X-ray absorption near-edge spectroscopic study of nickel catalysts

International Nuclear Information System (INIS)

Soldatov, Alexander V.; Smolentsev, Grigory; Kravtsova, Antonina; Yalovega, Galina; Feiters, Martin C.; Metselaar, Gerald A.; Joly, Yves

2006-01-01

Ni-isocyanide and Ni-acac complexes have been studied by X-ray absorption spectroscopy. Theoretical analysis has been done using self-consistent full multiple scattering (MS) approach within both muffin-tin (MT) model of the potential and non-MT finite deference method. For the isocyanide complex, it was shown that MS theoretical spectra reproduce all structural details of the X-ray absorption near-edge structure (XANES), but also that it is important to consider the non-MT effects in the potential for a correct simulation of the shape of the pre-edge structures. The contribution of a non-constant potential in the interstitial regions is extremely important for the interpretation of the XANES of Ni(acac) 2

Theoretical Mn K-edge XANES for Li2MnO3: DFT + U study

International Nuclear Information System (INIS)

Tamura, Tomoyuki; Ohwaki, Tsukuru; Ito, Atsushi; Ohsawa, Yasuhiko; Kobayashi, Ryo; Ogata, Shuji

2012-01-01

Spectral features of Mn K-edge x-ray absorption near-edge structure (XANES) for Li 2 MnO 3 were calculated using the first-principles full projector augmented wave method with the general gradient approximation plus U method. We demonstrated that the U parameter affects the spectral features in the pre-edge region while it does not affect those in the major absorption region. From the comparison with the experimental spectra and those of reference compounds, we showed that the spectral features of Mn K-edge XANES and the differences in the valence state can be reproduced well. (paper)

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

Energy Technology Data Exchange (ETDEWEB)

Liang, Xianqing, E-mail: lxq@gxu.edu.cn [Guangxi Colleges and Universities Key Laboratory of Novel Energy Materials and Related Technology, College of Physics Science and Technology, Guangxi University, Nanning 530004 (China); Guangxi Collaborative Innovation Center of Structure and Property for New Energy and Materials, School of Material Science and Engineering, Guilin University of Electronic Technology, Guilin 541004 (China); Pan, Deyou; Lao, Ming; Liang, Shuiying [Guangxi Colleges and Universities Key Laboratory of Novel Energy Materials and Related Technology, College of Physics Science and Technology, Guangxi University, Nanning 530004 (China); Huang, Dan; Zhou, Wenzheng; Guo, Jin [Guangxi Colleges and Universities Key Laboratory of Novel Energy Materials and Related Technology, College of Physics Science and Technology, Guangxi University, Nanning 530004 (China); Guangxi Collaborative Innovation Center of Structure and Property for New Energy and Materials, School of Material Science and Engineering, Guilin University of Electronic Technology, Guilin 541004 (China)

2017-05-15

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

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

Energy Technology Data Exchange (ETDEWEB)

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

1999-07-01

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

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

International Nuclear Information System (INIS)

Wu, Z.; Marcelli, A.; Cibin, G.; Mottana, A.; Rome Univ. Roma Tre, Rome; Paris, E.; Giuli, G.

1999-01-01

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

X-ray absorption near edge structure (XANES) study of some hydroxamic mixed ligand copper complexes

International Nuclear Information System (INIS)

Mishra, A; Parsai, N; Shrivastava, B D; Soni, N

2012-01-01

With the advent of modern bright synchrotron radiation sources, 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 four hydroxamic mixed ligand copper complexes have been performed at the recently developed BL-8 Dispersive EXAFS beamline at 2.5 GeV Indus-2 synchrotron at RRCAT, Indore, India. 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 complexes have been determined. The values of the chemical shift suggest that copper is in oxidation state +2 in all of the complexes. The chemical shift data has been utilized to estimate effective nuclear charge on copper atom. The order of the chemical shifts has been correlated to the relative ionic character of the bonding in these complexes.

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

Science.gov (United States)

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

2018-03-01

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

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

International Nuclear Information System (INIS)

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

1995-01-01

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

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

Science.gov (United States)

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

1995-05-01

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

Determination of Cr(VI) in wood specimen: A XANES study at the Cr K edge

International Nuclear Information System (INIS)

Strub, E.; Plarre, R.; Radtke, M.; Reinholz, U.; Riesemeier, H.; Schoknecht, U.; Urban, K.; Juengel, P.

2008-01-01

The content of chromium in different oxidation states in chromium-treated wood was studied with XANES (X-ray absorption near-edge structure) measurements at the Cr K absorption edge. It could be shown that wood samples treated with Cr(VI) (pine and beech) did still contain a measurable content of Cr(VI) after four weeks conditioning. If such wood samples were heat exposed for 2 h with 135 deg. C prior conditioning, Cr(VI) was no longer detected by XANES, indicating a complete reduction to chromium (III)

X-ray absorption spectroscopy: EXAFS and XANES - A versatile tool to study the atomic and electronic structure of materials

International Nuclear Information System (INIS)

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

1990-01-01

X-ray absorption spectroscopy (XAS) had been an essential tool to gather spectroscopic information about atomic energy level structure in the early decades of this century. The correct interpretation of the oscillatory structure in the x-ray absorption cross-section above the absorption edge has transformed XAS from a spectroscopic tool to a structural technique. EXAFS (Extended X-ray Absorption Fine Structure) yields information about the interatomic distances, near neighbor coordination numbers, and lattice dynamics. XANES (X-ray Absorption Near Edge Structure), on the other hand, gives information about the valence state, energy bandwidth and bond angles. Today, there are about 50 experimental stations in various synchrotrons around the world dedicated to collecting x-ray absorption data from the bulk and surfaces of solids and liquids. In this chapter, they will give the basic principles of XAS, explain the information content of essentially two different aspects of the absorption process leading to EXAFS and XANES, and discuss the source and sample limitations

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

Directory of Open Access Journals (Sweden)

Siwatt Pongpiachan

2012-01-01

Full Text Available 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.

Silicon K-edge XANES spectra of silicate minerals

Science.gov (United States)

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

1995-03-01

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

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

Science.gov (United States)

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

2015-07-01

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

Structural disorder and electronic hybridization in NicMg1-cO solid solutions probed by XANES at the oxygen K edge

International Nuclear Information System (INIS)

Chen Dongliang; Zhong Jun; Chu Wangsheng; Wu Ziyu; Kuzmin, Alexei; Mironova-Ulmane, Nina; Marcelli, Augusto

2007-01-01

A series of Ni c Mg 1-c O solid solutions has been studied for the first time looking at the structural disorder by means of x-ray absorption near-edge-structure (XANES) spectroscopy at the oxygen K edge. The experimental XANES signals were analysed within the full multiple scattering formalism and were interpreted taking into account clusters of up to 15 coordination shells around an absorbing oxygen atom. The substitution of nickel atoms by magnesium atoms results in a dramatic decrease of the empty density of states in the conduction band close to the Fermi level due to an exchange of the 3d(Ni)-2p(O) interaction with 3p(Mg)-2p(O). Besides, a simultaneous small decrease of the 3d(Ni)-2p(O) hybridization is also induced by the lattice expansion, determined by the difference in ionic radii between nickel and magnesium ions

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

Science.gov (United States)

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

2018-05-01

Gold and silver sulfoselenides are of interest as materials with high ionic conductivity and promising magnetoresistive, thermoelectric, optical, and other physico-chemical properties, which are strongly dependent on composition and structure. Here, we applied X-ray photoelectron spectroscopy and Ag L3 X-ray absorption near-edge structure (XANES) to study the electronic structures of low-temperature compounds and solid solutions Ag2SxSe1-x (0 compounds; in particular, the Ag L3-edge peak is about 35% lower for AgAuS relative to Ag2S. At the same time, the Au 4f binding energy and, therefore, charge at Au(I) sites increase with increasing S content due to the transfer of electron density from Au to Ag atoms. It was concluded that the effects mainly originate from shortening of the metal-chalcogen and especially the Ausbnd Ag interatomic distances in substances having similar coordination geometry.

Studies on absorption coefficient near edge of multi elements

International Nuclear Information System (INIS)

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

2005-01-01

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

Studies on absorption coefficient near edge of multi elements

Science.gov (United States)

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

2005-12-01

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

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

Science.gov (United States)

Xiong, Wenhui; Peng, Jian; Hu, Yongfeng

2012-02-15

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

Near edge x-ray spectroscopy theory

International Nuclear Information System (INIS)

1994-01-01

We propose to develop a quantitative theory of x-ray spectroscopies in the near edge region, within about 100 eV of threshold. These spectroscopies include XAFS (X-ray absorption fine structure), photoelectron diffraction (PD), and diffraction anomalous fine structure (DAFS), all of which are important tools for structural studies using synchrotron radiation x-ray sources. Of primary importance in these studies are many-body effects, such as the photoelectron self-energy, and inelastic losses. A better understanding of these quantities is needed to obtain theories without adjustable parameters. We propose both analytical and numerical calculations, the latter based on our x-ray spectroscopy codes FEFF

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

Directory of Open Access Journals (Sweden)

Siwatt Pongpiachan

2012-01-01

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

Sulfur K-edge absorption spectroscopy on selected biological systems; Schwefel-K-Kanten-Absorptionsspektroskopie an ausgewaehlten biologischen Systemen

Energy Technology Data Exchange (ETDEWEB)

Lichtenberg, Henning

2008-07-15

Sulfur is an essential element in organisms. In this thesis investigations of sulfur compounds in selected biological systems by XANES (X-ray Absorption Near Edge Structure) spectroscopy are reported. XANES spectroscopy at the sulfur K-edge provides an excellent tool to gain information about the local environments of sulfur atoms in intact biological samples - no extraction processes are required. Spatially resolved measurements using a Kirkpatrick-Baez mirror focusing system were carried out to investigate the infection of wheat leaves by rust fungi. The results give information about changes in the sulfur metabolism of the host induced by the parasite and about the extension of the infection into visibly uninfected plant tissue. Furthermore, XANES spectra of microbial mats from sulfidic caves were measured. These mats are dominated by microbial groups involved in cycling sulfur. Additionally, the influence of sulfate deprivation and H{sub 2}S exposure on sulfur compounds in onion was investigated. To gain an insight into the thermal degradation of organic material the influence of roasting of sulfur compounds in coffee beans was studied. (orig.)

EXAFS and XANES analysis of plutonium and cerium edges from titanate ceramics for fissile materials disposal

International Nuclear Information System (INIS)

Fortner, J. A.; Kropf, A. J.; Bakel, A. J.; Hash, M. C.; Aase, S. B.; Buck, E. C.; Chamerlain, D. B.

1999-01-01

We report x-ray absorption near edge structure (XANES) and extended x-ray absorption fine structure (EXAFS) spectra from the plutonium L III edge and XANES from the cerium L II edge in prototype titanate ceramic hosts. The titanate ceramics studied are based upon the hafnium-pyrochlore and zirconolite mineral structures and will serve as an immobilization host for surplus fissile materials, containing as much as 10 weight % fissile plutonium and 20 weight % (natural or depleted) uranium. Three ceramic formulations were studied: one employed cerium as a ''surrogate'' element, replacing both plutonium and uranium in the ceramic matrix, another formulation contained plutonium in a ''baseline'' ceramic formulation, and a third contained plutonium in a formulation representing a high-impurity plutonium stream. The cerium XANES from the surrogate ceramic clearly indicates a mixed III-IV oxidation state for the cerium. In contrast, XANES analysis of the two plutonium-bearing ceramics shows that the plutonium is present almost entirely as Pu(IV) and occupies the calcium site in the zirconolite and pyrochlore phases. The plutonium EXAFS real-space structure shows a strong second-shell peak, clearly distinct from that of PuO 2 , with remarkably little difference in the plutonium crystal chemistry indicated between the baseline and high-impurity formulations

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

Science.gov (United States)

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

2015-06-01

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

Debris of potassium–magnesium silicate glass generated by femtosecond laser-induced ablation in air: An analysis by near edge X-ray absorption spectroscopy, micro Raman and energy dispersive X-ray spectroscopy

International Nuclear Information System (INIS)

Grehn, M.; Seuthe, T.; Reinhardt, F.; Höfner, M.; Griga, N.; Eberstein, M.; Bonse, J.

2014-01-01

The redeposited material (debris) resulting from ablation of a potassium–magnesium silicate glass upon scanning femtosecond laser pulse irradiation (130 fs, 800 nm) in air environment is investigated by means of three complementary surface analytical methods. Changes in the electronic band structure of the glass constituent Magnesium (Mg) were identified by X-ray Absorption Near Edge Structure spectroscopy (XANES) using synchrotron radiation. An up-shift of ≈0.8 eV of a specific Magnesium K-edge absorption peak in the spectrum of the redeposited material along with a significant change in its leading edge position was detected. In contrast, the surface left after laser ablation exhibits a downshift of the peak position by ≈0.9 eV. Both observations may be related to a change of the Mg coordinative state of the laser modified/redeposited glass material. The presence of carbon in the debris is revealed by micro Raman spectroscopy (μ-RS) and was confirmed by energy dispersive X-ray spectroscopy (EDX). These observations are attributed to structural changes and chemical reactions taking place during the ablation process.

Mn K-edge XANES spectroscopy of photosynthetic water oxidation enzyme in the S0-, S1-, S2- and S3-states induced by flash excitation

International Nuclear Information System (INIS)

Ono, Taka-aki; Noguchi, Takumi; Inoue, Yorinao; Kusunoki, Masami; Matsushita, Tadashi; Oyanagi, Hiroyuki.

1993-01-01

Electronic and structural rearrangement of the Mn-cluster during the four step oxidation of water in photosynthetic oxygen evolution was studied by XANES spectroscopy. The Mn K-edge energy of the spectrum was changed with flash number to show a clear quadruple oscillation, indicating a periodic change in oxidation and electronic state of the Mn-cluster depending on Joliot and Kok's oxygen clock. (author)

Structural disorder and electronic hybridization in Ni{sub c}Mg{sub 1-c}O solid solutions probed by XANES at the oxygen K edge

Energy Technology Data Exchange (ETDEWEB)

Chen Dongliang [Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China); Zhong Jun [Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China); Chu Wangsheng [Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China); Wu Ziyu [Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China); Kuzmin, Alexei [Institute of Solid State Physics, University of Latvia, Kengaraga 8, LV-1063 Riga (Latvia); Mironova-Ulmane, Nina [Institute of Solid State Physics, University of Latvia, Kengaraga 8, LV-1063 Riga (Latvia); Marcelli, Augusto [Laboratori Nazionali di Frascati, Istituto Nazionale di Fisica Nucleare, PO Box 13, 00044 Frascati (Italy)

2007-09-05

A series of Ni{sub c}Mg{sub 1-c}O solid solutions has been studied for the first time looking at the structural disorder by means of x-ray absorption near-edge-structure (XANES) spectroscopy at the oxygen K edge. The experimental XANES signals were analysed within the full multiple scattering formalism and were interpreted taking into account clusters of up to 15 coordination shells around an absorbing oxygen atom. The substitution of nickel atoms by magnesium atoms results in a dramatic decrease of the empty density of states in the conduction band close to the Fermi level due to an exchange of the 3d(Ni)-2p(O) interaction with 3p(Mg)-2p(O). Besides, a simultaneous small decrease of the 3d(Ni)-2p(O) hybridization is also induced by the lattice expansion, determined by the difference in ionic radii between nickel and magnesium ions.

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

Energy Technology Data Exchange (ETDEWEB)

J Prietzel; J Thieme; D Paterson

2011-12-31

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

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

Science.gov (United States)

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

2017-10-01

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

Study of oxidation states of the transition metals in a series of Prussian blue analogs using x-ray absorption near edge structure (XANES) spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Adak, S. [Department of Physics, New Mexico State University, Las Cruces, NM, 88003 (United States); Hartl, M., E-mail: monika.hartl@esss.se [European Spallation Source ESS AB, 22100, Lund (Sweden); Manuel Lujan Jr. Neutron Scattering Center (LANSCE-LC), Los Alamos National Laboratory, Los Alamos, NM, 87545 (United States); Daemen, L. [Spallation Neutron Source, Oak Ridge National Laboratory, Oak Ridge, TN, 37830 (United States); Manuel Lujan Jr. Neutron Scattering Center (LANSCE-LC), Los Alamos National Laboratory, Los Alamos, NM, 87545 (United States); Fohtung, E.; Nakotte, H. [Department of Physics, New Mexico State University, Las Cruces, NM, 88003 (United States)

2017-01-15

Highlights: • Systematic XANES measurements on Prussian blue analogs shows oxidation state of transition metals. • Cobal-iron bimetallic hexacyanometallates show unexpected oxidation states. • Iron(II) ions in hexacyanometallates(III) show varying spin state depending on their bond to the “N” end or “C” end of the cyanide ligand. • Thermal expansion coefficients have been linked to the XANES results. - Abstract: There have been renewed interests in metal-organic framework classes of materials such as Prussian blue analogues (PBAs) due to their potential usage in energy storage applications. In particular, due to their high surface areas, controllable structures and excellent electrochemical properties, PBAs such as hexacyanometalates M{sup II}{sub 3}[A{sup III}(CN){sub 6}]{sub 2*}nH{sub 2}O (M = Mn, Fe, Co, Ni, Cu, Zn; A = Co, Fe, Cr; n = no. of water molecules present), M{sup II}{sub 2}[Fe{sup II}(CN){sub 6}]{sub 2*}nH{sub 2}O (M = Mn, Co, Ni, Cu, Zn) and mixed hexacyanometalates(III) (Fe{sub 1-x}Co{sub x}){sub 3}[B{sup III}(CN){sub 6}]{sub 2}·nH{sub 2}O (x = 0.25, 0.5, 0.75; B = Co, Fe) could have possible usage as a new class of cathode and even anode materials for rechargeable batteries. Detailed knowledge of the oxidation states of the transition metals in PBAs is required to improve efficiency and durability of such devices. Furthermore, a link between the thermal expansion observed in these materials and the oxidation state of the transition metal is of interest to synthesize materials with a desired thermal expansion behavior, Here we demonstrate the use of Synchrotron based X-ray absorption near-edge structure (XANES) spectra to identify transition metal oxidation states. Our analysis reveals the presence of divalent, trivalent and/or mixed valence transition metals in the materials as well as high-spin and low-spin complexes.

XANES analysis of dried and calcined bones

International Nuclear Information System (INIS)

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

2013-01-01

The structure of dried and calcined bones from chicken, bovine, deer, pig, sheep and chamois was examined using X-ray Absorption Near Edge Structure (XANES) spectroscopy. The oxygen K-edge absorption edge indicates that the surface of dried bone has a larger proportion of carbonate than the interior that is made up of phosphates. The phosphorus L and K edge clearly indicate that pyrophosphates, α-tricalcium phosphate (α-TCP) and hydrogen phosphates of Ca do not exist in either the dried bone or calcined bone and phosphorus exists as either β-tricalcium phosphate (β-TCP) or hydroxyapatite, both in the dried and calcined conditions. The Ca K-edge analysis indicates that β-TCP is the likely form of phosphate in both the dried and calcined conditions. - Highlights: • For the first time bones of five different species of vertebrates have been compared in both the dried and calcined states. • O, P and Ca edges detail the local coordination of these atoms in dried and calcined bone. • O K-edge shows that the surface of bone has more CO 3 while the interior has more PO 4 . • P and Ca edges eliminate the presence of pyrophosphates and confirmed the presence of HA and β-TCP. • The stability of these phosphates on calcination has been examined using XANES

XANES analysis of dried and calcined bones

Energy Technology Data Exchange (ETDEWEB)

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

2013-10-15

The structure of dried and calcined bones from chicken, bovine, deer, pig, sheep and chamois was examined using X-ray Absorption Near Edge Structure (XANES) spectroscopy. The oxygen K-edge absorption edge indicates that the surface of dried bone has a larger proportion of carbonate than the interior that is made up of phosphates. The phosphorus L and K edge clearly indicate that pyrophosphates, α-tricalcium phosphate (α-TCP) and hydrogen phosphates of Ca do not exist in either the dried bone or calcined bone and phosphorus exists as either β-tricalcium phosphate (β-TCP) or hydroxyapatite, both in the dried and calcined conditions. The Ca K-edge analysis indicates that β-TCP is the likely form of phosphate in both the dried and calcined conditions. - Highlights: • For the first time bones of five different species of vertebrates have been compared in both the dried and calcined states. • O, P and Ca edges detail the local coordination of these atoms in dried and calcined bone. • O K-edge shows that the surface of bone has more CO{sub 3} while the interior has more PO{sub 4}. • P and Ca edges eliminate the presence of pyrophosphates and confirmed the presence of HA and β-TCP. • The stability of these phosphates on calcination has been examined using XANES.

Europium-151 Moessbauer spectroscopic and XANES investigation of europium-exchanged Y-zeolite

International Nuclear Information System (INIS)

Berry, F.J.; Marco, J.F.; Steel, A.T.

1994-01-01

Eu 3+ in ca. 10 wt% europium-exchanged Y-zeolite is partially reduced by treatment in hydrogen at 600 C to Eu 2+ . The reduction of Eu 3+ is more readily achieved in Y-zeolite than in europium(III) oxide. The discrepancy in the extent of reduction as revealed by 151 Eu Moessbauer spectroscopy and near edge X-ray absorption fine structure (XANES) is associated with any difference in the recoil free fractions of Eu 2+ and Eu 3+ which may exist at 298 K and the enhanced sensitivity of the XANES to changes in the europium oxidation state. (orig.)

Determination of the products from the oxidation of aqueous hydrogen sulfide by sulfur K-edge XANES spectroscopy

International Nuclear Information System (INIS)

Vairavamurthy, A.; Manowitz, B.; Jeon, Yongseog; Zhou, Weiqing.

1993-01-01

The application of synchrotron radiation based XANES spectroscopy is described for determining the products formed from oxidation of aqueous sulfide.This technique allows simultaneous characterization of all the different forms of sulfur both qualitatively and quantitatively. Thus, it is superior to other commonly used techniques, such as chromatography, which are usually targeted at specific compounds. Since the use of XANES-based technique is relatively new in geochemistry, we present here an overview of the principles of the technique as well as the approach used for quantitative analysis. We studied the sulfide oxidation under conditions of high sulfide to oxygen ratio using 0.1 M sulfide solutions and the catalytic effects of sea sand, Fe 2+ , and Ni 2+ , were also examined. Significant results obtained from this study are presented to illustrate the value of the XANES technique for the determination of the products formed from the oxidation of sulfide at high concentrations

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

Energy Technology Data Exchange (ETDEWEB)

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

2016-12-15

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

High-resolution Al L2,3-edge x-ray absorption near edge structure spectra of Al-containing crystals and glasses: coordination number and bonding information from edge components

International Nuclear Information System (INIS)

Weigel, C; Calas, G; Cormier, L; Galoisy, L; Henderson, G S

2008-01-01

High-resolution Al L 2,3 -edge x-ray absorption near edge structure (XANES) spectra have been measured in selected materials containing aluminium in 4-, 5- and 6-coordination. A shift of 1.5 eV is observed between the onset of [4] Al and [6] Al L 2,3 -edge XANES, in agreement with the magnitude of the shift observed at the Al K-edge. The differences in the position and shape of low-energy components of Al L 2,3 -edge XANES spectra provide a unique fingerprint of the geometry of the Al site and of the nature of Al-O chemical bond. The high resolution allows the calculation of electronic parameters such as the spin-orbit coupling and exchange energy using intermediate coupling theory. The electron-hole exchange energy decreases in tetrahedral as compared to octahedral symmetry, in relation with the increased screening of the core hole in the former. Al L 2,3 -edge XANES spectra confirm a major structural difference between glassy and crystalline NaAlSi 2 O 6 , with Al in 4- and 6-coordination, respectively, Al coordination remaining unchanged in NaAl 1-x Fe x Si 2 O 6 glasses, as Fe is substituted for Al

X-ray absorption near-edge spectroscopy of plutonium solid species

International Nuclear Information System (INIS)

Kropf, A. J.

1998-01-01

We present XANES at the L III edge for four plutonium solid phases: Pu(III)F 3 , Pu(IV)O 2 , NaPu(V)O 2 CO 3 , and Ba 3 Pu(VI)O 6 . These correspond to the four important oxidation states in the process chemistry and environmental chemistry of plutonium. By a fitting method that uses an arc tangent function and gaussian curves, it was possible to reproducibly determine the edge energy and distinguish among the four oxidation states. These data demonstrate a 1.85 ± 0.20 eV shift per oxidation state

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

Science.gov (United States)

Zhan, Fei; Tao, Ye; Zhao, Haifeng

2017-07-01

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

X-ray Absorption Spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Yano, Junko; Yachandra, Vittal K.

2009-07-09

This review gives a brief description of the theory and application of X-ray absorption spectroscopy, both X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS), especially, pertaining to photosynthesis. The advantages and limitations of the methods are discussed. Recent advances in extended EXAFS and polarized EXAFS using oriented membranes and single crystals are explained. Developments in theory in understanding the XANES spectra are described. The application of X-ray absorption spectroscopy to the study of the Mn4Ca cluster in Photosystem II is presented.

XANES at the silicon k-edge in the kaolin-meta kaolin-geopolymer system

International Nuclear Information System (INIS)

Lima, F.T.; Silva, F.J.; Thaumaturgo, C.

2005-01-01

The geo polymer synthesis process optimization pretends to control the re logical and mechanical properties. The Al/Si ratio is the main variable that governs the geo polymerization process. This control occurs by changing temperature, pressure and chemical composition of the geo polymer. Thermal analysis (DTA/DSC), microscopic (SEM/TEM) and spectroscopic (FTIR, XRD, SAXS, EXAFS and XANES) techniques have been used to characterize these inorganic systems. In this work, XANES spectra of the k-edge silicon (Si) of the kaolin-meta kaolin-geo polymer are presented. The XANES spectra provides the oxidation state and structural information about the present studied atom: Silicon (Si). (author)

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

Science.gov (United States)

Zhang, Renqin; McEwen, Jean-Sabin

2018-05-22

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

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

Energy Technology Data Exchange (ETDEWEB)

Sigircik, Gokmen, E-mail: gsigircik@cu.edu.tr [Chemistry Department, University of Cukurova, 01330 Adana (Turkey); Erken, Ozge [Department of Physics, Faculty Science and Letters, Adiyaman University, 02040 Adiyaman (Turkey); Tuken, Tunc [Chemistry Department, University of Cukurova, 01330 Adana (Turkey); Gumus, Cebrail [Physics Department, University of Cukurova, 01330 Adana (Turkey); Ozkendir, Osman M. [Department of Energy Systems Engineering Tarsus Technology Faculty, Mersin University, 33400 Tarsus (Turkey); Ufuktepe, Yuksel [Physics Department, University of Cukurova, 01330 Adana (Turkey)

2015-06-15

Highlights: • Deposition mechanism of nano-structured ZnO films has been investigated in the absence and presence of chloride ions from aqueous solution. • Uniform and well-defined ZnO nano-towers and rods have been obtained via electrochemical deposition. • The presence of chloride ions altered the nucleation rate of ZnO particles on ITO substrates and resulting crystallographic properties. • Comparing the rod and tower nano-structured ZnO thin films, the excitation behavior of valance band electrons is different. - Abstract: Deposition mechanism of nano-structured ZnO films has been investigated in the absence and presence of chloride ions from aqueous solution. The resulting opto-electronic properties were interpreted extensively, using X-ray diffraction (XRD), X-ray Absorption Near Edge Spectroscopy (XANES), field emission scanning electron microscopy (FE-SEM), UV-Visible spectroscopy and four probe techniques. The ZnO deposition is mass transport controlled process and the interaction of chloride ions with the surface has great influence on diffusion kinetics, considering the substantial species (Zn{sup 2+} and OH{sup −}) involved in the construction of ZnO film. This effect does not change major lattice parameters, as shown with detailed analysis of XRD data. However, the texture coefficient (T{sub c}) (0 0 2) value is higher in presence of chloride ions containing synthesis solution which gave vertically aligned, well defined and uniformly dispersed nanorods structure. The calculated E{sub g} values are in the range 3.28–3.41 eV and 3.22–3.31 eV for ZnO nanorods and nanotowers synthesized at different deposition periods, respectively. Furthermore, the charge mobility values regarding the deposition periods were measured to be in the ranges from 130.4 to 449.2 cm{sup 2} V{sup −1} s{sup −1} and 126.2 to 204.7 cm{sup 2} V{sup −1} s{sup −1} for nanorods and nanotowers, respectively. From XANES results, it was shown that the Zn K-edge

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

International Nuclear Information System (INIS)

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

2015-01-01

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

Multiple Scattering Approach to Polarization Dependence of F K-Edge XANES Spectra for Highly Oriented Polytetrafluoroethylene (PTFE) Thin Film

International Nuclear Information System (INIS)

Nagamatsu, S.; Ono, M.; Kera, S.; Okudaira, K. K.; Fujikawa, T.; Ueno, N.

2007-01-01

The polarization dependence of F K-edge X-ray absorption near edge structure (XANES) spectra of highly-oriented thin-film of polytetrafluoroethylene (PTFE) has been analyzed by using multiple scattering theory. The spectra show clear polarization dependence due to the highly-oriented structure. The multiple scattering calculations reflects a local structure around an absorbing atom. The calculated results obtained by considering intermolecular-interactions are in good agreement with the observed polarization-dependence. We have also analyzed structural models of the radiation damaged PTFE films

Determination of Chemical States of Mercury on Activated Carbon Using XANES

International Nuclear Information System (INIS)

Takaoka, Masaki; Takeda, Nobuo; Oshita, Kazuyuki; Yamamoto, Takashi; Tanaka, Tsunehiro; Uruga, Tomoya

2007-01-01

Although the adsorption of mercury vapor onto activated carbon is a widely used technology to prevent environmental release, the adsorption mechanism is not clearly understood. In this study, we determined the chemical states of mercury on two kinds of activated carbon using X-ray absorption near-edge spectroscopy (XANES) to elucidate the adsorption mechanism. The adsorption experiments of elemental mercury onto activated carbon were conducted under air and nitrogen atmospheres at temperatures of 20 and 160 deg. C. Two types of activated carbon were prepared. X-ray absorption fine structure (XAFS) measurements were carried out on beamline BL01B1 at SPring-8. Hg-LIII edge XANES spectra suggested that chemical adsorption of elemental mercury on the activated carbon occurred in the 20-160 deg. C temperature range. According to the XANES spectra, a difference occurred in the chemical states of mercury between AC no. 1 and AC no. 2. The Hg XANES spectra on AC no. 1 were similar to those of Hg2Cl2 and HgS, and the Hg XANES spectra on AC no. 2 were similar to that of HgO, which suggested that nitric acid treatment removed sulfur from AC no. 1 and functional groups that were strong oxidizers on the surface of AC no. 2 created HgO. According to the EXAFS oscillation, a difference occurred in the chemical states of mercury on AC no. 1 between 20 and 160 deg. C. We found that impurities and oxidant functional groups on activated carbon play key roles in mercury adsorption

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

CERN Document Server

Noro, H; Nagoshi, M

2002-01-01

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

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

International Nuclear Information System (INIS)

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

2017-01-01

In this study, we have investigated polymorphic silica (SiO 2 ) 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 (λ CuKα =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. (paper)

Fate and chemical speciation of antimony (Sb) during uptake, translocation and storage by rye grass using XANES spectroscopy.

Science.gov (United States)

Ji, Ying; Sarret, Géraldine; Schulin, Rainer; Tandy, Susan

2017-12-01

Antimony (Sb) is a contaminant of increased prevalence in the environment, but there is little knowledge about the mechanisms of its uptake and translocation within plants. Here, we applied for the synchrotron based X-ray absorption near-edge structure (XANES) spectroscopy to analyze the speciation of Sb in roots and shoots of rye grass (Lolium perenne L. Calibra). Seedlings were grown in nutrient solutions to which either antimonite (Sb(III)), antimonate (Sb(V)) or trimethyl-Sb(V) (TMSb) were added. While exposure to Sb(III) led to around 100 times higher Sb accumulation in the roots than the other two treatments, there was no difference in total Sb in the shoots. Antimony taken up in the Sb(III) treatment was mainly found as Sb-thiol complexes (roots: >76% and shoots: 60%), suggesting detoxification reactions with compounds such as glutathione and phytochelatins. No reduction of accumulated Sb(V) was found in the roots, but half of the translocated Sb was reduced to Sb(III) in the Sb(V) treatment. Antimony accumulated in the TMSb treatment remained in the methylated form in the roots. By synchrotron based XANES spectroscopy, we were able to distinguish the major Sb compounds in plant tissue under different Sb treatments. The results help to understand the translocation and transformation of different Sb species in plants after uptake and provide information for risk assessment of plant growth in Sb contaminated soils. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

Science.gov (United States)

Šipr, Ondřej; Vackář, Jiří; Kuzmin, Alexei

2016-11-01

Polarization-dependent damping of the fine structure in the Cu K-edge spectrum of creatinium tetrachlorocuprate [(creat) 2 CuCl 4 ] 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.

X-ray absorption near-edge structure of GaN with high Mn concentration grown on SiC

International Nuclear Information System (INIS)

Sancho-Juan, O; Cantarero, A; Garro, N; Cros, A; Martinez-Criado, G; Salome, M; Susini, J; Olguin, D; Dhar, S

2009-01-01

By means of x-ray absorption near-edge structure (XANES) several Ga 1-x Mn x N (0.03 2 ↑ band localized in the gap region, and the corresponding anti-bonding state t 2 ↓, which seem to be responsible for the double structure which appears at the pre-edge absorption region. The shoulders and main absorption peak of the XANES spectra are attributed to transitions from the Mn(1s) band to the conduction bands, which are partially dipole allowed because of the Mn(4p) contribution to these bands.

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

International Nuclear Information System (INIS)

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

2013-01-01

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.

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

Science.gov (United States)

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.

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

International Nuclear Information System (INIS)

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

2016-01-01

Lanthanide silicates have been hydrothermally synthesized using Cu and Ni containers. Chemical formulae of the synthesized compounds correspond to K 3 Eu[Si 6 O 15 ] 2H 2 O, HK 6 Eu[Si 10 O 25 ], K 7 Sm 3 [Si 12 O 32 ], K 2 Sm[AlSi 4 O 12 ] 0.375H 2 O, K 4 Yb 2 [Si 8 O 21 ], K 4 Ce 2 [Al 2 Si 8 O 24 ]. The oxidation state of lanthanides (Eu, Ce, Tb, Sm, Yb) in these silicates has been determined using XANES spectroscopy at the Eu, Ce, Tb, Sm, Yb, L 3 - edges. The experimental XANES spectra were recorded using the synchrotron radiation source ANKA (Karlsruhe Institute of Technology) and the X-ray laboratory spectrometer Rigaku R- XAS. By comparing the absorption edge energies and white line intensities of the silicates with the ones of reference spectra the oxidation state of lanthanides Eu, Ce, Tb, Sm, Yb has been found to be equal to +3 in all investigated silicates except of the Ce-containing silicate from the run in Cu container where the cerium oxidation state ranges from +3 (Ce in silicate apatite and in a KCe silicate with Si 12 O 32 layers) to +4 (starting CeO 2 or oxidized Ce 2 O 3 ). (paper)

Cl K-edge XANES spectra of atmospheric rust on Fe, Fe-Cr and Fe-Ni alloys exposed to saline environment

International Nuclear Information System (INIS)

Konishi, Hiroyuki; Mizuki, Jun'ichiro; Yamashita, Masato; Uchida, Hitoshi

2004-01-01

Cl K-edge XANES measurements of atmospheric corrosion products (rust) formed on Fe, Fe-Ni and Fe-Cr alloys in chloride pollution have been performed using synchrotron radiation in order to clarify roles of anticorrosive alloying elements and of Cl in the corrosion resistance of weathering steel. The spectra of binary alloys show a shoulder structure near the absorption edge. The intensity of the shoulder peak depends on the kind and amount of the alloying element, whereas the energy position is invariant. This indicates that Cl is not combined directly with alloying elements in the rust. (author)

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

Science.gov (United States)

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

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

Lattice positions of Sn in Cu2ZnSnS4 nanoparticles and thin films studied by synchrotron X-ray absorption near edge structure analysis

Science.gov (United States)

Zillner, E.; Paul, A.; Jutimoosik, J.; Chandarak, S.; Monnor, T.; Rujirawat, S.; Yimnirun, R.; Lin, X. Z.; Ennaoui, A.; Dittrich, Th.; Lux-Steiner, M.

2013-06-01

Lattice positions of Sn in kesterite Cu2ZnSnS4 and Cu2SnS3 nanoparticles and thin films were investigated by XANES (x-ray absorption near edge structure) analysis at the S K-edge. XANES spectra were analyzed by comparison with simulations taking into account anti-site defects and vacancies. Annealing of Cu2ZnSnS4 nanoparticle thin films led to a decrease of Sn at its native and defect sites. The results show that XANES analysis at the S K-edge is a sensitive tool for the investigation of defect sites, being critical in kesterite thin film solar cells.

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

Science.gov (United States)

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

2014-11-01

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

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

Science.gov (United States)

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

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

CERN Document Server

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

2001-01-01

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

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

DEFF Research Database (Denmark)

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

2011-01-01

residue (CR) incorporation and farmyard manure (FYM) application, with equal applications of mineral nutrients were included in the study. In the new data treatment method, internally calibrated spectra of dilute solutions (30 mm) of model compounds were used to fit the sample spectra. This greatly...... the opposite trend was observed. Sulphur XANES spectroscopy of acetylacetone extracts of physically protected and unprotected organic S in two of the soils revealed that physical protection was not related to S speciation; however, intermediate forms of oxidized S species appeared to accumulate in the residual...

Difference between Cr and Ni K-edge XANES spectra of rust layers formed on Fe-based binary alloys exposed to Cl-rich environment

International Nuclear Information System (INIS)

Konishi, Hiroyuki; Mizuki, Jun'ichiro; Yamashita, Masato; Uchida, Hitoshi

2005-01-01

The rust layer formed on weathering steel possesses a strong protective ability against corrosives in an atmospheres. This ability is related to the structure of the rust layer. The difference in the protective ability of a rust layer. The difference in the protective ability of a rust layer in a Cl-rich environment between conventional weathering steel containing Cr and advanced weathering steel containing Ni is believed to be caused by the differences in local structural and chemical properties between alloying elements. Cr and Ni, in the rust layer. In order to examine the effect of these alloying elements on the structure of the rust layer formed on steel in a Cl-rich environment, we have performed Cr and Ni K-edge X-ray absorption near-edge structure (XANES) measurements for the rust layer of Fe-Cr and Fe-Ni binary alloys exposed to a Cl-rich atmosphere using synchrotron radiation. The results of the Cr K-edge XANES measurements for the rust layer of Fe-Cr binary alloys show that the atomic geometry around Cr depends on the concentration of Cr. Therefore, it is expected that the local structure around Cr in the rust layer is unstable. On the other hand, from the results of the Ni K-edge XANES measurements for the rust layer of Fe-Ni binary alloys. Ni is considered to be positioned at a specific site in the crystal structure of a constituent of the rust layer, such as akaganeite or magnetite. As a consequence, Ni negligibly interacts with Cl - ions in the rust layer. (author)

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.

Science.gov (United States)

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

Structure of spinel at high temperature using in-situ XANES study at the Al and Mg K-edge

Energy Technology Data Exchange (ETDEWEB)

Ligny, D de [Universite Claude Bernard Lyon 1, LPCML, 69622 Villeurbanne (France); Neuville, D R [Physique des Mineraux et Magmas, Geochimie-Cosmochimie, CNRS-IPGP, 4 place Jussieu, 75005 Paris (France); Flank, A-M; Lagarde, P, E-mail: deligny@pcml.univ-lyon1.f [Synchrotron SOLEIL, L' Orme des Merisiers, Saint Aubin, 91192 France (France)

2009-11-15

We present structural information obtained on spinel at high temperature (298-2400 K) using in situ XANES at the Mg and Al K-edge. Spinel, {sup [4]}(Al{sub x},Mg{sub 1-x}){sup [6]}(Al{sub 2-x},Mg{sub x})O{sub 4}, with increasing temperature, show a substitution of Mg by Al and Al by Mg in their respective sites. This substitution corresponds to an inversion of the Mg and Al sites. Furthermore, both experiments at the Al and Mg K-edges are in good agreement with XANES calculation made using FDMNES code.

Quantitative Interpretation of X-ray Absorption Near Structure Continuation Progress Report for 1st year 9/15/98-9/14/99

International Nuclear Information System (INIS)

Rehr, John J.; Bare, Simon; Stocht, Joachim

1999-01-01

OAK-B135 Quantitative Interpretation of X-ray Absorption Near Structure Continuation Progress Report for 1st year 9/15/98-9/14/99. This paper proposes to develop two industrial research collaborations to further develop the FEFF8 x-ray spectroscopy code to achieve a quantitative interpretation of x-ray absorption near edge structure (XANES) in materials of interest in energy research: (a) Quantitative interpretation of XANES for heterogeneous catalysts and disordered materials; and (b) quantitative interpretation of white-lines in XANES. The paper also outlines significant results achieved during the first Grant year

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

Energy Technology Data Exchange (ETDEWEB)

Booth, C. H.; Medling, S. A.; Jiang, Yu; Bauer, E. D.; Tobash, P. H.; Mitchell, J. N.; Veirs, D. K.; Wall, M. A.; Allen, P. G.; Kas, J. J.; Sokaras, D.; Nordlund, D.; Weng, T. -C.

2014-06-24

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

K-XANES study of YBa2Cu3O6.96 system

International Nuclear Information System (INIS)

Mishra, A.; Varshney, D.; Shivkumar, K.M.; Pandey, D.

1998-01-01

The copper K-edge x-ray absorption near edge structure (XANES) has been recorded in both CuO and YBaCuO samples on Cauchois type spectrograph with 0.4 m radius of curvature and a laboratory source of x-rays. The sample of YBa 2 Cu 3 ) 6.96 (T c =91K) were prepared by solid state route. The Cu K-XANES measurements were made on the powdered sample. The x-ray parameters, e.g., K-edge shift (ΔE k ), shift of principal absorption maximum (δE K ) and edge-width (δE A ) with reference to metal K-edge have been reported. The value of edge-shift of YBaCuO is larger than parent CuO. Also the smaller value of edge-width in YBaCuO is indicative of its ionic character. (author)

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

Science.gov (United States)

Valotto, Gabrio; Cattaruzza, Elti; Bardelli, Fabrizio

2017-02-01

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

Characterization of phosphorus species in sediments from the Arabian Sea oxygen minimum zone: Combining sequential extractions and X-ray spectroscopy

NARCIS (Netherlands)

Kraal, Peter; Bostick, Benjamin C.; Behrends, Thilo; Reichart, Gert-Jan; Slomp, Caroline P.

2015-01-01

The bulk phosphorus (P) distribution in sediment samples from the oxygen minimum zone of the northern Arabian Sea was determined using two methods: sequential chemical extraction (the ‘SEDEX’ procedure) and X-ray absorption near-edge structure (XANES) spectroscopy of the phosphorus K-edge. Our

Temperature dependent changes of the Mn 3d and 4p bands near $T_{c}$ in Colossal Magnetoresistance systems : a XANES study of $La_{1-x}Ca_{x}MnO_{3}$

NARCIS (Netherlands)

Bridges, F; Booth, C. H.; Kwei, G. H.; Neumeier, J. J.; Sawatzky, G. A.

2000-01-01

Abstract: We report high-resolution X-ray Absorption Near Edge Structure (XANES)measurements at the Mn K-edge as a function of temperature, forLa$_{1-x}$Ca$_x$MnO$_3$ samples, with a focus mainly on the pre-edge region.Small peaks labeled A$_1$-A$_3$ are observed which corresponds to

Vanadium K XANES of synthetic olivine: Valence determinations and crystal orientation effects

International Nuclear Information System (INIS)

Sutton, S.R.; Newville, M.

2005-01-01

Vanadium can exist in a large number of valence states in nature (2+?, 3+, 4+ and 5+) and determinations of V valence is therefore valuable in defining the oxidation states of earth and planetary materials over a large redox range. Synchrotron-based x-ray absorption near edge structure (XANES) spectroscopy is well-suited for measurements of V valence with ∼micrometer spatial resolution and ∼ppm elemental sensitivity. Applications of microXANES have been demonstrated for basaltic glasses. Applications to minerals are feasible but complicated by orientation effects (e.g. due to polarization of the synchrotron x-ray beam) and some results for spinel have been reported. Here we report initial results for olivine from laboratory crystallization ex-periments. The goal is to define the valence partition-ing between olivine and melt and quantify the magnitude of orientation effects, the latter tested by measuring grains at a variety of orientations in the same charge.

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

Science.gov (United States)

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

2017-12-01

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

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

Science.gov (United States)

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

2014-01-01

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

Sn-L3 EDGE and Fe K edge XANES spectra of the surface layer of ancient Chinese black mirror Heiqigu

International Nuclear Information System (INIS)

Gaowei Mengjia; Liu Yuzhen; Chu Wangsheng; Wu Ziyu; Wang Changsui

2009-01-01

The Chinese ancient black mirror known as Heiqigu was studied by x-ray-absorption near-edge structure spectroscopy and results were reported. The Sn-L 3 edge and Fe K edge spectra further confirmed the Schottky-type defect model in the Heiqigu surface system. And it was suggested that the surface layer of the mirror was a combined structure of oxidation of Sn(IV) and Sn(II). (authors)

X-ray absorption near-edge structure of hexagonal ternary phases in sputter-deposited TiAlN films

Energy Technology Data Exchange (ETDEWEB)

Gago, R., E-mail: rgago@icmm.csic.es [Instituto de Ciencia de Materiales de Madrid, Consejo Superior de Investigaciones Científicas, E-28049 Madrid (Spain); Soldera, F. [Department of Materials Science and Engineering, Saarland University, D-66123 Saarbruecken (Germany); Hübner, R.; Lehmann, J.; Munnik, F. [Institute of Ion Beam Physics and Materials Research, Helmholtz-Zentrum Dresden-Rossendorf, D-01314 Dresden (Germany); Vázquez, L. [Instituto de Ciencia de Materiales de Madrid, Consejo Superior de Investigaciones Científicas, E-28049 Madrid (Spain); Redondo-Cubero, A. [Instituto Tecnológico e Nuclear, Instituto Superior Técnico, Universidade Técnica de Lisboa, 2686-953 Sacavém (Portugal); Endrino, J.L. [Instituto de Ciencia de Materiales de Madrid, Consejo Superior de Investigaciones Científicas, E-28049 Madrid (Spain); Abengoa Research S.L., c/Energía Solar 1, Palmas Altas, E-41014 Seville (Spain)

2013-06-05

Highlights: ► Growth of ternary TiAlN films with nearly single-phase wurzite structure. ► Soft X-rays XANES measurements of ternary TiAlN films with wurzite structure. ► Identification of ternary TiAlN hexagonal phases by XANES. ► Correlation of XANES measurements with reported theoretical calculations. -- Abstract: Titanium aluminium nitride (TiAlN) coatings have been grown by reactive (Ar/N{sub 2}) direct-current magnetron sputtering from a Ti{sub 50}Al{sub 50} compound target. The film composition has been quantified by ion beam analysis showing the formation of Al-rich nitrides (Ti/Al ∼ 0.3), with stoichiometric films for N{sub 2} contents in the gas mixture equal or above ∼25%. The surface morphology of the films has been imaged by atomic force microscopy, showing very smooth surfaces with roughness values below 2 nm. X-ray and electron diffraction patterns reveal that the films are nanocrystalline with a wurzite (w) structure of lattice parameters larger (∼2.5%) than those for w-AlN. The lattice expansion correlates with the Ti/Al ratio in stoichiometric films, which suggests the incorporation of Ti into w-AlN. The atomic environments around Ti, Al and N sites have been extracted from the X-ray absorption near-edge structure (XANES) by recording the Ti2p, Al1s and N1s edges, respectively. The analysis of the XANES spectral lineshape and comparison with reported theoretical calculations confirm the formation of a ternary hexagonal phase.

Pressure-induced coordination change of Ti in silicate glass: a XANES study

OpenAIRE

Paris, Eleonora; Dingwell, Donald B.; Seifert, Friedrich; Mottana, Annibale; Romano, Claudia

1994-01-01

The effect of pressure on titanium coordination in glasses, with composition K2TiSi4O11, quenched isobarically from liquids equilibrated at high pressure (5, 10, 15, 20, 25, 30 kbar respectively) and T=1600° C has been investigated by X-ray absorption spectroscopy (XAS). The XANES spectra collected at the Ti K-edge clearly show a variation with pressure that is related to changes in the geometrical environment around the Ti atoms. By comparison with spectra of standard materials, the XANES sp...

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

Science.gov (United States)

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

2018-04-01

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

Fe K-edge XANES of Maya blue pigment

Science.gov (United States)

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

2005-08-01

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

Fe K-edge XANES of Maya blue pigment

International Nuclear Information System (INIS)

Rio, M. Sanchez del; Sodo, A.; Eeckhout, S.G.; Neisius, T.; Martinetto, P.; Dooryhee, E.; Reyes-Valerio, C.

2005-01-01

The utilization of techniques used in Materials Science for the characterization of artefacts of interest for cultural heritage is getting more and more attention nowadays. One of the products of the ancient Maya chemistry is the 'Maya blue' pigment, made with natural indigo and palygorskite. This pigment is different from any other pigment used in other parts of the world. It is durable and acid-resistant, and still keeps many secrets to scientists even though it has been studied for more than 50 years. Although the pigment is basically made of palygorskite Si 8 (Mg 2 Al 2 )O 20 (OH) 2 (OH 2 ) 4 .4H 2 O and an organic colourant (indigo: C 16 H 10 N 2 O 2 ), a number of other compounds have been found in previous studies on archaeological samples, like other clays and minerals, iron nanoparticles, iron oxides, impurities of transition metals (Cr, Mn, Ti, V), etc. We measured at the ESRF ID26 beamline the Fe K-edge XANES spectra of the blue pigment in ancient samples. They are compared to XANES spectra of Maya blue samples synthesized under controlled conditions, and iron oxides usually employed as pigments (hematite and goethite). Our results show that the iron found in ancient Maya blue pigment is related to the Fe exchanged in the palygorskite clay. We did not find iron in metallic form or goethite in archaeological Maya blue

Utilization of synchrotron radiation in analytical chemistry. Soft X-ray emission and absorption spectroscopy

International Nuclear Information System (INIS)

Muramatsu, Yasuji

2015-01-01

Synchrotron soft X-ray spectroscopy includes three major types of spectroscopy such as X-ray absorption spectroscopy (XAS), X-ray emission spectroscopy (XES), and X-ray photoelectron spectroscopy (XPS). This paper takes up XAS and XES of soft X-rays, and briefly describes the principle. XAS is roughly classified into XANES (X-ray absorption near-edge structure) and EXAFS (extended X-ray absorption fine structure), and XANES is mainly used in the analysis based on XAS of soft X-rays. As the examples of the latest soft X-ray analyses, the following are introduced: (1) bandgap of boron implantation diamond and the local structure of boron, (2) catalytic sites in solid fuel cell carbon electrode, and (3) soft X-ray analysis under atmospheric pressure. (A.O.)

Fe K-edge XANES of Maya blue pigment

Energy Technology Data Exchange (ETDEWEB)

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

2005-08-15

The utilization of techniques used in Materials Science for the characterization of artefacts of interest for cultural heritage is getting more and more attention nowadays. One of the products of the ancient Maya chemistry is the 'Maya blue' pigment, made with natural indigo and palygorskite. This pigment is different from any other pigment used in other parts of the world. It is durable and acid-resistant, and still keeps many secrets to scientists even though it has been studied for more than 50 years. Although the pigment is basically made of palygorskite Si{sub 8}(Mg{sub 2}Al{sub 2})O{sub 20}(OH){sub 2}(OH{sub 2}){sub 4}.4H{sub 2}O and an organic colourant (indigo: C{sub 16}H{sub 10}N{sub 2}O{sub 2}), a number of other compounds have been found in previous studies on archaeological samples, like other clays and minerals, iron nanoparticles, iron oxides, impurities of transition metals (Cr, Mn, Ti, V), etc. We measured at the ESRF ID26 beamline the Fe K-edge XANES spectra of the blue pigment in ancient samples. They are compared to XANES spectra of Maya blue samples synthesized under controlled conditions, and iron oxides usually employed as pigments (hematite and goethite). Our results show that the iron found in ancient Maya blue pigment is related to the Fe exchanged in the palygorskite clay. We did not find iron in metallic form or goethite in archaeological Maya blue.

Si K-edge XANES study of SiOxCyHz amorphous polymeric materials

International Nuclear Information System (INIS)

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

2007-01-01

This work reports on x-ray absorption spectroscopy study at the Si K edge of several amorphous SiO x C y H z polymers prepared by plasma-enhanced chemical-vapor deposition with different C/O ratios. SiO 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

X-ray absorption near-edge structure of GaN with high Mn concentration grown on SiC

Science.gov (United States)

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

2009-07-01

By means of x-ray absorption near-edge structure (XANES) several Ga1-xMnxN (0.03edges. All samples studied present a similar Mn ionization state, very close to 2+, and tetrahedral coordination. In order to interpret the near-edge structure, we have performed ab initio calculations using the full potential linear augmented plane wave method as implemented in the Wien2k code. The calculations show the appearance of a Mn bonding \\mathrm {t_{2}}\\uparrow band localized in the gap region, and the corresponding anti-bonding state \\mathrm {t_{2}}\\downarrow , which seem to be responsible for the double structure which appears at the pre-edge absorption region. The shoulders and main absorption peak of the XANES spectra are attributed to transitions from the Mn(1s) band to the conduction bands, which are partially dipole allowed because of the Mn(4p) contribution to these bands.

XANES and XMCD studies of FeRh and CoRh nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Smekhova, A; Wilhelm, F; Rogalev, A [European Synchrotron Radiation Facility, Grenoble Cedex 9, 38043 (France); Atamena, N; Ciuculescu, D; Amiens, C [Laboratoire de Chimie de Coordination, UPR 8241-CNRS, Toulouse Cedex 04, 31077 (France); Lecante, P, E-mail: smeal@esrf.f [Centre d' Elaboration de Materiaux et d' Etudes Structurales, UPR 8011-CNRS, Toulouse Cedex 04, 31055 (France)

2010-01-01

Element-selective magnetic properties of new core-shell bimetallic MRh (M=Fe or Co) nanoparticles (NP{sub S}) of 50/50 composition with either M-Rh or Rh-M core/shell order and an average diameter of {approx}2 nm have been investigated by X-ray Absorption Spectroscopy (XANES) and X-Ray Magnetic Circular Dichroism (XMCD) technique. XANES spectra at the Rh L{sub 2,3} edges exhibit the same characteristic features for all systems having the Rh metal enriched shell. XMCD experiments at the same edges have shown that 4d states of Rh atoms acquire a magnetic moment as a result of hybridization with iron or cobalt 3d states. As expected the value of this induced moment depends on the 3d transition metal and on the core/shell chemical order in the nanoparticle.

The P K-near edge absorption spectra of phosphates

Science.gov (United States)

Franke, R.; Hormes, J.

1995-12-01

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

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

Science.gov (United States)

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.

Transfer characterization of sulfur from coal-burning emission to plant leaves by PIXE and XANES

Energy Technology Data Exchange (ETDEWEB)

Bao, L.M.; Zhang, G.L.; Zhang, Y.X.; Li, Y.; Lin, J.; Liu, W.; Cao, Q.C.; Zhao, Y.D.; Ma, C.Y.; Han, Y. [Chinese Academy of Sciences, Shanghai (China). Shanghai Institute of Applied Physics

2009-11-15

The impact of coal-burning emission on sulfur in camphor leaves was investigated using Proton Induced X-ray Emission (PIXE) and synchrotron radiation technique X-ray Absorption Near-Edge Structure (XANES) spectroscopy. The PIXE results show that the sulfur concentrations in the leaves collected at the polluted site are significantly higher than those in controls. The sulfur XANES spectra show the presence of organic (disulfides, thiols, thioethers, sulfonates and sulfoxides) and inorganic sulfur (sulfates) in the leaves. The inorganic sulfur in the leaves of camphor tree polluted by coal combustion is 15% more than that of the control site. The results suggest that the long-term coal-burning pollution resulted in an enhanced content of the total sulfur and sulfate in the leaves, and the uptake of sulfur by leaves had exceeded the metabolic requirement of plants and the excess of sulfur was stored as SO{sub 4}2{sup -}. It can monitor the sulfur pollution in atmosphere.

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

Energy Technology Data Exchange (ETDEWEB)

Ramakrishnan, Girish; Wu, Qiyuan; Moon, Juhyuk; Orlov, Alexander

2017-07-01

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

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

Science.gov (United States)

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

2007-12-01

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

Correlated XANES, TEM, and NanoSIMS of presolar graphite grains

Science.gov (United States)

Groopman, Evan E.; Nittler, Larry R.

2018-01-01

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

X-ray absorption near-edge structure of GaN with high Mn concentration grown on SiC

Energy Technology Data Exchange (ETDEWEB)

Sancho-Juan, O; Cantarero, A; Garro, N; Cros, A [Materials Science Institute, University of Valencia, PO Box 22085, E46071 Valencia (Spain); Martinez-Criado, G; Salome, M; Susini, J [European Synchrotron Radiation Facility, 6 rue Jules Horowitz, 38043 Grenoble (France); Olguin, D [Dept. de Fisica, CINVESTAV-IPN, 07300 Mexico D F (Mexico); Dhar, S [Experimentalphysik, Universitaet Duisburg-Essen, Lotharstrasse 1, 47057 Duisburg (Germany)

2009-07-22

By means of x-ray absorption near-edge structure (XANES) several Ga{sub 1-x}Mn{sub x}N (0.03edges. All samples studied present a similar Mn ionization state, very close to 2+, and tetrahedral coordination. In order to interpret the near-edge structure, we have performed ab initio calculations using the full potential linear augmented plane wave method as implemented in the Wien2k code. The calculations show the appearance of a Mn bonding t{sub 2}arrow up band localized in the gap region, and the corresponding anti-bonding state t{sub 2}arrow down, which seem to be responsible for the double structure which appears at the pre-edge absorption region. The shoulders and main absorption peak of the XANES spectra are attributed to transitions from the Mn(1s) band to the conduction bands, which are partially dipole allowed because of the Mn(4p) contribution to these bands.

In situ X-ray near-edge absorption spectroscopy investigation of the state of charge of all-vanadium redox flow batteries.

Science.gov (United States)

Jia, Chuankun; Liu, Qi; Sun, Cheng-Jun; Yang, Fan; Ren, Yang; Heald, Steve M; Liu, Yadong; Li, Zhe-Fei; Lu, Wenquan; Xie, Jian

2014-10-22

Synchrotron-based in situ X-ray near-edge absorption spectroscopy (XANES) has been used to study the valence state evolution of the vanadium ion for both the catholyte and anolyte in all-vanadium redox flow batteries (VRB) under realistic cycling conditions. The results indicate that, when using the widely used charge-discharge profile during the first charge process (charging the VRB cell to 1.65 V under a constant current mode), the vanadium ion valence did not reach V(V) in the catholyte and did not reach V(II) in the anolyte. Consequently, the state of charge (SOC) for the VRB cell was only 82%, far below the desired 100% SOC. Thus, such incompletely charged mix electrolytes results in not only wasting the electrolytes but also decreasing the cell performance in the following cycles. On the basis of our study, we proposed a new charge-discharge profile (first charged at a constant current mode up to 1.65 V and then continuously charged at a constant voltage mode until the capacity was close to the theoretical value) for the first charge process that achieved 100% SOC after the initial charge process. Utilizing this new charge-discharge profile, the theoretical charge capacity and the full utilization of electrolytes has been achieved, thus having a significant impact on the cost reduction of the electrolytes in VRB.

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

Energy Technology Data Exchange (ETDEWEB)

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

2016-01-01

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

Speciation of uranium after microbial action by XANES and XPS

International Nuclear Information System (INIS)

Dodge, C.J.; Francis, A.J.; Lu, F.; Halada, G.P.; Kagwade, S.V.; Clayton, C.R.

1993-01-01

The speciation of radionuclides and toxic metals in wastes subjected to microbial action is important in determining the extent of stabilization in a disposal environment. As part of an ongoing study, we investigated the reduction of uranium by a Clostridium sp. using X-ray absorption neat edge spectroscopy (XANES) at the National Synchrotron Light Source (NSLS) and X-ray photoelectron spectroscopy (XPS). XPS analysis of uranyl acetate containing hexavalent uranium exhibited a binding energy of 382.0eV at the U 4f 7/2 peak. The sample incubated in the presence of bacteria was shifted to lower binding energy (380.6eV), confirming the reduction of U 6+ to U 4+ at the bacterial surface. XANES analysis, using an electron yield detector, was performed at the M v absorption edge (3d-->5f). The absorption peak energy of the sample exhibited a shift from 3551.1eV to 3550.1eV which is higher than uranium metal (3549.6eV ) but lower than U 4+ (3550.4eV). This indicates the presence of U 3+ which is probably located beneath the surface within the biomass. Anaerobic bacterial treatment of wastes containing uranyl ion can result in the stabilization of uranium

The Electronic Properties and L3 XANES of Au and Nano-Au

International Nuclear Information System (INIS)

Yiu, Y.M.; Zhang, P.; Sham, T.K.

2004-01-01

The electronic properties of Au crystal and nano Au have been investigated by theory and experiment. Molecularly capped nano-Au was synthesized using the two-phase method. Au nano-particles have been characterized by X-Ray Diffraction (XRD) and Transmission Electron Microscopy (TEM). They retain the fcc crystal structure. Their sizes have been determined to be in a range from 5.5 nm to 1.7 nm. The L3 X-ray Absorption Near Edge Structure (XANES) of nano-Au and Au foil have been recorded using synchrotron radiation, and examined by theoretical calculation based on the first principles. Both theory and experiment show that the nano-Au particles have essentially all the Au L3 XANES features of bulk Au in the near edge region with less pronounced resonance peaks. It is also shown that nano Au exhibits lower 4f binding energy than bulk Au in good agreement with quantum confined Au systems reported previously.

Ce-doped nanoparticles of TiO2: Rutile-to-brookite phase transition and evolution of Ce local-structure studied with XRD and XANES

International Nuclear Information System (INIS)

Kityakarn, Sutasinee; Worayingyong, Attera; Suramitr, Anwaraporn; Smith, M.F.

2013-01-01

The crystal and electronic structural changes undergone by TiO 2 nanoparticles when Ce is introduced were studied using X-ray diffraction (XRD) and X-ray absorption near-edge spectroscopy (XANES). A small amount of Ce (less than 1% molar concentration) resulted in i/a significant reduction of the average size of the TiO 2 nanoparticles and ii/a phase transition in which brookite replaced rutile as the minority phase component (anatase was the majority phase component at all Ce concentrations studied up to 10% molar concentration). The Ce L3 edge XANES revealed changes in the local environment of Ce impurities. As Ce concentration was increased the fraction of Ce that have formal valence of +3 decreased and, for the remaining Ce with valence +4, the 4f orbitals became less-strongly hybridized with the p-orbitals of oxygen neighbors. The results have implications for photocatalytic and gas sensing properties of Ce-doped TiO 2 . - Highlights: ► Ce-doping: TiO 2 nanoparticles shrink and minority phase changes rutile-> brookite. ► XANES reveals phase change for arbitrarily small particles (while XRD fails). ► As Ce added: fraction of Ce +3 dopants falls, hybridization of Ce +4 with O weakens

EXAFS and XANES analysis of oxides at the nanoscale

Directory of Open Access Journals (Sweden)

Alexei Kuzmin

2014-11-01

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

Investigation of the Role of Hole Doping in Different High Temperature Superconducting Systems Using XANES Technique

International Nuclear Information System (INIS)

Hamdan, N.M.; Hasan, A.; Faiz, M.; Salim, M.A.; Hussain, Z.

2004-01-01

X-ray Absorption Near edge Structure (XANES) technique was used to study the role of hole doping in F-doped Hg-1223 and the Ce-doped Tl-1223. Oxygen k-edge and Cu L2,3-edge structures were thoroughly investigated. The pre-edge features of O k-edge spectra, as a function of doping, reveal important information about the projected local density of unoccupied states on the O sites in the region close to the absorption edge, which is a measure of O 2p hole concentration in the valance band. Furthermore, the Cu L2,3 absorption edge provides useful information about the valance state of Cu which is also related to the hole state in the CuO 2 planes. In this work, we will discuss these XANES results in these systems and correlate the observed improvements in the superconducting properties to the electronic structure in the CuO2 planes

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

Science.gov (United States)

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

2013-04-01

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

Atomic-layer-resolved analysis of surface magnetism by diffraction spectroscopy

International Nuclear Information System (INIS)

Matsui, Fumihiko; Matsushita, Tomohiro; Daimon, Hiroshi

2010-01-01

X-ray absorption near edge structure (XANES) and X-ray magnetic circular dichroism (XMCD) measurements by Auger-electron-yield detection are powerful analysis tools for the electronic and magnetic structures of surfaces, but all the information from atoms within the electron mean-free-path range is summed into the obtained spectrum. In order to investigate the electronic and magnetic structures of each atomic layer at subsurface, we have proposed a new method, diffraction spectroscopy, which is the combination of X-ray absorption spectroscopy and Auger electron diffraction (AED). From a series of measured thickness dependent AED patterns, we deduced a set of atomic-layer-specific AED patterns arithmetically. Based on these AED patterns, we succeeded in disentangling obtained XANES and XMCD spectra into those from different atomic layers.

A XANES study of cobalt speciation state in blue-and-white glazes from 16th to 17th century Chinese porcelains

Energy Technology Data Exchange (ETDEWEB)

Figueiredo, M.O., E-mail: ondina.figueiredo@lneg.pt [CENIMAT/I3N, Faculty Sciences and Technology, New University of Lisbon, Campus da Caparica, 2829-516 Caparica (Portugal); National Laboratory of Energy and Geology (LNEG), Apartado 7586, 2721-866 Alfragide (Portugal); Silva, T.P. [National Laboratory of Energy and Geology (LNEG), Apartado 7586, 2721-866 Alfragide (Portugal); CENIMAT/I3N, Faculty Sciences and Technology, New University of Lisbon, Campus da Caparica, 2829-516 Caparica (Portugal); Veiga, J.P. [CENIMAT/I3N, Faculty Sciences and Technology, New University of Lisbon, Campus da Caparica, 2829-516 Caparica (Portugal)

2012-04-15

Highlights: Black-Right-Pointing-Pointer Speciation of cobalt in ancient Chinese porcelain glazes studied by X-ray absorption near-edge spectroscopy. Black-Right-Pointing-Pointer Blue pigmenting role of tetrahedral Co{sup 2+} ions. Black-Right-Pointing-Pointer Uncertainties in deducing a formal valence state for cobalt ions from the edge energy. - Abstract: The composition of cobalt blue pigments used in ancient blue-and-white Chinese glazes is known to have changed between the 14th and the 17th century and ratios of some main chemical components plus trace elements are relevant guide-lines to establish the porcelain manufacture period. Once archaeological findings of Chinese porcelains can contribute to set up dating processes, a study of blue-and-white porcelain shards recovered during recent excavations in Lisbon Old-City was carried out by non-destructive laboratory X-ray fluorescence spectrometry for chemical characterization, combined with X-ray absorption spectroscopy (XAS) using synchrotron radiation to ascertain the formal valence and coordination of pigmenting cobalt ions. Following a preliminary extended X-ray absorption fine-structure study that revealed a coordination of divalent cobalt ions slightly above four, a detailed analysis of the near-edge region of Co 1s X-ray absorption spectra (XANES) was carried out on the blue-and-white glazes from those archaeological Chinese porcelain fragments. Pre-edge features and edge details are discussed in comparison with XANES spectra obtained from model compounds with well known crystal structure - Co{sub 3}O{sub 4}, CoAl{sub 2}O{sub 4} and Co{sub 2}SiO{sub 4}, plus a cobalt-based blue pigment (cerulean). Present chemical data validate the manufacture period of studied Chinese porcelains advanced by Art Historians on the single basis of stylistic features (late 16th and medium 17th century). Spectroscopic results confirm a coordination environment of pigmenting Co{sup 2+} ions close to tetrahedral and

A XANES study of cobalt speciation state in blue-and-white glazes from 16th to 17th century Chinese porcelains

International Nuclear Information System (INIS)

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

2012-01-01

Highlights: ► Speciation of cobalt in ancient Chinese porcelain glazes studied by X-ray absorption near-edge spectroscopy. ► Blue pigmenting role of tetrahedral Co 2+ ions. ► Uncertainties in deducing a formal valence state for cobalt ions from the edge energy. - Abstract: The composition of cobalt blue pigments used in ancient blue-and-white Chinese glazes is known to have changed between the 14th and the 17th century and ratios of some main chemical components plus trace elements are relevant guide-lines to establish the porcelain manufacture period. Once archaeological findings of Chinese porcelains can contribute to set up dating processes, a study of blue-and-white porcelain shards recovered during recent excavations in Lisbon Old-City was carried out by non-destructive laboratory X-ray fluorescence spectrometry for chemical characterization, combined with X-ray absorption spectroscopy (XAS) using synchrotron radiation to ascertain the formal valence and coordination of pigmenting cobalt ions. Following a preliminary extended X-ray absorption fine-structure study that revealed a coordination of divalent cobalt ions slightly above four, a detailed analysis of the near-edge region of Co 1s X-ray absorption spectra (XANES) was carried out on the blue-and-white glazes from those archaeological Chinese porcelain fragments. Pre-edge features and edge details are discussed in comparison with XANES spectra obtained from model compounds with well known crystal structure – Co 3 O 4 , CoAl 2 O 4 and Co 2 SiO 4 , plus a cobalt-based blue pigment (cerulean). Present chemical data validate the manufacture period of studied Chinese porcelains advanced by Art Historians on the single basis of stylistic features (late 16th and medium 17th century). Spectroscopic results confirm a coordination environment of pigmenting Co 2+ ions close to tetrahedral and substantiate the dual role of cobalt as network former plus modifier in the glaze of ancient Chinese porcelains.

Polarized X-ray absorption spectroscopy of single-crystal Mn(V) complexes relevant to the oxygen-evolving complex of photosystem II

DEFF Research Database (Denmark)

Yano, Junko; Robblee, John; Pushkar, Yulia

2007-01-01

High-valent Mn-oxo species have been suggested to have a catalytically important role in the water splitting reaction which occurs in the Photosystem II membrane protein. In this study, five- and six-coordinate mononuclear Mn(V) compounds were investigated by polarized X-ray absorption spectroscopy...... structure of the metal site was then studied by measuring the polarization dependence of X-ray absorption near-edge spectroscopy (XANES) pre-edge spectra (1s to 3d transition) and comparing with the results of density functional theory (DFT) calculations. The Mn(V)-nitrido compound, in which the manganese......-edge peak. This component was interpreted as a 1s to 3d(xz,yz) transition with 4px,y mixing, due to the displacement of the Mn atom out of the equatorial plane. The XANES results have been correlated to DFT calculations, and the spectra have been simulated using a TD (time-dependent)-DFT approach...

Surface structure of alpha-Fe sub 2 O sub 3 nanocrystal observed by O K-edge X-ray absorption spectroscopy

CERN Document Server

Zhang, J; Ibrahim, K; Abbas, M I; Ju, X

2003-01-01

X-ray absorption near edge structure (XANES) spectra is used as a probe of surface structure of alpha-Fe sub 2 O sub 3 nanocrystal, prepared by sol-gel method. We present O K-edge XANES of alpha-Fe sub 2 O sub 3 in nanocrystal and bulk by total electron yield at the photoemission station of Beijing Synchrotron Radiation Facility. The spectrum of alpha-Fe sub 2 O sub 3 shows a splitting of the pre-edge structure, which is interpreted as two subsets of Fe 3d t sub 2 sub g and e sub g orbitals in oxygen octahedral (O sub h) crystal field, and is also sensitive to long-range order effects. However, no distinguishable splitting of the pre-edge peak of nanocrystal alpha-Fe sub 2 O sub 3 is observed. This suggests that there exists the distorted octahedral coordination around Fe sites and also the long-range disorder due to the surface as compared with bulk alpha-Fe sub 2 O sub 3.

In situ XANES studies of TiO{sub 2}/Fe{sub 3}O{sub 4}-C during photocatalytic degradation of trichloroethylene

Energy Technology Data Exchange (ETDEWEB)

Hsu, T.-F.; Hsiung, T.-L. [Department of Environmental Engineering, National Cheng Kung University, Tainan 70101, Taiwan (China); Wang, James [Department of Biomedical Engineering, University of Southern California, Los Angeles 90007 (United States); Huang, C.-H. [Department of Environmental Engineering, National Cheng Kung University, Tainan 70101, Taiwan (China); Paul Wang, H., E-mail: wanghp@mail.ncku.edu.t [Department of Environmental Engineering, National Cheng Kung University, Tainan 70101, Taiwan (China); Sustainable Environmental Research Center, National Cheng Kung University, Tainan 70101, Taiwan (China)

2010-07-21

Mainly anatase and Fe{sub 3}O{sub 4} in the magnetic photocatalysts (TiO{sub 2} on Fe{sub 3}O{sub 4}-C core-shell nanoparticles (TiO{sub 2}/Fe{sub 3}O{sub 4}-C)) are observed by X-ray powder diffraction (XRD) spectroscopy. The Ti K-edge least-square fitted XANES spectra of the TiO{sub 2}/Fe{sub 3}O{sub 4}-C photocatalyst indicate that the main titanium species are nanosize TiO{sub 2} (9 nm) (77%) and bulky TiO{sub 2} (23%). Speciation of titanium in the TiO{sub 2}/Fe{sub 3}O{sub 4}-C during photocatalytic degradation of 100 ppm of trichloroethylene (TCE) has also been studied by in situ X-ray absorption near-edge structural (XANES) spectroscopy. TiO{sub 2} is not perturbed during the course of photocatalysis. However, it is worth to note that during photocatalytic degradation of TCE, about 33% of FeO and 67% of Fe{sub 3}O{sub 4} are observed in the photocatalyst. It seems that the carbon layer on the TiO{sub 2}/Fe{sub 3}O{sub 4}-C photocatalysts can reduce the possibility for photoexcited electron-hole recombination as usually found on the relatively narrow bandgap of ferric oxide during photocatalysis.

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

Energy Technology Data Exchange (ETDEWEB)

Flank, A-M; Trcera, N; Itie, J-P; Lagarde, P [Synchrotron Soleil, L' Orme des Merisiers, BP 48, 91192 Gif sur Yvette (France); Brunet, F [Laboratoire de Geologie, CNRS-ENS-UMR8538, 24 rue Lhommond, 75005 Paris (France); Irifune, T [Geodynamics Research Center, Ehime University, Matsuyama 790-8577 (Japan)

2009-11-15

Phosphorus, a group V element, has always been found so far in minerals, biological systems and synthetic compounds with an oxygen coordination number of four (i.e, PO{sub 4} groups). We demonstrate here using phosphorus K-edge XANES spectroscopy that this element can also adopt a six-fold oxygen coordination (i.e, PO{sub 6} groups). This new coordination was achieved in AlPO{sub 4} doped SiO{sub 2} stishovite synthesized at 18 GPa and 1873 K and quenched down to ambient conditions. The well-crystallized P-bearing stishovite grains (up to 100{mu}m diameter) were embedded in the back-transformation products of high pressure form of AlPO{sub 4} matrix. They were identified by elemental mapping ({mu}-XRF). {mu}-XANES spectra collected at the Si and P K edges in the Si rich region with a very low concentration of P present striking resemblance, Si itself being characteristic of pure stishovite. We can therefore infer that phosphorus in the corresponding stishovite crystal is involved in an octahedral coordination made of six oxygen atoms. First principle XANES calculations using a plane-wave density functional formalism with core-hole effects treated in a supercell approach at the P K edge for a P atom substituting an Si one in the stishovite structure confirm this assertion. This result shows that in the lower-mantle where all silicon is six-fold coordinated, phosphorus has the crystal-chemical ability to remain incorporated into silicate structures.

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

Science.gov (United States)

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

2009-11-01

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

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

International Nuclear Information System (INIS)

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

2009-01-01

Phosphorus, a group V element, has always been found so far in minerals, biological systems and synthetic compounds with an oxygen coordination number of four (i.e, PO 4 groups). We demonstrate here using phosphorus K-edge XANES spectroscopy that this element can also adopt a six-fold oxygen coordination (i.e, PO 6 groups). This new coordination was achieved in AlPO 4 doped SiO 2 stishovite synthesized at 18 GPa and 1873 K and quenched down to ambient conditions. The well-crystallized P-bearing stishovite grains (up to 100μm diameter) were embedded in the back-transformation products of high pressure form of AlPO 4 matrix. They were identified by elemental mapping (μ-XRF). μ-XANES spectra collected at the Si and P K edges in the Si rich region with a very low concentration of P present striking resemblance, Si itself being characteristic of pure stishovite. We can therefore infer that phosphorus in the corresponding stishovite crystal is involved in an octahedral coordination made of six oxygen atoms. First principle XANES calculations using a plane-wave density functional formalism with core-hole effects treated in a supercell approach at the P K edge for a P atom substituting an Si one in the stishovite structure confirm this assertion. This result shows that in the lower-mantle where all silicon is six-fold coordinated, phosphorus has the crystal-chemical ability to remain incorporated into silicate structures.

An X-ray absorption near-edge structure (XANES) study of the Sn L_3 edge in zirconium alloy oxide films formed during autoclave corrosion

International Nuclear Information System (INIS)

Hulme, Helen; Baxter, Felicity; Babu, R. Prasath; Denecke, Melissa A.; Gass, Mhairi; Steuwer, Axel; Norén, Katarina; Carlson, Stefan; Preuss, Michael

2016-01-01

Highlights: • Characterisation of tin speciation in zirconium alloy metal and oxide films using Sn L_3-XANES. • Chemical environment of tin in Zircaloy-4 and ZIRLO™ oxide films shown to be similar. • Tin in the oxide films is present in both the di- and tetravalent states and oxidises progressively with oxide-layer growth. - Abstract: Application of Sn L_3-XANES to study the oxidation state of alloying additions of tin (1–1.2 wt%) in <2 μm oxide layers formed on nuclear grade zirconium alloy has been demonstrated. Data obtained for metallic and corroded ZIRLO™ (1 wt% Sn) and Zircaloy-4 (1.2 wt% Sn) indicate tin has a similar chemical speciation in both metal alloys but this differs in the oxidised surface layers. By recording XANES at various incident angles to vary the photon penetration depth and amount of the oxide layer probed in the measurement, the authors found evidence that the oxidation of tin progresses with increasing oxide thickness.

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

Science.gov (United States)

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

2014-01-01

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

Scanning tunneling microscopy and spectroscopy studies of graphite edges

International Nuclear Information System (INIS)

Niimi, Y.; Matsui, T.; Kambara, H.; Tagami, K.; Tsukada, M.; Fukuyama, Hiroshi

2005-01-01

We studied experimentally and theoretically the electronic local density of states (LDOS) near single-step edges at the surface of exfoliated graphite. In scanning tunneling microscopy measurements, we observed the (3x3)R30 o and honeycomb superstructures extending over 3-4-bar nm both from the zigzag and armchair edges. Calculations based on a density-functional-derived non-orthogonal tight-binding model show that these superstructures can coexist if the two types of edges admix each other in real graphite step edges. Scanning tunneling spectroscopy measurements near the zigzag edge reveal a clear peak in the LDOS at an energy below the Fermi energy by 20-bar meV. No such a peak was observed near the armchair edge. We concluded that this peak corresponds to the 'edge state' theoretically predicted for graphene ribbons, since a similar prominent LDOS peak due to the edge state is obtained by the first principles calculations

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.

Science.gov (United States)

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. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

International Nuclear Information System (INIS)

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

2008-01-01

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 Fe 2+ in the bulk glass of the vessels, and in the oxidized form Fe 3+ in the decorations, indicating that these glass artefacts were produced in at least two distinct processing steps under different furnace conditions. (orig.)

Study on atomic and electronic structures of ceramic materials using spectroscopy, microscopy, and first principles calculation

International Nuclear Information System (INIS)

Mizoguchi, Teruyasu

2011-01-01

In this review, following two topics are introduced: 1) experimental and theoretical electron energy loss (EEL) near edge structures (ELNES) and X-ray absorption near edge structures (XANES), and 2) atomic and electronic structure analysis of ceramic interface by combing spectroscopy, microscopy, and first principles calculation. In the ELNES/XANES calculation, it is concluded that inclusion of core-hole effect in the calculation is essential. By combining high energy resolution observation and theoretical calculation, detailed analysis of the electronic structure is achieved. In addition, overlap population (OP) diagram is used to interpret the spectrum. In the case of AlN, sharp and intense first peak of N-K edge is found to reflect narrow dispersion of the conduction band bottom. By applying ELNES and the OP diagram to Cu/Al 2 O 3 heterointerface, it is revealed that intensity of prepeak in O-K edge is inverse proportional to interface strength. The relationships between atomic structure and defect energetics at SrTiO 3 grain boundary are also investigated, and reveal that the formation behavior of Ti vacancy is sensitive to the structural distortion. In addition, by using state-of-the-art spectroscopy, microscopy, and first principles calculations, atomic scale visualization of fluorine dopant in LaFeOAs and first principles calculation of HfO 2 phase transformation are demonstrated. (author)

XANES investigation of Chinese faience excavated from Peng State Cemetery site in Western Zhou Period (BC1046–BC771)

International Nuclear Information System (INIS)

Hao, Wentao; Yang, Yimin; Zhu, Jian; Gu, Zhou; Xie, Yaoting; Zhang, Jing; Wang, Lihua

2014-01-01

Highlights: • We analyzed faience of Peng State archaeological cemetery site in Western Zhou Dynasty (BC1046–BC771). • We investigated the chemical composition and oxidation state by energy dispersive X-ray fluorescence (EDXRF) and X-ray absorption near edge spectroscopy (XANES), respectively. • The coloring element in both beads is copper in +2 valence, and the color divergence of these two beads may originate from different local chemical environments of Cu 2+ . • Chinese faience in this period is the earliest glaze with copper colorant. - Abstract: As a special kind of glazed ceramic, faience has an important role to play in the technological trajectory that eventually leads to the development of ancient glass. In China, faience products first emerged in early Western Zhou Dynasty (1046BC–771BC), and their great significance as well as brilliant colors varying between blue and green attracted a lot of scholars. However, scientific researches on the color source of Chinese faience in view of microstructure characterization are quite few. In the present work, analyses by energy dispersive X-ray fluorescence (EDXRF) and X-ray absorption near edge spectroscopy (XANES) were carried out on two faience beads with relatively blue and green color, respectively, both of which were excavated from Peng State archaeological cemetery site in Western Zhou Dynasty. The results show that the coloring element in both beads is copper with +2 valence, and the color divergence of these two beads may originate from different local chemical environments of Cu 2+ . It is suggested that the faience in this period is the earliest glaze with copper colorant in China

XANES investigation of Chinese faience excavated from Peng State Cemetery site in Western Zhou Period (BC1046–BC771)

Energy Technology Data Exchange (ETDEWEB)

Hao, Wentao; Yang, Yimin [Key Laboratory of Vertebrate Evolution and Human Origins of Chinese Academy of Sciences, Institute of Vertebrate Paleontology and Paleoanthropology, Chinese Academy of Sciences, Beijing 100044 (China); Department of Scientific History and Archaeometry, University of Chinese Academy of Sciences, Beijing 100049 (China); Zhu, Jian, E-mail: jzhu@ucas.ac.cn [Key Laboratory of Vertebrate Evolution and Human Origins of Chinese Academy of Sciences, Institute of Vertebrate Paleontology and Paleoanthropology, Chinese Academy of Sciences, Beijing 100044 (China); Department of Scientific History and Archaeometry, University of Chinese Academy of Sciences, Beijing 100049 (China); Gu, Zhou [Key Laboratory of Vertebrate Evolution and Human Origins of Chinese Academy of Sciences, Institute of Vertebrate Paleontology and Paleoanthropology, Chinese Academy of Sciences, Beijing 100044 (China); Department of Scientific History and Archaeometry, University of Chinese Academy of Sciences, Beijing 100049 (China); Xie, Yaoting [Institute of Archaeology of Shanxi Province, Taiyuan 030001 (China); Zhang, Jing [Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China); Wang, Lihua [Shanghai Synchrotron Radiation Facility, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201204 (China)

2014-10-15

Highlights: • We analyzed faience of Peng State archaeological cemetery site in Western Zhou Dynasty (BC1046–BC771). • We investigated the chemical composition and oxidation state by energy dispersive X-ray fluorescence (EDXRF) and X-ray absorption near edge spectroscopy (XANES), respectively. • The coloring element in both beads is copper in +2 valence, and the color divergence of these two beads may originate from different local chemical environments of Cu{sup 2+}. • Chinese faience in this period is the earliest glaze with copper colorant. - Abstract: As a special kind of glazed ceramic, faience has an important role to play in the technological trajectory that eventually leads to the development of ancient glass. In China, faience products first emerged in early Western Zhou Dynasty (1046BC–771BC), and their great significance as well as brilliant colors varying between blue and green attracted a lot of scholars. However, scientific researches on the color source of Chinese faience in view of microstructure characterization are quite few. In the present work, analyses by energy dispersive X-ray fluorescence (EDXRF) and X-ray absorption near edge spectroscopy (XANES) were carried out on two faience beads with relatively blue and green color, respectively, both of which were excavated from Peng State archaeological cemetery site in Western Zhou Dynasty. The results show that the coloring element in both beads is copper with +2 valence, and the color divergence of these two beads may originate from different local chemical environments of Cu{sup 2+}. It is suggested that the faience in this period is the earliest glaze with copper colorant in China.

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

International Nuclear Information System (INIS)

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

2016-01-01

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 L 3 and M 4 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-O axial bond length for the magnetite compared to the maghemite system are present too. (paper)

Femtosecond X-ray Absorption Spectroscopy at a Hard X-ray Free Electron Laser

DEFF Research Database (Denmark)

Lemke, Henrik T.; Bressler, Christian; Chen, Lin X.

2013-01-01

X-ray free electron lasers (XFELs) deliver short (current (SASE based) XFELs, they can be used for measuring high......-quality X-ray absorption data and we report femtosecond time-resolved X-ray absorption near-edge spectroscopy (XANES) measurements of a spin-crossover system, iron(II) tris(2,2'-bipyridine) in water. The data indicate that the low-spin to high-spin transition can be modeled by single-exponential kinetics...

X-ray and vibrational spectroscopy of manganese complexes relevant to the oxygen-evolving complex of photosynthesis

Energy Technology Data Exchange (ETDEWEB)

Visser, Hendrik [Univ. of California, Berkeley, CA (United States)

2001-01-01

Manganese model complexes, relevant to the oxygen-evolving complex (OEC) in photosynthesis, were studied with Mn K-edge X-ray absorption near-edge spectroscopy (XANES), Mn Kb X-ray emission spectroscopy (XES), and vibrational spectroscopy. A more detailed understanding was obtained of the influence of nuclearity, overall structure, oxidation state, and ligand environment of the Mn atoms on the spectra from these methods. This refined understanding is necessary for improving the interpretation of spectra of the OEC. Mn XANES and Kb XES were used to study a di-(mu)-oxo and a mono-(mu)-oxo di-nuclear Mn compound in the (III,III), (III,IV), and (IV,IV) oxidation states. XANES spectra show energy shifts of 0.8 - 2.2 eV for 1-electron oxidation-state changes and 0.4 - 1.8 eV for ligand-environment changes. The shifts observed for Mn XES spectra were approximately 0.21 eV for oxidation state-changes and only approximately 0.04 eV for ligand-environment changes. This indicates that Mn Kb XES i s more sensitive to the oxidation state and less sensitive to the ligand environment of the Mn atoms than XANES. These complimentary methods provide information about the oxidation state and the ligand environment of Mn atoms in model compounds and biological systems. A versatile spectroelectrochemical apparatus was designed to aid the interpretation of IR spectra of Mn compounds in different oxidation states. The design, based on an attenuated total reflection device, permits the study of a wide spectral range: 16,700 (600 nm) - 225

Soft X-ray excited colour-centre luminescence and XANES studies of calcium oxide

International Nuclear Information System (INIS)

Ko, J.Y.P.; Heigl, F.; Yiu, Y.M.; Zhou, X.-T.; Regier, T.; Blyth, R.I.R.; Sham, T.-K.

2007-01-01

In this study, we show that colour centres can be produced by irradiating calcium oxide with soft X-rays from a synchrotron radiation source. Using the X-ray excited optical Iuminescence (XEOL) technique, two colour centres, F-centre, and F + -centre can be identified. These colour centres emit photons at characteristic wavelengths. In addition, by performing time-resolved XEOL (TRXEOL), we are able to reveal timing and decay characteristics of the colour centres. We also present X-ray absorption near-edge structure (XANES) spectra collected across oxygen K-edge, calcium L 3,2 -edge, and calcium K-edge. Experimental results are compared with density functional theory (DFT) calculations. (author)

Structural study of thin films prepared from tungstate glass matrix by Raman and X-ray absorption spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Montanari, Bianca; Barbosa, Anne J.; Ribeiro, Sidney J.L.; Messaddeq, Younes [Departamento de Quimica Geral e Inorganica, Instituto de Quimica, UNESP, CP 355, CEP 14800-900 Araraquara, SP (Brazil); Poirier, Gael [Departamento de Ciencias Exatas, UNIFAL-MG, CEP 37130-000 Alfenas, MG (Brazil)], E-mail: gael@unifal-mg.edu.br; Li, Maximo S. [Instituto de Fisica, USP, CP 369, CEP 13560-970 Sao Carlos, SP (Brazil)

2008-06-30

Thin films were prepared using glass precursors obtained in the ternary system NaPO{sub 3}-BaF{sub 2}-WO{sub 3} and the binary system NaPO{sub 3}-WO{sub 3} with high concentrations of WO{sub 3} (above 40% molar). Vitreous samples have been used as a target to prepare thin films. Such films were deposited using the electron beam evaporation method onto soda-lime glass substrates. Several structural characterizations were performed by Raman spectroscopy and X-ray Absorption Near Edge Spectroscopy (XANES) at the tungsten L{sub I} and L{sub III} absorption edges. XANES investigations showed that tungsten atoms are only sixfold coordinated (octahedral WO{sub 6}) and that these films are free of tungstate tetrahedral units (WO{sub 4}). In addition, Raman spectroscopy allowed identifying a break in the linear phosphate chains as the amount of WO{sub 3} increases and the formation of P-O-W bonds in the films network indicating the intermediary behavior of WO{sub 6} octahedra in the film network. Based on XANES data, we suggested a new attribution of several Raman absorption bands which allowed identifying the presence of W-O{sup -} and W=O terminal bonds and a progressive apparition of W-O-W bridging bonds for the most WO{sub 3} concentrated samples (above 40% molar) attributed to the formation of WO{sub 6} clusters.

Determination of redox-active centers in praseodymium doped ceria by in situ-XANES spectroscopy

DEFF Research Database (Denmark)

Kiebach, Wolff-Ragnar; Chatzichristodoulou, Christodoulos; Werchmeister, Rebecka Maria Larsen

2012-01-01

Praseodymium doped ceria, a material of interest for electrochemical flue gas purification, was investigated with in situ X-ray Absorption Near Edge Structure spectroscopy between room temperature and 500°C in air and diluted nitrogen(II) oxide (NO/Ar) (1% NO in Ar). For temperatures above 400°C...

Characterization of iron speciation in urban and rural single particles using XANES spectroscopy and micro X-ray fluorescence measurements: investigating the relationship between speciation and fractional iron solubility

OpenAIRE

Oakes, M.; Weber, R. J.; Lai, B.; Russell, A.; Ingall, E. D.

2012-01-01

Soluble iron in fine atmospheric particles has been identified as a public health concern by participating in reactions that generate reactive oxygen species (ROS). The mineralogy and oxidation state (speciation) of iron have been shown to influence fractional iron solubility (soluble iron/total iron). In this study, iron speciation was determined in single particles at urban and rural sites in Georgia USA using synchrotron-based techniques, such as X-ray Absorption Near-Edge Structure (XANES...

HIGHER ORDER SPECIATION EFFECTS ON PLUTONIUM L3 X-RAY ABSORPTION NEAR EDGE SPECTRA.

Energy Technology Data Exchange (ETDEWEB)

Conradson, Steven D.; Abney, Kent D.; Begg, Bruce D.; Brady, Erik D.; Clark, David L.; den Auwer, Christophe; Ding, Mei; Dorhout, Peter K.; Espinosa-Faller, Francisco J.; Gordon, Pamela L.; Hess, Nancy J.; Hess, Ryan F.; Keogh, D. Webster; Lander, Gerard H.; Lupinetti, Anthony J.; Neu, Mary P.; Palmer, Phillip D.; Paviet-Hartmann, Patricia; Reilly, Sean D.; Runde, Wolfgang H.; Tait, C. Drew; Veirs, D. Kirk

2003-06-09

Pu L{sub 3} X-ray Near Edge Absorption Spectra for Pu(0-VII) are reported for more than 50 chalcogenides, chlorides, hydrates, hydroxides, nitrates, carbonates, oxy-hydroxides, and other compounds both as solids and in solution, and substituted in zirconlite, perovksite, and borosilicate glass. This large data base extends the known correlations between the energy and shape of these spectra from the usual association of the XANES with valence and site symmetry to higher order chemical effects. Because of the large number of compounds of these different types a number of novel and unexpected behaviors are observed.

Modeling of XANES-spectra with the FEFF-program

Energy Technology Data Exchange (ETDEWEB)

Bosman, E; Thieme, J, E-mail: e.bosman@gmx.d, E-mail: jthieme@gwdg.d [Institute for X-Ray Physics, Georg-August-University Gottingen, Friedrich-Hund-Platz 1, 37077 Gottingen (Germany)

2009-09-01

The aim of this project is the calculation of the absorption coefficient {mu} of x-ray absorption spectra as a function of energy and a comparison with experimental data. A characteristic fine structure can be found in x-ray absorption spectra (XAS) consisting of the XANES (X-Ray Absorption Near Edge Structure) and the EXAFS (Extended X-Ray Absorption Fine Structure) region. XANES is characterized by multiple scattering and provides information about coordination chemistry and bonding angles of the irradiated sample. The program FEFF 8.4 was used for the calculations of the absorption K-edge spectra. FEFF was generated for ab initio multiple scattering calculations of X-ray Absorption Fine Structure (XAFS) of atom-clusters. The code yields scattering amplitudes, phases and other quantities. We computed {mu} at the K-edge of several elements like Ti, S and Fe. For this purpose, clusters of Na{sub 2}SO{sub 4}, Ba{sub 2}TiO{sub 4}, FeS{sub 2}, CaSO{sub 2} 2(H {sub 2}O) were used, working with several space groups. Some of the calculations are consistent with the results of the experiments, but others show energy shifts in the range of some eV. In summary, the FEFF calculations and the experimental data exhibit similarities as well as deviations. By using trimming parameters, deviations could be eliminated to a certain extent, which will be presented.

Analysis of electronic structure of amorphous InGaZnO/SiO2 interface by angle-resolved X-ray photoelectron spectroscopy

International Nuclear Information System (INIS)

Ueoka, Y.; Ishikawa, Y.; Maejima, N.; Matsui, F.; Matsui, H.; Yamazaki, H.; Urakawa, S.; Horita, M.; Daimon, H.; Uraoka, Y.

2013-01-01

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

Structural investigations of LiFePO4 electrodes and in situ studies by Fe X-ray absorption spectroscopy

International Nuclear Information System (INIS)

Deb, Aniruddha; Bergmann, Uwe; Cramer, S.P.; Cairns, Elton J.

2005-01-01

Fe K-edge X-ray absorption near edge spectroscopy (XANES) and extended X-ray absorption fine structure (EXAFS) have been performed on electrodes containing LiFePO 4 to determine the local atomic and electronic structure and their stability with electrochemical cycling. A versatile electrochemical in situ cell has been constructed for long-term soft and hard X-ray experiments for the structural investigation on battery electrodes during the lithium-insertion/extraction processes. The device is used here for an X-ray absorption spectroscopic study of lithium insertion/extraction in a LiFePO 4 electrode, where the electrode contained about 7.7 mg of LiFePO 4 on a 20 μm thick Al-foil. Fe K-edge X-ray absorption near edge spectroscopy (XANES) and extended X-ray absorption fine structure (EXAFS) have been performed on this electrode to determine the local atomic and electronic structure and their stability with electrochemical cycling. The initial state (LiFePO 4 ) showed iron to be in the Fe 2+ state corresponding to the initial state (0.0 mAh) of the cell, whereas in the delithiated state (FePO 4 ) iron was found to be in the Fe 3+ state corresponding to the final charged state (3 mAh). XANES region of the XAS spectra revealed a high spin configuration for the two states (Fe (II), d 6 and Fe (III), d 5 ). The results confirm that the olivine structure of the LiFePO 4 and FePO 4 is retained by the electrodes in agreement with the XRD observations reported previously. These results confirm that LiFePO 4 cathode material retains good structural short-range order leading to superior cycling capability

Redox Chemisty of Tantalum Clusters on Silica Characterized by X-ray Absorption Spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Nemana,S.; Gates, B.

2006-01-01

SiO{sub 2}-supported clusters of tantalum were synthesized from adsorbed Ta(CH{sub 2}Ph){sub 5} by treatment in H{sub 2} at 523 K. The surface species were characterized by X-ray absorption spectroscopy (extended X-ray absorption fine structure (EXAFS) spectroscopy and X-ray absorption near edge spectroscopy (XANES)) and ultraviolet-visible spectroscopy. The EXAFS data show that SiOO{sub 2}-supported tantalum clusters were characterized by a Ta-Ta coordination number of approximately 2, consistent with the presence of tritantalum clusters, on average. When these were reduced in H{sub 2} and reoxidized in O{sub 2}, the cluster nuclearity remained essentially unchanged, although reduction and oxidation occurred, respectively, as shown by XANES and UV-vis spectra; in the reoxidation, the tantalum oxidation state change was approximately two electronic charges per tritantalum cluster. The data demonstrate an analogy between the chemistry of group 5 metals on the SiO{sub 2} support and their chemistry in solution, as determined by the group of Cotton.

Characterization of rust layer formed on Fe, Fe-Ni and Fe-Cr alloys exposed to Cl-rich environment by Cl and Fe K-edge XANES measurements

International Nuclear Information System (INIS)

Konishi, Hiroyuki; Mizuki, Jun'ichiro; Yamashita, Masato; Uchida, Hitoshi

2005-01-01

Chloride in atmosphere considerably reduces the corrosion resistance of conventional weathering steel containing a small amount of Cr. Ni is an effective anticorrosive element for improving the corrosion resistance of steel in a Cl-rich environment. In order to clarify the structure of the protective rust layer of weathering steel, Cl and Fe K-edge X-ray absorption near edge structure (XANES) spectra of atmospheric corrosion products (rust) formed on Fe, Fe-Ni and Fe-Cr alloys exposed to Cl-rich atmosphere were measured. The Fe K-XANES measurements enable the characterization of mixture of iron oxides such as rust. The chemical composition of the rust was determined by performing pattern fitting of the measured spectra. All the rust is composed mainly of goethite, akaganeite, lepidocrocite and magnetite. Among these iron oxides, akaganeite in particular is the major component in the rust. Additionally, the amount of akaganeite in the rust of Fe-Ni alloy is much greater than that in rust of Fe-Cr alloy. Akaganeite is generally considered to facilitate the corrosion of steel, but our results indicate that akaganeite in the rust of Fe-Ni alloy is quantitatively different from that in rust of Fe-Cr alloy and does not facilitate the corrosion of steel. The shoulder peak observed in Cl K-XANES spectra reveals that the rust contains a chloride other than akaganeite. The energy of the shoulder peak does not correspond to that of any well-known chlorides. In the measured spectra, there is no proof that Cl, by combining with the alloying element, inhibits the alloying element from acting in corrosion resistance. The shoulder peak appears only when the content of the alloying element is lower than a certain value. This suggests that the generation of the unidentified chloride is related to the corrosion rate of steel. (author)

Effect of metal ion on the structure and function of LiPDF: The study of the fine structure around the metal site using XANES

International Nuclear Information System (INIS)

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

2010-01-01

We used X-ray absorption near edge structure (XANES) spectroscopy to investigate the metal-dependent enzymatic activity of the peptide deformylase from Leptospira interrogans (LiPDF). Ab initio full multiple scattering calculations performed by MXAN are applied to obtain the local structure of the cobalt-containing LiPDF (Co-LiPDF) and zinc-containing LiPDF (Zn-LiPDF) around the metal sites in pH9.0 buffer solution. The result shows the cobalt-wat1 (the bond water molecule) distance of Co-LiPDF is 1.89 A, much shorter than that of Zn-LiPDF, 2.50 A. That is an essential factor for its low catalytic activity.

Effect of metal ion on the structure and function of LiPDF: The study of the fine structure around the metal site using XANES

Energy Technology Data Exchange (ETDEWEB)

Wang Yu [Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China); National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei 230029 (China); Chu Wangsheng, E-mail: cws@ihep.ac.c [Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China); Yang Feifei; Yu Meijuan; Zhao Haifeng [Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China); Gong Weimin [National Laboratory of Biomacromolecules, Institute of Biophysics, Chinese Academy of Sciences, Beijing 100101 (China); Dong Yuhui; Xie Yaning [Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China); Wu, Ziyu, E-mail: wuzy@ustc.edu.c [National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei 230029 (China); Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China)

2010-07-21

We used X-ray absorption near edge structure (XANES) spectroscopy to investigate the metal-dependent enzymatic activity of the peptide deformylase from Leptospira interrogans (LiPDF). Ab initio full multiple scattering calculations performed by MXAN are applied to obtain the local structure of the cobalt-containing LiPDF (Co-LiPDF) and zinc-containing LiPDF (Zn-LiPDF) around the metal sites in pH9.0 buffer solution. The result shows the cobalt-wat1 (the bond water molecule) distance of Co-LiPDF is 1.89 A, much shorter than that of Zn-LiPDF, 2.50 A. That is an essential factor for its low catalytic activity.

A structural study of ceramic oxides by X-ray absorption spectroscopy

International Nuclear Information System (INIS)

Akhtar, M.J.

1995-01-01

A detailed structural study of ceramic oxides is presented by employing X-ray Absorption Spectroscopy (XAS). In the present work X-ray Absorption Near Edge Structure (XANES) is used for the investigation of valence state of metal cations; whereas, Extended X-ray Absorption Fine Structure EXAFS) is employed for the determination for bond lengths, coordination numbers and nature of the elements present in the near neighbour shells surrounding the absorbing atom. These results show that local environment of dopant and host cations are different; and this variation in local structure depends on the nature and concentration of the dopant ions. (author)

Mn L2,3-edge X-ray absorption spectroscopic studies on charge-discharge mechanism of Li2MnO3

International Nuclear Information System (INIS)

Kubobuchi, Kei; Mogi, Masato; Imai, Hideto; Ikeno, Hidekazu; Tanaka, Isao; Mizoguchi, Teruyasu

2014-01-01

The redox reaction of Mn in Li 2 MnO 3 was studied by X-ray absorption spectroscopy and ab initio multiplet calculation. Associated with the de-intercalation of Li-ion, small but clear spectral changes were observed in Mn-L 2,3 X-ray absorption near edge structure (XANES). The systematic ab initio multiplet calculations of Mn-L 2,3 XANES revealed that the spectral changes in the experiment could not simply be ascribed to the change of the valency from Mn 4+ to Mn 5+ but can be explained well by the changes of local atomic structures around Mn 4+ due to the Li de-intercalation. Our results suggest that the electronic state of oxygen should change during charging in Li 2 MnO 3

Active Ti Species in TiCl3-Doped NaAlH4. Mechanism for Catalyst Deactivation

NARCIS (Netherlands)

Balde, C.P.; Stil, H.A.; van der Eerden, A.M.J.; de Jong, K.P.; Bitter, J.H.

2007-01-01

The nature of the active Ti species in TiCl3-doped NaAlH4, a promising hydrogen storage material, was studied as a function of the desorption temperature with Ti K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy, Ti K-edge X-ray absorption near-edge structure (XANES) spectroscopy,

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

Energy Technology Data Exchange (ETDEWEB)

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

2011-12-31

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

Nanoscale Phase Separation and Lattice Complexity in VO2: The Metal–Insulator Transition Investigated by XANES via Auger Electron Yield at the Vanadium L23-Edge and Resonant Photoemission

Directory of Open Access Journals (Sweden)

Augusto Marcelli

2017-12-01

Full Text Available Among transition metal oxides, VO2 is a particularly interesting and challenging correlated electron material where an insulator to metal transition (MIT occurs near room temperature. Here we investigate a 16 nm thick strained vanadium dioxide film, trying to clarify the dynamic behavior of the insulator/metal transition. We measured (resonant photoemission below and above the MIT transition temperature, focusing on heating and cooling effects at the vanadium L23-edge using X-ray Absorption Near-Edge Structure (XANES. The vanadium L23-edges probe the transitions from the 2p core level to final unoccupied states with 3d orbital symmetry above the Fermi level. The dynamics of the 3d unoccupied states both at the L3- and at the L2-edge are in agreement with the hysteretic behavior of this thin film. In the first stage of the cooling, the 3d unoccupied states do not change while the transition in the insulating phase appears below 60 °C. Finally, Resonant Photoemission Spectra (ResPES point out a shift of the Fermi level of ~0.75 eV, which can be correlated to the dynamics of the 3d// orbitals, the electron–electron correlation, and the stability of the metallic state.

XANES study on the electronic states of carbon nanotube and related materials

Energy Technology Data Exchange (ETDEWEB)

Imamura, M [National Inst. of Mater. and Chem. Res., Ibaraki (Japan); Shimada, H [National Inst. of Mater. and Chem. Res., Ibaraki (Japan); Matsubayashi, H [National Inst. of Mater. and Chem. Res., Ibaraki (Japan); Yumura, M [National Inst. of Mater. and Chem. Res., Ibaraki (Japan); Uchida, K [National Inst. of Mater. and Chem. Res., Ibaraki (Japan); Oshima, S [National Inst. of Mater. and Chem. Res., Ibaraki (Japan); Kuriki, Y [National Inst. of Mater. and Chem. Res., Ibaraki (Japan); Yoshimura, Y [National Inst. of Mater. and Chem. Res., Ibaraki (Japan); Sato, T [National Inst. of Mater. and Chem. Res., Ibaraki (Japan); Nishijima, A [National Inst. of Mater. and Chem. Res., Ibaraki (Japan)

1995-03-01

The C K-edge XANES spectra of carbon nanotubes and two fullerenes are presented . The XANES of the nanotubes is quite different from those of fullerenes, but analogous to that of HOPG. The difference in the 1s{yields}{pi}{sup *} transition is discussed in conjunction with the structural features. ((orig.)).

Effect of Cu insertion on structural, local electronic/atomic structure and photocatalyst properties of TiO{sub 2}, ZnO and Ni(OH){sub 2} nanostructures: XANES-EXAFS study

Energy Technology Data Exchange (ETDEWEB)

Sharma, Aditya; Varshney, Mayora [Advanced Analysis Centre, Korea Institute of Science and Technology, Seoul, 02792 (Korea, Republic of); Shin, Hyun Joon, E-mail: shj001@postech.ac.kr [Pohang Accelerator Laboratory (POSTECH), Pohang, 37673 (Korea, Republic of); Lee, Byeong-Hyeon [Advanced Analysis Centre, Korea Institute of Science and Technology, Seoul, 02792 (Korea, Republic of); Chae, Keun Hwa, E-mail: khchae@kist.re.kr [Advanced Analysis Centre, Korea Institute of Science and Technology, Seoul, 02792 (Korea, Republic of); Won, Sung Ok, E-mail: sowon@kist.re.kr [Advanced Analysis Centre, Korea Institute of Science and Technology, Seoul, 02792 (Korea, Republic of)

2017-04-15

We report detailed investigations on the synthesis, structural, morphology, electronic/atomic structure and photocatalyst properties of Cu doped TiO{sub 2}, ZnO and Ni(OH){sub 2} nanostructures. All of the samples were synthesized by using the chemical precipitation method. Samples were characterized by X-ray diffraction (XRD), transmission electron microscope (TEM), X-ray absorption near edge structure (XANES), extended X-ray absorption fine structure (EXAFS) and photocatalyst measurements. XRD studies revealed single phase nature of the samples and omitted the presence of trivial metallic or binary oxide phases. TiO{sub 2} set of samples have shown nanorod kind of morphology, however TEM images of ZnO and Ni(OH){sub 2} set of samples depicted the spherical morphology of particles. XANES spectra at the Cu K-edge and Cu L-edge, along with the atomic multiplet calculations, revealed the predominance of Cu{sup 2+} ions in all of the samples, within the entire doping range. Ti L-edge and Ti K-edge XANES confirmed the existence of Ti{sup 4+} ions in the pure and Cu doped TiO{sub 2} samples with anatase local structure. Zn L-edge XANES results confirmed the divalent character of Zn ions in the pure and Cu doped ZnO, which is further validated by the Zn K-edge XANES. Ni L-edge and Ni K-edge XANES conveyed the +2 valence state of Ni ions in the pure and Cu doped Ni (OH){sub 2} samples. EXAFS analysis at the Cu K-edge nullifies the formation of Cu metallic clusters and other trivial phases, suggesting random distribution of Cu atoms in the oxide materials. Though, local atomic arrangement of Cu ions is disparate in the different oxide compounds. As an application of the pure and Cu doped TiO{sub 2}, ZnO and Ni(OH){sub 2} nanostructures, towards the degradation of water pollutant dyes, we demonstrate that all of the samples can serve as effective photocatalyst materials towards the degradation of methyl orange aqueous pollutant dye under the UV-light irradiation

Electronic structure of Pt-Co cathode catalysts in membrane electrolyte assembly observed by X-ray absorption fine structure spectroscopy with different probing depth

International Nuclear Information System (INIS)

Kobayashi, M.; Hidai, S.; Niwa, H.; Harada, Y.; Oshima, M.; Ofuchi, H.; Nakamori, Y.; Aoki, T.

2010-01-01

Electronic structures of Pt-Co cathode and Pt-Ru anode catalysts in membrane electrolyte assemblies (MEAs) for polymer electrolyte fuel cell have been investigated using X-ray absorption near edge structure (XANES) spectroscopy, and the changes of electronic structures accompanied with degradation have been observed by comparison between spectra obtained by fluorescence-yield (FY) and conversion-electron-yield (CEY) methods, probing depths of which are several hundreds μm and ∼100 nm, respectively. The Co K XANES spectra of the as-fabricated MEA show that the Co atoms in the cathode are metallic and oxidized Co ions exist at the interface between the cathode and electrolyte. The spectra of the long-time operated MEA suggest that the oxidation of Co makes progress with degradation of the cathode catalysts. In contrast to the Co K XANES spectra, the line shape of the Ru K XANES spectra is unchanged even after the long-time operation.

Investigating the Geochemical Model for Molybdenum Mineralization in the JEB Tailings Management Facility at McClean Lake, Saskatchewan: An X-ray Absorption Spectroscopy Study.

Science.gov (United States)

Blanchard, Peter E R; Hayes, John R; Grosvenor, Andrew P; Rowson, John; Hughes, Kebbi; Brown, Caitlin

2015-06-02

The geochemical model for Mo mineralization in the JEB Tailings Management Facility (JEB TMF), operated by AREVA Resources Canada at McClean Lake, Saskatchewan, was investigated using X-ray Absorption Near-Edge Spectroscopy (XANES), an elemental-specific technique that is sensitive to low elemental concentrations. Twenty five samples collected during the 2013 sampling campaign from various locations and depths in the TMF were analyzed by XANES. Mo K-edge XANES analysis indicated that the tailings consisted primarily of Mo(6+) species: powellite (CaMoO4), ferrimolybdite (Fe2(MoO4)3·8H2O), and molybdate adsorbed on ferrihydrite (Fe(OH)3 - MoO4). A minor concentration of a Mo(4+) species in the form of molybdenite (MoS2) was also present. Changes in the Mo mineralization over time were inferred by comparing the relative amounts of the Mo species in the tailings to the independently measured aqueous Mo pore water concentration. It was found that ferrimolybdite and molybdate adsorbed on ferrihydrite initially dissolves in the TMF and precipitates as powellite.

The 1s x-ray absorption pre-edge structures in transition metal oxides

NARCIS (Netherlands)

de Groot, Frank|info:eu-repo/dai/nl/08747610X; Vanko, Gyoergy; Glatzel, Pieter

2009-01-01

We develop a general procedure to analyse the pre-edges in 1s x-ray absorption near edge structure (XANES) of transition metal oxides and coordination complexes. Transition metal coordination complexes can be described from a local model with one metal ion. The 1s 3d quadrupole transitions are

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

International Nuclear Information System (INIS)

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

2014-01-01

A new experimental set-up enabling microfocus fluorescence XANES mapping and microfocus XRD mapping on the same sample at beamline I18 at Diamond Light Source is described. To demonstrate this set-up the heterogeneous mineralogy in calcium carbonate granules excreted by the earthworm Lumbricus terrestris has been analysed. Data analysis methods have been developed which enable µXRD and µXANES two-dimensional maps to be compared. The use of fluorescence full spectral micro-X-ray absorption near-edge structure (µXANES) mapping is becoming more widespread in the hard energy regime. This experimental method using the Ca K-edge combined with micro-X-ray diffraction (µXRD) mapping of the same sample has been enabled on beamline I18 at Diamond Light Source. This combined approach has been used to probe both long- and short-range order in calcium carbonate granules produced by the earthworm Lumbricus terrestris. In granules produced by earthworms cultured in a control artificial soil, calcite and vaterite are observed in the granules. However, granules produced by earthworms cultivated in the same artificial soil amended with 500 p.p.m. Mg also contain an aragonite. The two techniques, µXRD and µXANES, probe different sample volumes but there is good agreement in the phase maps produced

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

Energy Technology Data Exchange (ETDEWEB)

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

2014-01-01

A new experimental set-up enabling microfocus fluorescence XANES mapping and microfocus XRD mapping on the same sample at beamline I18 at Diamond Light Source is described. To demonstrate this set-up the heterogeneous mineralogy in calcium carbonate granules excreted by the earthworm Lumbricus terrestris has been analysed. Data analysis methods have been developed which enable µXRD and µXANES two-dimensional maps to be compared. The use of fluorescence full spectral micro-X-ray absorption near-edge structure (µXANES) mapping is becoming more widespread in the hard energy regime. This experimental method using the Ca K-edge combined with micro-X-ray diffraction (µXRD) mapping of the same sample has been enabled on beamline I18 at Diamond Light Source. This combined approach has been used to probe both long- and short-range order in calcium carbonate granules produced by the earthworm Lumbricus terrestris. In granules produced by earthworms cultured in a control artificial soil, calcite and vaterite are observed in the granules. However, granules produced by earthworms cultivated in the same artificial soil amended with 500 p.p.m. Mg also contain an aragonite. The two techniques, µXRD and µXANES, probe different sample volumes but there is good agreement in the phase maps produced.

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

Science.gov (United States)

Tanaka, Isao; Mizoguchi, Teruyasu; Yamamoto, Tomoyuki

2009-03-01

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

Using Synchrotron-based X-ray Absorption Spectrometry to Identify the Arsenic Chemical Forms in Mine Waste Materials

International Nuclear Information System (INIS)

Matanitobua, Vitukawalu P.; Noller, Barry N.; Chiswell, Barry; Ng, Jack C.; Bruce, Scott L.; Huang, Daphne; Riley, Mark; Harris, Hugh H.

2007-01-01

X-ray Absorption Near Edge Spectroscopy (XANES) gives arsenic form directly in the solid phase and has lower detection limits than extraction techniques. An important and common application of XANES is to use the shift of the edge position to determine the valence state. XANES speciation analysis is based on fitting linear combinations of known spectra from model compounds to determine the ratios of valence states and/or phases present. As(V)/As(III) ratios were determined for various Australian mine waste samples and dispersed mine waste samples from river/creek sediments in Vatukoula, Fiji

TEM and XANES study of MOVPE grown InAIN layers with different indium content

International Nuclear Information System (INIS)

Kret, S; Wolska, A; Klepka, M T; Letrouit, A; Ivaldi, F; Szczepańska, A; Carlin, J-F; Kaufmann, N A K; Grandjean, N

2011-01-01

We present structure and spatially resolved composition studies by TEM (Transmission Electron Microscopy) and XANES (X-ray Absorption Near Edge Structure) of InAIN MOVPE (Metal-Organic Vapor Phase Epitaxy) epilayers containing 16-27 at% of indium. Investigations of the In L 3 edge by synchrotron radiation absorption show a significant change of the post-edge structure depending on the indium content. We attribute this to the solubility limit and phase separation in this system. Our measurements suggest that the critical composition is 18% for our growth conditions. HRTEM cross-sectional and EDX investigations confirm such phase separation as well as the changing of the structure from 2D growth to columnar like growth for the sample with the highest indium content.

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

Energy Technology Data Exchange (ETDEWEB)

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

2017-03-01

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

X-ray absorption spectroscopy and high-energy XRD study of the local environment of copper in antibacterial copper-releasing degradable phosphate glasses

OpenAIRE

Pickup, David M.; Ahmed, Ifty; Fitzgerald, Victoria; Moss, Rob M.; Wetherall, Karen; Knowles, Jonathan C.; Smith, Mark E.; Newport, Robert J.

2006-01-01

Phosphate-based glasses of the general formula Na2O-CaO-P2O5 are degradable in an aqueous environment, and therefore can act as antibacterial materials through the inclusion of ions such as copper. In this study, CuO and Cu2O were added to Na2O-CaO-P2O5 glasses (1-20 mol% Cu) and X-ray absorption spectroscopy (XAS) and high-energy X-ray diffraction (HEXRD) used to probe the local environment of the copper ions. Copper K-edge X-ray absorption near-edge structure (XANES) spectra confirm the oxi...

The local structure of Ca-Na pyroxenes. 2-Xanes studies at the Mg and A1 K edges

International Nuclear Information System (INIS)

Mottana, A.; Cibin, G.; Paris, E.; Giuli, G.; Florence Univ., Florence

1999-01-01

X-ray absorption spectra at the Mg and A1 K edges have been recorded on synthetic endmember diopside (Di) and jadeite (Jd) and on a series of natural Fe-poor Ca-Na clinopyroxenes compositionally straddling the Jd-Di join. The spectra of C2/c members of the series (C-omphacites) are different from having P2/n symmetry (P-omphacites). Differences can be explained by theoretical spectra calculated via the multiple-scattering formalism on atomic clusters with at least 89 atoms, extending to a. 0.62 nm away from the Mg viz. A1 absorber: Xanes detects in these systems medium- rather than short-range order-disorder relationships. Near-edge features of C-omphacites reflect the single-type of octahedral arrangement of the back scattering nearest-neighbours (six O atoms) around the absorber (Mg resp. A1) at the centre of the cluster (site M1). Others arise again from medium-range order. P-omphacites show more complicated spectra than C-omphacites. Their additional features reflect the increased local disorder around the probed atom (Mg resp. A1) induced by the two alternative M1, M11 configurations of the six O atoms forming the first co-ordination spheres. Mg and A1 are confirmed to be preferentially partitioned in the M1 resp. M11 site of the P-omphacite crystal structure, however never exclusively, but in a ratio close to 85:15 (plus or minus 10%) that implies a certain degree of local disorder. Changes in the relative heights of some prominent features are more evident in the A1 than in the Mg K-edge spectra. They are diagnostic to qualitatively distinguish C-from P-omphacites

The local structure of Ca-Na pyroxenes. 2-Xanes studies at the Mg and A1 K edges

Energy Technology Data Exchange (ETDEWEB)

Mottana, A. [Rome Univ. Roma Tre, Rome (Italy). Dipt. di Scienze Geologiche; Murata, T. [Kyoto University of Education, Kyoto (Japan). Dept. of Physics; Marcelli, A. [Istituto Nazionale di Fisica Nucleare, Frascati, RM (Italy). Laboratori Nazionali di Frascati; Wu, Z.Y. [Istituto Nazionale di Fisica Nucleare, Frascati, RM (Italy). Laboratori Nazionali di Frascati]|[Laboratoire Piere Suee, Gif-sur Yvette Cedex, (France); Cibin, G. [Istituto Nazionale di Fisica Nucleare, Frascati, RM (Italy). Laboratori Nazionali di Frascati; Paris, E. [Camerino Univ., Camerino, MC (Italy). Dipt. di Scienze della Terra; Giuli, G. [Camerino Univ., Camerino, MC (Italy). Dipt. di Scienze della Terra]|[Florence Univ., Florence (Italy). Dipt. di Scienze della Terra

1999-07-01

X-ray absorption spectra at the Mg and A1 K edges have been recorded on synthetic end member diopside (Di) and jadeite (Jd) and on a series of natural Fe-poor Ca-Na clinopyroxenes compositionally straddling the Jd-Di join. The spectra of C2/c members of the series (C-omphacites) are different from having P2/n symmetry (P-omphacites). Differences can be explained by theoretical spectra calculated via the multiple-scattering formalism on atomic clusters with at least 89 atoms, extending to a. 0.62 nm away from the Mg viz. A1 absorber: Xanes detects in these systems medium- rather than short-range order-disorder relationships. Near-edge features of C-omphacites reflect the single-type of octahedral arrangement of the back scattering nearest-neighbours (six O atoms) around the absorber (Mg resp. A1) at the centre of the cluster (site M1). Others arise again from medium-range order. P-omphacites show more complicated spectra than C-omphacites. Their additional features reflect the increased local disorder around the probed atom (Mg resp. A1) induced by the two alternative M1, M11 configurations of the six O atoms forming the first co-ordination spheres. Mg and A1 are confirmed to be preferentially partitioned in the M1 resp. M11 site of the P-omphacite crystal structure, however never exclusively, but in a ratio close to 85:15 (plus or minus 10%) that implies a certain degree of local disorder. Changes in the relative heights of some prominent features are more evident in the A1 than in the Mg K-edge spectra. They are diagnostic to qualitatively distinguish C-from P-omphacites.

Surface and in-depth characterization of lithium-ion battery cathodes at different cycle states using confocal micro-X-ray fluorescence-X-ray absorption near edge structure analysis

International Nuclear Information System (INIS)

Menzel, Magnus; Schlifke, Annalena; Falk, Mareike; Janek, Jürgen; Fröba, Michael; Fittschen, Ursula Elisabeth Adriane

2013-01-01

The cathode material LiNi 0.5 Mn 1.5 O 4 for lithium-ion batteries has been studied with confocal micro-X-ray fluorescence (CMXRF) combined with X-ray absorption near edge structure (XANES) at the Mn-K edge and the Ni-K edge. This technique allows for a non-destructive, spatially resolved (x, y and z) investigation of the oxidation states of surface areas and to some extent of deeper layers of the electrode. Until now CMXRF-XANES has been applied to a limited number of applications, mainly geo-science. Here, we introduce this technique to material science applications and show its performance to study a part of a working system. A novel mesoporous LiNi 0.5 Mn 1.5 O 4 material was cycled (charged and discharged) to investigate the effects on the oxidation states at the cathode/electrolyte interface. With this approach the degradation of Mn 3+ to Mn 4+ only observable at the surface of the electrode could be directly shown. The spatially resolved non-destructive analysis provides knowledge helpful for further understanding of deterioration and the development of high voltage battery materials, because of its nondestructive nature it will be also suitable to monitor processes during battery cycling. - Highlights: • The potential of confocal micro-XRF-XANES for spatial resolved species analysis in a part of a working system is shown. • The spatial resolution enables differentiation of the oxidized interface from deeper layers. • With the analytical technique confocal micro-XRF-XANES 3D in-situ analyses of working systems are feasible. • The multidimensional and nondestructive analysis of Li-ion battery cathodes is shown. • The analysis will allow for a deeper understanding of processes at interfaces in battery science and others

Surface and in-depth characterization of lithium-ion battery cathodes at different cycle states using confocal micro-X-ray fluorescence-X-ray absorption near edge structure analysis

Energy Technology Data Exchange (ETDEWEB)

Menzel, Magnus; Schlifke, Annalena [Institut für Anorganische und Angewandte Chemie, Universität Hamburg, Martin-Luther-King-Platz 6, 20146 Hamburg (Germany); Falk, Mareike; Janek, Jürgen [Physikalisch-Chemisches Institut, Justus-Liebig-Universität Gießen, Heinrich-Buff-Ring 58, 35392 Gießen (Germany); Fröba, Michael, E-mail: froeba@chemie.uni-hamburg.de [Institut für Anorganische und Angewandte Chemie, Universität Hamburg, Martin-Luther-King-Platz 6, 20146 Hamburg (Germany); Fittschen, Ursula Elisabeth Adriane, E-mail: ursula.fittschen@chemie.uni-hamburg.de [Institut für Anorganische und Angewandte Chemie, Universität Hamburg, Martin-Luther-King-Platz 6, 20146 Hamburg (Germany)

2013-07-01

The cathode material LiNi{sub 0.5}Mn{sub 1.5}O{sub 4} for lithium-ion batteries has been studied with confocal micro-X-ray fluorescence (CMXRF) combined with X-ray absorption near edge structure (XANES) at the Mn-K edge and the Ni-K edge. This technique allows for a non-destructive, spatially resolved (x, y and z) investigation of the oxidation states of surface areas and to some extent of deeper layers of the electrode. Until now CMXRF-XANES has been applied to a limited number of applications, mainly geo-science. Here, we introduce this technique to material science applications and show its performance to study a part of a working system. A novel mesoporous LiNi{sub 0.5}Mn{sub 1.5}O{sub 4} material was cycled (charged and discharged) to investigate the effects on the oxidation states at the cathode/electrolyte interface. With this approach the degradation of Mn{sup 3+} to Mn{sup 4+} only observable at the surface of the electrode could be directly shown. The spatially resolved non-destructive analysis provides knowledge helpful for further understanding of deterioration and the development of high voltage battery materials, because of its nondestructive nature it will be also suitable to monitor processes during battery cycling. - Highlights: • The potential of confocal micro-XRF-XANES for spatial resolved species analysis in a part of a working system is shown. • The spatial resolution enables differentiation of the oxidized interface from deeper layers. • With the analytical technique confocal micro-XRF-XANES 3D in-situ analyses of working systems are feasible. • The multidimensional and nondestructive analysis of Li-ion battery cathodes is shown. • The analysis will allow for a deeper understanding of processes at interfaces in battery science and others.

Chemical state analysis of heat-treated 6, 13-bis(triisopropylsilylethynyl) pentacene investigated by XPS valence band spectra, XANES spectra and first-principles calculation

International Nuclear Information System (INIS)

Muro, Maiko; Natsume, Yutaka; Kikuma, Jun; Setoyama, Hiroyuki

2014-01-01

X-ray photoelectron spectroscopy (XPS) valence band spectra reflect the chemical bonding states. To take this advantage, we tried to interpret experimental spectra by the occupied density of states (DOS) based on first principles calculation. In this work, we discussed XPS and X-ray Absorption Near Edge Structure (XANES) spectra of 6, 13-bis(triisopropylsilylethynyl) pentacene (TIPS-Pen), which is well known as an organic semiconductor. We studied chemical structure change of TIPS-Pen caused by heat-treatment at 300degC under nitrogen and under the air. It has been suggested that the structural change of pentacene skeleton by Diels-Alder type reaction occurs in both cases. In addition, the sample heat-treated under the air showed desorption of the isopropyl group and increase of oxygen concentration. (author)

Mn L{sub 2,3}-edge X-ray absorption spectroscopic studies on charge-discharge mechanism of Li{sub 2}MnO{sub 3}

Energy Technology Data Exchange (ETDEWEB)

Kubobuchi, Kei, E-mail: kubobuchi@nissan-arc.co.jp [NISSAN ARC Ltd., 1 Natsushima, Yokosuka 237-0061 (Japan); Institute of Industrial Science, The University of Tokyo, 4-6-1 Komaba, Meguro, Tokyo 153-8505, Japan. (Japan); Mogi, Masato; Imai, Hideto [NISSAN ARC Ltd., 1 Natsushima, Yokosuka 237-0061 (Japan); Ikeno, Hidekazu [Osaka Prefecture University, 1-2 Gakuen-cho, Naka-ku, Sakai, Osaka 599-8570 (Japan); Tanaka, Isao [Department of Materials Science and Engineering, Kyoto University, Yoshida-Honmachi, Sakyo-ku, Kyoto 606-8501 (Japan); Mizoguchi, Teruyasu, E-mail: teru@iis.u-tokyo.ac.jp [Institute of Industrial Science, The University of Tokyo, 4-6-1 Komaba, Meguro, Tokyo 153-8505, Japan. (Japan)

2014-02-03

The redox reaction of Mn in Li{sub 2}MnO{sub 3} was studied by X-ray absorption spectroscopy and ab initio multiplet calculation. Associated with the de-intercalation of Li-ion, small but clear spectral changes were observed in Mn-L{sub 2,3} X-ray absorption near edge structure (XANES). The systematic ab initio multiplet calculations of Mn-L{sub 2,3} XANES revealed that the spectral changes in the experiment could not simply be ascribed to the change of the valency from Mn{sup 4+} to Mn{sup 5+} but can be explained well by the changes of local atomic structures around Mn{sup 4+} due to the Li de-intercalation. Our results suggest that the electronic state of oxygen should change during charging in Li{sub 2}MnO{sub 3}.

Nanoindentation near the edge

Science.gov (United States)

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

2009-01-01

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

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

Directory of Open Access Journals (Sweden)

Martínez, A.

2009-06-01

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

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

International Nuclear Information System (INIS)

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

2011-01-01

Urological cancers comprise approximately one-third of all cancers diagnosed in men worldwide and out of these, prostate cancer is the most common one (). 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. - Highlights: → Different forms of sulphur has been found in prostate cancer cells. → FEFF8 code and LAPW method gave fairly good correspondence with the experiment. → LAPW is able to reproduce the fine structure of the absorption spectra. → Calculated DOS showed the influence of core atom on the shape of XANES spectra.

Parameter study of self-absorption effects in Total Reflection X-ray Fluorescence-X-ray Absorption Near Edge Structure analysis of arsenic

International Nuclear Information System (INIS)

Meirer, F.; Pepponi, G.; Streli, C.; Wobrauschek, P.; Kregsamer, P.; Zoeger, N.; Falkenberg, G.

2008-01-01

Total reflection X-ray Fluorescence (TXRF) analysis in combination with X-ray Absorption Near Edge Structure (XANES) analysis is a powerful method to perform chemical speciation studies at trace element levels. However, when measuring samples with higher concentrations and in particular standards, damping of the oscillations is observed. In this study the influence of self-absorption effects on TXRF-XANES measurements was investigated by comparing measurements with theoretical calculations. As(V) standard solutions were prepared at various concentrations and dried on flat substrates. The measurements showed a correlation between the damping of the oscillations and the As mass deposited. A Monte-Carlo simulation was developed using data of the samples shapes obtained from confocal white light microscopy. The results showed good agreement with the measurements; they confirmed that the key parameters are the density of the investigated atom in the dried residues and the shape of the residue, parameters that combined define the total mass crossed by a certain portion of the incident beam. The study presents a simple approach for an a priori evaluation of the self-absorption in TXRF X-ray absorption studies. The consequences for Extended X-ray Absorption Fine Structure (EXAFS) and XANES measurements under grazing incidence conditions are discussed, leading to the conclusion that the damping of the oscillations seems to make EXAFS of concentrated samples non feasible. For XANES 'fingerprint' analysis samples should be prepared with a deposited mass and sample shape leading to an acceptable absorption for the actual investigation

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

Science.gov (United States)

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

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

Science.gov (United States)

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

2014-01-01

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

3D local structure around copper site of rabbit prion-related protein: Quantitative determination by XANES spectroscopy combined with multiple-scattering calculations

International Nuclear Information System (INIS)

Cui, P.X.; Lian, F.L.; Wang, Y.; Wen, Yi; Chu, W.S.; Zhao, H.F.; Zhang, S.; Li, J.; Lin, D.H.; Wu, Z.Y.

2014-01-01

Prion-related protein (PrP), a cell-surface copper-binding glycoprotein, is considered to be responsible for a number of transmissible spongiform encephalopathies (TSEs). The structural conversion of PrP from the normal cellular isoform (PrP C ) to the post-translationally modified form (PrP Sc ) is thought to be relevant to Cu 2+ binding to histidine residues. Rabbits are one of the few mammalian species that appear to be resistant to TSEs, because of the structural characteristics of the rabbit prion protein (RaPrP C ) itself. Here we determined the three-dimensional local structure around the C-terminal high-affinity copper-binding sites using X-ray absorption near-edge structure combined with ab initio calculations in the framework of the multiple-scattering (MS) theory. Result shows that two amino acid resides, Gln97 and Met108, and two histidine residues, His95 and His110, are involved in binding this copper(II) ion. It might help us understand the roles of copper in prion conformation conversions, and the molecular mechanisms of prion-involved diseases. - Highlights: ► The first structure of the metal ion binding site in RaPrP fifth copper-binding site. ► Quantitative determination by XANES spectroscopy combined with ab initio calculations. ► Provide a proof of the roles of copper in prion conformation conversions. ► Provide a proof of the molecular mechanisms of prion-involved diseases

Near-Edge X-ray Absorption Fine Structure Spectroscopy of Diamondoid Thiol Monolayers on Gold

Energy Technology Data Exchange (ETDEWEB)

Willey, T M; Fabbri, J; Lee, J I; Schreiner, P; Fokin, A A; Tkachenko, B A; Fokina, N A; Dahl, J; Carlson, B; Vance, A L; Yang, W; Terminello, L J; van Buuren, T; Melosh, N

2007-11-27

Diamondoids, hydrocarbon molecules with cubic-diamond-cage structures, have unique properties with potential value for nanotechnology. The availability and ability to selectively functionalize this special class of nanodiamond materials opens new possibilities for surface-modification, for high-efficiency field emitters in molecular electronics, as seed crystals for diamond growth, or as robust mechanical coatings. The properties of self-assembled monolayers (SAMs) of diamondoids are thus of fundamental interest for a variety of emerging applications. This paper presents the effects of thiol substitution position and polymantane order on diamondoid SAMs on gold using near-edge X-ray absorption fine structure spectroscopy (NEXAFS) and X-ray photoelectron spectroscopy (XPS). A framework to determine both molecular tilt and twist through NEXAFS is presented and reveals highly ordered diamondoid SAMs, with the molecular orientation controlled by the thiol location. C 1s and S 2p binding energies are lower in adamantane thiol than alkane thiols on gold by 0.67 {+-} 0.05 eV and 0.16 {+-} 0.04 eV respectively. These binding energies vary with diamondoid monolayer structure and thiol substitution position, consistent with different amounts of steric strain and electronic interaction with the substrate. This work demonstrates control over the assembly, in particular the orientational and electronic structure, providing a flexible design of surface properties with this exciting new class of diamond clusters.

Origin of improved scintillation efficiency in (Lu,Gd).sub.3./sub.(Ga,Al).sub.5./sub.O.sub.12./sub.:Ce multicomponent garnets: an X-ray absorption near edge spectroscopy (XANES) study

Czech Academy of Sciences Publication Activity Database

Wu, Y.; Luo, J.; Nikl, Martin; Ren, G.

2014-01-01

Roč. 2, č. 1 (2014), "012101-1"-"012101-8" ISSN 2166-532X R&D Projects: GA MŠk LH12185 Institutional support: RVO:68378271 Keywords : scintillator * multicomponent garnet * Ce 4+ * XANES Subject RIV: BM - Solid Matter Physics ; Magnetism

Resonant X-ray emission spectroscopy in Dy compounds

International Nuclear Information System (INIS)

Tanaka, Satoshi; Okada, Kozo; Kotani, Akio.

1994-01-01

The excitation spectrum of the L 3 -M 5 X-ray emission of Dy compounds in the pre-edge region of Dy L 3 X-ray absorption near edge structure (L 3 -XANES) is theoretically investigated based upon the coherent second order optical formula with multiplet coupling effects. The spectral broadening of the excitation spectrum is determined by the M 5 core hole lifetime, being free from the L 3 core hole lifetime. The fine pre-edge structure of the L 3 edge due to the 2p→4f quadrupole transition can be seen in the excitation spectrum, while this structure is invisible in the conventional XANES, in agreement with the recent experimental results. We clarify the conditions for the excitation spectrum to be regarded as the absorption spectrum with a smaller width. The resonant X-ray emission spectra for various incident photon energies around the L 3 edge are also calculated. (author)

XANES analysis of calcium and sodium phosphates and silicates and hydroxyapatite-Bioglass (registered) 45S5 co-sintered bioceramics

International Nuclear Information System (INIS)

Demirkiran, Hande; Hu Yongfeng; Zuin, Lucia; Appathurai, Narayana; Aswath, Pranesh B.

2011-01-01

Bioglass (registered) 45S5 was co-sintered with hydroxyapatite at 1200 deg. C. When small amounts ( 5 (PO 4 ) 2 SiO 4 and Na 3 Ca 6 (PO 4 ) 5 in an amorphous silicate matrix respectively. These chemistries show improved bioactivity compared to hydroxyapatite and are the subject of this study. The structure of several crystalline calcium and sodium phosphates and silicates as well as the co-sintered hydroxyapatite-Bioglass (registered) 45S5 bioceramics were examined using XANES spectroscopy. The nature of the crystalline and amorphous phases were studied using silicon (Si) and phosphorus (P) K- and L 2,3 -edge and calcium (Ca) K-edge XANES. Si L 2,3 -edge spectra of sintered bioceramic compositions indicates that the primary silicates present in these compositions are sodium silicates in the amorphous state. From Si K-edge spectra, it is shown that the silicates are in a similar structural environment in all the sintered bioceramic compositions with 4-fold coordination. Using P L 2,3 -edge it is clearly shown that there is no evidence of sodium phosphate present in the sintered bioceramic compositions. In the P K-edge spectra, the post-edge shoulder peak at around 2155 eV indicates that this shoulder to be more defined for calcium phosphate compounds with decreasing solubility and increasing thermodynamic stability. This shoulder peak is more noticeable in hydroxyapatite and β-TCP indicating greater stability of the phosphate phase. The only spectra that does not show a noticeable peak is the composition with Na 3 Ca 6 (PO 4 ) 5 in a silicate matrix indicating that it is more soluble compared to the other compositions.

Identifying anthropogenic uranium compounds using soft X-ray near-edge absorption spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Ward, Jesse D.; Bowden, Mark; Tom Resch, C.; Eiden, Gregory C.; Pemmaraju, C. D.; Prendergast, David; Duffin, Andrew M.

2017-01-01

Uranium ores mined for industrial use are typically acid-leached to produce yellowcake and then converted into uranium halides for enrichment and purification. These anthropogenic chemical forms of uranium are distinct from their mineral counterparts. The purpose of this study is to use soft X-ray absorption spectroscopy to characterize several common anthropogenic uranium compounds important to the nuclear fuel cycle. Non-destructive chemical analyses of these compounds is important for process and environmental monitoring and X-ray absorption techniques have several advantages in this regard, including element-specificity, chemical sensitivity, and high spectral resolution. Oxygen K-edge spectra were collected for uranyl nitrate, uranyl fluoride, and uranyl chloride, and fluorine K-edge spectra were collected for uranyl fluoride and uranium tetrafluoride. Interpretation of the data is aided by comparisons to calculated spectra. These compounds have unique spectral signatures that can be used to identify unknown samples.

Functional Groups Quantification of Chondritic Organics by XANES Spectroscopy

Science.gov (United States)

Le Guillou, C.; Bernard, S.

2017-07-01

We have developed a new method to quantify the functional group concentration of organics using STXM-XANES. Applied to IOM and in situ FIB sections measurement, it reveals a lower aromaticity than expected from previous NMR results (35% vs. 60%).

Improved edge charge exchange recombination spectroscopy in DIII-D.

Science.gov (United States)

Chrystal, C; Burrell, K H; Grierson, B A; Haskey, S R; Groebner, R J; Kaplan, D H; Briesemeister, A

2016-11-01

The charge exchange recombination spectroscopy diagnostic on the DIII-D tokamak has been upgraded with the addition of more high radial resolution view chords near the edge of the plasma (r/a > 0.8). The additional views are diagnosed with the same number of spectrometers by placing fiber optics side-by-side at the spectrometer entrance with a precise separation that avoids wavelength shifted crosstalk without the use of bandpass filters. The new views improve measurement of edge impurity parameters in steep gradient, H-mode plasmas with many different shapes. The number of edge view chords with 8 mm radial separation has increased from 16 to 38. New fused silica fibers have improved light throughput and clarify the observation of non-Gaussian spectra that suggest the ion distribution function can be non-Maxwellian in low collisionality plasmas.

Towards a comprehensive X-ray approach for studying the photosynthetic manganese complex-XANES, K{alpha}/K{beta}/K{beta}-satellite emission lines, RIXS, and comparative computational approaches for selected model complexes

Energy Technology Data Exchange (ETDEWEB)

Zaharieva, I; Chernev, P; Risch, M; Gerencser, L; Haumann, M; Dau, H [Free University Berlin, FB Physik, Arnimallee 14, D-14195 Berlin (Germany); Berggren, G; Shevchenko, D; Anderlund, M [Dept. of Photochemistry and Molecular Science, Uppsala University, Box 523, S-751 20 Uppsala (Sweden); Weng, T C, E-mail: holger.dau@fu-berlin.d, E-mail: michael.haumann@fu-berlin.d [European Synchrotron Radiation Facility, BP 220, F-38043 Grenoble Cedex (France)

2009-11-15

Advanced X-ray spectroscopy experiments can contribute to elucidation of the mechanism of water oxidation in biological (tetra-manganese complex of Photosystem II) and artificial systems. Although the electronic structure of the catalytic metal site is of high interest, it is experimentally not easily accessible. Therefore, we and other researchers are working towards a comprehensive approach involving a combination of methods, namely (1) quantitative analysis of X-ray absorption near-edge structure (XANES) spectra collected at the K-edge and, in the long run, at the L-edge of manganese; (2) high-resolution X-ray emission spectroscopy (XES) of K{alpha} and K{beta} lines, (3) two-dimensional resonant inelastic X-ray scattering (RIXS) spectra. Collection of these spectroscopic data sets requires state-of-the-art synchrotron radiation facilities as well as experimental strategies to minimize the radiation-induced modifications of the samples. Data analysis requires the use and development of appropriate theoretical tools. Here, we present exemplary data collected for three multi-nuclear synthetic Mn complexes with the Mn ions in the oxidation states II, III, and IV, and for Mn{sup VII} of the permanganate ion. Emission spectra are calculated for the Mn{sup VII} ion using both multiple-scattering (MS) approach and time-dependent density functional theory (TDDFT).

X-ray absorption near edge structure study on Acutolysin-C, a zinc-metalloproteinase from Agkistrodon acutus venom: Insight into the acid-inactive mechanism

International Nuclear Information System (INIS)

Zhao Wei; Chu Wangsheng; Li Shujun; Liu Yiwei; Gao Bin; Niu Liwen; Teng Maikun; Benfatto, Maurizio; Hu Tiandou; Wu Ziyu

2007-01-01

Acutolysin-C, a snake-venom zinc metalloproteinase, displays a distinct pH-dependent proteolytic activity, which has been tentatively assigned to a structural change of the zinc-containing catalytic center. In this work we compare X-ray absorption near-edge structure (XANES) experimental spectra at the Zn K-edge and theoretical calculations of solutions at different pH values. The experimental data show clear differences confirmed by a best fit using the MXAN procedure. The results show that, when pH decreases from pH 8.0 to pH 3.0, the zinc-coordinating catalytic water molecule moves far from the Glu143 residue that is considered to play an essential role in the proteolytic process. Data suggests that this is the possible mechanism that deactivates the metalloproteinase

Molecular environment of iodine in naturally iodinated humic substances: Insight from X-ray absorption spectroscopy

International Nuclear Information System (INIS)

Schlegel, Michel L.; Mercier-Bion, Florence; Barre, Nicole; Reiller, Pascal; Moulin, Valerie

2006-01-01

The molecular environment of iodine in reference inorganic and organic compounds, and in dry humic and fulvic acids (HAs and FAs) extracted from subsurface and deep aquifers was probed by iodine L-3-edge X-ray absorption spectroscopy. The X-ray absorption near-edge structure (XANES) of iodine spectra from HAs and FAs resembled those of organic references and displayed structural features consistent with iodine forming covalent bonds with organic molecules. Simulation of XANES spectra by linear combination of reference spectra suggested the predominance of iodine forming covalent bonds to aromatic rings (aromatic-bound iodine). Comparison of extended X-ray absorption fine structure (EXAFS) spectra of reference and samples further showed that iodine was surrounded by carbon shells at distances comparable to those for references containing aromatic-bound iodine. Quantitative analysis of EXAFS spectra indicated that iodine was bound to about one carbon at a distance d(I-C) of 2.01(4)-2.04(9) angstrom, which was comparable to the distances observed for aromatic-bound iodine in references (1.99(1)-2.07(6) angstrom), and significantly shorter than that observed for aliphatic-bound iodine (2.15(2)-2.16(2) angstrom). These results are in agreement with previous conclusions from X-ray photoelectron spectroscopy and from electro-spray ionization mass spectrometry. These results collectively suggest that the aromatic-bound iodine is stable in the various aquifers of this study. (authors)

Correlation of the oxidation state of cerium in sol-gel glasses as a function of thermal treatment via optical spectroscopy and XANES studies.

Science.gov (United States)

Assefa, Zerihun; Haire, R G; Caulder, D L; Shuh, D K

2004-07-01

Sol-gel glass matrices containing lanthanides have numerous technological applications and their formation involves several chemical facets. In the case of cerium, its ability to exist in two different oxidation states or in mixed valence state provides additional complexities for the sol-gel process. The oxidation state of cerium present during different facets of preparation of sol-gel glasses, and also as a function of the starting oxidation state of cerium added, were studied both by optical spectroscopy and X-ray absorption near-edge structures (XANES). The findings acquired by each approach were compared. The primary focus was on the redox chemistries associated with sample preparation, gelation, and thermal treatment. When Ce3+ is introduced into the starting sols, the trivalent state normally prevails in the wet and room temperature-dried gels. Heating in air at >100 degrees C can generate a light yellow coloration with partial oxidation to the tetravalent state. Above 200 degrees C and up to approximately 1000 degrees C, cerium is oxidized to its tetravalent state. In contrast, when tetravalent cerium is introduced into the sol, both the wet and room temperature-dried gels lose the yellow-brown color of the initial ceric ammonium nitrate solution. When the sol-gel is heated to 110 degrees C it turns yellowish as the cerium tends to be re-oxidized. The yellow color is believed to represent the effect of oxidation and oligomerization of the cerium-silanol units in the matrix. The luminescence properties are also affected by these changes, the details of which are reported herein.

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

Energy Technology Data Exchange (ETDEWEB)

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

2007-01-31

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

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

International Nuclear Information System (INIS)

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

2007-01-01

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

Evidence for Topological Edge States in a Large Energy Gap near the Step Edges on the Surface of ZrTe_{5}

Directory of Open Access Journals (Sweden)

R. Wu

2016-05-01

Full Text Available Two-dimensional topological insulators with a large bulk band gap are promising for experimental studies of quantum spin Hall effect and for spintronic device applications. Despite considerable theoretical efforts in predicting large-gap two-dimensional topological insulator candidates, none of them have been experimentally demonstrated to have a full gap, which is crucial for quantum spin Hall effect. Here, by combining scanning tunneling microscopy/spectroscopy and angle-resolved photoemission spectroscopy, we reveal that ZrTe_{5} crystal hosts a large full gap of ∼100  meV on the surface and a nearly constant density of states within the entire gap at the monolayer step edge. These features are well reproduced by our first-principles calculations, which point to the topologically nontrivial nature of the edge states.

Extended x-ray absorption fine structure spectroscopy and x-ray absorption near edge spectroscopy study of aliovalent doped ceria to correlate local structural changes with oxygen vacancies clustering

Energy Technology Data Exchange (ETDEWEB)

Shirbhate, S. C.; Acharya, S. A., E-mail: saha275@yahoo.com [Department of Physics, Rashtrasant Tukadoji Maharaj Nagpur University, Nagpur 440033 (India); Yadav, A. K. [Atomic and molecular Physics Division, Bhabha Atomic Research Centre, Mumbai 400085 (India)

2016-04-04

This study provides atomic scale insight to understand the role of aliovalent dopants on oxygen vacancies clustering and dissociation mechanism in ceria system in order to enhance the performance of oxy-ion conductor. Dopants induced microscale changes in ceria are probed by extended X-ray absorption fine structure spectroscopy, X-ray absorption near edge spectra, and Raman spectroscopy. The results are explored to establish a correlation between atomic level structural changes (coordination number, interatomic spacing) → formation of dimer and trimer type cation-oxygen vacancies defect complex (intrinsic and extrinsic) → dissociation of oxygen vacancies from defect cluster → ionic conductivity temperature. It is a strategic approach to understand key physics of ionic conductivity mechanism in order to reduce operating temperature of electrolytes for intermediate temperature (300–450 °C) electrochemical devices for the first time.

Sulphur XANES Analysis of Cultured Human Prostate Cancer Cells

International Nuclear Information System (INIS)

Kwiatek, W.M.; Podgorczyk, M.; Paluszkiewicz, Cz.; Balerna, A.; Kisiel, A.

2008-01-01

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. (authors)

Near band edge emission characteristics of sputtered nano-crystalline ZnO films

International Nuclear Information System (INIS)

Kunj, Saurabh; Sreenivas, K.

2016-01-01

Sputtered zinc oxide (ZnO) thin films deposited on unheated glass substrate under different sputtering gas mixtures (Ar+O_2) have been investigated using X-ray diffraction and photo luminescence spectroscopy. Earlier reported studies on ZnO films prepared by different techniques exhibit either a sharp/broad near band edge (NBE) emission peak depending on the crystalline quality of the film. In the present study zinc oxide films, grown on unheated substrates, are seen to possess a preferred (002) orientation with a microstructure consisting of clustered nano-sized crystallites. The splitting in the near band edge emission (NBE) into three characteristic peaks is attributed to quantum confinement effect, and is observed specifically under an excitation of 270 nm. Deep level emission (DLE) in the range 400 to 700 nm is not observed indicating absence of deep level radiative defects.

Near band edge emission characteristics of sputtered nano-crystalline ZnO films

Science.gov (United States)

Kunj, Saurabh; Sreenivas, K.

2016-05-01

Sputtered zinc oxide (ZnO) thin films deposited on unheated glass substrate under different sputtering gas mixtures (Ar+O2) have been investigated using X-ray diffraction and photo luminescence spectroscopy. Earlier reported studies on ZnO films prepared by different techniques exhibit either a sharp/broad near band edge (NBE) emission peak depending on the crystalline quality of the film. In the present study zinc oxide films, grown on unheated substrates, are seen to possess a preferred (002) orientation with a microstructure consisting of clustered nano-sized crystallites. The splitting in the near band edge emission (NBE) into three characteristic peaks is attributed to quantum confinement effect, and is observed specifically under an excitation of 270 nm. Deep level emission (DLE) in the range 400 to 700 nm is not observed indicating absence of deep level radiative defects.

Near band edge emission characteristics of sputtered nano-crystalline ZnO films

Energy Technology Data Exchange (ETDEWEB)

Kunj, Saurabh; Sreenivas, K. [Department of Physics & Astrophysics, University of Delhi, Delhi 110007 INDIA (India)

2016-05-06

Sputtered zinc oxide (ZnO) thin films deposited on unheated glass substrate under different sputtering gas mixtures (Ar+O{sub 2}) have been investigated using X-ray diffraction and photo luminescence spectroscopy. Earlier reported studies on ZnO films prepared by different techniques exhibit either a sharp/broad near band edge (NBE) emission peak depending on the crystalline quality of the film. In the present study zinc oxide films, grown on unheated substrates, are seen to possess a preferred (002) orientation with a microstructure consisting of clustered nano-sized crystallites. The splitting in the near band edge emission (NBE) into three characteristic peaks is attributed to quantum confinement effect, and is observed specifically under an excitation of 270 nm. Deep level emission (DLE) in the range 400 to 700 nm is not observed indicating absence of deep level radiative defects.

Electronic structure of copper phthalocyanine : An experimental and theoretical study of occupied and unoccupied levels

NARCIS (Netherlands)

Evangelista, Fabrizio; Carravetta, Vincenzo; Stefani, Giovanni; Jansik, Branislav; Alagia, Michele; Stranges, Stefano; Ruocco, Alessandro

2007-01-01

An experimental and theoretical study of the electronic structure of copper phthalocyanine (CuPc) molecule is presented. We performed x-ray photoemission spectroscopy (XPS) and photoabsorption [x-ray absorption near-edge structure (XANES)] gas phase experiments and we compared the results with

Charge mechanism analysis of lithium ion secondary battery. X-ray absorption spectroscopy and first-principles calculations

International Nuclear Information System (INIS)

Kubobuchi, Kei; Imai, Hideto

2015-01-01

Redox reaction behaviors of a lithium ion secondary battery were investigated by K-edge in-situ XANES and L-edge XANES measurements combined with ab initio XANES simulation. During the charge process, the shape of K-edge XANES spectra was found to change, suggesting contribution of Mn 3d electron to charge and discharge. The detailed analysis based on first-principles electronic structure calculation and ab initio XANES simulation, however, indicated that valence change of Mn is little and rather O largely contribute to the reaction. (author)

First Ti-XANES analyses of refractory inclusions from Murchison

International Nuclear Information System (INIS)

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

2009-01-01

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 3+ and Ti 4+ can coexist, making the valence of Ti a valuable indicator of f O2 conditions during formation of nebular materials. The Ti 3+ /Ti 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 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 12 O 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 3+ /Ti 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 3+ /Ti 4+ ratios have not been previously measured. Analysis of these samples allows comparison of Ti valence of (1

XANES analysis of calcium and sodium phosphates and silicates and hydroxyapatite-Bioglass (registered) 45S5 co-sintered bioceramics

Energy Technology Data Exchange (ETDEWEB)

Demirkiran, Hande [Graduate Student, Materials Science and Engineering Department, University of Texas at Arlington, Arlington, TX (United States); Hu Yongfeng; Zuin, Lucia [Beamline Scientist, Canadian Light Source, Saskatoon, SK (Canada); Appathurai, Narayana [Beamline Scientist, Synchrotron Radiation Center, Madison, WI (United States); Aswath, Pranesh B., E-mail: aswath@uta.edu [Materials Science and Engineering Department, University of Texas at Arlington, Arlington, TX (United States)

2011-03-12

Bioglass (registered) 45S5 was co-sintered with hydroxyapatite at 1200 deg. C. When small amounts (< 5 wt.%) of Bioglass (registered) 45S5 was added it behaved as a sintering aid and also enhanced the decomposition of hydroxyapatite to {beta}-tricalcium phosphate. However when 10 wt.% and 25 wt.% Bioglass (registered) 45S5 was used it resulted in the formation of Ca{sub 5}(PO{sub 4}){sub 2}SiO{sub 4} and Na{sub 3}Ca{sub 6}(PO{sub 4}){sub 5} in an amorphous silicate matrix respectively. These chemistries show improved bioactivity compared to hydroxyapatite and are the subject of this study. The structure of several crystalline calcium and sodium phosphates and silicates as well as the co-sintered hydroxyapatite-Bioglass (registered) 45S5 bioceramics were examined using XANES spectroscopy. The nature of the crystalline and amorphous phases were studied using silicon (Si) and phosphorus (P) K- and L{sub 2,3}-edge and calcium (Ca) K-edge XANES. Si L{sub 2,3}-edge spectra of sintered bioceramic compositions indicates that the primary silicates present in these compositions are sodium silicates in the amorphous state. From Si K-edge spectra, it is shown that the silicates are in a similar structural environment in all the sintered bioceramic compositions with 4-fold coordination. Using P L{sub 2,3}-edge it is clearly shown that there is no evidence of sodium phosphate present in the sintered bioceramic compositions. In the P K-edge spectra, the post-edge shoulder peak at around 2155 eV indicates that this shoulder to be more defined for calcium phosphate compounds with decreasing solubility and increasing thermodynamic stability. This shoulder peak is more noticeable in hydroxyapatite and {beta}-TCP indicating greater stability of the phosphate phase. The only spectra that does not show a noticeable peak is the composition with Na{sub 3}Ca{sub 6}(PO{sub 4}){sub 5} in a silicate matrix indicating that it is more soluble compared to the other compositions.

The silicon neighborhood across the a-Si:H to {mu}c-Si transition by X-ray absorption spectroscopy (XAS)

Energy Technology Data Exchange (ETDEWEB)

Tessler, Leandro R.; Wang Qi; Branz, Howard M

2003-04-22

We report a synchrotron X-ray absorption spectroscopy study of the average neighborhood of Si near the transition from a-Si:H to {mu}c-Si on wedge-shaped samples prepared by hot-wire CVD in a chamber using a movable shutter. The thickness of the wedge varies from 30 to 160 nm. Nucleation of {mu}c-Si occurs at a critical thickness of approximately 100 nm. X-Ray absorption was measured at the Si K-edge (1.84 keV) by total electron photoemission yield. The absorption oscillations in the EXAFS region are very similar to all along the wedge. Analysis indicates an average tetrahedral first neighbor shell with radial disorder decreasing with crystallization. In the near-edge (XANES) region multiple scattering effects appear at the onset of crystallinity. Unlike single crystal silicon, these effects involve only double scattering within the first neighbor shell, indicating an ill-formed second shell in {mu}c-Si.

Hg L3 XANES Study of Mercury Methylation in Shredded Eichhornia Crassipes

International Nuclear Information System (INIS)

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

2008-01-01

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 HgCl 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 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 expensive than shredding

Pyrimidine and halogenated pyrimidines near edge x-ray absorption fine structure spectra at C and N K-edges: experiment and theory

International Nuclear Information System (INIS)

Bolognesi, P.; O'Keeffe, P.; Ovcharenko, Y.; Coreno, M.; Avaldi, L.; Feyer, V.; Plekan, O.; Prince, K. C.; Zhang, W.; Carravetta, V.

2010-01-01

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.

Localization and chemical forms of cadmium in plant samples by combining analytical electron microscopy and X-ray spectromicroscopy

Energy Technology Data Exchange (ETDEWEB)

Isaure, Marie-Pierre [Section d' Application des Traceurs, LITEN, CEA-Grenoble, 17, rue des Martyrs, 38054 Grenoble cedex 9 (France) and Environmental Geochemistry Group, LGIT, UMR 5559, Universite J. Fourier and CNRS, BP 53, 38041 Grenoble cedex 9 (France)]. E-mail: mpisaure@ujf-grenoble.fr; Fayard, Barbara [Laboratoire de Physique des Solides, UMR 8502 Universite Paris Sud, 91405 Orsay (France); European Synchrotron Radiation Facility, ID-21, BP220, 38043 Grenoble (France); Sarret, Geraldine [Environmental Geochemistry Group, LGIT, UMR 5559, Universite J. Fourier and CNRS, BP 53, 38041 Grenoble cedex 9 (France); Pairis, Sebastien [Laboratoire de Cristallographie, UPR 5031, 25 Avenue des Martyrs, BP 166, 38042 Grenoble cedex 9 (France); Bourguignon, Jacques [Laboratoire de Physiologie Cellulaire Vegetale, UMR 5168 CEA/CNRS/INRA/UJF, DRDC, CEA-Grenoble, 17 Avenue des Martyrs, 38054 Grenoble cedex 9 (France)

2006-12-15

Cadmium (Cd) is a metal of high toxicity for plants. Resolving its distribution and speciation in plants is essential for understanding the mechanisms involved in Cd tolerance, trafficking and accumulation. The model plant Arabidopsis thaliana was exposed to cadmium under controlled conditions. Elemental distributions in the roots and in the leaves were determined using scanning electron microscopy coupled with energy dispersive X-ray microanalysis (SEM-EDX), and synchrotron-based micro X-ray fluorescence ({mu}-XRF), which offers a better sensitivity. The chemical form(s) of cadmium was investigated using Cd L{sub III}-edge (3538 eV) micro X-ray absorption near edge structure ({mu}-XANES) spectroscopy. Plant {mu}-XANES spectra were fitted by linear combination of Cd reference spectra. Biological sample preparation and conditioning is a critical point because of possible artifacts. In this work we compared freeze-dried samples analyzed at ambient temperature and frozen hydrated samples analyzed at -170 deg. C. Our results suggest that in the roots Cd is localized in vascular bundles, and coordinated to S ligands. In the leaves, trichomes (epidermal hairs) represent the main compartment of Cd accumulation. In these specialized cells, {mu}-XANES results show that the majority of Cd is bound to O/N ligands likely provided by the cell wall, and a minor fraction could be bound to S-containing ligands. No significant difference in Cd speciation was observed between freeze-dried and frozen hydrated samples. This work illustrates the interest and the sensitivity of Cd L{sub III}-edge XANES spectroscopy, which is applied here for the first time to plant samples. Combining {mu}-XRF and Cd L{sub III}-edge {mu}-XANES spectroscopy offers promising tools to study Cd storage and trafficking mechanisms in plants and other biological samples.

Time-resolved X-ray absorption spectroscopy for the study of solid state reactions: synthesis of nanocrystalline barium titanate and thermal decomposition of ammonium hexachlorometallate compounds; Zeitaufgeloeste Roentgenabsorptionspektroskopie zur Untersuchung von Festkoerperreaktionen: Synthese von nanokristallinem Bariumtitanat und thermische Zersetzung von Ammoniumhexachlorometallat-Verbindungen

Energy Technology Data Exchange (ETDEWEB)

Rumpf, H.

2001-07-01

This report presents investigations on the mechanism of two different types of solid-state reactions: At first, barium titanate nanopowders were prepared through a combined polymerization and pyrolysis of a metallo-organic precursor. The mean particle size d{sub m} could be adjusted by choosing appropriate reaction temperatures and tempering atmospheres. In the present in situ study of this particular solid-phase reaction, X-ray absorption near edge structure (XANES) spectroscopy at the Ti K and Ba L{sub 3}-edges was applied in the preparation route of BaTiO{sub 3} nanopowders. A pronounced distortion of the lattice symmetry was found to occur in very fine BaTiO{sub 3} nanopowders (d{sub m} < 20 nm). Secondly, in situ XANES investigations were carried out at the Cl K, Pd L{sub 3}, Rh L{sub 3}, and Pt L{sub 3}-edges to study the mechanism of the thermal decomposition of ammonium hexachlorometallates. The results exceed structural information obtained by in situ X-ray diffraction methods and thermal analysis. Feff8 multiple scattering simulations have been carried out to disclose new intermediate phases of unknown reference compounds. (orig.)

Iron, nitrogen and silicon doped diamond like carbon (DLC) thin films: A comparative study

International Nuclear Information System (INIS)

Ray, Sekhar C.; Pong, W.F.; Papakonstantinou, P.

2016-01-01

The X-ray absorption near edge structure (XANES), X-ray photoelectron spectroscopy (XPS), valence band photoemission (VB-PES) and Raman spectroscopy results show that the incorporation of nitrogen in pulsed laser deposited diamond like carbon (DLC) thin films, reverts the sp"3 network to sp"2 as evidenced by an increase of the sp"2 cluster and I_D/I_G ratio in C K-edge XANES and Raman spectra respectively which reduces the hardness/Young's modulus into the film network. Si-doped DLC film deposited in a plasma enhanced chemical vapour deposition process reduces the sp"2 cluster and I_D/I_G ratio that causes the decrease of hardness/Young's modulus of the film structure. The Fe-doped DLC films deposited by dip coating technique increase the hardness/Young's modulus with an increase of sp"3-content in DLC film structure. - Highlights: • Fe, N and Si doped DLC films deposited by dip, PLD and PECVD methods respectively • DLC:Fe thin films have higher hardness/Young's modulus than DLC:N(:Si) thin films. • sp"3 and sp"2 contents are estimated from C K-edge XANES and VB-PES measurements.

[Chlorine speciation and concentration in cultivated soil in the northeastern China studied by X-ray absorption near edge structure].

Science.gov (United States)

Li, Jing; Lang, Chun-Yan; Ma, Ling-Ling; Xu, Dian-Dou; Zheng, Lei; Lu, Yu-Nanz; Cui Li-Rui; Zhang, Xiao-Meng

2014-10-01

A procedure has been proposed to determine chlorine speciation and concentration in soil with X-ray absorption near edge structure (XANES), and this method was applied to study the cultivated soil (bog, dark brown and black cultivated soil) in the Northeastern China. Qualitative analysis was carried out by least-squares fitting of sample spectra with standard spectra of three model compounds (NaCl, 3-chloropropionic acid, chlorophenol red). Linear correlation between the absolute fluorescence intensity of a series of NaCl standards and the Cl concentration was used as quantification standard for measuring the total Cl concentration in samples. The detection limits,relative standard deviation (RSD), recoveries were 2 mg · kg(-1), 0%-5% and 77%-133%, respectively. The average concentration of total Cl was 19 mg · kg(-1). The average relative content was as high as 61% of organochlorine with the concentration of 1-2 times as high as the concentration of inorganic chloride. The distribution trend of the total Cl, inorganic chloride and organic chlorine in different types of soil was: bog arable soil > dark brown soil > black soil. In conclusion, XANES is a reliable method to nondestructively characterize the speciation and concentration of chlorine in soil, which would provide some basic data for the future study of the chlorine's biogeochemical transformations.

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

Science.gov (United States)

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

2017-03-01

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

Effect of iron oxide reductive dissolution on the transformation and immobilization of arsenic in soils: New insights from X-ray photoelectron and X-ray absorption spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Fan, Jian-Xin [Key Laboratory of Soil Environment and Pollution Remediation, Institute of Soil Science, Chinese Academy of Sciences, Nanjing 210008 (China); School of River and Ocean Engineering, Chongqing Jiaotong University, Chongqing 400074 (China); Wang, Yu-Jun, E-mail: yjwang@issas.ac.cn [Key Laboratory of Soil Environment and Pollution Remediation, Institute of Soil Science, Chinese Academy of Sciences, Nanjing 210008 (China); Liu, Cun [Key Laboratory of Soil Environment and Pollution Remediation, Institute of Soil Science, Chinese Academy of Sciences, Nanjing 210008 (China); Wang, Li-Hua; Yang, Ke [Synchrotron Radiation Facility, Shanghai Institute of Applied Physics, Chinese Academy of sciences, Shanghai 201204 (China); Zhou, Dong-Mei, E-mail: dmzhou@issas.ac.cn [Key Laboratory of Soil Environment and Pollution Remediation, Institute of Soil Science, Chinese Academy of Sciences, Nanjing 210008 (China); Li, Wei; Sparks, Donald L. [Environmental Soil Chemistry Group, Delaware Environmental Institute and Department of Plant and Soil Sciences, University of Delaware, Newark, DE 19717-1303 United States (United States)

2014-08-30

Graphical abstract: - Highlights: • Immobility and transformation of As on different Eh soils were investigated. • μ-XRF, XANES, and XPS were used to gain As distribution and speciation in soil. • Sorption capacity of As on anaerobic soil was much higher than that on oxic soil. • Fe oxides reductive dissolution is a key factor for As sorption and transformation. - Abstract: The geochemical behavior and speciation of arsenic (As) in paddy soils is strongly controlled by soil redox conditions and the sequestration by soil iron oxyhydroxides. Hence, the effects of iron oxide reductive dissolution on the adsorption, transformation and precipitation of As(III) and As(V) in soils were investigated using batch experiments and synchrotron based techniques to gain a deeper understanding at both macroscopic and microscopic scales. The results of batch sorption experiments revealed that the sorption capacity of As(V) on anoxic soil was much higher than that on control soil. Synchrotron based X-ray fluorescence (μ-XRF) mapping studies indicated that As was heterogeneously distributed and was mainly associated with iron in the soil. X-ray absorption near edge structure (XANES), micro-X-ray absorption near edge structure (μ-XANES) and X-ray photoelectron spectroscopy (XPS) analyses revealed that the primary speciation of As in the soil is As(V). These results further suggested that, when As(V) was introduced into the anoxic soil, the rapid coprecipitation of As(V) with ferric/ferrous ion prevented its reduction to As(III), and was the main mechanism controlling the immobilization of As. This research could improve the current understanding of soil As chemistry in paddy and wetland soils.

Effect of iron oxide reductive dissolution on the transformation and immobilization of arsenic in soils: New insights from X-ray photoelectron and X-ray absorption spectroscopy

International Nuclear Information System (INIS)

Fan, Jian-Xin; Wang, Yu-Jun; Liu, Cun; Wang, Li-Hua; Yang, Ke; Zhou, Dong-Mei; Li, Wei; Sparks, Donald L.

2014-01-01

Graphical abstract: - Highlights: • Immobility and transformation of As on different Eh soils were investigated. • μ-XRF, XANES, and XPS were used to gain As distribution and speciation in soil. • Sorption capacity of As on anaerobic soil was much higher than that on oxic soil. • Fe oxides reductive dissolution is a key factor for As sorption and transformation. - Abstract: The geochemical behavior and speciation of arsenic (As) in paddy soils is strongly controlled by soil redox conditions and the sequestration by soil iron oxyhydroxides. Hence, the effects of iron oxide reductive dissolution on the adsorption, transformation and precipitation of As(III) and As(V) in soils were investigated using batch experiments and synchrotron based techniques to gain a deeper understanding at both macroscopic and microscopic scales. The results of batch sorption experiments revealed that the sorption capacity of As(V) on anoxic soil was much higher than that on control soil. Synchrotron based X-ray fluorescence (μ-XRF) mapping studies indicated that As was heterogeneously distributed and was mainly associated with iron in the soil. X-ray absorption near edge structure (XANES), micro-X-ray absorption near edge structure (μ-XANES) and X-ray photoelectron spectroscopy (XPS) analyses revealed that the primary speciation of As in the soil is As(V). These results further suggested that, when As(V) was introduced into the anoxic soil, the rapid coprecipitation of As(V) with ferric/ferrous ion prevented its reduction to As(III), and was the main mechanism controlling the immobilization of As. This research could improve the current understanding of soil As chemistry in paddy and wetland soils

X-ray absorption fine structure (XAFS) studies of cobalt silicide thin films

International Nuclear Information System (INIS)

Naftel, S.J.; Coulthard, I.; Hu, Y.; Sham, T.K.; Zinke-Allmang, M.

1998-01-01

Cobalt silicide thin films, prepared on Si(100) wafers, have been studied by X-ray absorption near edge structures (XANES) at the Si K-, L 2,3 - and Co K-edges utilizing both total electron (TEY) and fluorescence yield (FLY) detection as well as extended X-ray absorption fine structure (EXAFS) at the Co K-edge. Samples made using DC sputter deposition on clean Si surfaces and MBE were studied along with a bulk CoSi 2 sample. XANES and EXAFS provide information about the electronic structure and morphology of the films. It was found that the films studied have essentially the same structure as bulk CoSi 2 . Both the spectroscopy and materials characterization aspects of XAFS (X-ray absorption fine structures) are discussed

Depth distribution of secondary phases in kesterite Cu2ZnSnS4 by angle-resolved X-ray absorption spectroscopy

Directory of Open Access Journals (Sweden)

J. Just

2017-12-01

Full Text Available The depth distribution of secondary phases in the solar cell absorber material Cu2ZnSnS4 (CZTS is quantitatively investigated using X-ray Absorption Near Edge Structure (XANES analysis at the K-edge of sulfur at varying incidence angles. Varying information depths from several nanometers up to the full thickness is achieved. A quantitative profile of the phase distribution is obtained by a self-consistent fit of a multilayer model to the XANES spectra for different angles. Single step co-evaporated CZTS thin-films are found to exhibit zinc and copper sulfide secondary phases preferentially at the front or back interfaces of the film.

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

International Nuclear Information System (INIS)

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

1992-01-01

The high-resolution Ca L 2,3 x-ray-absorption near-edge-structure (XANES) spectrum of a Bi 2 Sr 2 CaCu 2 O 8 single crystal has been measured by use of a magnetic-projection x-ray microscope probing a surface area of 200x200 μm 2 . The Ca L 2,3 XANES spectrum is analyzed by performing a multiple-scattering XANES calculation in real space and comparing the results with the spectrum of CaF 2 . Good agreement between the calculated and experimental crystal-field splitting Δ f of the Ca 3d final states is found and the splitting is shown to be smaller by 0.5 eV than in the initial state. The Ca 3d partial density of states is found to be close to the Fermi level in the initial state. The Ca-O(in plane) distance is shown to be a critical parameter associated with the shift of the Ca 3d states relative to the Fermi level; in particular, we have studied the effect of the out-of-plane dimpling mode of the in-plane oxygen atoms O(in plane) that will move the Ca 3d states on or off the Fermi level. This mode can therefore play a role in modulating the charge transfer between the two CuO 2 planes separated by the Ca ions

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

Energy Technology Data Exchange (ETDEWEB)

Borg, A; King, P L; Pianetta, P; Lindau, I; Mitzi, D B

1992-01-01

The high-resolution Ca L(2,3) x-ray-absorption near-edge-structure (XANES) spectrum of a Bi2Sr2CaCu2O8 single crystal has been measured by use of a magnetic-projection x-ray microscope probing a surface area of 200x200 micrometers square. The Ca L(2,3) XANES spectrum is analyzed by performing a multiple-scattering XANES calculation in real space and comparing the results with the spectrum of CaF2. Good agreement between the calculated and experimental crystal-field splitting Delta f of the Ca 3d final states is found and the splitting is shown to be smaller by 0.5 eV than in the initial state. The Ca 3d partial density of states is found to be close to the Fermi level in the initial state. The Ca-O (in plane) distance is shown to be a critical parameter associated with the shift of the Ca 3d states relative to the Fermi level; in particular, the authors have studied the effect of the out-of-plane dimpling mode of the in-plane oxygen atoms O(in plane) that will move the Ca 3d states on or off the Fermi level. This mode can therefore play a role in modulating the charge transfer between the two CuO2 planes separated by the Ca ions.

Kinetics of iron redox reactions in silicate liquids: A high-temperature X-ray absorption and Raman spectroscopy study

Energy Technology Data Exchange (ETDEWEB)

Magnien, V. [Physique des Mineraux et Magmas, CNRS-IPGP, 4 place Jussieu, 75252 Paris cedex 05 (France); CEA VALRHO Marcoule, SCDV, LEBV, BP 17171, 30207 Bagnols/Ceze (France); Neuville, D.R. [Physique des Mineraux et Magmas, CNRS-IPGP, 4 place Jussieu, 75252 Paris cedex 05 (France)]. E-mail: neuville@ipgp.jussieu.fr; Cormier, L. [IMPMC, CNRS UMR 7590, Universites Paris 6 and 7 and IPGP, 4 place Jussieu, 75252 Paris cedex 05 (France); Roux, J. [Physique des Mineraux et Magmas, CNRS-IPGP, 4 place Jussieu, 75252 Paris cedex 05 (France); Hazemann, J.-L. [Laboratoire de cristallographie, UPR 5031, CNRS, 38043 Grenoble (France); Pinet, O. [CEA VALRHO Marcoule, SCDV, LEBV, BP 17171, 30207 Bagnols/Ceze (France); Richet, P. [Physique des Mineraux et Magmas, CNRS-IPGP, 4 place Jussieu, 75252 Paris cedex 05 (France)

2006-06-30

The oxidation kinetics of a Fe-bearing supercooled liquid of the system SiO{sub 2}-CaO-MgO-Na{sub 2}O-FeO has been determined near the glass transition range by X-ray absorption near edge structure (XANES) and Raman spectroscopies. Both techniques yield room-temperature iron redox ratios in accord with wet chemical, Moessbauer and electron microprobe analyses. Similar oxidation kinetics have also been observed with both methods. At constant temperature, the kinetics obey an exponential law with a characteristic time that follows an Arrhenian temperature dependence. As redox changes are too fast to be accounted for in terms of diffusion of either ionic or molecular oxygen, these results lend further support to the idea that the rate-limiting factor for oxidation near the glass transition is diffusion of network-modifying cations along with a flux of electron holes.

Effects of higher-coordination shells in garnets detected by XAS at the Al K-edge

International Nuclear Information System (INIS)

Marcelli, A.; Wu, Z.; Mottana, A.; Giuli, G.; Paris, E.; Seifert, F.

1996-03-01

The aluminium 1 s x-ray-absorption spectra of a series of garnets, pyrope, almandine, spessartine and grossular, are compared to full multiple-scattering calculation using cluster models. An overall good agreement between experiment and calculation, extended also to the edge region,is obtained in the energy range in up to 60 e V above the threshold, provided cluster containing at least 40 atoms are used. The analysis of these garnet XAS spectra provides clear evidence on the effect of probe, XANES spectroscopy at the edge of low Z elements appears to be a perfect tool to investigate the role played by atoms located in higher-coordination shells

Effects of higher-coordination shells in garnets detected by XAS at the Al K-edge

Energy Technology Data Exchange (ETDEWEB)

Marcelli, A. [Istituto Nazionale di Fisica Nucleare, Frascati (Italy). Lab. Nazionale di Frascati; Wu, Z. [CNRS UMR 110, Laboratoire de Chimie des Solides, Nantes Cedex (France). Institut de materiaux de Nantes; Mottana, A. [Roma III Univ., Rome (Italy). Dipartimento di Scienze Geologiche; Giuli, G.; Paris, E. [Camerino Univ., Camerino (Italy).Diparimento di Scienze della Terra; Seifert, F [Univ. Bayreuth, Bayreuth (Italy). Bayerisches Geoinstitut (Germany)

1996-03-01

The aluminium 1 s x-ray-absorption spectra of a series of garnets, pyrope, almandine, spessartine and grossular, are compared to full multiple-scattering calculation using cluster models. An overall good agreement between experiment and calculation, extended also to the edge region,is obtained in the energy range in up to 60 e V above the threshold, provided cluster containing at least 40 atoms are used. The analysis of these garnet XAS spectra provides clear evidence on the effect of probe, XANES spectroscopy at the edge of low Z elements appears to be a perfect tool to investigate the role played by atoms located in higher-coordination shells.

X-ray absorption spectroscopy in biological systems. Opportunities and limitations

Energy Technology Data Exchange (ETDEWEB)

Bovenkamp, Gudrun Lisa

2013-05-15

X-ray absorption spectroscopy has become more important for applications in the material sciences, geology, environmental science and biology, specifically in the field of molecular biology. The scope of this thesis is to add more experimental evidence in order to show how applicable X-ray absorption near edge structure (XANES) is to biology. Two biological systems were investigated, at the molecular level, lead uptake in plants and the effect of silver on bacteria. This investigation also included an analysis of the sensitivity of Pb L{sub 3}- and Ag L{sub 3}-XANES spectra with regard to their chemical environment. It was shown that Pb L{sub 3}- and Ag L{sub 3}-XANES spectra are sensitive to an environment with at least differences in the second coordination shell. The non-destructive and element specific properties of XANES are the key advantages that were very important for this investigation. However, in both projects the adequate selection of reference compounds, which required in some cases a chemical synthesis, was the critical factor to determine the chemical speciation and, finally, possible uptake and storage mechanisms for plants and antibacterial mechanisms of silver. The chemical environment of Pb in roots and leaves of plants from four different plant families and a lichen from a former lead mining site in the Eifel mountains in Germany was determined using both solid compounds and aqueous solutions of different ionic strength, which simulate the plant environment. The results can be interpreted in such a way that lead is sorbed on the surface of cell walls. Silver bonding as reaction with Staphylococcus aureus, Listeria monocytogenes, and Escherichia coli bacteria was determined using inorganic silver compounds and synthesized silver amino acids. Silver binds to sulfur, amine and carboxyl groups in amino acids.

X-ray absorption spectroscopy in biological systems. Opportunities and limitations

International Nuclear Information System (INIS)

Bovenkamp, Gudrun Lisa

2013-05-01

X-ray absorption spectroscopy has become more important for applications in the material sciences, geology, environmental science and biology, specifically in the field of molecular biology. The scope of this thesis is to add more experimental evidence in order to show how applicable X-ray absorption near edge structure (XANES) is to biology. Two biological systems were investigated, at the molecular level, lead uptake in plants and the effect of silver on bacteria. This investigation also included an analysis of the sensitivity of Pb L 3 - and Ag L 3 -XANES spectra with regard to their chemical environment. It was shown that Pb L 3 - and Ag L 3 -XANES spectra are sensitive to an environment with at least differences in the second coordination shell. The non-destructive and element specific properties of XANES are the key advantages that were very important for this investigation. However, in both projects the adequate selection of reference compounds, which required in some cases a chemical synthesis, was the critical factor to determine the chemical speciation and, finally, possible uptake and storage mechanisms for plants and antibacterial mechanisms of silver. The chemical environment of Pb in roots and leaves of plants from four different plant families and a lichen from a former lead mining site in the Eifel mountains in Germany was determined using both solid compounds and aqueous solutions of different ionic strength, which simulate the plant environment. The results can be interpreted in such a way that lead is sorbed on the surface of cell walls. Silver bonding as reaction with Staphylococcus aureus, Listeria monocytogenes, and Escherichia coli bacteria was determined using inorganic silver compounds and synthesized silver amino acids. Silver binds to sulfur, amine and carboxyl groups in amino acids.

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

Energy Technology Data Exchange (ETDEWEB)

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

2000-12-01

A key question for the understanding of photosynthetic water oxidation is whether the four oxidizing equivalents necessary to oxidize water to dioxygen are accumulated on the four Mn ions of the oxygen evolving complex (OEC), or whether some ligand-centered oxidations take place before the formation and release of dioxygen during the S₃ → [S₄] → S₀ transition. Progress in instrumentation and flash sample preparation allowed us to apply Mn Kβ X-ray emission spectroscopy (Kb XES) to this problem for the first time. The Kβ XES results, in combination with Mn X-ray absorption near-edge structure (XANES) and electron paramagnetic resonance (EPR) data obtained from the same set of samples, show that the S₂ → S₃ transition, in contrast to the S₀ → S₁ and S₁ → S₂ transitions, does not involve a Mn-centered oxidation. This is rationalized by manganese μ-oxo bridge radical formation during the S₂ → S₃ transition. Using extended X-ray absorption fine structure (EXAFS) spectroscopy, the local environment of the Mn atoms in the S₀ state has been structurally characterized. These results show that the Mn-Mn distance in one of the di-μ-oxo-bridged Mn-Mn moieties increases from 2.7 Å in the S₁} state to 2.85 Å in the S₀ state. Furthermore, evidence is presented that shows three di-μ-oxo binuclear Mn₂ clusters may be present in the OEC, which is contrary to the widely held theory that two such clusters are present in the OEC. The EPR properties of the S₀ state have been investigated and a characteristic ''multiline'' signal in the S₀ state has been discovered in the presence of methanol. This provides the first direct confirmation that the native S₀ state is paramagnetic. In addition, this signal was simulated using parameters derived from three

Interpretation of the U L3-edge EXAFS in uranium dioxide using molecular dynamics and density functional theory simulations

International Nuclear Information System (INIS)

Bocharov, Dmitry; Chollet, Melanie; Krack, Matthias; Bertsch, Johannes; Grolimund, Daniel; Martin, Matthias; Kuzmin, Alexei; Purans, Juris; Kotomin, Eugene

2016-01-01

X-ray absorption spectroscopy is employed to study the local structure of pure and Cr-doped UO 2 at 300 K. The U L 3 -edge EXAFS spectrum is interpreted within the multiplescattering (MS) theory using the results of the classical and ab initio molecular dynamics simulations, allowing us to validate the accuracy of theoretical models. The Cr K-edge XANES is simulated within the full-multiple-scattering formalism considering a substitutional model (Cr at U site). It is shown that both unrelaxed and relaxed structures, produced by ab initio density functional theory (DFT) calculations, fail to describe the experiment. (paper)

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

International Nuclear Information System (INIS)

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

2007-01-01

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 deg. C

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

Science.gov (United States)

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

2016-01-01

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

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

Science.gov (United States)

Sindhupakorn, Bura; Thienpratharn, Suwittaya; Kidkhunthod, Pinit

2017-10-01

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

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

Science.gov (United States)

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

2017-09-01

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

Local electronic and geometric structures of silicon atoms implanted in graphite

International Nuclear Information System (INIS)

Baba, Yuji; Sekiguchi, Tetsuhiro; Shimoyama, Iwao

2002-01-01

Low-energy Si + ions were implanted in highly oriented pyrolitic graphite (HOPG) up to 1% of surface atomic concentration, and the local electronic and geometric structures around the silicon atoms were in situ investigated by means of the Si K-edge X-ray absorption near-edge structure (XANES) and X-ray photoelectron spectroscopy using linearly polarized synchrotron radiation. The resonance peak appeared at 1839.5 eV in the Si K-edge XANES spectra for Si + -implanted HOPG. This energy is lower than those of the Si 1s→σ * resonance peaks in any other Si-containing materials. The intensity of the resonance peak showed strong polarization dependence, which suggests that the final state orbitals around the implanted Si atoms have π * -like character. It is concluded that the σ-type Si-C bonds produced by the Si + -ion implantation are nearly parallel to the graphite plane, and Si x C phase forms two-dimensionally spread graphite-like layer with sp 2 bonds

Multiple scattering approach to X-ray absorption spectroscopy

International Nuclear Information System (INIS)

Benfatto, M.; Wu Ziyu

2003-01-01

In this paper authors present the state of the art of the theoretical background needed for analyzing X-ray absorption spectra in the whole energy range. The multiple-scattering (MS) theory is presented in detail with some applications on real systems. Authors also describe recent progress in performing geometrical fitting of the XANES (X-ray absorption near-edge structure) energy region and beyond using a full multiple-scattering approach

X-ray spectroscopy of solids under pressure. Annual progress report, August 1983-July 1984

International Nuclear Information System (INIS)

Ingalls, R.L.

1984-01-01

X-ray absorption studies of several materials as a function of pressure have been performed. Of particular interest has been the EXAFS (extended x-ray absorption fine structure) and XANES (x-ray absorption near edge structure). Materials studied include the alkali halides, NaBr and RbCl, zinc blend semiconductors ZnSe and CuBr and mixed-valence materials SmS and SmSe. In the former, the volume dependence of bond lengths and their mean square fluctuations were determined from the EXAFS. In the latter materials the XANES exhibited the pressure induced change from the Sm 2+ configuration to Sm 3+

Synchrotron applications in wood preservation and deterioration

Science.gov (United States)

Barbara L. Illman

2003-01-01

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

Using Fluorescence XANES Measurement to Correct the Content of Hexavalent Chromium in Chromate Conversion Coatings Determined by Diphenyl Carbazide Color Test

International Nuclear Information System (INIS)

Nishino, Junichi; Ofuchi, Hironori; Taniguchi, Yosuke; Honma, Tetsuo; Sekikawa, Toshikazu; Otani, Haruka; Bando, Akio

2007-01-01

The Restriction of the use of certain Hazardous Substances (RoHS) directive will take effect on July 1 of this year. From that date, the use of chromate conversion coatings containing hexavalent chromium will not be permitted. By comparing the concentration of Cr6+ determined by the diphenyl carbazide color test and by fluorescence XANES (X-Ray Absorption Near Edge Structure) measurement, we can correct for the Cr6+ content of the color test. This will enable the use of the diphenyl carbazide color test to check product shipments in compliance with the RoHS directive

Molecular characterization of copper in soils using X-ray absorption spectroscopy

International Nuclear Information System (INIS)

Strawn, Daniel G.; Baker, Leslie L.

2009-01-01

Bioavailability of Cu in the soil is a function of its speciation. In this paper we investigated Cu speciation in six soils using X-ray absorption near edge structure (XANES), extended X-ray absorption fine structure (EXAFS), and synchrotron-based micro X-ray fluorescence (μ-XRF). The XANES and EXAFS spectra in all of the soils were the same. μ-XRF results indicated that the majority of the Cu particles in the soils were not associated with calcium carbonates, Fe oxides, or Cu sulfates. Principal component analysis and target transform of the XANES and EXAFS spectra suggested that Cu adsorbed on humic acid (HA) was an acceptable match. Thus it appears that Cu in all of the soils is primarily associated with soil organic matter (SOM). Theoretical fitting of the molecular structure in the soil EXAFS spectra revealed that the Cu in the soils existed as Cu atoms bound in a bidentate complex to O or N functional groups. - Copper speciation in six soils was investigated using XANES, EXAFS, and μ-XRF.

Iron, nitrogen and silicon doped diamond like carbon (DLC) thin films: A comparative study

Energy Technology Data Exchange (ETDEWEB)

Ray, Sekhar C., E-mail: Raysc@unisa.ac.za [Department of Physics, College of Science, Engineering and Technology, University of South Africa, Private Bag X6, Florida, 1710, Science Campus, Christiaan de Wet and Pioneer Avenue, Florida Park, Johannesburg (South Africa); Pong, W.F. [Department of Physics, Tamkang University, Tamsui 251, New Taipei City, Taiwan (China); Papakonstantinou, P. [Nanotechnology and Integrated Bio-Engineering Centre, University of Ulster, Shore Road, Newtownabbey BT37 0QB (United Kingdom)

2016-07-01

The X-ray absorption near edge structure (XANES), X-ray photoelectron spectroscopy (XPS), valence band photoemission (VB-PES) and Raman spectroscopy results show that the incorporation of nitrogen in pulsed laser deposited diamond like carbon (DLC) thin films, reverts the sp{sup 3} network to sp{sup 2} as evidenced by an increase of the sp{sup 2} cluster and I{sub D}/I{sub G} ratio in C K-edge XANES and Raman spectra respectively which reduces the hardness/Young's modulus into the film network. Si-doped DLC film deposited in a plasma enhanced chemical vapour deposition process reduces the sp{sup 2} cluster and I{sub D}/I{sub G} ratio that causes the decrease of hardness/Young's modulus of the film structure. The Fe-doped DLC films deposited by dip coating technique increase the hardness/Young's modulus with an increase of sp{sup 3}-content in DLC film structure. - Highlights: • Fe, N and Si doped DLC films deposited by dip, PLD and PECVD methods respectively • DLC:Fe thin films have higher hardness/Young's modulus than DLC:N(:Si) thin films. • sp{sup 3} and sp{sup 2} contents are estimated from C K-edge XANES and VB-PES measurements.

Speciation of copper and zinc in size-fractionated atmospheric particulate matter using total reflection mode X-ray absorption near-edge structure spectrometry

International Nuclear Information System (INIS)

Osan, Janos; Meirer, Florian; Groma, Veronika; Toeroek, Szabina; Ingerle, Dieter; Streli, Christina; Pepponi, Giancarlo

2010-01-01

The health effects of aerosol depend on the size distribution and the chemical composition of the particles. Heavy metals of anthropogenic origin are bound to the fine aerosol fraction (PM 2.5 ). The composition and speciation of aerosol particles can be variable in time, due to the time-dependence of anthropogenic sources as well as meteorological conditions. Synchrotron-radiation total reflection X-ray fluorescence (SR-TXRF) provides very high sensitivity for characterization of atmospheric particulate matter. X-ray absorption near-edge structure (XANES) spectrometry in conjunction with TXRF detection can deliver speciation information on heavy metals in aerosol particles collected directly on the reflector surface. The suitability of TXRF-XANES for copper and zinc speciation in size-fractionated atmospheric particulate matter from a short sampling period is presented. For high size resolution analysis, atmospheric aerosol particles were collected at different urban and rural locations using a 7-stage May cascade impactor having adapted for sampling on Si wafers. The thin stripe geometry formed by the particulate matter deposited on the May-impactor plates is ideally suited to SR-TXRF. Capabilities of the combination of the May-impactor sampling and TXRF-XANES measurements at HASYLAB Beamline L to Cu and Zn speciation in size-fractionated atmospheric particulate matter are demonstrated. Information on Cu and Zn speciation could be performed for elemental concentrations as low as 140 pg/m 3 . The Cu and Zn speciation in the different size fraction was found to be very distinctive for samples of different origin. Zn and Cu chemical state typical for soils was detected only in the largest particles studied (2-4 μm fraction). The fine particles, however, contained the metals of interest in the sulfate and nitrate forms.

A laboratory-based hard x-ray monochromator for high-resolution x-ray emission spectroscopy and x-ray absorption near edge structure measurements

Energy Technology Data Exchange (ETDEWEB)

Seidler, G. T., E-mail: seidler@uw.edu; Mortensen, D. R.; Remesnik, A. J.; Pacold, J. I.; Ball, N. A.; Barry, N.; Styczinski, M.; Hoidn, O. R. [Physics Department, University of Washington, Seattle, Washington 98195-1560 (United States)

2014-11-15

We report the development of a laboratory-based Rowland-circle monochromator that incorporates a low power x-ray (bremsstrahlung) tube source, a spherically bent crystal analyzer, and an energy-resolving solid-state detector. This relatively inexpensive, introductory level instrument achieves 1-eV energy resolution for photon energies of ∼5 keV to ∼10 keV while also demonstrating a net efficiency previously seen only in laboratory monochromators having much coarser energy resolution. Despite the use of only a compact, air-cooled 10 W x-ray tube, we find count rates for nonresonant x-ray emission spectroscopy comparable to those achieved at monochromatized spectroscopy beamlines at synchrotron light sources. For x-ray absorption near edge structure, the monochromatized flux is small (due to the use of a low-powered x-ray generator) but still useful for routine transmission-mode studies of concentrated samples. These results indicate that upgrading to a standard commercial high-power line-focused x-ray tube or rotating anode x-ray generator would result in monochromatized fluxes of order 10{sup 6}–10{sup 7} photons/s with no loss in energy resolution. This work establishes core technical capabilities for a rejuvenation of laboratory-based hard x-ray spectroscopies that could have special relevance for contemporary research on catalytic or electrical energy storage systems using transition-metal, lanthanide, or noble-metal active species.

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

Science.gov (United States)

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

2013-08-07

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

The valence state of Yb metal under high pressure determined by XANES measurement up to 34.6 GPa

International Nuclear Information System (INIS)

Fuse, Akinori; Nakamoto, Go; Kurisu, Makio; Ishimatsu, Naoki; Tanida, Hajime

2004-01-01

The purpose of this study was to accurately determine the valency of Yb at high pressure and room temperature and to clarify the relation between the valence state and the crystal structure of Yb metal. L III -edge X-ray absorption near-edge structure (XANES) spectra were measured to determine the valence state of Yb metal in the pressure range from 0 to 34.6 GPa at room temperature, using a diamond anvil cell (DAC) and synchrotron radiation at SPring-8. In the fcc phase, Yb metal exhibits mixed valence (the mean valence ν-bar >2.1). At the fcc-to-bcc phase transition, a 0.1 jump is found in ν-bar. In the bcc phase, ν-bar(P) is an increasing function of pressure with downward curvature, reaching only 2.55 at 26 GPa. The ν-bar is only 2.65 in the hcp phase at 34.6 GPa. A tendency for saturation in ν-bar(P) to values smaller than 3.0 is found

Influence of the core-hole effect on optical properties of magnesium oxide (MgO) near the Mg L-edge region.

Science.gov (United States)

Sinha, Mangalika; Modi, Mohammed H; Ghosh, Haranath; Yadav, P K; Gupta, R K

2018-05-01

The influence of the core-hole effect on optical properties of magnesium oxide (MgO) is established through experimental determination of optical constants and first-principles density functional theory studies. Optical constants (δ and β) of MgO thin film are measured in the spectral region 40-300 eV using reflectance spectroscopy techniques at the Indus-1 synchrotron radiation source. The obtained optical constants show strong core exciton features near the Mg L-edge region, causing significant mismatch with Henke's tabulated values. On comparing the experimentally obtained optical constants with Henke's tabulated values, an edge shift of ∼3.0 eV is also observed. Distinct evidence of effects of core exciton on optical constants (δ and β) in the near Mg L-edge absorption spectra are confirmed through first-principles simulations.

California gull chicks raised near colony edges have elevated stress levels

Science.gov (United States)

Herring, Garth; Ackerman, Joshua T.

2011-01-01

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

Soft X-ray induced chemical modification of polysaccharides in vascular plant cell walls

International Nuclear Information System (INIS)

Cody, George D.; Brandes, Jay; Jacobsen, Chris; Wirick, Susan

2009-01-01

Scanning transmission X-ray microscopy and micro carbon X-ray Absorption Near Edge Spectroscopy (C-XANES) can provide quantitative information regarding the distribution of the biopolymers cellulose, hemicellulose, and lignin in vascular plant cell walls. In the case of angiosperms, flowering plants, C-XANES may also be able to distinguish variations in lignin monomer distributions throughout the cell wall. Polysaccharides are susceptible to soft X-ray irradiation induced chemical transformations that may complicate spectral analysis. The stability of a model polysaccharide, cellulose acetate, to variable doses of soft X-rays under conditions optimized for high quality C-XANES spectroscopy was investigated. The primary chemical effect of soft X-ray irradiation on cellulose acetate involves mass loss coincident with de-acetylation. A lesser amount of vinyl ketone formation also occurs. Reduction in irradiation dose via defocusing does enable high quality pristine spectra to be obtained. Radiation induced chemical modification studies of oak cell wall reveals that cellulose and hemicellulose are less labile to chemical modification than cellulose acetate. Strategies for obtaining pristine C-XANES spectra of polysaccharides are presented.

Chemical Heterogeneity of a Large Cluster IDP: Clues to its Formation History Using X-ray Fluorescence Mapping and XANES Spectroscopy

Science.gov (United States)

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

2013-01-01

Chondritic porous IDPs may be among the most primitive objects found in our solar system [1]. They consist of many micron to submicron minerals, glasses and carbonaceous matter [2,3,4,5,6,7] with > 10(exp 4) grains in a 10 micron cluster [8]. Speculation on the environment where these fine grained, porous IDPs formed varies with possible sources being presolar dusty plasma clouds, protostellar condensation, solar asteroids or comets [4,6,9]. Also, fine grained dust forms in our solar system today [10,11]. Isotopic anomalies in some particles in IDPs suggest an interstellar source[4,7,12]. IDPs contain relic particles left from the dusty plasma that existed before the protostellar disk formed and other grains in the IDPs formed later after the cold dense nebula cloud collapsed to form our protostar and other grains formed more recently. Fe and CR XANES spectroscopy is used here to investigate the oxygen environment in a large (>50 10 micron or larger sub-units) IDP. Conclusions: Analyzing large (>50 10 micron or larger sub-units) CP IDPs gives one a view on the environments where these fine dust grains formed which is different from that found by only analyzing the small, 10 micron IDPs. As with cluster IDP L2008#5 [3], L2009R2 cluster #13 appears to be an aggregate of grains that sample a diversity of solar and perhaps presolar environments. Sub-micron, grain by grain measurement of trace element contents and elemental oxidation states determined by XANES spectroscopy offers the possibility of understanding the environments in which these grains formed when compared to standard spectra. By comparing thermodynamic modeling of condensates with analytical data an understanding of transport mechanisms operating in the early solar system may be attained.

Kinetics of iron redox reaction in silicate melts: A high temperature Xanes study on an alkali basalt

Energy Technology Data Exchange (ETDEWEB)

Cochain, B; Neuville, D R; Roux, J; Strukelj, E; Richet, P [Physique des Mineraux et Magmas, Geochimie-Cosmochimie, CNRS-IPGP, 4 place Jussieu, 75005 Paris (France); Ligny, D de [Universite Claude Bernard Lyon 1, LPCML, F-69622 Villeurbanne (France); Baudelet, F, E-mail: cochain@ipgp.jussieu.f [Synchrotron SOLEIL, L' Orme des Merisiers, Saint Aubin (France)

2009-11-15

In Earth and Materials sciences, iron is the most important transition element. Glass and melt properties are strongly affected by iron content and redox state with the consequence that some properties (i.e. viscosity, heat capacity, crystallization...) depend not only on the amounts of Fe{sup 2+} and Fe{sup 3+}, but also on the coordination state of these ions. In this work we investigate iron redox reactions through XANES experiments at the K-edge of iron. Using a high-temperature heating device, pre-edge of XANES spectra exhibits definite advantages to make in-situ measurements and to determine the evolution of redox state with time, temperature and composition of synthetic silicate melts. In this study, new kinetics measurements are presented for a basalt melt from the 31,000-BC eruption of the Puy de Lemptegy Volcano in France. These measurements have been made between 773 K and at superliquidus temperatures up to 1923 K.

Kinetics of iron redox reaction in silicate melts: A high temperature Xanes study on an alkali basalt

International Nuclear Information System (INIS)

Cochain, B; Neuville, D R; Roux, J; Strukelj, E; Richet, P; Ligny, D de; Baudelet, F

2009-01-01

In Earth and Materials sciences, iron is the most important transition element. Glass and melt properties are strongly affected by iron content and redox state with the consequence that some properties (i.e. viscosity, heat capacity, crystallization...) depend not only on the amounts of Fe 2+ and Fe 3+ , but also on the coordination state of these ions. In this work we investigate iron redox reactions through XANES experiments at the K-edge of iron. Using a high-temperature heating device, pre-edge of XANES spectra exhibits definite advantages to make in-situ measurements and to determine the evolution of redox state with time, temperature and composition of synthetic silicate melts. In this study, new kinetics measurements are presented for a basalt melt from the 31,000-BC eruption of the Puy de Lemptegy Volcano in France. These measurements have been made between 773 K and at superliquidus temperatures up to 1923 K.

Study of apical oxygen atoms in a spin-ladder cuprate compound by X-ray absorption spectroscopy near the Cu K edge

Energy Technology Data Exchange (ETDEWEB)

Hatterer, C.J.; Eustache, B.; Collin, L.; Beuran, C.F.; Partiot, C.; Germain, P.; Xu, X.Z.; Lagues, M. [CNRS, Paris (France). Surfaces et Supraconducteurs; Michalowicz, A. [Laboratoire de Physique des Milieux Desordonnes, Universite Paris XII Val-de-Marne, 61 avenue du general de Gaulle, 94010, Creteil Cedex (France)]|[LURE, Universite Paris Sud, 91405, Orsay Cedex (France); Moscovici, J. [Laboratoire de Physique des Milieux Desordonnes, Universite Paris XII Val-de-Marne, 61 avenue du general de Gaulle, 94010, Creteil Cedex (France); Deville Cavellin, C. [CNRS, Paris (France). Surfaces et Supraconducteurs]|[Laboratoire d`Electronique, Universite Paris XII Val-de-Marne, 61 av. du general de Gaulle, 94010, Creteil Cedex (France); Traverse, A. [LURE, Universite Paris Sud, 91405, Orsay Cedex (France)

1997-04-01

The structure of high-T{sub c} superconducting cuprate compounds is based on CuO{sub 2} planes alternating with blocks that behave as charge reservoirs. The apical oxygen atoms which belong to these reservoirs are suspected to play a role in the mechanism of superconductivity. It thus seems necessary to measure the amount of apical oxygen atoms in various compounds, as a function of the superconducting properties. Polarisation dependent X-ray absorption spectroscopy (XAS) measurements were performed near the Cu K-edge on three types of phases. We collected information about the neighbourhood of the copper atom in the cuprate planes and in the direction perpendicular to these planes. Two of these phases have well known structures: Bi2212 in which copper atoms are on a pyramidal site and infinite layer phase, a square planar cuprate without apical oxygen. We used the obtained results as reference data to study a new copper-rich phase related to the spin-ladder series. (orig.)

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

Science.gov (United States)

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

2017-01-01

The 1959 summit eruption of Kīlauea Volcano exhibited high lava fountains of gas-rich, primitive magma, containing olivine + chromian spinel in highly vesicular brown glass. Microprobe analysis of these samples shows that euhedral rims on olivine phenocrysts, in direct contact with glass, vary significantly in forsterite (Fo) content, at constant major-element melt composition, as do unzoned groundmass olivine crystals. Ferric/total iron (Fe+ 3/FeT)ratios for matrix and interstitial glasses, plus olivine-hosted glass inclusions in eight 1959 scoria samples have been determined by micro X-ray absorption near-edge structure spectroscopy (μ-XANES). These data show that much of the variation in Fo content reflects variation in oxidation state of iron in the melt, which varies with sulfur concentration in the glass and (locally) with proximity to scoria edges in contact with air. Data for 24 olivine-melt pairs in the better-equilibrated samples from later in the eruption show KD averaging 0.280 ± 0.03 for the exchange of Fe and Mg between olivine and melt, somewhat displaced from the value of 0.30 ± 0.03 given by Roeder and Emslie (1970). This may reflect the low SiO2 content of the 1959 magmas, which is lower than that in most Kīlauea tholeiites. More broadly, we show the potential of μ-XANES and electron microprobe to revisit and refine the value of KD in natural systems.The observed variations of Fe+ 3/FeT ratios in the glasses reflect two distinct processes. The main process, sulfur degassing, produces steady decrease of the Fe+ 3/FeT ratio. Melt inclusions in olivine are high in sulfur (1060–1500 ppm S), with Fe+ 3/FeT = 0.160–0.175. Matrix glasses are degassed (mostly S eruption and (2) the melts originally had Fe+ 3/FeT ≥ 0.175, consistent with oxygen fugacity (fO2) at least 0.4 log units above the fayalite-magnetite-quartz (FMQ) buffer at 1 atm and magmatic temperature of 1200 °C.The second process is interaction between the

Electronic structures of ultra-thin silicon carbides deposited on graphite

International Nuclear Information System (INIS)

Baba, Y.; Sekiguchi, T.; Shimoyama, I.; Nath, Krishna G.

2004-01-01

Electronic structures of ultra-thin silicon carbide films have been investigated by X-ray photoelectron spectroscopy (XPS) and Si K-edge X-ray absorption near edge structure (XANES) using linearly polarized synchrotron soft X-rays. Silicon carbide films were deposited on the surface of highly oriented pyrolytic graphite (HOPG) by ion beam deposition method. Tetramethylsilane (Si(CH 3 ) 4 ) was used as a discharge gas. The XPS and XANES features for the thick layers were similar to those for the bulk SiC. For sub-monolayered films, the Si 1s binding energy in XPS was higher by 2.5 eV than that for bulk SiC. This suggests the existence of low-dimensional SiC x where the silicon atoms are more positively charged than those in bulk SiC. After annealing the sub-monolayered film at 850 deg. C, a new peak appeared around 1840 eV in the XANES spectrum. The energy of this new peak was lower than those for any other silicon compounds. The low-energy feature of the XANES peak suggests the existence of π*-like orbitals around the silicon atom. On the basis of the polarization dependencies of the XANES spectra, it was revealed that the direction of the π*-like orbitals are nearly perpendicular to the surface. We conclude that sub-monolayered SiC x film exhibits flat-lying structure of which configuration is similar to a single sheet of graphite

X-ray absorption fine structure (XAFS) spectroscopy: a tool for structural studies in material sciences (abstract)

International Nuclear Information System (INIS)

Akhtar, M.J.

2011-01-01

XAFS spectroscopy has revealed itself as a powerful technique for structural characterization of the local atomic environment of individual atomic species, including bond distances, coordination numbers and type of nearest neighbors surrounding the central atom. This technique is particularly useful for materials that show considerable structural and chemical disorder. XAFS spectroscopy has found extensive applications in determining the local atomic and electronic structure of the absorbing centers (atoms) in the materials science, physics, chemistry, biology and geophysics. X-ray absorption edges contain a variety of information on the chemical state and the local structure of the absorbing atom. On the higher energy side of an absorption edge fine structure is observed due to backscattering of the emitted photoelectron. The post-edge region can be divided into two parts. The X-ray Absorption Near Edge Structure (XANES) which extends up to 50 eV of an absorption edge, the spectrum is interpreted in terms of the appropriate components of the local density of states, which would be expected to be sensitive to the valence state of the atom. The intensity, shape and location of the absorption edge features provide information on the valence state, electronic structure and coordination geometry of the absorbing atom.The Extended X-ray Absorption Fine Structure (EXAFS) region is dominated by the single scattering processes and extends up to 1000 eV above the edge and provides information on the radial distribution (coordination number, radial distance and type of neighboring atoms) around the central atom. The results on perovskite based and spinel ferrites systems will be presented, where valence state and cation distributions are determined; the present study will show focus on SrFeO/sub 3/, MnFe/sub 2/O/sub 4/ and Zn/sub 1-x/Ni/sub x/Fe/sub 2/O/sub 4/ materials. (author)

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

Energy Technology Data Exchange (ETDEWEB)

Vjunov, Aleksei; Wang, Meng; Govind, Niranjan; Huthwelker, Thomas; Shi, Hui; Mei, Donghai; Fulton, John L.; Lercher, Johannes A.

2017-10-23

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

Investigation of the nanoscale two-component ZnS-ZnO heterostructures by means of HR-TEM and X-ray based analysis

Science.gov (United States)

Pankin, I. A.; Polozhentsev, O. E.; Soldatov, M. A.; Bugaev, A. L.; Tsaturyan, A.; Lomachenko, K. A.; Guda, A. A.; Budnyk, A. P.; Lamberti, C.; Soldatov, A. V.

2018-06-01

This article is devoted to the spectroscopic characterization of ZnS-ZnO nanoscale heterostructures synthesized by the microwave-assisted solvothermal method. The synthesized samples were investigated by means of X-ray powder diffraction (XRPD), high energy resolution fluorescence detected X-ray absorption near-edge-structure (HERFD-XANES) spectroscopy, valence-to-core X-ray emission spectroscopy (VtC-XES) and high resolution transmission electron microscopy (HR-TEM) as well as energy dispersive X-ray spectroscopy (EDX). The average crystallite size estimated by the broadening of XRPD peaks increases from 2.7 nm to 3.7 nm in the temperature range from 100 °C to 150 °C. HR-TEM images show that nanoparticles are arranged in aggregates with the 60-200 nm size. Theoretical estimation shows that the systems synthesized at higher temperatures more prone to the agglomeration. The full profile Reitveld analysis of XRPD data reveals the formation of hexagonal zinc sulfide structure, whereas electron diffraction data reveal also the formation of cubic zinc sulfide and claim the polymorphous character of the system. High energy resolution Zn K-edge XANES data unambiguously demonstrate the presence of a certain amount of the zinc oxide which is likely to have an amorphous structure and could not be detected by XRPD. Qualitative analysis of XANES data allows deriving ZnS/ZnO ratio as a function of synthesis temperature. EDX analysis depicts homogeneous distribution of ZnS and amorphous ZnO phases across the conglomerates. A complementary element-selective valence to core X-ray emission spectroscopy evidences formation of two-component system and confirms estimations of ZnS/ZnO fractions obtained by linear combination fit of XANES data.

Magnetite Crisis in Miniature: Vanadium, Sulfur, and Iron Valence State Measurements in Melt Inclusions from Nyamuragira Volcano (D.R. Congo, Africa)

Science.gov (United States)

Head, E.; Lanzirotti, A.; Sutton, S.; Newville, M.

2017-12-01

Sulfur (S), vanadium (V), and iron (Fe) K-edge micro-X-ray absorption near edge structure (micro-XANES) spectroscopy of melt inclusions (MI) from Nyamuragira volcano (D.R. Congo, Africa) shows that diffusive loss of H from olivine-hosted melt inclusions may lead to crystallization of submicron magnetite and sulfide crystallites that are imperceptible petrographically or via electron microscopy. Micro-XANES was used to constrain the evolution of oxygen fugacity (fO2) and sulfur speciation for MI preserved in Nyamuragira tephra (1986 and 2006) and lava (1938 and 1948). The S, V, and Fe valence state oxybarometry for 1938, 1948, and 2006 MI are all consistent with equilibration at FMQ-1, and sulfur in MI from these three eruptions are sulfide-dominated (water loss in olivine-hosted MIs.

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

Science.gov (United States)

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

2017-09-01

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

Liquid microjet synchrotron-radiation spectroscopy for biomolecules in water solution 2

International Nuclear Information System (INIS)

Shimada, Hiroyuki; Ukai, Masatoshi

2014-01-01

A new spectroscopic research of radiation induced damage on DNA and its constituent molecules is proposed, which is made possible using a liquid microjet technique for bio-solution under vacuum in combination with synchrotron-radiation aided site-selective excitation. The latter part of the proposal article describes the present state of research on the selective primary radiation interaction by looking at base moieties of nucleotides. X-ray absorption near edge structure (XANES) spectra at energies around the nitrogen K-edge for nucleotides, adenosine-5'-monophosphate (AMP), guanosine-5'-monophosophate (GMP), cytidine-5'-monophosophate (CMP), and adenosine-5'-triphosphate (ATP) in aqueous solutions are presented. Selective excitation of a base moiety using a synchrotron radiation allows us to investigate the interaction of the base moiety with water solvent. We discuss the change of spectral character of XANES which reveals to the structural change of the base moiety under different pH environmental condition of water solution. Through the present research a scope for cooperative direct and indirect primary radiation effects is given. (author)

The coordination of sulfur in synthetic and biogenic Mg calcites: The red coral case

Science.gov (United States)

Perrin, J.; Rivard, C.; Vielzeuf, D.; Laporte, D.; Fonquernie, C.; Ricolleau, A.; Cotte, M.; Floquet, N.

2017-01-01

Sulfur has been recognized in biogenic calcites for a long time. However, its structural position is matter of debate. For some authors, sulfur is a marker of the organic matrix while it is part of the calcite structure itself for others. To better understand the place of sulfur in calcite, sulfated magnesian calcites (S-MgCalcite) have been synthetized at high pressure and temperature and studied by μ-XANES spectroscopy. S-MgCalcite XANES spectra show two different types of sulfur: sulfate (SO42-) as a predominant species and a small contribution of sulfite (SO32-), both substituting for carbonate ions in the calcite structure. To address the question of the position of sulfur in biogenic calcites, the oxidation states of sulfur in the skeleton and organic tissues of Corallium rubrum have been investigated by micro X-ray fluorescence (μ-XRF) and sulfur K-edge micro X-ray absorption near edge structure (μ-XANES) spectroscopy at the European Synchrotron Radiation Facility (ESRF, Grenoble, France) on beamline ID21. In the skeleton, sulfur is mainly present as oxidized sulfur SO42- (+VI), plus a weak sulfite contribution. XANES spectra indicate that sulfur is inorganically incorporated as sulfur structurally substituted to carbonate ions (SSS). Although an organic matrix is present in the red coral skeleton, reduced organic sulfur could not be detected by μ-XANES spectroscopy in the skeleton probably due to low organic/inorganic sulfur ratio. In the organic tissues surrounding the skeleton, several sulfur oxidation states have been detected including disulfide (S-S), thioether (R-S-CH3), sulfoxide (SO2), sulfonate (SO2O-) and sulfate (SO42-). The unexpected occurrence of inorganic sulfate within the organic tissues suggests the presence of pre-organized organic/inorganic complexes in the circulatory system of the red coral, precursors to biomineralization ahead of the growth front.

Electronic structure of polycrystalline cadmium dichloride studied by X-ray spectroscopies and ab initio calculations

International Nuclear Information System (INIS)

Demchenko, I.N.; Chernyshova, M.; Stolte, W.C.; Speaks, D.T.; Derkachova, A.

2012-01-01

The electronic structure of cadmium dichloride has been studied by X-ray absorption near edge structure (XANES) and, for the first time, by resonant inelastic X-ray scattering (RIXS) at the Cl K edge. Good agreement was obtained between the non-resonant X-ray emission (XES) along with XANES experimental spectra and the calculated Cl 3p local partial density of states (DOS). The calculations were performed using the full-potential linearized-augmented-plane-wave with the local orbitals (FP-(L)APW l o) method utilized in the WIEN2k code. It was shown that the position of the RIXS band in CdCl 2 follows a linear dispersion according to the Raman–Stokes law if the excitation energy is tuned below the absorption threshold. The situation changes for core excitation above the photoabsorption threshold where the dispersion relation is split into two branches. The position of the resonant contribution does not depend on the excitation energy, while the excitonic sideband follows the Raman–Stoke law. Combined XANES and RIXS measurements compared to calculated band structure allowed us to determine the direct band gap of CdCl 2 to be at 5.7 ± 0.05 eV. -- Highlights: ► XANES at the K edge of Cl and related emission KV band interpreted within the ab initio DFT formalism. ► Two dominant contributions observed in RIXS data: the resonant and the excitonic ones. ► The dispersion relation below the absorption threshold follows Raman–Stokes law. ► Dispersion above the threshold splits into two qualitatively different relations. ► Overlapping of XAS spectrum with RIXS one makes possible to estimate direct band gap value to be 5.7 eV.

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

Energy Technology Data Exchange (ETDEWEB)

Fittschen, U.E.A. [Department of Chemistry, University of Hamburg, Martin-Luther-King-Platz 6, 20146 Hamburg (Germany)], E-mail: ursula.fittschen@chemie.uni-hamburg.de; Meirer, F. [Atominstitut, Vienna University of Technology, Stadionallee 2, 1020 Wien (Austria)], E-mail: fmeirer@ati.ac.at; Streli, C. [Atominstitut, Vienna University of Technology, Stadionallee 2, 1020 Wien (Austria)], E-mail: streli@ati.ac.at; Wobrauschek, P. [Atominstitut, Vienna University of Technology, Stadionallee 2, 1020 Wien (Austria)], E-mail: wobi@ati.ac.at; Thiele, J. [Department of Chemistry, University of Hamburg, Martin-Luther-King-Platz 6, 20146 Hamburg (Germany)], E-mail: Julian.Thiele@gmx.de; Falkenberg, G. [Hamburger Synchrotronstrahlungslabor at Deutsches Elektronen-Synchrotron DESY, Notkestr. 85, 22603 Hamburg (Germany)], E-mail: falkenbe@mail.desy.de; Pepponi, G. [ITC-irst, Via Sommarive 18, 38050 Povo (Trento) (Italy)], E-mail: pepponi@itc.it

2008-12-15

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 {mu}m, 8.0-2.0 {mu}m, 2.0-0.13 {mu}m 0.13-0.015 {mu}m (aerodynamic particle size) and 15-30 nm, 30-60 nm, 60-130 nm, 130-250 nm, 250-500 nm, 0.5-1 {mu}m, 1-2 {mu}m, 2-4 {mu}m, 4-8 {mu}m, 8-16 {mu}m. 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

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

International Nuclear Information System (INIS)

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

2008-01-01

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

X-ray Absorption Spectroscopy Characterization of Electrochemical Processes in Renewable Energy Storage and Conversion Devices

Energy Technology Data Exchange (ETDEWEB)

Farmand, Maryam [George Washington Univ., Washington, DC (United States)

2013-05-19

The development of better energy conversion and storage devices, such as fuel cells and batteries, is crucial for reduction of our global carbon footprint and improving the quality of the air we breathe. However, both of these technologies face important challenges. The development of lower cost and better electrode materials, which are more durable and allow more control over the electrochemical reactions occurring at the electrode/electrolyte interface, is perhaps most important for meeting these challenges. Hence, full characterization of the electrochemical processes that occur at the electrodes is vital for intelligent design of more energy efficient electrodes. X-ray absorption spectroscopy (XAS) is a short-range order, element specific technique that can be utilized to probe the processes occurring at operating electrode surfaces, as well for studying the amorphous materials and nano-particles making up the electrodes. It has been increasingly used in recent years to study fuel cell catalysts through application of the and #916; and mgr; XANES technique, in combination with the more traditional X-ray Absorption Near Edge Structure (XANES) and Extended X-ray Absorption Fine Structure (EXAFS) techniques. The and #916; and mgr; XANES data analysis technique, previously developed and applied to heterogeneous catalysts and fuel cell electrocatalysts by the GWU group, was extended in this work to provide for the first time space resolved adsorbate coverages on both electrodes of a direct methanol fuel cell. Even more importantly, the and #916; and mgr; technique was applied for the first time to battery relevant materials, where bulk properties such as the oxidation state and local geometry of a cathode are followed.

Degradation in carbon stocks near tropical forest edges.

Science.gov (United States)

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

2015-12-18

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

Manganese speciation in Diplodon chilensis patagonicus shells: a XANES study

Science.gov (United States)

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

2009-04-01

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

On the state of iron in a clinoptilolite

International Nuclear Information System (INIS)

Marco, J.F.; Gracia, M.; Gancedo, J.R.; Gonzalez-Carreno, T.; Arcoya, A.; Seoane, X.L.

1995-01-01

The characterization of an iron-containing natural zeolitic sample from the deposit of Tasajeras (Cuba) has been carried out by means of X-ray powder diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), X-ray photoelectron spectroscopy (XPS), 57 Fe Moessbauer spectroscopy and Fe K-edge X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS). The results show that iron is mainly located (ca. 96%) as Fe 3+ in an octahedral site of the clinoptilolite framework. No evidence of tetrahedrally coordinated Fe 3+ was found. The remaining 4% Fe is located as Fe 2+ in an extraframework octahedral site, probably as a solvated ion, within the clinoptilolite structure. (orig.)

Retention and chemical speciation of uranium in an oxidized wetland sediment from the Savannah River Site

Energy Technology Data Exchange (ETDEWEB)

Li, Dien; Seaman, John C.; Chang, Hyun-Shik; Jaffe, Peter R.; Koster van Groos, Paul; Jiang, De-Tong; Chen, Ning; Lin, Jinru; Arthur, Zachary; Pan, Yuanming; Scheckel, Kirk G.; Newville, Matthew; Lanzirotti, Antonio; Kaplan, Daniel I.

2014-05-01

Uranium speciation and retention mechanism onto Savannah River Site (SRS) wetland sediments was studied using batch (ad)sorption experiments, sequential extraction desorption tests and U L{sub 3}-edge X-ray absorption near-edge structure (XANES) spectroscopy of contaminated wetland sediments. U was highly retained by the SRS wetland sediments. In contrast to other similar but much lower natural organic matter (NOM) sediments, significant sorption of U onto the SRS sediments was observed at pH <4 and pH >8. Sequential extraction tests indicated that the U(VI) species were primarily associated with the acid soluble fraction (weak acetic acid extractable) and NOM fraction (Na-pyrophosphate extractable). Uranium L3- edge XANES spectra of the U-retained sediments were nearly identical to that of uranyl acetate. The primary oxidation state of U in these sediments was as U(VI), and there was little evidence that the high sorptive capacity of the sediments could be ascribed to abiotic or biotic reduction to the less soluble U(IV) species. The molecular mechanism responsible for the high U retention in the SRS wetland sediments is likely related to the chemical bonding of U to organic carbon.

Coupled-cluster response theory for near-edge x-ray-absorption fine structure of atoms and molecules

DEFF Research Database (Denmark)

Coriani, Sonia; Christiansen, Ove; Fransson, Thomas

2012-01-01

triple corrected excitation energies CCSDR(3). This work is a first step toward the extension of these theoretical electronic structure methods of well-established high accuracy in UV-vis absorption spectroscopies to applications concerned with x-ray radiation. From the imaginary part of the linear...... response function, the near K-edge x-ray absorption spectra of neon, water, and carbon monoxide are determined and compared with experiment. Results at the CCSD level show relative peak intensities in good agreement with experiment with discrepancies in transition energies due to incomplete treatment...

Transport Measurements and Synchrotron-Based X-Ray Absorption Spectroscopy of Iron Silicon Germanide Grown by Molecular Beam Epitaxy

Science.gov (United States)

Elmarhoumi, Nader; Cottier, Ryan; Merchan, Greg; Roy, Amitava; Lohn, Chris; Geisler, Heike; Ventrice, Carl, Jr.; Golding, Terry

2009-03-01

Some of the iron-based metal silicide and germanide phases have been predicted to be direct band gap semiconductors. Therefore, they show promise for use as optoelectronic materials. We have used synchrotron-based x-ray absorption spectroscopy to study the structure of iron silicon germanide films grown by molecular beam epitaxy. A series of Fe(Si1-xGex)2 thin films (2000 -- 8000å) with a nominal Ge concentration of up to x = 0.04 have been grown. X-ray absorption near edge structure (XANES) and extended x-ray absorption fine structure (EXAFS) measurements have been performed on the films. The nearest neighbor co-ordination corresponding to the β-FeSi2 phase of iron silicide provides the best fit with the EXAFS data. Temperature dependent (20 coefficient was calculated. Results suggest semiconducting behavior of the films which is consistent with the EXAFS results.

X-ray spectroscopic and magnetic studies of RBaCo_2O_5_._5, R = Pr, Nd, Sm, Gd and Y

International Nuclear Information System (INIS)

Ganorkar, S.; Priolkar, K. R.; Sarode, P. R.; Emura, S.

2016-01-01

The structural and magnetic properties of layered perovskites of the type RBaCo_2O_5_+_δ with δ ≤0.5 (R=Pr, Nd, Sm, Gd and Y) have been investigated. The samples were prepared by the sol-gel method and characterized by X-ray diffraction, magnetization and X-ray absorption near edge structure (XANES) spectroscopy. It is found that the magnetic properties depend on the size of the rare-earth ion. The critical size of the rare-earth ion introduces structural distortion which affects the Co-O hybridization in these layered perovskites. The detailed analysis of experimental and calculated XANES spectra throws some light on spin states of Co ions in these perovskites.

The nature of ancient Egyptian copper-containing carbon inks is revealed by synchrotron radiation based X-ray microscopy

OpenAIRE

Christiansen , Thomas; Cotte , Marine; Loredo-Portales , René; Lindelof , Poul ,; Mortensen , Kell; Ryholt , Kim; Larsen , Sine

2017-01-01

International audience; For the first time it is shown that carbon black inks on ancient Egyptian papyri from different time periods and geographical regions contain copper. The inks have been investigated using synchrotron-based micro X-ray fluorescence (XRF) and micro X-ray absorption near-edge structure spectroscopy (XANES) at the European Synchrotron Radiation Facility (ESRF). The composition of the copper-containing carbon inks showed no significant differences that could be related to t...

New insights into the sorption mechanism of cadmium on red mud

International Nuclear Information System (INIS)

Luo Lei; Ma Chenyan; Ma Yibing; Zhang Shuzhen; Lv Jitao; Cui Mingqi

2011-01-01

Effectiveness and mechanism of cadmium (Cd) sorption on original, acidified and ball milling nano-particle red muds were investigated using batch sorption experiments, sequential extraction analysis and X-ray absorption near edge structure (XANES) spectroscopy. The maximum sorption capacity of Cd was 0.16, 0.19, and 0.21 mol/kg for the original, acidified, and nano-particle red muds at pH 6.5, respectively. Both acidification and ball-milling treatments significantly enhanced Cd sorption and facilitated transformation of Cd into less extractable fractions. The Cd L III -edge XANES analysis indicated the formation of inner-sphere complexes of Cd similar to XCdOH (X represents surface groups on red mud) on the red mud surfaces although outer-sphere complexes of Cd were the primary species. This work shed light on the potential application of red mud to remediate Cd-contaminated soils and illustrated the promising tool of XANES spectroscopy for speciation of multicomponent systems of environmental relevance. - Graphical abstract: Display Omitted Highlights: → Red mud has a strong affinity for Cd contaminants. → Ball-milling treatments significantly enhance Cd sorption on red mud. → Cadmium partially formed inner-sphere complexes on the red mud surfaces. → Red mud can be used to remediate Cd contaminated soils effectively. - Cadmium can be strongly sorbed and partially forms inner-sphere complexes on red mud.

Molecular speciation of phosphorus in organic amendments and amended soils using nuclear magnetic resonance and X-ray absorption spectroscopies

International Nuclear Information System (INIS)

Ajibove, B.

2007-01-01

Characterization of phosphorus (P) in organic amendments is essential for environmentally sustainable fertilization of agricultural soils. The sequential chemical extraction (SCE) technique commonly used for P characterization does not provide any direct molecular information about P species. Studies were conducted to characterize P species in organic amendments and amended soils at a molecular level. The SCE was used to fractionate P in organic amendments including biosolids, hog, dairy and beef cattle manures, and poultry litter. The extracts were analyzed for total P and P species using inductively coupled plasma - optical emission spectroscopy (ICP-OES) and solution 31 P nuclear magnetic resonance (NMR) spectroscopy, respectively. The relative proportions of P species in intact organic amendments and residues after each extraction, and calcareous soils amended with organic amendments and monoammonium phosphate (MAP) were estimated using the synchrotron-based P 1s X-ray absorption near edge structure (XANES) spectroscopy. The solution 31 P NMR provided a detailed characterization of organic P in the non-labile NaOH and HCl fractions of organic amendments, but was limited in characterizing the labile fractions of most of these organic amendments due to their proneness to alkaline hydrolysis. The XANES analysis, however, identified the actual chemical species constituting the labile P that was only characterized as inorganic P or orthophosphates by sequential extraction and solution 31 P NMR. In the amended Vertisolic and Chernozemic soils, XANES analysis estimated 'soluble and adsorbed P' as the dominant P species. For the Vertisolic soil, both the unamended and soil amended with biosolids and MAP contained hydroxyapatite (HAP). In addition, soil amended with biosolids, hog and dairy manures contained β-tricalcium phosphate (TRICAL), a more soluble CaP than HAP. TRICAL was found in all amended soils except in that amended with hog manure, while HAP was present

Fe distribution and speciation in human nails

Energy Technology Data Exchange (ETDEWEB)

Katsikini, M., E-mail: katsiki@auth.g [Aristotle University of Thessaloniki, School of Physics, 54124 Thessaloniki (Greece); Pinakidou, F.; Mavromati, E.; Paloura, E.C. [Aristotle University of Thessaloniki, School of Physics, 54124 Thessaloniki (Greece); Gioulekas, D. [Aristotle University of Thessaloniki, Medical School, 54124 Thessaloniki (Greece); Grolimund, D. [Swiss Light Source, Paul Scherer Institut, 5232 Villigen (Switzerland)

2010-02-15

Micro-X-ray Fluorescence (mu-XRF) and Fe-K edge micro-X-ray Absorption Near Edge Structure (mu-XANES) spectroscopies are applied for the study of the distribution and the spatially-resolved bonding environment of Fe in human nails. The mu-XRF maps reveal that Fe forms islands where its concentration is up to six times higher than in the rest of the sample. Comparison of the map characteristics of two nails that belong to healthy and ill donors (affected by lung cancer), reveals that there is no significant variation in the size distribution of the Fe-rich inclusions contrary to their spatial density which is found higher in the nail of the ill donor. However, a relation between the variations of the spatial density and the illness can not be established due to the small number of the studied samples. The analysis of the Fe-K mu-XANES spectra reveals that the bonding environment of Fe varies between the samples and between different spots of the same sample with different Fe concentration. The characteristics of the pre-edge peak in the Fe-K XANES spectra indicate the presence of both Fe{sup +3} and Fe{sup +2} that participate in the formation of distorted octahedra. Finally, the area under the pre-edge peak depends linearly on the position of the absorption edge indicating variation of the Fe ligation between the samples and/or between different spots in the same sample.

Characterization of yellow and colorless decorative glasses from the Temple of the Emerald Buddha, Bangkok, Thailand

Science.gov (United States)

Klysubun, Wantana; Ravel, Bruce; Klysubun, Prapong; Sombunchoo, Panidtha; Deenan, Weeraya

2013-06-01

Yellow and colorless ancient glasses, which were once used to decorate the Temple of the Emerald Buddha, Bangkok, Thailand, around 150 years ago, are studied to unravel the long-lost glass-making recipes and manufacturing techniques. Analyses of chemical compositions, using synchrotron x-ray fluorescence (SRXRF), indicate that the Thai ancient glasses are soda lime silica glasses (60 % SiO2; 10 % Na2O; 10 % CaO) bearing lead oxide between 2-16 %. Iron (1.5-9.4 % Fe2O3) and manganese (1.7 % MnO) are present in larger abundance than the other 3 d transition metals detected (0.04-0.2 %). K-edge x-ray absorption near edge spectroscopy (XANES) and extended x-ray absorption fine structure spectroscopy (EXAFS) provide conclusive evidence on the oxidation states of Fe being 3+ and Mn being 2+ and on short-length tetrahedral structures around the cations. This suggests that iron is used as a yellow colorant with manganese as a decolorant. L 3-edge XANES results reveal the oxidation states of lead as 2+. The results from this work provide information crucial for replicating these decorative glasses for the future restoration of the Temple of the Emerald Buddha.

Biosorption of Cr(VI) by coconut coir: Spectroscopic investigation on the reaction mechanism of Cr(VI) with lignocellulosic material

International Nuclear Information System (INIS)

Shen, Ying-Shuian; Wang, Shan-Li; Huang, Shiuh-Tsuen; Tzou, Yu-Min; Huang, Jang-Hung

2010-01-01

In this study, the removal mechanism of Cr(VI) from water by coconut coir (CC) was investigated using X-ray photoelectron spectroscopy (XPS), Cr K-edge X-ray absorption near edge structure (XANES) and FTIR spectroscopy. The results showed that, upon reaction with CC at pH 3, Cr(VI) was reduced to Cr(III), which was either bound to CC or released back into solution. As revealed by the FTIR spectra of CC before and after reacting with Cr(VI), the phenolic methoxyl and hydroxyl groups of lignin in CC are the dominant drivers of Cr(VI) reduction, giving rise to carbonyl and carboxyl groups on CC. These functional groups can subsequently provide binding sites for Cr(III) resulting from Cr(VI) reduction. In conjunction with forming complexes with carbonyl and carboxyl groups, the formation of Cr(III) hydroxide precipitate could also readily occur as revealed by the linear combination fitting of the Cr K-edge XANES spectrum using a set of reference compounds. The phenolic groups in lignin are responsible for initiating Cr(VI) reduction, so lignocellulosic materials containing a higher amount of phenolic groups are expected to be more effective scavengers for removal of Cr(VI) from the environment.

Biosorption of Cr(VI) by coconut coir: Spectroscopic investigation on the reaction mechanism of Cr(VI) with lignocellulosic material

Energy Technology Data Exchange (ETDEWEB)

Shen, Ying-Shuian [Department of Soil and Environmental Sciences, National Chung Hsing University, 250 Kuo Kuang Road, Taichung 40227, Taiwan (China); Wang, Shan-Li, E-mail: slwang@nchu.edu.tw [Department of Soil and Environmental Sciences, National Chung Hsing University, 250 Kuo Kuang Road, Taichung 40227, Taiwan (China); Huang, Shiuh-Tsuen [Department of Soil and Environmental Sciences, National Chung Hsing University, 250 Kuo Kuang Road, Taichung 40227, Taiwan (China); Department of Science Application and Dissemination, National Taichung University, Taichung, Taiwan (China); Tzou, Yu-Min; Huang, Jang-Hung [Department of Soil and Environmental Sciences, National Chung Hsing University, 250 Kuo Kuang Road, Taichung 40227, Taiwan (China)

2010-07-15

In this study, the removal mechanism of Cr(VI) from water by coconut coir (CC) was investigated using X-ray photoelectron spectroscopy (XPS), Cr K-edge X-ray absorption near edge structure (XANES) and FTIR spectroscopy. The results showed that, upon reaction with CC at pH 3, Cr(VI) was reduced to Cr(III), which was either bound to CC or released back into solution. As revealed by the FTIR spectra of CC before and after reacting with Cr(VI), the phenolic methoxyl and hydroxyl groups of lignin in CC are the dominant drivers of Cr(VI) reduction, giving rise to carbonyl and carboxyl groups on CC. These functional groups can subsequently provide binding sites for Cr(III) resulting from Cr(VI) reduction. In conjunction with forming complexes with carbonyl and carboxyl groups, the formation of Cr(III) hydroxide precipitate could also readily occur as revealed by the linear combination fitting of the Cr K-edge XANES spectrum using a set of reference compounds. The phenolic groups in lignin are responsible for initiating Cr(VI) reduction, so lignocellulosic materials containing a higher amount of phenolic groups are expected to be more effective scavengers for removal of Cr(VI) from the environment.

Biosorption of Cr(VI) by coconut coir: spectroscopic investigation on the reaction mechanism of Cr(VI) with lignocellulosic material.

Science.gov (United States)

Shen, Ying-Shuian; Wang, Shan-Li; Huang, Shiuh-Tsuen; Tzou, Yu-Min; Huang, Jang-Hung

2010-07-15

In this study, the removal mechanism of Cr(VI) from water by coconut coir (CC) was investigated using X-ray photoelectron spectroscopy (XPS), Cr K-edge X-ray absorption near edge structure (XANES) and FTIR spectroscopy. The results showed that, upon reaction with CC at pH 3, Cr(VI) was reduced to Cr(III), which was either bound to CC or released back into solution. As revealed by the FTIR spectra of CC before and after reacting with Cr(VI), the phenolic methoxyl and hydroxyl groups of lignin in CC are the dominant drivers of Cr(VI) reduction, giving rise to carbonyl and carboxyl groups on CC. These functional groups can subsequently provide binding sites for Cr(III) resulting from Cr(VI) reduction. In conjunction with forming complexes with carbonyl and carboxyl groups, the formation of Cr(III) hydroxide precipitate could also readily occur as revealed by the linear combination fitting of the Cr K-edge XANES spectrum using a set of reference compounds. The phenolic groups in lignin are responsible for initiating Cr(VI) reduction, so lignocellulosic materials containing a higher amount of phenolic groups are expected to be more effective scavengers for removal of Cr(VI) from the environment. 2010 Elsevier B.V. All rights reserved.

Challenges in the noninvasive detection of body composition using near-infrared spectroscopy

Directory of Open Access Journals (Sweden)

Wenliang Chen

2014-11-01

Full Text Available Noninvasive detection of body composition plays a significant role in the improvement of life quality and reduction in complications of the patients, and the near-infrared (NIR spectroscopy, with the advantages of painlessness and convenience, is considered as the most promising tool for the online noninvasive monitoring of body composition. However, quite different from other fields of online detection using NIR spectroscopy, such as food safety and environment monitoring, noninvasive detection of body composition demands higher precision of the instruments as well as more rigorousness of measurement conditions. Therefore, new challenges emerge when NIR spectroscopy is applied to the noninvasive detection of body composition, which, in this paper, are first concluded from the aspects of measurement methods, measurement conditions, instrument precision, multi-component influence, individual difference and novel weak-signal extraction method based on our previous research in the cutting-edge field of NIR noninvasive blood glucose detection. Moreover, novel ideas and approaches of our group to solve these problems are introduced, which may provide evidence for the future development of noninvasive blood glucose detection, and further contribute to the noninvasive detection of other body compositions using NIR spectroscopy.

Na-Ion Intercalation and Charge Storage Mechanism in 2D Vanadium Carbide

Energy Technology Data Exchange (ETDEWEB)

Bak, Seong-Min [Chemistry Division, Brookhaven National Laboratory, Upton NY 11973 USA; Qiao, Ruimin [Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley CA 94720 USA; Yang, Wanli [Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley CA 94720 USA; Lee, Sungsik [X-Ray Science Division, Argonne National Laboratory, Argonne IL 60439 USA; Yu, Xiqian [Institute of Physics, Chinese Academy of Science, Beijing 100190 China; Anasori, Babak [Department of Material Science and Engineering, A.J. Drexel Nanomaterials Institute, Drexel University, Philadelphia PA 19104 USA; Lee, Hungsui [Chemistry Division, Brookhaven National Laboratory, Upton NY 11973 USA; Gogotsi, Yury [Department of Material Science and Engineering, A.J. Drexel Nanomaterials Institute, Drexel University, Philadelphia PA 19104 USA; Yang, Xiao-Qing [Chemistry Division, Brookhaven National Laboratory, Upton NY 11973 USA

2017-07-14

Two-dimensional vanadium carbide MXene containing surface functional groups (denoted as V2CTx, where Tx are surface functional groups) was synthesized and studied as anode material for Na-ion batteries. V2CTx anode exhibits reversible charge storage with good cycling stability and high rate capability through electrochemical test. The charge storage mechanism of V2CTx material during Na+ intercalation/deintercalation and the redox reaction of vanadium were studied using a combination of synchrotron based X-ray diffraction (XRD), hard X-ray absorption near edge spectroscopy (XANES) and soft X-ray absorption spectroscopy (sXAS). Experimental evidence of a major contribution of redox reaction of vanadium to the charge storage and the reversible capacity of V2CTx during sodiation/desodiation process have been provided through V K-edge XANES and V L2,3-edge sXAS results. A correlation between the CO32- content and Na+ intercalation/deintercalation states in the V2CTx electrode observed from C and O K-edge in sXAS results imply that some additional charge storage reactions may take place between the Na+-intercalated V2CTx and the carbonate based non-aqueous electrolyte. The results of this study will provide valuable information for the further studies on V2CTx as anode material for Na-ion batteries and capacitors.

Electronic Structure from Iron L-edge Spectroscopy : An Example of Spin Transition Evidenced by Soft X-ray Absorption Spectroscopy

NARCIS (Netherlands)

Cartier dit Moulin, Ch.; Flank, A.M.; Rudolf, P.; Chen, C.T.

1993-01-01

Soft X-ray Absorption Spectroscopy at the transition metal L2,3 edges provides information about the 3d unoccupied states by dipole allowed transitions. We have recorded iron L2,3 edges in order to follow the reversible thermal spin interconversion (S=2 S=0) of the Fe(II)(o-phenantroline)2(NCS)2.

Sintering process of Eu doped luminescent glass prepared from porous glass

International Nuclear Information System (INIS)

Akai, T; Murakami, M; Yamashita, M; Okajima, T; Umesaki, N

2011-01-01

Eu doped high silica glass prepared by sintering porous glass exhibits blue luminescence with high quantum efficiency. In this work, we studied effects of sintering temperature on valance state of europium ion. To investigate a change of valance state of Eu, X-ray absorption near edge structure (XANES) spectroscopy measurements were carried out. Intensity of blue emission at around 430nm drastically increases when the sintering temperature is above 1000 deg. C. From XANES spectra, it is found that almost all the Eu exist as Eu 3+ in a samples sintered below 900 deg. C, while more than 70% of Eu exist as Eu 2+ in the sample sintered at 1050 deg. C and 1100 deg. C. The drastic change of oxidation state of europium ion between 900 and 1050 deg. C is discussed in relation to the structural change probed by infrared (IR) spectroscopy.

Electronic structure of titania aerogels: Soft x-ray absorption study

International Nuclear Information System (INIS)

Kucheyev, S.O.; Van Buuren, T.V.; Baumann, T.F.; Satcher, J.H.; Willey, T.M.; Muelenberg, R.W.; Felter, T.E.; Poco, J.E.; Gammon, S.A.; Terminello, L.J.

2004-01-01

Full text: Titania aerogels - a somewhat extreme form of nanoporous TiO 2 - are open-cell solid foams derived from highly crosslinked gels by drying them under supercritical conditions. In this presentation, the unoccupied electronic states of TiO 2 aerogels are studied by soft x-ray absorption near-edge structure (XANES) spectroscopy. High-resolution O K-edge and Ti L 2,3 -edge XANES spectra of aerogels are compared with those of rutile, anatase, and unrelaxed amorphous phases of full- density TiO 2 . Results show that all the main spectroscopic features of aerogels, reflecting the element-specific partial density of empty electronic states and correlation effects, can be attributed to the absence of long-range order in stoichiometric amorphous TiO 2 . Based on these results, we discuss the effects of short- and long-range order on the electronic structure of TiO 2 . This work was performed under the auspices of the U.S. Department of Energy by the University of California, Lawrence Livermore National Laboratory under Contract No. W-7405-Eng-48

Redox chemistry of a binary transition metal oxide (AB2O4): a study of the Cu(2+)/Cu(0) and Fe(3+)/Fe(0) interconversions observed upon lithiation in a CuFe2O4 battery using X-ray absorption spectroscopy.

Science.gov (United States)

Cama, Christina A; Pelliccione, Christopher J; Brady, Alexander B; Li, Jing; Stach, Eric A; Wang, Jiajun; Wang, Jun; Takeuchi, Esther S; Takeuchi, Kenneth J; Marschilok, Amy C

2016-06-22

Copper ferrite, CuFe2O4, is a promising candidate for application as a high energy electrode material in lithium based batteries. Mechanistic insight on the electrochemical reduction and oxidation processes was gained through the first X-ray absorption spectroscopic study of lithiation and delithiation of CuFe2O4. A phase pure tetragonal CuFe2O4 material was prepared and characterized using laboratory and synchrotron X-ray diffraction, Raman spectroscopy, and transmission electron microscopy. Ex situ X-ray absorption spectroscopy (XAS) measurements were used to study the battery redox processes at the Fe and Cu K-edges, using X-ray absorption near-edge structure (XANES), extended X-ray absorption fine structure (EXAFS), and transmission X-ray microscopy (TXM) spectroscopies. EXAFS analysis showed upon discharge, an initial conversion of 50% of the copper(ii) to copper metal positioned outside of the spinel structure, followed by a migration of tetrahedral iron(iii) cations to octahedral positions previously occupied by copper(ii). Upon charging to 3.5 V, the copper metal remained in the metallic state, while iron metal oxidation to iron(iii) was achieved. The results provide new mechanistic insight regarding the evolution of the local coordination environments at the iron and copper centers upon discharging and charging.

Investigating the local structure of B-site cations in (1-x)BaTiO3-xBiScO3 and (1-x)PbTiO3-xBiScO3 using X-ray absorption spectroscopy

Science.gov (United States)

Blanchard, Peter E. R.; Grosvenor, Andrew P.

2018-05-01

The structural properties of (1-x)BaTiO3-xBiScO3 and (1-x)PbTiO3-xBiScO3 were investigated using powder X-ray diffraction and X-ray absorption spectroscopy. Diffraction measurements confirmed that substituting small amounts of BiScO3 into BaTiO3 initially stabilizes a cubic phase at x = 0.2 before impurity phases begin to form at x = 0.5. BiScO3 substitution also resulted in noticeable changes in the local coordination environment of Ti4+. X-ray absorption near-edge spectroscopy (XANES) analysis showed that replacing Ti4+ with Sc3+ results in an increase in the off-centre displacement of Ti4+ cations. Surprisingly, BiScO3 substitution has no effect on the displacement of the Ti4+ cation in the (1-x)PbTiO3-xBiScO3 solid solution.

XAS Studies of Arsenic in the Environment

International Nuclear Information System (INIS)

Charnock, J. M.; Polya, D. A.; Gault, A. G.; Morgan, A. J.

2007-01-01

Arsenic is present in low concentrations in much of the Earth's crust and changes in its speciation are vital to understanding its transport and toxicity in the environment. We have used X-ray absorption spectroscopy to investigate the coordination sites of arsenic in a wide variety of samples, including soil and earthworm tissues from arsenic-contaminated land, and human hair and nail samples from people exposed to arsenic in Cambodia. Our results confirm the effectiveness of using X-ray absorption near edge structure (XANES) and X-ray absorption fine structure (EXAFS) spectroscopy to determine speciation changes in environmental samples

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

Science.gov (United States)

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

2002-05-01

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

High-resolution parallel electron energy-loss spectroscopy of MnL2,3-edges in inorganic manganese compounds

International Nuclear Information System (INIS)

Garvie, L.A.J.; Craven, A.J.

1994-01-01

Parallel electron energy-loss spectroscopy (PEELS) in a scanning transmission electron microscope (STEM) was used to record the Mn L 2,3 -edges from a range of natural and synthetic manganese containing materials, covering valences 0, II, III, IV and VII, with an energy resolution of ca. 0.5 eV. The Mn L 2,3 electron-loss near-edge structure (ELNES) of these edges provided a sensitive fingerprint of its valence. The Mn 2+ L 2,3 -edges show little sensitivity to the local site symmetry of the ligands surrounding the manganese. This is illustrated by comparing the Mn L 2,3 -edges from 4-, 6-and 8-fold coordinated Mn 2+ . In contrast, the Mn L 3 -edges from Mn 3+ and Mn 4+ containing minerals exhibited ELNES that are interpreted in terms of a crystals-field splitting of the 3d electrons, governed by the symmetry of the surrounding ligands. The Mn L 3 -edges for octahedrally coordinated Mn 2+ , Mn 3+ and Mn 4+ showed variations in their ELNES that were sensitive to the crystal-field strength. The crystal-field strength (10Q) was measured from these edges and compared very well with published optically determinted values. The magnitude of 10Dq measured from the Mn L 3 -edges and their O K-edge prepeaks of the manganese oxides were almost identical. This further confirms that the value of 10Dq measured at the Mn L 3 -edge is correct. Selected spectra are compared with theoretical 2p atomic multiplet spectra and the differences and similarities are explained in terms of the covalency and site symmetry of the manganese. The Mn L 3 -edges allow the valence of the manganese to be ascertained, even in multivalent state materials, and can also be used to dtermin 10Dq. (orig.)

An alternative preparation method for ion exchanged catalysts: Solid state redox reaction

DEFF Research Database (Denmark)

Schneider, E.; Hagen, A.; Grunwaldt, J.-D.

2004-01-01

A new method for modifying zeolites with zinc is proposed. The solid state redox reaction between metallic zinc and ZSM-5 zeolites with different Si/Al ratios was investigated by temperature programmed hydrogen evolution (TPHE), X-ray absorption near edge structure (XANES) and diffuse reflectance...... infrared Fourier transform spectroscopy (DRIFTS). The evolution of hydrogen was detected at temperatures above 620 K. The source of hydrogen was the solid state redox reaction of the metal with protons of the support. The samples exhibit catalytic activity in ethane aromatization indicating that zinc...... should be located at the same sites as in catalysts prepared by conventional methods. Combination of XANES and catalytic activity point to zinc being mainly present in tetrahedral geometry under reaction conditions....

Recovery of zinc in phosphor wastes via electrokinetic treatments

International Nuclear Information System (INIS)

Yu, M.Y.; Wang, H. Paul; Chen, C.Y.; Hsiung, T.-L.; Wei, Yu-Ling; Tai, H.-S.; Chiang, K.-C.

2007-01-01

Speciation of zinc in phosphor wastes during electrokinetic treatments has been studied by in situ X-ray absorption near edge structure (XANES) spectroscopy in the present work. The least-square fits of the in situ XANES spectra show that the major zinc species in the phosphor waste are ZnS (77%), ZnO (10%), and Zn(OH) 2 (13%). During the electrokinetic treatment for 90 min, 25% of ZnS and 4% of ZnO are dissolved. About 42% of zinc is enriched on the cathode under the electric field (5 V/cm). Prolonging the electrokinetic treatment time to 4 h under the electric field of 5 V/cm, at least 80% of zinc in the phosphor waste can be recovered

X-ray and photoelectron spectroscopy of the structure, reactivity, and electronic structure of semiconductor nanocrystals

Energy Technology Data Exchange (ETDEWEB)

Hamad, Kimberly Sue [Univ. of California, Berkeley, CA (United States)

2000-01-01

Semiconductor nanocrystals are a system which has been the focus of interest due to their size dependent properties and their possible use in technological applications. Many chemical and physical properties vary systematically with the size of the nanocrystal and thus their study enables the investigation of scaling laws. Due to the increasing surface to volume ratio as size is decreased, the surfaces of nanocrystals are expected to have a large influence on their electronic, thermodynamic, and chemical behavior. In spite of their importance, nanocrystal surfaces are still relatively uncharacterized in terms of their structure, electronic properties, bonding, and reactivity. Investigation of nanocrystal surfaces is currently limited by what techniques to use, and which methods are suitable for nanocrystals is still being determined. This work presents experiments using x-ray and electronic spectroscopies to explore the structure, reactivity, and electronic properties of semiconductor (CdSe, InAs) nanocrystals and how they vary with size. Specifically, x-ray absorption near edge spectroscopy (XANES) in conjunction with multiple scattering simulations affords information about the structural disorder present at the surface of the nanocrystal. X-ray photoelectron spectroscopy (XPS) and ultra-violet photoelectron spectroscopy (UPS) probe the electronic structure in terms of hole screening, and also give information about band lineups when the nanocrystal is placed in electric contact with a substrate. XPS of the core levels of the nanocrystal as a function of photo-oxidation time yields kinetic data on the oxidation reaction occurring at the surface of the nanocrystal.

Near-Field Spectroscopy with Nanoparticles Deposited by AFM

Science.gov (United States)

Anderson, Mark S.

2008-01-01

An alternative approach to apertureless near-field optical spectroscopy involving an atomic-force microscope (AFM) entails less complexity of equipment than does a prior approach. The alternative approach has been demonstrated to be applicable to apertureless near-field optical spectroscopy of the type using an AFM and surface enhanced Raman scattering (SERS), and is expected to be equally applicable in cases in which infrared or fluorescence spectroscopy is used. Apertureless near-field optical spectroscopy is a means of performing spatially resolved analyses of chemical compositions of surface regions of nanostructured materials. In apertureless near-field spectroscopy, it is common practice to utilize nanostructured probe tips or nanoparticles (usually of gold) having shapes and dimensions chosen to exploit plasmon resonances so as to increase spectroscopic-signal strengths. To implement the particular prior approach to which the present approach is an alternative, it is necessary to integrate a Raman spectrometer with an AFM and to utilize a special SERS-active probe tip. The resulting instrumentation system is complex, and the tasks of designing and constructing the system and using the system to acquire spectro-chemical information from nanometer-scale regions on a surface are correspondingly demanding.

Quantitative results near the band edges of disordered systems

International Nuclear Information System (INIS)

Economou, E.N.; Soukoulis, C.M.; Cohen, M.H.; Zdetsis, A.D.

1985-01-01

By combining the coherent-potential approximation, the potential-well analogy, and theories for the near tail in the density of states, we obtain, for the first time, explicitly quantitative results for the various quantities of interest near the band edges of disordered systems. These results exhibit a certain universality and can be expressed in terms of simple analytic functions, provided that disorder is not larger than about (1/5) of the bandwidth

Near Infrared Spectroscopy as a Hemodynamic Monitor in Critical Illness.

Science.gov (United States)

Ghanayem, Nancy S; Hoffman, George M

2016-08-01

The objectives of this review are to discuss the technology and clinical interpretation of near infrared spectroscopy oximetry and its clinical application in patients with congenital heart disease. MEDLINE and PubMed. Near infrared spectroscopy provides a continuous noninvasive assessment of tissue oxygenation. Over 20 years ago, near infrared spectroscopy was introduced into clinical practice for monitoring cerebral oxygenation during cardiopulmonary bypass in adults. Since that time, the utilization of near infrared spectroscopy has extended into the realm of pediatric cardiac surgery and is increasingly being used in the cardiac ICU to monitor tissue oxygenation perioperatively.

'Beam-emission spectroscopy' diagnostics also measure edge fast-ion light

International Nuclear Information System (INIS)

Heidbrink, W W; Bortolon, A; McKee, G R; Smith, D R

2011-01-01

Beam-emission spectroscopy (BES) diagnostics normally detect fluctuations in the light emitted by an injected neutral beam. Under some circumstances, however, light from fast ions that charge exchange in the high neutral-density region at the edge of the plasma make appreciable contributions to the BES signals. This 'passive' fast-ion D α (FIDA) light appears in BES signals from both the DIII-D tokamak and the National Spherical Torus Experiment (NSTX). One type of passive FIDA light is associated with classical orbits that traverse the edge. Another type is caused by instabilities that expel fast ions from the core; this light can complicate measurement of the instability eigenfunction.

Ultrafast stimulated Raman spectroscopy in the near-infrared region

International Nuclear Information System (INIS)

Takaya, Tomohisa

2016-01-01

A number of electronic transitions in the near-infrared wavelength region are associated with migration or delocalization of electrons in large molecules or molecular systems. Time-resolved near-infrared Raman spectroscopy will be a powerful tool for investigating the structural dynamic of samples with delocalized electrons. However, the sensitivity of near-infrared spontaneous Raman spectrometers is significantly low due to an extremely small probability of Raman scattering and a low sensitivity of near-infrared detectors. Nonlinear Raman spectroscopy is one of the techniques that can overcome the sensitivity problems and enable us to obtain time-resolved Raman spectra in resonance with near-IR transitions. In this article, the author introduces recent progress of ultrafast time-resolved near-infrared stimulated Raman spectroscopy. Optical setup, spectral and temporal resolution, and applications of the spectrometer are described. (author)

Dehydration of the Uranyl Peroxide Studtite, [UO₂(η²-O₂)(H₂O)₂]·2H₂O, Affords a Drastic Change in the Electronic Structure: A Combined X-ray Spectroscopic and Theoretical Analysis

Energy Technology Data Exchange (ETDEWEB)

Vitova, Tonya [Institute for Nuclear Waste Disposal (INE), Hermann-von-Helmholtz-Platz 1, D-76344 Eggenstein-Leopoldshafen, Germany; Pidchenko, Ivan [Institute for Nuclear Waste Disposal (INE), Hermann-von-Helmholtz-Platz 1, D-76344 Eggenstein-Leopoldshafen, Germany; Biswas, Saptarshi [School; Beridze, George [Institute of Energy and Climate Research,; JARA High-Performance Computing, Schinkelstrasse 2, 52062 Aachen, Germany; Dunne, Peter W. [School; Schild, Dieter [Institute for Nuclear Waste Disposal (INE), Hermann-von-Helmholtz-Platz 1, D-76344 Eggenstein-Leopoldshafen, Germany; Wang, Zheming [Pacific Northwest National Laboratory, MSIN K8-96, P.O. Box 999, Richland, Washington 99352, United States; Kowalski, Piotr M. [Institute of Energy and Climate Research,; JARA High-Performance Computing, Schinkelstrasse 2, 52062 Aachen, Germany; Baker, Robert J. [School

2018-02-05

The dehydration of studtite, [UO₂(2-O₂)(H₂O)2]·2H₂O, to metastudtite, [UO₂(2-O₂)(H₂O)₂], uranyl peroxide minerals that are major oxidative alteration phases of UO2 under conditions of geological storage, has been studied using X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy. XPS of the U 4f region shows small but significant differences between studtite and metastudtite, with the 4f binding energy of studtite the highest reported for a uranyl mineral studied by this technique. Further information on the changes in the electronic structure was elucidated using U M4-edge High Energy Resolution XANES (HR-XANES) spectroscopy, which directly probes f-orbital states. The transition from the 3d to the 5f* orbital is sensitive to variations of the U=Oaxial bond length and to changes in the bond covalency. We report evidences that the covalence in the uranyl fragment decreases upon dehydration. Photoluminescence spectroscopy at near liquid helium temperatures reveals significant spectral differences between the two materials, correlating with the X-ray spectroscopy results. A theoretical investigation has been conducted on the structures of both studtite and metastudtite and benchmarked to the HR-XANES spectra. These illustrate the sensitivity of the 3d to the 5f * transition towards U=Oaxial bond variation.

Simulated dry deposition of nitric acid near forest edges

NARCIS (Netherlands)

DeJong, JJM; Klaassen, W; Jong, J.J.M. de

1997-01-01

Dry deposition is simulated to understand and generalize observations of enhanced deposition of air pollution near forest edges. Nitric acid is taken as an example as its deposition velocity is often assumed to be determined by turbulent transport only. The simulations are based on the

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

International Nuclear Information System (INIS)

Wang, Xin

1996-12-01

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

Characterization of Functionalized Self-Assembled Monolayers and Surface-Attached Interlocking Molecules Using Near-Edge X-ray Absorption Fine Structure Spectroscopy

International Nuclear Information System (INIS)

Willey, T; Willey, T

2004-01-01

Quantitative knowledge of the fundamental structure and substrate binding, as well as the direct measurement of conformational changes, are essential to the development of self-assembled monolayers (SAMs) and surface-attached interlocking molecules, catenanes and rotaxanes. These monolayers are vital to development of nano-mechanical, molecular electronic, and biological/chemical sensor applications. This dissertation investigates properties of functionalized SAMs in sulfur-gold based adsorbed molecular monolayers using quantitative spectroscopic techniques including near-edge x-ray absorption fine structure spectroscopy (NEXAFS) and x-ray photoelectron spectroscopy (XPS). The stability of the gold-thiolate interface is addressed. A simple model SAM consisting of dodecanethiol adsorbed on Au(111) degrades significantly in less than 24 hours under ambient laboratory air. S 2p and O 1s XPS show the gold-bound thiolates oxidize to sulfinates and sulfonates. A reduction of organic material on the surface and a decrease in order are observed as the layer degrades. The effect of the carboxyl vs. carboxylate functionalization on SAM structure is investigated. Carboxyl-terminated layers consisting of long alkyl-chain thiols vs. thioctic acid with short, sterically separated, alkyl groups are compared and contrasted. NEXAFS shows a conformational change, or chemical switchability, with carboxyl groups tilted over and carboxylate endgroups more upright. Surface-attached loops and simple surface-attached rotaxanes are quantitatively characterized, and preparation conditions that lead to desired films are outlined. A dithiol is often insufficient to form a molecular species bound at each end to the substrate, while a structurally related disulfide-containing polymer yields surface-attached loops. Similarly, spectroscopic techniques show the successful production of a simple, surface-attached rotaxane that requires a ''molecular riveting'' step to hold the mechanically attached

Local Structure of Cerium in Aluminophosphate and Silicophosphate Glasses

International Nuclear Information System (INIS)

Rygel, Jennifer L.; Chen, Yongsheng; Pantano, Carlo G.; Shibata, Tomohiro; Du, Jincheng; Kokou, Leopold; Woodman, Robert; Belcher, James

2011-01-01

The local structure of cerium in two systematic compositional series of glasses, nominally CeP 3 O 9 -AlP 3 O 9 and CeP 3 O 9 -SiP 2 O 7 , was interrogated using X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure (XAFS) spectroscopy. XPS revealed that, for glasses melted in air, ≥95% of cerium ions are Ce 3+ . This was independently confirmed using X-ray absorption near edge spectroscopy (XANES). Ce K-edge extended X-ray absorption fine structure (EXAFS) has been used to determine the local structure of Ce 3+ . Near the metaphosphate composition, cerium was found to have an average cerium coordination number of ∼7.0 and an average cerium-oxygen bond length of 2.41 (angstrom). The average cerium coordination number and average cerium-oxygen bond distance were found to increase with decreasing cerium concentration in both compositional series. Rare-earth clustering is suggested based on numerical calculations for glasses containing ≥14 and ≥15 mol% Ce 2 O 3 for the aluminophosphate and silicophosphate series, respectively.

Green's function asymptotics near the internal edges of spectra of periodic elliptic operators. Spectral edge case

KAUST Repository

Kuchment, Peter

2012-06-21

Precise asymptotics known for the Green\\'s function of the Laplace operator have found their analogs for periodic elliptic operators of the second order at and below the bottom of the spectrum. Due to the band-gap structure of the spectra of such operators, the question arises whether similar results can be obtained near or at the edges of spectral gaps. As the result of this work shows, this is possible at a spectral edge when the dimension d ≥ 3. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Green's function asymptotics near the internal edges of spectra of periodic elliptic operators. Spectral edge case

KAUST Repository

Kuchment, Peter; Raich, Andrew

2012-01-01

Precise asymptotics known for the Green's function of the Laplace operator have found their analogs for periodic elliptic operators of the second order at and below the bottom of the spectrum. Due to the band-gap structure of the spectra of such operators, the question arises whether similar results can be obtained near or at the edges of spectral gaps. As the result of this work shows, this is possible at a spectral edge when the dimension d ≥ 3. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Lifshitz singularities in random harmonic chains: periodic amplitudes near the band edge and near special frequencies

International Nuclear Information System (INIS)

Nieuwenhuizen, T.M.; Luck, J.M.

1987-01-01

The authors give a complete description of the scaling behavior of the integrated density of states of random harmonic chains with random masses near the band edge omega/sub max/ and near special frequencies omega/sub s/. There are four different situations: omega upward arrow omega/sub max/, omega upward arrow omega/sub s/, omega upward arrow omega/sub s/ (critical case), omega upward arrow omega/sub s/ (general case). Their analytic results have the form of infinite sums involving Fourier coefficients of the scaling behavior of the Dyson-Schmidt function at the special frequency or the band edge. Binary mass distributions are considered in detail in the limit of a small fraction rho of light masses. Their predictions are compared with extensive numerical data

Near-infrared spectroscopy during peripheral vascular surgery

DEFF Research Database (Denmark)

Eiberg, J P; Schroeder, T V; Vogt, K C

1997-01-01

Near-infrared spectroscopy was performed perioperatively on the dorsum of the foot in 14 patients who underwent infrainguinal bypass surgery using a prosthesis or the greater saphenous vein. Dual-wavelength continuous light spectroscopy was used to assess changes in tissue saturation before, duri...

Femtosecond Near Edge X-ray Absorption Measurement of the VO2 Phase Transition

International Nuclear Information System (INIS)

Cavalleri, A.; Chong, H.H.W.; Fourmaux, S.; Glover, T.E.; Heimann, P.A; Kieffer, J.C.; Padmore, H.A.; Schoenlein, R.W.

2004-01-01

The authors measure the insulator-to-metal transition in VO 2 using femtosecond Near-Edge X-ray Absorption. Sliced pulses of synchrotron radiation are used to detect the photo-induced dynamics at the 516-eV Vanadium L 3 edge

Universality in invariant random-matrix models: Existence near the soft edge

International Nuclear Information System (INIS)

Kanzieper, E.; Freilikher, V.

1997-01-01

We consider two non-Gaussian ensembles of large Hermitian random matrices with strong level confinement and show that near the soft edge of the spectrum both scaled density of states and eigenvalue correlations follow so-called Airy laws inherent in the Gaussian unitary ensemble. This suggests that the invariant one-matrix models should display universal eigenvalue correlations in the soft-edge scaling limit. copyright 1997 The American Physical Society

XANES Studies of Mn K and L3,2 Edges in the (Ga,Mn)As Layers Modified by High Temperature Annealing

International Nuclear Information System (INIS)

Wolska, A.; Lawniczak-Jablonska, K.; Klepka, M.T.; Jakiela, R.; Demchenko, I.N.; Sadowski, J.; Holub-Krappe, E.; Persson, A.; Arvanitis, D.

2008-01-01

Ga 1-x Mn x As is commonly considered as a promising material for microelectronic applications utilizing the electron spin. One of the ways that allow increasing the Curie temperature above room temperature is to produce second phase inclusions. In this paper Ga 1-x Mn x As samples containing precipitations of ferromagnetic MnAs are under consideration. We focus on the atomic and electronic structure around the Mn atoms relating to the cluster formation. The changes in the electronic structure of the Mn, Ga and As atoms in the (Ga,Mn)As layers after high temperature annealing were determined by X-ray absorption near edge spectroscopy. The experimental spectra were compared with the predictions of ab initio full multiple scattering theory using the FEFF 8.4 code. The nominal concentration of the Mn atoms in the investigated samples was 6% and 8%. We do not ob- serve changes in the electronic structure of Ga and As introduced by the presence of the Mn atoms. We find, in contrast, considerable changes in the electronic structure around the Mn atoms. Moreover, for the first time it was possible to indicate the preferred interstitial positions of the Mn atoms. (authors)

Near-infrared spectroscopy for cocrystal screening

DEFF Research Database (Denmark)

Allesø, Morten; Velaga, Sitaram; Alhalaweh, Amjad

2008-01-01

Near-infrared (NIR) spectroscopy is a well-established technique for solid-state analysis, providing fast, noninvasive measurements. The use of NIR spectroscopy for polymorph screening and the associated advantages have recently been demonstrated. The objective of this work was to evaluate...... the analytical potential of NIR spectroscopy for cocrystal screening using Raman spectroscopy as a comparative method. Indomethacin was used as the parent molecule, while saccharin and l-aspartic acid were chosen as guest molecules. Molar ratios of 1:1 for each system were subjected to two types of preparative...... retained in a physical mixture with the guest molecule, while liquid-assisted cogrinding did not induce any changes in the crystal lattice. The good chemical peak selectivity of Raman spectroscopy allowed a straightforward interpretation of sample data by analyzing peak positions and comparing to those...

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

Science.gov (United States)

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

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

Science.gov (United States)

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

2018-06-01

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

Temperature dependent evolution of the local electronic structure of atmospheric plasma treated carbon nanotubes: Near edge x-ray absorption fine structure study

International Nuclear Information System (INIS)

Roy, S. S.; Papakonstantinou, P.; Okpalugo, T. I. T.; Murphy, H.

2006-01-01

Near edge x-ray absorption fine structure (NEXAFS) spectroscopy has been employed to obtain the temperature dependent evolution of the electronic structure of acid treated carbon nanotubes, which were further modified by dielectric barrier discharge plasma processing in an ammonia atmosphere. The NEXAFS studies were performed from room temperature up to 900 deg. C. The presence of oxygen and nitrogen containing functional groups was observed in C K edge, N K edge, and O K edge NEXAFS spectra of the multiwalled carbon nanotubes. The N K edge spectra revealed three types of π* features, the source of which was decisively identified by their temperature dependent evolution. It was established that these features are attributed to pyridinelike, NO, and graphitelike structures, respectively. The O K edge indicated that both carbonyl (C=O), π*(CO), and ether C-O-C, σ*(CO), functionalities were present. Upon heating in a vacuum to 900 deg. C the π*(CO) resonances disappeared while the σ*(CO) resonances were still present confirming their higher thermal stability. Heating did not produce a significant change in the π* feature of the C K edge spectrum indicating that the tabular structure of the nanotubes is essentially preserved following the thermal decomposition of the functional groups on the nanotube surface

Photographic infrared spectroscopy and near infrared photometry of Be stars

International Nuclear Information System (INIS)

Swings, J.P.

1976-01-01

Two topics are tackled in this presentation: spectroscopy and photometry. The following definitions are chosen: photographic infrared spectroscopy (wavelengths Hα<=lambda<1.2 μ); near infrared photometry (wavebands: 1.6 μ<=lambda<=20 μ). Near infrared spectroscopy and photometry of classical and peculiar Be stars are discussed and some future developments in the field are outlined. (Auth.)

Oxidation states of Fe and Ti in blue sapphire

International Nuclear Information System (INIS)

Wongrawang, P; Wongkokua, W; Monarumit, N; Thammajak, N; Wathanakul, P

2016-01-01

X-ray absorption near-edge spectroscopy (XANES) can be used to study the oxidation state of a dilute system such as transition metal defects in solid-state samples. In blue sapphire, Fe and Ti are defects that cause the blue color. Inter-valence charge transfer (IVCT) between Fe 2+ and Ti 4+ has been proposed to describe the optical color’s origin. However, the existence of divalent iron cations has not been thoroughly investigated. Fluorescent XANES is therefore employed to study K-edge absorptions of Fe and Ti cations in various blue sapphire samples including natural, synthetic, diffused and heat-treated sapphires. All the samples showed an Fe absorption edge at 7124 eV, corresponding to the Fe 3+ state; and Ti at 4984 eV, corresponding to Ti 4+ . From these results, we propose Fe 3+ -Ti 4+ mixed acceptor states located at 1.75 eV and 2.14 eV above the valence band of corundum, that correspond to 710 nm and 580 nm bands of UV–vis absorption spectra, to describe the cause of the color of blue sapphire. (paper)

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

Science.gov (United States)

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

2014-01-01

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

Automated on-line L-edge measurement of SNM concentration for near-real-time accounting

International Nuclear Information System (INIS)

Russo, P.A.; Marks, T. Jr.; Stephens, M.M.; Baker, A.L.; Cobb, D.D.

1982-09-01

An L-edge densitometer has been modified, tested, and demonstrated for on-line assay of special nuclear material concentration in flowing solution streams. The demonstration was part of a larger demonstration of near-real-time nuclear materials accounting during a continuous, week-long, cold operation of the Barnwell facility. The L-edge data were automatically analyzed and the results were transmitted to the materials accounting computer once every 5.5 min for the duration of the cold run. This report compares the results of the L-edge analyses with the delayed results obtained from destructive analysis of samples withdrawn from the same process line. Comparisons are also made with the results obtained in near real time from an automated process control instrument installed in series with the L-edge densitometer. The performance of the L-edge instrument was reliable throughout the continuous operation. The assay precision was consistent with that predicted by the counting statistics of the measurement. The results of the L-edge assays show good agreement with those of the destructive assays. A gradually varying discrepancy (of a few percent) between the L-edge and the process control results remains unexplained

The competitive growth of cubic domains in Ti(1-x)AlxN films studied by diffraction anomalous near-edge structure spectroscopy.

Science.gov (United States)

Pinot, Y; Tuilier, M-H; Pac, M-J; Rousselot, C; Thiaudière, D

2015-11-01

Titanium and aluminium nitride films deposited by magnetron sputtering generally grow as columnar domains made of oriented nanocrystallites with cubic or hexagonal symmetry depending on Al content, which are embedded in more disordered grain boundaries. The substitution of Al atoms for Ti in the cubic lattice of the films improves their resistance to wear and oxidation, allowing their use as protective coatings. Ti K-edge X-ray absorption spectroscopy, which probes both crystallized and more disordered grain boundaries, and X-ray diffraction anomalous fine structure, which is sensitive to short- and long-range order within a given crystallized domain, are carried out on a set of Ti(1-x)AlxN films deposited by magnetron sputtering on Si substrates. Attention is paid to the shape of the pre-edge region, which is sensitive to the symmetry of the site occupied by Ti atoms, either octahedral in face-centred-cubic Ti-rich (TiN, Ti0.54Al0.46N) samples or tetrahedral in hexagonal-close-packed Al-rich (Ti0.32Al0.68N) films. In order to obain information on the titanium environment in the well crystallized areas, subtraction of the smooth part of the energy-dependent structure factor for the Bragg reflections is applied to the pre-edge region of the diffraction anomalous data in order to restore their spectroscopic appearance. A flat pre-edge is related to the typical octahedral environment of Ti atoms for cubic reflections. The difference observed between pre-edge spectra associated with face-centred-cubic 200 and 111 Bragg reflections of Ti0.54Al0.46N is assigned to Ti enrichment of 111 large well ordered domains compared with the more disordered 200 ones. The sharp peak observed in the spectrum recorded from the hexagonal 002 peak of Ti0.32Al0.68N can be regarded as a standard for the pure tetrahedral Ti environment in hexagonal-close-packed nitride.

Ordered and disordered models of local structure around Ag cations in silver borate glasses based on x-ray absorptio n near-edge structure spectroscopy

Czech Academy of Sciences Publication Activity Database

Šipr, Ondřej; Dalba, G.; Rocca, F.

2004-01-01

Roč. 69, - (2004), 134201/1-134201/16 ISSN 0163-1829 R&D Projects: GA ČR GA202/02/0841 Institutional research plan: CEZ:AV0Z1010914 Keywords : disordered systems * structural analysis * XANES * silver * borate glass es Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.075, year: 2004

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

Energy Technology Data Exchange (ETDEWEB)

1993-10-01

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

Photoreflectance study of the near-band-edge transitions of chemical vapor deposition-grown mono- and few-layer MoS{sub 2} films

Energy Technology Data Exchange (ETDEWEB)

Lin, Kuang-I, E-mail: kilin@mail.ncku.edu.tw [Center for Micro/Nano Science and Technology, National Cheng Kung University, Tainan 70101, Taiwan (China); Chen, Yen-Jen; Wang, Bo-Yan; Cheng, Yung-Chen [Department of Materials Science, National University of Tainan, Tainan 70005, Taiwan (China); Chen, Chang-Hsiao, E-mail: chsiaoc@fcu.edu.tw [Department of Automatic Control Engineering, Feng Chia University, Taichung 40724, Taiwan (China)

2016-03-21

Room-temperature photoreflectance (PR) and reflectance (R) spectroscopy are utilized to investigate the near-band-edge transitions of molybdenum disulfide (MoS{sub 2}) thin films grown on sapphire substrates by a hot-wall chemical vapor deposition system. The layer thickness and optical properties of the MoS{sub 2} thin films are confirmed by Raman spectroscopy, atomic force microscope, and photoluminescence (PL) analysis. The B exciton shows relatively weak PL intensity in comparing with the A exciton even for monolayer MoS{sub 2} films. In the R spectrum of few‐layer MoS{sub 2}, it is not possible to clearly observe exciton related features. The PR spectra have two sharp, derivative-like features on a featureless background. Throughout the PR lineshape fitting, the transition energies are designated as the A and B excitons at the K-point of the Brillouin zone, but at room temperature there seems to be no distinguishable feature corresponding to an H‐point transition for the mono- and few-layer MoS{sub 2} films unlike in bulk. These transition energies are slightly larger than those obtained by PL, which is attributed to the Stokes shifts related to doping level. The obtained values of valence-band spin-orbit splitting are in good agreement with those from other experimental methods. By comparing the PR lineshapes, the dominant modulation mechanism is attributed to variations of the exciton transition energies due to change in the built-in electric field. On the strength of this study, PR spectroscopy is demonstrated as a powerful technique for characterizing the near-band-edge transitions of MoS{sub 2} from monolayer to bulk.

Origin of the chemical shift in X-ray absorption near-edge spectroscopy at the Mn K-Edge in manganese oxide compounds

NARCIS (Netherlands)

de Vries, AH; Hozoi, L.; Broer, R.

2003-01-01

The absorption edge in Mn K-edge X-ray absorption spectra of manganese oxide compounds shows a shift of several electronvolts in going from MnO through LaMnO3 to CaMnO3. On the other hand, in X-ray photoelectron spectra much smaller shifts are observed. To identify the mechanisms that cause the

XNAES and XPS studies on modification of SWCNTS upon gas-phase purification treatments

International Nuclear Information System (INIS)

Liang Xianqing; Wu Ziyu; Zhong Jun; Zhao Ting; Yao Peng; Ibrahim, K.; Qian Haijie

2009-01-01

A systematic characterization of single-walled carbon nanotubes (SWCNTs) after successive purification steps, including air oxidation at 350 degree C, hydrochloric acid etching and 600 degree C annealing in Ar, have been performed combining X-ray absorption near-edge structure (XANES) and X-ray photoelectron spectroscopy (XPS). The results indicated that the modification degree of SWCNTs increased after the purification procedures, but decreased significantly by annealing in Ar. It also showed that the SWCNTs could bond with chlorine atoms during the hydrochloric acid etching and suggested this modification may be importance for the applications. (authors)

Automated on-line L-edge measurement of SNM concentration for near-real-time accounting

International Nuclear Information System (INIS)

Russo, P.A.; Marks, T. Jr.; Stephens, M.M.; Hsue, S.T.; Baker, A.L.; Cobb, D.D.

1982-01-01

The L-edge densitometer developed at Los Alamos National Laboratory has been modified, tested, and demonstrated for on-line assay of special nuclear material concentration in flowing solution streams. The demonstration was part of a larger demonstration of near-real-time nuclear materials accounting during a continuous, week-long, cold operation of the Allied General Nuclear Services facility in Barnwell, South Carolina. The L-edge data were automatically analyzed and the results were transmitted to the materials accounting computer once every 5.5 min for the duration of the cold run. This report compares the results of the L-edge analyses with the delayed results obtained from destructive analysis of samples withdrawn from the same process line. Comparisons are also made with the results obtained in near real time from an automated process control instrument installed in series with the L-edge densitometer. The performance of the L-edge instrument was reliable throughout the continous operation. The assay precision was consistent with that predicted by the counting statistics of the measurement. The results of the L-edge assays show good agreement with those of the destructive assays. A gradually varying discrepancy (of a few percent) between the L-edge and the process control results remains unexplained. 9 figures

Ag K- and L3-edge XAFS study on Ag species in Ag/Ga2O3 photocatalysts

International Nuclear Information System (INIS)

Yamamoto, M; Yamamoto, N; Yoshida, T; Nomoto, T; Yamamoto, A; Yoshida, H; Yagi, S

2016-01-01

Ag loaded Ga 2 O 3 (Ag/Ga 2 O 3 ) shows photocatalytic activity for reduction of CO 2 with water. Ag L 3 -edge XANES and K-edge EXAFS spectra were measured for various Ag/Ga 2 O 3 samples, which suggested that structural and chemical states of Ag species varied with the loading amount of Ag and the preparation method. The Ag species were metallic Ag particles with an AgGaO 2 -like interface structure in the sample with high loading amount of Ag while predominantly Ag metal clusters in the sample with low loading amount of Ag. The XANES feature just above the edge represented the interaction between the Ag species and the Ga 2 O 3 surface, showing that the Ag metal clusters had more electrons in the d -orbitals by interacting with the Ga 2 O 3 surface, which would contribute the high photocatalytic activity. (paper)

Solution XAS Analysis for Exploring the Active Species in Homogeneous Vanadium Complex Catalysis

Science.gov (United States)

Nomura, Kotohiro; Mitsudome, Takato; Tsutsumi, Ken; Yamazoe, Seiji

2018-06-01

Selected examples in V K-edge X-ray Absorption Near Edge Structure (XANES) analysis of a series of vanadium complexes containing imido ligands (possessing metal-nitrogen double bond) in toluene solution have been introduced, and their pre-edge and the edge were affected by their structures and nature of ligands. Selected results in exploring the oxidation states of the active species in ethylene dimerization/polymerization using homogeneous vanadium catalysts [consisting of (imido)vanadium(V) complexes and Al cocatalysts] by X-ray absorption spectroscopy (XAS) analyses have been introduced. It has been demonstrated that the method should provide more clear information concerning the active species in situ, especially by combination with the other methods (NMR and ESR spectra, X-ray crystallographic analysis, and reaction chemistry), and should be powerful tool for study of catalysis mechanism as well as for the structural analysis in solution.

100 years of X-rays, 20 years of absorption spectroscopy with the synchrotron radiation: history, principles and a few examples of applications

International Nuclear Information System (INIS)

Michalowicz, A.; Moscovici, J.; Mimouni, A.

1995-01-01

The centenary of the discovery of X-rays is the occasion to summarize the history of X-ray absorption spectroscopy (XAS) and its development on synchrotron radiation sources, to give the underlying principles and to illustrate the possible uses of this spectroscopy by three examples: (a) the structural characterization of disordered spin transition coordination compounds by EXAFS spectroscopy; (b) the ligand binding to vitamin B 12 by XANES spectroscopy; and (c) the chemical analysis of sulfur compounds included in fly-ashes by low-energy XANES spectroscopy. (authors). 23 refs., 8 figs

Modification of SrTiO3 single-crystalline surface after plasma flow treatment

Energy Technology Data Exchange (ETDEWEB)

Levin, Alexandr A.; Weissbach, Torsten; Leisegang, Tilmann; Meyer, Dirk C. [Institut fuer Strukturphysik, Technische Universitaet Dresden, 01062 Dresden (Germany); Kulagin, Nikolay A. [Kharkiv National University for Radioelectronics, av. Shakespeare 6-48, 61045 Kharkiv (Ukraine); Langer, Enrico [Institut fuer Festkoerperphysik, Technische Universitaet Dresden, 01062 Dresden (Germany)

2009-07-01

Surface of pure and transition metal-doped SrTiO3(STO) single crystals before and after hydrogen plasma-flow treatment (energy of 5..20 J/cm2) is investigated by wide-angle X-ray diffraction (WAXRD), fluorescence X-ray absorption near edge structure (XANES) and scanning electron microscopy (SEM) techniques. Plasma treatment results in the formation of a textured polycrystalline layer at the surface of the single-crystalline samples with different orientation. The formation of the quasi-ordered structures consisting of nanoscale-sized pyramids is observed by SEM. XANES evidences the change of the valency of the part of Ti4+ to Ti3+ due to the plasma treatment. The data obtained together with results of X-ray spectroscopy measurements gives evidences of the change of stoichiometry of the STO samples resulting in a change of their physical properties after plasma treatment.

Eigenfunctions in disordered systems near the mobility edge

International Nuclear Information System (INIS)

Brezini, A.

1982-08-01

A model is proposed to calculate the average probability and the average size of the localization domain for an electron being localized at a given site in a Cayley tree lattice. The numerical results are presented in the limit of weak disorder in the case of Cauchy distribution for site energies. Attention is paid to the states near the mobility edge in the localized regime. Particularly, features exhibited in the linear chain case are observed for the first time for higher dimensions. (author)

XRF and XANES Data for Kaplan U Paper

Science.gov (United States)

The dataset contains two XRF images of iron and uranium distribution on plant roots and a database of XANES data used to produce XANES spectra figure for Figure 7 in the published paper.This dataset is associated with the following publication:Kaplan, D., R. Kukkadapu, J. Seaman, B. Arey, A. Dohnalkova, S. Buettner, D. Li, T. Varga, K. Scheckel, and P. Jaffe. Iron Mineralogy and Uranium-Binding Environment in the Rhizosphere of a Wetland Soil. D. Barcelo SCIENCE OF THE TOTAL ENVIRONMENT. Elsevier BV, AMSTERDAM, NETHERLANDS, 569: 53-64, (2016).

Chlorine levels and species in fine and size resolved atmospheric particles by X-ray absorption near-edge structure spectroscopy analysis in Beijing, China.

Science.gov (United States)

Ouyang, Jie; Yang, Guo-Sheng; Ma, Ling-Ling; Luo, Min; Zheng, Lei; Huo, Qing; Zhao, Yi-Dong; Hu, Tian-Dou; Cai, Zhen-Feng; Xu, Dian-Dou

2018-04-01

An understanding of the species of chlorine is crucial in the metropolis-Beijing, which is suffering serious haze pollution with high frequency. Particulate Matters (PMs) with five different sizes were collected in Beijing from July 2009 to March 2016, and characterized non-destructively by X-ray absorption near edge structure spectroscopy. PM 2.5 contributed for the major PMs mass in spring and summer, PM 0.5-1.0 and PM 1.0-2.5 contributed for the major PMs mass in autumn and winter. The concentrations of the three chlorine species were in the order of inorganic chlorine (Cl inorg ) > aliphatic chlorine (Cl ali ) > aromatic chlorine (Cl aro ), indicating that Cl inorg constituted the primary chlorine fraction and less toxic Cl ali constituted the primary total organic chlorine (Cl ali  + Cl aro , abbreviated as Cl org ) in the PMs in Beijing. In addition, these three chlorine species exhibited identical seasonal variation in PM 2.5 : winter > autumn > spring > summer. Wet precipitation is an important factor to result in the lower mass concentrations of these three chlorine species in summer. The temporal variations of both size resolved PM mass concentrations and chlorine species concentrations suggested that the air pollution prevention and control in Beijing has just won initial success. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

CERN Document Server

O'Grady, W E

1999-01-01

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

Cu k-edge studies of the charge carries in Th-doped cuprate system R2-xThxCuO4-δ (R = Nd, Sm and Gd)

International Nuclear Information System (INIS)

Liang, G.; Yi, Y.; Jardim, R.F.; Wang, L.V.

1999-01-01

To further study the charge carrier concentration in electron doped cuprate superconductors, a systematic x-ray absorption near edge structure (XANES) measurement has been carried out on Th-doped superconductor system R 2-x Th x CuO 4-δ (R = Nd, Sm, and Gd). The XANES results show that, similar to the Ce-doped compounds, while the intensity of the Cu 1+ 4p π feature increase with the increase of the Th doping level x, the intensities of the Cu 2+ 4p π and 4p σ features decreases. This clearly indicates that the electrons doped by the Th atoms are injected into the local Cu 3d-orbitals. The normalized Cu 1+ 4p π intensity data show that the Cu 1+ concentration in the Th-doped compound series with different R-elements is linearly proportional to the Th doping-level x. The data suggest that both Ce and Th donate the same fraction of electrons into the Cu sites

Direct speciation analysis of arsenic in sub-cellular compartments using micro-X-ray absorption spectroscopy

International Nuclear Information System (INIS)

Bacquart, Thomas; Deves, Guillaume; Ortega, Richard

2010-01-01

Identification of arsenic chemical species at a sub-cellular level is a key to understanding the mechanisms involved in arsenic toxicology and antitumor pharmacology. When performed with a microbeam, X-ray absorption near-edge structure (μ-XANES) enables the direct speciation analysis of arsenic in sub-cellular compartments avoiding cell fractionation and other preparation steps that might modify the chemical species. This methodology couples tracking of cellular organelles in a single cell by confocal or epifluorescence microscopy with local analysis of chemical species by μ-XANES. Here we report the results obtained with a μ-XANES experimental setup based on Kirkpatrick-Baez X-ray focusing optics that maintains high flux of incoming radiation (>10 11 ph/s) at micrometric spatial resolution (1.5x4.0 μm 2 ). This original experimental setup enabled the direct speciation analysis of arsenic in sub-cellular organelles with a 10 -15 g detection limit. μ-XANES shows that inorganic arsenite, As(OH) 3 , is the main form of arsenic in the cytosol, nucleus, and mitochondrial network of cultured cancer cells exposed to As 2 O 3 . On the other hand, a predominance of As(III) species is observed in HepG2 cells exposed to As(OH) 3 with, in some cases, oxidation to a pentavalent form in nuclear structures of HepG2 cells. The observation of intra-nuclear mixed redox states suggests an inter-individual variability in a cell population that can only be evidenced with direct sub-cellular speciation analysis.

Tribochemical behaviors of phosphite esters and their combinations with alkyl amines

International Nuclear Information System (INIS)

Fu, Xisheng; Sun, Lingguo; Zhou, Xuguang; Li, Jianchang; Fan, Bingji; Ren, Tianhui

2015-01-01

Highlights: • Investigating the differences of tribological performance between phosphite ester and their combinations with alkyl amines. • The combination of SEM and EDS was used to investigate the worn surface morphology and detect the element distributions and content on the steel surface. • The chemical compositions of the thermal films and tribofilms were characterized by TEY P L-edge and FY P K-edge XANES spectroscopy. • A phosphate and polyphosphate tribofilm was formed after rubbing times of even 10 s, and being formed completely after rubbing times of 10 min. • Phosphite ester forms short-chain polyphosphates, and ammonium phosphite produces medium-chain polyphosphates in the tribfilm. - Abstract: The tribochemical behaviors of dioctylphosphite ester and ditetradecylphosphite ester together with their corresponding combinations with alkyl amines were studied. The results of tribological evaluations showed that the phosphite ester with long alkyl chain exhibited better antiwear performance but worse extreme pressure property than that of the phosphite ester with short alkyl chain. The combinations showed better antiwear performance but worse extreme pressure property than their corresponding phosphite esters. Scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) were used to investigate the worn surface morphology and the content as well as the distribution of active elements. It can be found that the prorupt edges of worn surface are enriched with phosphoric-oxygenic compounds and less phosphoric-oxygenic compounds were detected in the valley. X-ray absorption near-edge structure (XANES) spectroscopy was employed to explore the chemical nature of the worn surface. The results show that a tribofilm composed of phosphates and polyphosphates is formed on the worn surface. Furthermore, the tribofilm is generated even in a rubbing of 10 s and is formed completely after 10 min rubbing.

Theoretical XANES Study of the Activated Nickel (t-Amylisocyanide) Molecule

International Nuclear Information System (INIS)

Glover, J. L.; Chantler, C. T.; Soldatov, A. V.; Smolentsev, G.; Feiters, M. C.

2007-01-01

XANES is one of the most powerful techniques for investigating the active centres of non-crystalline systems such as synthetic catalysts and enzymes. We have investigated XANES for an active species in the Ni-catalyzed polymerization of isocyanides, the activated Ni (t-amylisocyanide) complex, using two of the most popular theoretical approaches. This is a very large cluster for which it is extremely difficult to derive a converged solution using the Finite Difference Method. The cluster has been linked to important chemical developments for catalysts for isocyanide polymerization. Predicted XANES for the nano-cluster are compared with experimental data, providing an important test for different theoretical approaches. Developments of a finite element method gave excellent agreement with the experimental data, while simpler models were relatively unsuccessful

X-Ray Absorption Near-Edge Structure (XANES) of Calcium L3,2 Edges of Various Calcium Compounds and X-Ray Excited Optical Luminescence (XEOL) Studies of Luminescent Calcium Compounds

International Nuclear Information System (INIS)

Ko, J. Y. Peter; Zhou Xingtai; Sham, T.-K.; Heigl, Franziskus; Regier, Tom; Blyth, Robert

2007-01-01

X-ray absorption at calcium L3,2 edges of various calcium compounds were measured using a high resolution Spherical Grating Monochromator (SGM) at the Canadian Light Source (CLS). We observe that each compound has its unique fine structure of L3,2 edges. This uniqueness is due to differences in local structure of compounds. We also performed (X-ray Excited Optical Luminescence) XEOL of selected luminescent calcium compounds to investigate their optical properties. XEOL is a photon-in-photon-out technique in which the optical luminescence that is excited by tunable x-rays from a synchrotron light source is monitored. Depending on excitation energy of the x-ray, relative intensities of luminescence peaks vary. Recent findings of the results will be presented here

The aquatic hyphomycete Heliscus lugdunensis protects its hyphae tip cells from cadmium: A micro X-ray fluorescence and X-ray absorption near edge structure spectroscopy study

Science.gov (United States)

Isaure, Marie-Pierre; Leyh, Benjamin; Salomé, Murielle; Krauss, Gerd-Joachim; Schaumlöffel, Dirk; Dobritzsch, Dirk

2017-11-01

Aquatic fungi can be used to evaluate the functioning of natural ecosystems. Heliscus lugdunensis is an early colonizer of allochthone leafs. Since this aquatic hyphomycete is able to develop in metal contaminated habitats and tolerates cadmium, it appears to be a good candidate to investigate adaptation to metal pollution. This study aimed at examining the sequestration of Cd in the hyphae of H. lugdunensis, and particularly the role of the tip cells. For that, H. lugdunensis growth was evaluated under various Cd concentrations, and a combination of synchrotron micro X-ray fluorescence and X-ray absorption near edge structure spectroscopy was carried out to determine the compartments of Cd accumulation and the Cd chemical species, respectively. Results showed that the hyphal tip cells were depleted in Cd, and that the metal was stored in older cells. Cd was mainly associated with sulfur ligands and to a lesser extent bound to phosphates and carboxyl/hydroxyl groups from cell wall and/or organic acids. Finally, the aquatic fungus was able to maintain the tip cell as a functional system, thus allowing the colonization of contaminated environments.

Investigation of the effect of the incorporated Fe atoms in the ion-beam induced nanopatterns on Si(001)

Energy Technology Data Exchange (ETDEWEB)

Khanbabaee, Behnam; Biermanns, Andreas; Pietsch, Ullrich [Siegen Univ. (Germany). Festkoerperphysik; Cornejo, Marina; Frost, Frank [Leibniz-Institute fuer Oberflaechenmodifizierung e.V. (IOM), Leipzig (Germany)

2012-07-01

Ion beam erosion of semiconductor surfaces can modify the surface and depends on main sputtering parameters; different surface topographies such as ripple or dot like pattern are fabricated on the surface. Recent experiments have shown that the incorporation of foreign metallic atoms during the sputtering process plays a crucial role in pattern formation on surfaces. In the result of investigation we report on the depth profile of Fe atoms incorporated in sputtering process on Si(100) with low energy Kr ion beam. X-ray reflectivity (XRR) measurements determine the concentration profile of Fe atoms. X-ray absorption near edge spectroscopy (XANES) at the Fe K-edge (7112 eV) shows the formation of Fe rich silicide near surface region. X-ray photoelectron spectroscopy (XPS) shows a shift in the binding energy of Si2p levels at the surface compared top bulk confirming the formation of different phases of Fe-silicide on tope and below the surface. The depth profiles obtained by XRR are compared to results obtained by complementary secondary-ion mass spectrometry (SIMS).

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

Science.gov (United States)

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

2018-06-01

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

Investigation of the electronic structure of high-temperature superconductors and related transition metal oxides with near-edge x-ray absorption spectroscopy

International Nuclear Information System (INIS)

Gerhold, S.

2001-01-01

The unoccupied electronic structure and its orbital character has been studied with polarization-dependent near-edge x-ray absorption spectroscopy (NEXAFS) for selected high-temperature superconductors (HTSC) and related transition metal oxides. Although YBa 2 Cu 3 O 7-δ (Y-123) is arguably the best-investigated HTSC a conclusive NEXAFS study on how partial substitution of Cu by other transition metals affects the electronic structure has sorely been missing. The study presented here on a series of well characterized YBa 2 Cu 3-x Fe x O y single crystals shows that the cause for T c suppression is not at all magnetic pair breaking but charge carrier depletion, primarily in the chains; effects from disorder cannot be excluded. Annealing at high oxygen pressure increases along with oxygen content both the hole concentration and T c . Fe 3d-O 2p-derived states contribute prominently to the spectra for all polarizations a few eV above E F . Iron prefers a trivalent state in Y-123; upon reduction a spin transition can be observed. As YBa 2 Cu 3-x Fe x O y single crystals cannot be detwinned it is very difficult to distinguish between contributions from planes and chains to the spectra. In this situation thin films grown with a reduced degree of twinning ('twin-poor') allow more detailed investigations. An extended self-absorption correction was developed for fluorescence yield NEXAFS on epitactical HTSC thin films. Its application to twin-poor Y-123 thin films demonstrates that (apart from the effect of residual twins) the spectral information is equivalent to that of detwinned single crystals for a range of optimum film thicknesses, and this in turn allows to augment the NEXAFS study of YBa 2 Cu 3-x Fe x O y with spectra for corresponding twin-poor thin films. The system Ca 2-x (Sr,La) x RuO 4 is structurally related to the HTSCs; the development of its unoccupied electronic structure with x was investigated in this work, with emphasis on the metal

Manganese L-edge X-ray absorption spectroscopy of manganese catalase from Lactobacillus plantarum and mixed valence manganese complexes

Energy Technology Data Exchange (ETDEWEB)

Grush, M.M.; Chen, J.; George, S.J. [Univ. of California, Davis, CA (United States)] [and others

1996-01-10

The first Mn L-edge absorption spectra of a Mn metalloprotein are presented in this paper. Both reduced and superoxidized Mn catalase have been examined by fluorescence-detected soft X-ray absorption spectroscopy, and their Mn L-edge spectra are dramatically different. The spectrum of reduced Mn(II)Mn(II) catalase has been interpreted by ligand field atomic multiplet calculations and by comparison to model compound spectra. The analysis finds a 10 Dq value of nearly 1.1 eV, consistent with coordination by predominately nitrogen and oxygen donor ligands. For interpretation of mixed valence Mn spectra, an empirical simulation procedure based on the addition of homovalent model compound spectra has been developed and was tested on a variety of Mn complexes and superoxidized Mn catalase. This routine was also used to determine the oxidation state composition of the Mn in [Ba{sub 8}Na{sub 2}ClMn{sub 16}(OH){sub 8}(CO{sub 3}){sub 4}L{sub 8}] .53 H{sub 2}O (L=1,3-diamino-2-hydroxypropane-N,N,N`N`-tetraacetic acid). 27 refs., 6 figs.

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

International Nuclear Information System (INIS)

Jacobs, G.; Chaney, J.A.; Patterson, P.M.; Das, T.K.; Maillot, J.C.; Davis, B.H.

2004-01-01

The addition of platinum metal to cobalt/alumina-based Fischer-Tropsch synthesis (FTS) catalysts increases both the reduction rate and, consequently, the density of active cobalt sites. Platinum also lowers the temperature of the two-step conversion of cobalt oxide to cobalt metal observed in temperature programmed reduction (TPR) as Co 3 O 4 to CoO and CoO to Co 0 . The interaction of the alumina support with cobalt oxide ultimately determines the active site density of the catalyst surface. This interaction can be controlled by varying the cobalt loading and dispersion, selecting supports with differing surface areas or pore sizes, or changing the noble metal promoter. However, the active site density is observed to depend primarily on the cluster size and extent of reduction, and there is a direct relationship between site density and FTS rate. In this work, in situ extended X-ray absorption fine structure (EXAFS) at the L III edge of Pt was used to show that isolated Pt atoms interact with supported cobalt clusters without forming observable Pt-Pt bonds. K-edge EXAFS was also used to verify that the cobalt cluster size increases slightly for those systems with Pt promotion. X-ray absorption near-edge spectroscopy (XANES) was used to examine the remaining cobalt clusters after the first stage of TPR, and it revealed that the species were almost entirely cobalt (II) oxide. After the second stage of TPR to form cobalt metal, a residual oxide persists in the sample, and this oxide has been identified as cobalt (II) aluminate using X-ray photoelectron spectroscopy (XPS). Sequential in situ reduction of promoted and unpromoted systems was also monitored through XPS, and Pt was seen to increase the extent of cobalt reduction by a factor of two. (orig.)

Circularly polarized near-field optical mapping of spin-resolved quantum Hall chiral edge states.

Science.gov (United States)

Mamyouda, Syuhei; Ito, Hironori; Shibata, Yusuke; Kashiwaya, Satoshi; Yamaguchi, Masumi; Akazaki, Tatsushi; Tamura, Hiroyuki; Ootuka, Youiti; Nomura, Shintaro

2015-04-08

We have successfully developed a circularly polarized near-field scanning optical microscope (NSOM) that enables us to irradiate circularly polarized light with spatial resolution below the diffraction limit. As a demonstration, we perform real-space mapping of the quantum Hall chiral edge states near the edge of a Hall-bar structure by injecting spin polarized electrons optically at low temperature. The obtained real-space mappings show that spin-polarized electrons are injected optically to the two-dimensional electron layer. Our general method to locally inject spins using a circularly polarized NSOM should be broadly applicable to characterize a variety of nanomaterials and nanostructures.

Photoabsorption spectra of potassium and rubidium near the K-edge

International Nuclear Information System (INIS)

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

1995-01-01

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

μ-XRF and μ-XANES at calcification fronts of human articular cartilage

International Nuclear Information System (INIS)

Streli, C.; Zoeger, N.; Wobrauschek, P.; Jokubonis, C.; Pepponi, G.; Falkenberg, G.; Simon, P.; Roschger, P.; Tampieri, A.

2006-01-01

fronts of human calcified tissue. The finding of elevated Pb levels in cartilage compared to the subchondral region of the bone (about 10 times higher) motivated a study on the chemical speciation of Pb in both compartments of calcified human tissue. Comparing results from micro x-ray Absorption Near Edge Structure (μXANES) measurements in the tidemark with the ones from adequate standard materials gives information on the chemical bond of Pb in human cartilage. Results from a first μ-XANES experiment carried out at HASYLAB beamline L will be presented in this paper. μ-XANES scans at the tidemark of a femoral head and patella, and on a set of standard materials namely Pb-hydroxyapatite, PbO, PbS, PbCO 3 , and PbSO 4 have been compared and will be presented. Although suffering from weak counting statistics one could estimate from the results, that most of the accumulated Pb in the tidemark is bound to hydroxyapatite. (author)

Influence of near-edge processes in the elemental analysis using X

Indian Academy of Sciences (India)

The near-edge processes, such as X-ray absorption fine structure (XAFS) andresonant ... away from the shell/subshell ionization thresholds of the attenuator element. ... The influence of XAFS to the attenuation coefficient depends upon the ...

X-Ray Absorption Spectroscopy of Fe-Substituted Allophane and Imogolite

Science.gov (United States)

Baker, L. L.; Strawn, D. G.; Nickerson, R. D.; McDaniel, P.

2011-12-01

Martian rocks and sediments contain weathering products including clay minerals formed as a result of interaction between rocks and water, and these materials can act as important indicators of past surface conditions on Mars. Weathering of terrestrial volcanic rocks similar to those on Mars produces nano-sized, variably hydrated aluminosilicate and iron oxide minerals, including allophane, imogolite, halloysite, hisingerite, and ferrihydrite. The nanoaluminosilicates can contain isomorphically substituted Fe, which may affect their spectral and physical properties as well as their eventual recrystallization products. Detection and quantification of such minerals in natural environments on Earth is difficult due to their variable chemical composition and lack of long-range crystalline order. Their accurate detection and quantification on Mars requires a better understanding of how composition affects their spectral properties and evolution to more crystalline phases. Aluminosilicate nanoparticles of varying composition were synthesized with isomorphically substituted Fe at Fe:Al ratios of 1:100. Allophanes were synthesized with Al:Si ratios of 2:1, 1:1, and 1:3. The substituted Fe was probed using Fe K-edge X-ray absorption fine structure spectroscopy (XAFS). The XAFS spectrum contains information about the molecular environment surrounding the target atom, and is an ideal technique for studying poorly crystalline materials that are difficult to characterize using bulk methods such as XRD. The near-edge (XANES) and extended (EXAFS) portions of the XAFS spectrum were examined, and allophane backscattering paths were fit using coordinates for a modified nanoball model (1). XANES spectra rule out ferrihydrite in the synthetic samples, suggesting all Fe was incorporated into the aluminosilicate structure. The XAFS results suggest that Fe substituted into the allophane structure is present as Fe(III) in octahedral coordination in a well-ordered sheet. Some Fe

Introduction of spectroscopic photoemission and low energy electron microscope in SPring-8

International Nuclear Information System (INIS)

Guo, FangZhun; Kobayashi, Keisuke; Kinoshita, Toyohiko

2005-01-01

An upright configuration SPELEEM (Spectroscopic PhotoEmission and Low Energy Electron Microscope) has been introduced in SPring-8 in the framework of the nanotechnology support project of Ministry of Education, Culture, Sport, Science and Technology (MEXT), Japan. SPELEEM combines microscopy, spectroscopy and diffraction in one system, which allows a comprehensive characterization of the specimen. The combination of SPELEEM and polarized (circularly or linearly) soft X-rays in SPring-8 is expected to realize the highest performance. The characteristics of SPELEEM and typical results, for example nano-XANES (X-ray absorption near edge structure) of Fe oxide on Fe(100) surface, nano-XPS (X-ray photoemission spectroscopy) of indium (In) on Si(111) and antiferro-magnetic domain structure images of NiO(001) single crystal, are reported. (author)

Sulfur K-edge X-ray absorption spectroscopy as an experimental probe for S-nitroso proteins

International Nuclear Information System (INIS)

Szilagyi, Robert K.; Schwab, David E.

2005-01-01

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

Ion charge-state production and photoionization near the K edge in argon and potassium

International Nuclear Information System (INIS)

Berry, H.G.; Azuma, Y.; Cowan, P.L.; Gemmell, D.S.; LeBrun, T.; Amusia, M.Y.

1994-01-01

We have measured the time-of-flight charge distributions of ions of argon and potassium following x-ray absorption at energies near their respective K edges. We confirm previously observed enhancements of the higher charge states at energies up to 100 eV below the K edge in argon. The measurements confirm recent calculations suggesting excitation of a virtual 1s state in this energy range

Characterization of local chemistry and disorder in synthetic and natural α-Al2O3 materials by X-ray absorption near edge structure spectroscopy

International Nuclear Information System (INIS)

Mottana, A.; Murata, T.

1997-11-01

X-ray absorption fine spectra at the Al K-edge were measured experimentally on and calculated theoretically via the multiple-scattering formalism for a chemically pure and physically perfect synthetic α-Al 2 O 3 (α-alumina), a natural 'ruby/sapphire' (corundum) and a series of artificial 'corundum' produced for technical purposes and used as geochemical standards. The Al K-edge spectra differ despite of the identical coordination (short-range arrangement) assumed by O around Al, and vary slightly in relation to the slightly different chemistries of the materials (substitutional defects) as well as on account of the location taken by foreign atoms in the structural lattices (positional defects). A quantitative treatment of the observed changes is made in terms of short-range modification of the coordination polyhedron and of medium- to long-range modifications in the overall structure; both of them induced by substitutions. In some technical 'corundums', the impurities of admixed 'β-alumina', where Al is both in four- and six-fold coordination, produce another small but detectable effect on Al K-edges. Therefore, XAFS spectroscopy proves its potentials for both measuring a light element such as Al, and detecting minor coordination changes and substitutions (ca. 1∼3 wt.% as oxide) of the absorber by dilute other atoms, at least under favorable conditions as those occurring in this system are

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

Science.gov (United States)

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

2004-01-01

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

The Silicon Environment in Silica Polymorphs, Aluminosilicate Crystals and Melts: An In Situ High Temperature XAS Study

International Nuclear Information System (INIS)

Cormier, L.; Neuville, D. R.; Roux, J.; Ligny, D. de; Henderson, G. S.; Flank, A.-M.; Lagarde, P.

2007-01-01

High temperature X-ray absorption spectroscopy at the Si K-edge has been used to obtain in situ information on SiO2 phase transitions upon heating. Important modifications are observed for the XANES spectra of the high temperature polymorphs, in relation to disordering of the SiO4 tetrahedra beyond the short-range correlations. This paper also presents the XANES spectra of anorthite (CaAl2Si2O8) from room temperature up to the melt (1900 K). This study shows the possibilities for determining the Si environment in crystals and glasses up to the liquid state using in situ XANES measurements

Microimaging and tomography with chemical speciation

Energy Technology Data Exchange (ETDEWEB)

Rau, C. E-mail: rau@esrf.fr; Somogyi, A.; Simionovici, A

2003-01-01

Materials science deals with the study of the morphology of samples, their chemical composition and the relation between both. One general problem is the preservation of the sample throughout the different analyses, like it is often the case for classical chemical analysis. Destruction-free chemical speciation in three dimensions with micrometer resolution can be achieved by combining X-ray spectroscopy and imaging techniques. Highly brilliant radiation is needed for this purpose available at 3rd generation synchrotrons such as the ESRF. X-ray absorption near-edge spectroscopy (XANES) is a non-destructive well-known and established technique in chemistry. By scanning the X-ray energy in the vicinity (50-100 eV) of the absorption edge of an element, information can be obtained about the oxidation state of the probed atoms. The (conventional) technique mainly employed until now applies to homogeneous, specifically prepared flat samples where the measured signal can be considered as the average over the whole irradiated volume. This restriction for samples is partially released when the XANES method is combined with imaging techniques. 2D resolved data is acquired using area detectors or by scanning with a focussed beam. X-ray absorption tomography is a method of choice for investigating the 3D structure of objects and its dual energy version is used for getting information about the 3D distribution of a given element within the sample. Although the combination of XANES and tomography seems to be a natural extension of dual-energy tomography, in practice several experimental problems have to be overcome in order to obtain useable data. In the following we describe the results of XANES imaging and tomography obtained measuring a phantom sample of pure molybdenum compounds using a FreLoN 2000 camera system at the ESRF undulator beamline ID22. This system allowed making volume resolved distinctions between different oxidation states with spatial resolution in the

Chemistry of uranium in evaporation pond sediment in the San Joaquin Valley, California, USA, using x-ray fluorescence and XANES techniques

International Nuclear Information System (INIS)

Duff, M.C.; Amrhein, C.; Bertsch, P.M.; Hunter, D.B.

1997-01-01

Evaporation ponds in the San Joaquin Valley (SJV), CA, used for the disposal of irrigation drainage waters, contain elevated levels of uranium. The ponds are filled periodically and support algae which upon evaporation become incorporated in the sediments as layers of decaying organic matter. This rich source of organic matter promotes reducing conditions in the sediments. Our research was conducted to characterize oxidation/reduction reactions that affect soluble and sediment U(IV)/U(VI) concentrations in the SJV ponds. Studies were done to (1) determine soluble U(Vl)/U(IV) in waters in contact with a pond sediment subjected to changes in redox status, (2) observe U solid oxidation state as a reducing pond sediment underwent (in vitro) oxidation, and (3) determine U solid oxidation state with respect to depth in pond surface sediment layers. Low pressure ion-exchange chromatography with an eluent of 0.125 M H 2 C 2 O 4 /0.25 M HNO 3 was used for the separation of U(IV) and U(VI) oxidation states in the drainage waters. Soluble U(VI) and U(IV) coexisted in sediment suspensions exposed to changes in redox potential (Eh) (-260 mV to +330 mV), and U(VI) was highly soluble in the oxidized, surface pond sediments. X-ray near edge absorption spectroscopy (XANES) showed that the U solid phases were 25% U(IV) and 75% U(VI) and probably a mixed solid [U 3 O 8(s) ] in highly reducing pond sediments. Sediment U(IV) increased slightly with depth in the surface pond sediment layers suggesting a gradual reduction of U(VI) to U(IV) with time. Under oxidized conditions, this mixed oxidation-state solid was highly soluble. 59 refs., 6 figs., 1 tab

Radiobiological investigations of soft X-rays near carbon, nitrogen, oxygen K-shell edges on Aspergillus oryzae spores

International Nuclear Information System (INIS)

Chen, L.; Jiang, S. P.; Wan, L. B.; Ma, X. D.; Li, M. F.

2008-01-01

Soft X-rays at carbon, nitrogen, oxygen K-shell edges have special radiobiological effects. Using Aspergillus oryzae spores as sample, the radiation effects of soft X-rays near the K-shell edges of C, N and O elements from synchrotron radiation were investigated. Also the dose depositions of different X-ray energies in spore were discussed. At the same time, the spores were irradiated by gamma rays from 60 Co and relative biological effects were compared with those produced by soft X-rays. The results showed that soft X-rays near K-shell edges of O element had higher ability of radiation damage than that of X-rays near K-shell edges of C and N elements as compared with one another. But they all had higher killing abilities per unit dose than that of gamma rays from 60 Co. The relative biological effects (RBEs), the comparison of dose to gamma rays at 10% survival level, of the three soft X-rays were 1.65, 1.73 and 1.91, respectively. (authors)

Imperial College near infrared spectroscopy neuroimaging analysis framework.

Science.gov (United States)

Orihuela-Espina, Felipe; Leff, Daniel R; James, David R C; Darzi, Ara W; Yang, Guang-Zhong

2018-01-01

This paper describes the Imperial College near infrared spectroscopy neuroimaging analysis (ICNNA) software tool for functional near infrared spectroscopy neuroimaging data. ICNNA is a MATLAB-based object-oriented framework encompassing an application programming interface and a graphical user interface. ICNNA incorporates reconstruction based on the modified Beer-Lambert law and basic processing and data validation capabilities. Emphasis is placed on the full experiment rather than individual neuroimages as the central element of analysis. The software offers three types of analyses including classical statistical methods based on comparison of changes in relative concentrations of hemoglobin between the task and baseline periods, graph theory-based metrics of connectivity and, distinctively, an analysis approach based on manifold embedding. This paper presents the different capabilities of ICNNA in its current version.

Real-Time Speciation of Uranium During Active Bioremediation and U(IV) Reoxidation

International Nuclear Information System (INIS)

Komlos, J.; Mishra, B.; Lanzirotti, A.; Myneni, S.; Jaffe, P.

2008-01-01

The biological reduction of uranium from soluble U(VI) to insoluble U(IV) has shown potential to prevent uranium migration in groundwater. To gain insight into the extent of uranium reduction that can occur during biostimulation and to what degree U(IV) reoxidation will occur under field relevant conditions after biostimulation is terminated, X-ray absorption near edge structure (XANES) spectroscopy was used to monitor: (1) uranium speciation in situ in a flowing column while active reduction was occurring; and (2) in situ postbiostimulation uranium stability and speciation when exposed to incoming oxic water. Results show that after 70 days of bioreduction in a high (30 mM) bicarbonate solution, the majority (>90%) of the uranium in the column was immobilized as U(IV). After acetate addition was terminated and oxic water entered the column, in situ real-time XANES analysis showed that U(IV) reoxidation to U(VI) (and subsequent remobilization) occurred rapidly (on the order of minutes) within the reach of the oxygen front and the spatial and temporal XANES spectra captured during reoxidation allowed for real-time uranium reoxidation rates to be calculated.

Effects of Sulfation Level on the Desulfation Behavior of Presulfated Pt-BaO/Al2O3 Lean

International Nuclear Information System (INIS)

Kim, D.; Szanyi, J.; Kwak, J.; Wang, X.; Hanson, J.; Engelhard, M.; Peden, C.

2009-01-01

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

XAS study of TiO2-based nanomaterials

Science.gov (United States)

Schneider, K.; Zajac, D.; Sikora, M.; Kapusta, Cz.; Michalow-Mauke, K.; Graule, Th.; Rekas, M.

2015-07-01

X-Ray Absorption Spectroscopy studies of the W (0-1 at% W) and Mo-doped TiO2 (0-1 at% Mo) nanoparticle specimens at the K edges of titanium and molybdenum as well as at the L2 L3 edges of tungsten are presented. The materials were prepared with Flame Spray Synthesis process by oxidation of metal-organic precursors. The Ti:K edge spectra in the XANES range show pre-edge and post-edge features characteristic for anatase. A decrease of the amplitude of the EXAFS function with doping is observed and attributed to a softening of the crystal lattice. The Mo EXAFS functions show a considerable decrease of the second-neighbour-shell peak with increasing Mo content, which is attributed to an increased number of cation vacancies. For tungsten a less pronounced effect is observed. The Mo and W XANES spectra do not show noticeable changes with doping level, which indicates their unchanged oxidation states.

X-ray absorption spectroscopy on the calcium cofactor to the manganese cluster in photosynthetic oxygen evolution

Energy Technology Data Exchange (ETDEWEB)

Cinco, Roehl M. [Univ. of California, Berkeley, CA (United States)

1999-12-01

Along with Mn, calcium and chloride ions are necessary cofactors for oxygen evolution in Photosystem II (PS II). To further test and verify whether Ca is close to the Mn cluster, the authors substituted strontium for Ca and probed from the Sr point of view for any nearby Mn. The extended X-ray absorption fine structure (EXAFS) of Sr-reactivated PS II indicates major differences between the intact and NH₂OH-treated samples. In intact samples, the Fourier transform of the Sr EXAFS shows a Fourier peak that is missing in inactive samples. This peak II is best simulated by two Mn neighbors at a distance of 3.5 Angstrom, confirming the proximity of Ca (Sr) cofactor to the Mn cluster. In addition, polarized Sr EXAFS on oriented Sr-reactivated samples shows this peak II is dichroic: large magnitude at 10 degrees (angle between the PS II membrane normal and the x-ray electric field vector) and small at 80 degrees. Analysis of the dichroism yields the relative angle between the Sr-Mn vector and membrane normal (23 degrees ± 4 degrees), and the isotropic coordination number for these layered samples. X-ray absorption spectroscopy has also been employed to assess the degree of similarity between the manganese cluster in PS II and a family of synthetic manganese complexes containing the distorted cubane [Mn₄O₃X] core (X = benzoate, acetate, methoxide, hydroxide, azide, fluoride, chloride or bromide). In addition, Mn₄O₃Cl complexes containing three or six terminal Cl ligands at three of the Mn were included in this study. The EXAFS method detects the small changes in the core structures as X is varied in this series, and serves to exclude these distorted cubanes of C3v symmetry as a topological model for the Mn catalytic cluster. The sulfur K-edge x-ray absorption near-edge structure (XANES) spectra for the amino acids cysteine, methionine, their corresponding oxidized forms cystine and methionine sulfoxide, and

Investigation of the hydrothermal crystallisation of the perovskite solid solution NaCe{sub 1−x}La{sub x}Ti{sub 2}O{sub 6} and its defect chemistry

Energy Technology Data Exchange (ETDEWEB)

Harunsani, Mohammad H. [Department of Chemistry, University of Warwick, Coventry CV4 7AL (United Kingdom); Woodward, David I. [Department of Physics, University of Warwick, Coventry CV4 7Al (United Kingdom); Peel, Martin D.; Ashbrook, Sharon E. [School of Chemistry, and EaStCHEM University of St. Andrews, North Haugh, St. Andrews, KY16 9ST (United Kingdom); Walton, Richard I., E-mail: r.i.walton@warwick.ac.uk [Department of Chemistry, University of Warwick, Coventry CV4 7AL (United Kingdom)

2013-11-15

Perovskites of nominal composition NaCe{sub 1−x}La{sub x}Ti{sub 2}O{sub 6} (0≤x≤1) crystallise directly under hydrothermal conditions at 240 °C. Raman spectroscopy shows distortion from the ideal cubic structure and Rietveld analysis of powder X-ray and neutron diffraction reveals that the materials represent a continuous series in rhombohedral space group R3-bar c. Ce L{sub III}-edge X-ray absorption near edge structure spectroscopy shows that while the majority of cerium is present as Ce{sup 3+} there is evidence for Ce{sup 4+}. The paramagnetic Ce{sup 3+} affects the chemical shift and line width of {sup 23}Na MAS NMR spectra, which also show with no evidence for A-site ordering. {sup 2}H MAS NMR of samples prepared in D{sub 2}O shows the inclusion of deuterium, which IR spectroscopy shows is most likely to be as D{sub 2}O. The deuterium content is highest for the cerium-rich materials, consistent with oxidation of some cerium to Ce{sup 4+} to provide charge balance of A-site water. - Graphical abstract: A multi-element A-site perovskite crystallises directly from aqueous, basic solutions at 240 °C; while the paramagnetic effect of Ce{sup 3+} on the {sup 23}Na NMR shows a homogeneous solid-solution, the incorporation of A-site water is also found from {sup 2}H NMR and IR, with oxidation of some cerium to charge balance proved by XANES spectroscopy. Display Omitted - Highlights: • Direct hydrothermal synthesis allows crystallisation of a perovskite solid-solution. • XANES spectroscopy shows some oxidation of Ce{sup 3+} to Ce{sup 4+}. • The paramagnetism of Ce{sup 3+} shifts and broadens the {sup 23}Na solid-state NMR. • The perovskite materials incorporate water as an A-site defect.

Final Report on Small Particle Speciation for Forensics Analysis by Soft X-ray Scanning Transmission X-ray Microscopy

Energy Technology Data Exchange (ETDEWEB)

Pacold, J. I. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Altman, A. B. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States); Donald, S B [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Dai, Z. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Davisson, M. L. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Holliday, K S [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Knight, K. B. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Kristo, M. J. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Minasian, S. G. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Nelson, A J [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Tyliszczak, T [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Booth, C. H. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Shuh, D. K. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

2016-09-30

Materials of interest for nuclear forensic science are often highly heterogeneous, containing complex mixtures of actinide compounds in a wide variety of matrices. Scanning transmission X-ray microscopy (STXM) is ideally suited to study such materials, as it can be used to chemically image specimens by acquiring X-ray absorption near-edge spectroscopy (XANES) data with 25 nm spatial resolution. In particular, STXM in the soft X-ray synchrotron radiation regime (approximately 120 – 2000 eV) can collect spectroscopic information from the actinides and light elements in a single experiment. Thus, STXM combines the chemical sensitivity of X-ray absorption spectroscopy with high spatial resolution in a single non-destructive characterization method. This report describes the application of STXM to a broad range of nuclear materials. Where possible, the spectroscopic images obtained by STXM are compared with information derived from other analytical methods, and used to make inferences about the process history of each material. STXM measurements can yield information including the morphology of a sample, “elemental maps” showing the spatial distribution of major chemical constituents, and XANES spectra from localized regions of a sample, which may show spatial variations in chemical composition.

Speciation of copper diffused in a bi-porous molecular sieve

International Nuclear Information System (INIS)

Huang, C.-H.; Paul Wang, H.; Wei, Y.-L.; Chang, J.-E.

2010-01-01

To better understand diffusion of copper in the micro- and mesopores, speciation of copper in a bi-porous molecular sieve (BPMS) possessing inter-connecting 3-D micropores (0.50-0.55 nm) and 2-D mesopores (4.1 nm) has been studied by X-ray absorption near edge structure (XANES) spectroscopy. It is found that about 77% (16% of CuO nanoparticles and 61% of CuO clusters) and 23% (CuO ads ) of copper can be diffused into the meso- and micropores, respectively, in the BPMS. At least two diffusion steps in the BPMS may be involved: (i) free diffusion of copper in the mesopores and (ii) diffusion-controlled copper migrating into the micropores of the BPMS. The XANES data also indicate that diffusion rate of copper in the BPMS (4.68x10 -5 g/s) is greater than that in the ZSM-5 (1.11x10 -6 g/s) or MCM-41 (1.17x10 -5 g/s).

High spin state driven magnetism and thermoelectricity in Mn doped topological insulator Bi2Se3

Science.gov (United States)

Maurya, V. K.; Dong, C. L.; Chen, C. L.; Asokan, K.; Patnaik, S.

2018-06-01

We report on the synthesis, and structural - magnetic characterizations of Mn doped Bi2Se3 towards achieving a magnetically doped topological insulator. High quality single crystals of MnxBi2-xSe3 (x = 0, 0.03, 0.05, 0.1) are grown and analysed by X-ray diffraction (XRD), Low Energy Electron Diffraction (LEED), Scanning electron microscopy (SEM), and X-ray absorption near-edge structure spectroscopy (XANES). Magnetic properties of these samples under ZFC-FC protocol and isothermal magnetization confirm ferromagnetic correlation above x = 0.03 value. XANES measurements confirm that the dopant Mn is in Mn2+ state. This is further reconfirmed to be in high spin state by fitting magnetic data with Brillouin function for J = 5/2. Both Hall and Seebeck measurements indicate a sign change of charge carriers above x = 0.03 value of Mn doping. We propose Mn doped Bi2Se3 to be a potential candidate for electromagnetic and thermoelectric device applications involving topological surface states.

Synchrotron X-ray Absorption and In Vitro Bioactivity of Magnetic Macro/Mesoporous Bioactive Glasses

Directory of Open Access Journals (Sweden)

Thanida Charoensuk

2015-12-01

Full Text Available Iron oxides in macro/mesoporous bioactive glasses were characterized by synchrotron X-ray absorption near edge structure (XANES spectroscopy. This magnetic phase was introduced by adding Fe(NO33 9H2O during the sol-gel synthesis. The obtained bioactive glass scaffolds exhibited superparamagnetism, in which the magnetization was increased with the increase in the Fe molar ratio from 10 to 20%. The linear combination fits of the XANES spectra indicated that the increase in the Fe molar ratio to 20% enhanced the γ-Fe2O3 formation at the expense of the α- Fe2O3 phase. This variation also promoted the formation of fine-grained bone-like apatites on the surface of the scaffolds in the in vitro test. The apatite growth between three and seven days was confirmed by the changing elemental compositions. However, the highest magnetic proportion led to the distortion of the skeleton walls and the collapse of the porous networks.

Characterization of metal-functionalized flax orbitide as a new candidate for light-emitting semiconductor

International Nuclear Information System (INIS)

Bauer, Robert; Bazylewski, Paul; Chang, Gap Soo; Jadhav, Pramodkumar; Shen, Jianheng; Okinyo-Owiti, Denis Paskal; Reaney, Martin; Yang, Jian; Sammynaiken, Ramaswami

2015-01-01

Organic materials display promise in numerous electronic applications, complimentary to traditional semi-conducting materials. Cyclolinopeptides show promise in light-emitting applications as an organic semiconductor. Photoluminescence measurements indicate charge transfer between the peptide and the metal, resulting in an increase in intensity of the emission from around the metal in the Cyclolinopeptide complex. Complementary X-ray absorption near-edge spectroscopy (XANES) shows a change in occupation of energy states in the peptide when complexed with the metal, indicating charge transfer, but peak positions show the peptide is not chemically changed by the metal. Combining X-ray emission and XANES provides element specific partial density of states, to estimate the element specific energy gap which is the proposed emission range for the peptide material. Organic light emitting diode devices have been fabricated, although no measurable emission has been seen as of yet. The devices have diode like current-voltage characteristics showing the peptide is semi-conducting with a threshold voltage of approximately 2.5 V. (paper)

Speciation of copper diffused in a bi-porous molecular sieve

Science.gov (United States)

Huang, C.-H.; Paul Wang, H.; Wei, Y.-L.; Chang, J.-E.

2010-07-01

To better understand diffusion of copper in the micro- and mesopores, speciation of copper in a bi-porous molecular sieve (BPMS) possessing inter-connecting 3-D micropores (0.50-0.55 nm) and 2-D mesopores (4.1 nm) has been studied by X-ray absorption near edge structure (XANES) spectroscopy. It is found that about 77% (16% of CuO nanoparticles and 61% of CuO clusters) and 23% (CuO ads) of copper can be diffused into the meso- and micropores, respectively, in the BPMS. At least two diffusion steps in the BPMS may be involved: (i) free diffusion of copper in the mesopores and (ii) diffusion-controlled copper migrating into the micropores of the BPMS. The XANES data also indicate that diffusion rate of copper in the BPMS (4.68×10 -5 g/s) is greater than that in the ZSM-5 (1.11×10 -6 g/s) or MCM-41 (1.17×10 -5 g/s).

Rapid Mapping of Lithiation Dynamics in Transition Metal Oxide Particles with Operando X-ray Absorption Spectroscopy

Science.gov (United States)

Nowack, Lea; Grolimund, Daniel; Samson, Vallerie; Marone, Federica; Wood, Vanessa

2016-02-01

Since the commercialization of lithium ion batteries (LIBs), layered transition metal oxides (LiMO2, where M = Co, Mn, Ni, or mixtures thereof) have been materials of choice for LIB cathodes. During cycling, the transition metals change their oxidation states, an effect that can be tracked by detecting energy shifts in the X-ray absorption near edge structure (XANES) spectrum. X-ray absorption spectroscopy (XAS) can therefore be used to visualize and quantify lithiation kinetics in transition metal oxide cathodes; however, in-situ measurements are often constrained by temporal resolution and X-ray dose, necessitating compromises in the electrochemistry cycling conditions used or the materials examined. We report a combined approach to reduce measurement time and X-ray exposure for operando XAS studies of lithium ion batteries. A highly discretized energy resolution coupled with advanced post-processing enables rapid yet reliable identification of the oxidation state. A full-field microscopy setup provides sub-particle resolution over a large area of battery electrode, enabling the oxidation state within many transition metal oxide particles to be tracked simultaneously. Here, we apply this approach to gain insights into the lithiation kinetics of a commercial, mixed-metal oxide cathode material, nickel cobalt aluminium oxide (NCA), during (dis)charge and its degradation during overcharge.

Iron and Arsenic Speciation During As(III) Oxidation by Manganese Oxides in the Presence of Fe(II): Molecular-Level Characterization Using XAFS, Mössbauer, and TEM Analysis

Energy Technology Data Exchange (ETDEWEB)

Wu, Yun [Environmental Soil Chemistry Research Group, Delaware Environmental Institute, University of Delaware, Newark, Delaware 19716, United States; Kukkadapu, Ravi K. [Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, Washington 99354, United States; Livi, Kenneth J. T. [The High-Resolution Analytical Electron Microbeam Facility, Department of Earth and Planetary Sciences, The Johns Hopkins University, Baltimore, Maryland 21218, United States; Xu, Wenqian [Department of Chemistry, Brookhaven National Lab, Upton, New York 11796, United States; Li, Wei [Environmental Soil Chemistry Research Group, Delaware Environmental Institute, University of Delaware, Newark, Delaware 19716, United States; Key Laboratory of Surficial Geochemistry, Ministry of Education, School of Earth Sciences and Engineering, Nanjing University, Nanjing 210046, People’s Republic of China; Sparks, Donald L. [Environmental Soil Chemistry Research Group, Delaware Environmental Institute, University of Delaware, Newark, Delaware 19716, United States

2018-01-17

The redox state and speciation of metalloid arsenic (As) determine its toxicity and mobility. Knowledge of biogeochemical processes influencing the As redox state is therefore important to understand and predict its environmental behavior. Many previous studies examined As(III) oxidation by various Mn-oxides, but little is known the environmental influences (e.g. co-existing ions) on such process. In this study, we investigated the mechanisms of As(III) oxidation by a poorly crystalline hexagonal birnessite (δ-MnO2) in the presence of Fe(II) using X-ray absorption spectroscopy (XAS), Mössbauer spectroscopy and transmission electron microscopy (TEM) coupled with energy-dispersive X-ray spectroscopy (EDS). As K-edge X-ray absorption near edge spectroscopy (XANES) analysis revealed that, at low Fe(II) concentration (100 μM), As(V) was the predominant As species on the solid phase, while at higher Fe(II) concentration (200-1000 μM), both As(III) and As(V) were sorbed on the solid phase. As K-edge extended X-ray absorption fine structure spectroscopy (EXAFS) analysis showed an increasing As-Mn/Fe distance over time, indicating As prefers to bind with the newly formed Fe(III)-(hydr)oxides. As adsorbed on Fe(III)-(hydr)oxides as a bidentate binuclear corner-sharing complex. Both Mössbauer and TEM-EDS investigations demonstrated that the oxidized Fe(III) products formed during Fe(II) oxidation by δ-MnO2 were predominantly ferrihydrite, goethite, and ferric arsenate like compounds. However, Fe EXAFS analysis also suggested the formation of a small amount of lepidocrocite. The Mn K-edge XANES data indicated that As(III) and Fe(II) oxidation occurs as a two electron transfer with δ-MnO2 and the observed Mn(III) is due to conproportionation of surface sorbed Mn(II) with Mn(IV) in δ-MnO2 structure. This study reveals that the mechanisms of As(III) oxidation by δ-MnO2 in the presence of Fe(II) are very complex, involving many simultaneous reactions, and the formation of

Exafs studies of coprecipitation and adsorption reactions of Tc

Energy Technology Data Exchange (ETDEWEB)

Bunker, D.J.; Jones, M.J.; Livens, F.R.; Collison, D. [Manchester Univ. (United Kingdom). Dept. of Chemistry; Pattrick, R.A.D. [Manchester Univ., Dept. of Earth Sciences (United Kingdom); Charnock, J.M. [CLRC Daresbury Laboratoire, Warrington Cheshire (United Kingdom)

2000-07-01

Adsorption and coprecipitation reactions may be a simple way of removing [TcO{sub 4}]{sup -} from aqueous solution. The effectiveness of a range of potential adsorbents and precipitants has been evaluated and some are capable of near quantitative (>98%) removal of [TcO{sub 4}){sup -} from solution. X-ray absorption near edge structure (XANES) has been used to determine Tc oxidation states and extended X-ray absorption fine structure spectroscopy (EXAFS) has been used to identify the local environment of Tc. The absorption edge position has been determined, using [PPh{sub 4}][TcO{sub 4}], TcS{sub 2} and Tc{sub 2}S{sub 7} as model compounds, and is diagnostic of Tc oxidation state. In a series of experiments investigating FeS coprecipitation, Tc was reduced to oxidation state (IV) and its local environment resembled that in TcO{sub 2} (6 O atoms at approximately 2.0 Angstrom). (authors)

NeptuniumV Retention by Siderite under Anoxic Conditions: Precipitation of NpO2-Like Nanoparticles and of NpIV Pentacarbonate.

Science.gov (United States)

Scheinost, Andreas C; Steudtner, Robin; Hübner, René; Weiss, Stephan; Bok, Frank

2016-10-04

The Np V retention by siderite, an Fe II carbonate mineral with relevance for the near-field of high-level radioactive waste repositories, was investigated under anoxic conditions. Batch sorption experiments show that siderite has a high affinity for aqueous Np V O 2 + across pH 7 to 13 as expressed by solid-water distribution coefficients, log R d, > 5, similar to the log R d determined for the (solely) tetravalent actinide Th on calcite, suggesting reduction of Np V to Np IV by siderite. Np L 3 -edge X-ray absorption near edge (XANES) spectroscopy conducted in a pH range typical for siderite-containing host rocks (7-8), confirmed the tetravalent Np oxidation state. Extended X-ray absorption fine-structure (EXAFS) spectroscopy revealed a local structure in line with NpO 2 -like nanoparticles with diameter nanoparticles (∼10 -9 M), along with their negligible surface charge at neutral pH conditions which favors particle aggregation, suggest an efficient retention of Np in the near-field of radioactive waste repositories. When Np V was added to ferrous carbonate solution, the subsequent precipitation of siderite did not lead to a structural incorporation of Np IV by siderite, but caused precipitation of a Np IV pentacarbonate phase.

Electronic structure analysis of UO2 by X-ray absorption spectroscopy

International Nuclear Information System (INIS)

Ozkendir, O.M.

2009-01-01

Full text: Due to the essential role of Actinides in nuclear science and technology, electronic and structural investigations of actinide compounds attract major interest in science. Electronic structure of actinide compounds have important properties due to narrow 5f states which play key role in bonding with anions. The properties of Uranium has been a subject of enduring interest due to its being a major importance as a nuclear fuel and is the highest numbered element which can be found naturally on earth. UO 2 forms as a secondary uranyl group occurred during metamictization of uranium oxide compounds [1].Uranium oxide thin films have been investigated by X-ray Absorption Fine Structure spectroscopy (XAFS) [2]. The full multiple scattering approach has been applied to the calculation of U L3 edge spectra of UO 2 . The calculations are based on different choices of one electron potentials according to Uranium coordinations by using the real space multiple scattering method FEFF 8.2 code [3,4]. U L3-edge absorption spectrum in UO 2 is compared with U L3-edges in USiO 4 and UTe which are chosen due to their different electronic and chemical structures.We have found prominent changes in the XANES spectra of Uranium oxide thin films due to valency properties. Such observed changes are explained by considering the structural, electronic and spectroscopic properties. (author)

Chemical state of mercury and selenium in sewage sludge ash based P-fertilizers

Energy Technology Data Exchange (ETDEWEB)

Vogel, Christian, E-mail: cv.vogel@yahoo.de [Division 4.4 Thermochemical Residues Treatment and Resource Recovery, Bundesanstalt für Materialforschung und −prüfung (BAM), Unter den Eichen 87, 12205 Berlin (Germany); Krüger, Oliver; Herzel, Hannes [Division 4.4 Thermochemical Residues Treatment and Resource Recovery, Bundesanstalt für Materialforschung und −prüfung (BAM), Unter den Eichen 87, 12205 Berlin (Germany); Amidani, Lucia [ESRF—The European Synchrotron, 71 Avenue des Martyrs, 38000 Grenoble (France); Adam, Christian [Division 4.4 Thermochemical Residues Treatment and Resource Recovery, Bundesanstalt für Materialforschung und −prüfung (BAM), Unter den Eichen 87, 12205 Berlin (Germany)

2016-08-05

Highlights: • Mercury bonded to carbon/organic material was detected in some sewage sludge ashes. • After thermochemcial treatment some mercury remains stabilized in the SSA matrix. • Analysis of the chemical state of mercury and selenium in highly diluted samples. - Abstract: Phosphorus-fertilizers from secondary resources such as sewage sludge ash (SSA) will become more important in the future as they could substitute conventional fertilizers based on the nonrenewable resource phosphate rock. Thermochemical approaches were developed which remove heavy metals from SSA prior to its fertilizer application on farmlands. We analyzed the chemical state of mercury and selenium in SSA before and after thermochemical treatment under different conditions for P-fertilizer production by X-ray absorption near edge structure (XANES) spectroscopy. In some incineration plants the mercury loaded carbon adsorber from off-gas cleaning was collected together with the SSA for waste disposal. SSAs from those plants contained mercury mainly bound to carbon/organic material. The other SSAs contained inorganic mercury compounds which are most probably stabilized in the SSA matrix and were thus not evaporated during incineration. During thermochemical treatment, carbon-bound mercury was removed quantitatively. In contrast, a certain immobile fraction of inorganic mercury compounds remained in thermochemically treated SSA, which were not clearly identified. HgSe might be one of the inorganic compounds, which is supported by results of Se K-edge XANES spectroscopy. Furthermore, the chemical state of selenium in the SSAs was very sensitive to the conditions of the thermochemical treatment.

The influence of desulfovibrio desulfuricans on neptunium chemistry

International Nuclear Information System (INIS)

Soderholm, L.; Williams, C.; Antonio, M. R.; Tischler, M. L.; Markos, M.

1999-01-01

The role of biotic Np(V) reduction is studied in light of its potential role in the environmental immobilization of this hazardous radionuclide. The speciation of Np in Desulfovibrio desulfuricans cultures is compared with Np speciation in the spent medium and in the uninoculated medium. Precipitates formed in all three samples. Optical spectroscopy and X-ray absorption near edge structure (XANES) were used to determine that Np(V) is almost quantitatively reduced in all three samples and that the precipitate is an amorphous Np(IV) species. These results demonstrate that the reduction of Np is independent of Desulfovibrio desulfuricans. The underlying chemistry associated with these results is discussed

HOPS 136: An edge-on orion protostar near the end of envelope infall

Energy Technology Data Exchange (ETDEWEB)

Fischer, William J.; Megeath, S. Thomas [Department of Physics and Astronomy, University of Toledo, Toledo, OH (United States); Tobin, John J. [National Radio Astronomy Observatory, Charlottesville, VA (United States); Hartmann, Lee; Kounkel, Marina [Department of Astronomy, University of Michigan, Ann Arbor, MI (United States); Stutz, Amelia M. [Max-Planck-Institut für Astronomie, Heidelberg (Germany); Poteet, Charles A. [New York Center for Astrobiology, Rensselaer Polytechnic Institute, Troy, NY (United States); Ali, Babar [NHSC/IPAC/Caltech, Pasadena, CA (United States); Osorio, Mayra [Instituto de Astrofísica de Andalucía, CSIC, Granada (Spain); Manoj, P. [Department of Astronomy and Astrophysics, Tata Institute of Fundamental Research, Mumbai (India); Remming, Ian [Department of Astronomy and Astrophysics, University of Chicago, Chicago, IL (United States); Stanke, Thomas [ESO, Garching bei München (Germany); Watson, Dan M., E-mail: wjfischer@gmail.com [Department of Physics and Astronomy, University of Rochester, Rochester, NY (United States)

2014-02-01

Edge-on protostars are valuable for understanding the disk and envelope properties of embedded young stellar objects, since the disk, envelope, and envelope cavities are all distinctly visible in resolved images and well constrained in modeling. Comparing Two Micron All Sky Survey, Wide-field Infrared Survey Explorer, Spitzer, Herschel, and APEX photometry and an IRAM limit from 1.2 to 1200 μm, Spitzer spectroscopy from 5 to 40 μm, and high-resolution Hubble imaging at 1.60 and 2.05 μm to radiative transfer modeling, we determine envelope and disk properties for the Class I protostar HOPS 136, an edge-on source in Orion's Lynds 1641 region. The source has a bolometric luminosity of 0.8 L {sub ☉}, a bolometric temperature of 170 K, and a ratio of submillimeter to bolometric luminosity of 0.8%. Via modeling, we find a total luminosity of 4.7 L {sub ☉} (larger than the observed luminosity due to extinction by the disk), an envelope mass of 0.06 M {sub ☉}, and a disk radius and mass of 450 AU and 0.002 M {sub ☉}. The stellar mass is highly uncertain but is estimated to fall between 0.4 and 0.5 M {sub ☉}. To reproduce the flux and wavelength of the near-infrared scattered-light peak in the spectral energy distribution, we require 5.4 × 10{sup –5} M {sub ☉} of gas and dust in each cavity. The disk has a large radius and a mass typical of more evolved T Tauri disks in spite of the significant remaining envelope. HOPS 136 appears to be a key link between the protostellar and optically revealed stages of star formation.

[Near infrared spectroscopy study on water content in turbine oil].

Science.gov (United States)

Chen, Bin; Liu, Ge; Zhang, Xian-Ming

2013-11-01

Near infrared (NIR) spectroscopy combined with successive projections algorithm (SPA) was investigated for determination of water content in turbine oil. Through the 57 samples of different water content in turbine oil scanned applying near infrared (NIR) spectroscopy, with the water content in the turbine oil of 0-0.156%, different pretreatment methods such as the original spectra, first derivative spectra and differential polynomial least squares fitting algorithm Savitzky-Golay (SG), and successive projections algorithm (SPA) were applied for the extraction of effective wavelengths, the correlation coefficient (R) and root mean square error (RMSE) were used as the model evaluation indices, accordingly water content in turbine oil was investigated. The results indicated that the original spectra with different water content in turbine oil were pretreated by the performance of first derivative + SG pretreatments, then the selected effective wavelengths were used as the inputs of least square support vector machine (LS-SVM). A total of 16 variables selected by SPA were employed to construct the model of SPA and least square support vector machine (SPA-LS-SVM). There is 9 as The correlation coefficient was 0.975 9 and the root of mean square error of validation set was 2.655 8 x 10(-3) using the model, and it is feasible to determine the water content in oil using near infrared spectroscopy and SPA-LS-SVM, and an excellent prediction precision was obtained. This study supplied a new and alternative approach to the further application of near infrared spectroscopy in on-line monitoring of contamination such as water content in oil.

Nature of the eigenstates near the mobility edge in random binary alloys

International Nuclear Information System (INIS)

Dahmani, L.; Sebbani, M.; Brezini, A.

1986-06-01

We present a calculation of the probability of non-diffusion and the localization length in a disordered Cayley tree in the case of a binary alloy distribution for the site energies. Particular attention is paid to the states near the mobility edge E c and numerical data for the critical exponent υ of the localization length are deduced. (author)

Xanes and SR-XRF Study of Skin as a Barrier to Ultra-Fine Nanocrystals of TiO2

International Nuclear Information System (INIS)

Kwiatek, W.M.; Lekki, J.; Stachura, Z.; Hanson, A.; Ablett, J.

2007-01-01

Nanocrystalline TiO 2 is commonly used in cosmetic industry as a photoprotective agent. With recent advances in nanomaterial processing, the size of TiO 2 crystals decreased into the nanometre regime. There is no satisfactory evidence that crystals of such small size are harmless to the human population. An EU project NANODERM has been launched where several techniques have been applied to investigate the possibility of particle penetration through the protective horny layer into vital skin regions. Skin biopsies of the animal and human skin have been collected after exposition to formulations containing TiO 2 nanocrystals. The Ti depth distributions were measured by electron and ion microscopy. The microscopy studies did not detect penetration into vital tissue of healthy skin what does not exclude a possibility that TiO 2 could penetrate pathological skin with lowered barrier efficiency. Due to literature the physical effect of the UV irradiation of the TiO 2 nanoparticle is the shift from 4 th to 3 rd oxidation state of the Ti. Titanium at 3 rd oxidation state interact with environment producing free radicals and Reactive Oxygen Species. In order to quantify the oxidation state shift, XANES experiments were carried out with commercially available TiO 2 nanocrystals (6 - 100 nm size), both in anatase and rutile phase. The samples were irradiated with X-rays with, and without accompanying UV illumination at the NSLS X27A beam line. The corresponding XANES spectra were registered and the absorption edge was compared in UV - illuminated and not illuminated spectra. A shift of about 1 eV in the absorption edge position of the rutile sample exposed to UVA light (365 nm, 20 mW/cm 2 ) has been measured and attributed to the changed electron configuration. However, the direction of the shift detected in measured samples was opposite to the expected. (author)

Effects of phonon broadening on x-ray near-edge spectra in molecular crystals

Science.gov (United States)

Vinson, John; Jach, Terrence; Elam, Tim; Denlinger, Jonathon

2014-03-01

Calculations of near-edge x-ray spectra are often carried out using the average atomic coordinates from x-ray or neutron scattering experiments or from density functional theory (DFT) energy minimization. This neglects disorder from thermal and zero-point vibrations. Here we look at the nitrogen K-edge of ammonium chloride and ammonium nitrate, comparing Bethe-Salpeter calculations of absorption and fluorescence to experiment. We find that intra-molecular vibrational effects lead to significant, non-uniform broadening of the spectra, and that for some features zero-point motion is the primary source of the observed shape.

Near-infrared spectroscopy

Directory of Open Access Journals (Sweden)

Virendra Jain

2015-01-01

Full Text Available Tissue ischaemia can be a significant contributor to increased morbidity and mortality. Conventional oxygenation monitoring modalities measure systemic oxygenation, but regional tissue oxygenation is not monitored. Near-infrared spectroscopy (NIRS is a non-invasive monitor for measuring regional oxygen saturation which provides real-time information. There has been increased interest in the clinical application of NIRS following numerous studies that show improved outcome in various clinical situations especially cardiac surgery. Its use has shown improved neurological outcome and decreased postoperative stay in cardiac surgery. Its usefulness has been investigated in various high risk surgeries such as carotid endarterectomy, thoracic surgeries, paediatric population and has shown promising results. There is however, limited data supporting its role in neurosurgical population. We strongly feel, it might play a key role in future. It has significant advantages over other neuromonitoring modalities, but more technological advances are needed before it can be used more widely into clinical practice.

Theory of L -edge spectroscopy of strongly correlated systems

Science.gov (United States)

Lüder, Johann; Schött, Johan; Brena, Barbara; Haverkort, Maurits W.; Thunström, Patrik; Eriksson, Olle; Sanyal, Biplab; Di Marco, Igor; Kvashnin, Yaroslav O.

2017-12-01

X-ray absorption spectroscopy measured at the L edge of transition metals (TMs) is a powerful element-selective tool providing direct information about the correlation effects in the 3 d states. The theoretical modeling of the 2 p →3 d excitation processes remains to be challenging for contemporary ab initio electronic structure techniques, due to strong core-hole and multiplet effects influencing the spectra. In this work, we present a realization of the method combining the density-functional theory with multiplet ligand field theory, proposed in Haverkort et al. [Phys. Rev. B 85, 165113 (2012), 10.1103/PhysRevB.85.165113]. In this approach, a single-impurity Anderson model (SIAM) is constructed, with almost all parameters obtained from first principles, and then solved to obtain the spectra. In our implementation, we adopt the language of the dynamical mean-field theory and utilize the local density of states and the hybridization function, projected onto TM 3 d states, in order to construct the SIAM. The developed computational scheme is applied to calculate the L -edge spectra for several TM monoxides. A very good agreement between the theory and experiment is found for all studied systems. The effect of core-hole relaxation, hybridization discretization, possible extensions of the method as well as its limitations are discussed.

Measurement of the effective atomic numbers of compounds with cerium near to the absorption edge

International Nuclear Information System (INIS)

Polat, Recep; Icelli, Orhan

2010-01-01

In order to measure atomic, molecular and electronic cross-section; the effective atomic number, density of electron and absorption jump factor, we have first measured μ t values of compounds which are determined by mixture rule using transmission method. In order to measure experimentally the effective atomic number within absorption jump factors of compounds with Ce, the X-ray source used Am-241 whose gamma rays were stopped at secondary source (Sm), thus producing Kα and Kβ X-ray emission. The most crucial finding in this study is that measurement of the effective atomic number is not appropriate near to the absorption edge and the effective atomic number is affected by near to the absorption edge. The results obtained have been compared with theoretical values.

Evidence for the incorporation of lead into barite from waste rock pile materials

Energy Technology Data Exchange (ETDEWEB)

COURTIN-NOMADE, ALEXANDRA; SOUBRAND-COLIN, MARILYNE; MARCUS, MATTHEW A.; FAKRA, SIRINE .C

2008-01-21

Because Pb is one of the most toxic elements and is found as a major contaminant in mining environments, this study aims to identify the distribution of this element in host phases issued from the alteration of mine wastes. The sampling location was a former mine near Oakland, California (USA). This mine was once a source of sulfide minerals from which sulfuric acid was made. The material discussed in this paper was collected in iron hardpans that were formed within the waste rock pile resulting from the excavation work. In most contaminated environments (soils, mine waste), secondary metal-bearing phases arising from alteration processes are usually fine-grained (from 10 {micro}m to less than 1 {micro}m) and highly heterogeneous, requiring the use of micron-scale techniques. We performed micro-Raman spectroscopy, microscanning X-ray diffraction (SXRD), and microextended X-ray near edge spectroscopy (XANES) to determine the relationships between Pb and a Ba/Fe-rich host phase. Micro-Raman spectroscopy suggests that Pb is preferentially incorporated into barite rather than goethite. Results from micro-Raman experiments show the high sensitivity of this analytical tool to the incorporation of Pb into barite by being especially sensitive to the variations of the S-O bond and showing the characteristic bands due to the contribution of Pb. This association is confirmed and is well-illustrated by micro-SXRD mineral species maps showing the correlation between Pb and barite. Microfocused XANES indicates that Pb is present as Pb{sup 2+}, agreeing with the in situ physicochemical parameters.

Radiation damages during synchrotron X-ray micro-analyses of Prussian blue and zinc white historic paintings: detection, mitigation and integration

Energy Technology Data Exchange (ETDEWEB)

Gervais, Claire [Bern University of the Arts, Bern (Switzerland); Thoury, Mathieu [IPANEMA, USR 3461 CNRS/MCC, Synchrotron SOLEIL, Gif-sur-Yvette (France); Reguer, Solenn; Gueriau, Pierre [Synchrotron SOLEIL, Gif-sur-Yvette (France); Mass, Jennifer [Winterthur Museum and Country Estate, Conservation Department, Winterthur, DE (United States)

2015-11-15

High-flux synchrotron techniques allow microspectroscopic analyses of artworks that were not feasible even a few years ago, allowing for a more detailed characterization of their constituent materials and a better understanding of their chemistry. However, interaction between high-flux photons and matter at the sub-microscale can generate damages which are not visually detectable. We show here different methodologies allowing to evidence the damages induced by microscopic X-ray absorption near-edge structure spectroscopy analysis (μXANES) at the Fe and Zn K-edges of a painting dating from the turn of the twentieth century containing Prussian blue and zinc white. No significant degradation of the pigments was noticed, in agreement with the excellent condition of the painting. However, synchrotron radiation damages occurred at several levels, from chemical changes of the binder, modification of crystal defects in zinc oxide, to Prussian blue photoreduction. They could be identified by using both the μXANES signal during analysis and with photoluminescence imaging in the deep ultraviolet and visible ranges after analysis. We show that recording accurately damaged areas is a key step to prevent misinterpretation of results during future re-examination of the sample. We conclude by proposing good practices that could help in integrating radiation damage avoidance into the analytical pathway. (orig.)

Edge electron density profiles and fluctuations measured by two-dimensional beam emission spectroscopy in the KSTAR

Energy Technology Data Exchange (ETDEWEB)

Nam, Y. U., E-mail: yunam@nfri.re.kr; Wi, H. M. [National Fusion Research Institute, Daejeon (Korea, Republic of); Zoletnik, S.; Lampert, M. [Wigner RCP Institute for Particle and Nuclear Physics, Budapest (Hungary); Kovácsik, Ákos [Institute of Nuclear Techniques, Budapest Technical University, Budapest (Hungary)

2014-11-15

Beam emission spectroscopy (BES) system in Korea Superconducting Tokamak Advanced Research (KSTAR) has recently been upgraded. The background intensity was reduced from 30% to 2% by suppressing the stray lights. This allows acquisition of the relative electron density profiles on the plasma edge without background subtraction from the beam power modulation signals. The KSTAR BES system has its spatial resolution of 1 cm, the temporal resolution of 2 MHz, and a total 32 channel (8 radial × 4 poloidal) avalanche photo diode array. Most measurements were done on the plasma edge, r/a ∼ 0.9, with 8 cm radial measurement width that covers the pedestal range. High speed density profile measurements reveal temporal behaviors of fast transient events, such as the precursors of edge localized modes and the transitions between confinement modes. Low background level also allows analysis of the edge density fluctuation patterns with reduced background fluctuations. Propagation of the density structures can be investigated by comparing the phase delays between the spatially distributed channels.

Crop type influences edge effects on the reproduction of songbirds in sagebrush habitat near agriculture

Directory of Open Access Journals (Sweden)

Elly C. Knight

2014-06-01

Full Text Available Extensive fragmentation of the sagebrush shrubsteppe of western North America could be contributing to observed population declines of songbirds in sagebrush habitat. We examined whether habitat fragmentation impacts the reproduction of songbirds in sagebrush edge habitat near agriculture, and if potential impacts vary depending on the adjacent crop type. Specifically, we evaluated whether nest abundance and nest survival varied between orchard edge habitat, vineyard edge habitat, and interior habitat. We then examined whether the local nest predator community and vegetation could explain the differences detected. We detected fewer nests in edge than interior habitat. Nest abundance per songbird was also lower in edge than interior habitat, although only adjacent to vineyards. Nest predation was more frequent in orchard edge habitat than vineyard edge or interior habitat. Predators identified with nest cameras were primarily snakes, however, reduced nest survival in orchard edge habitat was not explained by differences in the abundance of snakes or any other predator species identified. Information theoretic analysis of daily survival rates showed that greater study plot shrub cover and lower grass height at nests were partially responsible for the lower rate of predation-specific daily nest survival rate (PDSR observed in orchard edge habitat, but additional factors are likely important. Results of this study suggest that different crop types have different edge effects on songbirds nesting in sagebrush shrubsteppe, and that these reproductive edge effects may contribute to observed declines of these species. Habitat managers should avoid the creation of new orchard-sagebrush habitat edges to avoid further impacts on already declining songbird populations.

Gd doping induced weak ferromagnetic ordering in ZnS nanoparticles synthesized by low temperature co-precipitation technique

Energy Technology Data Exchange (ETDEWEB)

Kaur, Palvinder [Department of Physics, Punjabi University, Patiala, Punjab, 147002 (India); Kumar, Sanjeev, E-mail: sanjeev04101977@gmail.com [Applied Science Department, PEC University of Technology, Chandigarh, 160012 (India); Chen, Chi-Liang, E-mail: chen.cl@nsrrc.org.tw [National Synchrotron Radiation Research Center (NSRRC), Hsinchu, 30076, Taiwan (China); Yang, Kai-Siang [National Synchrotron Radiation Research Center (NSRRC), Hsinchu, 30076, Taiwan (China); Department of Mechanical Engineering, National Taipei University of Technology, Taipei, Taiwan (China); Wei, Da-Hua [Department of Mechanical Engineering, National Taipei University of Technology, Taipei, Taiwan (China); Dong, Chung-Li [Department of Physics, Tamkang University, Tamsui, Taiwan (China); Srivastava, C. [Materials Engineering Department, Indian Institute of Science, Bangalore, 560012 (India); Rao, S.M. [Department of Physics, Punjabi University, Patiala, Punjab, 147002 (India); Institute of Physics, Academia Sinica, Taipei, 11529, Taiwan (China)

2017-01-15

Zn{sub 1−x}Gd{sub x}S nanoparticles with Gd concentration x = 0.00, 0.02 and 0.04 were synthesized by the chemical co-precipitation technique using thioglycerol as capping agent. X-ray diffraction (XRD), transmission electron microscopy (TEM), photoluminescence (PL) spectroscopy, X-ray absorption near-edge structure (XANES) and vibrating sample magnetometer (VSM) were employed to characterize the as synthesized Gd doped ZnS nanoparticles. XRD and TEM studies show the formation of cubic ZnS nanoparticles with an average size in the range 5–10 nm. The doping did not alter the phase of the ZnS. The PL spectra of doped ZnS nanoparticles showed the presence of sulphur vacancies in the lattice. XANES of Gd doped ZnS nanoparticles depicts spectral changes may arise from charge transfer between host Zn and dopant Gd ions. A VSM study shows that the weak ferromagnetic behaviour increases with increase in Gd doping ZnS nanoparticles. - Highlights: • Gd doped ZnS nanoparticles synthesized using co-precipitation technique. • PL studies depict sulphur and zinc vacancies in Gd doped ZnS nanoparticles. • XANES studies depict the charge transfer between host Zn and dopant Gd ions. • Room temperature weak ferromagnetism is observed in Gd doped ZnS nanoparticles.

Dependence of the Ce(iii)/Ce(iv) ratio on intracellular localization in ceria nanoparticles internalized by human cells

KAUST Repository

Ferraro, Daniela

2017-01-09

CeO2 nanoparticles (CNPs) have been investigated as promising antioxidant agents with significant activity in the therapy of diseases involving free radicals or oxidative stress. However, the exact mechanism responsible for CNP activity has not been completely elucidated. In particular, in situ evidence of modification of the oxidative state of CNPs in human cells and their evolution during cell internalization and subsequent intracellular distribution has never been presented. In this study we investigated modification of the Ce(iii)/Ce(iv) ratio following internalization in human cells by X-ray absorption near edge spectroscopy (XANES). From this analysis on cell pellets, we observed that CNPs incubated for 24 h showed a significant increase in Ce(iii). By coupling on individual cells synchrotron micro-X-ray fluorescence (μXRF) with micro-XANES (μXANES) we demonstrated that the Ce(iii)/Ce(iv) ratio is also dependent on CNP intracellular localization. The regions with the highest CNP concentrations, suggested to be endolysosomes by transmission electron microscopy, were characterized by Ce atoms in the Ce(iv) oxidation state, while a higher Ce(iii) content was observed in regions surrounding these areas. These observations suggest that the interaction of CNPs with cells involves a complex mechanism in which different cellular areas play different roles.

Dependence of the Ce(iii)/Ce(iv) ratio on intracellular localization in ceria nanoparticles internalized by human cells

KAUST Repository

Ferraro, Daniela; Tredici, Ilenia G.; Ghigna, Paolo; Castillio-Michel, Hiram; Falqui, Andrea; Di Benedetto, Cristiano; Alberti, Giancarla; Ricci, Vittorio; Anselmi-Tamburini, Umberto; Sommi, Patrizia

2017-01-01

CeO2 nanoparticles (CNPs) have been investigated as promising antioxidant agents with significant activity in the therapy of diseases involving free radicals or oxidative stress. However, the exact mechanism responsible for CNP activity has not been completely elucidated. In particular, in situ evidence of modification of the oxidative state of CNPs in human cells and their evolution during cell internalization and subsequent intracellular distribution has never been presented. In this study we investigated modification of the Ce(iii)/Ce(iv) ratio following internalization in human cells by X-ray absorption near edge spectroscopy (XANES). From this analysis on cell pellets, we observed that CNPs incubated for 24 h showed a significant increase in Ce(iii). By coupling on individual cells synchrotron micro-X-ray fluorescence (μXRF) with micro-XANES (μXANES) we demonstrated that the Ce(iii)/Ce(iv) ratio is also dependent on CNP intracellular localization. The regions with the highest CNP concentrations, suggested to be endolysosomes by transmission electron microscopy, were characterized by Ce atoms in the Ce(iv) oxidation state, while a higher Ce(iii) content was observed in regions surrounding these areas. These observations suggest that the interaction of CNPs with cells involves a complex mechanism in which different cellular areas play different roles.

Gd doping induced weak ferromagnetic ordering in ZnS nanoparticles synthesized by low temperature co-precipitation technique

International Nuclear Information System (INIS)

Kaur, Palvinder; Kumar, Sanjeev; Chen, Chi-Liang; Yang, Kai-Siang; Wei, Da-Hua; Dong, Chung-Li; Srivastava, C.; Rao, S.M.

2017-01-01

Zn_1_−_xGd_xS nanoparticles with Gd concentration x = 0.00, 0.02 and 0.04 were synthesized by the chemical co-precipitation technique using thioglycerol as capping agent. X-ray diffraction (XRD), transmission electron microscopy (TEM), photoluminescence (PL) spectroscopy, X-ray absorption near-edge structure (XANES) and vibrating sample magnetometer (VSM) were employed to characterize the as synthesized Gd doped ZnS nanoparticles. XRD and TEM studies show the formation of cubic ZnS nanoparticles with an average size in the range 5–10 nm. The doping did not alter the phase of the ZnS. The PL spectra of doped ZnS nanoparticles showed the presence of sulphur vacancies in the lattice. XANES of Gd doped ZnS nanoparticles depicts spectral changes may arise from charge transfer between host Zn and dopant Gd ions. A VSM study shows that the weak ferromagnetic behaviour increases with increase in Gd doping ZnS nanoparticles. - Highlights: • Gd doped ZnS nanoparticles synthesized using co-precipitation technique. • PL studies depict sulphur and zinc vacancies in Gd doped ZnS nanoparticles. • XANES studies depict the charge transfer between host Zn and dopant Gd ions. • Room temperature weak ferromagnetism is observed in Gd doped ZnS nanoparticles.

Surface-Enhanced Raman Spectroscopy of Dye and Thiol Molecules Adsorbed on Triangular Silver Nanostructures: A Study of Near-Field Enhancement, Localization of Hot-Spots, and Passivation of Adsorbed Carbonaceous Species

Directory of Open Access Journals (Sweden)

Manuel R. Gonçalves

2012-01-01

Full Text Available Surface-enhanced Raman spectroscopy (SERS of thiols and dye molecules adsorbed on triangular silver nanostructures was investigated. The SERS hot-spots are localized at the edges and corners of the silver triangular particles. AFM and SEM measurements permit to observe many small clusters formed at the edges of triangular particles fabricated by nanosphere lithography. Finite-element calculations show that near-field enhancements can reach values of more than 200 at visible wavelengths, in the gaps between small spherical particles and large triangular particles, although for the later no plasmon resonance was found at the wavelengths investigated. The regions near the particles showing strong near-field enhancement are well correlated with spatial localization of SERS hot-spots done by confocal microscopy. Silver nanostructures fabricated by thermal evaporation present strong and fast fluctuating SERS activity, due to amorphous carbon contamination. Thiols and dye molecules seem to be able to passivate the undesired SERS activity on fresh evaporated silver.

Characterization of structural properties of U and Pu in model systems by advanced synchrotron based X-ray spectroscopy

International Nuclear Information System (INIS)

Pidchenko, Ivan

2016-01-01

This dissertation presents the investigations of different U and Pu model systems relevant for safety assessment studies of nuclear waste repositories using the X-ray based synchrotron techniques: U and Pu L_3/M_4_,_5 edges HR-XANES, L_3 edge EXAFS and 3d4f RIXS as well as other complementary techniques, including XPS, XRD, SEM, TEM and UV-Vis-NIR techniques.

Selenium Accumulation, Distribution, and Speciation in Spineless Prickly Pear Cactus: A Drought- and Salt-Tolerant, Selenium-Enriched Nutraceutical Fruit Crop for Biofortified Foods1[OA

Science.gov (United States)

Bañuelos, Gary S.; Fakra, Sirine C.; Walse, Spencer S.; Marcus, Matthew A.; Yang, Soo In; Pickering, Ingrid J.; Pilon-Smits, Elizabeth A.H.; Freeman, John L.

2011-01-01

The organ-specific accumulation, spatial distribution, and chemical speciation of selenium (Se) were previously unknown for any species of cactus. We investigated Se in Opuntia ficus-indica using inductively coupled plasma mass spectrometry, microfocused x-ray fluorescence elemental and chemical mapping (μXRF), Se K-edge x-ray absorption near-edge structure (XANES) spectroscopy, and liquid chromatography-mass spectrometry (LC-MS). μXRF showed Se concentrated inside small conic, vestigial leaves (cladode tips), the cladode vasculature, and the seed embryos. Se K-edge XANES demonstrated that approximately 96% of total Se in cladode, fruit juice, fruit pulp, and seed is carbon-Se-carbon (C-Se-C). Micro and bulk XANES analysis showed that cladode tips contained both selenate and C-Se-C forms. Inductively coupled plasma mass spectrometry quantification of Se in high-performance liquid chromatography fractions followed by LC-MS structural identification showed selenocystathionine-to-selenomethionine (SeMet) ratios of 75:25, 71:29, and 32:68, respectively in cladode, fruit, and seed. Enzymatic digestions and subsequent analysis confirmed that Se was mainly present in a “free” nonproteinaceous form inside cladode and fruit, while in the seed, Se was incorporated into proteins associated with lipids. μXRF chemical mapping illuminated the specific location of Se reduction and assimilation from selenate accumulated in the cladode tips into the two LC-MS-identified C-Se-C forms before they were transported into the cladode mesophyll. We conclude that Opuntia is a secondary Se-accumulating plant whose fruit and cladode contain mostly free selenocystathionine and SeMet, while seeds contain mainly SeMet in protein. When eaten, the organic Se forms in Opuntia fruit, cladode, and seed may improve health, increase Se mineral nutrition, and help prevent multiple human cancers. PMID:21059825

Selenium Accumulation, Distribution, and Speciation in Spineless Prickly Pear Cactus: A Drought- and Salt-Tolerant, Selenium-Enriched Nutraceutical Fruit Crop for Biofortified Foods

Energy Technology Data Exchange (ETDEWEB)

Banuelos, Gary S.; Fakra, Sirine C.; Walse, Spencer S.; Marcus, Matthew A.; Yang, Soo In; Pickering, Ingrid J.; Pilon-Smits, Elizabeth A.H.; Freeman, John L.

2011-07-01

The organ-specific accumulation, spatial distribution, and chemical speciation of selenium (Se) were previously unknown for any species of cactus. We investigated Se in Opuntia ficus-indica using inductively coupled plasma mass spectrometry, microfocused x-ray fluorescence elemental and chemical mapping ({micro}XRF), Se K-edge x-ray absorption near-edge structure (XANES) spectroscopy, and liquid chromatography-mass spectrometry (LC-MS). {micro}XRF showed Se concentrated inside small conic, vestigial leaves (cladode tips), the cladode vasculature, and the seed embryos. Se K-edge XANES demonstrated that approximately 96% of total Se in cladode, fruit juice, fruit pulp, and seed is carbon-Se-carbon (C-Se-C). Micro and bulk XANES analysis showed that cladode tips contained both selenate and C-Se-C forms. Inductively coupled plasma mass spectrometry quantification of Se in high-performance liquid chromatography fractions followed by LC-MS structural identification showed selenocystathionine-to-selenomethionine (SeMet) ratios of 75:25, 71:29, and 32:68, respectively in cladode, fruit, and seed. Enzymatic digestions and subsequent analysis confirmed that Se was mainly present in a 'free' nonproteinaceous form inside cladode and fruit, while in the seed, Se was incorporated into proteins associated with lipids. {micro}XRF chemical mapping illuminated the specific location of Se reduction and assimilation from selenate accumulated in the cladode tips into the two LC-MS-identified C-Se-C forms before they were transported into the cladode mesophyll. We conclude that Opuntia is a secondary Se-accumulating plant whose fruit and cladode contain mostly free selenocystathionine and SeMet, while seeds contain mainly SeMet in protein. When eaten, the organic Se forms in Opuntia fruit, cladode, and seed may improve health, increase Se mineral nutrition, and help prevent multiple human cancers.

Optical second-harmonic and reflectance-anisotropy spectroscopy of molecular adsorption at Si(001) step-edges

Energy Technology Data Exchange (ETDEWEB)

Ehlert, Robert; Kwon, Jinhee; Downer, Michael C. [University of Texas at Austin, Department of Physics, Austin, TX 78712-1081 (United States)

2008-07-01

Reflectance-anisotropy spectroscopy (RAS) and spectroscopic second harmonic generation (SHG) are used to probe a single-domain reconstructed stepped Si(001) surface offcut 6 toward[110] before and after dissociative adsorption of H{sub 2} at the D{sub B} step edges. Preliminary analysis with a simplified bond hyperpolarizability model supports the mutual consistency of RA and SHG spectra and suggests that hydrogen termination redistributes oscillator strength from the chemically active step dangling bond into the step back bonds. The data provide a benchmark for first-principles calculations of the optical response of stepped Si surfaces to step edge molecular adsorption. (copyright 2008 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

Phyllosilicates and Amorphous Gel in the Nakhlites

Science.gov (United States)

Hicks, L. J.; Bridges, J. C.; Gurman, S. J.

2013-09-01

Previous studies of the nakhlite martian meteorites have revealed hydrothermal minerals present within the fractures of the olivine minerals and the mesostasis. The olivine fractures of the Lafayette nakhlite reveal variations with initial deposits of siderite on the fracture walls, followed by crystalline phyllosilicates (smectite), and finishing with a rapidly cooled amorphous silicate gel within the central regions of the fractures. The mesostasis fractures of Lafayette also contain a crystalline phyllosilicate (serpentine). The amorphous gel is the most abundant secondary phase within the fractures of the other nakhlites [1, 2]. By studying nine nakhlite samples, including Lafayette, Governador Valadares, Nakhla, Y-000593, Y-000749, Miller-Range 03346, NWA 817, NWA 998, and NWA 5790, our aim is to constrain the identity of the phyllosilicate secondary phase minerals found throughout the nakhlite martian meteorites. This is achieved using methods including Electron Probe Micro-analysis (EPMA); X-ray Absorption Near-Edge Structure (Fe-K XANES) spectroscopy measured using Beamline I-18 at the Diamond Light Source synchrotron; and the use of Transmission Electron Microscopy (TEM) at the University of Leicester for High-Resolution (HR) imaging and Selected Area Electron Diffraction (SAED). BF studying nine nakhlite samples, including Lafayette, Governador Valadares, Nakhla, Y-000593, Y-000749, Miller-Range 03346, NWA 817, NWA 998, and NWA 5790, our aim is to constrain the identity of the phyllosilicate secondary phase minerals found throughout the nakhlite martian meteorites. This is achieved using methods including Electron Probe Micro-analysis (EPMA); X-ray Absorption Near-Edge Structure (Fe-K XANES) spectroscopy measured using Beamline I-18 at the Diamond Light Source synchrotron; and the use of Transmission Electron Microscopy (TEM) at the University of Leicester for High-Resolution (HR) imaging and Selected Area Electron Diffraction (SAED).

Depósito de TiN sobre herramientas de corte para uso industrial

Directory of Open Access Journals (Sweden)

Auger, M. A.

2004-04-01

Full Text Available TiN coatings on stainless steel blades for glass fibre cutting have been investigated in this work. The aim was to improve their mechanical properties and increase the tool time life, decreasing in this way the production stops. Reactive magnetron sputtering has been the deposition technique. TiN films chemical composition has been determined by AES (Auger Electron Spectroscopy, RBS (Rutherford Backscattering Spectroscopy and XANES (X-Ray Spectroscopy Near the Absorption Edge, and it has been correlated to the gas mixture composition in the vacuum chamber. Crystalline structure has been determined by X-Ray Diffraction, and the films morphology has been observed by SEM (Scanning Electron Microscopy. The hardness coating has been extracted from nanoindentation measurements, giving a 21.54±1.04 GPa hardness value, typical for TiN in the literature. Factory proofs for coated cutting blades show a 67% lifetime increase.

En este trabajo se han estudiado láminas de TiN crecidas sobre cuchillas de acero inoxidable empleadas en el corte de fibra de vidrio, para mejorar sus propiedades mecánicas y aumentar el tiempo de vida de la herramienta, reduciendo de este modo las paradas de producción. La técnica de depósito utilizada ha sido la de sputtering magnetrón reactivo. La composición química de las capas de TiN ha sido determinada mediante medidas de Espectroscopía Auger, RBS (Rutherford Backscattering Spectroscopy y XANES (X-Ray Spectroscopy Near the Absorption Edge y se ha relacionado con la composición de la mezcla gaseosa presente en la cámara de reacción. La estructura cristalina se ha determinado mediante Difracción de Rayos X, y mediante la técnica de SEM (Scanning Electron Microscopy se ha observado la morfología de las capas. La dureza del recubrimiento se ha calculado a partir de medidas de nanoindentación, obteniéndose un valor de 21.54±1.04 GPa, típico en la literatura para el TiN. Los resultados de la prueba en f

Effect of atomic vibrations in XANES: polarization-dependent damping of the fine structure at the Cu K-edge of (creat).sub.2./sub.CuCl.sub.4./sub.

Czech Academy of Sciences Publication Activity Database

Šipr, Ondřej; Vackář, Jiří; Kuzmin, A.

2016-01-01

Roč. 23, č. 6 (2016), s. 1433-1439 ISSN 1600-5775 R&D Projects: GA MŠk LD15097 Institutional support: RVO:68378271 Keywords : XANES * vibrations * multiple-scattering formalism Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.011, year: 2016

Crystallographic Analysis of a Japanese Sword by using Bragg Edge Transmission Spectroscopy

Science.gov (United States)

Shiota, Yoshinori; Hasemi, Hiroyuki; Kiyanagi, Yoshiaki

Neutron imaging using a pulsed neutron source can give crystallographic information over wide area of a sample by analysing position dependent transmission spectra. With the use of a Bragg edge imaging method we non-destructively obtained crystallographic information of a Japanese sword, signed by Bishu Osafune Norimitsu, in order to know position dependent crystallographic characteristics and to check usefulness of the method for the Japanese sword investigation. Strong texture appeared on the back side. On the other hand in the middle area almost isotropic feature appeared and edge side showed feature between them. Rather isotropic area in the centre area gradually reduced from the grip side to the tip side. The crystallite size was smaller near the edge and became larger towards the back side. The smaller crystallite size will be due to quenching around the edge and this trend disappeared in the grip (nakago) area. The larger crystallite size will be due to strong hammering. Coarse grains were also observed directly as transmission images with the use of a high spatial resolution detector. The spatial distribution of the grains was not uniform but the reason have not been understood. Furthermore, a white area around a tip area was proved to be a void by looking at the Brag edge transmission spectra. This void may be formed during forging process of two kinds of steel. It is suggested that consideration on differences in the texture and the crystallite size depending on position will give information to clarify the manufacturing process, and Bragg edge analysis will be a profitable tool for research of Japanese sword.

Near-infrared spectroscopy for cocrystal screening. A comparative study with Raman spectroscopy.

Science.gov (United States)

Allesø, Morten; Velaga, Sitaram; Alhalaweh, Amjad; Cornett, Claus; Rasmussen, Morten A; van den Berg, Frans; de Diego, Heidi Lopez; Rantanen, Jukka

2008-10-15

Near-infrared (NIR) spectroscopy is a well-established technique for solid-state analysis, providing fast, noninvasive measurements. The use of NIR spectroscopy for polymorph screening and the associated advantages have recently been demonstrated. The objective of this work was to evaluate the analytical potential of NIR spectroscopy for cocrystal screening using Raman spectroscopy as a comparative method. Indomethacin was used as the parent molecule, while saccharin and l-aspartic acid were chosen as guest molecules. Molar ratios of 1:1 for each system were subjected to two types of preparative methods. In the case of saccharin, liquid-assisted cogrinding as well as cocrystallization from solution resulted in a stable 1:1 cocrystalline phase termed IND-SAC cocrystal. For l-aspartic acid, the solution-based method resulted in a polymorphic transition of indomethacin into the metastable alpha form retained in a physical mixture with the guest molecule, while liquid-assisted cogrinding did not induce any changes in the crystal lattice. The good chemical peak selectivity of Raman spectroscopy allowed a straightforward interpretation of sample data by analyzing peak positions and comparing to those of pure references. In addition, Raman spectroscopy provided additional information on the crystal structure of the IND-SAC cocrystal. The broad spectral line shapes of NIR spectra make visual interpretation of the spectra difficult, and consequently, multivariate modeling by principal component analysis (PCA) was applied. Successful use of NIR/PCA was possible only through the inclusion of a set of reference mixtures of parent and guest molecules representing possible solid-state outcomes from the cocrystal screening. The practical hurdle related to the need for reference mixtures seems to restrict the applicability of NIR spectroscopy in cocrystal screening.

Absolute spectroscopy near 7.8 μm with a comb-locked extended-cavity quantum-cascade-laser.

Science.gov (United States)

Lamperti, Marco; AlSaif, Bidoor; Gatti, Davide; Fermann, Martin; Laporta, Paolo; Farooq, Aamir; Marangoni, Marco

2018-01-22

We report for the first time the frequency locking of an extended-cavity quantum-cascade-laser (EC-QCL) to a near-infrared frequency comb. The locked laser source is exploited to carry out molecular spectroscopy around 7.8 μm with a line-centre frequency combined uncertainty of ~63 kHz. The strength of the approach, in view of an accurate retrieval of line centre frequencies over a spectral range as large as 100 cm -1 , is demonstrated on the P(40), P(18) and R(31) lines of the fundamental rovibrational band of N 2 O covering the centre and edges of the P and R branches. The spectrometer has the potential to be straightforwardly extended to other spectral ranges, till 12 μm, which is the current wavelength limit for commercial cw EC-QCLs.

Absolute spectroscopy near 7.8 μm with a comb-locked extended-cavity quantum-cascade-laser

KAUST Repository

Lamperti, Marco; Alsaif, Bidoor; Gatti, Davide; Fermann, Martin; Laporta, Paolo; Farooq, Aamir; Marangoni, Marco

2018-01-01

We report for the first time the frequency locking of an extended-cavity quantum-cascade-laser (EC-QCL) to a near-infrared frequency comb. The locked laser source is exploited to carry out molecular spectroscopy around 7.8 μm with a line-centre frequency combined uncertainty of ~63 kHz. The strength of the approach, in view of an accurate retrieval of line centre frequencies over a spectral range as large as 100 cm-1, is demonstrated on the P(40), P(18) and R(31) lines of the fundamental rovibrational band of N2O covering the centre and edges of the P and R branches. The spectrometer has the potential to be straightforwardly extended to other spectral ranges, till 12 μm, which is the current wavelength limit for commercial cw EC-QCLs.

Absolute spectroscopy near 7.8 μm with a comb-locked extended-cavity quantum-cascade-laser

KAUST Repository

Lamperti, Marco

2018-01-16

We report for the first time the frequency locking of an extended-cavity quantum-cascade-laser (EC-QCL) to a near-infrared frequency comb. The locked laser source is exploited to carry out molecular spectroscopy around 7.8 μm with a line-centre frequency combined uncertainty of ~63 kHz. The strength of the approach, in view of an accurate retrieval of line centre frequencies over a spectral range as large as 100 cm-1, is demonstrated on the P(40), P(18) and R(31) lines of the fundamental rovibrational band of N2O covering the centre and edges of the P and R branches. The spectrometer has the potential to be straightforwardly extended to other spectral ranges, till 12 μm, which is the current wavelength limit for commercial cw EC-QCLs.

Micron to Mine: Synchrotron Science for Mineral Exploration, Production, and Remediation

Science.gov (United States)

Banerjee, N.; Van Loon, L.; Flynn, T.

2017-12-01

Synchrotron science for mineral exploration, production, and remediation studies is a powerful tool that provides industry with relevant micron to macro geochemical information. Synchrotron micro X-ray fluorescence (SR-µXRF) offers a direct, high-resolution, rapid, and cost-effective chemical analysis while preserving the context of the sample by mapping ore minerals with ppm detection limits. Speciation of trace and deleterious elements can then be probed using X-ray absorption near-edge structure (XANES) spectroscopy. Large-scale (tens of cm) µXRF mapping and XANES analysis of samples collected at various mine locations have been undertaken to address questions regarding mineralization history to develop novel trace element exploration vectors. This information provides integral insights into trace element associations with ore minerals, local redox conditions responsible for mineralization, and mineralizing mechanisms. Gold is commonly intimately associated with sulfide mineralization (e.g., pyrite, arsenopyrite, etc.) and is present both as inclusions and filling fractures in sulfide grains. Gold may also occur as nanoparticles and/or in the sulfide mineral crystal lattice, known as "invisible gold". Understanding the nature and distribution of invisible gold in ore is integral to processing efficiency. The high flux and energy of a synchrotron light source allows for the detection of invisible gold by µXRF, and can probe its nature (metallic Au0 vs. lattice bound Au1+) using XANES spectroscopy. The long-term containment and management of arsenic is necessary to protect the health of both humans and the environment. Understanding the relationship of arsenic mineralization to gold deposits can lead to more sophisticated planning for mineral processing and the eventual storage of gangue materials. µXANES spectroscopy is an excellent tool for determining arsenic speciation within the context of the sample. Mineral phases such as arsenopyrite, scorodite, and

The microspectroscopy beamline for the Australian synchrotron project

International Nuclear Information System (INIS)

Boldeman, J.W.; Ryan, C.; Cohen, D.D.

2005-01-01

A new multi-million dollar synchrotron facility is currently being built in Clayton, Victoria. This is a 3GeV electron machine, it will be a world class machine and contain state of the art beamline facilities for both Australian and overseas scientists. It is due for completion in mid-2007. This specialised beamline will provide sub-micron spatial resolution with the highest flux possible. It will combine 2D mapping with micro X-ray fluorescence (μ-XRF), micro X-ray absorption near edge spectroscopy (μ-XANES) and micro X-ray absorption fine structure spectroscopy (μ-XAFS) for elemental and chemical analysis to solve scientific problems that can only be understood using X-ray beams with sub-micron resolutions. In this paper we describe some key beamline components and give details about their performance specifications. 7 refs., 4 figs.; 1 tab

Crystal and electronic structure study of Mn doped wurtzite ZnO nanoparticles

Directory of Open Access Journals (Sweden)

O.M. Ozkendir

2016-08-01

Full Text Available The change in the crystal and electronic structure properties of wurtzite ZnO nanoparticles was studied according to Mn doping in the powder samples. The investigations were conducted by X-ray Absorption Fine Structure Spectroscopy (XAFS technique for the samples prepared with different heating and doping processes. Electronic analysis was carried out by the collected data from the X-ray Absorption Near-Edge Structure Spectroscopy (XANES measurements. Additional crystal structure properties were studied by Extended-XAFS (EXAFS analysis. Longer heating periods for the undoped wurtzite ZnO samples were determined to own stable crystal geometries. However, for some doped samples, the distortions in the crystal were observed as a result of the low doping amounts of Mn which was treated as an impurity. Besides, the changes in oxygen locations were determined to create defects and distortions in the samples.

Cerebral near infrared spectroscopy oximetry in extremely preterm infants

DEFF Research Database (Denmark)

Hyttel-Sorensen, Simon; Pellicer, Adelina; Alderliesten, Thomas

2015-01-01

OBJECTIVE: To determine if it is possible to stabilise the cerebral oxygenation of extremely preterm infants monitored by cerebral near infrared spectroscopy (NIRS) oximetry. DESIGN: Phase II randomised, single blinded, parallel clinical trial. SETTING: Eight tertiary neonatal intensive care unit...

[Application of near-infrared spectroscopy in golf turfgrass management].

Science.gov (United States)

Li, Shu-Ying; Han, Jian-Guo

2008-07-01

The management of golf course is different from other turfs. Its particularity lies in its higher and more precise requirement during maintenance compare with other turfs. In case something happened to turf of golf course, more effective and higher speed detecting and resolution are required. Only the data about turf growth and environment were mastered precisely in time, the friendly environmental and scientific management goal could be completed effectively and economically. The near infrared spectroscopy is a new kind of effective, convenient and non-destructive analytical method in the turfgrass management of golf course in recent years. Many factors of turf-soil system in golf course could be determined by near infrared spectroscopy at the same time. In this paper, the existing literature that use of near infrared spectroscopy to study turfgrass and soil nutrient content, soil hygroscopic moisture, feasible fertilizer application time and rate, to fix the time and volume of irrigation, turfgrass visual quality evaluation, turfgrass disease prediction and prevention were reviewed. Most researchers considered the nutrition condition of turf impacted the visual and playing quality of golf course directly and then indirectly influenced most of assistant cultivation such as fertilization, mowing and irrigation and so on. The using of NIRS can detect the nutrient content of turfgrass effectively and estimate the nutrient is excessive or deficient quickly. And then the feasible time and rate of fertilizers can be decided. Comparing with the common judgment ways based on the season fertilization and visual estimation, the using of NIRS can reduce the application of fertilizers on the base of keeping the same turf quality simultaneously. NIRS can analysis many items of soil such as moisture, elements concentration, textures on the spot by the thousands. This method can get lots of cover-all data non-destructively. What's more, NIRS can analysis soil betimes quickly

Formation of silicon nanocrystals in multilayer nanoperiodic a-SiO{sub x}/insulator structures from the results of synchrotron investigations

Energy Technology Data Exchange (ETDEWEB)

Turishchev, S. Yu., E-mail: tsu@phys.vsu.ru; Terekhov, V. A.; Koyuda, D. A. [Voronezh State University (Russian Federation); Ershov, A. V.; Mashin, A. I. [Lobachevsky State University of Nizhny Novgorod (Russian Federation); Parinova, E. V.; Nesterov, D. N. [Voronezh State University (Russian Federation); Grachev, D. A.; Karabanova, I. A. [Lobachevsky State University of Nizhny Novgorod (Russian Federation); Domashevskaya, E. P. [Voronezh State University (Russian Federation)

2017-03-15

The problem of the efficiency of the controllable formation of arrays of silicon nanoparticles is studied on the basis of detailed investigations of the electronic structure of multilayer nanoperiodic a-SiO{sub x}/SiO{sub 2}, a-SiO{sub x}/Al{sub 2}O{sub 3}, and a-SiO{sub x}/ZrO{sub 2} compounds. Using synchrotron radiation and the X-ray absorption near edge structure (XANES) spectroscopy technique, a modification is revealed for the investigated structures under the effect of high-temperature annealing at the highest temperature of 1100°C; this modification is attributed to the formation of silicon nanocrystals in the layers of photoluminescent multilayer structures.

Species authentication and geographical origin discrimination of herbal medicines by near infrared spectroscopy: A review

OpenAIRE

Wang, Pei; Yu, Zhiguo

2015-01-01

Near infrared (NIR) spectroscopy as a rapid and nondestructive analytical technique, integrated with chemometrics, is a powerful process analytical tool for the pharmaceutical industry and is becoming an attractive complementary technique for herbal medicine analysis. This review mainly focuses on the recent applications of NIR spectroscopy in species authentication of herbal medicines and their geographical origin discrimination. Keywords: Near infrared spectroscopy, Herbal medicine, Species...

Food Safety Evaluation Based on Near Infrared Spectroscopy and Imaging: A Review.

Science.gov (United States)

Fu, Xiaping; Ying, Yibin

2016-08-17

In recent years, due to the increasing consciousness of food safety and human health, much progress has been made in developing rapid and nondestructive techniques for the evaluation of food hazards, food authentication, and traceability. Near infrared (NIR) spectroscopy and imaging techniques have gained wide acceptance in many fields because of their advantages over other analytical techniques. Following a brief introduction of NIR spectroscopy and imaging basics, this review mainly focuses on recent NIR spectroscopy and imaging applications for food safety evaluation, including (1) chemical hazards detection; (2) microbiological hazards detection; (3) physical hazards detection; (4) new technology-induced food safety concerns; and (5) food traceability. The review shows NIR spectroscopy and imaging to be effective tools that will play indispensable roles for food safety evaluation. In addition, on-line/real-time applications of these techniques promise to be a huge growth field in the near future.

Near-infrared spectroscopy can reveal increases in brain activity related to animal-assisted therapy.

Science.gov (United States)

Morita, Yuka; Ebara, Fumio; Morita, Yoshimitsu; Horikawa, Etsuo

2017-08-01

[Purpose] Previous studies have indicated that animal-assisted therapy can promote recovery of psychological, social, and physiological function in mental disorders. This study was designed as a pilot evaluation of the use of near-infrared spectroscopy to objectively identify changes in brain activity that could mediate the effect of animal-assisted therapy. [Subjects and Methods] The participants were 20 healthy students (10 males and 10 females; age 19-21 years) of the Faculty of Agriculture, Saga University. Participants were shown a picture of a Tokara goat or shack (control) while prefrontal cortical oxygenated haemoglobin levels (representing neural activity) were measured by near-infrared spectroscopy. [Results] The prefrontal cortical near-infrared spectroscopy signal was significantly higher during viewing of the animal picture than during a rest condition or during viewing of the control picture. [Conclusion] Our results suggest that near-infrared spectroscopy can be used to objectively identify brain activity changes during human mentation regarding animals; furthermore, these preliminary results suggest the efficacy of animal-assisted therapy could be related to increased activation of the prefrontal cortex.

Quantifying cerebral hypoxia by near-infrared spectroscopy tissue oximetry

DEFF Research Database (Denmark)

Rasmussen, Martin B.; Eriksen, Vibeke R.; Andresen, Bjørn

2017-01-01

Tissue oxygenation estimated by near-infrared spectroscopy (NIRS) is a volume-weighted mean of the arterial and venous hemoglobin oxygenation. In vivo validation assumes a fixed arterial-to-venous volume-ratio (AV-ratio). Regulatory cerebro-vascular mechanisms may change the AV-ratio. We used...

Defect induced structural inhomogeneity, ultraviolet light emission and near-band-edge photoluminescence broadening in degenerate In2O3 nanowires

Science.gov (United States)

Mukherjee, Souvik; Sarkar, Ketaki; Wiederrecht, Gary P.; Schaller, Richard D.; Gosztola, David J.; Stroscio, Michael A.; Dutta, Mitra

2018-04-01

We demonstrate here defect induced changes on the morphology and surface properties of indium oxide (In2O3) nanowires and further study their effects on the near-band-edge (NBE) emission, thereby showing the significant influence of surface states on In2O3 nanostructure based device characteristics for potential optoelectronic applications. In2O3 nanowires with cubic crystal structure (c-In2O3) were synthesized via carbothermal reduction technique using a gold-catalyst-assisted vapor-liquid-solid method. Onset of strong optical absorption could be observed at energies greater than 3.5 eV consistent with highly n-type characteristics due to unintentional doping from oxygen vacancy ({V}{{O}}) defects as confirmed using Raman spectroscopy. A combination of high resolution transmission electron microscopy, x-ray photoelectron spectroscopy and valence band analysis on the nanowire morphology and stoichiometry reveals presence of high-density of {V}{{O}} defects on the surface of the nanowires. As a result, chemisorbed oxygen species can be observed leading to upward band bending at the surface which corresponds to a smaller valence band offset of 2.15 eV. Temperature dependent photoluminescence (PL) spectroscopy was used to study the nature of the defect states and the influence of the surface states on the electronic band structure and NBE emission has been discussed. Our data reveals significant broadening of the NBE PL peak consistent with impurity band broadening leading to band-tailing effect from heavy doping.

Predicting rapeseed oil content with near-infrared spectroscopy

Directory of Open Access Journals (Sweden)

Roberta Rossato

2013-12-01

Full Text Available The objective of this work was to establish a calibration equation and to estimate the efficiency of near-infrared reflectance (NIR spectroscopy for evaluating rapeseed oil content in Southern Brazil. Spectral data from 124 half-sib families were correlated with oil contents determined by the chemical method. The accuracy of the equation was verified by coefficient of determination (R² of 0.92, error of calibration (SEC of 0.78, and error of performance (SEP of 1.22. The oil content of ten genotypes, which were not included in the calibration with NIR, was similar to the one obtained by the standard chemical method. NIR spectroscopy is adequate to differentiate oil content of rapeseed genotypes.

A high resolution x-ray fluorescence spectrometer for near edge absorption studies

International Nuclear Information System (INIS)

Stojanoff, V.; Hamalainen, K.; Siddons, D.P.; Hastings, J.B.; Berman, L.E.; Cramer, S.; Smith, G.

1991-01-01

A high resolution fluorescence spectrometer using a Johann geometry in a back scattering arrangement was developed. The spectrometer, with a resolution of 0.3 eV at 6.5 keV, combined with an incident beam, with a resolution of 0.7 eV, form the basis of a high resolution instrument for measuring x-ray absorption spectra. The advantages of the instrument are illustrated with the near edge absorption spectrum of dysprosium nitrate. 10 refs., 4 figs

Electronic structure and field emission properties of nitrogen doped graphene nano-flakes (GNFs:N) and carbon nanotubes (CNTs:N)

Energy Technology Data Exchange (ETDEWEB)

Ray, Sekhar C., E-mail: Raysc@unisa.ac.za [Department of Physics, College of Science, Engineering and Technology, University of South Africa, Private Bag X6, Florida, 1710, Science Campus, Christiaan de Wet and Pioneer Avenue, Florida Park, Johannesburg (South Africa); Pong, W.F. [Department of Physics, Tamkang University, Tamsui 251, New Taipei City, Taiwan (China); Papakonstantinou, P. [Nanotechnology and Integrated Bio-Engineering Centre, University of Ulster, Shore Road, Newtownabbey BT37 0QB (United Kingdom)

2016-09-01

Highlights: • Nitrogen doped graphene nano-flakes (GNFs:N) and carbon nano-tubes (CNTs:N) are used to study the electronic/bonding structure along with their defects state. • The I{sub D}/I{sub G} ratio obtained from Raman spectroscopy used for the study of the defects states of CNTs:N than GNFs:N. • The electron field emission result shows that the turn on electric field is lower in case of CNTs:N than GNFs:N. • All results are good agreement with XANES and the results obtained from Raman spectra. - Abstract: Substitution of hetero-atom doping is a promising route to modulate the outstanding material properties of carbon nanotubes and graphene for customized applications. Nitrogen-doping has been introduced to ensure tunable work-function, enhanced n-type carrier concentration, diminished surface energy, and manageable polarization. Along with the promising assessment of N-doping effects, research on the N-doped carbon based composite structures is emerging for the synergistic integration with various functional materials. Nitrogen undoped/doped graphene nano-flakes (GNFs/GNFs:N) and multiwall carbon nano-tubes (MWCNTs/MWCNTs:N) are used for comparative study of their electronic/bonding structure along with their defects state. X-ray absorption near edge structure (XANES) spectroscopy shows that the GNFs:N produce mainly pyridine like structure; whereas MWCNTs:N shows graphitic nitrogen atoms are attached with the carbon lattice. The I{sub D}/I{sub G} ratio obtained from Raman spectroscopy shows that the defects is higher in MWCNTs:N than GNFs:N. The electron field emission result shows that the turn on electric field is lower (higher electron emission current) in case of MWCNTs:N than GNFs:N and are good agreement with XANES and the results obtained from Raman spectra.

Non-equilibrium solid-to-plasma transition dynamics using XANES diagnostic

Energy Technology Data Exchange (ETDEWEB)

Dorchies, F., E-mail: dorchies@celia.u-bordeaux1.fr [Univ. Bordeaux, CNRS, CEA, CELIA (Centre Lasers Intenses et Applications), UMR 5107, F-33400 Talence (France); Recoules, V. [CEA-DAM-DIF, F-91297 Arpajon (France)

2016-10-31

The advent of femtosecond lasers has shed new light on non-equilibrium high energy density physics. The ultrafast energy absorption by electrons and the finite rate of their energy transfer to the lattice creates non-equilibrium states of matter, triggering a new class of non-thermal processes from the ambient solid up to extreme conditions of temperature and pressure, referred as the warm dense matter regime. The dynamical interplay between electron and atomic structures is the key issue that drives the ultrafast phase transitions dynamics. Bond weakening or bond hardening are predicted, but strongly depends on the material considered. Many studies have been conducted but this physics is still poorly understood. The experimental tools used up-to-now have provided an incomplete insight. Pure optical techniques measure only indirectly atomic motion through changes in the dielectric function whereas X-ray or electron diffraction only probes the average long-range order. This review is dedicated to recent developments in time-resolved X-ray absorption near-edge spectroscopy, which is expected to give a more complete picture by probing simultaneously the modifications of the near-continuum electron and local atomic structures. Results are reported for three different types of metals (simple, transition and noble metals) in which a confrontation has been carried out between measurements and ab initio simulations.

Species authentication and geographical origin discrimination of herbal medicines by near infrared spectroscopy: A review

Directory of Open Access Journals (Sweden)

Pei Wang

2015-10-01

Full Text Available Near infrared (NIR spectroscopy as a rapid and nondestructive analytical technique, integrated with chemometrics, is a powerful process analytical tool for the pharmaceutical industry and is becoming an attractive complementary technique for herbal medicine analysis. This review mainly focuses on the recent applications of NIR spectroscopy in species authentication of herbal medicines and their geographical origin discrimination. Keywords: Near infrared spectroscopy, Herbal medicine, Species authentication, Geographical origin discrimination, Quality control

Predictions of the near edge transport shortfall in DIII-D L-mode plasmas using the trapped gyro-Landau-fluid model

Energy Technology Data Exchange (ETDEWEB)

Kinsey, J. E. [CompX, P.O. Box 2672, Del Mar, California 92014 (United States); Staebler, G. M.; Candy, J.; Petty, C. C.; Waltz, R. E. [General Atomics, P.O. Box 85608, San Diego, California 92186-5608 (United States); Rhodes, T. L. [Physics Department and PSTI, University of California, Los Angeles, California 90095 (United States)

2015-01-15

Previous studies of DIII-D L-mode plasmas have shown that a transport shortfall exists in that our current models of turbulent transport can significantly underestimate the energy transport in the near edge region. In this paper, the Trapped Gyro-Landau-Fluid (TGLF) drift wave transport model is used to simulate the near edge transport in a DIII-D L-mode experiment designed to explore the impact of varying the safety factor on the shortfall. We find that the shortfall systematically increases with increasing safety factor and is more pronounced for the electrons than for the ions. Within the shortfall dataset, a single high current case has been found where no transport shortfall is predicted. Reduced neutral beam injection power has been identified as the key parameter separating this discharge from other discharges exhibiting a shortfall. Further analysis shows that the energy transport in the L-mode near edge region is not stiff according to TGLF. Unlike the H-mode core region, the predicted temperature profiles are relatively more responsive to changes in auxiliary heating power. In testing the fidelity of TGLF for the near edge region, we find that a recalibration of the collision model is warranted. A recalibration improves agreement between TGLF and nonlinear gyrokinetic simulations performed using the GYRO code with electron-ion collisions. The recalibration only slightly impacts the predicted shortfall.

Properties on the edge: graphene edge energies, edge stresses, edge warping, and the Wulff shape of graphene flakes

International Nuclear Information System (INIS)

Branicio, Paulo S; Jhon, Mark H; Gan, Chee Kwan; Srolovitz, David J

2011-01-01

It has been shown that the broken bonds of an unreconstructed graphene edge generate compressive edge stresses leading to edge warping. Here, we investigate edge energies and edge stresses of graphene nanoribbons with arbitrary orientations from armchair to zigzag, considering both flat and warped edge shapes in the presence and absence of hydrogen. We use the second generation reactive empirical bond order potential to calculate the edge energies and stresses for clean and hydrogenated edges. Using these energies, we perform a Wulff construction to determine the equilibrium shapes of flat graphene flakes as a function of hydrogen chemical potential. While edge stresses for clean, flat edges are compressive, they become tensile if allowed to warp. Conversely, we find that edge energies change little (∼1%) with edge warping. Hydrogenation of the edges virtually eliminates both the edge energy and edge stresses. For warped edges an approximately linear relationship is found between amplitudes and wavelengths. The equilibrium shape of a graphene flake is determined by the value of the hydrogen chemical potential. For very small (and large) values of it the flakes have a nearly hexagonal (dodecagon) shape with zigzag oriented edges, while for intermediate values graphene flakes are found with complex shapes

On-Line Monitoring of Fermentation Processes by Near Infrared and Fluorescence Spectroscopy

DEFF Research Database (Denmark)

Svendsen, Carina

Monitoring and control of fermentation processes is important to ensure high product yield, product quality and product consistency. More knowledge on on-line analytical techniques such as near infrared and fluorescence spectroscopy is desired in the fermentation industry to increase the efficiency...... of on-line monitoring systems. The primary aim of this thesis is to elucidate and explore the dynamics in fermentation processes by spectroscopy. Though a number of successful on-line lab-scale monitoring systems have been reported, it seems that several challenges are still met, which limits the number...... of full-scale systems implemented in industrial fermentation processes. This thesis seeks to achieve a better understanding of the techniques near infrared and fluorescence spectroscopy and thereby to solve some of the challenges that are encountered. The thesis shows the advantages of applying real...

Effect of motion artifacts and their correction on near-infrared spectroscopy oscillation data

DEFF Research Database (Denmark)

Selb, Juliette; Yücel, Meryem A; Phillip, Dorte

2015-01-01

Functional near-infrared spectroscopy is prone to contamination by motion artifacts (MAs). Motion correction algorithms have previously been proposed and their respective performance compared for evoked rain activation studies. We study instead the effect of MAs on "oscillation" data which...... in the frequency band around 0.1 and 0.04 Hz, suggesting a physiological origin for the difference. We emphasize the importance of considering MAs as a confounding factor in oscillation-based functional near-infrared spectroscopy studies....

μ-XRF imaging and μ-XANES analysis of root of arsenic hyperaccumulator fern (Pteris vittata L.) by using synchrotron radiation

International Nuclear Information System (INIS)

Kitajima, Nobuyuki; Onuma, Ryoko; Hokura, Akiko; Nakai, Izumi; Terada, Yasuko

2006-01-01

Pteris vittata L. is known as a peculiar fern which have high performance to accumulate arsenic, a toxic heavy metal, in its plant body. This fern is expected as a strong candidate plant for a technology of phytoremediation due to its hyperaccumulation ability (over 2% arsenic concentration with dry weight basis). In this study, the distribution of arsenic in a horizontal cross-section of root was examined by μ-SR-XRF imaging, and a valence change from surface to centre of the root was revealed by the As-K edge μ-XANES spectra. All the measurements were carried out utilizing X-ray microbeam (1.1 μm x 1.3 μm) from the undulator source at BL37XU in SPring-8 (JASRI, Japan). Arsenic was detected on whole area of root tissue from surface to centre, and mainly distributed within the structure through a cell wall. A comparison of XANES spectra of the 8 points in the root tissue at high As level with those of the reference compounds (As 2 O 3 and H 3 AsO 4 ), revealed that As (V) uptaken by root was reduced to As (III) immediately, and existed as a mixture of As (III) and As (V). Furthermore, it was indicated that their ratios As (III)/As (V) increased remarkably at the boundary area between the cortex and the central cylinder. (author)

Practical guide to interpretive near-infrared spectroscopy

CERN Document Server

Workman, Jr, Jerry

2007-01-01

Containing focused, comprehensive coverage, Practical Guide to Interpretive Near-Infrared Spectroscopy gives you the tools necessary to interpret NIR spectra. The authors present extensive tables, charts, and figures with NIR absorption band assignments and structural information for a broad range of functional groups, organic compounds, and polymers. They include visual spectral representation of all major compound functional groupings and NIR frequency ranges. Organized by functional group type and chemical structure, based on standard compound classification, the chapters are easy to

Diameter-dependence of the electronic structures of the ZnO nanorods

International Nuclear Information System (INIS)

Chiou, J.W.; Kumar, K.P.K.; Jan, J.C.; Tsai, H.M.; Bao, C.W.; Pong, W.F.; Tsai, M.-H.; Hong, I.-H.; Klauser, R.; Lee, J.F.; Wu, J.J.; Liu, S.C.

2004-01-01

Full text: O K-, Zn L3- and K-edges x-ray absorption near-edge structure (XANES) spectra and scanning photoelectron microscopy (SPEM) spectra were measured for the ZnO nanorods with various diameters to study their electronic structures. Analysis of the XANES spectra revealed that charge transfer from the O 2p to Zn 3d states is enhanced with the decrease of the nanorod diameter. The charge transfer due to O 2p-Zn 3d hybridization is found to be compensated by the Zn 4p to O 2p charge transfer due to O 2p-Zn 4p rehybridization in consistence with the Zn 3d SPEM results. The valence-band photoemission spectra show changes in the electronic structures, especially near to the Fermi level, with the decrease of the nanorod diameter due to surface effect and/or local electrostatic polarization

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

Science.gov (United States)

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

2016-02-01

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

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

International Nuclear Information System (INIS)

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

2004-01-01

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

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

Science.gov (United States)

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

2004-05-01

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

Composition-driven Cu-speciation and reducibility in Cu-CHA zeolite catalysts: a multivariate XAS/FTIR approach to complexity† †Electronic supplementary information (ESI) available: Sample description and synthesis details, experimental setup for in situ XAS and FTIR spectroscopy, details on the MCR-ALS method, details on DFT-assisted XANES simulations, details on the determination of N pure by PCA, MCR-ALS results for downsized and upsized component spaces, additional information to support the assignment of theoretical XANES curves, details on EXAFS analysis, details on IR spectral deconvolution. See DOI: 10.1039/c7sc02266b Click here for additional data file.

Science.gov (United States)

Martini, A.; Lomachenko, K. A.; Pankin, I. A.; Negri, C.; Berlier, G.; Beato, P.; Falsig, H.; Bordiga, S.; Lamberti, C.

2017-01-01

The small pore Cu-CHA zeolite is attracting increasing attention as a versatile platform to design novel single-site catalysts for deNOx applications and for the direct conversion of methane to methanol. Understanding at the atomic scale how the catalyst composition influences the Cu-species formed during thermal activation is a key step to unveil the relevant composition–activity relationships. Herein, we explore by in situ XAS the impact of Cu-CHA catalyst composition on temperature-dependent Cu-speciation and reducibility. Advanced multivariate analysis of in situ XANES in combination with DFT-assisted simulation of XANES spectra and multi-component EXAFS fits as well as in situ FTIR spectroscopy of adsorbed N2 allow us to obtain unprecedented quantitative structural information on the complex dynamics during the speciation of Cu-sites inside the framework of the CHA zeolite. PMID:29147509

Gasoline classification using near infrared (NIR) spectroscopy data: Comparison of multivariate techniques

Energy Technology Data Exchange (ETDEWEB)

Balabin, Roman M., E-mail: balabin@org.chem.ethz.ch [Department of Chemistry and Applied Biosciences, ETH Zurich, 8093 Zurich (Switzerland); Safieva, Ravilya Z. [Gubkin Russian State University of Oil and Gas, 119991 Moscow (Russian Federation); Lomakina, Ekaterina I. [Faculty of Computational Mathematics and Cybernetics, Lomonosov Moscow State University, 119992 Moscow (Russian Federation)

2010-06-25

Near infrared (NIR) spectroscopy is a non-destructive (vibrational spectroscopy based) measurement technique for many multicomponent chemical systems, including products of petroleum (crude oil) refining and petrochemicals, food products (tea, fruits, e.g., apples, milk, wine, spirits, meat, bread, cheese, etc.), pharmaceuticals (drugs, tablets, bioreactor monitoring, etc.), and combustion products. In this paper we have compared the abilities of nine different multivariate classification methods: linear discriminant analysis (LDA), quadratic discriminant analysis (QDA), regularized discriminant analysis (RDA), soft independent modeling of class analogy (SIMCA), partial least squares (PLS) classification, K-nearest neighbor (KNN), support vector machines (SVM), probabilistic neural network (PNN), and multilayer perceptron (ANN-MLP) - for gasoline classification. Three sets of near infrared (NIR) spectra (450, 415, and 345 spectra) were used for classification of gasolines into 3, 6, and 3 classes, respectively, according to their source (refinery or process) and type. The 14,000-8000 cm{sup -1} NIR spectral region was chosen. In all cases NIR spectroscopy was found to be effective for gasoline classification purposes, when compared with nuclear magnetic resonance (NMR) spectroscopy or gas chromatography (GC). KNN, SVM, and PNN techniques for classification were found to be among the most effective ones. Artificial neural network (ANN-MLP) approach based on principal component analysis (PCA), which was believed to be efficient, has shown much worse results. We hope that the results obtained in this study will help both further chemometric (multivariate data analysis) investigations and investigations in the sphere of applied vibrational (infrared/IR, near-IR, and Raman) spectroscopy of sophisticated multicomponent systems.

Gasoline classification using near infrared (NIR) spectroscopy data: Comparison of multivariate techniques

International Nuclear Information System (INIS)

Balabin, Roman M.; Safieva, Ravilya Z.; Lomakina, Ekaterina I.

2010-01-01

Near infrared (NIR) spectroscopy is a non-destructive (vibrational spectroscopy based) measurement technique for many multicomponent chemical systems, including products of petroleum (crude oil) refining and petrochemicals, food products (tea, fruits, e.g., apples, milk, wine, spirits, meat, bread, cheese, etc.), pharmaceuticals (drugs, tablets, bioreactor monitoring, etc.), and combustion products. In this paper we have compared the abilities of nine different multivariate classification methods: linear discriminant analysis (LDA), quadratic discriminant analysis (QDA), regularized discriminant analysis (RDA), soft independent modeling of class analogy (SIMCA), partial least squares (PLS) classification, K-nearest neighbor (KNN), support vector machines (SVM), probabilistic neural network (PNN), and multilayer perceptron (ANN-MLP) - for gasoline classification. Three sets of near infrared (NIR) spectra (450, 415, and 345 spectra) were used for classification of gasolines into 3, 6, and 3 classes, respectively, according to their source (refinery or process) and type. The 14,000-8000 cm -1 NIR spectral region was chosen. In all cases NIR spectroscopy was found to be effective for gasoline classification purposes, when compared with nuclear magnetic resonance (NMR) spectroscopy or gas chromatography (GC). KNN, SVM, and PNN techniques for classification were found to be among the most effective ones. Artificial neural network (ANN-MLP) approach based on principal component analysis (PCA), which was believed to be efficient, has shown much worse results. We hope that the results obtained in this study will help both further chemometric (multivariate data analysis) investigations and investigations in the sphere of applied vibrational (infrared/IR, near-IR, and Raman) spectroscopy of sophisticated multicomponent systems.

Depth profile investigation of the incorporated iron atoms during Kr{sup +} ion beam sputtering on Si (001)

Energy Technology Data Exchange (ETDEWEB)

Khanbabaee, B., E-mail: khanbabaee@physik.uni-siegen.de [Solid State Physics, University of Siegen, D-57068 Siegen (Germany); Arezki, B.; Biermanns, A. [Solid State Physics, University of Siegen, D-57068 Siegen (Germany); Cornejo, M.; Hirsch, D. [Leibniz-Institut für Oberflächenmodifizierung e. V. (IOM), Permoserstraße 15, D-04318 Leipzig (Germany); Lützenkirchen-Hecht, D. [Abteilung Physik, Bergische Universität Wuppertal, D-42097 Wuppertal (Germany); Frost, F. [Leibniz-Institut für Oberflächenmodifizierung e. V. (IOM), Permoserstraße 15, D-04318 Leipzig (Germany); Pietsch, U. [Solid State Physics, University of Siegen, D-57068 Siegen (Germany)

2013-01-01

We investigate the incorporation of iron atoms during nano-patterning of Si surfaces induced by 2 keV Kr{sup +} ion beam erosion under an off-normal incidence angle of 15°. Considering the low penetration depth of the ions, we have used X-ray reflectivity (XRR) and X-ray absorption near edge spectroscopy (XANES) under grazing-incidence angles in order to determine the depth profile and phase composition of the incorporated iron atoms in the near surface region, complemented by secondary ion mass spectrometry and atomic force microscopy. XRR analysis shows the accumulation of metallic atoms within a near surface layer of a few nanometer thickness. We verify that surface pattern formation takes place only when the co-sputtered Fe concentration exceeds a certain limit. For high Fe concentration, the ripple formation is accompanied by the enhancement of Fe close to the surface, whereas no Fe enhancement is found for low Fe concentration at samples with smooth surfaces. Modeling of the measured XANES spectra reveals the appearance of different silicide phases with decreasing Fe content from the top towards the volume. - Highlights: ► We investigate the incorporation of iron atoms during nano-patterning of Si surfaces. ► Pattern formation occurs when the areal density of Fe exceeds a certain threshold. ► X-ray reflectivity shows a layering at near surface due to incorporated Fe atoms. ► It is shown that the patterning is accompanied with the appearance of Fe-rich silicide.

Electronic structure of Ni/sub 3/Al and Ni/sub 3/Ga alloys

CERN Document Server

Pong, W F; Chang, Y K; Tsai, M H; Hsieh, H H; Pieh, J Y; Tseng, P K; Lee, J F; Hsu, L S

1999-01-01

This work investigates the charge transfer and Al(Ga) p-Ni d hybridization effects in the intermetallic Ni/sub 3/Al(Ni/sub 3/Ga) alloy using the NiL/sub 3.2/- and K-edge and Al(Ga)K X-ray absorption near edge structure (XANES) measurements. We find that the intensity of white-line features at the NiL/sub 3.2/-edge in the Ni/sub 3/Al(Ni /sub 3/Ga) alloy decreased in comparison with that of pure Ni, which can be attributed to the enhancement of Ni3d states filling and the depletion of the density of Ni 3d unoccupied states in the Ni/sub 3 /Al(Ni/sub 3/Ga) alloy. Two clear features are also observed in the Ni/sub 3/Al(Ni/sub 3/Ga) XANES spectrum at the Al(Ga) K-edge, which can be assigned to the Al(Ga) unoccupied 3p (4p) states and their hybridized states with the Ni 3d/4sp states above the Fermi level in Ni/sub 3/Al(Ni/sub 3/Ga). The threshold at Al K-edge XANES for Ni/sub 3/Al clearly shifts towards higher photon energies relative to that of pure Al, indicating that Al loses charges upon forming Ni/sub 3 /Al. ...

Cold crucible induction melter test for crystalline ceramic waste form fabrication: A feasibility assessment

Energy Technology Data Exchange (ETDEWEB)

Amoroso, Jake W., E-mail: jake.amoroso@srnl.doe.gov [Savannah River National Laboratory, Aiken, SC 29808 (United States); Marra, James; Dandeneau, Christopher S. [Savannah River National Laboratory, Aiken, SC 29808 (United States); Brinkman, Kyle; Xu, Yun [Clemson University, Clemson, SC 29634 (United States); Tang, Ming [Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Maio, Vince [Idaho National Laboratory, Idaho Falls, ID 83415 (United States); Webb, Samuel M. [Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Menlo Park, CA 94086 (United States); Chiu, Wilson K.S. [University of Connecticut, Storrs, Connecticut 06269-3139 (United States)

2017-04-01

The first scaled proof-of-principle cold crucible induction melter (CCIM) test to process a multiphase ceramic waste form from a simulated combined (Cs/Sr, lanthanide and transition metal fission products) commercial used nuclear fuel waste stream was recently conducted in the United States. X-ray diffraction, 2-D X-ray absorption near edge structure (XANES), electron microscopy, inductively coupled plasma-atomic emission spectroscopy (and inductively coupled plasma-mass spectroscopy for Cs), and product consistency tests were used to characterize the fabricated CCIM material. Characterization analyses confirmed that a crystalline ceramic with a desirable phase assemblage was produced from a melt using a CCIM. Primary hollandite, pyrochlore/zirconolite, and perovskite phases were identified in addition to minor phases rich in Fe, Al, or Cs. The material produced in the CCIM was chemically homogeneous and displayed a uniform phase assemblage with acceptable aqueous chemical durability.

Structure of alumina supported vanadia catalysts for oxidative dehydrogenation of propane prepared by flame spray pyrolysis

DEFF Research Database (Denmark)

Høj, Martin; Jensen, Anker Degn; Grunwaldt, Jan-Dierk

2013-01-01

.%. The catalysts were subsequently characterized by BET surface area, X-ray diffraction (XRD), Raman, UV–vis diffuse reflectance and X-ray absorption spectroscopy (XAS) as well as measurement of the catalytic performance. The catalysts had specific surface areas from 143 to 169 m2/g corresponding to average......A series of five vanadia on alumina catalysts for oxidative dehydrogenation of propane to propene were synthesized by flame spray pyrolysis (FSP) using vanadium(III)acetylacetonate and aluminium(III)acetylacetonate dissolved in toluene as precursors. The vanadium loading was 2, 3, 5, 7.5 and 10wt...... X-ray absorption near edge structure (XANES) spectroscopy showed that the vanadia can be reduced when operating at low oxygen concentrations. The catalyst performance was determined in fixed bed reactors with an inlet gas composition of C3H8/O2/N2=5/25/70. The main products were propene, CO and CO2...

Surface-Enhanced Raman Spectroscopy of Dye and Thiol Molecules Adsorbed on Triangular Silver Nano structures: A Study of Near-Field Enhancement, Localization of Hot-Spots, and Passivation of Adsorbed Carbonaceous Species

International Nuclear Information System (INIS)

Goncalves, M.R.; Marti, O.; Fabian Enderle, F.

2012-01-01

Surface-enhanced Raman spectroscopy (SERS) of thiols and dye molecules adsorbed on triangular silver nanostructures was investigated. The SERS hot-spots are localized at the edges and corners of the silver triangular particles. AFM and SEM measurements permit to observe many small clusters formed at the edges of triangular particles fabricated by nanosphere lithography. Finite-element calculations show that near-field enhancements can reach values of more than 200 at visible wavelengths, in the gaps between small spherical particles and large triangular particles, although for the later no plasmon resonance was found at the wavelengths investigated. The regions near the particles showing strong near-field enhancement are well correlated with spatial localization of SERS hot-spots done by confocal microscopy. Silver nanostructures fabricated by thermal evaporation present strong and fast fluctuating SERS activity, due to amorphous carbon contamination. Thiols and dye molecules seem to be able to passivate the undesired SERS activity on fresh evaporated silver. excitation: by far-field illumination of metal nanostructures or rough metal Raman scattering cross-section of gold-palladium target Temporal Fluctuation in SERS Temporal and spectral fluctuations.

Burned bones forensic investigations employing near infrared spectroscopy

OpenAIRE

Cascant, Mari Merce; Rubio, Sonia; Gallello, Gianni; Pastor, Agustin; Garrigues, Salvador; De la Guardia, Miguel

2017-01-01

The use of near infrared (NIR) spectroscopy was evaluated, by using chemometric tools, for the study of the environmental impact on burned bones. Spectra of internal and external parts of burned bones, together with sediment samples, were treated by Principal Component Analysis and cluster classification as exploratory techniques to select burned bone samples, less affected by environmental processes, to properly carry out forensic studies. Partial Least Square Discriminant Analysis was used ...

A Cross-Sectional Survey of Near-Infrared Spectroscopy Use in Pediatric Cardiac ICUs in the United Kingdom, Ireland, Italy, and Germany.

Science.gov (United States)

Hoskote, Aparna U; Tume, Lyvonne N; Trieschmann, Uwe; Menzel, Christoph; Cogo, Paola; Brown, Katherine L; Broadhead, Michael W

2016-01-01

Despite the increasing use of near-infrared spectroscopy across pediatric cardiac ICUs, there is significant variability and equipoise with no universally accepted management algorithms. We aimed to explore the use of near-infrared spectroscopy in pediatric cardiac ICUs in the United Kingdom, Ireland, Italy, and Germany. A cross-sectional multicenter, multinational electronic survey of one consultant in each pediatric cardiac ICU. Pediatric cardiac ICUs in the United Kingdom and Ireland (n = 13), Italy (n = 12), and Germany (n = 33). Questionnaire targeted to establish use, targets, protocols/thresholds for intervention, and perceived usefulness of near-infrared spectroscopy monitoring. Overall, 42 of 58 pediatric cardiac ICUs (72%) responded: United Kingdom and Ireland, 11 of 13 (84.6%); Italy, 12 of 12 (100%); and Germany, 19 of 33 (57%, included all major centers). Near-infrared spectroscopy usage varied with 35% (15/42) reporting that near-infrared spectroscopy was not used at all (7/42) or occasionally (8/42); near-infrared spectroscopy use was much less common in the United Kingdom (46%) when compared with 78% in Germany and all (100%) in Italy. Only four units had a near-infrared spectroscopy protocol, and 18 specifically used near-infrared spectroscopy in high-risk patients; 37 respondents believed that near-infrared spectroscopy added value to standard monitoring and 23 believed that it gave an earlier indication of deterioration, but only 19 would respond based on near-infrared spectroscopy data alone. Targets for absolute values and critical thresholds for intervention varied widely between units. The reasons cited for not or occasionally using near-infrared spectroscopy were expense (n = 6), limited evidence and uncertainty on how it guides management (n = 4), difficulty in interpretation, and unreliability of data (n = 3). Amongst the regular or occasional near-infrared spectroscopy users (n = 35), 28 (66%) agreed that a multicenter study is warranted

Kinetic and transport theory near the tokamak edge