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Sample records for k-edge xanes studies

  1. Aluminium K-Edge XANES Study of Mica Preiswerkite

    SciTech Connect

    Wu, Z.; Marcelli, A.; Cibin, G.; Mottana, A.; Della Ventura, G.; /SLAC, SSRl

    2006-10-27

    We present the Al K-edge XANES spectrum of synthetic mica with mixed fourfold coordinated and sixfold coordinated Al (preiswerkite). Experimental analysis and multiple scattering simulations of XANES spectra demonstrate that octahedral contributions may overlap the tetrahedral ones so that the lower energy structures in mixed coordination compounds may be associated to Al octahedral site. This unexpected behavior can be explained as due to a large local distortion of the Al octahedral site.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

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

    2011-12-01

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

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

    PubMed

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

    2016-08-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

  7. Mn K-edge XANES study of the La1-xCaxMnO3 colossal magnetoresistive manganites

    NASA Astrophysics Data System (ADS)

    Ignatov, A. Yu.; Ali, N.; Khalid, S.

    2001-07-01

    We report Mn K-edge x-ray absorption near edge structure (XANES) calculations of the La1-xCaxMnO3 manganites considering three pair correlations, according to the three fundamental degrees of freedom governing their unusual electronic properties, namely, the electronic structure of the unoccupied states probed by the Mn K-edge profile versus (i) local atomic distortions; (ii) local magnetic ordering; and (iii) the charge-transfer nature of the Mn-O bonds. The calculations are accompanied by Mn K-edge XANES measurements in the temperature range 30-300 K. The main features of the absorption edge can be qualitatively reproduced in terms of single-electron multiple-scattering calculations for an 87-atom cluster. Lattice polaronic distortions in La0.7Ca0.3MnO3 are simulated assuming a strongly distorted orthorhombic structure above and an almost undistorted rhombohedral structure below Tc. The results roughly reproduce the energy ``shift'' across Tc observed experimentally. Mn K-edge spin-polarized XANES spectra of the x=0, 0.3, and 1 samples are presented. An energy splitting between the majority- and minority-spin spectra of 0.5-1.1 eV contributes to the total XANES broadening below the Néel (Curie) temperature. A small feature B3 standing approximately 6 eV above the main absorption peak is beyond the scope of single-electron calculations; it is assigned to a shake-up transition. To illustrate, the calculated Mn K edge is obtained as the convolution product of the single-electron XANES and the spectrum of many-body excitations in the Mn-O electronic states upon the sudden switching on of the Mn 1s core hole. We investigate the charge-transfer (CT) versus. Mott-Hubbard-type ground state using the Ud, Δ, and the Tdp parameters determined by previous Mn 2p x-ray photoemission spectroscopy measurements and find that LaMnO3 should be viewed as a CT-type insulator with a substantial O 2p component in the ground state. In light of these results the controversial issue of

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

    NASA Astrophysics Data System (ADS)

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

    2013-04-01

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

  9. Ca and S K-edge XANES studies of calcite-acid mine water interactions

    SciTech Connect

    Myneni, S.C.B.; Perera, R.C.C.

    1997-04-01

    Heavy metal-rich acidic waters (SO{sub 4}{sup 2{minus}}, AsO{sub 4}{sup 3{minus}}, SeO{sub 4}{sup 2{minus}}, Fe{sup 2+}, Fe{sup 3+}, Al{sup 3+}, Cu{sup 2+}, Zn{sup 2+}, Cd{sup 2+}) and related ochreous coatings are common around abandoned sulfide and coal mine sites. This is mainly caused by the natural weathering of pyrite (FeS{sub 2}), arsenopyrite (FeAsS), and other metal sulfide containing shales. Acid generation in the case of pyrite can be explained by a general reaction: FeS{sub 2} + 3.5 O{sub 2} + H{sub 2}O {leftrightarrow} Fe{sup 2+} + SO{sub 4}{sup 2{minus}} + 2H{sup +}. Also, these low pH waters interact with the soils, and mobilize their soluble elements. One of the common remediation strategies is to allow these acid waters to react with limestone (CaCO{sub 3}-rich rock) and neutralize the pH and precipitate out soluble metals. Yet, the associated problem is the precipitation of Fe and Al oxides and hydroxy sulfate coatings on limestone surfaces, which block calcite reactive sites, and make them ineffective a few hours after initiation of treatment. The main objectives of this research are to examine: (1) the chemistry of limestone surface coatings, and (2) their toxic metal uptake and the conditions that inhibit their formation. Previous molecular studies using X-ray diffraction, and vibrational spectroscopy on limestone surface coatings (sampled from Athens, OH) indicate that the surface-most layer (the layer in contact with water) is composed of schwertmannite (Fe(III)-hydroxy sulfate) like phases. However, white, X-ray amorphous; Al-, sulfate- and carbonate-rich; and Ca-poor phases appeared at the interface between the limestone and the iron oxide coatings. The structure, morphology, and coordination chemistry of component major and trace elements of these white precipitate phases have not previously been examined.

  10. Phosphorus K-edge XANES spectroscopy of mineral standards

    PubMed Central

    Ingall, Ellery D.; Brandes, Jay A.; Diaz, Julia M.; de Jonge, Martin D.; Paterson, David; McNulty, Ian; Elliott, W. Crawford; Northrup, Paul

    2011-01-01

    Phosphorus K-edge X-ray absorption near-edge structure (XANES) spectroscopy was performed on phosphate mineral specimens including (a) twelve specimens from the apatite group covering a range of compositional variation and crystallinity; (b) six non-apatite calcium-rich phosphate minerals; (c) 15 aluminium-rich phosphate minerals; (d) ten phosphate minerals rich in either reduced iron or manganese; (e) four phosphate minerals rich in either oxidized iron or manganese; (f) eight phosphate minerals rich in either magnesium, copper, lead, zinc or rare-earth elements; and (g) four uranium phosphate minerals. The identity of all minerals examined in this study was independently confirmed using X-ray powder diffraction. Minerals were distinguished using XANES spectra with a combination of pre-edge features, edge position, peak shapes and post-edge features. Shared spectral features were observed in minerals with compositions dominated by the same specific cation. Analyses of apatite-group minerals indicate that XANES spectral patterns are not strongly affected by variations in composition and crystallinity typical of natural mineral specimens. PMID:21335905

  11. Phosphorus K-edge XANES Spectroscopy of Mineral Standards

    SciTech Connect

    E Ingall; J Brandes; J Diaz; M de Jonge; D Paterson; I McNulty; C Elliott; P Northrup

    2011-12-31

    Phosphorus K-edge X-ray absorption near-edge structure (XANES) spectroscopy was performed on phosphate mineral specimens including (a) twelve specimens from the apatite group covering a range of compositional variation and crystallinity; (b) six non-apatite calcium-rich phosphate minerals; (c) 15 aluminium-rich phosphate minerals; (d) ten phosphate minerals rich in either reduced iron or manganese; (e) four phosphate minerals rich in either oxidized iron or manganese; (f) eight phosphate minerals rich in either magnesium, copper, lead, zinc or rare-earth elements; and (g) four uranium phosphate minerals. The identity of all minerals examined in this study was independently confirmed using X-ray powder diffraction. Minerals were distinguished using XANES spectra with a combination of pre-edge features, edge position, peak shapes and post-edge features. Shared spectral features were observed in minerals with compositions dominated by the same specific cation. Analyses of apatite-group minerals indicate that XANES spectral patterns are not strongly affected by variations in composition and crystallinity typical of natural mineral specimens.

  12. Sulphur Speciation and Turnover in Soils: Evidence from Sulphur K-Edge XANES Spectroscopy and Isotope Dilution Studies

    SciTech Connect

    Zhao,F.; Lehmann, J.; Solomon, D.; Fox, M.; McGrath, S.

    2005-01-01

    Sulphur K-edge X-ray absorption near edge structure (XANES) spectroscopy was used to quantify S species in humic substance extracts from ten soils from the UK, China and New Zealand, which differ in land use and agricultural management. XANES spectroscopy showed the presence of most reduced (sulphides, disulphides, thiols and thiophenes), intermediate (sulphoxides and sulphonates) and highly oxidised S (ester sulphates) forms, with the three groups representing 14-32%, 33-50% and 22-53% of the organic S in the humic substance extracts, respectively. Land use had a profound influence on the relative proportions of S species. Well-drained arable soils generally had a higher proportion of organic S present in the most oxidised form than the grassland soils collected nearby, whereas paddy soils showed a more reduced profile due to episodic flooding. In the Broadbalk Classical Experiment at Rothamsted, reversion of an arable system to grassland or woodland in the 1880s resulted in an increase of the most reduced and intermediate S species at the expense of the most oxidised S species. Long-term applications of farmyard manure to an arable plot also shifted S species from the most oxidised to the intermediate and the most reduced species. Sulphur immobilization and gross mineralization were determined in seven soils using the {sup 35}S isotope dilution method. Gross mineralization during a 53-day incubation correlated more closely with the amounts of the most reduced and intermediate S species than with the most oxidised S species, suggesting that the former (C-bonded S) were the main source of organic S for mineralization in the short-term.

  13. Sulphur Speciation and Turnover in Soils: Evidence from Sulfur K-Edge XANES Spectroscopy and Isotope Dilution Studies

    SciTech Connect

    Zhao,F.; Lehmann, J.; Solomon, D.; Fox, M.; McGrath, S.

    2006-01-01

    Sulphur K-edge X-ray absorption near edge structure (XANES) spectroscopy was used to quantify S species in humic substance extracts from ten soils from the UK, China and New Zealand, which differ in land use and agricultural management. XANES spectroscopy showed the presence of most reduced (sulphides, disulphides, thiols and thiophenes), intermediate (sulphoxides and sulphonates) and highly oxidised S (ester sulphates) forms, with the three groups representing 14-32%, 33-50% and 22-53% of the organic S in the humic substance extracts, respectively. Land use had a profound influence on the relative proportions of S species. Well-drained arable soils generally had a higher proportion of organic S present in the most oxidised form than the grassland soils collected nearby, whereas paddy soils showed a more reduced profile due to episodic flooding. In the Broadbalk Classical Experiment at Rothamsted, reversion of an arable system to grassland or woodland in the 1880s resulted in an increase of the most reduced and intermediate S species at the expense of the most oxidised S species. Long-term applications of farmyard manure to an arable plot also shifted S species from the most oxidised to the intermediate and the most reduced species. Sulphur immobilisation and gross mineralisation were determined in seven soils using the {sup 35}S isotope dilution method. Gross mineralisation during a 53-day incubation correlated more closely with the amounts of the most reduced and intermediate S species than with the most oxidised S species, suggesting that the former (C-bonded S) were the main source of organic S for mineralisation in the short-term.

  14. K-edge EXAFS and XANES studies of Cu in CdTe thin-film solar cells

    NASA Astrophysics Data System (ADS)

    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.

  15. Adsorption of boric acid on pure and humic acid coated am-Al(OH)3: A boron K-edge XANES study.

    PubMed

    Xu, Dani; Peak, Derek

    2007-02-01

    The fate and mobility of boric acid in the environment is largely controlled by adsorption reactions with soil organic matter and soil minerals to form surface complexes (Soil Sci Soc. Am. J. 1991, 55, 1582; Geochim. Cosmochim. Acta 2002, 67, 2551; Soil Sci. Soc. Am. J. 1995, 59, 405; Environ. Sci. Technol. 1995, 29, 302). In this study, boric acid adsorption on pure am-Al(OH)3 and 5% (w/w) humic acid (HA) coated am-Al(OH)3 were investigated both as a function of pH (4.5-11) and initial boric acid concentration (0-4.5 mmol L(-1)). Batch adsorption isotherm experiments were also conducted with samples exposed to atmospheric CO2 and anaerobic (N2) conditions to examine the effects of dissolved CO2 on boric acid adsorption. Boron (B) K-edge X-ray absorption near-edge structure (XANES) spectroscopy was used to investigate the coordination of boric acid adsorbed at mineral/water interfaces. The XANES spectra of boric acid adsorption samples showed that both trigonally and tetrahedrally coordinated B complexes were present on the mineral surface. Both macroscopic and spectroscopic experiments revealed that the combination of HA coating on am-Al(OH)3 and dissolved CO2 decreased boric acid adsorption compared to adsorption on pure am-Al(OH)3.

  16. Utilization of 'elemental' sulfur by different phototrophic sulfur bacteria (Chromatiaceae, Ectothiorhodospiraceae): A sulfur K-edge XANES spectroscopy study

    NASA Astrophysics Data System (ADS)

    Franz, B.; Lichtenberg, H.; Dahl, C.; Hormes, J.; Prange, A.

    2009-11-01

    Phototrophic sulfur bacteria are generally able to use elemental sulfur as an electron donor for anoxygenic photosynthesis. Elemental sulfur is mainly a mixture of cyclo-octasulfur and polymeric sulfur. The purple sulfur bacterium Allochromatium vinosum strongly prefers the polymeric sulfur fraction showing that sulfur speciation has a strong influence on availability of elemental sulfur. X-ray absorption near edge structure (XANES) spectroscopy was used to investigate whether polymeric sulfur is also the preferred sulfur species in other purple sulfur bacteria belonging to the families Chromatiaceae and Ecothiorodospiraceae. The cultures were fed with 50 mM of elemental sulfur consisting of 68% polymeric sulfur and 30% cyclo-octasulfur. In all cultures, elemental sulfur was converted into intra- or extracellular sulfur globules, respectively, and further oxidized to sulfate. Sulfate concentrations were determined by HPLC and turbidometric assays, respectively. However, the added elemental sulfur was only partly used by the bacteria, one part of the 'elemental sulfur' remained in the cultures and was not taken up. XANES spectroscopy revealed that only the polymeric sulfur fraction was taken up by all cultures investigated. This strongly indicates that polymeric 'chain-like' sulfur is the form preferably used by phototrophic sulfur bacteria.

  17. Mn K-edge XANES studies of La1-xAxMnO3 systems (A=Ca, Ba, Pb)

    NASA Astrophysics Data System (ADS)

    Bridges, F.; Booth, C. H.; Anderson, M.; Kwei, G. H.; Neumeier, J. J.; Snyder, J.; Mitchell, J.; Gardner, J. S.; Brosha, E.

    2001-06-01

    We present Mn K-edge x-ray absorption near-edge structure (XANES) data for a number of manganite systems as a function of temperature. The 1s absorption edge for the Ca-substituted samples is very sharp, almost featureless, and shifts uniformly upwards with increasing Ca content. The interpretation of this result is controversial because the lack of structure appears difficult to reconcile with a mixture of Mn+3 and Mn+4 ions or with several different Mn-O bond lengths at high T. We propose a possible solution in terms of covalency and considerable overlap of the Mn p states (mostly Mn 4p). The manganite preedge structure is quite similar to that for a large number of other Mn compounds, with two or three small peaks that are ascribed to 1s-3d weakly allowed dipole transitions plus possibly a small quadrupole component. The weak dipole transitions are explained as arising from a hybridization of the Mn 4p state of the excited atom with an odd symmetry combination of Mn 3d states on adjacent Mn atoms. The first preedge peak A1 has a small shift to higher energy with increasing valence while the next peak A2 is nearly independent of dopant concentration at 300 K. However, for the colossal magnetoresistance (CMR) samples the A2 preedge peak shifts to a lower energy below the ferromagnetic transition temperature Tc, resulting in a decrease in the A2-A1 splitting by ~0.4 eV. This indicates a change in the higher-energy 3d bands, most likely the minority spin eg, plus some change in covalency. In addition, the amplitudes are temperature dependent for the CMR materials, with the change in A1, A2 correlated with the change in sample magnetization. For the charge ordered (CO) sample, the analysis suggests that the change in the preedge is produced by a distortion that increases below TCO. We discuss these results in terms of some of the theoretical models that have been proposed and other recent XANES studies.

  18. B K-Edge XANES of Superstructural Units in Borate Glasses

    SciTech Connect

    Sipr, O.; Simunek, A.; Rocca, F.

    2007-02-02

    The potential of x-ray absorption near-edge structure (XANES) spectroscopy for studying medium range order in borate glasses is assessed by theoretical modelling of the spectra. B K edge XANES is calculated in case that B atoms are located in isolated BO3 and BO4 units and in case that B atom are located in superstructural units of 9-15 atoms. It is found that boroxol ring and diborate and ditriborate superstructural units give rise to spectra which differ from spectra obtained by a mere superposition of spectra of isolated BO3 and BO4 units. On the other hand, spectra of pentaborate and triborate units do not differ significantly from spectra of isolated BO3 and BO4.

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

    PubMed

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

    2013-09-05

    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.

  20. Si K-edge XANES study of SiO{sub x}C{sub y}H{sub z} amorphous polymeric materials

    SciTech Connect

    Chaboy, J.; Barranco, A.; Yanguas-Gil, A.; Yubero, F.; Gonzalez-Elipe, A. R.

    2007-02-15

    This work reports on x-ray absorption spectroscopy study at the Si K edge of several amorphous SiO{sub x}C{sub y}H{sub z} polymers prepared by plasma-enhanced chemical-vapor deposition with different C/O ratios. SiO{sub 2} and SiC have been used as reference materials. The comparison of the experimental Si K-edge x-ray absorption near-edge structure spectra with theoretical computations based on multiple scattering theory has allowed us to monitor the modification of the local coordination around Si as a function of the overall C/O ratio in this kind of materials.

  1. Mn K-edge XANES and Kbeta XES studies of two Mn-oxo binuclear complexes: investigation of three different oxidation states relevant to the oxygen-evolving complex of photosystem II.

    PubMed

    Visser, H; Anxolabéhère-Mallart, E; Bergmann, U; Glatzel, P; Robblee, J H; Cramer, S P; Girerd, J J; Sauer, K; Klein, M P; Yachandra, V K

    2001-07-25

    Two structurally homologous Mn compounds in different oxidation states were studied to investigate the relative influence of oxidation state and ligand environment on Mn K-edge X-ray absorption near-edge structure (XANES) and Mn Kbeta X-ray emission spectroscopy (Kbeta XES). The two manganese compounds are the di-mu-oxo compound [L'2Mn(III)O2Mn(IV)L'2](ClO4)3, where L' is 1,10-phenanthroline (Cooper, S. R.; Calvin, M. J. Am. Chem. Soc. 1977, 99, 6623-6630) and the linear mono-mu-oxo compound [LMn(III)OMn(III)L](ClO4)2, where L- is the monoanionic N,N-bis(2-pyridylmethyl)-N'-salicylidene-1,2-diaminoethane ligand (Horner, O.; Anxolabéhère-Mallart, E.; Charlot, M. F.; Tchertanov, L.; Guilhem, J.; Mattioli, T. A.; Boussac, A.; Girerd, J.-J. Inorg. Chem. 1999, 38, 1222-1232). Preparative bulk electrolysis in acetonitrile was used to obtain higher oxidation states of the compounds: the Mn(IV)Mn(IV) species for the di-mu-oxo compound and the Mn(III)Mn(IV) and Mn(IV)Mn(IV) species for the mono-mu-oxo compound. IR, UV/vis, EPR, and EXAFS spectra were used to determine the purity and integrity of the various sample solutions. The Mn K-edge XANES spectra shift to higher energy upon oxidation when the ligand environment remains similar. However, shifts in energy are also observed when only the ligand environment is altered. This is achieved by comparing the di-mu-oxo and linear mono-mu-oxo Mn-Mn moieties in equivalent oxidation states, which represent major structural changes. The magnitude of an energy shift due to major changes in ligand environment can be as large as that of an oxidation-state change. Therefore, care must be exercised when correlating the Mn K-edge energies to manganese oxidation states without taking into account the nature of the ligand environment and the overall structure of the compound. In contrast to Mn K-edge XANES, Kbeta XES spectra show less dependence on ligand environment. The Kbeta1,3 peak energies are comparable for the di-mu-oxo and mono

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

    PubMed

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

    2014-08-01

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

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

    SciTech Connect

    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.

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

    PubMed

    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.

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

    PubMed

    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.

  6. Sulfur K-edge XANES for methylene blue in photocatalytic reaction over WO3 nanomaterials

    NASA Astrophysics Data System (ADS)

    Komori, K.; Yoshida, T.; Nomoto, T.; Yamamoto, M.; Tsukada, C.; Yagi, S.; Yajima, M.; Kajita, S.; Ohno, N.

    2015-12-01

    We investigated the photocatalysis of dendritic nanostructured WO3/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*(S-C) peak in the XANES spectra reduced and a new peak originated from SO42- 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 SO42- ion. After the adsorption reaction in the dark, the XANES spectra of the sample surfaces showed a sharp π*(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 WO3/W composite materials even under NIR light irradiation.

  7. Determining the Sulfur species in the dispersants Corexit 9500A and 9527A applying S K-edge XANES spectroscopy

    NASA Astrophysics Data System (ADS)

    Bovenkamp-Langlois, Lisa; Roy, Amitava

    2016-05-01

    The dispersants Corexit 9500A and 9527A were used extensively during the Deepwater Horizon oil spill in the Gulf of Mexico. Sulfur K-edge X-ray absorption near edge structure (XANES) spectroscopy was used to investigate the dispersants for the sulfur based components. The main sulfur containing component should be dioctyl sodium sulfosuccinate (DOSS). S K-edge XANES analysis shows that indeed the major sulfur species in both kinds of Corexit (9500A and 9527A) is sulfonic acid which is a part of DOSS. In addition some fraction of sulfone was detected.

  8. Li K-Edge XANES Spectra of Lithium Niobate and Lithium Tantalite

    SciTech Connect

    Mizota, H.; Ito, Y.; Tochio, T.; Handa, K.; Takekawa, S.; Kitamura, K.

    2007-02-02

    The x-ray emission with the single crystal of lithium niobate (LiNbO3) or lithium tantalite (LiTaO3) by thermal changes in a vacuum system is closely concerned with the electronic state of each crystal. Therefore, lithium K-edge x-ray absorption near edge structures (XANES) spectra of these materials were measured in the region from 50 eV to 90 eV by means of total electron yield method (T.E.Y.), using the extremely soft x-ray. Samples were powder of lithium carbonate (Li2CO3) and single crystal of lithium fluoride (LiF), LiNbO3 and LiTaO3 in order to compare the shapes of these XANES spectra. Various peak structures appear in these spectra in the range from 55 eV to 80 eV and each spectrum has different shapes as a result of the difference of bond length and bond angles for the atoms which are in less than 60 nm from the absorbing atom. The relationship between these spectra and the electronic states was discussed by FEFF 8.

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

    PubMed

    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.

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

    PubMed Central

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

    2014-01-01

    The potentiality of high energy XANES (X-ray absorption near edge structure) as a structural tool for lanthanoid-containing systems has been explored. The K-edge XANES spectra of La3+, Gd3+, and Lu3+ 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 38 (La) to 65 (Lu) keV, the large widths of the core hole states do not appreciably reduce the potential structural information of XANES data. We show that, for lanthanoid compounds, accurate structural parameters are obtained from the analysis of K-edge XANES signal if a deconvolution procedure is carried out. We found that in solid octakis(DMSO) lanthanoid(III) iodides the Ln3+ ions are coordinated by eight DMSO ligands arranged in a quite symmetric fashion. In DMSO solution the Ln3+ ions retain a regular eight-coordination structure and the coordination number does not change along the series. At variance with water the second coordination shell has been found to provide a negligible contribution to the XANES spectra of Ln3+ ions in DMSO solution. PMID:23657739

  11. Ab initio and experimental pre-edge investigations of the Mn K -edge XANES in oxide-type materials

    NASA Astrophysics Data System (ADS)

    Farges, François

    2005-04-01

    Mn K edge ab initio FEFF8.2 calculations of the pre-edge features of the x-ray-absorption near-edge structure (XANES) region were undertaken for a series of Mn-bearing oxide-type compounds. The aim of the study is to provide a reliable method for determining quantitative and accurate redox and symmetry information for manganese. In agreement with multiplet calculations by Glatzel and co-workers, FEFF8.2 predicts a doublet and a triplet for Mn(II) and Mn(III) in octahedral symmetry, respectively, in agreement with high-resolution XANES experiments. Site distortion increases notably the contribution from dipolar transitions and, consequently, the pre-edge feature integrated area. An even more intense pre-edge feature is calculated and measured for the Td symmetry (singletlike). For Mn(IV), a triplet is predicted and measured for the Oh symmetry. However, additional transitions are found in Mn(IV)-rich compounds, that are related to metal-metal transitions. These transitions overlap strongly with the “true pre-edge,” making extraction of redox and symmetry information for Mn(IV) more challenging. However, a model of the pre-edge with pseudo-Voigt functions of fixed calculated width (based on core-hole lifetime and experimental resolution) helps to separate the contributions related to first-neighbor symmetry from those of the metal-metal pairs. Application to multivalent defective manganese oxide materials suggests that the pre-edge information varies linearly as a function of Mn redox state or symmetry but varies nonlinearly as a function of both parameters. Finally, the polymerization of the manganese networks can be estimated from the metal-metal transitions found in the pre-edge region.

  12. Ab initio and experimental pre-edge investigations of the Mn K-edge XANES in oxide-type materials

    SciTech Connect

    Farges, Francois

    2005-04-15

    Mn K edge ab initio FEFF8.2 calculations of the pre-edge features of the x-ray-absorption near-edge structure (XANES) region were undertaken for a series of Mn-bearing oxide-type compounds. The aim of the study is to provide a reliable method for determining quantitative and accurate redox and symmetry information for manganese. In agreement with multiplet calculations by Glatzel and co-workers, FEFF8.2 predicts a doublet and a triplet for Mn(II) and Mn(III) in octahedral symmetry, respectively, in agreement with high-resolution XANES experiments. Site distortion increases notably the contribution from dipolar transitions and, consequently, the pre-edge feature integrated area. An even more intense pre-edge feature is calculated and measured for the T{sub d} symmetry (singletlike). For Mn(IV), a triplet is predicted and measured for the O{sub h} symmetry. However, additional transitions are found in Mn(IV)-rich compounds, that are related to metal-metal transitions. These transitions overlap strongly with the 'true pre-edge', making extraction of redox and symmetry information for Mn(IV) more challenging. However, a model of the pre-edge with pseudo-Voigt functions of fixed calculated width (based on core-hole lifetime and experimental resolution) helps to separate the contributions related to first-neighbor symmetry from those of the metal-metal pairs. Application to multivalent defective manganese oxide materials suggests that the pre-edge information varies linearly as a function of Mn redox state or symmetry but varies nonlinearly as a function of both parameters. Finally, the polymerization of the manganese networks can be estimated from the metal-metal transitions found in the pre-edge region.

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

    PubMed

    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.

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

    SciTech Connect

    Pendyala, Venkat Ramana Rao; Jacobs, Gary; Ma, Wenping; Sparks, Dennis E.; Shafer, Wilson D.; Khalid, Syed; Xiao, Qunfeng; Hu, Yongfeng; Davis, Burtron H.

    2016-07-23

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

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

    DOE PAGES

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

    2016-07-23

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

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

    SciTech Connect

    Pendyala, Venkat Ramana Rao; Jacobs, Gary; Ma, Wenping; Sparks, Dennis E.; Shafer, Wilson D.; Khalid, Syed; Xiao, Qunfeng; Hu, Yongfeng; Davis, Burtron H.

    2016-07-23

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

  17. Measurement of sulfur L2,3 and carbon K edge XANES in a polythiophene film using a high harmonic supercontinuum.

    PubMed

    Johnson, A S; Miseikis, L; Wood, D A; Austin, D R; Brahms, C; Jarosch, S; Strüber, C S; Ye, P; Marangos, J P

    2016-11-01

    We use a high harmonic generated supercontinuum in the soft X-ray region to measure X-ray absorption near edge structure (XANES) spectra in polythiophene (poly(3-hexylthiophene)) films at multiple absorption edges. A few-cycle carrier-envelope phase-stable laser pulse centered at 1800 nm was used to generate a stable soft X-ray supercontinuum, with amplitude gating limiting the generated pulse duration to a single optical half-cycle. We report a quantitative transmission measurement of the sulfur L2,3 edge over the range 160-200 eV and the carbon K edge from 280 to 330 eV. These spectra show all the features previously reported in the XANES spectra of polythiophene, but for the first time they are measured with a source that has an approximately 1 fs pulse duration. This study opens the door to measurements that can fully time-resolve the photoexcited electronic dynamics in these systems.

  18. Measurement of sulfur L2,3 and carbon K edge XANES in a polythiophene film using a high harmonic supercontinuum

    PubMed Central

    Johnson, A. S.; Miseikis, L.; Wood, D. A.; Austin, D. R.; Brahms, C.; Jarosch, S.; Strüber, C. S.; Ye, P.; Marangos, J. P.

    2016-01-01

    We use a high harmonic generated supercontinuum in the soft X-ray region to measure X-ray absorption near edge structure (XANES) spectra in polythiophene (poly(3-hexylthiophene)) films at multiple absorption edges. A few-cycle carrier-envelope phase-stable laser pulse centered at 1800 nm was used to generate a stable soft X-ray supercontinuum, with amplitude gating limiting the generated pulse duration to a single optical half-cycle. We report a quantitative transmission measurement of the sulfur L2,3 edge over the range 160–200 eV and the carbon K edge from 280 to 330 eV. These spectra show all the features previously reported in the XANES spectra of polythiophene, but for the first time they are measured with a source that has an approximately 1 fs pulse duration. This study opens the door to measurements that can fully time-resolve the photoexcited electronic dynamics in these systems. PMID:27822487

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

    PubMed

    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.

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

    SciTech Connect

    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.

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

    SciTech Connect

    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.

    2016-06-13

    Gallium-modified zeolites are known catalysts for the dehydrogenation of alkanes, reactivity that finds industrial application in the aromatization of light alkanes by Ga-ZSM5. While the role of gallium cations in alkane activation is well known, the oxidation state and coordination environment of gallium under reaction conditions has been the subject of debate. Edge shifts in Ga K-edge XANES spectra acquired under reaction conditions have long been interpreted as evidence for reduction of Ga(III) to Ga(I). However, a change in oxidation state is not the only factor that can give rise to a change in the XANES spectrum. In order 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. Furthermore, these findings apply both to gallium-impregnated zeolite catalysts and to silica-supported single site gallium catalysts, the latter of which is found to be active and selective for dehydrogenation of propane and hydrogenation of propylene.

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

    DOE PAGES

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

    2016-06-13

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

  3. Humic sulfur in eutrophic bay sediments: Characterization by sulfur stable isotopes and K-edge XANES spectroscopy

    NASA Astrophysics Data System (ADS)

    Zhu, Mao-Xu; Chen, Liang-Jin; Yang, Gui-Peng; Huang, Xiang-Li; Ma, Chen-Yan

    2014-02-01

    Organic sulfur (OS) is an important sedimentary sulfur pool in marine sediments and chemical extractions are often used for quantification of various OS pools, however, OS sources and mechanisms of OS formation are not well understood. In this study, sulfur stable isotope and sulfur X-ray absorption near edge structure (XANES) spectroscopy were combined to investigate the sources and speciation of humic-acid sulfur (HA-S) and fulvic-acid sulfur (FA-S) in sediments of eutrophic Jiaozhou Bay. Whilst there may be some indication that eutrophication has enhanced FA-S burial in the sediment, this has not substantially modified the characteristically low humic sulfur (i.e., HA-S + FA-S) contents of the sediments. Sulfur isotopic compositions indicate that both HA-S and FA-S are mixtures of diagenetic and biosynthetic OS in origin; HA-S is dominated by biosynthetic sulfur and FA-S by diagenetic source. Sulfur isotopic compositions and contents of pyrite and diagenetic OS indicate that inhibition of sulfurization by pyrite formation, if any, appears insignificant. XANES analysis suggests that the contents of high oxidized OS (i.e., sulfones and ester-sulfates) and strongly reduced OS species are comparable in the HA-S, whereas the FA-S is dominated by strongly reduced OS as a result of enhanced sulfurization.

  4. Evolution of phosphorus complexation and mineralogy during (hydro)thermal treatments of activated and anaerobically digested sludge: Insights from sequential extraction and P K-edge XANES.

    PubMed

    Huang, Rixiang; Tang, Yuanzhi

    2016-09-01

    (Hydro)thermal treatments of sewage sludge is a promising option that can simultaneously target safe waste disposal, energy recovery, and nutrient recovery/recycling. The speciation of phosphorus (P) in sludge is of great relevance to P reclamation/recycling and soil application of sludge-derived products, thus it is critical to understand the effects of different treatment techniques and conditions on P speciation. This study systematically characterized P speciation (i.e. complexation and mineral forms) in chars derived from pyrolysis and hydrothermal carbonization (HTC) of municipal sewage sludges. Combined sequential extraction and P K-edge X-ray absorption near edge structure (XANES) spectroscopy analysis revealed the dependence of P transformation on treatment conditions and metal composition in the feedstocks. Pyrolysis of sludges decreased the relative abundance of phytic acid while increased the abundance of Al-associated P. HTC thoroughly homogenized and exposed P for interaction with various metals/minerals, with the final P speciation closely related to the composition/speciation of metals and their affinities to P. Results from this study revealed the mechanisms of P transformation during (hydro)thermal treatments of sewage sludges, and might be applicable to other biosolids. It also provided fundamental knowledge basis for the design and selection of waste management strategies for better P (re)cycling and reclamation.

  5. Redox Reaction in Silicate Melts Monitored by ``Static'' In-Situ Fe K-Edge XANES up to 1180°C

    NASA Astrophysics Data System (ADS)

    Wilke, Max; Partzsch, Georg M.; Welter, Edmund; Farges, François

    2007-02-01

    A new experimental setup to measure in-situ kinetics of redox reactions in silicate melts is presented. To study the progress of the Fe-redox reaction, the variation of the signal is recorded at an energy, where the difference between the spectra of the oxidized and reduced Fe in the melt is largest ("static XANES"). To control the redox conditions, the gas atmosphere could be changed between to types of gases using computer-controlled valves (N2:H2 and air, respectively). In this way, a number of reduction/oxidation cycles can be monitored in-situ and continuously. Applied at the Fe K-edge in molten silicates, we obtained a set of high quality data, which includes the very first steps of the redox reaction. An Avrami-type equation is used to investigate rate-controlling parameters for the iron oxidation/reduction kinetics for two melts (basaltic and Na trisilicate) for temperatures up to 1180°C.

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

    PubMed Central

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

    2016-01-01

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

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed

    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.

  9. Investigation of soil legacy phosphorus transformation in long-term agricultural fields using sequential fractionation, P K-edge XANES and solution P NMR spectroscopy.

    PubMed

    Liu, Jin; Hu, Yongfeng; Yang, Jianjun; Abdi, Dalel; Cade-Menun, Barbara J

    2015-01-06

    Understanding legacy phosphorus (P) build-up and draw-down from long-term fertilization is essential for effective P management. Using replicated plots from Saskatchewan, Canada, with P fertilization from 1967 to 1995 followed by either P fertilization or P cessation (1995-2010), soil P was characterized in surface and subsurface layers using sequential fractionation, P K-edge X-ray absorption near-edge structure (XANES) and solution (31)P nuclear magnetic resonance (P NMR) spectroscopy. Legacy P from a 28-year build-up was sufficient for 15 years of wheat cultivation, resulting in no significant differences in crop yield in 2010. In surface soils, soil test (Olsen) P decreased significantly in unfertilized plots compared with 1995, which was reflected in declining aluminum (hydr)oxide-associated inorganic P by fractionation and XANES. Furthermore, XANES analysis revealed a decrease of calcium-associated P in 2010-unfertilized soils at both depths and an increase of Fe (hydr)oxides-associated P in the 2010-fertilized and -unfertilized surface soils relative to the 1995 soils. Increased total organic P and orthophosphate diesters by P NMR and accumulated inositol hexaphosphate by XANES were observed in surface soils with P fertilization cessation. In subsurface soils, few legacy P transformations were detected. These results provide important information about legacy P to improve agricultural sustainability while mitigating water quality deterioration.

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

    SciTech Connect

    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{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.

  11. Retention mechanisms of citric acid in ternary kaolinite-Fe(III)-citrate acid systems using Fe K-edge EXAFS and L3,2-edge XANES spectroscopy

    DOE PAGES

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

    2016-05-23

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

  12. Insights into molecular chemistry of Chiapas amber using infrared-light microscopy, PIXE/RBS, and sulfur K-edge XANES spectroscopy

    NASA Astrophysics Data System (ADS)

    Riquelme, Francisco; Northrup, Paul; Ruvalcaba-Sil, José Luis; Stojanoff, Vivian; Peter Siddons, D.; Alvarado-Ortega, Jesús

    2014-07-01

    Chiapas amber is a natural occurring fossil resin structurally composed of long macromolecule chains with semicrystalline phases associated with both fossil and polymerization process. The most conspicuous characteristic of this fossil polymer is that it preserves ancient organic inclusions. In the present work, PIXE/RBS spectrometry (particle-induced X-ray emission/Rutherford backscattering) were combined with complementary K-edge XANES spectroscopy (X-ray absorption near-edge structure) to identify the amount of sulfur in Chiapas amber. Initially, the amber samples were examined using infrared reflected photomicrography. Amber is transparent to infrared light and so embedded plants and animals are easily visible, showing them in extraordinary detail, as if they were immersed in a water-like solution. The PIXE/RBS data show that the proportion of sulfur in amber is significantly higher than that found in recently formed resins, consistent with the biogeochemical process that transforms the resin into amber during long-term burial in geological deposits. The sulfur K-edge XANES spectra from amber confirm the sulfur abundance and reveal sulfur species in the reduced and intermediate oxidation states in amber. Almost no oxidized sulfur was found, whereas the recent resins show mostly oxidized sulfur fractions. This indicates that labile oxidized sulfur decays during fossilization and resin maturation must occur under conditions of oxygen depletion. The implications of the presence of sulfur in amber for organic preservation is also discussed here. Sulfur compounds work as a polymer additive that promotes intense resin solidification. This restricts the early oxidant-specific biodegradation of the embedded biomatter and, over geological time, provides greater stability against chemical changes.

  13. Ab initio x-ray absorption near-edge structure study of Ti K-edge in rutile.

    PubMed

    Chaboy, J; Nakajima, N; Tezuka, Y

    2007-07-04

    This work reports a theoretical x-ray absorption near-edge structure (XANES) spectroscopy study at the Ti K-edge in TiO(2) rutile. We present detailed ab initio computations of the Ti K-edge XANES spectrum performed within the multiple-scattering framework. An extensive discussion is presented concerning the size of the cluster needed to reproduce the experimental spectrum, especially regarding the split main absorption line. In addition, the role of the exchange and correlation potential (ECP) in reproducing all the experimental XANES features is discussed. The best agreement between experimental data and computations is obtained by using real ECP potentials, i.e. the energy-dependent Dirac-Hara exchange potential, or by using only the real part of the energy-dependent Hedin-Lundqvist complex potential, together with an additional imaginary constant to account for the core-hole lifetime and the experimental resolution. The addition of the imaginary part of the HL potential worsens the agreement between the experimental and calculated spectra, indicating the failure of the complex part of the Hedin-Lundqvist ECP in accounting for the electron damping in these systems.

  14. Contribution of molecular dynamics simulations and ab initio calculations to the interpretation of Mg K-edge experimental XANES in K(2)O-MgO-3SiO(2) glass.

    PubMed

    Trcera, Nicolas; Rossano, Stéphanie; Madjer, Karim; Cabaret, Delphine

    2011-06-29

    The structural environment of Mg in a K-bearing silicate glass of composition K(2)MgSi(3)O(8) is investigated by x-ray absorption near-edge structure (XANES) spectroscopy at the Mg K-edge. XANES calculations are performed using a plane-wave electronic structure code, and a structural model obtained by classical molecular dynamics coupled to ab initio relaxation. Bond valence theory is used to validate plausible environments within the structural models. Comparison between the experimental and calculated spectra enables us to conclude that the Mg atoms are located in distorted tetrahedral sites. Site distortions are found to be correlated to the theoretical shift of the XANES edge position.

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

  16. Parameters Influencing Sulfur Speciation in Environmental Samples Using Sulfur K-Edge X-Ray Absorption Near-Edge Structure

    PubMed Central

    Pongpiachan, Siwatt; Thumanu, Kanjana; Kositanont, Charnwit; Schwarzer, Klaus; Prietzel, Jörg; Hirunyatrakul, Phoosak; Kittikoon, Itthipon

    2012-01-01

    This paper aims to enhance the credibility of applying the sulfur K-edge XANES spectroscopy as an innovative “fingerprint” for characterizing environmental samples. The sensitivities of sulfur K-edge XANES spectra of ten sulfur compound standards detected by two different detectors, namely, Lytle detector (LyD) and Germanium detector (GeD), were studied and compared. Further investigation on “self-absorption” effect revealed that the maximum sensitivities of sulfur K-edge XANES spectra were achieved when diluting sulfur compound standards with boron nitride (BN) at the mixing ratio of 0.1%. The “particle-size” effect on sulfur K-edge XANES spectrum sensitivities was examined by comparing signal-to-noise ratios of total suspended particles (TSP) and particulate matter of less than 10 millionths of a meter (PM10) collected at three major cities of Thailand. The analytical results have demonstrated that the signal-to-noise ratios of sulfur K-edge XANES spectra were positively correlated with sulfate content in aerosols and negatively connected with particle sizes. The combination of hierarchical cluster analysis (HCA) and principal component analysis (PCA) has proved that sulfur K-edge XANES spectrum can be used to characterize German terrestrial soils and Andaman coastal sediments. In addition, this study highlighted the capability of sulfur K-edge XANES spectra as an innovative “fingerprint” to distinguish tsunami backwash deposits (TBD) from typical marine sediments (TMS). PMID:23193498

  17. 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

    SciTech Connect

    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.

  18. Pressure Induced Phase Transition in PbTiO3 Studied by X-ray Absorption Spectroscopy at the Ti K edge

    SciTech Connect

    Dhaussy, A. C.; Marinel, S.; Veres, A.; Jaouen, N.; Itie, J. P.; Rogalev, A.

    2007-01-19

    The Ti-K edge X-ray Absorption Near Edge Structure (XANES) for CaTiO3 and PbTiO3 have been measured under high pressure in a diamond anvil cell at room temperature. Despite the huge absorption from the diamond cell and the sample high quality XANES allows us to observe that in CaTiO3 no change occurs when applying pressure, at the opposite of PbTiO3 in which the pre-edge features vary strongly. It allows studying the phase transition from ferroelectric to paraelectric phase in PbTiO3 from the local point of view. Under pressure the change in intensity of the pre-edge indicates qualitatively that the Ti atom is moving toward the centre of the oxygen octahedron along the c-axis.

  19. Retention mechanisms of citric acid in ternary kaolinite-Fe(III)-citrate acid systems using Fe K-edge EXAFS and L3,2-edge XANES spectroscopy

    SciTech Connect

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

    2016-05-23

    Organic carbon (OC) stability in tropical soils is strongly interlinked with multivalent cation interaction and mineral association. Low molecular weight organic acids (LMWOAs) represent the readily biodegradable OC. Therefore, investigating retention mechanisms of LMWOAs in mineral-cation-LMWOAs systems is critical to understanding soil C cycling. Given the general acidic conditions and dominance of kaolinite in tropical soils, we investigated the retention mechanisms of citric acid (CA) in kaolinite-Fe(III)-CA systems with various Fe/CA molar ratios at pH ~3.5 using Fe K-edge EXAFS and L-3,2-edge XANES techniques. With Fe/CA molar ratios >2, the formed ferrihydrite mainly contributed to CA retention through 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. In conclusion, these findings will enhance our understanding of the dynamics of CA and other LMWOAs in tropical soils.

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

    PubMed

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

    2012-01-30

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

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

    NASA Astrophysics Data System (ADS)

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

    2013-05-01

    Phosphorus (P) is a crucial element for life on Earth, and the bioavailability of P in terrestrial ecosystems, which is dependent on the soil P stock and its speciation, may limit ecosystem productivity and succession. In our study, for the first time a direct speciation of soil P in two glacier foreland chronosequences has been conducted using synchrotron-based X-ray Absorption Near-Edge Structure (XANES) spectroscopy. The chronosequences are located in the forefields of Hailuogou Glacier (Gongga Shan, China) and Damma Glacier (Swiss Alps). The age since deglaciation of the investigated soils ranges from 0 to 120 years at Hailuogou, and from 15 to >700 years at Damma. Differences in climate conditions (cooler at Damma, in contrast to Hailuogou precluding the establishment of forest in advanced ecosystem succession stages) and in the chemical composition of the parent material result in different soil contents of total P and Fe/Al oxyhydroxides, which are much smaller at Damma than at Hailuogou. Nevertheless, both chronosequences show similar trends of their topsoil P status with increasing soil age. Our study reveals a rapid change of topsoil P speciation in glacier retreat areas already during initial stages of pedogenesis: Initially dominating bedrock-derived apatite-P and Al-bound P is depleted; Fe-bound P and particularly organically-bound P is accumulated. Organic P strongly dominates in the topsoil of the mature soils outside the proglacial area of Damma Glacier (age 700-3000 years), and already 50 years after deglacation in the topsoil of the retreat area of Hailuogou Glacier. A key factor for the change in topsoil P speciation is the establishment of vegetation, resulting in soil organic matter (SOM) accumulation as well as accelerated soil acidification and apatite dissolution by organic acids, which are produced by SOM-degrading micro-organisms, mykorrhiza fungi, and plant roots. Particularly the succession of grassland to forest seems to accelerate the

  2. XANES studies of oxidation states of sulfur in aquatic and soil humic substances

    SciTech Connect

    Xia, K.; Weesner, F.; Bleam, W.F.; Helmke, P.A.; Bloom, P.R.; Skyllberg, U.L.

    1998-09-01

    Sulfur K-edge x-ray absorption near-edge structure spectroscopy (XANES) was used to identify multiple organic S oxidation states in aquatic and soil humic substances. The XANES results suggest that S in humic substances exists in four major oxidation groups similar to sulfate ester, sulfonate, sulfoxide, and thiol-sulfide. Thiol S cannot be separated from sulfide X and must be considered as a single thiol-sulfide peak. The second derivative spectra suggest the existence of thiophene and sulfone S. The relative quantities of each major S form in humic samples were estimated based on the integrated cross section of each s {r_arrow} p transition peak corresponding to different S oxidation states in the S K-edge XANES spectra. The XANES results of the four humic samples used in this study appear to reflect the environmental settings where the humic substances originally formed. The percentage of the most reduced organic S (thiol-sulfide and possibly thiophene) in humic substances follows the sequence:aquatic samples > organic soil sample > mineral soil sample. The percentage of most oxidized S (sulfate group) was the greatest in the humic substance from a mineral soil and the lowest in the aquatic humic substances.

  3. Photon counting x-ray imaging with K-edge filtered x-rays: A simulation study.

    PubMed

    Atak, Haluk; Shikhaliev, Polad M

    2016-03-01

    In photon counting (PC) x-ray imaging and computed tomography (CT), the broad x-ray spectrum can be split into two parts using an x-ray filter with appropriate K-edge energy, which can improve material decomposition. Recent experimental study has demonstrated substantial improvement in material decomposition with PC CT when K-edge filtered x-rays were used. The purpose of the current work was to conduct further investigations of the K-edge filtration method using comprehensive simulation studies. The study was performed in the following aspects: (1) optimization of the K-edge filter for a particular imaging configuration, (2) effects of the K-edge filter parameters on material decomposition, (3) trade-off between the energy bin separation, tube load, and beam quality with K-edge filter, (4) image quality of general (unsubtracted) images when a K-edge filter is used to improve dual energy (DE) subtracted images, and (5) improvements with K-edge filtered x-rays when PC detector has limited energy resolution. The PC x-ray images of soft tissue phantoms with 15 and 30 cm thicknesses including iodine, CaCO3, and soft tissue contrast materials, were simulated. The signal to noise ratio (SNR) of the contrast elements was determined in general and material-decomposed images using K-edge filters with different atomic numbers and thicknesses. The effect of the filter atomic number and filter thickness on energy separation factor and SNR was determined. The boundary conditions for the tube load and halfvalue layer were determined when the K-edge filters are used. The material-decomposed images were also simulated using PC detector with limited energy resolution, and improvements with K-edge filtered x-rays were quantified. The K-edge filters with atomic numbers from 56 to 71 and K-edge energies 37.4-63.4 keV, respectively, can be used for tube voltages from 60 to 150 kVp, respectively. For a particular tube voltage of 120 kVp, the Gd and Ho were the optimal filter materials

  4. Mn K-edge XANES spectroscopy of a photosynthetic O2-evolving complex. High-quality pre-edge features and distinct fine structures in the S1- and S2-states.

    PubMed

    Kusunoki, M; Ono, T; Matsushita, T; Oyanagi, H; Inoue, Y

    1990-10-01

    High-resolution XANES (X-ray Absorption Near Edge Structure) spectroscopy for Mn in the S1 and S2 states of the spinach photosynthetic O2-evolving complex revealed distinct features in K-edge spectra, when a high signal-to-noise (S/N) ratio of ca. 80 with a low and constant background-to-signal (B/S) ratio of 0.15 to 0.18 was attained. Six features resolved in each S-state spectrum involve a pre-edge feature due to 1s----3d transitions, a main-edge feature possibly due to 1s----4s transitions and four fine structures superimposed on the principal absorption bands due to 1s----4p* transitions. The high-quality pre-edge features were analyzed according to a parametric ligand-field theory in comparison with those of some typical authentic Mn complexes. It was deduced that i) all of the four Mn ions in the S1-state are octahedrally coordinated and two of them constitute a di-mu-oxo bridged Mn(III, III) dimeric subunit; ii) the bridged Mn(III) ions are further bridged by a deprotonated water dimer, (HOHOH)-, and coordinated by imidazole-N and carboxylate-O- on the opposite side of the Mn atom from the di-mu-oxo bridge; iii) the other two Mn ions exist in the form of Mn(III) monomeric subunits; and iv) upon the S1----S2 transition, only the bridged Mn(III,III) is oxidized to Mn(III,IV). The distinct change in the principal absorption band shape upon the S1----S2 transition is briefly discussed to obtain the XANES evidence for a tetrameric Mn-cluster.

  5. Morphology-dependent luminescence from ZnO nanostructures - An X-ray excited optical luminescence study at the Zn K-edge

    SciTech Connect

    Lobacheva, Olga; Murphy, Michael W; Ko, Jun Young Peter; Sham, Tsun-Kong

    2009-08-28

    ZnO nanostructures have been synthesized by thermal evaporation on Si substrates. It is found that the morphologies of the nanostructures are governed by growth conditions such as temperature, carrier-gas flow rate, and the nature of the substrate (with and without a catalyst). We report X-ray excited optical luminescence from ZnO nanostructures of distinctly different morphologies in the energy and time domain using excitation photon energies across the Zn K-edge. X-ray excited optical luminescence (XEOL) and X-ray absorption near edge structure (XANES) study has clearly shown the morphology dependence of the ZnO optical properties. A correlation of luminescence with morphology, size, and crystallinity emerges.

  6. Preliminary study of an angiographic and angio-tomographic technique based on K-edge filters

    SciTech Connect

    Golosio, Bruno; Brunetti, Antonio; Oliva, Piernicola; Carpinelli, Massimo; Luca Masala, Giovanni; Meloni, Francesco; Battista Meloni, Giovanni

    2013-08-14

    Digital Subtraction Angiography is commonly affected by artifacts due to the patient movements during the acquisition of the images without and with the contrast medium. This paper presents a preliminary study on an angiographic and angio-tomographic technique based on the quasi-simultaneous acquisition of two images, obtained using two different filters at the exit of an X-ray tube. One of the two filters (K-edge filter) contains the same chemical element used as a contrast agent (gadolinium in this study). This filter absorbs more radiation with energy just above the so called K-edge energy of gadolinium than the radiation with energy just below it. The other filter (an aluminium filter in this study) is simply used to suppress the low-energy contribution to the spectrum. Using proper calibration curves, the two images are combined to obtain an image of the contrast agent distribution. In the angio-tomographic application of the proposed technique two images, corresponding to the two filter types, are acquired for each viewing angle of the tomographic scan. From the two tomographic reconstructions, it is possible to obtain a three-dimensional map of the contrast agent distribution. The technique was tested on a sample consisting of a rat skull placed inside a container filled with water. Six small cylinders with 4.7 mm internal diameter containing the contrast medium at different concentrations were placed inside the skull. In the plain angiographic application of the technique, five out of six cylinders were visible, with gadolinium concentration down to 0.96%. In the angio-tomographic application, all six cylinders were visible, with gadolinium concentration down to 0.49%. This preliminary study shows that the proposed technique can provide images of the contrast medium at low concentration without most of the artifacts that are present in images produced by conventional techniques. The results encourage further investigation on the feasibility of a clinical

  7. Preliminary study of an angiographic and angio-tomographic technique based on K-edge filters

    NASA Astrophysics Data System (ADS)

    Golosio, Bruno; Oliva, Piernicola; Brunetti, Antonio; Luca Masala, Giovanni; Carpinelli, Massimo; Meloni, Francesco; Battista Meloni, Giovanni

    2013-08-01

    Digital Subtraction Angiography is commonly affected by artifacts due to the patient movements during the acquisition of the images without and with the contrast medium. This paper presents a preliminary study on an angiographic and angio-tomographic technique based on the quasi-simultaneous acquisition of two images, obtained using two different filters at the exit of an X-ray tube. One of the two filters (K-edge filter) contains the same chemical element used as a contrast agent (gadolinium in this study). This filter absorbs more radiation with energy just above the so called K-edge energy of gadolinium than the radiation with energy just below it. The other filter (an aluminium filter in this study) is simply used to suppress the low-energy contribution to the spectrum. Using proper calibration curves, the two images are combined to obtain an image of the contrast agent distribution. In the angio-tomographic application of the proposed technique two images, corresponding to the two filter types, are acquired for each viewing angle of the tomographic scan. From the two tomographic reconstructions, it is possible to obtain a three-dimensional map of the contrast agent distribution. The technique was tested on a sample consisting of a rat skull placed inside a container filled with water. Six small cylinders with 4.7 mm internal diameter containing the contrast medium at different concentrations were placed inside the skull. In the plain angiographic application of the technique, five out of six cylinders were visible, with gadolinium concentration down to 0.96%. In the angio-tomographic application, all six cylinders were visible, with gadolinium concentration down to 0.49%. This preliminary study shows that the proposed technique can provide images of the contrast medium at low concentration without most of the artifacts that are present in images produced by conventional techniques. The results encourage further investigation on the feasibility of a clinical

  8. K-edge digital subtraction imaging with dichromatic x-ray sources: SNR and dose studies

    NASA Astrophysics Data System (ADS)

    Sarnelli, A.; Elleaume, H.; Taibi, A.; Gambaccini, M.; Bravin, A.

    2006-09-01

    The aim of the present work is to analytically evaluate the signal to noise ratio (SNR) and the delivered dose in K-edge digital subtraction imaging (KES) using two types of x-ray sources: a monochromatic x-ray source (available at synchrotron radiation facilities and considered as gold standard) and a quasi-monochromatic compact source. The energy separation ΔE between the two monochromatic beams is 1 keV and 4 keV for the two sources, respectively. The evaluation has been performed for both radiography and computed tomography. Different geometries have been studied to mimic clinical situations. In mammography, a pathology perfused by a contrast agent has been modelled; in angiography, a vessel superimposed to a ventricle or a stand-alone artery stenosis has been studied. The SNR and the skin dose have been calculated as a function of the detail diameter, the contrast agent (iodine and gadolinium), and its concentration in the tissues. Results show that for ΔE = 4 keV a slightly higher delivered dose is required to obtain the same SNR with respect to ΔE < 1 keV. A similar study has been performed for KES-CT. Computer simulations of CT images performed with Snark software are shown to validate the analytical calculations.

  9. Copper blue in an ancient glass bead: a XANES study

    NASA Astrophysics Data System (ADS)

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

    2006-06-01

    The blue colour in ancient soda-lime glasses has been attributed to the presence of copper and/or cobalt but the origin of different shades is not yet fully interpreted. As a contribution to this question, a non-destructive X-ray absorption study at [ Cu]K-edge was undertaken on the blue (turquoise) layer from a “Nueva Cadiz” type tubular glass bead dated pre-XVII century where copper is the unique colouring agent. Minerals configuring two distinct blue tonalities due to Cu (2+) in similar square coordination were selected as basic model compounds: azurite, which is a classical navy-blue pigment used in ancient wall paintings over plaster, and chalcanthite, displaying exactly the same turquoise-blue tonality of tubular glass beads manufactured since the Egyptian Antiquity. Theoretical modelling of the XAFS spectra was undertaken using the FEFF code. The IFEFFIT software package was used for fitting the calculated spectra to experimental data. EXAFS results are discussed in view of the crystal structures of copper minerals chosen to model the speciation state and structural situation of that element prevailing in the turquoise-blue archaeological glass. Special attention is focused on the difficulties in theoretical modelling [ Cu]K-XANES spectra of ancient glasses with different colourings.

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

    NASA Technical Reports Server (NTRS)

    Ruckman, Mark W.; Hepp, Aloysius F.

    1990-01-01

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

  11. Photoabsorption study of Bacillus megaterium, DNA and Related Biological Materials in the Phosphorus K-edge Region

    NASA Technical Reports Server (NTRS)

    Frigo, Sean P.; McNulty,Ian; Richmond, Robert C.; Ehret, Charles F.

    2003-01-01

    We have measured the x-ray transmission spectra of several biologically related samples in the phosphorus K-edge absorption region. These include red phosphorus, hydrated sodium phosphate (Na3PO4 12 H2O), deoxyribonucleic acid (DNA), adenosinetriphosphate (ATP), diolylphosphatidyl choline (DOPC), and Bacillus megaterium spores. Red phosphorus essentially displays an edge-jump. All other spectra are similar in form and energy position, where each is dominated by a narrower, more intense first peak and a broader but less intense second peak. The corresponding K-edge absorption thresholds are shifted towards higher energy relative to that for red phosphorus, as expected for increasing degrees of phosphorus oxidation. The B.meguterium spectrum has aspects common to both the phosphate and DNA spectra and is therefore interpreted as a composite of spectra arising from DNA/RNA and phosphates within the spore. The B. megaterium spore spectrum provides needed information for resonant radiation damage studies in the phosphorus K-edge absorption region by identifying candidate photoexcitations. In addition, the absorption spectra will be useful in macromolecular crystallography studies employing anomalous dispersion effects at the phosphorus K-edge.

  12. Photoabsorption Study of Bacillus megaterium, DNA and Related Biological Materials in the Phosphorus K-edge Region

    NASA Technical Reports Server (NTRS)

    Frigo, Sean P.; McNulty, Ian; Richmond, Robert C.; Ehret, Charles F.

    2002-01-01

    We have measured the x-ray transmission spectra of several biologically related samples in the phosphorus K-edge absorption region. These include elemental red phosphorus, hydrated sodium phosphate (Na3PO4.12H2O), deoxyribonucleic acid (DNA), adenosinetriphosphate (ATP), diolylphosphatidyl choline (DOPC), and Bacillus megaterium spores. Elemental red phosphorus essentially displays an edge-jump. All other spectra are similar in form and energy position. Each spectrum for these substances is dominated by a narrower, more intense first peak and a broader but less intense second peak. The corresponding K-edge absorption thresholds are shifted towards higher energy relative to that for elemental red phosphorus, as expected for increasing degrees of phosphorus oxidation. The B. megaterium spectrum has aspects common to both the phosphate and DNA spectra and is therefore interpreted as a composite of spectra arising from DNA/RNA and phosphates within the spore. The B. megaterium spore spectrum provides needed information for resonant radiation damage studies in the phosphorus K-edge absorption region by identifying candidate photoexcitations. In addition,the absorption spectra will be useful in macromolecular crystallography studies employing anomalous dispersion effects at the phosphorus K-edge.

  13. Photoabsorption Study of Bacillus megaterium, DNA and Related Biological Materials in the Phosphorus K-edge Region

    NASA Technical Reports Server (NTRS)

    Frigo, Sean P.; McNulty, Ian; Richmond, Robert C.; Ehret, Charles F.

    2002-01-01

    We have measured the x-ray transmission spectra of several biologically related samples in the phosphorus K-edge absorption region. These include elemental red phosphorus, hydrated sodium phosphate (Na3PO4.12H2O), deoxyribonucleic acid (DNA), adenosinetriphosphate (ATP), diolylphosphatidyl choline (DOPC), and Bacillus megaterium spores. Elemental red phosphorus essentially displays an edge-jump. All other spectra are similar in form and energy position. Each spectrum for these substances is dominated by a narrower, more intense first peak and a broader but less intense second peak. The corresponding K-edge absorption thresholds are shifted towards higher energy relative to that for elemental red phosphorus, as expected for increasing degrees of phosphorus oxidation. The B. megaterium spectrum has aspects common to both the phosphate and DNA spectra and is therefore interpreted as a composite of spectra arising from DNA/RNA and phosphates within the spore. The B. megaterium spore spectrum provides needed information for resonant radiation damage studies in the phosphorus K-edge absorption region by identifying candidate photoexcitations. In addition,the absorption spectra will be useful in macromolecular crystallography studies employing anomalous dispersion effects at the phosphorus K-edge.

  14. Studies on effective atomic numbers, electron densities from mass attenuation coefficients near the K edge in some samarium compounds.

    PubMed

    Akman, F; Durak, R; Turhan, M F; Kaçal, M R

    2015-07-01

    The effective atomic numbers and electron densities of some samarium compounds were determined using the experimental total mass attenuation coefficient values near the K edge in the X-ray energy range from 36.847 up to 57.142 keV. The measurements, in the region from 36.847 to 57.142 keV, were done in a transmission geometry utilizing the Kα2, Kα1, Kβ1 and Kβ2 X-rays from different secondary source targets excited by the 59.54 keV gamma-photons from an Am-241 annular source. This paper presents the first measurement of the effective atomic numbers and electron densities for some samarium compounds near the K edge. The results of the study showed that the measured values were in good agreement with the theoretically calculated ones. Copyright © 2015 Elsevier Ltd. All rights reserved.

  15. Zn K edge and O K edge x-ray absorption spectra of ZnO surfaces: implications for nanorods.

    PubMed

    Šipr, O; Rocca, F

    2011-08-10

    Zn K edge and O K edge x-ray absorption near-edge structure (XANES) spectra of ZnO surfaces are calculated. The difference between theoretical XANES for ZnO surfaces and ZnO bulk is then compared to the earlier observed differences between experimental XANES for ZnO nanostructures and ZnO bulk as taken from the literature. It follows from our calculations that the differences between the experimental XANES of bulk ZnO and nanocrystalline ZnO is not due to the enhanced role of the surfaces in nanostructures. Rather, the difference in XANES has to reflect differences in the local geometry around the photoabsorbing sites. The dependence of XANES of ZnO surfaces on the polarization of the incoming radiation is also investigated theoretically and found to be similar as in the bulk.

  16. Model compound vulcanization studied by XANES

    NASA Astrophysics Data System (ADS)

    Taweepreda, W.; Nu-Mard, R.; Pattanasiriwisawa, W.; Songsiriritthigul, P.

    2009-11-01

    Squalene has been used as a model compound for the investigation of sulphur crosslink in the vulcanization process. The effects of the accelerator on the crosslink were deduced from the sulfur K-edge absorption spectra. The majority of the crosslinks for the squalene vulcanized with ZDEC or TMTD is likely disulfidic, while that vulcanized with CBS or MBTS is monosulfidic.

  17. Removing arsenic from synthetic groundwater with iron electrocoagulation: an Fe and As K-edge EXAFS study.

    PubMed

    van Genuchten, Case M; Addy, Susan E A; Peña, Jasquelin; Gadgil, Ashok J

    2012-01-17

    Electrocoagulation (EC) using iron electrodes is a promising arsenic removal strategy for Bangladesh groundwater drinking supplies. EC is based on the rapid in situ dissolution of a sacrificial Fe(0) anode to generate iron precipitates with a high arsenic sorption affinity. We used X-ray absorption spectroscopy (XAS) to investigate the local coordination environment (<4.0 Å) of Fe and As in EC precipitates generated in synthetic Bangladesh groundwater (SBGW). Fe and As K-edge EXAFS spectra were found to be similar between samples regardless of the large range of current density (0.02, 1.1, 5.0, 100 mA/cm(2)) used to generate samples. Shell-by-shell fits of the Fe K-edge EXAFS spectra indicated that EC precipitates consist of primarily edge-sharing FeO(6) octahedra. The absence of corner-sharing FeO(6) octahedra implies that EC precipitates resemble nanoscale clusters (polymers) of edge-sharing octahedra that efficiently bind arsenic. Shell-by-shell fits of As K-edge EXAFS spectra show that arsenic, initially present as a mixture of As(III) and As(V), forms primarily binuclear, corner-sharing As(V) surface complexes on EC precipitates. This specific coordination geometry prevents the formation of FeO(6) corner-sharing linkages. Phosphate and silicate, abundant in SBGW, likely influence the structure of EC precipitates in a similar way by preventing FeO(6) corner-sharing linkages. This study provides a better understanding of the structure, reactivity, and colloidal stability of EC precipitates and the behavior of arsenic during EC. The results also offer useful constraints for predicting arsenic remobilization during the long-term disposal of EC sludge.

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

    PubMed

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

    2012-07-01

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

  19. A XANES study of Cu speciation in high-temperature brines using synthetic fluid inclusions

    SciTech Connect

    Berry, Andrew J.; Hack, Alistair C.; Mavrogenes, John A.; Newville, Matthew; Sutton, Stephen R.

    2010-12-03

    Cu K-edge X-ray absorption near edge structure (XANES) spectra were recorded from individual synthetic brine fluid inclusions as a function of temperature up to 500 C. The inclusions serve as sample cells for high-temperature spectroscopic studies of aqueous Cu-Cl speciation. Cu{sup +} and Cu{sup 2+} can both be identified from characteristic pre-edge features. Mixed oxidation states can be deconvoluted using linear combinations of Cu{sup +} and Cu{sup 2+} spectra. This work illustrates how complex Cu XANES spectra can be interpreted successfully. Cu{sup 2+} is the stable oxidation state in solution at room temperature and Cu{sup +} at high temperatures. The change in oxidation state with temperature was completely reversible. Cu{sup +} was found to occur exclusively as the linear species [CuCl{sub 2}]{sup -} in solutions containing KCl with Cu:Cl ratios up to 1:6. In the absence of K{sup +}, there is evidence for higher order coordination of Cu{sup +}, in particular the tetrahedral complex [CuCl{sub 4}]{sup 3-}. The importance of such complexes in natural ore-forming fluids is yet to be determined, but may explain the vapor-phase partitioning of Cu as a Cl complex from a Cl-rich brine.

  20. Partial-ion-yield studies of SOCl2 following x-ray absorption around the S and Cl K edges

    NASA Astrophysics Data System (ADS)

    Bowen, K. P.; Stolte, W. C.; Lago, A. F.; Dávalos, J. Z.; Piancastelli, M. N.; Lindle, D. W.

    2012-11-01

    We present a series of photoabsorption and partial-ion-yield experiments on thionyl chloride, SOCl2, at both the sulfur and chlorine K edges. The photoabsorption results exhibit better resolution than previously published data, leading to alternate spectral assignments for some of the features, particularly in the Rydberg-series region. Based on measured fragmentation patterns, we suggest the LUMO, of a' character, is delocalized over the entire molecular skeleton. Unusual behavior of the S2 + fragment hints at a relatively localized bond rupture (the S-O bond below the S K edge and the S-Cl bonds below the Cl K edge) following excitation to some of the higher lying intermediate states.

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

    NASA Astrophysics Data System (ADS)

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

    2017-01-01

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

  2. EPR studies of 5-bromouracil crystal after irradiation with X rays in the bromine K-edge region.

    PubMed

    Yokoya, Akinari; Takakura, Kaoru; Watanabe, Ritsuko; Akamatsu, Ken; Ito, Takashi

    2004-10-01

    Radicals induced in a single crystal of 5-bromouracil (BrUra) by synchrotron soft X rays in the bromine K-edge region (13.461-13.482 keV) were investigated using the X-band EPR method. The crystal was irradiated at three peak energies of the absorption spectrum at room temperature or at 80 K. A hydrogen abstraction radical derived from N1 of the pyrimidine ring was commonly observed for all of the energies used, though with some variation in quantity. Similar characteristics were also observed in the EPR signal for the off-K-edge low-energy (13.42 keV) and (60)Co gamma rays used for comparison. When irradiated at 80 K, a much larger exposure (roughly 10 times) of soft X rays was needed to obtain the same signal intensity as that observed at room temperature. EPR signals were not detectable with gamma irradiation at liquid nitrogen temperature.

  3. Local environment about O atoms in Pr-Y-Ba-Cu-O films studied by O K-edge XAFS

    SciTech Connect

    Krol, A.; Soo, Y. L.; Huang, S; Ming, Z. H.; Song, L. W.; Kao, Y. H.; Smith, G. C.

    1992-09-01

    The local environment about oxygen atoms in Pr{sub x}Y{sub 1-x}Ba{sub 2}Cu{sub 3}O{sub 7} films obtained by laser ablation has been investigated by means of the x-ray absorption fine structure (XAFS) spectroscopy at the O K-edge. It has been found that the Pr atoms do not substitute for the Cu atoms nor form interstitial defects in the CuO{sub 2} planes and that the presence of Pr dopant does not disturb the local environment of oxygen.

  4. Structure of Alkali Borate Glasses at High Pressure: B and Li K-Edge Inelastic X-Ray Scattering Study

    SciTech Connect

    Lee, Sung Keun; Eng, Peter J.; Mao, Ho-kwang; Meng, Yue; Shu, Jinfu

    2008-06-16

    We report the first in situ boron K-edge inelastic x-ray scattering (IXS) spectra for alkali borate glasses (Li{sub 2}B{sub 4}O{sub 7}) at high pressure up to 30 GPa where pressure-induced coordination transformation from three-coordinated to four-coordinated boron was directly probed. Coordination transformation (reversible upon decompression) begins around 5 GPa and the fraction of four-coordinated boron increases with pressure from about 50% (at 1 atm) to more than 95% (at 30 GPa) with multiple densification mechanisms, evidenced by three distinct pressure ranges for (d{sup [4]}B/dP){sub T}. The lithium K-edge IXS spectrum for Li-borate glasses at 5 GPa shows IXS features similar to that at 1 atm, suggesting that the Li environment does not change much with pressure up to 5 GPa. These results provide improved understanding of the structure of low-z glass at high pressure.

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

    PubMed

    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.

  6. Vulcanization reaction of squalene and S8 powder studied by Sulfur K-edge NEXAFS under liquid phase

    NASA Astrophysics Data System (ADS)

    Yagi, S.; Menjo, Y.; Tsukada, C.; Ogawa, S.; Kutluk, G.; Namatame, H.; Taniguchi, M.

    2015-03-01

    Vulcanized rubber materials are useful in our surroundings. However, detail structure and reaction are not revealed even in present. Since squalene molecule possesses some same properties compared with natural rubber, we have prepared the samples of vulcanized squalene at 140 °C for several hours. To understand the vulcanization reaction,sulfur K-edge NEXAFS measurements have been carried out for the vulcanized squalene under liquid phase with He-path system and fluorescence detection mode. Moreover, we have tried curve fitting analysis of NEXAFS spectra. The results indicate that the squalene has been vulcanized by the S8 molecule at 140 °C and the S8 molecule length is shortened from 8 to 5-6 after the vulcanization reaction.

  7. Chemical Bonding In Amorphous Si Coated-carbon Nanotube As Anodes For Li ion Batteries: A XANES Study

    SciTech Connect

    Zhou, Jigang; Hu, Yongfeng; Li, Xiaolin; Wang, Chong M.; Zuin, Lucia

    2014-03-11

    The chemical bonding nature and its evolution upon electrochemical cycling in amorphous Si coated-carbon nanotube (Si-CNT) anode has been investigated using comprehensive X-ray absorption spectroscopy (XANES) at Si L- and K-edges along with C and O K-edges. The Si nanolayer on CNT is found to be anchored to CNT via Si-O-C bonding. This bond weakens upon electrochemical cycling accompanied with generation of Li2CO3 on the surface of Si-CNT. Those findings are crucial in designing further improved Si-C composite anode for lithium ion battery.

  8. XANES study of Fe-implanted strontium titanate

    NASA Astrophysics Data System (ADS)

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

    2014-03-01

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

  9. XANES study of Fe-implanted strontium titanate

    SciTech Connect

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

    2014-03-31

    Properties of strontium titanate SrTiO{sub 3} (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.

  10. Carbon K-Edge XANES Spectromicroscopy of Natural Graphite

    SciTech Connect

    Brandes,J.; Cody, G.; Rumble, D.; Haberstroh, P.; Wirick, S.; Gelinas, Y.; Morais-Cabral, J.

    2008-01-01

    The black carbon continuum is composed of a series of carbon-rich components derived from combustion or metamorphism and characterized by contrasting environmental behavior and susceptibility to oxidation. In this work, we present a micro-scale density fractionation method that allows isolating the small quantities of soot-like and graphitic material usually found in natural samples. Organic carbon and {delta}{sup 13}C mass balance calculations were used to quantify the relative contributions of the two fractions to thermally-stable organic matter from a series of aquatic sediments. Varying proportions of soot-like and graphitic material were found in these samples, with large variations in {delta}{sup 13}C signatures suggesting important differences in their origin and/or dynamics in the environment.

  11. XANES: Solid state mineral analysis

    NASA Astrophysics Data System (ADS)

    Bell, Peter M.

    Researchers in the field of mineral physics have become aware of new analytical techniques for studying the electronic structure of solids; one such technique is the X ray absorption fine structure (XFAS) method. In this technique the fine structure of the X ray K-edge, for example, can b e employed as a critical probe of t h e intricacies of a crystal structure (P. A. Lee, P. H. Citrin, P. Eisenberger, and B. M. Kincaid, Rev. Mod. Phys., 53, 799, 1981).A similar, related technique, X ray absorption near-edge spectroscopy (XANES), is a relatively unknown method of studying the electronic structure of solids. XANES is new, and due to its complex nature, data on all but very simple solids have not yet been applied rigorously. Among the first XANES results on minerals is the recent study reported by G. Knapp, B. Veal, H. Pan, and T. Klipper (Solid State Comm. 44, 1343, 1982) on perovskites, magnesiowustites, and other 3d oxides in the zircon and spinel groups. The interpretation of these results is still semiquantitative, being based on ground state and basic selection rule considerations. The results show, however, a strong correlation between near-edge spectra and crystal structure.

  12. Determination of the S-ZnO structural interaction in thiol-capped ZnO nanoparticles: a sulfur K-edge XAS study.

    PubMed

    Guglieri, Clara; Aquilanti, Giuliana; Díaz-Moreno, Sofía; Chaboy, J

    2017-02-03

    ZnO nanoparticles capped with thiol molecules display room temperature ferromagnetism which has been associated with the structural details of the interface formed between the organic molecule and the ZnO core. Although the local order around sulfur atoms at the ZnS/ZnO interface has been related to the occurrence of the ferromagnetic like behavior, no direct structural determination has been obtained yet. We report here a detailed x-ray absorption spectroscopy study performed at the sulfur K-edge to determine the local structure around the sulfur atoms in these systems and how it is modified by varying the length of the organic molecule.

  13. Determination of the S-ZnO structural interaction in thiol-capped ZnO nanoparticles: a sulfur K-edge XAS study

    NASA Astrophysics Data System (ADS)

    Guglieri, Clara; Aquilanti, Giuliana; Díaz-Moreno, Sofía; Chaboy, J.

    2017-02-01

    ZnO nanoparticles capped with thiol molecules display room temperature ferromagnetism which has been associated with the structural details of the interface formed between the organic molecule and the ZnO core. Although the local order around sulfur atoms at the ZnS/ZnO interface has been related to the occurrence of the ferromagnetic like behavior, no direct structural determination has been obtained yet. We report here a detailed x-ray absorption spectroscopy study performed at the sulfur K-edge to determine the local structure around the sulfur atoms in these systems and how it is modified by varying the length of the organic molecule.

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

    PubMed

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

    2015-08-19

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

  15. Effect of x-ray energy dispersion in digital subtraction imaging at the iodine K-edge--A Monte Carlo study

    SciTech Connect

    Prino, F.; Ceballos, C.; Cabal, A.; Sarnelli, A.; Gambaccini, M.; Ramello, L.

    2008-01-15

    The effect of the energy dispersion of a quasi-monochromatic x-ray beam on the performance of a dual-energy x-ray imaging system is studied by means of Monte Carlo simulations using MCNPX (Monte Carlo N-Particle eXtended) version 2.6.0. In particular, the case of subtraction imaging at the iodine K-edge, suitable for angiographic imaging application, is investigated. The average energies of the two beams bracketing the iodine K-edge are set to the values of 31.2 and 35.6 keV corresponding to the ones obtained with a compact source based on a conventional x-ray tube and a mosaic crystal monochromator. The energy dispersion of the two beams is varied between 0 and 10 keV of full width at half-maximum (FWHM). The signal and signal-to-noise ratio produced in the simulated images by iodine-filled cavities (simulating patient vessels) drilled in a PMMA phantom are studied as a function of the x-ray energy dispersion. The obtained results show that, for the considered energy separation of 4.4 keV, no dramatic deterioration of the image quality is observed with increasing x-ray energy dispersion up to a FWHM of about 2.35 keV. The case of different beam energies is also investigated by means of fast simulations of the phantom absorption.

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

    NASA Astrophysics Data System (ADS)

    Groopman, Evan Edward

    surrounded by turbostratic graphite within a low-density SN graphite grain. Nanocrystalline cores consisting of randomly-oriented 2-4 nm sheets of graphene and surrounded by concentric shells of graphite have been observed in high-density presolar graphite grains from Asymptotic Giant Branch stars, whose grains are typically microstructurally distinct from SN graphite grains. These vastly different stellar environments briefly formed similar nanocrystalline structures before diverging in the structure of their mantling graphite to be typical of AGB and SN grains. While relatively few correlated NanoSIMS and TEM studies have been performed previously, which this research thesis aims to expand, my collaborators and I also endeavored to add a third correlated technique, STXM/XANES, which had previously not been applied to presolar grains. XANES allows for the investigation of molecular bonds, which we used to help infer physical and chemical properties of stellar ejecta. I investigated the C K-edge and Ti L-edge of molecular bonds in both presolar graphite grains and their TiC subgrains. The presolar graphite grains, while overwhelmingly composed of aromatic C molecules, host a wide variety of minor organic molecules. Considering the large isotopic anomalies in the grains, these minor components are not likely due to contamination. I also investigated the valence state of Ti in Ti-rich subgrains and plan to work towards illuminating the effect that V in solid solution has upon the TiC bonds.

  17. Interaction between Pt nanoparticles and carbon nanotubes An X-ray absorption near edge structures (XANES) study

    NASA Astrophysics Data System (ADS)

    Zhou, Jigang; Zhou, Xingtai; Sun, Xuhui; Li, Ruying; Murphy, Michael; Ding, Zhifeng; Sun, Xueliang; Sham, Tsun-Kong

    2007-04-01

    The interaction between Pt and carbon in Pt nanoparticles (NPs)-carbon nanotubes (CNTs) composite has been investigated with Pt M 3-edge and C K-edge X-ray absorption near edge structures (XANES) recorded in surface-sensitive total electron yield (TEY) and bulk-sensitive fluorescence yield (FLY). XANES in TEY shows that Pt NPs on CNTs have a fcc structure and the white-line features of the XANES strongly support that the crystalline Pt NPs interact with CNTs through synergic bonding involving charge redistribution between C 2p-derived states and Pt 5d bands. Such interaction facilitates the immobilization of Pt NPs on CNT surface without generating oxygenated functional groups.

  18. A Monte Carlo simulation study of an improved K-edge log-subtraction X-ray imaging using a photon counting CdTe detector

    NASA Astrophysics Data System (ADS)

    Lee, Youngjin; Lee, Amy Candy; Kim, Hee-Joung

    2016-09-01

    Recently, significant effort has been spent on the development of photons counting detector (PCD) based on a CdTe for applications in X-ray imaging system. The motivation of developing PCDs is higher image quality. Especially, the K-edge subtraction (KES) imaging technique using a PCD is able to improve image quality and useful for increasing the contrast resolution of a target material by utilizing contrast agent. Based on above-mentioned technique, we presented an idea for an improved K-edge log-subtraction (KELS) imaging technique. The KELS imaging technique based on the PCDs can be realized by using different subtraction energy width of the energy window. In this study, the effects of the KELS imaging technique and subtraction energy width of the energy window was investigated with respect to the contrast, standard deviation, and CNR with a Monte Carlo simulation. We simulated the PCD X-ray imaging system based on a CdTe and polymethylmethacrylate (PMMA) phantom which consists of the various iodine contrast agents. To acquired KELS images, images of the phantom using above and below the iodine contrast agent K-edge absorption energy (33.2 keV) have been acquired at different energy range. According to the results, the contrast and standard deviation were decreased, when subtraction energy width of the energy window is increased. Also, the CNR using a KELS imaging technique is higher than that of the images acquired by using whole energy range. Especially, the maximum differences of CNR between whole energy range and KELS images using a 1, 2, and 3 mm diameter iodine contrast agent were acquired 11.33, 8.73, and 8.29 times, respectively. Additionally, the optimum subtraction energy width of the energy window can be acquired at 5, 4, and 3 keV for the 1, 2, and 3 mm diameter iodine contrast agent, respectively. In conclusion, we successfully established an improved KELS imaging technique and optimized subtraction energy width of the energy window, and based on

  19. K-edge densitometer (KED)

    SciTech Connect

    Sprinkle, J.K.; Hansen, W.J.

    1993-02-11

    In 1979, a K-edge densitometer (KED) was installed by the Safeguards Assay group from Los Alamos National Laboratory in the PNC reprocessing plant at Tokai-mura, Japan. It uses an active nondestructive assay technique, KED, to measure the plutonium concentration of the product solution. The measurement uncertainty of an assay depends on the count time chosen, but can be 0.5% or better. The computer hardware and software were upgraded in 1992. This manual describes the operation of the instrument, with an emphasis on the user interface to the software.

  20. Dispersive x-ray absorption studies at the Fe K-edge on the iron chalcogenide superconductor FeSe under pressure.

    PubMed

    Bendele, M; Marini, C; Joseph, B; Simonelli, L; Dore, P; Pascarelli, S; Chikovani, M; Pomjakushina, E; Conder, K; Saini, N L; Postorino, P

    2013-10-23

    The local structure and the electronic properties of FeSe under hydrostatic pressure were studied by means of dispersive x-ray absorption measurements at the Fe K-edge. The pressure dependence of the x-ray absorption near edge structure features seems to follow the behavior of the superconducting transition temperature Tc. The local structure, that has an important impact on the superconducting properties, appears to fall into two regimes: the pressure dependence of the Fe-Fe bond distance shows a clear change in the compressibility at p ∼ 5 GPa; in contrast, the Fe-Se bond distance decreases continuously with increasing pressure with a lower compressibility than the Fe-Fe bond. The results suggest that the pressure dependent changes in Tc of FeSe are closely related to the changes in local structure.

  1. Light-induced relaxation of photolyzed carbonmonoxy myoglobin: a temperature-dependent x-ray absorption near-edge structure (XANES) study.

    PubMed

    Arcovito, A; Lamb, D C; Nienhaus, G U; Hazemann, J L; Benfatto, M; Della Longa, S

    2005-04-01

    X-ray absorption near-edge structure (XANES) spectra at the Fe K-edge have been measured and compared on solution samples of horse carbonmonoxy-myoglobin and its photoproducts, prepared by two different photolysis protocols: 1), extended illumination at low temperature (15 K) by white light; and 2), slow-cool from 140 to 10 K at a rate of 0.5 K/min while illuminating the sample with a 532-nm continuous-wave laser source. CO recombination has been followed while increasing the temperature at a rate of 1.2 K/min. After extended illumination at 15 K, a single process is observed, corresponding to CO recombination from a completely photolyzed species with CO bound to the primary docking site (formally B-state, in agreement with previous x-ray diffraction studies). The temperature peak for this single process is approximately 50 K. Using slow-cool illumination, data show a two-state recombination curve, the two temperature peaks being roughly assigned to 50 K and 110 K. These results are in good agreement with previous FTIR studies using temperature-derivative spectroscopy. The XANES spectroscopic markers probe structural differences between the photoproduct induced by extended illumination at 15 K and the photoproduct induced by slow-cool illumination. These differences in the XANES data have been interpreted as due to light-induced Fe-heme relaxation that does not involve CO migration from the B-state. A quantitative description of the unrelaxed and relaxed B-states, including the measurements of the Fe-N(p), Fe-N(His), and Fe-CO distances, and the out-of-plane Fe displacement, has been obtained via a procedure (MXAN) recently developed by us. This work shows that XANES, being able to extract both kinetic and structural parameters in a single experiment, is a powerful tool for structural dynamic studies of proteins.

  2. High Pressure XANES studies on Mn dopeHigh Pressure XANES studies on Mn doped Bi2 Te3

    NASA Astrophysics Data System (ADS)

    Light, Brian; Kumar, Ravhi; Baker, Jason; Dharmalingam, Prabhakaran; Park, Changyong; Unlv Team; Hpcat; Carnegie Institute Of Washington Collaboration

    Bi2Te3, Bi2Se3, and Sb2Te3 are narrow band-gap semiconductors have been extensively studied along with their alloys due to their promising technological applications as thermoelectric materials. More recently pressure induced superconductivity and structural transition have been observed in these materials around 7 GPa [1, 2]. Here we have performed high pressure x-ray near edge spectroscopy (XANES) measurements at Bi L-III edge on Mn (0.1) doped Bi2Te3 samples to understand the variation of the Bi valence across the pressure induced superconductivity regime. We have inferred notable changes in the Bi valence at high pressure conditions. The results will be discussed in detail. Work at the University of Nevada Las Vegas (ALC) is funded by U.S. Department of Energy Award DE-SC0001928. Portions of this work were performed at HPCAT (Sector 16), Advanced Photon Source (APS), Argonne National Laboratory. HPCAT is supported by DOE-BES, DOE-NNSA, NSF, and the W.M. Keck Foundation. APS is supported by DOE-BES, under Contract No. DE-AC02-06CH1135.

  3. Sulfur K-Edge XAS Studies of the Effect of DNA Binding on the [Fe 4 S 4 ] Site in EndoIII and MutY

    DOE PAGES

    Ha, Yang; Arnold, Anna R.; Nuñez, Nicole N.; ...

    2017-07-18

    S K-edge X-ray absorption spectroscopy (XAS) was used to study the [Fe4S4] clusters in the DNA repair glycosylases EndoIII and MutY to evaluate the effects of DNA binding and solvation on Fe–S bond covalencies (i.e., the amount of S 3p character mixed into the Fe 3d valence orbitals). Increased covalencies in both iron–thiolate and iron–sulfide bonds would stabilize the oxidized state of the [Fe4S4] clusters. Our results are compared to those on previously studied [Fe4S4] model complexes, ferredoxin (Fd), and to new data on high-potential iron–sulfur protein (HiPIP). A limited decrease in covalency is observed upon removal of solvent watermore » from EndoIII and MutY, opposite to the significant increase observed for Fd, where the [Fe4S4] cluster is solvent exposed. Importantly, in EndoIII and MutY, a large increase in covalency is observed upon DNA binding, which is due to the effect of its negative charge on the iron–sulfur bonds. Furthermore, in EndoIII, this change in covalency can be quantified and makes a significant contribution to the observed decrease in reduction potential found experimentally in DNA repair proteins, enabling their HiPIP-like redox behavior.« less

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

    NASA Astrophysics Data System (ADS)

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

    2009-04-01

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

  5. Extended X- ray absorption fine structure study at the K-edge of copper in mixed ligand complexes having benzimidazole as one of the ligands

    NASA Astrophysics Data System (ADS)

    Hinge, V. K.; Joshi, S. K.; Nitin Nair, N.; Singh Verma, Vikram; Shrivastava, B. D.; Prasad, J.; Srivastava, K.

    2014-09-01

    Extended X-ray absorption fine structure (EXAFS) spectra have been studied at the K-edge of copper in some of its biologically important complexes, viz., [Cu(BzImH)4X2] and [Cu(BzIm)2], where X= Cl, Br, 1/2SO4, ClO4, NO3, and BzIm = Benzimidazolato anion. The spectra have been recorded using a bent crystal 0.4 m Cauchois-type transmission spectrograph. The positions of EXAFS maxima and minima have been used to determine the bond lengths in the complexes with the help of three different methods, namely, Levy's, Lytle's and Lytle, Sayers and Stern's (L.S.S.) methods. The phase uncorrected bond lengths have also been determined from Fourier transforms of the experimental spectra. The results obtained from these methods have been discussed and it has been found that the results obtained by L.S.S. method are comparable with the results obtained by Fourier transformation method and that these two methods give phase uncorrected bond lengths.

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

  7. Measurement of X-ray mass attenuation coefficient of nickel around the K-edge using synchrotron radiation based X-ray absorption study

    NASA Astrophysics Data System (ADS)

    Roy, Bunty Rani; Rajput, Parasmani; Jha, S. N.; Nageswara Rao, A. S.

    2015-09-01

    The work presents the X-ray absorption fine structure (XAFS) technique for measuring the X-ray mass attenuation coefficient of nickel metal foil in the X-ray energy range of 8271.2-8849.4 eV using scanning XAFS beam line (BL-09) at Indus-2 synchrotron radiation source facility, Raja Ramanna Centre for Advanced Technology (RRCAT) at Indore, India. The result represents the X-ray mass attenuation coefficient data for 0.02 mm thick Ni metal foil in the XAFS region of Ni K-edge. However, the results are compared to theoretical values using X-COM. There is a maximum deviation which is found exactly near the K-edge jump and decreases as we move away from the absorption edge. Oscillatory structure appears just above the observed absorption edge i.e., 8348.7 eV and is confined to around 250 eV above the edge.

  8. Optimization of K-edge imaging for vulnerable plaques using gold nanoparticles and energy resolved photon counting detectors: a simulation study.

    PubMed

    Alivov, Yahya; Baturin, Pavlo; Le, Huy Q; Ducote, Justin; Molloi, Sabee

    2014-01-06

    We investigated the effect of different imaging parameters, such as dose, beam energy, energy resolution and the number of energy bins, on the image quality of K-edge spectral computed tomography (CT) of gold nanoparticles (GNP) accumulated in an atherosclerotic plaque. A maximum likelihood technique was employed to estimate the concentration of GNP, which served as a targeted intravenous contrast material intended to detect the degree of the plaque's inflammation. The simulation studies used a single-slice parallel beam CT geometry with an x-ray beam energy ranging between 50 and 140 kVp. The synthetic phantoms included small (3 cm in diameter) cylinder and chest (33 × 24 cm(2)) phantoms, where both phantoms contained tissue, calcium and gold. In the simulation studies, GNP quantification and background (calcium and tissue) suppression tasks were pursued. The x-ray detection sensor was represented by an energy resolved photon counting detector (e.g., CdZnTe) with adjustable energy bins. Both ideal and more realistic (12% full width at half maximum (FWHM) energy resolution) implementations of the photon counting detector were simulated. The simulations were performed for the CdZnTe detector with a pixel pitch of 0.5-1 mm, which corresponds to a performance without significant charge sharing and cross-talk effects. The Rose model was employed to estimate the minimum detectable concentration of GNPs. A figure of merit (FOM) was used to optimize the x-ray beam energy (kVp) to achieve the highest signal-to-noise ratio with respect to the patient dose. As a result, the successful identification of gold and background suppression was demonstrated. The highest FOM was observed at the 125 kVp x-ray beam energy. The minimum detectable GNP concentration was determined to be approximately 1.06 µmol mL(-1) (0.21 mg mL(-1)) for an ideal detector and about 2.5 µmol mL(-1) (0.49 mg mL(-1)) for a more realistic (12% FWHM) detector. The studies show the optimal

  9. Optimization of the K-edge imaging for vulnerable plaques using gold nanoparticles and energy-resolved photon counting detectors: a simulation study

    PubMed Central

    Alivov, Yahya; Baturin, Pavlo; Le, Huy Q.; Ducote, Justin; Molloi, Sabee

    2014-01-01

    We investigated the effect of different imaging parameters such as dose, beam energy, energy resolution, and number of energy bins on image quality of K-edge spectral computed tomography (CT) of gold nanoparticles (GNP) accumulated in an atherosclerotic plaque. Maximum likelihood technique was employed to estimate the concentration of GNP, which served as a targeted intravenous contrast material intended to detect the degree of plaque's inflammation. The simulations studies used a single slice parallel beam CT geometry with an X-ray beam energy ranging between 50 and 140 kVp. The synthetic phantoms included small (3 cm in diameter) cylinder and chest (33x24 cm2) phantom, where both phantoms contained tissue, calcium, and gold. In the simulation studies GNP quantification and background (calcium and tissue) suppression task were pursued. The X-ray detection sensor was represented by an energy resolved photon counting detector (e.g., CdZnTe) with adjustable energy bins. Both ideal and more realistic (12% FWHM energy resolution) implementations of photon counting detector were simulated. The simulations were performed for the CdZnTe detector with pixel pitch of 0.5-1 mm, which corresponds to the performance without significant charge sharing and cross-talk effects. The Rose model was employed to estimate the minimum detectable concentration of GNPs. A figure of merit (FOM) was used to optimize the X-ray beam energy (kVp) to achieve the highest signal-to-noise ratio (SNR) with respect to patient dose. As a result, the successful identification of gold and background suppression was demonstrated. The highest FOM was observed at 125 kVp X-ray beam energy. The minimum detectable GNP concentration was determined to be approximately 1.06 μmol/mL (0.21 mg/mL) for an ideal detector and about 2.5 μmol/mL (0.49 mg/mL) for more realistic (12% FWHM) detector. The studies show the optimal imaging parameters at lowest patient dose using an energy resolved photon counting detector

  10. Charge-transfer and Mott-Hubbard Excitations in FeBo{sub 3} : Fe K-edge resonant Inelastic x-ray scattering study.

    SciTech Connect

    Kim, J.; Shvydko, Y.

    2011-06-06

    Momentum-resolved resonant inelastic x-ray scattering (RIXS) spectroscopy has been carried out successfully at the Fe K-edge for the first time. The RIXS spectra of a FeBO{sub 3} single crystal reveal a wealth of information on {approx} 1-10 eV electronic excitations. The IXS signal resonates when the incident photon energy approaches the pre-edge (1s{sup -}-3d) and the main-edge (1s{sup -}-4p) of the Fe K-edge absorption spectrum. The RIXS spectra measured at the pre-edge and the main-edge show quantitatively different dependences on the incident photon energy, momentum transfer, photon polarization, and temperature. We present a multielectron analysis of the Mott-Hubbard (MH) and charge transfer (CT) excitations, and calculate their energies. Electronic excitations observed in the pre-edge and main-edge RIXS spectra are interpreted as MH and CT excitations, respectively. We propose the electronic structure around the chemical potential in FeBO{sub 3} based on the experimental data.

  11. Experimental versus ab initio x-ray absorption of iron-doped zirconia: Trends in O K -edge spectra as a function of iron doping

    NASA Astrophysics Data System (ADS)

    Douma, D. H.; Ciprian, R.; Lamperti, A.; Lupo, P.; Cianci, E.; Sangalli, D.; Casoli, F.; Nasi, L.; Albertini, F.; Torelli, P.; Debernardi, A.

    2014-11-01

    We present an experimental study of x-ray absorption near edge structure (XANES) at L2 ,3,M2 ,3, and K edges of, respectively, Fe, Zr, and O in iron-doped zirconia (ZrO2:Fe ) for different Fe dopant concentrations x (from x ˜6 % to x ˜25 % at.) and make the comparison with ab initio simulations at the O K -edge. The x-ray magnetic circular dichroism (XMCD) measurements show no evidence of ferromagnetic (FM) order for all the analyzed samples in agreement with our ab initio simulations, which show an antiferromagnetic (AFM) order. We found that substituting Zr with Fe atoms leads to a radical change in the O K -edge XANES spectrum, especially in the pre-edge region where a pre-edge peak appears. This pre-edge peak is ascribed to dipole transitions from O 1 s to O 2 p states that are hybridized with the unoccupied Fe 3 d states. Both theoretical and experimental results reveal that the intensity of the pre-edge peak increases with Fe concentration, suggesting the increase of unoccupied Fe 3 d states. The increase of Fe concentration increases oxygen vacancies as required for charge neutrality and consequently improves AFM ordering. According to our first-principles calculations, the effect of one Fe atom is mostly localized in the first oxygen shell and vanishes as one moves far from it. Thus the increase of the O K -pre-edge peak with increasing Fe concentration is due to the increase of percentage of oxygen atoms that are near neighbors to Fe atoms.

  12. Three-dimensional local structure of photoexcited Cu diimine complex refined by quantitative XANES analysis.

    SciTech Connect

    Smolentsev, G.; Soldatov, A. V.; Chen, L. X.; Chemical Sciences and Engineering Division; Southern Federal Univ.; Northwestern Univ.

    2008-05-28

    The structural details of [Cu(dmp){sub 2}]{sup +} (dmp = 2,9-dimethyl-1,10-phenanthroline) at its metal-to-ligand charge-transfer (MLCT) excited-state in acetonitrile were extracted using quantitative analysis of Cu K-edge X-ray adsorption near edge structure (XANES). The study combines two techniques: fitting experimental XANES spectra with a multidimensional interpolation approximation, and calculating theoretical XANES spectra with molecular potentials beyond the muffin-tin approximation. The results of the study show that the best fit of the experimental XANES data must include a solvent molecule binding to the Cu with a short Cu-N distance of 2.00 {angstrom}. This confirms that the formation of an exciplex is responsible for the excited-state quenching in coordinating solvents, such as acetonitrile. Moreover, the calculations suggest that the formation of this exciplex state is accompanied by significant rocking distortions of the dmp ligands resulting in a 108{sup o} angle between the N(solvent)-Cu bond and the C{sub 2} symmetry axis of the dmp ligand. This combined approach allows us to extract molecular configurations that would otherwise be missed in a conventional qualitative XANES analysis.

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

    NASA Astrophysics Data System (ADS)

    Taylor, Kevin; Byrne, Patrick; Hudson-Edwards, Karen

    2015-04-01

    Chromium is generally common within the urban sediment cascade as a result of abundant industrial and transport-related sources. The risks that Cr-bearing particles pose to ecosystems and humans depend on the solid phase chemical speciation of Cr in the particles. In this study, we use bulk chemical digests, sequential chemical extraction analysis, electron microscopy, electron microprobe and microfocus XANES analysis to describe the solid-phase speciation of Cr in urban particulate matter from both aquatic sediment and road dust sediment (RDS) in Manchester, UK. Cr-bearing grains within RDS are predominantly iron oxide grains, commonly of goethite or haematite mineralogy, but Cr-bearing silicate glass grains are also present. Iron oxide glass grains most likely have sorbed Cr, and derive from the rusting of Cr-steel particles from vehicles. Electron microprobe analysis indicates concentrations of Cr up to 3200 μg/g in these grains, and XANES analysis indicates that Cr(III) is the dominant oxidation state, with some trace amounts of Cr(VI). Cr-bearing grains within aquatic sediments are dominated by alumino-silicate glass grains derived from industrial waste. These grains contain Cr-rich areas with up to 19% Cr2O3 and XANES analysis indicates that Cr is present as Cr(III). The dominance of Cr(III) in these urban particulate grains suggests limited bioavailability or toxicity. However, the presence within two markedly different grain types (iron oxides and silicate glasses) indicates that the long-term geochemical behaviour and environmental risk of RDS and the aquatic sediments studied are likely to be quite different. These findings highlight the importance of understanding sources of metal contaminants in urban environments and the geochemical processes that affect their transfer through the urban sediment cascade and the wider river basin.

  14. S K-edge X-ray absorption studies of tetranuclear iron-sulfur clusters: mu-sulfide bonding and its contribution to electron delocalization.

    PubMed

    Glaser, T; Rose, K; Shadle, S E; Hedman, B; Hodgson, K O; Solomon, E I

    2001-01-24

    X-ray absorption spectroscopy (XAS) at the sulfur ( approximately 2470 eV) and chlorine ( approximately 2822 eV) K-edges has been applied to a series of 4Fe-4S model complexes. These are compared to 2Fe-2S model complexes to obtain insight into the localized ground state in the mixed-valence dimer versus the delocalized ground state in the mixed-valence tetramer. The preedges of hypothetical delocalized mixed-valence dimers [Fe(2)S(2)](+) are estimated using trends from experimental data and density functional calculations, for comparison to the delocalized mixed-valence tetramer [Fe(4)S(4)](2+). The differences between these two mixed-valence sites are due to the change of the sulfide-bridging mode from micro(2) to micro(3). The terminal chloride and thiolate ligands are used as spectator ligands for the electron density of the iron center. From the intensity of the preedge, the covalency of the terminal ligands is found to increase in the tetramer as compared to the dimer. This is associated with a higher effective nuclear charge on the iron in the tetramer (derived from the energies of the preedge). The micro(3)-bridging sulfide in the tetramer has a reduced covalency per bond (39%) as compared to the micro(2)-bridging sulfide in the dimer (51%). A simple perturbation model is used to derive a quadratic dependence of the superexchange coupling constant J on the covalency of the metal ions with the bridging ligands. This relationship is used to estimate the superexchange contribution in the tetramer (J = -156 cm(-)(1)) as compared to the mixed-valence dimer (J = -360 cm(-)(1)). These results, combined with estimates for the double exchange and the vibronic coupling contributions of the dimer sub-site of the tetramer, lead to a delocalized S(t) = (9)/(2) spin ground state for the mixed-valence dimer in the tetramer. Thus, the decrease in the covalency, hence the superexchange pathway associated with changing the bridging mode of the sulfides from micro(2) to micro

  15. ELNES investigations of the oxygen K-edge in spinels.

    PubMed

    Docherty, F T; Craven, A J; McComb, D W; Skakle, J

    2001-02-01

    The results of a systematic study of the oxygen K-edge electron energy-loss spectroscopy (ELNES) from a series of aluminium- and chromium-containing spinels are presented. Extra fine structure in the region up to 10 eV above the edge onset is observed for the chromium-containing compounds and is assigned to transitions to states created by mixing of oxygen 2p and metal 3d orbitals. The experimental data has been simulated using the multiple scattering code, FEFF8. Good agreement was obtained in the case of magnesium aluminate, but relatively poor agreement was obtained in the case of the chromites. The possible fingerprints in the oxygen K-edge ELNES corresponding to a high degree of inversion the spinel structure and to a tetragonal distortion of the cubic structure are discussed.

  16. Mn K-Edge X-ray Absorption Studies of Oxo- and Hydroxo-manganese(IV) Complexes: Experimental and Theoretical Insights into Pre-Edge Properties

    PubMed Central

    2015-01-01

    Mn K-edge X-ray absorption spectroscopy (XAS) was used to gain insights into the geometric and electronic structures of [MnII(Cl)2(Me2EBC)], [MnIV(OH)2(Me2EBC)]2+, and [MnIV(O)(OH)(Me2EBC)]+, which are all supported by the tetradentate, macrocyclic Me2EBC ligand (Me2EBC = 4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane). Analysis of extended X-ray absorption fine structure (EXAFS) data for [MnIV(O)(OH)(Me2EBC)]+ revealed Mn–O scatterers at 1.71 and 1.84 Å and Mn–N scatterers at 2.11 Å, providing the first unambiguous support for the formulation of this species as an oxohydroxomanganese(IV) adduct. EXAFS-determined structural parameters for [MnII(Cl)2(Me2EBC)] and [MnIV(OH)2(Me2EBC)]2+ are consistent with previously reported crystal structures. The Mn pre-edge energies and intensities of these complexes were examined within the context of data for other oxo- and hydroxomanganese(IV) adducts, and time-dependent density functional theory (TD-DFT) computations were used to predict pre-edge properties for all compounds considered. This combined experimental and computational analysis revealed a correlation between the Mn–O(H) distances and pre-edge peak areas of MnIV=O and MnIV–OH complexes, but this trend was strongly modulated by the MnIV coordination geometry. Mn 3d-4p mixing, which primarily accounts for the pre-edge intensities, is not solely a function of the Mn–O(H) bond length; the coordination geometry also has a large effect on the distribution of pre-edge intensity. For tetragonal MnIV=O centers, more than 90% of the pre-edge intensity comes from excitations to the Mn=O σ* MO. Trigonal bipyramidal oxomanganese(IV) centers likewise feature excitations to the Mn=O σ* molecular orbital (MO) but also show intense transitions to 3dx2–y2 and 3dxy MOs because of enhanced 3d-4px,y mixing. This gives rise to a broader pre-edge feature for trigonal MnIV=O adducts. These results underscore the importance of reporting experimental pre-edge areas

  17. Mn K-edge X-ray absorption studies of oxo- and hydroxo-manganese(IV) complexes: experimental and theoretical insights into pre-edge properties.

    PubMed

    Leto, Domenick F; Jackson, Timothy A

    2014-06-16

    Mn K-edge X-ray absorption spectroscopy (XAS) was used to gain insights into the geometric and electronic structures of [Mn(II)(Cl)2(Me2EBC)], [Mn(IV)(OH)2(Me2EBC)](2+), and [Mn(IV)(O)(OH)(Me2EBC)](+), which are all supported by the tetradentate, macrocyclic Me2EBC ligand (Me2EBC = 4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane). Analysis of extended X-ray absorption fine structure (EXAFS) data for [Mn(IV)(O)(OH)(Me2EBC)](+) revealed Mn-O scatterers at 1.71 and 1.84 Å and Mn-N scatterers at 2.11 Å, providing the first unambiguous support for the formulation of this species as an oxohydroxomanganese(IV) adduct. EXAFS-determined structural parameters for [Mn(II)(Cl)2(Me2EBC)] and [Mn(IV)(OH)2(Me2EBC)](2+) are consistent with previously reported crystal structures. The Mn pre-edge energies and intensities of these complexes were examined within the context of data for other oxo- and hydroxomanganese(IV) adducts, and time-dependent density functional theory (TD-DFT) computations were used to predict pre-edge properties for all compounds considered. This combined experimental and computational analysis revealed a correlation between the Mn-O(H) distances and pre-edge peak areas of Mn(IV)═O and Mn(IV)-OH complexes, but this trend was strongly modulated by the Mn(IV) coordination geometry. Mn 3d-4p mixing, which primarily accounts for the pre-edge intensities, is not solely a function of the Mn-O(H) bond length; the coordination geometry also has a large effect on the distribution of pre-edge intensity. For tetragonal Mn(IV)═O centers, more than 90% of the pre-edge intensity comes from excitations to the Mn═O σ* MO. Trigonal bipyramidal oxomanganese(IV) centers likewise feature excitations to the Mn═O σ* molecular orbital (MO) but also show intense transitions to 3dx(2)-y(2) and 3dxy MOs because of enhanced 3d-4px,y mixing. This gives rise to a broader pre-edge feature for trigonal Mn(IV)═O adducts. These results underscore the importance of

  18. Carbon K-edge Spectra of Carbonate Minerals

    SciTech Connect

    Brandes, J.; Wirick, S; Jacobsen, C

    2010-01-01

    Carbon K-edge X-ray spectroscopy has been applied to the study of a wide range of organic samples, from polymers and coals to interstellar dust particles. Identification of carbonaceous materials within these samples is accomplished by the pattern of resonances in the 280-320 eV energy region. Carbonate minerals are often encountered in the study of natural samples, and have been identified by a distinctive resonance at 290.3 eV. Here C K-edge and Ca L-edge spectra from a range of carbonate minerals are presented. Although all carbonates exhibit a sharp 290 eV resonance, both the precise position of this resonance and the positions of other resonances vary among minerals. The relative strengths of the different carbonate resonances also vary with crystal orientation to the linearly polarized X-ray beam. Intriguingly, several carbonate minerals also exhibit a strong 288.6 eV resonance, consistent with the position of a carbonyl resonance rather than carbonate. Calcite and aragonite, although indistinguishable spectrally at the C K-edge, exhibited significantly different spectra at the Ca L-edge. The distinctive spectral fingerprints of carbonates provide an identification tool, allowing for the examination of such processes as carbon sequestration in minerals, Mn substitution in marine calcium carbonates (dolomitization) and serpentinization of basalts.

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

    SciTech Connect

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

    2015-05-07

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

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

    PubMed

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

    2015-05-07

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

  1. 279 - Xanes Studies on UV-Irradiated Interstellar Ice Analogs: A Comparison to STARDUST Samples

    NASA Technical Reports Server (NTRS)

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

    2010-01-01

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

  2. IN SITU STUDIES OF CORROSION USING X-RAY ABSORPTION NEAR SPECTROSCOPY (XANES)

    SciTech Connect

    ISAACS, H.S.; SCHMUKI, P.; VIRTANEN, S.

    2001-03-25

    Applications of x-ray absorption near-edge spectroscopy (XANES) and the design of cells for in situ corrosion studies are reviewed. Passive films studies require very thin metal or alloy layers be used having a thickness of the order of the films formed because of penetration of the x-ray beam into the metal substrate. The depth of penetration in water also limits the thickness of solutions that can be used because of water reduces the x-ray intensity. Solution thickness must also be limited in studies of conversion layer formation studies because the masking of the Cr in solution. Illustrative examples are taken from the anodic behavior of Al-Cr alloys, the growth of passive films on Fe and stainless steels, and the formation of chromate conversion layers on Al.

  3. A XANES and EXAFS Study of Hydration and Ion Pairing in Ambient Aqueous MnBr[subscript 2] Solutions

    SciTech Connect

    Chen, Yongsheng; Fulton, John L.; Partenheimer, Walter

    2008-09-25

    Extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge structure (XANES) spectroscopies were used to probe the first-shell coordination structure of Mn(II) in aqueous MnBr{sub 2} solutions at ambient conditions from very dilute to the near saturation limit. The Mn K-edge EXAFS spectra for 0.05 and 0.2 m solutions showed that there was no Br(-I) in the first shell, and that the Mn(II) was fully hydrated with six water molecules in an octahedral arrangement. In contrast, for 6 m solution, the coordination number of water was reduced to about 5, and an average of about one bromine atom was present in the first shell as a contact ion pair. The 1s {yields} 4p transition at 6545.5 eV confirmed the observation of Mn-Br contact ion pairs at high concentrations and the 1s {yields} 3d transition at 6539.5 eV showed that the first shell coordination symmetry remained octahedral even in the presence of Mn-Br ion pairs.

  4. XAF/XANES studies of plutonium-loaded sodalite/glass composite waste forms.

    SciTech Connect

    Aase, S. B.; Kropf, A. J.; Lewis, M. A.; Reed, D. T.; Richmann, M. K.

    1999-07-14

    A sodalite/glass ceramic waste form has been developed to immobilize highly radioactive nuclear wastes in chloride form, as part of an electrochemical cleanup process. Simulated waste forms have been fabricated which contain plutonium and are representative of the salt from the electrometallurgical process to recover uranium from spent nuclear fuel. X-ray absorption fine structure spectroscopy (XAFS) and x-ray absorption near-edge spectroscopy (XANES) studies were performed to determine the location, oxidation state and form of the plutonium within these waste forms. Plutonium, in the non-fission-element case, was found to segregate as plutonium(IV) oxide with a crystallite size of at least 20 nm. With fission elements present, the crystallite size was about 2 nm. No plutonium was observed within the sodalite or glass in the waste form.

  5. Vanadium K Xanes Studies of EET79001 Impact-Melt Glasses Revisited

    NASA Technical Reports Server (NTRS)

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

    2016-01-01

    Some impact-melt glasses in shergottites are rich in Martian atmospheric noble gases and sulfur suggesting a possible association with regolith-derived secondary mineral assemblages in the shocked samples. Previously, we studied two glasses, # 506 (Lith C in Lith A) and # 507 (Lith C in Lith B) from EET79001 [1,2] and suggested that sulfur initially existed as sulfate in the glass precursor materials and, on shock-melting of the precursors, the sulfate was reduced to sulfides in the shock glasses. To examine the validity of this hypothesis, we used V K microXANES techniques to measure the valence states of vanadium in the Lith C glasses from Lith A and Lith B in EET79001 [3] to complement and com-pare with previous analogous measurements on,78 glass (Lith C in Lith A) [4,5]. We reported the preliminary results in [3]. Vanadium is ideal for addressing the redox issue because it has multiple valence states and is a well-studied element. Vanadium in basalts exists mostly as V(sup 3+), V(sup 4+) and V(sup 5+) in terrestrial samples, mainly as V(sup 3+) with minor V(sup 2+) and minor V(sup 4+) in lunar samples and as roughly equal mixtures of V(sup 3+) and V(sup 4+) in Martian meteorites. In this report, we discuss the application of the V K XANES results to decipher the nature of shock reduction occurring in the silicate glasses during the impact process.

  6. Optical XAFS of ZnO Nanowires at the Zn K-Edge and Related Phenomena

    SciTech Connect

    Heigl, F.; Sun, X.H.J; Lam, S.; Sham, T.K.; Gordon, R.; Brewe, D.; Rosenberg, R.; Shenoy, G.; Yablonskikh, M.; MacNaughton, J.; Moewes, A.

    2008-10-06

    We report x-ray excited optical luminescence (XEOL) from one-dimensional nanostructures of ZnO excited with photon energies across the Zn K-edge. The optical luminescence shows an UV and a green emission band characteristic of near band edge and defect emission, respectively. The optical channels were used in turn to monitor the Zn K-edge XAFS to high k values. The densities of states of oxygen character in the valence band were also studied with x-ray emission spectroscopy (XES). The Zn K-edge decay dynamics was examined with time-resolved x-ray excited optical luminescence.

  7. Investigation of the mica x-ray absorption near-edge structure spectral features at the Al K-edge

    NASA Astrophysics Data System (ADS)

    Wu, Ziyu; Marcelli, A.; Cibin, G.; Mottana, A.; Della Ventura, G.

    2003-10-01

    Near-edge features of Al x-ray absorption near-edge structure (XANES) spectra in aluminosilicate compounds with mixed coordination number are usually assigned to a fourfold coordinated site contribution followed by a sixfold coordinated site contribution that is displaced towards higher energy because of the increasing ligand nucleus potentials, neglecting possible contributions due to bond distance variations and local geometrical distortion. Here we present and discuss the Al K-edge XANES spectra of synthetic micas with either fourfold coordinated Al (phlogopite), or with sixfold coordinated Al (polylithionite), as well as with mixed coordination (preiswerkite). Multiple scattering simulations of XANES spectra demonstrate that octahedral contributions may overlap the tetrahedral ones so that the lower energy structures in mixed coordination compounds may be associated with the octahedral sites. This unexpected behaviour can be described as due to the effect of a significant reduction of the ligand field strength (i.e. large local distortion and Al-O bond distances).

  8. From the S2 molecule to its condensed molecular and polymerized phases: An x-ray absorption study at the S K edge

    NASA Astrophysics Data System (ADS)

    Karnatak, R. C.

    1997-01-01

    X-ray K absorption spectra of sulfur have been studied in its vapour and molecular and polymerized solid phases. The spectrum of the S2 molecule is discussed in the light of the p orbital energies and the s-p orbital energy differences of some second and third period elements. The cyclic and chain forms of sulfur show some similarity in σ* line structure and a marked difference in their near edge structure due to different number of S atoms surrounding a central atom in these allotropic forms. The results are discussed in the light of different vapour to condensed phase deposition processes. The role of planar cis and trans isomers of an intermediate tetrasulfur cluster, crucial for the formation of a chain or cyclic variety, is stressed.

  9. Drug-nanocarrier interaction--tracking the local structure of calcium silicate upon ibuprofen loading with X-ray absorption near edge structure (XANES).

    PubMed

    Guo, Xiaoxuan; Wu, Jin; Yiu, Yun-Mui; Hu, Yongfeng; Zhu, Ying-Jie; Sham, Tsun-Kong

    2013-09-28

    The interaction between drug carrier and drug molecules is fundamental for the study of drug delivery, drug targeting, and drug release. Until now, little has been known about the interaction at the molecular level. X-Ray absorption near edge structure (XANES) spectroscopy is a sensitive tool for identifying this interaction. Herein, we report the use of calcium and silicon K-edge X-ray absorption near edge structure (XANES) spectroscopy to investigate how drug molecules interact with different functional groups in calcium silicate hydrate and anhydrous calcium silicate nanocarriers with different morphologies. Significant changes are observed in the XANES spectra after drug loading; ibuprofen (IBU) loading leads to the ordering of silicates locally and there is loss of hydrates during the IBU loading processes.

  10. Core-to-Rydberg band shift and broadening of hydrogen bonded ammonia clusters studied with nitrogen K-edge excitation spectroscopy

    SciTech Connect

    Yamanaka, Takeshi; Takahashi, Osamu; Tabayashi, Kiyohiko; Namatame, Hirofumi; Taniguchi, Masaki; Tanaka, Kenichiro

    2012-01-07

    Nitrogen 1s (N ls) core-to-Rydberg excitation spectra of hydrogen-bonded clusters of ammonia (AM) have been studied in the small cluster regime of beam conditions with time-of-flight (TOF) fragment-mass spectroscopy. By monitoring partial-ion-yield spectra of cluster-origin products, ''cluster'' specific excitation spectra could be recorded. Comparison of the ''cluster'' band with ''monomer'' band revealed that the first resonance bands of clusters corresponding to N 1s{yields} 3sa{sub 1}/3pe of AM monomer are considerably broadened. The changes of the experimental core-to-Rydberg transitions {Delta}FWHM (N 1s{yields} 3sa{sub 1}/3pe) ={approx}0.20/{approx}0.50 eV compare well with the x ray absorption spectra of the clusters generated by using density functional theory (DFT) calculation. The broadening of the core-to-Rydberg bands in small clusters is interpreted as being primarily due to the splitting of non-equivalent core-hole N 1s states caused by both electrostatic core-hole and hydrogen-bonding (H{sub 3}N{center_dot}{center_dot}{center_dot}H-NH{sub 2}) interactions upon dimerization. Under Cs dimer configuration, core-electron binding energy of H-N (H-donor) is significantly decreased by the intermolecular core-hole interaction and causes notable redshifts of core-excitation energies, whereas that of lone-pair nitrogen (H-acceptor) is slightly increased and results in appreciable blueshifts in the core-excitation bands. The result of the hydrogen-bonding interaction strongly appears in the n-{sigma}* orbital correlation, destabilizing H-N donor Rydberg states in the direction opposite to the core-hole interaction, when excited N atom with H-N donor configuration strongly possesses the Rydberg component of anti-bonding {sigma}* (N-H) character. Contributions of other cyclic H-bonded clusters (AM){sub n} with n{>=} 3 to the spectral changes of the N 1s{yields} 3sa{sub 1}/3pe bands are also examined.

  11. Pressure-Induced Amorphisation in San Carlos Olivine: a XANES Study.

    NASA Astrophysics Data System (ADS)

    Kantor, I.; Torchio, R.

    2014-12-01

    Olivine (Mg,Fe)2SiO4 is one of the main rock-forming minerals of the Earth crust and is often used as a model compound of the whole silicate part of our planet. In equilibrium conditions in the Earth interior olivine undergoes a series of phase transitions and further breaks into ferropericlase and bridgmanite phases at about 25 GPa. All these transitions are responsible for major seismic discontinuities in the Earth. However, if olivine in compressed at temperature that is too low to overcome kinetic barrier, it preserves its original structureuntil ~35 GPa and then gradually becomes amorphous. This transformation have been observed before by mean of X-ray diffraction and Raman spectroscopy, but very little is known about the amorphisation mechanism and the local structure of (Mg,Fe)2SiO4 glass under high pressure. We performed a combined XANES and Raman spectroscopic study of a pressure-induced amorphisation is natural olivine sample (Mg0.92Fe0.08)2SiO4 from San Carlos location. Despite the fact that this natural sample has very low iron concentration and therefore absorption jump was quite small (about 0.06), a decent quality XANES spectra were recorded in transmission mode on the energy-dispercive beamline ID24 at the ESRF usind a diamond anvil cell technique. The amorphisation process can be clearly seen in Raman spectra as a significant broadening and further disappearance of the Raman peaks starting from 35-40 GPa, in perfect agreement with the previous literature data. The most interesting result is a dramatic change of the near-edge structure of X-ray absorption spectra. Since XAS is sensitive to the local structure only, one would not expect significant changes in spectra (apart for some broadening) if only long-range order in the material is lost. Our experimental results indicate that pressure-induced amorphisation in olivine is accomplished with a significant variation of the local atomic structure around Fe cation, probably forming effective

  12. Carbon K-Edge Scanning Transmission X-ray Spectromicroscopy (STXM) of Uranium Binding to Bacterial Cells

    NASA Astrophysics Data System (ADS)

    Gillow, J.; Wirick, S.; Feser, M.; Jacobsen, C.; Francis, A.

    2002-12-01

    The sorption of uranium by bacteria was studied by interrogation of the C K-absorption edge using scanning transmission x-ray spectromicroscopy (STXM). The unique imaging and spectroscopy capability of STXM was used to elucidate the chemical environment of C in the bacterial cell. Washed whole cells and cell wall preparations of bacteria commonly found in soil environments including Pseudomonas fluorescens, Bacillus subtilis, the facultative anaerobe Shewanella putrefaciens and the strict anaerobe Clostridium sp. were exposed to uranyl nitrate at pH 5. After washing to remove potential surface precipitates and non-bonded uranium the cells and walls were dried onto TEM gridx. Standards (uranyl salts and organic complexes), bacterial cells unexposed, and U-exposed cells were analyzed by STXM at 280-310 eV with the C K-edge x-ray absorption near-edge spectroscopy (XANES) examined for evidence of U in the C coordination environment. Principle spectral features of the bacteria included the 285 eV C=C and 288 eV C=O 1s-π * resonances due to the major C function groups that comprise the bacterial cell wall. There was no change in peak position of 1s-π * spectral features for whole cells or cell walls when U was present. This indicates that U does not exert an influence on the electron resonance of C when bonded as carboxylate species at the bacterial cell surface. This finding is supported by the analysis of uranyl citrate and uranyl alanine standards. The extended x-ray absorption fine structure spectroscopy region of the C K-edge of bacterial cells exposed to U shows slight changes in spectral features at >290 eV. Other absorption edges accessible by soft x-ray spectroscopy were examined; U was detected at it's NV (736.2 eV) and NIV (778.3 eV) edges however there was poor resolution of U associated with the bacteria. Analysis at the O K-edge (529 eV) provided evidence for metal-ligand interaction and forms the basis for further study to gain a molecular

  13. Automated analysis of XANES: A feasibility study of Au reference compounds

    NASA Astrophysics Data System (ADS)

    Chang, S.-Y.; Molleta, L. B.; Booth, S. G.; Uehara, A.; Mosselmans, J. F. W.; Ignatyev, K.; Dryfe, R. A. W.; Schroeder, S. L. M.

    2016-05-01

    With the advent of high-throughput and imaging core level spectroscopies (including X-ray absorption spectroscopy, XAS, as well as electron energy loss spectroscopy, EELS), automated data processing, visualisation and analytics will become a necessity. As a first step towards these objectives we examined the possibilities and limitations of a simple automated XANES peak fitting procedure written in MATLAB, for the parametrisation of XANES features, including ionisation potentials as well as the energies and intensities of electronic transitions. Using a series of Au L3-edge XANES reference spectra we show that most of the relevant information can be captured through a small number of rules applied to constrain the fits. Uncertainty in this strategy arises mostly when the ionisation potential (IP) overlaps with weak electronic transitions or features in the continuum beyond the IP, which can result in ambiguity through multiple equally good fits.

  14. In Situ XANES Study of CuO/TiO2 Thin Films During Photodegradation of Methylene Blue

    SciTech Connect

    Hsiung Tungli; Wang, H. Paul; Wei Yuling

    2007-02-02

    Speciation of copper in the CuO/TiO2 thin film (synthesized by the doctor-blade deposition method) during photocatalytic decomposition of methylene blue has been studied by in situ X-ray absorption near-edge structural (XANES) spectroscopy. During the UV/VIS radiation (90 min), in the presence of methylene blue, a decrease of Cu(II) and an increases of Cu(0) and Cu(I) fractions in the CuO/TiO2 thin film are observed by in situ XANES. The r-space Fourier transformation EXAFS (extend X-ray absorption fine structural) spectra also show that the bond distance of Cu-O in the thin film is decreased by 0.03 A during photocatalytic degradation of methylene blue.

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

    NASA Astrophysics Data System (ADS)

    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.

  16. X-ray absorption near edge spectroscopy at the Mn K-edge in highly homogeneous GaMnN diluted magnetic semiconductors

    NASA Astrophysics Data System (ADS)

    Sancho-Juan, O.; Cantarero, A.; Martínez-Criado, G.; Olguín, D.; Garro, N.; Cros, A.; Salomé, M.; Susini, J.; Dhar, S.; Ploog, K.

    We have studied by X-ray absorption spectroscopy the local environment of Mn in highly homogeneous Ga1-xMnxN (0.06 < x < 0.14) thin epilayers grown by molecular beam epitaxy on [0001] SiC substrates. The measurements were performed in fluorescence mode around the Ga and Mn K-edges. In this report, we focus our attention to the X-ray absorption near edge spectroscopy (XANES) results. The comparison of the XANES spectra corresponding to the Ga and Mn edges indicates that Mn is substitutional to Ga in all samples studied. The XANES spectra measured at the Mn absorption edge shows in the near-edge region a double peak and a shoulder below the absorption edge and the main absorption peak after the edge, separated around 15 eV above the pre-edge structure. We have compared the position of the edge with that of MnO (Mn2+) and Mn2O3 (Mn3+). All samples studied present the same Mn oxidation state, 2+. In order to interprete the near-edge structure, we have performed ab initio calculations with a 2 × 2 × 1 supercell (?6% Mn) using the full potential linear augmented plane wave method as implemented in the Wien2k code. The calculations show the appearance of Mn anti-bonding t2g bands, which are responsible for the pre-edge absorption. The shoulder and main absorption peaks are due to transitions from the valence band 1s-states of Mn to the p-contributions of the conduction bands.

  17. X-ray absorption near-edge structure (XANES) spectroscopy study of the interaction of silver ions with Staphylococcus aureus, Listeria monocytogenes, and Escherichia coli.

    PubMed

    Bovenkamp, Gudrun Lisa; Zanzen, Ulrike; Krishna, Katla Sai; Hormes, Josef; Prange, Alexander

    2013-10-01

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

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

    PubMed Central

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

    2013-01-01

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

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

    SciTech Connect

    Robblee, John Henry

    2000-12-01

    states of Mn in the S0 state. The dichroic nature of X-rays from synchrotron radiation and single-crystal Mn complexes have been exploited to selectively probe Mn-ligand bonds using XANES and EXAFS spectroscopy. The results from single-crystal Mn complexes show that dramatic dichroism exists in these complexes, and are suggestive of a promising future for single-crystal studies of PS II.

  20. Total electron yield XANES of zinc-blende MnTe

    NASA Astrophysics Data System (ADS)

    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. Ligand binding processes in hemoglobin. Chemical reactivity of iron studied by XANES spectroscopy.

    PubMed Central

    Pin, S; Valat, P; Cortes, R; Michalowicz, A; Alpert, B

    1985-01-01

    K-absorption edge of coordinated ions exhibits a fine structure (through the use of XANES, or x-ray absorption near edge structures) that reflects the electronic repartition and the chemical reactivity of these ions. Comparative analysis of iron K-absorption-edge shape for hemoglobin derivatives with different ligand affinity suggests strongly that in hemoglobin, iron-forms with high and low affinity are highly improbable. PMID:4092074

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

    NASA Astrophysics Data System (ADS)

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

    2013-04-01

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

  3. Temperature and radiation effects at the fluorine K-edge in LiF

    DOE PAGES

    Schwartz, Craig P.; Ponce, Francisco; Friedrich, Stephan; ...

    2017-05-30

    Here, the fluorine K-edge of LiF is studied both experimentally and theoretically as a function of temperature. Instantaneous thermal fluctuations in atomic positions are shown in molecular dynamics simulations to increase in amplitude from 0.029 to 0.064 nm in the temperature range from 40 to 298 K. This is sufficient to cause instantaneous deviations from local octahedral atomic symmetry in this rock-salt crystal, resulting in altered electronic structure. The lowered symmetry of the lowest core-excited states of fluorine atoms is evident in X-ray absorption spectra at the F K-edge. In addition, sufficient radiation exposure produces a new X-ray absorption peak,more » below the F K-edge of LiF, which is assigned to defects in LiF based on both calculations and comparison to previous experiments.« less

  4. Magnetic circular x-ray dichroisms of Fe-Ni alloys at K edge.

    SciTech Connect

    Freeman, A. J.; Gofron, K. J.; Kimball, C. W.; Lee, P. L.; Montano, P. A.; Rao, F.; Wang, X.

    1997-04-03

    Magnetic Circular X-ray Dichroism (MCXD) studies at K edges of Fe-Ni alloys reveal changes of the MCXD signal with composition and crystal structure. We observe that the signal at the invar composition is of comparable strength as other compositions. Moreover, the edge position is strongly dependent on lattice constant. First principles calculations demonstrate that the shape and strength of the signal strongly depends on the crystal orientation, composition, and lattice constant. We find direct relation between the MCXD signal and the p DOS. We find that the MCXD at K edge probes the magnetism due to itinerant electrons.

  5. Mammographic x-ray unit kilovoltage test tool based on k-edge absorption effect.

    PubMed

    Napolitano, Mary E; Trueblood, Jon H; Hertel, Nolan E; David, George

    2002-09-01

    A simple tool to determine the peak kilovoltage (kVp) of a mammographic x-ray unit has been designed. Tool design is based on comparing the effect of k-edge discontinuity of the attenuation coefficient for a series of element filters. Compatibility with the mammography accreditation phantom (MAP) to obtain a single quality control film is a second design objective. When the attenuation of a series of sequential elements is studied simultaneously, differences in the absorption characteristics due to the k-edge discontinuities are more evident. Specifically, when the incident photon energy is higher than the k-edge energy of a number of the elements and lower than the remainder, an inflection may be seen in the resulting attenuation data. The maximum energy of the incident photon spectra may be determined based on this inflection point for a series of element filters. Monte Carlo photon transport analysis was used to estimate the photon transmission probabilities for each of the sequential k-edge filter elements. The photon transmission corresponds directly to optical density recorded on mammographic x-ray film. To observe the inflection, the element filters chosen must have k-edge energies that span a range greater than the expected range of the end point energies to be determined. For the design, incident x-ray spectra ranging from 25 to 40 kVp were assumed to be from a molybdenum target. Over this range, the k-edge energy changes by approximately 1.5 keV between sequential elements. For this design 21 elements spanning an energy range from 20 to 50 keV were chosen. Optimum filter element thicknesses were calculated to maximize attenuation differences at the k-edge while maintaining optical densities between 0.10 and 3.00. Calculated relative transmission data show that the kVp could be determined to within +/-1 kV. To obtain experimental data, a phantom was constructed containing 21 different elements placed in an acrylic holder. MAP images were used to determine

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

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  8. Electron yield XAFS study of evaporated Co/Pd multilayers with various thickness ratios of Co to Pd sublayers: Simulations of the Co K-edge XAFS and fourier transforms

    SciTech Connect

    Choi, M. . Dept. of Physics); Joo, J.H. . Materials Design Lab.); Kim, S.K.; Kang, J.S.; Lee, Y.P. ); Shin, S.C. ); Heald, S.M.

    1992-01-01

    Electron-yield XAFS measurements using the NSLS were made on e-beam evaporated Co/Pd multilayers with various sublayer thicknesses and different thickness ratios of Co to Pd sublayers. The Co K-edge and the Pd K-edge XAFS data were obtained for the Co/Pd multilayers with sublayer thicknesses of 3[Angstrom]/ 4[Angstrom], 15[Angstrom]/4[Angstrom], 3[Angstrom]/15[Angstrom], 2.1[Angstrom]/13.5[Angstrom], and 2.2[Angstrom]/4.5[Angstrom]. Fourier transforms of Co K XAFS for most samples show a splitting of major peak, and the magnitude ratio of these split peaks varies systematically with the thickness ratio of the Pd sublayer to the Co sublayer, whereas the Fourier transforms of the Pd K XAFS for the same samples do not show a splitting of peaks. As a preliminary analysis, the Co K XAFS and the split peaks in the Fourier transform for the Co/Pd(3[Angstrom]/4[Angstrom]) case were simulated by using the FEFF calculations, and the Co K XAFS and the major peak in the fourier transform for the Co/Pd(15[Angstrom]/4[Angstrom]) case were also simulated consistently.

  9. Electron yield XAFS study of evaporated Co/Pd multilayers with various thickness ratios of Co to Pd sublayers: Simulations of the Co K-edge XAFS and fourier transforms

    SciTech Connect

    Choi, M.; Joo, J.H.; Kim, S.K.; Kang, J.S.; Lee, Y.P.; Shin, S.C.; Heald, S.M.

    1992-11-01

    Electron-yield XAFS measurements using the NSLS were made on e-beam evaporated Co/Pd multilayers with various sublayer thicknesses and different thickness ratios of Co to Pd sublayers. The Co K-edge and the Pd K-edge XAFS data were obtained for the Co/Pd multilayers with sublayer thicknesses of 3{Angstrom}/ 4{Angstrom}, 15{Angstrom}/4{Angstrom}, 3{Angstrom}/15{Angstrom}, 2.1{Angstrom}/13.5{Angstrom}, and 2.2{Angstrom}/4.5{Angstrom}. Fourier transforms of Co K XAFS for most samples show a splitting of major peak, and the magnitude ratio of these split peaks varies systematically with the thickness ratio of the Pd sublayer to the Co sublayer, whereas the Fourier transforms of the Pd K XAFS for the same samples do not show a splitting of peaks. As a preliminary analysis, the Co K XAFS and the split peaks in the Fourier transform for the Co/Pd(3{Angstrom}/4{Angstrom}) case were simulated by using the FEFF calculations, and the Co K XAFS and the major peak in the fourier transform for the Co/Pd(15{Angstrom}/4{Angstrom}) case were also simulated consistently.

  10. Li K-edge X-ray absorption near edge structure spectra for a library of lithium compounds applied in lithium batteries

    NASA Astrophysics Data System (ADS)

    Wang, Dongniu; Zuin, Lucia

    2017-01-01

    Lithium ion batteries (LIB) have achieved great success as energy supply systems in portable devices and in electrical vehicles. Identifying the local chemical structures of elemental lithium in lithium compounds is beneficial for improving understanding of battery components and performance. Herein, a library of Li K-edge X-ray absorption near edge structure (XANES) of lithium compounds relevant to Li-ion batteries is reported. Materials described include lithium metals (anode), Li-containing cathodes, electrolytes and solid electrolyte interphase (SEI). The results illustrate the characteristic spectral features stemming from the various electronic structures and chemical environment of lithium atoms for each and every possible battery component. XANES spectra of Sn based anode after discharging reveal the appearance of Li2CO3 on electrode surface. X-ray damage on sensitive lithium species is also assessed; the results reveal that more attention should be paid to irradiation effects to conduct XANES measurements for battery materials properly.

  11. The efficacy of K-edge filters in diagnostic radiology.

    PubMed

    Williamson, B D; van Doorn, T

    1994-12-01

    The application of K-edge filters in diagnostic radiology has been investigated by many workers for over twenty years. These investigations have analysed the effects of such filters on image quality and radiation dose as well as the practicalities of their application. This paper presents a synopsis of the published works and concludes that K-edge filters do not perceptibly improve image quality and make only limited reductions in patient dose. K-edge filters are also costly to purchase and potentially result in a reduction in the cost effectiveness of x-ray examinations by increasing the x-ray tube loading. Equivalent contrast enhancement and dose reductions can be achieved by the assiduous choice of non-selective filters.

  12. Polychrome glass from Etruscan sites: first non-destructive characterization with synchrotron μ-XRF, μ-XANES and XRPD

    NASA Astrophysics Data System (ADS)

    Arletti, R.; Vezzalini, G.; Quartieri, S.; Ferrari, D.; Merlini, M.; Cotte, M.

    2008-07-01

    This work is devoted to the characterization of a suite of very rare, highly decorated and coloured glass vessels and beads from the VII to the IV century BC. The most serious difficulty in developing this study was that any sampling even micro-sampling was absolutely forbidden. As a consequence, the mineralogical and chemical nature of chromophores and opacifiers present in these Iron Age finds were identified by means of the following synchrotron-based, strictly non-destructive, techniques: micro X-ray fluorescence (μ-XRF), Fe K-edge micro X-ray absorption near edge spectroscopy (μ-XANES) and X-ray powder diffraction (XRPD). The μ-XRF mapping evidenced high levels of Pb and Sb in the yellow decorations and the presence of only Sb in the white and light-blue ones. Purple and black glass show high amounts of Mn and Fe, respectively. The XRPD analyses confirmed the presence of lead and calcium antimonates in yellow, turquoise and white decorations. Fe K-edge μ-XANES spectra were collected in different coloured parts of the finds, thus enabling the mapping of the oxidation state of these elements across the samples. In most of the samples iron is present in the reduced form Fe2+ in the bulk glass of the vessels, and in the oxidized form Fe3+ in the decorations, indicating that these glass artefacts were produced in at least two distinct processing steps under different furnace conditions.

  13. Sulfur poisoning mechanism of steam reforming catalysts: an X-ray absorption near edge structure (XANES) spectroscopic study.

    PubMed

    Chen, Yongsheng; Xie, Chao; Li, Yan; Song, Chunshan; Bolin, Trudy B

    2010-06-07

    The present XANES study aims at elucidating the roles of carbon deposits and metal sulfides in the catalyst deactivation in steam reforming reactions with the presence of sulfur. CeO(2)-Al(2)O(3)-supported Ni and Rh-based catalysts were tested in steam reforming of liquid hydrocarbon fuel containing 350 ppm sulfur for H(2) production at 800 degrees C. The Rh catalyst demonstrated much better sulfur tolerance than the Ni catalyst. XANES revealed that there are various sulfur species (metal sulfide, sulfonate, sulfate and organic sulfide) on the used Ni and Rh catalysts. Metal sulfide and organic sulfide are the dominant sulfur species on the Ni catalyst whereas sulfonate and sulfate predominate on the Rh catalyst. Meanwhile organic sulfide and sulfate are also observed on the support alone. Furthermore, there are more carbon deposits formed in the presence of sulfur on both catalysts. More carboxyl groups occur on the carbon deposits formed on the same catalyst when there is no sulfur in the fuel. From correlation analysis of the amounts of nickel sulfide and carbon deposits along with the relative catalytic activity loss, we conclude that sulfur causes the initial deactivation of the Ni catalyst by metal sulfide formation in the first few hours while build-up of carbon deposits contributes mainly to the subsequent deactivation.

  14. Fragmentation of HCl following excitation at the chlorine K edge

    SciTech Connect

    Hansen, D.L.; Arrasate, M.E.; Cotter, J.P.

    1997-04-01

    A space-focused time-of-flight (TOF) mass spectrometer was used to study the relaxation dynamics of HCl following excitation in the vicinity of the Cl-K edge ({approximately}2.8 keV) using x-rays from B.L. 9.3.1. At the lowest resonant excitation to a {sigma}{sup *} antibonding orbital (1{sigma} {r_arrow} 6{sigma}), a significant fraction of the excited molecules decay by emission of a neutral H atom. While neutral-H emission has been observed for shallow core levels (e.g., Cl 2p in HCl), the authors believe this to be the first observation of neutral-atom emission as a significant decay channel following resonant excitation of a deep core hole. The dissociation of neutral hydrogen atoms raises the issue of how effectively dissociation competes with Auger decay in the relaxation of these deep core levels (i.e., Cl 1s). Graphical evidence is presented to support the dissociation agrument. In addition, trends in fractional ion yields from Photo-Ion Photo-Ion COincidence (PIPICO) spectra suggest the presence of post-collision interaction (PCI). While, electron spectroscopy studies are required to confirm the observation of this effect, the authors believe this to be the first evidence of PCI moderated dissociation in molecules.

  15. On the Structure of the Iron K-Edge

    NASA Technical Reports Server (NTRS)

    Palmeri, P.; Mendoza, C.; Kallman, T. R.; Bautista, M. A.; White, Nicholas E. (Technical Monitor)

    2002-01-01

    It is shown that the commonly held view of a sharp Fe K edge must be modified if the decay pathways of the series of resonances converging to the K thresholds are adequately taken into account. These resonances display damped Lorentzian profiles of nearly constant widths that are smeared to impose continuity across the threshold. By modeling the effects of K damping on opacities, it is found that the broadening of the K edge grows with the ionization level of the plasma, and the appearance at high ionization of a localized absorption feature at 7.2 keV is identified as the Kbeta unresolved transition array.

  16. Unoccupied-band narrowing in Na and its effect on the x-ray-absorption K edge

    SciTech Connect

    Citrin, P.H.; Wertheim, G.K.; Hashizume, T.; Sette, F.; MacDowell, A.A.; Comin, F.

    1988-08-22

    The first Na K-edge absorption measurements are reported. The data reveal a narrowing of the unfilled density of states analogous to that observed in a recent photoemission study of the conduction band and in very good agreement with new band-structure calculations. The narrowing is found to be essential for obtaining compatibility among the K-edge threshold exponent, the L/sub 2,3/-edge exponent, and the singularity index in core-level photoemission.

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

    PubMed

    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.

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

    SciTech Connect

    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

  19. Hg L3 XANES study of mercury methylation in shredded Eichhornia crassipes.

    PubMed

    Rajan, Michael; Darrow, Jeannine; Hua, Michael; Barnett, Brandy; Mendoza, Miguel; Greenfield, Ben K; Andrews, Joy C

    2008-08-01

    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 HgCl2 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 L3 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 expensive than

  20. New methodological approach for the vanadium K-edge X-ray absorption near-edge structure interpretation: application to the speciation of vanadium in oxide phases from steel slag.

    PubMed

    Chaurand, Perrine; Rose, Jérôme; Briois, Valérie; Salome, Murielle; Proux, Olivier; Nassif, Vivian; Olivi, Luca; Susini, Jean; Hazemann, Jean-Louis; Bottero, Jean-Yves

    2007-05-17

    This paper presents a comparison between several methods dedicated to the interpretation of V K-edge X-ray absorption near-edge structure (XANES) features. V K-edge XANES spectra of several V-bearing standard compounds were measured in an effort to evaluate advantages and limits of each method. The standard compounds include natural minerals and synthetic compounds containing vanadium at various oxidation state (from +3 to +5) and in different symmetry (octahedral, tetrahedral, and square pyramidal). Correlations between normalized pre-edge peak area and its centroid position have been identified as the most reliable method for determining quantitative and accurate redox and symmetry information for vanadium. This methodology has been previously developed for the Fe K edge. It is also well adapted for the V K edge and is less influenced by the standard choice than other methods. This methodology was applied on an "environmental sample," i.e., a well-crystallized leached steel slag containing vanadium as traces. Micro-XANES measurements allowed elucidating the microdistribution of vanadium speciation in leached steel slag. The vanadium exhibits an important evolution from the unaltered to the altered phases. Its oxidation state increases from +3 to +5 together with the decrease of its symmetry (from octahedral to tetrahedral).

  1. First approach to studies of sulphur electron DOS in prostate cancer cell lines and tissues studied by XANES

    NASA Astrophysics Data System (ADS)

    Kwiatek, Wojciech M.; Czapla, Joanna; Podgórczyk, Magdalena; Kisiel, Andrzej; Konior, Jerzy; Balerna, Antonella

    2011-10-01

    Urological cancers comprise approximately one-third of all cancers diagnosed in men worldwide and out of these, prostate cancer is the most common one ( WHO World Cancer Report, 2008). Several risk factors such as age, hormone levels, environmental conditions and family history are suspected to play a role in the onset of this disease of otherwise obscure aetiology. It is therefore the medical need that drives multidisciplinary research in this field, carried out by means of various experimental and theoretical techniques. Out of many relevant factors, it is believed that sulphur can take an important part in cancer transformations. We have investigated the prostate cancer cell lines and tissues, along with selected organic and inorganic compounds used as references, by the X-ray absorption fine structure spectroscopy near the sulphur edge energy region. Particularly, the comparison of the experimental results collected during XANES measurements and theoretical calculations of electron density of states with use of the FEFF8 code and LAPW (linearised augmented plane-wave) method has been performed and in this work the first results of our studies are presented.

  2. XANES Speciation of P in Environmental Samples: An Assessment of Filter Media for on-Site Wastewater Treatment

    SciTech Connect

    Eveborn, D.; Gustafsson, J; Hesterberg, D; Hillier, S

    2009-01-01

    X-ray absorption near edge structure (XANES) spectroscopy is a useful technique for characterization of chemical species of phosphorus in complex environmental samples. To develop and evaluate bed filters as sustainable on-site wastewater treatment solutions, our objective in this study was to determine the chemical forms of accumulated phosphorus in a selection of promising filter materials: Filtralite P, Filtra P, Polonite, Absol, blast furnace slag, and wollastonite. Full-scale operational wastewater-treatment systems were sampled and in addition, filter samples collected from laboratory studies provided access to additional media and complementary samples. Phosphorus species were characterized using phosphorus K-edge XANES spectroscopy, complemented by X-ray powder diffraction (XRPD) and attenuated total reflectance Fourier-transform infrared spectroscopy (ATR-FTIR). No systematic differences could be seen in the results between laboratory- and full-scale samples. All six filter media contained significant amounts of crystalline calcium phosphates. Some samples also contained amorphous calcium phosphate (>60% of total P in Absol). In Filtralite P and blast furnace slag, more than 35% of the accumulated phosphorus was associated with Fe or Al. Both the power and shortcomings of XANES analysis for characterizing P species in these filter media are discussed.

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

    NASA Astrophysics Data System (ADS)

    Denoeud, Adrien

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

  4. Spectral CT Using Multiple Balanced K-Edge Filters

    PubMed Central

    Rakvongthai, Yothin; Worstell, William; Fakhri, Georges El; Bian, Junguo; Lorsakul, Auranuch; Ouyang, Jinsong

    2015-01-01

    Our goal is to validate a spectral CT system design that uses a conventional X-ray source with multiple balanced K-edge filters. By performing a simultaneously synthetic reconstruction in multiple energy bins, we obtained a good agreement between measurements and model expectations for a reasonably complex phantom. We performed simulation and data acquisition on a phantom containing multiple rods of different materials using a NeuroLogica CT scanner. Five balanced K-edge filters including Molybdenum, Cerium, Dysprosium, Erbium, and Tungsten were used separately proximal to the X-ray tube. For each sinogram bin, measured filtered vector can be defined as a product of a transmission matrix, which is determined by the filters and is independent of the imaging object, and energy-binned intensity vector. The energy-binned sinograms were then obtained by inverting the transmission matrix followed by a multiplication of the filter measurement vector. For each energy bin defined by two consecutive K-edges, a synthesized energy-binned attenuation image was obtained using filtered back-projection reconstruction. The reconstructed attenuation coefficients for each rod obtained from the experiment was in good agreement with the corresponding simulated results. Furthermore, the reconstructed attenuation coefficients for a given energy bin, agreed with National Institute of Standards and Technology reference values when beam hardening within the energy bin is small. The proposed cost-effective system design using multiple balanced K-edge filters can be used to perform spectral CT imaging at clinically relevant flux rates using conventional detectors and integrating electronics. PMID:25252276

  5. Simulating Cl K-edge X-ray absorption spectroscopy in MCl62- (M= U, Np, Pu) complexes and UOCl5- using time-dependent density functional theory

    SciTech Connect

    Govind, Niranjan; De Jong, Wibe A.

    2014-02-21

    We report simulations of the X-ray absorption near edge structure (XANES) at the Cl K-edge of actinide hexahalides MCl62- (M = U, Np, Pu) and the UOCl5- complex using linear-response time-dependent density functional theory (LR-TDDFT) extended for core excitations. To the best of our knowledge, these are the first calculations of the Cl K-edge spectra of NpCl62- and PuCl62-. In addition, the spectra are simulated with and without the environmental effects of the host crystal as well as ab initio molecular dynamics (AIMD) to capture the dynamical effects due to atomic motion. The calculated spectra are compared with experimental results, where available and the observed trends are discussed.

  6. Structure of assemblies of metal nanowires in mesoporous alumina membranes studied by EXAFS, XANES, X-ray diffraction and SAXS.

    PubMed

    Benfield, Robert E; Grandjean, Didier; Dore, John C; Esfahanian, Hamid; Wu, Zhonghua; Kröll, Michael; Geerkens, Marcus; Schmid, Günter

    2004-01-01

    Mesoporous alumina membranes ("anodic aluminium oxide", or "AAO") are made by anodic oxidation of aluminium metal. These membranes contain hexagonal arrays of parallel non-intersecting cylindrical pores perpendicular to the membrane surface. By varying the anodisation voltage, the pore diameters are controllable within the range 5-250 nm. We have used AAO membranes as templates for the electrochemical deposition of metals within the pores to produce nanowires. These represent assemblies of one-dimensional quantum wires with prospective applications in electronic, optoelectronic and magnetic devices. Detailed characterisation of the structures of these nanowire assemblies on a variety of length scales is essential to understand their physical properties and evaluate their possible applications. We have used EXAFS, XANES, WAXS, high energy X-ray diffraction and SAXS to study their structure and bonding. In this paper we report the results of our studies of four different nanowire systems supported in AAO membranes. These are the ferromagnetic metals iron and cobalt, the superconducting metal tin, and the semiconductor gallium nitride. Iron nanowires in pores of diameter over the range 12 nm-72 nm are structurally very similar to bcc bulk iron. They have a strong preferred orientation within the alumina pores. Their XANES shows significant differences from that of bulk iron, showing that the electronic structure of the iron nanowires depends systematically on their diameter. Cobalt nanowires are composed of a mixture of hcp and fcc phases, but the ratio of the two phases does not depend in a simple way on the pore diameter or preparation conditions. In bulk cobalt, the fcc beta-phase is normally stable only at high temperatures. Strong preferred orientation of the c-axis in the pores was found. Tin nanowires in alumina membranes with pores diameters between 12 nm and 72 nm have a tetragonal beta-structure at ambient temperature and also at 80 K. Magnetic

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

    NASA Astrophysics Data System (ADS)

    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

  8. Anisotropy of chemical bonds in collagen molecules studied by X-ray absorption near-edge structure (XANES) spectroscopy.

    PubMed

    Lam, Raymond S K; Metzler, Rebecca A; Gilbert, Pupa U P A; Beniash, Elia

    2012-03-16

    Collagen type I fibrils are the major building blocks of connective tissues. Collagen fibrils are anisotropic supramolecular structures, and their orientation can be revealed by polarized light microscopy and vibrational microspectroscopy. We hypothesized that the anisotropy of chemical bonds in the collagen molecules, and hence their orientation, might also be detected by X-ray photoemission electron spectromicroscopy (X-PEEM) and X-ray absorption near-edge structure (XANES) spectroscopy, which use linearly polarized synchrotron light. To test this hypothesis, we analyzed sections of rat-tail tendon, composed of parallel arrays of collagen fibrils. The results clearly indicate that XANES-PEEM is sensitive to collagen fibril orientation and, more specifically, to the orientations of carbonyl and amide bonds in collagen molecules. These data suggest that XANES-PEEM is a promising technique for characterizing the chemical composition and structural organization at the nanoscale of collagen-based connective tissues, including tendons, cartilage, and bone.

  9. XANES Measurements of Cr Valence in Olivine and their Applications to Planetary Basalts (Invited)

    NASA Astrophysics Data System (ADS)

    Bell, A. S.; Burger, P.; Le, L.; Shearer, C. K.; Papike, J.; Sutton, S. R.; Newville, M.; Jones, J. H.

    2013-12-01

    The oxidation state and partitioning behavior of trace Cr in terrestrial and planetary basaltic magmas has long been a subject of petrologic inquiry. We have performed a series of experiments designed to examine the relationship between oxygen fugacity and the ratio of divalent to trivalent Cr present in olivine crystals grown from a basaltic liquid. The experimental olivine crystals were grown at fO2 values ranging from IW-1 to IW+3.4. The melt composition used in this work was modeled after the bulk composition of the primitive, basaltic martian meteorite Yamato 980459 (Y-98). Chromium valence in the olivine crystals was measured with X-ray-Absorption-Near-Edge-Spectroscopy (XANES) at the Advanced Photon Source, Argonne National Laboratory. Chromium K-edge XANES data were acquired with the x-ray microprobe of GSECARS beamline 13-ID-E. Beam focusing was accomplished with dynamically-figured Kirkpatrick-Baez focusing mirrors; this configuration yielded a beam focused to a final spot size of ~ 4 μm2. Results from the XANES measurements indicate that the ratio of divalent to trivalent Cr in the olivine is systematically correlated with fO2 in a manner that is consistent with the expected redox systematics for Cr2+- Cr3+ in the melt. In this way, measurements of the Cr2+/Cr3+ in olivine phenocrysts can indirectly reveal information about the Cr valence ratio and fO2 the liquid from which it grew even in the absence of a quenched melt phase. Although the results from the experiments presented in this work specifically apply to the Yamato 98 parental liquid, the concepts and XANES analytical techniques used in this study present a novel, generalized methodology that may be applicable to any olivine-bearing basalt. Furthermore, the XANES based measurements are made on a micron-scale, thus potential changes of the Cr2+/Cr3+ in the melt occurring during crystallization may be recorded in detail.

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

    PubMed

    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.

  11. A XANES study of the structural role of lead in glazes from decorated tiles, XVI to XVIII century manufacture

    NASA Astrophysics Data System (ADS)

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

    2006-05-01

    Aged lead-rich, tin-opacified glazes from polychrome tiles manufactured in the 16th 18th century were studied to ascertain the structural role of lead. Glaze fragments with white, blue, yellow, brown and green colouring were analysed using non-destructive X-ray techniques, both laboratorial X-ray diffraction to identify crystalline components and synchrotron-based. Elemental analyses by synchrotron radiation X-ray fluorescence were performed at the former LURE photon microprobe (line D15A at DCI, in Orsay). The instrumental set-up of beamline BM29 at the ESRF, in Grenoble, was applied to collect X-ray absorption spectra at the Pb L3-edge. Natural minerals and synthetics with known crystal structure were used as model oxy-compounds to configure different formal valences and coordinations of lead ions by oxygen anions, and to interpret the effects upon details of X-ray absorption near-edge spectroscopy (XANES) spectra. Experimental evidence supports the general conclusion that lead is hosted by the glassy matrix, irrespective of the glaze colour. Furthermore, it was concluded that lead ions assume coordinations higher than usual for silica glasses, acting as network modifiers in the silica-lime-alkali glasses of ancient tile glazes.

  12. Investigation of S H bonds in biologically important compounds by sulfur K-edge X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Prange, A.; Dahl, C.; Trüper, H. G.; Behnke, M.; Hahn, J.; Modrow, H.; Hormes, J.

    2002-09-01

    X-ray Absorption Near Edge Structure (XANES) spectroscopy, often provides a direct correlation between observed resonances in the spectrum and molecular bonds in the sample. This can be used as a fingerprint for the presence of a given molecular environment of the absorber atom in a sample. As the white line is found at similar energy positions for S C and S H bonds, this approach is impossible when both types of bond are present simultaneously, as often in biological systems. To develop a criterium for the presence of S H bonds in such samples, reduced glutathione, reduced coenzyme A, cysteine and their corresponding oxidized forms were investigated using sulfur K-edge XANES, revealing a unique feature at 2 475.8 eV in the respective difference spectra. To correlate this structure to S H bonds, H2S and H2S2 were measured, whose difference spectrum also shows a structure at this energy position, whereas it is not present throughout a variety of C S C/C S S C environments. Theoretical investigations suggest its correlation to a Rydberg transition occurring in the case of a S H bond. Using this criterium, the presence of S H bonds is in the purple sulfur bacterium Allochromatium vinosum during oxidation of intracellular accumulated sulfur, is proved, as expected from biological considerations.

  13. A Carbon-XANES Study of IDP Organic Diversity: Evidence for Multiple Sources of Early Solar System Organic Matter

    NASA Astrophysics Data System (ADS)

    Flynn, G. J.; Wirick, S.; Keller, L. P.

    2013-09-01

    We identified >30 distinct C-XANES spectra, differing in positions, relative areas, and widths of C=O and C=C absorptions, in a single ultramicrotome section of a CP IDP, suggesting multiple sources for organic matter in the early solar system.

  14. Solvation structure of Zn(2+) and Cu(2+) ions in acetonitrile: a combined EXAFS and XANES study.

    PubMed

    D'Angelo, Paola; Migliorati, Valentina

    2015-03-12

    The solvation structure of Zn(2+) and Cu(2+) in acetonitrile has been determined by a combined approach using both X-ray absorption near edge structure (XANES) and the extended X-ray absorption fine structure (EXAFS) spectroscopy. For the former cation, an octahedral geometry of the acetonitrile solvate complex has been found with a Zn-N distance of 2.12(1) Å. For the Cu(2+) solvates the EXAFS technique has been found to be not able to provide a conclusive determination of the coordination numbers and polyhedral environment, while the analysis of the XANES spectra unambiguously shows the existence of an axially elongated square pyramidal coordination, ruling out the previously proposed octahedral Jahn-Teller (JT) distorted geometry. The Cu-N distances obtained are 2.00(1) and 2.28(2) Å for the equatorial and axial ligands, respectively, and the EXAFS and XANES techniques find values of the bond distances in good agreement. The XANES technique has proven to be extremely powerful in providing a reliable resolution of solution structure for dynamic ion complexes.

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

    NASA Astrophysics Data System (ADS)

    Morina, Ardian; Zhao, Hongyuan; Mosselmans, J. Fred W.

    2014-04-01

    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.

  16. Micro-XANES Determination of Fe Oxidation State in MORB and its Relationship to Water Content

    NASA Astrophysics Data System (ADS)

    Posner, E. S.; Cottrell, E.; Kelley, K. A.; Ruebush, E.

    2009-12-01

    We report the oxidation state of iron and H2O content for a global suite of mid-ocean ridge basalt (MORB) glasses in order to assess the relationship between water and oxidation state in mantle-derived basalts unaffected by subduction zone processes. Fe3+/ΣFe ratios were determined with Fe K-edge μX-ray absorption near-edge structure spectroscopy (μXANES). Fe oxidation state was previously determined with microcolorimetry and/or direct titration on a subset of the samples. Fe3+/ΣFe ratios determined using the Mossbauer-based μXANES basalt calibration averaged 0.16±0.01 (n=46) and negatively correlate with MgO suggesting the influence of olivine fractionation. The subset of samples also analyzed by colorimetry ranged from 0.04-0.15 compared to 0.13-0.17 with XANES (n=27) and those also analyzed by direct titration ranged from 0.09-0.14 compared to 0.14-0.17 with XANES (n=9). To investigate the cause of these offsets, Fe3+/ΣFe ratios were determined directly by Mossbauer spectroscopy on two hand-picked, aphyric MORB glass separates and were found to be identical within error to values determined by μXANES. Experimentally equilibrated basaltic glasses from the original study of Kress and Carmichael (CMP, 1991), for which Fe3+/ΣFe ratios were determined by microcolorimetry, were also found to yield Fe3+/ΣFe ratios identical to those determined by μXANES within error. Acid digestion of olivine microphenocrysts in natural MORB samples may lead to an offset between XANES, which samples only glass, and wet-chemical determinations of Fe3+/ΣFe ratios. For example, acid digestion of 20% Fo85 olivine is sufficient to cause the observed offset between XANES and direct titration. Total H2O content, determined with FTIR on the same suite of glasses, shows no correlation with iron oxidation state globally (n=46) or locally within a cogenetic suite (n=10, CHEPR, EPR 6°-13° N, 6-9wt% MgO). In contrast, subduction-influenced back-arc basin (BABB) settings show clear

  17. Ni K-Edge XANES Analyses of Residual Ni Catalyst in Carbon Nanofiber Using Full Multiple Scattering Theory

    SciTech Connect

    Ushiro, Mayuko; Ohminami, Kenryo; Nagamatsu, Shin-ichi; Fujikawa, Takashi; Asakura, Kiyotaka

    2007-02-02

    Residual Ni species after Ni removal treatment of carbon nanofibers have been investigated by use of XAFS analyses. Most of the Ni impurities are in Ni monomer which is located on defects in carbon nanofibers. The XAFS analyses combined with the multiple scattering theory give useful information on nano-structures of small amount species. Molecular orbital calculation also support the results from the XAFS analyses.

  18. K-Edge Subtraction Angiography with Synchrotron X-Rays

    SciTech Connect

    Giacomini, John C.

    1996-12-31

    The purpose of this project was to utilize dual energy, monochromatic X-rays produced from synchrotrons radiation in order to obtain noninvasive medical imaging. The application of synchrotrons radiation to medical imaging is based on the principle of iodine dichromography, first described by Bertil Jacobson of the Karolinska Institute in 1953. Medical imaging using synchrotrons radiation and K-edge dichromography was pioneered at Stanford University under the leadership of Dr. Ed Rubenstein, and the late Nobel Laureate in Physics, Dr. Robert Hofstadter. With progressive refinements in hardware, clinical-quality images were obtained of human coronary arteries utilizing peripheral injections of iodinated contrast agent. These images even now are far superior to those being presented by investigators using MRI as an imaging tool for coronary arteries. However, new supplies and instruments in the cardiac catheterization laboratory have served to transform coronary angiography into an outpatient procedure, with relatively little morbidity. We extended the principles learned with coronary angiography to noninvasive imaging of the human bronchial tree. For these images, we utilized xenon as the contrast agent, as it has a K-edge very similar to that of iodine. In this case, there is no true competing diagnostic test, and pulmonary neoplasm is an enormous public health concern. In early experiments, we demonstrated remarkably clear images of the human bronchial tree. These images have been shown internationally; however, funding difficulties primarily with the Department of Energy have not allowed for progression of this promising avenue of research. One potential criticism of the project is that in order to obtain these images, we utilized national laboratories. Some have questioned whether this would lead to a practical imaging modality. However, we have shown that the technology exists to allow for construction of a miniature storage ring, with a superconducting

  19. Portable X-Ray, K-Edge Heavy Metal Detector

    SciTech Connect

    Fricke, V.

    1999-10-25

    The X-Ray, K-Edge Heavy Metal Detection System was designed and built by Ames Laboratory and the Center for Nondestructive Evaluation at Iowa State University. The system uses a C-frame inspection head with an X-ray tube mounted on one side of the frame and an imaging unit and a high purity germanium detector on the other side. the inspection head is portable and can be easily positioned around ventilation ducts and pipes up to 36 inches in diameter. Wide angle and narrow beam X-ray shots are used to identify the type of holdup material and the amount of the contaminant. Precise assay data can be obtained within minutes of the interrogation. A profile of the containerized holdup material and a permanent record of the measurement are immediately available.

  20. XANES spectroscopy as a tool to trace phosphorus transformation during soil genesis and mountain ecosystem development from lake sediments

    NASA Astrophysics Data System (ADS)

    Giguet-Covex, C.; Poulenard, J.; Chalmin, E.; Arnaud, F.; Rivard, C.; Jenny, J.-P.; Dorioz, J.-M.

    2013-10-01

    The aim of this study is to investigate phosphorus (P) species modifications triggered by soil genesis and mountain ecosystem development after glacial retreat using a lake sediment archive (Lake Anterne, North French Alps). Five lake sediment samples, representative of different stages of soil and ecosystem development, were selected for P speciation analyses. Furthermore, a sequence of current soils from the catchment was analyzed to better constrain our interpretations of the lacustrine archive. Synchrotron techniques (X-ray Fluorescence (XRF) mapping and P K-edge X-ray absorption near edge structure (XANES) spectroscopy) were applied to lake sediments, soils, and standards (mineral and organic) to distinguish between different P species. The results show that soil development during the first millennia of the Holocene triggered increased P species diversity. At the onset of the Holocene, P was present as apatite when rocks and leptosols dominated the catchment. Pedogenic processes then led to apatite dissolution and the formation of large amounts of P on metal/clay-organic complexes. P geochemistry during the main step of soil genesis (early leptosols dominated by apatite, low weathered cambisols with P mainly adsorbed on iron oxides, highly weathered podzols with large amounts of P on Al/Fe/clay organic complexes) is thus clearly recorded in lake sediments. P K-edge XANES spectroscopy is particularly relevant as qualitative method to study P species in soils and lake sediments at high spatial resolution. Such resolution is needed to reveal the diversity of small P particles and like this better characterize the P cycle and improve our understanding of ecosystem evolution.

  1. Neutral dissociation of hydrogen following photoexcitation of HCl at the chlorine K edge

    SciTech Connect

    Hansen, D.L.; Arrasate, M.E.; Martin, R.; Vanderford, B.; Lindle, D.W.; Cotter, J.; Neill, P.; Fisher, G.R.; Perera, R.C.; Leung, K.T.; Levin, J.C.; Sellin, I.A.; Simon, M.; Simon, M.; Uehara, Y.; Whitfield, S.B.

    1998-04-01

    Time-of-flight mass spectroscopy was used to study the relaxation dynamics of HCl following photoexcitation in the vicinity of the Cl K edge ({approximately}2.8keV) using monochromatic synchrotron radiation. At the lowest resonant excitation to the 6{sigma}{sup {asterisk}} antibonding orbital, almost half of the excited molecules decay by emission of a neutral H atom, mostly in coincidence with a highly charged Cl{sup n+} ion. The present work demonstrates that neutral-atom emission can be a significant decay channel for excited states with very short lifetimes (1 fs). {copyright} {ital 1998} {ital The American Physical Society}

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

    SciTech Connect

    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.

  3. NanoSIMS, TEM, and XANES studies of a unique presolar supernova graphite grain

    SciTech Connect

    Groopman, Evan; Bernatowicz, Thomas; Zinner, Ernst; Nittler, Larry R.

    2014-07-20

    We report on isotopic and microstructural investigations of a unique presolar supernova (SN) graphite grain, referred to as G6, isolated from the Orgueil CI chondrite. G6 contains complex heterogeneities in its isotopic composition and in its microstructure. Nano-scale secondary ion mass spectrometer isotope images of ultramicrotome sections reveal heterogeneities in its C, N, and O isotopic compositions, including anomalous shell-like structures. Transmission electron microscope studies reveal a nanocrystalline core surrounded by a turbostratic graphite mantle, the first reported nanocrystalline core from a low-density SN graphite grain. Electron diffraction analysis shows that the nanocrystalline core consists of randomly oriented 2-4 nm graphene particles, similar to those in cores of high-density (HD) presolar graphite grains from asymptotic giant branch stars. G6's core also exhibits evidence for planar stacking of these graphene nano-sheets with a domain size up to 4.5 nm, which was unobserved in the nanocrystalline cores of HD graphite grains. We also report on X-ray absorption near-edge structure measurements of G6. The complex isotopic- and micro-structure of G6 provides evidence for mixing and/or granular transport in SN ejecta.

  4. Biotransformations of antidiabetic vanadium prodrugs in mammalian cells and cell culture media: A XANES spectroscopic study

    DOE PAGES

    Levina, Aviva; McLeod, Andrew I.; Pulte, Anna; ...

    2015-04-23

    The antidiabetic activities of vanadium(V) and -(IV) prodrugs are determined by their ability to release active species upon interactions with components of biological media. The first X-ray absorption spectroscopic study of the reactivity of typical vanadium (V) antidiabetics, vanadate ([VVO4]3–, A) and a vanadium(IV) bis(maltolato) complex (B), with mammalian cell cultures has been performed using HepG2 (human hepatoma), A549 (human lung carcinoma), and 3T3-L1 (mouse adipocytes and preadipocytes) cell lines, as well as the corresponding cell culture media. X-ray absorption near-edge structure data were analyzed using empirical correlations with a library of model vanadium(V), -(IV), and -(III) complexes. Both Amore » and B ([V] = 1.0 mM) gradually converged into similar mixtures of predominantly five- and six-coordinate VV species (~75% total V) in a cell culture medium within 24 h at 310 K. Speciation of V in intact HepG2 cells also changed with the incubation time (from ~20% to ~70% VIV of total V), but it was largely independent of the prodrug used (A or B) or of the predominant V oxidation state in the medium. Subcellular fractionation of A549 cells suggested that VV reduction to VIV occurred predominantly in the cytoplasm, while accumulation of VV in the nucleus was likely to have been facilitated by noncovalent bonding to histone proteins. The nuclear VV is likely to modulate the transcription process and to be ultimately related to cell death at high concentrations of V, which may be important in anticancer activities. Mature 3T3-L1 adipocytes (unlike for preadipocytes) showed a higher propensity to form VIV species, despite the prevalence of VV in the medium. Lastly, the distinct V biochemistry in these cells is consistent with their crucial role in insulin-dependent glucose and fat metabolism and may also point to an endogenous role of V in adipocytes.« less

  5. Biotransformations of antidiabetic vanadium prodrugs in mammalian cells and cell culture media: A XANES spectroscopic study

    SciTech Connect

    Levina, Aviva; McLeod, Andrew I.; Pulte, Anna; Aitken, Jade B.; Lay, Peter A.

    2015-04-23

    The antidiabetic activities of vanadium(V) and -(IV) prodrugs are determined by their ability to release active species upon interactions with components of biological media. The first X-ray absorption spectroscopic study of the reactivity of typical vanadium (V) antidiabetics, vanadate ([VVO4]3–, A) and a vanadium(IV) bis(maltolato) complex (B), with mammalian cell cultures has been performed using HepG2 (human hepatoma), A549 (human lung carcinoma), and 3T3-L1 (mouse adipocytes and preadipocytes) cell lines, as well as the corresponding cell culture media. X-ray absorption near-edge structure data were analyzed using empirical correlations with a library of model vanadium(V), -(IV), and -(III) complexes. Both A and B ([V] = 1.0 mM) gradually converged into similar mixtures of predominantly five- and six-coordinate VV species (~75% total V) in a cell culture medium within 24 h at 310 K. Speciation of V in intact HepG2 cells also changed with the incubation time (from ~20% to ~70% VIV of total V), but it was largely independent of the prodrug used (A or B) or of the predominant V oxidation state in the medium. Subcellular fractionation of A549 cells suggested that VV reduction to VIV occurred predominantly in the cytoplasm, while accumulation of VV in the nucleus was likely to have been facilitated by noncovalent bonding to histone proteins. The nuclear VV is likely to modulate the transcription process and to be ultimately related to cell death at high concentrations of V, which may be important in anticancer activities. Mature 3T3-L1 adipocytes (unlike for preadipocytes) showed a higher propensity to form VIV species, despite the prevalence of VV in the medium. Lastly, the distinct V biochemistry in these cells is consistent with their crucial role in insulin-dependent glucose and fat metabolism and may also point to an endogenous role of V in

  6. Biotransformations of Antidiabetic Vanadium Prodrugs in Mammalian Cells and Cell Culture Media: A XANES Spectroscopic Study.

    PubMed

    Levina, Aviva; McLeod, Andrew I; Pulte, Anna; Aitken, Jade B; Lay, Peter A

    2015-07-20

    The antidiabetic activities of vanadium(V) and -(IV) prodrugs are determined by their ability to release active species upon interactions with components of biological media. The first X-ray absorption spectroscopic study of the reactivity of typical vanadium (V) antidiabetics, vanadate ([V(V)O4](3-), A) and a vanadium(IV) bis(maltolato) complex (B), with mammalian cell cultures has been performed using HepG2 (human hepatoma), A549 (human lung carcinoma), and 3T3-L1 (mouse adipocytes and preadipocytes) cell lines, as well as the corresponding cell culture media. X-ray absorption near-edge structure data were analyzed using empirical correlations with a library of model vanadium(V), -(IV), and -(III) complexes. Both A and B ([V] = 1.0 mM) gradually converged into similar mixtures of predominantly five- and six-coordinate V(V) species (∼75% total V) in a cell culture medium within 24 h at 310 K. Speciation of V in intact HepG2 cells also changed with the incubation time (from ∼20% to ∼70% V(IV) of total V), but it was largely independent of the prodrug used (A or B) or of the predominant V oxidation state in the medium. Subcellular fractionation of A549 cells suggested that V(V) reduction to V(IV) occurred predominantly in the cytoplasm, while accumulation of V(V) in the nucleus was likely to have been facilitated by noncovalent bonding to histone proteins. The nuclear V(V) is likely to modulate the transcription process and to be ultimately related to cell death at high concentrations of V, which may be important in anticancer activities. Mature 3T3-L1 adipocytes (unlike for preadipocytes) showed a higher propensity to form V(IV) species, despite the prevalence of V(V) in the medium. The distinct V biochemistry in these cells is consistent with their crucial role in insulin-dependent glucose and fat metabolism and may also point to an endogenous role of V in adipocytes.

  7. Biotransformations of Antidiabetic Vanadium Prodrugs in Mammalian Cells and Cell Culture Media: A XANES Spectroscopic Study

    PubMed Central

    2016-01-01

    The antidiabetic activities of vanadium(V) and -(IV) prodrugs are determined by their ability to release active species upon interactions with components of biological media. The first X-ray absorption spectroscopic study of the reactivity of typical vanadium (V) antidiabetics, vanadate ([VVO4]3–, A) and a vanadium(IV) bis(maltolato) complex (B), with mammalian cell cultures has been performed using HepG2 (human hepatoma), A549 (human lung carcinoma), and 3T3-L1 (mouse adipocytes and preadipocytes) cell lines, as well as the corresponding cell culture media. X-ray absorption near-edge structure data were analyzed using empirical correlations with a library of model vanadium(V), -(IV), and -(III) complexes. Both A and B ([V] = 1.0 mM) gradually converged into similar mixtures of predominantly five- and six-coordinate VV species (∼75% total V) in a cell culture medium within 24 h at 310 K. Speciation of V in intact HepG2 cells also changed with the incubation time (from ∼20% to ∼70% VIV of total V), but it was largely independent of the prodrug used (A or B) or of the predominant V oxidation state in the medium. Subcellular fractionation of A549 cells suggested that VV reduction to VIV occurred predominantly in the cytoplasm, while accumulation of VV in the nucleus was likely to have been facilitated by noncovalent bonding to histone proteins. The nuclear VV is likely to modulate the transcription process and to be ultimately related to cell death at high concentrations of V, which may be important in anticancer activities. Mature 3T3-L1 adipocytes (unlike for preadipocytes) showed a higher propensity to form VIV species, despite the prevalence of VV in the medium. The distinct V biochemistry in these cells is consistent with their crucial role in insulin-dependent glucose and fat metabolism and may also point to an endogenous role of V in adipocytes. PMID:25906315

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

    PubMed

    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.

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

    PubMed Central

    Pongpiachan, Siwatt; Thumanu, Kanjana; Na Pattalung, Warangkana; Hirunyatrakul, Phoosak; Kittikoon, Itthipon; Ho, Kin Fai; Cao, Junji

    2012-01-01

    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. PMID:22988545

  10. Probing the electronic and geometric structure of ferric and ferrous myoglobins in physiological solutions by Fe K-edge absorption spectroscopy.

    PubMed

    Lima, Frederico A; Penfold, Thomas J; van der Veen, Renske M; Reinhard, Marco; Abela, Rafael; Tavernelli, Ivano; Rothlisberger, Ursula; Benfatto, Maurizio; Milne, Christopher J; Chergui, Majed

    2014-01-28

    We present an iron K-edge X-ray absorption study of carboxymyoglobin (MbCO), nitrosylmyoglobin (MbNO), oxymyoglobin (MbO2), cyanomyoglobin (MbCN), aquomet myoglobin (metMb) and unligated myoglobin (deoxyMb) in physiological media. The analysis of the XANES region is performed using the full-multiple scattering formalism, implemented within the MXAN package. This reveals trends within the heme structure, absent from previous crystallographic and X-ray absorption analysis. In particular, the iron-nitrogen bond lengths in the porphyrin ring converge to a common value of about 2 Å, except for deoxyMb whose bigger value is due to the doming of the heme. The trends of the Fe-Nε (His93) bond length is found to be consistent with the effect of ligand binding to the iron, with the exception of MbNO, which is explained in terms of the repulsive trans effect. We derive a high resolution description of the relative geometry of the ligands with respect to the heme and quantify the magnitude of the heme doming in the deoxyMb form. Finally, time-dependent density functional theory is used to simulate the pre-edge spectra and is found to be in good agreement with the experiment. The XAS spectra typically exhibit one pre-edge feature which arises from transitions into the unoccupied dσ and dπ - πligand* orbitals. 1s → dπ transitions contribute weakly for MbO2, metMb and deoxyMb. However, despite this strong Fe d contribution these transitions are found to be dominated by the dipole (1s → 4p) moment due to the low symmetry of the heme environment.

  11. Investigation of X-ray fluorescence computed tomography (XFCT) and K-edge imaging.

    PubMed

    Bazalova, Magdalena; Kuang, Yu; Pratx, Guillem; Xing, Lei

    2012-08-01

    This work provides a comprehensive Monte Carlo study of X-ray fluorescence computed tomography (XFCT) and K-edge imaging system, including the system design, the influence of various imaging components, the sensitivity and resolution under various conditions. We modified the widely used EGSnrc/DOSXYZnrc code to simulate XFCT images of two acrylic phantoms loaded with various concentrations of gold nanoparticles and Cisplatin for a number of XFCT geometries. In particular, reconstructed signal as a function of the width of the detector ring, its angular coverage and energy resolution were studied. We found that XFCT imaging sensitivity of the modeled systems consisting of a conventional X-ray tube and a full 2-cm-wide energy-resolving detector ring was 0.061% and 0.042% for gold nanoparticles and Cisplatin, respectively, for a dose of ∼ 10 cGy. Contrast-to-noise ratio (CNR) of XFCT images of the simulated acrylic phantoms was higher than that of transmission K-edge images for contrast concentrations below 0.4%.

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

    NASA Astrophysics Data System (ADS)

    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

  13. Second Generation Gold Nanobeacons for Robust K-Edge Imaging with Multi-Energy CT

    PubMed Central

    Schirra, Carsten O.; Senpan, Angana; Roessl, Ewald; Thran, Axel; Stacy, Allen J.; Wu, Lina; Proska, Roland; Pan, Dipanjan

    2012-01-01

    Spectral CT is the newest advancement in CT imaging technology, which enhances traditional CT images with the capability to image and quantify certain elements based on their distinctive K-edge energies. K-edge imaging feature recognizes high accumulations of targeted elements and presents them as colorized voxels against the normal grayscale X-ray background offering promise to overcome the relatively low inherent contrast within soft tissue and distinguish the high attenuation of calcium from contrast enhanced targets. Towards this aim, second generation gold nanobeacons (GNB2), which incorporate at least five times more metal than the previous generation was developed. The particles were synthesized as lipid-encapsulated, vascularly constrained (>120 nm) nanoparticle incorporating tiny gold nanoparticles (2–4 nm) within a polysorbate core. The choice of core material dictated to achieve a higher metal loading. The particles were thoroughly characterized by physicochemical techniques. This study reports one of the earlier examples of spectral CT imaging with gold nanoparticles demonstrating the potential for targeted in vitro and in vivo imaging and eliminates calcium interference with CT. The use of statistical image reconstruction shows high SNR may allow dose reduction and/or faster scan times. PMID:23185109

  14. Iron in Silicate Glasses: Systematic Analysis of Pre-Edge And Xanes Features

    SciTech Connect

    Farges, F.; Rossano, S.; Wilke, M.; Lefrere, Y.; Brown, G.E., Jr.; /SLAC, SSRL

    2006-10-27

    A large number (67) of silicate glasses containing variable amounts of iron oxide were studied by high-resolution XANES spectroscopy at the Fe K-edge to determine an accurate method to derive redox information from pre-edge features. The glass compositions studied mimic geological magmas, ranging from basaltic to rhyolitic, dry and hydrous, with variable quench rates. The studied glasses also include more chemically simple calco-sodic silicate glass compositions. The Fe contents range from 30 wt.% to less than 2000 ppm. For most of the series of composition studied, the pre-edge information varies linearly with redox, even under high-resolution conditions. The average coordination of Fe(II) is often similar to its Fe(III) counterpart except in highly polymerized glasses because of the strong influence exerted by the tetrahedral framework on iron's sites. Natural volcanic glasses (from various volcanoes around the world) show similar variations. The average coordination of Fe(II) is often comprised between 4.5 and 5. Fe(III) shows larger variations in coordination (4 to 6, depending on composition). Bond valence models are proposed to predict the average coordination of Fe based on composition. Molecular dynamics simulations (Born-Mayer-Huggins) potentials were carried out on some compositions to estimate the magnitude of disorder effects (both static and thermal) in the XAFS analysis. XANES calculations based on the MD simulations and FEFF 8.2 show large variations in the local structures around Fe. Also, 5-coordinated Fe(III) is found to be an important moiety in ferrisilicate glasses. For Fe(II), discrepancies between glass and melt are larger and are related to its greater structural relaxation at T{sub g}. Also, a strong destructive interference between network formers and modifiers explain the relatively weak intensity of the next-nearest neighbors contributions in the experimental spectra.

  15. Phosphorus Speciation in Manure and Manure-Amended Soils Using XANES Spectroscopy

    SciTech Connect

    Sato,S.; Solomon, D.; Hyland, C.; Ketterings, Q.; Lehmann, J.

    2005-01-01

    Previous studies suggested an increase in the proportion of calcium phosphates (CaP) of the total phosphorus (P) pool in soils with a long-term poultry manure application history versus those with no or limited application histories. To understand and predict long-term P accumulation and release dynamics in these highly amended soils, it is important to understand what specific P species are being formed. We assessed forms of CaP formed in poultry manure and originally acidic soil in response to different lengths of mostly poultry manure applications using P K-edge X-ray absorption near-edge structure (XANES) spectroscopy. Phosphorus K-edge XANES spectra of poultry manure showed no evidences of crystalline P minerals but dominance of soluble CaP species and free and weakly bound phosphates (aqueous phosphate and phosphate adsorbed on soil minerals). Phosphate in an unamended neighboring forest soil (pH 4.3) was mainly associated with iron (Fe) compounds such as strengite and Fe-oxides. Soils with a short-term manure history contained both Fe-associated phosphates and soluble CaP species such as dibasic calcium phosphate (DCP) and amorphous calcium phosphate (ACP). Long-term manure application resulted in a dominance of CaP forms confirming our earlier results obtained with sequential extractions, and a transformation from soluble to more stable CaP species such as {beta}-tricalcium calcium phosphate (TCP). Even after long-term manure application (>25 yr and total P in soil up to 13 307 mg kg{sup -1}), however, none of the manure-amended soils showed the presence of crystalline CaP. With a reduction or elimination of poultry manure application to naturally acidic soils, the pH of the soil is likely to decrease, thereby increasing the solubility of Ca-bonded inorganic P minerals. Maintaining a high pH is therefore an important strategy to minimize P leaching in these soils.

  16. In situ S-K XANES study of polymer electrolyte fuel cells: changes in the chemical states of sulfonic groups depending on humidity.

    PubMed

    Isegawa, Kazuhisa; Nagami, Tetsuo; Jomori, Shinji; Yoshida, Masaaki; Kondoh, Hiroshi

    2016-09-14

    Changes in the chemical states of sulfonic groups of Nafion in polymer electrolyte fuel cells (PEFCs) under gas-flowing conditions were studied using in situ S-K XANES spectroscopy. The applied potential to the electrodes and the humidity of the cell were changed under flowing H2 gas in the anode and He gas in the cathode. While the potential shows no significant effect on the S-K XANES spectra, the humidity is found to induce reversible changes in the spectra. Comparison of the spectral changes with simulations based on the density functional theory calculations indicates that the humidity influences the chemical state of the sulfonic group; under wet conditions the sulfonic group is in the form of a sulfonate ion. By drying treatment the sulfonate ion binds to hydrogen and becomes sulfonic acid. Furthermore, a small fraction of the sulfonic acid irreversibly decomposes to atomic sulfur. The peak energy of the atomic sulfur suggests that the generated atomic sulfur is adsorbed on the Pt catalyst surfaces.

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

    NASA Astrophysics Data System (ADS)

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

    2009-11-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2005-11-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  20. Quantitative analysis of sulfur functional groups in natural organic matter by XANES spectroscopy

    NASA Astrophysics Data System (ADS)

    Manceau, Alain; Nagy, Kathryn L.

    2012-12-01

    Two new approaches to quantify sulfur functionalities in natural organic matter from S K-edge XANES spectroscopy are presented. In the first, the K-edge spectrum is decomposed into Gaussian and two arctangent functions, as in the usual Gaussian curve fitting (GCF) method, but the applicability of the model is improved by a rigorous simulation procedure that constrains the model-fit to converge toward chemically and physically realistic values. Fractions of each type of functionality are obtained after spectral decomposition by correcting Gaussian areas for the change in X-ray absorption cross-section with increasing oxidation state. This correction is made using published calibration curves and a new curve obtained in this study. Calibration-induced errors, inherent to the choice of a particular curve, are typically lower than 5% of total sulfur for oxidized species (e.g., sulfate), may reach 10% for organic reduced sulfur, and may be as high as 30-40% for inorganic reduced sulfur. A generic curve, which reduces the calibration-induced uncertainty by a factor of two on data collected to avoid X-ray overabsorption, is derived. In the second analytical scheme, the K-edge spectrum is partitioned into a weighted sum of component species, as in the usual linear combination fitting (LCF) method, but is fit to an extended database of reference spectra under the constraint of non-negativity in the loadings (Combo fit). The fraction of each sulfur functionality is taken as the sum of all positive fractions of references with similar oxidation state of sulfur. The two proposed methods are applied to eight humic and fulvic acids from the International Humic Substances Society (IHSS). The nature and fractions of sulfur functionalities obtained by the two analytical approaches are consistent with each other. The accuracy of the derived values, expressed as the difference in values of a fraction obtained on the same material by the two independent methods, is on average 4.5 ± 3

  1. Reducing radiation dose by application of optimized low-energy x-ray filters to K-edge imaging with a photon counting detector.

    PubMed

    Choi, Yu-Na; Lee, Seungwan; Kim, Hee-Joung

    2016-01-21

    K-edge imaging with photon counting x-ray detectors (PCXDs) can improve image quality compared with conventional energy integrating detectors. However, low-energy x-ray photons below the K-edge absorption energy of a target material do not contribute to image formation in the K-edge imaging and are likely to be completely absorbed by an object. In this study, we applied x-ray filters to the K-edge imaging with a PCXD based on cadmium zinc telluride for reducing radiation dose induced by low-energy x-ray photons. We used aluminum (Al) filters with different thicknesses as the low-energy x-ray filters and implemented the iodine K-edge imaging with an energy bin of 34-48 keV at the tube voltages of 50, 70 and 90 kVp. The effects of the low-energy x-ray filters on the K-edge imaging were investigated with respect to signal-difference-to-noise ratio (SDNR), entrance surface air kerma (ESAK) and figure of merit (FOM). The highest value of SDNR was observed in the K-edge imaging with a 2 mm Al filter, and the SDNR decreased as a function of the filter thicknesses. Compared to the K-edge imaging with a 2 mm Al filter, the ESAK was reduced by 66%, 48% and 39% in the K-edge imaging with a 12 mm Al filter for 50 kVp, 70 kVp and 90 kVp, respectively. The FOM values, which took into account the ESAK and SDNR, were maximized for 8, 6 to 8 and 4 mm Al filters at 50 kVp, 70 kVp and 90 kVp, respectively. We concluded that the use of an optimal low-energy filter thickness, which was determined by maximizing the FOM, could significantly reduce radiation dose while maintaining image quality in the K-edge imaging with the PCXD.

  2. Using X-ray Microscopy and Hg L3 XANES to study Hg Binding in the Rhizosphere of Spartina Cordgrass

    PubMed Central

    Patty, Cynthia; Barnett, Brandy; Mooney, Bridget; Kahn, Amanda; Levy, Silvio; Liu, Yijin; Pianetta, Piero; Andrews, Joy C

    2009-01-01

    San Francisco Bay has been contaminated historically by mercury from mine tailings as well as contemporary industrial sources. Native Spartina foliosa and non-native S. alterniflora-hybrid cordgrasses are dominant florae within the SF Bay estuary environment. Understanding mercury uptake and transformations in these plants will help to characterize the significance of their roles in mercury biogeochemical cycling in the estuarine environment. Methylated mercury can be biomagnified up the food web, resulting in levels in sport fish up to one million times greater than in surrounding waters and resulting in advisories to limit fish intake. Understanding the uptake and methylation of mercury in the plant rhizosphere can yield insight into ways to manage mercury contamination. The transmission x-ray microscope on beamline 6-2 at the Stanford Synchrotron Radiation Lightsource (SSRL) was used to obtain absorption contrast images and 3D tomography of Spartina foliosa roots that were exposed to 1 ppm Hg (as HgCl2) hydroponically for one week. Absorption contrast images of micron-sized roots from S. foliosa revealed dark particles, and dark channels within the root, due to Hg absorption. 3D tomography showed that the particles are on the root surface, and slices from the tomographic reconstruction revealed that the particles are hollow, consistent with microorganisms with a thin layer of Hg on the surface. Hg L3 XANES of ground-up plant roots and Hg L3 micro-XANES from microprobe analysis of micron-sized roots (60–120 microns in size) revealed three main types of speciation in both Spartina species: Hg-S ligation in a form similar to Hg(II) cysteine, Hg-S bonding as in cinnabar and metacinnabar, and methylmercury-carboxyl bonding in a form similar to methylmercury acetate. These results are interpreted within the context of obtaining a “snapshot” of mercury methylation in progress. PMID:19848152

  3. Using X-ray microscopy and Hg L3 XANES to study Hg binding in the rhizosphere of Spartina cordgrass.

    PubMed

    Patty, Cynthia; Barnett, Brandy; Mooney, Bridget; Kahn, Amanda; Levy, Silvio; Liu, Yijin; Pianetta, Piero; Andrews, Joy C

    2009-10-01

    San Francisco Bay has been contaminated historically by mercury from mine tailings as well as contemporary industrial sources. Native Spartina foliosa and non-native S. alterniflora-hybrid cordgrasses are dominant florae within the SF Bay estuary environment. Understanding mercury uptake and transformations in these plants will help to characterize the significance of their roles in mercury biogeochemical cycling in the estuarine environment. Methylated mercury can be biomagnified up the food web, resulting in levels in sport fish up to 1 million times greater than in surrounding waters and resulting in advisories to limit fish intake. Understanding the uptake and methylation of mercury in the plant rhizosphere can yield insight into ways to manage mercury contamination. The transmission X-ray microscope on beamline 6-2 at the Stanford Synchrotron Radiation Lightsource (SSRL) was used to obtain absorption contrast images and 3D tomography of Spartina foliosa roots that were exposed to 1 ppm Hg (as HgCl2) hydroponically for 1 week. Absorption contrast images of micrometer-sized roots from S. foliosa revealed dark particles, and dark channels within the root, due to Hg absorption. 3D tomography showed that the particles are on the root surface, and slices from the tomographic reconstruction revealed that the particles are hollow, consistent with microorganisms with a thin layer of Hg on the surface. Hg L3 XANES of ground-up plant roots and Hg L3 micro-XANES from microprobe analysis of micrometer-sized roots (60-120 microm in size) revealed three main types of speciation in both Spartina species: Hg-S ligation in a form similar to Hg(II) cysteine, Hg-S bonding as in cinnabar and metacinnabar, and methylmercury-carboxyl bonding in a form similar to methylmercury acetate. These results are interpreted within the context of obtaining a "snapshot" of mercury methylation in progress.

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

    DOE PAGES

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

    2017-01-26

    Here, the local structure about Fe(II) and Fe(III) in silicate melts was investigated in-situ using iron K-edge X-ray absorption near-edge structure (XANES) spectroscopy. An aerodynamic levitation and laser heating system was used to allow access to high temperatures without contamination, and was combined with a chamber and gas mixing system to allow the iron oxidation state, Fe3+/ΣFe, to be varied by systematic control of the atmospheric oxygen fugacity. Eleven alkali-free, mostly iron-rich and depolymerized base compositions were chosen for the experiments, including pure oxide FeO, olivines (Fe,Mg)2SiO4, pyroxenes (Fe,Mg)SiO3, calcic FeO-CaSiO3, and a calcium aluminosilicate composition, where total iron contentmore » is denoted by FeO for convenience. Melt temperatures varied between 1410 and 2160 K and oxygen fugacities between FMQ – 2.3(3) to FMQ + 9.1(3) log units (uncertainties in parentheses) relative to the fayalite-magnetite-β-quartz (FMQ) buffer.« less

  5. Polarized experimental and theoretical K-edge x-ray absorption studies of SO/sub 4//sup 2-/, ClO/sub 3//sup -/, S/sub 2/O/sub 3//sup 2-/, and S/sub 2/O/sub 6//sup 2-/

    SciTech Connect

    Tyson, T.A.; Roe, A.L.; Frank, P.; Hodgson, K.O.; Hedman, B.

    1989-04-01

    The first studies of the polarized sulfur and chlorine x-ray K-edge absorption spectra of the oxyanions SO/sub 4//sup 2-/ (sulfate), ClO/sub 3//sup -/ (chlorate), S/sub 2/O/sub 3//sup 2-/ (thiosulfate), and S/sub 2/O/sub 6//sup 2-/ (dithionate) are presented. To provide a basis for the interpretation of the experimental measurements, extended continuum multiple-scattering X..cap alpha.. computations were carried out. This approach enabled us to identify features in the absorption spectra both by symmetry and final-state type (final bound states or final continuum states). For the thiosulfate anion (which has two nonequivalent sulfur atoms) it proved possible to determine which sulfur atom is responsible for each of a series of well-resolved features in the polarized spectra. In addition, generalizing from the case of the chlorate anion, molecules in which the absorbing atom is not completely surrounded by ligands (''open clusters'') may have important contributions from the second shell of neighbors manifested as features in the continuum region of the spectrum.

  6. Small copper clusters studied by x-ray absorption near-edge structure

    NASA Astrophysics Data System (ADS)

    Oyanagi, H.; Sun, Z. H.; Jiang, Y.; Uehara, M.; Nakamura, H.; Yamashita, K.; Orimoto, Y.; Zhang, L.; Lee, C.; Fukano, A.; Maeda, H.

    2012-04-01

    The local structure of copper nanoparticles grown in organic solution by reducing Cu(II) hexafluoroacetylacetonate [Cu(hfac)2] was studied as-grown by the Cu K-edge x-ray absorption near-edge structure (XANES). Comparison of the experimental XANES spectra with reference materials indicated small copper clusters are formed by ligand-exchange with oleylamine and subsequent reducing by diphenylsilane. The multiple-scattering (MS) calculation for various model clusters consisting of 13-135 atoms suggests that small (13-19 atom) Cu clusters are stabilized without a large deformation.

  7. NO binding kinetics in myoglobin investigated by picosecond Fe K-edge absorption spectroscopy

    PubMed Central

    Silatani, Mahsa; Lima, Frederico A.; Penfold, Thomas J.; Rittmann, Jochen; Reinhard, Marco E.; Rittmann-Frank, Hannelore M.; Borca, Camelia; Grolimund, Daniel; Milne, Christopher J.; Chergui, Majed

    2015-01-01

    Diatomic ligands in hemoproteins and the way they bind to the active center are central to the protein’s function. Using picosecond Fe K-edge X-ray absorption spectroscopy, we probe the NO-heme recombination kinetics with direct sensitivity to the Fe-NO binding after 532-nm photoexcitation of nitrosylmyoglobin (MbNO) in physiological solutions. The transients at 70 and 300 ps are identical, but they deviate from the difference between the static spectra of deoxymyoglobin and MbNO, showing the formation of an intermediate species. We propose the latter to be a six-coordinated domed species that is populated on a timescale of ∼200 ps by recombination with NO ligands. This work shows the feasibility of ultrafast pump–probe X-ray spectroscopic studies of proteins in physiological media, delivering insight into the electronic and geometric structure of the active center. PMID:26438842

  8. Beyond carbon K-edge harmonic emission using a spatial and temporal synthesized laser field.

    PubMed

    Pérez-Hernández, J A; Ciappina, M F; Lewenstein, M; Roso, L; Zaïr, A

    2013-02-01

    We present numerical simulations of high-order harmonic generation in helium using a temporally synthesized and spatially nonhomogeneous strong laser field. The combination of temporal and spatial laser field synthesis results in a dramatic cutoff extension far beyond the usual semiclassical limit. Our predictions are based on the convergence of three complementary approaches: resolution of the three dimensional time dependent Schrödinger equation, time-frequency analysis of the resulting dipole moment, and classical trajectory extraction. A laser field synthesized both spatially and temporally has been proven capable of generating coherent extreme ultraviolet photons beyond the carbon K edge, an energy region of high interest as it can be used to initiate inner-shell dynamics and study time-resolved intramolecular attosecond spectroscopy.

  9. A balanced filterless K-edge energy window multilayer detector for dual energy computed tomography

    NASA Astrophysics Data System (ADS)

    Allec, Nicholas; Karim, Karim S.

    2010-04-01

    Ross (or balanced) filter-based systems have been studied extensively in the past, however they have only recently been studied for medical applications such as computed tomography and contrast-enhanced mammography. Balanced filters are filters composed of different materials which have thicknesses designed to match the attenuation for all radiation energies except those within a certain energy window (between the K-edges of the filter materials). Images obtained using different filters to attenuate the incident x-rays can be subtracted to obtain an image which contains information solely within the energy window. The disadvantage of this image acquisition method is the requirement of a separate exposure for each filter. This can lead to motion artifacts in the resulting image for example due to cardiac, respiratory, or patient movement. In this paper we investigate a filterless, multilayer detector design using the general concept of balanced filters. In the proposed detector, energy discrimination is achieved using stacked layers of different conversion materials. Similar to how the thicknesses of balanced filters are chosen, the thicknesses of the conversion layers are designed to match the attenuation of x-rays except between the K-edges of the conversion materials. Motion artifacts are suppressed in the final image due to the simultaneous acquisition of images on all layers during a single exposure. The proposed multilayer design can be used for a number of applications depending on the energy range of interest. To study the proposed design, we consider dual energy computed tomography (CT) using a gadolinium-based contrast agent.

  10. Picosecond sulfur K-edge X-ray absorption spectroscopy with applications to excited state proton transfer.

    PubMed

    Van Kuiken, Benjamin E; Ross, Matthew R; Strader, Matthew L; Cordones, Amy A; Cho, Hana; Lee, Jae Hyuk; Schoenlein, Robert W; Khalil, Munira

    2017-07-01

    Picosecond X-ray absorption (XA) spectroscopy at the S K-edge (∼2.4 keV) is demonstrated and used to monitor excited state dynamics in a small organosulfur molecule (2-Thiopyridone, 2TP) following optical excitation. Multiple studies have reported that the thione (2TP) is converted into the thiol (2-Mercaptopyridine, 2MP) following photoexcitation. However, the timescale and photochemical pathway of this reaction remain uncertain. In this work, time-resolved XA spectroscopy at the S K-edge is used to monitor the formation and decay of two transient species following 400 nm excitation of 2TP dissolved in acetonitrile. The first transient species forms within the instrument response time (70 ps) and decays within 6 ns. The second transient species forms on a timescale of ∼400 ps and decays on a 15 ns timescale. Time-dependent density functional theory is used to identify the first and second transient species as the lowest-lying triplet states of 2TP and 2MP, respectively. This study demonstrates transient S K-edge XA spectroscopy as a sensitive and viable probe of time-evolving charge dynamics near sulfur sites in small molecules with future applications towards studying complex biological and material systems.

  11. Picosecond sulfur K-edge X-ray absorption spectroscopy with applications to excited state proton transfer

    PubMed Central

    Van Kuiken, Benjamin E.; Ross, Matthew R.; Strader, Matthew L.; Cordones, Amy A.; Cho, Hana; Lee, Jae Hyuk; Schoenlein, Robert W.; Khalil, Munira

    2017-01-01

    Picosecond X-ray absorption (XA) spectroscopy at the S K-edge (∼2.4 keV) is demonstrated and used to monitor excited state dynamics in a small organosulfur molecule (2-Thiopyridone, 2TP) following optical excitation. Multiple studies have reported that the thione (2TP) is converted into the thiol (2-Mercaptopyridine, 2MP) following photoexcitation. However, the timescale and photochemical pathway of this reaction remain uncertain. In this work, time-resolved XA spectroscopy at the S K-edge is used to monitor the formation and decay of two transient species following 400 nm excitation of 2TP dissolved in acetonitrile. The first transient species forms within the instrument response time (70 ps) and decays within 6 ns. The second transient species forms on a timescale of ∼400 ps and decays on a 15 ns timescale. Time-dependent density functional theory is used to identify the first and second transient species as the lowest-lying triplet states of 2TP and 2MP, respectively. This study demonstrates transient S K-edge XA spectroscopy as a sensitive and viable probe of time-evolving charge dynamics near sulfur sites in small molecules with future applications towards studying complex biological and material systems. PMID:28529962

  12. Picosecond sulfur K-edge X-ray absorption spectroscopy with applications to excited state proton transfer

    DOE PAGES

    Van Kuiken, Benjamin E.; Ross, Matthew R.; Strader, Matthew L.; ...

    2017-05-08

    Picosecond X-ray absorption (XA) spectroscopy at the S K-edge (~2.4 keV) is demonstrated and used to monitor excited state dynamics in a small organosulfur molecule (2-Thiopyridone, 2TP) following optical excitation. Multiple studies have reported that the thione (2TP) is converted into the thiol (2-Mercaptopyridine, 2MP) following photoexcitation. However, the timescale and photochemical pathway of this reaction remain uncertain. In this work, time-resolved XA spectroscopy at the S K-edge is used to monitor the formation and decay of two transient species following 400nm excitation of 2TP dissolved in acetonitrile. The first transient species forms within the instrument response time (70 ps)more » and decays within 6 ns. The second transient species forms on a timescale of ~400 ps and decays on a 15 ns timescale. Time-dependent density functional theory is used to identify the first and second transient species as the lowestlying triplet states of 2TP and 2MP, respectively. This study demonstrates transient S K-edge XA spectroscopy as a sensitive and viable probe of time-evolving charge dynamics near sulfur sites in small molecules with future applications towards studying complex biological and material systems.« less

  13. Progressive Oxidation of Pyrite in Five Bituminous Coal Samples: An As XANES and 57Fe Mossbauer Spectroscopic Study

    SciTech Connect

    Kolker,A.; Huggins, F.

    2007-01-01

    Naturally occurring pyrite commonly contains minor substituted metals and metalloids (As, Se, Hg, Cu, Ni, etc.) that can be released to the environment as a result of its weathering. Arsenic, often the most abundant minor constituent in pyrite, is a sensitive monitor of progressive pyrite oxidation in coal. To test the effect of pyrite composition and environmental parameters on the rate and extent of pyrite oxidation in coal, splits of five bituminous coal samples having differing amounts of pyrite and extents of As substitution in the pyrite, were exposed to a range of simulated weathering conditions over a period 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 O{sub 2} atmosphere; (3) room atmosphere (relative humidity {approx}20-60%); and (4) room atmosphere with samples wetted periodically with double-distilled water. Sample splits were removed after one month, nine months, and 17 months to monitor the extent of As and Fe oxidation using As X-ray absorption near-edge structure (XANES) spectroscopy and {sup 57}Fe Mossbauer spectroscopy, respectively. Arsenic XANES spectroscopy shows progressive oxidation of pyritic As to arsenate, with wetted samples showing the most rapid oxidation. {sup 57}Fe Mossbauer spectroscopy also shows a much greater proportion of Fe{sup 3+} forms (jarosite, Fe{sup 3+} sulfate, FeOOH) for samples stored under wet conditions, but much less

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

    USGS Publications Warehouse

    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

  15. Killing of Bacillus Megaterium Spores by X-Rays at the Phosphorus K-Edge

    NASA Technical Reports Server (NTRS)

    Richmond, Robert C.; Frigo, Sean P.; Ehret, Charles F.; Rose, M. Franklin (Technical Monitor)

    2001-01-01

    This study continues a progression of experiments on the radiation-induced killing of bacterial spores that began at the Argonne National Laboratory in 1957. A series of aliquots of Bacillus megaterium spores were prepared onto polycarbonate filters and irradiated with photons of 2159 eV compared to 2140 eV energy on the 2-IDB beamline at the Advanced Photon Source. Flux density was approximately 10 photons/sec/mm . The phosphorous K-edge absorption spectrum in these spores was determined to peak at 2159 eV, wheras 2140 eV was determined to be outside that absorption spectrum. Spores on filters were irradiated at ambient conditions, and were either immediately plated for colony formation after irradiation, or were held for postirradiation exposure to oxygen prior to plating. Slopes of survival curves from the four conditions of irradiation, i.e., two photon energies each comparing immediate plating vs postirradiation holding, were used for quantitative determination of differences in rates of spore killing over a range of radiation doses. It was found that spores irradiated at the phosphorus K-edge were killed 20% more efficiently than when irradiated with 2140eV photons, and this was true for both immediate plating and postirradiation holding in air. Postirradiation holding in air increased killing efficiency by about 12% for both photon energies compared to plating immediately after irradiation. The increase of killing efficiency with postirradiation holding is less than expected from earlier experiments using relatively low-flux X-rays, and raises the possibility of dose-mitigation by radical-radical recombination in the case of high-flux X-rays from the synchrotron.

  16. Killing of Bacillus Megaterium Spores by X-rays at the Phosphorus K-edge

    NASA Technical Reports Server (NTRS)

    Richmond, Robert C.; Frigo, Sean P.; Ehret, Charles F.; Rose, M. Franklin (Technical Monitor)

    2001-01-01

    This study continues a progression of experiments on the radiation-induced killing of bacterial spores that began at the Argonne National Laboratory in 1957. A series of aliquots of Bacillus megaterium spores were prepared onto polycarbonate filters and irradiated with photons of 2159 eV compared to 2140 eV energy on the 2-IDB beamline at the Advanced Photon Source. Flux density was approximately 10(exp 18) photons/sec/sq mm. The phosphorous K-edge absorption spectrum in these spores was determined to peak at 2159 eV, wheras 2140 eV was determined to be outside that absorption spectrum. Spores on filters were irradiated at ambient conditions, and were either immediately plated for colony formation after irradiation, or were held for postirradiation exposure to oxygen prior to plating. Slopes of survival curves from the four conditions of irradiation, i.e., two photon energies each comparing immediate plating vs postirradiation holding, were used for quantitative determination of differences in rates of spore killing over a range of radiation doses. It was found that spores irradiated at the phosphorus K-edge were killed 20% more efficiently than when irradiated with 2140 eV photons, and this was true for both immediate plating and postirradiation holding in air. Postirradiation holding in air increased killing efficiency by about 12% for both photon energies compared to plating immediately after irradiation. The increase of killing efficiency with postirradiation holding is less than expected from earlier experiments using relatively low-flux X-rays, and raises the possibility of dose-mitigation by radical-radical recombination in the case of high-flux X-rays from the synchrotron.

  17. Killing of Bacillus Megaterium Spores by X-Rays at the Phosphorus K-Edge

    NASA Technical Reports Server (NTRS)

    Richmond, Robert C.; Frigo, Sean P.; Ehret, Charles F.; Rose, M. Franklin (Technical Monitor)

    2001-01-01

    This study continues a progression of experiments on the radiation-induced killing of bacterial spores that began at the Argonne National Laboratory in 1957. A series of aliquots of Bacillus megaterium spores were prepared onto polycarbonate filters and irradiated with photons of 2159 eV compared to 2140 eV energy on the 2-IDB beamline at the Advanced Photon Source. Flux density was approximately 10 photons/sec/mm . The phosphorous K-edge absorption spectrum in these spores was determined to peak at 2159 eV, wheras 2140 eV was determined to be outside that absorption spectrum. Spores on filters were irradiated at ambient conditions, and were either immediately plated for colony formation after irradiation, or were held for postirradiation exposure to oxygen prior to plating. Slopes of survival curves from the four conditions of irradiation, i.e., two photon energies each comparing immediate plating vs postirradiation holding, were used for quantitative determination of differences in rates of spore killing over a range of radiation doses. It was found that spores irradiated at the phosphorus K-edge were killed 20% more efficiently than when irradiated with 2140eV photons, and this was true for both immediate plating and postirradiation holding in air. Postirradiation holding in air increased killing efficiency by about 12% for both photon energies compared to plating immediately after irradiation. The increase of killing efficiency with postirradiation holding is less than expected from earlier experiments using relatively low-flux X-rays, and raises the possibility of dose-mitigation by radical-radical recombination in the case of high-flux X-rays from the synchrotron.

  18. Killing of Bacillus Megaterium Spores by X-rays at the Phosphorus K-edge

    NASA Technical Reports Server (NTRS)

    Richmond, Robert C.; Frigo, Sean P.; Ehret, Charles F.; Rose, M. Franklin (Technical Monitor)

    2001-01-01

    This study continues a progression of experiments on the radiation-induced killing of bacterial spores that began at the Argonne National Laboratory in 1957. A series of aliquots of Bacillus megaterium spores were prepared onto polycarbonate filters and irradiated with photons of 2159 eV compared to 2140 eV energy on the 2-IDB beamline at the Advanced Photon Source. Flux density was approximately 10(exp 18) photons/sec/sq mm. The phosphorous K-edge absorption spectrum in these spores was determined to peak at 2159 eV, wheras 2140 eV was determined to be outside that absorption spectrum. Spores on filters were irradiated at ambient conditions, and were either immediately plated for colony formation after irradiation, or were held for postirradiation exposure to oxygen prior to plating. Slopes of survival curves from the four conditions of irradiation, i.e., two photon energies each comparing immediate plating vs postirradiation holding, were used for quantitative determination of differences in rates of spore killing over a range of radiation doses. It was found that spores irradiated at the phosphorus K-edge were killed 20% more efficiently than when irradiated with 2140 eV photons, and this was true for both immediate plating and postirradiation holding in air. Postirradiation holding in air increased killing efficiency by about 12% for both photon energies compared to plating immediately after irradiation. The increase of killing efficiency with postirradiation holding is less than expected from earlier experiments using relatively low-flux X-rays, and raises the possibility of dose-mitigation by radical-radical recombination in the case of high-flux X-rays from the synchrotron.

  19. Comparison of quantitative k-edge empirical estimators using an energy-resolved photon-counting detector

    NASA Astrophysics Data System (ADS)

    Zimmerman, Kevin C.; Gilat Schmidt, Taly

    2016-03-01

    Using an energy-resolving photon counting detector, the amount of k-edge material in the x-ray path can be estimated using a process known as material decomposition. However, non-ideal effects within the detector make it difficult to accurately perform this decomposition. This work evaluated the k-edge material decomposition accuracy of two empirical estimators. A neural network estimator and a linearized maximum likelihood estimator with error look-up tables (A-table method) were evaluated through simulations and experiments. Each estimator was trained on system-specific calibration data rather than specific modeling of non-ideal detector effects or the x-ray source spectrum. Projections through a step-wedge calibration phantom consisting of different path lengths through PMMA, aluminum, and a k-edge material was used to train the estimators. The estimators were tested by decomposing data acquired through different path lengths of the basis materials. The estimators had similar performance in the chest phantom simulations with gadolinium. They estimated four of the five densities of gadolinium with less than 2mg/mL bias. The neural networks estimates demonstrated lower bias but higher variance than the A-table estimates in the iodine contrast agent simulations. The neural networks had an experimental variance lower than the CRLB indicating it is a biased estimator. In the experimental study, the k-edge material contribution was estimated with less than 14% bias for the neural network estimator and less than 41% bias for the A-table method.

  20. Behavior and mechanism of arsenate adsorption on activated natural siderite: evidences from FTIR and XANES analysis.

    PubMed

    Zhao, Kai; Guo, Huaming

    2014-02-01

    Activated natural siderite (ANS) was used to investigate its characteristics and mechanisms of As(V) adsorption from aqueous solution. Batch tests were carried out to determine effects of contact time, initial As(V) concentration, temperature, pH, background electrolyte, and coexisting anions on As(V) adsorption. Arsenic(V) adsorption on ANS well-fitted pseudo-second-order kinetics. ANS showed a high-adsorption capacity of 2.19 mg/g estimated from Langmuir isotherm at 25 °C. Thermodynamic studies indicated that As(V) adsorption on ANS was spontaneous, favorable, and endothermic. ANS adsorbed As(V) efficiently in a relatively wide pH range between 2.0 and 10.0, although the removal efficiency was slightly higher in acidic conditions than that in basic conditions. Effects of background electrolyte and coexisting anions were not significant within the concentration ranges observed in high As groundwater. Results of XRD and Fe K-edge XANES analysis suggested ANS acted as an Fe(II)/(III) hybrid system, which was quite effective in adsorbing As from aqueous solution. There was no As redox transformation during adsorption, although Fe(II) oxidation occurred in the system. Two infrared bands at 787 and 872 cm(-1) after As(V) adsorption suggested that As(V) should be predominantly adsorbed on ANS via inner-sphere bidendate binuclear surface complexes.

  1. Calculation and Interpretation of XANES

    NASA Astrophysics Data System (ADS)

    Ravel, B.; Rehr, J. J.

    1997-03-01

    A real space multiple-scattering (MS) approach for ab initio calculations and for the interpretation of x-ray absorption near edge structure (XANES) is presented. The method is based on full-MS calculations of the electron density matrix ρ(E). Our approach uses the exact Rehr-Albers [Phys. Rev. B, 41, 8139, (1990)] separable representation of the free propagator G together with atomic scattering t-matrices from uc(FEFF7) [Phys. Rev. B52, 2995 (1995)]. This method yields a parallel treatment both of XANES and local electronic structure, including local densities of states (LDOS) and charge transfer. With this method XANES for large clusters can be calculated efficiently. A scattering theoretic interpretation is presented using the separation of both XANES and LDOS into central site and scattering parts, i.e., μ(E)=μ_c(E)[1+\\chi(E)] and ρ(E)=ρ_c(E)[1+\\chi(E)], where \\chi(E) is the XAFS function and both μc and ρc are smooth backgrounds. Charge transfer is interpreted in terms of the scattering part \\chi, and hence is related to features in XANES. Calculations for several materials are presented and compared with LMTO band-structure calculations and with experiment.

  2. Application of X-ray K-edge densitometry in D and D operations

    SciTech Connect

    Jensen, T.; Aljundi, T.; Gray, J.N. |

    1998-12-31

    K-edge densitometry is a nondestructive assay technique which provides accurate measurement of heavy metal contamination in pipes, containers, and other items encountered in D and D operations. A prototype mobile K-edge instrument has been built and demonstrated in several applications. Results from measurements of uranium in pipes and spent reactor fuel plates, and quantification of mercury and lead in waste drums are presented. In this report the authors briefly describe the theory behind K-edge densitometry. They follow that with a description of the prototype system they have developed, and a presentation of results from demonstrations of this system. They conclude with a discussion of the potential for application of K-edge analysis in D and D operations.

  3. Simultaneous x-ray fluorescence and K-edge CT imaging with photon-counting detectors

    NASA Astrophysics Data System (ADS)

    Li, Liang; Li, Ruizhe; Zhang, Siyuan; Chen, Zhiqiang

    2016-10-01

    Rapid development of the X-ray phonon-counting detection technology brings tremendous research and application opportunities. In addition to improvements in conventional X-ray imaging performance such as radiation dose utilization and beam hardening correction, photon-counting detectors allows significantly more efficient X-ray fluorescence (XRF) and K-edge imaging, and promises a great potential of X-ray functional, cellular and molecular imaging. XRF is the characteristic emission of secondary X-ray photons from a material excited by initial X-rays. The phenomenon is widely used for chemical and elemental analysis. K-edge imaging identifies a material based on its chemically-specific absorption discontinuity over X-ray photon energy. In this paper, we try to combine XRF and K-edge signals from the contrast agents (e.g., iodine, gadolinium, gold nanoparticles) to simultaneously realize XFCT and K-edge CT imaging for superior image performance. As a prerequisite for this dual-modality imaging, the accurate energy calibration of multi-energy-bin photon-counting detectors is critically important. With the measured XRF data of different materials, we characterize the energy response function of a CZT detector for energy calibration and spectrum reconstruction, which can effectively improve the energy resolution and decrease the inconsistence of the photon counting detectors. Then, a simultaneous K-edge and X-ray fluorescence CT imaging (SKYFI) experimental setup is designed which includes a cone-beam X-ray tube, two separate photon counting detector arrays, a pin-hole collimator and a rotation stage. With a phantom containing gold nanoparticles the two types of XFCT and K-edge CT datasets are collected simultaneously. Then, XFCT and K-edge CT images are synergistically reconstructed in a same framework. Simulation results are presented and quantitative analyzed and compared with the separate XFCT and K-edge CT results.

  4. Interpretation of O K-edge EELS in zircon using a structural variation approach

    SciTech Connect

    Spence, John C.H; Jiang, Nan

    2009-12-01

    This work describes an approach to interpret the near-edge fine structure of electron energy-loss spectroscopy (EELS) of O K-edge in zircon using a structural variation method. The positions and intensities of several peaks in the O K-edge EELS spectrum are assigned to specific structural parameters. It suggests that the near-edge structures in EELS can be used to measure atomic structure changes.

  5. Interpretation of O K-edge EELS in zircon using a structural variation approach.

    PubMed

    Jiang, Nan; Spence, John C H

    2009-12-01

    This work describes an approach to interpret the near-edge fine structure of electron energy-loss spectroscopy (EELS) of O K-edge in zircon using a structural variation method. The positions and intensities of several peaks in the O K-edge EELS spectrum are assigned to specific structural parameters. It suggests that the near-edge structures in EELS can be used to measure atomic structure changes.

  6. Field demonstration of a portable, X-ray, K-edge heavy-metal detector

    SciTech Connect

    Jensen, T.; Aljundi, T.; Whitmore, C.; Zhong, H.; Gray, J.N.

    1997-03-31

    Under the Characterization, Monitoring, and Sensor Technology Crosscutting Program, the authors have designed and built a K-edge heavy metal detector that measures the level of heavy metal contamination inside closed containers in a nondestructive, non-invasive way. The device employs a volumetric technique that takes advantage of the X-ray absorption characteristics of heavy elements, and is most suitable for characterization of contamination inside pipes, processing equipment, closed containers, and soil samples. The K-edge detector is a fast, efficient, and cost-effective in situ characterization tool. More importantly, this device will enhance personnel safety while characterizing radioactive and toxic waste. The prototype K-edge system was operated at the Materials and Chemistry Laboratory User Facility at the Oak Ridge K-25 Site during February 1997. Uranium contaminated pipes and valves from a UF{sub 6} feed facility were inspected using the K-edge technique as well as a baseline nondestructive assay method. Operation of the K-edge detector was demonstrated for uranium contamination ranging from 10 to 6,000 mg/cm{sup 2} and results from the K-edge measurements were found to agree very well with nondestructive assay measurements.

  7. Ce K edge XAS of ceria-based redox materials under realistic conditions for the two-step solar thermochemical dissociation of water and/or CO2.

    PubMed

    Rothensteiner, Matthäus; Sala, Simone; Bonk, Alexander; Vogt, Ulrich; Emerich, Hermann; van Bokhoven, Jeroen A

    2015-10-28

    X-ray absorption spectroscopy was used to characterise ceria-based materials under realistic conditions present in a reactor for solar thermochemical two-step water and carbon dioxide splitting. A setup suitable for in situ measurements in transmission mode at the cerium K edge from room temperature up to 1773 K is presented. Time-resolved X-ray absorption near-edge structure (XANES) data, collected for a 10 mol% hafnium-doped ceria sample (Ce0.9Hf0.1O2-δ) during reduction at 1773 K in a flow of inert gas and during re-oxidation by CO2 at 1073 K, enables the quantitative determination of the non-stoichiometry δ of the fluorite-type structure. XANES analysis suggests the formation of the hexagonal Ce2O3 phase upon reduction in 2% hydrogen/helium at 1773 K. We discuss the experimental limitations and possibilities of high-temperature in situ XAS at edges of lower energy as well as the importance of the technique for understanding and improving the properties of ceria-based oxygen storage materials for thermochemical solar energy conversion.

  8. Linear combination of XANES for quantitative analysis of Ti-Si binary oxides.

    PubMed

    Lee, J S; Kim, W B; Choi, S H

    2001-03-01

    A new method is demonstrated for the quantification of Ti-O-Si and Ti-O-Ti bonds in Ti-Si binary oxides. It is based on the linear combination of two reference X-ray absorption near-edge structure (XANES) spectra at the Ti K edge. The proper selection of a Ti-O-Si reference material is most important for the successful application of this method. Three Ti-Si binary oxide systems have been analysed by the new method: Ti-Si mixed oxides, titania supported on silica and Ti-substituted MCM-41 (crystalline mesoporous molecular sieve material invented by Mobil) with various Ti contents.

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  10. Absolute determination of charge-coupled device quantum detection efficiency using Si K-edge x-ray absorption fine structure

    SciTech Connect

    Dunn, J; Steel, A B

    2012-05-06

    We report a method to determine the quantum detection efficiency and the absorbing layers on a front-illuminated charge-coupled device (CCD). The CCD under study, as part of a crystal spectrometer, measures intense continuum x-ray emission from a picosecond laser-produced plasma and spectrally resolves the Si K-edge x-ray absorption fine structure features due to the electrode gate structure of the device. The CCD response across the Si K-edge shows a large discontinuity as well as a number of oscillations that are identified individually and uniquely from Si, SiO{sub 2}, and Si{sub 3}N{sub 4} layers. From the spectral analysis of the structure and K-edge discontinuity, the active layer thickness and the different absorbing layers thickness can be determined precisely. A precise CCD detection model from 0.2-10 keV can be deduced from this highly sensitive technique.

  11. Exact Multiple Scattering XANES Calculations

    NASA Astrophysics Data System (ADS)

    Ravel, B.; Rehr, J. J.

    1996-03-01

    Ab initio calculations of X-ray absorption near-edge structure (XANES), are made by inverting the full multiple-scattering (MS) matrix G=(1-G_0t)-1G_0. Our approach uses the fast, quickly convergent Rehr-Albers(J.J. Rehr and R.C. Albers, Phys. Rev. B, 41), 8139, (1990) separable representation of the free electron propagator G0 together with atomic scattering t-matrices from the FEFF6 code,(S. I. Zabinsky, et al., Phys. Rev. B52), 2995 (1995). which are calculated within the muffin-tin approximation with overlapped atom potentials. With this technique XANES spectra and its polarization dependence can be calculated in reasonable cpu time on large clusters. Good agreement with the XANES spectra of several sample compounds is obtained. This strategy is also used to determine the local densities of states ρ(E, r ) from the full MS matrix. From ρ(E, r ) we calculate the Fermi energies and estimate charge transfer for our sample clusters. The prospect of quantitative analysis of XANES spectra and its preedge features is discussed.

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

    PubMed

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  14. Strong excitonic interactions in the oxygen K-edge of perovskite oxides.

    PubMed

    Tomita, Kota; Miyata, Tomohiro; Olovsson, Weine; Mizoguchi, Teruyasu

    2017-07-01

    Excitonic interactions of the oxygen K-edge electron energy-loss near-edge structure (ELNES) of perovskite oxides, CaTiO3, SrTiO3, and BaTiO3, together with reference oxides, MgO, CaO, SrO, BaO, and TiO2, were investigated using a first-principles Bethe-Salpeter equation calculation. Although the transition energy of oxygen K-edge is high, strong excitonic interactions were present in the oxygen K-edge ELNES of the perovskite oxides, whereas the excitonic interactions were negligible in the oxygen K-edge ELNES of the reference compounds. Detailed investigation of the electronic structure suggests that the strong excitonic interaction in the oxygen K-edge ELNES of the perovskite oxides is caused by the directionally confined, low-dimensional electronic structure at the Ti-O-Ti bonds. Copyright © 2016 Elsevier B.V. All rights reserved.

  15. Study of XANES near Ta-L edges in LiTaO3 through thermal wave, fluorescence and first principles

    NASA Astrophysics Data System (ADS)

    Kane, S. R.; Kumar, Shailendra; Ghosh, Haranath; Singh, Ajit Kumar; Tiwari, M. K.

    2016-01-01

    X-ray absorption near-edge spectra (XANES) of Ta-L2 and L3 edges in LiTaO3 (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-L3 and Ta-L2 absorption edges, measured by thermal waves and fluorescence, differ. Possible origins of these differences are discussed.

  16. Structural investigation of high-valent manganese-salen complexes by UV/Vis, Raman, XANES, and EXAFS spectroscopy.

    PubMed

    Feth, Martin P; Bolm, Carsten; Hildebrand, Jens P; Köhler, Manuela; Beckmann, Oliver; Bauer, Matthias; Ramamonjisoa, Rivo; Bertagnolli, Helmut

    2003-03-17

    XANES and EXAFS spectroscopic studies at the Mn-K- and Br-K-edge of reaction products of (S,S)-(+)-N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminomanganese(III) chloride ([(salen)Mn(III)Cl], 1) and (S,S)-(+)-N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminomanganese(III) bromide ([(salen)Mn(III)Br], 2) with 4-phenylpyridine N-oxide (4-PPNO) and 3-chloroperoxybenzoic acid (MCPBA) are reported. The reaction of the Mn(III) complexes with two equivalents of 4-PPNO leads to a hexacoordinated compound, in which the manganese atom is octahedrally coordinated by four oxygen/nitrogen atoms of the salen ligand at an average distance of approximately 1.90 A and two additional, axially bonded oxygen atoms of the 4-PPNO at 2.25 A. The oxidation state of this complex was determined as approximately +IV by a comparative study of Mn(III) and Mn(V) reference compounds. The green intermediate obtained in reactions of MCPBA and solutions of 1 or 2 in acetonitrile was investigated with XANES, EXAFS, UV/Vis, and Raman spectroscopy, and an increase of the coordination number of the manganese atoms from 4 to 5 and the complete abstraction of the halide was observed. A formal oxidation state of IV was deduced from the relative position of the pre-edge 1s-->3d feature of the X-ray absorption spectrum of the complex. The broad UV/Vis band of this complex in acetonitrile with lambda(max)=648 nm was consistent with a radical cation structure, in which a MCPBA molecule was bound to the Mn(IV) central atom. An oxomanganese(V) or a dimeric manganese(IV) species was not detected.

  17. 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

    SciTech Connect

    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

  18. Electronic structure of Al-doped ZnO transparent conductive thin films studied by x-ray absorption and emission spectroscopies

    SciTech Connect

    Huang, W. H.; Sun, S. J.; Chiou, J. W.; Chou, H.; Chan, T. S.; Lin, H.-J.; Kumar, Krishna; Guo, J.-H.

    2011-11-15

    This study used O K-, Zn L{sub 3}-, Zn K-, and Al K-edges x-ray absorption near-edge structure (XANES) and O K-edge x-ray emission spectroscopy (XES) measurements to investigate the electronic structure of transparent Al-doped ZnO (AZO) thin film conductors. The samples were prepared on glass substrates at a low temperature near 77 K by using a standard RF sputtering method. High-purity Ne (5N) was used as the sputtering gas. The crystallography of AZO thin films gradually transformed from the ZnO wurtize structure to an amorphous structure during sample deposition, which suggests the suitability to grow on flexible substrates, eliminating the severe degradation due to fragmentation by repeated bending. The O K- and Zn L{sub 3}-edges XANES spectra of AZO thin films revealed a decrease in the number of both O 2p and Zn 3d unoccupied states when the pressure of Ne was increased from 5 to 100 mTorr. In contrast, Al K-edges XANES spectra showed that the number of unoccupied states of Al 3p increased in conjunction with the pressure of Ne, indicating an electron transfer from Al to O atoms, and suggesting that Al doping increases the negative effective charge of oxygen ions. XES and XANES spectra of O 2p states at the O K-edge also revealed that Al doping not only raised the conduction-band-minimum, but also increased the valence-band-maximum and the band-gap. The results indicate that the reduction in conductivity of AZO thin films is due to the generation of ionic characters, the increase in band-gap, and the decrease in density of unoccupied states of oxygen.

  19. Identification of Uranyl Minerals Using Oxygen K-Edge X Ray Absorption Spectroscopy

    SciTech Connect

    Ward, Jesse D.; Bowden, Mark E.; Resch, Charles T.; Smith, Steven C.; McNamara, Bruce K.; Buck, Edgar C.; Eiden, Gregory C.; Duffin, Andrew M.

    2016-03-01

    Uranium analysis is consistently needed throughout the fuel cycle, from mining to fuel fabrication to environmental monitoring. Although most of the world’s uranium is immobilized as pitchblende or uraninite, there exists a plethora of secondary uranium minerals, nearly all of which contain the uranyl cation. Analysis of uranyl compounds can provide clues as to a sample’s facility of origin and chemical history. X-ray absorption spectroscopy is one technique that could enhance our ability to identify uranium minerals. Although there is limited chemical information to be gained from the uranium X-ray absorption edges, recent studies have successfully used ligand NEXAFS to study the physical chemistry of various uranium compounds. This study extends the use of ligand NEXAFS to analyze a suite of uranium minerals. We find that major classes of uranyl compounds (carbonate, oxyhydroxide, silicate, and phosphate) exhibit characteristic lineshapes in the oxygen K-edge absorption spectra. As a result, this work establishes a library of reference spectra that can be used to classify unknown uranyl minerals.

  20. Absorption and scattering by interstellar dust in the silicon K-edge of GX 5-1

    NASA Astrophysics Data System (ADS)

    Zeegers, S. T.; Costantini, E.; de Vries, C. P.; Tielens, A. G. G. M.; Chihara, H.; de Groot, F.; Mutschke, H.; Waters, L. B. F. M.; Zeidler, S.

    2017-03-01

    Context. We study the absorption and scattering of X-ray radiation by interstellar dust particles, which allows us to access the physical and chemical properties of dust. The interstellar dust composition is not well understood, especially on the densest sight lines of the Galactic plane. X-rays provide a powerful tool in this study. Aims: We present newly acquired laboratory measurements of silicate compounds taken at the Soleil synchrotron facility in Paris using the Lucia beamline. The dust absorption profiles resulting from this campaign were used in this pilot study to model the absorption by interstellar dust along the line of sight of the low-mass X-ray binary GX 5-1. Methods: The measured laboratory cross-sections were adapted for astrophysical data analysis and the resulting extinction profiles of the Si K-edge were implemented in the SPEX spectral fitting program. We derive the properties of the interstellar dust along the line of sight by fitting the Si K-edge seen in absorption in the spectrum of GX 5-1. Results: We measured the hydrogen column density towards GX 5-1 to be 3.40 ± 0.1 × 1022 cm-2. The best fit of the silicon edge in the spectrum of GX 5-1 is obtained by a mixture of olivine and pyroxene. In this study, our modeling is limited to Si absorption by silicates with different Mg:Fe ratios. We obtained an abundance of silicon in dust of 4.0 ± 0.3 × 10-5 per H atom and a lower limit for total abundance, considering both gas and dust of >4.4 × 10-5 per H atom, which leads to a gas to dust ratio of >0.22. Furthermore, an enhanced scattering feature in the Si K-edge may suggest the presence of large particles along the line of sight.

  1. K-edge ratio method for identification of multiple nanoparticulate contrast agents by spectral CT imaging

    PubMed Central

    Ghadiri, H; Ay, M R; Shiran, M B; Soltanian-Zadeh, H

    2013-01-01

    Objective: Recently introduced energy-sensitive X-ray CT makes it feasible to discriminate different nanoparticulate contrast materials. The purpose of this work is to present a K-edge ratio method for differentiating multiple simultaneous contrast agents using spectral CT. Methods: The ratio of two images relevant to energy bins straddling the K-edge of the materials is calculated using an analytic CT simulator. In the resulting parametric map, the selected contrast agent regions can be identified using a thresholding algorithm. The K-edge ratio algorithm is applied to spectral images of simulated phantoms to identify and differentiate up to four simultaneous and targeted CT contrast agents. Results: We show that different combinations of simultaneous CT contrast agents can be identified by the proposed K-edge ratio method when energy-sensitive CT is used. In the K-edge parametric maps, the pixel values for biological tissues and contrast agents reach a maximum of 0.95, whereas for the selected contrast agents, the pixel values are larger than 1.10. The number of contrast agents that can be discriminated is limited owing to photon starvation. For reliable material discrimination, minimum photon counts corresponding to 140 kVp, 100 mAs and 5-mm slice thickness must be used. Conclusion: The proposed K-edge ratio method is a straightforward and fast method for identification and discrimination of multiple simultaneous CT contrast agents. Advances in knowledge: A new spectral CT-based algorithm is proposed which provides a new concept of molecular CT imaging by non-iteratively identifying multiple contrast agents when they are simultaneously targeting different organs. PMID:23934964

  2. SR high-speed K-edge subtraction angiography in the small animal (abstract)

    NASA Astrophysics Data System (ADS)

    Takeda, T.; Akisada, M.; Nakajima, T.; Anno, I.; Ueda, K.; Umetani, K.; Yamaguchi, C.

    1989-07-01

    To assess the ability of the high-speed K-edge energy subtraction system which was made at beamline 8C of Photon Factory, Tsukuba, we performed an animal experiment. Rabbits were used for the intravenous K-edge subtraction angiography. In this paper, the actual images of the artery obtained by this system, are demonstrated. The high-speed K-edge subtraction system consisted of movable silicon (111) monocrystals, II-ITV, and digital memory system. Image processing was performed by 68000-IP computer. The monochromatic x-ray beam size was 50×60 mm. Photon energy above and below iodine K edge was changed within 16 ms and 32 frames of images were obtained sequentially. The rabbits were anaesthetized by phenobarbital and a 5F catheter was inserted into inferior vena cava via the femoral vein. 1.5 ml/kg of contrast material (Conlaxin H) was injected at the rate of 0.5 ml/kg/s. TV images were obtained 3 s after the starting point of injection. By using this system, the clear K-edge subtracted images were obtained sequentially as a conventional DSA system. The quality of the images were better than that obtained by DSA. The dynamical blood flow was analyzed, and the best arterial image could be selected from the sequential images. The structures of aortic arch, common carotid arteries, right subclavian artery, and internal thoracic artery were obtained at the chest. Both common carotid arteries and vertebral arteries were recorded at the neck. The diameter of about 0.3-0.4 mm artery could be clearly revealed. The high-speed K-edge subtraction system demonstrates the very sharp arterial images clearly and dynamically.

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

    NASA Astrophysics Data System (ADS)

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

    2013-09-01

    Ni doped, Li doped and (Li, Ni) codoped ZnO thin films were successfully grown using a pulsed laser deposition technique. Undoped and doped ZnO thin films were investigated using extended x-ray absorption fine structure (EXAFS) and x-ray absorption near edge spectroscopy (XANES). Preliminary investigations on the Zn K-edge of the undoped and doped ZnO thin films revealed that doping has not influenced the average Zn-Zn bond length and Debye-Waller factor. This shows that both Ni and Li doping do not appreciably affect the average local environment of Zn. All the doped ZnO thin films exhibited more than 50% of substitutional Ni, with a maximum of 77% for 2% Ni and 2% Li doped ZnO thin film. The contribution of Ni metal to the EXAFS signal clearly reveals the presence of Ni clusters. The Ni-Ni distance in the Ni0 nanoclusters, which are formed in the film, is shorter with respect to the reference Ni metal foil and the Debye-Waller factor is higher. Both facts perfectly reflect what is expected for metal nanoparticles. At the highest doping concentration (5%), the presence of Li favors the growth of a secondary NiO phase. Indeed, 2% Ni and 5% Li doped ZnO thin film shows %Nisub = 75 ± 11, %Nimet = 10 ± 8, %NiO = 15 ± 8. XANES studies further confirm that the substitutional Ni is more than 50% in all the samples. These results explain the observed magnetic properties.

  4. Molecular anisotropy effects in carbon K-edge scattering: depolarized diffuse scattering and optical anisotropy

    SciTech Connect

    Stone, Kevin H.

    2014-07-14

    Some polymer properties, such as conductivity, are very sensitive to short- and intermediate-range orientational and positional ordering of anisotropic molecular functional groups, and yet means to characterize orientational order in disordered systems are very limited. We demonstrate that resonant scattering at the carbon K-edge is uniquely sensitive to short-range orientation correlations in polymers through depolarized scattering at high momentum transfers, using atactic polystyrene as a well-characterized test system. Depolarized scattering is found to coexist with unpolarized fluorescence, and to exhibit pronounced anisotropy. We also quantify the spatially averaged optical anisotropy from low-angle reflectivity measurements, finding anisotropy consistent with prior visible, x-ray absorption, and theoretical studies. The average anisotropy is much smaller than that in the depolarized scattering and the two have different character. Both measurements exhibit clear spectral signatures from the phenyl rings and the polyethylene-like backbone. Discussion focuses on analysis considerations and prospects for using this depolarized scattering for studies of disorder in soft condensed matter.

  5. Molecular anisotropy effects in carbon K-edge scattering: Depolarized diffuse scattering and optical anisotropy

    NASA Astrophysics Data System (ADS)

    Stone, Kevin H.; Kortright, Jeffrey B.

    2014-09-01

    Some polymer properties, such as conductivity, are very sensitive to short- and intermediate-range orientational and positional ordering of anisotropic molecular functional groups, and yet means to characterize orientational order in disordered systems are very limited. We demonstrate that resonant scattering at the carbon K edge is uniquely sensitive to short-range orientation correlations in polymers through depolarized scattering at high momentum transfers, using atactic polystyrene as a well-characterized test system. Depolarized scattering is found to coexist with unpolarized fluorescence and to exhibit pronounced anisotropy. We also quantify the spatially averaged optical anisotropy from low-angle reflectivity measurements, finding anisotropy consistent with prior visible, x-ray absorption, and theoretical studies. The average anisotropy is much smaller than that in the depolarized scattering and the two have different character. Both measurements exhibit clear spectral signatures from the phenyl rings and the polyethylenelike backbone. Discussion focuses on analysis considerations and prospects for using this depolarized scattering for studies of disorder in soft condensed matter.

  6. Inelastic scattering at the B K edge of hexagonal BN

    SciTech Connect

    Jia, J.J.; Callcott, T.A.; Zhou, L.

    1997-04-01

    Many recent soft x-ray fluorescence (SXF) studies have shown that inelastic scattering processes make important contributions to the observed spectra for excitation near the x-ray threshold. These effects are all attributed to a process, usually called an electronic Raman scattering (ERS) process, in which energy is lost to an electronic excitation. The theory has been described using second order perturbation theory by Tulkki and Aberg. In different materials, the detailed nature of the electronic excitation producing the energy loss may be very different. In crystalline Si, diamond and graphite, changes in spectral shape and dispersion of spectral features with variation of the excitation energy are observed, which are attributed to k conservation between the photoelectron generated in the excitation process and the valence hole remaining after the coupled emission process. Hence the process is strongly localized in k-space. In haxagonal boron nitride, which has a lattice and band structure very similar to graphite, inelastic scattering produces very different effects on the observed spectra. Here, the inelastic losses are coupled to a strong resonant elastic scattering process, in which the intermediate state is a localized core exciton and the final state is a localized valence exciton, so that the electronic excitation is strongly localized in real rather than reciprocal space.

  7. Studies of valence of selected rare earth silicides determined using Si K and Pd/Rh L2,3 XANES and LAPW numerical studies

    NASA Astrophysics Data System (ADS)

    Zajdel, P.; Kisiel, A.; Szytuła, A.; Goraus, J.; Balerna, A.; Banaś, A.; Starowicz, P.; Konior, J.; Cinque, G.; Grilli, A.

    2015-12-01

    We report on the investigation of Si and Pd/Rh chemical environments using X-ray Absorption Near Edge Spectroscopy in two different families of rare earth silicides R2PdSi3 (R = Ce, Nd, Tb, Dy, Ho, Er) and HoRh2-xPdxSi2 (x = 0, 0.5, 0.75, 1.0, 1.5, 1.8, 2.0). The Si K, Pd L3 and Rh L3 absorption edges were recorded in order to follow their changes upon the variation of 4f and 4d5s electron numbers. In both cases it was found that the Si K edge was shifted ≈0.5 eV toward lower energies, relative to pure silicon. In the first family, the shift decreases with increasing number of f-electrons, while the Si K edge remains constant upon rhodium-palladium substitution. In all cases the Pd L3 edge was shifted to higher energies relative to metallic Pd. No visible change in the Pd L3 position was observed either with a varying 4f electron count or upon Pd/Rh substitution. Also, the Rh L3 edge did not change. For two selected members, Ho2PdSi3 and HoPd2Si2, the Wien2K'09 (LDA + U) package was used to calculate the electronic structure and the absorption edges. Si K edges were reproduced well for both compounds, while Pd L3 only exhibited a fair agreement for the second compound. This discrepancy between the Pd L3 theory and experiment for the Ho2PdSi3 sample can be attributed to the specific ordered superstructure used in the numerical calculations. The observed changes indicate that despite possessing a formal inter-metallic character, the chemical bond between the R-Si and R-Pd interactions are different. The variation and the direction of the chemical shift of the Si K edge suggests a weak ionic character of the R-Si bonds, in agreement with the localized character of the 4f electrons. In turn, the changes of the Pd/Rh edge are consistent with a metallic band that is affected by its long range chemical environment.

  8. K-edge subtraction angiography with synchrotron x-rays: Final technical report, (February 1, 1984 to January 31, 1987)

    SciTech Connect

    Hofstadter, R

    1987-09-01

    The aim was the development of an angiographic method and appropriate equipment for imaging with x-rays the coronary arteries in a non-invasive manner. Successive steps involved studies with phantoms, live animals and finally with human subjects. Clinical evaluation of human coronary arteries remains a goal of this and a continuing project, and steps along the way to such an achievement are in process. Transvenous injection of a dye using the method of iodine dichromography near 33.2 keV, the K-edge of iodine, forms the basis of the method. 11 refs.

  9. K-edge Subtraction Angiography with Synchrotron X-Rays: Final Technical Report, (February 1, 1984 to January 31, 1987)

    DOE R&D Accomplishments Database

    Hofstadter, R.

    1987-09-01

    The aim was the development of an angiographic method and appropriate equipment for imaging with x-rays the coronary arteries in a non-invasive manner. Successive steps involved studies with phantoms, live animals and finally with human subjects. Clinical evaluation of human coronary arteries remains a goal of this and a continuing project, and steps along the way to such an achievement are in process. Transvenous injection of a dye using the method of iodine dichromography near 33.2 keV, the K-edge of iodine, forms the basis of the method

  10. Photoabsorption spectra of potassium and rubidium near the K-edge

    SciTech Connect

    Azuma, Y.; Berry, H.G.; Cowan, P.L.

    1995-08-01

    We have used a high-temperature circulating heat-pipe absorption cell together with monochromatized X-ray beams at the X24A and X23A2 beam lines at the NSLS to obtain photoabsorption spectra of potassium and rubidium at their K- and KM-edges. The photon-energy ranges lay near 3600 eV and 15200 eV, respectively. We have also obtained first measurements of the LII and LIII edges in cesium. Although the K-edge photoabsorptions of the rare gases have been studied, there is little previous work on other atomic vapors. Most of the edges and resonance peaks that we observed have now been identified using Dirac Hartree-Fock calculations. As a check, we have compared these results with those obtained previously in closed-shell rare-gas absorption spectra. The absolute energies were obtained through a calibration of the X24A systems using measurements of several metal L-edges in the 3200-5000 eV energy range. We found that the 4p resonance in potassium is significantly enhanced compared with the corresponding situation in argon. Likewise, the 5p resonance in krypton is unresolved from the background ionization cross section, whereas it is well resolved in rubidium. As suggested by Amusia, these enhancements may be due to the enhanced potential seen in the excited state of the alkali systems as a result of the presence of an s-electron which reduces the nuclear shielding.

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

    PubMed

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

    2016-04-05

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

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

  13. Composition-dependent structure of polycrystalline magnetron-sputtered V–Al–C–N hard coatings studied by XRD, XPS, XANES and EXAFS

    PubMed Central

    Krause, Bärbel; Darma, Susan; Kaufholz, Marthe; Mangold, Stefan; Doyle, Stephen; Ulrich, Sven; Leiste, Harald; Stüber, Michael; Baumbach, Tilo

    2013-01-01

    V–Al–C–N hard coatings with high carbon content were deposited by reactive radio-frequency magnetron sputtering using an experimental combinatorial approach, deposition from a segmented sputter target. The composition-dependent coexisting phases within the coating were analysed using the complementary methods of X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), X-ray absorption near-edge spectroscopy (XANES) and extended X-ray absorption fine-structure spectroscopy (EXAFS). For the analysis of the X-ray absorption near-edge spectra, a new approach for evaluation of the pre-edge peak was developed, taking into account the self-absorption effects in thin films. Within the studied composition range, a mixed face-centred cubic (V,Al)(C,N) phase coexisting with a C–C-containing phase was observed. No indication of hexagonal (V,Al)(N,C) was found. The example of V–Al–C–N demonstrates how important a combination of complementary methods is for the detection of coexisting phases in complex multi-element coatings. PMID:24046506

  14. Composition-dependent structure of polycrystalline magnetron-sputtered V-Al-C-N hard coatings studied by XRD, XPS, XANES and EXAFS.

    PubMed

    Krause, Bärbel; Darma, Susan; Kaufholz, Marthe; Mangold, Stefan; Doyle, Stephen; Ulrich, Sven; Leiste, Harald; Stüber, Michael; Baumbach, Tilo

    2013-08-01

    V-Al-C-N hard coatings with high carbon content were deposited by reactive radio-frequency magnetron sputtering using an experimental combinatorial approach, deposition from a segmented sputter target. The composition-dependent coexisting phases within the coating were analysed using the complementary methods of X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), X-ray absorption near-edge spectroscopy (XANES) and extended X-ray absorption fine-structure spectroscopy (EXAFS). For the analysis of the X-ray absorption near-edge spectra, a new approach for evaluation of the pre-edge peak was developed, taking into account the self-absorption effects in thin films. Within the studied composition range, a mixed face-centred cubic (V,Al)(C,N) phase coexisting with a C-C-containing phase was observed. No indication of hexagonal (V,Al)(N,C) was found. The example of V-Al-C-N demonstrates how important a combination of complementary methods is for the detection of coexisting phases in complex multi-element coatings.

  15. Environmental applications of XANES: Speciation of {Tc} in cement after chemical treatment and Se after bacterial uptake

    SciTech Connect

    Shuh, D.K.; Kaltsoyannis, N.; Bucher, J.J.

    1994-03-01

    XANES (X-ray Absorption Near Edge Spectroscopy) has been employed to evaluate the efficacy of a process designed to encapsulate and reduce {Tc}O{sub 4}{sup {minus}} in cement matrices, thereby immobilizing {Tc}. The oxidation state of Se following.bioremediation of Se by bacteria has also been determined by XANES. The XANES measurements were performed at the Stanford Synchrotron Radiation Laboratory (SSRL) and the National Synchrotron Light Source (NSLS) at the respective K edges of {Tc} (21.0 keV) and Se (12.7 keV). Comparison of the XANES spectra of Tc in untreated cement to Tc in slag treated cement and to the chemical shifts of reference materials, shows that the oxidation state of {Tc} is the same in both cements. Thus, the addition of a reducing agent to the cement formulation does not significantly reduce the {Tc}O{sub 4} The common soil bacterium, Bacillus subtilis, is known to incorporate Se on or within the cell wall when exposed to a SE(IV) solution. The Se XANES spectra of B. subtilis, as well as bacillus isolated from selenium rich soil, show that the organisms reduce selenite to the red allotrope of elemental Se.

  16. X-ray studies on optical and structural properties of ZnO nanostructured thin films

    NASA Astrophysics Data System (ADS)

    Larcheri, S.; Armellini, C.; Rocca, F.; Kuzmin, A.; Kalendarev, R.; Dalba, G.; Graziola, R.; Purans, J.; Pailharey, D.; Jandard, F.

    2006-01-01

    X-ray absorption near-edge fine structure (XANES) studies have been carried out on nanostructured ZnO thin films prepared by atmospheric pressure chemical vapour deposition (APCVD). Films have been characterized by X-ray diffraction (XRD) and optical luminescence spectroscopy exciting with laser light (PL) or X-ray (XEOL). According to XRD measurements, all the APCVD samples reveal a highly (002) oriented crystalline structure. The samples have different thickness (less than 1 μm) and show significant shifts of the PL and XEOL bands in the visible region. Zn K-edge XANES spectra were recorded using synchrotron radiation at BM08 of ESRF (France), by detecting photoluminescence yield (PLY) and X-ray fluorescence yield (FLY). The differences between the PLY- and FLY-XANES confirm the possibility of studying the local environment in the luminescence centres and to correlate the structural and optical properties of ZnO nanostructured samples.

  17. Electronic structure and hybridization of CaS by means of X-ray absorption spectroscopy at Ca and S K-edges.

    PubMed

    Xu, Wei; Liu, Lijuan; Cui, Mingqi; Zheng, Lei; Hu, Yongfeng; Marcelli, Augusto; Wu, Ziyu

    2013-01-01

    The cubic calcium sulfide (CaS) is a well known system and an attractive building block material for many luminescence technological applications. However, it is essential to achieve an accurate understanding of its electronic structure in order to engineer its band structure for optimized applications. Here a study of the electronic structure of CaS by means of X-ray absorption spectroscopy performed at both Ca and S K-edges, and calculations performed in the framework of the multiple-scattering theory and of the finite difference method are presented. At the Ca K-edge the presence of an anomalous d states feature is discussed while in the S K-edge spectrum the presence of a pre-edge shoulder owing to the hybridization among Ca d states and S p states is pointed out. Although the l-projected density of states of CaS is in good agreement with previous first-principles calculations, the standard muffin-tin potential is inadequate to reproduce near-edge structures at both Ca and S K-edges in this system. Indeed, with its highly symmetric and less compact structure, CaS is characterized by a large set of collinear atomic configurations that pose severe constraints on the construction of the atomic potential. On the contrary, the finite-difference method with no muffin-tin approximation is more suitable for X-ray absorption calculations in this system.

  18. Dispersion corrections of the copper K edge measured by Fresnel diffraction.

    PubMed

    Lee, Wah-Keat; Cloetens, Peter; Schlenker, Michel

    2004-01-01

    Dispersion corrections to the atomic scattering factors for the copper K edge have been measured by a new technique, Fresnel diffraction. Fresnel diffraction fringes were measured at several sample-detector distances as a function of energy across the copper K-absorption edge. The dispersion corrections were obtained from optimizing a least-squares fit of Fresnel fringe simulations to the measured data.

  19. Ion yields for tetramethylgermane exposed to x-rays near the Ge K-edge

    SciTech Connect

    Holroyd, R.A.; Preses, J.M.; Sham, T.K.

    2000-03-30

    Free ion yields were measured for tetramethylgermane (TMG) in both the liquid and vapor phase and for Kr gas exposed to X-rays. The X-ray energy was varied across the K-edges of Ge and Kr, respectively. In Kr the relative W value increases slightly at the K-edge, which is at 14.3 keV. In liquid TMG the observed ion yield drops at the Ge K-edge (11.1 keV) and shows two minima separated by 10 eV. This ion-yield spectrum is a mirror image of the absorption spectrum, as represented by the gas-phase ion-yield spectrum. The observation of such an inverted spectrum in liquids is shown to be due in large part to inefficiency of collection of charges. This is a consequence of the large Ge cross sections above the edge which concentrates the region of irradiation near the entrance window, increasing the local dose rate and enhancing recombination. The yield of excited states in mixtures of TMG and toluene drops at the Ge K-edge by the amount expected considering the large X-ray fluorescence yield.

  20. Observation of yttrium oxide nanoparticles in cabbage (Brassica oleracea) through dual energy K-edge subtraction imaging

    SciTech Connect

    Chen, Yunyun; Sanchez, Carlos; Yue, Yuan; de Almeida, Mauricio; González, Jorge M.; Parkinson, Dilworth Y.; Liang, Hong

    2016-03-25

    Background: The potential transfer of engineered nanoparticles (ENPs) from plants into the food chain has raised widespread concerns. In order to investigate the effects of ENPs on plants, young cabbage plants (Brassica oleracea) were exposed to a hydroponic system containing yttrium oxide (yttria) ENPs. The objective of this study was to reveal the impacts of NPs on plants by using K-edge subtraction imaging technique. Results: Using synchrotron dual-e nergy X-ray micro-tomography with K-edge subtraction technique, we studied the uptake, accumulation, distribution and concentration mapping of yttria ENPs in cabbage plants. It was found that yttria ENPs were uptaken by the cabbage roots but did not effectively transferred and mobilized through the cabbage stem and leaves. This could be due to the accumulation of yttria ENPs blocked at primary-lateral-root junction. Instead, non-yttria minerals were found in the xylem vessels of roots and stem. Conclusions: Synchrotron dual-energy X-ray micro-tomography is an effective method to observe yttria NPs inside the cabbage plants in both whole body and microscale level. Furthermore, the blockage of a plant's roots by nanoparticles is likely the first and potentially fatal environmental effect of such type of nanoparticles.

  1. Observation of yttrium oxide nanoparticles in cabbage (Brassica oleracea) through dual energy K-edge subtraction imaging.

    PubMed

    Chen, Yunyun; Sanchez, Carlos; Yue, Yuan; de Almeida, Mauricio; González, Jorge M; Parkinson, Dilworth Y; Liang, Hong

    2016-03-25

    The potential transfer of engineered nanoparticles (ENPs) from plants into the food chain has raised widespread concerns. In order to investigate the effects of ENPs on plants, young cabbage plants (Brassica oleracea) were exposed to a hydroponic system containing yttrium oxide (yttria) ENPs. The objective of this study was to reveal the impacts of NPs on plants by using K-edge subtraction imaging technique. Using synchrotron dual-energy X-ray micro-tomography with K-edge subtraction technique, we studied the uptake, accumulation, distribution and concentration mapping of yttria ENPs in cabbage plants. It was found that yttria ENPs were uptaken by the cabbage roots but did not effectively transferred and mobilized through the cabbage stem and leaves. This could be due to the accumulation of yttria ENPs blocked at primary-lateral-root junction. Instead, non-yttria minerals were found in the xylem vessels of roots and stem. Synchrotron dual-energy X-ray micro-tomography is an effective method to observe yttria NPs inside the cabbage plants in both whole body and microscale level. Furthermore, the blockage of a plant's roots by nanoparticles is likely the first and potentially fatal environmental effect of such type of nanoparticles.

  2. Observation of yttrium oxide nanoparticles in cabbage (Brassica oleracea) through dual energy K-edge subtraction imaging

    DOE PAGES

    Chen, Yunyun; Sanchez, Carlos; Yue, Yuan; ...

    2016-03-25

    Background: The potential transfer of engineered nanoparticles (ENPs) from plants into the food chain has raised widespread concerns. In order to investigate the effects of ENPs on plants, young cabbage plants (Brassica oleracea) were exposed to a hydroponic system containing yttrium oxide (yttria) ENPs. The objective of this study was to reveal the impacts of NPs on plants by using K-edge subtraction imaging technique. Results: Using synchrotron dual-e nergy X-ray micro-tomography with K-edge subtraction technique, we studied the uptake, accumulation, distribution and concentration mapping of yttria ENPs in cabbage plants. It was found that yttria ENPs were uptaken by themore » cabbage roots but did not effectively transferred and mobilized through the cabbage stem and leaves. This could be due to the accumulation of yttria ENPs blocked at primary-lateral-root junction. Instead, non-yttria minerals were found in the xylem vessels of roots and stem. Conclusions: Synchrotron dual-energy X-ray micro-tomography is an effective method to observe yttria NPs inside the cabbage plants in both whole body and microscale level. Furthermore, the blockage of a plant's roots by nanoparticles is likely the first and potentially fatal environmental effect of such type of nanoparticles.« less

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

    NASA Astrophysics Data System (ADS)

    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

  4. Molecular conformation changes in alkylthiol ligands as a function of size in gold nanoparticles: X-ray absorption studies

    SciTech Connect

    Ramallo-Lopez, J. M.; Giovanetti, L. J.; Requejo, F. G.; Isaacs, S. R.; Shon, Y. S.; Salmeron, M.

    2006-08-15

    The bonding of hexanethiols to gold nanoparticles of 1.5, 2.0, and 3 nm was studied using x-ray absorption near-edge spectroscopy (XANES) and extended x-ray absorption fine structure (EXAFS). The XANES spectra revealed that a substantial fraction of weakly bound hexanethiol molecules are present in addition to those forming covalent bonds with Au atoms. The weakly bound molecules can be removed by washing in dichloromethane. After removal of the weakly bound molecules the S K-edge XANES reveals peaks due to S-Au and S-C bonds with intensities that change as a function of particle size. Au L{sub 3}-edge EXAFS results indicate that these changes follow the changes in coordination number of Au to the S atoms at the surface of the particles.

  5. Long-range chemical sensitivity in the sulfur K-edge X-ray absorption spectra of substituted thiophenes.

    PubMed

    George, Graham N; Hackett, Mark J; Sansone, Michael; Gorbaty, Martin L; Kelemen, Simon R; Prince, Roger C; Harris, Hugh H; Pickering, Ingrid J

    2014-09-11

    Thiophenes are the simplest aromatic sulfur-containing compounds and are stable and widespread in fossil fuels. Regulation of sulfur levels in fuels and emissions has become and continues to be ever more stringent as part of governments' efforts to address negative environmental impacts of sulfur dioxide. In turn, more effective removal methods are continually being sought. In a chemical sense, thiophenes are somewhat obdurate and hence their removal from fossil fuels poses problems for the industrial chemist. Sulfur K-edge X-ray absorption spectroscopy provides key information on thiophenic components in fuels. Here we present a systematic study of the spectroscopic sensitivity to chemical modifications of the thiophene system. We conclude that while the utility of sulfur K-edge X-ray absorption spectra in understanding the chemical composition of sulfur-containing fossil fuels has already been demonstrated, care must be exercised in interpreting these spectra because the assumption of an invariant spectrum for thiophenic forms may not always be valid.

  6. Long-Range Chemical Sensitivity in the Sulfur K-Edge X-ray Absorption Spectra of Substituted Thiophenes

    PubMed Central

    2015-01-01

    Thiophenes are the simplest aromatic sulfur-containing compounds and are stable and widespread in fossil fuels. Regulation of sulfur levels in fuels and emissions has become and continues to be ever more stringent as part of governments’ efforts to address negative environmental impacts of sulfur dioxide. In turn, more effective removal methods are continually being sought. In a chemical sense, thiophenes are somewhat obdurate and hence their removal from fossil fuels poses problems for the industrial chemist. Sulfur K-edge X-ray absorption spectroscopy provides key information on thiophenic components in fuels. Here we present a systematic study of the spectroscopic sensitivity to chemical modifications of the thiophene system. We conclude that while the utility of sulfur K-edge X-ray absorption spectra in understanding the chemical composition of sulfur-containing fossil fuels has already been demonstrated, care must be exercised in interpreting these spectra because the assumption of an invariant spectrum for thiophenic forms may not always be valid. PMID:25116792

  7. Stability of mineral fibres in contact with human cell cultures. An in situ μXANES, μXRD and XRF iron mapping study.

    PubMed

    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. Copyright © 2016 Elsevier Ltd. All rights reserved.

  8. Experimental and theoretical XANES of CdSxSe1-x nanostructures

    NASA Astrophysics Data System (ADS)

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

    2014-03-01

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

  9. The Ti environment in natural hibonite: XANES spectroscopy and computer modelling

    NASA Astrophysics Data System (ADS)

    Kravtsova, Antonina N.; Soldatov, Alexander V.; Walker, Andrew M.; Berry, Andrew J.

    2016-05-01

    The local atomic structure around Ti in Ti-bearing hibonite (CaAl12O19) was studied using X-ray absorption near-edge structure (XANES) spectroscopy and computer modelling. Structural models of the direct substitution of Al by Ti3+, Al by Ti4+ charge balanced by the coupled substitution of Mg2+ for Al, and small Ti clusters were considered. The Ti K-XANES spectra of natural hibonite with different Ti concentration were recorded. Theoretical Ti K- XANES spectra for structural models of hibonite were calculated. It was shown that the theoretical Ti K-XANES spectra for a model with Ti at the five-coordinated M2 site are in agreement with the experimental XANES spectra of hibonite with low concentrations of Ti, while the theoretical spectra for a structural model of clustered Ti are in agreement with the experimental spectra of hibonite with higher Ti contents.

  10. Photon counting spectral CT: improved material decomposition with K-edge-filtered x-rays

    NASA Astrophysics Data System (ADS)

    Shikhaliev, Polad M.

    2012-03-01

    Photon counting spectral computed tomography (PCSCT) provides material selective CT imaging at a single CT scan and fixed tube voltage. The PCSCT data are acquired in several energy ranges (bins) arranged over the x-ray spectrum. The quasi-monoenergetic CT images are acquired in these energy bins and are used for material decomposition. The PCSCT exhibits inherent limitations when material decomposition is performed using energy bins. For effective material decomposition, the energy bins used for material decomposition should be sufficiently narrow and well separated. However, when narrow bins are used, a large fraction of the detected x-ray counts is lost and statistical noise is increased. Alternatively, the x-ray spectrum can be split into a few larger bins with no gap in between and all detected x-ray photons can be used for material decomposition. However, in this case the energy bins are too wide and not well separated, which results in suboptimal material decomposition. The above contradictory requirements can be resolved if the x-ray photons are physically removed from the regions of the energy spectrum between the energy bins. Such a selective removal can be performed using filtration of the x-ray beam by high-Z filter materials with appropriate positions of K-edge energies. The K-edge filtration of x-rays can, therefore, provide necessary gaps between the energy bins with no dose penalty to the patient. In the current work, we proposed using selective K-edge filtration of x-rays in PCSCT and performed the first experimental investigation of this approach. The PCSCT system included a cadmium zinc telluride semiconductor detector with 2 × 256 pixels and 1 × 1 mm2 pixel size, and five energy bins. The CT phantom had 14 cm diameter and included contrast elements of iodine, gold and calcifications with clinically relevant concentrations. The tube voltages of 60, 90 and 120 kVp were used. K-edge filters based on Ba (Ek = 37.44 keV) were used for a 60 kVp tube

  11. Real time /ital K/-edge subtraction x-ray imaging

    SciTech Connect

    Fukagawa, H.; Noda, C.; Suzuki, Y.; Hasegawa, S.; Ando, M.; Hyodo, K.; Nishimura, K.; Akisada, M.; Takenaka, E.; Hosaka, R.; and others

    1989-07-01

    This paper describes an x-ray /ital K/-edge subtraction television system for noninvasive angiography utilizing synchrotron radiation. The phantom, including contrast material (iodine), is irradiated by monochromatized dual-energy x-ray flux, alternately, using a high speed monochromator. The monochromator consists of a silicon crystal plate vibrating at 15 Hz so that the phantom is irradiated by the x-ray flux of 150 eV above and below the /ital K/-edge photon energy of iodine, 15 times per second. As an x-ray detector, TV cameras optically coupled to an x-ray image intensifier are used and the video signal is processed to display the subtraction image of pairs of successive images in real time. This system was fully implemented and moving phantoms were examined. Both the time interval between the energy change and the exposure time of each image has been shortened to 2 ms.

  12. Ca K-Edge XAS as a Probe of Calcium Centers in Complex Systems

    PubMed Central

    2014-01-01

    Herein, Ca K-edge X-ray absorption spectroscopy (XAS) is developed as a means to characterize the local environment of calcium centers. The spectra for six, seven, and eight coordinate inorganic and molecular calcium complexes were analyzed and determined to be primarily influenced by the coordination environment and site symmetry at the calcium center. The experimental results are closely correlated to time-dependent density functional theory (TD-DFT) calculations of the XAS spectra. The applicability of this methodology to complex systems was investigated using structural mimics of the oxygen-evolving complex (OEC) of PSII. It was found that Ca K-edge XAS is a sensitive probe for structural changes occurring in the cubane heterometallic cluster due to Mn oxidation. Future applications to the OEC are discussed. PMID:25492398

  13. Photon counting spectral CT: improved material decomposition with K-edge-filtered x-rays.

    PubMed

    Shikhaliev, Polad M

    2012-03-21

    Photon counting spectral computed tomography (PCSCT) provides material selective CT imaging at a single CT scan and fixed tube voltage. The PCSCT data are acquired in several energy ranges (bins) arranged over the x-ray spectrum. The quasi-monoenergetic CT images are acquired in these energy bins and are used for material decomposition. The PCSCT exhibits inherent limitations when material decomposition is performed using energy bins. For effective material decomposition, the energy bins used for material decomposition should be sufficiently narrow and well separated. However, when narrow bins are used, a large fraction of the detected x-ray counts is lost and statistical noise is increased. Alternatively, the x-ray spectrum can be split into a few larger bins with no gap in between and all detected x-ray photons can be used for material decomposition. However, in this case the energy bins are too wide and not well separated, which results in suboptimal material decomposition. The above contradictory requirements can be resolved if the x-ray photons are physically removed from the regions of the energy spectrum between the energy bins. Such a selective removal can be performed using filtration of the x-ray beam by high-Z filter materials with appropriate positions of K-edge energies. The K-edge filtration of x-rays can, therefore, provide necessary gaps between the energy bins with no dose penalty to the patient. In the current work, we proposed using selective K-edge filtration of x-rays in PCSCT and performed the first experimental investigation of this approach. The PCSCT system included a cadmium zinc telluride semiconductor detector with 2 × 256 pixels and 1 × 1 mm(2) pixel size, and five energy bins. The CT phantom had 14 cm diameter and included contrast elements of iodine, gold and calcifications with clinically relevant concentrations. The tube voltages of 60, 90 and 120 kVp were used. K-edge filters based on Ba (E(k) = 37.44 keV) were used for a 60 k

  14. Hybrid-K-edge/X-ray Fluorescense Densitometry with Laser-Compton Scattered X-rays

    SciTech Connect

    Dr. Khalid Chouffani El Fassi

    2010-08-29

    The quantitative verification of the accountancy of fissile nuclear materials through independent measurements represents one of the key elements of nuclear materials Safeguards. Elemental probes of materials of interest to non-proliferation are critical to research strategy in order to identify sensitive advanced instrumentation detection technologies. Advanced instrumentation for material detection and accountability are needed for use in fuel cycle facilities for real-time in-process monitoring of separations-partitioning, fuels fabrication as well as for traditional safeguards activities. Radiation-based NDA (non-destructive analysis) techniques can provide some vital information about nuclear materials much more quickly, cheaply and safely than chemical or radio chemical analysis. Hybrid K-edge densitometry (HKED) is currently the most accurate nondestructive inspection technique that provides sensitive quantification of heavy metal contamination. HKED in a technique that exploits both K-edge absorption and X-ray fluorescence (XRF) and allows simultaneously greater elemental specificity and lower detection limits

  15. Structural Properties and Charge Distribution of the Sodium Uranium, Neptunium, and Plutonium Ternary Oxides: A Combined X-ray Diffraction and XANES Study.

    PubMed

    Smith, Anna L; Martin, Philippe; Prieur, Damien; Scheinost, Andreas C; Raison, Philippe E; Cheetham, Anthony K; Konings, Rudy J M

    2016-02-15

    The charge distributions in α-Na2UO4, Na3NpO4, α-Na2NpO4, Na4NpO5, Na5NpO6, Na2PuO3, Na4PuO5, and Na5PuO6 are investigated in this work using X-ray absorption near-edge structure (XANES) spectroscopy at the U-L3, Np-L3, and Pu-L3 edges. In addition, a Rietveld refinement of monoclinic Na2PuO3, in space group C2/c, is reported for the first time, and the existence of the isostructural Na2NpO3 phase is revealed. In contrast to measurements in solution, the number of published XANES data for neptunium and plutonium solid phases with a valence state higher than IV is very limited. The present results cover a wide range of oxidation states, namely, IV to VII, and can serve as reference for future investigations. The sodium actinide series show a variety of local coordination geometries, and correlations between the shape of the XANES spectra and the local structural environments are discussed herein.

  16. Ca K-Edge XAS as a Probe of Calcium Centers in Complex Systems

    DOE PAGES

    Martin-Diaconescu, Vlad; Gennari, Marcello; Gerey, Bertrand; ...

    2014-12-10

    Calcium K-edge pre-edges coupled with TD-DFT theoretical calculation of spectra provide a powerful approach for the characterization of complex calcium centers in inorganic and bioinorganic chemistry. Herein, Ca K-edge X-ray absorption spectroscopy (XAS) is developed as a means to characterize the local environment of calcium centers. The spectra for six, seven, and eight coordinate inorganic and molecular calcium complexes were analyzed and determined to be primarily influenced by the coordination environment and site symmetry at the calcium center. The experimental results are closely correlated to time-dependent density functional theory (TD-DFT) calculations of the XAS spectra. The applicability of this methodologymore » to complex systems was investigated using structural mimics of the oxygen-evolving complex (OEC) of PSII. It was found that Ca K-edge XAS is a sensitive probe for structural changes occurring in the cubane heterometallic cluster due to Mn oxidation. Future applications to the OEC are discussed.« less

  17. Energy-Discriminating Gadolinium K-Edge X-ray Computed Tomography System

    NASA Astrophysics Data System (ADS)

    Matsukiyo, Hiroshi; Watanabe, Manabu; Sato, Eiichi; Osawa, Akihiro; Enomoto, Toshiyuki; Nagao, Jiro; Abderyim, Purkhet; AIzawa, Katsuo; Hitomi, Keitaro; Tanaka, Etsuro; Mori, Hidezo; Kawai, Toshiaki; Ogawa, Akira; Takahashi, Kiyomi; Sato, Shigehiro; Onagawa, Jun

    2010-02-01

    An energy-discriminating K-edge X-ray computed tomography (CT) system is useful for increasing the contrast resolution of a target region utilizing contrast media and for reducing the absorbed dose for patients. The CT system is of the first-generation type of detector using cadmium telluride (CdTe). CT is performed by repeated translations and rotations of an object. Penetrating X-ray photons from the object are detected by a CdTe detector, and event signals of X-ray photons are produced using charge-sensitive and shaping amplifiers. Both photon energy and energy width are selected out using a multichannel analyzer, and the number of photons is counted by a countercard. To perform energy discrimination, a low-dose-rate X-ray generator for photon counting was developed. Its maximum tube voltage and minimum tube current were 110 kV and 1 µA, respectively. In energy-discriminating CT, the tube voltage and tube current were 100 kV and 20 µA, respectively, and the X-ray intensity was 2.98 µGy/s at a distance of 1.0 m from the source and a tube voltage of 100 kV. The demonstration of enhanced gadolinium K-edge X-ray CT was carried out by selecting photons with energies just beyond the gadolinium K-edge energy of 50.3 keV.

  18. Energy-Discriminating Gadolinium K-Edge X-ray Computed Tomography System

    NASA Astrophysics Data System (ADS)

    Hiroshi Matsukiyo,; Manabu Watanabe,; Eiichi Sato,; Akihiro Osawa,; Toshiyuki Enomoto,; Jiro Nagao,; Purkhet Abderyim,; Katsuo AIzawa,; Keitaro Hitomi,; Etsuro Tanaka,; Hidezo Mori,; Toshiaki Kawai,; Akira Ogawa,; Kiyomi Takahashi,; Shigehiro Sato,; Jun Onagawa,

    2010-02-01

    An energy-discriminating K-edge X-ray computed tomography (CT) system is useful for increasing the contrast resolution of a target region utilizing contrast media and for reducing the absorbed dose for patients. The CT system is of the first-generation type of detector using cadmium telluride (CdTe). CT is performed by repeated translations and rotations of an object. Penetrating X-ray photons from the object are detected by a CdTe detector, and event signals of X-ray photons are produced using charge-sensitive and shaping amplifiers. Both photon energy and energy width are selected out using a multichannel analyzer, and the number of photons is counted by a countercard. To perform energy discrimination, a low-dose-rate X-ray generator for photon counting was developed. Its maximum tube voltage and minimum tube current were 110 kV and 1 μA, respectively. In energy-discriminating CT, the tube voltage and tube current were 100 kV and 20 μA, respectively, and the X-ray intensity was 2.98 μGy/s at a distance of 1.0 m from the source and a tube voltage of 100 kV. The demonstration of enhanced gadolinium K-edge X-ray CT was carried out by selecting photons with energies just beyond the gadolinium K-edge energy of 50.3 keV.

  19. K-edge x-ray absorption spectra of Cs and Xe

    SciTech Connect

    Gomilsek, J. Padeznik; Kodre, A.; Arcon, I.; Hribar, M.

    2003-10-01

    X-ray absorption spectrum of cesium vapor in the K-edge region is measured in a stainless steel cell. The spectrum is free of the x-ray absorption fine structure signal and shows small features analogous to those in the spectrum of the neighbor noble gas Xe. Although the large natural width of the K vacancy (>10 eV) washes out most of the details, fingerprints of multielectron excitations can be recognized at energies close to Dirac-Fock estimates of doubly excited states 1s4(d,p,s) and 1s3(d,p). Among these, the 1s3p excitation 1000 eV above the K edge in both spectra is the deepest double excitation observed so far. Within the K-edge profile, some resolution is recovered with numerical deconvolution of the spectra, revealing the coexcitation of the 5(p,s) electrons, and even the valence 6s electron in Cs. As in homologue elements, three-electron excitations, either as separate channels or as configuration admixtures are required to explain some spectral features in detail.

  20. Self-Supported Copper Oxide Electrocatalyst for Water Oxidation at Low Overpotential and Confirmation of Its Robustness by Cu K-edge X-ray Absorption Spectroscopy

    SciTech Connect

    Liu, Xiang; Cui, Shengsheng; Sun, Zijun; Ren, Yang; Zhang, Xiaoyi; Du, Pingwu

    2016-01-21

    Developing efficient water oxidation catalysts made of earth-abundant elements is a demanding challenge that should be met to fulfill the promise of water splitting for clean energy. Herein we report an annealing approach to synthesize binder-free, self-supported heterogeneous copper oxide (CuO) on conductive electrodes for oxygen evolution reaction (OER), producing electrodes with excellent electrocatalytic properties such as high efficiency, low overpotential, and good stability. The catalysts were grown in situ on fluorine-doped tin oxide (FTO) by electrodeposition from a simple Cu(II) salt solution, followed by annealing at a high temperature. Under optimal conditions, the CuO-based OER catalyst shows an onset potential of <0.58 V (vs Ag/AgCl) in 1.0 M KOH at pH 13.6. From the Tafel plot, the required overpotentials for current densities of 0.1 and 1.0 mA/cm2 are only 360 and 430 mV, respectively. The structure and the presence of a CuO motif in the catalyst have been identified by high-energy X-ray diffraction (HE-XRD), Cu K-edge X-ray absorption (XAS) spectra including X-ray absorption near-edge structure (XANES), and extended X-ray absorption fine structure (EXAFS). To the best of our knowledge, this represents the best catalytic activity for CuO-based OER catalysts to date.

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

    SciTech Connect

    Glazoff, Michael V.

    2016-03-14

    Abstract Transition aluminas doped with Cr find widespread application in the dehydrogenation industry, while La-stabilized transition aluminas are used extensively for high temperature application as catalytic supports. In this work, a detailed synchrotron XAFS-spectroscopy studies were conducted to shed light upon the atomic mechanisms of catalysis and/or catalytic support stabilization. It has been demonstrated that in the samples of different transition aluminas doped with Cr, the atoms of chromium 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 row “gamma – chi – theta – eta-alumina” the change of properties (in particular, of the coloration of different samples) takes place because of dramatic reduction in the average size of Cr clusters and, possibly, their appearance on the Al2O3 surface. It has been also demonstrated that the substantial change in the local coordination of the La atoms in the samples of gamma-alumina doped with La, takes place only upon heating up to 1400°C, thereby making 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). It has been proved 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 amounts of this expensive 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 bulk of alumina crystal, could be a major reason of the increased thermal stability of gamma

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

    DOE PAGES

    Glazoff, Michael V.

    2016-03-14

    Abstract Transition aluminas doped with Cr find widespread application in the dehydrogenation industry, while La-stabilized transition aluminas are used extensively for high temperature application as catalytic supports. In this work, a detailed synchrotron XAFS-spectroscopy studies were conducted to shed light upon the atomic mechanisms of catalysis and/or catalytic support stabilization. It has been demonstrated that in the samples of different transition aluminas doped with Cr, the atoms of chromium 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 row “gamma – chi – theta –more » eta-alumina” the change of properties (in particular, of the coloration of different samples) takes place because of dramatic reduction in the average size of Cr clusters and, possibly, their appearance on the Al2O3 surface. It has been also demonstrated that the substantial change in the local coordination of the La atoms in the samples of gamma-alumina doped with La, takes place only upon heating up to 1400°C, thereby making 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). It has been proved 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 amounts of this expensive 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 bulk of alumina crystal, could be a major reason of the increased thermal stability of

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

    NASA Astrophysics Data System (ADS)

    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

  4. Vanadium K-edge X-ray-absorption spectroscopy of the functioning and thionine-oxidized forms of the VFe-protein of the vanadium nitrogenase from Azotobacter chroococcum.

    PubMed Central

    Arber, J M; Dobson, B R; Eady, R R; Hasnain, S S; Garner, C D; Matsushita, T; Nomura, M; Smith, B E

    1989-01-01

    Vanadium K-edge X-ray-absorption spectra were collected for samples of thionine-oxidized, super-reduced (during enzyme turnover) and dithionite-reduced VFe-protein of the vanadium nitrogenase of Azotobacter chroococcum (Acl*). Both the e.x.a.f.s and the x.a.n.e.s. (X-ray-absorption near-edge structure) are consistent with the vanadium being present as part of a VFeS cluster; the environment of the vanadium is not changed significantly in different oxidation states of the protein. The vanadium atom is bound to three oxygen (or nitrogen), three sulphur and three iron atoms at 0.215(3), 0.231(3) and 0.275(3) nm respectively. PMID:2730564

  5. Nb K-edge x-ray absorption investigation of the pressure induced amorphization in A-site deficient double perovskite La1/3NbO3.

    PubMed

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

    2016-02-03

    Nb K-edge x-ray absorption spectroscopy is utilized to investigate the changes in the local structure of the A-site deficient double perovskite La1/3NbO3 which undergoes a pressure induced irreversible amorphization. EXAFS results show that with increasing pressure up to 7.5 GPa, the average Nb-O bond distance decreases in agreement with the expected compression and tilting of the NbO6 octahedra. On the contrary, above 7.5 GPa, the average Nb-O bond distance show a tendency to increase. Significant changes in the Nb K-edge XANES spectrum with evident low energy shift of the pre-peak and the absorption edge is found to happen in La1/3NbO3 above 6.3 GPa. These changes evidence a gradual reduction of the Nb cations from Nb(5+) towards Nb(4+) above 6.3 GPa. Such a valence change accompanied by the elongation of the average Nb-O bond distances in the octahedra, introduces repulsion forces between non-bonding adjacent oxygen anions in the unoccupied A-sites. Above a critical pressure, the Nb reduction mechanism can no longer be sustained by the changing local structure and amorphization occurs, apparently due to the build-up of local strain. EXAFS and XANES results indicate two distinct pressure regimes having different local and electronic response in the La1/3NbO3 system before the occurence of the pressure induced amorphization at  ∼14.5 GPa.

  6. Nb K-edge x-ray absorption investigation of the pressure induced amorphization in A-site deficient double perovskite La1/3NbO3

    NASA Astrophysics Data System (ADS)

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

    2016-02-01

    Nb K-edge x-ray absorption spectroscopy is utilized to investigate the changes in the local structure of the A-site deficient double perovskite La1/3NbO3 which undergoes a pressure induced irreversible amorphization. EXAFS results show that with increasing pressure up to 7.5 GPa, the average Nb-O bond distance decreases in agreement with the expected compression and tilting of the NbO6 octahedra. On the contrary, above 7.5 GPa, the average Nb-O bond distance show a tendency to increase. Significant changes in the Nb K-edge XANES spectrum with evident low energy shift of the pre-peak and the absorption edge is found to happen in La1/3NbO3 above 6.3 GPa. These changes evidence a gradual reduction of the Nb cations from Nb5+ towards Nb4+ above 6.3 GPa. Such a valence change accompanied by the elongation of the average Nb-O bond distances in the octahedra, introduces repulsion forces between non-bonding adjacent oxygen anions in the unoccupied A-sites. Above a critical pressure, the Nb reduction mechanism can no longer be sustained by the changing local structure and amorphization occurs, apparently due to the build-up of local strain. EXAFS and XANES results indicate two distinct pressure regimes having different local and electronic response in the La1/3NbO3 system before the occurence of the pressure induced amorphization at  ˜14.5 GPa.

  7. Comparison of iodine K-edge subtraction and fluorescence subtraction imaging in an animal system

    NASA Astrophysics Data System (ADS)

    Zhang, H.; Zhu, Y.; Bewer, B.; Zhang, L.; Korbas, M.; Pickering, I. J.; George, G. N.; Gupta, M.; Chapman, D.

    2008-09-01

    K-Edge Subtraction (KES) utilizes the discontinuity in the X-ray absorption across the absorption edge of the selected contrast element and creates an image of the projected density of the contrast element from two images acquired just above and below the K-edge of the contrast element. KES has proved to be powerful in coronary angiography, micro-angiography, bronchography, and lymphatic imaging. X-ray fluorescence imaging is a successful technique for the detection of dilute quantities of elements in specimens. However, its application at high X-ray energies (e.g. at the iodine K-edge) is complicated by significant Compton background, which may enter the energy window set for the contrast material's fluorescent X-rays. Inspired by KES, Fluorescence Subtraction Imaging (FSI) is a technique for high-energy (>20 keV) fluorescence imaging using two different incident beam energies just above and below the absorption edge of a contrast element (e.g. iodine). The below-edge image can be assumed as a "background" image, which includes Compton scatter and fluorescence from other elements. The above-edge image will contain nearly identical spectral content as the below-edge image but will contain the additional fluorescence of the contrast element. This imaging method is especially promising with thick objects with dilute contrast materials, significant Compton background, and/or competing fluorescence lines from other materials. A quality factor is developed to facilitate the comparison. The theoretical value of the quality factor sets the upper limit that an imaging method can achieve when the noise is Poisson limited. The measured value of this factor makes two or more imaging methods comparable. Using the Hard X-ray Micro-Analysis (HXMA) beamline at the Canadian Light Source (CLS), the techniques of FSI and KES were critically compared, with reference to radiation dose, image acquisition time, resolution, signal-to-noise ratios, and quality factor.

  8. A Bremsstrahlung Spectrometer using k-edge and Differential Filters with Image plate dosimeters

    SciTech Connect

    Chen, C; Mackinnon, A; Beg, F; Chen, H; Key, M; King, J A; Link, A; MacPhee, A; Patel, P; Porkolab, M; Stephens, R; VanWoerkom, L; Akli, K; Freeman, R

    2008-05-02

    A Bremsstrahlung spectrometer using k-edge and differential filtering has been used with Image Plate dosimeters to measure the x-ray fluence from short-pulse laser/target interactions. An electron spectrometer in front of the Bremsstrahlung spectrometer deflects electrons from the x-ray line of sight and simultaneously measures the electron spectrum. The response functions were modeled with the Monte Carlo code Integrated Tiger Series 3.0 and the dosimeters calibrated with radioactive sources. Electron distributions with slope temperatures in the MeV range are inferred from the Bremsstrahlung spectra.

  9. A Bremsstrahlung spectrometer using k-edge and differential filters with image plate dosimeters

    SciTech Connect

    Chen, C. D.; Porkolab, M.; King, J. A.; Beg, F. N.; Key, M. H.; Chen, H.; Mackinnon, A. J.; MacPhee, A. G.; Patel, P. K.; Akli, K. U.; Stephens, R. B.; Freeman, R. R.; Link, A.; Van Woerkom, L. D.

    2008-10-15

    A Bremsstrahlung spectrometer using k-edge and differential filtering has been used with image plate dosimeters to measure the x-ray fluence from short-pulse laser/target interactions. An electron spectrometer in front of the Bremsstrahlung spectrometer deflects electrons from the x-ray line of sight and simultaneously measures the electron spectrum. The response functions were modeled with the Monte Carlo code INTEGRATED TIGER SERIES 3.0 and the dosimeters calibrated with radioactive sources. An electron distribution with a slope temperature of 1.3 MeV is inferred from the Bremsstrahlung spectra.

  10. X-ray, K-edge measurement of uranium concentration in reactor fuel plates

    SciTech Connect

    Jensen, T.; Aljundi, T.; Whitmore, C.; Zhong, H.; Gray, J.N.

    1997-11-26

    Under the Characterization, Monitoring, and Sensor Technology Crosscutting Program, the authors have designed and built a K-edge heavy-metal detector that measures the level of heavy-metal content inside closed containers in a nondestructive, non-invasive way. They have applied this technique to measurement of the amount of uranium in stacks of reactor fuel plates containing nuclear materials of different enrichments and alloys. They have obtained good agreement with expected uranium concentrations ranging from 60 mg/cm{sup 2} to 3,000 mg/cm{sup 2}, and have demonstrated that the instrument can operate in a high radiation field (> 200 mR/hr).

  11. Performance of the HERMES beamline at the carbon K-edge

    NASA Astrophysics Data System (ADS)

    Swaraj, S.; Belkhou, R.; Stanescu, S.; Rioult, M.; Besson, A.; Hitchcock, A. P.

    2017-06-01

    Contamination of soft X-rays beamline optics due to carbon cracking and deposition under X- ray irradiation is especially critical for spectromicroscopy operations near the carbon K-absorption edge from organic materials, polymers and nanoparticles. In this paper we present the strategy and procedure followed on the HERMES beamline (Synchrotron SOLEIL) to minimize carbon contamination of the beamline optics. Measurements on a complex organic test sample are reported to demonstrate the performance of the beamline at the carbon K-edge in imaging, spectroscopy and spectromicroscopy modes.

  12. Sensitivity of photon-counting based K-edge imaging in X-ray computed tomography.

    PubMed

    Roessl, Ewald; Brendel, Bernhard; Engel, Klaus-Jürgen; Schlomka, Jens-Peter; Thran, Axel; Proksa, Roland

    2011-09-01

    The feasibility of K-edge imaging using energy-resolved, photon-counting transmission measurements in X-ray computed tomography (CT) has been demonstrated by simulations and experiments. The method is based on probing the discontinuities of the attenuation coefficient of heavy elements above and below the K-edge energy by using energy-sensitive, photon counting X-ray detectors. In this paper, we investigate the dependence of the sensitivity of K-edge imaging on the atomic number Z of the contrast material, on the object diameter D , on the spectral response of the X-ray detector and on the X-ray tube voltage. We assume a photon-counting detector equipped with six adjustable energy thresholds. Physical effects leading to a degradation of the energy resolution of the detector are taken into account using the concept of a spectral response function R(E,U) for which we assume four different models. As a validation of our analytical considerations and in order to investigate the influence of elliptically shaped phantoms, we provide CT simulations of an anthropomorphic Forbild-Abdomen phantom containing a gold-contrast agent. The dependence on the values of the energy thresholds is taken into account by optimizing the achievable signal-to-noise ratios (SNR) with respect to the threshold values. We find that for a given X-ray spectrum and object size the SNR in the heavy element's basis material image peaks for a certain atomic number Z. The dependence of the SNR in the high- Z basis-material image on the object diameter is the natural, exponential decrease with particularly deteriorating effects in the case where the attenuation from the object itself causes a total signal loss below the K-edge. The influence of the energy-response of the detector is very important. We observed that the optimal SNR values obtained with an ideal detector and with a CdTe pixel detector whose response, showing significant tailing, has been determined at a synchrotron differ by factors of

  13. Vibrationally resolved NEXAFS at C and N K-edges of pyridine, 2-fluoropyridine and 2,6-difluoropyridine: A combined experimental and theoretical assessment

    SciTech Connect

    Baiardi, Alberto; Mendolicchio, Marco; Barone, Vincenzo; Fronzoni, Giovanna; Cardenas Jimenez, Gustavo Adolfo; Stener, Mauro; Grazioli, Cesare; Simone, Monica de; Coreno, Marcello

    2015-11-28

    In the present work, the near edge X-ray absorption spectroscopy (NEXAFS) spectra at both C and N K-edges of pyridine, 2-fluoropyridine, and 2,6-difluoropyridine have been studied both experimentally and theoretically. From an electronic point of view, both transition potential density functional theory and time-dependent density functional theory approaches lead to reliable results provided that suitable basis sets and density functionals are employed. In this connection, the global hybrid B3LYP functional in conjunction with the EPR-III basis set appears particularly suitable after constant scaling of the band positions. For the N K-edge, vertical energies obtained at these levels and broadened by symmetric Gaussian distributions provide spectra in reasonable agreement with the experiment. Vibronic contributions further modulate the band-shapes leading to a better agreement with the experimental results, but are not strictly necessary for semi-quantitative investigations. On the other hand, vibronic contributions are responsible for strong intensity redistribution in the NEXAFS C K-edge spectra, and their inclusion is thus mandatory for a proper description of experiments. In this connection, the simple vertical gradient model is particularly appealing in view of its sufficient reliability and low computational cost. For more quantitative results, the more refined vertical Hessian approach can be employed, and its effectiveness has been improved thanks to a new least-squares fitting approach.

  14. Study of Cu chemical state inside single neurons from Parkinson's disease and control substantia nigra using the micro-XANES technique.

    PubMed

    Chwiej, Joanna; Adamek, Dariusz; Szczerbowska-Boruchowska, Magdalena; Krygowska-Wajs, Anna; Bohic, Sylvain; Lankosz, Marek

    2008-01-01

    Parkinson's disease (PD) is referred to as idiopathic disorder, which means that its causes have not been found yet. However, a few processes such as oxidative stress, protein aggregation and mitochondrial dysfunction are suspected to lead to the atrophy and death of substantia nigra (SN) neurons in case of this neurodegenerative disorder. Cu is a trace element whose role in the pathogenesis of PD is widely discussed. The investigation of Cu oxidation state inside single nerve cells from SN of PD and control cases may shed some new light on the role of this element in PD. The differences in Cu chemical state were investigated with the use of X-ray absorption near edge structure (XANES) spectroscopy. The least-square fitting method was applied for the analysis of XANES spectra. The comparison of the positions of white line, multiple scattering and pre-edge peak maximum at the energy scale did not reveal the existence of differences in Cu chemical state between PD and control samples. However, it was found that most of the Cu inside SN neurons occurs in tetrahedral environment and probably as Cu(II).

  15. K-edge eliminated material decomposition method for dual-energy X-ray CT.

    PubMed

    Zhao, Tiao; Li, Liang; Chen, Zhiqiang

    2017-09-01

    In medical dual-energy CT, projection-domain decomposition is typically used to process the acquired two projection datasets. However, when a high atomic-number contrast-agent is introduced, its K-edge discontinuity challenges this method. In this work, we take advantage of the fact that the contrast agent and its solvent are known in advance and propose to first decompose the attenuation coefficient functions of the contrast agent and its solvent to estimate the attenuation contribution of the K-shell photoelectric. Then, the contribution of the K-edge attenuation to the projection data is eliminated and the problem is decomposed to determine the attenuation coefficient functions of the other biological materials. Numerical experiments are shown to verify that the proposed method can give better results with less artifacts than the result of the direct projection-domain decomposition. Moreover, the variances of the decomposition coefficients, which is the index of the noise level of the decomposition coefficient image on the contrast regions, are smaller. Copyright © 2017. Published by Elsevier Ltd.

  16. Animal experiments by K-edge subtraction angiography by using SR (abstract)

    NASA Astrophysics Data System (ADS)

    Anno, I.; Akisada, M.; Takeda, T.; Sugishita, Y.; Kakihana, M.; Ohtsuka, S.; Nishimura, K.; Hasegawa, S.; Takenaka, E.; Hyodo, K.; Ando, M.

    1989-07-01

    Ischemic heart disease is one of the most popular and lethal diseases for aged peoples in the world, and is usually diagnosed by transarterial selective coronary arteriography. However, it is rather invasive and somewhat dangerous, so that the selective coronary arteriography is not feasible for prospective screening of coronary occlusive heart disease. Conventional digital subtraction angiography (DSA) is widely known as a relatively noninvasive and useful technique is making a diagnosis of arterial occlusive disease, especially in making the diagnosis of ischemic heart disease. Conventional intravenous subtraction angiography by temporal subtraction, however, has several problems when applying to the moving objects. Digital subtraction method using high-speed switching above and below the K edge could be the ideal approach to this solution. We intend to make a synchrotron radiation digital K-edge subtraction angiography in the above policy, and to apply it to the human coronary ischemic disease on an outpatient basis. The principles and experimental systems have already been described in detail by our coworkers. Our prototype experimental system is situated at the AR (accumulation ring) for TRISTAN project of high energy physics. The available beam size is 70 mm by 120 mm. The electron energy of AR is 6.5 GeV and average beam current is approximately 10 mA. This paper will show the animal experiments of our K-edge subtraction system, and discuss some problems and technical difficulties. Three dogs, weighing approximately 15 kg, were examined to evaluate the ability of our prototype synchrotron radiation DSA unit, that we are now constructing. The dogs were anaesthetized with pentobarbital sodium, intravenously (30 mg/kg). Six french-sized (1.52 mm i.d.) pigtail catheter with multiple side holes were introduced via the right femoral vein into the right atrium by the cutdown technique under conventional x-ray fluoroscopic control. Respiration of the dogs was

  17. XANES evidence for oxidation of Cr(III) to Cr(VI) by Mn-oxides in a lateritic regolith developed on serpentinized ultramafic rocks of New Caledonia.

    PubMed

    Fandeur, Dik; Juillot, Farid; Morin, Guillaume; Olivi, Luca; Cognigni, Andrea; Webb, Samuel M; Ambrosi, Jean-Paul; Fritsch, Emmanuel; Guyot, François; Brown, Gordon E

    2009-10-01

    Although several laboratory studies showed that Mn-oxides are capable of oxidizing Cr(II) to Cr(VI), very few have reported evidence for such a reaction in natural systems. This study presents new evidence for this redox reaction between Cr(III) and Mn-oxides in a lateritic regolith developed on ultramafic rocks in New Caledonia. The studied lateritic regolith presents several units with contrasting amounts of major (Fe, Al, Si, and Mg) and trace (Mn, Cr, Ni, Co) elements, which are related to varying mineralogical compositions. Bulk XANES analyses show the occurrence of Cr(VI) (up to 20 wt % of total chromium) in the unit of the regolith which is also enriched in Mn (up to 21.7 wt % MnO), whereas almost no Cr(VI) is detected elsewhere. X-ray powder diffraction indicates that the large amounts of Mn in this unit of the regolith are due to the occurrence of Mn-oxides (identified as a mixture of asbolane, lithiophorite and birnessite) and Mn K-edge XANES data indicate that Mn occurs mainly as Mn(IV) in this unit, although small amounts of Mn(III) could also be detected. These results strongly suggest a direct role of the Mn-oxides on the occurrence of Cr(VI) through a redox reaction between Cr(III) and Mn(IV) and/or Mn(III). Owing to the much larger toxicity and solubility of Cr(VI), such a co-occurrence of Cr and Mn-oxides in these soils could then represent an important risk for the environment. However, the significant amounts of Cr(VI) released after reacting the samples from the studied sequence with a 0.1 M (NH)4H2PO4 solution, designed to remove tightly sorbed chromate species, suggest that Cr(VI) mainly occurs as sorption complexes. This hypothesis is reinforced by spatially resolved XANES analyses, which show that Cr(VI) is associated with both Mn- and Fe-oxides, and especially at the boundary between these two mineral species. Such a distribution of Cr(VI) suggests a possible readsorption of Cr(VI) onto surrounding Fe-oxyhydroxides (mainly goethite) after

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

    NASA Astrophysics Data System (ADS)

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

    2013-04-01

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

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

    PubMed

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

    2013-01-30

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

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

    PubMed

    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.

  1. Properties of pure and sulfided NiMoO{sub 4} and CoMoO{sub 4} catalysts: TPR, XANES and time-resolved XRD studies

    SciTech Connect

    Chaturvedi, S.; Rodriguez, J.A.; Hanson, J.C.; Albornoz, A.; Brito, J.L.

    1998-12-31

    X-ray absorption near-edge spectroscopy (XANES) was used to characterize the structural and electronic properties of a series of cobalt- and nickel-molybdate catalysts (AMoO{sub 4}.nH{sub 2}O, {alpha}-AMoO{sub 4}, {beta}-AMoO{sub 4}; A=Co or Ni). The results of XANES indicate that the Co and Ni atoms are in octahedral sites in all these compounds, while the coordination of Mo varies from octahedral in the {alpha}-phases to tetrahedral in the {beta}-phases and hydrate. Time-resolved x-ray diffraction shows a direct transformation of the hydrates into the {beta}-AMoO{sub 4} compounds (following a kinetics of first order) at temperatures between 200 and 350{degrees}C. This is facilitated by the similarities that the AMoO{sub 4}.nH{sub 2}O and H{sub 2} at temperatures between 400 and 600{degrees}C, forming gaseous water oxides in which the oxidation state of Co and Ni remains +2 while that of Mo is reduced to +5 or +4. After exposing {alpha}-NiMoO{sub 4} and {beta}-NiMoO{sub 4} to H{sub 2}S, both metals get sulfided and a NiMoS{sub x} phase is formed. For the {beta} phase of NiMoO{sub 4} the sulfidation of Mo is more extensive than for the {alpha} phase, making the former a better precursor for catalysts of hydrodesulfurization reactions.

  2. Characterization of atmospheric aerosols using Synchroton radiation total reflection X-ray fluorescence and Fe K-edge total reflection X-ray fluorescence-X-ray absorption near-edge structure

    NASA Astrophysics Data System (ADS)

    Fittschen, U. E. A.; Meirer, F.; Streli, C.; Wobrauschek, P.; Thiele, J.; Falkenberg, G.; Pepponi, G.

    2008-12-01

    In this study a new procedure using Synchrotron total reflection X-ray fluorescence (SR-TXRF) to characterize elemental amounts in atmospheric aerosols down to particle sizes of 0.015 um is presented. The procedure was thoroughly evaluated regarding bounce off effects and blank values. Additionally the potential of total reflection X-ray fluorescence-X-ray absorption near edge structure (SR-TXRF-XANES) for speciation of FeII/III down to amounts of 34 pg in aerosols which were collected for 1 h is shown. The aerosols were collected in the city of Hamburg with a low pressure Berner impactor on Si carriers covered with silicone over time periods of 60 and 20 min each. The particles were collected in four and ten size fractions of 10.0-8.0 μm, 8.0-2.0 μm, 2.0-0.13 μm 0.13-0.015 μm (aerodynamic particle size) and 15-30 nm, 30-60 nm, 60-130 nm, 130-250 nm, 250-500 nm, 0.5-1 μm, 1-2 μm, 2-4 μm, 4-8 μm, 8-16 μm. Prior to the sampling "bounce off" effects on Silicone and Vaseline coated Si carriers were studied with total reflection X-ray fluorescence. According to the results silicone coated carriers were chosen for the analysis. Additionally, blank levels originating from the sampling device and the calibration procedure were studied. Blank levels of Fe corresponded to 1-10% of Fe in the aerosol samples. Blank levels stemming from the internal standard were found to be negligible. The results from the Synchroton radiation total reflection X-ray fluorescence analysis of the aerosols showed that 20 min of sampling time gave still enough sample material for elemental determination of most elements. For the determination of the oxidation state of Fe in the aerosols different Fe salts were prepared as a reference from suspensions in isopropanol. The results from the Fe K-edge Synchroton radiation total reflection X-ray fluorescence-X-ray absorption near-edge structure analysis of the aerosol samples showed that mainly Fe(III) was present in all particle size fractions.

  3. Reduction and re-oxidation of Cu/Al2O3 catalysts investigated with quick-scanning XANES and EXAFS

    NASA Astrophysics Data System (ADS)

    Stötzel, J.; Lützenkirchen-Hecht, D.; Frahm, R.; Kimmerle, B.; Baiker, A.; Nachtegaal, M.; Beier, M. J.; Grunwaldt, J.-D.

    2009-11-01

    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.

  4. An energy dispersive bent Laue monochromator for K-edge subtraction imaging

    SciTech Connect

    Samadi, Nazanin; Martinson, Mercedes; Bassey, Bassey; Gomez, Ariel; Belev, George; Chapman, Dean

    2016-07-27

    K-Edge Subtraction (KES) is a powerful synchrotron imaging method that allows the quantifiable determination of a contrast element (e.g. iodine) and matrix material (usually represented as water) in both projection imaging and computed tomography. A bent Laue monochromator has been developed that has very good focal and energy dispersive properties for KES. Approximately 5% of the vertical beam profile is involved in “edge crossing” energies, thus no splitter is employed as has been done with previous implementations where approximately 33% of the beam size was blocked. The beam can be narrowed vertically allowing a smaller crossover angle than a splitter based system which minimizes artifacts. The combination of good spatial resolution, energy dispersive properties, flux and a unique approach to data analysis make this system nearly ideal for KES.

  5. Exotic sources of x-rays for iodine K-edge angiography

    SciTech Connect

    Carr, R.

    1993-08-01

    Digital Subtractive Angiography (DSA) has been performed to image human coronary arteries using wiggler radiation from electron storage rings. The significant medical promise of this procedure motivates the development of smaller and less costly x-ray sources. Several exotic sources are candidates for consideration, using effects such as Cherenkov, channeling, coherent bremsstrahlung, laser backscattering, microundulator, parametric, Smith-Purcell, and transition radiation. In this work we present an analysis of these effects as possible sources of intense x-rays at the iodine K-edge at 33.169 key. The criteria we use are energy, efficiency, flux, optical properties, and technical realizability. For each of the techniques, we find that they suffer either from low flux, a low energy cutoff, target materials heating, too high electron beam energy requirement, optical mismatch to angiography, or a combination of these. We conclude that the foreseeable state-of-the-art favors a compact storage ring design.

  6. Measurement of an inverse Compton scattering source local spectrum using k-edge filters

    SciTech Connect

    Golosio, Bruno; Oliva, Piernicola; Carpinelli, Massimo; Endrizzi, Marco; Delogu, Pasquale; Pogorelsky, Igor; Yakimenko, Vitaly

    2012-04-16

    X-ray sources based on the inverse Compton scattering process are attracting a growing interest among scientists, due to their extremely fast pulse, quasi-monochromatic spectrum, and relatively high intensity. The energy spectrum of the x-ray beam produced by inverse Compton scattering sources in a fixed observation direction is a quasi-monochromatic approximately Gaussian distribution. The mean value of this distribution varies with the scattering polar angle between the electron beam direction and the x-ray beam observation direction. Previous works reported experimental measurements of the mean energy as a function of the polar angle. This work introduces a method for the measurement of the whole local energy spectrum (i.e., the spectrum in a fixed observation direction) of the x-ray beam yielded by inverse Compton scattering sources, based on a k-edge filtering technique.

  7. The potential for neurovascular intravenous angiography using K-edge digital subtraction angiography

    NASA Astrophysics Data System (ADS)

    Schültke, E.; Fiedler, S.; Kelly, M.; Griebel, R.; Juurlink, B.; LeDuc, G.; Estève, F.; Le Bas, J.-F.; Renier, M.; Nemoz, C.; Meguro, K.

    2005-08-01

    Background: Catheterization of small-caliber blood vessels in the central nervous system can be extremely challenging. Alternatively, intravenous (i.v.) administration of contrast agent is minimally invasive and therefore carries a much lower risk for the patient. With conventional X-ray equipment, volumes of contrast agent that could be safely administered to the patient do not allow acquisition of high-quality images after i.v. injection, because the contrast bolus is extremely diluted by passage through the heart. However, synchrotron-based digital K-edge subtraction angiography does allow acquisition of high-quality images after i.v. administration of relatively small doses of contrast agent. Materials and methods: Eight adult male New Zealand rabbits were used for our experiments. Animals were submitted to both angiography with conventional X-ray equipment and synchrotron-based digital subtraction angiography. Results: With conventional X-ray equipment, no contrast was seen in either cerebral or spinal blood vessels after i.v. injection of iodinated contrast agent. However, using K-edge digital subtraction angiography, as little as 1 ml iodinated contrast agent, when administered as i.v. bolus, yielded images of small-caliber blood vessels in the central nervous system (both brain and spinal cord). Conclusions: If it would be possible to image blood vessels of the same diameter in the central nervous system of human patients, the synchrotron-based technique could yield high-quality images at a significantly lower risk for the patient than conventional X-ray imaging. Images could be acquired where catheterization of feeding blood vessels has proven impossible.

  8. X-ray absorption spectroscopic study of new high-Tc superconducting intercalation compound of (HgX2)0.5Bi2Sr2CaCu2Oy(X=Br,I)

    NASA Astrophysics Data System (ADS)

    Choy, Jin-Ho; Park, Nam-Gyu; Hwang, Seong-Ju; Hwang, Sung-Ho; Kim, Dong-Hoon

    1996-06-01

    We have systematically performed x-ray absorption spectroscopic (XAS) studies on the new mercuric halide intercalated superconductors, (HgX2)0.5Bi2Sr2CaCu2Oy with X equals Br and I, in order to investigate the electronic and crystal structure of these compounds. The present Hg LIII-edge EXAFS results indicate that the mercury is coordinated with two bromide or iodide ligands with bond length of 2.46 angstrom for the HgBr2-intercalate and 2.65 angstrom for the HgI2-one. This is the first example of linear molecular salt of HgX2 stabilized in the solid lattice. According to the I LI- and Br K-edge x-ray absorption near edge structure (XANES) spectroscopic studies, a small amount of electron transfer from the intercalant HgX2 to the host lattice could be observed upon intercalation, resulting in the negatively charged state of (HgX2)(delta -). The Cu K-edge EXAFS analysis reveals that the bond distance of Cu-Oaxial is slightly shortened upon intercalation, reflecting the oxidation of (Cu-O) layer, which is well consistent with the I LI- and Br K-edge XANES results.

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

    PubMed

    Xiong, Wenhui; Peng, Jian; Hu, Yongfeng

    2012-02-15

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

  10. Nickel site distribution and clustering in synthetic double-chain silicates by experimental and theoretical XANES spectroscopy

    NASA Astrophysics Data System (ADS)

    Giuli, Gabriele; Paris, Eleonora; Ziyu, Wu; Berrettoni, Mario; della Ventura, Giancarlo; Mottana, Annibale

    2000-09-01

    The crystal-chemical role of Ni in synthetic potassium-richterites within the join K(CaNa)Mg4Ni[Si8O22](OH)2-K(CaNa)Ni5[Si8O22](OH)2 has been investigated by XAS (x-ray-absorption spectroscopy). From a structural point of view these materials are classified as double-chain silicates and belong to the amphiboles group. X-ray absorption near-edge structure (XANES) spectra recorded at the Ni K edge show variations that can be related to the Ni-Mg substitution at the octahedral M sites of these amphi-boles. Theoretical XANES spectra, calculated on the basis of the multiple-scattering theory, reproduce very well the experimental spectra, and allow us to understand the relationships between XANES features and the chemical and structural environments around the photoabsorbing ion. The combination of XAS experiments and theoretical calculations provides information on the Ni partitioning between the three octahedral sites and on the local chemistry around the absorber.

  11. Local structure of ball-milled LaNi{sub 5} hydrogen storage material by Ni K-edge EXAFS

    SciTech Connect

    Joseph, B.; Iadecola, A.; Schiavo, B.; Cognigni, A.; Olivi, L.; D'Ali Staiti, G.; Saini, N.L.

    2010-07-15

    Local structure of the nanostructured LaNi{sub 5} hydrogen storage alloys, prepared by ball-milling, has been studied using Ni K-edge extended X-ray absorption fine structure spectroscopy. Results indicate that the ball-milling up to 100 h results in the production of nanoparticles characterized by large atomic disorder and slightly reduced unit-cell volume, compared to the bulk LaNi{sub 5}. High temperature annealing appears to help in partial recovery of atomic order in the ball-milled samples; however, long-time ball-milled samples retain large disorder even after the high temperature annealing. The results suggest that the large disorder and the reduced unit-cell volume might be causing a higher energy-barrier for the hydride-phase formation in the long time ball-milled LaNi{sub 5} powders. - Graphical Abstract: X-ray diffraction (XRD) pattern (left panel) and Fourier transforms of the Ni K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy (right panel) of bulk LaNi{sub 5} hydrogen storage material (structure model is given in the middle) together with the same after 100 h ball-milling. Milled samples show a remarkable reduction intensity and broadening of the XRD peaks. Substantial damping of the amplitude and a slight shrinkage of the profile are observed in the EXAFS spectrum. These results indicate that the ball-milling up to 100 h results in the production of nanoparticles characterized by slightly reduced unit-cell volume and substantial atomic disorder compared to the bulk LaNi5. High temperature annealing appears to help in partial recovery of atomic order in the ball-milled samples; however, long-time ball-milled samples retain the disorder even after the high temperature annealing. The results suggest that the large disorder and the reduced unit-cell volume might be causing a higher energy-barrier for the hydride-phase formation in the long-time ball-milled LaNi{sub 5} powders.

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

    PubMed

    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.

  13. Field flatteners fabricated with a rapid prototyper for K-edge subtraction imaging of small animals

    NASA Astrophysics Data System (ADS)

    Zhu, Ying; Zhang, Honglin; Bewer, Brian; Florin Gh. Popescu, Bogdan; Nichol, Helen; Chapman, Dean

    2008-04-01

    One of the difficulties in X-ray imaging is the need to record a wide dynamic range of intensities on the detector. For example, some rays may miss the object being imaged entirely while others may suffer many orders of magnitude attenuation in passing through. In K-edge subtraction (KES) [E. Rubenstein, et al., Trans. Am. Clin. Climatol. Assoc. 97 (1985) 27.] imaging subtle differences in transmission through an object about the absorption edge of an element are used to create an image of the projected density of that element. This is done by a logarithmic subtraction of images acquired with energies above and below the absorption edge. For KES, the detector must register this transmitted intensity range in a linear manner for the subtraction method to be successful. The range of intensities which may strike the detector has inspired the concept of a field flattener. A field flattener is a device placed in the beam path that attenuates the input monochromatic beam to equalize X-ray absorption due to differences in the density of soft and hard tissues of an object before it passes through the object and thus achieves a flattened image. This removes the need for a wide dynamic range linear detector and allows detectors with modest performance to be used successfully in KES applications. The field flattener improves the S/ N ratio since X-ray exposures can be increased up to detector saturation. However, a field flattener removes anatomical information from each raw image (above or below K-edge) that may provide useful landmarks. Using rapid prototyping technology, two sets of field flatteners were fabricated and used in a KES experiment. This paper describes the procedure to design and fabricate field flatteners based on animal images from X-ray computed tomography (CT). Analysis of experimental data and KES images of a rat head with and without the field flattener are also presented. The results show a promising improvement of S/ N ratio using a field flattener

  14. Fe K-edge X-ray resonant magnetic scattering from Ba(Fe1−xCox)2As2 superconductors

    SciTech Connect

    Kim, Min Gyu; Kreyssig, Andreas; Lee, Yongbin; McQueeney, Robert J.; Harmon, Bruce N.; Goldman, Alan I.

    2012-06-15

    We present an X-ray resonant magnetic scattering study at the Fe-K absorption edge of the BaFe2As2 compound. The energy spectrum of the resonant scattering, together with our calculation using the full-potential linear-augmented plane wave method with a local density functional suggests that the observed resonant scattering arises from electric dipole (E1) transitions. We discuss the role of Fe K-edge X-ray resonant magnetic scattering in understanding the relationship between the structure and the antiferromagnetic transition in the doped Ba(Fe1−xCox)2As2 superconductors.

  15. Resonant inelastic x-ray scattering on iso-C₂H₂Cl₂ around the chlorine K-edge: structural and dynamical aspects.

    PubMed

    Kawerk, Elie; Carniato, Stéphane; Journel, Loïc; Marchenko, Tatiana; Piancastelli, Maria Novella; Žitnik, Matjaž; Bučar, Klemen; Bohnic, Rok; Kavčič, Matjaž; Céolin, Denis; Khoury, Antonio; Simon, Marc

    2014-10-14

    We report a theoretical and experimental study of the high resolution resonant K(α) X-ray emission lines around the chlorine K-edge in gas phase 1,1-dichloroethylene. With the help of ab initio electronic structure calculations and cross section evaluation, we interpret the lowest lying peak in the X-ray absorption and emission spectra. The behavior of the K(α) emission lines with respect to frequency detuning highlights the existence of femtosecond nuclear dynamics on the dissociative Potential Energy Surface of the first K-shell core-excited state.

  16. Oxygen K edge scattering from bulk comb diblock copolymer reveals extended, ordered backbones above lamellar order-disorder transition

    SciTech Connect

    Kortright, Jeffrey Barrett; Sun, Jing; Spencer, Ryan K.; Jiang, Xi; Zuckermann, Ronald N.

    2016-12-14

    The evolution of molecular morphology in bulk samples of comb diblock copolymer pNdc12-b-pNte21 across the lamellar order-disorder transition (ODT) is studied using resonant x-ray scattering at the oxygen K edge, with the goal of determining whether the molecules remain extended or collapse above the ODT. The distinct spectral resonances of carbonyl oxygen on the backbone and ether oxygen in the pNte side chains combine with their different site symmetry within the molecule to yield strong differences in bulk structural sensitivity at all temperatures. Comparison with simple models for the disordered phase clearly reveals that disordering at the ODT corresponds to loss of positional order of molecules with extended backbones that retain orientational order, rather than backbone collapse into a locally isotropic disordered phase. This conclusion is facilitated directly by the distinct structural sensitivity at the two resonances. Lastly, we discuss the roles of depolarized scattering in enhancing this sensitivity, and background fluorescence in limiting dynamic range, in oxygen resonant scattering.

  17. Oxygen K edge scattering from bulk comb diblock copolymer reveals extended, ordered backbones above lamellar order-disorder transition

    DOE PAGES

    Kortright, Jeffrey Barrett; Sun, Jing; Spencer, Ryan K.; ...

    2016-12-14

    The evolution of molecular morphology in bulk samples of comb diblock copolymer pNdc12-b-pNte21 across the lamellar order-disorder transition (ODT) is studied using resonant x-ray scattering at the oxygen K edge, with the goal of determining whether the molecules remain extended or collapse above the ODT. The distinct spectral resonances of carbonyl oxygen on the backbone and ether oxygen in the pNte side chains combine with their different site symmetry within the molecule to yield strong differences in bulk structural sensitivity at all temperatures. Comparison with simple models for the disordered phase clearly reveals that disordering at the ODT corresponds tomore » loss of positional order of molecules with extended backbones that retain orientational order, rather than backbone collapse into a locally isotropic disordered phase. This conclusion is facilitated directly by the distinct structural sensitivity at the two resonances. Lastly, we discuss the roles of depolarized scattering in enhancing this sensitivity, and background fluorescence in limiting dynamic range, in oxygen resonant scattering.« less

  18. High-resolution molybdenum K-edge X-ray absorption spectroscopy analyzed with time-dependent density functional theory.

    PubMed

    Lima, Frederico A; Bjornsson, Ragnar; Weyhermüller, Thomas; Chandrasekaran, Perumalreddy; Glatzel, Pieter; Neese, Frank; DeBeer, Serena

    2013-12-28

    X-ray absorption spectroscopy (XAS) is a widely used experimental technique capable of selectively probing the local structure around an absorbing atomic species in molecules and materials. When applied to heavy elements, however, the quantitative interpretation can be challenging due to the intrinsic spectral broadening arising from the decrease in the core-hole lifetime. In this work we have used high-energy resolution fluorescence detected XAS (HERFD-XAS) to investigate a series of molybdenum complexes. The sharper spectral features obtained by HERFD-XAS measurements enable a clear assignment of the features present in the pre-edge region. Time-dependent density functional theory (TDDFT) has been previously shown to predict K-pre-edge XAS spectra of first row transition metal compounds with a reasonable degree of accuracy. Here we extend this approach to molybdenum K-edge HERFD-XAS and present the necessary calibration. Modern pure and hybrid functionals are utilized and relativistic effects are accounted for using either the Zeroth Order Regular Approximation (ZORA) or the second order Douglas-Kroll-Hess (DKH2) scalar relativistic approximations. We have found that both the predicted energies and intensities are in excellent agreement with experiment, independent of the functional used. The model chosen to account for relativistic effects also has little impact on the calculated spectra. This study provides an important calibration set for future applications of molybdenum HERFD-XAS to complex catalytic systems.

  19. XANES spectra of metal phytate compounds

    USDA-ARS?s Scientific Manuscript database

    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...

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

    PubMed

    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.

  1. Using X-ray, K-edge densitometry in spent fuel characterization

    SciTech Connect

    Jensen, T.; Aljundi, T.; Gray, J.N.

    1998-06-01

    There are instances where records for spent nuclear fuel are incomplete, as well as cases where fuel assemblies have deteriorated during storage. To bring these materials into compliance for long term storage will require determination of parameters such as enrichment, total fissionable material, and burnup. To obtain accurate estimates of these parameters will require the combination of information from different inspection techniques. A method which can provide an accurate measure of the total uranium in the spent fuel is X-ray K-edge densitometry. To assess the potential for applying this method in spent fuel characterization, the authors have measured the amount of uranium in stacks of reactor fuel plates containing nuclear materials of different enrichments and alloys. They have obtained good agreement with expected uranium concentrations ranging from 60 mg/cm{sup 2} to 3,000 mg/cm{sup 2}, and have demonstrated that these measurements can be made in a high radiation field (> 200 mR/hr).

  2. Demonstration of enhanced K-edge angiography using a cerium target x-ray generator

    SciTech Connect

    Sato, Eiichi; Tanaka, Etsuro; Mori, Hidezo; Kawai, Toshiaki; Ichimaru, Toshio; Sato, Shigehiro; Takayama, Kazuyoshi; Ido, Hideaki

    2004-11-01

    The cerium target x-ray generator is useful in order to perform enhanced K-edge angiography using a cone beam because K-series characteristic x rays from the cerium target are absorbed effectively by iodine-based contrast mediums. The x-ray generator consists of a main controller, a unit with a Cockcroft-Walton circuit and a fixed anode x-ray tube, and a personal computer. The tube is a glass-enclosed diode with a cerium target and a 0.5-mm-thick beryllium window. The maximum tube voltage and current were 65 kV and 0.4 mA, respectively, and the focal-spot sizes were 1.0x1.3 mm. Cerium K{alpha} lines were left using a barium sulfate filter, and the x-ray intensity was 0.48 {mu}C/kg at 1.0 m from the source with a tube voltage of 60 kV, a current of 0.40 mA, and an exposure time of 1.0 s. Angiography was performed with a computed radiography system using iodine-based microspheres. In coronary angiography of nonliving animals, we observed fine blood vessels of approximately 100 {mu}m with high contrasts.

  3. Prediction of Iron K-Edge Absorption Spectra Using Time-Dependent Density Functional Theory

    SciTech Connect

    George, S.DeBeer; Petrenko, T.; Neese, F.

    2009-05-14

    Iron K-edge X-ray absorption pre-edge features have been calculated using a time-dependent density functional approach. The influence of functional, solvation, and relativistic effects on the calculated energies and intensities has been examined by correlation of the calculated parameters to experimental data on a series of 10 iron model complexes, which span a range of high-spin and low-spin ferrous and ferric complexes in O{sub h} to T{sub d} geometries. Both quadrupole and dipole contributions to the spectra have been calculated. We find that good agreement between theory and experiment is obtained by using the BP86 functional with the CP(PPP) basis set on the Fe and TZVP one of the remaining atoms. Inclusion of solvation yields a small improvement in the calculated energies. However, the inclusion of scalar relativistic effects did not yield any improved correlation with experiment. The use of these methods to uniquely assign individual spectral transitions and to examine experimental contributions to backbonding is discussed.

  4. Time-Dependent Density Functional Calculations of Ligand K-Edge X-Ray Absorption Spectra

    SciTech Connect

    DeBeer George, S.; Petrenko, T.; Neese, F.

    2007-07-10

    X-ray absorption spectra (XAS) at the Cl and S K edge and Mo L edge have been calculated at the TDDFT level for a series of dioxomolybdenum complexes LMoO{sub 2}X (L = hydrotris(3,5-dimethyl-1-pyrazolyl)borate, X = Cl, SCH{sub 2}Ph, OPh), which play an important role in modeling the catalytic cycle of the sulfite oxidase enzyme. Also, the XAS spectra of model molecules of the Mo complexes have been simulated and interpreted in terms of the Mo 4d orbital splitting, in order to find possible correlations with the spectral pattern of the complexes. Comparison with the available experimental data allows us to assess the performances of the present computational scheme to describe the core excitations in large bioinorganic systems. The theoretical interpretation of the spectral features of both the metal and ligand core excitations in terms of the oscillator strength distribution provides important insight into the covalency of the metal-ligand bond.

  5. Theoretical simulations of oxygen K -edge resonant inelastic x-ray scattering of kaolinite

    NASA Astrophysics Data System (ADS)

    Ertan, Emelie; Kimberg, Victor; Gel'mukhanov, Faris; Hennies, Franz; Rubensson, Jan-Erik; Schmitt, Thorsten; Strocov, Vladimir N.; Zhou, Kejin; Iannuzzi, Marcella; Föhlisch, Alexander; Odelius, Michael; Pietzsch, Annette

    2017-04-01

    Near-edge x-ray absorption fine structure (NEXAFS) and resonant inelastic x-ray scattering (RIXS) measurements at the oxygen K edge were combined with theoretical spectrum simulations, based on periodic density functional theory and nuclear quantum dynamics, to investigate the electronic structure and chemical bonding in kaolinite Al2Si2O5 (OH) 4. We simulated NEXAFS spectra of all crystallographically inequivalent oxygen atoms in the crystal and RIXS spectra of the hydroxyl groups. Detailed insight into the ground-state potential energy surface of the electronic states involved in the RIXS process were accessed by analyzing the vibrational excitations, induced by the core excitation, in quasielastic scattering back to the electronic ground state. In particular, we find that the NEXAFS pre-edge is dominated by features related to OH groups within the silica and alumina sheets, and that the vibrational progression in RIXS can be used to selectively probe vibrational modes of this subclass of OH groups. The signal is dominated by the OH stretching mode, but also other lower vibrational degrees of freedom, mainly hindered rotational modes, contribute to the RIXS signal.

  6. Comparative study of experimental and theoretical analysis of EXAFS data of copper complexes using FT method

    NASA Astrophysics Data System (ADS)

    Mishra, A.; Mishra, S.; Kekre, P.; Choudhary, Pankaj

    2014-09-01

    The X-ray absorption spectra at the K-edge for a series of copper mixed ligand, having hydroxypyridine as one of the ligands, have been investigated in the laboratory X-ray spectroscopic set-up. In the series only X-ray absorption near edge structure (XANES) parameters and bond length using modified Lytle, Levy's and LSS methods were calculated. In the present study the bond lengths are calculated by Fourier Transform method theoretically using IFEFFIT software and compared with experimental results.

  7. K-edge imaging with the XPAD3 hybrid pixel detector, direct comparison of CdTe and Si sensors.

    PubMed

    Cassol, F; Portal, L; Graber-Bolis, J; Perez-Ponce, H; Dupont, M; Kronland, C; Boursier, Y; Blanc, N; Bompard, F; Boudet, N; Buton, C; Clémens, J C; Dawiec, A; Debarbieux, F; Delpierre, P; Hustache, S; Vigeolas, E; Morel, C

    2015-07-21

    We investigate the improvement from the use of high-Z CdTe sensors for pre-clinical K-edge imaging with the hybrid pixel detectors XPAD3. We compare XPAD3 chips bump bonded to Si or CdTe sensors in identical experimental conditions. Image performance for narrow energy bin acquisitions and contrast-to-noise ratios of K-edge images are presented and compared. CdTe sensors achieve signal-to-noise ratios at least three times higher than Si sensors within narrow energy bins, thanks to their much higher detection efficiency. Nevertheless Si sensors provide better contrast-to-noise ratios in K-edge imaging when working at equivalent counting statistics, due to their better estimation of the attenuation coefficient of the contrast agent. Results are compared to simulated data in the case of the XPAD3/Si detector. Good agreement is observed when including charge sharing between pixels, which have a strong impact on contrast-to-noise ratios in K-edge images.

  8. X-ray Absorption Spectroscopy at the Sulfur K-Edge: A New Tool to Investigate the Biochemical Mechanisms of Neurodegeneration

    PubMed Central

    2012-01-01

    Sulfur containing molecules such as thiols, disulfides, sulfoxides, sulfonic acids, and sulfates may contribute to neurodegenerative processes. However, previous study in this field has been limited by the lack of in situ analytical techniques. This limitation may now be largely overcome following the development of synchrotron radiation X-ray absorption spectroscopy at the sulfur K-edge, which has been validated as a novel tool to investigate and image the speciation of sulfur in situ. In this investigation, we build the foundation required for future application of this technique to study and image the speciation of sulfur in situ within brain tissue. This study has determined the effect of sample preparation and fixation methods on the speciation of sulfur in thin sections of rat brain tissue, determined the speciation of sulfur within specific brain regions (brain stem and cerebellum), and identified sulfur specific markers of peroxidative stress following metal catalyzed reactive oxygen species production. X-ray absorption spectroscopy at the sulfur K-edge is now poised for an exciting new range of applications to study thiol redox, methionine oxidation, and the role of taurine and sulfatides during neurodegeneration. PMID:22860187

  9. Extraction of local coordination structure in a low-concentration uranyl system by XANES.

    PubMed

    Zhang, Linjuan; Zhou, Jing; Zhang, Jianyong; Su, Jing; Zhang, Shuo; Chen, Ning; Jia, Yunpeng; Li, Jiong; Wang, Yu; Wang, Jian Qiang

    2016-05-01

    Obtaining structural information of uranyl species at an atomic/molecular scale is a critical step to control and predict their physical and chemical properties. To obtain such information, experimental and theoretical L3-edge X-ray absorption near-edge structure (XANES) spectra of uranium were studied systematically for uranyl complexes. It was demonstrated that the bond lengths (R) in the uranyl species and relative energy positions (ΔE) of the XANES were determined as follows: ΔE1 = 168.3/R(U-Oax)(2) - 38.5 (for the axial plane) and ΔE2 = 428.4/R(U-Oeq)(2) - 37.1 (for the equatorial plane). These formulae could be used to directly extract the distances between the uranium absorber and oxygen ligand atoms in the axial and equatorial planes of uranyl ions based on the U L3-edge XANES experimental data. In addition, the relative weights were estimated for each configuration derived from the water molecule and nitrate ligand based on the obtained average equatorial coordination bond lengths in a series of uranyl nitrate complexes with progressively varied nitrate concentrations. Results obtained from XANES analysis were identical to that from extended X-ray absorption fine-structure (EXAFS) analysis. XANES analysis is applicable to ubiquitous uranyl-ligand complexes, such as the uranyl-carbonate complex. Most importantly, the XANES research method could be extended to low-concentration uranyl systems, as indicated by the results of the uranyl-amidoximate complex (∼40 p.p.m. uranium). Quantitative XANES analysis, a reliable and straightforward method, provides a simplified approach applied to the structural chemistry of actinides.

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

    NASA Technical Reports Server (NTRS)

    Ruckman, Mark W.; Hepp, Aloysius F.

    1991-01-01

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

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

    NASA Technical Reports Server (NTRS)

    Ruckman, Mark W.; Hepp, Aloysius F.

    1991-01-01

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

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

    NASA Technical Reports Server (NTRS)

    Ruckman, Mark W.; Hepp, Aloysius F.

    1991-01-01

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

  13. Double-core ionization and excitation above the sulphur K-edge in ?, ? and ?

    NASA Astrophysics Data System (ADS)

    Reynaud, Cécile; Gaveau, Marc-André; Bisson, Kristel; Millié, Philippe; Nenner, Irène; Bodeur, Suzanne; Archirel, Pierre; Lévy, Bernard

    1996-11-01

    Experimental and theoretical results are reported on double-core excitation and ionization processes in some sulphur containing molecules. X-ray absorption spectra have been recorded at the sulphur K-edge using synchrotron radiation delivered by the DCI ring at LURE (Orsay, France). Absolute x-ray absorption cross sections have been determined for gas phase 0953-4075/29/22/017/img12, 0953-4075/29/22/017/img13 and 0953-4075/29/22/017/img14 molecules in the 2400 - 2800 eV region. Several narrow features are observed far from the edge and assigned to 0953-4075/29/22/017/img15 double-core excited states. Two series of states are present corresponding to the triplet and singlet configurations, due to the core 1s - 2p exchange term. The energy, width and intensity of the features are strongly molecule dependent. In the case of 0953-4075/29/22/017/img12, a theoretical determination of all the single- and double-core vacancy ionization potentials has been performed using a new theoretical approach which makes it possible to solve the convergence problem inherent in a simple SCF calculation. Results compare favourably with available experimental values. In particular, the singlet - triplet separation is correctly predicted for all the double-core ionized states. The relation between the double-core relaxation energies and the associated single-core relaxation values is discussed. Finally, the double-core excited state energies are determined within a Z + 2 core equivalent model, allowing a full assignment of the 0953-4075/29/22/017/img15 experimental spectra of 0953-4075/29/22/017/img12.

  14. Energy-Specific Equation-of-Motion Coupled-Cluster Methods for High-Energy Excited States: Application to K-edge X-ray Absorption Spectroscopy.

    PubMed

    Peng, Bo; Lestrange, Patrick J; Goings, Joshua J; Caricato, Marco; Li, Xiaosong

    2015-09-08

    Single-reference techniques based on coupled-cluster (CC) theory, in the forms of linear response (LR) or equation of motion (EOM), are highly accurate and widely used approaches for modeling valence absorption spectra. Unfortunately, these equations with singles and doubles (LR-CCSD and EOM-CCSD) scale as O(N⁶), which may be prohibitively expensive for the study of high-energy excited states using a conventional eigensolver. In this paper, we present an energy-specific non-Hermitian eigensolver that is able to obtain high-energy excited states (e.g., XAS K-edge spectrum) at low computational cost. In addition, we also introduce an improved trial vector for iteratively solving the EOM-CCSD equation with a focus on high-energy eigenstates. The energy-specific EOM-CCSD approach and its low-scaling alternatives are applied to calculations of carbon, nitrogen, oxygen, and sulfur K-edge excitations. The results are compared to other implementations of CCSD for excited states, energy-specific linear response time-dependent density functional theory (TDDFT), and experimental results with multiple statistical metrics are presented and evaluated.

  15. Spectral line shapes of U M2 - and As K -edge resonant x-ray scattering in the two antiferromagnetic phases of UAs

    NASA Astrophysics Data System (ADS)

    Normile, P. S.; Wilkins, S. B.; Detlefs, B.; Mannix, D.; Blackburn, E.; Bouchenoire, L.; Bernhoeft, N.; Lander, G. H.

    2007-05-01

    We present resonant x-ray scattering measurements on uranium arsenide at the U M2 and As K absorption edges. The studies at both edges relate to aspects of the hybridization (involving the 5f states) in UAs. At the U M2 edge, the spectral line shapes are found to differ between the two antiferromagnetic phases of UAs. In the “type-I” phase, the line shapes may be fitted using a single resonant component, whereas in the “type-IA” phase, a second resonant component, 3.5eV above the first component, is required to fit the line shapes in the rotated polarization (σ→π) scattering channel. The possibility that the single (first) component in the type-I (type-IA) phase corresponds to E2 scattering due to the ordered 5f magnetic-dipole moments and that in the type-IA phase the second component represents an E1 process involving polarized 6d (U) states is considered. Similar line shapes are observed for the two antiferromagnetic phases at the As K edge, a result which is in discordance with a recent theoretical prediction. The experimentally observed As K -edge line shape has an asymmetrical form in both phases, which possibly relates to As 4p -band effects unaccounted for in the theory.

  16. Evaluation of spectral photon counting computed tomography K-edge imaging for determination of gold nanoparticle biodistribution in vivo.

    PubMed

    Si-Mohamed, Salim; Cormode, David P; Bar-Ness, Daniel; Sigovan, Monica; Naha, Pratap C; Langlois, Jean-Baptiste; Chalabreysse, Lara; Coulon, Philippe; Blevis, Ira; Roessl, Ewald; Erhard, Klaus; Boussel, Loic; Douek, Philippe

    2017-07-20

    Spectral photon counting computed tomography (SPCCT) is an emerging medical imaging technology. SPCCT scanners record the energy of incident photons, which allows specific detection of contrast agents due to measurement of their characteristic X-ray attenuation profiles. This approach is known as K-edge imaging. Nanoparticles formed from elements such as gold, bismuth or ytterbium have been reported as potential contrast agents for SPCCT imaging. Furthermore, gold nanoparticles have many applications in medicine, such as adjuvants for radiotherapy and photothermal ablation. In particular, longitudinal imaging of the biodistribution of nanoparticles would be highly attractive for their clinical translation. We therefore studied the capabilities of a novel SPCCT scanner to quantify the biodistribution of gold nanoparticles in vivo. PEGylated gold nanoparticles were used. Phantom imaging showed that concentrations measured on gold images correlated well with known concentrations (slope = 0.94, intercept = 0.18, RMSE = 0.18, R(2) = 0.99). The SPCCT system allowed repetitive and quick acquisitions in vivo, and follow-up of changes in the AuNP biodistribution over time. Measurements performed on gold images correlated with the inductively coupled plasma-optical emission spectrometry (ICP-OES) measurements in the organs of interest (slope = 0.77, intercept = 0.47, RMSE = 0.72, R(2) = 0.93). TEM results were in agreement with the imaging and ICP-OES in that much higher concentrations of AuNPs were observed in the liver, spleen, bone marrow and lymph nodes (mainly in macrophages). In conclusion, we found that SPCCT can be used for repetitive and non-invasive determination of the biodistribution of gold nanoparticles in vivo.

  17. X-ray diffraction and X-ray K-absorption near edge studies of Copper (II) Micro cyclic Carbamide complexes.

    NASA Astrophysics Data System (ADS)

    Malviya, P. K.; Sharma, P.; Mishra, A.; Bhalse, D.

    2016-10-01

    Synthesis of metal complexes [Cu (Carbamide)] (X = Br, Cl, NO3, SO4,CH3COO) by the chemical root method. The XRD data have been recorded at DAE, IUC Indore.XANES spectra have been recorded at the K-edge of Cu using the dispersive beam line at 2.5GeV Indus-2 synchrotron radiation source RRCAT (Raja Ramanna Center for Advance Technology), Indore, India. XRD and XANES data have been analysed using the computer software Origin 8.0 professional and Athena. X-ray diffraction studies of all the complexes are indicative of their crystalline nature. The crystalline size of the samples is estimated using the Scherer's formula. The values of the chemical shifts suggest that copper is in oxidation state +2 in all of the complexes.

  18. Electronic structure and optical properties of 2,5,8,11-tetra-tert-butylperylene polyhedral crystals from x-ray absorption near-edge structure and x-ray excited optical luminescence studies

    NASA Astrophysics Data System (ADS)

    Lv, Jingyu; Ko, Peter J. Y.; Zhang, Ying; Liu, Lijia; Zhang, Xiujuan; Zhang, Xiaohong; Sun, Xuhui; Sham, T. K.

    2011-06-01

    X-ray absorption near-edge structure (XANES) and x-ray excited optical luminescence (XEOL) have been used to study the optical properties of 2,5,8,11-tetra-tert-butylperylene (TBPe) polyhedral crystals with morphology varies from cube to rhombic dodecahedron. Benefit from the high resolution of synchrotron radiation spectroscopy, C 1s to π∗ and σ∗ transitions from different carbon sites in TBPe can be clearly distinguished in the carbon K-edge XANES. XEOL studies reveal that different crystals exhibit multiple emission bands with different branching ratio. It is also found that all the polyhedral crystals exhibit a weak luminescence in the near infrared, which is absent in the powder sample.

  19. Probing single magnon excitations in Sr₂IrO₄ using O K-edge resonant inelastic x-ray scattering

    DOE PAGES

    Liu, X.; Dean, M. P. M.; Liu, J.; ...

    2015-04-28

    Resonant inelastic X-ray scattering (RIXS) at the L-edge of transition metal elements is now commonly used to probe single magnon excitations. Here we show that single magnon excitations can also be measured with RIXS at the K-edge of the surrounding ligand atoms when the center heavy metal elements have strong spin-orbit coupling. This is demonstrated with oxygen K-edge RIXS experiments on the perovskite Sr₂IrO₄, where low energy peaks from single magnon excitations were observed. This new application of RIXS has excellent potential to be applied to a wide range of magnetic systems based on heavy elements, for which the L-edgemore » RIXS energy resolutions in the hard X-ray region is usually poor.« less

  20. Probing single magnon excitations in Sr₂IrO₄ using O K-edge resonant inelastic x-ray scattering

    SciTech Connect

    Liu, X.; Dean, M. P. M.; Liu, J.; Chiuzbaian, S. G.; Jaouen, N.; Nicolaou, A.; Yin, W. G.; Rayan Serrao, C.; Ramesh, R.; Ding, H.; Hill, J. P.

    2015-04-28

    Resonant inelastic X-ray scattering (RIXS) at the L-edge of transition metal elements is now commonly used to probe single magnon excitations. Here we show that single magnon excitations can also be measured with RIXS at the K-edge of the surrounding ligand atoms when the center heavy metal elements have strong spin-orbit coupling. This is demonstrated with oxygen K-edge RIXS experiments on the perovskite Sr₂IrO₄, where low energy peaks from single magnon excitations were observed. This new application of RIXS has excellent potential to be applied to a wide range of magnetic systems based on heavy elements, for which the L-edge RIXS energy resolutions in the hard X-ray region is usually poor.

  1. Sulfur K-edge X-ray absorption spectroscopy as an experimental probe for S-nitroso proteins

    SciTech Connect

    Szilagyi, Robert K. . E-mail: Szilagyi@Montana.EDU; Schwab, David E.

    2005-04-29

    X-ray absorption spectroscopy at the sulfur K-edge (2.4-2.6 keV) provides a sensitive and specific technique to identify S-nitroso compounds, which have significance in nitric oxide-based cell signaling. Unique spectral features clearly distinguish the S-nitroso-form of a cysteine residue from the sulfhydryl-form or from a methionine thioether. Comparison of the sulfur K-edge spectra of thiolate, thiol, thioether, and S-nitroso thiolate compounds indicates high sensitivity of energy positions and intensities of XAS pre-edge features as determined by the electronic environment of the sulfur absorber. A new experimental setup is being developed for reaching the in vivo concentration range of S-nitroso thiol levels in biological samples.

  2. Intermolecular bonding of hemin in solution and in solid state probed by N K-edge X-ray spectroscopies.

    PubMed

    Golnak, Ronny; Xiao, Jie; Atak, Kaan; Stevens, Joanna S; Gainar, Adrian; Schroeder, Sven L M; Aziz, Emad F

    2015-11-21

    X-ray absorption/emission spectroscopy (XAS/XES) at the N K-edge of iron protoporphyrin IX chloride (FePPIX-Cl, or hemin) has been carried out for dissolved monomers in DMSO, dimers in water and for the solid state. This sequence of samples permits identification of characteristic spectral features associated with the hemin intermolecular bonding. These characteristic features are further analyzed and understood at the molecular orbital (MO) level based on the DFT calculations.

  3. Three-dimensional labeling of newly formed bone using synchrotron radiation barium K-edge subtraction imaging

    NASA Astrophysics Data System (ADS)

    Panahifar, Arash; Swanston, Treena M.; Pushie, M. Jake; Belev, George; Chapman, Dean; Weber, Lynn; Cooper, David M. L.

    2016-07-01

    Bone is a dynamic tissue which exhibits complex patterns of growth as well as continuous internal turnover (i.e. remodeling). Tracking such changes can be challenging and thus a high resolution imaging-based tracer would provide a powerful new perspective on bone tissue dynamics. This is, particularly so if such a tracer can be detected in 3D. Previously, strontium has been demonstrated to be an effective tracer which can be detected by synchrotron-based dual energy K-edge subtraction (KES) imaging in either 2D or 3D. The use of strontium is, however, limited to very small sample thicknesses due to its low K-edge energy (16.105 keV) and thus is not suitable for in vivo application. Here we establish proof-of-principle for the use of barium as an alternative tracer with a higher K-edge energy (37.441 keV), albeit for ex vivo imaging at the moment, which enables application in larger specimens and has the potential to be developed for in vivo imaging of preclinical animal models. New bone formation within growing rats in 2D and 3D was demonstrated at the Biomedical Imaging and Therapy bending magnet (BMIT-BM) beamline of the Canadian Light Source synchrotron. Comparative x-ray fluorescence imaging confirmed those patterns of uptake detected by KES. This initial work provides a platform for the further development of this tracer and its exploration of applications for in vivo development.

  4. In situ Fe K-edge X-ray absorption fine structure of a pyrite electrode in a Li/polyethylene oxide (LiClO{sub 4})/FeS{sub 2} battery environment

    SciTech Connect

    Totir, D.; Bae, I.T.; Hu, Y.; Scherson, D.A.; Antonio, M.R.

    1996-12-31

    Electronic and structural properties of materials generated by the reduction and subsequent oxidation of pyrite in a lithium-based solid polymer electrolyte have been examined by in situ fluorescence Fe K-edge X-ray absorption fine structure (XAFS) in a FeS{sub 2}/Li battery environment. The XAFS results obtained are consistent with the formation of metallic iron as one of the products of the full (4-electron) discharge, in agreement with information reported in other laboratories. Extended X-ray absorption fine structure (EXAFS) data reveal that a subsequent 2-electron or 4-electron recharge generates a species with a Fe-S bond distance identical to that of pyrite, d(Fe-S) = 2.259 {angstrom}, with no other clearly detectable interactions due to more distant atoms. Based on the similarities between the metrical parameters and other features in the X-ray absorption near edge structure (XANES), the ferrous sites in these species appear to be tetrahedrally coordinated, as in chalcopyrite (CuFeS{sub 2}), for which d(Fe-S) is 2.257 {angstrom}, and, thus, different than in Li{sub 2} FeS{sub 2}, a material that exhibits longer Fe-S distances.

  5. Characterization of phosphorus species in biosolids and manures using XANES spectroscopy.

    PubMed

    Shober, Amy L; Hesterberg, Dean L; Sims, J Thomas; Gardner, Sheila

    2006-01-01

    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(4) sorbed to Al hydroxides, and phytic acid in lime-stabilized biosolids and manures; hydroxylapatite, PO(4) sorbed on ferrihydrite, and phytic acid in lime- and Fe-treated biosolids; and PO(4) sorbed on ferrihydrite, hydroxylapatite, beta-tricalcium phosphate (beta-TCP), and often PO(4) sorbed to Al hydroxides in Fe-treated and digested biosolids. Strong relationships existed between the proportions of XANES PO(4) sorbed to Al hydroxides and NH(4)Cl- + NH(4)F-extractable P, XANES PO(4) sorbed to ferrihydrite + phytic acid and NaOH-extractable P, and XANES hydroxylapatite + beta-TCP and dithionite-citrate-bicarbonate (DCB)- + H(2)SO(4)-extractable P (r(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.

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

    SciTech Connect

    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.

  7. Study of Strong Electrolytes by X-Ray Spectroscopy at the C1 K-Edge.

    DTIC Science & Technology

    1984-05-23

    Utah Salt Lake City, Utah 84112 Donald E. Mains Naval Weapons Support Center Electrochemical Power Sources Division Crane, Indiana 47522 S. Ruby ...Department of Physics University of Puerto Rico Rio Piedras , Puerto Rico 00931 Dr. Joseph Gordon, II I8M Corporation K33/281 5600 Cottle Road San

  8. C1 K-Edge X-Ray Absorption Studies of Concentrated Ferric Chloride Solutions.

    DTIC Science & Technology

    1984-05-23

    Sources Division 111 Chapel Street Crane, Indiana 47522 Newton, Massachusetts 02158 S. Ruby Or. Aaron Wold DOE (STOR) Department of Chemistry M.S. 66025...Puerto Rico Washington State University Rio Piedras , Puerto Rico 00931 Pullman, Washington 99164 Dr. Joseph Gordon, II Dr. Carl Kannewurf IBM Corporation

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

    NASA Astrophysics Data System (ADS)

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

    2003-01-01

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

  10. Theory and the Experimental Confirmation of the Local Electronic Structure of the Multiferroic PbVO3, a New Member of PbTiO3 Family, Studied by X-ray Near Edge Absorption Structure: I

    NASA Astrophysics Data System (ADS)

    Alam, Sher; Ahmad, Javed; Ohya, Yutaka; Dong, Chungli; Hsu, Chih-Chin; Lee, Jyh-Fu; Mutsuhiro, Shima; Miki, Kazuki; Al-Deyab, Salem S.; Guo, Jinghua; Nishimura, Chikashi

    2012-07-01

    Recently, an interesting multiferroic system PbVO3 [A. A. Belik et al.: Chem. Mater. 17 (2005) 269] has been successfully prepared using a high-pressure and high-temperature technique. The crystallographic features of PbVO3 were reported. In this note, we concentrate on the theoretical and the experimental X-ray near edge absorption structure (XANES) spectra by considering the K-edge of Vanadium. The tetragonality (c/a=1.229 at 300 K) of PbVO3 is the largest in the PbTiO3 family of compounds. Thus, one is led naturally to examine the effects of the changes in the tetragonality and axial oxygen position on the electronic structure (i.e., XANES spectrum). We study these effects in two ways. At a given temperature, we vary the tetragonality and the axial oxygen position, and quantify the changes in terms of the XANES difference spectrum. Secondly, we compute the XANES spectra at three different temperatures, namely, 90, 300, and 530 K, and quantify the changes in terms of the difference spectrum. We note that in this compound the tetragonality increases almost monotonically with temperature from 12 to 570 K, without transition to the cubic phase under ambient pressure. A key objective of the current investigation is to gain an understanding of various absorption features in the vicinity of the K-edge of V, in terms of valence, local site symmetry, local coordination geometry, local bond distances, charge transfer, and local projected density of states. We consider both the polarized and unpolarized XANES spectra, theoretically. The experiment was performed on the polycrystalline material after the theoretical investigation. In short, we have performed a local electronic study, theoretical as well as experimental, which complements the crystallographic features reported recently for PbVO3. The local electronic study given here is supplemented and enhanced by the O-K edge results indicated in the accompanying Paper II, which gives both the experimental and theoretical

  11. Electronic structure of KD2xH2(1-x)PO4 studied by soft x-ray absorption and emission spectroscopies

    SciTech Connect

    Kucheyev, S O; Bostedt, C F; van Buuren, T; Willey, T M; Land, T A; Terminello, L J; Felter, T E; Hamza, A V; Demos, S G; Nelson, A J

    2004-04-27

    The surface and bulk electronic structure of tetragonal (at 300 K) and orthorhombic (at 77 K) KD{sub 2x}H{sub 2(1-x)}PO{sub 4} single crystals (so-called KDP and DKDP), with a deuteration degree x of 0.0, 0.3, and 0.6, is studied by soft x-ray absorption near-edge structure (XANES) and non-resonant soft x-ray emission (XES) spectroscopies. High-resolution O K-edge, P L{sub 2,3}-edge, and K L{sub 2,3}-edge XANES and XES spectra reveal that the element-specific partial density of states in the conduction and valence bands is essentially independent of deuteration x. We give assignment of XANES and XES peaks based on previous molecular orbital and band-structure calculations. Projected densities of states in the conduction band also appear to be essentially identical for tetragonal (at 300 K) and orthorhombic (at 77 K) phases, consistent with previous band structure calculations. However, a decrease in sample temperature from 300 to 77 K results in an {approx} 0.5 eV shift in the valence band edge (probed by XES), with negligible changes to the conduction band edge (probed by XANES). Results also show that high-intensity x-ray irradiation results in decomposition of these hydrogen-bonded materials into water and KPO{sub 3} cyclo- and polyphosphates.

  12. X-ray absorption spectroscopy by full-field X-ray microscopy of a thin graphite flake: Imaging and electronic structure via the carbon K-edge

    PubMed Central

    Hitchock, Adam P; Ke, Xiaoxing; Van Tendeloo, Gustaaf; Ewels, Chris P; Guttmann, Peter

    2012-01-01

    Summary We demonstrate that near-edge X-ray-absorption fine-structure spectra combined with full-field transmission X-ray microscopy can be used to study the electronic structure of graphite flakes consisting of a few graphene layers. The flake was produced by exfoliation using sodium cholate and then isolated by means of density-gradient ultracentrifugation. An image sequence around the carbon K-edge, analyzed by using reference spectra for the in-plane and out-of-plane regions of the sample, is used to map and spectrally characterize the flat and folded regions of the flake. Additional spectral features in both π and σ regions are observed, which may be related to the presence of topological defects. Doping by metal impurities that were present in the original exfoliated graphite is indicated by the presence of a pre-edge signal at 284.2 eV. PMID:23016137

  13. Communication: Near edge x-ray absorption fine structure spectroscopy of aqueous adenosine triphosphate at the carbon and nitrogen K-edges.

    PubMed

    Kelly, Daniel N; Schwartz, Craig P; Uejio, Janel S; Duffin, Andrew M; England, Alice H; Saykally, Richard J

    2010-09-14

    Near edge x-ray absorption fine structure (NEXAFS) spectroscopy at the nitrogen and carbon K-edges was used to study the hydration of adenosine triphosphate in liquid microjets. The total electron yield spectra were recorded as a function of concentration, pH, and the presence of sodium, magnesium, and copper ions (Na(+)/Mg(2+)/Cu(2+)). Significant spectral changes were observed upon protonation of the adenine ring, but not under conditions that promote π-stacking, such as high concentration or presence of Mg(2+), indicating that NEXAFS is insensitive to the phenomenon. Intramolecular inner-sphere association of Cu(2+) did create observable broadening of the nitrogen spectrum, whereas outer-sphere association with Mg(2+) did not.

  14. Pyrimidine and halogenated pyrimidines near edge x-ray absorption fine structure spectra at C and N K-edges: experiment and theory

    SciTech Connect

    Bolognesi, P.; O'Keeffe, P.; Ovcharenko, Y.; Coreno, M.; Avaldi, L.; Feyer, V.; Plekan, O.; Prince, K. C.; Zhang, W.; Carravetta, V.

    2010-07-21

    The inner shell excitation of pyrimidine and some halogenated pyrimidines near the C and N K-edges has been investigated experimentally by near edge x-ray absorption fine structure spectroscopy and theoretically by density functional theory calculations. The selected targets, 5-Br-pyrimidine, 2-Br-pyrimidine, 2-Cl-pyrimidine, and 5-Br-2-Cl-pyrimidine, allow the effects of the functionalization of the pyrimidine ring to be studied either as a function of different halogen atoms bound to the same molecular site or as a function of the same halogen atom bound to different molecular sites. The results show that the individual characteristics of the different spectra of the substituted pyrimidines can be rationalized in terms of variations in electronic and geometrical structures of the molecule depending on the localization and the electronegativity of the substituent.

  15. Pyrimidine and halogenated pyrimidines near edge x-ray absorption fine structure spectra at C and N K-edges: experiment and theory.

    PubMed

    Bolognesi, P; O'Keeffe, P; Ovcharenko, Y; Coreno, M; Avaldi, L; Feyer, V; Plekan, O; Prince, K C; Zhang, W; Carravetta, V

    2010-07-21

    The inner shell excitation of pyrimidine and some halogenated pyrimidines near the C and N K-edges has been investigated experimentally by near edge x-ray absorption fine structure spectroscopy and theoretically by density functional theory calculations. The selected targets, 5-Br-pyrimidine, 2-Br-pyrimidine, 2-Cl-pyrimidine, and 5-Br-2-Cl-pyrimidine, allow the effects of the functionalization of the pyrimidine ring to be studied either as a function of different halogen atoms bound to the same molecular site or as a function of the same halogen atom bound to different molecular sites. The results show that the individual characteristics of the different spectra of the substituted pyrimidines can be rationalized in terms of variations in electronic and geometrical structures of the molecule depending on the localization and the electronegativity of the substituent.

  16. Submicrometer hyperspectral X-ray imaging of heterogeneous rocks and geomaterials: applications at the Fe k-edge.

    PubMed

    De Andrade, Vincent; Susini, Jean; Salomé, Murielle; Beraldin, Olivier; Rigault, Cecile; Heymes, Thomas; Lewin, Eric; Vidal, Olivier

    2011-06-01

    Because of their complex genesis, rocks and geomaterials are commonly polycrystalline heterogeneous systems, with various scale-level chemical and structural heterogeneities. Like most other μ-analytical techniques relying on scanning instruments with pencil-beam, the X-ray absorption near edge structure (XANES) technique allows elemental oxidation states to be probed with high spatial resolution but suffers from long acquisition times, imposing practical limits on the field of view. Now, regions of interest of sample are generally several orders of magnitude larger than the beam size. Here, we show the potential of coupling XANES and full-field absorption radiographies with a large hard X-ray beam. Thanks to a new setup, which allows both the acquisition of a XANES image stack and the execution of polarization contrast imaging, 1 to 4 mega-pixel crystallographic orientations and Fe oxidation state mapping corrected from polarization effects are obtained in a couple of hours on polycrystalline materials with submicrometric resolution. The demonstration is first carried out on complex metamorphic rocks, where Fe(3+)/Fe(total) images reveal subtle redox variations within single mineralogical phases. A second application concerns a bentonite analogue considered for nuclear waste and CO(2) storage. Proportion mappings of finely mixed phases are extracted from hyperspectral data, imaging the spatial progress of reaction processes essential for the safety of such storage systems.

  17. Tetrahalide Complexes of the [U(NR)(2)]2+ Ion: Synthesis, Theory, and Chlorine K-Edge X-ray Absorption Spectroscopy

    SciTech Connect

    Spencer, Liam P.; Yang, Ping; Minasian, Stefan G.; Jilek, Robert E.; Batista, Enrique R.; Boland, Kevin S.; Boncella, James M.; Conradson, S. D.; Clark, David L.; Hayton, Trevor W.; Kozimor, Stosh A.; Martin, Richard L.; MacInnes, Molly M.; Olson, Angela C.; Scott, Brian L.; Shuh, D. K.; Wilkerson, Marianne P.

    2013-02-13

    Synthetic routes to salts containing uranium bisimido tetrahalide anions [U(NR)(2)X-4](2-) (X = Cl-, Br-) and non-coordinating NEt4+ and PPh4+ countercations are reported. In general, these compounds can be prepared from U(NR)(2)I-2(THF)(x) (x = 2 and R = 'Bu, Ph; x = 3 and R = Me) upon addition of excess halide. In addition to providing stable coordination complexes with Cl-, the [U(NMe)(2)](2 +) cation also reacts with Br- to form stable [NEt4](2)[U(NMe)(2)Br-4] complexes. These materials were used as a platform to compare electronic structure and bonding in [U(NR)(2)](2+) with [UO2](2+). Specifically, Cl K-edge X-ray absorption spectroscopy (XAS) and both ground-state and time-dependent hybrid density functional theory (DFT and TDDFT) were used to probe U-Cl bonding interactions in [PPh4](2)[U((NBu)-Bu-t)(2)Cl-4] and [PPh4](2)[UO2Cl4]. The DFT and XAS results show the total amount of Cl 3p character mixed with the U 5f orbitals was roughly 7-10% per U-Cl bond for both compounds, which shows that moving from oxo to imido has little effect on orbital mixing between the U 5f and equatorial Cl 3p orbitals. The results are presented in the context of recent Cl K-edge XAS and DFT studies on other hexavalent uranium chloride systems with fewer oxo or imido ligands.

  18. Sulfur K-Edge XAS and DFT Calculations on NitrileHydratase: Geometric and Electronic Structure of the Non-heme Iron Active Site

    SciTech Connect

    Dey, Abhishek; Chow, Marina; Taniguchi, Kayoko; Lugo-Mas, Priscilla; Davin, Steven; Maeda, Mizuo; Kovacs, Julie A.; Odaka, Masafumi; Hodgson, Keith O.; Hedman, Britt; Solomon, Edward I.; /SLAC, SSRL

    2006-09-28

    The geometric and electronic structure of the active site of the non-heme iron enzyme nitrile hydratase (NHase) is studied using sulfur K-edge XAS and DFT calculations. Using thiolate (RS{sup -})-, sulfenate (RSO{sup -})-, and sulfinate (RSO{sub 2}{sup -})-ligated model complexes to provide benchmark spectral parameters, the results show that the S K-edge XAS is sensitive to the oxidation state of S-containing ligands and that the spectrum of the RSO- species changes upon protonation as the S-O bond is elongated (by {approx}0.1 {angstrom}). These signature features are used to identify the three cysteine residues coordinated to the low-spin Fe{sup III} in the active site of NHase as CysS{sup -}, CysSOH, and CysSO{sub 2}{sup -} both in the NO-bound inactive form and in the photolyzed active form. These results are correlated to geometry-optimized DFT calculations. The pre-edge region of the X-ray absorption spectrum is sensitive to the Z{sub eff} of the Fe and reveals that the Fe in [FeNO]{sup 6} NHase species has a Z{sub eff} very similar to that of its photolyzed Fe{sup III} counterpart. DFT calculations reveal that this results from the strong {pi} back-bonding into the {pi}* antibonding orbital of NO, which shifts significant charge from the formally t{sub 2}{sup 6} low-spin metal to the coordinated NO.

  19. Estimation of basis line-integrals in a spectral distortion-modeled photon counting detector using low-rank approximation-based x-ray transmittance modeling: K-edge imaging application.

    PubMed

    Lee, Okkyun; Kappler, Steffen; Polster, Christoph; Taguchi, Katsuyuki

    2017-08-29

    Photon counting detectors (PCD) provide multiple energy-dependent measurements for estimating basis lineintegrals. However, the measured spectrum is distorted from the spectral response effect (SRE) via charge sharing, K-fluorescence emission, etc. Thus, in order to avoid bias and artifacts in images, the SRE needs to be compensated. For this purpose, we recently developed a computationally efficient three-step algorithm for PCD-CT without contrast agents by approximating smooth x-ray transmittance using low-order polynomial bases. It compensated the SRE by incorporating the SRE model in a linearized estimation process and achieved nearly the minimum variance and unbiased (MVU) estimator. In this paper, we extend the three-step algorithm to K-edge imaging applications by designing optimal bases using a low-rank approximation to model x-ray transmittances with arbitrary shapes (i.e., smooth without the K-edge or discontinuous with the K-edge). The bases can be used to approximate the x-ray transmittance and to linearize the PCD measurement modeling and then the three-step estimator can be derived as in the previous approach: Estimating the xray transmittance in the first step, estimating basis line-integrals including that of the contrast agent in the second step, and correcting for a bias in the third step. We demonstrate that the proposed method is more accurate and stable than the low-order polynomial-based approaches with extensive simulation studies using gadolinium for the K-edge imaging application. We also demonstrate that the proposed method achieves nearly MVU estimator, and is more stable than the conventional maximum likelihood estimator in high attenuation cases with fewer photon counts.

  20. Atomistic origins of pressure-induced changes in the O K -edge x-ray Raman scattering features of Si O2 and MgSi O3 polymorphs: Insights from ab initio calculations

    NASA Astrophysics Data System (ADS)

    Yi, Yoo Soo; Lee, Sung Keun

    2016-09-01

    Despite its fundamental importance in condensed matter physics and geophysical implications, establishing the systematic and direct link between the pressure-induced structural changes in crystalline and noncrystalline low-z oxides and their corresponding evolution in O K -edge core-electron excitation features under extreme compression has been challenging. Here we calculated the site-resolved partial density of states and O K -edge x-ray Raman scattering (XRS) spectra for two of the important oxide phases in the Earth's lower mantle, MgSi O3 bridgmanite and post-bridgmanite, up to 120 GPa using ab initio calculations, revealing the electronic origins of the O K -edge features for oxides under compression. The absorption threshold (EA) and band gap increase linearly with a decrease in the O-O distance in diverse Si O2 and MgSi O3 high-pressure phases [EA(eV ) ≈-10.9 dO-O(Å ) +34.4 ] , providing a predictive relationship between the EA and the O-O distances in the oxide at high pressure. Despite densification, upon isobaric phase transition from bridgmanite to post-bridgmanite at 120 GPa, a decrease in band gap results in a decrease in edge energy because of an increase in O-O distance. The oxygen proximity is a useful structural proxy of oxide densification upon compression, as it explains the pressure-induced changes in O K -edge XRS features of crystalline and amorphous Si O2 and MgSi O3 at high pressures. These results can be applied to studies of the pressure-bonding transitions in a wide range of oxides under extreme compression.

  1. Isotope effects in liquid water probed by transmission mode x-ray absorption spectroscopy at the oxygen K-edge

    NASA Astrophysics Data System (ADS)

    Schreck, Simon; Wernet, Philippe

    2016-09-01

    The effects of isotope substitution in liquid water are probed by x-ray absorption spectroscopy at the O K-edge as measured in transmission mode. Confirming earlier x-ray Raman scattering experiments, the D2O spectrum is found to be blue shifted with respect to H2O, and the D2O spectrum to be less broadened. Following the earlier interpretations of UV and x-ray Raman spectra, the shift is related to the difference in ground-state zero-point energies between D2O and H2O, while the difference in broadening is related to the difference in ground-state vibrational zero-point distributions. We demonstrate that the transmission-mode measurements allow for determining the spectral shapes with unprecedented accuracy. Owing in addition to the increased spectral resolution and signal to noise ratio compared to the earlier measurements, the new data enable the stringent determination of blue shift and broadening in the O K-edge x-ray absorption spectrum of liquid water upon isotope substitution. The results are compared to UV absorption data, and it is discussed to which extent they reflect the differences in zero-point energies and vibrational zero-point distributions in the ground-states of the liquids. The influence of the shape of the final-state potential, inclusion of the Franck-Condon structure, and differences between liquid H2O and D2O resulting from different hydrogen-bond environments in the liquids are addressed. The differences between the O K-edge absorption spectra of water from our transmission-mode measurements and from the state-of-the-art x-ray Raman scattering experiments are discussed in addition. The experimentally extracted values of blue shift and broadening are proposed to serve as a test for calculations of ground-state zero-point energies and vibrational zero-point distributions in liquid H2O and D2O. This clearly motivates the need for new calculations of the O K-edge x-ray absorption spectrum of liquid water.

  2. Resonant inelastic X-ray scattering spectrometer with 25meV resolution at the Cu K -edge

    DOE PAGES

    Ketenoglu, Didem; Harder, Manuel; Klementiev, Konstantin; ...

    2015-06-27

    An unparalleled resolution is reported with an inelastic X-ray scattering instrument at the CuK-edge. Based on a segmented concave analyzer, featuring single-crystal quartz (SiO2) pixels, the spectrometer delivers a resolution near 25meV (FWHM) at 8981eV. Besides the quartz analyzer, the performance of the spectrometer relies on a four-bounce Si(553) high-resolution monochromator and focusing Kirkpatrick–Baez optics. The measured resolution agrees with the ray-tracing simulation of an ideal spectrometer. The performance of the spectrometer is demonstrated by reproducing the phonon dispersion curve of a beryllium single-crystal.

  3. Isotope effects in liquid water probed by transmission mode x-ray absorption spectroscopy at the oxygen K-edge.

    PubMed

    Schreck, Simon; Wernet, Philippe

    2016-09-14

    The effects of isotope substitution in liquid water are probed by x-ray absorption spectroscopy at the O K-edge as measured in transmission mode. Confirming earlier x-ray Raman scattering experiments, the D2O spectrum is found to be blue shifted with respect to H2O, and the D2O spectrum to be less broadened. Following the earlier interpretations of UV and x-ray Raman spectra, the shift is related to the difference in ground-state zero-point energies between D2O and H2O, while the difference in broadening is related to the difference in ground-state vibrational zero-point distributions. We demonstrate that the transmission-mode measurements allow for determining the spectral shapes with unprecedented accuracy. Owing in addition to the increased spectral resolution and signal to noise ratio compared to the earlier measurements, the new data enable the stringent determination of blue shift and broadening in the O K-edge x-ray absorption spectrum of liquid water upon isotope substitution. The results are compared to UV absorption data, and it is discussed to which extent they reflect the differences in zero-point energies and vibrational zero-point distributions in the ground-states of the liquids. The influence of the shape of the final-state potential, inclusion of the Franck-Condon structure, and differences between liquid H2O and D2O resulting from different hydrogen-bond environments in the liquids are addressed. The differences between the O K-edge absorption spectra of water from our transmission-mode measurements and from the state-of-the-art x-ray Raman scattering experiments are discussed in addition. The experimentally extracted values of blue shift and broadening are proposed to serve as a test for calculations of ground-state zero-point energies and vibrational zero-point distributions in liquid H2O and D2O. This clearly motivates the need for new calculations of the O K-edge x-ray absorption spectrum of liquid water.

  4. Characterization of Sulfur Compounds in Coffee Beans by Sulfur K-XANES Spectroscopy

    NASA Astrophysics Data System (ADS)

    Lichtenberg, H.; Prange, A.; Modrow, H.; Hormes, J.

    2007-02-01

    In this `feasibility study' the influence of roasting on the sulfur speciation in Mexican coffee beans was investigated by sulfur K-XANES Spectroscopy. Spectra of green and slightly roasted beans could be fitted to a linear combination of `standard' reference spectra for biological samples, whereas longer roasting obviously involves formation of additional sulfur compounds in considerable amounts.

  5. Characterization of Sulfur Compounds in Coffee Beans by Sulfur K-XANES Spectroscopy

    SciTech Connect

    Lichtenberg, H.; Hormes, J.; Prange, A.; Modrow, H.

    2007-02-02

    In this 'feasibility study' the influence of roasting on the sulfur speciation in Mexican coffee beans was investigated by sulfur K-XANES Spectroscopy. Spectra of green and slightly roasted beans could be fitted to a linear combination of 'standard' reference spectra for biological samples, whereas longer roasting obviously involves formation of additional sulfur compounds in considerable amounts.

  6. Near-coincident K-line and K-edge energies as ionization diagnostics for some high atomic number plasmas

    SciTech Connect

    Pereira, N. R.; Weber, B. V.; Phipps, D. G.; Schumer, J. W.; Seely, J. F.; Carroll, J. J.; Vanhoy, J. R.; Slabkowska, K.; Polasik, M.

    2012-10-15

    For some high atomic number atoms, the energy of the K-edge is tens of eVs higher than the K-line energy of another atom, so that a few eV increase in the line's energy results in a decreasing transmission of the x-ray through a filter of the matching material. The transmission of cold iridium's Asymptotically-Equal-To 63.287 keV K{alpha}{sub 2} line through a lutetium filter is 7% lower when emitted by ionized iridium, consistent with an energy increase of {Delta}{epsilon} Asymptotically-Equal-To 10{+-}1 eV associated with the ionization. Likewise, the transmission of the K{beta}{sub 1} line of ytterbium through a near-coincident K-edge filter changes depending on plasma parameters that should affect the ionization. Systematic exploration of filter-line pairs like these could become a unique tool for diagnostics of suitable high energy density plasmas.

  7. Experimental feasibility of multi-energy photon-counting K-edge imaging in pre-clinical computed tomography

    NASA Astrophysics Data System (ADS)

    Schlomka, J. P.; Roessl, E.; Dorscheid, R.; Dill, S.; Martens, G.; Istel, T.; Bäumer, C.; Herrmann, C.; Steadman, R.; Zeitler, G.; Livne, A.; Proksa, R.

    2008-08-01

    Theoretical considerations predicted the feasibility of K-edge x-ray computed tomography (CT) imaging using energy discriminating detectors with more than two energy bins. This technique enables material-specific imaging in CT, which in combination with high-Z element based contrast agents, opens up possibilities for new medical applications. In this paper, we present a CT system with energy detection capabilities, which was used to demonstrate the feasibility of quantitative K-edge CT imaging experimentally. A phantom was imaged containing PMMA, calcium-hydroxyapatite, water and two contrast agents based on iodine and gadolinium, respectively. Separate images of the attenuation by photoelectric absorption and Compton scattering were reconstructed from energy-resolved projection data using maximum-likelihood basis-component decomposition. The data analysis further enabled the display of images of the individual contrast agents and their concentrations, separated from the anatomical background. Measured concentrations of iodine and gadolinium were in good agreement with the actual concentrations. Prior to the tomographic measurements, the detector response functions for monochromatic illumination using synchrotron radiation were determined in the energy range 25 keV-60 keV. These data were used to calibrate the detector and derive a phenomenological model for the detector response and the energy bin sensitivities.

  8. Probing ultrafast ππ*/nπ* internal conversion in organic chromophores via K-edge resonant absorption

    DOE PAGES

    Wolf, T. J. A.; Myhre, R. H.; Cryan, J. P.; ...

    2017-06-22

    Many photoinduced processes including photosynthesis and human vision happen in organic molecules and involve coupled femtosecond dynamics of nuclei and electrons. Organic molecules with heteroatoms often possess an important excited-state relaxation channel from an optically allowed ππ* to a dark nπ* state. The ππ*/nπ* internal conversion is difficult to investigate, as most spectroscopic methods are not exclusively sensitive to changes in the excited-state electronic structure. Here, we report achieving the required sensitivity by exploiting the element and site specificity of near-edge soft X-ray absorption spectroscopy. As a hole forms in the n orbital during ππ*/nπ* internal conversion, the absorption spectrummore » at the heteroatom K-edge exhibits an additional resonance. We demonstrate the concept using the nucleobase thymine at the oxygen K-edge, and unambiguously show that ππ*/nπ* internal conversion takes place within (60 ± 30) fs. Furthermore, high-level-coupled cluster calculations confirm the method’s impressive electronic structure sensitivity for excited-state investigations.« less

  9. Probing ultrafast ππ*/nπ* internal conversion in organic chromophores via K-edge resonant absorption.

    PubMed

    Wolf, T J A; Myhre, R H; Cryan, J P; Coriani, S; Squibb, R J; Battistoni, A; Berrah, N; Bostedt, C; Bucksbaum, P; Coslovich, G; Feifel, R; Gaffney, K J; Grilj, J; Martinez, T J; Miyabe, S; Moeller, S P; Mucke, M; Natan, A; Obaid, R; Osipov, T; Plekan, O; Wang, S; Koch, H; Gühr, M

    2017-06-22

    Many photoinduced processes including photosynthesis and human vision happen in organic molecules and involve coupled femtosecond dynamics of nuclei and electrons. Organic molecules with heteroatoms often possess an important excited-state relaxation channel from an optically allowed ππ* to a dark nπ* state. The ππ*/nπ* internal conversion is difficult to investigate, as most spectroscopic methods are not exclusively sensitive to changes in the excited-state electronic structure. Here, we report achieving the required sensitivity by exploiting the element and site specificity of near-edge soft X-ray absorption spectroscopy. As a hole forms in the n orbital during ππ*/nπ* internal conversion, the absorption spectrum at the heteroatom K-edge exhibits an additional resonance. We demonstrate the concept using the nucleobase thymine at the oxygen K-edge, and unambiguously show that ππ*/nπ* internal conversion takes place within (60 ± 30) fs. High-level-coupled cluster calculations confirm the method's impressive electronic structure sensitivity for excited-state investigations.Many photo-induced processes such as photosynthesis occur in organic molecules, but their femtosecond excited-state dynamics are difficult to track. Here, the authors exploit the element and site selectivity of soft X-ray absorption to sensitively follow the ultrafast ππ*/nπ* electronic relaxation of hetero-organic molecules.

  10. XRD and xanes studies of copper complexes using (diethyl 4-amino-1-phenyl-1H-pyrazole-3,5 dicarboxylate) as ligand

    NASA Astrophysics Data System (ADS)

    Mishra, Ashutosh; Jain, Garima

    2013-06-01

    X-ray diffraction (XRD) and X-ray absorption spectroscopic (XAS) studies have been done on three copper complexes using (diethyl 4-amino-1-phenyl-1H-pyrazole-3,5 dicarboxylate) as ligand. The X-ray diffraction studies of copper complexes have been recorded using Rigaku RINT-2000 X-ray diffractometer equipped with a rotating anode with tube voltage of 40 kV and current of 100 mA. The X-ray absorption spectra of the complexes have been recorded at Raja Ramanna Centre for Advanced Technology (RRCAT), Indore and is called beamline.

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

    NASA Astrophysics Data System (ADS)

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

    2014-11-01

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

  12. Effect of Particle Size Upon Pt/SiO2 Catalytic Cracking of n-Dodecane Under Supercritical Conditions: in situ SAXS and XANES Studies

    SciTech Connect

    Lee, Sungwon; Lee, Sungsik; Kumbhalkar, Mrunmayi; Wiaderek, Kamila M.; Dumesic, James A; Winans, Randall E.

    2017-01-01

    The endothermic cracking and dehydrogenation of n-dodecane is investigated over well-defined nanometer size platinum catalysts supported on SiO2 to study the particle size effects in the catalytic cracking reaction, with simultaneous in situ monitoring of the particle size and oxidation state of the working catalysts by in situ SAXS (small angle X-ray scattering) and XAS (X-ray absorption spectroscopy). The selectivity toward olefins products was found dominant in the 1 nm size platinum catalysts, whereas paraffins are dominant in the 2 nm catalysts. This reveals a strong correlation between catalytic performance and catalyst size as well as the stability of the nanoparticles in supercritical condition of n-dodecane. The presented results suggest that controlling the size and geometric structure of platinum nanocatalysts could lead to a fundamentally new level of understanding of nanoscale materials by monitoring the catalysts in realistic reaction conditions.

  13. XANES and micro-Raman spectroscopy study of the barium titanosilicates BaTiSi2O7 and BaTiSi4O11

    NASA Astrophysics Data System (ADS)

    Viani, A.; Pollastri, S.; Macova, P.; Palermo, A.; Peréz-Estébanez, M.; Gualtieri, A. F.

    2016-04-01

    The coordination environment around Ti4+ in the photoluminescent compound BaTiSi2O7 and in BaTiSi4O11 was investigated with X-ray absorption near-edge structure spectroscopy and micro-Raman spectroscopy. The presence of VTi in TiO5 pyramidal units with one short Ti-O bond involving the apical oxygen was detected in both compounds. Interpretation of the vibrational signal from the silicate framework suggested that BaTiSi4O11 is a metasilicate containing building units of SiO4 tetrahedra, which are larger than in other barium titanosilicates. These results confirmed the same structural environment of Ti4+ as recently disclosed by structure refinement of BaTiSi2O7 and provided new insights into the unknown structure of BaTiSi4O11 in the light of the study of its physical properties as potential functional material.

  14. Analyzing organic sulfur in coal/char: Integrated mild gasification/XANES methods. Technical report, 1 March--31 May 1994

    SciTech Connect

    Palmer, S.R.; Huffman, G.P.

    1994-09-01

    The overall goal of this study is to improve the understanding of sulfur in coals/chars via the use of combined advanced non-destructive and advanced destructive methods of sulfur analysis. This study combines selective oxidation, analytical pyrolysis, and sulfur X-ray Absorption Near Edge Structure Spectroscopy (XANES) analysis. Samples with a wide variety of sulfur contents, (0.63% to 4.40%) have been prepared for use in this study. This includes steam gasification chars, oxidized coals and desulfurized coals as well of the original unaltered coals. Mild pyrolysis and preliminary XANES data shows that the sulfur chemistry of gasification chars is significantly different from that of the original coals. Mild pyrolysis of the samples that were oxidized with peroxyacetic acid showed that the level of simple thiophene structures observed in the pyrolysis products declines with increasing levels of oxidation. Sulfur XANES spectra of treated samples showed various effects depending on the treatment severity. For the less severely treated samples (demineralization and solvent extraction), the XANES spectra were similar, although not identical, to the untreated coal spectra, whereas the more severe treatments (steam at 450 C; peroxyacetic acid at 25 C) showed preferential oxidation of one or more sulfur-bearing phases in the original coal. Additional samples have recently been examined by XANES and W-band EPR and the data is currently being processed and evaluated.

  15. Automated Chemical Analysis of Internally Mixed Aerosol Particles Using X-ray Spectromicroscopy at the Carbon K-Edge

    SciTech Connect

    Gilles, Mary K; Moffet, R.C.; Henn, T.; Laskin, A.

    2011-01-20

    We have developed an automated data analysis method for atmospheric particles using scanning transmission X-ray microscopy coupled with near edge X-ray fine structure spectroscopy (STXM/NEXAFS). This method is applied to complex internally mixed submicrometer particles containing organic and inorganic material. Several algorithms were developed to exploit NEXAFS spectral features in the energy range from 278 to 320 eV for quantitative mapping of the spatial distribution of elemental carbon, organic carbon, potassium, and noncarbonaceous elements in particles of mixed composition. This energy range encompasses the carbon K-edge and potassium L2 and L3 edges. STXM/NEXAFS maps of different chemical components were complemented with a subsequent analysis using elemental maps obtained by scanning electron microscopy coupled with energy dispersive X-ray analysis (SEM/EDX). We demonstrate the application of the automated mapping algorithms for data analysis and the statistical classification of particles.

  16. Resonant inelastic X-ray scattering spectrometer with 25 meV resolution at the Cu K-edge

    PubMed Central

    Ketenoglu, Didem; Harder, Manuel; Klementiev, Konstantin; Upton, Mary; Taherkhani, Mehran; Spiwek, Manfred; Dill, Frank-Uwe; Wille, Hans-Christian; Yavaş, Hasan

    2015-01-01

    An unparalleled resolution is reported with an inelastic X-ray scattering instrument at the Cu K-edge. Based on a segmented concave analyzer, featuring single-crystal quartz (SiO2) pixels, the spectrometer delivers a resolution near 25 meV (FWHM) at 8981 eV. Besides the quartz analyzer, the performance of the spectrometer relies on a four-bounce Si(553) high-resolution monochromator and focusing Kirkpatrick–Baez optics. The measured resolution agrees with the ray-tracing simulation of an ideal spectrometer. The performance of the spectrometer is demonstrated by reproducing the phonon dispersion curve of a beryllium single-crystal. PMID:26134800

  17. Bethe-Salpeter equation calculations of resonant inelastic x-ray scattering at the nitrogen K edge

    NASA Astrophysics Data System (ADS)

    Vinson, John; Jach, Terrence; Elam, Tim; Denlinger, Jonathon

    2013-03-01

    We present theoretical calculations of resonant inelastic x-ray scattering (RIXS) at the nitrogen K edge of several materials along with direct comparison to experimental results. Our approach is based on a Bethe-Salpeter equation formalism, and our calculations are carried out using an extension of the OCEAN package,[1] including both intermediate and final-state excitonic effects. By building upon a DFT basis we include ground-state effects without system-dependent fitting parameters. We are able to account for the general trends and features seen in experiment. A more ad hoc account of other contributions to the measured spectra, primarily phonon coupling, is attempted, but this highlights some current shortcomings limiting fully ab initio calculations of the near-edge x-ray spectra of extended systems.

  18. Iron K-edge X-ray absorption spectroscopy of the iron-molybdenum cofactor of nitrogenase from Klebsiella pneumoniae.

    PubMed Central

    Arber, J M; Flood, A C; Garner, C D; Gormal, C A; Hasnain, S S; Smith, B E

    1988-01-01

    Iron K-edge X-ray absorption data for the iron-molybdenum cofactor ('FeMoco') from Klebsiella pneumoniae reported here provide the first evidence for long-range structural order in the cofactor [Fe...Fe(Mo) = 0.368 nm in addition to Fe...S = 0.22 nm and Fe...Fe(Mo) = 0.27 nm] and, in contrast with previously published data [Antonio, Teo, Orme-Johnson, Nelson, Groh, Lindahl, Kauzlarich & Averill (1982) J. Am. Chem. Soc. 104, 4703-4705], indicate that most of the iron centres are not co-ordinated to light (oxygen, nitrogen) atoms. This demonstrates that presently available chemical models for FeMoco are inadequate. PMID:3046607

  19. Quantum Monte Carlo for the x-ray absorption spectrum of pyrrole at the nitrogen K-edge

    SciTech Connect

    Zubarev, Dmitry Yu.; Austin, Brian M.; Lester, William A. Jr.

    2012-04-14

    Fixed-node diffusion Monte Carlo (FNDMC) is used to simulate the x-ray absorption spectrum of a gas-phase pyrrole molecule at the nitrogen K-edge. Trial wave functions for core-excited states are constructed from ground-state Kohn-Sham determinants substituted with singly occupied natural orbitals from configuration interaction with single excitations calculations of the five lowest valence-excited triplet states. The FNDMC ionization potential (IP) is found to lie within 0.3 eV of the experimental value of 406.1 {+-} 0.1 eV. The transition energies to anti-bonding virtual orbitals match the experimental spectrum after alignment of IP values and agree with the existing assignments.

  20. Phosphine and phosphine oxide groups in metal-organic frameworks detected by P K-edge XAS.

    PubMed

    Morel, F L; Pin, S; Huthwelker, T; Ranocchiari, M; van Bokhoven, J A

    2015-02-07

    Phosphine metal-organic frameworks (P-MOFs) are crystalline porous coordination polymers that contain phosphorus functional groups within their pores. We present the use of X-ray absorption spectroscopy (XAS) at the P K-edge to determine the phosphine to phosphine oxide ratio in two P-MOFs with MIL-101 topology. The phosphorus oxidation state is of particular interest as it strongly influences the coordination affinity of these materials for transition metals. This method can determine the oxidation state of phosphorus even when the material contains paramagnetic nuclei, differently from NMR spectroscopy. We observed that phosphine in LSK-15 accounts for 72 ± 4% of the total phosphorus groups and that LSK-12 contains only phosphine oxide.

  1. Oxygen K-edge fine structures of water by x-ray Raman scattering spectroscopy under pressure conditions

    SciTech Connect

    Fukui, Hiroshi; Huotari, Simo; Andrault, Denis; Kawamoto, Tatsuhiko

    2007-10-07

    Fine structure of the oxygen K edge was investigated for water at ambient pressure, 0.16, 0.21, 0.27, 0.47, and 0.60 GPa using x-ray Raman scattering spectroscopy (XRS). Similarity in near-edge structures at 0.16 and 0.60 GPa suggests little difference in the electronic state of oxygen in the low-pressure and high-pressure forms of water. Yet, we observed significant variation of preedge structure of the XRS spectra with compression. The intensity of the preedge peak at 535.7 eV has a minimal value at around 0.3 GPa, indicating that the number of hydrogen bonding increases first and then decreases as a function of pressure.

  2. Spectroscopic studies of cathode materials for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Totir, Dana Alexa

    2000-10-01

    Structural changes that occur during electrochemical cycling of lithium-ion battery cathode materials have been investigated using in situ spectroscopic techniques. A new method was developed for the preparation of carbon and binder free cathodes utilizing powder materials of interest for commercial batteries. The extraordinary quality of the cyclic voltammetric curves recorded for this type of electrodes during the in situ measurements allows direct correlations to be made between the state of charge of the material and its structural and electronic characteristics. LiCoO2, LiMn2O4 and LiCo0.15Ni 0.85O2 electrodes were evaluated using cycling voltammetry and the mean diffusion coefficient for Li-ions in the lattice (DLi) was calculated for LiMn2O4. LiMn2O4 electrodes prepared by this technique have been studied in situ using Mn K-edge XAS. Data analysis for the species formed at different potentials indicated a contraction of the lattice associated with the increase in the oxidation state of manganese. In situ Raman spectra of particles of LiMn2O 4, and LiCoO2 embedded in Au and also of KS-44 graphite and carbon microfibers MCF28 embedded in thermally annealed Ni have been recorded as a function of the applied potential. Fe K-edge XAFS of pyrite electrodes in a Li/PEO(LiClO4)/FeS 2 cell and S K-edge XANES measurements of a FeS2 electrode in a non-aqueous electrolyte have been acquired as a function of the state of charge. The studies have clearly evidenced the formation of metallic Fe and Li2S as intermediates after 4 e- discharge and the formation of Li2FeS2 after 2 e- recharge. While Fe K-edge studies have indicated that there is no change in the Fe environment and oxidation state upon 4 e- recharge, the results obtained from S K-edge studies are inconclusive for this stage. Finally, in situ Co K-edge XAFS data were obtained for the first time during the electrochemical cycling of electrodeposited Co(OH) 2 films in alkaline solutions. The results support

  3. First-principles XANES simulations of spinel zinc ferrite with a disordered cation distribution

    SciTech Connect

    Nakashima, Seisuke; Fujita, Koji; Tanaka, Katsuhisa; Hirao, Kazuyuki; Yamamoto, Tomoyuki; Tanaka, Isao

    2007-05-01

    Theoretical calculations of Zn K and Fe K x-ray absorption near-edge structures (XANES) using a first-principles method have been performed to evaluate the degree of cation disordering in spinel zinc ferrite (ZnFe{sub 2}O{sub 4}) thin film prepared by a sputtering method, ZnFe{sub 2}O{sub 4} thin films annealed at elevated temperatures, and ZnFe{sub 2}O{sub 4} bulk specimen prepared by a solid-state reaction. Using the full-potential linearized augmented plane-wave + local orbitals method, a theoretical spectrum is generated for the tetrahedral and octahedral environments for each of the two cations. The experimental XANES spectrum of the thin film annealed at 800 deg. C as well as that of bulk specimen is successfully reproduced by using either the theoretical spectrum for Zn{sup 2+} on the tetrahedral site (A site) or that for Fe{sup 3+} on the octahedral site (B site), which is indicative of the normal spinel structure. For the as-deposited film, on the other hand, excellent agreement between theoretical and experimental spectra is obtained by considering the presence of either ion in both the A and B sites. The degree of cation disordering, x, defined as [Zn{sub 1-x}{sup 2+}Fe{sub x}{sup 3+}]{sub A}[Zn{sub x}{sup 2+}Fe{sub 2-x}{sup 3+}]{sub B}O{sub 4}, is estimated to be approximately 0.6 in the as-deposited film, which is consistent with the analysis of the extended x-ray absorption fine structure on the Zn K edge. Curious magnetic properties as we previously observed for the as-deposited thin film--i.e., ferrimagnetic behaviors accompanied by large magnetization at room temperature and cluster spin-glass-like behavior--are discussed in connection with disordering of Zn{sup 2+} and Fe{sup 3+} ions in the spinel-type structure.

  4. Asymptotically-Equal-To 10 eV ionization shift in Ir K{alpha}{sub 2} from a near-coincident Lu K-edge

    SciTech Connect

    Pereira, N. R.; Weber, B. V.; Phipps, D.; Schumer, J. W.; Seely, J. F.; Carroll, J. J.; VanHoy, J. R.; Slabkowska, K.; Polasik, M.

    2012-10-15

    Close to an x-ray filter's K-edge the transmission depends strongly on the photon energy. For a few atom pairs, the K-edge of one is only a few tens of eV higher than a K-line energy of another, so that a small change in the line's energy becomes a measurable change in intensity behind such a matching filter. Lutetium's K-edge is Asymptotically-Equal-To 27 eV above iridium's K{alpha}{sub 2} line, Asymptotically-Equal-To 63.287 keV for cold Ir. A Lu filter reduces this line's intensity by Asymptotically-Equal-To 10 % when it is emitted by a plasma, indicating an ionization shift {Delta}E Asymptotically-Equal-To 10{+-}1 eV.

  5. Photoconductivity measurements of x-ray absorption fine structures in liquids in the soft x-ray region: Si and Cl K-edge

    SciTech Connect

    Sham, T.K.; Xiong, J.Z.; Feng, X.H.; Holroyd, R.A.; Yang, B.X.

    1992-12-31

    Photoconductivity measurements of X-ray absorption fine structures (XAFS) at the Si and Cl K-edge have been carried out in a liquid cell for (CH{sub 3}){sub 4},Si [(CH{sub 3}){sub 3}Si]{sub 4}Si and eitheras a pure liquid or 2,2,4-trimethylpentane solution. It is found that for the pure liquids and their concentrated hydrocarbon solutions, all K-edge XAFS spectra are inverted as expected under the condition of total absorption. A sharp conductivity dip is also observed in CCl{sub 4} at the Cl K-edge. The concentration dependence of the XAFS spectrum of CCl{sub 4} is reported. These results are discussed in terms of soft X-ray induced ion yields of the solute and solvent molecules in liquids.

  6. Photoconductivity measurements of x-ray absorption fine structures in liquids in the soft x-ray region: Si and Cl K-edge

    SciTech Connect

    Sham, T.K.; Xiong, J.Z.; Feng, X.H. . Dept. of Chemistry); Holroyd, R.A. ); Yang, B.X. )

    1992-01-01

    Photoconductivity measurements of X-ray absorption fine structures (XAFS) at the Si and Cl K-edge have been carried out in a liquid cell for (CH[sub 3])[sub 4],Si [(CH[sub 3])[sub 3]Si][sub 4]Si and eitheras a pure liquid or 2,2,4-trimethylpentane solution. It is found that for the pure liquids and their concentrated hydrocarbon solutions, all K-edge XAFS spectra are inverted as expected under the condition of total absorption. A sharp conductivity dip is also observed in CCl[sub 4] at the Cl K-edge. The concentration dependence of the XAFS spectrum of CCl[sub 4] is reported. These results are discussed in terms of soft X-ray induced ion yields of the solute and solvent molecules in liquids.

  7. Oxygen K-edge absorption spectra of small molecules in the gas phase

    SciTech Connect

    Yang, B.X.; Kirz, J.; Sham, T.K.

    1986-01-01

    The absorption spectra of O/sub 2/, CO, CO/sub 2/ and OCS have been recorded in a transmission mode in the energy region from 500 to 950 eV. Recent observation of EXAFS in these molecules is confirmed in this study. 7 refs., 3 figs.

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

    NASA Astrophysics Data System (ADS)

    Tamura, Tomoyuki; Kohyama, Masanori; Ogata, Shuji

    2017-07-01

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

  9. Postcollision-interaction effects in HCl following photofragmentation near the chlorine K edge

    SciTech Connect

    Hansen, D.L.; Arrasate, M.E.; Martin, R.; Vanderford, B.; Lindle, D.W.; Levin, J.C.; Sellin, I.A.; Neill, P; Perera, R.C.C. Leung, K.T. Simon, M. Simon, M. Uehara, Y. Whitfield, S.B.

    1998-06-01

    Ion time-of-flight mass spectroscopy was used to study the relaxation dynamics of HCl following photoexcitation in the vicinity of the Cl K threshold ({approx}2.8 keV). Detailed observations of molecular fragmentation mediated by postcollision interaction between a photoelectron and an Auger electron are presented, evidenced by the recapture of Cl K photoelectrons by either Cl{sup n+} or H{sup +} dissociation fragments. {copyright} {ital 1998} {ital The American Physical Society}

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

    NASA Technical Reports Server (NTRS)

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

    2014-01-01

    . The natures of the macromolecular carbon in the solid inclusions observed by C-XANES are consistent with the previous studies showing that the carbonaceous solid inclusions have not originated from Monahans parent body [1-3], and have various origins, including various chondritic meteorite parent bodies as well as other unknown source(s).

  11. A valence state evaluation of a positive electrode material in an Li-ion battery with first-principles K- and L-edge XANES spectral simulations and resonance photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Kubobuchi, Kei; Mogi, Masato; Matsumoto, Masashi; Baba, Teruhisa; Yogi, Chihiro; Sato, Chikai; Yamamoto, Tomoyuki; Mizoguchi, Teruyasu; Imai, Hideto

    2016-10-01

    X-ray absorption near edge structure (XANES) analysis is an element-specific method for proving electronic state mostly in the field of applied physics, such as battery and catalysis reactions, where the valence change plays an important role. In particular, many results have been reported for the analysis of positive electrode materials of Li-ion batteries, where multiple transition materials contribute to the reactions. However, XANES analysis has been limited to identifying the valence state simply in comparison with reference materials. When the shape of XANES spectra shows complicated changes, we were not able to identify the valence states or estimate the valence quantitatively, resulting in insufficient reaction analysis. To overcome such issues, we propose a valence state evaluation method using K- and L-edge XANES analysis with first-principles simulations. By using this method, we demonstrated that the complicated reaction mechanism of Li(Ni1/3Co1/3Mn1/3)O2 can be successfully analyzed for distinguishing each contribution of Ni, Co, Mn, and O to the redox reactions during charge operation. In addition to the XANES analysis, we applied resonant photoelectron spectroscopy (RPES) and diffraction anomalous fine structure spectroscopy (DAFS) with first-principles calculations to the reaction analysis of Co and Mn, which shows no or very little contribution to the redox. The combination of RPES and first-principles calculations successfully enables us to confirm the contribution of Co at high potential regions by electively observing Co 3d orbitals. Through the DAFS analysis, we deeply analyzed the spectral features of Mn K-edges and concluded that the observed spectral shape change for Mn does not originate from the valence change but from the change in distribution of wave functions around Mn upon Li extraction.

  12. 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.

    PubMed

    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

  13. Vanadium K-edge X-ray absorption spectroscopy of bromoperoxidase from Ascophyllum nodosum

    SciTech Connect

    Arber, J.M.; de Boer, E.; Garner, C.D.; Hasnain, S.S.; Wever, R. )

    1989-09-19

    Bromoperoxidase from Ascophyllum nodusum was the first vanadium-containing enzyme to be isolated. X-ray absorption spectra have now been collected in order to investigate the coordination of vanadium in the native, native plus bromide, native plus hydrogen peroxide, and dithionite-reduced forms of the enzyme. The edge and X-ray absorption near-edge structures show that, in the four samples studied, it is only on reduction of the native enzyme that the metal site is substantially altered. In addition, these data are consistent with the presence of vanadium(IV) in the reduced enzyme and vanadium(V) in the other samples. Extended X-ray absorption fine structure data confirm that there are structural changes at the metal site on reduction of the native enzyme, notably a lengthening of the average inner-shell distance, and the presence of terminal oxygen together with histidine and oxygen-donating residues.

  14. Quadrupole transition in the Dy L{sub 3} edge observed by lifetime-broadening-suppressed XANES spectroscopy

    SciTech Connect

    Hayashi, Hisashi; Takeda, Rumi; Kawata, Masaki; Udagawa, Yasuo; Kawamura, Naomi; Watanabe, Yasuhiro; Nanao, Susumu

    2004-10-15

    Lifetime-broadening-suppressed x-ray absorption near edge structure (LBS-XANES) spectroscopy is applied to the Dy L{sub 3} edge, where multiplet nature of the final state as well as lifetime-broadening distorts the band shape. It was found that, by determining appropriate final state density function from observed the L{alpha} band shape, LBS-XANES spectra can be obtained and 2p{yields}4f quadrupole transition is unequivocally observed as a separate peak. It has been proved from the present results that LBS-XANES spectroscopy is very versatile; transitions with multiplet final states can be studied by the use of hard x-rays and forbidden transitions obscured by intense dipole-allowed transitions can be revealed. Implications for resonant inelastic x-ray scattering (RIXS) spectra are also discussed in terms of RIXS contour plot and the Kramers-Heisenberg equation.

  15. Improving material separation of high-flux whole-body photon counting computed tomography by K-edge pre-filtration

    NASA Astrophysics Data System (ADS)

    Polster, C.; Gutjahr, R.; Berner, M.; Flohr, T.; Hertel, M.; Kappler, S.; Stierstorfer, K.; Dietrich, O.

    2017-03-01

    Photon-counting detectors in computed tomography (CT) allow for measuring the energy of the incident xray photons within certain energy windows. This information can be used to enhance contrast or reconstruct CT images of different material bases. Compared to energy-integrating CT-detectors, pixel dimensions have to be smaller to limit the negative effect of pulse pile-up at high X-ray fluxes. Unfortunately, reducing the pixel size leads to increased K-escape and charge sharing effects. As a consequence, an incident X-ray may generate more than one detector signal, and with deteriorated energy information. In earlier simulation studies it has been shown that these limitations can be mitigated by optimizing the X-ray spectrum using K-edge pre-filtration. In the current study, we have used a whole-body research CT scanner with a high-flux capable photon-counting detector, in which for the first time a pre-patient hafnium filter was installed. Our measurement results demonstrate substantial improvement of the material decomposition capability at comparable dose levels. The results are in agreement with the predictions provided in simulations.

  16. Quantitative spectral K-edge imaging in preclinical photon-counting x-ray computed tomography.

    PubMed

    de Vries, Anke; Roessl, Ewald; Kneepkens, Esther; Thran, Axel; Brendel, Bernhard; Martens, Gerhard; Proska, Roland; Nicolay, Klaas; Grüll, Holger

    2015-04-01

    The objective of this study was to investigate the feasibility and the accuracy of spectral computed tomography (spectral CT) to determine the tissue concentrations and localization of high-attenuation, iodine-based contrast agents in mice. Iodine tissue concentrations determined with spectral CT are compared with concentrations measured with single-photon emission computed tomography (SPECT) and inductively coupled plasma mass spectrometry (ICP-MS). All animal procedures were performed according to the US National Institutes of Health principles of laboratory animal care and were approved by the ethical review committee of Maastricht, The Netherlands. Healthy Swiss mice (n = 4) were injected with an iodinated emulsion radiolabeled with indium as multimodal contrast agent for CT and SPECT. The CT and SPECT scans were acquired using a dedicated small-animal SPECT/CT system. Subsequently, scans were performed with a preclinical spectral CT scanner equipped with a photon-counting detector and 6 energy threshold levels. Quantitative data analysis of SPECT and spectral CT scans were obtained using 3-dimensional volumes-of-interest drawing methods. The ICP-MS on dissected organs was performed to determine iodine uptake per organ and was compared with the amounts determined from spectral CT and SPECT. Iodine concentrations obtained with image-processed spectral CT data correlated well with data obtained either with noninvasive SPECT imaging (slope = 0.96, r = 0.75) or with ICP-MS (slope = 0.99, r = 0.89) in tissue samples. This preclinical proof-of-concept study shows the in vivo quantification of iodine concentrations in tissues using spectral CT. Our multimodal imaging approach with spectral CT and SPECT using radiolabeled iodinated emulsions together with ICP-based quantification allows a direct comparison of all methods. Benchmarked against ICP-MS data, spectral CT in the present implementation shows a slight underestimation of organ iodine concentrations compared

  17. Site-selective photofragmentation of chlorinated polymeric films observed around the chlorine K-edge

    NASA Astrophysics Data System (ADS)

    Arantes, C.; Mendes, L. A. V.; Pinho, R. R.; Ferreira, M.; de Souza, G. G. B.; Rocha, A. B.; Rocco, M. L. M.

    2013-03-01

    Photon stimulated ion desorption (PSID) and Near-edge X-ray absorption fine structure (NEXAFS) studies have been performed on poly(vinyl chloride) (PVC) and poly(vinyl dichloride) (PVDC) around the chlorine 1s-edge. Experiments were performed using a synchrotron source operating in the single-bunch mode and a time-of-flight mass spectrometry for ion analysis. Cl+ ion yields, as a function of the photon energy, reproduce the photoabsorption spectrum, showing significant increase at the 1s-resonance. Edge-jump ratios, defined as the ratio between edge-jumps (intensity ratio of the yields between above and below the absorption edge) of two different transitions, for Cl+ ion yields were much higher than the equivalent electron yields, indicating site-selectivity in C-Cl bond breaking for both polymers, as a result of efficient spectator Auger decay. The expected isotope ratio of 3:1 for chlorine was measured for PVC. The interpretation of the NEXAFS spectrum was assisted by quantum mechanical calculations at a multireference perturbation theory level.

  18. K edge absorption spectra of sulphur in vapour, molecular and polymerized solid phases

    NASA Astrophysics Data System (ADS)

    Durand, J. M.; Olivier-Fourcade, J.; Jumas, J. C.; Womes, M.; Teodorescu, C. M.; Elafif, A.; Esteva, J. M.; Karnatak, R. C.

    1996-12-01

    X-ray K absorption spectra of sulphur have been studied in its vapour, molecular and polymerized solid phases. The vapour phase of sulphur containing 0953-4075/29/23/019/img11 molecules yields a K spectrum which is similar to that of the 0953-4075/29/23/019/img12 molecule. This observation suggests a 0953-4075/29/23/019/img13 ground state of 0953-4075/29/23/019/img11, which is in agreement with that obtained from optical spectra. Different line splittings in the spectra of these molecules are discussed in the light of the p orbital and s - p orbital energy differences of some second- and third-period elements. While the condensed phase spectrum of 0953-4075/29/23/019/img12 remains unchanged, the observed K spectrum of condensed 0953-4075/29/23/019/img11 differs considerably from its vapour phase. This abrupt change in the bonding between the S atoms in the condensed phase is typical behaviour of sulphur and indicates the formation of two directional covalent bonds and creation of 0953-4075/29/23/019/img17 and 0953-4075/29/23/019/img18 lone pairs. This behaviour is, in fact, a clear distinction between the chemistries of sulphur and that of its homologue oxygen. The cyclic and chain forms of sulphur show some similarity in 0953-4075/29/23/019/img19 line structure and a marked difference in their near-edge structure due to a different number of S atoms surrounding a central atom in these allotropic forms.

  19. Resonant inelastic x-ray scattering on iso-C{sub 2}H{sub 2}Cl{sub 2} around the chlorine K-edge: Structural and dynamical aspects

    SciTech Connect

    Kawerk, Elie E-mail: ekawerk@units.it; Carniato, Stéphane; Journel, Loïc; Marchenko, Tatiana; Simon, Marc; Piancastelli, Maria Novella; Žitnik, Matjaž; Bučar, Klemen; Bohnic, Rok; and others

    2014-10-14

    We report a theoretical and experimental study of the high resolution resonant K{sub α} X-ray emission lines around the chlorine K-edge in gas phase 1,1-dichloroethylene. With the help of ab initio electronic structure calculations and cross section evaluation, we interpret the lowest lying peak in the X-ray absorption and emission spectra. The behavior of the K{sub α} emission lines with respect to frequency detuning highlights the existence of femtosecond nuclear dynamics on the dissociative Potential Energy Surface of the first K-shell core-excited state.

  20. In situ site-selective transition metal K-edge XAS: a powerful probe of the transformation of mixed-valence compounds.

    PubMed

    Bordage, Amélie; Trannoy, Virgile; Proux, Olivier; Vitoux, Hugo; Moulin, Robinson; Bleuzen, Anne

    2015-07-14

    We present herein the first in situ site-selective XAS experiment performed on a proof-of-principle transformation of a mixed-valence compound: the calcination of the K0.1Co(II)4[Co(III)(CN)6]2.7·20H2O Prussian Blue analogue (containing Co(2+) and Co(3+) ions in two different Oh sites) into Co3O4 (containing Co(2+) ions in a Td site and Co(3+) in an Oh site). By recording the Co K-edge X-ray absorption spectra using a spectrometer aligned at the Co Kβ1,3 emission line, the evolution of each species was singly monitored from 20 °C up to the oxide formation. The experimental spectrum of the Co(2+)(Td) and Co(3+) (Oh) species in Co3O4 is reported for the first time. Our results demonstrate the possibilities offered by site-selective XAS for the investigation of chemical transformations and the study of materials under working conditions whenever the chemical element of interest is present in several states and/or sites.

  1. Structural studies in the BaO-B 2O 3-TiO 2 system by XAS and 11B-NMR

    NASA Astrophysics Data System (ADS)

    Maia, L. J. Q.; Mastelaro, V. R.; Schneider, J. F.; Parent, P.; Laffon, C.

    2005-05-01

    The structure of barium-titanium-metaborate xBaO- xB 2O 3- yTiO 2 ( y=0%, 4%, 8%, 16% and x=50- y/2) amorphous and crystallized powders, obtained using a polymeric precursor method, was investigated by Ti and B K-edge X-ray absorption spectroscopy (XAS) and 11B-NMR high-resolution techniques. XANES study of amorphous samples shows that Ti 4+ ions exist as [4]Ti species associated to [6]Ti and [5]Ti species in a practically equivalent amount. After crystallization, titanium environment is predominately composed by [6]Ti species. According to XANES results obtained at the B K-edge, the fraction of boron in tetrahedral sites ( [4]B) reduces as the amount of TiO 2 is increased from x=0% to 4%, with a consequent increase of boron in trigonal sites ( [3]B). By a combination of 11B-NMR spin-echo and triple quantum magic angle spinning (3Q-MAS) techniques, the detailed borate speciation was determined as consisting in [4]B and two kind of trigonal sites, [3]B A and [3]B B, corresponding, respectively, to borates sharing three and two O atoms with other boron units. NMR results reveal not only the reduction in boron coordination also seen by XANES but also the simultaneous reduction in the condensation degree of trigonal units, when the Ti content is increased in the glass. In crystallized samples, β-BaB 2O 4 and BaTi(BO 3) 2 phases were identified and quantified by 11B-NMR.

  2. Amorphisation mechanism of a flint aggregate during the alkali-silica reaction: X-ray diffraction and X-ray absorption XANES contributions

    SciTech Connect

    Verstraete, J.; Khouchaf, L.; Bulteel, D.; Garcia-Diaz, E.; Flank, A.M; Tuilier, M.H

    2004-04-01

    Flint samples at different stages of the Alkali-Silica Reaction were prepared and analyzed by X-ray diffraction (XRD) and silicon K-edge X-ray absorption near edge structure techniques (XANES). The results are compared to those of measurements performed on alpha quartz c-SiO{sub 2} and rough flint aggregate. The molar fraction of Q{sub 3} sites is determined as a function of the time of reaction. Up to 14 h of attack, the effect of the reaction seems of little importance. From 30 to 168 h, we showed an acceleration of the effect of the reaction on the crystal structure of the aggregate resulting in an amorphisation of the crystal. During this period, the amorphous fraction increases linearly with the number of Q{sub 3} sites. The results of the XANES confirm the amorphisation of the aggregate during the reaction and show the presence of silicon in a tetrahedral environment of oxygen whatever the time of attack.

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

    SciTech Connect

    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.

  4. The determination of dopant ion valence distributions in insulating crystals using XANES measurements.

    PubMed

    Hughes-Currie, Rosa B; Ivanovskikh, Konstantin V; Wells, Jon-Paul R; Reid, Michael F; Gordon, Robert A

    2016-04-06

    Ytterbium-doped wide-bandgap fluoride crystals CaF2, SrF2 and NaMgF3 have been measured using x-ray absorption near edge structure (XANES) on the L3 edge to determine the ratio of trivalent to divalent Yb ions present in the crystals. This study improves upon previous XANES measurements of dopant ion valency by taking into account the x-ray emission transition probabilities for the divalent and trivalent species instead of simply assuming that the relative concentrations may be determined by the ratio of the x-ray excitation band areas. Trivalent to divalent ratios as high as 5 are inferred even at low total dopant ion concentrations of 0.05 mol% Yb.

  5. The determination of dopant ion valence distributions in insulating crystals using XANES measurements

    NASA Astrophysics Data System (ADS)

    Hughes-Currie, Rosa B.; Ivanovskikh, Konstantin V.; Wells, Jon-Paul R.; Reid, Michael F.; Gordon, Robert A.

    2016-04-01

    Ytterbium-doped wide-bandgap fluoride crystals CaF2, SrF2 and NaMgF3 have been measured using x-ray absorption near edge structure (XANES) on the L3 edge to determine the ratio of trivalent to divalent Yb ions present in the crystals. This study improves upon previous XANES measurements of dopant ion valency by taking into account the x-ray emission transition probabilities for the divalent and trivalent species instead of simply assuming that the relative concentrations may be determined by the ratio of the x-ray excitation band areas. Trivalent to divalent ratios as high as 5 are inferred even at low total dopant ion concentrations of 0.05 mol% Yb.

  6. A 23Na magic angle spinning nuclear magnetic resonance, XANES, and high-temperature X-ray diffraction study of NaUO3, Na4UO5, and Na2U2O7.

    PubMed

    Smith, A L; Raison, P E; Martel, L; Charpentier, T; Farnan, I; Prieur, D; Hennig, C; Scheinost, A C; Konings, R J M; Cheetham, A K

    2014-01-06

    The valence state of uranium has been confirmed for the three sodium uranates NaU(V)O3/[Rn](5f(1)), Na4U(VI)O5/[Rn](5f(0)), and Na2U(VI)2O7/[Rn](5f(0)), using X-ray absorption near-edge structure (XANES) spectroscopy. Solid-state (23)Na magic angle spinning nuclear magnetic resonance (MAS NMR) measurements have been performed for the first time, yielding chemical shifts at -29.1 (NaUO3), 15.1 (Na4UO5), and -14.1 and -19 ppm (Na1 8-fold coordinated and Na2 7-fold coordinated in Na2U2O7), respectively. The [Rn]5f(1) electronic structure of uranium in NaUO3 causes a paramagnetic shift in comparison to Na4UO5 and Na2U2O7, where the electronic structure is [Rn]5f(0). A (23)Na multi quantum magic angle spinning (MQMAS) study on Na2U2O7 has confirmed a monoclinic rather than rhombohedral structure with evidence for two distinct Na sites. DFT calculations of the NMR parameters on the nonmagnetic compounds Na4UO5 and Na2U2O7 have permitted the differentiation between the two Na sites of the Na2U2O7 structure. The linear thermal expansion coefficients of all three compounds have been determined using high-temperature X-ray diffraction: αa = 22.7 × 10(-6) K(-1), αb = 12.9 × 10(-6) K(-1), αc = 16.2 × 10(-6) K(-1), and αvol = 52.8 × 10(-6) K(-1) for NaUO3 in the range 298-1273 K; αa = 37.1 × 10(-6) K(-1), αc = 6.2 × 10(-6) K(-1), and αvol = 81.8 × 10(-6) K(-1) for Na4UO5 in the range 298-1073 K; αa = 6.7 × 10(-6) K(-1), αb = 14.4 × 10(-6) K(-1), αc = 26.8 × 10(-6) K(-1), αβ = -7.8 × 10(-6) K(-1), and αvol = -217.6 × 10(-6) K(-1) for Na2U2O7 in the range 298-573 K. The α to β phase transition reported for the last compound above about 600 K was not observed in the present studies, either by high-temperature X-ray diffraction or by differential scanning calorimetry.

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

    NASA Technical Reports Server (NTRS)

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

    2011-01-01

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

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

    NASA Technical Reports Server (NTRS)

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

    2011-01-01

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

  9. High-speed K-edge angiography achieved with tantalum K-series characteristic x rays (Honorable Mention Poster Award)

    NASA Astrophysics Data System (ADS)

    Sato, Eiichi; Tanaka, Etsuro; Mori, Hidezo; Kawai, Toshiaki; Inoue, Takashi; Ogawa, Akira; Sato, Shigehiro; Takayama, Kazuyoshi; Ido, Hideaki

    2005-04-01

    The tantalum plasma flash x-ray generator is useful in order to perform high-speed K-edge angiography using cone beams because Kα rays from the tantalum target are absorbed effectively by gadolinium-based contrast media. In the flash x-ray generator, a 150 nF condenser is charged up to 80 kV by a power supply, and flash x rays are produced by the discharging. The x-ray tube is a demountable diode, and the turbomolecular pump evacuates air from the tube with a pressure of approximately 1 mPa. Since the electric circuit of the high-voltage pulse generator employs a cable transmission line, the high-voltage pulse generator produces twice the potential of the condenser charging voltage. When the charging voltage was increased, the K-series characteristic x-ray intensities of tantalum increased. The K lines were clean and intense, and hardly any bremsstrahlung rays were detected. The x-ray pulse widths were approximately 100 ns, and the time-integrated x-ray intensity had a value of approximately 300 μGy at 1.0 m from the x-ray source with a charging voltage of 80 kV. Angiography was performed using a film-less computed radiography (CR) system and gadolinium-based contrast media. In angiography of non-living animals, we observed fine blood vessels of approximately 100 μm with high contrasts.

  10. Resonant soft x-ray reflectivity of Me/B4C multilayers near the boron K edge

    SciTech Connect

    Ksenzov, Dmitriy; Schlemper, Christoph; Pietsch, Ullrich

    2010-09-01

    Energy dependence of the optical constants of boron carbide in the short period Ru/B4C and Mo/B4C multilayers (MLs) are evaluated from complete reflectivity scans across the boron K edge using the energy-resolved photon-in-photon-out method. Differences between the refractive indices of the B4Cmaterial inside and close to the surface are obtained from the peak profile of the first order ML Bragg peak and the reflection profile near the critical angle of total external reflection close to the surface. Where a Mo/B4C ML with narrow barrier layers appears as a homogeneous ML at all energies, a Ru/B4C ML exhibits another chemical nature of boron at the surface compared to the bulk. From evaluation of the critical angle of total external reflection in the energy range between 184 and 186 eV, we found an enriched concentration of metallic boron inside the Ru-rich layer at the surface, which is not visible in other energy ranges.

  11. Photoionization of Ne Atoms and Ne+ Ions Near the K Edge: Precision Spectroscopy and Absolute Cross-sections

    NASA Astrophysics Data System (ADS)

    Müller, Alfred; Bernhardt, Dietrich; Borovik, Alexander, Jr.; Buhr, Ticia; Hellhund, Jonas; Holste, Kristof; Kilcoyne, A. L. David; Klumpp, Stephan; Martins, Michael; Ricz, Sandor; Seltmann, Jörn; Viefhaus, Jens; Schippers, Stefan

    2017-02-01

    Single, double, and triple photoionization of Ne+ ions by single photons have been investigated at the synchrotron radiation source PETRA III in Hamburg, Germany. Absolute cross-sections were measured by employing the photon-ion merged-beams technique. Photon energies were between about 840 and 930 eV, covering the range from the lowest-energy resonances associated with the excitation of one single K-shell electron up to double excitations involving one K- and one L-shell electron, well beyond the K-shell ionization threshold. Also, photoionization of neutral Ne was investigated just below the K edge. The chosen photon energy bandwidths were between 32 and 500 meV, facilitating the determination of natural line widths. The uncertainty of the energy scale is estimated to be 0.2 eV. For comparison with existing theoretical calculations, astrophysically relevant photoabsorption cross-sections were inferred by summing the measured partial ionization channels. Discussion of the observed resonances in the different final ionization channels reveals the presence of complex Auger-decay mechanisms. The ejection of three electrons from the lowest K-shell-excited Ne+(1s2{s}22{p}6{}2{{{S}}}1/2) level, for example, requires cooperative interaction of at least four electrons.

  12. Photoionization of Ne Atoms and Ne + Ions Near the K Edge: PrecisionSpectroscopy and Absolute Cross-sections

    DOE PAGES

    Müller, Alfred; Bernhardt, Dietrich; Borovik, Alexander; ...

    2017-02-17

    Single, double, and triple photoionization of Ne + ions by single photons have been investigated at the synchrotron radiation source PETRA III in Hamburg, Germany. Absolute cross-sections were measured by employing the photon-ion merged-beams technique. Photon energies were between about 840 and 930 eV, covering the range from the lowest-energy resonances associated with the excitation of one single K-shell electron up to double excitations involving one K- and one L-shell electron, well beyond the K-shell ionization threshold. Also, photoionization of neutral Ne was investigated just below the K edge. The chosen photon energy bandwidths were between 32 and 500 meV,more » facilitating the determination of natural line widths. The uncertainty of the energy scale is estimated to be 0.2 eV. For comparison with existing theoretical calculations, astrophysically relevant photoabsorption cross-sections were inferred by summing the measured partial ionization channels. Discussion of the observed resonances in the different final ionization channels reveals the presence of complex Auger-decay mechanisms. The ejection of three electrons from the lowest K-shell-excited Ne + (1s2s2p6 2S1/2) level, for example, requires cooperative interaction of at least four electrons.« less

  13. Local electronic structure of aqueous zinc acetate: oxygen K-edge X-ray absorption and emission spectroscopy on micro-jets.

    PubMed

    Golnak, Ronny; Atak, Kaan; Suljoti, Edlira; Hodeck, Kai F; Lange, Kathrin M; Soldatov, Mikhail A; Engel, Nicholas; Aziz, Emad F

    2013-06-07

    Oxygen K-edge X-ray absorption, emission, and resonant inelastic X-ray scattering spectra were measured to site selectively gain insights into the electronic structure of aqueous zinc acetate solution. The character of the acetate ion and the influence of zinc and water on its local electronic structure are discussed.

  14. Correction: Ligand K-edge XAS, DFT, and TDDFT analysis of pincer linker variations in Rh(i) PNP complexes: reactivity insights from electronic structure.

    PubMed

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

    2016-07-21

    Correction for 'Ligand K-edge XAS, DFT, and TDDFT analysis of pincer linker variations in Rh(i) PNP complexes: reactivity insights from electronic structure' by Jason M. Keith, Scott R. Daly, et al., Dalton Trans., 2016, 45, 9774-9785.

  15. XANES Identification of Plutonium Speciation in RFETS Samples

    SciTech Connect

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

    2009-06-03

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

  16. SU-C-207-06: In Vivo Quantification of Gold Nanoparticles Using K-Edge Imaging Via Spectrum Shaping by Gold Filter

    SciTech Connect

    Chen, H; Cormack, R; Bhagwat, M; Berbeco, R

    2015-06-15

    Purpose: Gold nanoparticles (AuNP) are multifunctional platforms ideal for drug delivery, targeted imaging and radiosensitization. We have investigated quantitative imaging of AuNPs using on board imager (OBI) cone beam computed tomography (CBCT). To this end, we also present, for the first time, a novel method for k-edge imaging of AuNP by filter-based spectral shaping. Methods: We used a digital 25 cm diameter water phantom, embedded with 3 cm spheres filled with AuNPs of different concentrations (0 mg/ml – 16 mg/ml). A poly-energetic X-ray spectrum of 140 kVp from a conventional X-ray tube is shaped by balanced K-edge filters to create an excess of photons right above the K-edge of gold at 80.7 keV. The filters consist of gold, tin, copper and aluminum foils. The phantom with appropriately assigned attenuation coefficients is forward projected onto a detector for each energy bin and then integrated. FKD reconstruction is performed on the integrated projections. Scatter, detector efficiency and noise are included. Results: We found that subtracting the results of two filter sets (Filter A:127 µm gold foil with 254 µm tin, 330 µm copper and 1 mm aluminum, and Filter B: 635 µm tin with 264 µm copper and 1 mm aluminum), provides substantial image contrast. The resulting filtered spectra match well below 80.7 keV, while maintaining sufficient X-ray quanta just above that. Voxel intensities of AuNP containing spheres increase linearly with AuNP concentration. K-edge imaging provides 18% more sensitivity than the tin filter alone, and 38% more sensitivity than the gold filter alone. Conclusion: We have shown that it is feasible to quantitatively detect AuNP distributions in a patient-sized phantom using clinical CBCT and K-edge spectral shaping.

  17. Enhanced k-edge angiography utilizing a superfluorescent x-ray generator with a gadolinium-target tube

    NASA Astrophysics Data System (ADS)

    Sato, Eiichi; Germer, Rudolf; Obara, Haruo; Tanaka, Etsuro; Mori, Hidezo; Kawai, Toshiaki; Inoue, Takashi; Ogawa, Akira; Sato, Shigehiro; Takayama, Kazuyoshi

    2007-01-01

    The gadolinium plasma flash x-ray generator is useful for performing high-speed enhanced K-edge angiography using cone beams because K-series characteristic x-rays from the gadolinium target are absorbed effectively by iodine-based contrast media. In the flash x-ray generator, a 150 nF condenser is charged up to 80 kV by a power supply, and flash x-rays are produced by the discharging. The x-ray tube is a demountable cold-cathode diode, and the turbomolecular pump evacuates air from the tube with a pressure of approximately 1 mPa. Since the electric circuit of the high-voltage pulse generator employs a cable transmission line, the high-voltage pulse generator produces twice the potential of the condenser charging voltage. At a charging voltage of 80 kV, the estimated maximum tube voltage and current are approximately 160 kV and 40 kA, respectively. When the charging voltage was increased, the K-series characteristic x-ray intensities of gadolinium increased. Bremsstrahlung x-ray intensity rate decreased with increasing the charging voltage, and clean K lines were produced with a charging voltage of 80 kV. The x-ray pulse widths were approximately 100 ns, and the time-integrated x-ray intensity had a value of approximately 500 μGy at 1.0 m from the x-ray source with a charging voltage of 80 kV. Angiography was performed using a filmless computed radiography (CR) system and iodine-based contrast media. In the angiography of nonliving animals, we observed fine blood vessels of approximately 100 μm with high contrasts.

  18. K-edge angiography utilizing a tungsten plasma X-ray generator in conjunction with gadolinium-based contrast media

    NASA Astrophysics Data System (ADS)

    Sato, Eiichi; Hayasi, Yasuomi; Tanaka, Etsuro; Mori, Hidezo; Kawai, Toshiaki; Inoue, Takashi; Ogawa, Akira; Sato, Shigehiro; Takayama, Kazuyoshi; Onagawa, Jun; Ido, Hideaki

    2006-11-01

    The tungsten plasma flash X-ray generator is useful in order to perform high-speed enhanced K-edge angiography using cone beams because K-series characteristic X-rays from the tungsten target are absorbed effectively by gadolinium-based contrast media. In the flash X-ray generator, a 150 nF condenser is charged up to 80 kV by a power supply, and flash X-rays are produced by the discharging. The X-ray tube is a demountable diode, and the turbomolecular pump evacuates air from the tube with a pressure of approximately 1 mPa. Since the electric circuit of the high-voltage pulse generator employs a cable transmission line, the high-voltage pulse generator produces twice the potential of the condenser charging voltage. At a charging voltage of 80 kV, the estimated maximum tube voltage and current were approximately 160 kV and 40 kA, respectively. When the charging voltage was increased, the characteristic X-ray intensities of tungsten K α lines increased. The K α lines were clean, and hardly any bremsstrahlung rays were detected. The X-ray pulse widths were approximately 110 ns, and the time-integrated X-ray intensity had a value of approximately 0.35 mGy at 1.0 m from the X-ray source with a charging voltage of 80 kV. Angiography was performed using a film-less computed radiography (CR) system and gadolinium-based contrast media. In angiography of non-living animals, we observed fine blood vessels of approximately 100 μm with high contrasts.

  19. Trace metal analysis by laser ablation-inductively coupled plasmamass spectrometry and x-ray K-edge densitometry of forensic samples

    SciTech Connect

    Berry, Jonna Elizabeth

    2016-10-25

    This dissertation describes a variety of studies on the determination of trace elements in samples with forensic importance. Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) was used to determine the trace element composition of numerous lipstick samples. Lipstick samples were determined to be homogeneous. Most lipstick samples of similar colors were readily distinguishable at a 95% confidence interval based on trace element composition. Numerous strands of a multi-strand speaker cable were analyzed by LA-ICP-MS. The strands in this study are spatially heterogeneous in trace element composition. In actual forensic applications, the possibility of spatial heterogeneity must be considered, especially in cases where only small samples (e.g., copper wire fragments after an explosion) are available. The effects of many unpredictable variables, such as weather, temperature, and human activity, on the retention of gunshot residue (GSR) around projectile wounds were assessed with LAICP- MS. Skin samples around gunshot and stab wounds and larvae feeding in and around the wounds on decomposing pig carcasses were analyzed for elements consistent with GSR (Sb, Pb, Ba, and Cu). These elements were detected at higher levels in skin and larvae samples around the gunshot wounds compared to the stab wounds for an extended period of time throughout decomposition in both a winter and summer study. After decomposition, radiographic images of the pig bones containing possible damage from bullets revealed metallic particles embedded within a number of bones. Metallic particles within the bones were analyzed with x-ray, K-edge densitometry and determined to contain lead, indicating that bullet residue can be retained throughout decomposition and detected within bones containing projectile trauma.

  20. Speciation Mapping of Environmental Samples Using XANES Imaging

    EPA Science Inventory

    Fast X-ray detectors with large solid angles and high dynamic ranges open the door to XANES imaging, in which millions of spectra are collected to image the speciation of metals at micrometre resolution, over areas up to several square centimetres. This paper explores how such mu...

  1. Speciation Mapping of Environmental Samples Using XANES Imaging

    EPA Science Inventory

    Fast X-ray detectors with large solid angles and high dynamic ranges open the door to XANES imaging, in which millions of spectra are collected to image the speciation of metals at micrometre resolution, over areas up to several square centimetres. This paper explores how such mu...

  2. In-operando synchronous time-multiplexed O K-edge x-ray absorption spectromicroscopy of functioning tantalum oxide memristors

    SciTech Connect

    Kumar, Suhas; Graves, Catherine E.; Strachan, John Paul Williams, R. Stanley; Kilcoyne, A. L. David; Tyliszczak, Tolek; Nishi, Yoshio

    2015-07-21

    Memristors are receiving keen interest because of their potential varied applications and promising large-scale information storage capabilities. Tantalum oxide is a memristive material that has shown promise for high-performance nonvolatile computer memory. The microphysics has been elusive because of the small scale and subtle physical changes that accompany conductance switching. In this study, we probed the atomic composition, local chemistry, and electronic structure of functioning tantalum oxide memristors through spatially mapped O K-edge x-ray absorption. We developed a time-multiplexed spectromicroscopy technique to enhance the weak and possibly localized oxide modifications with spatial and spectral resolutions of <30 nm and 70 meV, respectively. During the initial stages of conductance switching of a micrometer sized crosspoint device, the spectral changes were uniform within the spatial resolution of our technique. When the device was further driven with millions of high voltage-pulse cycles, we observed lateral motion and separation of ∼100 nm-scale agglomerates of both oxygen interstitials and vacancies. We also demonstrate a unique capability of this technique by identifying the relaxation behavior in the material during electrical stimuli by identifying electric field driven changes with varying pulse widths. In addition, we show that changes to the material can be localized to a spatial region by modifying its topography or uniformity, as against spatially uniform changes observed here during memristive switching. The goal of this report is to introduce the capability of time-multiplexed x-ray spectromicroscopy in studying weak-signal transitions in inhomogeneous media through the example of the operation and temporal evolution of a memristor.

  3. Cu K-edge X-ray Absorption Spectroscopy Reveals Differential Copper Coordimation Within Amyloid-beta Oligomers Compared to Amyloid-beta Monomers

    SciTech Connect

    J Shearer; P Callan; T Tran; V Szalai

    2011-12-31

    The fatal neurodegenerative disorder Alzheimer's disease (AD) has been linked to the formation of soluble neurotoxic oligomers of amyloid-{beta} (A{beta}) peptides. These peptides have high affinities for copper cations. Despite their potential importance in AD neurodegeneration few studies have focused on probing the Cu{sup 2+/1+} coordination environment within A{beta} oligomers. Herein we present a Cu K-edge X-ray absorption spectroscopic study probing the copper-coordination environment within oligomers of A{beta}(42) (sequence: DAEFRHDSGYEVHHQKLVFFAEDVGSNKGAIIGLMVGGVVIA). We find that the Cu{sup 2+} cation is contained within a square planar mixed N/O ligand environment within A{beta}(42) oligomers, which is similar to the copper coordination environment of the monomeric forms of {l_brace}Cu{sup II}A{beta}(40){r_brace} and {l_brace}Cu{sup II}A{beta}(16){r_brace}. Reduction of the Cu{sup 2+} cation within the A{beta}(42) oligomers to Cu{sup 1+} yields a highly dioxygen sensitive copper-species that contains Cu{sup 1+} in a tetrahedral coordination geometry. This can be contrasted with monomers of {l_brace}Cu{sup I}A{beta}(40){r_brace} and {l_brace}Cu{sup I}A{beta}(16){r_brace}, which contain copper in a dioxygen inert linear bis-histidine ligand environment [Shearer and Szalai, J. Am. Chem. Soc., 2008, 130, 17826]. The biological implications of these findings are discussed.

  4. In-operando synchronous time-multiplexed O K-edge x-ray absorption spectromicroscopy of functioning tantalum oxide memristors

    NASA Astrophysics Data System (ADS)

    Kumar, Suhas; Graves, Catherine E.; Strachan, John Paul; Kilcoyne, A. L. David; Tyliszczak, Tolek; Nishi, Yoshio; Williams, R. Stanley

    2015-07-01

    Memristors are receiving keen interest because of their potential varied applications and promising large-scale information storage capabilities. Tantalum oxide is a memristive material that has shown promise for high-performance nonvolatile computer memory. The microphysics has been elusive because of the small scale and subtle physical changes that accompany conductance switching. In this study, we probed the atomic composition, local chemistry, and electronic structure of functioning tantalum oxide memristors through spatially mapped O K-edge x-ray absorption. We developed a time-multiplexed spectromicroscopy technique to enhance the weak and possibly localized oxide modifications with spatial and spectral resolutions of <30 nm and 70 meV, respectively. During the initial stages of conductance switching of a micrometer sized crosspoint device, the spectral changes were uniform within the spatial resolution of our technique. When the device was further driven with millions of high voltage-pulse cycles, we observed lateral motion and separation of ˜100 nm-scale agglomerates of both oxygen interstitials and vacancies. We also demonstrate a unique capability of this technique by identifying the relaxation behavior in the material during electrical stimuli by identifying electric field driven changes with varying pulse widths. In addition, we show that changes to the material can be localized to a spatial region by modifying its topography or uniformity, as against spatially uniform changes observed here during memristive switching. The goal of this report is to introduce the capability of time-multiplexed x-ray spectromicroscopy in studying weak-signal transitions in inhomogeneous media through the example of the operation and temporal evolution of a memristor.

  5. Multivariate curve resolution analysis for interpretation of dynamic Cu K-edge X-ray absorption spectroscopy spectra for a Cu doped V(2)O(5) lithium battery.

    PubMed

    Conti, Paolo; Zamponi, Silvia; Giorgetti, Marco; Berrettoni, Mario; Smyrl, William H

    2010-05-01

    Vanadium pentoxide materials prepared through sol-gel processes act as excellent intercalation hosts for lithium as well as polyvalent cations. A chemometric approach has been applied to study the X-ray absorption near-edge structure (XANES) evolution during in situ scanning of the Cu(0.1)V(2)O(5) xerogel/Li ions battery. Among the more common techniques, the fixed size windows evolving factor analysis (FSWEFA) permits the number of species involved in the experiment to be determined and the range of existence of each of them. This result, combined with the constraints of the invariance of the total concentration and non-negativity of both concentrations and spectra, enabled us to obtain the spectra of the pure components using a multivariate curve resolution refined by an alternate least squares fitting procedure. This allowed the normalized concentration profile to be understood. This data treatment evidenced the occurrence, for the first time, of three species during the battery charging. This fact finds confirmation by comparison of the pure spectra with the experimental ones. Extended X-ray absorption fine structure (EXAFS) analysis confirms the occurrence of three different chemical environments of Cu during battery charging.

  6. XAFS STUDIES OF NICKEL AND SULFUR SPECIATION IN RESIDENTIAL OIL FLY-ASH PARTICULATE MATTERS (ROFA PM)

    EPA Science Inventory

    XAFS spectroscopy has been employed to evaluate the effect of fuel compositions and combustion conditions on the amount, form, and distribution of sulfur and nickel in size-fractionated ROFA PM. Analysis of S K-edge XANES establish that sulfate is abundant in all PM. However, dep...

  7. XAFS STUDIES OF NICKEL AND SULFUR SPECIATION IN RESIDENTIAL OIL FLY-ASH PARTICULATE MATTERS (ROFA PM)

    EPA Science Inventory

    XAFS spectroscopy has been employed to evaluate the effect of fuel compositions and combustion conditions on the amount, form, and distribution of sulfur and nickel in size-fractionated ROFA PM. Analysis of S K-edge XANES establish that sulfate is abundant in all PM. However, dep...

  8. Imaging Taurine in the Central Nervous System Using Chemically Specific X-ray Fluorescence Imaging at the Sulfur K-Edge

    SciTech Connect

    Hackett, Mark J.; Paterson, Phyllis G.; Pickering, Ingrid J.; George, Graham N.

    2016-11-15

    A method to image taurine distributions within the central nervous system and other organs has long been sought. Since taurine is small and mobile, it cannot be chemically “tagged” and imaged using conventional immuno-histochemistry methods. Combining numerous indirect measurements, taurine is known to play critical roles in brain function during health and disease and is proposed to act as a neuro-osmolyte, neuro-modulator, and possibly a neuro-transmitter. Elucidation of taurine’s neurochemical roles and importance would be substantially enhanced by a direct method to visualize alterations, due to physiological and pathological events in the brain, in the local concentration of taurine at or near cellular spatial resolution in vivo or in situ in tissue sections. We thus have developed chemically specific X-ray fluorescence imaging (XFI) at the sulfur K-edge to image the sulfonate group in taurine in situ in ex vivo tissue sections. To our knowledge, this represents the first undistorted imaging of taurine distribution in brain at 20 μm resolution. We report quantitative technique validation by imaging taurine in the cerebellum and hippocampus regions of the rat brain. Further, we apply the technique to image taurine loss from the vulnerable CA1 (cornus ammonis 1) sector of the rat hippocampus following global brain ischemia. The location-specific loss of taurine from CA1 but not CA3 neurons following ischemia reveals osmotic stress may be a key factor in delayed neurodegeneration after a cerebral ischemic insult and highlights the significant potential of chemically specific XFI to study the role of taurine in brain disease.

  9. Imaging Taurine in the Central Nervous System Using Chemically Specific X-ray Fluorescence Imaging at the Sulfur K-Edge.

    PubMed

    Hackett, Mark J; Paterson, Phyllis G; Pickering, Ingrid J; George, Graham N

    2016-11-15

    A method to image taurine distributions within the central nervous system and other organs has long been sought. Since taurine is small and mobile, it cannot be chemically "tagged" and imaged using conventional immuno-histochemistry methods. Combining numerous indirect measurements, taurine is known to play critical roles in brain function during health and disease and is proposed to act as a neuro-osmolyte, neuro-modulator, and possibly a neuro-transmitter. Elucidation of taurine's neurochemical roles and importance would be substantially enhanced by a direct method to visualize alterations, due to physiological and pathological events in the brain, in the local concentration of taurine at or near cellular spatial resolution in vivo or in situ in tissue sections. We thus have developed chemically specific X-ray fluorescence imaging (XFI) at the sulfur K-edge to image the sulfonate group in taurine in situ in ex vivo tissue sections. To our knowledge, this represents the first undistorted imaging of taurine distribution in brain at 20 μm resolution. We report quantitative technique validation by imaging taurine in the cerebellum and hippocampus regions of the rat brain. Further, we apply the technique to image taurine loss from the vulnerable CA1 (cornus ammonis 1) sector of the rat hippocampus following global brain ischemia. The location-specific loss of taurine from CA1 but not CA3 neurons following ischemia reveals osmotic stress may be a key factor in delayed neurodegeneration after a cerebral ischemic insult and highlights the significant potential of chemically specific XFI to study the role of taurine in brain disease.

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

    SciTech Connect

    Popa, Karin; Raison, Philippe E.; Martel, Laura; Martin, Philippe M.; Solari, Pier L.; Bouëxière, Daniel; Konings, Rudy J.M.; Somers, Joseph

    2015-10-15

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

  11. Reaction of H{sub 2} and H{sub 2}S with CoMoO{sub 4} and NiMoO{sub 4}: TPR, XANES, time-resolved XRD, and molecular-orbital studies

    SciTech Connect

    Rodriguez, J.A.; Chaturvedi, S.; Hanson, J.C.; Brito, J.L.

    1999-02-04

    The combination of two metals in an oxide matrix can produce materials with novel physical and chemical properties. The reactivity of a series of cobalt and nickel molybdates ({alpha}-AMoO{sub 4}, {beta}-AMoO{sub 4}, and AmoO{sub 4}{center_dot}nH{sub 2}O; A = Co or Ni) toward H{sub 2} and H{sub 2}S was examined using temperature programmed reduction (TPR), synchrotron-based X-ray powder diffraction (XRD), and X-ray absorption near-edge-spectroscopy (XANES). In general, the cobalt and nickel molybdates are more reactive toward H{sub 2} and easier to reduce than pure molybdenum oxides: MoO{sub 2} < MoO{sub 3} < CoMoO{sub 4} < NiMoO{sub 4}. The interaction of H{sub 2} with surfaces of {alpha}-NiMoO{sub 4}, {alpha}-CoMoO{sub 4}, and {alpha}-MoO{sub 3} was investigated using ab initio SCF calculations and cluster models. The mixed-metal oxides are easier to reduce due to the combination of two factors. First, it is easier to adsorb and dissociate H{sub 2} on Ni or Co sites than on Mo sites of an oxide. And second, as a result of differences in the strength of the metal-oxygen bonds, it is easier to remove oxygen as water from the nickel and cobalt molybdates than from MoO{sub 3} or MoO{sub 2}. The extra reactivity that the Co and Ni atoms provide also makes the rate of sulfidation of the cobalt and nickel molybdates faster than that of pure molybdenum oxides. For the adsorption of H{sub 2}S, HS, and S on {alpha}-NiMoO{sub 4} and {alpha}-MoO{sub 3} clusters, the results of ab initio SCF calculations show bigger bonding energies on the Ni sites than on the Mo sites. In these systems, the oxidation state of the Ni atoms is substantially lower (i.e., larger electron density) than that of the Mo atoms, favoring the formation of Ni {r_arrow} SH and Ni {r_arrow} S dative bonds. Results of time-resolved XRD and XANES indicate that the reduced AMoO{sub 4} compounds can be regenerated by reaction with O{sub 2} at high temperatures (350--450 C). A similar procedure (S{sub a} + O

  12. Probing single magnon excitations in Sr2IrO4 using O K-edge resonant inelastic x-ray scattering

    NASA Astrophysics Data System (ADS)

    Liu, X.; Dean, M. P. M.; Liu, J.; Chiuzbăian, S. G.; Jaouen, N.; Nicolaou, A.; Yin, W. G.; Rayan Serrao, C.; Ramesh, R.; Ding, H.; Hill, J. P.

    2015-05-01

    Resonant inelastic x-ray scattering (RIXS) at the L-edge of transition metal elements is now commonly used to probe single magnon excitations. Here we show that single magnon excitations can also be measured with RIXS at the K-edge of the surrounding ligand atoms when the center heavy metal elements have strong spin-orbit coupling. This is demonstrated with oxygen K-edge RIXS experiments on the perovskite Sr2IrO4, where low energy peaks from single magnon excitations were observed. This new application of RIXS has excellent potential to be applied to a wide range of magnetic systems based on heavy elements, for which the L-edge RIXS energy resolution in the hard x-ray region is usually poor.

  13. Optical properties of boron carbide near the boron K edge evaluated by soft-x-ray reflectometry from a Ru/B4C multilayer

    SciTech Connect

    Ksenzov, Dmitriy; Panzner, Tobias; Schlemper, Christoph; Morawe, Christian; Pietsch, Ullrich

    2009-12-10

    Soft-x-ray Bragg reflection from two Ru/B4C multilayers with 10 and 63 periods was used for independent determination of both real and imaginary parts of the refractive index n = 1 -{delta} + i{beta} close to the boron K edge ({approx}188 eV). Prior to soft x-ray measurements, the structural parameters of the multilayers were determined by x-ray reflectometry using hard x rays. For the 63-period sample, the optical properties based on the predictions made for elemental boron major deviations were found close to the K edge of boron for the 10-period sample explained by chemical bonding of boron to B4C and various boron oxides.

  14. Performance of computed tomography for contrast agent concentration measurements with monochromatic x-ray beams: comparison of K-edge versus temporal subtraction

    NASA Astrophysics Data System (ADS)

    Elleaume, H.; Charvet, A. M.; Corde, S.; Estève, F.; LeBas, J. F.

    2002-09-01

    We investigated the performance of monochromatic computed tomography for the quantification of contrast agent concentrations. Two subtraction methods (K-edge subtraction and temporal subtraction) were evaluated and compared theoretically and experimentally in terms of detection limit, precision and accuracy. Measurements were performed using synchrotron x-rays with Lucite phantoms (10 cm and 17.5 cm in diameter) containing iodine or gadolinium solutions ranging from 50 μg ml-1 to 5 mg ml-1. The experiments were carried out using monochromators developed at the European Synchrotron Radiation Facility (ESRF) medical beamline. The phantoms were imaged either above and below the contrast agent K-edge, or before and after the addition of the contrast agent. Both methods gave comparable performance for phantoms less than 10 cm in diameter. For large phantoms, equivalent to a human head, the temporal subtraction is more suitable for detecting elements such as iodine, keeping a reasonable x-ray dose delivered to the phantom. A good agreement was obtained between analytical calculations, simulations and measurements. The beam harmonic content was taken into account in the simulations. It explains the performance degradation with high contrast agent concentrations. The temporal subtraction technique has the advantage of energy tunability and is well suited for imaging elements, such as iodine or gadolinium, in highly absorbing samples. For technical reasons, the K-edge method is preferable when the imaged organ is moving since the two measurements can be performed simultaneously, which is mandatory for obtaining a good subtraction.

  15. Sulfur K-edge x-ray absorption spectroscopy: A spectroscopic tool to examine the redox state of S-containing metabolites in vivo

    PubMed Central

    Rompel, Annette; Cinco, Roehl M.; Latimer, Matthew J.; McDermott, Ann E.; Guiles, R. D.; Quintanilha, Alexandre; Krauss, Ronald M.; Sauer, Kenneth; Yachandra, Vittal K.; Klein, Melvin P.

    1998-01-01

    The sulfur K-edge x-ray absorption spectra for the amino acids cysteine and methionine and their corresponding oxidized forms cystine and methionine sulfoxide are presented. Distinct differences in the shape of the edge and the inflection point energy for cysteine and cystine are observed. For methionine sulfoxide the inflection point energy is 2.8 eV higher compared with methionine. Glutathione, the most abundant thiol in animal cells, also has been investigated. The x-ray absorption near-edge structure spectrum of reduced glutathione resembles that of cysteine, whereas the spectrum of oxidized glutathione resembles that of cystine. The characteristic differences between the thiol and disulfide spectra enable one to determine the redox status (thiol to disulfide ratio) in intact biological systems, such as unbroken cells, where glutathione and cyst(e)ine are the two major sulfur-containing components. The sulfur K-edge spectra for whole human blood, plasma, and erythrocytes are shown. The erythrocyte sulfur K-edge spectrum is similar to that of fully reduced glutathione. Simulation of the plasma spectrum indicated 32% thiol and 68% disulfide sulfur. The whole blood spectrum can be simulated by a combination of 46% disulfide and 54% thiol sulfur. PMID:9600928

  16. In situ removal of carbon contamination from a chromium-coated mirror: ideal optics to suppress higher-order harmonics in the carbon K-edge region.

    PubMed

    Toyoshima, Akio; Kikuchi, Takashi; Tanaka, Hirokazu; Mase, Kazuhiko; Amemiya, Kenta

    2015-11-01

    Carbon-free chromium-coated optics are ideal in the carbon K-edge region (280-330 eV) because the reflectivity of first-order light is larger than that of gold-coated optics while the second-order harmonics (560-660 eV) are significantly suppressed by chromium L-edge and oxygen K-edge absorption. Here, chromium-, gold- and nickel-coated mirrors have been adopted in the vacuum ultraviolet and soft X-ray branch beamline BL-13B at the Photon Factory in Tsukuba, Japan. Carbon contamination on the chromium-coated mirror was almost completely removed by exposure to oxygen at a pressure of 8 × 10(-2) Pa for 1 h under irradiation of non-monochromated synchrotron radiation. The pressure in the chamber recovered to the order of 10(-7) Pa within a few hours. The reflectivity of the chromium-coated mirror of the second-order harmonics in the carbon K-edge region (560-660 eV) was found to be a factor of 0.1-0.48 smaller than that of the gold-coated mirror.

  17. An X-ray absorption spectroscopic study of the metal site preference in Al{sub 1-x}Ga{sub x}FeO{sub 3}

    SciTech Connect

    Walker, James D.S.; Grosvenor, Andrew P.

    2013-01-15

    Magnetoelectric materials have potential for being introduced into next generation technologies, especially memory devices. The AFeO{sub 3} (Pna2{sub 1}; A=Al, Ga) system has received attention to better understand the origins of magnetoelectric coupling. The magnetoelectric properties this system exhibits depend on the amount of anti-site disorder present, which is affected by the composition and the method of synthesis. In this study, Al{sub 1-x}Ga{sub x}FeO{sub 3} was synthesized by the ceramic method and studied by X-ray absorption spectroscopy. Al L{sub 2,3}-, Ga K-, and Fe K-edge spectra were collected to examine how the average metal coordination number changes with composition. Examination of XANES spectra from Al{sub 1-x}Ga{sub x}FeO{sub 3} indicate that with increasing Ga content, Al increasingly occupies octahedral sites while Ga displays a preference for occupying the tetrahedral site. The Fe K-edge spectra indicate that more Fe is present in the tetrahedral site in AlFeO{sub 3} than in GaFeO{sub 3}, implying more anti-site disorder is present in AlFeO{sub 3}. - Graphical abstract: Al{sub 1-x}Ga{sub x}FeO{sub 3} has been investigated by XANES. Through examination of Al L{sub 2,3}-, Ga K-, and Fe K-edge XANES spectra, it was found that more anti-site disorder of the Fe atoms is present in AlFeO{sub 3} compared to in GaFeO{sub 3}. Highlights: Black-Right-Pointing-Pointer Al{sub 1-x}Ga{sub x}FeO{sub 3} was investigated by X-ray absorption spectroscopy. Black-Right-Pointing-Pointer Ga prefers to occupy the tetrahedral site in Al{sub 1-x}Ga{sub x}FeO{sub 3}. Black-Right-Pointing-Pointer Fe prefers to occupy the octahedral sites in Al{sub 1-x}Ga{sub x}FeO{sub 3} as x increases. Black-Right-Pointing-Pointer More anti-site disorder is present in AlFeO{sub 3} compared to in GaFeO{sub 3.}.

  18. Effects of Composition on Fe XANES Redox Calibrations in Glasses

    NASA Astrophysics Data System (ADS)

    McCanta, M. C.; Dyar, M. D.; Breves, E.

    2013-12-01

    The oxidation state of volcanic materials on a planet reflects the degree of oxidation of the magma source region and, possibly, the additional effects of magma interaction with the near surface environment. Constraining fO2 in geologic samples can be both difficult and subject to large uncertainties, with the choice of oxybarometer often limited by the phase assemblage present. Many current methods for estimating magmatic fO2 rely on Fe2+/Fe3+ partitioning in silicate melts or between crystals and melt as a function of fO2 (e.g., Sack et al., 1980; Kress and Carmichael, 1991). However, use of oxybarometers is limited by the difficulty in measuring Fe2+/Fe3+ ratios in situ at micro-scales. Fe titration and Mössbauer techniques allow for bulk measurements but require large amounts of material and do not allow for investigation of zoning or fO2 variations at microscales. Synchrotron micro-XANES spectroscopy (SmX), which uses the shape of the Fe K absorption XANES edge, offers great promise making these measurements on standard thin sections. However, because melt composition and structure have an effect on Fe3+/ΣFe (e.g., Kilinc et al., 1983; Borisov and McCammon, 2010), especially under oxidizing conditions, SmX requires calibration samples with compositions similar to those of the unknowns being studied. To address this need, a suite of 33 synthetic glasses covering a wide range of geologically-relevant compositions was generated under varying fO2 conditions. Runs were conducted in a 1-atm gas mixing furnace using the Pt (fO2 ≥ QFM) or Re (fO2 < QFM) wire-loop technique. Three oxygen fugacities were considered for each composition: air, quartz-fayalite-magnetite (QFM), and iron-wustite (IW). The fO2 values were fixed either by flowing air or an H2-CO2 gas mixture pegged at the QFM or IW buffer for the maximum temperature of an experiment with the gas composition held constant during quench. Samples were held above their melting temperatures for 6 hours, drop

  19. Local atomic structure investigation of AlFeCuCrMgx (0.5, 1, 1.7) high entropy alloys: X-ray absorption spectroscopy study

    NASA Astrophysics Data System (ADS)

    Maulik, Ornov; Patra, N.; Bhattacharyya, D.; Jha, S. N.; Kumar, Vinod

    2017-02-01

    The present paper reports local atomic structure investigation of novel AlFeCuCrMgx (x=0.5, 1, 1.7) high entropy alloys (HEAs) produced by mechanical alloying using Fe, Cr and Cu K-edge X-ray absorption near edge spectroscopy (XANES) and extended x-ray absorption fine structure (EXAFS) spectroscopy. XANES spectra measured at Fe and Cr K-edges resemble that of the respective pure metal foils, while the spectrum measured at Cu K-edge manifests the presence of some other phases in the as-milled alloys. The radial distribution functions (RDFs) obtained from Fourier transformation of EXAFS spectra support the formation of disordered BCC structure.

  20. High-precision determination of iron oxidation state in silicate glasses using XANES

    SciTech Connect

    Cottrell, Elizabeth; Kelley, Katherine A.; Lanzirotti, Antonio; Fischer, Rebecca A.

    2009-11-04

    Fe K-edge X-ray absorption near-edge structure (XANES) and Moessbauer spectra were collected on natural basaltic glasses equilibrated over a range of oxygen fugacity (QFM - 3.5 to QFM + 4.5). The basalt compositions and fO{sub 2} conditions were chosen to bracket the natural range of redox conditions expected for basalts from mid-ocean ridge, ocean island, back-arc basin, and arc settings, in order to develop a high-precision calibration for the determination of Fe{sup 3+}/{Sigma}Fe in natural basalts. The pre-edge centroid energy, corresponding to the 1s {yields} 3d transition, was determined to be the most robust proxy for Fe oxidation state, affording significant advantages compared to the use of other spectral features. A second-order polynomial models the correlation between the centroid and Fe{sup 3+}/{Sigma}Fe, yielding a precision of {+-} 0.0045 in Fe{sup 3+}/{Sigma}Fe for glasses with Fe{sup 3+}/{Sigma}Fe > 8%, which is comparable to the precision of wet chemistry. This high precision relies on a Si (311) monochromator to better define the Fe{sup 2+} and Fe{sup 3+} transitions, accurate and robust modeling of the pre-edge feature, dense fO{sub 2}-coverage and compositional appropriateness of reference glasses, and application of a non-linear drift correction. Through re-analysis of the reference glasses across three synchrotron beam sessions, we show that the quoted precision can be achieved (i.e., analyses are reproducible) across multiple synchrotron beam sessions, even when spectral collection conditions (detector parameters or sample geometry) change. Rhyolitic glasses were also analyzed and yield a higher centroid energy at a given Fe{sup 3+}/{Sigma}Fe than basalts, implying that major variations in melt structure affect the relationship between centroid position and Fe{sup 3+}/{Sigma}Fe, and that separate calibrations are needed for the determination of oxidation state in basalts and rhyolites.

  1. Properties of impurity-bearing ferrihydrite II: Insights into the surface structure and composition of pure, Al- and Si-bearing ferrihydrite from Zn(II) sorption experiments and Zn K-edge X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Cismasu, A. Cristina; Levard, Clément; Michel, F. Marc; Brown, Gordon E.

    2013-10-01

    Naturally occurring ferrihydrite often contains impurities such as Al and Si, which can impact its chemical reactivity with respect to metal(loid) adsorption and (in)organic or microbially induced reductive dissolution. However, the surface composition of impure ferrihydrites is not well constrained, and this hinders our understanding of the factors controlling the surface reactivity of these nanophases. In this study, we conducted Zn(II) adsorption experiments combined with Zn K-edge X-ray absorption spectroscopy measurements on pure ferrihydrite (Fh) and Al- or Si-bearing ferrihydrites containing 10 and 20 mol% Al or Si (referred to as 10AlFh, 20AlFh and 10SiFh, 20SiFh) to evaluate Zn(II) uptake in relation to Zn(II) speciation at their surfaces. Overall, Zn(II) uptake at the surface of AlFh is similar to that of pure Fh, and based on Zn K-edge EXAFS data, Zn(II) speciation at the surface of Fh and AlFh also appears similar. Binuclear bidentate IVZn-VIFe complexes (at ∼3.46 Å (2C[1]) and ∼3.25 Å (2C[2])) were identified at low Zn(II) surface coverages from Zn K-edge EXAFS fits. With increasing Zn(II) surface coverage, the number of second-neighbor Fe ions decreased, which was interpreted as indicating the formation of IVZn polymers at the ferrihydrite surface, and a deviation from Langmuir uptake behavior. Zn(II) uptake at the surface of SiFh samples was more significant than at Fh and AlFh surfaces, and was attributed to the formation of outer-sphere complexes (on average 24% of sorbed Zn). Although similar Zn-Fe/Zn distances were obtained for the Zn-sorbed SiFh samples, the number of Fe second neighbors was lower in comparison with Fh. The decrease in second-neighbor Fe is most pronounced for sample 20SiFh, suggesting that the amount of reactive surface Fe sites diminishes with increasing Si content. Although our EXAFS results shown here do not provide evidence for the existence of Zn-Al or Zn-Si complexes, their presence is not excluded for Zn-sorbed Al

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

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

    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

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

    PubMed

    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.

  5. Iron speciation in human cancer cells by K-edge total reflection X-ray fluorescence-X-ray absorption near edge structure analysis

    NASA Astrophysics Data System (ADS)

    Polgári, Zs.; Meirer, F.; Sasamori, S.; Ingerle, D.; Pepponi, G.; Streli, C.; Rickers, K.; Réti, A.; Budai, B.; Szoboszlai, N.; Záray, G.

    2011-03-01

    X-ray absorption near edge structure (XANES) analysis in combination with synchrotron radiation induced total reflection X-ray fluorescence (SR-TXRF) acquisition was used to determine the oxidation state of Fe in human cancer cells and simultaneously their elemental composition by applying a simple sample preparation procedure consisting of pipetting the cell suspension onto the quartz reflectors. XANES spectra of several inorganic and organic iron compounds were recorded and compared to that of different cell lines. The XANES spectra of cells, independently from the phase of cell growth and cell type were very similar to that of ferritin, the main Fe store within the cell. The spectra obtained after CoCl 2 or NiCl 2 treatment, which could mimic a hypoxic state of cells, did not differ noticeably from that of the ferritin standard. After 5-fluorouracil administration, which could also induce an oxidative-stress in cells, the absorption edge position was shifted toward higher energies representing a higher oxidation state of Fe. Intense treatment with antimycin A, which inhibits electron transfer in the respiratory chain, resulted in minor changes in the spectrum, resembling rather the N-donor Fe-α,α'-dipyridyl complex at the oxidation energy of Fe(III), than ferritin. The incorporation of Co and Ni in the cells was followed by SR-TXRF measurements.

  6. Theory of K-edge resonant inelastic x-ray scattering and its application for La0.5Sr1.5MnO4

    NASA Astrophysics Data System (ADS)

    Seman, T. F.; Liu, X.; Hill, J. P.; van Veenendaal, M.; Ahn, K. H.

    2013-03-01

    We present a formula based on tight-binding approach for the calculation of K-edge resonant inelastic x-ray scattering spectrum for transition metal oxides, by extending the previous result [K. H. Ahn, A. J. Fedro, and M. van Veenendaal, Phys. Rev. B 79, 045103 (2009).] to include explicit momentum dependence and a basis with multiple core hole sites. We apply this formula to layered charge, orbital, and spin ordered manganites, La0.5Sr1.5MnO4. The K-edge RIXS spectrum is found not periodic with respect to the actual reciprocal lattice, but approximately periodic with respect to the reciprocal lattice for the hypothetical unit cell with one core hole site. With experimental strcuture and reasonable tight-binding parameters, we obtain good agreement with experimental data, in particular, with regards to the large variation of the intensity with momentum. We find that the screening in La0.5Sr1.5MnO4 is highly localized around the core hole site and demonstrate the potential of K-edge RIXS as a probe for the screening dynamics in materials. Work supported by US.DOE Contr. DE-AC02-98CH10886 (X.L.,J.H.), US.DOE Award DE-FG02-03ER46097 (M.v.V.), CMCSN under Grants DE-FG02-08ER46540 & DE-SC0007091 (T.S.,K.A.,M.v.V.), Argonne XSD Visitor Prog.(K.A.), US.DOE Contr. DE-AC02-06CH11357 (X.L.,J.H).

  7. Ligand K-edge XAS, DFT, and TDDFT analysis of pincer linker variations in Rh(i) PNP complexes: reactivity insights from electronic structure.

    PubMed

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

    2016-06-14

    Here we report P K-edge, Cl K-edge, and Rh L3-edge X-ray absorption spectroscopy (XAS) data for Rh[C5H3N-2,6-(XP(t)Bu2)2]Cl, where X = O ((tBu)PONOP; ) or CH2 ((tBu)PNP; ). Solid-state XAS data for and were compared to density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations to identify how changing the PNP pincer linker from O to CH2 affected electronic structure and bonding at Rh(i). Pronounced differences in XAS peak intensities and energies were observed. The P K-edge XAS data revealed a large increase in Rh 4dx(2)-y(2) and P 3p orbital-mixing (Rh-P σ*) in compared to , and pronounced transition energy variations reflected marked differences in orbital energies and compositions. By comparison, the Cl K-edge XAS data revealed only subtle differences in Rh-Cl covalency, although larger splitting between the Rh-Cl π* and σ* transitions was observed in . Analysis of the occupied MOs from DFT (HOMO, HOMO-1, HOMO-2, and HOMO-3) and comparison to the unoccupied MOs involved in XAS revealed a relatively uniform energy increase (ca. 0.3-0.5 eV) for all five 4d-derived molecular orbitals in Rh((tBu)PNP)Cl () compared to Rh((tBu)PONOP)Cl (). The energy shift was relatively invariant with respect to differences in orbital symmetry, bonding type (σ or π), and orbital mixing, which suggested that the increase could be attributed to electrostatic effects. The change in d-orbital energies are consistent with known reactivity differences of Rh((tBu)PONOP)(+) and Rh((tBu)PNP)(+) towards CO, H2, and CH2Cl2, and are explained here by considering how d-orbital energies affect covalent L → M σ bonding and M → L π backbonding.

  8. Indirect Probing of defects in unipolar resistive switching NiOx thin films by Ni K-edge resonant inelastic x-ray scattering

    SciTech Connect

    Jung, Ranju; Phark, Soo-Hyong; Kim, Dong-Wood; Upton, Mary; Casa, Diego; Gog, Thomas; Kim, Jungho

    2015-02-01

    We present observations of the Ni K-edge resonant inelastic X-ray scattering (RIXS) in NiOx thin films showing unipolar resistive switching (RS). The RIXS spectra of RS NiOx thin films can be described in terms of crystal field (dd) and charge transfer (CT) excitations. We found distorted dd excitations in the films' pristine state before electroforming, and identical excitations for high and low resistance states after electroforming. This suggests that the RS property of NiOx thin film is related to defects in pristine NiOx films, and RS occurs in local nanosized spots too small to be detected by RIXS.

  9. Auger electron and photoabsorption spectra of glycine in the vicinity of the oxygen K-edge measured with an X-FEL

    NASA Astrophysics Data System (ADS)

    Sanchez-Gonzalez, A.; Barillot, T. R.; Squibb, R. J.; Kolorenč, P.; Agaker, M.; Averbukh, V.; Bearpark, M. J.; Bostedt, C.; Bozek, J. D.; Bruce, S.; Carron Montero, S.; Coffee, R. N.; Cooper, B.; Cryan, J. P.; Dong, M.; Eland, J. H. D.; Fang, L.; Fukuzawa, H.; Guehr, M.; Ilchen, M.; Johnsson, A. S.; Liekhus-S, C.; Marinelli, A.; Maxwell, T.; Motomura, K.; Mucke, M.; Natan, A.; Osipov, T.; Östlin, C.; Pernpointner, M.; Petrovic, V. S.; Robb, M. A.; Sathe, C.; Simpson, E. R.; Underwood, J. G.; Vacher, M.; Walke, D. J.; Wolf, T. J. A.; Zhaunerchyk, V.; Rubensson, J.-E.; Berrah, N.; Bucksbaum, P. H.; Ueda, K.; Feifel, R.; Frasinski, L. J.; Marangos, J. P.

    2015-12-01

    We report the first measurement of the near oxygen K-edge auger spectrum of the glycine molecule. Our work employed an x-ray free electron laser as the photon source operated with input photon energies tunable between 527 and 547 eV. Complete electron spectra were recorded at each photon energy in the tuning range, revealing resonant and non-resonant auger structures. Finally ab initio theoretical predictions are compared with the measured above the edge auger spectrum and an assignment of auger decay channels is performed.

  10. Analyzing organic sulfur in coal/char: Integrated mild degradation/XANES methods. Final technical report, September 1, 1993--November 30, 1994

    SciTech Connect

    Palmer, S.R.; Huffman, G.P.

    1994-12-31

    The overall goal of this study is to improve the understanding of sulfur in coals/chars via the use of combined advanced nondestructive and advanced destructive methods of sulfur analysis. This study combines selective oxidation, analytical pyrolysis, and sulfur X-ray Absorption Near Edge Structure Spectroscopy (XANES) analysis. Samples with a wide variety of sulfur contents, (0.63%--4.40%) have been prepared for use in this study. This includes steam gasification chars, oxidized coals and desulfurized coals as well of the original unaltered coals. Mild pyrolysis and XANES data shows that the sulfur chemistry of gasification chars is significantly different from that of the original coals. Mild pyrolysis of the samples that were oxidized with peroxyacetic acid showed that the level of simple thiophene structures observed in the pyrolysis products declines with increasing levels of oxidation. Sulfur XANES spectra of treated samples showed various effects depending on the treatment severity. The XANES spectra of less severely treated samples were similar, although not identical, to the untreated coal spectra. XANES of gasification chars indicated conversion of pyrite to pyrrhotite, removal of organic sulfide sulfur and dissolution of soluble inorganic sulfur species during gasification. Mild oxidation with peroxyacetic acid results in preferential oxidation of sulfide forms before thiophene forms but increasing oxidation severity leads to virtually all sulfur species being oxidized. Good agreement between W-band EPR and XANES data for aromatic sulfur contents were obtained. The TPR analysis of coal indicated that organic sulfur was present as alkyl-aryl sulfide, aryl-aryl sulfides, simple thiophenes and condensed thiophenes. TPR shows that non-thiophenic compounds are removed by PAA oxidation, and that the longer the oxidation is performed the greater is the removal of non-thiophenic sulfur structures.

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

    NASA Technical Reports Server (NTRS)

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

    1993-01-01

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

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

    NASA Technical Reports Server (NTRS)

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

    1993-01-01

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

  13. Local disorder investigation in NiS(2-x)Se(x) using Raman and Ni K-edge x-ray absorption spectroscopies.

    PubMed

    Marini, C; Joseph, B; Caramazza, S; Capitani, F; Bendele, M; Mitrano, M; Chermisi, D; Mangialardo, S; Pal, B; Goyal, M; Iadecola, A; Mathon, O; Pascarelli, S; Sarma, D D; Postorino, P

    2014-11-12

    We report on Raman and Ni K-edge x-ray absorption investigations of a NiS(2-x)Se(x) (with x = 0.00, 0.50/0.55, 0.60, and 1.20) pyrite family. The Ni K-edge absorption edge shows a systematic shift going from an insulating phase (x = 0.00 and 0.50) to a metallic phase (x = 0.60 and 1.20). The near-edge absorption features show a clear evolution with Se doping. The extended x-ray absorption fine structure data reveal the evolution of the local structure with Se doping which mainly governs the local disorder. We also describe the decomposition of the NiS(2-x)Se(x) Raman spectra and investigate the weights of various phonon modes using Gaussian and Lorentzian profiles. The effectiveness of the fitting models in describing the data is evaluated by means of Bayes factor estimation. The Raman analysis clearly demonstrates the disorder effects due to Se alloying in describing the phonon spectra of NiS(2-x)Se(x) pyrites.

  14. Quantum simulation of thermally-driven phase transition and oxygen K-edge x-ray absorption of high-pressure ice

    PubMed Central

    Kang, Dongdong; Dai, Jiayu; Sun, Huayang; Hou, Yong; Yuan, Jianmin

    2013-01-01

    The structure and phase transition of high-pressure ice are of long-standing interest and challenge, and there is still a huge gap between theoretical and experimental understanding. The quantum nature of protons such as delocalization, quantum tunneling and zero-point motion is crucial to the comprehension of the properties of high-pressure ice. Here we investigated the temperature-induced phase transition and oxygen K-edge x-ray absorption spectra of ice VII, VIII and X using ab initio path-integral molecular dynamics simulations. The tremendous difference between experiments and the previous theoretical predictions is closed for the phase diagram of ice below 300 K at pressures up to 110 GPa. Proton tunneling assists the proton-ordered ice VIII to transform into proton-disordered ice VII where only thermal activated proton-transfer cannot occur. The oxygen K edge with its shift is sensitive to the order-disorder transition, and therefore can be applied to diagnose the dynamics of ice structures. PMID:24253589

  15. Quantum simulation of thermally-driven phase transition and oxygen K-edge x-ray absorption of high-pressure ice.

    PubMed

    Kang, Dongdong; Dai, Jiayu; Sun, Huayang; Hou, Yong; Yuan, Jianmin

    2013-11-20

    The structure and phase transition of high-pressure ice are of long-standing interest and challenge, and there is still a huge gap between theoretical and experimental understanding. The quantum nature of protons such as delocalization, quantum tunneling and zero-point motion is crucial to the comprehension of the properties of high-pressure ice. Here we investigated the temperature-induced phase transition and oxygen K-edge x-ray absorption spectra of ice VII, VIII and X using ab initio path-integral molecular dynamics simulations. The tremendous difference between experiments and the previous theoretical predictions is closed for the phase diagram of ice below 300 K at pressures up to 110 GPa. Proton tunneling assists the proton-ordered ice VIII to transform into proton-disordered ice VII where only thermal activated proton-transfer cannot occur. The oxygen K edge with its shift is sensitive to the order-disorder transition, and therefore can be applied to diagnose the dynamics of ice structures.

  16. Probing the K-edge of a laser heated aluminum plasma using X-rays from betatron oscillations in a laser wakefield accelerator with femtosecond resolution

    NASA Astrophysics Data System (ADS)

    Behm, Keegan; Hussein, Amina; Zhao, Tony; Hill, Edward; Maksimchuk, Anatoly; Nees, John; Yanovsky, Victor; Mangles, Stuart; Krushelnick, Karl; Thomas, Alexander; CenterUltrafast Optical Science Team; Plasmas Group Team

    2016-10-01

    Presented here are data from a two-beam pump-probe experiment. We used synchrotron-like X-rays created by betatron oscillations to probe a thin metal foil that is pumped by the secondary laser beam. The Hercules Ti:Sapphire laser facility was operated with a pulse duration of 34 fs and a power of 80 TW split. A 75-25 beam splitter was used to drive a laser wakefield accelerator and heat the secondary target. We observed opacity changes around the K-edge of thin aluminum foil as it was heated by an ultrafast pump laser. To understand how the opacity is changing with heating and expansion of the plasma, the delay between the two laser paths was adjusted on a femtosecond time scale from 50 to 400 fs. Experimental data for aluminum shows variation in opacity around the K-edge with changes in the probe delay. The transmitted synchrotron-like spectrum was measured using single photon counting on an X-ray CCD camera and was available on a shot-by-shot basis. The success of this work demonstrates a practical application for X-rays produced from betatron oscillations in a wakefield accelerator. U.S. Department of Energy and the National Nuclear Security Administration.

  17. Multiple pre-edge structures in Cu K -edge x-ray absorption spectra of high- Tc cuprates revealed by high-resolution x-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Gougoussis, C.; Rueff, J.-P.; Calandra, M.; D'Astuto, M.; Jarrige, I.; Ishii, H.; Shukla, A.; Yamada, I.; Azuma, M.; Takano, M.

    2010-06-01

    Using high-resolution x-ray absorption spectroscopy and state-of-the-art electronic structure calculations we demonstrate that the pre-edge region at the Cu K edge of high- Tc cuprates is composed of several excitations invisible in standard x-ray absorption spectra. We consider in detail the case of Ca2-xCuO2Cl2 and show that the many pre-edge excitations (two for c -axis polarization, four for in-plane polarization and out-of-plane incident x-ray momentum) are dominated by off-site transitions and intersite hybridization. This demonstrates the relevance of approaches beyond the single-site model for the description of the pre edges of correlated materials. Finally, we show the occurrence of a doubling of the main edge peak that is most visible when the polarization is along the c axis. This doubling, that has not been seen in any previous absorption data in cuprates, is not reproduced by first-principles calculations. We suggest that this peak is due to many-body charge-transfer excitations while all the other visible far-edge structures are single particle in origin. Our work indicates that previous interpretations of the Cu K -edge x-ray absorption spectra in high- Tc cuprates can be profitably reconsidered.

  18. Femtosecond probing around the K-edge of a laser heated plasma using X-rays from betatron oscillations in a laser wakefield accelerator

    NASA Astrophysics Data System (ADS)

    Behm, Keegan; Zhao, Tony; Maksimchuk, Anatoly; Yanovsky, Victor; Nees, John; Mangles, Stuart; Krushelnick, Karl; Thomas, Alexander; CenterUltrafast Optical Science Team; Plasmas Group Team

    2015-11-01

    Presented here are data from a two-beam pump-probe experiment. We used synchrotron-like X-rays created by betatron oscillations to probe a thin metal foil that is pumped by the secondary laser beam. The Hercules Ti:Sapph laser facility was operated with a pulse duration of 34 fs and a power of 65 TW split to drive a laser wakefield accelerator and heat the secondary target. We observed opacity changes around the K-edge of thin foils as they were heated by an ultrafast pump laser. To understand how the opacity is changing with heating and expansion of the plasma, the delay between the two laser paths was adjusted on a fs and ps time scale. Experimental data for polyvinylidene chloride (PVDC) and aluminum show variations in opacity around the Cl and Al K-edges with changes in the probe delay. The transmitted synchrotron-like spectrum was measured using single photon counting on an X-ray CCD camera and was available on a shot-by-shot basis. The success of this work demonstrates a practical application for X-rays produced from betatron oscillations in a wakefield accelerator. The compact size of these ``table-top'' accelerators and the ultrashort nature of the generated X-ray pulses allows pump-probe experiments that can probe events that occur on the femtosecond time scale.

  19. Structure of shock compressed model basaltic glass: Insights from O K-edge X-ray Raman scattering and high-resolution 27Al NMR spectroscopy

    SciTech Connect

    Lee, Sung Keun; Park, Sun Young; Kim, Hyo-Im; Tschauner, Oliver; Asimow, Paul; Bai, Ligang; Xiao, Yuming; Chow, Paul

    2012-05-29

    The detailed atomic structures of shock compressed basaltic glasses are not well understood. Here, we explore the structures of shock compressed silicate glass with a diopside-anorthite eutectic composition (Di{sub 64}An{sub 36}), a common Fe-free model basaltic composition, using oxygen K-edge X-ray Raman scattering and high-resolution {sup 27}Al solid-state NMR spectroscopy and report previously unknown details of shock-induced changes in the atomic configurations. A topologically driven densification of the Di{sub 64}An{sub 36} glass is indicated by the increase in oxygen K-edge energy for the glass upon shock compression. The first experimental evidence of the increase in the fraction of highly coordinated Al in shock compressed glass is found in the {sup 27}Al NMR spectra. This unambiguous evidence of shock-induced changes in Al coordination environments provides atomistic insights into shock compression in basaltic glasses and allows us to microscopically constrain the magnitude of impact events or relevant processes involving natural basalts on Earth and planetary surfaces.

  20. Evaluation of hexavalent chromium extraction method EPA method 3060A for soils using XANES spectroscopy.

    PubMed

    Malherbe, Julien; Isaure, Marie-Pierre; Séby, Fabienne; Watson, Russell P; Rodriguez-Gonzalez, Pablo; Stutzman, Paul E; Davis, Clay W; Maurizio, Chiara; Unceta, Nora; Sieber, John R; Long, Stephen E; Donard, Olivier F X

    2011-12-15

    Hexavalent chromium (Cr(VI)) occurrence in soils is generally determined using an extraction step to transfer it to the liquid phase where it is more easily detected and quantified. In this work, the performance of the most common extraction procedure (EPA Method 3060A) using NaOH-Na(2)CO(3) solutions is evaluated using X-ray absorption near edge structure spectroscopy (XANES), which enables the quantification of Cr(VI) directly in the solid state. Results obtained with both methods were compared for three solid samples with different matrices: a soil containing chromite ore processing residue (COPR), a loamy soil, and a paint sludge. Results showed that Cr(VI) contents determined by the two methods differ significantly, and that the EPA Method 3060A procedure underestimated the Cr(VI) content in all studied samples. The underestimation is particularly pronounced for COPR. Low extraction yield for EPA Method 3060A was found to be the main reason. The Cr(VI) present in COPR was found to be more concentrated in magnetic phases. This work provides new XANES analyses of SRM 2701 and its extraction residues for the purpose of benchmarking EPA 3060A performance.

  1. High-Resolution Fe XANES Pre-Edge Spectroscopy of Micas

    NASA Astrophysics Data System (ADS)

    Tucker, J. M.; Dyar, M. D.; Gunter, M.; Delaney, J. S.; Lanzirotti, A.

    2009-12-01

    Fe XANES (X-Ray Absorption Near-Edge Structure) spectroscopy has the potential to yield information on Fe valence states and coordination geometry in minerals at microscales smaller than 10 μm. In this study, component peaks in Fe-Kα XANES pre-edge spectra of micas with varying compositions are examined to relate area-weighted pre-edge peaks present at the three optical orientations to Fe3+/Fe2+ ratios, cation site occupancies and mica structural features. Samples studied include three dioctahedral (Fe occupancy in M2 only) and three trioctahedral micas (Fe occupancy in both M1 and M2) with well-known chemistries: two illites, one muscovite, one annite, and two phlogopites with Fe3+/total Fe ranging from 11% to 75%. Mössbauer data determined that Fe3+and Fe2+ were present in the M sites of all samples except one tetra-ferriphlogopite, which is dominated by tetrahedral Fe3+ with a small amount of octahedral Fe3+. Samples were mounted on goniometer heads and the three optical orientations were determined using a spindle stage. XANES spectra were acquired with polarized x-rays parallel to each of the three optical orientations. Incident x-rays were tuned using a Si(311) monochromator at beamline X26A at the National Synchrotron Light Source at Brookhaven National Laboratory. XANES spectra were collected in fluorescence mode using a 9-element high purity Ge solid state detector array. Spectra were edge-step normalized and corrected for self-absorption using the FLUO algorithm. Differences between the tetra-ferriphlogopite spectra and the other high Fe3+ samples allow peaks due to tetrahedral Fe3+ and octahedral Fe3+ to be identified. The energy of the tetrahedral Fe3+ peak is higher by ~0.5 eV in the X direction than in Y and Z and its area is also much greater in the X orientation, suggesting that those transitions are favored perpendicular to c. Comparison of spectra of the other dioctahedral and trioctahedral micas allows peaks due to Fe3+ and Fe2+ in M1 and M2

  2. Sulphur XANES Analysis of Cultured Human Prostate Cancer Cells

    NASA Astrophysics Data System (ADS)

    Kwiatek, W. M.; Podgórczyk, M.; Paluszkiewicz, Cz.; Balerna, A.; Kisiel, A.

    2008-08-01

    Prostate cancer is one of the most commonly diagnosed cancers in men throughout the world. It is believed that changes to the structure of protein binding sites, altering its metabolism, may play an important role in carcinogenesis. Sulphur, often present in binding sites, can influence such changes through its chemical speciation. Hence there is a need for precise investigation of coordination environment of sulphur. X-ray absorption near edge structure spectroscopy offers such possibility. Cell culture samples offer histologically well defined areas of good homogeneity, suitable for successful and reliable X-ray absorption near edge structure analysis. This paper presents sulphur speciation data collected from three different human prostate cancer cell lines (PC-3, LNCaP and DU-145). Sulphur X-ray absorption near edge structure analysis was performed on K-edge structure. The spectra of cells were compared with those of cancerous tissue and with organic substances as well as inorganic compounds.

  3. New structural insights into the iron-molybdenum cofactor from azotobacter vinelandii nitrogenase through sulfur K and molybdenum L x-ray absorption edge studies

    SciTech Connect

    Hedman, B.; Frank, P.; Gheller, S.F.; Roe, A.L.; Newton, W.E.; Hodgson, K.O.

    1988-06-08

    The electronic and structural nature of sulfur and molybdenum in the FeMO cofactor (FeMO-co) isolated from Azotobacter vinelandii MoFe protein has been studied by X-ray absorption edge and near-edge spectroscopy (referred to herein collectively as XANES) at the sulfur K and molybdenum L/sub 3/ and L/sub 2/ absorption edges. In contrast to the relatively poor resolution found for X-ray absorption edges at higher energies (e.g., several electronvolts at the molybdenum K edge at 20 keV), resolution in the 2.5-3.0-keV region is significantly improved (e.g., 0.5 eV at the sulfur K edge at 2.47 keV), resulting in more edge structure with higher sensitivity to changes in electronic and structural environment. In order to record spectra from dilute samples at these low energies, an experimental method that takes advantage of the higher flux synchrotron radiation from an undulator magnet has been developed. XANES spectra have been recorded for FeMo-co in the oxidized (ox) and semireduced (s-r) forms and, for comparison, a number of inorganic complexes containing molybdenum and sulfur. To remove the interference of dithionite, its decomposition products, and other small, unbound molecules from the FeMo-co spectrum, an anaerobic column chromatographic method of purification has been developed. The spectrum of dithionite-free FeMo-co in the oxidized form could thus be recorded.

  4. Magnetite biomineralization in Magnetospirillum gryphiswaldense: time-resolved magnetic and structural studies.

    PubMed

    Fdez-Gubieda, M Luisa; Muela, Alicia; Alonso, Javier; García-Prieto, Ana; Olivi, Luca; Fernández-Pacheco, Rodrigo; Barandiarán, José Manuel

    2013-04-23

    Magnetotactic bacteria biosynthesize magnetite nanoparticles of high structural and chemical purity that allow them to orientate in the geomagnetic field. In this work we have followed the process of biomineralization of these magnetite nanoparticles. We have performed a time-resolved study on magnetotactic bacteria Magnetospirillum gryphiswaldense strain MSR-1. From the combination of magnetic and structural studies by means of Fe K-edge X-ray absorption near edge structure (XANES) and high-resolution transmission electron microscopy we have identified and quantified two phases of Fe (ferrihydrite and magnetite) involved in the biomineralization process, confirming the role of ferrihydrite as the source of Fe ions for magnetite biomineralization in M. gryphiswaldense. We have distinguished two steps in the biomineralization process: the first, in which Fe is accumulated in the form of ferrihydrite, and the second, in which the magnetite is rapidly biomineralized from ferrihydrite. Finally, the XANES analysis suggests that the origin of the ferrihydrite could be at bacterial ferritin cores, characterized by a poorly crystalline structure and high phosphorus content.

  5. Spectroscopic study of the polymerization of intercalated anilinium ions in different montmorillonite clays

    NASA Astrophysics Data System (ADS)

    do Nascimento, Gustavo M.; Temperini, Marcia L. A.

    2011-09-01

    The polymerization of the intercalated aniline ions was studied in three different clays, Swy2-montmorillonite (MMT), synthetic mica-montmorillonite (Syn1) and pillarized Swy2-montmorillonite (PILC). PANI is formed between the MMT and Syn1 clay layers, being confirmed by the shift of d001 peak in the X-ray pattern. X-ray Absorption near to Si K edge (Si K XANES) data show that the structures of clays are preserved after the polymerization process and in addition to the SEM images show that morphologies of the clays are maintained after polymerization, indicating no polymerization in their external surface. UV-vis-NIR and resonance Raman data display that the PANI formed in Syn1 galleries has higher amount of phenazinic rings than observed for PANI intercalated in montmorillonite (MMT) clay. No polymer formation was detected in the PILC. N K XANES and EPR spectroscopies show the presence of azo and radical nitrogen in intercalated PANI chains. Hence, the results are rationalized considering the structural differences between the clays for understanding the role of the anilinium polymerization within the clays galleries.

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

    NASA Astrophysics Data System (ADS)

    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

  7. The Be K-edge in beryllium oxide and chalcogenides: soft x-ray absorption spectra from first-principles theory and experiment.

    PubMed

    Olovsson, W; Weinhardt, L; Fuchs, O; Tanaka, I; Puschnig, P; Umbach, E; Heske, C; Draxl, C

    2013-08-07

    We have carried out a theoretical and experimental investigation of the beryllium K-edge soft x-ray absorption fine structure of beryllium compounds in the oxygen group, considering BeO, BeS, BeSe, and BeTe. Theoretical spectra are obtained ab initio, through many-body perturbation theory, by solving the Bethe-Salpeter equation (BSE), and by supercell calculations using the core-hole approximation. All calculations are performed with the full-potential linearized augmented plane-wave method. It is found that the two different theoretical approaches produce a similar fine structure, in good agreement with the experimental data. Using the BSE results, we interpret the spectra, distinguishing between bound core-excitons and higher energy excitations.

  8. Ag K-edge EXAFS analysis of DNA-templated fluorescent silver nanoclusters: insight into the structural origins of emission tuning by DNA sequence variations.

    PubMed

    Neidig, Michael L; Sharma, Jaswinder; Yeh, Hsin-Chih; Martinez, Jennifer S; Conradson, Steven D; Shreve, Andrew P

    2011-08-10

    DNA-templated silver nanoclusters are promising biological fluorescence probes due to their useful fluorescence properties, including tunability of emission wavelength through DNA template sequence variations. Ag K-edge EXAFS analysis of DNA-templated silver nanoclusters has been used to obtain insight into silver nanocluster bonding, size, and structural correlations to fluorescence. The results indicate the presence of small silver nanoclusters (<30 silver atoms) containing Ag-Ag bonds and Ag-N/O ligations to DNA. The DNA sequence used leads to differences in silver-DNA ligation as well as silver nanocluster size. The results support a model in which cooperative effects of both Ag-DNA ligation and variations in cluster size lead to the tuning of the fluorescence emission of DNA-templated silver nanoclusters.

  9. Observation of momentum-dependent charge excitations in hole-doped cuprates using resonant inelastic x-ray scattering at the oxygen K edge

    NASA Astrophysics Data System (ADS)

    Ishii, Kenji; Tohyama, Takami; Asano, Shun; Sato, Kentaro; Fujita, Masaki; Wakimoto, Shuichi; Tustsui, Kenji; Sota, Shigetoshi; Miyawaki, Jun; Niwa, Hideharu; Harada, Yoshihisa; Pelliciari, Jonathan; Huang, Yaobo; Schmitt, Thorsten; Yamamoto, Yoshiya; Mizuki, Jun'ichiro

    2017-09-01

    We investigate electronic excitations in La2 -x(Br,Sr ) xCuO4 using resonant inelastic x-ray scattering (RIXS) at the oxygen K edge. RIXS spectra of the hole-doped cuprates show clear momentum dependence below 1 eV. The broad spectral weight exhibits positive dispersion and shifts to higher energy with increasing hole concentration. Theoretical calculation of the dynamical charge structure factor on oxygen orbitals in a three-band Hubbard model is consistent with the experimental observation of the momentum and doping dependence, and therefore the momentum-dependent spectral weight is ascribed to intraband charge excitations which have been observed in electron-doped cuprates. Our results confirm that the momentum-dependent charge excitations exist on the order of the transfer energy (t ), and the broad spectral line shape indicates damped and incoherent character of the charge excitations at the energy range in the doped Mott insulators.

  10. X-ray natural linear dichroism of graphitic materials across the carbon K-edge: Correction for perturbing high-order harmonics

    NASA Astrophysics Data System (ADS)

    Jansing, C.; Mertins, H. C.; Gaupp, A.; Sokolov, A.; Gilbert, M. C.; Wahab, H.; Timmers, H.

    2016-05-01

    Reflectivity measurements on graphitic materials such as graphene at energies across the carbon K-edge are frustrated by significant intensity loss due to adventitious carbon on beamline mirrors. Such intensity reduction enhances effects due to perturbing high-order harmonics in the beam. These effects distort the actual structure of the reflectance curve. In order to overcome this limitation, a correction technique has been developed and demonstrated first with measurements for highly ordered pyrolytic graphite. The same approach may be applied to other graphitic materials such as graphene and it may be used with other synchrotron beamlines. The fraction of high-order harmonics was determined by passing the incident beam through a 87 nm thin silicon nitride absorber that can be well modeled. Using the corrected measurements the x-ray natural linear dichroism of the sample has been determined.

  11. Unraveling the nature of charge excitations in La2CuO4 with momentum-resolved Cu K-edge resonant inelastic X-ray scattering

    SciTech Connect

    Chen, Cheng-Chien

    2011-03-01

    Results of model calculations using exact diagonalization reveal the orbital character of states associated with different Raman loss peaks in Cu K-edge resonant inelastic X-ray scattering (RIXS) from La{sub 2}CuO{sub 4}. The model includes electronic orbitals necessary to highlight non-local Zhang-Rice singlet, charge transfer and d-d excitations, as well as states with apical oxygen 2p{sub z} character. The dispersion of these excitations is discussed with prospects for resonant final state wave-function mapping. A good agreement with experiments emphasizes the substantial multi-orbital character of RIXS profiles in the energy transfer range 1-6 eV.

  12. Ligand K-edge X-ray absorption spectroscopy and DFT calculations on [Fe3S4]0,+ clusters: delocalization, redox, and effect of the protein environment.

    PubMed

    Dey, Abhishek; Glaser, Thorsten; Moura, Jose J-G; Holm, Richard H; Hedman, Britt; Hodgson, Keith O; Solomon, Edward I

    2004-12-29

    Ligand K-edge XAS of an [Fe3S4]0 model complex is reported. The pre-edge can be resolved into contributions from the mu(2)S(sulfide), mu(3)S(sulfide), and S(thiolate) ligands. The average ligand-metal bond covalencies obtained from these pre-edges are further distributed between Fe(3+) and Fe(2.5+) components using DFT calculations. The bridging ligand covalency in the [Fe2S2]+ subsite of the [Fe3S4]0 cluster is found to be significantly lower than its value in a reduced [Fe2S2] cluster (38% vs 61%, respectively). This lowered bridging ligand covalency reduces the superexchange coupling parameter J relative to its value in a reduced [Fe2S2]+ site (-146 cm(-1) vs -360 cm(-1), respectively). This decrease in J, along with estimates of the double exchange parameter B and vibronic coupling parameter lambda2/k(-), leads to an S = 2 delocalized ground state in the [Fe3S4]0 cluster. The S K-edge XAS of the protein ferredoxin II (Fd II) from the D. gigas active site shows a decrease in covalency compared to the model complex, in the same oxidation state, which correlates with the number of H-bonding interactions to specific sulfur ligands present in the active site. The changes in ligand-metal bond covalencies upon redox compared with DFT calculations indicate that the redox reaction involves a two-electron change (one-electron ionization plus a spin change of a second electron) with significant electronic relaxation. The presence of the redox inactive Fe(3+) center is found to decrease the barrier of the redox process in the [Fe3S4] cluster due to its strong antiferromagnetic coupling with the redox active Fe2S2 subsite.

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

    NASA Astrophysics Data System (ADS)

    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.

  14. Time-dependent X-ray absorption spectroscopic (XAS) study on the transformation of zinc basic salt into bis(N-oxopyridine-2-thionato) zinc (II).

    PubMed

    Paek, Seung-Min; Jo, Won-Young; Park, Man; Choy, Jin-Ho

    2007-11-01

    Solid transchelation reaction was established for the synthesis of bis(N-oxopyridine-2-thionato) zinc (II), commonly known as zinc pyrithione (ZPT), to control particle size using zinc basic salt (ZBS) and aqueous sodium pyrithione solution. Distinguished from ZPT particles prepared by usual precipitation reaction, the obtained ZPT nanoparticles exhibited very narrow size distribution. X-ray absorption spectroscopy (XAS) at Zn K-edge was systematically examined to elucidate time-dependent local structural evolution during solid transchelation reaction. X-ray absorption near edge structure (XANES) analysis clearly revealed that local environment around zinc atoms transformed into pentahedron as reaction proceeded. Based on quantitative X-ray diffraction and XANES analysis, we made structural models. Theoretical XAS spectrum calculated with FEFF code could reproduce experimental one, suggesting that XAS analysis could be very powerful tool to probe phase transformation. Furthermore, according to extended X-ray absorption fine structure (EXAFS) fitting results, Zn-O distance in reaction products gradually increased from 1.96 to 2.07 angstroms, suggesting that zinc atoms bounded with oxygen ones in ZBS were transchelated with pyrithione ligands. This study could be a strong evidence for the usefulness of XAS to study time-dependent structural transformation of nanocrystalline materials.

  15. Local structure and La L1 and L3-edge XANES spectra of lanthanum complex oxides.

    PubMed

    Asakura, Hiroyuki; Shishido, Tetsuya; Teramura, Kentaro; Tanaka, Tsunehiro

    2014-06-16

    La L1 and L3-edge X-ray absorption near-edge structure (XANES) of various La oxides were classified according to the local configuration of La. We found a correlation between both of the areas of the pre-edge peaks of the La L1-edge XANES spectra and the full width at half-maximum of white line of La L3-edge XANES spectra and the local configuration of La. Theoretical calculation of the XANES spectra and local density of states reveals the difference of La L1 and L3-edge XANES spectra of various La compounds is related to the p-d hybridization of the unoccupied band and broadening of the d band of La induced by the difference of local configuration. In addition, simplified bond angle analysis parameters defined by the angles of the La atom and the two adjacent oxygen atoms are correlated to the pre-edge peak intensity of the La L1-edge XANES spectra. These results indicate that quantitative analysis of La L1 and L3-edge XANES spectra could be an indicator of the local structure of La materials.

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

    NASA Astrophysics Data System (ADS)

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

    2013-04-01

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

  17. micro-XANES and micro-XRF investigations of metal binding mechanisms in biosolids.

    PubMed

    Hettiarachchi, G M; Scheckel, K G; Ryan, J A; Sutton, S R; Newville, M

    2006-01-01

    Micro-X-ray fluorescence (micro-XRF) microprobe analysis and micro-X-ray absorption near-edge structure (micro-XANES) spectroscopy were employed to identify Fe and Mn phases and their association with selected metals in two biosolids (limed composted [LC] and Nu-Earth) before and after treatment to remove organic carbon (OC). Spatial correlations derived from elemental mapping of XRF images showed strong correlations between Fe and Cd, Cr, Pb, or Zn (r2= 0.65-0.92) before and after removal of most of the OC. The strong correlation between Fe and Cu that was present in intact samples disappeared after OC removal, suggesting that Cu was associated with OC coatings that may have been present on Fe compounds. Except for Fe and Cr, the spatial correlations of metals with Mn were improved after treatment to remove OC, indicating that the treatment may have altered more than the OC in the system. The Fe micro-XANES spectra of the intact biosolids sample showed that every point had varying mixtures of Fe(II and III) species and no two points were identical. The lack of uniformity in Fe species in the biosolids sample illustrates the complexity of the materials and the difficulty of studying biosolids using conventional analytical tools or chemical extraction techniques. Still, these microscopic observations provide independent information supporting the previous laboratory and field hypothesis that Fe compounds play a major role in retention of environmentally important trace elements in biosolids. This could be due to co-precipitation of the metals with Fe, adsorption of metals by Fe compounds, or a combination of both mechanisms.

  18. High resolution short focal distance Bent Crystal Laue Analyzer for copper K edge x-ray absorption spectroscopy

    SciTech Connect

    Kujala, N. G.; Barrea, R. A.; Karanfil, C.

    2011-06-15

    We have developed a compact short focal distance Bent Crystal Laue Analyzer (BCLA) for Cu speciation studies of biological systems with specific applications to cancer biology. The system provides high energy resolution and high background rejection. The system is composed of an aluminum block serving as a log spiral bender for a 15 micron thick Silicon 111 crystal and a set of soller slits. The energy resolution of the BCLA--about 14 eV at the Cu K{alpha} line-- allows resolution of the Cu K{alpha}{sub 1} and CuK{alpha}{sub 2} lines. The system is easily aligned by using a set of motorized XYZ linear stages. Two operation modes are available: incident energy scans (IES) and emission energy scans (EES). IES allows scanning of the incident energy while the BCLA system is maintained at a preselected fixed position - typically CuK{alpha}{sub 1} line. EES is used when the incident energy is fixed and the analyzer is scanned to provide the peak profile of the emission lines of Cu.

  19. Octahedral versus tetrahedral coordination of Al in synthetic micas determined by XANES

    SciTech Connect

    Mottana, A.; Ventura, G.D.; Robert, J.L.

    1997-05-01

    We used the JUMBO monochromator at SSRL to measure the Al K-edge X-ray absorption spectra of synthetic micas having variable Al content and occupancy, from 0 to 2/3 in the octahedral M positions, and 0 to 2/3 in the tetrahedral T positions. The measured Al K edges differ markedly, but the differences may have a common explanation: (1) Micas containing 1/3 Al in M or {1/4} Al in T have K edges that differ in the energy and intensity of the first two features, which are related to interaction of Al with its first-shell nearest neighbors (O and OH or F). They are nearly identical to the K edges of reference minerals such as albite (tetrahedral Al only) or grossular (octahedral Al only). (2) Micas containing Al in both M and T have K edges that can be interpreted as a weighed combination of the simple edges. 39 refs., 4 figs., 1 tab.

  20. Induction of DNA strand breaks, base lesions and clustered damage sites in hydrated plasmid DNA films by ultrasoft X rays around the phosphorus K edge.

    PubMed

    Yokoya, Akinari; Cunniffe, Siobhan M T; Watanabe, Ritsuko; Kobayashi, Katsumi; O'Neill, Peter

    2009-09-01

    To characterize the DNA damage induced by K-shell ionization of phosphorus atom in DNA backbone on the level of hydration, the yields of DNA strand breaks and base lesions arising from the interaction of ultrasoft X rays with energies around the phosphorus K edge were determined using dry and fully hydrated pUC18 plasmid DNA samples. Base lesions and bistranded clustered DNA damage sites were revealed by postirradiation treatment with the base excision repair proteins endonuclease III (Nth) and formamidopyrimidine-DNA glycosylase (Fpg). The yield of prompt single-strand breaks (SSBs) with dry DNA irradiated at the phosphorus K resonance energy (2153 eV) is about one-third that below the phosphorus K edge (2147 eV). The yields of prompt double-strand breaks (DSBs) were found to be less dependent on the X-ray energy, with the yields being about two times lower when irradiated at 2153 eV. Heat-labile sites were not produced in detectable amounts. The yields of base lesions were dependent on the energy of the X rays, especially when the DNA was fully hydrated. Bistranded clustered DNA damage sites, revealed enzymatically as additional DSBs, were produced in dry as well as in hydrated DNA with all three energies of X rays. The yields of these enzyme-sensitive sites were also lower when irradiated at the phosphorus K resonance energy. On the other hand, the yields of prompt SSBs and enzyme-sensitive sites for the two off-resonance energies were, larger than those determined previously for gamma radiation. The results indicate that the photoelectric effect caused by X rays and dense ionization and excitation events along the tracks of low-energy secondary electrons are more effective at inducing SSBs and enzyme-sensitive sites. The complex types of damage, prompt and enzymatically induced DSBs, are preferentially induced by phosphorus K resonance at 2153 eV rather than simple SSBs and isolated base lesions, particularly in hydrated conditions. It is concluded that not

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

    NASA Astrophysics Data System (ADS)

    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.

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

    SciTech Connect

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

    2009-03-23

    Ti valence in refractory phases is an important recorder of redox conditions in the early solar nebula. We report the valence of Ti in pyroxene, spinel and hibonite in spinel-hibonite and spinel-pyroxene inclusions and in a coarse hibonite grain. A system of solar composition is so reducing that Ti{sup 3+} and Ti{sup 4+} can coexist, making the valence of Ti a valuable indicator of f{sub O2} conditions during formation of nebular materials. The Ti{sup 3+}/Ti{sup 4+} ratios observed in the Ti-rich phases fassaite and rhoenite in coarse-grained refractory inclusions from CV3 chondrites have been shown to be quantitatively consistent 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

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

    NASA Technical Reports Server (NTRS)

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

    1993-01-01

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

  4. Low-temperature spin-state transition in LaCoO{sub 3} investigated using resonant x-ray absorption at the Co K edge

    SciTech Connect

    Medarde, M.; Pomjakushina, E.; Conder, K.; Dallera, C.; Grioni, M.; Voigt, J.; Podlesnyak, A.; Neisius, Th.; Tjernberg, O.; Barilo, S. N.

    2006-02-01

    LaCoO{sub 3} displays two broad anomalies in the DC magnetic susceptibility {chi}{sup DC}, occurring, respectively, around 50 K and 500 K. We have investigated the first of them within the 10 KK-edge XAS reports, our data show the existence of abrupt changes around 50 K which can be nicely correlated with the anomaly in {chi}{sup DC}. To our knowledge, this is the first time that a clear, quantitative relationship between the temperature dependence of the magnetic susceptibility and that of the XAS spectra is reported. The intensity changes in the preedge region, which are consistent with a transition from a lower to a higher spin state, have been analyzed using a minimal model including the Co 3d and O 2p hybridization in the initial state. The temperature dependence of the Co magnetic moment obtained from the estimated e{sub g} and t{sub 2g} occupations could be satisfactorily reproduced. Also, the decrease of the Co 3d and O 2p hybridization by increasing temperature obtained from this simple model compares favorably with the values estimated from thermal evolution of the crystallographic structure.

  5. Solvation Effects on S K-edge XAS Spectra of Fe-S Proteins: Normal and Inverse Effects on WT and Mutant Rubredoxin

    PubMed Central

    Sun, Ning; Dey, Abhishek; Xiao, Zhiguang; Wedd, Anthony G.; Hodgson, Keith O.; Hedman, Britt; Solomon, Edward I.

    2010-01-01

    S K-edge X-ray Absorption Spectroscopy (XAS) was performed on wild type Cp rubredoxin and its Cys->Ser mutants in both solution and lyophilized forms. For wild type rubredoxin and for the mutants where an interior cysteine residue (C6 or C39) is substituted by serine, a normal solvent effect is observed, that is, the S covalency increases upon lyophilization. For the mutants where a solvent accessible surface cysteine residue is substituted by serine, the S covalency decreases upon lyophilization which is an inverse solvent effect. Density functional theory (DFT) calculations reproduce these experimental results and show that the normal solvent effect reflects the covalency decrease due to solvent H-bonding to the surface thiolates and that the inverse solvent effect results from the covalency compensation from the interior thiolates. With respect to the Cys->Ser substitution, the S covalency decreases. Calculations indicate that the stronger bonding interaction of the alkoxide with the Fe relative to that of thiolate increases the energy of the Fe d orbitals and reduces their bonding interaction with the remaining cysteines. The solvent effects support a surface solvent tuning contribution to electron transfer and the Cys->Ser result provides an explanation for the change in properties of related iron-sulfur sites with this mutation. PMID:20726554

  6. Dual-energy fluorescent x-ray computed tomography system with a pinhole design: Use of K-edge discontinuity for scatter correction

    PubMed Central

    Sasaya, Tenta; Sunaguchi, Naoki; Thet-Lwin, Thet-; Hyodo, Kazuyuki; Zeniya, Tsutomu; Takeda, Tohoru; Yuasa, Tetsuya

    2017-01-01

    We propose a pinhole-based fluorescent x-ray computed tomography (p-FXCT) system with a 2-D detector and volumetric beam that can suppress the quality deterioration caused by scatter components. In the corresponding p-FXCT technique, projections are acquired at individual incident energies just above and below the K-edge of the imaged trace element; then, reconstruction is performed based on the two sets of projections using a maximum likelihood expectation maximization algorithm that incorporates the scatter components. We constructed a p-FXCT imaging system and performed a preliminary experiment using a physical phantom and an I imaging agent. The proposed dual-energy p-FXCT improved the contrast-to-noise ratio by a factor of more than 2.5 compared to that attainable using mono-energetic p-FXCT for a 0.3 mg/ml I solution. We also imaged an excised rat’s liver infused with a Ba contrast agent to demonstrate the feasibility of imaging a biological sample. PMID:28272496

  7. Dual-energy fluorescent x-ray computed tomography system with a pinhole design: Use of K-edge discontinuity for scatter correction

    NASA Astrophysics Data System (ADS)

    Sasaya, Tenta; Sunaguchi, Naoki; Thet-Lwin, Thet-; Hyodo, Kazuyuki; Zeniya, Tsutomu; Takeda, Tohoru; Yuasa, Tetsuya

    2017-03-01

    We propose a pinhole-based fluorescent x-ray computed tomography (p-FXCT) system with a 2-D detector and volumetric beam that can suppress the quality deterioration caused by scatter components. In the corresponding p-FXCT technique, projections are acquired at individual incident energies just above and below the K-edge of the imaged trace element; then, reconstruction is performed based on the two sets of projections using a maximum likelihood expectation maximization algorithm that incorporates the scatter components. We constructed a p-FXCT imaging system and performed a preliminary experiment using a physical phantom and an I imaging agent. The proposed dual-energy p-FXCT improved the contrast-to-noise ratio by a factor of more than 2.5 compared to that attainable using mono-energetic p-FXCT for a 0.3 mg/ml I solution. We also imaged an excised rat’s liver infused with a Ba contrast agent to demonstrate the feasibility of imaging a biological sample.

  8. An unambiguous signature in molecular frame photoelectron angular distributions of core hole localization in fluorine K-edge photoionization of CF4

    NASA Astrophysics Data System (ADS)

    McCurdy, C. W.; Rescigno, T. N.; Trevisan, C. S.; Lucchese, R. R.

    2016-05-01

    Molecular Frame Photoelectron Angular Distributions (MFPADs) are calculated using the Complex Kohn variational method for core-hole ionization of the carbon and fluorines in CF4 at photoelectron energies below 15 eV. The angular distributions for localized versus delocalized core-hole creation on the four equivalent fluorines are radically different. A strong propensity for the dissociation to take place via the mechanism hν +CF4 -->CF 4 + +e- -->CF 3 + +F(1s-1) -->CF 3 + +F+ + 2e- in which a core excited neutral fluorine atom ionizes during or after dissociation creates the conditions for experimental observation of core hole localization. Comparison with recent unpublished experiments at the Advanced Light Source that measured the Recoil Frame Photoelectron Angular Distributions (averaged over CF3 rotations around the recoil axis) for fluorine K-edge ionization gives unambiguous evidence that these experiments directly observed the creation of an almost completely localized core hole on the dissociating fluorine atom when the molecule was initially photoionized. Work supported by USDOE, OBES Chemical Sciences, Geosciences, and Biosciences Division.

  9. Crystal Stability and Pressure-Induced Phase Transitions in Scheelite AWO4(A=Ca,Sr,Ba,Pb,Eu) Binary Oxides. I: A Review of Recent ab initio Calculations, ADXRD, XANES, and Raman Studies

    SciTech Connect

    Lopez-Solano,J.; Rodriguez-Hernandez, P.; Radescu, S.; Mujica, A.; Munoz, A.; Errandonea, D.; Manjon, F.; Pellicer-Porres, J.; Garro, N.; et al.

    2007-01-01

    The structural properties of CaWO{sub 4}, SrWO{sub 4}, BaWO{sub 4}, PbWO{sub 4}, and EuWO{sub 4} scintillating crystals under pressure have been studied by X-ray powder diffraction, X-ray absorption near-edge structure measurements, Raman spectroscopy, and ab initio density functional theory calculations. The results obtained from these studies will be reviewed here and their differences and similitudes discussed.

  10. EXAFS and XANES analysis of oxides at the nanoscale

    PubMed Central

    Kuzmin, Alexei; Chaboy, Jesús

    2014-01-01

    Worldwide research activity at the nanoscale is triggering the appearance of new, and frequently surprising, materials properties in which the increasing importance of surface and interface effects plays a fundamental role. This opens further possibilities in the development of new multifunctional materials with tuned physical properties that do not arise together at the bulk scale. Unfortunately, the standard methods currently available for solving the atomic structure of bulk crystals fail for nanomaterials due to nanoscale effects (very small crystallite sizes, large surface-to-volume ratio, near-surface relaxation, local lattice distortions etc.). As a consequence, a critical reexamination of the available local-structure characterization methods is needed. This work discusses the real possibilities and limits of X-ray absorption spectroscopy (XAS) analysis at the nanoscale. To this end, the present state of the art for the interpretation of extended X-ray absorption fine structure (EXAFS) is described, including an advanced approach based on the use of classical molecular dynamics and its application to nickel oxide nanoparticles. The limits and possibilities of X-ray absorption near-edge spectroscopy (XANES) to determine several effects associated with the nanocrystalline nature of materials are discussed in connection with the development of ZnO-based dilute magnetic semiconductors (DMSs) and iron oxide nanoparticles. PMID:25485137

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

    NASA Technical Reports Server (NTRS)

    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.