenkov, A P; Konarev, P V; Meshkov, A A; Benazeth, S; Purans, J

    2000-01-01

    Temperature-dependent X-ray absorption investigations were made on the Bi L sub 3 -edge in Ba sub 1 sub - sub x K sub x BiO sub 3 with x=0.0, 0.4 and 0.5. For the superconducting samples (x=0.4 and 0.5) it has been found that the local structure differs from the ideal cubic in contrast to the neutron and X-ray diffraction data. The provided analysis of the EXAFS spectra indicates that the oxygen atoms move in double-well potential produced by the existence of two non-equivalent octahedral types of the oxygen environment of bismuth. The vibrations in such a potential lead to modulations of the Bi-O lengths with low frequency which is determined by the soft oxygen octahedron rotation mode frequency. This induces strong electron-phonon interaction and may be the reason for relatively high-temperature transition (T sub c approx 30 K) to the superconducting state.

  12. Quick-EXAFS setup at the SuperXAS beamline for in situ X-ray absorption spectroscopy with 10 ms time resolution

    Science.gov (United States)

    Müller, Oliver; Nachtegaal, Maarten; Just, Justus; Lützenkirchen-Hecht, Dirk; Frahm, Ronald

    2016-01-01

    The quick-EXAFS (QEXAFS) method adds time resolution to X-ray absorption spectroscopy (XAS) and allows dynamic structural changes to be followed. A completely new QEXAFS setup consisting of monochromator, detectors and data acquisition system is presented, as installed at the SuperXAS bending-magnet beamline at the Swiss Light Source (Paul Scherrer Institute, Switzerland). The monochromator uses Si(111) and Si(311) channel-cut crystals mounted on one crystal stage, and remote exchange allows an energy range from 4.0 keV to 32 keV to be covered. The spectral scan range can be electronically adjusted up to several keV to cover multiple absorption edges in one scan. The determination of the Bragg angle close to the position of the crystals allows high-accuracy measurements. Absorption spectra can be acquired with fast gridded ionization chambers at oscillation frequencies of up to 50 Hz resulting in a time resolution of 10 ms, using both scan directions of each oscillation period. The carefully developed low-noise detector system yields high-quality absorption data. The unique setup allows both state-of-the-art QEXAFS and stable step-scan operation without the need to exchange whole monochromators. The long-term stability of the Bragg angle was investigated and absorption spectra of reference materials as well as of a fast chemical reaction demonstrate the overall capabilities of the new setup. PMID:26698072

  13. Quick-EXAFS setup at the SuperXAS beamline for in situ X-ray absorption spectroscopy with 10 ms time resolution.

    Science.gov (United States)

    Müller, Oliver; Nachtegaal, Maarten; Just, Justus; Lützenkirchen-Hecht, Dirk; Frahm, Ronald

    2016-01-01

    The quick-EXAFS (QEXAFS) method adds time resolution to X-ray absorption spectroscopy (XAS) and allows dynamic structural changes to be followed. A completely new QEXAFS setup consisting of monochromator, detectors and data acquisition system is presented, as installed at the SuperXAS bending-magnet beamline at the Swiss Light Source (Paul Scherrer Institute, Switzerland). The monochromator uses Si(111) and Si(311) channel-cut crystals mounted on one crystal stage, and remote exchange allows an energy range from 4.0 keV to 32 keV to be covered. The spectral scan range can be electronically adjusted up to several keV to cover multiple absorption edges in one scan. The determination of the Bragg angle close to the position of the crystals allows high-accuracy measurements. Absorption spectra can be acquired with fast gridded ionization chambers at oscillation frequencies of up to 50 Hz resulting in a time resolution of 10 ms, using both scan directions of each oscillation period. The carefully developed low-noise detector system yields high-quality absorption data. The unique setup allows both state-of-the-art QEXAFS and stable step-scan operation without the need to exchange whole monochromators. The long-term stability of the Bragg angle was investigated and absorption spectra of reference materials as well as of a fast chemical reaction demonstrate the overall capabilities of the new setup.

  14. Unified ZnO Q-dot growth mechanism from simultaneous UV-Vis and EXAFS monitoring of sol-gel reactions induced by different alkali base

    Science.gov (United States)

    Caetano, Bruno L.; Silva, Marlon N.; Santilli, Celso V.; Briois, Valérie; Pulcinelli, Sandra H.

    2016-11-01

    This article aims to give experimental evidences of the universality of main steps involved in ZnO nanoparticles formation and growth from sol-gel process. In this way, we revisit the effect of the alkali base (LiOH, NaOH, KOH) used to induce the hydrolysis-condensation reaction in order to unfold the ZnO Q-dot formation mechanisms by using simultaneous time resolved monitoring of zinc species and Q-dot size by combining EXAFS and UV-Vis spectroscopy. Irrespective of the alkali base used, nucleation and growth of ZnO Q-dots occur by consumption of zinc oxy-acetate precursor. Higher amounts of ZnO nanocrystal are produced as the strength of the base increases. After achieving the steady state equilibrium regime the Q-dot growth occurs initially by oriented attachment coalescence mechanism followed by the Ostwald ripening coarsening. The dependence of the formation and growth mechanisms on the base strength allows the fine tuning of the Q-dot size and photoluminescence properties.

  15. Insight to ternary complexes of co-adsorption of norfloxacin and Cu(II) onto montmorillonite at different pH using EXAFS.

    Science.gov (United States)

    Pei, Zhi-Guo; Shan, Xiao-Quan; Zhang, Shu-Zhen; Kong, Jing-Jing; Wen, Bei; Zhang, Jing; Zheng, Li-Rong; Xie, Ya-Ning; Janssens, Koen

    2011-02-15

    Co-adsorption of norfloxacin (Nor) and Cu(II) on montmorillonite at pH 4.5, 7.0 and 9.0 was studied by integrated batch adsorption experiments and extended X-ray absorption fine structure (EXAFS) spectroscopy. Under such pH conditions the dominant species of Nor are cation (Nor(+)), zwitterion (Nor(±)), and anion (Nor(-)), respectively. Results indicated that Nor sorption decreased with an increase of solution pH. The presence of Cu(II) slightly suppressed the Nor(+) sorption at pH 4.5, while increased Nor(±) and Nor(-)sorption on montmorillonite at pH 7.0 and 9.0, respectively. In contrast, Nor increased Cu(II) adsorption at pH 4.5, but had little effect on the adsorption of Cu(II) on montmorillonite at pH 7.0 and 9.0. Spectroscopic results showed that, at pH 4.5, Nor(+) was sorbed on montmorillonite by the formation of outer-sphere montmorillonite-Nor-Cu(II) ternary surface complex. At pH 7.0, montmorillonite-Nor-Cu(II) and montmorillonite-Cu(II)-Nor ternary surface complexes co-exist. At pH 9.0, montmorillonite-Cu(II)-Nor ternary surface complex was likely formed, which was different to Cu(II)(Nor)(2) precipitate of the solution. Copyright © 2010 Elsevier B.V. All rights reserved.

  16. EXAFS analysis of cations distribution in structure of Co1-xNixFe2O4 nanoparticles obtained by hydrothermal method in aloe vera extract solution

    Science.gov (United States)

    Wongpratat, Unchista; Maensiri, Santi; Swatsitang, Ekaphan

    2016-09-01

    Effect of cations distribution upon EXAFS analysis on magnetic properties of Co1-xNixFe2O4 (x = 0, 0.25, 0.50, 0.75 and 1.0) nanoparticles prepared by the hydrothermal method in aloe vera extract solution were studied. XRD analysis confirmed a pure phase of cubic spinel ferrite of all samples. Changes in lattice parameter and particle size depended on the Ni content with partial substitution and site distributions of Co2+, Ni2+ ions of different ionic radii at both tetrahedral and octahedral sites in the crystal structure. Particle sizes of samples estimated by TEM images were found to be in the range of 10.87-62.50 nm. The VSM results at room temperature indicated the ferrimagnetic behavior of all samples. Superparamagnetic behavior was observed in NiFe2O4 sample. The coercivity (Hc) and remanance (Mr) values were related to the particle sizes of samples. The saturation magnetization (Ms) was increased by a factor of 1.4 to a value of 57.57 emu/g, whereas the coercivity (Hc) was decreased by a factor of 20 to a value of 63.15 Oe for a sample with x = 0.75. In addition to the cations distribution, the increase of aspect ratio (surface to volume ratio) due to the decrease of particle size could significantly affect the magnetic properties of the materials.

  17. Recent advances and applications in the analysis of organic C and N using soft X-ray XANES

    Science.gov (United States)

    Gillespie, A. W.; Dynes, J.; Regier, T. Z.; Boyko, T.; Chevrier, D. K.; Peak, D.

    2014-12-01

    Determining the chemical speciation of carbon and nitrogen in environmental samples is important for understanding the role of organic matter in contamination mobility and nutrient cycling. Despite these important applications, bulk soft X-ray absorption spectroscopy, particularly at the carbon K-edge has not been extensively applied to environmental samples until recently. The primary reasons for this gap is the lack of beamline endstations that are suitable for 'dirty' samples and the technical challenges related to acquiring and normalizing spectra from dilute samples. X-ray absorption spectroscopy (XAS) at the C K-edge probes the local bonding environment of C and N. Bulk XAS techniques permit for high throughput, the study of whole soils and high sampling density. These analyses are complementary to X-ray transmission microscopy (STXM) techniques which are limited by low throughput, thin particles (<100 nm) and low sampling density. In many projects, these bulk XAS measurements may be essential to understanding large scale processes in soils such as the global C cycle. Technical challenges have been largely overcome through the use of customized energy selective silicon drift detectors which enable the carbon signal to be detected separately from the signals from higher order light such as oxygen (i.e., partial fluorescence yield). Accurate normalization is now possible using the X-ray scattering signal from Au coated Si wafers as the Io. The radiation dose was minimized using a monochromator slew scanning mode in conjunction with the development of software tools to automatically sample of multiple pristine spots on a sample. Technical developments and recent applications will be presented, showing how bulk C and N XAS is now positioned to contribute significantly to advancing the characterization of organic matter in soils and environmental samples.

  18. Coordination of the uranyl ion in solution and ionic liquids : a combined UV-Vis absorption and EXAFS study

    OpenAIRE

    Servaes, Kelly

    2007-01-01

    The uranyl ion (UO22+) has been extensively studied for decades and nowadays it is still a hot topic in a number of contemporary issues like nuclear waste treatment and the Balkan syndrome. Therefore, besides our fundamental interest in this complex system, the aim of this study was to provide a convenient and straightforward approach to identify the structure of various uranyl complexes formed in solution. To achieve this goal, spectroscopic techniques like UV-Vis absorption spectroscopy, ...

  19. Carbon XANES Data from Six Aerogel Picokeystones Cut from the Top and Bottom Sides of the Stardust Comet Sample Tray

    Science.gov (United States)

    Wirick, S.; Flynn, G. J.; Frank, D.; Sandford, S. A.; Zolensky, M. E.; Tsou, P.; Peltzer, C.; Jacobsen, C.

    2009-01-01

    Great care and a large effort was made to minimize the amount of organic matter contained within the flight aerogel used to collect Comet 81P/Wild 2 samples. Even so, by the very nature of the production process and silica aerogel s affinity for volatile organics keeping silica aerogel free from organics is a monumental task. Silica aerogel from three production batches was flown on the Stardust sample return mission. All 3 types had layered densities varying from 5mg/ml to 50 mg/ml where the densest aerogel was farthest away from the collection area. A 2 step gelation process was used to make the flight aerogel and organics used in this process were tetraethylorthosilicate, ethanol and acetonitrile. Both ammonium hydroxide and nitric acid were also used in the aerogel production process. The flight aerogel was baked at JPL at 300 C for 72 hours, most of the baking was done at atmosphere but twice a day the oven was pumped to 10 torr for hour [1]. After the aerogel was baked it was stored in a nitrogen purged cabinet until flight time. One aerogel cell was located in the SRC away from any sample collection area as a witness to possible contamination from out gassing of the space craft, re-entry gases and any other organic encounter. This aerogel was aerogel used in the interstellar collection sample tray and is the least dense of the 3 batches of aerogel flown. Organics found in the witness tile include organics containing Si-CH3 bonds, amines and PAHS. Besides organic contamination, hot spots of calcium were reported in the flight aerogel. Carbonates have been detected in comet 81P/Wild2 samples . During preflight analyses, no technique was used to analyze for carbonates in aerogel. To determine if the carbonates found in 81P/Wild2 samples were from the comet, it is necessary to analyze the flight aerogel for carbonate as well as for organics.

  20. Quantitative investigation of two metallohydrolases by X-ray absorption spectroscopy near-edge spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, W. [Hefei National Laboratory for Physical Sciences at Microscale and School of Life Sciences, University of Science and Technology of China, Hefei, Anhui 230027 (China); Chu, W.S.; Yang, F.F.; Yu, M.J.; Chen, D.L.; Guo, X.Y. [Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China); Zhou, D.W.; Shi, N. [Hefei National Laboratory for Physical Sciences at Microscale and School of Life Sciences, University of Science and Technology of China, Hefei, Anhui 230027 (China); Marcelli, A. [Istituto Nazionale di Fisica Nucleare, Laboratori Nazionali di Frascati, P.O. Box 13, Frascati 00044 (Italy); Niu, L.W.; Teng, M.K. [Hefei National Laboratory for Physical Sciences at Microscale and School of Life Sciences, University of Science and Technology of China, Hefei, Anhui 230027 (China); Gong, W.M. [Institute of Biophysics, Chinese Academy of Sciences, Beijing 100101 (China); Benfatto, M. [Istituto Nazionale di Fisica Nucleare, Laboratori Nazionali di Frascati, P.O. Box 13, Frascati 00044 (Italy); Wu, Z.Y. [Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China); Istituto Nazionale di Fisica Nucleare, Laboratori Nazionali di Frascati, P.O. Box 13, Frascati 00044 (Italy)], E-mail: wuzy@ihep.ac.cn

    2007-09-21

    The last several years have witnessed a tremendous increase in biological applications using X-ray absorption spectroscopy (BioXAS), thanks to continuous advancements in synchrotron radiation (SR) sources and detector technology. However, XAS applications in many biological systems have been limited by the intrinsic limitations of the Extended X-ray Absorption Fine Structure (EXAFS) technique e.g., the lack of sensitivity to bond angles. As a consequence, the application of the X-ray absorption near-edge structure (XANES) spectroscopy changed this scenario that is now continuously changing with the introduction of the first quantitative XANES packages such as Minut XANES (MXAN). Here we present and discuss the XANES code MXAN, a novel XANES-fitting package that allows a quantitative analysis of experimental data applied to Zn K-edge spectra of two metalloproteins: Leptospira interrogans Peptide deformylase (LiPDF) and acutolysin-C, a representative of snake venom metalloproteinases (SVMPs) from Agkistrodon acutus venom. The analysis on these two metallohydrolases reveals that proteolytic activities are correlated to subtle conformation changes around the zinc ion. In particular, this quantitative study clarifies the occurrence of the LiPDF catalytic mechanism via a two-water-molecules model, whereas in the acutolysin-C we have observed a different proteolytic activity correlated to structural changes around the zinc ion induced by pH variations.

  1. Quantitative investigation of two metallohydrolases by X-ray absorption spectroscopy near-edge spectroscopy

    Science.gov (United States)

    Zhao, W.; Chu, W. S.; Yang, F. F.; Yu, M. J.; Chen, D. L.; Guo, X. Y.; Zhou, D. W.; Shi, N.; Marcelli, A.; Niu, L. W.; Teng, M. K.; Gong, W. M.; Benfatto, M.; Wu, Z. Y.

    2007-09-01

    The last several years have witnessed a tremendous increase in biological applications using X-ray absorption spectroscopy (BioXAS), thanks to continuous advancements in synchrotron radiation (SR) sources and detector technology. However, XAS applications in many biological systems have been limited by the intrinsic limitations of the Extended X-ray Absorption Fine Structure (EXAFS) technique e.g., the lack of sensitivity to bond angles. As a consequence, the application of the X-ray absorption near-edge structure (XANES) spectroscopy changed this scenario that is now continuously changing with the introduction of the first quantitative XANES packages such as Minut XANES (MXAN). Here we present and discuss the XANES code MXAN, a novel XANES-fitting package that allows a quantitative analysis of experimental data applied to Zn K-edge spectra of two metalloproteins: Leptospira interrogans Peptide deformylase ( LiPDF) and acutolysin-C, a representative of snake venom metalloproteinases (SVMPs) from Agkistrodon acutus venom. The analysis on these two metallohydrolases reveals that proteolytic activities are correlated to subtle conformation changes around the zinc ion. In particular, this quantitative study clarifies the occurrence of the LiPDF catalytic mechanism via a two-water-molecules model, whereas in the acutolysin-C we have observed a different proteolytic activity correlated to structural changes around the zinc ion induced by pH variations.

  2. Papers from U.S. Department of Energy Science Undergraduate Laboratory Internship Program (SULI) 2010

    Energy Technology Data Exchange (ETDEWEB)

    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 -} in 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.

  3. High-Resolution Structure of the Photosynthetic Mn4Ca Catalyst from X-ray Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Yachandra, Vittal; Yano, Junko; Kern, Jan; Pushkar, Yulia; Sauer, Kenneth; Glatzel, Pieter; Bergmann, Uwe; Messinger, Johannes; Zouni, Athina; Yachandra, Vittal K.

    2007-08-01

    The application of high-resolution X-ray spectroscopy methods to study the photosynthetic water oxidizing complex, which contains a unique hetero-nuclear catalytic Mn4Ca cluster, are described. Issues of X-ray damage especially at the metal sites in the Mn4Ca cluster are discussed. The structure of the Mn4Ca catalyst at high-resolution which has so far eluded attempts of determination by X-ray diffraction, EXAFS and other spectroscopic techniques has been addressed using polarized EXAFS techniques applied to oriented PS II membrane preparations and PS II single crystals. A review of how the resolution of traditional EXAFS techniques can be improved, using methods such as range-extended EXAFS is presented, and the changes that occur in the structure of the cluster as it advances through the catalytic cycle are described. X-ray absorption and emission techniques (XANES and K? emission) have been used earlier to determine the oxidation states of the Mn4Ca cluster, and in this report we review the use of X-ray resonant Raman spectroscopy to understand the electronic structure of the Mn4Ca cluster as it cycles through the intermediate S-states.

  4. Ti K-edge XANES study of the local environment of titanium in bioresorbable TiO2-CaO-Na2O-P2O5 glasses.

    Science.gov (United States)

    Pickup, David M; Abou Neel, Ensanya A; Moss, Robert M; Wetherall, Kate M; Guerry, Paul; Smith, Mark E; Knowles, Jonathan C; Newport, Robert J

    2008-04-01

    Ti K-edge XANES (X-ray absorption near edge structure) spectroscopy has been used to study the local coordination of titanium in biocompatible and bioresorbable TiO2-CaO-Na2O-P2O5 glasses. Both conventional melt-quenched glasses of composition (TiO2)x(CaO)0.30(Na2O)0.20-x(P2O5)0.50, where x = 0.01, 0.03 and 0.05, and sol-gel derived (TiO2)0.25(CaO)0.25(P2O5)0.50 glass have been studied. The results show that in all the materials studied, titanium is surrounded by an octahedron of oxygen atoms. Further analysis reveals that the TiO6 site in the amorphous samples is not heavily distorted relative to that in rutile, anatase or CaSiTiO5. The spectra from the (TiO2)0.25(CaO)0.25(P2O5)0.50 sol-gel samples reveal greater distortion in the TiO6 site in the dried gel compared to the heat-treated sol-gel glass. The XANES spectra from melt-quenched glass samples soaked in distilled water for various times do not shown any evidence of degradation of the titanium site over periods of up to 14 days.

  5. Full multiple scattering analysis of XANES at the Cd L3 and O K edges in CdO films combined with a soft-x-ray emission investigation

    Energy Technology Data Exchange (ETDEWEB)

    Demchenko, I. N.; Denlinger, J. D.; Chernyshova, M.; Yu, K. M.; Speaks, D. T.; Olalde-Velasco, P.; Hemmers, O.; Walukiewicz, W.; Derkachova, A.; Lawniczak-Jablonska, K.

    2010-07-05

    X-ray absorption near edge structure (XANES) at the cadmium L3 and oxygen K edges for CdO thin films grown by pulsed laser deposition method, is interpreted within the real-space multiple scattering formalism, FEFF code. The features in the experimental spectra are well reproduced by calculations for a cluster of about six and ten coordination shells around the absorber for L3 edge of Cd and K edge of O, respectively. The calculated projected electronic density of states is found to be in good agreement with unoccupied electronic states in experimental data and allows to conclude that the orbital character of the lowest energy of the conductive band is Cd-5s-O-2p. The charge transfer has been quantified and not purely ionic bonding has been found. Combined XANES and resonant inelastic x-ray scattering measurements allow us to determine the direct and indirect band gap of investigated CdO films to be {approx}2.4-eV and {approx}0.9-eV, respectively.

  6. Experimental techniques; Techniques experimentales

    Energy Technology Data Exchange (ETDEWEB)

    Roussel-Chomaz, P. [GANIL CNRS/IN2P3, CEA/DSM, 14 - Caen (France)

    2007-07-01

    This lecture presents the experimental techniques, developed in the last 10 or 15 years, in order to perform a new class of experiments with exotic nuclei, where the reactions induced by these nuclei allow to get information on their structure. A brief review of the secondary beams production methods will be given, with some examples of facilities in operation or under project. The important developments performed recently on cryogenic targets will be presented. The different detection systems will be reviewed, both the beam detectors before the targets, and the many kind of detectors necessary to detect all outgoing particles after the reaction: magnetic spectrometer for the heavy fragment, detection systems for the target recoil nucleus, {gamma} detectors. Finally, several typical examples of experiments will be detailed, in order to illustrate the use of each detector either alone, or in coincidence with others. (author)

  7. Influences of different environmental parameters on the sorption of trivalent metal ions on bentonite: batch sorption, fluorescence, EXAFS and EPR studies.

    Science.gov (United States)

    Verma, P K; Pathak, P N; Mohapatra, P K; Godbole, S V; Kadam, R M; Veligzhanin, A A; Zubavichus, Y V; Kalmykov, S N

    2014-04-01

    The presence of long-lived radionuclides in natural aquatic systems is of great environmental concern in view of their possible migration into biospheres of mankind. Trivalent actinides such as (241/243)Am can contribute a great deal to radioactivity for several thousand years. This migration is significantly influenced by various factors such as pH, complexing ions present in aquatic environments, and the sorption of species involving radionuclides by sediments around water bodies. Clay minerals such as bentonite are known to be highly efficient in radionuclide retention and hence are suitable candidates for backfill materials. This study presents experimental results on the interaction of Eu(iii) and Gd(iii) (chemical analogs of Am(iii) and Cm(iii)) with bentonite clay under varying experimental conditions of contact time, pH, and the presence of complexing anions such as humic acid (HA) and citric acid (cit). The sorption of HA on bentonite decreased with increasing the pH from 2 to 8, which was attributed to electrostatic interactions between HA and the bentonite surfaces. The sorption of Eu(iii) on bentonite colloids showed marginal variation with pH (>95%). However, a decrease in Eu(iii) sorption was observed in the presence of HA beyond pH 5 due to the increased aqueous complexation of Eu(iii) with deprotonated HA in the aqueous phase. The complexation of Eu(iii) with citrate ions was studied using Time Resolved Laser induced Fluorescence Spectroscopy (TRLFS) to explain the sorption data. Extended X-ray absorption fine structure (EXAFS) and electron paramagnetic resonance (EPR) investigations were carried out to understand the local chemical environment surrounding Eu(iii) and Gd(iii) (EPR probe) sorbed on bentonite under different experimental conditions. Surface complexation modelling shows the predominant formation of ≡XOEu(+2) (silanol) up to pH < 7, and beyond which ≡YOEu(OH)(+) (aluminol) is responsible for the quantitative sorption of Eu(iii) onto

  8. Structure and reactivity of framework and extraframework iron in Fe-silicalite as investigated by spectroscopic and physicochemical methods

    Energy Technology Data Exchange (ETDEWEB)

    Bordiga, S.; Buzzoni, R.; Geobaldo, F.; Giamello, E. [Universita di Torino (Italy)] [and others

    1996-02-01

    The application of IR, Raman, UV-visible, EPR, XANES, EXAFS, and TPR techniques to the determination of the Fe{sup 3+} local environment in Fe-silicalite is described and discussed. These methods give information concerning the structural changes of the zeolitic structure, upon thermal treatments and interaction with adsorbates. In particular the effect of template burning at 773 K or at 973 K on the local Fe{sup 3+} environment has been discussed in detail. The reactivity of the zeolite towards NH{sub 3} has also been discussed. 64 refs., 11 figs., 3 tabs.

  9. 黑漆古铜镜表面层的X射线近边吸收谱分析%Sn-L3 EDGE and Fe K edge XANES spectra of the surface layer of ancient Chinese black mirror Heiqigu

    Institute of Scientific and Technical Information of China (English)

    高魏梦佳; 刘渝珍; 储旺盛; 吴自玉; 王昌燧

    2009-01-01

    利用同步辐射X射线吸收(XANES)近边分析,探讨了黑漆古铜镜表面层某些原子周边的信息.Sn原子L3边XANES谱的分析,进一步证明黑漆古铜镜表面SnO2晶格中存在以肖托基缺陷的形式存在掺杂的Fe原子,Sn原子的外层轨道空态少于标样SnO2,被部分填充.Sn原子与O原子的结合程度较标样SnO2低,黑漆古铜镜表面是由Sn(IV)与Sn(II)的氧化态共同组成的稳定结构.

  10. XAFS Study of the Al K-Edge in NaAlH4

    NARCIS (Netherlands)

    Balde, C.P.; Mijovilovich, A.E.; Koningsberger, D.C.; van der Eerden, A.M.J.; Smith, A.D.; de Jong, K.P.; Bitter, J.H.

    2007-01-01

    Al K-edge (1561.1 eV) XANES and EXAFS spectra of unoxidized NaAlH4, a hydrogen storage material, have been recorded in He atmosphere in a special in situ low-energy cell. The XANES spectrum of NaAlH4 is reported and compared to that of oxidized NaAlH4, thus illustrating the power of XANES spectrosco

  11. Characterization techniques for graphene-based materials in catalysis

    Directory of Open Access Journals (Sweden)

    Maocong Hu

    2017-06-01

    Full Text Available Graphene-based materials have been studied in a wide range of applications including catalysis due to the outstanding electronic, thermal, and mechanical properties. The unprecedented features of graphene-based catalysts, which are believed to be responsible for their superior performance, have been characterized by many techniques. In this article, we comprehensively summarized the characterization methods covering bulk and surface structure analysis, chemisorption ability determination, and reaction mechanism investigation. We reviewed the advantages/disadvantages of different techniques including Raman spectroscopy, X-ray photoelectron spectroscopy (XPS, Fourier transform infrared spectroscopy (FTIR and Diffuse Reflectance Fourier Transform Infrared Spectroscopy (DRIFTS, X-Ray diffraction (XRD, X-ray absorption near edge structure (XANES and X-ray absorption fine structure (XAFS, atomic force microscopy (AFM, scanning electron microscopy (SEM, transmission electron microscopy (TEM, high-resolution transmission electron microscopy (HRTEM, ultraviolet-visible spectroscopy (UV-vis, X-ray fluorescence (XRF, inductively coupled plasma mass spectrometry (ICP, thermogravimetric analysis (TGA, Brunauer–Emmett–Teller (BET, and scanning tunneling microscopy (STM. The application of temperature-programmed reduction (TPR, CO chemisorption, and NH3/CO2-temperature-programmed desorption (TPD was also briefly introduced. Finally, we discussed the challenges and provided possible suggestions on choosing characterization techniques. This review provides key information to catalysis community to adopt suitable characterization techniques for their research.

  12. On the molecular basis of the activity of the antimalarial drug chloroquine: EXAFS-assisted DFT evidence of a direct Fe-N bond with free heme in solution

    Science.gov (United States)

    Macetti, Giovanni; Rizzato, Silvia; Beghi, Fabio; Silvestrini, Lucia; Lo Presti, Leonardo

    2016-02-01

    4-aminoquinoline antiplasmodials interfere with the biocrystallization of the malaria pigment, a key step of the malaria parasite metabolism. It is commonly believed that these drugs set stacking π···π interactions with the Fe-protoporphyrin scaffold of the free heme, even though the details of the heme:drug recognition process remain elusive. In this work, the local coordination of Fe(III) ions in acidic solutions of hematin at room temperature was investigated by extended x-ray absorption fine structure (EXAFS) spectroscopy in the 4.0-5.5 pH range, both in the presence and in the absence of the antimalarial drug chloroquine. EXAFS results were complemented by DFT simulations in polarizable continuum media to model solvent effects. We found evidence that a complex where the drug quinoline nitrogen is coordinated with the iron center might coexist with formerly proposed adduct geometries, based on stacking interactions. Charge-assisted hydrogen bonds among lateral chains of the two molecules play a crucial role in stabilizing this complex, whose formation is favored by the presence of lipid micelles. The direct Fe-N bond could reversibly block the axial position in the Fe 1st coordination shell in free heme, acting as an inhibitor for the crystallization of the malaria pigment without permanently hampering the catalytic activity of the redox center. These findings are discussed in the light of possible implications on the engineering of drugs able to thwart the adaptability of the malaria parasite against classical aminoquinoline-based therapies.

  13. X-ray Absorption Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Yano, Junko; Yachandra, Vittal K.

    2009-07-09

    This review gives a brief description of the theory and application of X-ray absorption spectroscopy, both X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS), especially, pertaining to photosynthesis. The advantages and limitations of the methods are discussed. Recent advances in extended EXAFS and polarized EXAFS using oriented membranes and single crystals are explained. Developments in theory in understanding the XANES spectra are described. The application of X-ray absorption spectroscopy to the study of the Mn4Ca cluster in Photosystem II is presented.

  14. Annealed Crystallization of Ni-B and Ni-Ce-B Ultrafine Amorphous Alloys Studied by EXAFS%EXAFS研究Ni-B和Ni-Ce-B 超细非晶态合金的退火晶化

    Institute of Scientific and Technical Information of China (English)

    王晓光; 闫文胜; 钟文杰; 张新夷; 韦世强

    2001-01-01

    EXAFS technique was used to quantitatively determine the local structure evolutions of Ni-B and Ni-Ce-B ultrafine amorphous alloys prepared by chemical reduction during the annealed process. The results show that the average bond length Rj, coordination number N, thermal disorder factor σT and static disorder factor σS are 0.275 nm, 11.9, 0.006 9 nm, 0.034 nm; 0.215 nm, 2.7, 0.005 5 nm, 0.003 8 nm, and 0.276 nm, 12.4, 0.006 7 nm, 0.035 nm; 0.214 nm, 2.9, 0.005 8 nm, 0.004 2 nm for the Ni-Ni and Ni-B first neighbor shells of Ni-B and Ni-Ce-B ultrafine amorphous alloys, respectively. It is indicated that the σS of Ni-Ni shell is rather larger, about four or five times as large as that of σT, and one order larger than that of σS of Ni-B shell. Ni-B sample is crystallized after being annealed at 300 ℃, and its RNi—Ni as well as σS are 0.254 nm and 0.011 nm, respectively. However, the crystallization temperature of Ni-Ce-B sample increases about 100 ℃ due to the addition of 0.3% Ce element. The local structure around Ni atom for the Ni-B sample annealed at 500 ℃ is fully similar to that of Ni foil. For the Ni-Ce-B samples annealed at 500 ℃, the σS of Ni-Ni shell is 0.007 3 nm and the N of Ni-B shell is 1.2. It implies that the Ni lattice produced from the crystallization of Ni-Ce-B amorphous alloys is significantly distorted and the interaction between Ni and B atoms is strongly increased by the effect of Ce element.%采用同步辐射EXAFS技术定量地研究化学还原法制备的Ni-B 和Ni-Ce-B超细非晶态合金中Ni原子的局域环境结构随退火温度升高而产生的变化. 结果表明, 对于Ni-B和Ni-Ce-B超细非晶态合金初始样品: Ni-Ni最邻近配位壳层的平均键长RNi—Ni、 配位数N、 热无序σT、 结构无序σS分别为0.275 nm, 11.9, 0.006 9 nm, 0.034 nm; 0.276 nm, 12.4, 0.006 7 nm, 0.035 nm. Ni-B最邻近配位壳层的RNi—B, N, σT, σS分别为0.215 nm, 2.7, 0.005 5 nm, 0.003 8 nm; 0

  15. Use of synchrotron XANES and Cr-doped coal to further confirm the vaporization of organically bound Cr and the formation of chromium(VI) during coal oxy-fuel combustion.

    Science.gov (United States)

    Chen, Juan; Jiao, Facun; Zhang, Lian; Yao, Hong; Ninomiya, Yoshihiko

    2012-03-20

    Through the use of synchrotron XANES and Cr-doped brown coal, extensive efforts have been made to clarify the volatility of organically bound Cr during oxy-fuel combustion and the mode of occurrence and leachability of Cr in resulting fly ashes. As the continuation of our previous study using raw coal, the Cr-doped coal has been tested in this study to improve the signal-to-noise ratio for Cr K-edge XANES spectra, and hence the accuracy for Cr(VI) quantification. As has been confirmed, the abundant CO(2) as a balance gas for oxy-firing has the potential to inhibit the decomposition of organically bound Cr, thereby favoring its retention in solid ash. It also has the potential to promote the oxidation of Cr(III) to Cr(VI) to a minor extent. Increasing the oxygen partial pressure, particularly in the coexistence of HCl in flue gas, favored the oxidation of Cr(III) into gaseous Cr(VI)-bearing species such as CrO(2)Cl(2). Regarding the solid impurities including Na(2)SO(4) and CaO, Na(2)SO(4) has proven to preferentially capture the Cr(III)-bearing species at a low furnace temperature such as 600 °C. Its promoting effect on the oxidation of Cr(III) to Cr(VI), although thermodynamically available at the temperatures examined here, is negligible in a lab-scale drop tube furnace (DTF), where the particle residence time is extremely short. In contrast, CaO has proven facilitating the capture of Cr(VI)-bearing species particularly oxychloride vapors at 1000 °C, forming Ca chromate with the formulas of CaCrO(4) and Ca(3)(CrO(4))(2) via a direction stabilization of Cr(VI) oxychloride vapor by CaO particle or an indirect oxidation of Cr(III) via the initial formation of Ca chromite. The fly ash collected from the combustion of Cr-doped coal alone has a lower water solubility (i.e., 58.7%) for its Cr(VI) species, due to the formation of Ba/Pb chromate and/or the incorporation of Cr(VI) vapor into a slagging phase which is water-insoluble. Adding CaO to coal increased the

  16. Mechanical properties and microstructure of TiC/amorphous hydrocarbon nanocomposite coatings.

    Energy Technology Data Exchange (ETDEWEB)

    Meng, W. J.; Tittsworth, R. C.; Rehn, L. E.; Materials Science Division; Louisana State Univ.

    2000-12-01

    Using the techniques of reactive magnetron sputter deposition and inductively coupled plasma (ICP) assisted hybrid physical vapor deposition (PVD)/chemical vapor deposition (CVD), we have synthesized a wide variety of metal-free amorphous hydrocarbon (a-C:H) and Ti-containing hydrocarbon (Ti-C:H) coatings. Coating elastic modulus and hardness have been measured by the technique of instrumented nanoindentation and related to Ti and hydrogen compositions. We show that both metal and hydrogen compositions significantly influence the mechanical properties of Ti-C:H coatings. The microstructure of Ti-C:H coatings is further characterized by transmission electron microscopy (TEM), X-ray absorption near edge structure (XANES) spectroscopy, and extended X-ray absorption fine structure (EXAFS) spectroscopy. XANES spectroscopy and high-resolution TEM examination of Ti-C:H specimens shows that the dissolution limit of Ti atoms in an a-C:H matrix is between 0.9 and 2.5 at.%. Beyond the Ti dissolution limit, precipitation of nanocrystalline B1-TiC cluster occurs and Ti-C:H coatings are in fact TiC/a-C:H thin film nanocomposites. Measurements of the average Ti bonding environment in TiC/a-C:H nanocomposites by EXAFS spectroscopy are consistent with a microstructure in which bulk-like B1-TiC clusters are embedded in an a-C:H matrix.

  17. Dependence of copper species on the nature of the support for dispersed CuO catalysts.

    Science.gov (United States)

    Gervasini, Antonella; Manzoli, Maela; Martra, Gianmario; Ponti, Alessandro; Ravasio, Nicoletta; Sordelli, Laura; Zaccheria, Federica

    2006-04-20

    Copper catalysts prepared by chemisorption-hydrolysis technique over silica (Cu/Si) and silica-alumina (Cu/SiAl) supports were studied to understand the role of the support on the nature and surface properties of the copper species stabilized on their surfaces. The morphological and surface properties of the copper phases have been characterized by complementary techniques, such as HRTEM, EXAFS-XANES, EPR, XPS, and FTIR. For the FTIR investigation, molecular probes (CO and NO) were also adsorbed on the surfaces to test the reactivity of the copper species. Moreover, the catalytic performances of the two catalysts have been compared in the HC-SCR reaction (NO reduction by C(2)H(4)) performed in highly oxidant conditions. The superior activity and selectivity of the supported silica-alumina catalyst with respect to that supported on silica could be related with the different nature of the copper species stabilized on the two supports, as emerged from the results obtained from the spectroscopic investigations. Small and well-dispersed CuO particles were present on silica, whereas isolated copper ions predominated on silica-alumina, likely in regions rich in alumina that made some exchangeable sites available, as indicated by FTIR spectra of adsorbed CO. The less positive global charge of copper species on Cu/SiAl than in Cu/Si has been confirmed by EPR, XPS, and EXAFS-XANES analyses.

  18. Distinction of Metal Species of Phytate by Solid-State Spectroscopic Techniques

    Energy Technology Data Exchange (ETDEWEB)

    He,Z.; Honeycutt, W.; Zhang, T.; Pellechia, P.; Caliebe, W.

    2007-01-01

    Solid-state {sup 31}P nuclear magnetic resonance (NMR) and x-ray absorption near edge structure (XANES) spectroscopies have provided knowledge on metal speciation of inorganic P. No effort has been made, however, to accurately assign speciated metal phytates (inositol hexaphosphoric acid salts) using these advanced techniques. Phytate is a predominant form of organic P in animal manure, soil, and other organic substances as each year 51 million Mg of phytate are formed in crops and fruits globally. Currently, the interactions and fate of phytate in the environment are poorly understood. Here we show the solid-state spectral characteristics of six metal phytates. Both spectra were affected by the metal species of the phytates, as significant differences were observed in the shape and position of spectra among the metal phytates. Reference spectra of these pure metal phytate compounds may help in identifying metal species of phytate in environmental samples by these advanced spectroscopic technologies.

  19. Insight From EXAFS and the Multi Site Complexation Model (MUSIC) Into the Discrepancy Between SCM-Predicted and Experimental pH-Dependent Ni Sorption to Hydrous Manganese Oxyhydroxide

    Science.gov (United States)

    Haack, E. A.; Smith, D. S.; Trainor, T. P.; Warren, L. A.

    2003-12-01

    Hydrous manganese oxyhydroxides (HMO) are receiving increasing attention from both geomicrobiologists, due to the importance of microbial catalysis in their formation, and trace element geochemists, due to their importance as trace metal sorbents in a wide number of environments. Accurate models of the mechanisms of trace metal sequestration in association with HMO are thus required for an overall understanding of metal reactive transport. We have examined the utility of a surface complexation model to describe pH-dependent Ni sorption to synthetic HMO, a layered oxide comparable in structure to microbially-catalyzed Mn oxide. Surface complexation models (SCM) have successfully reproduced metal and proton binding curves to a number of geochemically relevant solids, including bacteria and mineral surfaces. However, because these models are derived from potentiometric titrations, they have intrinsic limitations; very high and very low proton affinity sites cannot be characterized. Results from our study indicated that Ni sorption to HMO could not be described by assuming Ni sorption to the SCM-derived proton binding sites. Ni sorption capacity of the solid far exceeded proton binding capacity at low pH values. Examination of the Ni-sorbed HMO samples with EXAFS indicated that the discrepancy between Ni sorption and proton binding could not be ascribed to the precipitation of a separate Ni solid phase. Rather, all at pH values examined (2.0, 4.0 and 6.5) Ni sorbed above/below layer vacancies in the MnO6 octahedral layers of HMO, as interlayer tridentate corner-sharing complexes. At circumneutral pH (6.5), Ni also substituted directly for structural Mn. A theoretical pKa spectrum was derived for HMO using the multi site complexation model (MUSIC) and proton affinity constants for surface functional groups relevant for Ni sorption, as constrained by EXAFS, were identified. Ni sorption as an interlayer complex occurred at sites with very high proton affinity, thus

  20. Seleno-auranofin (Et3PAuSe-tagl): synthesis, spectroscopic (EXAFS, 197Au Mössbauer, 31P, 1H, 13C, and 77Se NMR, ESI-MS) characterization, biological activity, and rapid serum albumin-induced triethylphosphine oxide generation.

    Science.gov (United States)

    Hill, David T; Isab, Anvarhusein A; Griswold, Don E; DiMartino, Michael J; Matz, Elizabeth D; Figueroa, Angel L; Wawro, Joyce E; DeBrosse, Charles; Reiff, William M; Elder, Richard C; Jones, Benjamin; Webb, James W; Shaw, C Frank

    2010-09-06

    Seleno-auranofin (SeAF), an analogue of auranofin (AF), the orally active antiarthritic gold drug in clinical use, was synthesized and has been characterized by an array of physical techniques and biological assays. The Mössbauer and extended X-ray absorption fine structure (EXAFS) parameters of the solid compound demonstrate a linear P-Au-Se coordination environment at a gold(I) center, analogous to the structure of auranofin. The (31)P, (13)C, and (1)H NMR spectra of SeAF in chloroform solution closely resemble those of auranofin. The (77)Se spectrum consists of a singlet at 481 ppm, consistent with a metal-bound selenolate ligand. The absence of (2)J(PSe) coupling in the (31)P and (77)Se spectra may arise from dynamic processes occurring in solution or because the (2)J(PSe) coupling constants are smaller than the observed bandwidths. Electrospray ionization mass spectrometry (ESI-MS) spectra of SeAF in 50:50 methanol-water exhibited strong signals for [(Et(3)P)(2)Au](+), [(Et(3)PAu)(2)-mu-Se-tagl](+), and [Au(Se-tagl)(2)](-), which arise from ligand scrambling reactions. Three assays of the anti-inflammatory activity of SeAF allowed comparison to AF. SeAF exhibited comparable activity in the topically administered murine arachadonic acid-induced and phorbol ester-induced anti-inflammatory assays but was inactive in the orally administered carrageenan-induced assay in rats. However, in vivo serum gold levels were comparable in the rat, suggesting that differences between the in vivo metabolism of the two compounds, leading to differences in transport to the inflamed site, may account for the differential activity in the carrageenan-induced assay. Reactions of serum albumin, the principal transport protein of gold in the serum, demonstrated formation of AlbSAuPEt(3) at cysteine 34 and provided evidence for facile reduction of disulfide bonds at cysteine 34 and very rapid formation of Et(3)P=O, a known metabolite of auranofin.

  1. Acquired Techniques

    DEFF Research Database (Denmark)

    Lunde Nielsen, Espen; Halse, Karianne

    2013-01-01

    Acquired Techniques - a Leap into the Archive, at Aarhus School of Architecture. In collaboration with Karianne Halse, James Martin and Mika K. Friis. Following the footsteps of past travelers this is a journey into tools and techniques of the architectural process. The workshop will focus upon...... architectural production as a conglomerate of various analogue and digital methods, and provide the basics, the tips/tricks - and how the tool themselves becomes operational for spatial/thematic investigations. Eventually, this will become a city, exhibition and phamplet inhabited by the (by...

  2. Translation Techniques

    Directory of Open Access Journals (Sweden)

    Marcia Pinheiro

    2015-05-01

    Full Text Available In this paper, we discuss three translation techniques: literal, cultural, and artistic. Literal translation is a well-known technique, which means that it is quite easy to find sources on the topic. Cultural and artistic translation may be new terms. Whilst cultural translation focuses on matching contexts, artistic translation focuses on matching reactions. Because literal translation matches only words, it is not hard to find situations in which we should not use this technique.  Because artistic translation focuses on reactions, judging the quality of an artistic translation work is one of the most difficult things one can do. We end up having a score of complexity and humanity for each one of the mentioned techniques: Literal translation would be the closest thing we have to the machines world and artistic translation would be the closest thing we have to the purely human world. By creating these classifications and studying the subtleties of each one of them, we are adding degrees of quality to our courses and to translation as a professional field. The main contribution of this paper is then the formalization of such a piece of knowledge. We, however, also lay the foundations for studies of this type.

  3. Experimental Techniques

    CERN Document Server

    Engelfried, J

    1999-01-01

    In this course we will give examples for experimental techniques used in particle physics experiments. After a short introduction, we will discuss applications in silicon microstrip detectors, wire chambers, and single photon detection in Ring Imaging Cherenkov (RICH) counters. A short discussion of the relevant physics processes, mainly different forms of energy loss in matter, is enclosed.

  4. Atomic structure of glassy Mg60Cu30Y10 investigated with EXAFS, x-ray and neutron diffraction, and reverse Monte Carlo simulations

    DEFF Research Database (Denmark)

    Jovari, P.; Saksl, K.; Pryds, Nini;

    2007-01-01

    Short range order of amorphous Mg60Cu30Y10 was investigated by x-ray and neutron diffraction, Cu and Y K-edge x-ray absorption fine structure measurements, and the reverse Monte Carlo simulation technique. We found that Mg-Mg and Mg-Cu nearest neighbor distances are very similar to values found i...

  5. Electronic and atomic structures of the Sr3Ir4Sn13 single crystal: A possible charge density wave material

    Science.gov (United States)

    Wang, H.-T.; Srivastava, M. K.; Wu, C.-C.; Hsieh, S.-H.; Wang, Y.-F.; Shao, Y.-C.; Liang, Y.-H.; Du, C.-H.; Chiou, J.-W.; Cheng, C.-M.; Chen, J.-L.; Pao, C.-W.; Lee, J.-F.; Kuo, C. N.; Lue, C. S.; Wu, M.-K.; Pong, W.-F.

    2017-01-01

    X-ray scattering (XRS), x-ray absorption near-edge structure (XANES) and extended x-ray absorption fine structure (EXAFS) spectroscopic techniques were used to study the electronic and atomic structures of the high-quality Sr3Ir4Sn13 (SIS) single crystal below and above the transition temperature (T* ≈ 147 K). The evolution of a series of modulated satellite peaks below the transition temperature in the XRS experiment indicated the formation of a possible charge density wave (CDW) in the (110) plane. The EXAFS phase derivative analysis supports the CDW-like formation by revealing different bond distances [Sn1(2)-Sn2] below and above T* in the (110) plane. XANES spectra at the Ir L3-edge and Sn K-edge demonstrated an increase (decrease) in the unoccupied (occupied) density of Ir 5d-derived states and a nearly constant density of Sn 5p-derived states at temperatures T atomic structures and the CDW-like phase in the SIS single crystal. PMID:28106144

  6. Structure and Bonding in Amorphous Cr1-xCx Nanocomposite Thin Films: X-ray Absorption Spectra and First-Principles Calculation

    CERN Document Server

    Olovsson, Weine; Magnuson, Martin

    2016-01-01

    The local structure and chemical bonding in two-phase amorphous Cr$_{1-x}$C$_{x}$ nanocomposite thin films are investigated by Cr $K$-edge ($1s$) X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopies in comparison to theory. By utilizing the computationally efficient \\textit{stochastic quenching} (SQ) technique, we reveal the complexity of different Cr-sites in the transition metal carbides, highlighting the need for large scale averaging to obtain theoretical XANES and EXAFS spectra for comparison with measurements. As shown in this work, it is advantageous to use \\textit{ab initio} theory as an assessment to correctly model and fit experimental spectra and investigate the trends of bond lengths and coordination numbers in complex amorphous materials. With sufficient total carbon content ($\\geq$ 30 at\\%), we find that the short-range coordination in the amorphous carbide phase exhibit similarities to that of a Cr$_{7}$C$_{3\\pm{}y}$ structure, while e...

  7. Quick extended x-ray absorption fine structure instrument with millisecond time scale, optimized for in situ applications.

    Science.gov (United States)

    Khalid, S; Caliebe, W; Siddons, P; So, I; Clay, B; Lenhard, T; Hanson, J; Wang, Q; Frenkel, A I; Marinkovic, N; Hould, N; Ginder-Vogel, M; Landrot, G L; Sparks, D L; Ganjoo, A

    2010-01-01

    In order to learn about in situ structural changes in materials at subseconds time scale, we have further refined the techniques of quick extended x-ray absorption fine structure (QEXAFS) and quick x-ray absorption near edge structure (XANES) spectroscopies at beamline X18B at the National Synchrotron Light Source. The channel cut Si (111) monochromator oscillation is driven through a tangential arm at 5 Hz, using a cam, dc motor, pulley, and belt system. The rubber belt between the motor and the cam damps the mechanical noise. EXAFS scan taken in 100 ms is comparable to standard data. The angle and the angular range of the monochromator can be changed to collect a full EXAFS or XANES spectrum in the energy range 4.7-40.0 KeV. The data are recorded in ascending and descending order of energy, on the fly, without any loss of beam time. The QEXAFS mechanical system is outside the vacuum system, and therefore changing the mode of operation from conventional to QEXAFS takes only a few minutes. This instrument allows the acquisition of time resolved data in a variety of systems relevant to electrochemical, photochemical, catalytic, materials, and environmental sciences.

  8. Study of temperature dependent local structure by polarized Cu K-edge EXAFS measurements on La sub 2 sub - sub x Sr sub x CuO sub 4 (x=0.105, 0.13, 0.20)

    CERN Document Server

    Saini, N L; Bianconi, A; Oyanagi, H; Ito, T; Oka, K

    2003-01-01

    We have studied temperature dependent local structure of superconducting La sub 2 sub - sub x Sr sub x CuO sub 4 (0.105, 0.13, 0.20) single crystals by Cu K-edge extended x-ray absorption fine structure (EXAFS) measurements with polarization parallel to the in-plane Cu-O bonds. We find that, while underdoped crystals (x=0.105, 0.13) show anomalous temperature dependence, similar to the case of optimally doped system (x=0.15), overdoped crystal (x=0.20) does not reveal such anomaly. Correlated Debye-Waller factor (DWF) of the Cu-O bonds (distance broadening) has been used as an order parameter to determine characteristic local displacements in the CuO sub 2 plane. The amplitude of temperature dependent step-like increase in the DWF at low temperature decreases with increasing doping. It has been discussed that decreasing electron-lattice interaction with increasing doping, shown by angle resolved photoemission measurements, is closely related to the evolving anomalous local CuO sub 2 distortion and charge inho...

  9. Heat capacity measurement and EXAFS study of (U{sub 0.85}Mg{sub 0.15})O{sub 2{minus}x} for x = 0 and 0.1

    Energy Technology Data Exchange (ETDEWEB)

    Atita, Y; Matsui, T. [Nagoya Univ. (Japan); Ohno, H. [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Office of Synchrotron Radiation Facility Project; Kobayashi, K. [National Lab. for High Energy Physics, Tsukuba, Ibaraki (Japan). Photon Factory

    1997-03-01

    Heat capacities and electrical conductivities of (U{sub 0.85}Mg{sub 0.15})O{sub 2{minus}x} (x = 0 and 0.1) were measured simultaneously by means of a direct heating pulse calorimeter (DHPC) in the temperature range from 300 to 1500 K. Anomalous increases in the heat capacity curves of (U{sub 0.85}Mg{sub 0.15})O{sub 2{minus}x} (x = 0 and 0.1) were observed above about 800 and 1150 K, respectively. The values for the enthalpy of oxygen Frenkel defect formation were calculated from the excess heat capacity and were found to be similar to those for UO{sub 2} doped with rare earth elements. On the other hand, no anomaly was seen in the electrical conductivity curve around the onset temperature of the anomalous increase in the heat capacity. It was, therefore, concluded that the excess heat capacity originates from the predominant contribution of the formation of Frenkel pair-like defects of oxygen. An extended X-ray absorption fine structure (EXAFS) experiment shows a different environment of oxygen around uranium and magnesium, and this should be a cause of the onset temperature difference.

  10. Phase diagram and EXAFS study of La sub 0 sub . sub 7 Ca sub 0 sub . sub 3 sub - sub x Ba sub x MnO sub 3 manganites

    CERN Document Server

    Ulyanov, A N; Yang, D S

    2003-01-01

    The phase diagram and local structure of La sub 0 sub . sub 7 Ca sub 0 sub . sub 3 sub - sub x Ba sub x MnO sub 3 (x=0; 0.03; 0.06; ... 0.3) lanthanum manganites were studies. The Curie temperature, T sub c , of the compositions showed a sharp change near the concentrational structural orthorhombic-rhombohedral phase transition. Maximums of dispersion, sigma sub M sub n sub - sub O sup 2 , and asymmetry, sigma M sub n sub - sub O sup 3 , of pair distribution function for the Mn-O bond distances of MnO sub 6 octahedron on x-dependence were observed by extended X-ray absorption fine structure (EXAFS) analysis. The maximum of sigma sub M sub n sub - sub O sup 2 is caused by increase of dynamic rms displacements of Mn-O bond distances near the T sub c. The observed x dependence of sigma sub M sub n sub - sub O sup 3 reflects the reduction of charge carriers mobility at approaching to T sub c. (author)

  11. Intensity techniques

    DEFF Research Database (Denmark)

    Jacobsen, Finn

    2008-01-01

    The Handbook of Signal Processing in Acoustics will compile the techniques and applications of signal processing as they are used in the many varied areas of Acoustics. The Handbook will emphasize the interdisciplinary nature of signal processing in acoustics. Each Section of the Handbook...... will present topics on signal processing which are important in a specific area of acoustics. These will be of interest to specialists in these areas because they will be presented from their technical perspective, rather than a generic engineering approach to signal processing. Non-specialists, or specialists...... from different areas, will find the self-contained chapters accessible and will be interested in the similarities and differences between the approaches and techniques used in different areas of acoustics....

  12. Electrochemical Techniques

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Gang; Lin, Yuehe

    2008-07-20

    Sensitive and selective detection techniques are of crucial importance for capillary electrophoresis (CE), microfluidic chips, and other microfluidic systems. Electrochemical detectors have attracted considerable interest for microfluidic systems with features that include high sensitivity, inherent miniaturization of both the detection and control instrumentation, low cost and power demands, and high compatibility with microfabrication technology. The commonly used electrochemical detectors can be classified into three general modes: conductimetry, potentiometry, and amperometry.

  13. Redox and speciation mapping of rock thin sections using high spatial resolution full-field imaging technique

    Science.gov (United States)

    de Andrade, V.; Susini, J.; Salomé, M.; Beraldin, O.; Heymes, T.; Lewin, E.

    2009-04-01

    Because of their complex genesis, natural rocks are the most often heterogeneous systems, with various scale-level heterogeneities for both chemistry and structure. In the last decade, the dramatic improvements of hyperspectral imaging techniques provided new tools for accurate material characterisation. Most of these micro- and nano- analytical techniques rely on scanning instruments, which offer high spatial resolution but suffer from long acquisition times imposing practical limits on the field of view. Conversely, full-field imaging techniques rely on a fast parallel acquisition but have limited resolution. Although soft X-ray full-field microscopes based on Fresnel zone plates are commonly used for high resolution imaging, its combination with spectroscopy is challenging and 2D chemical mapping still difficult. For harder X-rays, lensless X-ray microscope based on simple propagation geometry is easier and can be readily used for 2D spectro-microscopy. A full-field experimental setup was optimized at the ESRF-ID21 beamline to image iron redox and speciation distributions in rocks thin sections. The setup comprises a Si111 or Si220 (E = 0.4 eV) monochromator, a special sample stage and a sensitive camera associated with a brand new GGG:Eu light conversion scintillator and high magnification visible light optics. The pixel size ranges from 1.6 to 0.16 m according to the optic used. This instrument was used to analyse phyllosilicates and oxides of metamorphic sediments coming from the Aspromonte nappes-pile in Calabria. Iron chemical state distributions were derived - from images of 1000 Ã- 2000 Ã- 30 m3 rock thin sections - by subtraction of absorption images above and below the Fe K-edge. Using an automatic stitching reconstruction, a wide field image (4Ã-3 mm2 with a 1 m2 resolution for a total of about 12 millions pixels) of Fetotal elemental distribution was produced. Moreover, -XANES analyses (more than 1 million individual -XANES spectra) were performed

  14. Crystal and electronic structure study of AgAu and AgCu bimetallic alloy thin films by X-ray techniques

    Energy Technology Data Exchange (ETDEWEB)

    Ozkendir, O. Murat, E-mail: ozkendir@gmail.com [Mersin University, Faculty of Technology, Energy Systems Engineering, Tarsus (Turkey); Mersin University, Institute of Natural Science, Department of Nanotechnology and Advanced Materials, Mersin (Turkey); Cengiz, E. [Karadeniz Technical University, Faculty of Science, Department of Physics, Trabzon (Turkey); Yalaz, E. [Mersin University, Institute of Natural Science, Department of Nanotechnology and Advanced Materials, Mersin (Turkey); Söğüt, Ö.; Ayas, D.H. [Kahramanmaraş Sütçü İmam Üniversitesi, Faculty of Science and Letters, Department of Physics, Kahramanmaraş (Turkey); Thammajak, B. Nirawat [Synchrotron Light Research Institute (Public Organisation), 111 University Avenue, T. Suranaree, A. Muang, Nakhon Ratchasima 30000 (Thailand)

    2016-05-15

    Highlights: • Crystal and electronic properties of bimetallic AgCu and AgAu alloy thin films were studied. • Both AgCu and AgAu bimetallic samples were determined to have cubic crystal geometry. • Strong influence of Cu and Au atoms on the electronic structure of the Ag atoms were determined. - Abstract: Crystal and electronic structure properties of bimetallic AgAu and AgCu alloy thin films were investigated by X-ray spectroscopic techniques. The aim of this study is to probe the influence of Au or Cu atoms on the electronic behaviors of Ag ions in bimetallic alloy materials that yields different crystal properties. To identify the mechanisms causing crystal phase transitions, study were supported by the collected EXAFS (Extended X-ray Absorption Fine Structure) data. Crystal structures of both Cu and Au doped bimetallic Ag samples were determined mainly in cubic geometry with “Fm3m” space group. Through the Ag–Au and Ag–Cu molecular interactions during bimetallic alloy formations, highly overlapped electronic levels that supports large molecular band formations were observed with different ionization states. Besides, traces of the d–d interactions in Au rich samples were determined as the main interplay in the broad molecular bond formations. The exact atomic locations and types in the samples were determined by EXAFS studies and supported by the performed calculations with FEFF scientific code.

  15. In situ characterization of uranium and americium oxide solid solution formation for CRMP process: first combination of in situ XRD and XANES measurements.

    Science.gov (United States)

    Caisso, Marie; Picart, Sébastien; Belin, Renaud C; Lebreton, Florent; Martin, Philippe M; Dardenne, Kathy; Rothe, Jörg; Neuville, Daniel R; Delahaye, Thibaud; Ayral, André

    2015-04-14

    Transmutation of americium in heterogeneous mode through the use of U1-xAmxO2±δ ceramic pellets, also known as Americium Bearing Blankets (AmBB), has become a major research axis. Nevertheless, in order to consider future large-scale deployment, the processes involved in AmBB fabrication have to minimize fine particle dissemination, due to the presence of americium, which considerably increases the risk of contamination. New synthesis routes avoiding the use of pulverulent precursors are thus currently under development, such as the Calcined Resin Microsphere Pelletization (CRMP) process. It is based on the use of weak-acid resin (WAR) microspheres as precursors, loaded with actinide cations. After two specific calcinations under controlled atmospheres, resin microspheres are converted into oxide microspheres composed of a monophasic U1-xAmxO2±δ phase. Understanding the different mechanisms during thermal conversion, that lead to the release of organic matter and the formation of a solid solution, appear essential. By combining in situ techniques such as XRD and XAS, it has become possible to identify the key temperatures for oxide formation, and the corresponding oxidation states taken by uranium and americium during mineralization. This paper thus presents the first results on the mineralization of (U,Am) loaded resin microspheres into a solid solution, through in situ XAS analysis correlated with HT-XRD.

  16. Chemical ordering in Pd81Ge19 metallic glass studied by reverse Monte-Carlo modelling of XRD, ND and EXAFS experimental data

    Science.gov (United States)

    Pethes, Ildikó; Kaban, Ivan; Stoica, Mihai; Beuneu, Brigitte; Jóvári, Pál

    2016-10-01

    Pd81Ge19 metallic glass was investigated by neutron diffraction, x-ray diffraction and extended x-ray absorption fine structure spectroscopy at the Ge K-edge. Large scale structural models were obtained by fitting the three measurements simultaneously in the framework of the reverse Monte Carlo simulation technique. It was found that the experimental data sets can be adequately fitted without Ge-Ge nearest neighbours. Mean Pd-Pd and Pd-Ge distances are 2.80 ± 0.02 Å and 2.50 ± 0.02 Å, respectively. The total average coordination number of Pd is 12.1 ± 0.5 while Ge is surrounded by 10.6 ± 1.1 Pd atoms. The coordination numbers calculated from partial pair correlation functions were compared to those obtained by Voronoi tessellation method. It was found that the latter technique overestimates the number of nearest neighbours by about 20% due to the significant contribution of distant pairs.

  17. Combinatorial techniques

    CERN Document Server

    Sane, Sharad S

    2013-01-01

    This is a basic text on combinatorics that deals with all the three aspects of the discipline: tricks, techniques and theory, and attempts to blend them. The book has several distinctive features. Probability and random variables with their interconnections to permutations are discussed. The theme of parity has been specially included and it covers applications ranging from solving the Nim game to the quadratic reciprocity law. Chapters related to geometry include triangulations and Sperner's theorem, classification of regular polytopes, tilings and an introduction to the Eulcidean Ramsey theory. Material on group actions covers Sylow theory, automorphism groups and a classification of finite subgroups of orthogonal groups. All chapters have a large number of exercises with varying degrees of difficulty, ranging from material suitable for Mathematical Olympiads to research.

  18. Atomic structure of glassy Mg60Cu30Y10 investigated with EXAFS, x-ray and neutron diffraction, and reverse Monte Carlo simulations

    DEFF Research Database (Denmark)

    Jovari, P.; Saksl, K.; Pryds, Nini

    2007-01-01

    Short range order of amorphous Mg60Cu30Y10 was investigated by x-ray and neutron diffraction, Cu and Y K-edge x-ray absorption fine structure measurements, and the reverse Monte Carlo simulation technique. We found that Mg-Mg and Mg-Cu nearest neighbor distances are very similar to values found...... studied by differential scanning calorimetry and in situ x-ray powder diffraction. The alloy shows a glass transition and three crystallization events, the first and dominant one at 456 K corresponding to eutectic crystallization of at least three phases: Mg2Cu and most likely cubic MgY and CuMgY....

  19. Experimental Techniques

    DEFF Research Database (Denmark)

    Wyer, Jean

    2013-01-01

    Gas-phase ion spectroscopy requires specialised apparatus, both when it comes to measuring photon absorption and light emission (fluorescence). The reason is much lower ion densities compared to solution-phase spectroscopy. In this chapter different setups are described, all based on mass spectro...... in data interpretation, and the advantages and disadvantages of the different techniques are clarified. New instrumental developments involving cryo-cooled storage rings, which show great promise for the future, are briefly touched upon.......Gas-phase ion spectroscopy requires specialised apparatus, both when it comes to measuring photon absorption and light emission (fluorescence). The reason is much lower ion densities compared to solution-phase spectroscopy. In this chapter different setups are described, all based on mass...... to circumvent this is discussed based on a chemical approach, namely tagging of ammonium groups by crown ether. Prompt dissociation can sometimes be identified from the total beam depletion differing from that due to statistical dissociation. Special emphasis in this chapter is on the limitations and pitfalls...

  20. XAS study on copper red in ancient glass beads from Thailand.

    Science.gov (United States)

    Klysubun, Wantana; Thongkam, Yatima; Pongkrapan, Sorapong; Won-in, Krit; T-Thienprasert, Jiraroj; Dararutana, Pisutti

    2011-03-01

    Glass has been used in ornaments and decorations in Thailand for thousands of years, being discovered in several archeological sites and preserved in museums throughout the country. To date only a few of them have been examined by conventional methods for their compositions and colorations. In this work we report for the first time an advanced structural analysis of Thai ancient glass beads using synchrotron X-ray absorption spectroscopy (XAS) and energy-dispersive X-ray (EDX) spectrometry. Four samples of ancient glass beads were selected from four different archeological sites in three southern provinces (Ranong, Krabi and Pang-nga) of Thailand. Archaeological dating indicated that they were made more than 1,300 years ago. A historically known method for obtaining a red color is to add compounds containing transition elements such as gold, copper, and chromium. For our samples, EDX spectrometry data revealed existing fractions of iron, copper, zinc, and chromium in ascending order. Thus, copper was selectively studied by XAS as being potentially responsible for the red color in the glass beads. K-shell X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) of copper were recorded in fluorescence mode using an advanced 13-element germanium detector. Comparisons with XANES spectra of reference compounds identified two major forms of copper, monovalent copper and a metallic cluster, dispersed in the glass matrix. The cluster dimension was approximated on the basis of structural modeling and a theoretical XANES calculation. As a complement, EXAFS spectra were analyzed to determine the first-shell coordination around copper. XAS was proven to be an outstanding, advanced technique that can be applied to study nondestructively archaeological objects to understand their characteristics and how they were produced in ancient times.

  1. Fabrication of Nd∶Lu2O3 Nano-ceramic and the EXAFS Research%Nd∶Lu2O3纳米陶瓷的制备和EXAFS研究

    Institute of Scientific and Technical Information of China (English)

    周鼎; 徐家跃; 金敏; 江国健; 申慧

    2013-01-01

    Nd doped Lu2O3 nanocrystalline powders were synthesized by a wet chemical processing derived by mixed solution of NH4OH + NH4HCO3. The powders are uniform and the average size is about 40 nm. Green compacts were sintered in flowing H2 atmosphere by two-step sintering at T1 = 1720 ℃, T2 = 1620 ℃ for 12 h. Translucent nano-ceramic was obtained, which present a stronger luminescent intensity in fluorescence spectrum, comparing to the micron ceramic. EXAFS research showed that with decreasing grain size, higher degree of disorder factor of the local environment of Nd atoms doped in the nano-ceramic was discovered. The nano-ceramic X-ray absorption coefficient of the same photon energy is less than a micron ceramic.%通过氨水加碳酸氢铵复合沉淀剂合成了Nd3+掺杂的氧化镥纳米晶粉体.经马弗炉900℃煅烧2h,获得了分散性好、晶粒尺寸约为40nm的高质量的Nd∶Lu2O3纳米晶粉体.采用无压流动H2气氛对所得素坯进行两步烧结致密化(T1=1720℃,T2=1620℃)获得了半透明的纳米Lu2O3陶瓷.荧光光谱表明在808nm波长激发下,纳米陶瓷发光强度明显超过微米级陶瓷.同步辐射研究表明,随着晶粒尺寸减小,纳米陶瓷中Nd原子的局域环境混乱度增大,无序度相对变大.在Nd掺杂浓度相同情况下,对同一光子能量的X射线吸收系数纳米陶瓷小于微米级陶瓷.

  2. Reactivity of Fe-binuclear complexes in over-exchanged Fe/ZSM5, studied by in situ XAFS spectroscopy Part 1: Heat treatment in He and O2

    NARCIS (Netherlands)

    Koningsberger, D.C.; Battiston, A.A.; Bitter, J.H.; Heijboer, W.M.; Groot, F.M.F. de

    2003-01-01

    The structure of the iron species in mildly calcined over-exchanged Fe/ZSM5, prepared by CVD of FeCl3, was studied during heat treatments in He or O2/He (50:50) by coupling in situ Fe K edge HR-XANES and EXAFS. The majority of iron appears to be present as Fe-binuclear complexes. EXAFS shows that

  3. Reactivity of Binuclear Fe-Complexes in Over-Exhanged Fe/ZSM5 Studied by In Situ XAFS Spectroscopy : Part 1: Heat Treatment in He and O2

    NARCIS (Netherlands)

    Koningsberger, D.C.; Battiston, A.A.; Bitter, J.H.; Heijboer, W.M.; Groot, F.M.F. de

    2003-01-01

    The structure of the iron species in mildly calcined over-exchanged Fe/ZSM5, prepared by CVD of FeCl3, was studied during heat treatments in He or O2/He (50:50) by coupling in situ Fe K edge HR-XANES and EXAFS. The majority of iron appears to be present as Fe-binuclear complexes. EXAFS shows that

  4. Optical and local structural study of Gd doped ZrO{sub 2} thin films deposited by RF magnetron sputtering technique

    Energy Technology Data Exchange (ETDEWEB)

    Haque, S. Maidul, E-mail: skmaidulhaque@gmail.com; Shinde, D. D.; Misal, J. S. [Atomic & Molecular Physics Division, Bhabha Atomic Research Centre, VIZAG Centre, Visakhapatnam-530012 (India); Jha, S. N.; Bhattacharyya, D.; Sahoo, N. K. [Atomic & Molecular Physics Division, Bhabha Atomic Research Centre. Mumbai – 400094 (India)

    2015-06-24

    ZrO{sub 2} samples with 0, 7, 9, 11, 13 % Gd doping have been prepared by RF magnetron sputtering deposition technique for solid oxide fuel cell application. The optical properties of the samples have been studied by transmission spectrophotometry and spectroscopic ellipsometry while the local structure surrounding Zr sites has been characterized by extended x-ray absorption fine structure (EXAFS) measurement at Zr K edge with synchrotron radiation. It has been observed that beyond 11% Gd doping, band gap decreases and refractive index increases significantly and also oxygen and Zr coordinations surrounding Zr sites increase which indicates the formation of Gd clustering in ZrO{sub 2} matrix beyond this doping concentration.

  5. EXAFS analysis of cations distribution in structure of Co{sub 1−x}Ni{sub x}Fe{sub 2}O{sub 4} nanoparticles obtained by hydrothermal method in aloe vera extract solution

    Energy Technology Data Exchange (ETDEWEB)

    Wongpratat, Unchista [Materials Science and Nanotechnology Program, Faculty of Science, Khon Kaen University, Khon Kaen 40002 (Thailand); Maensiri, Santi [School of Physics, Institute of Science, Suranaree University, Nakhonratchasima 30000 (Thailand); Swatsitang, Ekaphan, E-mail: ekaphan@kku.ac.th [Materials Science and Nanotechnology Program, Faculty of Science, Khon Kaen University, Khon Kaen 40002 (Thailand); Integrated Nanotechnology Research Center, Department of Physics, Faculty of Science, Khon Kaen University, Khon Kaen 40002 Thailand (Thailand)

    2016-09-01

    Graphical abstract: It is obvious from the M–H curves at room temperature of Co{sub 1−x}Ni{sub x}Fe{sub 2}O{sub 4} (x = 0, 0.25, 0.50, 0.75 and 1.0) nanoparticles that partially substitution of the lower Bohr magneton (2 μ{sub B}) and smaller atomic radii (0.55 Å at A site, 0.69 Å at B site) of Ni{sup 2+} ions on the higher Bohr magneton (3 μ{sub B}) and larger atomic radii (0.58 Å at A site, 0.74 Å at B site) of Co{sup 2+} ions can increase the saturation magnetization (M{sub s}) of sample with x = 0.75 to approximately 1.4 times of sample with x = 0, due to the increase of the aspect ratio (surface to volume) of nanoparticles, as a result of particle size decreasing from 37.03 to 12.63 nm. In addition to this, the ferrimagnetic behavior of CoFe{sub 2}O{sub 4} has been changed to superparamagnetic behavior with the dramatic decrease of the coercivity from 1365.60 to 63.15 Oe. - Highlights: • Magnetic behavior of Co{sub 1−x}Ni{sub x}Fe{sub 2}O{sub 4} NPs depends on Ni content and size of NPs. • Distribution of Co{sup 2+} and Ni{sup 2+} ions in the structure results in the increase of M{sub s}. • Superparamagnetic behavior is observed with increasing of the aspect ratio. • M{sub s} is increased by a factor 1.4 to a value of 57.57 emu/g in Co{sub 0.25}Ni{sub 0.75}Fe{sub 2}O{sub 4}. • H{sub c} is decreased by a factor 20 to a value of 63.15 Oe in Co{sub 0.25}Ni{sub 0.75}Fe{sub 2}O{sub 4}. - Abstract: Effect of cations distribution upon EXAFS analysis on magnetic properties of Co{sub 1−x}Ni{sub x}Fe{sub 2}O{sub 4} (x = 0, 0.25, 0.50, 0.75 and 1.0) nanoparticles prepared by the hydrothermal method in aloe vera extract solution were studied. XRD analysis confirmed a pure phase of cubic spinel ferrite of all samples. Changes in lattice parameter and particle size depended on the Ni content with partial substitution and site distributions of Co{sup 2+}, Ni{sup 2+} ions of different ionic radii at both tetrahedral and octahedral sites in the

  6. X-ray Absorption Spectroscopy Characterization of Electrochemical Processes in Renewable Energy Storage and Conversion Devices

    Energy Technology Data Exchange (ETDEWEB)

    Farmand, Maryam [George Washington Univ., Washington, DC (United States)

    2013-05-19

    The development of better energy conversion and storage devices, such as fuel cells and batteries, is crucial for reduction of our global carbon footprint and improving the quality of the air we breathe. However, both of these technologies face important challenges. The development of lower cost and better electrode materials, which are more durable and allow more control over the electrochemical reactions occurring at the electrode/electrolyte interface, is perhaps most important for meeting these challenges. Hence, full characterization of the electrochemical processes that occur at the electrodes is vital for intelligent design of more energy efficient electrodes. X-ray absorption spectroscopy (XAS) is a short-range order, element specific technique that can be utilized to probe the processes occurring at operating electrode surfaces, as well for studying the amorphous materials and nano-particles making up the electrodes. It has been increasingly used in recent years to study fuel cell catalysts through application of the and #916; and mgr; XANES technique, in combination with the more traditional X-ray Absorption Near Edge Structure (XANES) and Extended X-ray Absorption Fine Structure (EXAFS) techniques. The and #916; and mgr; XANES data analysis technique, previously developed and applied to heterogeneous catalysts and fuel cell electrocatalysts by the GWU group, was extended in this work to provide for the first time space resolved adsorbate coverages on both electrodes of a direct methanol fuel cell. Even more importantly, the and #916; and mgr; technique was applied for the first time to battery relevant materials, where bulk properties such as the oxidation state and local geometry of a cathode are followed.

  7. X-ray absorption studies of battery materials

    Energy Technology Data Exchange (ETDEWEB)

    McBreen, J.

    1996-10-01

    X-ray absorption spectroscopy (XAS) is ideal for {ital in}{ital situ} studies of battery materials because both the probe and signal are penetrating x rays. The advantage of XAS being element specific permits investigation of the environment of a constituent element in a composite material. This makes it very powerful for studying electrode additives and corrosion of individual components of complex metal hydride alloys. The near edge part of the spectrum (XANES) provides information on oxidation state and site symmetry of the excited atom. This is particularly useful in study of corrosion and oxidation changes in cathode materials during charge/discharge cycle. Extended fine structure (EXAFS) gives structural information. Thus the technique provides both chemical and structural information. Since XAS probes only short range order, it can be applied to study of amorphous electrode materials and electrolytes. This paper discusses advantages and limitations of the method, as well as some experimental aspects.

  8. Cation distribution in Ni{sub 1−x}Zn{sub x}Fe{sub 2}O{sub 4} using X-ray absorption spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Yadav, A. K., E-mail: akyadav@barc.gov.in; Jha, S. N.; Bhattacharyya, D.; Sahoo, N. K. [Atomic and Molecular Physics Division, Bhabha Atomic Research Centre, Mumbai - 400094 (India); Jadhav, J.; Biswas, S. [Department of Physics, The LNM Institute of Information Technology, Jaipur-302031 (India)

    2014-04-24

    Spinel ferrite samples of Ni{sub 1−x}Zn{sub x}Fe{sub 2}O{sub 4} (for x=0.2, 0.4, 0.5, 0.6 and 0.8) nanoparticles prepared by a novel chemical synthesis method have been characterized by X-ray Absorption Spectroscopy (XAS) technique to investigate the distribution of cations in the unit cell. XANES region clearly shows that as Ni concentration increases, the pre-edge feature, which is a characteristic of tetrahedral coordination of Fe, is enhanced. A quantitative determination of the relative occupancy of iron cation in the octahedral and tetrahedral sites of the spinel structure was obtained from EXAFS data analysis. It has been found that as atomic fraction of Ni is increased from 0.2 to 0.8, Fe occupancy at tetrahedral to octahedral sites is increased from 13:87 and to 39:61.

  9. Operando characterization of batteries using x-ray absorption spectroscopy: advances at the beamline XAFS at synchrotron Elettra

    Science.gov (United States)

    Aquilanti, Giuliana; Giorgetti, Marco; Dominko, Robert; Stievano, Lorenzo; Arčon, Iztok; Novello, Nicola; Olivi, Luca

    2017-02-01

    X-ray absorption spectroscopy is a synchrotron radiation based technique that is able to provide information on both local structure and electronic properties in a chemically selective manner. It can be used to characterize the dynamic processes that govern the electrochemical energy storage in batteries, and to shed light on the redox chemistry and changes in structure during galvanostatic cycling to design cathode materials with improved properties. Operando XAS studies have been performed at beamline XAFS at Elettra on different systems. For Li-ion batteries, a multiedge approach revealed the role of the different cathode components during the charge and discharge of the battery. In addition, Li-S batteries for automotive applications were studied. Operando sulfur K-edge XANES and EXAFS analysis was used to characterize the redox chemistry of sulfur, and to relate the electrochemical mechanism to its local structure.

  10. Crystal and electronic structure study of Mn doped wurtzite ZnO nanoparticles

    Institute of Scientific and Technical Information of China (English)

    O.M. Ozkendir; S. Yildirimcan; A. Yuzer; K. Ocakoglu

    2016-01-01

    The change in the crystal and electronic structure properties of wurtzite ZnO nanoparticles was studied according to Mn doping in the powder samples. The investigations were conducted by X-ray Absorption Fine Structure Spectroscopy (XAFS) technique for the samples prepared with different heating and doping processes. Electronic analysis was carried out by the collected data from the X-ray Absorption Near-Edge Structure Spectroscopy (XANES) measurements. Additional crystal structure properties were studied by Extended-XAFS (EXAFS) analysis. Longer heating periods for the undoped wurtzite ZnO samples were determined to own stable crystal geometries. However, for some doped samples, the distortions in the crystal were observed as a result of the low doping amounts of Mn which was treated as an impurity. Besides, the changes in oxygen locations were determined to create defects and distor-tions in the samples.

  11. Crystal and electronic structure study of Mn doped wurtzite ZnO nanoparticles

    Directory of Open Access Journals (Sweden)

    O.M. Ozkendir

    2016-08-01

    Full Text Available The change in the crystal and electronic structure properties of wurtzite ZnO nanoparticles was studied according to Mn doping in the powder samples. The investigations were conducted by X-ray Absorption Fine Structure Spectroscopy (XAFS technique for the samples prepared with different heating and doping processes. Electronic analysis was carried out by the collected data from the X-ray Absorption Near-Edge Structure Spectroscopy (XANES measurements. Additional crystal structure properties were studied by Extended-XAFS (EXAFS analysis. Longer heating periods for the undoped wurtzite ZnO samples were determined to own stable crystal geometries. However, for some doped samples, the distortions in the crystal were observed as a result of the low doping amounts of Mn which was treated as an impurity. Besides, the changes in oxygen locations were determined to create defects and distortions in the samples.

  12. Microprobe techniques for speciation analysis and geochemical characterization of mine environments: the mercury district of Almadén in Spain.

    Science.gov (United States)

    Bernaus, Anna; Gaona, Xavier; Esbrí, José Maria; Higueras, Pablo; Falkenberg, Gerald; Valiente, Manuel

    2006-07-01

    Metallurgic calcines with very high mercury and methylmercury content from the Almadén mining district were analyzed by synchrotron-based microprobe techniques. Information about mercury speciation was obtained by micro-EXAFS (microscopic extended X-ray absorption fine structure) spectroscopy, whereas elemental associations were evaluated by micro-XRF (microscopic X-ray fluorescence analysis) mapping. Complementary characterization methodologies, including X-ray diffraction (XRD), inductively coupled plasma-optical spectroscopy (ICP-OES), as well as a sequential extraction scheme (SES), were used to predict the potential availability of mercury. Analysis of total metal content revealed extremely high concentrations of mercury and iron (between 7 and 35 and 65-70 g kg(-1), respectively) and high zinc concentrations (2.2-2.5 g kg(-1)), whereas other metals such as copper, nickel, and lead were found at low concentration levels (30-300 mg kg(-1)). Micro-EXAFS results indicate that cinnabar (HgS(red)) is one of the main species within the studied mercury-rich particles (5-89% of total mercury content), together with more soluble mercury compounds such as Hg3(SO4)02 (schuetteite) and HgO (5-55% of total mercury content). Additionally, element-specific micro-XRF maps of selected mercury-rich particles in the studied samples revealed an evident correlation among Hg-Pb-Ni (and S), indicating a possible geochemical linkage of these elements. Correlations were also found among Fe-Mn and Hg, which have been attributed to sorption of mercury onto oxyhydroxides of Fe and Mn. This finding was supported by results from a sequential extraction scheme, where a significant

  13. Stress Management Techniques

    Directory of Open Access Journals (Sweden)

    Czesław Czabała

    2016-05-01

    Of all the stress management techniques people used mostly those included in the categories of “problem solving”, “vicarious gratification” and “distancing”. This points to the use of techniques that require no effort but are not fully effective. It could be so that they have not skills to use other techniques, or are aware that such techniques exist.

  14. Radiologic imaging technique

    Energy Technology Data Exchange (ETDEWEB)

    Bushong, S.C. (Dept. of Radiology, Baylor College of Medicine, Houston, TX (US)); Eastman, T.R. (Agfagavert Inc., Irving, TX (US))

    1990-01-01

    The authors focus on the subject of clinical radiographic technique. Emphasizing correct radiographic technique, it's heavily illustrated with radiographs that demonstrate proper exposure and show what happens when exposure variables are changed. A key feature is a discussion and evaluation of radiographic technique charts. Basic technique charts are provided for every body part examined.

  15. Structural characterization of Bi{sub 2}Te{sub 3} and Sb{sub 2}Te{sub 3} as a function of temperature using neutron powder diffraction and extended X-ray absorption fine structure techniques

    Energy Technology Data Exchange (ETDEWEB)

    Mansour, A. N. [Naval Surface Warfare Center, Carderock Division, West Bethesda, Maryland 20817 (United States); Wong-Ng, W. [Materials Measurement Science Division National Institute of Standards and Technology, Gaithersburg, Maryland 20899 (United States); Huang, Q. [Center for Neutron Research National Institute of Standards and Technology, Gaithersburg, Maryland 20899 (United States); Tang, W. [Zhejiang Sci-Tech University, Hangzhou, Zhejiang 310018 (China); Thompson, A.; Sharp, J. [Marlow Industries, Inc Dallas, Texas 75238 (United States)

    2014-08-28

    The structure of Bi{sub 2}Te{sub 3} (Seebeck coefficient Standard Reference Material (SRM™ 3451)) and the related phase Sb{sub 2}Te{sub 3} have been characterized as a function of temperature using the neutron powder diffraction (NPD) and the extended X-ray absorption fine structure (EXAFS) techniques. The neutron structural studies were carried out from 20 K to 300 K for Bi{sub 2}Te{sub 3} and from 10 K to 298 K for Sb{sub 2}Te{sub 3}. The EXAFS technique for studying the local structure of the two compounds was conducted from 19 K to 298 K. Bi{sub 2}Te{sub 3} and Sb{sub 2}Te{sub 3} are isostructural, with a space group of R3{sup ¯}m. The structure consists of repeated quintuple layers of atoms, Te2-M-Te1-M-Te2 (where M = Bi or Sb) stacking along the c-axis of the unit cell. EXAFS was used to examine the bond distances and static and thermal disorders for the first three shells of Bi{sub 2}Te{sub 3} and Sb{sub 2}Te{sub 3} as a function of temperature. The temperature dependencies of thermal disorders were analyzed using the Debye and Einstein models for lattice vibrations. The Debye and Einstein temperatures for the first two shells of Bi{sub 2}Te{sub 3} are similar to those of Sb{sub 2}Te{sub 3} within the uncertainty in the data. However, the Debye and Einstein temperatures for the third shell of Bi-Bi are significantly lower than those of the third shell of Sb-Sb. The Einstein temperature for the third shell is consistent with a soft phonon mode in both Bi{sub 2}Te{sub 3} and Sb{sub 2}Te{sub 3}. The lower Einstein temperature of Bi-Bi relative to Sb-Sb is consistent with the lower value of thermal conductivity of Bi{sub 2}Te{sub 3} relative to Sb{sub 2}Te{sub 3}.

  16. Synchrotron x-ray sources and new opportunities in the soil and environmental sciences

    Energy Technology Data Exchange (ETDEWEB)

    Schulze, D. (Purdue Univ., Lafayette, IN (USA)); Anderson, S. (Michigan State Univ., East Lansing, MI (USA)); Mattigod, S. (Pacific Northwest Lab., Richland, WA (USA))

    1990-07-01

    This report contains the following papers: characteristics of the advanced photon source and comparison with existing synchrotron facilities; x-ray absorption spectroscopy: EXAFS and XANES -- A versatile tool to study the atomic and electronic structure of materials; applications of x-ray spectroscopy and anomalous scattering experiments in the soil and environmental sciences; X-ray fluorescence microprobe and microtomography.

  17. Tools & techniques--statistics: propensity score techniques.

    Science.gov (United States)

    da Costa, Bruno R; Gahl, Brigitta; Jüni, Peter

    2014-10-01

    Propensity score (PS) techniques are useful if the number of potential confounding pretreatment variables is large and the number of analysed outcome events is rather small so that conventional multivariable adjustment is hardly feasible. Only pretreatment characteristics should be chosen to derive PS, and only when they are probably associated with outcome. A careful visual inspection of PS will help to identify areas of no or minimal overlap, which suggests residual confounding, and trimming of the data according to the distribution of PS will help to minimise residual confounding. Standardised differences in pretreatment characteristics provide a useful check of the success of the PS technique employed. As with conventional multivariable adjustment, PS techniques cannot account for confounding variables that are not or are only imperfectly measured, and no PS technique is a substitute for an adequately designed randomised trial.

  18. Surface science techniques

    CERN Document Server

    Bracco, Gianangelo

    2013-01-01

    The book describes the experimental techniques employed to study surfaces and interfaces. The emphasis is on the experimental method. Therefore all chapters start with an introduction of the scientific problem, the theory necessary to understand how the technique works and how to understand the results. Descriptions of real experimental setups, experimental results at different systems are given to show both the strength and the limits of the technique. In a final part the new developments and possible extensions of the techniques are presented. The included techniques provide microscopic as well as macroscopic information. They cover most of the techniques used in surface science.

  19. Introduction to perturbation techniques

    CERN Document Server

    Nayfeh, Ali H

    2011-01-01

    Similarities, differences, advantages and limitations of perturbation techniques are pointed out concisely. The techniques are described by means of examples that consist mainly of algebraic and ordinary differential equations. Each chapter contains a number of exercises.

  20. Relaxation Techniques for Health

    Science.gov (United States)

    ... R S T U V W X Y Z Relaxation Techniques for Health Share: On This Page What’s the ... Bottom Line? How much do we know about relaxation techniques? A substantial amount of research has been done ...

  1. Semiconductor Research Experimental Techniques

    CERN Document Server

    Balkan, Naci

    2012-01-01

    The book describes the fundamentals, latest developments and use of key experimental techniques for semiconductor research. It explains the application potential of various analytical methods and discusses the opportunities to apply particular analytical techniques to study novel semiconductor compounds, such as dilute nitride alloys. The emphasis is on the technique rather than on the particular system studied.

  2. Characterization of microstructure and mechanical behavior of sputter deposited Ti-containing amorphous carbon coatings.

    Energy Technology Data Exchange (ETDEWEB)

    Feng, B.; Cao, D. M.; Meng, W. J.; Xu, J.; Tittsworth, R. C.; Rehn, L. E.; Baldo, P. M.; Doll, G. L.; Materials Science Division; Louisiana State Univ.; The Timken Company

    2001-12-03

    We report on the characterization of microstructure and mechanical properties of sputter deposited Ti-containing amorphous carbon (Ti-aC) coatings as a function of Ti composition. Ti-aC coatings have been deposited by unbalanced magnetron sputter deposition, in an industrial-scale four-target coating deposition system. The composition and microstructure of the Ti-aC coatings have been characterized in detail by combining the techniques of Rutherford backscattering spectrometry (RBS) and hydrogen elastic recoil detection (ERD), transmission electron microscopy (TEM), X-ray absorption near edge structure (XANES) spectroscopy and extended X-ray absorption fine structure (EXAFS) spectroscopy. At Ti compositions <4at.%, Ti atoms dissolve in an amorphous carbon (a-C) matrix. The dissolution limit of Ti atoms in an a-C matrix is determined to be between 4 and 8 at.%. At Ti compositions >8 at.%, XANES and EXAFS data indicate that the average Ti atomic bonding environment in Ti-aC coatings resembles that in cubic B1-TiC, consistent with TEM observation of precipitation of TiC nanocrystallites in the a-C matrix. Beyond the Ti dissolution limit, the Ti-aC coatings are nanocomposites with nanocrystalline TiC clusters embedded in an a-C matrix. A large scale, quasi one-dimensional composition modulation in the Ti-aC coatings was observed due to the particular coating deposition geometry. Elastic stiffness and hardness of the Ti-aC coatings were measured by instrumented nanoindentation and found to vary systematically as a function of Ti composition. Unlubricated friction coefficient of Ti-aC coatings against WC-Co balls was found to increase as the Ti composition increases. As Ti composition increases, the overall mechanical behavior of the Ti-aC coatings becomes more TiC-like.

  3. Electronic structure determination using an assembly of conventional and synchrotron techniques: The case of a xanthate complex

    Science.gov (United States)

    Juncal, Luciana C.; Avila, José; Asensio, Maria Carmen; Della Védova, Carlos O.; Romano, Rosana M.

    2017-06-01

    The electronic properties of the coordination complex nickel (II) bis-n-propylxanthate, Ni(CH3(CH2)2OC(S)S)2, were studied by a combination of complementary experimental (both laboratory and synchrotron based techniques) and theoretical methods. Energy differences between HOMOs and LUMOs were determined from UV-visible spectroscopy. The assignment of the transitions were performed with the aid of TD-DFT calculations and based in symmetry considerations. The analysis of the Raman excitation profiles of selected vibrational modes of the complex, taken in resonance with a particular electronic transition, was found to reinforce the electronic assignment. Experimental binding energies of inner and core electrons were determined by PES measurements. Ni K-edge, S K-edge, Ni L-edge, O K-edge and C K-edge XANES spectra were interpreted in terms of the promotion of core electrons to unoccupied electronic levels. An experimental quantitative molecular orbital diagram was constructed using the information extracted from the different techniques.

  4. Low current beam techniques

    Energy Technology Data Exchange (ETDEWEB)

    Saint, A.; Laird, J.S.; Bardos, R.A.; Legge, G.J.F. [Melbourne Univ., Parkville, VIC (Australia). School of Physics; Nishijima, T.; Sekiguchi, H. [Electrotechnical Laboratory, Tsukuba (Japan).

    1993-12-31

    Since the development of Scanning Transmission Microscopy (STIM) imaging in 1983 many low current beam techniques have been developed for the scanning (ion) microprobe. These include STIM tomography, Ion Beam Induced Current, Ion Beam Micromachining and Microlithography and Ionoluminense. Most of these techniques utilise beam currents of 10{sup -15} A down to single ions controlled by beam switching techniques This paper will discuss some of the low beam current techniques mentioned above, and indicate, some of their recent applications at MARC. A new STIM technique will be introduced that can be used to obtain Z-contrast with STIM resolution. 4 refs., 3 figs.

  5. Structural Characterization of Biogenic Manganese Oxides Produced in Sea Water

    Science.gov (United States)

    Webb, S. M.; Bargar, J. R.; Tebo, B. M.

    2003-12-01

    Manganese oxides have been coined as the "scavengers of the sea" and play important roles in both marine and freshwater systems. Natural manganese oxide nanoparticles and grain coatings are ubiquitous in the environment and profoundly impact the quality of sediments via their ability to degrade and sequester contaminants. These oxides are believed to form dominantly via oxidation of Mn(II) by marine and freshwater bacteria and have extremely high sorptive capacities for heavy metals. We have used XANES, EXAFS, and synchrotron (SR)-XRD techniques to study biogenic manganese oxides produced by spores of the marine Bacillus sp., strain SG-1 in seawater as a function of reaction time under fully in-situ conditions. The primary biogenic solid-phase Mn oxide product is a hexagonal layered phyollomanganate with an oxidation state similar to that in delta-MnO2. XRD data show the biooxides to have a phyllomanganate 10 basal plane spacing, suggesting the interlayer is hydrated and contains calcium. As the experiment continues, the initial biooxide changes to show triclinic symmetry. Fits to these EXAFS spectra suggest the octahedral layers have low Mn octahedral site vacancies in the lattice and the latyers bend to accommodate Jahn-Teller distortions creating the change in symmetry. The oxides observed in this study as models of Mn(II) bio-oxidation may be representative of the most abundant manganese oxide phase suspended in the oxic and sub-oxic zones of the oceanic water column.

  6. Hard X-ray micro-spectroscopy at Berliner Elektronenspeicherring für Synchrotronstrahlung II

    Science.gov (United States)

    Erko, A.; Zizak, I.

    2009-09-01

    The capabilities of the X-ray beamlines at Berliner Elektronenspeicherring für Synchrotronstrahlung II (BESSY II) for hard X-ray measurements with micro- and nanometer spatial resolution are reviewed. The micro-X-ray fluorescence analysis (micro-XRF), micro-extended X-ray absorption fine structure (micro-EXAFS), micro-X-ray absorption near-edge structure (micro-XANES) as well as X-ray standing wave technique (XSW), X-ray beam induced current (XBIC) in combination with micro-XRF and micro-diffraction as powerful methods for organic and inorganic sample characterization with synchrotron radiation are discussed. Mono and polycapillary optical systems were used for fine X-ray focusing down to 1 µm spot size with monochromatic and white synchrotron radiation. Polycapillary based confocal detection was applied for depth-resolved micro-XRF analysis with a volume resolution down to 3.4 · 10 - 6 mm 3. Standing wave excitation in waveguides was also applied to nano-EXAFS measurements with depth resolution on the order of 1 nm. Several examples of the methods and its applications in material research, biological investigations and metal-semiconductor interfaces analysis are given.

  7. Characterization of yellow and colorless decorative glasses from the Temple of the Emerald Buddha, Bangkok, Thailand

    Science.gov (United States)

    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.

  8. Full quantitative multiple-scattering analysis of X-ray absorption spectra: application to potassium hexacyanoferrat(II) and -(III) complexes.

    Science.gov (United States)

    Hayakawa, Kuniko; Hatada, Keisuke; D'Angelo, Paola; Della Longa, Stefano; Natoli, Calogero R; Benfatto, Maurizio

    2004-12-01

    A recently developed method to the full quantitative analysis of the XAS spectra extending from the absorption edge to the high-energy region is presented. This method is based on the use of two independent approaches to the analysis of the EXAFS and XANES data, the well-known GNXAS and the newly developed MXAN procedures. Herein, we report the application of this technique to two iron complexes of known structure where multiple-scattering effects are prominent, the potassium hexacyanoferrat(II) and -(III) crystals and aqueous solutions. The structural parameters obtained from refinements using the two methods are equal and compare quite well with crystallographic values. Small discrepancies between the experimental and calculated XANES spectra have been observed, and their origin has been investigated in the framework of non-muffin-tin correction. The ligand dependence of the theoretical spectra has been also examined. Analysis of the whole energy range of the XAS spectra has been found to be useful in elucidating both the type of ligands and the geometry of iron sites. These results are of particular use in studying the geometrical environment of metallic sites in proteins and complexes of chemical interest.

  9. Clasroom Observation Techniques

    OpenAIRE

    Akbayrak, Burcu

    1999-01-01

    In this article observation techniques as a data collecting tool used in social and educational research are examined and discussed. First the concepts and purposes of the observation technique are explained and later systematic and non-systematic observation techniques are described. Two research projects conducted in the classroom are then summarized. These are ‘ORACLE’ (Observational Research and Classroom Learning Evaluation Project), and ‘PRINDEP’ (Primary Needs Independent Evaluation Pr...

  10. Microbe-Clay Mineral Reactions and Characterization Techniques

    Science.gov (United States)

    Dong, H.; Zhang, G.; Ji, S.; Jaisi, D.; Kim, J.

    2008-12-01

    Clays and clay minerals are ubiquitous in soils, sediments, and sedimentary rocks. They play an important role in environmental processes such as nutrient cycling, plant growth, contaminant migration, organic matter maturation, and petroleum production. The changes in the oxidation state of the structural iron in clay minerals, in part, control their physical and chemical properties in natural environments, such as clay particle flocculation, dispersion, swelling, hydraulic conductivity, surface area, cation and anion exchange capacity, and reactivity towards organic and inorganic contaminants. The structural ferric iron [Fe(III)] in clay minerals can be reduced either chemically or biologically. Many different chemical reductants have been tried, but the most commonly used agent is dithionite. Biological reductants are bacteria, including dissimilatory iron reducing prokaryotes (DIRP) and sulfate-reducing bacteria (SRB). A wide variety of DIRP have been used to reduce ferric iron in clay minerals, including mesophilic, thermophilic, and hyperthermophilic prokaryotes. Multiple clay minerals have been used for microbial reduction studies, including smectite, nontronite (iron-rich smectite variety), illite, illite/smectite, chlorite, and their various mixtures. All these clay minerals are reducible by microorganisms under various conditions with smectite (nontronite) being the most reducible. The reduction extent and rate of ferric iron in clay minerals are measured by wet chemistry, and the reduced clay mineral products are typically characterized with chemical methods, X-ray diffraction, scanning and transmission electron microscopy, Mössbauer spectroscopy, Fourier Transform Infrared Spectroscopy (FTIR), UV-vis spectroscopy, and synchrotron-based techniques (such as EXAFS). Microbially reduced smectites (nontronites) have been found to be reactive in reducing a variety of organic and inorganic contaminants. Degradable organic contaminants include pesticides

  11. Persian fencing techniques

    Directory of Open Access Journals (Sweden)

    Manouchehr Moshtagh Khorasani

    2012-07-01

    Full Text Available There are numerous manuscripts, poems and stories that describe, specifically and in detail, the different techniques used in Persian swordsmanship. The present article explains the origins and the techniques of Persian swordsmanship. The article also describes the traditional code of conduct for Persian warriors. Additionally, it describes an array of techniques that were deployed in actual combat in Iran’s history. Some of these techniques are represented via the miniatures that are reproduced herein. This is the first article on Persian swordsmanship published in any periodical.

  12. Principles of fluorescence techniques

    CERN Document Server

    2016-01-01

    Fluorescence techniques are being used and applied increasingly in academics and industry. The Principles of Fluorescence Techniques course will outline the basic concepts of fluorescence techniques and the successful utilization of the currently available commercial instrumentation. The course is designed for students who utilize fluorescence techniques and instrumentation and for researchers and industrial scientists who wish to deepen their knowledge of fluorescence applications. Key scientists in the field will deliver theoretical lectures. The lectures will be complemented by the direct utilization of steady-state and lifetime fluorescence instrumentation and confocal microscopy for FLIM and FRET applications provided by leading companies.

  13. UIAGM Ropehandling Techniques.

    Science.gov (United States)

    Cloutier, K. Ross

    The Union Internationale des Associations des Guides de Montagne's (UIAGM) rope handling techniques are intended to form the standard for guiding ropework worldwide. These techniques have become the legal standard for instructional institutions and commercial guiding organizations in UIAGM member countries: Austria, Canada, France, Germany, Great…

  14. Emerging optical nanoscopy techniques

    Directory of Open Access Journals (Sweden)

    Montgomery PC

    2015-09-01

    Full Text Available Paul C Montgomery, Audrey Leong-Hoi Laboratoire des Sciences de l'Ingénieur, de l'Informatique et de l'Imagerie (ICube, Unistra-CNRS, Strasbourg, France Abstract: To face the challenges of modern health care, new imaging techniques with subcellular resolution or detection over wide fields are required. Far field optical nanoscopy presents many new solutions, providing high resolution or detection at high speed. We present a new classification scheme to help appreciate the growing number of optical nanoscopy techniques. We underline an important distinction between superresolution techniques that provide improved resolving power and nanodetection techniques for characterizing unresolved nanostructures. Some of the emerging techniques within these two categories are highlighted with applications in biophysics and medicine. Recent techniques employing wider angle imaging by digital holography and scattering lens microscopy allow superresolution to be achieved for subcellular and even in vivo, imaging without labeling. Nanodetection techniques are divided into four subcategories using contrast, phase, deconvolution, and nanomarkers. Contrast enhancement is illustrated by means of a polarized light-based technique and with strobed phase-contrast microscopy to reveal nanostructures. Very high sensitivity phase measurement using interference microscopy is shown to provide nanometric surface roughness measurement or to reveal internal nanometric structures. Finally, the use of nanomarkers is illustrated with stochastic fluorescence microscopy for mapping intracellular structures. We also present some of the future perspectives of optical nanoscopy. Keywords: microscopy, imaging, superresolution, nanodetection, biophysics, medical imaging

  15. Emerging optical nanoscopy techniques

    Science.gov (United States)

    Montgomery, Paul C; Leong-Hoi, Audrey

    2015-01-01

    To face the challenges of modern health care, new imaging techniques with subcellular resolution or detection over wide fields are required. Far field optical nanoscopy presents many new solutions, providing high resolution or detection at high speed. We present a new classification scheme to help appreciate the growing number of optical nanoscopy techniques. We underline an important distinction between superresolution techniques that provide improved resolving power and nanodetection techniques for characterizing unresolved nanostructures. Some of the emerging techniques within these two categories are highlighted with applications in biophysics and medicine. Recent techniques employing wider angle imaging by digital holography and scattering lens microscopy allow superresolution to be achieved for subcellular and even in vivo, imaging without labeling. Nanodetection techniques are divided into four subcategories using contrast, phase, deconvolution, and nanomarkers. Contrast enhancement is illustrated by means of a polarized light-based technique and with strobed phase-contrast microscopy to reveal nanostructures. Very high sensitivity phase measurement using interference microscopy is shown to provide nanometric surface roughness measurement or to reveal internal nanometric structures. Finally, the use of nanomarkers is illustrated with stochastic fluorescence microscopy for mapping intracellular structures. We also present some of the future perspectives of optical nanoscopy. PMID:26491270

  16. Scientific techniques in Egyptology

    Energy Technology Data Exchange (ETDEWEB)

    Newton, G.W.A.

    1987-04-01

    The paper concerns the contribution made by scientific method to Egyptology, in the areas of dating, provenance and medicine. The dating techniques, the analysis techniques and the use of radiology to determine the lifestyle of ancient Egyptians are all described. (U.K.).

  17. Techniques for Teachers Section

    Science.gov (United States)

    Tait, A., Ed.

    1973-01-01

    Includes a simple technique to demonstrate Millikan's oil drop experiment, an environmental studies experiment to measure dissolved oxygen in water samples, and a technique to demonstrate action-reaction. Science materials described are the Pol-A-Star Tomiscope, Nuffield chemistry film loops, air pucks and pH meters. (JR)

  18. Reliability prediction techniques

    Energy Technology Data Exchange (ETDEWEB)

    Whittaker, B.; Worthington, B.; Lord, J.F.; Pinkard, D.

    1986-01-01

    The paper demonstrates the feasibility of applying reliability assessment techniques to mining equipment. A number of techniques are identified and described and examples of their use in assessing mining equipment are given. These techniques include: reliability prediction; failure analysis; design audit; maintainability; availability and the life cycle costing. Specific conclusions regarding the usefulness of each technique are outlined. The choice of techniques depends upon both the type of equipment being assessed and its stage of development, with numerical prediction best suited for electronic equipment and fault analysis and design audit suited to mechanical equipment. Reliability assessments involve much detailed and time consuming work but it has been demonstrated that the resulting reliability improvements lead to savings in service costs which more than offset the cost of the evaluation.

  19. [New microbiological techniques].

    Science.gov (United States)

    Schubert, S; Wieser, A; Bonkat, G

    2017-06-01

    Microbiological diagnostic procedures have changed rapidly in recent years. This is especially true in the field of molecular diagnostics. Classical culture-based techniques are still the gold standard in many areas; however, they are already complemented by automated and also molecular techniques to guarantee faster and better quality results. The most commonly used techniques include real-time polymerase chain reaction (RT-PCR) based systems and nucleic acid hybridization. These procedures are used most powerfully from direct patient samples or in assays to detect the presence of nonculturable or fastidious organisms. Further techniques such as DNA sequencing are not yet used routinely for urological samples and can be considered experimental. However, in conjunction with dropping prices and further technical developments, these techniques promise to be used much more in the near future. Regarding bacterial identification from culture, mass spectrometry (MALDI-TOF MS) has become the technique of choice in recent years especially in Europe. It has tremendously shortened the time to result. This is now going to be extended to antibiotic susceptibility testing. This is of paramount importance in view of ever rising antimicrobial resistance rates. Techniques described in this review offer a faster and better microbiological diagnosis. Such continuous improvements are critical especially in times of cost pressure and rising antimicrobial resistance rates. It is in our interest to provide the best possible care for patients and in this regard a good and effective communication between the laboratory and the clinician is of vital importance.

  20. Optimisation d'une nanotechnologie liée à la post combustion automobile : étude par EXAFS, RMN & DRX de catalyseurs industriels Zn/Al2O3

    Science.gov (United States)

    Bazin, D.; Revel, R.; Klur, I.; Pourpoint, A.

    2002-07-01

    In this paper, we report a structural characterisation of an industrial catalyst conducted through the combined use of different characterisation techniques i.e. ^{27}Al Nuclear Magnetic Resonance (NMR), X-Ray Diffraction (XRD) and High Resolution Transmission Electronic Microscopy (HRTEM). The usual characterisation techniques help to restrict the problem but do not precisely show the structure of the supported system "Zn"/Al2O3. For example, ^{27}Al NMR shows the occupation of tetrahedral site by zinc through a modification of the occupation of tetrahedral and octahedral site by aluminium atoms. Unfortunately this technique is not able to determine the size of the zinc based metal oxide cluster. A more appropriate technique, such as X-ray absorption spectroscopy is thus necessary. In fact, we show that only the complete set of data leads to major information regarding the cation distribution as well as the electronic state of the metal atoms. Nous présentons une étude de matériaux nanodivisés industriels initiée à l'aide de techniques de caractérisation classiques (Microscopie électronique haute résolution, Résonance Magnétique Nucléaire, Diffraction des rayons X) et affinée par une technique spécifique au rayonnement synchrotron, la spectroscopie d'absorption X. Le catalyseur industriel est obtenu par dispersion à l'échelle atomique d'atomes de zinc à la surface d'une yc alumine de grande surface spécifique (> 200m^2/g). Le fait qu'une similarité structurale existe entre le support et le composé défini obtenu par insertion du cation dans la matrice rend quasi-inopérante la DRX classique. La RMN de l'aluminium par contre constitue une technique de choix puisque l'occupation par le zinc de sites tétraédriques se traduit par l'occupation plus conséquente de sites octaédriques par l'aluminium. Néanmoins, la taille des cristallites de "ZnAl2O4", les possibilités d'inversion (limitées ici car le zinc occupe préférentiellement les sites t

  1. Complexing mechanism of the lanthanide cations Eu3+, Gd3+, and Tb3+ with 1,4,7,10-tetrakis(carboxymethyl)-1,4,7,10-tetraazacyclododecane (dota)-characterization of three successive complexing phases: study of the thermodynamic and structural properties of the complexes by potentiometry, luminescence spectroscopy, and EXAFS.

    Science.gov (United States)

    Moreau, Juliette; Guillon, Emmanuel; Pierrard, Jean-Claude; Rimbault, Jean; Port, Marc; Aplincourt, Michel

    2004-10-11

    Complexation of the lanthanides Eu3+, Gd3+, and Tb3+ with 1,4,7,10-tetrakis(carboxymethyl)-1,4,7,10-tetraazacyclododecane (dota) has been studied in solution by using potentiometry, luminescence spectrometry, and EXAFS. Three series of successive complexes were characterized by at least two of these methods: the immediate [LnHn(dota)](n-1)+** and intermediate [LnHn(dota)](n-1)+* complexes with 0 potentiometry. From the results, a complexation mechanism involving three steps has been proposed. In the [LnHn(dota)](n-1)+** complexes that are instantaneously formed, the lanthanide is bound to four oxygen atoms of the carboxylate groups and to five water molecules. These species evolve rapidly: the lanthanide moves into the macrocycle cavity, two new bonds are formed with two nitrogen atoms diametrically opposed in the tetraaza cycle and only three water molecules remain bound to the lanthanide in the [LnHn(dota)](n-1)+* (0

  2. GROUP PROFILE Computer Technique

    Directory of Open Access Journals (Sweden)

    Andrey V. Sidorenkov

    2015-01-01

    Full Text Available This article contains a description of the structure, the software and functional capabilities, and the scope and purposes of application of the Group Profile (GP computer technique. This technique rests on a conceptual basis (the microgroup theory, includes 16 new and modified questionnaires, and a unique algorithm, tied to the questionnaires, for identification of informal groups. The GP yields a wide range of data about the group as a whole (47 indices, each informal group (43 indices, and each group member (16 indices. The GP technique can be used to study different types of groups: production (work groups, design teams, military units, etc., academic (school classes, student groups, and sports.

  3. Spectrometric techniques 2

    CERN Document Server

    Vanasse, George A

    2013-01-01

    Spectrometric Techniques, Volume II provides information pertinent to vacuum ultraviolet techniques to complete the demonstration of the diversity of methods available to the spectroscopist interested in the ultraviolet visible and infrared spectral regions. This book discusses the specific aspects of the technique of Fourier transform spectroscopy.Organized into five chapters, this volume begins with an overview of the large number of systematic effects in the recording of an interferogram. This text then examines the design approach for a Fourier transform spectrometer with focus on optics.

  4. Computer techniques for electromagnetics

    CERN Document Server

    Mittra, R

    1973-01-01

    Computer Techniques for Electromagnetics discusses the ways in which computer techniques solve practical problems in electromagnetics. It discusses the impact of the emergence of high-speed computers in the study of electromagnetics. This text provides a brief background on the approaches used by mathematical analysts in solving integral equations. It also demonstrates how to use computer techniques in computing current distribution, radar scattering, and waveguide discontinuities, and inverse scattering. This book will be useful for students looking for a comprehensive text on computer techni

  5. Separation techniques: Chromatography

    Science.gov (United States)

    Coskun, Ozlem

    2016-01-01

    Chromatography is an important biophysical technique that enables the separation, identification, and purification of the components of a mixture for qualitative and quantitative analysis. Proteins can be purified based on characteristics such as size and shape, total charge, hydrophobic groups present on the surface, and binding capacity with the stationary phase. Four separation techniques based on molecular characteristics and interaction type use mechanisms of ion exchange, surface adsorption, partition, and size exclusion. Other chromatography techniques are based on the stationary bed, including column, thin layer, and paper chromatography. Column chromatography is one of the most common methods of protein purification. PMID:28058406

  6. Internal septorhinoplasty technique.

    Science.gov (United States)

    Waite, Peter D

    2012-02-01

    The internal septorhinoplasty was the standard operating procedure until the popularity of the external or open rhinoplasty technique. The internal technique of the rhinoplasty should be in the armamentarium of every cosmetic surgeon. There will always be indications for both internal and external rhinoplasty. The advantages of the internal technique are several. Rhinoplasty should be treatment planned based on the individual diagnosis. With experience, most surgeons find the internal rhinoplasty to be successful and extremely rewarding. A simple internal rhinoplasty will produce a good result and satisfied patients.

  7. Spectrometric techniques 4

    CERN Document Server

    Vanasse, George A

    2013-01-01

    Spectrometric Techniques, Volume IV discusses three widely diversified areas of spectrometric techniques. The book focuses on three spectrometric methods. Chapter 1 discusses the phenomenology and applications of Coherent Anti-Stokes Raman Spectroscopy (CARS), the most commonly used optical technique that exploit the Raman effect. The second chapter is concerned with diffraction gratings and mountings for the Vacuum Ultraviolet Spectral Region. Chapter 3 accounts the uses of mass spectrometry, detectors, types of spectrometers, and ion sources. Physicists and chemists will find the book a go

  8. Approximation techniques for engineers

    CERN Document Server

    Komzsik, Louis

    2006-01-01

    Presenting numerous examples, algorithms, and industrial applications, Approximation Techniques for Engineers is your complete guide to the major techniques used in modern engineering practice. Whether you need approximations for discrete data of continuous functions, or you''re looking for approximate solutions to engineering problems, everything you need is nestled between the covers of this book. Now you can benefit from Louis Komzsik''s years of industrial experience to gain a working knowledge of a vast array of approximation techniques through this complete and self-contained resource.

  9. Spectrometric techniques 3

    CERN Document Server

    Vanasse, George A

    2013-01-01

    Spectrometric Techniques, Volume III presents the applications of spectrometric techniques to atmospheric and space studies. This book reviews the spectral data processing and analysis techniques that are of broad applicability.Organized into five chapters, this volume begins with an overview of the instrumentation used for obtaining field data. This text then reviews the contribution that space-borne spectroscopy in the thermal IR has made to the understanding of the planets. Other chapters consider the instruments that have recorded the planetary emission spectra. This book discusses as well

  10. Plant tissue culture techniques

    Directory of Open Access Journals (Sweden)

    Rolf Dieter Illg

    1991-01-01

    Full Text Available Plant cell and tissue culture in a simple fashion refers to techniques which utilize either single plant cells, groups of unorganized cells (callus or organized tissues or organs put in culture, under controlled sterile conditions.

  11. Symbolic rewriting techniques

    CERN Document Server

    Weispfenning, Volker; Grabmeier, Johannes

    1998-01-01

    Symbolic rewriting techniques are methods for deriving consequences from systems of equations, and are of great use when investigating the structure of the solutions. Such techniques appear in many important areas of research within computer algebra: • the Knuth-Bendix completion for groups, monoids and general term-rewriting systems, • the Buchberger algorithm for Gröbner bases, • the Ritt-Wu characteristic set method for ordinary differential equations, and • the Riquier-Janet method for partial differential equations. This volume contains invited and contributed papers to the Symbolic Rewriting Techniques workshop, which was held at the Centro Stefano Franscini in Ascona, Switzerland, from April 30 to May 4, 1995. That workshop brought together 40 researchers from various areas of rewriting techniques, the main goal being the investigation of common threads and methods. Following the workshops, each contribution was formally refereed and 14 papers were selected for publication.

  12. Plant tissue culture techniques

    OpenAIRE

    Rolf Dieter Illg

    1991-01-01

    Plant cell and tissue culture in a simple fashion refers to techniques which utilize either single plant cells, groups of unorganized cells (callus) or organized tissues or organs put in culture, under controlled sterile conditions.

  13. Reversible Data Hiding Techniques

    Directory of Open Access Journals (Sweden)

    Dhananjay Yadav

    2012-03-01

    Full Text Available Reversible data hiding is a technique that is used to hide data inside an image. The data is hidden in such a way that the exact or original data is not visible. The hidden data can be retrieved as and when required. There are several methods that are used in reversible data hiding techniques like Watermarking, Lossless embedding and encryption. In this paper we present a review of reversible watermarking techniques and show different methods that are used to get reversible data hiding technique with higher embedding capacity and invisible objects. Watermark need not be hidden. Watermarking can be applied to 1. Images, 2. Text, 3. Audio/video, 4. Software.

  14. RFCM Techniques Chamber Facility

    Data.gov (United States)

    Federal Laboratory Consortium — FUNCTION: Provides the capability to develop radio-frequency countermeasure (RFCM) techniques in a controlled environment from 2.0 to 40.0 GHz. The configuration of...

  15. INTERNAL ENVIRONMENT ANALYSIS TECHNIQUES

    National Research Council Canada - National Science Library

    Caescu Stefan Claudiu; Popescu Andrei; Ploesteanu Mara Gabriela

    2011-01-01

    .... Objectives of the Research The main purpose of the study of the analysis techniques of the internal environment is to provide insight on those aspects that are of strategic importance to the organization...

  16. Microwave Breast Imaging Techniques

    DEFF Research Database (Denmark)

    Zhurbenko, Vitaliy; Rubæk, Tonny

    2010-01-01

    This paper outlines the applicability of microwave radiation for breast cancer detection. Microwave imaging systems are categorized based on their hardware architecture. The advantages and disadvantages of various imaging techniques are discussed. The fundamental tradeoffs are indicated between v...

  17. Renal Tumor Biopsy Technique

    Institute of Scientific and Technical Information of China (English)

    Lei Zhang; Xue-Song Li; Li-Qun Zhou

    2016-01-01

    Objective:To review hot issues and future direction of renal tumor biopsy (RTB) technique.Data Sources:The literature concerning or including RTB technique in English was collected from PubMed published from 1990 to 2015.Study Selection:We included all the relevant articles on RTB technique in English,with no limitation of study design.Results:Computed tomography and ultrasound were usually used for guiding RTB with respective advantages.Core biopsy is more preferred over fine needle aspiration because of superior accuracy.A minimum of two good-quality cores for a single renal tumor is generally accepted.The use of coaxial guide is recommended.For biopsy location,sampling different regions including central and peripheral biopsies are recommended.Conclusion:In spite of some limitations,RTB technique is relatively mature to help optimize the treatment of renal tumors.

  18. Microwave Breast Imaging Techniques

    DEFF Research Database (Denmark)

    Zhurbenko, Vitaliy; Rubæk, Tonny

    2010-01-01

    This paper outlines the applicability of microwave radiation for breast cancer detection. Microwave imaging systems are categorized based on their hardware architecture. The advantages and disadvantages of various imaging techniques are discussed. The fundamental tradeoffs are indicated between...

  19. Relaxation techniques for stress

    Science.gov (United States)

    ... problems such as high blood pressure, stomachaches, headaches, anxiety, and depression. Using relaxation techniques can help you feel calm. These exercises can also help you manage stress and ease the effects of stress on your body.

  20. Optimization techniques in statistics

    CERN Document Server

    Rustagi, Jagdish S

    1994-01-01

    Statistics help guide us to optimal decisions under uncertainty. A large variety of statistical problems are essentially solutions to optimization problems. The mathematical techniques of optimization are fundamentalto statistical theory and practice. In this book, Jagdish Rustagi provides full-spectrum coverage of these methods, ranging from classical optimization and Lagrange multipliers, to numerical techniques using gradients or direct search, to linear, nonlinear, and dynamic programming using the Kuhn-Tucker conditions or the Pontryagin maximal principle. Variational methods and optimiza

  1. Apollo Onboard Navigation Techniques

    Science.gov (United States)

    Interbartolo, Michael

    2009-01-01

    This viewgraph presentation reviews basic navigation concepts, describes coordinate systems and identifies attitude determination techniques including Primary Guidance, Navigation and Control System (PGNCS) IMU management and Command and Service Module Stabilization and Control System/Lunar Module (LM) Abort Guidance System (AGS) attitude management. The presentation also identifies state vector determination techniques, including PGNCS coasting flight navigation, PGNCS powered flight navigation and LM AGS navigation.

  2. Gulliver, medium, technique

    OpenAIRE

    Bullard, Paddy

    2016-01-01

    In the four Parts of Gulliver’s Travels the narrator attends closely to the manual skills, crafts and techniques of the different countries visited and to the materials and instruments by which they are mediated. The patterned, motif-like presentation of these observations and their rich contextual background, historical and literary, indicate their special significance. These references to technique play an important, previously underappreciated roll in Gulliver. They form a thematic connect...

  3. Separation techniques: Chromatography

    OpenAIRE

    Coskun, Ozlem

    2016-01-01

    Chromatography is an important biophysical technique that enables the separation, identification, and purification of the components of a mixture for qualitative and quantitative analysis. Proteins can be purified based on characteristics such as size and shape, total charge, hydrophobic groups present on the surface, and binding capacity with the stationary phase. Four separation techniques based on molecular characteristics and interaction type use mechanisms of ion exchange, surface adsorp...

  4. Techniques for colorectal anastomosis

    Institute of Scientific and Technical Information of China (English)

    Yik-Hong; Ho; Mohamed; Ahmed; Tawfi; k; Ashour

    2010-01-01

    Colorectal anastomotic leak remains one of the most feared post-operative complications, particularly after anterior resection of the rectum with, the shift from abdomino-peritoneal resections to total mesorectal excision and primary anastomosis. The literature fails to demonstrate superiority of stapled over hand-sewn techniques in colorectal anastomosis, regardless of the level of anastomosis, although a high stricture rate was noted in the former technique. Thus, improvements in safety aspects of anastom...

  5. Computer assisted audit techniques

    Directory of Open Access Journals (Sweden)

    Dražen Danić

    2008-12-01

    Full Text Available The purpose of this work is to point to the possibilities of more efficient auditing. In the encirclement of more and more intensive use of computer techniques that help to CAAT all the aims and the volume of auditing do not change when the audit is done in the computer-informatics environment. The computer assisted audit technique (CAATs can improve the efficiency and productivity of audit procedures. In the computerized information system, the CAATs are the ways in which an auditor can use computer to gather or as help in gathering auditing evidence. There are more reasons why the auditors apply computer techniques that help in auditing. Most often, they do it to achieve improvement of auditing efficiency when the data volume is large. It depends on several factors whether the auditors will apply the computer techniques that help auditing and to what degree respectively. If they do it, the most important are the computer knowledge, professional skill, experience of auditors, and availability of computer technique, and adequacy of computer supports, infeasibility of hand tests, efficiency and time limit. Through several examples from practice, we showed the possibilities of ACL as one of the CAAT tools.

  6. Element distribution and iron speciation in mature wheat grains (Triticum aestivum L.) using synchrotron X-ray fluorescence microscopy mapping and X-ray absorption near-edge structure (XANES) imaging.

    Science.gov (United States)

    De Brier, Niels; Gomand, Sara V; Donner, Erica; Paterson, David; Smolders, Erik; Delcour, Jan A; Lombi, Enzo

    2016-08-01

    Several studies have suggested that the majority of iron (Fe) and zinc (Zn) in wheat grains are associated with phytate, but a nuanced approach to unravel important tissue-level variation in element speciation within the grain is lacking. Here, we present spatially resolved Fe-speciation data obtained directly from different grain tissues using the newly developed synchrotron-based technique of X-ray absorption near-edge spectroscopy imaging, coupling this with high-definition μ-X-ray fluorescence microscopy to map the co-localization of essential elements. In the aleurone, phosphorus (P) is co-localized with Fe and Zn, and X-ray absorption near-edge structure imaging confirmed that Fe is chelated by phytate in this tissue layer. In the crease tissues, Zn is also positively related to P distribution, albeit less so than in the aleurone. Speciation analysis suggests that Fe is bound to nicotianamine rather than phytate in the nucellar projection, and that more complex Fe structures may also be present. In the embryo, high Zn concentrations are present in the root and shoot primordium, co-occurring with sulfur and presumably bound to thiol groups. Overall, Fe is mainly concentrated in the scutellum and co-localized with P. This high resolution imaging and speciation analysis reveals the complexity of the physiological processes responsible for element accumulation and bioaccessibility.

  7. Radiation techniques for acromegaly

    Directory of Open Access Journals (Sweden)

    Minniti Giuseppe

    2011-12-01

    Full Text Available Abstract Radiotherapy (RT remains an effective treatment in patients with acromegaly refractory to medical and/or surgical interventions, with durable tumor control and biochemical remission; however, there are still concerns about delayed biochemical effect and potential late toxicity of radiation treatment, especially high rates of hypopituitarism. Stereotactic radiotherapy has been developed as a more accurate technique of irradiation with more precise tumour localization and consequently a reduction in the volume of normal tissue, particularly the brain, irradiated to high radiation doses. Radiation can be delivered in a single fraction by stereotactic radiosurgery (SRS or as fractionated stereotactic radiotherapy (FSRT in which smaller doses are delivered over 5-6 weeks in 25-30 treatments. A review of the recent literature suggests that pituitary irradiation is an effective treatment for acromegaly. Stereotactic techniques for GH-secreting pituitary tumors are discussed with the aim to define the efficacy and potential adverse effects of each of these techniques.

  8. Telescopes and Techniques

    CERN Document Server

    Kitchin, C R

    2013-01-01

    Telescopes and Techniques has proved itself in its first two editions, having become probably one of the most widely used astronomy texts, both for amateur astronomers and astronomy and astrophysics undergraduates. Both earlier editions of the book were widely used for introductory practical astronomy courses in many universities. In this Third Edition the author guides the reader through the mathematics, physics and practical techniques needed to use today's telescopes (from the smaller models to the larger instruments installed in many colleges) and how to find objects in the sky. Most of the physics and engineering involved is described fully and requires little prior knowledge or experience. Both visual and electronic imaging techniques are covered, together with an introduction to how data (measurements) should be processed and analyzed. A simple introduction to radio telescopes is also included. Brief coverage of the more advanced topics of photometry and spectroscopy are included, but mainly to enable ...

  9. Vibrating wire alignment technique

    CERN Document Server

    Xiao-Long, Wang; lei, Wu; Chun-Hua, Li

    2013-01-01

    Vibrating wire alignment technique is a kind of method which through measuring the spatial distribution of magnetic field to do the alignment and it can achieve very high alignment accuracy. Vibrating wire alignment technique can be applied for magnet fiducialization and accelerator straight section components alignment, it is a necessary supplement for conventional alignment method. This article will systematically expound the international research achievements of vibrating wire alignment technique, including vibrating wire model analysis, system frequency calculation, wire sag calculation and the relation between wire amplitude and magnetic induction intensity. On the basis of model analysis this article will introduce the alignment method which based on magnetic field measurement and the alignment method which based on amplitude and phase measurement. Finally, some basic questions will be discussed and the solutions will be given.

  10. Neuronavigation. Principles. Surgical technique.

    Science.gov (United States)

    Ivanov, Marcel; Ciurea, Alexandru Vlad

    2009-01-01

    Neuronavigation and stereotaxy are techniques designed to help neurosurgeons precisely localize different intracerebral pathological processes by using a set of preoperative images (CT, MRI, fMRI, PET, SPECT etc.). The development of computer assisted surgery was possible only after a significant technological progress, especially in the area of informatics and imagistics. The main indications of neuronavigation are represented by the targeting of small and deep intracerebral lesions and choosing the best way to treat them, in order to preserve the neurological function. Stereotaxis also allows lesioning or stimulation of basal ganglia for the treatment of movement disorders. These techniques can bring an important amount of confort both to the patient and to the neurosurgeon. Neuronavigation was introduced in Romania around 2003, in four neurosurgical centers. We present our five-years experience in neuronavigation and describe the main principles and surgical techniques.

  11. Communication Analysis modelling techniques

    CERN Document Server

    España, Sergio; Pastor, Óscar; Ruiz, Marcela

    2012-01-01

    This report describes and illustrates several modelling techniques proposed by Communication Analysis; namely Communicative Event Diagram, Message Structures and Event Specification Templates. The Communicative Event Diagram is a business process modelling technique that adopts a communicational perspective by focusing on communicative interactions when describing the organizational work practice, instead of focusing on physical activities1; at this abstraction level, we refer to business activities as communicative events. Message Structures is a technique based on structured text that allows specifying the messages associated to communicative events. Event Specification Templates are a means to organise the requirements concerning a communicative event. This report can be useful to analysts and business process modellers in general, since, according to our industrial experience, it is possible to apply many Communication Analysis concepts, guidelines and criteria to other business process modelling notation...

  12. Novel Foraminal Expansion Technique

    Science.gov (United States)

    Senturk, Salim; Ciplak, Mert; Oktenoglu, Tunc; Sasani, Mehdi; Egemen, Emrah; Yaman, Onur; Suzer, Tuncer

    2016-01-01

    The technique we describe was developed for cervical foraminal stenosis for cases in which a keyhole foraminotomy would not be effective. Many cervical stenosis cases are so severe that keyhole foraminotomy is not successful. However, the technique outlined in this study provides adequate enlargement of an entire cervical foraminal diameter. This study reports on a novel foraminal expansion technique. Linear drilling was performed in the middle of the facet joint. A small bone graft was placed between the divided lateral masses after distraction. A lateral mass stabilization was performed with screws and rods following the expansion procedure. A cervical foramen was linearly drilled medially to laterally, then expanded with small bone grafts, and a lateral mass instrumentation was added with surgery. The patient was well after the surgery. The novel foraminal expansion is an effective surgical method for severe foraminal stenosis. PMID:27559460

  13. Novel food processing techniques

    Directory of Open Access Journals (Sweden)

    Vesna Lelas

    2006-12-01

    Full Text Available Recently, a lot of investigations have been focused on development of the novel mild food processing techniques with the aim to obtain the high quality food products. It is presumed also that they could substitute some of the traditional processes in the food industry. The investigations are primarily directed to usage of high hydrostatic pressure, ultrasound, tribomechanical micronization, microwaves, pulsed electrical fields. The results of the scientific researches refer to the fact that application of some of these processes in particular food industry can result in lots of benefits. A significant energy savings, shortening of process duration, mild thermal conditions, food products with better sensory characteristics and with higher nutritional values can be achieved. As some of these techniques act also on the molecular level changing the conformation, structure and electrical potential of organic as well as inorganic materials, the improvement of some functional properties of these components may occur. Common characteristics of all of these techniques are treatment at ambient or insignificant higher temperatures and short time of processing (1 to 10 minutes. High hydrostatic pressure applied to various foodstuffs can destroy some microorganisms, successfully modify molecule conformation and consequently improve functional properties of foods. At the same time it acts positively on the food products intend for freezing. Tribomechanical treatment causes micronization of various solid materials that results in nanoparticles and changes in structure and electrical potential of molecules. Therefore, the significant improvement of some rheological and functional properties of materials occurred. Ultrasound treatment proved to be potentially very successful technique of food processing. It can be used as a pretreatment to drying (decreases drying time and improves functional properties of food, as extraction process of various components

  14. Clustering Techniques in Bioinformatics

    Directory of Open Access Journals (Sweden)

    Muhammad Ali Masood

    2015-01-01

    Full Text Available Dealing with data means to group information into a set of categories either in order to learn new artifacts or understand new domains. For this purpose researchers have always looked for the hidden patterns in data that can be defined and compared with other known notions based on the similarity or dissimilarity of their attributes according to well-defined rules. Data mining, having the tools of data classification and data clustering, is one of the most powerful techniques to deal with data in such a manner that it can help researchers identify the required information. As a step forward to address this challenge, experts have utilized clustering techniques as a mean of exploring hidden structure and patterns in underlying data. Improved stability, robustness and accuracy of unsupervised data classification in many fields including pattern recognition, machine learning, information retrieval, image analysis and bioinformatics, clustering has proven itself as a reliable tool. To identify the clusters in datasets algorithm are utilized to partition data set into several groups based on the similarity within a group. There is no specific clustering algorithm, but various algorithms are utilized based on domain of data that constitutes a cluster and the level of efficiency required. Clustering techniques are categorized based upon different approaches. This paper is a survey of few clustering techniques out of many in data mining. For the purpose five of the most common clustering techniques out of many have been discussed. The clustering techniques which have been surveyed are: K-medoids, K-means, Fuzzy C-means, Density-Based Spatial Clustering of Applications with Noise (DBSCAN and Self-Organizing Map (SOM clustering.

  15. Advanced Techniques in Biophysics

    CERN Document Server

    Arrondo, José Luis R

    2006-01-01

    Technical advancements are basic elements in our life. In biophysical studies, new applications and improvements in well-established techniques are being implemented every day. This book deals with advancements produced not only from a technical point of view, but also from new approaches that are being taken in the study of biophysical samples, such as nanotechniques or single-cell measurements. This book constitutes a privileged observatory for reviewing novel applications of biophysical techniques that can help the reader enter an area where the technology is progressing quickly and where a comprehensive explanation is not always to be found.

  16. Simple Driving Techniques

    DEFF Research Database (Denmark)

    Rosendahl, Mads

    2002-01-01

    -like language. Our aim is to extract a simple notion of driving and show that even in this tamed form it has much of the power of more general notions of driving. Our driving technique may be used to simplify functional programs which use function composition and will often be able to remove intermediate data......Driving was introduced as a program transformation technique by Valentin Turchin in some papers around 1980. It was intended for the programming language REFAL and used in metasystem transitions based on super compilation. In this paper we present one version of driving for a more conventional lisp...

  17. Radiographic constant exposure technique

    DEFF Research Database (Denmark)

    Domanus, Joseph Czeslaw

    1985-01-01

    The constant exposure technique has been applied to assess various industrial radiographic systems. Different X-ray films and radiographic papers of two producers were compared. Special attention was given to fast film and paper used with fluorometallic screens. Radiographic image quality...... was tested by the use of ISO wire IQI's and ASTM penetrameters used on Al and Fe test plates. Relative speed and reduction of kilovoltage obtained with the constant exposure technique were calculated. The advantages of fast radiographic systems are pointed out...

  18. Surface science techniques

    CERN Document Server

    Walls, JM

    2013-01-01

    This volume provides a comprehensive and up to the minute review of the techniques used to determine the nature and composition of surfaces. Originally published as a special issue of the Pergamon journal Vacuum, it comprises a carefully edited collection of chapters written by specialists in each of the techniques and includes coverage of the electron and ion spectroscopies, as well as the atom-imaging methods such as the atom probe field ion microscope and the scanning tunnelling microscope. Surface science is an important area of study since the outermost surface layers play a crucial role

  19. Brachytherapy applications and techniques

    CERN Document Server

    Devlin, Phillip M

    2015-01-01

    Written by the foremost experts in the field, this volume is a comprehensive text and practical reference on contemporary brachytherapy. The book provides detailed, site-specific information on applications and techniques of brachytherapy in the head and neck, central nervous system, breast, thorax, gastrointestinal tract, and genitourinary tract, as well as on gynecologic brachytherapy, low dose rate and high dose rate sarcoma brachytherapy, vascular brachytherapy, and pediatric applications. The book thoroughly describes and compares the four major techniques used in brachytherapy-intraca

  20. Modern recording techniques

    CERN Document Server

    Huber, David Miles

    2013-01-01

    As the most popular and authoritative guide to recording Modern Recording Techniques provides everything you need to master the tools and day to day practice of music recording and production. From room acoustics and running a session to mic placement and designing a studio Modern Recording Techniques will give you a really good grounding in the theory and industry practice. Expanded to include the latest digital audio technology the 7th edition now includes sections on podcasting, new surround sound formats and HD and audio.If you are just starting out or looking for a step up