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

NASA Astrophysics Data System (ADS)

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

2013-04-01

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

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

PubMed

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

2016-03-07

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

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

PubMed

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

2016-04-05

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

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

NASA Technical Reports Server (NTRS)

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

2010-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2017-05-01

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

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

PubMed

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

2016-08-01

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

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

NASA Astrophysics Data System (ADS)

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

2016-08-01

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

XANES Identification of Plutonium Speciation in RFETS Samples

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

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

2009-06-03

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

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

PubMed

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

2018-03-01

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

Phosphorus K-edge XANES spectroscopy of mineral standards

PubMed Central

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

2011-01-01

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

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

PubMed

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

2015-07-01

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

Understanding of sub-band gap absorption of femtosecond-laser sulfur hyperdoped silicon using synchrotron-based techniques

PubMed Central

Limaye, Mukta V.; Chen, S. C.; Lee, C. Y.; Chen, L. Y.; Singh, Shashi B.; Shao, Y. C.; Wang, Y. F.; Hsieh, S. H.; Hsueh, H. C.; Chiou, J. W.; Chen, C. H.; Jang, L. Y.; Cheng, C. L.; Pong, W. F.; Hu, Y. F.

2015-01-01

The correlation between sub-band gap absorption and the chemical states and electronic and atomic structures of S-hyperdoped Si have been extensively studied, using synchrotron-based x-ray photoelectron spectroscopy (XPS), x-ray absorption near-edge spectroscopy (XANES), extended x-ray absorption fine structure (EXAFS), valence-band photoemission spectroscopy (VB-PES) and first-principles calculation. S 2p XPS spectra reveal that the S-hyperdoped Si with the greatest (~87%) sub-band gap absorption contains the highest concentration of S2− (monosulfide) species. Annealing S-hyperdoped Si reduces the sub-band gap absorptance and the concentration of S2− species, but significantly increases the concentration of larger S clusters [polysulfides (Sn2−, n > 2)]. The Si K-edge XANES spectra show that S hyperdoping in Si increases (decreased) the occupied (unoccupied) electronic density of states at/above the conduction-band-minimum. VB-PES spectra evidently reveal that the S-dopants not only form an impurity band deep within the band gap, giving rise to the sub-band gap absorption, but also cause the insulator-to-metal transition in S-hyperdoped Si samples. Based on the experimental results and the calculations by density functional theory, the chemical state of the S species and the formation of the S-dopant states in the band gap of Si are critical in determining the sub-band gap absorptance of hyperdoped Si samples. PMID:26098075

Synchrotron applications in wood preservation and deterioration

Treesearch

Barbara L. Illman

2003-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

Stoichiometry of mercury-thiol complexes on bacterial cell envelopes

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

Mishra, Bhoopesh; Shoenfelt, Elizabeth; Yu, Qiang

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

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

EPA Science Inventory

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

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

Treesearch

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

2016-01-01

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

Magnesium K-edge XANES spectroscopy of geological standards.

PubMed

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

2013-09-01

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

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

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

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

2015-06-24

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

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

NASA Astrophysics Data System (ADS)

Valotto, Gabrio; Cattaruzza, Elti; Bardelli, Fabrizio

2017-02-01

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

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

PubMed

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

2015-06-02

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

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

NASA Astrophysics Data System (ADS)

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

1997-02-01

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

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

NASA Astrophysics Data System (ADS)

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

2008-02-01

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

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

PubMed

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

2013-01-30

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

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

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

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

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

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

DOE PAGES

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

2017-12-12

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

XAS Studies of Arsenic in the Environment

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

Charnock, J. M.; School of Earth, Atmospheric and Environmental Sciences, University of Manchester, Oxford Road, Manchester, M13 9PL; Polya, D. A.

2007-02-02

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

Speciation and Elemental Mapping of Metal Containing Aerosols

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

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

NASA Astrophysics Data System (ADS)

Sindhupakorn, Bura; Thienpratharn, Suwittaya; Kidkhunthod, Pinit

2017-10-01

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

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

PubMed

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

2016-01-01

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

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

NASA Astrophysics Data System (ADS)

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

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

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

DOE PAGES

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

2017-09-29

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

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

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

Timoshenko, Janis; Lu, Deyu; Lin, Yuewei

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

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

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

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

2016-03-24

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

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

PubMed

Valotto, Gabrio; Cattaruzza, Elti; Bardelli, Fabrizio

2017-02-15

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

Site-selective XAFS spectroscopy tuned to surface active sites of Cu/ZnO and Cr/SiO2 catalysts.

PubMed

Izumi, Y; Nagamori, H; Kiyotaki, F; Minato, T

2001-03-01

XAFS (X-ray absorption fine structure) spectra were measured by using the fluorescence spectrometer for the emitted X-ray from sample. The chemical shifts between Cu0 and Cu1 and between CrIII and CrVI were evaluated. Tuning the fluorescence spectrometer to each energy, the Cu0 and CuI site-selective XANES for Cu/ZnO catalyst were measured. The first one was similar to the XANES of Cu metal and the second one was the 5 : 5 average of XANES for CuI sites + Cu metal. The population ratio of copper site of the Cu/ZnO catalyst was found to be Cu metal: Cu2O : CuI atomically dispersed on surface = 70(+/-23) : 22(+/-14) : 8(+/-5). Site-selective XANES for CrIII site of Cr/SiO2 catalyst was also studied.

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

NASA Technical Reports Server (NTRS)

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

2011-01-01

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

Sulfur Speciation in Biochars by Very High Resolution Benchtop Kα X-ray Emission Spectroscopy.

PubMed

Holden, William M; Seidler, Gerald T; Cheah, Singfoong

2018-05-30

The analytical chemistry of sulfur-containing materials poses substantial technical challenges, especially due to the limitations of 33 S NMR and the time-intensive preparations required for wet-chemistry analyses. A number of prior studies have found that synchrotron-based X-ray absorption near edge structure (XANES) measurements can give detailed speciation of sulfur chemistry in such cases. However, due to the obvious access limitations, synchrotron XANES of sulfur cannot be part of routine analytical practice across the chemical sciences community. Here, in a study of the sulfur chemistry in biochars, we compare and contrast the chemical inferences available from synchrotron XANES with that given by benchtop, extremely high resolution wavelength-dispersive X-ray fluorescence (WD-XRF) spectroscopy, also often called X-ray emission spectroscopy (XES). While the XANES spectra have higher total information content, often giving differentiation between different moieties having the same oxidation state, the lower sensitivity of the S Kα XES to coordination and local structure provides pragmatic benefit for the more limited goal of quantifying the S oxidation state distribution. Within that constrained metric, we find good agreement between the two methods. As the sulfur concentrations were as low as 150 ppm, these measurements provide proof-of-principle for characterization of the sulfur chemistry of biochars and potential applications to other areas such as soils, batteries, catalysts, and fossil fuels and their combustion products.

Sulfur Speciation in Biochars by Very High Resolution Benchtop Ka X-Ray Emission Spectroscopy

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

Cheah, Singfoong; Holden, William M.; Seidler, Gerald T.

The analytical chemistry of sulfur-containing materials poses substantial technical challenges, especially due to the limitations of 33S NMR and the time-intensive preparations required for wet-chemistry analyses. A number of prior studies have found that synchrotron-based X-ray absorption near edge structure (XANES) measurements can give detailed speciation of sulfur chemistry in such cases. However, due to the obvious access limitations, synchrotron XANES of sulfur cannot be part of routine analytical practice across the chemical sciences community. Here, in a study of the sulfur chemistry in biochars, we compare and contrast the chemical inferences available from synchrotron XANES with that given bymore » benchtop, extremely high resolution wavelength-dispersive X-ray fluorescence (WD-XRF) spectroscopy, also often called X-ray emission spectroscopy (XES). While the XANES spectra have higher total information content, often giving differentiation between different moieties having the same oxidation state, the lower sensitivity of the S Ka XES to coordination and local structure provides pragmatic benefit for the more limited goal of quantifying the S oxidation state distribution. Within that constrained metric, we find good agreement between the two methods. As the sulfur concentrations were as low as 150 ppm, these measurements provide proof-of-principle for characterization of the sulfur chemistry of biochars and potential applications to other areas such as soils, batteries, catalysts, and fossil fuels and their combustion products.« less

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

NASA Astrophysics Data System (ADS)

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

2017-10-01

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

XANES analysis of dried and calcined bones.

PubMed

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

2013-10-01

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

THE DISTRIBUTION, SOLID-PHASE SPECIATION, AND DESORPTION/DISSOLUTION OF AS IN IRON-BASED DRINKING WATER TREATMENT MEDIA 1

EPA Science Inventory

Arsenic concentrations (Total Recoverable As by EPA Method 3051, soluble, Toxicity Characteristic Leaching Procedure extractable) and solid-phase speciation (by X-ray Absorption Near-Edge Spectroscopy-XANES) were assessed as a function of depth through Fe-media beds for two comme...

THE DISTRIBUTION, SOLID-PHASE SPECIATION, AND DESORPTION/DISSOLUTION OF AS IN IRON-BASED TREATMENT MEDIA

EPA Science Inventory

Arsenic concentrations (Total Recoverable As by EPA Method 3051) and solid-phase speciation (by X-ray Absorption Near-Edge Spectroscopy-XANES) were assessed as a function of depth through Fe-media beds for two commercially available products from pilot-scale field tests. These re...

THE DISTRIBUTION, SOLID-PHASE SPECIATION, AND DESORPTION/DISSOLUTION OF AS IN IRON-BASED DRINKING WATER TREATMENT MEDIA - JOURNAL

EPA Science Inventory

Arsenic concentrations (Total Recoverable As by EPA Method 3051, soluble, Toxicity Characteristic Leaching Procedure extractable) and solid-phase speciation (by X-ray Absorption Near-Edge Spectroscopy-XANES) were assessed as a function of depth through Fe-media beds for two comme...

THE DISTRIBUTION AND SOLID-PHASE SPECIATION OF AS IN IRON-BASED TREATMENT MEDIA

EPA Science Inventory

Arsenic concentrations (Total Recoverable As by EPA Method 3051) and solid-phase speciation (by X-ray Absorption Near-Edge Spectroscopy-XANES) were assessed as a function of depth through Fe-media beds for two commercially available products from pilot-scale field tests. These r...

Chemical Modification of Graphene Oxide by Nitrogenation: An X-ray Absorption and Emission Spectroscopy Study

DOE PAGES

Chuang, Cheng-Hao; Ray, Sekhar C.; Mazumder, Debarati; ...

2017-02-10

Nitrogen-doped graphene oxides (GO:N x) were synthesized by a partial reduction of graphene oxide (GO) using urea [CO(NH 2) 2 ]. Their electronic/bonding structures were investigated using X-ray absorption near-edge structure (XANES), valence-band photoemission spectroscopy (VB-PES), X-ray emission spectroscopy (XES) and resonant inelastic X-ray scattering (RIXS). During GO:N x synthesis, different nitrogen-bonding species, such as pyrrolic/graphitic-nitrogen, were formed by replacing of oxygen-containing functional groups. At lower N-content (2.7 at%), pyrrolic-N, owing to surface and subsurface diffusion of C, N and NH is deduced from various X-ray spectroscopies. In contrast, at higher N-content (5.0 at%) graphitic nitrogen was formed in whichmore » each N-atom trigonally bonds to three distinct sp 2 -hybridized carbons with substitution of the N-atoms for C atoms in the graphite layer. Upon nitrogen substitution, the total density of state close to Fermi level is increased to raise the valence-band maximum, as revealed by VB-PES spectra, indicating an electron donation from nitrogen, molecular bonding C/N/O coordination or/and lattice structure reorganization in GO:N x . The well-ordered chemical environments induced by nitrogen dopant are revealed by XANES and RIXS measurements.« less

Investigation of nanoparticulate silicon as printed layers using scanning electron microscopy, transmission electron microscopy, X-ray absorption spectroscopy and X-ray photoelectron spectroscopy

DOE PAGES

Unuigbe, David M.; Harting, Margit; Jonah, Emmanuel O.; ...

2017-08-21

The presence of native oxide on the surface of silicon nanoparticles is known to inhibit charge transport on the surfaces. Scanning electron microscopy (SEM) studies reveal that the particles in the printed silicon network have a wide range of sizes and shapes. High-resolution transmission electron microscopy reveals that the particle surfaces have mainly the (111)- and (100)-oriented planes which stabilizes against further oxidation of the particles. X-ray absorption spectroscopy (XANES) and X-ray photoelectron spectroscopy (XPS) measurements at the O 1s-edge have been utilized to study the oxidation and local atomic structure of printed layers of silicon nanoparticles which were milledmore » for different times. XANES results reveal the presence of the +4 (SiO 2) oxidation state which tends towards the +2 (SiO) state for higher milling times. Si 2pXPS results indicate that the surfaces of the silicon nanoparticles in the printed layers are only partially oxidized and that all three sub-oxide, +1 (Si 2O), +2 (SiO) and +3 (Si 2O 3), states are present. The analysis of the change in the sub-oxide peaks of the silicon nanoparticles shows the dominance of the +4 state only for lower milling times.« less

Chemical Modification of Graphene Oxide by Nitrogenation: An X-ray Absorption and Emission Spectroscopy Study

NASA Astrophysics Data System (ADS)

Chuang, Cheng-Hao; Ray, Sekhar C.; Mazumder, Debarati; Sharma, Surbhi; Ganguly, Abhijit; Papakonstantinou, Pagona; Chiou, Jau-Wern; Tsai, Huang-Ming; Shiu, Hung-Wei; Chen, Chia-Hao; Lin, Hong-Ji; Guo, Jinghua; Pong, Way-Faung

2017-02-01

Nitrogen-doped graphene oxides (GO:Nx) were synthesized by a partial reduction of graphene oxide (GO) using urea [CO(NH2)2]. Their electronic/bonding structures were investigated using X-ray absorption near-edge structure (XANES), valence-band photoemission spectroscopy (VB-PES), X-ray emission spectroscopy (XES) and resonant inelastic X-ray scattering (RIXS). During GO:Nx synthesis, different nitrogen-bonding species, such as pyrrolic/graphitic-nitrogen, were formed by replacing of oxygen-containing functional groups. At lower N-content (2.7 at%), pyrrolic-N, owing to surface and subsurface diffusion of C, N and NH is deduced from various X-ray spectroscopies. In contrast, at higher N-content (5.0 at%) graphitic nitrogen was formed in which each N-atom trigonally bonds to three distinct sp2-hybridized carbons with substitution of the N-atoms for C atoms in the graphite layer. Upon nitrogen substitution, the total density of state close to Fermi level is increased to raise the valence-band maximum, as revealed by VB-PES spectra, indicating an electron donation from nitrogen, molecular bonding C/N/O coordination or/and lattice structure reorganization in GO:Nx. The well-ordered chemical environments induced by nitrogen dopant are revealed by XANES and RIXS measurements.

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

PubMed

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

2015-09-01

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

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

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

Ramakrishnan, Girish; Wu, Qiyuan; Moon, Juhyuk

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

A Study of Ziegler–Natta Propylene Polymerization Catalysts by Spectroscopic Methods

PubMed Central

Tkachenko, Olga P.; Kucherov, Alexey V.; Kustov, Leonid M.; Virkkunen, Ville; Leinonen, Timo; Denifl, Peter

2017-01-01

Ziegler–Natta polymerization catalysts were characterized by a complex of surface- and bulk-sensitive methods (DRIFTS, XPS, ESR, and XAS = XANES + EXAFS). A diffuse-reflectance Fourier-transform IR spectroscopy (DRIFTS) study showed the presence of strong Lewis acid sites in different concentrations and absence of strong basic sites in the polymerization catalysts. X-ray photoelectron spectroscopy (XPS), electron-spin resonance (ESR), and (X-ray absorption near-edge structure (XANES) analysis revealed the presence of Ti4+, Ti3+, Ti2+, and Ti1+ species in the surface layers and in the bulk of catalysts. The samples under study differ drastically in terms of the number of ESR-visible paramagnetic sites. The EXAFS study shows the presence of a Cl atom as a nearest neighbor of the absorbing Ti atom. PMID:28772850

Disentangling atomic-layer-specific x-ray absorption spectra by Auger electron diffraction spectroscopy

NASA Astrophysics Data System (ADS)

Matsui, Fumihiko; Matsushita, Tomohiro; Kato, Yukako; Hashimoto, Mie; Daimon, Hiroshi

2009-11-01

In order to investigate the electronic and magnetic structures of each atomic layer at subsurface, we have proposed a new method, Auger electron diffraction spectroscopy, which is the combination of x-ray absorption spectroscopy (XAS) and Auger electron diffraction (AED) techniques. We have measured a series of Ni LMM AED patterns of the Ni film grown on Cu(001) surface for various thicknesses. Then we deduced a set of atomic-layer-specific AED patterns in a numerical way. Furthermore, we developed an algorithm to disentangle XANES spectra from different atomic layers using these atomic-layer-specific AED patterns. Surface and subsurface core level shift were determined for each atomic layer.

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

PubMed Central

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

2013-01-01

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

Influence of oxygen on growth of carbon thin films

NASA Astrophysics Data System (ADS)

Kumar, Prabhat; Gupta, Mukul; Phase, D. M.; Stahn, Jochen

2018-04-01

In this work we studied the influence of oxygen gas on growth of carbon thin films in a magnetron sputtering process. X-ray absorption spectroscopy (XAS), x-ray and neutron reflectivity techniques were used to probe carbon thin films deposited with and without oxygen at room temperature. XAS in particularly x-ray absorption near edge spectroscopy (XANES) is powerful technique to identify the nature of hybridization of carbon atoms with other elements. In a XANES pattern, presence of C=O and C-O bonds is generally observed in spite of the fact that oxygen has not been deliberately included in the growth process. In order to confirm the presence of such features, we introduced a small amount of oxygen at 1% during the growth of carbon thin films. Though such additions do not affect the number density as observed by x-ray and neutron reflectivity, they severally affect the C K-edge spectra as evidenced by an enhancement in carbon-oxygen hybridization. Observed results are helpful in analyzing the C K-edge spectra more confidently.

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

Sulfur (S), vanadium (V), and iron (Fe) K-edge micro-X-ray absorption near edge structure (micro-XANES) spectroscopy of melt inclusions (MI) from Nyamuragira volcano (D.R. Congo, Africa) shows that diffusive loss of H from olivine-hosted melt inclusions may lead to crystallization of submicron magnetite and sulfide crystallites that are imperceptible petrographically or via electron microscopy. Micro-XANES was used to constrain the evolution of oxygen fugacity (fO2) and sulfur speciation for MI preserved in Nyamuragira tephra (1986 and 2006) and lava (1938 and 1948). The S, V, and Fe valence state oxybarometry for 1938, 1948, and 2006 MI are all consistent with equilibration at FMQ-1, and sulfur in MI from these three eruptions are sulfide-dominated (< 9% sulfate). However, Fe and V micro-XANES data for 1986 MI appear to be more reduced by 1-2 log units, while S micro-XANES data indicate more variable sulfate content. The 1986 results are best explained by diffusive loss of H from the entrapped melt. Submicron magnetite forms as Fe oxidizes in the melt in response to the loss of H, and V strongly partitions into these magnetite nanolites due to its compatibility. The nanolites are consistently analyzed within the beam volume and, thus, the measured V XANES appears more ordered. Magnetite crystallization from the melt also triggers precipitation of crystalline FeS phases within the inclusion, leading to a more ordered S XANES spectra as well. This may suggest a different magma storage history for the 1986 eruption compared to the others. Results demonstrate that coupled S, V, and Fe micro-XANES analysis of alkalic MI can provide accurate measures of the fO2 of entrapped melts, and that S and V micro-XANES spectroscopy are potentially highly sensitive tools for identifying diffusive water loss in olivine-hosted MIs.

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

NASA Astrophysics Data System (ADS)

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

2002-05-01

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

EXAFS and XANES analysis of oxides at the nanoscale.

PubMed

Kuzmin, Alexei; Chaboy, Jesús

2014-11-01

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

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

NASA Astrophysics Data System (ADS)

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

2018-06-01

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

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

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

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). Themore » spin polarization in K fluorescence could be used to generate spin selective XANES or spin-polarized EXAFS, which provides a new measure of the spin density, or the nature of magnetic neighboring atoms. Finally, dramatic line-sharpening effects by the combination of absorption and emission processes allow observation of structure that is normally unobservable. All these unique characters can enormously simplify a complex x-ray spectrum. Applications of this novel technique have generated information from various transition-metal model compounds to metalloproteins. The absorption and emission spectra by high resolution fluorescence detection are interdependent. The ligand field multiplet model has been used for the analysis of K{alpha} and K{beta} emission spectra. First demonstration on different chemical states of Fe compounds has shown the applicability of site selectivity and spin polarization. Different interatomic distances of the same element in different chemical forms have been detected using site-selective EXAFS.« less

Direct deconvolution of two-state pump-probe X-ray absorption spectra and the structural changes in a 100 ps transient of Ni(II)-tetramesitylporphyrin.

PubMed

Della-Longa, S; Chen, L X; Frank, P; Hayakawa, K; Hatada, K; Benfatto, M

2009-05-04

Full multiple scattering (FMS) Minuit XANES (MXAN) has been combined with laser pump-probe K-edge X-ray absorption spectroscopy (XAS) to determine the structure of photoexcited Ni(II)tetramesitylporphyrin, Ni(II)TMP, in dilute toluene solution. It is shown that an excellent simulation of the XANES spectrum is obtained, excluding the lowest-energy bound-state transitions. In ground-state Ni(II)TMP, the first-shell and second-shell distances are, respectively, d(Ni-N) = (1.93 +/- 0.02) A and d(Ni-C) = (2.94 +/- 0.03) A, in agreement with a previous EXAFS result. The time-resolved XANES difference spectrum was obtained (1) from the spectra of Ni(II)TMP in its photoexcited T(1) state and its ground state, S(0). The XANES difference spectrum has been analyzed to obtain both the structure and the fraction of the T(1) state. If the T(1) fraction is kept fixed at the value (0.37 +/- 0.10) determined by optical transient spectroscopy, a 0.07 A elongation of the Ni-N and Ni-C distances [d(Ni-N) and d(Ni-C)] is found, in agreement with the EXAFS result. However, an evaluation of both the distance elongation and the T(1) fraction can also be obtained using XANES data only. According to experimental evidence, and MXAN simulations, the T(1) fraction is (0.60 +/- 0.15) with d(Ni-N) = (1.98 +/- 0.03) A (0.05 A elongation). The overall uncertainty of these results depends on the statistical correlation between the distances and T(1) fraction, and the chemical shift of the ionization energy because of subtle changes of metal charge between the T(1) and S(0) states. The T(1) excited-state structure results, independently obtained without the excited-state fraction from optical transient spectroscopy, are still in agreement with previous EXAFS investigations. Thus, full multiple scattering theory applied through the MXAN formalism can be used to provide structural information, not only on the ground-state molecules but also on very short-lived excited states through differential analysis applied to transient photoexcited species from time-resolved experiments.

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

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

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

2016-12-12

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

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

PubMed

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

2013-08-07

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

XANES study of Fe-implanted strontium titanate

NASA Astrophysics Data System (ADS)

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

2014-03-01

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

XANES mapping of organic sulfate in three scleractinian coral skeletons

NASA Astrophysics Data System (ADS)

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

2003-01-01

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

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

NASA Technical Reports Server (NTRS)

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

2014-01-01

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

The characterization of Cr secondary oxide phases in ZnO films studied by X-ray spectroscopy and photoemission spectroscopy

NASA Astrophysics Data System (ADS)

Chiou, J. W.; Chang, S. Y.; Huang, W. H.; Chen, Y. T.; Hsu, C. W.; Hu, Y. M.; Chen, J. M.; Chen, C.-H.; Kumar, K.; Guo, J.-H.

2011-03-01

X-ray absorption near-edge structure (XANES), X-ray emission spectroscopy (XES), and X-ray photoemission spectroscopy (XPS) were used to characterize the Cr secondary oxide phases in ZnO films that had been prepared using a co-sputtering method. Analysis of the Cr L3,2-edge XANES spectra reveals that the intensity of white-line features decreases subtly as the sputtering power increases, indicating that the occupation of Cr 3 d orbitals increases with Cr concentration in (Zn, Cr)O films. The O K-edge spectra show that the intensity of XANES features of (Zn, Cr)O films is lower than those of ZnO film, suggesting enhanced occupation of O 2 p-derived states through O 2 p-Cr 3 d hybridization. The XES and XPS spectra indicate that the line shapes in the valence band of (Zn, Cr)O films are quite different from those of ZnO and that the Cr 2O 3 phase dominates the spinel structure of (Zn, Cr)O films increasingly as the Cr sputtering power is increased. Over all results suggest that the non-ferromagnetic behavior of (Zn, Cr)O films can be attributed to the dominant presence of Cr 2O 3, whereas the bulk comprise phase segregations of Cr 2O 3 and/or ZnCr 2O 4, which results them the most stable TM-doped ZnO material against etching.

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

NASA Astrophysics Data System (ADS)

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

2001-09-01

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

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

Pacold, J. I.; Altman, A. B.; Donald, S B

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 resolutionmore » 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.« less

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

PubMed

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

2007-04-01

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

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

USGS Publications Warehouse

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

2003-01-01

X-ray absorption near-edge spectroscopy (XANES) analysis of sorption complexes has the advantages of high sensitivity (10- to 20-fold greater than extended X-ray absorption fine structure [EXAFS] analysis) and relative ease and speed of data collection (because of the short k-space range). It is thus a potentially powerful tool for characterization of environmentally significant surface complexes and precipitates at very low surface coverages. However, quantitative analysis has been limited largely to "fingerprint" comparison with model spectra because of the difficulty of obtaining accurate multiple-scattering amplitudes for small clusters with high confidence. In the present work, calculations of the XANES for 50- to 200-atom clusters of structure from Zn model compounds using the full multiple-scattering code Feff 8.0 accurately replicate experimental spectra and display features characteristic of specific first-neighbor anion coordination geometry and second-neighbor cation geometry and number. Analogous calculations of the XANES for small molecular clusters indicative of precipitation and sorption geometries for aqueous Zn on ferrihydrite, and suggested by EXAFS analysis, are in good agreement with observed spectral trends with sample composition, with Zn-oxygen coordination and with changes in second-neighbor cation coordination as a function of sorption coverage. Empirical analysis of experimental XANES features further verifies the validity of the calculations. The findings agree well with a complete EXAFS analysis previously reported for the same sample set, namely, that octahedrally coordinated aqueous Zn2+ species sorb as a tetrahedral complex on ferrihydrite with varying local geometry depending on sorption density. At significantly higher densities but below those at which Zn hydroxide is expected to precipitate, a mainly octahedral coordinated Zn2+ precipitate is observed. An analysis of the multiple scattering paths contributing to the XANES demonstrates the importance of scattering paths involving the anion sublattice. We also describe the specific advantages of complementary quantitative XANES and EXAFS analysis and estimate limits on the extent of structural information obtainable from XANES analysis. ?? 2003 Elsevier Science Ltd.

Dehydration of the Uranyl Peroxide Studtite, [UO 2(η 2-O 2)(H 2O) 2]·2H 2O, Affords a Drastic Change in the Electronic Structure: A Combined X-ray Spectroscopic and Theoretical Analysis

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

Vitova, Tonya; Pidchenko, Ivan; Biswas, Saptarshi

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

Vanadium, sulfur, and iron valences in melt inclusions as a window into magmatic processes: A case study at Nyamuragira volcano, Africa

NASA Astrophysics Data System (ADS)

Head, Elisabet; Lanzirotti, Antonio; Newville, Matthew; Sutton, Stephen

2018-04-01

This study describes microscale sulfur (S), vanadium (V), and iron (Fe) K-edge X-ray absorption near edge structure (μ-XANES) spectroscopy measurements on olivine-hosted melt inclusions (MI) preserved in tephras (1986 and 2006) and lavas (1938 and 1948) erupted from Nyamuragira volcano (D.R. Congo, Africa). The S, V, and Fe spectroscopic data are used to constrain the evolution of oxygen fugacity (fO2) and sulfur speciation for the entrapped melts. Melt inclusions from lavas show evidence of post-entrapment crystallization and were thus reheated prior to μ-XANES analysis. The MI from tephra show no evidence of post-entrapment crystallization and were, therefore, not reheated. Sulfur, V, and Fe μ-XANES results from 1938, 1948, and 2006 eruptive materials are all similar within analytical uncertainty and provide similar average calculated melt fO2's based on XANES oxybarometry. However, olivine-hosted MI from the 1986 tephras yield significantly different S, V, and Fe XANES spectra when compared to MI from the other eruptions, with disagreement between calculated fO2's from the three valence state oxybarometers beyond the uncertainty of the calibration models. Their V μ-XANES spectra are also significantly more ordered and yield more reduced average V valence. The S μ-XANES spectra display a significantly more intense low-energy spectral resonance, which indicates differences in Fe-S bonding character, and greater variability in their measured sulfate content. These V and S spectroscopic features are best explained by crystallization of sub-micrometer magnetite and sulfide crystallites within the 1986 inclusions. The sensitivity of XANES spectroscopy to short-range order allows these crystallites to be recognized even though they are not easily detected by imaging analysis. This shows that V and S μ-XANES are potentially highly sensitive tools for identifying the presence of volumetrically minor amounts of spinel and sulfide within inclusions extracted from rapidly-cooled samples of tephra. Additionally, the observation that rehomogenized 1938 and 1948 inclusions from lava yield similar S, V, and Fe XANES spectra to the 2006 inclusions from tephra may be an encouraging indication that rehomogenization appears to have enabled the successful recovery of their pre-eruptive fO2, despite their complex post-eruptive histories.

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

NASA Astrophysics Data System (ADS)

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

2016-12-01

Although the chemical environments of elements in silicate melts at specific conditions of temperature, pressure and oxygen fugacity (fO2) are often inferred from measurements after quenching the melts to glasses, it is widely recognized that changes may occur during the quenching process, making measurements in situ at high pressure and temperature highly desirable. A case of importance in geochemistry is the speciation of uranium in silicate melts as a function of pressure. Evidence from mineral-melt partitioning and XANES (X-ray Absorption Near-Edge Structure) spectroscopy of glasses suggests that U5+ may be stable at low pressures in the Earth's crust (along with U4+ or U6+, depending on fO2) where basaltic liquids crystallize, but not in the Earth's upper mantle where peridotite partially melts to produce such liquids. To test these observations we recorded in situ transmission U and Th L3-edge XANES spectra of U and Th-doped silicate liquids at 1.6 GPa and 1350°C using the D-DIA apparatus at the X-ray Absorption Spectroscopy Beamline of the Australian Synchrotron. Data for thorium, which occurs exclusively as a tetravalent cation under terrestrial fO2 conditions, were collected as a `control' to monitor for changes in coordination. The cell assembly consisted of a boron-epoxy cube as pressure medium, alumina sleeve and cylindrical graphite heater. The starting mix, a powdered synthetic average MORB silicate glass doped with 2 wt.% of U and Th, was loaded into San Carlos olivine capsules along with solid oxygen buffers (either Re-ReO2 or Ru-RuO2) in a sandwich arrangement. The capsule was then placed inside the graphite heater and insulated with crushable MgO powder. Temperature was monitored using a type D thermocouple. U and Th L3-edge XANES spectra were recorded throughout the heating/compression cycle and then after quenching. Our preliminary assessment indicates that the U-XANES spectra recorded for the liquid in situ at high pressure and temperature and subsequently for the quenched glass are very similar, which would suggest no apparent change in uranium coordination and/or valence state on cooling/decompression.

Local Structure Determination of Carbon/Nickel Ferrite Composite Nanofibers Probed by X-ray Absorption Spectroscopy.

PubMed

Nilmoung, Sukunya; Kidkhunthod, Pinit; Maensiri, Santi

2015-11-01

Carbon/NiFe2O4 composite nanofibers have been successfully prepared by electrospinning method using a various concentration solution of Ni and Fe nitrates dispersed into polyacrylonitride (PAN) solution in N,N' dimethylformamide. The phase and mophology of PAN/NiFe2O4 composite samples were characterized and investigated by X-ray diffraction and scanning electron microscopy. The magnetic properties of the prepared samples were measured at ambient temperature by a vibrating sample magnetometer. It is found that all composite samples exhibit ferromagnetism. This could be local-structurally explained by the existed oxidation states of Ni2+ and Fe3+ in the samples. Moreover, local environments around Ni and Fe ions could be revealed by X-ray absorption spectroscopy (XAS) measurement including X-ray absorption near edge structure (XANES) and Extended X-ray absorption fine structure (EXAFS).

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

NASA Astrophysics Data System (ADS)

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

2017-01-01

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

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

PubMed

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

2014-08-30

The geochemical behavior and speciation of arsenic (As) in paddy soils is strongly controlled by soil redox conditions and the sequestration by soil iron oxyhydroxides. Hence, the effects of iron oxide reductive dissolution on the adsorption, transformation and precipitation of As(III) and As(V) in soils were investigated using batch experiments and synchrotron based techniques to gain a deeper understanding at both macroscopic and microscopic scales. The results of batch sorption experiments revealed that the sorption capacity of As(V) on anoxic soil was much higher than that on control soil. Synchrotron based X-ray fluorescence (μ-XRF) mapping studies indicated that As was heterogeneously distributed and was mainly associated with iron in the soil. X-ray absorption near edge structure (XANES), micro-X-ray absorption near edge structure (μ-XANES) and X-ray photoelectron spectroscopy (XPS) analyses revealed that the primary speciation of As in the soil is As(V). These results further suggested that, when As(V) was introduced into the anoxic soil, the rapid coprecipitation of As(V) with ferric/ferrous ion prevented its reduction to As(III), and was the main mechanism controlling the immobilization of As. This research could improve the current understanding of soil As chemistry in paddy and wetland soils. Copyright © 2014 Elsevier B.V. All rights reserved.

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

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

Vjunov, Aleksei; Wang, Meng; Govind, Niranjan

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

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

PubMed

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

2010-01-11

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

Editorial

NASA Astrophysics Data System (ADS)

Musilek, L.; Dunn, W. L.

2017-08-01

The selected proceedings of the 13th International Symposium on Radiation Physics (ISRP-13) are presented here across a broad range of important topics including: Fundamental processes in radiation physics, Theoretical investigations, New radiation sources, techniques & detectors, Absorption and fluorescence spectroscopy (XAFS, XANES, XRF Spectroscopy, Raman, Infrared …), Applications of radiation in material science, nano-science & nanotechnology, Applications of radiation in biology & medical science, Applications of radiation in space, earth, energy & environmental sciences, Applications of radiation in cultural heritage & art and Applications of radiation in industry. In total, 48 papers have been accepted for these proceedings.

Using X-ray absorption to probe sulfur oxidation states in complex molecules

NASA Astrophysics Data System (ADS)

Vairavamurthy, A.

1998-10-01

X-ray absorption near-edge structure (XANES) spectroscopy offers an important non-destructive tool for determining oxidation states and for characterizing chemical speciation. The technique was used to experimentally verify the oxidation states of sulfur in different types of complex molecules because there are irregularities and uncertainties in assigning the values traditionally. The usual practice of determining oxidation states involves using a set of conventional rules. The oxidation state is an important control in the chemical speciation of sulfur, ranging from -2 to +6 in its different compounds. Experimental oxidation-state values for various types of sulfur compounds, using their XANES peak-energy positions, were assigned from a scale in which elemental sulfur and sulfate are designated as 0 and +6, respectively. Because these XANES-based values differed considerably from conventionally determined oxidation states for most sulfur compounds, a new term 'oxidation index' was coined to describe them. The experimental values were closer to those conventional values obtained by assigning shared electrons to the more electronegative atoms than to those based on other customary rules for assigning them. Because the oxidation index is distinct and characteristic for each different type of sulfur functionality, it becomes an important parameter for characterizing sulfur species, and for experimentally verifying uncertain oxidation states.

Characterization of pentavalent and hexavalent americium complexes in nitric acid using X-ray absorption fine structure spectroscopy and first-principles modeling

DOE PAGES

Riddle, Catherine; Czerwinski, Kenneth; Kim, Eunja; ...

2016-01-18

We studied the speciation of pentavalent and hexavalent americium (Am) complexes in nitric acidicby X-ray absorption fine structure spectroscopy (XAFS), UV-visible spectroscopy, and density functional theory (DFT). Extended x-ray absorption fine structure (EXAFS) and x-ray absorption near edge structure (XANES) results were consistent with the presence of a mixture of AmO 2 + and AmO 2 2+ with only a small amount AmO 2 present. The resulting average bond distances we found were 1.71 Å for Am=O and 2.44 Å for Am-O. All-electron scalar relativistic calculations were also carried out using DFT to predict the equilibrium geometries and properties ofmore » the AmO 2 + and AmO 2 2+ aquo complexes. Calculated bond distances for the Am(VI) complex are in reasonable agreement with EXAFS data and the computed energy gaps between frontier molecular orbitals suggest a slightly higher kinetic stability and chemical hardness of Am(VI) compared to Am(V).« less

Elucidating the Nature of the Excited State of a Heteroleptic Copper Photosensitizer by using Time-Resolved X-ray Absorption Spectroscopy.

PubMed

Moonshiram, Dooshaye; Garrido-Barros, Pablo; Gimbert-Suriñach, Carolina; Picón, Antonio; Liu, Cunming; Zhang, Xiaoyi; Karnahl, Michael; Llobet, Antoni

2018-04-25

We report the light-induced electronic and geometric changes taking place within a heteroleptic Cu I photosensitizer, namely [(xant)Cu(Me 2 phenPh 2 )]PF 6 (xant=xantphos, Me 2 phenPh 2 =bathocuproine), by time-resolved X-ray absorption spectroscopy in the ps-μs time regime. Time-resolved X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) analysis enabled the elucidation of the electronic and structural configuration of the copper center in the excited state as well as its decay dynamics in different solvent conditions with and without triethylamine acting as a sacrificial electron donor. A three-fold decrease in the decay lifetime of the excited state is observed in the presence of triethylamine, showing the feasibility of the reductive quenching pathway in the latter case. A prominent pre-edge feature is observed in the XANES spectrum of the excited state upon metal to charge ligand transfer transition, showing an increased hybridization of the 3d states with the ligand p orbitals in the tetrahedron around the Cu center. EXAFS and density functional theory illustrate a significant shortening of the Cu-N and an elongation of the Cu-P bonds together with a decrease in the torsional angle between the xantphos and bathocuproine ligand. This study provides mechanistic time-resolved understanding for the development of improved heteroleptic Cu I photosensitizers, which can be used for the light-driven production of hydrogen from water. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

NASA Astrophysics Data System (ADS)

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

2009-11-01

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

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

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

The photodegradation of cadmium yellow paints in Henri Matisse's Le Bonheur de vivre (1905-1906)

NASA Astrophysics Data System (ADS)

Mass, Jennifer L.; Opila, Robert; Buckley, Barbara; Cotte, Marine; Church, Jonathan; Mehta, Apurva

2013-04-01

Evidence for the alteration of the yellow paints in Henri Matisse's Le Bonheur de vivre (1905-1906, The Barnes Foundation) has been observed since the 1990s. The changes in this iconic work of Matisse's Fauvist period include lightening, darkening, and flaking of the yellow paints. Handheld X-ray fluorescence (XRF) and multispectral imaging surveys reveal that the degradation is confined to cadmium yellow (CdS) paints. The discoloration of cadmium yellow paints in Impressionist, Post-Impressionist and early modernist work from the 1880s through the 1920s has been ascribed to the photo-oxidative degradation of CdS. Preliminary investigations of the degraded yellow paints in this work involved Cd LIII-edge X-ray Absorption Near Edge Spectroscopy (XANES) at the Stanford Synchrotron Radiation Light Source (SSRL Menlo Park, California) and Scanning Electron Microscopy-energy dispersive X-ray analysis (SEM-EDS) at the Winterthur Museum Scientific Research and Analysis Laboratory. To determine if the visual changes in the paints did in fact indicate photo-oxidative degradation and if different chemistries could be observed for the lightened versus darkened regions, synchrotron radiation-micro Fourier Transform InfraRed (SR-μFTIR) spectroscopy, X-ray Fluorescence (SR-μXRF) mapping and micro X-ray Absorption Near Edge Spectroscopy (μXANES) mapping at the Cd LIII-edge of the altered paint cross-sections were carried out at the European synchrotron radiation facility (ESRF, Grenoble, France) beamline ID-21. The goal is to elucidate the discoloration mechanisms observed in the paint using elemental and speciation mapping. The μXANES mapping and SR-FTIR imaging showed a substantial enrichment of CdCO3 in the off-white surface crust of the faded/discolored CdS paint. This suggests that the CdCO3 is present as an insoluble photodegradation product rather than solely a paint filler or starting reagent. Additionally, oxalates and sulfates were found to be concentrated at the alteration surface.

Uranium Redox Transformations after U(VI) Coprecipitation with Magnetite Nanoparticles.

PubMed

Pidchenko, Ivan; Kvashnina, Kristina O; Yokosawa, Tadahiro; Finck, Nicolas; Bahl, Sebastian; Schild, Dieter; Polly, Robert; Bohnert, Elke; Rossberg, André; Göttlicher, Jörg; Dardenne, Kathy; Rothe, Jörg; Schäfer, Thorsten; Geckeis, Horst; Vitova, Tonya

2017-02-21

Uranium redox states and speciation in magnetite nanoparticles coprecipitated with U(VI) for uranium loadings varying from 1000 to 10 000 ppm are investigated by X-ray absorption spectroscopy (XAS). It is demonstrated that the U M 4 high energy resolution X-ray absorption near edge structure (HR-XANES) method is capable to clearly characterize U(IV), U(V), and U(VI) existing simultaneously in the same sample. The contributions of the three different uranium redox states are quantified with the iterative transformation factor analysis (ITFA) method. U L 3 XAS and transmission electron microscopy (TEM) reveal that initially sorbed U(VI) species recrystallize to nonstoichiometric UO 2+x nanoparticles within 147 days when stored under anoxic conditions. These U(IV) species oxidize again when exposed to air. U M 4 HR-XANES data demonstrate strong contribution of U(V) at day 10 and that U(V) remains stable over 142 days under ambient conditions as shown for magnetite nanoparticles containing 1000 ppm U. U L 3 XAS indicates that this U(V) species is protected from oxidation likely incorporated into octahedral magnetite sites. XAS results are supported by density functional theory (DFT) calculations. Further characterization of the samples include powder X-ray diffraction (pXRD), scanning electron microscopy (SEM) and Fe 2p X-ray photoelectron spectroscopy (XPS).

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

NASA Astrophysics Data System (ADS)

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

2013-06-01

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

Structural Changes Correlated with Magnetic Spin State Isomorphism in the S2 State of the Mn4CaO5 Cluster in the Oxygen-Evolving Complex of Photosystem II

PubMed Central

Chatterjee, Ruchira; Han, Guangye; Kern, Jan; Gul, Sheraz; Fuller, Franklin D.; Garachtchenko, Anna; Young, Iris; Weng, Tsu-Chien; Nordlund, Dennis; Alonso-Mori, Roberto; Bergmann, Uwe; Sokaras, Dimosthenis; Hatakeyama, Makoto; Yachandra, Vittal K.; Yano, Junko

2016-01-01

The Mn4CaO5 cluster in Photosystem II catalyzes the four-electron redox reaction of water oxidation in natural photosynthesis. This catalytic reaction cycles through four intermediate states (Si, i = 0 to 4), involving changes in the redox state of the four Mn atoms in the cluster. Recent studies suggest the presence and importance of isomorphous structures within the same redox/intermediate S-state. It is highly likely that geometric and electronic structural flexibility play a role in the catalytic mechanism. Among the catalytic intermediates that have been identified experimentally thus far, there is clear evidence of such isomorphism in the S2 state, with a high-spin (5/2) (HS) and a low spin (1/2) (LS) form, identified and characterized by their distinct electron paramagnetic resonance (EPR spectroscopy) signals. We studied these two S2 isomers with Mn extended X-ray absorption fine structure (EXAFS) and absorption and emission spectroscopy (XANES/XES) to characterize the structural and electronic structural properties. The geometric and electronic structure of the HS and LS S2 states are different as determined using Mn EXAFS and XANES/XES, respectively. The Mn K-edge XANES and XES for the HS form are different from the LS and indicate a slightly lower positive charge on the Mn atoms compared to the LS form. Based on the EXAFS results which are clearly different, we propose possible structural differences between the two spin states. Such structural and magnetic redox-isomers if present at room temperature, will likely play a role in the mechanism for water-exchange/oxidation in photosynthesis. PMID:28044099

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

NASA Astrophysics Data System (ADS)

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

2005-11-01

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

Structural changes correlated with magnetic spin state isomorphism in the S 2 state of the Mn 4CaO 5 cluster in the oxygen-evolving complex of photosystem II

DOE PAGES

Chatterjee, Ruchira; Han, Guangye; Kern, Jan; ...

2016-05-09

The Mn 4CaO 5 cluster in photosystem II catalyzes the four-electron redox reaction of water oxidation in natural photosynthesis. This catalytic reaction cycles through four intermediate states (S i, i = 0 to 4), involving changes in the redox state of the four Mn atoms in the cluster. Recent studies suggest the presence and importance of isomorphous structures within the same redox/intermediate S-state. It is highly likely that geometric and electronic structural flexibility play a role in the catalytic mechanism. Among the catalytic intermediates that have been identified experimentally thus far, there is clear evidence of such isomorphism in themore » S2 state, with a high-spin (5/2) (HS) and a low spin (1/2) (LS) form, identified and characterized by their distinct electron paramagnetic resonance (EPR spectroscopy) signals. We studied these two S2 isomers with Mn extended X-ray absorption fine structure (EXAFS) and absorption and emission spectroscopy (XANES/XES) to characterize the structural and electronic structural properties. The geometric and electronic structure of the HS and LS S2 states are different as determined using Mn EXAFS and XANES/XES, respectively. The Mn K-edge XANES and XES for the HS form are different from the LS and indicate a slightly lower positive charge on the Mn atoms compared to the LS form. Based on the EXAFS results which are clearly different, we propose possible structural differences between the two spin states. As a result, such structural and magnetic redox-isomers if present at room temperature, will likely play a role in the mechanism for water-exchange/oxidation in photosynthesis.« less

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

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

Farmand, Maryam

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 spectroscopymore » (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.« less

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

PubMed

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

2015-08-19

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

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

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

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

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

Coordinated Analyses of Mineral-organic Matter Associations in Interplanetary Dust Particles

NASA Technical Reports Server (NTRS)

Nakamura-Messenger, K.; Herzog, G. F.; Smith, T.; Keller, L. P.; Flynn, G. J.; Khodja, H.; Taylor, S.; Wirick, S.; Messenger, S.

2012-01-01

Little is known about the timing and processes involved in the incorporation of organic matter with inorganic materials in early Solar System bodies. Recently, X-ray absorption near-edge spectroscopy (XANES) studies showed carbon-rich rims surrounding individual mineral grains in anhydrous IDPs [1,2]. These carbonaceous rims are believed to have formed prior to parent body formation and likely served to bond mineral grains during accretion into larger aggregates. We are exploring the nature of these carbonaceous rims through coordinated analyses of their chemistry, mineralogy, spectroscopy and isotopic characteristics. Here we report our preliminary mineralogical observations.

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

NASA Technical Reports Server (NTRS)

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

1993-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2013-04-01

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

Chemical Behavior of Sulfur in Minerals and Silicate Glasses Studied Using Inner Shell Spectroscopy

NASA Astrophysics Data System (ADS)

Alonso Mori, R.; Paris, E.; Glatzel, P.; Giuli, G.; Scaillet, B.

2008-12-01

Understanding the chemical behaviour of sulfur is of fundamental importance in explaining different geological mechanisms ranging from volcano-climatic interactions to the genesis of ore deposits. Understanding how sulphur behaves is also of great economic importance in industrial activities including glass-forming processes and the treatment of vitreous waste material from refuse incineration. The chemical behaviour of sulfur in minerals and glasses has been widely studied via X-ray absorption near edge structure (XANES) spectroscopy, which probes the unoccupied density of states and thus provides information on the oxidation state and local structure of the species under study. However, the XANES spectral shape is influenced by various effects, namely the local symmetry, the ligand type, even up to high coordination spheres, and the valence electron occupation, making it difficult to systematically analyze the different spectral contributions. We use X-ray emission spectroscopy (XES) as a complementary technique to avoid some of the inherent difficulties of XANES analysis, and to extract additional information on the electronic structure. The Kb lines, close to the K-edge, directly yield the p-density of occupied valence states, giving valuable information on the local coordination. We have compared XANES and Kb XES experimental data on sulfur- bearing minerals with ab initio quantum-chemical calculations based on density functional theory (DFT), in order to visualize the molecular orbitals and to extract information about the chemical bonding in these compounds. The S Ka emission lines, which arise from 2p to 1s transitions, are expected to be mostly free from chemical bond effects except for small energy shifts that reflect the valence orbital electron population via screening effects. S Ka shifts can be readily used to determine the speciation of sulfur in silicate glasses. The electronic configuration of the sulfur atoms is obtained by calculating the effective charge around the sulfur atom based on the Mulliken population analysis generated by DFT calculations, and then successfully correlated with the observed experimental shifts. In order to check these results using a theoretical framework other than DFT, we also performed calculations using a multiple scattering approach (FEFF8.4). X-ray absorption and emission spectroscopy has been applied to three series of peralkaline rhyolitic obsidians each with different alkali/alumina ratios ((Na2O + K2O)/Al2O3). The occurrence of sulfur was accurately determined by using the energy shift of the S Ka emission lines to make a quantitative analysis. We observe that we can follow the evolution of sulfur as a function of controlled formation conditions with respect to pressure, temperature or oxygen fugacity, and determine whether it is present as sulfate or sulfide. XANES and Kb emission lines also yield detailed information on the local chemistry and structure, and thus help us to understand the geochemical role of S in these systems.

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

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

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

2010-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2014-11-01

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

Estimating the number of pure chemical components in a mixture by X-ray absorption spectroscopy.

PubMed

Manceau, Alain; Marcus, Matthew; Lenoir, Thomas

2014-09-01

Principal component analysis (PCA) is a multivariate data analysis approach commonly used in X-ray absorption spectroscopy to estimate the number of pure compounds in multicomponent mixtures. This approach seeks to describe a large number of multicomponent spectra as weighted sums of a smaller number of component spectra. These component spectra are in turn considered to be linear combinations of the spectra from the actual species present in the system from which the experimental spectra were taken. The dimension of the experimental dataset is given by the number of meaningful abstract components, as estimated by the cascade or variance of the eigenvalues (EVs), the factor indicator function (IND), or the F-test on reduced EVs. It is shown on synthetic and real spectral mixtures that the performance of the IND and F-test critically depends on the amount of noise in the data, and may result in considerable underestimation or overestimation of the number of components even for a signal-to-noise (s/n) ratio of the order of 80 (σ = 20) in a XANES dataset. For a given s/n ratio, the accuracy of the component recovery from a random mixture depends on the size of the dataset and number of components, which is not known in advance, and deteriorates for larger datasets because the analysis picks up more noise components. The scree plot of the EVs for the components yields one or two values close to the significant number of components, but the result can be ambiguous and its uncertainty is unknown. A new estimator, NSS-stat, which includes the experimental error to XANES data analysis, is introduced and tested. It is shown that NSS-stat produces superior results compared with the three traditional forms of PCA-based component-number estimation. A graphical user-friendly interface for the calculation of EVs, IND, F-test and NSS-stat from a XANES dataset has been developed under LabVIEW for Windows and is supplied in the supporting information. Its possible application to EXAFS data is discussed, and several XANES and EXAFS datasets are also included for download.

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

PubMed

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

2014-03-01

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

Micron to Mine: Synchrotron Science for Mineral Exploration, Production, and Remediation

NASA Astrophysics Data System (ADS)

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 arsenic trioxide can be accurately identified as well as relative amounts determined. With this information the oxidation-reduction of arsenic-bearing compounds can be monitored to optimize management practices for the long-term capture of arsenic contaminants.

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

NASA Astrophysics Data System (ADS)

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.

Arsenic Re-Mobilization in Water Treatment Adsorbents Under Reducing Conditions: Part II, XAS and Modeling Study

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

Liu,S.; Jing, C.; Meng, X.

2008-01-01

The mechanism of arsenic re-mobilization in spent adsorbents under reducing conditions was studied using X-ray absorption spectroscopy and surface complexation model calculations. X-ray absorption near edge structure (XANES) spectroscopy demonstrated that As(V) was partially reduced to As(III) in spent granular ferric hydroxide (GFH), titanium dioxide (TiO2), activated alumina (AA) and modified activated alumina (MAA) adsorbents after 2 years of anaerobic incubation. As(V) was completely reduced to As(III) in spent granular ferric oxide (GFO) under 2-year incubation. The extended X-ray absorption fine structure (EXAFS) spectroscopy analysis showed that As(III) formed bidentate binuclear surface complexes on GFO as evidenced by an averagemore » As(III)-O bond distance of 1.78 Angstroms and As(III)-Fe distance of 3.34 Angstroms . The release of As from the spent GFO and TiO2 was simulated using the charge distribution multi-site complexation (CD-MUSIC) model. The observed redox ranges for As release and sulfate mobility were described by model calculations.« less

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

DOE PAGES

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

2015-10-23

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

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

NASA Astrophysics Data System (ADS)

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

2009-05-01

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

Developing V-Xanes Oxybarometry for Probing Materials Formed in Reducing Environments in the Early Solar Disk

NASA Technical Reports Server (NTRS)

Butterworth, A. L.; Gainsforth, Z.; Jilly-Rehak, C. E.; Righter, K.; Westphal, A. J.

2017-01-01

Vanadium exhibits four oxidation states (V(sup 2+), V(sup 3+), V(sup 4+) and V(sup 5+)) that have been shown to preferentially partition between melt phases dependent on redox conditions, spanning oxygen fugacity across more than 10 log units. We are developing synchrotron-based x-ray absorption spectroscopy of low-fugacity standards for the determination of V oxidation state in highly reducing conditions relevant to the early solar nebula.

Na-Ion Intercalation and Charge Storage Mechanism in Two-Dimensional Vanadium Carbide

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

Bak, Seong -Min; Qiao, Ruimin; Yang, W.

We synthesized two-dimensional vanadium carbide MXene containing surface functional groups (denoted as V 2CT x, where T x are surface functional groups) and studied as anode material for Na-ion batteries. V 2CT x anode exhibits reversible charge storage with good cycling stability and high rate capability through electrochemical test. Furthermore, the charge storage mechanism of V 2CT x 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 ofmore » redox reaction of vanadium to the charge storage and the reversible capacity of V 2CT x during sodiation/desodiation process have been provided through V K-edge XANES and V L2,3-edge sXAS results. A correlation between the CO 3 2- content and Na + intercalation/deintercalation states in the V 2CT x 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 V 2CT x and the carbonate based non-aqueous electrolyte. Our results of this study will provide valuable information for the further studies on V 2CT x as anode material for Na-ion batteries and capacitors.« less

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

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

Bak, Seong-Min; Qiao, Ruimin; Yang, Wanli

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 andmore » 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.« less

Na-Ion Intercalation and Charge Storage Mechanism in Two-Dimensional Vanadium Carbide

DOE PAGES

Bak, Seong -Min; Qiao, Ruimin; Yang, W.; ...

2017-07-14

We synthesized two-dimensional vanadium carbide MXene containing surface functional groups (denoted as V 2CT x, where T x are surface functional groups) and studied as anode material for Na-ion batteries. V 2CT x anode exhibits reversible charge storage with good cycling stability and high rate capability through electrochemical test. Furthermore, the charge storage mechanism of V 2CT x 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 ofmore » redox reaction of vanadium to the charge storage and the reversible capacity of V 2CT x during sodiation/desodiation process have been provided through V K-edge XANES and V L2,3-edge sXAS results. A correlation between the CO 3 2- content and Na + intercalation/deintercalation states in the V 2CT x 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 V 2CT x and the carbonate based non-aqueous electrolyte. Our results of this study will provide valuable information for the further studies on V 2CT x as anode material for Na-ion batteries and capacitors.« less

Selenium speciation in seleniferous agricultural soils under different cropping systems using sequential extraction and X-ray absorption spectroscopy.

PubMed

Qin, Hai-Bo; Zhu, Jian-Ming; Lin, Zhi-Qing; Xu, Wen-Po; Tan, De-Can; Zheng, Li-Rong; Takahashi, Yoshio

2017-06-01

Selenium (Se) speciation in soil is critically important for understanding the solubility, mobility, bioavailability, and toxicity of Se in the environment. In this study, Se fractionation and chemical speciation in agricultural soils from seleniferous areas were investigated using the elaborate sequential extraction and X-ray absorption near-edge structure (XANES) spectroscopy. The speciation results quantified by XANES technique generally agreed with those obtained by sequential extraction, and the combination of both approaches can reliably characterize Se speciation in soils. Results showed that dominant organic Se (56-81% of the total Se) and lesser Se(IV) (19-44%) were observed in seleniferous agricultural soils. A significant decrease in the proportion of organic Se to the total Se was found in different types of soil, i.e., paddy soil (81%) > uncultivated soil (69-73%) > upland soil (56-63%), while that of Se(IV) presented an inverse tendency. This suggests that Se speciation in agricultural soils can be significantly influenced by different cropping systems. Organic Se in seleniferous agricultural soils was probably derived from plant litter, which provides a significant insight for phytoremediation in Se-laden ecosystems and biofortification in Se-deficient areas. Furthermore, elevated organic Se in soils could result in higher Se accumulation in crops and further potential chronic Se toxicity to local residents in seleniferous areas. Copyright © 2017 Elsevier Ltd. All rights reserved.

Unusual heme iron-lipid acyl chain coordination in Escherichia coli flavohemoglobin.

PubMed

D'Angelo, Paola; Lucarelli, Debora; della Longa, Stefano; Benfatto, Maurizio; Hazemann, Jean Louis; Feis, Alessandro; Smulevich, Giulietta; Ilari, Andrea; Bonamore, Alessandra; Boffi, Alberto

2004-06-01

Escherichia coli flavohemoglobin is endowed with the notable property of binding specifically unsaturated and/or cyclopropanated fatty acids both as free acids or incorporated into a phospholipid molecule. Unsaturated or cyclopropanated fatty acid binding to the ferric heme results in a spectral change observed in the visible absorption, resonance Raman, extended x-ray absorption fine spectroscopy (EXAFS), and x-ray absorption near edge spectroscopy (XANES) spectra. Resonance Raman spectra, measured on the flavohemoglobin heme domain, demonstrate that the lipid (linoleic acid or total lipid extracts)-induced spectral signals correspond to a transition from a five-coordinated (typical of the ligand-free protein) to a hexacoordinated, high spin heme iron. EXAFS and XANES measurements have been carried out both on the lipid-free and on the lipid-bound protein to assign the nature of ligand in the sixth coordination position of the ferric heme iron. EXAFS data analysis is consistent with the presence of a couple of atoms in the sixth coordination position at 2.7 A in the lipid-bound derivative (bonding interaction), whereas a contribution at 3.54 A (nonbonding interaction) can be singled out in the lipid-free protein. This last contribution is assigned to the CD1 carbon atoms of the distal LeuE11, in full agreement with crystallographic data on the lipid-free protein at 1.6 A resolution obtained in the present work. Thus, the contributions at 2.7 A distance from the heme iron are assigned to a couple of carbon atoms of the lipid acyl chain, possibly corresponding to the unsaturated carbons of the linoleic acid.

Local atomic and electronic structures of epitaxial strained LaCoO3 thin films

NASA Astrophysics Data System (ADS)

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

2012-01-01

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

X-ray absorption spectroscopy and X-ray photoelectron spectroscopy studies of CaSO 4:Dy thermoluminescent phosphors

NASA Astrophysics Data System (ADS)

Bakshi, A. K.; Jha, S. N.; Olivi, L.; Phase, D. M.; Kher, R. K.; Bhattacharyya, D.

2007-11-01

Extended X-ray absorption fine structure (EXAFS) measurements have been carried out on CaSO4:Dy phosphor samples at the Dy L3 edge with synchrotron radiation. Measurements were carried out on a set of samples which were subjected to post-preparation annealing at different temperatures and for different cycles. The EXAFS data have been analysed to find the Dy-S and Dy-O bond lengths in the neighbourhood of the Dy atoms in a CaSO4 matrix. The observations from EXAFS measurements were verified with XANES and XPS techniques. On the basis of these measurements, efforts were made to explain the loss of thermoluminescence sensitivity of CaSO4:Dy phosphors after repeated cycles of annealing at 400 °C in air for 1 h.

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

NASA Astrophysics Data System (ADS)

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

2014-07-01

Chemical imaging, electronic structure and optical properties of ZnO/CdS nano-composites have been investigated using scanning transmission X-ray microscopy (STXM), X-ray absorption near-edge structure (XANES) and X-ray excited optical luminescence (XEOL) spectroscopy. STXM and XANES results confirm that the as-prepared product is ZnO/CdS core/shell nanowires (NWs), and further indicate that ZnS was formed on the surface of ZnO NWs as the interface between ZnO and CdS. The XEOL from ZnO/CdS NW arrays exhibits one weak ultraviolet (UV) emission at 375 nm, one strong green emission at 512 nm, and two broad infrared (IR) emissions at 750 and 900 nm. Combining XANES and XEOL, it is concluded that the UV luminescence is the near band gap emission (BGE) of ZnO; the green luminescence comes from both the BGE of CdS and defect emission (DE, zinc vacancies) of ZnO; the IR luminescence is attributed to the DE (bulk defect related to the S site) of CdS; ZnS contributes little to the luminescence of the ZnO/CdS NW arrays. Interestingly, the BGE and DE from oxygen vacancies of ZnO in the ZnO/CdS nano-composites are almost entirely quenched, while DE from zinc vacancies changes little.Chemical imaging, electronic structure and optical properties of ZnO/CdS nano-composites have been investigated using scanning transmission X-ray microscopy (STXM), X-ray absorption near-edge structure (XANES) and X-ray excited optical luminescence (XEOL) spectroscopy. STXM and XANES results confirm that the as-prepared product is ZnO/CdS core/shell nanowires (NWs), and further indicate that ZnS was formed on the surface of ZnO NWs as the interface between ZnO and CdS. The XEOL from ZnO/CdS NW arrays exhibits one weak ultraviolet (UV) emission at 375 nm, one strong green emission at 512 nm, and two broad infrared (IR) emissions at 750 and 900 nm. Combining XANES and XEOL, it is concluded that the UV luminescence is the near band gap emission (BGE) of ZnO; the green luminescence comes from both the BGE of CdS and defect emission (DE, zinc vacancies) of ZnO; the IR luminescence is attributed to the DE (bulk defect related to the S site) of CdS; ZnS contributes little to the luminescence of the ZnO/CdS NW arrays. Interestingly, the BGE and DE from oxygen vacancies of ZnO in the ZnO/CdS nano-composites are almost entirely quenched, while DE from zinc vacancies changes little. Electronic supplementary information (ESI) available: PL spectra of the ZnO NW arrays before/after CdS coating. S K-edge XANES spectra of the ZnO/CdS core/shell NW arrays. See DOI: 10.1039/c4nr02231a

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

DOE PAGES

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

2017-01-07

Here, the structure of molten Fe 2SiO 4+x has been studied using both high-energy X-ray diffraction and Fe K-edge X-ray absorption near-edge structure (XANES) spectroscopy, combined with aerodynamic levitation and laser beam heating. A wide range of Fe 3+ contents were accessed by varying the levitation and atmospheric gas composition. Diffraction measurements were made in the temperature ( T) and oxygen partial pressure ranges 1624(21) < T < 2183(94) K (uncertainties in parentheses) and –5.6(3) < ΔFMQ < +2.8(5) log units (relative to the Fayalite-Magnetite-Quartz buffer). Iron K-edge XANES measurements covered the ranges 1557(33) < T < 1994(36) K andmore » –2.1(3) < ΔFMQ < +4.4(3) log units. Fe 3+ contents, x = Fe 3+/ΣFe, estimated directly from the pre-edge peaks of the XANES spectra varied between 0.15(1) and 0.40(2). While these agree in some cases with semi-empirical models, notable discrepancies are discussed in the context of the redox kinetics and the limitations in both the models and in the calibrations used to derive oxidation state from XANES spectra. XANES pre-edge peak areas imply average Fe–O coordination numbers, n FeO, close to 5 for all Fe 3+/ΣFe. Diffraction measurements yielded values of 4.4(2) < n FeO < 4.7(1). There is limited evidence for a linear trend n FeO(x) = 4.46(3) + 0.4(1)x. Asymmetric Fe–O bond length distributions peak at around 1.96 Å and have a shoulder arising from longer interatomic distances. Mean r FeO lie close to 2.06 Å, consistent with n FeO close to 5. These observations suggest that Fe 2+ is less efficient at stabilizing tetrahedral Fe 3+ compared to large monovalent alkali cations. Comparison of in-situ XANES estimates of Fe 3+/ΣFe in the melts to those of the quenched solids obtained from XANES as well as Mössbauer spectroscopy indicate rapid oxidation during cooling, enabled by stirring of the melt by the levitation gas flow. As such, the oxidation state of hot komatiitic and other highly fluid melts may not be retained, even during rapid cooling, as it is for cooler basaltic and more silicic magmas.« less

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

NASA Technical Reports Server (NTRS)

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

2014-01-01

Monahans meteorite (H5) contains fluid inclusion- bearing halite (NaCl) crystals [1]. Microthermometry and Raman spectroscopy showed that the fluid in the inclusions is an aqueous brine and they were trapped near 25degC [1]. Their continued presence in the halite grains requires that their incorporation into the H chondrite asteroid was post metamorphism [2]. Abundant solid inclusions are also present in the halites. The solid inclusions include abundant and widely variable organics [2]. Analyses by Raman microprobe, SEM/EDX, synchrotron X-ray diffraction and TEM reveal that these grains include macromolecular carbon similar in structure to CV3 chondrite matrix carbon, aliphatic carbon compounds, olivine (Fo99-59), high- and low-Ca pyroxene, feldspars, magnetite, sulfides, lepidocrocite, carbonates, diamond, apatite and possibly the zeolite phillipsite [3]. Here we report organic analyses of these carbonaceous residues in Monahans halite using C-, N-, and O- X-ray absorption near edge structure (XANES). Samples and Methods: Approximately 100 nm-thick sections were extracted with a focused ion beam (FIB) at JSC from solid inclusions from Monahans halite. The sections were analyzed using the scanning transmission X-ray microscope (STXM) on beamline 5.3.2.2 at the Advanced Light Source, Lawrence Berkeley National Laboratory for XANES spectroscopy. Results and Discussion: C-XANES spectra of the solid inclusions show micrometer-scale heterogeneity, indicating that the macromolecular carbon in the inclusions have complex chemical variations. C-XANES features include 284.7 eV assigned to aromatic C=C, 288.4-288.8 eV assigned to carboxyl, and 290.6 eV assigned to carbonate. The carbonyl features obtained by CXANES might have been caused by the FIB used in sample preparation. No specific N-XANES features are observed. The CXANES spectra obtained from several areas in the FIB sections include type 1&2 chondritic IOM like, type 3 chondritic IOM like, and none of the above. The natures of the macromolecular carbon in the solid inclusions observed by C-XANES are consistent with the previous studies showing that the carbonaceous solid inclusions have not originated from Monahans parent body [1-3], and have various origins, including various chondritic meteorite parent bodies as well as other unknown source(s).

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

NASA Astrophysics Data System (ADS)

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

2017-04-01

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

Bone char effects on soil: sequential fractionations and XANES spectroscopy

NASA Astrophysics Data System (ADS)

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

2018-01-01

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

Noninvasive Synchrotron-Based X-ray Raman Scattering Discriminates Carbonaceous Compounds in Ancient and Historical Materials [ In situ synchrotron-based X-Ray Raman scattering discriminates carbonaceous compounds in ancient and historical materials

DOE PAGES

Gueriau, Pierre; Rueff, Jean -Pascal; Bernard, Sylvain; ...

2017-09-13

Carbon compounds are ubiquitous and occur in a diversity of chemical forms in many systems including ancient and historic materials ranging from cultural heritage to paleontology. Determining their speciation cannot only provide unique information on their origin but may also elucidate degradation processes. Synchrotron-based X-ray absorption near-edge structure (XANES) spectroscopy at the carbon K-edge (280–350 eV) is a very powerful method to probe carbon speciation. However, the short penetration depth of soft X-rays imposes stringent constraints on sample type, preparation, and analytical environment. A hard X-ray probe such as X-ray Raman scattering (XRS) can overcome many of these difficulties. Heremore » we report the use of XRS at ~6 keV incident energy to collect carbon K-edge XANES data and probe the speciation of organic carbon in several specimens relevant to cultural heritage and natural history. This methodology enables the measurement to be done in a nondestructive way, in air, and provides information that is not compromised by surface contamination by ensuring that the dominant signal contribution is from the bulk of the probed material. Using the backscattering geometry at large photon momentum transfer maximizes the XRS signal at the given X-ray energy and enhances nondipole contributions compared to conventional XANES, thereby augmenting the speciation sensitivity. The capabilities and limitations of the technique are discussed. As a result, we show that despite its small cross section, for a range of systems the XRS method can provide satisfactory signals at realistic experimental conditions. XRS constitutes a powerful complement to FT-IR, Raman, and conventional XANES spectroscopy, overcoming some of the limitations of these techniques.« less

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

PubMed Central

Sarangi, Ritimukta

2012-01-01

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

Time-resolved x-ray absorption spectroscopy: Watching atoms dance

NASA Astrophysics Data System (ADS)

Milne, Chris J.; Pham, Van-Thai; Gawelda, Wojciech; van der Veen, Renske M.; El Nahhas, Amal; Johnson, Steven L.; Beaud, Paul; Ingold, Gerhard; Lima, Frederico; Vithanage, Dimali A.; Benfatto, Maurizio; Grolimund, Daniel; Borca, Camelia; Kaiser, Maik; Hauser, Andreas; Abela, Rafael; Bressler, Christian; Chergui, Majed

2009-11-01

The introduction of pump-probe techniques to the field of x-ray absorption spectroscopy (XAS) has allowed the monitoring of both structural and electronic dynamics of disordered systems in the condensed phase with unprecedented accuracy, both in time and in space. We present results on the electronically excited high-spin state structure of an Fe(II) molecular species, [FeII(bpy)3]2+, in aqueous solution, resolving the Fe-N bond distance elongation as 0.2 Å. In addition an analysis technique using the reduced χ2 goodness of fit between FEFF EXAFS simulations and the experimental transient absorption signal in energy space has been successfully tested as a function of excited state population and chemical shift, demonstrating its applicability in situations where the fractional excited state population cannot be determined through other measurements. Finally by using a novel ultrafast hard x-ray 'slicing' source the question of how the molecule relaxes after optical excitation has been successfully resolved using femtosecond XANES.

Determination of oxidation state of iron in normal and pathologically altered human aortic valves

NASA Astrophysics Data System (ADS)

Czapla-Masztafiak, J.; Lis, G. J.; Gajda, M.; Jasek, E.; Czubek, U.; Bolechała, F.; Borca, C.; Kwiatek, W. M.

2015-12-01

In order to investigate changes in chemical state of iron in normal and pathologically altered human aortic valves X-ray absorption spectroscopy was applied. Since Fe is suspected to play detrimental role in aortic valve stenosis pathogenesis the oxidation state of this element has been determined. The experimental material consisted of 10 μm sections of valves excised during routine surgery and from autopsies. The experiment was performed at the MicroXAS beamline of the SLS synchrotron facility in Villigen (Switzerland). The Fe K-edge XANES spectra obtained from tissue samples were carefully analyzed and compared with the spectra of reference compounds containing iron in various chemical structures. The analysis of absorption edge position and shape of the spectra revealed that both chemical forms of iron are presented in valve tissue but Fe3+ is the predominant form. Small shift of the absorption edge toward higher energy in the spectra from stenotic valve samples indicates higher content of the Fe3+ form in pathological tissue. Such a phenomenon suggests the role of Fenton reaction and reactive oxygen species in the etiology of aortic valve stenosis. The comparison of pre-edge regions of XANES spectra for control and stenotic valve tissue confirmed no differences in local symmetry or spin state of iron in analyzed samples.

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

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

Hesterberg, Dean; McNulty, Ian; Thieme, Juergen

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

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

DOE PAGES

Hesterberg, Dean; McNulty, Ian; Thieme, Juergen

2017-07-27

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

Fate of zinc in an electroplating sludge during electrokinetic treatments.

PubMed

Liu, Shou-Heng; Wang, H Paul

2008-08-01

Chemical structure of zinc in the electrokinetic treatments of an electroplating sludge has been studied by in situ extended X-ray absorption fine structural (EXAFS) and X-ray absorption near edge structural (XANES) spectroscopies in the present work. The least-square fitted XANES spectra indicate that the main zinc compounds in the sludge were ZnCO(3) (75%), ZnOSiO(2) (17%) and Zn(OH)(2) (7%). Zinc in the sludge possessed a Zn-O bond distance of 2.07 A with a coordination number (CN) of 5. In the second shells, the bond distance of Zn-(O)-Si was 3.05 A (CN=2). An increase of Zn-(O)-Si (0.05 A) with a decrease of its CN (from 5 to <1) was found in the early stage of the electrokinetic treatment. Prolong the electrokinetic treatment time to 180 min, about 34% of Zn(II) was dissolved into the aqueous phase and about 68% of Zn(II) in the sludge (or 23% of total zinc) was migrated to the cathode under the electric field (5 V cm(-1)). The dissolution and electromigration rates of Zn(II) in the sludge were 1.0 and 0.6 mmol h(-1)g(-1) sludge, respectively during the electrokinetic treatment. This work also exemplifies the utilization of in situ EXAFS and XANES for revealing speciation and possible reaction pathways during the course of zinc recycling from the sludge by electrokinetic treatments.

Characterization by 27Al NMR, X-ray absorption spectroscopy, and density functional theory techniques of the species responsible for benzene hydrogenation in Y zeolite-supported carburized molybdenum catalysts.

PubMed

Rocha, Angela S; da Silva, Victor Teixeira; Eon, Jean G; de Menezes, Sônia M C; Faro, Arnaldo C; Rocha, Alexandre B

2006-08-17

Carburized molybdenum catalysts supported on a dealuminated NaH-Y zeolite were prepared by carburization under a 20% methane in hydrogen flow of two precursors obtained by adsorption of molybdenum hexacarbonyl, one containing 5 wt % and the other 10 wt % Mo, and a third one was prepared by impregnation with aqueous ammonium heptamolybdate, containing 5 wt % Mo. The three catalysts displayed very distinct behaviors in the benzene hydrogenation reaction at atmospheric pressure and 363 K. By using XANES spectroscopy at the molybdenum L edge, EXAFS and XANES spectroscopy at the molybdenum K edge, and 27Al solid-state NMR spectroscopy, it was shown that different carburized molybdenum species exist in each sample. In the catalyst containing 10 wt % Mo, formation of molybdenum carbide nanoparticles was observed, with an estimated diameter of 1.8 nm. In the catalyst containing 5 wt % Mo and prepared by carburization of adsorbed molybdenum hexacarbonyl, formation of molybdenum oxycarbide dimers is proposed. In the latter case, density functional theory calculations have led to a dimer structure which is compatible with EXAFS results. In the catalyst prepared by impregnation with ammonium heptamolybdate solution followed by carburization, the molybdenum seems to interact with extraframework alumina to produce highly disordered mixed molybdenum-aluminum oxycarbides.

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

NASA Astrophysics Data System (ADS)

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

2015-03-01

The distribution of trivalent and tetravalent cerium, Ce(III) and Ce(IV) respectively, in a lateritic profile from Madagascar, has been characterized by X-ray-absorption near-edge structure (XANES) spectroscopy at the Ce LIII-edge on the LUCIA beamline (SOLEIL synchrotron, France). XANES spectra were acquired on bulk-rock samples as well as on specific lateritic minerals or polymineral zones (in-situ measurements) of the tonalite bedrock and the three overlying weathered horizons (C-, B- and A-horizons). Geochemically, the bedrock, and the A- and C-horizons show similar rare earth element content (REE = 363-405 mg/kg). They also display the same positive Ce-anomaly (CeCN/Ce∗ = 1.12-1.45), which is therefore likely to be inherited from the bedrock. In the B-horizon, the higher REE content (REE = 2194 mg/kg) and the larger Ce-anomaly (CeCN/Ce∗ = 4.26) are consistent with an accumulation zone caused by the evaporation of groundwater during the dry season. There is a good agreement between the Ce(III)/Cetotal ratio (XCe(III)) deduced from the positive Ce-anomaly (bulk-rock geochemical data) and that derived from XANES spectroscopy on the same bulk-rock samples (BR-XCe(III)-XANES) in the bedrock, and the C- and B-horizons. In the A-horizon, XANES measurements on bulk rock and minerals revealed a higher BR-XCe(III)-XANES (up to 100%) compared to the XCe(III) deduced from geochemical data (XCe(III) = 79%). The preservation of a positive Ce-anomaly in the A-horizon suggests that the Ce mobilization and redistribution during weathering occurred with no significant Ce fractionation from other trivalent REE. Remarkably, the only investigated sample where cerianite is observed belongs to the B-horizon. Within this horizon, Ce oxidation state varies depending on the microstructural position (porosity, cracks, clay-rich groundmass). The highest Ce(IV) concentrations are measured in cerianite (and aluminophosphates) localized in pores at the vicinity of Mn-rich domains (XCe(III)-XANES = 30-51%). Therefore, Ce fractionation from other REE is attributed to a Ce oxidation and precipitation potentially assisted by oxyhydroxide scavenging. In the C-horizon, Ce(III) and Ce(IV) are mainly distributed in REE-minerals of the rhabdophane group found in pores and cracks. The similarity between the Ce(III) proportion of rhabdophane grains (XCe(III)-XANES = 74-89%) with that of the bedrock (BR-XCe(III)-XANES = 79%) suggests no significant fractionation of Ce(III) and Ce(IV) between solution and mineral during the successive stages of primary REE-mineral alteration, transport in solution and secondary precipitation in the incipient stages of weathering. Overall, our novel spectroscopic approach shows that Ce is not necessarily oxidized nor fractionated from other REE during weathering in lateritic conditions. This implies that like Ce(III), Ce(IV) can be mobilized in aqueous fluids during weathering, possibly thanks to complexation with organic molecules, and can precipitate together with Ce(III) in secondary REE-bearing minerals. The corollary is that (paleo)redox reconstructions in soils and/or sediments based on Ce-anomaly in weathered rocks or minerals must be interpreted with caution.

Operando characterization of batteries using x-ray absorption spectroscopy: advances at the beamline XAFS at synchrotron Elettra

NASA Astrophysics Data System (ADS)

Aquilanti, Giuliana; Giorgetti, Marco; Dominko, Robert; Stievano, Lorenzo; Arčon, Iztok; Novello, Nicola; Olivi, Luca

2017-02-01

X-ray absorption spectroscopy is a synchrotron radiation based technique that is able to provide information on both local structure and electronic properties in a chemically selective manner. It can be used to characterize the dynamic processes that govern the electrochemical energy storage in batteries, and to shed light on the redox chemistry and changes in structure during galvanostatic cycling to design cathode materials with improved properties. Operando XAS studies have been performed at beamline XAFS at Elettra on different systems. For Li-ion batteries, a multiedge approach revealed the role of the different cathode components during the charge and discharge of the battery. In addition, Li-S batteries for automotive applications were studied. Operando sulfur K-edge XANES and EXAFS analysis was used to characterize the redox chemistry of sulfur, and to relate the electrochemical mechanism to its local structure.

Redox chemistry of a binary transition metal oxide (AB 2 O 4 ): a study of the Cu 2+ /Cu 0 and Fe 3+ /Fe 0 interconversions observed upon lithiation in a CuFe 2 O 4 battery using X-ray absorption spectroscopy

DOE PAGES

Cama, Christina A.; Pelliccione, Christopher J.; Brady, Alexander B.; ...

2016-06-06

Copper ferrite, CuFe 2 O 4, 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 CuFe 2 O 4. A phase pure tetragonal CuFe 2 O 4 material was prepared and characterized using laboratory and synchrotron X-ray diffraction, Raman spectroscopy, and transmission electron microscopy. We used ex situ X-ray absorption spectroscopy (XAS) measurements to study the battery redox processes at the Fe and Cu K-edges, using X-ray absorption near-edge structuremore » (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). Then, upon charging to 3.5 V, the copper metal remained in the metallic state, while iron metal oxidation to iron(III) was achieved. Our results provide new mechanistic insight regarding the evolution of the local coordination environments at the iron and copper centers upon discharging and charging.« less

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.

PubMed

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.

XAS study of TiO2-based nanomaterials

NASA Astrophysics Data System (ADS)

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.

Enhanced Air Stability in REPb3 (RE = Rare Earths) by Dimensional Reduction Mediated Valence Transition.

PubMed

Subbarao, Udumula; Sarkar, Sumanta; Jana, Rajkumar; Bera, Sourav S; Peter, Sebastian C

2016-06-06

We conceptually selected the compounds REPb3 (RE = Eu, Yb), which are unstable in air, and converted them to the stable materials in ambient conditions by the chemical processes of "nanoparticle formation" and "dimensional reduction". The nanoparticles and the bulk counterparts were synthesized by the solvothermal and high-frequency induction furnace heating methods, respectively. The reduction of the particle size led to the valence transition of the rare earth atom, which was monitored through magnetic susceptibility and X-ray absorption near edge spectroscopy (XANES) measurements. The stability was checked by X-ray diffraction and thermogravimetric analysis over a period of seven months in oxygen and argon atmospheres and confirmed by XANES. The nanoparticles showed outstanding stability toward aerial oxidation over a period of seven months compared to the bulk counterpart, as the latter one is more prone to the oxidation within a few days.

Phase transitions in biogenic amorphous calcium carbonate.

PubMed

Gong, Yutao U T; Killian, Christopher E; Olson, Ian C; Appathurai, Narayana P; Amasino, Audra L; Martin, Michael C; Holt, Liam J; Wilt, Fred H; Gilbert, P U P A

2012-04-17

Crystalline biominerals do not resemble faceted crystals. Current explanations for this property involve formation via amorphous phases. Using X-ray absorption near-edge structure (XANES) spectroscopy and photoelectron emission microscopy (PEEM), here we examine forming spicules in embryos of Strongylocentrotus purpuratus sea urchins, and observe a sequence of three mineral phases: hydrated amorphous calcium carbonate (ACC · H(2)O) → dehydrated amorphous calcium carbonate (ACC) → calcite. Unexpectedly, we find ACC · H(2)O-rich nanoparticles that persist after the surrounding mineral has dehydrated and crystallized. Protein matrix components occluded within the mineral must inhibit ACC · H(2)O dehydration. We devised an in vitro, also using XANES-PEEM, assay to identify spicule proteins that may play a role in stabilizing various mineral phases, and found that the most abundant occluded matrix protein in the sea urchin spicules, SM50, stabilizes ACC · H(2)O in vitro.

Phase transitions in biogenic amorphous calcium carbonate

PubMed Central

Gong, Yutao U. T.; Killian, Christopher E.; Olson, Ian C.; Appathurai, Narayana P.; Amasino, Audra L.; Martin, Michael C.; Holt, Liam J.; Wilt, Fred H.; Gilbert, P. U. P. A.

2012-01-01

Crystalline biominerals do not resemble faceted crystals. Current explanations for this property involve formation via amorphous phases. Using X-ray absorption near-edge structure (XANES) spectroscopy and photoelectron emission microscopy (PEEM), here we examine forming spicules in embryos of Strongylocentrotus purpuratus sea urchins, and observe a sequence of three mineral phases: hydrated amorphous calcium carbonate (ACC·H2O) → dehydrated amorphous calcium carbonate (ACC) → calcite. Unexpectedly, we find ACC·H2O-rich nanoparticles that persist after the surrounding mineral has dehydrated and crystallized. Protein matrix components occluded within the mineral must inhibit ACC·H2O dehydration. We devised an in vitro, also using XANES-PEEM, assay to identify spicule proteins that may play a role in stabilizing various mineral phases, and found that the most abundant occluded matrix protein in the sea urchin spicules, SM50, stabilizes ACC·H2O in vitro. PMID:22492931

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

NASA Astrophysics Data System (ADS)

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

2017-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Evidence for Different Reaction Pathways for Liquid and Granular Micronutrients in a Calcareous Soil

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

Hettiarachchi, Ganga M.; McLaughlin, Mike J.; Scheckel, Kirk G.

2008-06-16

The benefits of Mn and Zn fluid fertilizers over conventional granular products in calcareous sandy loam soils have been agronomically demonstrated. We hypothesized that the differences in the effectiveness between granular and fluid Mn and Zn fertilizers is due to different Mn and Zn reaction processes in and around fertilizer granules and fluid fertilizer bands. We used a combination of several synchrotron-based x-ray techniques, namely, spatially resolved micro-x-ray fluorescence (?-XRF), micro-x-ray absorption near edge structure spectroscopy (?-XANES), and bulk-XANES and -extended x-ray absorption fine structure (EXAFS) spectroscopy, along with several laboratory-based x-ray techniques to speciate different fertilizer-derived Mn and Znmore » species in highly calcareous soils to understand the chemistry underlying the observed differential behavior of fluid and granular micronutrient forms. Micro-XRF mapping of soil-fertilizer reactions zones indicated that the mobility of Mn and Zn from liquid fertilizer was greater than that observed for equivalent granular sources of these micronutrients in soil. After application of these micronutrient fertilizers to soil, Mn and Zn from liquid fertilizers were found to remain in comparatively more soluble solid forms, such as hydrated Mn phosphate-like, Mn calcite-like, adsorbed Zn-like, and Zn silicate-like phases, whereas Mn and Zn from equivalent granular sources tended to transform into comparatively less soluble solid forms such as Mn oxide-like, Mn carbonate-like, and Zn phosphate-like phases.« less

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

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

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

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

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

DOE PAGES

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

2016-12-07

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

Speciation of metal(loid)s in environmental samples by X-ray absorption spectroscopy: a critical review.

PubMed

Gräfe, Markus; Donner, Erica; Collins, Richard N; Lombi, Enzo

2014-04-25

Element specificity is one of the key factors underlying the widespread use and acceptance of X-ray absorption spectroscopy (XAS) as a research tool in the environmental and geo-sciences. Independent of physical state (solid, liquid, gas), XAS analyses of metal(loid)s in complex environmental matrices over the past two decades have provided important information about speciation at environmentally relevant interfaces (e.g. solid-liquid) as well as in different media: plant tissues, rhizosphere, soils, sediments, ores, mineral process tailings, etc. Limited sample preparation requirements, the concomitant ability to preserve original physical and chemical states, and independence from crystallinity add to the advantages of using XAS in environmental investigations. Interpretations of XAS data are founded on sound physical and statistical models that can be applied to spectra of reference materials and mixed phases, respectively. For spectra collected directly from environmental matrices, abstract factor analysis and linear combination fitting provide the means to ascertain chemical, bonding, and crystalline states, and to extract quantitative information about their distribution within the data set. Through advances in optics, detectors, and data processing, X-ray fluorescence microprobes capable of focusing X-rays to micro- and nano-meter size have become competitive research venues for resolving the complexity of environmental samples at their inherent scale. The application of μ-XANES imaging, a new combinatorial approach of X-ray fluorescence spectrometry and XANES spectroscopy at the micron scale, is one of the latest technological advances allowing for lateral resolution of chemical states over wide areas due to vastly improved data processing and detector technology. Copyright © 2014. Published by Elsevier B.V.

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

NASA Astrophysics Data System (ADS)

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

2015-06-01

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

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

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

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

2005-03-15

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

In situ spectroscopic and solution analyses of the reductive dissolution of Mn02 by Fe(II)

USGS Publications Warehouse

Villinski, John E.; O'Day, Peggy A.; Corley, Timothy L.; Conklin, Martha H.

2001-01-01

The reductive dissolution of MnO2 by Fe(II) under conditions simulating acid mine drainage (pH 3, 100 mM SO42-) was investigated by utilizing a flow-through reaction cell and synchrotron X-ray absorption spectroscopy. This configuration allows collection of in situ, real-time X-ray absorption near-edge structure (XANES) spectra and bulk solution samples. Analysis of the solution chemistry suggests that the reaction mechanism changed (decreased reaction rate) as MnO2 was reduced and Fe(III) precipitated, primarily as ferrihydrite. Simultaneously, we observed an additional phase, with the local structure of jacobsite (MnFe2O4), in the Mn XANES spectra of reactants and products. The X-ray absorbance of this intermediate phase increased during the experiment, implying an increase in concentration. The presence of this phase, which probably formed as a surface coating, helps to explain the reduced rate of dissolution of manganese(IV) oxide. In natural environments affected by acid mine drainage, the formation of complex intermediate solid phases on mineral surfaces undergoing reductive dissolution may likewise influence the rate of release of metals to solution.

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

Unuigbe, David M.; Harting, Margit; Jonah, Emmanuel O.

The presence of native oxide on the surface of silicon nanoparticles is known to inhibit charge transport on the surfaces. Scanning electron microscopy (SEM) studies reveal that the particles in the printed silicon network have a wide range of sizes and shapes. High-resolution transmission electron microscopy reveals that the particle surfaces have mainly the (111)- and (100)-oriented planes which stabilizes against further oxidation of the particles. X-ray absorption spectroscopy (XANES) and X-ray photoelectron spectroscopy (XPS) measurements at the O 1s-edge have been utilized to study the oxidation and local atomic structure of printed layers of silicon nanoparticles which were milledmore » for different times. XANES results reveal the presence of the +4 (SiO 2) oxidation state which tends towards the +2 (SiO) state for higher milling times. Si 2pXPS results indicate that the surfaces of the silicon nanoparticles in the printed layers are only partially oxidized and that all three sub-oxide, +1 (Si 2O), +2 (SiO) and +3 (Si 2O 3), states are present. The analysis of the change in the sub-oxide peaks of the silicon nanoparticles shows the dominance of the +4 state only for lower milling times.« less

Microbial reduction of uranium (VI) by Bacillus sp. dwc-2: A macroscopic and spectroscopic study.

PubMed

Li, Xiaolong; Ding, Congcong; Liao, Jiali; Du, Liang; Sun, Qun; Yang, Jijun; Yang, Yuanyou; Zhang, Dong; Tang, Jun; Liu, Ning

2017-03-01

The microbial reduction of U(VI) by Bacillus sp. dwc-2, isolated from soil in Southwest China, was explored using transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and X-ray absorption near edge spectroscopy (XANES). Our studies indicated that approximately 16.0% of U(VI) at an initial concentration of 100mg/L uranium nitrate could be reduced by Bacillus sp. dwc-2 at pH8.2 under anaerobic conditions at room temperature. Additionally, natural organic matter (NOM) played an important role in enhancing the bioreduction of U(VI) by Bacillus sp. dwc-2. XPS results demonstrated that the uranium presented mixed valence states (U(VI) and U(IV)) after bioreduction, which was subsequently confirmed by XANES. Furthermore, the TEM and high resolution transmission electron microscopy (HRTEM) analysis suggested that the reduced uranium was bioaccumulated mainly within the cell and as a crystalline structure on the cell wall. These observations implied that the reduction of uranium may have a significant effect on its fate in the soil environment in which these bacterial strains occur. Copyright © 2016. Published by Elsevier B.V.

Damage and annealing recovery of boron-implanted ultra-shallow junction: The correlation between beam current and surface configuration

NASA Astrophysics Data System (ADS)

Chang, Feng-Ming; Wu, Zong-Zhe; Lin, Yen-Fu; Kao, Li-Chi; Wu, Cheng-Ta; JangJian, Shiu-Ko; Chen, Yuan-Nian; Lo, Kuang Yao

2018-03-01

The condition of the beam current in the implantation process is a key issue in the damage rate and structural evolution in the sequent annealing process, especially for ultra-shallow layers. In this work, we develop a compensative optical method combined with UV Raman, X-ray photoelectron spectroscopy (XPS), and X-ray absorption near edge spectroscopy (XANES) to inspect the influence of the beam current in the implantation process. The optima condition of the beam current in the implantation process is determined by higher effective Si-B bond portion in UV Raman spectra and less the peak of B-B bond in XPS spectra which is caused by B cluster defects. Results of XANES indicate that the B oxide layer is formed on the surface of the ultra-shallow junction. The defects in the ultra-shallow junction after annealing are analyzed by novel optical analyses, which cannot be inspected by a traditional thermal wave and resistance measurement. This work exhibits the structural variation of the ultra-shallow junction via a variant beam current and provides a valuable metrology in examining the chemical states and the effective activation in the implantation technology.

Phosphorus transformations in plant-based and bio-waste materials induced by pyrolysis.

PubMed

Robinson, James Stephen; Baumann, Karen; Hu, Yongfeng; Hagemann, Philipp; Kebelmann, Lutz; Leinweber, Peter

2018-01-01

Strategies are needed to increase the sustainability of phosphorus (P) fertiliser management in agriculture. This paper reports on the potential of pyrolysis treatment to recycle P from renewable materials previously regarded as wastes. The study used K-edge X-ray absorption near-edge structure (XANES) spectroscopy to examine chemical forms of P in the waste feedstock materials and corresponding biochars (pyrolysis at 480-500 °C) of four ligno-cellulosic, plant-based residues and five relatively P-rich livestock and water-treatment by-products, to acquire information on changes in potential P fertiliser value. Pyrolysis enriched P in the biochars by factors of 1.3-4.3, thus offering wide-ranging P fertiliser potential. XANES spectroscopy revealed hydroxyapatite (HAP) as one of the dominant chemical P compounds in the feedstocks, ranging from 14% (rice husks) to 98% (animal bone) of total P. For most materials, pyrolysis increased the proportion of HAP, and pyrophosphates were generated in several cases. These alterations possibly lead to diversity in the P solubility characteristics of the biochars if used as soil amendments; this is an important property of environmentally sound P fertilisers.

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

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

Sulfonates: A novel class of organic sulfur compounds in marine sediments

NASA Astrophysics Data System (ADS)

Vairavamurthy, Appathurai; Zhou, Weiqing; Eglinton, Timothy; Manowitz, Bernard

1994-11-01

X-ray absorption near-edge structure spectroscopy (XANES) used to measure sulfur speciation in a variety of organic-rich marine sediments has established sulfonates as a novel and major component of sedimentary organic sulfur. The origins of sulfonates in sediments are not clear, although both biological and geochemical mechanisms are possible. The accumulation of oxidized sulfonate sulfur in reducing marine sediments was not known previously; hence, a new perspective in sulfur geochemistry is established. The biogeochemical implications of the presence of sulfonates in marine sediments are discussed.

Ab initio modeling of nonequilibrium electron-ion dynamics of iron in the warm dense matter regime

NASA Astrophysics Data System (ADS)

Ogitsu, T.; Fernandez-Pañella, A.; Hamel, S.; Correa, A. A.; Prendergast, D.; Pemmaraju, C. D.; Ping, Y.

2018-06-01

The spatiotemporal electron and ion relaxation dynamics of iron induced by femtosecond laser pulses was studied using a one-dimensional two-temperature model (1D-TTM) where electron and ion temperature-dependent thermophysical parameters such as specific heat (C ), electron-phonon coupling (G ), and thermal conductivity (K ) were calculated with ab initio density-functional-theory (DFT) simulations. Based on the simulated time evolutions of electron and ion temperature distributions [Te(x ,t ) and Ti(x ,t ) ], the time evolution of x-ray absorption near-edge spectroscopy (XANES) was calculated and compared with experimental results reported by Fernandez-Pañella et al., where the slope of XANES spectrum at the onset of absorption (s ) was used due to its excellent sensitivity to the electron temperature. Our results indicate that the ion temperature dependence on G and C , which is largely neglected in the past studies, is very important for studying the nonequilibrium electron-ion relaxation dynamics of iron in warm dense matter (WDM) conditions. It is also shown that the 1 /s behavior becomes very sensitive to the thermal gradient profile, in other words, to the values of K in a TTM simulation, for target thickness of about two to four times the mean free path of conduction electrons. Our approach based on 1D-TTM and XANES simulations can be used to determine the optimal combination of target geometry and laser fluence for a given target material, which will enable us to tightly constrain the thermophysical parameters under electron-ion nonequilibrium WDM conditions.

Characterization of Sb-doped Bi(2)UO(6) solid solutions by X-ray diffraction and X-ray absorption spectroscopy.

PubMed

Misra, N L; Yadav, A K; Dhara, Sangita; Mishra, S K; Phatak, Rohan; Poswal, A K; Jha, S N; Sinha, A K; Bhattacharyya, D

2013-01-01

The preparation and characterization of Sb-doped Bi(2)UO(6) solid solutions, in a limited composition range, is reported for the first time. The solid solutions were prepared by solid-state reactions of Bi(2)O(3), Sb(2)O(3) and U(3)O(8) in the required stoichiometry. The reaction products were characterized by X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) measurements at the Bi and U L(3) edges. The XRD patterns indicate the precipitation of additional phases in the samples when Sb doping exceeds 4 at%. The chemical shifts of the Bi absorption edges in the samples, determined from the XANES spectra, show a systematic variation only up to 4 at% of Sb doping and support the results of XRD measurements. These observations are further supported by the local structure parameters obtained by analysis of the EXAFS spectra. The local structure of U is found to remain unchanged upon Sb doping indicating that Sb(+3) ions replace Bi(+3) during the doping of Bi(2)UO(6) by Sb.

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

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

Wu, Yun; Kukkadapu, Ravi K.; Livi, Kenneth J. T.

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 nearmore » 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 Fe(III)-(hydr)oxides plays a very important role in reducing As mobility.« less

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

NASA Astrophysics Data System (ADS)

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 < T < 350 K) magneto transport measurements were done on the Fe(Si1-xGex)2 thin films via Van Der Paw (VDP) Hall configuration using a 0.5-1T magnetic field and a current of 10-200 μA through indium ohmic contacts, the Hall coefficient was calculated. Results suggest semiconducting behavior of the films which is consistent with the EXAFS results.

Formation of Environmentally Persistent Free Radical (EPFR) in Iron(III) Cation-Exchanged Smectite Clay

PubMed Central

Nwosu, Ugwumsinachi G.; Roy, Amitava; dela Cruz, Albert Leo N.; Dellinger, Barry; Cook, Robert

2016-01-01

Environmentally persistent free radicals (EPFRs) have been found at a number of Superfund sites, with EPFRs being formed via a proposed redox process at ambient environmental conditions. The possibility of such a redox process taking place at ambient environmental conditions is studied utilizing a surrogate soil system of phenol and iron(III)-exchanged calcium montmorillonite clay, Fe(III)CaM. Sorption of phenol by the Fe(III)CaM is demonstrated by Fourier-transformed infra-red (FT-IR) spectroscopy, as evidenced by the peaks between 1345 cm−1 and 1595 cm−1, and at lower frequencies between 694 cm−1 and 806 cm−1, as well as X-ray diffraction (XRD) spectroscopy, as shown by an increase in interlayer spacing within Fe(III)CaM. The formation and characterization of the EPFRs is determined by electron paramagnetic resonance (EPR) spectroscopy, showing phenoxyl-type radical with a g-factor of 2.0034 and ΔHp-p of 6.1 G at an average concentration of 7.5 × 1017 spins/g. EPFRs lifetime data are indicative of oxygen and water molecules being responsible for EPFR decay. The change in the oxidation state of the iron redox center is studied by X-ray absorption near-edge structure (XANES) spectroscopy, showing that 23% of the Fe(III) is reduced to Fe(II). X-ray photoemission spectroscopy (XPS) results confirm the XANES results. These findings, when combined with the EPFR concentration data, demonstrate that the stoichiometry of the EPFR formation under the conditions of this study is 1.5 × 10−2 spins/Fe(II) atom. PMID:26647158

Formation of environmentally persistent free radical (EPFR) in iron(III) cation-exchanged smectite clay.

PubMed

Nwosu, Ugwumsinachi G; Roy, Amitava; dela Cruz, Albert Leo N; Dellinger, Barry; Cook, Robert

2016-01-01

Environmentally persistent free radicals (EPFRs) have been found at a number of Superfund sites, with EPFRs being formed via a proposed redox process at ambient environmental conditions. The possibility of such a redox process taking place at ambient environmental conditions is studied utilizing a surrogate soil system of phenol and iron(III)-exchanged calcium montmorillonite clay, Fe(III)CaM. Sorption of phenol by the Fe(III)CaM is demonstrated by Fourier-transformed infra-red (FT-IR) spectroscopy, as evidenced by the peaks between 1345 cm(-1) and 1595 cm(-1), and at lower frequencies between 694 cm(-1) and 806 cm(-1), as well as X-ray diffraction (XRD) spectroscopy, as shown by an increase in interlayer spacing within Fe(III)CaM. The formation and characterization of the EPFRs is determined by electron paramagnetic resonance (EPR) spectroscopy, showing phenoxyl-type radical with a g-factor of 2.0034 and ΔHP-P of 6.1 G at an average concentration of 7.5 × 10(17) spins per g. EPFRs lifetime data are indicative of oxygen and water molecules being responsible for EPFR decay. The change in the oxidation state of the iron redox center is studied by X-ray absorption near-edge structure (XANES) spectroscopy, showing that 23% of the Fe(III) is reduced to Fe(II). X-ray photoemission spectroscopy (XPS) results confirm the XANES results. These findings, when combined with the EPFR concentration data, demonstrate that the stoichiometry of the EPFR formation under the conditions of this study is 1.5 × 10(-2) spins per Fe(II) atom.

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

NASA Astrophysics Data System (ADS)

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

2013-12-01

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

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

PubMed

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

2012-01-30

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

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

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

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

2008-02-28

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

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

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

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

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

Robblee, John Henry

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

A X-Ray Absorption Study of Transition Metal Oxides

NASA Astrophysics Data System (ADS)

Bunker, Grant Byrd

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

Characterization of Sulfur Compounds in Coffee Beans by Sulfur K-XANES Spectroscopy

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

Lichtenberg, H.; Hormes, J.; Institute of Physics, University of Bonn, Nussallee 12, 53115 Bonn

2007-02-02

In this 'feasibility study' the influence of roasting on the sulfur speciation in Mexican coffee beans was investigated by sulfur K-XANES Spectroscopy. Spectra of green and slightly roasted beans could be fitted to a linear combination of 'standard' reference spectra for biological samples, whereas longer roasting obviously involves formation of additional sulfur compounds in considerable amounts.

Arsenic speciation in tissues of the hyperaccumulator P. calomelanos var. austroamericana using X-ray absorption spectroscopy.

PubMed

Kachenko, Anthony G; Gräfe, Markus; Singh, Balwant; Heald, Steve M

2010-06-15

The fate and chemical speciation of arsenic (As) during uptake, translocation, and storage by the As hyperaccumulating fern Pityrogramma calomelanos var. austroamericana (Pteridaceae) were examined using inductively coupled plasma-atomic emission spectrometry (ICP-AES) and synchrotron-based micro-X-ray absorption near edge structure (micro-XANES) and micro-X-ray fluorescence (micro-XRF) spectroscopies. Chemical analysis revealed total As concentration was ca. 6.5 times greater in young fronds (5845 mg kg(-1) dry weight (DW)) than in old fronds (903 mg kg(-1) DW). In pinnae, As concentration decreased from the base (6822 mg kg(-1) DW) to the apex (4301 mg kg(-1) DW) of the fronds. The results from micro-XANES and micro-XRF of living tissues suggested that more than 60% of arsenate (As(V)) absorbed was reduced to arsenite (As(III)) in roots, prior to transport through vascular tissues as As(V) and As(III). In pinnules, As(III) was the predominant redox species (72-90%), presumably as solvated, oxygen coordinated compounds. The presence of putative As(III)-sulphide (S(2-)) coordination throughout the fern tissues (4-25%) suggests that S(2-) functional groups may contribute in the biochemical reduction of As(V) to As(III) during uptake and transport at a whole-plant level. Organic arsenicals and thiol-rich compounds were not detected in the species and are unlikely to play a role in As hyperaccumulation in this fern. The study provides important insights into homeostatic regulation of As following As uptake in P. calomelanos var. austroamericana.

Imaging of drug loading distributions in individual microspheres of calcium silicate hydrate - an X-ray spectromicroscopy study

NASA Astrophysics Data System (ADS)

Guo, Xiaoxuan; Wang, Zhiqiang; Wu, Jin; Wang, Jian; Zhu, Ying-Jie; Sham, Tsun-Kong

2015-04-01

Imaging is one of the most direct and ideal ways to track drug loading distributions in drug carriers on the molecular level, which will facilitate the optimization of drug carriers and drug loading capacities. Herein, we report the mapping of an individual mesoporous calcium silicate hydrate (CSH) microsphere before and after the loading of ibuprofen (IBU) and the interactions between drug carriers and drug molecules simultaneously by scanning transmission X-ray microscopy (STXM). Nanoscaled X-ray absorption near edge structure (XANES) spectroscopy clearly indicates that IBU is bonded to calcium and silicate sites via carboxylic acid groups. More importantly, STXM has been successfully used to determine the absolute thickness of IBU, revealing its distribution in the CSH microsphere.Imaging is one of the most direct and ideal ways to track drug loading distributions in drug carriers on the molecular level, which will facilitate the optimization of drug carriers and drug loading capacities. Herein, we report the mapping of an individual mesoporous calcium silicate hydrate (CSH) microsphere before and after the loading of ibuprofen (IBU) and the interactions between drug carriers and drug molecules simultaneously by scanning transmission X-ray microscopy (STXM). Nanoscaled X-ray absorption near edge structure (XANES) spectroscopy clearly indicates that IBU is bonded to calcium and silicate sites via carboxylic acid groups. More importantly, STXM has been successfully used to determine the absolute thickness of IBU, revealing its distribution in the CSH microsphere. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr07471h

Spectromicroscopy of boron in human glioblastomas following administration of Na2B12H11SH.

PubMed

Gilbert, B; Perfetti, L; Fauchoux, O; Redondo, J; Baudat, P A; Andres, R; Neumann, M; Steen, S; Gabel, D; Mercanti, D; Ciotti, M T; Perfetti, P; Margaritondo, G; De Stasio, G

2000-07-01

Boron neutron capture therapy (BNCT) is an experimental, binary treatment for brain cancer which requires as the first step that tumor tissue is targeted with a boron-10 containing compound. Subsequent exposure to a thermal neutron flux results in destructive, short range nuclear reaction within 10 microm of the boron compound. The success of the therapy requires than the BNCT agents be well localized in tumor, rather than healthy tissue. The MEPHISTO spectromicroscope, which performs microchemical analysis by x-ray absorption near edge structure (XANES) spectroscopy from microscopic areas, has been used to study the distribution of trace quantities of boron in human brain cancer tissues surgically removed from patients first administered with the compound Na2B12H11SH (BSH). The interpretation of XANES spectra is complicated by interference from physiologically present sulfur and phosphorus, which contribute structure in the same energy range as boron. We addressed this problem with the present extensive set of spectra from S, B, and P in relevant compounds. We demonstrate that a linear combination of sulfate, phosphate and BSH XANES can be used to reproduce the spectra acquired on boron-treated human brain tumor tissues. We analyzed human glioblastoma tissue from two patients administered and one not administered with BSH. As well as weak signals attributed to BSH, x-ray absorption spectra acquired from tissue samples detected boron in a reduced chemical state with respect to boron in BSH. This chemical state was characterized by a sharp absorption peak at 188.3 eV. Complementary studies on BSH reference samples were not able to reproduce this chemical state of boron, indicating that it is not an artifact produced during sample preparation or x-ray exposure. These data demonstrate that the chemical state of BSH may be altered by in vivo metabolism.

Automated generation and ensemble-learned matching of X-ray absorption spectra

NASA Astrophysics Data System (ADS)

Zheng, Chen; Mathew, Kiran; Chen, Chi; Chen, Yiming; Tang, Hanmei; Dozier, Alan; Kas, Joshua J.; Vila, Fernando D.; Rehr, John J.; Piper, Louis F. J.; Persson, Kristin A.; Ong, Shyue Ping

2018-12-01

X-ray absorption spectroscopy (XAS) is a widely used materials characterization technique to determine oxidation states, coordination environment, and other local atomic structure information. Analysis of XAS relies on comparison of measured spectra to reliable reference spectra. However, existing databases of XAS spectra are highly limited both in terms of the number of reference spectra available as well as the breadth of chemistry coverage. In this work, we report the development of XASdb, a large database of computed reference XAS, and an Ensemble-Learned Spectra IdEntification (ELSIE) algorithm for the matching of spectra. XASdb currently hosts more than 800,000 K-edge X-ray absorption near-edge spectra (XANES) for over 40,000 materials from the open-science Materials Project database. We discuss a high-throughput automation framework for FEFF calculations, built on robust, rigorously benchmarked parameters. FEFF is a computer program uses a real-space Green's function approach to calculate X-ray absorption spectra. We will demonstrate that the ELSIE algorithm, which combines 33 weak "learners" comprising a set of preprocessing steps and a similarity metric, can achieve up to 84.2% accuracy in identifying the correct oxidation state and coordination environment of a test set of 19 K-edge XANES spectra encompassing a diverse range of chemistries and crystal structures. The XASdb with the ELSIE algorithm has been integrated into a web application in the Materials Project, providing an important new public resource for the analysis of XAS to all materials researchers. Finally, the ELSIE algorithm itself has been made available as part of veidt, an open source machine-learning library for materials science.

Solvation structure of the halides from x-ray absorption spectroscopy

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

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

2016-07-28

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

SUT-NANOTEC-SLRI beamline for X-ray absorption spectroscopy

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

Klysubun, Wantana; Kidkhunthod, Pinit; Tarawarakarn, Pongjakr

2017-04-04

The SUT-NANOTEC-SLRI beamline was constructed in 2012 as the flagship of the SUT-NANOTEC-SLRI Joint Research Facility for Synchrotron Utilization, co-established by Suranaree University of Technology (SUT), National Nanotechnology Center (NANOTEC) and Synchrotron Light Research Institute (SLRI). It is an intermediate-energy X-ray absorption spectroscopy (XAS) beamline at SLRI. The beamline delivers an unfocused monochromatic X-ray beam of tunable photon energy (1.25–10 keV). The maximum normal incident beam size is 13 mm (width) × 1 mm (height) with a photon flux of 3 × 10 8to 2 × 10 10 photons s -1(100 mA) -1varying across photon energies. Details of the beamlinemore » and XAS instrumentation are described. To demonstrate the beamline performance,K-edge XANES spectra of MgO, Al 2O 3, S 8, FeS, FeSO 4, Cu, Cu 2O and CuO, and EXAFS spectra of Cu and CuO are presented.« less

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

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

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

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

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

PubMed

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

2014-04-10

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

Photo-oxidative doping in π-conjugated zig-zag chain of carbon atoms with sulfur-functional group

NASA Astrophysics Data System (ADS)

Ikeura-Sekiguchi, Hiromi; Sekiguchi, Tetsuhiro

2017-12-01

Photo-oxidative doping processes were studied for the trans-polyacetylene backbone with the -SCH3 side group as a chemically representative of the precisely controlled S-functionalized zig-zag graphene nanoribbon edge. Sulfur K-edge X-ray absorption near edge structure (XANES) spectroscopy indicates that photochemical reaction of S-CH3 with atmospheric O2 forms selectively oxidized products such as -S(O)CH3 and -SO3- bound to the polyacetylene (PA) backbone. Using the correlation between the oxidation states of sulfur and the XANES peak positions, the partial charge distribution of CH3Sδ+-PAδ- has been estimated. Such positively charged sulfur atoms can attract higher electronegative oxygen atoms and expect to enhance the photooxidization capabilities. The formation of the -SO3- side group is evidently responsible for hole doping into the PA backbone. The results can provide some strategy for area-selective and controllable doping processes of atomic-scale molecular systems with the assistance of UV light.

High spin state driven magnetism and thermoelectricity in Mn doped topological insulator Bi2Se3

NASA Astrophysics Data System (ADS)

Maurya, V. K.; Dong, C. L.; Chen, C. L.; Asokan, K.; Patnaik, S.

2018-06-01

We report on the synthesis, and structural - magnetic characterizations of Mn doped Bi2Se3 towards achieving a magnetically doped topological insulator. High quality single crystals of MnxBi2-xSe3 (x = 0, 0.03, 0.05, 0.1) are grown and analysed by X-ray diffraction (XRD), Low Energy Electron Diffraction (LEED), Scanning electron microscopy (SEM), and X-ray absorption near-edge structure spectroscopy (XANES). Magnetic properties of these samples under ZFC-FC protocol and isothermal magnetization confirm ferromagnetic correlation above x = 0.03 value. XANES measurements confirm that the dopant Mn is in Mn2+ state. This is further reconfirmed to be in high spin state by fitting magnetic data with Brillouin function for J = 5/2. Both Hall and Seebeck measurements indicate a sign change of charge carriers above x = 0.03 value of Mn doping. We propose Mn doped Bi2Se3 to be a potential candidate for electromagnetic and thermoelectric device applications involving topological surface states.

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

PubMed

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

2014-12-12

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

Speciation of copper diffused in a bi-porous molecular sieve

NASA Astrophysics Data System (ADS)

Huang, C.-H.; Paul Wang, H.; Wei, Y.-L.; Chang, J.-E.

2010-07-01

To better understand diffusion of copper in the micro- and mesopores, speciation of copper in a bi-porous molecular sieve (BPMS) possessing inter-connecting 3-D micropores (0.50-0.55 nm) and 2-D mesopores (4.1 nm) has been studied by X-ray absorption near edge structure (XANES) spectroscopy. It is found that about 77% (16% of CuO nanoparticles and 61% of CuO clusters) and 23% (CuO ads) of copper can be diffused into the meso- and micropores, respectively, in the BPMS. At least two diffusion steps in the BPMS may be involved: (i) free diffusion of copper in the mesopores and (ii) diffusion-controlled copper migrating into the micropores of the BPMS. The XANES data also indicate that diffusion rate of copper in the BPMS (4.68×10 -5 g/s) is greater than that in the ZSM-5 (1.11×10 -6 g/s) or MCM-41 (1.17×10 -5 g/s).

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

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

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

2009-04-03

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

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

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

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

2009-04-30

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

Uranium association with iron-bearing phases in mill tailings from Gunnar, Canada.

PubMed

Othmane, Guillaume; Allard, Thierry; Morin, Guillaume; Sélo, Madeleine; Brest, Jessica; Llorens, Isabelle; Chen, Ning; Bargar, John R; Fayek, Mostafa; Calas, Georges

2013-11-19

The speciation of uranium was studied in the mill tailings of the Gunnar uranium mine (Saskatchewan, Canada), which operated in the 1950s and 1960s. The nature, quantification, and spatial distribution of uranium-bearing phases were investigated by chemical and mineralogical analyses, fission track mapping, electron microscopy, and X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopies at the U LIII-edge and Fe K-edge. In addition to uranium-containing phases from the ore, uranium is mostly associated with iron-bearing minerals in all tailing sites. XANES and EXAFS data and transmission electron microscopy analyses of the samples with the highest uranium concentrations (∼400-700 mg kg(-1) of U) demonstrate that uranium primarily occurs as monomeric uranyl ions (UO2(2+)), forming inner-sphere surface complexes bound to ferrihydrite (50-70% of the total U) and to a lesser extent to chlorite (30-40% of the total U). Thus, the stability and mobility of uranium at the Gunnar site are mainly influenced by sorption/desorption processes. In this context, acidic pH or alkaline pH with the presence of UO2(2+)- and/or Fe(3+)-complexing agents (e.g., carbonate) could potentially solubilize U in the tailings pore waters.

Arsenic speciation in sinter mineralization from a hydrothermal channel of El Tatio geothermal field, Chile

NASA Astrophysics Data System (ADS)

Alsina, Marco A.; Zanella, Luciana; Hoel, Cathleen; Pizarro, Gonzalo E.; Gaillard, Jean-François; Pasten, Pablo A.

2014-10-01

El Tatio geothermal field is the principal natural source of arsenic for the Loa River, the main surface water resource in the hyper-arid Atacama Desert (Antofagasta Region, Northern Chile). Prior investigations by bulk X-ray absorption spectroscopy have identified hydrous ferric oxides as the principal arsenic-containing phase in sinter material from El Tatio, suggesting sorption as the main mechanism for arsenic scavenging by the solid phases of these hot spring environments. Here we examine siliceous sinter material sampled from a hydrothermal channel using synchrotron based X-ray micro-probe techniques, including As and Fe Kα X-ray fluorescence (μ-XRF), As K-edge X-ray absorption near edge structure (μ-XANES), and X-ray diffraction (μ-XRD). Least-squares linear fitting of μ-XANES spectra shows that arsenic is predominantly present as arsenate sorbed on hydrous ferric oxides (63% molar proportion), but we also identify nodular arsenide micro-mineralizations (37% molar proportion) similar to loellingite (FeAs2), not previously detected during bulk-scale analysis of the sinter material. Presence of arsenide mineralizations indicates development of anoxic environments on the surface of the siliceous sinter, and suggests a more complex biogeochemistry for arsenic than previously observed for circum-neutral pH brine hot spring environments.

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

NASA Astrophysics Data System (ADS)

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

1981-11-01

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

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

NASA Astrophysics Data System (ADS)

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

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

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

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

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

2007-03-15

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

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

PubMed

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

2013-09-25

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

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

PubMed

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

2010-07-15

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

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

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

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

2015-10-15

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

ICE CHEMISTRY ON OUTER SOLAR SYSTEM BODIES: ELECTRON RADIOLYSIS OF N{sub 2}-, CH{sub 4}-, AND CO-CONTAINING ICES

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

Materese, Christopher K.; Cruikshank, Dale P.; Sandford, Scott A.

Radiation processing of the surface ices of outer Solar System bodies may be an important process for the production of complex chemical species. The refractory materials resulting from radiation processing of known ices are thought to impart to them a red or brown color, as perceived in the visible spectral region. In this work, we analyzed the refractory materials produced from the 1.2-keV electron bombardment of low-temperature N{sub 2}-, CH{sub 4}-, and CO-containing ices (100:1:1), which simulates the radiation from the secondary electrons produced by cosmic ray bombardment of the surface ices of Pluto. Despite starting with extremely simple icesmore » dominated by N{sub 2}, electron irradiation processing results in the production of refractory material with complex oxygen- and nitrogen-bearing organic molecules. These refractory materials were studied at room temperature using multiple analytical techniques including Fourier-transform infrared spectroscopy, X-ray absorption near-edge structure (XANES) spectroscopy, and gas chromatography coupled with mass spectrometry (GC-MS). Infrared spectra of the refractory material suggest the presence of alcohols, carboxylic acids, ketones, aldehydes, amines, and nitriles. XANES spectra of the material indicate the presence of carboxyl groups, amides, urea, and nitriles, and are thus consistent with the IR data. Atomic abundance ratios for the bulk composition of these residues from XANES analysis show that the organic residues are extremely N-rich, having ratios of N/C ∼ 0.9 and O/C ∼ 0.2. Finally, GC-MS data reveal that the residues contain urea as well as numerous carboxylic acids, some of which are of interest for prebiotic and biological chemistries.« less

Ice Chemistry on Outer Solar System Bodies: Electron Radiolysis of N2-, CH4-, and CO-Containing Ices

NASA Astrophysics Data System (ADS)

Materese, Christopher K.; Cruikshank, Dale P.; Sandford, Scott A.; Imanaka, Hiroshi; Nuevo, Michel

2015-10-01

Radiation processing of the surface ices of outer Solar System bodies may be an important process for the production of complex chemical species. The refractory materials resulting from radiation processing of known ices are thought to impart to them a red or brown color, as perceived in the visible spectral region. In this work, we analyzed the refractory materials produced from the 1.2-keV electron bombardment of low-temperature N2-, CH4-, and CO-containing ices (100:1:1), which simulates the radiation from the secondary electrons produced by cosmic ray bombardment of the surface ices of Pluto. Despite starting with extremely simple ices dominated by N2, electron irradiation processing results in the production of refractory material with complex oxygen- and nitrogen-bearing organic molecules. These refractory materials were studied at room temperature using multiple analytical techniques including Fourier-transform infrared spectroscopy, X-ray absorption near-edge structure (XANES) spectroscopy, and gas chromatography coupled with mass spectrometry (GC-MS). Infrared spectra of the refractory material suggest the presence of alcohols, carboxylic acids, ketones, aldehydes, amines, and nitriles. XANES spectra of the material indicate the presence of carboxyl groups, amides, urea, and nitriles, and are thus consistent with the IR data. Atomic abundance ratios for the bulk composition of these residues from XANES analysis show that the organic residues are extremely N-rich, having ratios of N/C ∼ 0.9 and O/C ∼ 0.2. Finally, GC-MS data reveal that the residues contain urea as well as numerous carboxylic acids, some of which are of interest for prebiotic and biological chemistries.

XAS Studies of Se Speciation in Selenite-Fed Rats

PubMed Central

Weekley, Claire M.; Aitken, Jade B.; Witting, Paul K.; Harris, Hugh H.

2014-01-01

The biological activity of selenium is dependent on its chemical form. Therefore, knowledge of Se chemistry in vivo is required for efficacious use of selenium compounds in disease prevention and treatment. Using X-ray absorption spectroscopy, Se speciation in the kidney, liver, heart, spleen, testis and red blood cells of rats fed control (~0.3 ppm Se) or selenite-supplemented (1 ppm or 5 ppm Se) diets for 3 or 6 weeks, was investigated. X-ray absorption spectroscopy revealed the presence of Se–Se and Se–C species in the kidney and liver, and Se–S species in the kidney, but not the liver. X-ray absorption near edge structure (XANES) spectra showed that there was variation in speciation in the liver and kidneys, but Se speciation was much more uniform in the remaining organs. Using principal component analysis (PCA) to interpret the Se K-edge X-ray absorption spectra, we were able to directly compare the speciation of Se in two different models of selenite metabolism – human lung cancer cells and rat tissues. The effects of Se dose, tissue type and duration of diet on selenium speciation in rat tissues were investigated, and a relationship between the duration of the diet (3 weeks versus 6 weeks) and selenium speciation was observed. PMID:25363824

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

NASA Astrophysics Data System (ADS)

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

2018-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2017-01-01

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

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

DOE PAGES

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

2016-01-28

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

Synthesis of nanocrystalline NiO/ZnO heterostructured composite powders by sol-gel auto combustion method and their characterizations

NASA Astrophysics Data System (ADS)

Tangcharoen, Thanit; Klysubun, Wantana; Kongmark, Chanapa

2018-03-01

Nanocrystalline NiO/ZnO heterostructured composite powders were prepared by the sol-gel auto combustion method, based on nickel and zinc nitrate precursors and using diethanolamine (DEA) as novel fuel. The composition of different NiO and ZnO ratios, ranging from 100/0, 95/5, 90/10, 80/20, 60/40, 50/50, 40/60, 20/80, 10/90, 5/95 to 0/100, were studied. The structural, chemical bonding, morphological, optical, and fluorescence properties including the local atomic structure of each calcined sample were systematically investigated by means of X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), UV-visible diffuse reflectance spectroscopy (UV-DRS), photoluminescence (PL) spectroscopy, and synchrotron X-ray absorption spectroscopy (XAS), respectively. For the ZnO concentration below 20%, both XRD and Raman spectroscopy results revealed only the NiO phase. This conformed to the observation of Zn K-edge and Ni K-edge X-ray absorption near edge structure (XANES). The Zn ions found in the samples of low ZnO concentration exhibited six-fold coordination with oxygen atoms rather than the four-fold coordination found in the wurtzite (WZ) structure of ZnO. In contrast, the Ni ions which are found in the samples of low NiO concentration (≤10%) are coordinated both tetrahedrally and octahedrally by four or six oxygen atoms, respectively, rather than the six-fold coordination which is usually observed for Ni ions in the rock salt (RS) form of NiO. All analytical results obtained from experimental XANES spectra were verified by the theoretical calculation of absorption spectra using the FEFF9.7 code. The UV-DRS results showed that there was an increase in the reflectance efficiency for both infrared and visible light conditions as the content of ZnO increases; meanwhile, the values for the energy gap (Eg) of all composite samples were higher than that of pure NiO and ZnO. In addition, the PL spectra revealed major blue emission bands observed at 490 nm when the excitation wavelength was 300 nm. As the ZnO phase developed, a variety of violet emission bands occurred within the range of 400 nm-450 nm, which was obviously related to the change in Eg. The intrinsic defects occurred in the NiO/ZnO composite powders were probably responsible for this phenomenon.

Studies on absorption coefficient near edge of multi elements

NASA Astrophysics Data System (ADS)

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

2005-12-01

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

Hydrogen-induced structural changes at the nickel site of the regulatory [NiFe] hydrogenase from Ralstonia eutropha detected by X-ray absorption spectroscopy.

PubMed

Haumann, Michael; Porthun, Antje; Buhrke, Thorsten; Liebisch, Peter; Meyer-Klaucke, Wolfram; Friedrich, Bärbel; Dau, Holger

2003-09-23

For the first time, the nickel site of the hydrogen sensor of Ralstonia eutropha, the regulatory [NiFe] hydrogenase (RH), was investigated by X-ray absorption spectroscopy (XAS) at the nickel K-edge. The oxidation state and the atomic structure of the Ni site were investigated in the RH in the absence (air-oxidized, RH(ox)) and presence of hydrogen (RH(+H2)). Incubation with hydrogen is found to cause remarkable changes in the spectroscopic properties. The Ni-C EPR signal, indicative of Ni(III), is detectable only in the RH(+H2) state. XANES and EXAFS spectra indicate a coordination of the Ni in the RH(ox) and RH(+H2) that pronouncedly differs from the one in standard [NiFe] hydrogenases. Also, the changes induced by exposure to H(2) are unique. A drastic modification in the XANES spectra and an upshift of the K-edge energy from 8339.8 (RH(ox)) to 8341.1 eV (RH(+H2)) is observed. The EXAFS spectra indicate a change in the Ni coordination in the RH upon exposure to H(2). One likely interpretation of the data is the detachment of one sulfur ligand in RH(+H2) and the binding of additional (O,N) or H ligands. The following Ni oxidation states and coordinations are proposed: five-coordinated Ni(II)(O,N)(2)S(3) for RH(ox) and six-coordinated Ni((III))(O,N)(3)X(1)S(2) [X being either an (O,N) or H ligand] for RH(+H2). Implications of the structural features of the Ni site of the RH in relation to its function, hydrogen sensing, are discussed.

Acetate- and thiol-capped monodisperse ruthenium nanoparticles: XPS, XAS, and HRTEM studies.

PubMed

Chakroune, Nassira; Viau, Guillaume; Ammar, Souad; Poul, Laurence; Veautier, Delphine; Chehimi, Mohamed M; Mangeney, Claire; Villain, Françoise; Fiévet, Fernand

2005-07-19

Monodisperse ruthenium nanoparticles were prepared by reduction of RuCl3 in 1,2-propanediol. The mean particle size was controlled by appropriate choice of the reduction temperature and the acetate ion concentration. Colloidal solutions in toluene were obtained by coating the metal particles with dodecanethiol. High-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), and X-ray absorption spectroscopy (XANES and EXAFS for the Ru K-absorption edge) were performed on particles of two different diameters, 2 and 4 nm, and in different environments, polyol/acetate or thiol. For particles stored in polyol/acetate XPS studies revealed superficial oxidation limited to one monolayer and a surface coating containing mostly acetate ions. Analysis of the EXAFS spectra showed both oxygen and ruthenium atoms around the ruthenium atoms with a Ru-Ru coordination number N smaller than the bulk value, as expected for fine particles. In the case of 2 nm acetate-capped particles N is consistent with particles made up of a metallic core and an oxidized monolayer. For 2 nm thiol-coated particles, a Ru-S bond was evidenced by XPS and XAS. For the 4 nm particles XANES and XPS studies showed that most of the ruthenium atoms are in the zerovalent state. Nevertheless, in both cases, when capped with thiol, the Ru-Ru coordination number inferred from EXAFS is much smaller than for particles of the same size stored in polyol. This is attributed to a structural disorganization of the particles by thiol chemisorption. HRTEM studies confirm the marked dependence of the structural properties of the ruthenium particles on their chemical environment; they show the acetate-coated particles to be single crystals, whereas the thiol-coated particles appear to be polycrystalline.

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

PubMed

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

2014-11-10

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

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

PubMed Central

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

2014-01-01

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

Probing the Electronic Structure of - and Electron-Doped High-Temperature Superconductors with Photoemission and X-Ray Absorption Spectroscopies

NASA Astrophysics Data System (ADS)

Lederman, Eli R.

1990-01-01

The electronic structures of hole- and electron -doped high temperature superconductors have been probed using x-ray absorption near-edge spectroscopy (XANES) and photoelectron emission spectroscopy (PES). These measurements have been performed on RBa_2Cu _3O_{rm 7-y} , La_{rm 2-x}Sr _{rm x}CuO _4 and Ln_{rm 2 -x}Ce_{rm x} CuO_{rm 4} for R = Y, Eu and Ln = Nd, Pr and Sm. The parameters x and y have been varied to include a range of hole and electron carrier densities and the undoped parent compounds. Previous XANES and PES results have indicated that unoccupied states of O 2p character can be associated with the carriers in the materials RBa_2 Cu_3O_{ rm 7-y} and La_{ rm 2-x}Sr_{rm x}CuO_4 and that the density of holes increases with O and Sr content, respectively. Conduction was hole-based in all known high-T_{ rm c} cuprates until the recent discovery of superconductivity in Ln_{rm 2-x}Ce_{rm x} CuO_4. Hall coefficient measurements have suggested that the carriers in this system are electrons added with Ce doping. It has been anticipated that these electron-doped materials will provide an important test for models of high temperature superconductivity. PES measurements are presented that show significant Cu 3d character in the valence band of these electron-based materials, but that the Cu^{2+} /Cu^{1+} ratio is unchanged by the level of Ce doping, indicating that doped electrons are itinerant rather than highly correlated. Resonant photoemission from the valence band indicates the presence of unoccupied O 2p states, but these holes are less abundant than in the hole-doped materials. Measurements of XANES at the O 1s edge suggest that unoccupied states of O 2p character in the electron -doped materials are not related to conduction in a simple way. The density of these holes is shown to decrease upon Ce doping and the process of reduction, despite the fact that both are necessary of superconductivity. Furthermore, whereas the O 2p holes are at E_{rm F} in the hole-doped materials, they are ~1 eV above E_{ rm F} in their electron-doped counterparts. A schematic of the band structure is proposed on the basis of these spectroscopic measurements.

Coupling MD Simulations and X-ray Absorption Spectroscopy to Study Ions in Solution

NASA Astrophysics Data System (ADS)

Marcos, E. Sánchez; Beret, E. C.; Martínez, J. M.; Pappalardo, R. R.; Ayala, R.; Muñoz-Páez, A.

2007-12-01

The structure of ionic solutions is a key-point in understanding physicochemical properties of electrolyte solutions. Among the reduced number of experimental techniques which can supply direct information on the ion environment, X-ray Absorption techniques (XAS) have gained importance during the last decades although they are not free of difficulties associated to the data analysis leading to provide reliable structures. Computer simulations of ions in solution is a theoretical alternative to provide information on the solvation structure. Thus, the use of computational chemistry can increase the understanding of these systems although an accurate description of ionic solvation phenomena represents nowadays a significant challenge to theoretical chemistry. We present: (a) the assignment of features in the XANES spectrum to well defined structural motif in the ion environment, (b) MD-based evaluation of EXAFS parameters used in the fitting procedure to make easier the structural resolution, and (c) the use of the agreement between experimental and simulated XANES spectra to help in the choice of a given intermolecular potential for Computer Simulations. Chemical problems examined are: (a) the identification of the second hydration shell in dilute aqueous solutions of highly-charged cations, such as Cr3+, Rh3+, Ir3+, (b) the invisibility by XAS of certain structures characterized by Computer Simulations but exhibiting high dynamical behavior and (c) the solvation of Br- in acetonitrile.

Coupling MD Simulations and X-ray Absorption Spectroscopy to Study Ions in Solution

NASA Astrophysics Data System (ADS)

Marcos, E. Sánchez; Beret, E. C.; Martínez, J. M.; Pappalardo, R. R.; Ayala, R.; Muñoz-Páez, A.

2007-11-01

The structure of ionic solutions is a key-point in understanding physicochemical properties of electrolyte solutions. Among the reduced number of experimental techniques which can supply direct information on the ion environment, X-ray Absorption techniques (XAS) have gained importance during the last decades although they are not free of difficulties associated to the data analysis leading to provide reliable structures. Computer simulations of ions in solution is a theoretical alternative to provide information on the solvation structure. Thus, the use of computational chemistry can increase the understanding of these systems although an accurate description of ionic solvation phenomena represents nowadays a significant challenge to theoretical chemistry. We present: (a) the assignment of features in the XANES spectrum to well defined structural motif in the ion environment, (b) MD-based evaluation of EXAFS parameters used in the fitting procedure to make easier the structural resolution, and (c) the use of the agreement between experimental and simulated XANES spectra to help in the choice of a given intermolecular potential for Computer Simulations. Chemical problems examined are: (a) the identification of the second hydration shell in dilute aqueous solutions of highly-charged cations, such as Cr3+, Rh3+, Ir3+, (b) the invisibility by XAS of certain structures characterized by Computer Simulations but exhibiting high dynamical behavior and (c) the solvation of Br- in acetonitrile.

Microwave-assisted synthesis of water-soluble, fluorescent gold nanoclusters capped with small organic molecules and a revealing fluorescence and X-ray absorption study

NASA Astrophysics Data System (ADS)

Helmbrecht, C.; Lützenkirchen-Hecht, D.; Frank, W.

2015-03-01

Colourless solutions of blue light-emitting, water-soluble gold nanoclusters (AuNC) were synthesized from gold colloids under microwave irradiation using small organic molecules as ligands. Stabilized by 1,3,5-triaza-7-phosphaadamantane (TPA) or l-glutamine (GLU), fluorescence quantum yields up to 5% were obtained. AuNC are considered to be very promising for biological labelling, optoelectronic devices and light-emitting materials but the structure-property relationships have still not been fully clarified. To expand the knowledge about the AuNC apart from their fluorescent properties they were studied by X-ray absorption spectroscopy elucidating the oxidation state of the nanoclusters' gold atoms. Based on curve fitting of the XANES spectra in comparison to several gold references, optically transparent fluorescent AuNC are predicted to be ligand-stabilized Au5+ species. Additionally, their near edge structure compared with analogous results of polynuclear clusters known from the literature discloses an increasing intensity of the feature close to the absorption edge with decreasing cluster size. As a result, a linear relationship between the cluster size and the X-ray absorption coefficient can be established for the first time.Colourless solutions of blue light-emitting, water-soluble gold nanoclusters (AuNC) were synthesized from gold colloids under microwave irradiation using small organic molecules as ligands. Stabilized by 1,3,5-triaza-7-phosphaadamantane (TPA) or l-glutamine (GLU), fluorescence quantum yields up to 5% were obtained. AuNC are considered to be very promising for biological labelling, optoelectronic devices and light-emitting materials but the structure-property relationships have still not been fully clarified. To expand the knowledge about the AuNC apart from their fluorescent properties they were studied by X-ray absorption spectroscopy elucidating the oxidation state of the nanoclusters' gold atoms. Based on curve fitting of the XANES spectra in comparison to several gold references, optically transparent fluorescent AuNC are predicted to be ligand-stabilized Au5+ species. Additionally, their near edge structure compared with analogous results of polynuclear clusters known from the literature discloses an increasing intensity of the feature close to the absorption edge with decreasing cluster size. As a result, a linear relationship between the cluster size and the X-ray absorption coefficient can be established for the first time. Electronic supplementary information (ESI) available: The deconvoluted reference spectra are given in ESI Fig. 1-9. See DOI: 10.1039/c4nr07051h

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

PubMed

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

2016-02-03

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

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

DOE PAGES

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

2017-01-26

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

Ground-state wave function of plutonium in PuSb as determined via x-ray magnetic circular dichroism

DOE PAGES

Janoschek, M.; Haskel, D.; Fernandez-Rodriguez, J.; ...

2015-01-14

Measurements of x-ray magnetic circular dichroism (XMCD) and x-ray absorption near-edge structure (XANES) spectroscopy at the Pu M₄,₅ edges of the ferromagnet PuSb are reported. Using bulk magnetization measurements and a sum rule analysis of the XMCD spectra, we determine the individual orbital [μ L = 2.8(1)μ B/Pu] and spin moments [μ S = –2.0(1)μ B/Pu] of the Pu 5f electrons for the first time. Atomic multiplet calculations of the XMCD and XANES spectra reproduce well the experimental data and are consistent with the experimental value of the spin moment. These measurements of L z and S z are inmore » excellent agreement with the values that have been extracted from neutron magnetic form factor measurements, and confirm the local character of the 5f electrons in PuSb. We demonstrate that a split M₅ as well as a narrow M₄ XMCD signal may serve as a signature of 5f electron localization in actinide compounds.« less

XANES study of elemental mercury oxidation over RuO 2/TiO 2 and selective catalytic reduction catalysts for mercury emissions control

DOE PAGES

Liu, Zhouyang; Li, Can; Sriram, Vishnu; ...

2016-07-25

Linear combination fitting of the X-ray Absorption Near Edge Spectroscopy (XANES) was used to quantify oxidized mercury species over RuO 2/TiO 2 and Selective Catalytic Reduction (SCR) catalysts under different simulated flue gas conditions. Halogen gases play a major role in mercury oxidation. In the absence of halogen gas, elemental mercury can react with sulfur that is contained in both the RuO2/TiO2 and SCR catalysts to form HgS and HgSO 4. In the presence of HCl or HBr gas, HgCl 2 or HgBr 2 is the main oxidized mercury species. When both HCl and HBr gases are present, HgBr2 ismore » the preferred oxidation product and no HgCl 2 can be found. The formation of HgO and HgS cannot be neglected with or without halogen gas. Other simulated flue gas components such as NO, NH 3, SO 2 and CO 2 do not have significant effect on oxidized mercury speciation when halogen gas is present.« less

Mobility of rare earth elements in mine drainage: Influence of iron oxides, carbonates, and phosphates.

PubMed

Edahbi, Mohamed; Plante, Benoît; Benzaazoua, Mostafa; Ward, Matthew; Pelletier, Mia

2018-05-01

The geochemical behavior of rare earth elements (REE) was investigated using weathering cells. The influence of sorption and precipitation on dissolved REE mobility and fractionation is evaluated using synthetic iron-oxides, carbonates, and phosphates. Sorption cell tests are conducted on the main lithologies of the expected waste rocks from the Montviel deposit. The sorbed materials are characterized using a scanning electron microscope (SEM) equipped with a microanalysis system (energy dispersive spectroscopy EDS) (SEM-EDS), X-ray diffraction (XRD), and X-ray absorption near edge structure (XANES) in order to understand the effect of the synthetic minerals on REE mobility. The results confirm that sorption and precipitation control the mobility and fractionation of REE. The main sorbent phases are the carbonates, phosphates (present as accessory minerals in the Montviel waste rocks), and iron oxides (main secondary minerals generated upon weathering of the Montviel lithologies). The XANES results show that REE are present as trivalent species after weathering. Thermodynamic equilibrium calculations results using Visual Minteq suggest that REE could precipitate as secondary phosphates (REEPO 4 ). Copyright © 2018 Elsevier Ltd. All rights reserved.

Problems with the thermogravimetric determination of oxygen stoichiometries in pure and rare-earth substituted La2RuO5

NASA Astrophysics Data System (ADS)

Riegg, S.; Müller, T.; Ebbinghaus, S. G.

2013-06-01

The oxygen stoichiometries of pure and rare-earth substituted La2RuO5 have been investigated by thermogravimetry (TG) in reducing atmosphere. Assuming that the observed total weight loss is caused by the reduction of Ru4+ to Ru-metal, remarkable oxygen deficiencies were calculated. These would correspond to ruthenium oxidation states significantly lower than the ones experimentally observed by XANES. To explain this discrepancy we investigated the reduction products by X-ray absorption spectroscopy (XAS). EXAFS measurements at the Ru-K edge revealed the presence of an X-ray amorphous ruthenium oxide, indicating an incomplete reduction. The apparent oxygen deficiencies obtained for pure and rare-earth substituted samples correlate with the amount of remaining ruthenium oxide. The presence of a ruthenium oxide species was furthermore verified by Ru-LIII XANES investigations. Our results show that the determination of oxygen contents by thermogravimetry might fail even for the easily reducable nobel metal oxides and therefore has to be applied with caution if the reaction products cannot be identified unambiguously.

Comparison of the Organic Composition of Cometary Samples with Residues Formed from the UV Irradiation of Astrophysical Ice Analogs

NASA Technical Reports Server (NTRS)

Milam, S. N.; Nuevo, M.; Sandford, S. A.; Cody, G. D.; Kilcoyne, A. L. D.; Stroud, R. M.; DeGregorio, B. T.

2010-01-01

The NASA Stardust mission successfully collected material from Comet 81P/Wild 2 [1], including authentic cometary grains [2]. X-ray absorption near-edge structure (XANES) spectroscopy analysis of these samples indicates the presence of oxygen-rich and nitrogen-rich organic materials, which contain a broad variety of functional groups (carbonyls, C=C bonds, aliphatic chains, amines, arnides, etc.) [3]. One component of these organics appears to contain very little aromatic carbon and bears some similarity to the organic residues produced by the irradiation of ices of interstellar/cometary composition, Stardust samples were also recently shown to contain glycine, the smallest biological amino acid [4]. Organic residues produced froth the UV irradiation of astrophysical ice analogs are already known to contain a large suite of organic molecules including amino acids [5-7], amphiphilic compounds (fatty acids) [8], and other complex species. This work presents a comparison between XANES spectra measured from organic residues formed in the laboratory with similar data of cometary samples collected by the Stardust mission

Multiconfigurational nature of 5f orbitals in uranium and plutonium intermetallics

PubMed Central

Booth, C.H.; Jiang, Yu; Wang, D.L.; Mitchell, J.N.; Tobash, P.H.; Bauer, E.D.; Wall, M.A.; Allen, P.G.; Sokaras, D.; Nordlund, D.; Weng, T.-C.; Torrez, M.A.; Sarrao, J.L.

2012-01-01

Uranium and plutonium’s 5f electrons are tenuously poised between strongly bonding with ligand spd-states and residing close to the nucleus. The unusual properties of these elements and their compounds (e.g., the six different allotropes of elemental plutonium) are widely believed to depend on the related attributes of f-orbital occupancy and delocalization for which a quantitative measure is lacking. By employing resonant X-ray emission spectroscopy (RXES) and X-ray absorption near-edge structure (XANES) spectroscopy and making comparisons to specific heat measurements, we demonstrate the presence of multiconfigurational f-orbital states in the actinide elements U and Pu and in a wide range of uranium and plutonium intermetallic compounds. These results provide a robust experimental basis for a new framework toward understanding the strongly-correlated behavior of actinide materials. PMID:22706643

Rapid Mapping of Lithiation Dynamics in Transition Metal Oxide Particles with Operando X-ray Absorption Spectroscopy.

PubMed

Nowack, Lea; Grolimund, Daniel; Samson, Vallerie; Marone, Federica; Wood, Vanessa

2016-02-24

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.

Rapid Mapping of Lithiation Dynamics in Transition Metal Oxide Particles with Operando X-ray Absorption Spectroscopy

PubMed Central

Nowack, Lea; Grolimund, Daniel; Samson, Vallerie; Marone, Federica; Wood, Vanessa

2016-01-01

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. PMID:26908198

Rapid Mapping of Lithiation Dynamics in Transition Metal Oxide Particles with Operando X-ray Absorption Spectroscopy

NASA Astrophysics Data System (ADS)

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.

Structural reconstruction of the catalytic center of LiPDF through multiple scattering calculation with MXAN

NASA Astrophysics Data System (ADS)

Guo, Xiaoyun; Chu, Wangsheng; Ma, Sixuan; Gong, Weimin; Benfatto, Maurizio; Hu, Tiandou; Xie, Yaning; Wu, ZiYu

2006-11-01

Peptide deformylase (PDF, EC 3.5.1.27) is essential for the normal growth of eubacterium but not for mammalians. Recently, PDF has been studied as a target for new antibiotics. In this paper, X-ray absorption spectroscopy was employed to determine the local structure around the zinc ion of PDF from Leptospira Interrogans in dry powder, because it is very difficult to obtain the crystallized sample of LiPDF. We performed X-ray absorption near edge structure (XANES) calculation and reconstructed successfully the local geometry of the active center, and the results from calculations show that a water molecule (Wat1) has moved towards the zinc ion and lies in the distance range to coordinate with the zinc ion weakly. In addition, the sensitivity of theoretical spectra to the different ligand bodies was evaluated in terms of goodness-of-fit.

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

NASA Astrophysics Data System (ADS)

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

2018-06-01

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

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

NASA Astrophysics Data System (ADS)

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

2013-04-01

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

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

PubMed

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

2014-05-01

Uranium speciation and retention mechanisms onto Savannah River Site (SRS) wetland sediments was studied using batch (ad)sorption experiments, sequential extraction, U L3-edge X-ray absorption near-edge structure (XANES) spectroscopy, fluorescence mapping and μ-XANES. Under oxidized conditions, U was highly retained by the SRS wetland sediments. In contrast to other similar but much lower natural organic matter (NOM) sediments, significant sorption of U onto the SRS sediments was observed at pH < 4 and pH > 8. Sequential extraction indicated that the U species were primarily associated with the acid soluble fraction (weak acetic acid extractable) and organic fraction (Na-pyrophosphate extractable). Uranium L3-edge XANES spectra of the U-bound sediments were nearly identical to that of uranyl acetate. Based on fluorescence mapping, U and Fe distributions in the sediment were poorly correlated, U was distributed throughout the sample and did not appear as isolated U mineral phases. The primary oxidation state of U in these oxidized sediments was U(VI), and there was little evidence that the high sorptive capacity of the sediments could be ascribed to abiotic or biotic reduction to the less soluble U(IV) species or to secondary mineral formation. Collectively, this study suggests that U may be strongly bound to wetland sediments, not only under reducing conditions by reductive precipitation, but also under oxidizing conditions through NOM-uranium bonding. Published by Elsevier Ltd.

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

NASA Astrophysics Data System (ADS)

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

2017-10-01

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

Cold crucible induction melter test for crystalline ceramic waste form fabrication: A feasibility assessment

DOE PAGES

Amoroso, Jake W.; Marra, James; Dandeneau, Christopher S.; ...

2017-01-18

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. We identified primary hollandite,more » pyrochlore/zirconolite, and perovskite phases 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.« less

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

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

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

2014-06-24

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

Characterization of a transient +2 sulfur oxidation state intermediate from the oxidation of aqueous sulfide

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

Vairavmurthy, M.A.; Zhou, Weiqing

1995-04-01

The oxidation H{sub 2}S to sulfate involves a net transfer of eight electrons and occurs through the formation of several partially oxidized intermediates with oxidation states ranging from {minus}1 to +5. Known intermediates include elemental sulfur (oxidation state 0), polysulfides (outer sulfur: {minus}1, inner sulfur: 0), sulfite (+4) and thiosulfate (outer sulfur: {minus}1, inner sulfur: +5). A noticeable gap in this series of intermediates is that of a +2 sulfur oxidation state oxoacid/oxoanion species, which was never detected experimentally. Here, we present evidence of the transient existence of +2 oxidation state intermediate in the Ni(II)-catalyzed oxidation of aqueous sulfide. X-raymore » absorption near-edge structure (XANES) spectroscopy and Fourier-transform-infrared (FT-IR) spectroscopy were used to characterize this species; they suggest that it has a sulfoxylate ion (SO{sub 2}{sup 2{minus}}) structure.« less

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

PubMed

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

2009-04-08

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

Reactivity of Chromium(III) Nutritional Supplements in Biological Media: An X-Ray Absorption Spectroscopic Study

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

Nguyen, A.; Mulyani, I.; Levina, A.

2009-05-22

Chromium(III) nutritional supplements are widely used due to their purported ability to enhance glucose metabolism, despite growing evidence on low activity and the potential genotoxicity of these compounds. Reactivities of Cr(III) complexes used in nutritional formulations, including [Cr3O(OCOEt)6(OH2)3]+ (A), [Cr(pic)3] (pic) = 2-pyridinecarboxylato(-) (B), and trans-[CrCl2(OH2)4]+ (CrCl3 {center_dot} 6H2O; C), in a range of natural and simulated biological media (artificial digestion systems, blood and its components, cell culture media, and intact L6 rat skeletal muscle cells) were studied by X-ray absorption near-edge structure (XANES) spectroscopy. The XANES spectroscopic data were processed by multiple linear-regression analyses with the use of amore » library of model Cr(III) compounds, and the results were corroborated by the results of X-ray absorption fine structure spectroscopy and electrospray mass spectrometry. Complexes A and B underwent extensive ligand-exchange reactions under conditions of combined gastric and intestinal digestion (in the presence of a semisynthetic meal, 3 h at 310 K), as well as in blood serum and in a cell culture medium (1-24 h at 310 K), with the formation of Cr(III) complexes with hydroxo and amino acid/protein ligands. Reactions of compounds A-C with cultured muscle cells led to similar ligand-exchange products, with at least part of Cr(III) bound to the surface of the cells. The reactions of B with serum greatly enhanced its propensity to be converted to Cr(VI) by biological oxidants (H2O2 or glucose oxidase system), which is proposed to be a major cause of both the insulin-enhancing activity and toxicity of Cr(III) compounds (Mulyani, I.; Levina, A.; Lay, P. A. Angew. Chem. Int. Ed. 2004, 43, 4504-4507). This finding enhances the current concern over the safety of consumption of large doses of Cr(III) supplements, particularly [Cr(pic)3].« less

Characterizing phosphorus speciation of Chesapeake Bay sediments using chemical extraction, 31P NMR, and X-ray absorption fine structure spectroscopy.

PubMed

Li, Wei; Joshi, Sunendra R; Hou, Guangjin; Burdige, David J; Sparks, Donald L; Jaisi, Deb P

2015-01-06

Nutrient contamination has been one of the lingering issues in the Chesapeake Bay because the bay restoration is complicated by temporally and seasonally variable nutrient sources and complex interaction between imported and regenerated nutrients. Differential reactivity of sedimentary phosphorus (P) pools in response to imposed biogeochemical conditions can record past sediment history and therefore a detailed sediment P speciation may provide information on P cycling particularly the stability of a P pool and the formation of one pool at the expense of another. This study examined sediment P speciation from three sites in the Chesapeake Bay: (i) a North site in the upstream bay, (ii) a middle site in the central bay dominated by seasonally hypoxic bottom water, and (iii) a South site at the bay-ocean boundary using a combination of sequential P extraction (SEDEX) and spectroscopic techniques, including (31)P NMR, P X-ray absorption near edge structure spectroscopy (XANES), and Fe extended X-ray absorption fine structure (EXAFS). Results from sequential P extraction reveal that sediment P is composed predominantly of ferric Fe-bound P and authigenic P, which was further confirmed by solid-state (31)P NMR, XANES, and EXAFS analyses. Additionally, solution (31)P NMR results show that the sediments from the middle site contain high amounts of organic P such as monoesters and diesters, compared to the other two sites, but that these compounds rapidly decrease with sediment depth indicating remineralized P could have precipitated as authigenic P. Fe EXAFS enabled to identify the changes in Fe mineral composition and P sinks in response to imposed redox condition in the middle site sediments. The presence of lepidocrocite, vermiculite, and Fe smectite in the middle site sediments indicates that some ferric Fe minerals can still be present along with pyrite and vivianite, and that ferric Fe-bound P pool can be a major P sink in anoxic sediments. These results provide improved insights into sediment P dynamics, particularly the rapid remineralization of organic P and the stability of Fe minerals and the ferric Fe-bound P pool in anoxic sediments in the Chesapeake Bay.

Optically detected X-ray absorption spectroscopy measurements as a means of monitoring corrosion layers on copper.

PubMed

Dowsett, Mark G; Adriaens, Annemie; Jones, Gareth K C; Poolton, Nigel; Fiddy, Steven; Nikitenko, Sergé

2008-11-15

XANES and EXAFS information is conventionally measured in transmission through the energy-dependent absorption of X-rays or by observing X-ray fluorescence, but secondary fluorescence processes, such as the emission of electrons and optical photons (e.g., 200-1000 nm), can also be used as a carrier of the XAS signatures, providing complementary information such as improved surface specificity. Where the near-visible photons have a shorter range in a material, the data will be more surface specific. Moreover, optical radiation may escape more readily than X-rays through liquid in an environmental cell. Here, we describe a first test of optically detected X-ray absorption spectroscopy (ODXAS) for monitoring electrochemical treatments on copper-based alloys, for example, heritage metals. Artificially made corrosion products deposited on a copper substrate were analyzed in air and in a 1% (w/v) sodium sesquicarbonate solution to simulate typical conservation methods for copper-based objects recovered from marine environments. The measurements were made on stations 7.1 and 9.2 MF (SRS Daresbury, UK) using the mobile luminescence end station (MoLES), supplemented by XAS measurements taken on DUBBLE (BM26 A) at the ESRF. The ODXAS spectra usually contain fine structure similar to that of XAS spectra measured in X-ray fluorescence. Importantly, for the compounds examined, the ODXAS is significantly more surface specific, and >98% characteristic of thin surface layers of 0.5-1.5-microm thickness in cases where X-ray measurements are dominated by the substrate. However, EXAFS and XANES from broadband optical measurements are superimposed on a high background due to other optical emission modes. This produces statistical fluctuations up to double what would be expected from normal counting statistics because the data retain the absolute statistical fluctuation in the original raw count, while losing up to 70% of their magnitude when background is removed. The problem may be solved in future through optical filtering to isolate the information-containing band, combined with the use of higher input X-ray fluxes available on third-generation light sources.

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

Frankaer, Christian Grundahl; Mossin, Susanne; Ståhl, Kenny

The level of structural detail around the metal sites in Ni{sup 2+} and Cu{sup 2+} T{sub 6} insulin derivatives was significantly improved by using a combination of single-crystal X-ray crystallography and X-ray absorption spectroscopy. Photoreduction and subsequent radiation damage of the Cu{sup 2+} sites in Cu insulin was followed by XANES spectroscopy. Using synchrotron radiation (SR), the crystal structures of T{sub 6} bovine insulin complexed with Ni{sup 2+} and Cu{sup 2+} were solved to 1.50 and 1.45 Å resolution, respectively. The level of detail around the metal centres in these structures was highly limited, and the coordination of water inmore » Cu site II of the copper insulin derivative was deteriorated as a consequence of radiation damage. To provide more detail, X-ray absorption spectroscopy (XAS) was used to improve the information level about metal coordination in each derivative. The nickel derivative contains hexacoordinated Ni{sup 2+} with trigonal symmetry, whereas the copper derivative contains tetragonally distorted hexacoordinated Cu{sup 2+} as a result of the Jahn–Teller effect, with a significantly longer coordination distance for one of the three water molecules in the coordination sphere. That the copper centre is of type II was further confirmed by electron paramagnetic resonance (EPR). The coordination distances were refined from EXAFS with standard deviations within 0.01 Å. The insulin derivative containing Cu{sup 2+} is sensitive towards photoreduction when exposed to SR. During the reduction of Cu{sup 2+} to Cu{sup +}, the coordination geometry of copper changes towards lower coordination numbers. Primary damage, i.e. photoreduction, was followed directly by XANES as a function of radiation dose, while secondary damage in the form of structural changes around the Cu atoms after exposure to different radiation doses was studied by crystallography using a laboratory diffractometer. Protection against photoreduction and subsequent radiation damage was carried out by solid embedment of Cu insulin in a saccharose matrix. At 100 K the photoreduction was suppressed by ∼15%, and it was suppressed by a further ∼30% on cooling the samples to 20 K.« less

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

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

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

2016-07-28

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

Ligand-tailored single-site silica supported titanium catalysts: Synthesis, characterization and towards cyanosilylation reaction

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

Xu, Wei; Li, Yani; Yu, Bo

2015-01-15

A successive anchoring of Ti(NMe{sub 2}){sub 4}, cyclopentadiene and a O-donor ligand, 1-hydroxyethylbenzene (PEA), 1,1′-bi-2-naphthol (Binol) or 2,3-dihydroxybutanedioic acid diethyl ester (Tartrate), on silica was conducted by SOMC strategy in moderate conditions. The silica, monitored by in-situ Fourier transform infrared spectroscopy (in-situ FT-IR), was pretreated at different temperatures (200, 500 and 800 °C). The ligand tailored silica-supported titanium complexes were characterized by in-situ FT-IR, {sup 13}C CP MAS-NMR, X-ray photoelectron spectroscopy (XPS), X-ray absorption near edge structure (XANES) and elemental analysis in detail, verifying that the surface titanium species are single sited. The catalytic activity of the ligand tailored single-sitemore » silica supported titanium complexes was evaluated by a cyanosilylation of benzaldehyde. The results showed that the catalytic activity is dependent strongly on the dehydroxylation temperatures of silica and the configuration of the ligands. - Graphical abstract: The ligand-tailored silica supported “single site” titanium complexes were synthesized by SOMC strategy and fully characterized. Their catalytic activity were evaluated by benzaldehyde silylcyanation. - Highlights: • Single-site silica supported Ti active species was prepared by SOMC technique. • O-donor ligand tailored Ti surface species was synthesized. • The surface species was characterized by XPS, {sup 13}C CP-MAS NMR, XANES etc. • Catalytic activity of the Ti active species in silylcyanation reaction was evaluated.« less

Correlated microanalysis of cometary organic grains returned by Stardust

NASA Astrophysics Data System (ADS)

de Gregorio, Bradley T.; Stroud, Rhonda M.; Cody, George D.; Nittler, Larry R.; David Kilcoyne, A. L.; Wirick, Sue

2011-09-01

Abstract- Carbonaceous matter in Stardust samples returned from comet 81P/Wild 2 is observed to contain a wide variety of organic functional chemistry. However, some of this chemical variety may be due to contamination or alteration during particle capture in aerogel. We investigated six carbonaceous Stardust samples that had been previously analyzed and six new samples from Stardust Track 80 using correlated transmission electron microscopy (TEM), X-ray absorption near-edge structure spectroscopy (XANES), and secondary ion mass spectroscopy (SIMS). TEM revealed that samples from Track 35 containing abundant aliphatic XANES signatures were predominantly composed of cometary organic matter infilling densified silica aerogel. Aliphatic organic matter from Track 16 was also observed to be soluble in the epoxy embedding medium. The nitrogen-rich samples in this study (from Track 22 and Track 80) both contained metal oxide nanoparticles, and are likely contaminants. Only two types of cometary organic matter appear to be relatively unaltered during particle capture. These are (1) polyaromatic carbonyl-containing organic matter, similar to that observed in insoluble organic matter (IOM) from primitive meteorites, interplanetary dust particles (IDPs), and in other carbonaceous Stardust samples, and (2) highly aromatic refractory organic matter, which primarily constitutes nanoglobule-like features. Anomalous isotopic compositions in some of these samples also confirm their cometary heritage. There also appears to be a significant labile aliphatic component of Wild 2 organic matter, but this material could not be clearly distinguished from carbonaceous contaminants known to be present in the Stardust aerogel collector.

Low toxic maghemite nanoparticles for theranostic applications.

PubMed

Kuchma, Elena A; Zolotukhin, Peter V; Belanova, Anna A; Soldatov, Mikhail A; Lastovina, Tatiana A; Kubrin, Stanislav P; Nikolsky, Anatoliy V; Mirmikova, Lidia I; Soldatov, Alexander V

2017-01-01

Iron oxide nanoparticles have numerous and versatile biological properties, ranging from direct and immediate biochemical effects to prolonged influences on tissues. Most applications have strict requirements with respect to the chemical and physical properties of such agents. Therefore, developing rational design methods of synthesis of iron oxide nanoparticles remains of vital importance in nanobiomedicine. Low toxic superparamagnetic iron oxide nanoparticles (SPIONs) for theranostic applications in oncology having spherical shape and maghemite structure were produced using the fast microwave synthesis technique and were fully characterized by several complementary methods (transmission electron microscopy [TEM], X-ray diffraction [XRD], dynamic light scattering [DLS], X-ray photoelectron spectroscopy [XPS], X-ray absorption near edge structure [XANES], Mossbauer spectroscopy, and HeLa cells toxicity testing). TEM showed that the majority of the obtained nanoparticles were almost spherical and did not exceed 20 nm in diameter. The averaged DLS hydrodynamic size was found to be ~33 nm, while that of nanocrystallites estimated by XRD waŝ16 nm. Both XRD and XPS studies evidenced the maghemite (γ-Fe 2 O 3 ) atomic and electronic structure of the synthesized nanoparticles. The XANES data analysis demonstrated the structure of the nanoparticles being similar to that of macroscopic maghemite. The Mossbauer spectroscopy revealed the γ-Fe 2 O 3 phase of the nanoparticles and vibration magnetometry study showed that reactive oxygen species in HeLa cells are generated both in the cytoplasm and the nucleus. Quasispherical Fe 3+ SPIONs having the maghemite structure with the average size of 16 nm obtained by using the fast microwave synthesis technique are expected to be of great value for theranostic applications in oncology and multimodal anticancer therapy.

Low toxic maghemite nanoparticles for theranostic applications

PubMed Central

Zolotukhin, Peter V; Belanova, Anna A; Soldatov, Mikhail A; Lastovina, Tatiana A; Kubrin, Stanislav P; Nikolsky, Anatoliy V; Mirmikova, Lidia I

2017-01-01

Background Iron oxide nanoparticles have numerous and versatile biological properties, ranging from direct and immediate biochemical effects to prolonged influences on tissues. Most applications have strict requirements with respect to the chemical and physical properties of such agents. Therefore, developing rational design methods of synthesis of iron oxide nanoparticles remains of vital importance in nanobiomedicine. Methods Low toxic superparamagnetic iron oxide nanoparticles (SPIONs) for theranostic applications in oncology having spherical shape and maghemite structure were produced using the fast microwave synthesis technique and were fully characterized by several complementary methods (transmission electron microscopy [TEM], X-ray diffraction [XRD], dynamic light scattering [DLS], X-ray photoelectron spectroscopy [XPS], X-ray absorption near edge structure [XANES], Mossbauer spectroscopy, and HeLa cells toxicity testing). Results TEM showed that the majority of the obtained nanoparticles were almost spherical and did not exceed 20 nm in diameter. The averaged DLS hydrodynamic size was found to be ~33 nm, while that of nanocrystallites estimated by XRD waŝ16 nm. Both XRD and XPS studies evidenced the maghemite (γ-Fe2O3) atomic and electronic structure of the synthesized nanoparticles. The XANES data analysis demonstrated the structure of the nanoparticles being similar to that of macroscopic maghemite. The Mossbauer spectroscopy revealed the γ-Fe2O3 phase of the nanoparticles and vibration magnetometry study showed that reactive oxygen species in HeLa cells are generated both in the cytoplasm and the nucleus. Conclusion Quasispherical Fe3+ SPIONs having the maghemite structure with the average size of 16 nm obtained by using the fast microwave synthesis technique are expected to be of great value for theranostic applications in oncology and multimodal anticancer therapy. PMID:28919740

The soft x-ray beamline at Frascati Labs

NASA Astrophysics Data System (ADS)

Cinque, Gianfelice; Burattini, Emilio; Grilli, Antonio; Dabagov, Sultan

2005-08-01

DAΦNE-Light is the Synchrotron Radiation laboratory at the Laboratori Nazionali di Frascati (LNF)1. Three beamlines were commissioned since spring 2003 to exploit parasitically the intense photon emission from DAΦNE, the 0.5 1 GeV storage ring routinely circulating over 1 A of electrons. The soft X-ray beamline utilizes a wiggler source and, by a double-crystal fixed-exit monochromator, it is operational in the distinguishing energy window 1.5 - 4 keV range to be extended from the "water window" toward 6 keV. At present, the research activity is focused on X-ray Absorption Spectroscopy (XAS): precisely, X-ray Absorption Near Edge Spectroscopy (XANES) on the inner electronic levels of light elements and transition metals from Al to Ge and both d- and f-shells of higher Z atoms. Preliminary tests of X-ray imaging have been performed in view of applying different focusing optics, namely policapillary systems in trasmission and/or bent mica diffractor in back-reflection, for X-ray microscopy and spectromicroscopy experiments. The use of polycapillary systems (lenses, halflenses, capillaries) for studying features of radiation transportation by such structures (X-ray channelling, focusing, bending, etc.) has been planned.

Pyrolysis Treatment of Chromite Ore Processing Residue by Biomass: Cellulose Pyrolysis and Cr(VI) Reduction Behavior.

PubMed

Zhang, Da-Lei; Zhang, Mei-Yi; Zhang, Chu-Hui; Sun, Ying-Jie; Sun, Xiao; Yuan, Xian-Zheng

2016-03-15

The pyrolysis treatment with biomass is a promising technology for the remediation of chromite-ore-processing residue (COPR). However, the mechanism of this process is still unclear. In this study, the behavior of pyrolysis reduction of Cr(VI) by cellulose, the main component of biomass, was elucidated. The results showed that the volatile fraction (VF) of cellulose, ie. gas and tar, was responsible for Cr(VI) reduction. All organic compounds, as well as CO and H2 in VF, potentially reduced Cr(VI). X-ray absorption near-edge structure (XANES) spectroscopy and extended X-ray absorption fine-structure (EXAFS) spectroscopy confirmed the reduction of Cr(VI) to Cr(III) and the formation of amorphous Cr2O3. The remnant Cr(VI) content in COPR can be reduced below the detection limit (2 mg/kg) by the reduction of COPR particle and extension of reaction time between VF and COPR. This study provided a deep insight on the co-pyrolysis of cellulose with Cr(VI) in COPR and an ideal approach by which to characterize and optimize the pyrolysis treatment for COPR by other organics.

Time-resolved X-Ray Absorption Spectroscopy of a Cobalt-Based Hydrogen Evolution System for Artificial Photosynthesis

NASA Astrophysics Data System (ADS)

Moonshiram, Dooshaye; Gimbert, Carolina; Lehmann, Carl; Southworth, Stephen; Llobet, Antoni; Argonne National Laboratory Team; Institut Català d'Investigació Química Collaboration

2015-03-01

Production of cost-effective hydrogen gas through solar power is an important challenge of the Department of Energy among other global industry initiatives. In natural photosynthesis, the oxygen evolving complex(OEC) can carry out four-electron water splitting to hydrogen with an efficiency of around 60%. Although, much progress has been carried out in determining mechanistic pathways of the OEC, biomimetic approaches have not duplicated Nature's efficiency in function. Over the past years, we have witnessed progress in developments of light harvesting modules, so called chromophore/catalytic assemblies. In spite of reportedly high catalytic activity of these systems, quantum yields of hydrogen production are below 40 % when using monochromatic light. Proper understanding of kinetics and bond making/breaking steps has to be achieved to improve efficiency of hydrogen evolution systems. This project shows the timing implementation of ultrafast X-ray absorption spectroscopy to visualize in ``real time'' the photo-induced kinetics accompanying a sequence of redox reactions in a cobalt-based molecular photocatalytic system. Formation of a Co(I) species followed by a Co(III) hydride species all the way towards hydrogen evolution is shown through time-resolved XANES.

Evolution of Eu valence and superconductivity in layered Eu0.5La0.5FBiS2 -xSex system

NASA Astrophysics Data System (ADS)

Mizuguchi, Y.; Paris, E.; Wakita, T.; Jinno, G.; Puri, A.; Terashima, K.; Joseph, B.; Miura, O.; Yokoya, T.; Saini, N. L.

2017-02-01

We have studied the effect of Se substitution on Eu valence in a layered Eu0.5La0.5FBiS2 -xSex superconductor using a combined analysis of x-ray absorption near-edge structure (XANES) and x-ray photoelectron spectroscopy (XPS) measurements. Eu L3-edge XANES spectra reveal that Eu is in the mixed valence state with coexisting Eu2 + and Eu3 +. The average Eu valence decreases sharply from ˜2.3 for x =0.0 to ˜2.1 for x =0.4 . Consistently, Eu 3 d XPS shows a clear decrease in the average valence by Se substitution. Bi 4 f XPS indicates that effective charge carriers in the BiCh2 (Ch = S, Se) layers are slightly increased by Se substitution. On the basis of the present results it has been discussed that the metallic character induced by Se substitution in Eu0.5La0.5FBiS2 -xSex is likely to be due to increased in-plane orbital overlap driven by reduced in-plane disorder that affects the carrier mobility.

Magnetic properties of Gd T2Zn20 (T =Fe , Co) investigated by x-ray diffraction and spectroscopy

NASA Astrophysics Data System (ADS)

Mardegan, J. R. L.; Francoual, S.; Fabbris, G.; Veiga, L. S. I.; Strempfer, J.; Haskel, D.; Ribeiro, R. A.; Avila, M. A.; Giles, C.

2016-01-01

We investigate the magnetic and electronic properties of the Gd T2Zn20 (T =Fe and Co) compounds using x-ray resonant magnetic scattering (XRMS), x-ray absorption near-edge structure (XANES), and x-ray magnetic circular dichroism (XMCD). The XRMS measurements reveal that GdCo2Zn20 has a commensurate antiferromagnetic spin structure with a magnetic propagation vector τ ⃗=(1/2 ,1/2 ,1/2 ) below the Néel temperature (TN˜ 5.7 K). Only the Gd ions carry a magnetic moment forming an antiferromagnetic structure with magnetic representation Γ6. For the ferromagnetic GdFe2Zn20 compound, an extensive investigation was performed at low temperature and under magnetic field using XANES and XMCD. A strong XMCD signal of about 12.5 % and 9.7 % is observed below the Curie temperature (TC˜85 K ) at the Gd L2 and L3 edges, respectively. In addition, a small magnetic signal of about 0.06 % of the jump is recorded at the Zn K edge, suggesting that the Zn 4 p states are spin polarized by the Gd 5 d extended orbitals.

Highly efficient Cu-decorated iron oxide nanocatalyst for low pressure CO 2 conversion

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

Halder, Avik; Kilianová, Martina; Yang, Bing

We report a nanoparticulate iron oxide based catalyst for CO2 conversion with high efficiency at low pressures and on the effect of the presence of copper on the catalyst's restructuring and its catalytic performance. In situ X-ray scattering reveals the restructuring of the catalyst at the nanometer scale. In situ X-ray absorption near edge structure (XANES) shows the evolution of the composition and oxidation state of the iron and copper components under reaction conditions along with the promotional effect of copper on the chemical transformation of the iron component. X-ray diffraction (XRD), XANES and Raman spectroscopy proved that the startingmore » nano catalyst is composed of iron oxides differing in chemical nature (alpha-Fe2O3, Fe3O4, FeO(OH)) and dimensionality, while the catalyst after CO2 conversion was identified as a mixture of alpha-Fe, Fe3C, and traces of Fe5C2. The significant increase of the rate CO2 is turned over in the presence of copper nanoparticles indicates that Cu nanoparticles activate hydrogen, which after spilling over to the neighbouring iron sites, facilitate a more efficient conversion of carbon dioxide.« less

Magnetic properties of GdT 2Zn 20 (T = Fe, Co) investigated by x-ray diffraction and spectroscopy

DOE PAGES

J. R. L. Mardegan; Fabbris, G.; Francoual, S.; ...

2016-01-26

In this study, we investigate the magnetic and electronic properties of the GdT 2Zn 20 (T=Fe and Co) compounds using x-ray resonant magnetic scattering (XRMS), x-ray absorption near-edge structure (XANES), and x-ray magnetic circular dichroism (XMCD). The XRMS measurements reveal that GdCo 2Zn 20 has a commensurate antiferromagnetic spin structure with a magnetic propagation vector →/ τ = (12,12,12) below the Néel temperature (T N ~ 5.7 K). Only the Gd ions carry a magnetic moment forming an antiferromagnetic structure with magnetic representation Γ 6. For the ferromagnetic GdFe 2Zn 20 compound, an extensive investigation was performed at low temperaturemore » and under magnetic field using XANES and XMCD. A strong XMCD signal of about 12.5% and 9.7% is observed below the Curie temperature (T C ~ 85K) at the Gd L 2 and L 3 edges, respectively. In addition, a small magnetic signal of about 0.06% of the jump is recorded at the Zn K edge, suggesting that the Zn 4p states are spin polarized by the Gd 5d extended orbitals.« less

Phase Changes of Monosulfoaluminate in NaCl Aqueous Solution

DOE PAGES

Yoon, Seyoon; Ha, Juyoung; Chae, Sejung Rosie; ...

2016-05-21

Monosulfoaluminate (Ca 4Al 2(SO 4)(OH) 12∙6H 2O) plays an important role in anion binding in Portland cement by exchanging its original interlayer ions (SO 4 2- and OH -) with chloride ions. In this study, scanning transmission X-ray microscope (STXM), X-ray absorption near edge structure (XANES) spectroscopy, and X-ray diffraction (XRD) were used to investigate the phase change of monosulfoaluminate due to its interaction with chloride ions. Pure monosulfoaluminate was synthesized and its powder samples were suspended in 0, 0.1, 1, 3, and 5 M NaCl solutions for seven days. At low chloride concentrations, a partial dissolution of monosulfoaluminate formedmore » ettringite, while, with increasing chloride content, the dissolution process was suppressed. As the NaCl concentration increased, the dominant mechanism of the phase change became ion exchange, resulting in direct phase transformation from monosulfoaluminate to Kuzel’s salt or Friedel’s salt. The phase assemblages of the NaCl-reacted samples were explored using thermodynamic calculations and least-square linear combination (LC) fitting of measured XANES spectra. A comprehensive description of the phase change and its dominant mechanism are discussed.« less

Mullite and Mullite Ceramics

DTIC Science & Technology

1994-01-01

possible. The here reported measurements were carried out with synchrotron radiation from the electron storage ring ELSA of the Bonn University. All...Physikalisches Institut der Universitdt Bonn , Bonn , Germany Measurements of X-ray absorption spectra near the absorption edge of a selected element (XANES

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

NASA Astrophysics Data System (ADS)

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

2017-11-01

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

Coupling CP-MD simulations and X-ray absorption spectroscopy: exploring the structure of oxaliplatin in aqueous solution.

PubMed

Beret, Elizabeth C; Provost, Karine; Müller, Diane; Marcos, Enrique Sánchez

2009-09-10

A combined experimental-theoretical approach applying X-ray absorption spectroscopy and ab initio molecular dynamics (CP-MD) simulations is used to get insight into the structural determination of oxaliplatin, a third-generation anticancer drug of the cisplatin family, in aqueous solution. Experimental Pt L(III)-edge EXAFS and XANES spectra of oxaliplatin in water are compared with theoretical XAS spectra. The latter are obtained as statistically averaged spectra computed for a set of selected snapshots extracted from the MD trajectory of ethyldiamineoxalatoplatinum(II) (EDO-Pt) in liquid water. This compound is a simplified structure of oxaliplatin, where the outer part of the cyclohexane ring contained in the cyclohexanediamine ligand of oxaliplatin has been removed. We show that EDO-Pt is an appropriate model to simulate the spectroscopical properties of oxaliplatin given that the cyclohexane ring does not generate particular features in neither the EXAFS nor the XANES spectra. The computation of average EXAFS spectra using structures from the MD simulation in which atoms are selected according to different cutoff radii around the Pt center allows the assignment of spectral features to particular structural motifs, both in k and R-spaces. The outer oxygen atoms of the oxalate ligand (R(Pt-O(II)) = 3.97 +/- 0.03 A) are responsible for a well-defined hump at around 6.5 A(-1) in the k(2)-weighted EXAFS spectrum. The conventional EXAFS analysis data procedure is reexamined by its application to the simulated average EXAFS spectra. The structural parameters resulting from the fit may then be compared with those obtained from the simulation, providing an estimation of the methodological error associated with the global fitting procedure. A thorough discussion on the synergy between the experimental and theoretical XAS approaches is presented, and evidence for the detection of a slight hydration structure around the Pt complex is shown, leading to the suggestion of a new challenge to experimental XAS measurements.

In situ spectroscopic characterization of Ni 1-xZn x/ZnO catalysts and their selectivity for acetylene semihydrogenation in excess ethylene

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

Spanjers, Charles S.; Sim, Richard S.; Sturgis, Nicholas P.

2015-10-30

The structures of ZnO-supported Ni catalysts were explored with in situ X-ray absorption spectroscopy, temperature-programmed reduction, X-ray diffraction, high-resolution transmission electron microscopy (HRTEM), scanning transmission electron microscopy, and electron energy loss spectroscopy. Calcination of nickel nitrate on a nanoparticulate ZnO support at 450 °C results in the formation of Zn-doped NiO (ca. N₀̣̣₈₅ Zn₀̣̣₁₅O) nanoparticles with the rock salt crystal structure. Subsequent in situ reduction monitored by X-ray absorption near-edge structure (XANES) at the Ni K edge reveals a direct transformation of the Zn-doped NiO nanoparticles to a face-centered cubic alloy, Ni 1-xZn x, at ~400 °C with x increasingmore » with increasing temperature. Both in situ XANES and ex situ HRTEM provide evidence for intermetallic β₁-NiZn formation at ~550 °C. In comparison to a Ni/SiO₂ catalyst, Ni/ZnO necessitates a higher temperature for the reduction of Ni II to Ni⁰, which highlights the strong interaction between Ni and the ZnO support. The catalytic activity for acetylene removal from an ethylene feed stream is decreased by a factor of 20 on Ni/ZnO in comparison to Ni/SiO₂. The decrease in catalytic activity of Ni/ZnO is accompanied by a reduced absolute selectivity to ethylene. H–D exchange measurements demonstrate a reduced ability of Ni/ZnO to dissociate hydrogen in comparison to Ni/SiO₂.These results of the catalytic experiments suggest that the catalytic properties are controlled, in part, by the zinc oxide support and stress the importance of reporting absolute ethylene selectivity for the catalytic semihydrogenation of acetylene in excess ethylene.« less

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

NASA Astrophysics Data System (ADS)

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

2017-02-01

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

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

NASA Astrophysics Data System (ADS)

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

2014-05-01

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

Preparation of γ-LiV2O5 from polyoxovanadate cluster Li7[V15O36(CO3)] as a high-performance cathode material and its reaction mechanism revealed by operando XAFS

NASA Astrophysics Data System (ADS)

Wang, Heng; Isobe, Jin; Shimizu, Takeshi; Matsumura, Daiju; Ina, Toshiaki; Yoshikawa, Hirofumi

2017-08-01

γ-phase LiV2O5, which shows superior electrochemical performance as cathode material in Li-ion batteries, was prepared by annealing the polyoxovanadate cluster Li7 [V15O36(CO3)]. The reaction mechanism was studied using operando X-ray absorption fine structure (XAFS), powder X-ray diffraction (PXRD), and X-ray photoelectron spectroscopy (XPS) analyses. The X-ray absorption near edge structure (XANES) and XPS results reveal that γ-LiV2O5 undergoes two-electron redox reaction per V2O5 pyramid unit, resulting in a large reversible capacity of 260 Ah/kg. The extended X-ray absorption fine structure (EXAFS) and PXRD analyses also suggest that the V-V distance slightly increases, due to the reduction of V5+ to V4+ during Li ion intercalation as the material structure is maintained. As a result, γ-LixV2O5 shows highly reversible electrochemical reaction with x = 0.1-1.9.

Morphology, stability, and X-ray absorption spectroscopic study of iron oxide (Hematite) nanoparticles prepared by micelle nanolithography

NASA Astrophysics Data System (ADS)

Bera, Anupam; Bhattacharya, Atanu; Tiwari, N.; Jha, S. N.; Bhattacharyya, D.

2018-03-01

Currently, considerable effort is being made towards synthesis and characterization of iron oxide nanoparticles. In this article, we report on the preparation and characterization of iron oxide nanoparticle (NP) arrays supported on natively oxidized Si(100) surface. The NPs are synthesized by reverse micelle nanolithography technique and are then deposited onto natively oxidized Si(100) surface via spin-coating. Plasma oxidation followed by high temperature annealing results in a unimodal size distribution of pseudohexagonally-ordered array of iron oxide NPs (with ∼14 nm mean diameter and ∼5 nm mean height). High temperature annealing does not fragment the NPs. Particles are sinter-resistant: the unimodal arrays are robust with respect to thermal treatment. X-ray absorption spectroscopy (XAS), including X-ray Absorption Near Edge Structure (XANES) and Extended X-ray Absorption Fine Structure (EXAFS), reveals that structure of the iron oxide particle resembles closely the hematite α-Fe2O3 structure. Furthermore, with the help of EXAFS spectra, we eliminate the possibility of γ-Fe2O3, Fe3O4, FeO and FeO(OH) structures for the NPs.

Applications of Hard X-ray Full-Field Transmission X-ray Microscopy at SSRL

NASA Astrophysics Data System (ADS)

Liu, Y.; Andrews, J. C.; Meirer, F.; Mehta, A.; Gil, S. Carrasco; Sciau, P.; Mester, Z.; Pianetta, P.

2011-09-01

State-of-the-art hard x-ray full-field transmission x-ray microscopy (TXM) at beamline 6-2C of Stanford Synchrotron Radiation Lightsource has been applied to various research fields including biological, environmental, and material studies. With the capability of imaging a 32-micron field-of-view at 30-nm resolution using both absorption mode and Zernike phase contrast, the 3D morphology of yeast cells grown in gold-rich media was investigated. Quantitative evaluation of the absorption coefficient was performed for mercury nanoparticles in alfalfa roots exposed to mercury. Combining XANES and TXM, we also performed XANES-imaging on an ancient pottery sample from the Roman pottery workshop at LaGraufesenque (Aveyron).

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

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

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

2008-01-01

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

X-ray absorption and Raman spectroscopy studies of molybdenum environments in borosilicate waste glasses

NASA Astrophysics Data System (ADS)

McKeown, David A.; Gan, Hao; Pegg, Ian L.

2017-05-01

Mo-containing high-level nuclear waste borosilicate glasses were investigated as part of an effort to improve Mo loading while avoiding yellow phase crystallization. Previous work showed that additions of vanadium decrease yellow phase formation and increases Mo solubility. X-ray absorption spectroscopy (XAS) and Raman spectroscopy were used to characterize Mo environments in HLW borosilicate glasses and to investigate possible structural relationships between Mo and V. Mo XAS spectra for the glasses indicate isolated tetrahedral Mo6+O4 with Mo-O distances near 1.75 Å. V XANES indicate tetrahedral V5+O4 as the dominant species. Raman spectra show composition dependent trends, where Mo-O symmetrical stretch mode frequencies (ν1) are sensitive to the mix of alkali and alkaline earth cations, decreasing by up to 10 cm-1 for glasses that change from Li+ to Na+ as the dominant network-modifying species. This indicates that MoO4 tetrahedra are isolated from the borosilicate network and are surrounded, at least partly, by Na+ and Li+. Secondary ν1 frequency effects, with changes up to 7 cm-1, were also observed with increasing V2O5 and MoO3 content. These secondary trends may indicate MoO4-MoO4 and MoO4-VO4 clustering, suggesting that V additions may stabilize Mo in the matrix with respect to yellow phase formation.

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

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

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

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

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

Favorito, Jessica E.; Luxton, Todd P.; Eick, Matthew J.

Selenium is a trace element found in western US soils, where ingestion of Se-accumulating plants has resulted in livestock fatalities. Therefore, a reliable understanding of Se speciation and bioavailability is critical for effective mitigation. Sequential extraction procedures (SEP) are often employed to examine Se phases and speciation in contaminated soils but may be limited by experimental conditions. We examined the validity of a SEP using X-ray absorption spectroscopy (XAS) for both whole and a sequence of extracted soils. The sequence included removal of soluble, PO4-extractable, carbonate, amorphous Fe-oxide, crystalline Fe-oxide, organic, and residual Se forms. For whole soils, XANES analysesmore » indicated Se(0) and Se(-II) predominated, with lower amounts of Se(IV) present, related to carbonates and Fe-oxides. Oxidized Se species were more elevated and residual/elemental Se was lower than previous SEP results from ICP-AES suggested. For soils from the SEP sequence, XANES results indicated only partial recovery of carbonate, Fe-oxide and organic Se. This suggests Se was incompletely removed during designated extractions, possibly due to lack of mineral solubilization or reagent specificity. Selenium fractions associated with Fe-oxides were reduced in amount or removed after using hydroxylamine HCl for most soils examined. XANES results indicate partial dissolution of solid-phases may occur during extraction processes. This study demonstrates why precautions should be taken to improve the validity of SEPs. Mineralogical and chemical characterizations should be completed prior to SEP implementation to identify extractable phases or mineral components that may influence extraction effectiveness. Sequential extraction procedures can be appropriately tailored for reliable quantification of speciation in contaminated soils.« less

Roman coloured and opaque glass: a chemical and spectroscopic study

NASA Astrophysics Data System (ADS)

Arletti, R.; Dalconi, M. C.; Quartieri, S.; Triscari, M.; Vezzalini, G.

2006-05-01

This work reports the results of an archaeometrical investigation of opaque Roman glass and is mainly focussed on the role of configuration and oxidation state of copper on the colour and opacity of red and green opaque finds (mosaic tesserae, game counters, and glass artefacts) from Sicily and Pompeii excavations. The glass fragments were characterised by EMPA, SEM-EDS, TEM, and XRPD analyses and the copper local environment was investigated using X-ray absorption spectroscopy. The analyses of high-resolution Cu-K edge XANES and EXAFS spectra suggest that, in red samples, copper is present as monovalent cations coordinated to the oxygen atoms of the glass framework, accompanied by metallic clusters. In green samples all the copper cations are incorporated in the glass matrix.

Uniaxial ferromagnetism of local uranium moments in hexagonal UBeGe

NASA Astrophysics Data System (ADS)

Gumeniuk, Roman; Yaresko, Alexander N.; Schnelle, Walter; Nicklas, Michael; Kvashnina, Kristina O.; Hennig, Christoph; Grin, Yuri; Leithe-Jasper, Andreas

2018-05-01

The new intermetallic uranium beryllium germanide UBeGe and its thorium analogon ThBeGe crystallize with the hexagonal ZrBeSi type of structure. Studies of magnetic, thermal, and transport properties were performed on polycrystalline samples between 1.8 and 750K. UBeGe is a uniaxial ferromagnet and there are indications for two magnetic transitions at TC(1 )≈160 K and TC(2 )≈150 K . The high paramagnetic effective moment μeff≈3.1 μB , x-ray absorption near-edge spectroscopy (XANES, 17-300 K), as well as theoretical DFT calculations indicate localized U 5 f2 states in UBeGe. ThBeGe is a diamagnetic metallic material with low density of states at the Fermi level.

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

NASA Astrophysics Data System (ADS)

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

2009-11-01

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

XANES analyses of silicon crystalline irradiated by nitrogen/oxygen ions.

PubMed

Yoshida, T; Hara, T; Li, T; Yoshida, H; Tanabe, T

2001-03-01

X-ray absorption techniques have been applied to the characterization of 5 keV nitrogen / oxygen ions implanted silicon samples. The depth selective measurement of XANES by recording in PEY mode and the quantitative analysis by superposition of XANES spectra were carried out to elucidate the depth profile of implanted ions. It has been revealed that the silicon nitride phase were formed in silicon after prolonged N+ irradiation and it extended over the deep part of the damaged region from the surface. On the other hand, for the O+ irradiation, silicon dioxide phase were produced only in the shallow part of the damaged region, i.e., the silicon dioxide phase likely broke off during the irradiation.

MAX: Multiplatform Applications for XAFS

NASA Astrophysics Data System (ADS)

Alain, Michalowicz; Jacques, Moscovici; Diane, Muller-Bouvet; Karine, Provost

2009-11-01

MAX is a new EXAFS and XANES analysis package, replacing our old "EXAFS pour le Mac" software suite. The major improvement is the ability to work with strictly the same code, compiled at once for Microsoft Windows, Apple MacOSX and LINUX systems, justifying the title "Multiplatform Applications for XAFS". It is organized as four modules: ABSORBIX (X-ray absorbance and fluorescence self-absorption calculations), CHEROKEE (EXAFS and XANES data treatment), ROUNDMIDNIGHT (EXAFS modeling and fit) and CRYSTALFFREV (from crystal structures and molecular modeling to FEFF EXAFS and XANES theoretical calculations). Most features developed in "EXAFS pour le Mac" are still available, but with much improvements in the user's interface, data treatment algorithms and new functionalities.

First X-Ray absorption spectroscopy results on Aeolian dust archived in Antarctica and Alpine firn cores

NASA Astrophysics Data System (ADS)

Marcelli, A.; Maggi, V.; Cibin, G.; Sala, M.; Marino, F.; Delmonte, B.

2006-12-01

We present the first x-ray absorption spectroscopy (XAS) data at the Fe K-edge collected on insoluble mineral dust from Talos Dome firn core (TDC, 159°04'E, 72°46'S, 2316 m a.s.l., mean accumulation rate 8 g cm-2 yr- 1), drilled in the framework of the International Trans Antarctic Scientific Expedition (ITASE), and from a Colle del Lys 2003 firn core (CDL03, 45°92'N, 7°86'E, 4248m a.s.l., mean accumulation rate 134 g cm-2 yr-1, Lys Glacier, Mt. Rosa, Italy). The low concentration of mineral particles, obtained by filtering each firn core melted samples on Nuclepore membranes in a 1000 class clean room, required a specific procedure to prepare the samples necessary to the successful collection of the XAS data. The firn samples were decontaminated in clean room under laminar flow bench by means of a ceramic knife and discarding the external part of the cores. Analyses of the insoluble particle content were performed by particle counter Beckman CounterãMultisizer III in order to defined concentration and size distribution of particles in each samples. A dedicated HV experimental chamber, devoted to the realization of XAS experiments on very low absorber concentration samples, was developed and realized in the framework of the CryoAlp collaboration at IMONT, the Italian National Institute for Mountains. The original experimental setup, thanks to the presence of an in-vacuum sample micromanipulator and special sample alignment and docking system installed for these experiments at the Stanford Synchrotron Radiation Laboratory at the beamline 6-2, allows both normal-incidence X-ray Fluorescence detection using a Ketek SDD detector having an energy resolution of about 150 eV and extremely low energy detection limit, and Total X-ray Reflection Fluorescence and Absorption Spectroscopy measurements. The high quality of the XANES experiments performed, using both normal incidence and Total Reflection XAS measurements, allowed recognizing iron-inclusion mineral fractions. Samples for Total Reflection XAS measurements were prepared just for this kind of measurements by depositing the insoluble mineral dust on clean Si wafer substrates. In addition, the XANES spectra show clear differences, corresponding to different samples mineral iron hosts, demonstrating that with this fully non-distructive technique, new information about the dust mineralogy at very low concentration can be performed. The analysis is then complementary to other well established techniques like XRD and PIXE.

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

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

Kolker,A.; Huggins, F.

2007-01-01

Naturally occurring pyrite commonly contains minor substituted metals and metalloids (As, Se, Hg, Cu, Ni, etc.) that can be released to the environment as a result of its weathering. Arsenic, often the most abundant minor constituent in pyrite, is a sensitive monitor of progressive pyrite oxidation in coal. To test the effect of pyrite composition and environmental parameters on the rate and extent of pyrite oxidation in coal, splits of five bituminous coal samples having differing amounts of pyrite and extents of As substitution in the pyrite, were exposed to a range of simulated weathering conditions over a period ofmore » 17 months. Samples investigated include a Springfield coal from Indiana (whole coal pyritic S = 2.13 wt.%; As in pyrite = detection limit (d.l.) to 0.06 wt.%), two Pittsburgh coal samples from West Virginia (pyritic S = 1.32-1.58 wt.%; As in pyrite = d.l. to 0.34 wt.%), and two samples from the Warrior Basin, Alabama (pyritic S = 0.26-0.27 wt.%; As in pyrite = d.l. to 2.72 wt.%). Samples were collected from active mine faces, and expected differences in the concentration of As in pyrite were confirmed by electron microprobe analysis. Experimental weathering conditions in test chambers were maintained as follows: (1) dry Ar atmosphere; (2) dry O{sub 2} atmosphere; (3) room atmosphere (relative humidity {approx}20-60%); and (4) room atmosphere with samples wetted periodically with double-distilled water. Sample splits were removed after one month, nine months, and 17 months to monitor the extent of As and Fe oxidation using As X-ray absorption near-edge structure (XANES) spectroscopy and {sup 57}Fe Mossbauer spectroscopy, respectively. Arsenic XANES spectroscopy shows progressive oxidation of pyritic As to arsenate, with wetted samples showing the most rapid oxidation. {sup 57}Fe Mossbauer spectroscopy also shows a much greater proportion of Fe{sup 3+} forms (jarosite, Fe{sup 3+} sulfate, FeOOH) for samples stored under wet conditions, but much less difference among samples stored under dry conditions in different atmospheres. The air-wet experiments show evidence of pyrite re-precipitation from soluble ferric sulfates, with As retention in the jarosite phase. Extents of As and Fe oxidation were similar for samples having differing As substitution in pyrite, suggesting that environmental conditions outweigh the composition and amount of pyrite as factors influencing the oxidation rate of Fe sulfides in coal.« less

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

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

XAS Investigations of PEM Fuel Cells

NASA Astrophysics Data System (ADS)

Roth, Christina; Ramaker, David E.

Polymer-electrolyte membrane (PEM) fuel cells are still far from an area-wide market launch due in part to long-term stability, reliability and cost issues. A more detailed knowledge of the underlying reaction mechanisms is expected to further their application, as it would allow for the design of tailor-made catalysts. However, this will only be possible by complementing traditional in situ studies on single-crystals in electrochemical cells with more sophisticated metal/electrolyte interfacial studies by novel spectroscopic methodologies, which can provide complementary insights into the behaviour of commercial catalysts under real fuel cell operating conditions. This review will focus on the advances of Xray absorption spectroscopy (XAS) in applied fuel cell research utilizing several examples. XAS enables both the nanoparticle morphology and the adsorbate coverage and binding site to be investigated with just one technique. The latter is possible when complementing the conventional extended X-ray absorption fine structure (EXAFS) analysis with the more novel Δμ XANES approach.

Effects of X-ray irradiation on the Eu3+ → Eu2+ conversion in CaAl2O4 phosphors

NASA Astrophysics Data System (ADS)

Gomes, Manassés A.; Carvalho, Jéssica C.; Andrade, Adriano B.; Rezende, Marcos V.; Macedo, Zélia S.; Valerio, Mário E. G.

2018-01-01

This paper reports structural and luminescence properties of Eu-doped CaAl2O4 produced by an alternative sol-gel method using coconut water. Results of differential thermal analysis (DTA), thermogravimetric analysis (TGA), and X-ray diffraction (XRD) allowed us to identify the best synthesis conditions for sample preparation. Simultaneous measurements of X-ray absorption spectroscopy (XAS) and X-ray excited optical luminescence (XEOL) were also performed in the X-ray energy range of the Eu LIII edge. Results from photoluminescence (PL) showed only the characteristic Eu3+ emission. However, radioluminescence emission spectra from Eu-doped CaAl2O4 shows a process of conversion of Eu3+ to Eu2+, which is induced by X-ray irradiation and is dependent on the radiation dose energy. X-ray absorption near edge structure (XANES) measurements corroborate Eu reduction due to irradiation, showing that only the Eu3+ ion is present in stable form in the CaAl2O4.

Ag XANES data of biosolids

EPA Pesticide Factsheets

The dataset contains energy and absorption data for XANES spectra indicated in Figure 1 of the manuscript.This dataset is associated with the following publication:Donner, E., K. Scheckel , R. Sekine, R. Popelka-Filcoff, J. Bennett, G. Brunetti, R. Naidu, S. McGrath, and E. Lombi. Non-labile silver species in biosolids remain stable throughout 50 years of weathering and ageing.. D.O. Carpenter, and E.Y. Zeng ENVIRONMENTAL POLLUTION. Elsevier Science Ltd, New York, NY, USA, 205: 78-86, (2015).

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

NASA Astrophysics Data System (ADS)

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

2015-06-01

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

In situ visualisation and characterisation of the capacity of highly reactive minerals to preserve soil organic matter (SOM) in colloids at submicron scale.

PubMed

Xiao, Jian; Wen, Yongli; Li, Huan; Hao, Jialong; Shen, Qirong; Ran, Wei; Mei, Xinlan; He, Xinhua; Yu, Guanghui

2015-11-01

Mineral-organo associations (MOAs) are a mixture of identifiable biopolymers associated with highly reactive minerals and microorganisms. However, the in situ characterization and correlation between soil organic matter (SOM) and highly reactive Al and Fe minerals are still unclear for the lack of technologies, particularly in the long-term agricultural soil colloids at submicron scale. We combined several novel techniques, including nano-scale secondary ion mass spectrometry (NanoSIMS), X-ray absorption near edge structure (XANES) and confocal laser scanning microscopy (CLSM) to characterise the capacity of highly reactive Al and Fe minerals to preserve SOM in Ferralic Cambisol in south China. Our results demonstrated that: (1) highly reactive minerals were strongly related to SOM preservation, while SOM had a more significant line correlation with the highly reactive Al minerals than the highly reactive Fe minerals, according to the regions of interest correlation analyses using NanoSIMS; (2) allophane and ferrihydrite were the potential mineral species to determine the SOM preservation capability, which was evaluated by the X-ray photoelectron spectroscopy (XPS) and Fe K-edge XANES spectroscopy techniques; and (3) soil organic biopolymers with dominant compounds, such as proteins, polysaccharides and lipids, were distributed at the rough and clustered surface of MOAs with high chemical and spatial heterogeneity according to the CLSM observation. Our results also promoted the understanding of the roles played by the highly reactive Al and Fe minerals in the spatial distribution of soil organic biopolymers and SOM sequestration. Copyright © 2015 Elsevier Ltd. All rights reserved.

The incorporation of plutonium in lanthanum zirconate pyrochlore

NASA Astrophysics Data System (ADS)

Gregg, Daniel J.; Zhang, Yingjie; Middleburgh, Simon C.; Conradson, Steven D.; Triani, Gerry; Lumpkin, Gregory R.; Vance, Eric R.

2013-11-01

The incorporation of plutonium (Pu) within lanthanum zirconate pyrochlore was investigated using air, argon, and N2-3.5%H2 sintering atmospheres together with Ca2+ and Sr2+ incorporation for charge compensation. The samples have been characterised in the first instance by X-ray diffraction (XRD), scanning electron microscopy (SEM) and diffuse reflectance spectroscopy (DRS). The results show Pu can be exchanged for La3+ on the A-site with and without charge compensation and for Zr4+ on the B-site. DRS measurements were made over the wavenumber range of 4000-19,000 cm-1 and the Pu in all air- and argon-sintered samples was found to be present as Pu4+ while that in samples sintered in N2-3.5%H2 was present as Pu3+. The Pu valence was confirmed for three of the samples using X-ray near-edge absorption spectroscopy (XANES). Pu valences >4+ were not observed in any of the samples.

Light, Molecules, Action: Using Ultrafast Uv-Visible and X-Ray Spectroscopy to Probe Excited State Dynamics in Photoactive Molecules

NASA Astrophysics Data System (ADS)

Sension, R. J.

2017-06-01

Light provides a versatile energy source capable of precise manipulation of material systems on size scales ranging from molecular to macroscopic. Photochemistry provides the means for transforming light energy from photon to process via movement of charge, a change in shape, a change in size, or the cleavage of a bond. Photochemistry produces action. In the work to be presented here ultrafast UV-Visible pump-probe, and pump-repump-probe methods have been used to probe the excited state dynamics of stilbene-based molecular motors, cyclohexadiene-based switches, and polyene-based photoacids. Both ultrafast UV-Visible and X-ray absorption spectroscopies have been applied to the study of cobalamin (vitamin B_{12}) based compounds. Optical measurements provide precise characterization of spectroscopic signatures of the intermediate species on the S_{1} surface, while time-resolved XANES spectra at the Co K-edge probe the structural changes that accompany these transformations.

Ligand-tailored single-site silica supported titanium catalysts: Synthesis, characterization and towards cyanosilylation reaction

NASA Astrophysics Data System (ADS)

Xu, Wei; Li, Yani; Yu, Bo; Yang, Jindou; Zhang, Ying; Chen, Xi; Zhang, Guofang; Gao, Ziwei

2015-01-01

A successive anchoring of Ti(NMe2)4, cyclopentadiene and a O-donor ligand, 1-hydroxyethylbenzene (PEA), 1,1‧-bi-2-naphthol (Binol) or 2,3-dihydroxybutanedioic acid diethyl ester (Tartrate), on silica was conducted by SOMC strategy in moderate conditions. The silica, monitored by in-situ Fourier transform infrared spectroscopy (in-situ FT-IR), was pretreated at different temperatures (200, 500 and 800 °C). The ligand tailored silica-supported titanium complexes were characterized by in-situ FT-IR, 13C CP MAS-NMR, X-ray photoelectron spectroscopy (XPS), X-ray absorption near edge structure (XANES) and elemental analysis in detail, verifying that the surface titanium species are single sited. The catalytic activity of the ligand tailored single-site silica supported titanium complexes was evaluated by a cyanosilylation of benzaldehyde. The results showed that the catalytic activity is dependent strongly on the dehydroxylation temperatures of silica and the configuration of the ligands.

Arsenic speciation in biological samples using XAS and mixed oxidation state calibration standards of inorganic arsenic.

PubMed

Parsons, J G; Lopez, M L; Castillo-Michel, H; Peralta-Videa, J R; Gardea-Torresdey, J L

2009-08-01

The speciation of elements without pre-edge features preformed with X-ray absorption near edge structure (XANES) can lead to problems when the energy difference between two species is small. The speciation of arsenic (As) in plant samples was investigated using the mixtures As2S3/As2O5, As2S3/As2O3, or As2O3/As2O5. The data showed that the energy separation (eV) between As2O5 and As2S3 was 5.8, between As2O3 and As2O5 was 3.6, and between As2S3 and As2O3 was 2.1. From the intensity of the white-line feature and the concentration of As species, calibration curves showing a limit of detection of approximately 10% were generated. In addition, an error of +/-10% was determined for the linear combination-XANES (LC-XANES) fitting technique. The difference between the LC-XANES fittings and calculations from the calibration curves was <10%. The data also showed that the speciation of As in a sample can be determined using EXAFS (extended X-ray absorption fine structure). Finally, it was also shown that both EXAFS and XANES of the sample should be examined to determine the true speciation of an element. Even though there is a difference of 2 eV between As(III) bound to O and As(III) bound to S, in the EXAFS region the As(III)-S and As(III)-O ligands are clearly visible. However, distinction between the As(III)-O and As(V)-O ligands in the EXAFS spectra was not clearly visible in this study.

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

NASA Astrophysics Data System (ADS)

Tanaka, Isao; Mizoguchi, Teruyasu; Yamamoto, Tomoyuki

2009-03-01

Both electron energy loss near edge structure (ELNES) spectroscopy and x-ray absorption near edge structure (XANES) spectroscopy provide information on the local structural and chemical environments of selected elements of interest. Recent technological progress in scanning transmission electron microscopy has enabled ELNES measurements with atomic column spatial resolution. Very dilute concentrations (nanograms per milliliter or ppb level) of dopants can be observed using third-generation synchrotron facilities when x-ray fluorescence is measured with highly efficient detectors. With such technical developments, ELNES and XANES have become established as essential tools in a large number of fields of natural science, including condensed matter physics, chemistry, mineralogy and materials science. In addition to these developments in experimental methodology, notable progress in reproducing spectra using theoretical methods has recently been made. Using first-principles methods, one can analyze and interpret spectra without reference to experiment. This is quite important since we are often interested in the analysis of exotic materials or specific atoms located at lattice discontinuities such as surfaces and interfaces, where appropriate experimental data are difficult to obtain. Using the structures predicted by reliable first-principles calculations, one can calculate theoretical ELNES and XANES spectra without too much difficulty even in such cases. Despite the fact that ELNES and XANES probe the same phenomenon—essentially the electric dipole transition from a core orbital to an unoccupied band—there have not been many opportunities for researchers in the two areas to meet and discuss. Theoretical calculations of ELNES spectra have been mainly confined to the electron microscopy community. On the other hand, the theory of XANES has been developed principally by researchers in the x-ray community. Publications describing the methods have been written more-or-less independently by the two communities. The three-day workshop on the Theoretical Calculation of ELNES and XANES (TEX2008) was planned to help remedy this situation. It aimed to demonstrate capability of state-of-the-art theoretical techniques to explain and predict ELNES and XANES spectra, and to allow deep discussion between scientists in the two communities. It also provided an excellent opportunity to introduce experimentalists to the computational techniques available. Invited talks and poster presentations by leading scientists were given on the first day, which was followed by tutorial sessions for five computer programs on the second and third days. Excellent lectures were given by Peter Blaha (Vienna, Austria) on the WIEN2k code, Chris J Pickard (St Andrews, UK) on the CASTEP code, John J Rehr (Seattle, USA) on the FEFF8 code, Frank de Groot (Utrecht, The Netherlands) on the CTM4XAS code, and Hidekazu Ikeno (Kyoto, Japan) on the first-principles CI-multiplet code. Thanks to the enthusiastic participation of more than 100 scientists from around the world, the workshop was a complete success. The aim of this special issue in Journal of Physics: Condensed Matter is to share with the readers the most up-to-date knowledge presented at the workshop. We believe this will prove useful as a reference for researchers in many different fields, as well as an overview of the current status and future directions of theoretical calculations for ELNES and XANES. TEX2008 was a satellite meeting of the First International Symposium on Advanced Microscopy and Theoretical Calculations (AMTC1) (Nagoya, Japan, 29-30 June 2008), which was held in commemoration of the establishment of the Nanostuctures Research Laboratory (NSRL) at the Japan Fine Ceramics Center (JFCC) and as a daughter event of EXPO 2005, Aichi, Japan. A Grant-in-Aid for Scientific Research on Priority Areas 'Nano Materials Science for Atomic-Scale Modification' from the Ministry of Education, Culture, Sports and Technology (MEXT) and support from the Chubu Economic Federation for the workshop are gratefully acknowledged.

New frontiers in water purification: highly stable amphopolycarboxyglycinate-stabilized Ag-AgCl nanocomposite and its newly discovered potential

NASA Astrophysics Data System (ADS)

Krutyakov, Yurii A.; Zherebin, Pavel M.; Kudrinskiy, Alexey A.; Zubavichus, Yan V.; Presniakov, Mikhail Yu; Yapryntsev, Alexey D.; Karabtseva, Anastasia V.; Mikhaylov, Dmitry M.; Lisichkin, Georgii V.

2016-09-01

A simple synthetic procedure for high-stable dispersions of porous composite Ag/AgCl nanoparticles stabilized with amphoteric surfactant sodium tallow amphopolycarboxyglycinate has been proposed for the first time. The prepared samples were characterized by UV-vis spectroscopy, x-ray powder diffraction (XRD), x-ray photoelectron spectroscopy, small area electron diffraction (SAED), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), and electron probe micro-analysis. In addition, measurements (carried out at the Kurchatov synchrotron radiation source stations) of the Ag K-edge extended x-ray absorption fine structure (EXAFS) and x-ray absorption near edge structure (XANES) spectra and XRD of the prepared nanoparticles have been performed. The obtained results suggest that small-sized Ag clusters are homogeneously distributed in the mass of the AgCl nanoparticle (~80 nm) formed during the synthesis. The Ag/AgCl dispersion demonstrates photocatalytic activity (with respect to methyl orange) and high bactericidal activity against E. coli. This activity is superior to the activity of both Ag and AgCl nanoparticles stabilized by the same surfactant. Thus, porous composite Ag/AgCl nanoparticles can be used as a multifunctional agent that is able to remove both pollutants and bacterium from water.

Inorganic polymers from laterite using activation with phosphoric acid and alkaline sodium silicate solution: Mechanical and microstructural properties

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

Lassinantti Gualtieri, Magdalena, E-mail: magdalena.gualtieri@unimore.it; Romagnoli, Marcello; Pollastri, Simone

2015-01-15

Geopolymers from laterite, an iron-rich soil available in developing countries, have great potential as building materials. In this work, laterite from Togo (Africa) was used to prepare geopolymers using both phosphoric acid and alkaline sodium silicate solution. Microstructural properties were investigated by scanning electron microscopy, X-ray powder diffraction and mercury porosimetry, whereas thermal properties were evaluated by thermal analyses. The local environment of iron was studied by X-ray Absorption Spectroscopy (XANES region). The mechanical properties were determined. Modulus of Rupture and Young's modulus fell in the ranges 3.3–4.5 MPa and 12–33 GPa, respectively, rendering the materials good candidates for constructionmore » purposes. Heating above 900 °C results in weight-gain, presumably due to iron redox reactions. X-ray Absorption Spectroscopy data evidence changes in the chemical and structural environments of iron following thermal treatment of geopolymers. These changes indicate interaction between the geopolymer structure and iron during heating, possibly leading to redox properties. -- Highlights: •Geopolymerization of laterite is promising for fabrication of building materials. •Both phosphoric acid and alkaline sodium silicate solution can be used for activation. •Thermally activated redox properties of the inorganic polymers were observed.« less

High-resolution x-ray absorption spectroscopy studies of metal compounds in neurodegenerative brain tissue

NASA Astrophysics Data System (ADS)

Collingwood, J. F.; Mikhaylova, A.; Davidson, M. R.; Batich, C.; Streit, W. J.; Eskin, T.; Terry, J.; Barrea, R.; Underhill, R. S.; Dobson, J.

2005-01-01

Fluorescence mapping and microfocus X-ray absorption spectroscopy are used to detect, locate and identify iron biominerals and other inorganic metal accumulations in neurodegenerative brain tissue at sub-cellular resolution (<5 microns). Recent progress in developing the technique is reviewed. Synchrotron X-rays are used to map tissue sections for metals of interest, and XANES and XAFS are used to characterise anomalous concentrations of the metals in-situ so that they can be correlated with tissue structures and disease pathology. Iron anomalies associated with biogenic magnetite, ferritin and haemoglobin are located and identified in an avian tissue model with a pixel resolution ~5 microns. Subsequent studies include brain tissue sections from transgenic Huntington's mice, and the first high-resolution mapping and identification of iron biominerals in human Alzheimer's and control autopsy brain tissue. Technical developments include use of microfocus diffraction to obtain structural information about biominerals in-situ, and depositing sample location grids by lithography for the location of anomalies by conventional microscopy. The combined techniques provide a breakthrough in the study of both intra- and extra-cellular iron compounds and related metals in tissue. The information to be gained from this approach has implications for future diagnosis and treatment of neurodegeneration, and for our understanding of the mechanisms involved.

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

Ozkendir, Osman Murat, E-mail: ozkendir@gmail.com

Highlights: • Crystal and electronic structure properties of Nd{sub x}Ti{sub 1−x}BO{sub 2+d} structure were investigated. • New crystal structures for Nd–Ti complexes are determined. • Distortions in the crystal structure were observed as a result of Boron shortage. • Prominent change in electronic properties of the samples with the increasing Nd amount. - Abstract: Neodymium substituted TiBO{sub 3} samples were investigated according to their crystal, electric and electronic properties. Studies were conducted by X-ray absorption fine structure spectroscopy (XAFS) technique for the samples with different substitutions in the preparation processes. To achieve better crystal structure results during the study, XRDmore » pattern results were supported by extended-XAFS (EXAFS) analysis. The electronic structure analysis were studied by X-ray absorption near-edge structure spectroscopy (XANES) measurements at the room temperatures. Due to the substituted Nd atoms, prominent changes in crystal structure, new crystal geometries for Nd-Ti complexes, phase transitions in the crystals structure were detected according to the increasing Nd substitutions in the samples. In the entire stages of the substitutions, Nd atoms were observed as governing the whole phenomena due to their dominant characteristics in Ti geometries. Besides, electrical resistivity decay was determined in the materials with the increasing amount of Nd substitution.« less

Speciation and distribution of arsenic and localization of nutrients in rice grains

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

Lombi, E.; Scheckel, K.G.; Pallon, J.

2012-09-05

Arsenic (As) contamination of rice grains and the generally low concentration of micronutrients in rice have been recognized as a major concern for human health. Here, we investigated the speciation and localization of As and the distribution of (micro)nutrients in rice grains because these are key factors controlling bioavailability of nutrients and contaminants. Bulk total and speciation analyses using high-pressure liquid chromatography (HPLC)-inductively coupled plasma mass spectrometry (ICP-MS) and X-ray absorption near-edge spectroscopy (XANES) was complemented by spatially resolved microspectroscopic techniques ({mu}-XANES, {mu}-X-ray fluorescence ({mu}-XRF) and particle induced X-ray emission (PIXE)) to investigate both speciation and distribution of As andmore » localization of nutrients in situ. The distribution of As and micronutrients varied between the various parts of the grains (husk, bran and endosperm) and was characterized by element-specific distribution patterns. The speciation of As in bran and endosperm was dominated by As(III)-thiol complexes. The results indicate that the translocation from the maternal to filial tissues may be a bottleneck for As accumulation in the grain. Strong similarities between the distribution of iron (Fe), manganese (Mn) and phosphorus (P) and between zinc (Zn) and sulphur (S) may be indicative of complexation mechanisms in rice grains.« less

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

NASA Astrophysics Data System (ADS)

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

2014-07-01

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

Imaging Catalytic Activation of CO 2 on Cu 2O (110): A First-Principles Study

DOE PAGES

Li, Liang; Zhang, Rui; Vinson, John; ...

2018-03-05

Balancing global energy needs against increasing greenhouse gas emissions requires new methods for efficient CO 2 reduction. While photoreduction of CO 2 is a viable approach for fuel generation, the rational design of photocatalysts hinges on precise characterization of the surface catalytic reactions. Cu 2O is a promising next-generation photocatalyst, but the atomic-scale description of the interaction between CO 2 and the Cu 2O surface is largely unknown, and detailed experimental measurements are lacking. In this study, density-functional-theory (DFT) calculations have been performed to identify the Cu 2O (110) surface stoichiometry that favors CO 2 reduction. To facilitate interpretation ofmore » scanning tunneling microscopy (STM) and X-ray absorption near-edge structures (XANES) measurements, which are useful for characterizing catalytic reactions, we present simulations based on DFT-derived surface morphologies with various adsorbate types. STM and XANES simulations were performed using the Tersoff Hamann approximation and Bethe-Salpeter equation (BSE) approach, respectively. The results provide guidance for observation of CO 2 reduction reaction on, and rational surface engineering of, Cu 2O (110). In conclusion, they also demonstrate the effectiveness of computational image and spectroscopy modeling as a predictive tool for surface catalysis characterization.« less

Imaging Catalytic Activation of CO 2 on Cu 2O (110): A First-Principles Study

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

Li, Liang; Zhang, Rui; Vinson, John

Balancing global energy needs against increasing greenhouse gas emissions requires new methods for efficient CO 2 reduction. While photoreduction of CO 2 is a viable approach for fuel generation, the rational design of photocatalysts hinges on precise characterization of the surface catalytic reactions. Cu 2O is a promising next-generation photocatalyst, but the atomic-scale description of the interaction between CO 2 and the Cu 2O surface is largely unknown, and detailed experimental measurements are lacking. In this study, density-functional-theory (DFT) calculations have been performed to identify the Cu 2O (110) surface stoichiometry that favors CO 2 reduction. To facilitate interpretation ofmore » scanning tunneling microscopy (STM) and X-ray absorption near-edge structures (XANES) measurements, which are useful for characterizing catalytic reactions, we present simulations based on DFT-derived surface morphologies with various adsorbate types. STM and XANES simulations were performed using the Tersoff Hamann approximation and Bethe-Salpeter equation (BSE) approach, respectively. The results provide guidance for observation of CO 2 reduction reaction on, and rational surface engineering of, Cu 2O (110). In conclusion, they also demonstrate the effectiveness of computational image and spectroscopy modeling as a predictive tool for surface catalysis characterization.« less

Radiation damages during synchrotron X-ray micro-analyses of Prussian blue and zinc white historic paintings: detection, mitigation and integration

NASA Astrophysics Data System (ADS)

Gervais, Claire; Thoury, Mathieu; Réguer, Solenn; Gueriau, Pierre; Mass, Jennifer

2015-11-01

High-flux synchrotron techniques allow microspectroscopic analyses of artworks that were not feasible even a few years ago, allowing for a more detailed characterization of their constituent materials and a better understanding of their chemistry. However, interaction between high-flux photons and matter at the sub-microscale can generate damages which are not visually detectable. We show here different methodologies allowing to evidence the damages induced by microscopic X-ray absorption near-edge structure spectroscopy analysis (μXANES) at the Fe and Zn K-edges of a painting dating from the turn of the twentieth century containing Prussian blue and zinc white. No significant degradation of the pigments was noticed, in agreement with the excellent condition of the painting. However, synchrotron radiation damages occurred at several levels, from chemical changes of the binder, modification of crystal defects in zinc oxide, to Prussian blue photoreduction. They could be identified by using both the μXANES signal during analysis and with photoluminescence imaging in the deep ultraviolet and visible ranges after analysis. We show that recording accurately damaged areas is a key step to prevent misinterpretation of results during future re-examination of the sample. We conclude by proposing good practices that could help in integrating radiation damage avoidance into the analytical pathway.

X-ray physico-chemical imaging during activation of cobalt-based Fischer-Tropsch synthesis catalysts

NASA Astrophysics Data System (ADS)

Beale, Andrew M.; Jacques, Simon D. M.; Di Michiel, Marco; Mosselmans, J. Frederick W.; Price, Stephen W. T.; Senecal, Pierre; Vamvakeros, Antonios; Paterson, James

2017-11-01

The imaging of catalysts and other functional materials under reaction conditions has advanced significantly in recent years. The combination of the computed tomography (CT) approach with methods such as X-ray diffraction (XRD), X-ray fluorescence (XRF) and X-ray absorption near-edge spectroscopy (XANES) now enables local chemical and physical state information to be extracted from within the interiors of intact materials which are, by accident or design, inhomogeneous. In this work, we follow the phase evolution during the initial reduction step(s) to form Co metal, for Co-containing particles employed as Fischer-Tropsch synthesis (FTS) catalysts; firstly, working at small length scales (approx. micrometre spatial resolution), a combination of sample size and density allows for transmission of comparatively low energy signals enabling the recording of `multimodal' tomography, i.e. simultaneous XRF-CT, XANES-CT and XRD-CT. Subsequently, we show high-energy XRD-CT can be employed to reveal extent of reduction and uniformity of crystallite size on millimetre-sized TiO2 trilobes. In both studies, the CoO phase is seen to persist or else evolve under particular operating conditions and we speculate as to why this is observed. This article is part of a discussion meeting issue 'Providing sustainable catalytic solutions for a rapidly changing world'.

Phase transitions in biogenic amorphous calcium carbonate

NASA Astrophysics Data System (ADS)

Gong, Yutao

Geological calcium carbonate exists in both crystalline phases and amorphous phases. Compared with crystalline calcium carbonate, such as calcite, aragonite and vaterite, the amorphous calcium carbonate (ACC) is unstable. Unlike geological calcium carbonate crystals, crystalline sea urchin spicules (99.9 wt % calcium carbonate and 0.1 wt % proteins) do not present facets. To explain this property, crystal formation via amorphous precursors was proposed in theory. And previous research reported experimental evidence of ACC on the surface of forming sea urchin spicules. By using X-ray absorption near-edge structure (XANES) spectroscopy and photoelectron emission microscopy (PEEM), we studied cross-sections of fresh sea urchin spicules at different stages (36h, 48h and 72h after fertilization) and observed the transition sequence of three mineral phases: hydrated ACC → dehydrated ACC → biogenic calcite. In addition, we unexpectedly found hydrated ACC nanoparticles that are surrounded by biogenic calcite. This observation indicates the dehydration from hydrated ACC to dehydrated ACC is inhibited, resulting in stabilization of hydrated ACC nanoparticles. We thought that the dehydration was inhibited by protein matrix components occluded within the biomineral, and we designed an in vitro assay to test the hypothesis. By utilizing XANES-PEEM, we found that SM50, the most abundant occluded matrix protein in sea urchin spicules, has the function to stabilize hydrated ACC in vitro.

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

PubMed

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

2012-07-01

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

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

Winter, Lea R.; Gomez, Elaine; Yan, Binhang

CO 2 hydrogenation over Fe-modified Ni/CeO 2 catalysts was investigated in a batch reactor using time-resolved in situ FTIR spectroscopy. Low loading of Ni/CeO 2 was associated with high selectivity to CO over CH 4, while higher Ni loading improved CO 2 hydrogenation activity with a reduced CO selectivity. X-ray absorption near-edge structure (XANES) analysis revealed Ni to be metallic for all catalysts including the CO-selective low loading 0.5% Ni catalyst, suggesting that the selectivity trend is due to structural rather than oxidation state effects. The loading amount of 1.5% Ni was selected for co-impregnation with Fe, based on themore » significant shift in product selectivity towards CH 4 for that loading amount, in order to shift the selectivity towards CO while maintaining high activity. Temperature programmed reduction (TPR) results indicated bimetallic interactions between Ni and Fe, and XANES analysis showed that about 70% of Fe in the bimetallic catalysts was oxidized. The Ni-Fe catalysts demonstrated improved selectivity towards CO without significantly compromising activity, coupling the high activity of Ni catalysts and the high CO selectivity of Fe. The general trends in Ni loading and bimetallic modification should guide efforts to develop non-precious metal catalysts for the selective production of CO by CO 2 hydrogenation.« less

Atomistic simulation and XAS investigation of Mn induced defects in Bi{sub 12}TiO{sub 20}

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

Rezende, Marcos V dos S.; Santos, Denise J.; Jackson, Robert A.

2016-06-15

This work reports an investigation of the valence and site occupancy of Mn dopants in Bi{sub 12}TiO{sub 20} (BTO: Mn) host using X-ray Absorption (XAS) and atomistic simulation techniques based on energy minimisation. X-ray Absorption Near Edge Structure (XANES) at the Mn K-edges gave typical results for Mn ions with mixed valences of 3+ and 4+. Extended X-ray Absorption Fine Structure (EXAFS) results indicated that Mn ions are probably substituted at Ti sites. Atomistic simulation was performed assuming the incorporation of Mn{sup 2+}, Mn{sup 3+} and Mn{sup 4+} ions at either Bi{sup 3+} or Ti{sup 4+} sites, and the resultsmore » were compared to XANES and EXAFS measurements. Electrical conductivity for pure and doped samples was used to evaluate the consistency of the proposed model. - Graphical abstract: The structure of Bi{sub 12}TiO{sub 20} (BTO). Display Omitted - Highlights: • Pure and Mn-doped Bi{sub 12}TiO{sub 20} samples were studied by experimental techniques combined with atomistic simulation. • Good agreement between experimental and simulation results was obtained. • XANES results suggest a mixture of 3+ and 4+ valences for Mn, occupying the Ti4+ site in both cases. • Charge compensation by holes is most energetically favoured, explaining the enhancement observed in AC dark conductivity.« less

Determining the Oxygen Fugacity of Lunar Pyroclastic Glasses Using Vanadium Valence - An Update

NASA Technical Reports Server (NTRS)

Karner, J. M.; Sutton, S. R.; Papike, J. J.; Shearer, C. K.; Jones, J. H.; Newville, M.

2004-01-01

We have been developing an oxygen barometer based on the valence state of V (V(2+), V(3+), V(4+), and V(5+)) in solar system basaltic glasses. The V valence is determined by synchrotron micro x-ray absorption near edge structure (XANES), which uses x-ray absorption associated with core-electronic transitions (absorption edges) to reveal a pre-edge peak whose intensity is directly proportional to the valence state of an element. XANES has advantages over other techniques that determine elemental valence because measurements can be made non-destructively in air and in situ on conventional thin sections at a micrometer spatial resolution with elemental sensitivities of approx. 100 ppm. Recent results show that fO2 values derived from the V valence technique are consistent with fO2 estimates determined by other techniques for materials that crystallized above the IW buffer. The fO2's determined by V valence (IW-3.8 to IW-2) for the lunar pyroclastic glasses, however, are on the order of 1 to 2.8 log units below previous estimates. Furthermore, the calculated fO2's decrease with increasing TiO2 contents from the A17 VLT to the A17 Orange glasses. In order to investigate these results further, we have synthesized lunar green and orange glasses and examined them by XANES.

The BALDER Beamline at the MAX IV Laboratory

NASA Astrophysics Data System (ADS)

Klementiev, K.; Norén, K.; Carlson, S.; Sigfridsson Clauss, K. G. V.; Persson, I.

2016-05-01

X-ray absorption spectroscopy (XAS) includes well-established methods to study the local structure around the absorbing element - extended X-ray absorption fine structure (EXAFS), and the effective oxidation number or to quantitatively determine the speciation of an element in a complex matrix - X-ray absorption near-edge structure (XANES). The increased brilliance and intensities available at the new generation of synchrotron light sources makes it possible to study, in-situ and in-operando, much more dilute systems with relevance for natural systems, as well as the micro-scale variability and dynamics of chemical reactions on the millisecond time-scale. The design of the BALDER beamline at the MAX IV Laboratory 3 GeV ring has focused on a high flux of photons in a wide energy range, 2.4-40 keV, where the K-edge is covered for the elements S to La, and the L 3-edge for all elements heavier than Sb. The overall design of the beamline will allow large flexibility in energy range, beam size and data collection time. The other focus of the beamline design is the possibility to perform multi-technique analyses on samples. Development of sample environment requires focus on implementation of auxiliary methods in such a way that techniques like Fourier transform infrared (FTIR) spectroscopy, UV-Raman spectroscopy, X-ray diffraction and/or mass spectrometry can be performed simultaneously as the XAS study. It will be a flexible system where different instruments can be plugged in and out depending on the needs for the particular investigation. Many research areas will benefit from the properties of the wiggler based light source and the capabilities to perform in-situ and in-operando measurements, for example environmental and geochemical sciences, nuclear chemistry, catalysis, materials sciences, and cultural heritage.

Uranium speciation as a function of depth in contaminated hanford sediments--a micro-XRF, micro-XRD, and micro- and bulk-XAFS study.

PubMed

Singer, David M; Zachara, John M; Brown, Gordon E

2009-02-01

The distribution and speciation of U and Cu in contaminated vadose zone and aquifer sediments from the U.S. DOE Hanford site (300 Area) were determined using a combination of synchrotron-based micro-X-ray fluorescence (microXRF) imaging, micro-X-ray absorption near edge structure (microXANES) spectroscopy, and micro-X-ray diffraction (microXRD) techniques combined with bulk U LIII-edge X-ray absorption fine structure (XAFS) spectroscopy. Samples were collected from within the inactive North Process Pond (NPP2) at 8 ft (2.4 m, NPP2-8) depth and 12 ft (3.7 m, NPP2-12) depth in the vadose zone, and fines were isolated from turbid groundwater just below the water Table (12-14 ft, approximately 4 m, NPP2-GW). microXRF imaging, microXRD, and microXANES spectroscopy revealed two major U occurrences within the vadose and groundwater zones: (1) low to moderate concentrations of U(VI) associated with fine-textured grain coatings that were consistently found to contain clinochlore (referred to here as chlorite) observed in all three samples, and (2) U(VI)-Cu(II) hotspots consisting of micrometer-sized particles associated with surface coatings on grains of muscovite and chlorite observed in samples NPP2-8' and NPP2-GW. In the aquifer fines (NPP2-GW), these particles were identified as cuprosklodowskite (cps: Cu[(UO2)(SiO2OH)]2 x 6H2O) and metatorbernite (mtb: Cu(UO2)2(PO4)2 x 8H2O). In contrast, the U-Cu-containing particles in the vadose zone were X-ray amorphous. Analyses of U LIII-edge XAFS spectra by linear-combination fitting indicated that U speciation consisted of (1) approximately 75% uranyl sorbed to chlorite and approximately 25% mtb-like X-ray amorphous U-Cu-phosphates (8 ft depth), (2) nearly 100% sorbed uranyl (12 ft depth), and (3) approximately 70% uranyl sorbed to chlorite and approximately 30% cps/mtb (groundwater zone). These findings suggest that dissolution of U(VI)-Cu(II)-bearing solids as well as desorption of U(VI), mainly from phyllosilicates, are important persistent sources of U(VI) to the associated uranium groundwater plume in Hanford Area 300.

How temperature determines formation of maghemite nanoparticles

NASA Astrophysics Data System (ADS)

Girod, Matthias; Vogel, Stefanie; Szczerba, Wojciech; Thünemann, Andreas F.

2015-04-01

We report on the formation of polymer-stabilized superparamagnetic single-core and multi-core maghemite nanoparticles. The particle formation was carried out by coprecipitation of Fe(II) and Fe(III) sulfate in a continuous aqueous process using a micromixer system. Aggregates containing 50 primary particles with sizes of 2 nm were formed at a reaction temperature of 30 °C. These particles aggregated further with time and were not stable. In contrast, stable single-core particles with a diameter of 7 nm were formed at 80 °C as revealed by small-angle X-ray scattering (SAXS) coupled in-line with the micromixer for particle characterization. X-ray diffraction and TEM confirmed the SAXS results. X-ray absorption near-edge structure spectroscopy (XANES) identified the iron oxide phase as maghemite.

Forcing Cesium into Higher Oxidation States Using Useful hard x-ray Induced Chemistry under High Pressure

NASA Astrophysics Data System (ADS)

Sneed, D.; Pravica, M.; Kim, E.; Chen, N.; Park, C.; White, M.

2017-10-01

This paper discusses our attempt to synthesize higher oxidation forms of cesium fluoride by pressurizing cesium fluoride in a fluorine-rich environment created via the x-ray decomposition of potassium tetrafluoroborate. This was done in order to confirm recent theoretical predictions of higher oxidation forms of CsFn. We discuss the development of a technique to produce molecular fluorine in situ via useful hard x-ray photochemistry, and the attempt to utilize this technique to form higher oxidation states of cesium fluoride. In order to verify the formation of the novel stoichiometric species of CsFn. X-ray Absorption Near Edge Spectroscopy (XANES) centered on the cesium K-edge was performed to probe the oxidation state of cesium as well as the local molecular coordination around Cs.

Selenium speciation in phosphate mine soils and evaluation of a sequential extraction procedure using XAFS.

PubMed

Favorito, Jessica E; Luxton, Todd P; Eick, Matthew J; Grossl, Paul R

2017-10-01

Selenium is a trace element found in western US soils, where ingestion of Se-accumulating plants has resulted in livestock fatalities. Therefore, a reliable understanding of Se speciation and bioavailability is critical for effective mitigation. Sequential extraction procedures (SEP) are often employed to examine Se phases and speciation in contaminated soils but may be limited by experimental conditions. We examined the validity of a SEP using X-ray absorption spectroscopy (XAS) for both whole and a sequence of extracted soils. The sequence included removal of soluble, PO 4 -extractable, carbonate, amorphous Fe-oxide, crystalline Fe-oxide, organic, and residual Se forms. For whole soils, XANES analyses indicated Se(0) and Se(-II) predominated, with lower amounts of Se(IV) present, related to carbonates and Fe-oxides. Oxidized Se species were more elevated and residual/elemental Se was lower than previous SEP results from ICP-AES suggested. For soils from the SEP sequence, XANES results indicated only partial recovery of carbonate, Fe-oxide and organic Se. This suggests Se was incompletely removed during designated extractions, possibly due to lack of mineral solubilization or reagent specificity. Selenium fractions associated with Fe-oxides were reduced in amount or removed after using hydroxylamine HCl for most soils examined. XANES results indicate partial dissolution of solid-phases may occur during extraction processes. This study demonstrates why precautions should be taken to improve the validity of SEPs. Mineralogical and chemical characterizations should be completed prior to SEP implementation to identify extractable phases or mineral components that may influence extraction effectiveness. Sequential extraction procedures can be appropriately tailored for reliable quantification of speciation in contaminated soils. Copyright © 2017 Elsevier Ltd. All rights reserved.

The oxidation state of Fe in MORB glasses and the oxygen fugacity of the upper mantle

NASA Astrophysics Data System (ADS)

Cottrell, Elizabeth; Kelley, Katherine A.

2011-05-01

Micro-analytical determination of Fe3+/∑Fe ratios in mid-ocean ridge basalt (MORB) glasses using micro X-ray absorption near edge structure (μ-XANES) spectroscopy reveals a substantially more oxidized upper mantle than determined by previous studies. Here, we show that global MORBs yield average Fe3+/∑Fe ratios of 0.16 ± 0.01 (n = 103), which trace back to primary MORB melts equilibrated at the conditions of the quartz-fayalite-magnetite (QFM) buffer. Our results necessitate an upward revision of the Fe3+/∑Fe ratios of MORBs, mantle oxygen fugacity, and the ferric iron content of the mantle relative to previous wet chemical determinations. We show that only 0.01 (absolute, or < 10%) of the difference between Fe3+/∑Fe ratios determined by micro-colorimety and XANES can be attributed to the Mössbauer-based XANES calibration. The difference must instead derive from a bias between micro-colorimetry performed on experimental vs. natural basalts. Co-variations of Fe3+/∑Fe ratios in global MORB with indices of low-pressure fractional crystallization are consistent with Fe3+ behaving incompatibly in shallow MORB magma chambers. MORB Fe3+/∑Fe ratios do not, however, vary with indices of the extent of mantle melting (e.g., Na2O(8)) or water concentration. We offer two hypotheses to explain these observations: The bulk partition coefficient of Fe3+ may be higher during peridotite melting than previously thought, and may vary with temperature, or redox exchange between sulfide and sulfate species could buffer mantle melting at ~ QFM. Both explanations, in combination with the measured MORB Fe3+/∑Fe ratios, point to a fertile MORB source with greater than 0.3 wt.% Fe2O3.

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

NASA Astrophysics Data System (ADS)

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

2013-04-01

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

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

NASA Astrophysics Data System (ADS)

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

1999-05-01

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

X-ray absorption and Raman spectroscopy studies of molybdenum environments in borosilicate waste glasses

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

McKeown, David A.; Gan, Hao; Pegg, Ian L.

2017-05-01

Mo-containing high-level nuclear waste borosilicate glasses were investigated as part of an effort to improve Mo loading while avoiding yellow phase crystallization. Previous work showed that additions of vanadium decrease yellow phase formation and increases Mo solubility. X-ray absorption spectroscopy (XAS) and Raman spectroscopy were used to characterize Mo environments in HLW borosilicate glasses and to investigate possible structural relationships between Mo and V. Mo XAS spectra for the glasses indicate isolated tetrahedral Mo6+O4 with Mo-O distances near 1.75 Å. V XANES indicate tetrahedral V5+O4 as the dominant species. Raman spectra show composition dependent trends, where Mo-O symmetrical stretch modemore » frequencies (ν1) are sensitive to the mix of alkali and alkaline earth cations, decreasing by up to 10 cm-1 for glasses that change from Li+ to Na+ as the dominant network-modifying species. This indicates that MoO4 tetrahedra are isolated from the borosilicate network and are surrounded, at least partly, by Na+ and Li+. Secondary ν1 frequency effects, with changes up to 7 cm-1, were also observed with increasing V2O5 and MoO3 content. These secondary trends may indicate MoO4-MoO4 and MoO4-VO4 clustering, suggesting that V additions may stabilize Mo in the matrix with respect to yellow phase formation.« less

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.

PubMed Central

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

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

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

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

2013-10-28

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

Copper uptake, intracellular localization, and speciation in marine microalgae measured by synchrotron radiation X-ray fluorescence and absorption microspectroscopy

DOE PAGES

Adams, Merrin S.; Dillon, Carolyn T.; Vogt, Stefan; ...

2016-07-20

Metal toxicity to aquatic organisms depends on the speciation of the metal and its binding to the critical receptor site(s) (biotic ligand) of the organism. The intracellular nature of the biotic ligand for Cu in microalgal cells was investigated using the high elemental sensitivity of microprobe synchrotron radiation X-ray fluorescence (SR-XRF) and X-ray absorption near-edge spectroscopy (XANES). The marine microalgae, Ceratoneis closterium, Phaeodactylum tricornutum, and Tetraselmis sp. were selected based on their varying sensitivities to Cu (72-h 50% population growth inhibitions of 8–47 μg Cu/L). Intracellular Cu in control cells was similar for all three species (2.5–3.2 × 10–15 gmore » Cu/cell) and increased 4-fold in C. closterium and Tetraselmis sp. when exposed to copper, but was unchanged in P. tricornutum (72-h exposure to 19, 40, and 40 μg Cu/L, respectively). Whole cell microprobe SR-XRF identified endogenous Cu in the central compartment (cytoplasm) of control (unexposed) cells. After Cu exposure, Cu was colocated with organelles/granules dense in P, S, Ca, and Si and this was clearly evident in thin sections of Tetraselmis sp. XANES indicated coexistence of Cu(I) and Cu(II) in control and Cu-exposed cells, with the Cu ligand (e.g., phytochelatin) in P. tricornutum different from that in C. closterium and Tetraselmis sp. Here, this study supports the hypothesis that Cu(II) is reduced to Cu(I) and that polyphosphate bodies and phytochelatins play a significant role in the internalization and detoxification of Cu in marine microalgae.« less

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

NASA Astrophysics Data System (ADS)

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

2011-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2017-04-01

Soil scientists see chemical characterization of phosphorus (e.g., chemical speciation) as a winning strategy to increase phosphorus use efficiency in agriculture, to understand the fate of applied P fertilizer in soils and to devise strategies to minimize P losses to the environment. Phosphorus (P) is majorly presented in soils as phosphate, bound to mineral components of soils such as Al-, Ca- and Fe-(hydr)oxides or associated with organic molecules, being thus generally referred to as organic phosphates. In addition, because of the turnover of P between plants and microbes, it delivers P back to soils as a mixture of species with high spatial and chemical heterogeneity, adding complexity to the determination of the P species contained in environmental samples. Therefore, due to the variety of forms that phosphate can present in soils, its precise chemical characterization can only be achieved using a set of analytical techniques. Although established methodologies (e. g., soil test P, sequential chemical fractionation, P isotherms) have been useful to subsidize information for the establishment of policies and guidelines for soil management and P fertilizers use, they have failed to provide detailed information on P chemistry and reactivity in soils in a more satisfactory manner, which are critical to predict P bioavailability to plants and loss potential to the environment. More recently, the association of wet chemistry analysis with spectroscopy and microscopy techniques has arguably represented the most successful means to chemically speciate phosphate in soils. This is because using qualitative (chemical speciation), quantitative (chemical fractionation) and spatial (microscopy) data allows for triangulation of information, thereby reducing bias and increasing validity of the results. The analysis framework that we propose in this study includes the use of (i) sequential chemical fractionation of soil P to determine the partitioning of P within the different P pools considered in the fractionation protocol, (ii) two synchrotron-based X-ray absorption spectroscopic techniques, XANES and EXAFS, for chemical characterization of the P forms and mineralogy of Fe-(hydr)oxides present in a sample, and (iii) Scanning Electron Microscopy and Energy-Dispersive spectroscopy, SEM/EDS, to provide complimentary information to corroborate and aid in the interpretation of our P XANES data. It was shown that the combination of techniques can assist us not only in the determination of the P chemical species present in a given material, but also to better understand the complex and dynamic processes to which P is subjected in soils. The association of spectroscopy (XANES and EXAFS) and microscopy (SEM/EDS) with wet chemistry data in this study was key to shift our understanding of the relationship between P and other soil mineral components from a macroscopic into a microscopic one. This represents a strong driving force to integrate the results of multi-analytical techniques into a more complete understanding of the systems under study. In addition, we provide a library of reference spectra for P K-edge XANES containing P sorbed to single and binary mixtures of mineral analogues intended to assist in the identification of P sorbed species commonly found in soils and sediments. Key-words: P K-edge XANES, Fe K-edge EXAFS, sequential chemical fractionation, soil phosphorus

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

Mukerjee, S.; Ziegelbauer, J; Arruda, T

Over the last few decades, researchers have made significant developments in producing more advanced electrocatalytic materials for power generation applications. For example, traditional fuel cell catalysts often involve high-priced precious metals such as Pt. However, in order for fuel cells to become commercially viable, there is a need to reduce or completely remove precious metal altogether. As a result, a myriad of novel, unconventional materials have been explored such as chalcogenides, porphyrins, and organic-metal-macrocycles for low/medium temperature fuel cells as well as enzymatic and microbial fuel cells. As these materials increasingly become more complex, researchers often find themselves in searchmore » of new characterization methods, especially those which are allow in situ and operando measurements with element specificity. One such method that has received much attention for analysis of electrocatalytic materials is X-ray absorption spectroscopy (XAS). XAS is an element specific, core level absorption technique which yields structural and electronic information. As a core electron method, XAS requires an extremely bright source, hence a synchrotron. The resulting intensity of synchrotron radiation allow for experiments to be conducted in situ, under electrochemically relevant conditions. Although a bulk-averaging technique requiring rigorous mathematical manipulation, XAS has the added benefit that it can probe materials which possess no long range order. This makes it ideal to characterize nano-scale electrocatalysts. XAS experiments are conducted by ramping the X-ray photon energy while measuring absorption of the incident beam the sample or by counting fluorescent photons released from a sample due to subsequent relaxation. Absorption mode XAS follows the Beer-Lambert Law, {mu}x = log(I{sub 0}/I{sub t}) (1) where {mu} is the absorption coefficient, x is the sample thickness and I{sub 0} and I{sub t} are the intensities of the incident and transmission beams respectively. When the energy of the incident X-rays exceed the electron binding energy (E{sub 0}) of the element under investigation, the electron is ejected from the core to available excited states in the form of a photoelectron with kinetic energy: E{sub k} = h? - E{sub 0} (2) with, E{sub k} being the kinetic energy of the released photoelectron and h? the energy of the incident beam. In general, the X-ray absorption spectrum is broken down into two distinct energy regions: the X-ray absorption near-edge structure or XANES (-50eV {le} E{sub 0} {le} 50eV) and the extended X-ray absorption fine-structure or EXAFS (50eV {le} E{sub 0} {le} {approx}1000eV). The XANES region is dominated by low-energy photoelectrons which undergo multiple scattering events. As such, it can reveal information about oxidation state, local symmetry, electronic structure, and the extent of oxidation of a material. Due to this complex multiple scattering, there is no simple XANES equation to describe it quantitatively. However, recent advancements in computers and the evolution of numerical methods such as the FEFF code have made possible reliable XANES simulations. Photoelectrons in the EXAFS region have high enough E{sub k} to undergo primarily single back-scattering events. These back-scattered photoelectrons interfere with the outgoing photoelectrons, causing the oscillations in the absorption spectrum. Using the previously developed EXAFS equations it is now possible to model EXAFS data to determine coordination numbers, bond distances, and mean-square disorder (commonly referred to as Debye-Waller factor). EXAFS data is often shown by Fourier Transforming KSpace into distance, r, space where the total magnitude is plotted against the radial coordinates. This allow for easy qualitative comparison of samples. Employing EXAFS on nanoscale materials has the added advantage that it can quantitatively illustrate changes in atom-atom coordination, which can be related to particle size or morphology. Overall this technique enables the measurement of both bulk and surface adsorbed species with element specificity under actual electrochemical operating conditions. Thus this represents the one of the most powerful methods to understand the exact role of the reaction center and degradation processes such as sintering and corrosion.« less

Effects of Sulfation Level on the Desulfation Behavior of Presulfated Pt-BaO/Al2O3 Lean

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

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

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 phasemore » 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.« less

Mineral associations and character of isotopically anomalous organic material in the Tagish Lake carbonaceous chondrite

NASA Astrophysics Data System (ADS)

Zega, Thomas J.; Alexander, Conel M. O.'D.; Busemann, Henner; Nittler, Larry R.; Hoppe, Peter; Stroud, Rhonda M.; Young, Andrea F.

2010-10-01

We report a coordinated analytical study of matrix material in the Tagish Lake carbonaceous chondrite in which the same small (⩽20 μm) fragments were measured by secondary ion mass spectrometry (SIMS), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS), electron energy-loss spectroscopy (EELS), and X-ray absorption near-edge spectroscopy (XANES). SIMS analysis reveals H and N isotopic anomalies (hotspots), ranging from hundreds to thousands of nanometers in size, which are present throughout the fragments. Although the differences in spatial resolution of the SIMS techniques we have used introduce some uncertainty into the exact location of the hotspots, in general, the H and N isotopic anomalies are spatially correlated with C enrichments, suggesting an organic carrier. TEM analysis, enabled by site-specific extraction using a focused-ion-beam scanning-electron microscope, shows that the hotspots contain an amorphous component, Fe-Ni sulfides, serpentine, and mixed-cation carbonates. TEM imaging reveals that the amorphous component occurs in solid and porous forms, EDS indicates that it contains abundant C, and EELS and XANES at the C K edge reveal that it is largely aromatic. This amorphous component is probably macromolecular C, likely the carrier of the isotopic anomalies, and similar to the material extracted from bulk samples as insoluble organic matter. However, given the large sizes of some of the hotspots, the disparity in spatial resolution among the various techniques employed in our study, and the phases with which they are associated, we cannot entirely rule out that some of the isotopic anomalies are carried by inorganic material, e.g., sheet silicates. The isotopic composition of the organic matter points to an initially primitive origin, quite possibly within cold interstellar clouds or the outer reaches of the solar protoplanetary disk. The association of organic material with secondary phases, e.g., serpentine and carbonates, suggests that the organic matter was susceptible to parent-body processing, and thus, isotopic dilution.

A Multi-spectroscopic Investigation of Sulphur Speciation in Silicate Glasses and Slags

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

Bingham, P.; Connelly, A; Hand, R

2010-01-01

Sulphur K-edge x-ray absorption near-edge structure (XANES), sulphur K{sub {alpha}} and K{sub {beta}} high resolution x-ray emission spectroscopies (XES), electron paramagnetic resonance (EPR) and optical absorption spectroscopies have been used to study the speciation of sulphur in a range of soda-lime-silica glasses and silicate slags. Several inorganic standards with known sulphur oxidation states and structural environments have also been analysed. Results confirm that the average oxidation state of sulphur in glasses decreases, as expected, in the order (colourless>light olive>dark olive>light amber>dark amber). This behaviour is consistent with decreasing S{sup 6+}/{Sigma}S ratio, which has been quantified by linear combination fitting ofmore » XES S K{alpha} spectra, and with analysed sulphur contents which exhibit a characteristic relationship with oxygen partial pressure, pO{sub 2}. A combination of S{sup 6+}, S{sup 5+}, S{sup 4+} and more reduced sulphur species has been detected in olive and amber glasses. The S{sup 4+} and S{sup 5+} species are most evident in olive-coloured glasses produced under moderately reducing conditions that coincide with minimum sulphur solubilities. The reduced form of sulphur, present in all reduced glasses, is interpreted as being present as S{sup 2-} on the basis of XANES, XES, EPR and optical measurements. An alternative interpretation of the data is that there is a continuum of less strongly reduced species, primarily S{sup +} and S{sup 2+}; this interpretation has less merit. In this paper we show that the established relationship that describes sulphur redox only in terms of S{sup 6+} and S{sup 2-}, and which states that only these two species co-exist over a narrow, moderately reducing range of pO{sub 2}, does not fully describe the behaviour of S in the industrial, non-equilibrated glasses studied. Hence this relationship requires slight modification for non-equilibrated systems to explain the existence of intermediate sulphur oxidation states such as S{sup 4+} and S{sup 5+}, particularly within the intermediate pO{sub 2} range that corresponds with sulphur solubility minima.« less

Speciation of Mg in biogenic calcium carbonates

NASA Astrophysics Data System (ADS)

Farges, F.; Meibom, A.; Flank, A.-M.; Lagarde, P.; Janousch, M.; Stolarski, J.

2009-11-01

A selection of marine biominerals, mostly aragonitic coral skeletons were probed at the Mg K-edge by XANES spectroscopy coupled to μXRF methods and compared to an extensive set of relevant model compounds (silicates, carbonates, oxides and organic). Extensive methodologies are required to better describe the speciation of Mg in those minerals. A combination of ab-initio XANES calculations for defective clusters around Mg in aragonite together with wavelets analyzes of the XANES region are required to robustly interpret the spectra. When using those methodologies, the speciation of Mg ranges from a magnesite-type environment in some scleractinian corals to an organic-type environment. In all environments, the Mg-domains probed appear to be less than 1 nm in size.

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

PubMed

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

2004-07-01

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

Vertical changes of the Co and Mn speciation along a lateritic regolith developed on peridotites (New Caledonia)

NASA Astrophysics Data System (ADS)

Dublet, Gabrielle; Juillot, Farid; Brest, Jessica; Noël, Vincent; Fritsch, Emmanuel; Proux, Olivier; Olivi, Luca; Ploquin, Florian; Morin, Guillaume

2017-11-01

Because they can host significant amounts of Co, the Mn-oxides are commonly considered as the major Co-bearing mineral species in lateritic environments. However, little is known about the process leading to the formation and/or the weathering of these Co-rich Mn-oxides. This lack of knowledge is mainly due to the fact that Co concentrations are too low in primary silicates for classical speciation analysis. In this study, we investigated both Co and Mn speciation in a 64 m thick lateritic regolith developed upon peridotites in New Caledonia, by combining High Energy Resolution Fluorescence Detection X-ray absorption Near Edge Structure (HERFD-XANES) spectroscopy at the Co K-edge with classical XANES spectroscopy at the Mn K-edge, bulk chemistry (ICP) and mineralogy (XRD). The results obtained provide new insights into the evolution of Co and Mn speciation as a function of the weathering stages. Co and Mn primarily occur as Co(II) and Mn(II,III) in olivine and serpentine in the bedrock. During the first weathering stage, these forms of Co and Mn are progressively oxidized toward Co(III) and Mn(III,IV), which occur mainly as Co(III)-bearing Mn(III/IV)-oxides in the transition between the saprolite and the laterite. In the uppermost lateritic horizons, long-time weathering resulted in a strong leaching of Co and Mn, and the remaining of these elements occurs as Co(II) and Mn(III) substituting for Fe(III) in goethite. This latter scavenging process emphasizes the importance of Fe-oxides for the long-term stabilization of Co and Mn in such deeply weathered laterites.

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

PubMed

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

2015-09-08

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

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

NASA Astrophysics Data System (ADS)

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

2007-12-01

Marine iron-oxyhydroxide/manganese-oxide crusts (Fe-Mn crusts) provide the richest known source of tellurium (Te). Te averages about 50 ppm in Fe-Mn crusts distributed globally, with concentrations locally up to 210 ppm. The sorption of Te onto Fe-Mn crusts likely controls the dominant redox species and concentration of Te in the global ocean (Hein et al., 2003). However, little is known about the mechanisms by which Te is sequestered by Fe-Mn crusts and Fe-Mn colloids in the water column, and then stabilized in the Fe/Mn oxyhydroxide/oxide framework. Two primary hypotheses are being tested: (a) Te(IV) is initially the predominant adsorbed species, which is subsequently oxidized on the Fe-oxyhydroxide and/or Mn oxide phases in natural systems and in sorption experiments. (b) Once oxidized, Te(VI) remains tightly bound to the Fe phase in Fe-Mn crusts as adsorbed surface complexes. These hypotheses are being examined by using the Stanford Synchrotron Radiation Laboratory's (SSRL) synchrotron-based XANES (x-ray absorption near-edge structure) spectroscopy to assess Te oxidation state in natural samples and samples in which Te(IV) and Te(VI) were sorbed onto synthetic and natural FeOOH and Mn oxides. EXAFS (extended x-ray absorption fine structure) spectroscopy is being used to resolve the local molecular-scale structure around Te in these same samples. Data have thus far been obtained for six Fe-Mn crusts from a variety of geographic locations and water depths of occurrence, with differing chemical compositions; and two model compounds, Te(IV) sorbed on FeOOH and Te(IV) sorbed on MnO2. XANES data show that for all six Fe-Mn crust samples, 85 to 100 percent of the Te occurs as Te(VI). For the model compounds, about 65 percent of the Te(IV) sorbed onto the MnO2 had oxidized to Te(VI) by the time (one week) the sample was analyzed, whereas Te sorbed onto FeOOH remained at about 100 percent Te(IV). The most striking result from the EXAFS data is that all spectra for the six Fe-Mn crust samples are virtually identical, regardless of location, depositional conditions, or chemical and mineralogical compositions. This uniformity indicates that the local structure around Te is similar for all samples and, therefore, the mode of incorporation of Te into the Fe-Mn crusts does not vary despite varying environments of formation. This implies that a single set of processes applies throughout the global ocean to the incorporation of Te into Fe-Mn crusts. Hein, J.R., Koschinsky, A., and Halliday, A.N., 2003, Geochim. Cosmochim. Acta 67: 1117-1127.

An X-ray absorption spectroscopic study of the metal site preference in Al1-xGaxFeO3

NASA Astrophysics Data System (ADS)

Walker, James D. S.; Grosvenor, Andrew P.

2013-01-01

Magnetoelectric materials have potential for being introduced into next generation technologies, especially memory devices. The AFeO3 (Pna21; A=Al, Ga) system has received attention to better understand the origins of magnetoelectric coupling. The magnetoelectric properties this system exhibits depend on the amount of anti-site disorder present, which is affected by the composition and the method of synthesis. In this study, Al1-xGaxFeO3 was synthesized by the ceramic method and studied by X-ray absorption spectroscopy. Al L2,3-, Ga K-, and Fe K-edge spectra were collected to examine how the average metal coordination number changes with composition. Examination of XANES spectra from Al1-xGaxFeO3 indicate that with increasing Ga content, Al increasingly occupies octahedral sites while Ga displays a preference for occupying the tetrahedral site. The Fe K-edge spectra indicate that more Fe is present in the tetrahedral site in AlFeO3 than in GaFeO3, implying more anti-site disorder is present in AlFeO3.

Thermal decomposition of ammonium hexachloroosmate.

PubMed

Asanova, T I; Kantor, I; Asanov, I P; Korenev, S V; Yusenko, K V

2016-12-07

Structural changes of (NH 4 ) 2 [OsCl 6 ] occurring during thermal decomposition in a reduction atmosphere have been studied in situ using combined energy-dispersive X-ray absorption spectroscopy (ED-XAFS) and powder X-ray diffraction (PXRD). According to PXRD, (NH 4 ) 2 [OsCl 6 ] transforms directly to metallic Os without the formation of any crystalline intermediates but through a plateau where no reactions occur. XANES and EXAFS data by means of Multivariate Curve Resolution (MCR) analysis show that thermal decomposition occurs with the formation of an amorphous intermediate {OsCl 4 } x with a possible polymeric structure. Being revealed for the first time the intermediate was subjected to determine the local atomic structure around osmium. The thermal decomposition of hexachloroosmate is much more complex and occurs within a minimum two-step process, which has never been observed before.

Forcing Cesium into Higher Oxidation States Using Useful hard x-ray Induced Chemistry under High Pressure

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

Sneed, D.; Pravica, M.; Kim, E.

This paper discusses our attempt to synthesize higher oxidation forms of cesium fluoride by pressurizing cesium fluoride in a fluorine-rich environment created via the x-ray decomposition of potassium tetrafluoroborate. This was done in order to confirm recent theoretical predictions of higher oxidation forms of CsFn. We discuss the development of a technique to produce molecular fluorine in situ via useful hard x-ray photochemistry, and the attempt to utilize this technique to form higher oxidation states of cesium fluoride. In order to verify the formation of the novel stoichiometric species of CsFn. X-ray Absorption Near Edge Spectroscopy (XANES) centered on themore » cesium K-edge was performed to probe the oxidation state of cesium as well as the local molecular coordination around Cs.« less

The irreversible formation of palladium carbide during hydrogenation of 1-pentyne over silica-supported palladium nanoparticles: in situ Pd K and L3 edge XAS.

PubMed

Tew, Min Wei; Nachtegaal, Maarten; Janousch, Markus; Huthwelker, Thomas; van Bokhoven, Jeroen A

2012-04-28

The catalytically active phase of silica-supported palladium catalysts in the selective and non-selective hydrogenation of 1-pentyne was determined using in situ X-ray absorption spectroscopy at the Pd K and L(3) edges. Upon exposure to alkyne, a palladium carbide-like phase rapidly forms, which prevents hydrogen to diffuse into the bulk of the nano-sized particles. Both selective and non-selective hydrogenation occur over carbided particles. The palladium carbide-like phase is stable under reaction conditions and only partially decomposes under high hydrogen partial pressure. Non-selective hydrogenation to pentane is not indicative of hydride formation. The palladium carbide phase was detected in the EXAFS analysis and the K edge XANES showed representative features. This journal is © the Owner Societies 2012

Local Structure and Surface Properties of CoxZn1-xO Thin Films for Ozone Gas Sensing.

PubMed

Catto, Ariadne C; Silva, Luís F da; Bernardi, Maria Inês B; Bernardini, Sandrine; Aguir, Khalifa; Longo, Elson; Mastelaro, Valmor R

2016-10-05

A detailed study of the structural, surface, and gas-sensing properties of nanostructured Co x Zn 1-x O films is presented. X-ray diffraction (XRD) analysis revealed a decrease in the crystallization degree with increasing Co content. The X-ray absorption near-edge structure (XANES) and X-ray photoelectron spectroscopies (XPS) revealed that the Co 2+ ions preferentially occupied the Zn 2+ sites and that the oxygen vacancy concentration increased as the amount of cobalt increased. Electrical measurements showed that the Co dopants not only enhanced the sensor response at low ozone levels (ca. 42 ppb) but also led to a decrease in the operating temperature and improved selectivity. The enhancement in the gas-sensing properties was attributed to the presence of oxygen vacancies, which facilitated ozone adsorption.

Experimental and theoretical XANES of CdSxSe1-x nanostructures

NASA Astrophysics Data System (ADS)

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

2014-03-01

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

Investigation of electronic and local structural changes during lithium uptake and release of nano-crystalline NiFe2O4 by X-ray absorption spectroscopy

NASA Astrophysics Data System (ADS)

Zhou, Dong; Permien, Stefan; Rana, Jatinkumar; Krengel, Markus; Sun, Fu; Schumacher, Gerhard; Bensch, Wolfgang; Banhart, John

2017-02-01

Nano-crystalline NiFe2O4 particles were synthesized and used as active electrode material for a lithium ion battery that showed a high discharge capacity of 1534 mAh g-1 and charge capacity of 1170 mAh g-1 during the 1st cycle. X-ray absorption spectroscopy including XANES and EXAFS were used to investigate electronic and local structural changes of NiFe2O4 during the 1st lithiation and de-lithiation process. As lithium is inserted into the structure, tetrahedral site Fe3+ ions are reduced to Fe2+ and moved from tetrahedral sites to empty octahedral sites, while Ni2+ ions are unaffected. As a consequence, the matrix spinel structure collapses and transforms to an intermediate rock-salt monoxide phase. Meanwhile, the inserted Li is partially consumed by the formation of SEI and other side reactions during the conversion reaction. With further lithiation, the monoxide phase is reduced to highly disordered metallic Fe/Ni nanoparticles with a number of nearest neighbors of 6.0(8) and 8.1(4) for Fe and Ni, respectively. During subsequent de-lithiation, the metal particles are individually re-oxidized to Fe2O3 and NiO phases instead to the original NiFe2O4 spinel phase.

Examination of Cr(VI) treatment by zero-valent iron using in situ, real-time X-ray absorption spectroscopy and Cr isotope measurements

NASA Astrophysics Data System (ADS)

Jamieson-Hanes, Julia H.; Lentz, Adam M.; Amos, Richard T.; Ptacek, Carol J.; Blowes, David W.

2014-10-01

A series of replicate flow-through cell experiments was conducted to characterize Cr isotope fractionation during Cr(VI) treatment by granular zero-valent iron (ZVI). Synthetic groundwater containing 50 mg L-1 Cr(VI) was pumped upward through a custom-made cell packed with ZVI under anaerobic conditions. The geochemical evolution of the system was monitored using pH and redox measurements, while aqueous effluent samples were retained for analysis of cations and Cr isotopes. Real-time, in situ X-ray absorption near edge structure (XANES) spectroscopy collected via a Kapton® window in the cell provided additional information on the speciation of the reaction products. Increases in δ53Cr values corresponding to decreases in Cr(VI) concentration suggested the occurrence of redox processes. Spectroscopic results correlated well with the isotope data, indicating reduction of Cr(VI) to Cr(III). The isotope data did not appear to follow a single trend. A two-stage system was proposed to explain the complex isotope trend, where the rapid Cr removal was associated with very little fractionation (ε = -0.2‰), whereas slower removal was associated with a greater degree of fractionation (ε = -1.2‰ to -1.5‰). Reactive transport modeling was used to quantify distinct isotope fractionation values (ε), differentiated by a significant change in the Cr removal rate.

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

PubMed

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

2014-10-22

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

Location and Electronic Nature of Phosphorus in the Si Nanocrystal − SiO2 System

PubMed Central

König, Dirk; Gutsch, Sebastian; Gnaser, Hubert; Wahl, Michael; Kopnarski, Michael; Göttlicher, Jörg; Steininger, Ralph; Zacharias, Margit; Hiller, Daniel

2015-01-01

Up to now, no consensus exists about the electronic nature of phosphorus (P) as donor for SiO2-embedded silicon nanocrystals (SiNCs). Here, we report on hybrid density functional theory (h-DFT) calculations of P in the SiNC/SiO2 system matching our experimental findings. Relevant P configurations within SiNCs, at SiNC surfaces, within the sub-oxide interface shell and in the SiO2 matrix were evaluated. Atom probe tomography (APT) and its statistical evaluation provide detailed spatial P distributions. For the first time, we obtain ionisation states of P atoms in the SiNC/SiO2 system at room temperature using X-ray absorption near edge structure (XANES) spectroscopy, eliminating structural artefacts due to sputtering as occurring in XPS. K energies of P in SiO2 and SiNC/SiO2 superlattices (SLs) were calibrated with non-degenerate P-doped Si wafers. results confirm measured core level energies, connecting and explaining XANES spectra with h-DFT electronic structures. While P can diffuse into SiNCs and predominantly resides on interstitial sites, its ionization probability is extremely low, rendering P unsuitable for introducing electrons into SiNCs embedded in SiO2. Increased sample conductivity and photoluminescence (PL) quenching previously assigned to ionized P donors originate from deep defect levels due to P. PMID:25997696

Tuning Ni-catalyzed CO 2 hydrogenation selectivity via Ni-ceria support interactions and Ni-Fe bimetallic formation

DOE PAGES

Winter, Lea R.; Gomez, Elaine; Yan, Binhang; ...

2017-10-16

CO 2 hydrogenation over Fe-modified Ni/CeO 2 catalysts was investigated in a batch reactor using time-resolved in situ FTIR spectroscopy. Low loading of Ni/CeO 2 was associated with high selectivity to CO over CH 4, while higher Ni loading improved CO 2 hydrogenation activity with a reduced CO selectivity. X-ray absorption near-edge structure (XANES) analysis revealed Ni to be metallic for all catalysts including the CO-selective low loading 0.5% Ni catalyst, suggesting that the selectivity trend is due to structural rather than oxidation state effects. The loading amount of 1.5% Ni was selected for co-impregnation with Fe, based on themore » significant shift in product selectivity towards CH 4 for that loading amount, in order to shift the selectivity towards CO while maintaining high activity. Temperature programmed reduction (TPR) results indicated bimetallic interactions between Ni and Fe, and XANES analysis showed that about 70% of Fe in the bimetallic catalysts was oxidized. The Ni-Fe catalysts demonstrated improved selectivity towards CO without significantly compromising activity, coupling the high activity of Ni catalysts and the high CO selectivity of Fe. The general trends in Ni loading and bimetallic modification should guide efforts to develop non-precious metal catalysts for the selective production of CO by CO 2 hydrogenation.« less

Insight into the Capacity Fading Mechanism of Amorphous Se 2 S 5 Confined in Micro/Mesoporous Carbon Matrix in Ether-Based Electrolytes

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

Xu, Gui-Liang; Ma, Tianyuan; Sun, Cheng-Jun

2016-04-13

In contrast to the stable cycle performance of space confined Se-based cathodes for lithium batteries in carbonate-based electrolytes, their common capacity fading in ether-based electrolytes has been paid less attention and not yet well-addressed so far. In this work, the lithiation/delithiation of amorphous Se2S5 confined in micro/mesoporous carbon (Se2S5/MPC) cathode was investigated by in situ X-ray near edge absorption spectroscopy (XANES) and theoretical calculations. The Se2S5/MPC composite was synthesized by a modified vaporization-condensation method to ensure a good encapsulation of Se2S5 into the pores of MPC host. In situ XANES results illustrated that the lithiation/delithiation reversibility of Se component wasmore » gradually decreased in ether-based electrolytes, leading to an aggravated formation of long-chain polyselenides during cycling and further capacity decay. Moreover, ab initio calculations revealed that the binding energy of polyselenides (Li2Sen) with carbon host is in an order of Li2Se6 > Li2Se4 > Li2Se. The insights into the failure mechanism of Se-based cathode gain in this work are expected to serve as a guide for future design on high performance Se-based cathodes.« less

Observation of high-spin mixed oxidation state of cobalt in ceramic Co3TeO6

NASA Astrophysics Data System (ADS)

Singh, Harishchandra; Ghosh, Haranath; Chandrasekhar Rao, T. V.; Sinha, A. K.; Rajput, Parasmani

2014-12-01

We report coexistence of high spin Co3+ and Co2+ in ceramic Co3TeO6 using X-ray Absorption Near Edge Structure (XANES), DC magnetization, and first principles ab-initio calculations. The main absorption line of cobalt Co K-edge XANES spectra, along with a linear combination fit, led us to estimate relative concentration of Co2+ and Co3+as 60:40. The pre edge feature of XANES spectrum shows crystal field splitting of ˜1.26 eV between eg and t2g states, suggesting a mixture of high spin states of both Co2+ and Co3+. Temperature dependent high field DC magnetization measurements reveal dominant antiferromagnetic order with two Neel temperatures (TN1 ˜ 29 K and TN2 ˜ 18 K), consistent with single crystal study. A larger effective magnetic moment is observed in comparison to that reported for single crystal (which contains only Co2+), supports our inference that Co3+ exists in high spin state. Furthermore, we show that both Co2+ and Co3+ being in high spin states constitute a favorable ground state through first principles ab-initio calculations, where Rietveld refined synchrotron X-ray diffraction data are used as input.

Communication: X-ray excited optical luminescence from TbCl3 at the giant resonance of terbium

NASA Astrophysics Data System (ADS)

Heigl, F.; Jürgensen, A.; Zhou, X.-T.; Hu, Y.-F.; Zuin, L.; Sham, T. K.

2013-02-01

We have studied the optical recombination channels of TbCl3 using x-ray excited optical luminescence at the N4,5 absorption edge of Tb (giant resonance) in both the energy and time domain. The luminescence exhibits a relatively fast 5D3, and a slow 5D4 decay channel in the blue and green, respectively. The rather short lifetime of the 5D3 state indicates that the decay is mainly driven by Tb-Tb ion interaction via non-radiative energy transfer (cross-relaxation). At the giant resonance the X-ray Absorption Near Edge Structure (XANES) recorded using partial photoluminescence yield is inverted. In the pre-edge region the contrast of the spectral feature is significantly better in optical XANES than in total electron yield. Changes in the intensity of 5D3-7F5 (544 nm) and 5D4-7F6 (382 nm) optical transitions as the excitation energy is tuned across the giant resonance are also noted. The results provide detailed insight into the dynamics of the optical recombination channels and an alternative method to obtain high sensitivity, high energy resolution XANES at the giant resonance of light emitting rare-earth materials.

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

NASA Astrophysics Data System (ADS)

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

2015-05-01

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

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

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

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

2015-05-07

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

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

PubMed

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

2015-05-01

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

X-Ray absorption spectroscopy quantitative analysis of biomimetic copper(II) complexes with tridentate nitrogen ligands mimicking the tris(imidazole) array of protein centres.

PubMed

Borghi, Elena; Casella, Luigi

2010-02-21

In this study copper(ii) complexes with the tridentate nitrogen ligand bis[2-(1-methylbenzimidazol-2-yl)ethyl]amine (2-BB) are considered as model compounds for the Cu-tris(imidazole) array found in several copper proteins. 2-BB chelates copper(ii) forming two six-membered rings and the complexes contain methanol, nitrite, azide and water as ancillary ligands; both the coordination numbers and stereochemistries differ in these complexes. Their key structural features were investigated by using full multiple-scattering theoretical analysis of the copper K-edge X-ray absorption spectrum with the MXAN code. We showed that using cluster sizes large enough to include all atoms of the ligand, the analysis of the XANES region can give both a structural model of the metal centre and map the structure of the 2-BB complexes. Complex [Cu(2-BB)(N(3))](+) provided a critical test through the comparison of the XANES simulation results with crystallographic data, thus permitting the extension of the method to the complex [Cu(2-BB)(H(2)O)(n)](+) (n = 1 or 2), for which crystallographic data are not available but is expected to bear a five-coordinated Cu(3N)(2O) core (n = 2). The structural data of [Cu(2-BB)(MeOH)(ClO(4))](+) and [Cu(2-BB)(NO(2))](+), both with a Cu(3N)(2O) core but with a different stereochemistry, were used as the starting parameters for two independent simulations of the XANES region of the [Cu(2-BB)(H(2)O)(2)](+) cation. The two structural models generated by simulation converge towards a structure for the aqua-cation with a lower coordination number. New calculations, where four-coordinated Cu(3N)(O) cores were considered as the starting structures, validated that the structure of the aqua-complex in the powder state has a copper(ii) centre with a four-coordinated Cu(3N)(O) core and a molecular formula [Cu(2-BB)(H(2)O)](ClO(4)).(H(2)O). A water solvation molecule, presumed to be disordered from the simulations with the two Cu(3N)(2O) cores, is present. The successful treatment of this Cu-2-BB complex system allows the extension of the method to other biomimetic compounds when a structural characterization is lacking.

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

NASA Astrophysics Data System (ADS)

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

2016-02-01

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

X-ray absorption spectroscopic studies on gold nanoparticles in mesoporous and microporous materials.

PubMed

Akolekar, Deepak B; Foran, Garry; Bhargava, Suresh K

2004-05-01

Au L(3)-edge X-ray absorption spectroscopic measurements were carried out over a series of mesoporous and microporous materials containing gold nanoparticles to investigate the effects of the host matrix and preparation methods on the properties of gold nanoparticles. The materials of structure type MCM-41, ZSM-5, SAPO-18 and LSX with varying framework composition containing low concentrations of gold nanoparticles were prepared and characterized. In these materials the size of the gold nanoparticles varied in the range approximately 1 to 4 nm. A series of gold nanoparticles within different mesoporous and microporous materials have been investigated using X-ray absorption fine structure (XANES, EXAFS) and other techniques. Information such as atomic distances, bonding and neighbouring environment obtained from XAFS measurements was useful in elucidating the nature and structure of gold nanoparticles on these catalytic materials. The influence of the high-temperature (823, 1113, 1273 K) treatment on gold nanoparticles inside the mesoporous matrix was investigated using the XAFS technique. The XAFS and XANES results confirm various characteristics of gold nanoparticles in these materials suitable for catalysis, fabrication of nanodevices and other applications.

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

NASA Astrophysics Data System (ADS)

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

2014-12-01

Redox state of magma is important to understand dynamics of volcanic eruptions because magma properties such as composition of degassed volatiles, stability field of minerals, and rheology of magma depend on redox state. To evaluate redox state of magma, Fe3+/ΣFe ratio [= Fe3+/( Fe3++ Fe2+)] of volcanic glass has been measured non-destructively by Fe-K edge μ-XANES (micro X-ray Absorption Near Edge Structure) spectroscopy (e.g., Cottrell and Kelly, 2011). We performed textural, compositional, and Fe-K edge μ-XANES analyses on volcanic ash to infer oxidation process of magma at shallow conduit during eruption at Bromo Volcano, Indonesia. The volcanic ash particles were collected in 24th March 2011 by real-time sampling from ongoing activity. The activity was characterized by strombolian eruption showing magma head ascended to near the ground surface. The ash sample contains two type of volcanic glasses named as Brown and Black glasses (BrG and BlG), based on their color. Textual analysis shows microlite crystallinities are same in the two type of glasses, ranging from 0 to 3 vol.%. EPMA analyses show that all of the glasses have almost identical andesitic composition with SiO2 = 60 wt.%. In contrast, Fe-K edge μ-XANES spectra with the analytical method by Ishibashi et al. (in prep) demonstrate that BrG (Fe3+/ΣFe = 0.20-0.26) is more oxidized than BlG (Fe3+/ΣFe = 0.32-0.60). From combination of the glass composition, the measured Fe3+/ΣFe ratio and 1060 degree C of temperature (Kress and Carmichael, 1991), the oxygen fugacities are estimated to be NNO and NNO+4 for BrG and BlG, respectively. The volcanic glasses preserve syn-eruptive physicochemical conditions by rapid quenching due to their small size ranging from 125 to 250 μm. Our results demonstrate that BrG and BlG magmas are textually and chemically identical but their redox conditions are different at the eruption. The oxidation of magma can be caused by following two processes; 1) diffusive transport of oxygen, and 2) dissociation reaction of hydrogen from magma head. The two processes should be easy to occur in shallower region of the conduit. Therefore we suggest BlG magma existed in shallower part of the conduit than BrG magma. The K-edge μ-XANES analysis can be strong tool for understanding on degassing and ascent process of magma at shallow conduit.

Arsenic sorption to nanoparticulate mackinawite (FeS): An examination of phosphate competition.

PubMed

Niazi, Nabeel Khan; Burton, Edward D

2016-11-01

Nanoparticulate mackinawite (FeS) can be an important host-phase for arsenic (As) in sulfidic, subsurface environments. Although not previously investigated, phosphate (PO 4 3- ) may compete with As for available sorption sites on FeS, thereby enhancing As mobility in FeS-bearing soils, sediments and groundwater systems. In this study, we examine the effect of PO 4 3- on sorption of arsenate (As(V)) and arsenite (As(III)) to nanoparticulate FeS at pH 6, 7 and 9. Results show that PO 4 3- (at 0.01-1.0 mM P) did not significantly affect sorption of either As(V) or As(III) to nanoparticulate FeS at initial aqueous As concentrations ranging from 0.01 to 1.0 mM. At pH 9 and 7, sorption of both As(III) and As(V) to nanoparticulate FeS was similar, with distribution coefficient (K d ) values spanning 0.76-15 L g -1 (which corresponds to removal of 87-98% of initial aqueous As(III) and As(V) concentrations). Conversely, at pH 6, the sorption of As(III) was characterized by substantially higher K d values (6.3-93.4 L g -1 ) than those for As(V) (K d  = 0.21-0.96 L g -1 ). Arsenic K-edge X-ray absorption near edge structure (XANES) spectroscopy indicated that up to 52% of the added As(V) was reduced to As(III) in As(V) sorption experiments, as well as the formation of minor amounts of an As 2 S 3 -like species. In As(III) sorption experiments, XANES spectroscopy also demonstrated the formation of an As 2 S 3 -like species and the partial oxidation of As(III) to As(V) (despite the strictly O 2 -free experimental conditions). Overall, the XANES data indicate that As sorption to nanoparticulate FeS involves several redox transformations and various sorbed species, which display a complex dependency on pH and As loading but that are not influenced by the co-occurrence of PO 4 3- . This study shows that nanoparticulate FeS can help to immobilize As(III) and As(V) in sulfidic subsurface environments where As co-exists with PO 4 3- . Copyright © 2016 Elsevier Ltd. All rights reserved.

Al Speciation in Silicate Melts: AlV a new Network Former?

NASA Astrophysics Data System (ADS)

Neuville, D. R.; Florian, P.; de Ligny, D.; Montouillout, V.; Massiot, D.

2009-05-01

The first human glasses were made 3500 BC. It was essentially sodo-lime silicate glass. To improve the chemical resistance, the thermal properties and increase the viscosity it is interesting to add aluminum in these silicates. But what is the speciation of the aluminum and how it varies according to the chemical composition and to the temperature? The aluminum appears essentially in four or five fold coordination in glasses and melts melted. The proportion of [5]Al varies according to the alkaline or to the earth-alkaline content and to the temperature. We shall present in a first part the influence of the network-modifier on the proportion of [5]Al and then we shall present some new results of absorption of high-temperature using NMR and XANES spectroscopy at the Al K-edge. Finally, from glass transition temperature measurements we propose to explain that [5]Al can be a new network former.

Chemical Composition and Oxidation State of Iron-Containing Aerosol Particles Over West Antarctic Peninsula

NASA Astrophysics Data System (ADS)

Fan, S.; Yu, S.; Lai, B.; Gao, Y.

2017-12-01

Iron is a limiting micronutrient element critical for the marine ecosystem. In the extensive high-nutrient low-chlorophyll (HNLC) regions of the Southern Ocean, the activities of phytoplankton are partly controlled by iron (Fe) from different sources, including atmospheric deposition. Among important properties of atmospheric Fe are the elemental composition and Fe oxidation state of Fe-containing aerosol particles, as these properties affect aerosol Fe solubility. To explore these issues, aerosol samples were collected at Palmer Station in West Antarctic Peninsula. Samples were analyzed by submicron synchrotron-based X-ray fluorescence (XRF) and X-ray absorption near edge structure (XANES) spectroscopy for the Fe oxidation state and elemental composition of aerosol particles. The morphological information of aerosol particles was also observed by the high-resolution fluorescence microscopy, revealing possible sources and formation processes of iron-containing particles. More detailed results will be discussed in this presentation.

Speciation of chromium compounds from humic acid-zeolite Y to an ionic liquid during extraction.

PubMed

Huang, Hsin-Liang; Wei, Yu Jhe

2018-03-01

By synchrotron X-ray absorption spectroscopy, chemical structures of hexavalent chromium (Cr(VI))/trivalent chromium (Cr(III)) adsorbed on humic acid (HA)-zeolite Y and extracted in an ionic liquid (1-butyl-3-methylimidazolium tetrafluoroborate ([C 4 mim][BF 4 ])) have been studied. By combining the competitive adsorption results and reduction of Cr(VI)-HA with the carboxyl groups of HA, Cr(III)-HA (58%) was shown to be the major compound in HA-zeolite Y using synchrotron X-ray absorption near-edge structure (XANES) spectroscopy. In an ionic liquid phase, the reduction of Cr(VI)-HA to Cr(III)-HA and the desorption of Cr(III) from HA were caused by [C 4 mim][BF 4 ]. The 9 F nuclear magnetic resonance (NMR) spectra show that the perturbation of the [C 4 mim][BF 4 ] anion was affected by the extractable chromium species. The formation of a Cr(III) ion affected the increase in the bond distance for the 1st shell CrO of the chromium species in [C 4 mim][BF 4 ] using extended X-ray absorption fine structure (EXAFS) spectroscopy. The changes in the non-extractable chromium species remaining in HA-zeolite Y were also caused by [C 4 mim][BF 4 ] during extraction. The desorption of the absorbed Cr(III) on HA and zeolite Y was observed to form Cr(III) ions. As the percentage of Cr(III) ions remaining in HA-zeolite Y increased, a slightly greater bond distance for CrO was found at 2.01 Å. The enhanced reduction of Cr(VI)-HA and desorption of Cr(III) adsorbed on the HA and zeolite Y to form Cr(III) ions were affected by [C 4 mim][BF 4 ]. Increased mobility of Cr(III) in the simulated soil can promote the migration of Cr(III) ions into the H 2 O during soil washing for remediation. Copyright © 2017 Elsevier Ltd. All rights reserved.

Selenium Accumulation, Distribution, and Speciation in Spineless Prickly Pear Cactus: A Drought- and Salt-Tolerant, Selenium-Enriched Nutraceutical Fruit Crop for Biofortified Foods1[OA

PubMed Central

Bañuelos, Gary S.; Fakra, Sirine C.; Walse, Spencer S.; Marcus, Matthew A.; Yang, Soo In; Pickering, Ingrid J.; Pilon-Smits, Elizabeth A.H.; Freeman, John L.

2011-01-01

The organ-specific accumulation, spatial distribution, and chemical speciation of selenium (Se) were previously unknown for any species of cactus. We investigated Se in Opuntia ficus-indica using inductively coupled plasma mass spectrometry, microfocused x-ray fluorescence elemental and chemical mapping (μXRF), Se K-edge x-ray absorption near-edge structure (XANES) spectroscopy, and liquid chromatography-mass spectrometry (LC-MS). μXRF showed Se concentrated inside small conic, vestigial leaves (cladode tips), the cladode vasculature, and the seed embryos. Se K-edge XANES demonstrated that approximately 96% of total Se in cladode, fruit juice, fruit pulp, and seed is carbon-Se-carbon (C-Se-C). Micro and bulk XANES analysis showed that cladode tips contained both selenate and C-Se-C forms. Inductively coupled plasma mass spectrometry quantification of Se in high-performance liquid chromatography fractions followed by LC-MS structural identification showed selenocystathionine-to-selenomethionine (SeMet) ratios of 75:25, 71:29, and 32:68, respectively in cladode, fruit, and seed. Enzymatic digestions and subsequent analysis confirmed that Se was mainly present in a “free” nonproteinaceous form inside cladode and fruit, while in the seed, Se was incorporated into proteins associated with lipids. μXRF chemical mapping illuminated the specific location of Se reduction and assimilation from selenate accumulated in the cladode tips into the two LC-MS-identified C-Se-C forms before they were transported into the cladode mesophyll. We conclude that Opuntia is a secondary Se-accumulating plant whose fruit and cladode contain mostly free selenocystathionine and SeMet, while seeds contain mainly SeMet in protein. When eaten, the organic Se forms in Opuntia fruit, cladode, and seed may improve health, increase Se mineral nutrition, and help prevent multiple human cancers. PMID:21059825

Selenium Accumulation, Distribution, and Speciation in Spineless Prickly Pear Cactus: A Drought- and Salt-Tolerant, Selenium-Enriched Nutraceutical Fruit Crop for Biofortified Foods

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

Banuelos, Gary S.; Fakra, Sirine C.; Walse, Spencer S.

The organ-specific accumulation, spatial distribution, and chemical speciation of selenium (Se) were previously unknown for any species of cactus. We investigated Se in Opuntia ficus-indica using inductively coupled plasma mass spectrometry, microfocused x-ray fluorescence elemental and chemical mapping ({micro}XRF), Se K-edge x-ray absorption near-edge structure (XANES) spectroscopy, and liquid chromatography-mass spectrometry (LC-MS). {micro}XRF showed Se concentrated inside small conic, vestigial leaves (cladode tips), the cladode vasculature, and the seed embryos. Se K-edge XANES demonstrated that approximately 96% of total Se in cladode, fruit juice, fruit pulp, and seed is carbon-Se-carbon (C-Se-C). Micro and bulk XANES analysis showed that cladode tipsmore » contained both selenate and C-Se-C forms. Inductively coupled plasma mass spectrometry quantification of Se in high-performance liquid chromatography fractions followed by LC-MS structural identification showed selenocystathionine-to-selenomethionine (SeMet) ratios of 75:25, 71:29, and 32:68, respectively in cladode, fruit, and seed. Enzymatic digestions and subsequent analysis confirmed that Se was mainly present in a 'free' nonproteinaceous form inside cladode and fruit, while in the seed, Se was incorporated into proteins associated with lipids. {micro}XRF chemical mapping illuminated the specific location of Se reduction and assimilation from selenate accumulated in the cladode tips into the two LC-MS-identified C-Se-C forms before they were transported into the cladode mesophyll. We conclude that Opuntia is a secondary Se-accumulating plant whose fruit and cladode contain mostly free selenocystathionine and SeMet, while seeds contain mainly SeMet in protein. When eaten, the organic Se forms in Opuntia fruit, cladode, and seed may improve health, increase Se mineral nutrition, and help prevent multiple human cancers.« less

Identification of different coordination geometries by XAFS in copper(II) complexes with trimesic acid

NASA Astrophysics Data System (ADS)

Gaur, A.; Klysubun, W.; Soni, Balram; Shrivastava, B. D.; Prasad, J.; Srivastava, K.

2016-10-01

X-ray absorption spectroscopy (XAS) is very useful in revealing the information about geometric and electronic structure of a transition-metal absorber and thus commonly used for determination of metal-ligand coordination. But XAFS analysis becomes difficult if differently coordinated metal centers are present in a system. In the present investigation, existence of distinct coordination geometries around metal centres have been studied by XAFS in a series of trimesic acid Cu(II) complexes. The complexes studied are: Cu3(tma)2(im)6 8H2O (1), Cu3(tma)2(mim)6 17H2O (2), Cu3(tma)2(tmen)3 8.5H2O (3), Cu3(tma) (pmd)3 6H2O (ClO4)3 (4) and Cu3(tma)2 3H2O (5). These complexes have not only Cu metal centres with different coordination but in complexes 1-3, there are multiple coordination geometries present around Cu centres. Using XANES spectra, different coordination geometries present in these complexes have been identified. The variation observed in the pre-edge features and edge features have been correlated with the distortion of the specific coordination environment around Cu centres in the complexes. XANES spectra have been calculated for the distinct metal centres present in the complexes by employing ab-initio calculations. These individual spectra have been used to resolve the spectral contribution of the Cu centres to the particular XANES features exhibited by the experimental spectra of the multinuclear complexes. Also, the variation in the 4p density of states have been calculated for the different Cu centres and then correlated with the features originated from corresponding coordination of Cu. Thus, these spectral features have been successfully utilized to detect the presence of the discrete metal centres in a system. The inferences about the coordination geometry have been supported by EXAFS analysis which has been used to determine the structural parameters for these complexes.

Degradation process of lead chromate in paintings by Vincent van Gogh studied by means of synchrotron X-ray spectromicroscopy and related methods. 1. Artificially aged model samples.

PubMed

Monico, Letizia; Van der Snickt, Geert; Janssens, Koen; De Nolf, Wout; Miliani, Costanza; Verbeeck, Johan; Tian, He; Tan, Haiyan; Dik, Joris; Radepont, Marie; Cotte, Marine

2011-02-15

On several paintings by artists of the end of the 19th century and the beginning of the 20th Century a darkening of the original yellow areas, painted with the chrome yellow pigment (PbCrO(4), PbCrO(4)·xPbSO(4), or PbCrO(4)·xPbO) is observed. The most famous of these are the various Sunflowers paintings Vincent van Gogh made during his career. In the first part of this work, we attempt to elucidate the degradation process of chrome yellow by studying artificially aged model samples. In view of the very thin (1-3 μm) alteration layers that are formed, high lateral resolution spectroscopic methods such as microscopic X-ray absorption near edge (μ-XANES), X-ray fluorescence spectrometry (μ-XRF), and electron energy loss spectrometry (EELS) were employed. Some of these use synchrotron radiation (SR). Additionally, microscopic SR X-ray diffraction (SR μ-XRD), μ-Raman, and mid-FTIR spectroscopy were employed to completely characterize the samples. The formation of Cr(III) compounds at the surface of the chrome yellow paint layers is particularly observed in one aged model sample taken from a historic paint tube (ca. 1914). About two-thirds of the chromium that is present at the surface has reduced from the hexavalent to the trivalent state. The EELS and μ-XANES spectra are consistent with the presence of Cr(2)O(3)·2H(2)O (viridian). Moreover, as demonstrated by μ-XANES, the presence of another Cr(III) compound, such as either Cr(2)(SO(4))(3)·H(2)O or (CH(3)CO(2))(7)Cr(3)(OH)(2) [chromium(III) acetate hydroxide], is likely.

X-ray absorption spectroscopy study of parent misfit-layered cobalt oxide [Sr₂O₂] q}CoO₂

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

Chou, Ta-Lei; Chan, Ting-Shan; Chen, Jin-Ming

Here we present a comprehensive X-ray absorption spectroscopy study carried out at Co-L₂,₃, Co-K, O-K and Sr-K edges for the parent misfit-layered cobalt oxide phase [Sr₂O₂]₀.₅₂CoO₂; comparison is made to another misfit-layered oxide [CoCa₂O₃]₀.₆₂CoO₂ and the perovskite oxide LaCoO₃. A high-quality sample of [Sr₂O₂]₀.₅₂CoO₂ was obtained through ultra-high-pressure synthesis using Sr₃Co₂O₆ and Sr(OH)₂∙8H₂O as starting materials. Different dosages of KClO₃ were mixed with the raw materials as an oxygen source and tested, but it was found that the window for the redox control of [Sr₂O₂]₀.₅₂CoO₂ is rather narrow. From Co-K and Co-L₂,₃ spectra a mixed III/IV valence state is revealedmore » for cobalt in [Sr₂O₂]₀.₅₂}CoO₂, but the average valence value is a little lower than in [CoCa₂O₃]₀.₆₂CoO₂. Then, Sr-K spectrum indicates that the [Sr₂O₂] double-layer block in [Sr₂O₂]₀.₅₂CoO₂ clearly deviates from the cubic SrO rock-salt structure, suggesting a more complicated coordination environment for strontium. This together with a somewhat low Co-valence value and the fact that the phase formation of [Sr₂O₂]₀.₅₂CoO₂ required the presence of Sr(OH)₂∙8H₂O in the high-pressure synthesis suggest that the [Sr₂O₂] block contains ---OH groups, i.e. [Sr₂(O,OH)₂]₀.₅₂CoO₂. - Graphical abstract: [Sr₂O₂]₀.₅₂CoO₂ obtained through high-pressure synthesis is a parent of misfit-layered cobalt oxides, such as [CoCa₂O₃]₀.₆₂CoO₂ or [M mA₂O 2+m] qCoO₂ in general. Our comprehensive X-ray absorption spectroscopy study shows that both [Sr₂O₂]₀.₅₂CoO₂ and [CoCa₂O₃]₀.₆₂CoO₂ possess mixed III/IV valence cobalt, but the average Co-valence is a little lower in the former. This is tentatively believed to be due to OH --- groups replacing part of O²⁻ ions in the [Sr₂O₂] layer block. Highlights: • [Sr₂O₂]₀.₅₂CoO₂ is a parent of misfit-layered cobalt oxides. • It is obtained by ultra-high-pressure synthesis from Sr₃Co₂O₆, Sr(OH)₂∙6H₂O and KClO₃. • Co-K and Co---L XANES spectra reveal lower than expected Co-valence value. • Sr-K XANES spectrum indicates that the [Sr₂O₂] block is not of simple rock-salt structure. • This block most probably contains ---OH --- groups, i.e. [Sr₂(O,OH)₂]₀.₅₂CoO₂.« less

Effects of calcium and phosphate on uranium(IV) oxidation: Comparison between nanoparticulate uraninite and amorphous UIV-phosphate

NASA Astrophysics Data System (ADS)

Latta, Drew E.; Kemner, Kenneth M.; Mishra, Bhoopesh; Boyanov, Maxim I.

2016-02-01

The mobility of uranium in subsurface environments depends strongly on its redox state, with UIV phases being significantly less soluble than UVI minerals. This study compares the oxidation kinetics and mechanisms of two potential products of UVI reduction in natural systems, a nanoparticulate UO2 phase and an amorphous UIV-Ca-PO4 analog to ningyoite (CaUIV(PO4)2·1-2H2O). The valence of U was tracked by X-ray absorption near-edge spectroscopy (XANES), showing similar oxidation rate constants for UIVO2 and UIV-phosphate in solutions equilibrated with atmospheric O2 and CO2 at pH 7.0 (kobs,UO2 = 0.17 ± 0.075 h-1 vs. kobs,UIVPO4 = 0.30 ± 0.25 h-1). Addition of up to 400 μM Ca and PO4 decreased the oxidation rate constant by an order of magnitude for both UO2 and UIV-phosphate. The intermediates and products of oxidation were tracked by electron microscopy, powder X-ray diffraction (pXRD), and extended X-ray absorption fine-structure spectroscopy (EXAFS). In the absence of Ca or PO4, the product of UO2 oxidation is Na-uranyl oxyhydroxide (under environmentally relevant concentrations of sodium, 15 mM NaClO4 and low carbonate concentration), resulting in low concentrations of dissolved UVI (<2.5 × 10-7 M). Oxidation of UIV-phosphate produced a Na-autunite phase (Na2(UO2)PO4·xH2O), resulting in similarly low dissolved U concentrations (<7.3 × 10-8 M). When Ca and PO4 are present in the solution, the EXAFS data and the solubility of the UVI phase resulting from oxidation of UO2 and UIV-phosphate are consistent with the precipitation of Na-autunite. Bicarbonate extractions and Ca K-edge X-ray absorption spectroscopy of oxidized solids indicate the formation of a Ca-UVI-PO4 layer on the UO2 surface and suggest a passivation layer mechanism for the decreased rate of UO2 oxidation in the presence of Ca and PO4. Interestingly, the extractions were unable to remove all of the oxidized U from partially oxidized UO2 solids, suggesting that oxidized U is distributed between the interior of the UO2 nanoparticles and the labile surface layer. Accounting for the entire pool of oxidized U by XANES is the likely reason for the higher UO2 oxidation rate constants determined here relative to prior studies. Our results suggest that the natural presence or addition of Ca and PO4 in groundwater could slow the rates of UIV oxidation, but that the rates are still fast enough to cause complete oxidation of UIV within days under fully oxygenated conditions.

Effects of calcium and phosphate on uranium(IV) oxidation: Comparison between nanoparticulate uraninite and amorphous U IV–phosphate

DOE PAGES

Latta, Drew E.; Kemner, Kenneth M.; Mishra, Bhoopesh; ...

2015-11-17

The mobility of uranium in subsurface environments depends strongly on its redox state, with U IV phases being significantly less soluble than U VI minerals. This study compares the oxidation kinetics and mechanisms of two potential products of U VI reduction in natural systems, a nanoparticulate UO 2 phase and an amorphous U IV–Ca–PO 4 analog to ningyoite (CaU IV(PO 4) 2·1–2H 2O). The valence of U was tracked by X-ray absorption near-edge spectroscopy (XANES), showing similar oxidation rate constants for U IVO 2 and U IV–phosphate in solutions equilibrated with atmospheric O 2 and CO 2 at pH 7.0more » (k obs,UO2 = 0.17 ± 0.075 h -1 vs. k obs,U IV PO4 = 0.30 ± 0.25 h -1). Addition of up to 400 μM Ca and PO 4 decreased the oxidation rate constant by an order of magnitude for both UO 2 and U IV–phosphate. The intermediates and products of oxidation were tracked by electron microscopy, powder X-ray diffraction (pXRD), and extended X-ray absorption fine-structure spectroscopy (EXAFS). In the absence of Ca or PO 4, the product of UO 2 oxidation is Na–uranyl oxyhydroxide (under environmentally relevant concentrations of sodium, 15 mM NaClO 4 and low carbonate concentration), resulting in low concentrations of dissolved U VI (<2.5 × 10 -7 M). Oxidation of U IV–phosphate produced a Na-autunite phase (Na 2(UO 2)PO 4·xH 2O), resulting in similarly low dissolved U concentrations (<7.3 × 10 -8 M). When Ca and PO 4 are present in the solution, the EXAFS data and the solubility of the UVI phase resulting from oxidation of UO 2 and UIV–phosphate are consistent with the precipitation of Na-autunite. Bicarbonate extractions and Ca K-edge X-ray absorption spectroscopy of oxidized solids indicate the formation of a Ca–UVI–PO 4 layer on the UO 2 surface and suggest a passivation layer mechanism for the decreased rate of UO 2 oxidation in the presence of Ca and PO 4. Interestingly, the extractions were unable to remove all of the oxidized U from partially oxidized UO 2 solids, suggesting that oxidized U is distributed between the interior of the UO 2 nanoparticles and the labile surface layer. Accounting for the entire pool of oxidized U by XANES is the likely reason for the higher UO 2 oxidation rate constants determined here relative to prior studies. In conclusion, our results suggest that the natural presence or addition of Ca and PO 4 in groundwater could slow the rates of U IV oxidation, but that the rates are still fast enough to cause complete oxidation of U IV within days under fully oxygenated conditions.« less

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

NASA Astrophysics Data System (ADS)

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

2016-01-01

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

Strontium hydroxyapatite and strontium carbonate as templates for the precipitation of calcium-phosphates in the absence and presence of fluoride

NASA Astrophysics Data System (ADS)

Sternitzke, Vanessa; Janousch, Markus; Heeb, Michèle B.; Hering, Janet G.; Johnson, C. Annette

2014-06-01

The heterogeneous precipitation of calcium-phosphates on calcium hydroxyapatite (Ca10(PO4)6(OH)2 or HAP) in the presence and absence of fluoride is important in the formation of bone and teeth, protection against tooth decay, dental and skeletal fluorosis and defluoridation of drinking water. Strontium hydroxyapatite (Sr10(PO4)6(OH)2 or SrHAP) and strontium carbonate (SrCO3) were used as calcium-free seed templates in precipitation experiments conducted with varying initial calcium-to-phosphate (Ca/P) or calcium-to-phosphate-to-fluoride (Ca/P/F) ratios. Suspensions of SrHAP or SrCO3 seed templates (which were calcium-limited for both templates and phosphate-limited in the case of SrCO3) were reacted at pH 7.3 (25 °C) over 3 days. The resulting solids were examined with Scanning Transmission Electron Microscopy (STEM), X-ray Diffraction (XRD), Fourier Transform Infrared (FTIR), and X-ray Photoelectron Spectroscopy (XPS), X-ray Absorption Near Edge Structure (XANES), and Extended X-ray Absorption Fine Structure spectroscopy (EXAFS). Calcium apatite was the predominant phase identified by all techniques independent of the added Ca/P ratios and of the presence of fluoride. It was not possible to make an unambiguous distinction between HAP and fluorapatite (Ca10(PO4)6F2, FAP). The apatite was calcium-deficient and probably contained some strontium.

X-Ray Absorption Spectroscopy of Fe-Substituted Allophane and Imogolite

NASA Astrophysics Data System (ADS)

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 substitution in tetrahedral sites occurs in allophane with Al:Si = 2:1, but not in higher-Si compositions. These results support the nanoball model for allophane (1) based on a rolled octahedral sheet and indicate that sheet is well ordered. They do not support proposed models of an incomplete octahedral sheet in high-Si allophanes. Analysis of Fe distribution suggests considerable Fe clustering in the octahedral sheet which increases with sample aging. This clustering could lead to eventual nucleation of a separate Fe (oxyhydr)oxide phase. (1) Creton et al. (2008) J Phys Chem C 112, 358.

Chemical fingerprinting of naphthenic acids and oil sands process waters-A review of analytical methods for environmental samples.

PubMed

Headley, J V; Peru, K M; Mohamed, M H; Frank, R A; Martin, J W; Hazewinkel, R R O; Humphries, D; Gurprasad, N P; Hewitt, L M; Muir, D C G; Lindeman, D; Strub, R; Young, R F; Grewer, D M; Whittal, R M; Fedorak, P M; Birkholz, D A; Hindle, R; Reisdorph, R; Wang, X; Kasperski, K L; Hamilton, C; Woudneh, M; Wang, G; Loescher, B; Farwell, A; Dixon, D G; Ross, M; Pereira, A Dos Santos; King, E; Barrow, M P; Fahlman, B; Bailey, J; McMartin, D W; Borchers, C H; Ryan, C H; Toor, N S; Gillis, H M; Zuin, L; Bickerton, G; Mcmaster, M; Sverko, E; Shang, D; Wilson, L D; Wrona, F J

2013-01-01

This article provides a review of the routine methods currently utilized for total naphthenic acid analyses. There is a growing need to develop chemical methods that can selectively distinguish compounds found within industrially derived oil sands process affected waters (OSPW) from those derived from the natural weathering of oil sands deposits. Attention is thus given to the characterization of other OSPW components such as oil sands polar organic compounds, PAHs, and heavy metals along with characterization of chemical additives such as polyacrylamide polymers and trace levels of boron species. Environmental samples discussed cover the following matrices: OSPW containments, on-lease interceptor well systems, on- and off-lease groundwater, and river and lake surface waters. There are diverse ranges of methods available for analyses of total naphthenic acids. However, there is a need for inter-laboratory studies to compare their accuracy and precision for routine analyses. Recent advances in high- and medium-resolution mass spectrometry, concomitant with comprehensive mass spectrometry techniques following multi-dimensional chromatography or ion-mobility separations, have allowed for the speciation of monocarboxylic naphthenic acids along with a wide range of other species including humics. The distributions of oil sands polar organic compounds, particularly the sulphur containing species (i.e., OxS and OxS2) may allow for distinguishing sources of OSPW. The ratios of oxygen- (i.e., Ox) and nitrogen-containing species (i.e., NOx, and N2Ox) are useful for differentiating organic components derived from OSPW from natural components found within receiving waters. Synchronous fluorescence spectroscopy also provides a powerful screening technique capable of quickly detecting the presence of aromatic organic acids contained within oil sands naphthenic acid mixtures. Synchronous fluorescence spectroscopy provides diagnostic profiles for OSPW and potentially impacted groundwater that can be compared against reference groundwater and surface water samples. Novel applications of X-ray absorption near edge spectroscopy (XANES) are emerging for speciation of sulphur-containing species (both organic and inorganic components) as well as industrially derived boron-containing species. There is strong potential for an environmental forensics application of XANES for chemical fingerprinting of weathered sulphur-containing species and industrial additives in OSPW.

Direct Synthesis of Novel and Reactive Sulfide-modified Nano Iron through Nanoparticle Seeding for Improved Cadmium-Contaminated Water Treatment

PubMed Central

Su, Yiming; Adeleye, Adeyemi S.; Huang, Yuxiong; Zhou, Xuefei; Keller, Arturo A.; Zhang, Yalei

2016-01-01

Magnetic sulfide-modified nanoscale zerovalent iron (S-nZVI) is of great technical and scientific interest because of its promising application in groundwater remediation, although its synthesis is still a challenge. We develop a new nanoparticle seeding method to obtain a novel and reactive nanohybrid, which contains an Fe(0) core covered by a highly sulfidized layer under high extent of sulfidation. Syntheses monitoring experiments show that seeding accelerates the reduction rate from Fe2+ to Fe0 by 19%. X-ray adsorption near edge structure (XANES) spectroscopy and extended X-ray absorption fine structure analyses demonstrate the hexahedral Fe-Fe bond (2.45 and 2.83 Å) formation through breaking down of the 1.99 Å Fe-O bond both in crystalline and amorphous iron oxide. The XANES analysis also shows 24.2% (wt%) of FeS with bond length of 2.4 Å in final nanohybrid. Both X-ray diffraction and Mössbauer analyses further confirm that increased nanoparticle seeding results in formation of more Fe0 crystals. Nano-SiO2 seeding brings down the size of single Fe0 grain from 32.4 nm to 18.7 nm, enhances final Fe0 content from 5.9% to 55.6%, and increases magnetization from 4.7 to 65.5 emu/g. The synthesized nanohybrid has high cadmium removal capacity and holds promising prospects for treatment of metal-contaminated water. PMID:27095387

Direct Synthesis of Novel and Reactive Sulfide-modified Nano Iron through Nanoparticle Seeding for Improved Cadmium-Contaminated Water Treatment

NASA Astrophysics Data System (ADS)

Su, Yiming; Adeleye, Adeyemi S.; Huang, Yuxiong; Zhou, Xuefei; Keller, Arturo A.; Zhang, Yalei

2016-04-01

Magnetic sulfide-modified nanoscale zerovalent iron (S-nZVI) is of great technical and scientific interest because of its promising application in groundwater remediation, although its synthesis is still a challenge. We develop a new nanoparticle seeding method to obtain a novel and reactive nanohybrid, which contains an Fe(0) core covered by a highly sulfidized layer under high extent of sulfidation. Syntheses monitoring experiments show that seeding accelerates the reduction rate from Fe2+ to Fe0 by 19%. X-ray adsorption near edge structure (XANES) spectroscopy and extended X-ray absorption fine structure analyses demonstrate the hexahedral Fe-Fe bond (2.45 and 2.83 Å) formation through breaking down of the 1.99 Å Fe-O bond both in crystalline and amorphous iron oxide. The XANES analysis also shows 24.2% (wt%) of FeS with bond length of 2.4 Å in final nanohybrid. Both X-ray diffraction and Mössbauer analyses further confirm that increased nanoparticle seeding results in formation of more Fe0 crystals. Nano-SiO2 seeding brings down the size of single Fe0 grain from 32.4 nm to 18.7 nm, enhances final Fe0 content from 5.9% to 55.6%, and increases magnetization from 4.7 to 65.5 emu/g. The synthesized nanohybrid has high cadmium removal capacity and holds promising prospects for treatment of metal-contaminated water.

Speciation and Distribution of Phosphorus in a Fertilized Soil: A Synchrotron-Based Investigation

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

Lombi, E.; Scheckel, K.G.; Armstrong, R.D.

2008-06-09

Phosphorus availability is often a limiting factor for crop production around the world. The efficiency of P fertilizers in calcareous soils is limited by reactions that decrease P availability; however, fluid fertilizers have recently been shown, in highly calcareous soils of southern Australia, to be more efficient for crop (wheat [Triticum aestivum L.]) P nutrition than granular products. To elucidate the mechanisms responsible for this differential response, an isotopic dilution technique (E value) coupled with a synchrotron-based spectroscopic investigation were used to assess the reaction products of a granular (monoammonium phosphate, MAP) and a fluid P (technical-grade monoammonium phosphate, TG-MAP)more » fertilizer in a highly calcareous soil. The isotopic exchangeability of P from the fluid fertilizer, measured with the E-value technique, was higher than that of the granular product. The spatially resolved spectroscopic investigation, performed using nano x-ray fluorescence and nano x-ray absorption near-edge structure (n-XANES), showed that P is heterogeneously distributed in soil and that, at least in this highly calcareous soil, it is invariably associated with Ca rather than Fe at the nanoscale. 'Bulk' XANES spectroscopy revealed that, in the soil surrounding fertilizer granules, P precipitation in the form of octacalcium phosphate and apatite-like compounds is the dominant mechanism responsible for decreases in P exchangeability. This process was less prominent when the fluid P fertilizer was applied to the soil.« less

Complete transformation of ZnO and CuO nanoparticles in culture medium and lymphocyte cells during toxicity testing.

PubMed

Ivask, Angela; Scheckel, Kirk G; Kapruwan, Pankaj; Stone, Vicki; Yin, Hong; Voelcker, Nicolas H; Lombi, Enzo

2017-03-01

Here, we present evidence on complete transformation of ZnO and CuO nanoparticles, which are among the most heavily studied metal oxide particles, during 24 h in vitro toxicological testing with human T-lymphocytes. Synchrotron radiation-based X-ray absorption near edge structure (XANES) spectroscopy results revealed that Zn speciation profiles of 30 nm and 80 nm ZnO nanoparticles, and ZnSO 4 - exposed cells were almost identical with the prevailing species being Zn-cysteine. This suggests that ZnO nanoparticles are rapidly transformed during a standard in vitro toxicological assay, and are sequestered intracellularly, analogously to soluble Zn. Complete transformation of ZnO in the test conditions was further supported by almost identical Zn spectra in medium to which ZnO nanoparticles or ZnSO 4 was added. Likewise, Cu XANES spectra for CuO and CuSO 4 -exposed cells and cell culture media were similar. These results together with our observation on similar toxicological profiles of ZnO and soluble Zn, and CuO and soluble Cu, underline the importance of dissolution and subsequent transformation of ZnO and CuO nanoparticles during toxicological testing and provide evidence that the nano-specific effect of ZnO and CuO nanoparticles is negligible in this system. We strongly suggest to account for this aspect when interpreting the toxicological results of ZnO and CuO nanoparticles.

Complete transformation of ZnO and CuO nanoparticles in ...

EPA Pesticide Factsheets

Here, we present evidence on complete transformation of ZnO and CuO nanoparticles, which are among the most heavily studied metal oxide particles, during 24 h in vitro toxicological testing with human T-lymphocytes. Synchrotron radiation-based X-ray absorption near edge structure (XANES) spectroscopy results revealed that Zn speciation profiles of 30 nm and 80 nm ZnO nanoparticles, and ZnSO4- exposed cells were almost identical with the prevailing species being Zn-cysteine. This suggests that ZnO nanoparticles are rapidly transformed during a standard in vitro toxicological assay, and are sequestered intracellularly, analogously to soluble Zn. Complete transformation of ZnO in the test conditions was further supported by almost identical Zn spectra in medium to which ZnO nanoparticles or ZnSO4 was added. Likewise, Cu XANES spectra for CuO and CuSO4-exposed cells and cell culture media were similar. These results together with our observation on similar toxicological profiles of ZnO and soluble Zn, and CuO and soluble Cu, underline the importance of dissolution and subsequent transformation of ZnO and CuO nanoparticles during toxicological testing and provide evidence that the nano-specific effect of ZnO and CuO nanoparticulates is negligible in this system. We strongly suggest to account for this aspect when interpreting the toxicological results of ZnO and CuO nanoparticles. Although a number of studies have discussed the transformation of nanoparticles during

Chromium-removal processes during groundwater remediation by a zerovalent iron permeable reactive barrier.

PubMed

Wilkin, Richard T; Su, Chunming; Ford, Robert G; Paul, Cynthia J

2005-06-15

Solid-phase associations of chromium were examined in core materials collected from a full-scale, zerovalent iron permeable reactive barrier (PRB) at the U.S. Coast Guard Support Center located near Elizabeth City, NC. The PRB was installed in 1996 to treat groundwater contaminated with hexavalent chromium. After eight years of operation, the PRB remains effective at reducing concentrations of Cr from average values >1500 microg L(-1) in groundwater hydraulically upgradient of the PRB to values <1 microg L(-1) in groundwater within and hydraulically downgradient of the PRB. Chromium removal from groundwater occurs at the leading edge of the PRB and also within the aquifer immediately upgradient of the PRB. These regions also witness the greatest amount of secondary mineral formation due to steep geochemical gradients that result from the corrosion of zerovalent iron. X-ray absorption near-edge structure (XANES) spectroscopy indicated that chromium is predominantly in the trivalent oxidation state, confirming that reductive processes are responsible for Cr sequestration. XANES spectra and microscopy results suggest that Cr is, in part, associated with iron sulfide grains formed as a consequence of microbially mediated sulfate reduction in and around the PRB. Results of this study provide evidence that secondary iron-bearing mineral products may enhance the capacity of zerovalent iron systems to remediate Cr in groundwater, either through redox reactions at the mineral-water interface or by the release of Fe(II) to solution via mineral dissolution and/or metal corrosion.

Immobilization of Cr(VI) and Its Reduction to Cr(III) Phosphate by Granular Biofilms Comprising a Mixture of Microbes

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

Nancharaiah, Y.V.; Francis, A.; Dodge, C.

2010-04-01

We assessed the potential of mixed microbial consortia, in the form of granular biofilms, to reduce chromate and remove it from synthetic minimal medium. In batch experiments, acetate-fed granular biofilms incubated aerobically reduced 0.2 mM Cr(VI) from a minimal medium at 0.15 mM day-1 g-1, with reduction of 0.17 mM day-1 g-1 under anaerobic conditions. There was negligible removal of Cr(VI) (i) without granular biofilms, (ii) with lyophilized granular biofilms, and (iii) with granules in the absence of an electron donor. Analyses by X-ray absorption near edge spectroscopy (XANES) of the granular biofilms revealed the conversion of soluble Cr(VI) tomore » Cr(III). Extended X-ray absorption fine-structure (EXAFS) analysis of the Cr-laden granular biofilms demonstrated similarity to Cr(III) phosphate, indicating that Cr(III) was immobilized with phosphate on the biomass subsequent to microbial reduction. The sustained reduction of Cr(VI) by granular biofilms was confirmed in fed-batch experiments. Our study demonstrates the promise of granular-biofilm-based systems in treating Cr(VI)-containing effluents and wastewater.« less

A first-principle calculation of the XANES spectrum of Cu2+ in water

NASA Astrophysics Data System (ADS)

La Penna, G.; Minicozzi, V.; Morante, S.; Rossi, G. C.; Stellato, F.

2015-09-01

The progress in high performance computing we are witnessing today offers the possibility of accurate electron density calculations of systems in realistic physico-chemical conditions. In this paper, we present a strategy aimed at performing a first-principle computation of the low energy part of the X-ray Absorption Spectroscopy (XAS) spectrum based on the density functional theory calculation of the electronic potential. To test its effectiveness, we apply the method to the computation of the X-ray absorption near edge structure part of the XAS spectrum in the paradigmatic, but simple case of Cu2+ in water. In order to keep into account the effect of the metal site structure fluctuations in determining the experimental signal, the theoretical spectrum is evaluated as the average over the computed spectra of a statistically significant number of simulated metal site configurations. The comparison of experimental data with theoretical calculations suggests that Cu2+ lives preferentially in a square-pyramidal geometry. The remarkable success of this approach in the interpretation of XAS data makes us optimistic about the possibility of extending the computational strategy we have outlined to the more interesting case of molecules of biological relevance bound to transition metal ions.

The binuclear nickel center in the A-cluster of acetyl-CoA synthase (ACS) and two biomimetic dinickel complexes studied by X-ray absorption and emission spectroscopy

NASA Astrophysics Data System (ADS)

Schrapers, P.; Mebs, S.; Ilina, Y.; Warner, D. S.; Wörmann, C.; Schuth, N.; Kositzki, R.; Dau, H.; Limberg, C.; Dobbek, H.; Haumann, M.

2016-05-01

Acetyl-CoA synthase (ACS) is involved in the bacterial carbon oxide conversion pathway. The binuclear nickel sites in ACS enzyme and two biomimetic synthetic compounds containing a Ni(II)Ni(II) unit (1 and 2) were compared using XAS/XES. EXAFS analysis of ACS proteins revealed similar Ni-N/O/S bond lengths and Ni-Ni/Fe distances as in the crystal structure in oxidized ACS, but elongated Ni-ligand bonds in reduced ACS, suggesting more reduced nickel species. The XANES spectra of ACS and the dinickel complexes showed overall similar shapes, but less resolved pre-edge and edge features in ACS, attributed to more distorted square-planar nickel sites in particular in reduced ACS. DFT calculation of pre-edge absorption and Kβ2,5 emission features reproduced the experimental spectra of the synthetic complexes, was sensitive even to the small geometry differences in 1 and 2, and indicated low-spin Ni(II) sites. Comparison of nickel sites in proteins and biomimetic compounds is valuable for deducing structural and electronic differences in response to ligation and redox changes.

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

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

Liu, Xiang; Cui, Shengsheng; Sun, Zijun

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

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

PubMed

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

2009-04-09

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

Silicon K-edge XANES spectra of silicate minerals

NASA Astrophysics Data System (ADS)

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

1995-03-01

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

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

PubMed

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

2013-07-01

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

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

PubMed Central

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

2014-01-01

The use of fluorescence full spectral micro-X-ray absorption near-edge 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. PMID:24365942

In-situ X-Ray Absorption Spectroscopy (XAS) Investigation of a Bifunctional Manganese Oxide Catalyst with High Activity for Electrochemical Water Oxidation and Oxygen Reduction

PubMed Central

Benck, Jesse D.; Gul, Sheraz; Webb, Samuel M.; Yachandra, Vittal K.; Yano, Junko; Jaramillo, Thomas F.

2013-01-01

In-situ x-ray absorption spectroscopy (XAS) is a powerful technique that can be applied to electrochemical systems, with the ability to elucidate the chemical nature of electrocatalysts under reaction conditions. In this study, we perform in-situ XAS measurements on a bifunctional manganese oxide (MnOx) catalyst with high electrochemical activity for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). Using x-ray absorption near edge structure (XANES) and extended x-ray absorption fine structure (EXAFS), we find that exposure to an ORR-relevant potential of 0.7 V vs. RHE produces a disordered Mn3II,III,IIIO4 phase with negligible contributions from other phases. After the potential is increased to a highly anodic value of 1.8 V vs. RHE, relevant to the OER, we observe an oxidation of approximately 80% of the catalytic thin film to form a mixed MnIII,IV oxide, while the remaining 20% of the film consists of a less oxidized phase, likely corresponding to unchanged Mn3II,III,IIIO4. XAS and electrochemical characterization of two thin film catalysts with different MnOx thicknesses reveals no significant influence of thickness on the measured oxidation states, at either ORR or OER potentials, but demonstrates that the OER activity scales with film thickness. This result suggests that the films have porous structure, which does not restrict electrocatalysis to the top geometric layer of the film. As the portion of the catalyst film that is most likely to be oxidized at the high potentials necessary for the OER is that which is closest to the electrolyte interface, we hypothesize that the MnIII,IV oxide, rather than Mn3II,III,IIIO4, is the phase pertinent to the observed OER activity. PMID:23758050

Comparison of the Manganese Cluster in Oxygen-Evolving Photosystem II with Distorted Cubane Manganese Compounds through X-ray Absorption Spectroscopy

PubMed Central

Cinco, Roehl M.; Rompel, Annette; Visser, Hendrik; Aromí, Guillem; Christou, George; Sauer, Kenneth; Klein, Melvin P.; Yachandra, Vittal K.

2014-01-01

X-ray absorption spectroscopy has been employed to assess the degree of similarity between the oxygen-evolving complex (OEC) in photosystem II (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). These [Mn4(μ3-O)3(μ3-X)] cubanes possess C3v symmetry except for the X = benzoate species, which is slightly more distorted with only Cs symmetry. In addition, Mn4O3Cl complexes containing three or six terminal Cl ligands at three of the Mn were included in this study. The Mn K-edge X-ray absorption near edge structure (XANES) from the oxygen-ligated complexes begin to resemble general features of the PS II (S1 state) spectrum, although the second derivatives are distinct from those in PS II. The extended X-ray absorption fine structure (EXAFS) of these Mn compounds also displays superficial resemblance to that of PS II, but major differences emerge on closer examination of the phases and amplitudes. The most obvious distinction is the smaller magnitude of the Fourier transform (FT) of the PS II EXAFS compared to the FTs from the distorted cubanes. Curve fitting of the Mn EXAFS spectra verifies the known core structures of the Mn cubanes, and shows that the number of the crucial 2.7 and 3.3 Å Mn–Mn distances differs from that observed in the OEC. The EXAFS method detects small changes in the core structures as X is varied in this series, and serves to exclude the distorted cubane of C3v symmetry as a topological model for the Mn catalytic cluster of the OEC. Instead, the method shows that even more distortion of the cubane framework, altering the ratio of the Mn–Mn distances, is required to resemble the Mn cluster in PS II. PMID:11671305

Structural study of the ammonium octafluoroneptunate, [NH 4] 4NpF 8

DOE PAGES

Poineau, Frederic; Silva, Chinthaka M.; Yeamans, Charles B.; ...

2016-04-21

The [NH 4] 4NpF 8 salt was prepared from the solid-state reaction of NpO 2 with NH 4HF 2 and characterized by powder X-ray diffraction and X-ray absorption fine structure spectroscopy. The diffraction results confirm the compound to be isostructural to [NH 4] 4UF 8 with the following lattice parameter (a = 13.054(4) Å, b = 6.681(2) Å, c = 13.676(5) Å, ß = 121.14 Å). For the first time, a Neptunium fluoride complex has been characterized by XAFS spectroscopy. The energy position of the white line and inflection of the XANES spectra of [NH 4] 4NpF 8 are consistentmore » with the presence of Np(IV). Adjustment of the EXAFS spectra indicates that the coordination number (7.4±1.5) and the average Np-F distance (2.26(1) Å) are consistent with the presence of the NpF8 dodecahedron. The average Np-F distance is ~0.02 Å shorter than the U-F distance in [NH 4] 4UF 8 and is a result of the actinide contraction.« less

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

Gianetti, Thomas L.; Nocton, Grégory; Minasian, Stefan G.

Reaction of the neutral diniobium benzene complex {[Nb(BDI)N tBu] 2(μ-C 6H 6)} (BDI = N,N'-diisopropylbenzene-β-diketiminate) with Ag[B(C 6F 5) 4] results in a single electron oxidation to produce a cationic diniobium arene complex, {[Nb(BDI)N tBu] 2(μ-C 6H 6)}{B(C 6F 5) 4}. Investigation of the solid state and solution phase structure using single-crystal X-ray diffraction, cyclic voltammetry, magnetic susceptibility, and multinuclear NMR spectroscopy indicates that the oxidation results in an asymmetric molecule with two chemically inequivalent Nb atoms. Further characterization using density functional theory (DFT) calculations, UV-visible, Nb L 3,2-edge X-ray absorption near-edge structure (XANES), and EPR spectroscopies supports assignment ofmore » a diniobium complex, in which one Nb atom carries a single unpaired electron that is not largely delocalized on the second Nb atom. During the oxidative transformation, one electron is removed from the δ-bonding HOMO, which causes a destabilization of the molecule and formation of an asymmetric product. Subsequent reactivity studies indicate that the oxidized product allows access to metal-based chemistry with substrates that did not exhibit reactivity with the starting neutral complex.« less

Evaluating the electronic structure of formal Ln II ions in Ln II(C 5H 4SiMe 3) 3 1– using XANES spectroscopy and DFT calculations

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

Fieser, Megan E.; Ferrier, Maryline Ghislaine; Su, Jing

Here, the isolation of [K(2.2.2-cryptand)][Ln(C 5H 4SiMe 3) 3], formally containing LnII, for all lanthanides (excluding Pm) was surprising given that +2 oxidation states are typically regarded as inaccessible for most 4f-elements. Herein, X-ray absorption near-edge spectroscopy (XANES), ground-state density functional theory (DFT), and transition dipole moment calculations are used to investigate the possibility that Ln(C 5H 4SiMe 3) 3 1– (Ln = Pr, Nd, Sm, Gd, Tb, Dy, Y, Ho, Er, Tm, Yb and Lu) compounds represented molecular Ln II complexes. Results from the ground-state DFT calculations were supported by additional calculations that utilized complete-active-space multi-configuration approach with second-ordermore » perturbation theoretical correction (CASPT2). Through comparisons with standards, Ln(C 5H 4SiMe 3) 3 1– (Ln = Sm, Tm, Yb, Lu, Y) are determined to contain 4f 6 5d 0 (Sm II), 4f 13 5d 0 (Tm II), 4f 14 5d 0 (Yb II), 4f 14 5d 1 (Lu II), and 4d 1 (Y II) electronic configurations. Additionally, our results suggest that Ln(C 5H 4SiMe 3) 3 1– (Ln = Pr, Nd, Gd, Tb, Dy, Ho, and Er) also contain Ln II ions, but with 4f n 5d 1 configurations (not 4f n +1 5d 0). In these 4f n 5d 1 complexes, the C 3h-symmetric ligand environment provides a highly shielded 5d-orbital of a' symmetry that made the 4f n 5d 1 electronic configurations lower in energy than the more typical 4f n+1 5d 0 configuration.« less

Ligand Noninnocence in Iron Corroles: Insights from Optical and X-ray Absorption Spectroscopies and Electrochemical Redox Potentials

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

Ganguly, Sumit; Giles, Logan J.; Thomas, Kolle E.

Two new series of iron meso-tris(para-X-phenyl)corrole (TpXPC) complexes, Fe[TpXPC]Ph and Fe[TpXPC]Tol, in which X=CF 3, H, Me, and OMe, and Tol=p-methylphenyl (p-tolyl), have been synthesized, allowing a multitechnique electronic–structural comparison with the corresponding FeCl, FeNO, and Fe 2(μ-O) TpXPC derivatives. Optical spectroscopy revealed that the Soret maxima of the FePh and FeTol series are insensitive to the phenyl para substituent, consistent with the presumed innocence of the corrole ligand in these compounds. Accordingly, we may be increasingly confident in the ability of the substituent effect criterion to serve as a probe of corrole noninnocence. Furthermore, four complexes—Fe[TPC]Cl, Fe[TPC](NO), {Fe[TPC]} 2O,more » and Fe[TPC]Ph—were selected for a detailed XANES investigation of the question of ligand noninnocence. The intensity-weighted average energy (IWAE) positions were found to exhibit rather modest variations (0.8 eV over the series of corroles). The integrated Fe-K pre-edge intensities, on the other hand, vary considerably, with a 2.5 fold increase for Fe[TPC]Ph relative to Fe[TPC]Cl and Fe[TPC](NO). Given the approximately C 4v local symmetry of the Fe in all the complexes, the large increase in intensity for Fe[TPC]Ph may be attributed to a higher number of 3d holes, consistent with an expected Fe IV-like description, in contrast to Fe[TPC]Cl and Fe[TPC](NO), in which the Fe is thought to be Fe III-like. In conclusion, these results afford strong validation of XANES as a probe of ligand noninnocence in metallocorroles. Electrochemical redox potentials, on the other hand, were found not to afford a simple probe of ligand noninnocence in Fe corroles.« less

Ligand Noninnocence in Iron Corroles: Insights from Optical and X-ray Absorption Spectroscopies and Electrochemical Redox Potentials

DOE PAGES

Ganguly, Sumit; Giles, Logan J.; Thomas, Kolle E.; ...

2017-10-06

Two new series of iron meso-tris(para-X-phenyl)corrole (TpXPC) complexes, Fe[TpXPC]Ph and Fe[TpXPC]Tol, in which X=CF 3, H, Me, and OMe, and Tol=p-methylphenyl (p-tolyl), have been synthesized, allowing a multitechnique electronic–structural comparison with the corresponding FeCl, FeNO, and Fe 2(μ-O) TpXPC derivatives. Optical spectroscopy revealed that the Soret maxima of the FePh and FeTol series are insensitive to the phenyl para substituent, consistent with the presumed innocence of the corrole ligand in these compounds. Accordingly, we may be increasingly confident in the ability of the substituent effect criterion to serve as a probe of corrole noninnocence. Furthermore, four complexes—Fe[TPC]Cl, Fe[TPC](NO), {Fe[TPC]} 2O,more » and Fe[TPC]Ph—were selected for a detailed XANES investigation of the question of ligand noninnocence. The intensity-weighted average energy (IWAE) positions were found to exhibit rather modest variations (0.8 eV over the series of corroles). The integrated Fe-K pre-edge intensities, on the other hand, vary considerably, with a 2.5 fold increase for Fe[TPC]Ph relative to Fe[TPC]Cl and Fe[TPC](NO). Given the approximately C 4v local symmetry of the Fe in all the complexes, the large increase in intensity for Fe[TPC]Ph may be attributed to a higher number of 3d holes, consistent with an expected Fe IV-like description, in contrast to Fe[TPC]Cl and Fe[TPC](NO), in which the Fe is thought to be Fe III-like. In conclusion, these results afford strong validation of XANES as a probe of ligand noninnocence in metallocorroles. Electrochemical redox potentials, on the other hand, were found not to afford a simple probe of ligand noninnocence in Fe corroles.« less

Evaluating the electronic structure of formal Ln II ions in Ln II(C 5H 4SiMe 3) 3 1– using XANES spectroscopy and DFT calculations

DOE PAGES

Fieser, Megan E.; Ferrier, Maryline Ghislaine; Su, Jing; ...

2017-06-30

Here, the isolation of [K(2.2.2-cryptand)][Ln(C 5H 4SiMe 3) 3], formally containing LnII, for all lanthanides (excluding Pm) was surprising given that +2 oxidation states are typically regarded as inaccessible for most 4f-elements. Herein, X-ray absorption near-edge spectroscopy (XANES), ground-state density functional theory (DFT), and transition dipole moment calculations are used to investigate the possibility that Ln(C 5H 4SiMe 3) 3 1– (Ln = Pr, Nd, Sm, Gd, Tb, Dy, Y, Ho, Er, Tm, Yb and Lu) compounds represented molecular Ln II complexes. Results from the ground-state DFT calculations were supported by additional calculations that utilized complete-active-space multi-configuration approach with second-ordermore » perturbation theoretical correction (CASPT2). Through comparisons with standards, Ln(C 5H 4SiMe 3) 3 1– (Ln = Sm, Tm, Yb, Lu, Y) are determined to contain 4f 6 5d 0 (Sm II), 4f 13 5d 0 (Tm II), 4f 14 5d 0 (Yb II), 4f 14 5d 1 (Lu II), and 4d 1 (Y II) electronic configurations. Additionally, our results suggest that Ln(C 5H 4SiMe 3) 3 1– (Ln = Pr, Nd, Gd, Tb, Dy, Ho, and Er) also contain Ln II ions, but with 4f n 5d 1 configurations (not 4f n +1 5d 0). In these 4f n 5d 1 complexes, the C 3h-symmetric ligand environment provides a highly shielded 5d-orbital of a' symmetry that made the 4f n 5d 1 electronic configurations lower in energy than the more typical 4f n+1 5d 0 configuration.« less

Iodate in calcite and vaterite: Insights from synchrotron X-ray absorption spectroscopy and first-principles calculations

NASA Astrophysics Data System (ADS)

Podder, J.; Lin, J.; Sun, W.; Botis, S. M.; Tse, J.; Chen, N.; Hu, Y.; Li, D.; Seaman, J.; Pan, Y.

2017-02-01

Calcium carbonates such as calcite are the dominant hosts of inorganic iodine in nature and are potentially important for the retention and removal of radioactive iodine isotopes (129I and 131I) in contaminated water. However, little is known about the structural environment of iodine in carbonates. In this study, iodate (IO3-) doped calcite and vaterite have been synthesized using the gel-diffusion method at three NaIO3 concentrations (0.002; 0.004; 0.008 M) and a pH value of 9.0, under ambient temperature and pressure. Inductively coupled plasma mass spectrometry (ICP-MS) analyses show that iodine is preferentially incorporated into calcite over vaterite. Synchrotron iodine K-edge X-ray absorption near-edge structure (XANES) spectra confirm that IO3- is the dominant iodine species in synthetic calcite and vaterite. Analyses of iodine K-edge extended X-ray absorption fine structure (EXAFS) data, complemented by periodic first-principles calculations at the density functional theory (DFT) levels, demonstrate that the I5+ ion of the IO3- group in calcite and vaterite is bonded by three and two additional O atoms (i.e., coordination numbers = 6 and 5), respectively, and is incorporated via the charged coupled substitution I5+ + Na+ ↔ C4+ + Ca2+, with the Na+ cation at a nearest Ca2+ site being the most energetically favorable configuration.

Chemical and structural characterization of copper adsorbed on mosses (Bryophyta).

PubMed

González, Aridane G; Jimenez-Villacorta, Felix; Beike, Anna K; Reski, Ralf; Adamo, Paola; Pokrovsky, Oleg S

2016-05-05

The adsorption of copper on passive biomonitors (devitalized mosses Hypnum sp., Sphagnum denticulatum, Pseudoscleropodium purum and Brachythecium rutabulum) was studied under different experimental conditions such as a function of pH and Cu concentration in solution. Cu assimilation by living Physcomitrella patents was also investigated. Molecular structure of surface adsorbed and incorporated Cu was studied by X-ray Absorption Spectroscopy (XAS). Devitalized mosses exhibited the universal adsorption pattern of Cu as a function of pH, with a total binding sites number 0.05-0.06 mmolg(dry)(-1) and a maximal adsorption capacity of 0.93-1.25 mmolg(dry)(-1) for these devitalized species. The Extended X-ray Absorption Fine Structure (EXAFS) fit of the first neighbor demonstrated that for all studied mosses there are ∼4.5 O/N atoms around Cu at ∼1.95 Å likely in a pseudo-square geometry. The X-ray Absorption Near Edge Structure (XANES) analysis demonstrated that Cu(II)-cellulose (representing carboxylate groups) and Cu(II)-phosphate are the main moss surface binding moieties, and the percentage of these sites varies as a function of solution pH. P. patens exposed during one month to Cu(2+) yielded ∼20% of Cu(I) in the form of Cu-S(CN) complexes, suggesting metabolically-controlled reduction of adsorbed and assimilated Cu(2+). Copyright © 2016 Elsevier B.V. All rights reserved.

Geometry of Pt(IV) in H 2PtCl 6 aqueous solution: An X-ray absorption spectroscopic investigation

NASA Astrophysics Data System (ADS)

Chen, Xing; Chu, Wangsheng; Wang, Lei; Wu, Ziyu

2009-02-01

The noble metal ions play an important role in many chemical reactions, but at the present time they represent also potentially new environmental contaminants. There is relatively little information available to adequately assess the potential health hazards, so that to evaluate the potential hazards and identify the necessary actions to reduce the risks associated with exposure to these metals and their compounds it is important to understand the local structure around noble metal ions. In this contribution, the local coordination around platinum (IV) ions e.g., Pt 4+ in aqueous solution, has been investigated by using X-ray absorption spectroscopy (XAS). X-ray absorption near-edge spectra (XANES) of both [PtCl 6] 2- and [PtCl 4(OH) 2] 2- in an aqueous solution have been calculated using FEFF8.2 and both are characterized by an octahedral geometry. From these calculations, we may also assign a characteristic post-edge feature to a contribution of Cl d-states. From the EXAFS analysis we also determined the corresponding Pt bond distances, e.g., 2.33 Å for the Pt-Cl distance and 2.03 Å for the Pt-O distance in these aqueous solutions. The same analysis provides evidence that the peaks in the Fourier transform at about 4.0 Å are due to multiple scattering collinear Cl-Pt-Cl contributions.

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

van Veelen, Arjen; Bargar, John R.; Law, Gareth T. W.

Polarization-dependent grazing incidence X-ray absorption spectroscopy (XAS) measurements were completed on oriented single crystals of magnesite [MgCO 3] and brucite [Mg(OH) 2] reacted with aqueous uranyl chloride above and below the solubility boundaries of schoepite (500, 50, and 5 ppm) at pH 8.3 and at ambient (P CO2 = 10 –3.5) or reduced partial pressures of carbon dioxide (P CO2 = 10 –4.5). X-ray absorption near edge structure (XANES) spectra show a striking polarization dependence (χ = 0° and 90° relative to the polarization plane of the incident beam) and consistently demonstrated that the uranyl molecule was preferentially oriented withmore » its O axial = U(VI) = O axial linkage at high angles (60–80°) to both magnesite (101¯4) and brucite (0001). Extended X-ray absorption fine structure (EXAFS) analysis shows that the “effective” number of U(VI) axial oxygens is the most strongly affected fitting parameter as a function of polarization. Furthermore, axial tilt in the surface thin films (thickness ~ 21 Å) is correlated with surface roughness [σ]. Our results show that hydrated uranyl(-carbonate) complexes polymerize on all of our experimental surfaces and that this process is controlled by surface hydroxylation. Lastly, these results provide new insights into the bonding configuration expected for uranyl complexes on the environmentally significant carbonate and hydroxide mineral surfaces.« less

Uranium immobilization and nanofilm formation on magnesium-rich minerals

DOE PAGES

van Veelen, Arjen; Bargar, John R.; Law, Gareth T. W.; ...

2016-03-18

Polarization-dependent grazing incidence X-ray absorption spectroscopy (XAS) measurements were completed on oriented single crystals of magnesite [MgCO 3] and brucite [Mg(OH) 2] reacted with aqueous uranyl chloride above and below the solubility boundaries of schoepite (500, 50, and 5 ppm) at pH 8.3 and at ambient (P CO2 = 10 –3.5) or reduced partial pressures of carbon dioxide (P CO2 = 10 –4.5). X-ray absorption near edge structure (XANES) spectra show a striking polarization dependence (χ = 0° and 90° relative to the polarization plane of the incident beam) and consistently demonstrated that the uranyl molecule was preferentially oriented withmore » its O axial = U(VI) = O axial linkage at high angles (60–80°) to both magnesite (101¯4) and brucite (0001). Extended X-ray absorption fine structure (EXAFS) analysis shows that the “effective” number of U(VI) axial oxygens is the most strongly affected fitting parameter as a function of polarization. Furthermore, axial tilt in the surface thin films (thickness ~ 21 Å) is correlated with surface roughness [σ]. Our results show that hydrated uranyl(-carbonate) complexes polymerize on all of our experimental surfaces and that this process is controlled by surface hydroxylation. Lastly, these results provide new insights into the bonding configuration expected for uranyl complexes on the environmentally significant carbonate and hydroxide mineral surfaces.« less

Uranium Immobilization and Nanofilm Formation on Magnesium-Rich Minerals.

PubMed

van Veelen, Arjen; Bargar, John R; Law, Gareth T W; Brown, Gordon E; Wogelius, Roy A

2016-04-05

Polarization-dependent grazing incidence X-ray absorption spectroscopy (XAS) measurements were completed on oriented single crystals of magnesite [MgCO3] and brucite [Mg(OH)2] reacted with aqueous uranyl chloride above and below the solubility boundaries of schoepite (500, 50, and 5 ppm) at pH 8.3 and at ambient (PCO2 = 10(-3.5)) or reduced partial pressures of carbon dioxide (PCO2 = 10(-4.5)). X-ray absorption near edge structure (XANES) spectra show a striking polarization dependence (χ = 0° and 90° relative to the polarization plane of the incident beam) and consistently demonstrated that the uranyl molecule was preferentially oriented with its Oaxial═U(VI)═Oaxial linkage at high angles (60-80°) to both magnesite (101̅4) and brucite (0001). Extended X-ray absorption fine structure (EXAFS) analysis shows that the "effective" number of U(VI) axial oxygens is the most strongly affected fitting parameter as a function of polarization. Furthermore, axial tilt in the surface thin films (thickness ∼ 21 Å) is correlated with surface roughness [σ]. Our results show that hydrated uranyl(-carbonate) complexes polymerize on all of our experimental surfaces and that this process is controlled by surface hydroxylation. These results provide new insights into the bonding configuration expected for uranyl complexes on the environmentally significant carbonate and hydroxide mineral surfaces.

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

PubMed Central

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

2014-01-01

Two structurally homologous Mn compounds in different oxidation states were studied to investigate the relative influence of oxidation state and ligand environment on Mn K-edge X-ray absorption near-edge structure (XANES) and Mn Kβ X-ray emission spectroscopy (Kβ XES). The two manganese compounds are the di-μ-oxo compound [L′2MnIIIO2MnIVL′2](ClO4)3, where L′ is 1,10-phenanthroline (Cooper, S. R.; Calvin, M. J. Am. Chem. Soc. 1977, 99, 6623–6630) and the linear mono-μ-oxo compound [LMnIIIOMnIIIL](ClO4)2, where L− is the monoanionic N,N-bis(2-pyridylmethyl)-N′-salicylidene-1,2-diaminoethane ligand (Horner, O.; Anxolabéhère-Mallart, E.; Charlot, M. F.; Tchertanov, L.; Guilhem, J.; Mattioli, T. A.; Boussac, A.; Girerd, J.-J. Inorg. Chem. 1999, 38, 1222–1232). Preparative bulk electrolysis in acetonitrile was used to obtain higher oxidation states of the compounds: the MnIVMnIV species for the di-μ-oxo compound and the MnIIIMnIV and MnIVMnIV species for the mono-μ-oxo compound. IR, UV/vis, EPR, and EXAFS spectra were used to determine the purity and integrity of the various sample solutions. The Mn K-edge XANES spectra shift to higher energy upon oxidation when the ligand environment remains similar. However, shifts in energy are also observed when only the ligand environment is altered. This is achieved by comparing the di-μ-oxo and linear mono-μ-oxo Mn–Mn moieties in equivalent oxidation states, which represent major structural changes. The magnitude of an energy shift due to major changes in ligand environment can be as large as that of an oxidation-state change. Therefore, care must be exercised when correlating the Mn K-edge energies to manganese oxidation states without taking into account the nature of the ligand environment and the overall structure of the compound. In contrast to Mn K-edge XANES, Kβ XES spectra show less dependence on ligand environment. The Kβ1,3 peak energies are comparable for the di-μ-oxo and mono-μ-oxo compounds in equivalent oxidation states. The energy shifts observed due to oxidation are also similar for the two different compounds. The study of the different behavior of the XANES pre-edge and main-edge features in conjunction with Kβ XES provides significant information about the oxidation state and character of the ligand environment of manganese atoms. PMID:11459481

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

NASA Astrophysics Data System (ADS)

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

2007-12-01

We demonstrate that the oxidation state of iron (Fe3+/ΣFe) can be determined with a precision of ±0.02 (10% relative) on natural basalt glasses at mantle-relevant fO2 using Fe K-edge X-ray absorption near edge structure (XANES) spectroscopy. This is equivalent to ±0.25 log unit resolution relative to the QFM buffer. Precise determination of the oxidation state over this narrow range (Fe3+/ΣFe=0.06-0.30) and at low fO2 (down to QFM-2) relies on appropriate standards, high spectral resolution, and highly reproducible methods for extracting the pre-edge centroid position. We equilibrated natural tholeiite powder in a CO/CO2 gas mixing furnace at 1350°C from QFM-3 to QFM+2 to create six glasses of known Fe3+/ΣFe, independently determined by Mössbauer spectroscopy. XANES spectra were collected at station X26A at NSLS, Brookhaven Natl. Lab, in fluorescence mode (9 element Ge array detector) using both Si(111) and Si(311) monochromators. Generally, the energy position of the 1s→3d (pre-edge) transition centroid is the most sensitive monitor of Fe oxidation state using XANES. For the mixture of Fe oxidation states in these glasses and the resulting coordination geometries, the pre-edge spectra are best defined by two multiple 3d crystal field transitions. The Si(311) monochromator, with higher energy resolution, substantially improved spectral resolution for the 1s→3d transition. Dwell times of 5s at 0.1eV intervals across the pre-edge region yielded spectra with the 1s→3d transition peaks clearly resolved. The pre-edge centroid position is highly sensitive to the background subtraction and peak fitting procedures. Differences in fitting models result in small but significant differences in the calculated peak area of each pre-edge multiplet, and the relative contribution of each peak to the calculated centroid. We assessed several schemes and obtained robust centroid positions by simultaneously fitting the background with a damped harmonic oscillator (DHO) function and pre-edge features with two Gaussians over a sub-sample of the pre-edge region (7110-7120 eV). We found that the relation between Fe3+/ΣFe and the centroid energy is non-linear over this fO2 range, which is expected if the coordination environment changes with oxidation state. ΔQFM is linearly related (R2=0.99) to the centroid position. This new calibration allows the oxidation states of natural mantle melts to be discriminated with high spatial resolution (9μm). We apply the new calibration to determination of Fe3+/ΣFe in natural basaltic glasses and olivine-hosted glass inclusions (Cottrell et al. & Kelley et al., this meeting).

Direct Determination of the Intracellular Oxidation State of Plutonium

PubMed Central

Gorman-Lewis, Drew; Aryal, Baikuntha P.; Paunesku, Tatjana; Vogt, Stefan; Lai, Barry; Woloschak, Gayle E.; Jensen, Mark P.

2013-01-01

Microprobe X-ray absorption near edge structure (μ-XANES) measurements were used to determine directly, for the first time, the oxidation state of intracellular plutonium in individual 0.1 μm2 areas within single rat pheochromocytoma cells (PC12). The living cells were incubated in vitro for 3 hours in the presence of Pu added to the media in different oxidation states (Pu(III), Pu(IV), and Pu(VI)) and in different chemical forms. Regardless of the initial oxidation state or chemical form of Pu presented to the cells, the XANES spectra of the intracellular Pu deposits was always consistent with tetravalent Pu even though the intracellular milieu is generally reducing. PMID:21755934

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

PubMed

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

2017-05-05

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

Incorporation of chromium into TiO{sub 2} nanopowders

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

Kollbek, Kamila, E-mail: biernack@agh.edu.pl; AGH University of Science and Technology, Academic Centre for Materials and Nanotechnology, Al. Mickiewicza 30, 30-059 Krakow; Sikora, Marcin

2015-04-15

Highlights: • Nanopowders of TiO{sub 2}:Cr with different amount of Cr dopant were obtained by flame spray synthesis, FSS. • Increase in the optical absorption and a shift of the absorption edge were observed upon Cr doping. • HERFD-XANES measurements indicated that the average valence state of titanium ions was preserved. • Increasing magnetic susceptibility of a paramagnetic character was observed upon Cr doping. - Abstract: The paper reports on the results of a study of optical, electronic and magnetic properties of TiO{sub 2} nanopowders doped with Cr ions. Diffused reflectance spectra reveal an increase in the optical absorption andmore » a shift of the absorption edge towards lower energies upon Cr doping. Direct information on the Ti electronic state and the symmetry of its nearest environment is obtained from XANES Ti K-edge spectra. Magnetic behaviour is probed by means of the temperature dependence of DC magnetic susceptibility. Increasing magnetic susceptibility of a paramagnetic character is observed upon increasing chromium doping. The Curie constant of TiO{sub 2}:10 at.% Cr sample (0.12 emu K/mol Oe) is lower than that expected for Cr{sup 3+} (0.1875 emu K/mol Oe) possibly due to the appearance of Cr{sup 4+} or the presence of the orbital contribution to the magnetic moment.« less

Fate and lability of silver in soils: Effect of ageing

EPA Science Inventory

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

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

PubMed

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

2015-12-21

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

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

NASA Astrophysics Data System (ADS)

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

1992-10-01

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

Speciation and characterization of arsenic in gold ores and cyanidation tailings using X-ray absorption spectroscopy

USGS Publications Warehouse

Paktunc, D.; Foster, A.; Heald, S.; Laflamme, G.

2004-01-01

The knowledge of mineralogy and molecular structure of As is needed to better understand the stability of As in wastes resulting from processing of gold ores. In this study, optical microscopy, scanning electron microscopy, electron microprobe, X-ray diffraction and X-ray absorption fine structure (XAFS) spectroscopy (including both XANES and EXAFS regimes) were employed to determine the mineralogical composition and local coordination environment of As in gold ores and process tailings from bench-scale tests designed to mimic a common plant practice. Arsenic-bearing minerals identified in the ores and tailings include iron (III) oxyhydroxides, scorodite (FeAsO4??2H2O), ferric arsenates, arseniosiderite (Ca2Fe3 (AsO4)3O2??3H2O), Ca-Fe arsenates, pharmacosiderite (KFe4 (AsO4)3(OH)4??6-7H2O), jarosite (K2Fe6(SO4)4 (OH)12) and arsenopyrite (FeAsS). Iron (III) oxyhydroxides contain variable levels of As from trace to about 22 wt% and Ca up to approximately 9 wt%. Finely ground ore and tailings samples were examined by bulk XAFS and selected mineral grains were analyzed by microfocused XAFS (micro-EXAFS) spectroscopy to reconcile the ambiguities of multiple As sources in the complex bulk EXAFS spectra. XANES spectra indicated that As occurs as As5+in all the samples. Micro-EXAFS spectra of individual iron (III) oxyhydroxide grains with varying As concentrations point to inner-sphere bidentate-binuclear arsenate complexes as the predominant form of As. There are indications for the presence of a second Fe shell corresponding to bidentate-mononuclear arrangement. Iron (III) oxyhydroxides with high As concentrations corresponding to maximum adsorption densities probably occur as nanoparticles. The discovery of Ca atoms around As in iron (III) oxyhydroxides at interatomic distances of 4.14-4.17 A?? and the coordination numbers suggest the formation of arseniosiderite-like nanoclusters by coprecipitation rather than simple adsorption of Ca onto iron (III) oxyhydroxides. Correlation of Ca with As in iron (III) oxyhydroxides as determined by electron microprobe analysis supports the coprecipitate origin for the presence of Ca in iron (III) oxyhydroxides. The samples containing higher abundances of ferric arsenates released higher As concentrations during the cyanidation tests. The presence of highly soluble ferric arsenates and Ca-Fe arsenates, and relatively unstable iron (III) oxyhydroxides with Fe/As molar ratios of less than 4 in the ore and process tailings suggests that not only the tailings in the impoundment will continue to release As, but also there is the potential for mobilization of As from the natural sources such as the unmined ore. ?? 2004 Elsevier Ltd.

Speciation and characterization of arsenic in gold ores and cyanidation tailings using X-ray absorption spectroscopy

NASA Astrophysics Data System (ADS)

Paktunc, Dogan; Foster, Andrea; Heald, Steve; Laflamme, Gilles

2004-03-01

The knowledge of mineralogy and molecular structure of As is needed to better understand the stability of As in wastes resulting from processing of gold ores. In this study, optical microscopy, scanning electron microscopy, electron microprobe, X-ray diffraction and X-ray absorption fine structure (XAFS) spectroscopy (including both XANES and EXAFS regimes) were employed to determine the mineralogical composition and local coordination environment of As in gold ores and process tailings from bench-scale tests designed to mimic a common plant practice. Arsenic-bearing minerals identified in the ores and tailings include iron (III) oxyhydroxides, scorodite (FeAsO 4·2H 2O), ferric arsenates, arseniosiderite (Ca 2Fe 3(AsO 4) 3O 2·3H 2O), Ca-Fe arsenates, pharmacosiderite (KFe 4(AsO 4) 3(OH) 4·6-7H 2O), jarosite (K 2Fe 6(SO 4) 4(OH) 12) and arsenopyrite (FeAsS). Iron (III) oxyhydroxides contain variable levels of As from trace to about 22 wt% and Ca up to approximately 9 wt%. Finely ground ore and tailings samples were examined by bulk XAFS and selected mineral grains were analyzed by microfocused XAFS (micro-EXAFS) spectroscopy to reconcile the ambiguities of multiple As sources in the complex bulk EXAFS spectra. XANES spectra indicated that As occurs as As 5+in all the samples. Micro-EXAFS spectra of individual iron (III) oxyhydroxide grains with varying As concentrations point to inner-sphere bidentate-binuclear arsenate complexes as the predominant form of As. There are indications for the presence of a second Fe shell corresponding to bidentate-mononuclear arrangement. Iron (III) oxyhydroxides with high As concentrations corresponding to maximum adsorption densities probably occur as nanoparticles. The discovery of Ca atoms around As in iron (III) oxyhydroxides at interatomic distances of 4.14-4.17 Å and the coordination numbers suggest the formation of arseniosiderite-like nanoclusters by coprecipitation rather than simple adsorption of Ca onto iron (III) oxyhydroxides. Correlation of Ca with As in iron (III) oxyhydroxides as determined by electron microprobe analysis supports the coprecipitate origin for the presence of Ca in iron (III) oxyhydroxides. The samples containing higher abundances of ferric arsenates released higher As concentrations during the cyanidation tests. The presence of highly soluble ferric arsenates and Ca-Fe arsenates, and relatively unstable iron (III) oxyhydroxides with Fe/As molar ratios of less than 4 in the ore and process tailings suggests that not only the tailings in the impoundment will continue to release As, but also there is the potential for mobilization of As from the natural sources such as the unmined ore.

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

PubMed

Zhang, Renqin; McEwen, Jean-Sabin

2018-05-22

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

Ab initio X-ray absorption modeling of Cu-SAPO-34: Characterization of Cu exchange sites under different conditions

DOE PAGES

Zhang, Renqin; Helling, Kathy; McEwen, Jean-Sabin

2016-03-29

Copper-exchanged SAPO-34 (Cu-SAPO-34) provides excellent catalytic activity and hydrothermal sta-bility in the selective catalytic reduction (SCR) of NOxby using NH3as a reductant. Here, we find that the6-membered ring (6MR) site is the most energetically favorable for a Cu+ion while the 8-memberedring (8MR) sites are less favorable by about 0.5 eV with respect to the 6MR site in Cu-SAPO-34. Uponadsorption of molecular species (H2O, O, OH, O2), the energy differences between Cu in the 8MR and 6MRsites decreases and almost disappears. Further, a thermodynamic phase diagram study shows that a Cu+ion bound to a single H2O molecule is the most stablemore » species at low oxygen potential values while aCu2+ion bound to 2 OH species is more stable when the oxygen chemical potential is sufficiently high. Bycomparing Cu K-edge XANES between Cu-SSZ-13 and Cu-SAPO-34 with Cu in different oxidation states,we conclude that it is difficult to differentiate the simulated XANES of Cu in these structures at a givenoxidation state. By studying the Cu K-edge XANES of several favorable structures in Cu-SAPO-34 in thepresence of adspecies, the simulated XANES results capture the real trend of the edge shift with oxidationstate and gives new insights into the experimentally determined XANES of Cu-SAPO-34 obtained understandard SCR conditions.« less

Oxidized derivatives of Octopus vulgaris and Carcinus aestuarii hemocyanins at pH 7.5 and related models by x-ray absorption spectroscopy.

PubMed Central

Borghi, Elena; Solari, Pier Lorenzo; Beltramini, Mariano; Bubacco, Luigi; Di Muro, Paolo; Salvato, Benedetto

2002-01-01

The binuclear copper sites of the met and met-azido derivatives of Octopus vulgaris and Carcinus aestuarii hemocyanins at pH 7.5 were characterized by high-resolution x-ray absorption spectroscopy in the low energy region (XANES) and in the higher region (EXAFS). The accuracy of the analysis of the data was tested with two mononuclear and six binuclear copper(II) complexes of the poly(benzimidazole) ligand systems 2-BB, L-5,5 and L-6,6 (Casella et al., 1993, Inorg. Chem. 32:2056-2067; 1996, Inorg. Chem. 35:1101-1113). Their structural and reactivity properties are related to those of the protein's derivatives. The results obtained for those models with resolved x-ray structure (the 2-BB-aquo and azido mononuclear complexes, and the binuclear L-5,5 Cu(II)-bis(hydroxo) (Casella et al., unpublished)), extends the validity of our approach to the other poly(benzimidazole)-containing complexes and to the hemocyanin derivatives. Comparison between the protein's and the complexes' data, support a description of the met-derivatives as a five-coordinated O-bridged binuclear copper(II) center and favors, for both species, a bis(hydroxo) structure with a 3-A Cu-Cu distance. For O. vulgaris met-azido derivative a mu-1,3 bridging mode for the ligand appears the most likely. The structural situation of C. aestuarii met-azido-derivative is less clear: a mu-1,1 mode is favored, but a terminal mode cannot be excluded. PMID:12023249

The mechanism of metal nanoparticle formation in plants: limits on accumulation

NASA Astrophysics Data System (ADS)

Haverkamp, R. G.; Marshall, A. T.

2009-08-01

Metal nanoparticles have many potential technological applications. Biological routes to the synthesis of these particles have been proposed including production by vascular plants, known as phytoextraction. While many studies have looked at metal uptake by plants, particularly with regard to phytoremediation and hyperaccumulation, few have distinguished between metal deposition and metal salt accumulation. This work describes the uptake of AgNO3, Na3Ag(S2O3)2, and Ag(NH3)2NO3 solutions by hydroponically grown Brassica juncea and the quantitative measurement of the conversion of these salts to silver metal nanoparticles. Using X-ray absorption near edge spectroscopy (XANES) to determine the metal speciation within the plants, combined with atomic absorption spectroscopy (AAS) for total Ag, the quantity of reduction of AgI to Ag0 is reported. Transmission electron microscopy (TEM) showed Ag particles of 2-35 nm. The factors controlling the amount of silver accumulated are revealed. It is found that there is a limit on the amount of metal nanoparticles that may be deposited, of about 0.35 wt.% Ag on a dry plant basis, and that higher levels of silver are obtained only by the concentration of metal salts within the plant, not by deposition of metal. The limit on metal nanoparticle accumulation, across a range of metals, is proposed to be controlled by the total reducing capacity of the plant for the reduction potential of the metal species and limited to reactions occurring at an electrochemical potential greater than 0 V (verses the standard hydrogen electrode).

Silver binding in argentiferous manganese oxide minerals investigated by synchrotron radiation X-ray absorption spectroscopy

NASA Astrophysics Data System (ADS)

Fan, Chenzi; Li, Qiaoying; Chu, Binbin; Lu, Guohui; Gao, Yuhong; Xu, Lingxiao

2018-02-01

The knowledge of the nature of silver occurrence and sites in argentiferous manganese oxides is significant for developing better process to extract silver from manganese-silver ores. Synchrotron radiation has been used to collect Ag K-edge X-ray absorption spectroscopy of three natural and five synthetic samples of silver-containing manganese oxide, basically in the phases of tunnel-type cryptomelane or todorokite and layer-type birnessite or chalcophanite. Data were also gathered on five standards including Ag foil, Ag2O, Ag2SO4, Ag2CO3, and AgNO3 to compare the local environments of Ag atoms with the samples. Ag K-edge XANES studies show that Ag is present in most of the samples in Ag+ oxidation state, except in the Ag-Tod sample through annealing step in the form of Ag0 nanoparticles which are also identified by TEM. The natural samples from Xiangguang manganese-silver ores exhibit similar coordination distances as the corresponding tunnel or layer structured synthetic samples. In the argentiferous cryptomelanes, silver cations do not occupy the tunnel centers like K+, but rather place on the common face sites of the cubic cage formed by MnO6 octahedra, coordinated with about four oxygen anions at 2.4 Å bond distances proved by the EXAFS results. In the silver-exchanged birnessites or natural argentiferous chalcophanite, silver cations probably occupy a tetrahedral coordination to interlayer O atoms and a position located above or below the vacant cavities in the Mn octahedra layers.

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

NASA Astrophysics Data System (ADS)

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

2013-04-01

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

Manganese(IV) Oxide Production by Acremonium sp. Strain KR21-2 and Extracellular Mn(II) Oxidase Activity

PubMed Central

Miyata, Naoyuki; Tani, Yukinori; Maruo, Kanako; Tsuno, Hiroshi; Sakata, Masahiro; Iwahori, Keisuke

2006-01-01

Ascomycetes that can deposit Mn(III, IV) oxides are widespread in aquatic and soil environments, yet the mechanism(s) involved in Mn oxide deposition remains unclear. A Mn(II)-oxidizing ascomycete, Acremonium sp. strain KR21-2, produced a Mn oxide phase with filamentous nanostructures. X-ray absorption near-edge structure (XANES) spectroscopy showed that the Mn phase was primarily Mn(IV). We purified to homogeneity a laccase-like enzyme with Mn(II) oxidase activity from cultures of strain KR21-2. The purified enzyme oxidized Mn(II) to yield suspended Mn particles; XANES spectra indicated that Mn(II) had been converted to Mn(IV). The pH optimum for Mn(II) oxidation was 7.0, and the apparent half-saturation constant was 0.20 mM. The enzyme oxidized ABTS [2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonic acid)] (pH optimum, 5.5; Km, 1.2 mM) and contained two copper atoms per molecule. Moreover, the N-terminal amino acid sequence (residues 3 to 25) was 61% identical with the corresponding sequence of an Acremonium polyphenol oxidase and 57% identical with that of a Myrothecium bilirubin oxidase. These results provide the first evidence that a fungal multicopper oxidase can convert Mn(II) to Mn(IV) oxide. The present study reinforces the notion of the contribution of multicopper oxidase to microbially mediated precipitation of Mn oxides and suggests that Acremonium sp. strain KR21-2 is a good model for understanding the oxidation of Mn in diverse ascomycetes. PMID:17021194

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

Adams, Merrin S.; Dillon, Carolyn T.; Vogt, Stefan

Metal toxicity to aquatic organisms depends on the speciation of the metal and its binding to the critical receptor site(s) (biotic ligand) of the organism. The intracellular nature of the biotic ligand for Cu in microalgal cells was investigated using the high elemental sensitivity of microprobe synchrotron radiation X-ray fluorescence (SR-XRF) and X-ray absorption near-edge spectroscopy (XANES). The marine microalgae, Ceratoneis closterium, Phaeodactylum tricornutum, and Tetraselmis sp. were selected based on their varying sensitivities to Cu (72-h 50% population growth inhibitions of 8–47 μg Cu/L). Intracellular Cu in control cells was similar for all three species (2.5–3.2 × 10–15 gmore » Cu/cell) and increased 4-fold in C. closterium and Tetraselmis sp. when exposed to copper, but was unchanged in P. tricornutum (72-h exposure to 19, 40, and 40 μg Cu/L, respectively). Whole cell microprobe SR-XRF identified endogenous Cu in the central compartment (cytoplasm) of control (unexposed) cells. After Cu exposure, Cu was colocated with organelles/granules dense in P, S, Ca, and Si and this was clearly evident in thin sections of Tetraselmis sp. XANES indicated coexistence of Cu(I) and Cu(II) in control and Cu-exposed cells, with the Cu ligand (e.g., phytochelatin) in P. tricornutum different from that in C. closterium and Tetraselmis sp. Here, this study supports the hypothesis that Cu(II) is reduced to Cu(I) and that polyphosphate bodies and phytochelatins play a significant role in the internalization and detoxification of Cu in marine microalgae.« less

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

Dublet, Gabrielle; Juillot, Farid; Brest, Jessica

Because they can host significant amounts of Co, the Mn-oxides are commonly considered as the major Co-bearing mineral species in lateritic environments. However, little is known about the process leading to the formation and/or the weathering of these Co-rich Mn-oxides. This lack of knowledge is mainly due to the fact that Co concentrations are too low in primary silicates for classical speciation analysis. In this study, we investigated both Co and Mn speciation in a 64 m thick lateritic regolith developed upon peridotites in New Caledonia, by combining High Energy Resolution Fluorescence Detection X-ray absorption Near Edge Structure (HERFD-XANES) spectroscopymore » at the Co K-edge with classical XANES spectroscopy at the Mn K-edge, bulk chemistry (ICP) and mineralogy (XRD). The results obtained provide new insights into the evolution of Co and Mn speciation as a function of the weathering stages. Co and Mn primarily occur as Co(II) and Mn(II,III) in olivine and serpentine in the bedrock. During the first weathering stage, these forms of Co and Mn are progressively oxidized toward Co(III) and Mn(III,IV), which occur mainly as Co(III)-bearing Mn(III/IV)-oxides in the transition between the saprolite and the laterite. In the uppermost lateritic horizons, long-time weathering resulted in a strong leaching of Co and Mn, and the remaining of these elements occurs as Co(II) and Mn(III) substituting for Fe(III) in goethite. Finally, this latter scavenging process emphasizes the importance of Fe-oxides for the long-term stabilization of Co and Mn in such deeply weathered laterites.« less

An X-ray Absorption Fine Structure study of Au adsorbed onto the non-metabolizing cells of two soil bacterial species

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

Song, Zhen; Kenney, Janice P.L.; Fein, Jeremy B.

2015-02-09

Gram-positive and Gram-negative bacterial cells can remove Au from Au(III)-chloride solutions, and the extent of removal is strongly pH dependent. In order to determine the removal mechanisms, X-ray Absorption Fine Structure (XAFS) spectroscopy experiments were conducted on non-metabolizing biomass of Bacillus subtilis and Pseudomonas putida with fixed Au(III) concentrations over a range of bacterial concentrations and pH values. X-ray Absorption Near Edge Structure (XANES) and Extended X-ray Absorption Fine Structure (EXAFS) data on both bacterial species indicate that more than 90% of the Au atoms on the bacterial cell walls were reduced to Au(I). In contrast to what has beenmore » observed for Au(III) interaction with metabolizing bacterial cells, no Au(0) or Au-Au nearest neighbors were observed in our experimental systems. All of the removed Au was present as adsorbed bacterial surface complexes. For both species, the XAFS data suggest that although Au-chloride-hydroxide aqueous complexes dominate the speciation of Au in solution, Au on the bacterial cell wall is characterized predominantly by binding of Au atoms to sulfhydryl functional groups and amine and/or carboxyl functional groups, and the relative importance of the sulfhydryl groups increases with increasing pH and with decreasing Au loading. The XAFS data for both microorganism species suggest that adsorption is the first step in the formation of Au nanoparticles by bacteria, and the results enhance our ability to account for the behavior of Au in bacteria-bearing geologic systems.« less

An X-ray Absorption Fine Structure study of Au adsorbed onto the non-metabolizing cells of two soil bacterial species

NASA Astrophysics Data System (ADS)

Song, Zhen; Kenney, Janice P. L.; Fein, Jeremy B.; Bunker, Bruce A.

2012-06-01

Gram-positive and Gram-negative bacterial cells can remove Au from Au(III)-chloride solutions, and the extent of removal is strongly pH dependent. In order to determine the removal mechanisms, X-ray Absorption Fine Structure (XAFS) spectroscopy experiments were conducted on non-metabolizing biomass of Bacillus subtilis and Pseudomonas putida with fixed Au(III) concentrations over a range of bacterial concentrations and pH values. X-ray Absorption Near Edge Structure (XANES) and Extended X-ray Absorption Fine Structure (EXAFS) data on both bacterial species indicate that more than 90% of the Au atoms on the bacterial cell walls were reduced to Au(I). In contrast to what has been observed for Au(III) interaction with metabolizing bacterial cells, no Au(0) or Au-Au nearest neighbors were observed in our experimental systems. All of the removed Au was present as adsorbed bacterial surface complexes. For both species, the XAFS data suggest that although Au-chloride-hydroxide aqueous complexes dominate the speciation of Au in solution, Au on the bacterial cell wall is characterized predominantly by binding of Au atoms to sulfhydryl functional groups and amine and/or carboxyl functional groups, and the relative importance of the sulfhydryl groups increases with increasing pH and with decreasing Au loading. The XAFS data for both microorganism species suggest that adsorption is the first step in the formation of Au nanoparticles by bacteria, and the results enhance our ability to account for the behavior of Au in bacteria-bearing geologic systems.

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

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

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

Primitive Oxygen-, Nitrogen-, and Organic-Rich Vein Preserved in a Xenolith Hosted in the Metamorphosed Carancas Meteorite

NASA Technical Reports Server (NTRS)

Chan, Q. H. S.; Zolensky, M. E.; Kebukawa, Y.; Franchi, I.; Wright, I.; Zhao, I.; Rahman, Z.; Utas, J.

2018-01-01

Primitive xenolithic CI-like carbonaceous (C) clasts are sometimes hosted within meteorites of a different origin (ordinary chondrite, ureilite, howardite, and eucrite). These xenoliths contain aggregates of macromolecular carbon (MMC), which are often present as discrete grains and exhibit a wide range of structural order and chemical compositions. The Carancas meteorite is a H4-5 that impacted south of Lake Titicaca, Peru in 2007. While the meteorite exhibits extensive recrystallization of the matrix indicating metamorphism, it contains dark, CI-like clasts that show no evidence of heating. Similar to other xenolithic clasts, the examined C clast of Carancas contains MMC, which however exists in the form of a vein-like structure dissimilar to the typical occurrence of MMC in meteorites. We investigated the organic and isotopic compositions of the organic-rich vein with C,N,O-X-ray absorption near-edge structure (XANES), Raman spectroscopy, and NanoSIMS, in order to constrain its possible origin.

Effect of Particle Size Upon Pt/SiO 2 Catalytic Cracking of n-Dodecane Under Supercritical Conditions: in situ SAXS and XANES Studies

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

Lee, Sungwon; Lee, Sungsik; Kumbhalkar, Mrunmayi

The endothermic cracking and dehydrogenation of n-dodecane is investigated over well-defined nanometer size platinum catalysts supported on SiO 2 to study the particle size effects in the catalytic cracking reaction, with simultaneous in situ monitoring of the particle size and oxidation state of the working catalysts by in situ SAXS (small angle X-ray scattering) and XAS (X-ray absorption spectroscopy). The selectivity toward olefins products was found dominant in the 1 nm size platinum catalysts, whereas paraffins are dominant in the 2 nm catalysts. This reveals a strong correlation between catalytic performance and catalyst size as well as the stability ofmore » the nanoparticles in supercritical condition of n-dodecane. The presented results suggest that controlling the size and geometric structure of platinum nanocatalysts could lead to a fundamentally new level of understanding of nanoscale materials by monitoring the catalysts in realistic reaction conditions.« less

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

Zhang, Zhicheng; Rao, Linfeng; Abney, Carter W.

Adsorbents developed for the recovery of uranium from seawater display poor selectivity over other transition metals present in the ocean, with vanadium particularly problematic. To improve selectivity, an indispensable step is the positive identification of metal binding environments following actual seawater deployment. In this work we apply x-ray absorption fine structure (XAFS) spectroscopy to directly investigate the vanadium binding environment on seawater-deployed polyamidoxime adsorbents. Comparison of the x-ray absorption near edge spectra (XANES) reveal marked similarities to recently a reported non-oxido vanadium (V) structure formed upon binding with cyclic imidedioxime, a byproduct of generating amidoxime functionalities. Density functional theory (DFT)more » calculations provided a series of putative vanadium binding environments for both vanadium (IV) and vanadium (V) oxidation states, and with both amidoxime and cyclic imidedioxime. Fits of the extended XAFS (EXAFS) data confirmed vanadium (V) is bound exclusively by the cyclic imidedioxime moiety in a 1:2 metal:ligand fashion, though a modest structural distortion is also observed compared to crystal structure data and computationally optimized geometries which is attributed to morphology effects from the polymer graft chain and the absence of crystal packing interactions. These results demonstrate that improved selectivity for uranium over vanadium can be achieved by suppressing the formation of cyclic imidedioxime during preparation of polyamidoxime adsorbents for seawater uranium recovery.« less

Fatigue of LiNi0.8Co0.15Al0.05O2 in commercial Li ion batteries

NASA Astrophysics Data System (ADS)

Kleiner, Karin; Dixon, Ditty; Jakes, Peter; Melke, Julia; Yavuz, Murat; Roth, Christina; Nikolowski, Kristian; Liebau, Verena; Ehrenberg, Helmut

2015-01-01

The degradation of LiNi0.8Co0.15Al0.05O2 (LNCAO), a cathode material in lithium-ion-batteries, was studied using in situ powder diffraction and in situ Ni K edge X-ray absorption spectroscopy (XAS). The fatigued material was taken from a 7 Ah battery which was cycled for 34 weeks under defined durability conditions. Meanwhile, a cell was stored, as reference, under controlled conditions without electrochemical treatment. The fatigued LNCAO used in this study showed a capacity loss of 26% ± 9% compared to the non-cycled material. During charge and discharge the local and the overall structure of LNCAO was investigated by X-ray near edge structure (XANES) analysis, the extended X-ray absorption fine structure (EXAFS) analysis and by using Rietveld refinement of in situ powder diffraction patterns. Both powder diffraction and XAS revealed additional, rhombohedral phases which do not change with electrochemical cycling. Moreover, a phase with the lattice parameters of fully lithiated LNCAO was still present in the fatigued material at high potentials, while it was absent in the non-fatigued reference material. The coexistence of these phases is described by domains within the LNCAO particles, in correlation with the observed fatigue.

Ultra-small plutonium oxide nanocrystals: an innovative material in plutonium science.

PubMed

Hudry, Damien; Apostolidis, Christos; Walter, Olaf; Janssen, Arne; Manara, Dario; Griveau, Jean-Christophe; Colineau, Eric; Vitova, Tonya; Prüssmann, Tim; Wang, Di; Kübel, Christian; Meyer, Daniel

2014-08-11

Apart from its technological importance, plutonium (Pu) is also one of the most intriguing elements because of its non-conventional physical properties and fascinating chemistry. Those fundamental aspects are particularly interesting when dealing with the challenging study of plutonium-based nanomaterials. Here we show that ultra-small (3.2±0.9 nm) and highly crystalline plutonium oxide (PuO2 ) nanocrystals (NCs) can be synthesized by the thermal decomposition of plutonyl nitrate ([PuO2 (NO3 )2 ]⋅3 H2 O) in a highly coordinating organic medium. This is the first example reporting on the preparation of significant quantities (several tens of milligrams) of PuO2 NCs, in a controllable and reproducible manner. The structure and magnetic properties of PuO2 NCs have been characterized by a wide variety of techniques (powder X-ray diffraction (PXRD), X-ray absorption fine structure (XAFS), X-ray absorption near edge structure (XANES), TEM, IR, Raman, UV/Vis spectroscopies, and superconducting quantum interference device (SQUID) magnetometry). The current PuO2 NCs constitute an innovative material for the study of challenging problems as diverse as the transport behavior of plutonium in the environment or size and shape effects on the physics of transuranium elements. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

USGS Publications Warehouse

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

2016-01-01

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

Reversal magnetization dependence with the Cr and Fe oxidation states in YFe1-xCrxO3 (0≤x≤1) perovskites

NASA Astrophysics Data System (ADS)

Fabian, F. A.; Pedra, P. P.; Moura, K. O.; Duque, J. G. S.; Meneses, C. T.

2016-06-01

In this work, we have carried out a detailed study of the magnetic and structural properties of YFe1-xCrxO3 (0≤x≤1) samples with orthorhombic structure obtained by co-precipitation method. Analysis of X-ray diffraction data using Rietveld refinement show that all samples present an orthorhombic crystal system with space group Pnma. Besides, we have observed a reduction of unit cell volume with increasing of the Cr concentration. SEM images show the formation of grains of micrometer order. X-ray Absorption near edge spectroscopy (XANES) measurements show a shift of absorption edge which can be indicate there is (i) different oxidation states to Fe and Cr ions and/or (ii) a changing in the point symmetry of Fe and Cr ions to the compounds. The magnetization measurements indicate a continuous decreasing of the magnetic transition temperature as function of chromium doping. The reversal magnetization effect was observed to concentrations around x=0.5. Besides, the deviation of the Curie-Weiss law and a weak ferromagnetic behavior observed at room temperature in the M vs H curves can be attributed to the strong magnetic interactions between the transition metals with different oxidation states.

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

PubMed Central

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

2009-01-01

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

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

PubMed

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

2009-10-01

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

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

NASA Astrophysics Data System (ADS)

Farges, François; Brown, Gordon E.

1997-05-01

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

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

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

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

2009-05-21

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

Observation of the origin of d0 magnetism in ZnO nanostructures using X-ray-based microscopic and spectroscopic techniques

NASA Astrophysics Data System (ADS)

Singh, Shashi B.; Wang, Yu-Fu; Shao, Yu-Cheng; Lai, Hsuan-Yu; Hsieh, Shang-Hsien; Limaye, Mukta V.; Chuang, Chen-Hao; Hsueh, Hung-Chung; Wang, Hsaiotsu; Chiou, Jau-Wern; Tsai, Hung-Ming; Pao, Chih-Wen; Chen, Chia-Hao; Lin, Hong-Ji; Lee, Jyh-Fu; Wu, Chun-Te; Wu, Jih-Jen; Pong, Way-Faung; Ohigashi, Takuji; Kosugi, Nobuhiro; Wang, Jian; Zhou, Jigang; Regier, Tom; Sham, Tsun-Kong

2014-07-01

Efforts have been made to elucidate the origin of d0 magnetism in ZnO nanocactuses (NCs) and nanowires (NWs) using X-ray-based microscopic and spectroscopic techniques. The photoluminescence and O K-edge and Zn L3,2-edge X-ray-excited optical luminescence spectra showed that ZnO NCs contain more defects than NWs do and that in ZnO NCs, more defects are present at the O sites than at the Zn sites. Specifically, the results of O K-edge scanning transmission X-ray microscopy (STXM) and the corresponding X-ray-absorption near-edge structure (XANES) spectroscopy demonstrated that the impurity (non-stoichiometric) region in ZnO NCs contains a greater defect population than the thick region. The intensity of O K-edge STXM-XANES in the impurity region is more predominant in ZnO NCs than in NWs. The increase in the unoccupied (occupied) density of states at/above (at/below) the conduction-band minimum (valence-band maximum) or the Fermi level is related to the population of defects at the O sites, as revealed by comparing the ZnO NCs to the NWs. The results of O K-edge and Zn L3,2-edge X-ray magnetic circular dichroism demonstrated that the origin of magnetization is attributable to the O 2p orbitals rather than the Zn d orbitals. Further, the local density approximation (LDA) + U verified that vacancies in the form of dangling or unpaired 2p states (due to Zn vacancies) induced a significant local spin moment in the nearest-neighboring O atoms to the defect center, which was determined from the uneven local spin density by analyzing the partial density of states of O 2p in ZnO.Efforts have been made to elucidate the origin of d0 magnetism in ZnO nanocactuses (NCs) and nanowires (NWs) using X-ray-based microscopic and spectroscopic techniques. The photoluminescence and O K-edge and Zn L3,2-edge X-ray-excited optical luminescence spectra showed that ZnO NCs contain more defects than NWs do and that in ZnO NCs, more defects are present at the O sites than at the Zn sites. Specifically, the results of O K-edge scanning transmission X-ray microscopy (STXM) and the corresponding X-ray-absorption near-edge structure (XANES) spectroscopy demonstrated that the impurity (non-stoichiometric) region in ZnO NCs contains a greater defect population than the thick region. The intensity of O K-edge STXM-XANES in the impurity region is more predominant in ZnO NCs than in NWs. The increase in the unoccupied (occupied) density of states at/above (at/below) the conduction-band minimum (valence-band maximum) or the Fermi level is related to the population of defects at the O sites, as revealed by comparing the ZnO NCs to the NWs. The results of O K-edge and Zn L3,2-edge X-ray magnetic circular dichroism demonstrated that the origin of magnetization is attributable to the O 2p orbitals rather than the Zn d orbitals. Further, the local density approximation (LDA) + U verified that vacancies in the form of dangling or unpaired 2p states (due to Zn vacancies) induced a significant local spin moment in the nearest-neighboring O atoms to the defect center, which was determined from the uneven local spin density by analyzing the partial density of states of O 2p in ZnO. Electronic supplementary information (ESI) available: Scanning photoelectron microscopy (SPEM) results of ZnO NCs and NWs. Computational details and calculated total and partial density of states (PDOS) of bulk wurtzite ZnO with oxygen anion vacancies (VO). See DOI: 10.1039/c4nr01961j

Electronic Structure of Manganese Corroles Revisited: X-ray Structures, Optical and X-ray Absorption Spectroscopies, and Electrochemistry as Probes of Ligand Noninnocence

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

Ganguly, Sumit; MCormick, Laura J.; Conradie, Jeanet

Presented herein is a detailed multitechnique investigation of ligand noninnocence in S = 3/2 manganese corrole derivatives at the formal Mn IV oxidation state. The Soret maxima of Mn[T pXPC]Cl (T pXPC = meso-tris( p-X-phenyl)corrole, where X = CF 3, H, Me, and OMe) were found to red-shift over a range of 37 nm with increasing electron-donating character of X. For Mn[T pXPC]Ph, in contrast, the complex Soret envelopes were found to be largely independent of X. These observations suggested a noninnocent corrole •2–-like ligand for the MnCl complexes and an innocent corrole 3– ligand for the MnPh complexes. Single-crystalmore » X-ray structures of three Mn[T pXPC]Cl complexes revealed skeletal bond-length alternations indicative of a noninnocent corrole, while no such alternation was observed for Mn[T pOMePC]Ph. B3LYP density functional theory (DFT) calculations on Mn[TPC]Cl yielded strong spatial separation of the α and β spin densities, consistent with an antiferromagnetically coupled Mn III-corrole •2– description. By comparison, relatively little spatial separation of the α and β spin densities was found for Mn[TPC]Ph, consistent with an essentially Mn IV-corrole 3– description. X-ray absorption of near-edge spectroscopy (XANES) revealed a moderate blue shift of 0.6 eV for the Mn K-pre-edge of Mn[T pCF 3PC]Ph and a striking enhancement of the pre-edge intensity, relative to Mn[T pCF 3PC]Cl, consistent with a more oxidized, i.e., Mn IV, center in Mn[T pCF 3PC]Ph. Time-dependent DFT calculations indicated that the enhanced intensity of the Mn K-pre-edge of Mn[T pCF 3PC]Ph results from the extra 3d z2 hole, which mixes strongly with the Mn 4p z orbital. Combined with similar results on Fe[TPC]Cl and Fe[TPC]Ph, the present study underscores the considerable potential of metal K-edge XANES in probing ligand noninnocence in first-row transition-metal corroles. As a result, cyclic voltammetry measurements revealed highly negative first reduction potentials for the Mn[T pXPC]Ph series (~–0.95 V) as well as large electrochemical HOMO-LUMO gaps of ~1.7 V. The first reductions, however, are irreversible, suggesting cleavage of the Mn–Ph bond.« less

Electronic Structure of Manganese Corroles Revisited: X-ray Structures, Optical and X-ray Absorption Spectroscopies, and Electrochemistry as Probes of Ligand Noninnocence

DOE PAGES

Ganguly, Sumit; MCormick, Laura J.; Conradie, Jeanet; ...

2018-06-06

Presented herein is a detailed multitechnique investigation of ligand noninnocence in S = 3/2 manganese corrole derivatives at the formal Mn IV oxidation state. The Soret maxima of Mn[T pXPC]Cl (T pXPC = meso-tris( p-X-phenyl)corrole, where X = CF 3, H, Me, and OMe) were found to red-shift over a range of 37 nm with increasing electron-donating character of X. For Mn[T pXPC]Ph, in contrast, the complex Soret envelopes were found to be largely independent of X. These observations suggested a noninnocent corrole •2–-like ligand for the MnCl complexes and an innocent corrole 3– ligand for the MnPh complexes. Single-crystalmore » X-ray structures of three Mn[T pXPC]Cl complexes revealed skeletal bond-length alternations indicative of a noninnocent corrole, while no such alternation was observed for Mn[T pOMePC]Ph. B3LYP density functional theory (DFT) calculations on Mn[TPC]Cl yielded strong spatial separation of the α and β spin densities, consistent with an antiferromagnetically coupled Mn III-corrole •2– description. By comparison, relatively little spatial separation of the α and β spin densities was found for Mn[TPC]Ph, consistent with an essentially Mn IV-corrole 3– description. X-ray absorption of near-edge spectroscopy (XANES) revealed a moderate blue shift of 0.6 eV for the Mn K-pre-edge of Mn[T pCF 3PC]Ph and a striking enhancement of the pre-edge intensity, relative to Mn[T pCF 3PC]Cl, consistent with a more oxidized, i.e., Mn IV, center in Mn[T pCF 3PC]Ph. Time-dependent DFT calculations indicated that the enhanced intensity of the Mn K-pre-edge of Mn[T pCF 3PC]Ph results from the extra 3d z2 hole, which mixes strongly with the Mn 4p z orbital. Combined with similar results on Fe[TPC]Cl and Fe[TPC]Ph, the present study underscores the considerable potential of metal K-edge XANES in probing ligand noninnocence in first-row transition-metal corroles. As a result, cyclic voltammetry measurements revealed highly negative first reduction potentials for the Mn[T pXPC]Ph series (~–0.95 V) as well as large electrochemical HOMO-LUMO gaps of ~1.7 V. The first reductions, however, are irreversible, suggesting cleavage of the Mn–Ph bond.« less

Novel Catalytic Mechanisms For The Chemical Reduction Of Carbon Dioxide To Energy-Dense Liquids

DTIC Science & Technology

2016-12-14

spectroscopy and X-ray crystallography . Synchrotron radiation techniques such as EXAFS and XANES are being used to characterize the structure and...Chemistry and Catalysis using Soft X-rays at LCLS” 23rd Congress and General Assembly of the International Union of Crystallography , Montreal (2014). A

Ba3Fe1.56Ir1.44O9: A Polar Semiconducting Triple Perovskite with Near Room Temperature Magnetic Ordering.

PubMed

Ferreira, Timothy; Carone, Darren; Huon, Amanda; Herklotz, Andreas; Stoian, Sebastian A; Heald, Steve M; Morrison, Gregory; Smith, Mark D; Loye, Hans-Conrad Zur

2018-05-29

The crystal chemistry and magnetic properties for two triple perovskites, Ba 3 Fe 1.56 Ir 1.44 O 9 and Ba 3 NiIr 2 O 9 , grown as large, highly faceted single crystals from a molten strontium carbonate flux, are reported. Unlike the idealized A 3 MM 2 'O 9 hexagonal symmetry characteristic of most triple perovskites, including Ba 3 NiIr 2 O 9, Ba 3 Fe 1.56 Ir 1.44 O 9 possesses significant site-disorder, resulting in a noncentrosymmetric polar structure with trigonal symmetry. The valence of iron and iridium in the heavily distorted Fe/Ir sites was determined to be Fe(III) and Ir(V) by X-ray absorption near edge spectroscopy (XANES). Density functional theory calculations were conducted to understand the effect of the trigonal distortion on the local Fe(III)O 6 electronic structure, and the spin state of iron was determined to be S = 5/2 by Mössbauer spectroscopy. Conductivity measurements indicate thermally activated semiconducting behavior in the trigonal perovskite. Magnetic properties were measured and near room temperature magnetic ordering (T N = 270 K) was observed for Ba 3 Fe 1.56 Ir 1.44 O 9 .

Electron localization in a mixed-valence diniobium benzene complex

DOE PAGES

Gianetti, Thomas L.; Nocton, Grégory; Minasian, Stefan G.; ...

2014-11-11

Reaction of the neutral diniobium benzene complex {[Nb(BDI)N tBu] 2(μ-C 6H 6)} (BDI = N,N'-diisopropylbenzene-β-diketiminate) with Ag[B(C 6F 5) 4] results in a single electron oxidation to produce a cationic diniobium arene complex, {[Nb(BDI)N tBu] 2(μ-C 6H 6)}{B(C 6F 5) 4}. Investigation of the solid state and solution phase structure using single-crystal X-ray diffraction, cyclic voltammetry, magnetic susceptibility, and multinuclear NMR spectroscopy indicates that the oxidation results in an asymmetric molecule with two chemically inequivalent Nb atoms. Further characterization using density functional theory (DFT) calculations, UV-visible, Nb L 3,2-edge X-ray absorption near-edge structure (XANES), and EPR spectroscopies supports assignment ofmore » a diniobium complex, in which one Nb atom carries a single unpaired electron that is not largely delocalized on the second Nb atom. During the oxidative transformation, one electron is removed from the δ-bonding HOMO, which causes a destabilization of the molecule and formation of an asymmetric product. Subsequent reactivity studies indicate that the oxidized product allows access to metal-based chemistry with substrates that did not exhibit reactivity with the starting neutral complex.« less

Combining μX-ray fluorescence, μXANES and μXRD to shed light on Zn2+ cations in cartilage and meniscus calcifications.

PubMed

Dessombz, Arnaud; Nguyen, Christelle; Ea, Hang-Korng; Rouzière, Stephan; Foy, Eddy; Hannouche, Didier; Réguer, Solene; Picca, Frederic-Emmanuel; Thiaudière, Dominique; Lioté, Frédéric; Daudon, Michel; Bazin, Dominique

2013-10-01

We aimed to examine the presence of Zn, a trace element, in osteoarthritis (OA) cartilage and meniscus from patients undergoing total knee joint replacement for primary OA. We mapped Ca(2+) and Zn(2+) at the mesoscopic scale by X-ray fluorescence microanalysis (μX-ray) to determine the spatial distribution of the 2 elements in cartilage, μX-ray absorption near edge structure spectroscopy to identify the Zn species, and μX-ray diffraction to determine the chemical nature of the calcification. Fourier transform infrared spectroscopy was used to determine the chemical composition of cartilage and meniscus. Ca(2+) showed a heterogeneous spatial distribution corresponding to the calcifications within cartilage (or meniscus) or at their surface. At least 2 Zn(2+) species were present: the first may correspond to Zn embedded in protein (different Zn metalloproteins are known to prevent calcification in biological tissues), and the second may be associated with a Zn trap in or at the surface of the calcification. Calcification present in OA cartilage may significantly modify the spatial distribution of Zn; part of the Zn may be trapped in the calcification and may alter the associated biological function of Zn metalloproteins. Copyright © 2013 Elsevier GmbH. All rights reserved.

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

Yoon, Songhak; Maegli, Alexandra E.; Karvonen, Lassi

Polycrystalline SrTiO{sub 3} and SrTi(O,F){sub 3} powders were synthesized by a solid-state reaction. A partial substitution of oxygen by nitrogen was subsequently carried out using thermal ammonolysis resulting in SrTi(N,O){sub 3} and SrTi(N,O,F){sub 3}. Powder X-ray diffraction (XRD) revealed a cubic perovskite structure with space group Pm-3m for all samples. The thermal ammonolysis slightly increased the lattice parameters, crystallite sizes and strain. As a result from the co-substitution of oxygen with nitrogen and fluorine for SrTi(N,O,F){sub 3}, highly distorted TiO{sub 6} octahedra were detected using X-ray absorption near edge structure (XANES) spectroscopy. The weakening of all active modes of themore » Raman spectra after thermal ammonolysis also indicated enhanced distortions in the local crystal structure. SrTi(N,O,F){sub 3} has the largest amount of nitrogen as well as fluorine among all four samples as determined by thermogravimetric analysis (TGA), elemental analysis and X-ray photoelectron spectroscopy (XPS). In the UV–vis spectra a distinctive shift of the absorption-edge energy was observed exclusively for the SrTi(N,O,F){sub 3} sample from 390 to 510 nm corresponding to a bandgap narrowing from 3.18 to 2.43 eV. - Graphical abstract: Figure shows the shift of the absorption-edge energy for the SrTi(N,O,F){sub 3} sample from 390 to 510 nm corresponding to a bandgap narrowing from 3.18 to 2.43 eV. Display Omitted - Highlights: • Synthesis of phase-pure SrTi(N,O,F){sub 3} via solid-state reaction. • The incorporated nitrogen contents increase by the presence of fluorine in SrTi(N,O,F){sub 3}. • Co-substitution with nitrogen and fluorine is beneficial for the bandgap narrowing compared to by only nitrogen or fluorine substitution.« less

The redox state of iron in the matrix of CI, CM and metamorphosed CM chondrites by XANES spectroscopy

NASA Astrophysics Data System (ADS)

Beck, P.; De Andrade, V.; Orthous-Daunay, F.-R.; Veronesi, G.; Cotte, M.; Quirico, E.; Schmitt, B.

2012-12-01

Carbonaceous chondrites record the action of water at some point of their petrological history. These meteorites are usually connected to low albedo asteroid, which present visible/near-IR absorption explained by iron related absorption within phyllosilicates and oxides. In order to obtain quantitative insight into the mineralogy of iron-bearing phases, we have measured X-ray absorption near-edge spectroscopy at the iron K-edge of matrix from carbonaceous chondrites. This method enables to constrain the redox state and environment of iron in these meteorites. For this study, we selected seven CM chondrites and the CI Orgueil, expected to span a range of aqueous alteration degrees. Our analysis of the pre-edge features show that the redox state of Orgueil (CI) is dominated by octahedral Fe and that the Fe3+/(Fe3++Fe2+) atomic ratio is above 80%. Full-inversion of the spectra suggests that the iron budget is dominated by iron oxides, with additional contributions from phyllosilicate. In the case of the CM, the iron speciation appears different that in the case of Orgueil. Cronstedtite is identified from the inversion of the spectra, and suggested by the presence of significant amount of tetrahedral Fe3+. Within the CM chondrites, a trend of aqueous alteration appears presents, and which is roughly correlated to the scheme defined by Rubin et al. (2007). This trend is characterized by an increase in the amount of iron oxides. Two shock metamorphosed CM are present in our dataset (PCA 91008, WIS 91600). If WIS 91600 does not appear distinguishable, from the CM trend, in the case of PCA 91008, shock metamorphism did impact the pre-edge intensity and an increased amount of anhydrous silicates is found. Although the matrix was dehydrated, significant amount of Fe3+ is still present, providing a memory of the aqueous alteration.

Platinum-mordenite catalysts for n-Hexane isomerization: Characterization by X-ray absorption spectroscopy and chemical probes

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

Otten, M.M.; Clayton, M.J.; Lamb, H.H.

Platinum-mordenite (Pt-MOR) catalysts were prepared from NH{sub 4}-MOR by ion exchange with (Pt{sup II}(NH{sub 3}){sub 4})(OH){sub 2}, calcination in O{sub 2} at 350{degrees}C, and reduction in H{sub 2} at 350{degrees}C. The resultant Pt-H-MOR was active for n-hexane isomerization and hydrocracking via bifunctional catalysis at 240-300{degrees}C and 1 atm. The observed activation energies for C{sub 6} branched-isomer formation are unusually low, suggesting that the isomerization rates were controlled by pore diffusion. A Pt-KH-MOR catalyst was prepared by ion exchange with aqueous KNO{sub 3} and re-reduction at 350{degrees}C; elemental analysis evidenced 90% exchange of protons for K{sup +} ions. The product distributionmore » and observed activation energies for C{sub 6} branched-isomer formation over Pt-KH-MOR are consistent with n-hexane isomerization via bifunctional catalysis. Hydrocracking was strongly suppressed, and light hydrocarbons were formed primarily by Pt-catalyzed hydrogenolysis. From in-situ extended X-ray absorption fine structure spectroscopy and H{sub 2} temperature-programmed desorption, we conclude that the Pt-MOR catalysts consist of small Pt clusters hosted within the mordenite crystals. The PtL{sub III}X-ray absorption near-edge structure (XANES) spectra of Pt-H-MOR and Pt-KH-MOR are closely similar, suggesting that the electronic structure of the Pt clusters is unaffected by mordenite acid-base chemistry. The infrared spectrum of CO adsorbed on Pt-H-MOR contains an intense band at 2084 cm{sup -1}, which is assigned to linear CO moieties on Pt clusters. The infrared spectrum of CO adsorbed on Pt-KH-MOR evidences a red shift of the linear CO band, which the authors suggest is due to electrostatic interactions between carbonyl O atoms and nearby K{sup +} ions. 45 refs., 9 figs., 6 tabs.« less

Tetra- and Hexavalent Uranium Forms Bidentate-Mononuclear Complexes with Particulate Organic Matter in a Naturally Uranium-Enriched Peatland.

PubMed

Mikutta, Christian; Langner, Peggy; Bargar, John R; Kretzschmar, Ruben

2016-10-04

Peatlands frequently serve as efficient biogeochemical traps for U. Mechanisms of U immobilization in these organic matter-dominated environments may encompass the precipitation of U-bearing mineral(oid)s and the complexation of U by a vast range of (in)organic surfaces. The objective of this work was to investigate the spatial distribution and molecular binding mechanisms of U in soils of an alpine minerotrophic peatland (pH 4.7-6.6, E h = -127 to 463 mV) using microfocused X-ray fluorescence spectrometry and bulk and microfocused U L 3 -edge X-ray absorption spectroscopy. The soils contained 2.3-47.4 wt % organic C, 4.1-58.6 g/kg Fe, and up to 335 mg/kg geogenic U. Uranium was found to be heterogeneously distributed at the micrometer scale and enriched as both U(IV) and U(VI) on fibrous and woody plant debris (48 ± 10% U(IV), x̅ ± σ, n = 22). Bulk U X-ray absorption near edge structure (XANES) spectroscopy revealed that in all samples U(IV) comprised 35-68% of total U (x̅ = 50%, n = 15). Shell-fit analyses of bulk U L 3 -edge extended X-ray absorption fine structure (EXAFS) spectra showed that U was coordinated to 1.3 ± 0.2 C atoms at a distance of 2.91 ± 0.01 Å (x̅ ± σ), which implies the formation of bidentate-mononuclear U(IV/VI) complexes with carboxyl groups. We neither found evidence for U shells at ∼3.9 Å, indicative of mineral-associated U or multinuclear U(IV) species, nor for a substantial P/Fe coordination of U. Our data indicates that U(IV/VI) complexation by natural organic matter prevents the precipitation of U minerals as well as U complexation by Fe/Mn phases at our field site, and suggests that organically complexed U(IV) is formed via reduction of organic matter-bound U(VI).

Electronic Structures and Optical Properties of α-Al2O3Nanowires

NASA Astrophysics Data System (ADS)

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

2013-04-01

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

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

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

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

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

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

PubMed

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

2016-09-14

Changes in the chemical states of sulfonic groups of Nafion in polymer electrolyte fuel cells (PEFCs) under gas-flowing conditions were studied using in situ S-K XANES spectroscopy. The applied potential to the electrodes and the humidity of the cell were changed under flowing H 2 gas in the anode and He gas in the cathode. While the potential shows no significant effect on the S-K XANES spectra, the humidity is found to induce reversible changes in the spectra. Comparison of the spectral changes with simulations based on the density functional theory calculations indicates that the humidity influences the chemical state of the sulfonic group; under wet conditions the sulfonic group is in the form of a sulfonate ion. By drying treatment the sulfonate ion binds to hydrogen and becomes sulfonic acid. Furthermore, a small fraction of the sulfonic acid irreversibly decomposes to atomic sulfur. The peak energy of the atomic sulfur suggests that the generated atomic sulfur is adsorbed on the Pt catalyst surfaces.

X-ray absorption Studies of Zinc species in Centella asiatica

NASA Astrophysics Data System (ADS)

Dehipawala, Sunil; Cheung, Tak; Hogan, Clayton; Agoudavi, Yao; Dehipawala, Sumudu

2013-03-01

Zinc is a very important mineral present in a variety of vegetables. It is an essential element in cellular metabolism and several bodily functions. We used X-ray fluorescence, and X-ray Absorption near Edge structure(XANES) to study the amount of zinc present in several leafy vegetables as well as its chemical environment within the plant. Main absorption edge position of XANES is sensitive to the oxidation state of zinc and is useful when comparing the type of zinc present in different vegetables to the standard zinc present in supplements. Normalized main edge height is proportional to the amount of zinc present in the sample. Several leafy greens were used in this study, such as Spinacia oleracea, Basella alba, Brassica oleracea, Cardiospermum halicacabumand Centella asiatica. All of these plant leaves contained approximately the same amount of zinc in the leaf portion of the plant and a slightly lower amount in the stems, except Centella asiatica. Both leaves and stems of the plant Centella asiatica contained nearly two times the zinc compared to other plants. Further investigation of zinc's chemical environment within Centella asiatica could lead to a much more efficient dietary consumption of zinc. Use of the National Synchrotron Light Source, Brookhaven National Laboratory, was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-98CH10886

Differential utilization and transformation of sulfur allotropes, μ-S and α-S8, by moderate thermoacidophile Sulfobacillus thermosulfidooxidans.

PubMed

Nie, Zhen-yuan; Liu, Hong-chang; Xia, Jin-lan; Zhu, Hong-rui; Ma, Chen-yan; Zheng, Lei; Zhao, Yi-dong; Qiu, Guan-zhou

2014-10-01

The utilization of amorphous μ-S and orthorhombic α-S8 by thermoacidophile Sulfobacillus thermosulfidooxidans was firstly investigated in terms of cell growth and sulfur oxidation behavior. The morphology and surface sulfur speciation transformation were evaluated by using scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform-infrared spectroscopy (FT-IR), Raman spectroscopy and sulfur K-edge X-ray absorption near edge structure (XANES) spectroscopy. The results showed that the strain grown on μ-S entered slower (about 1 day later) into the exponential phase, while grew faster in exponential phase and attained higher maximal cell density and lower pH than on α-S8. After bio-corrosion, both sulfur samples were evidently eroded, but only μ-S surface presented much porosity, while α-S8 maintained glabrous. μ-S began to be gradually converted into α-S8 from day 2 when the bacterial cells entered the exponential phase, with a final composition of 62.3% μ-S and 37.7% α-S8 on day 4 at the stationary phase. α-S8 was not found to transform into other species in the experiments with or without bacteria. These data indicated S. thermosulfidooxidans oxidized amorphous μ-S faster than orthorhombic α-S8, but the chain-like μ-S was transformed into cyclic α-S8 by S. thermosulfidooxidans. Copyright © 2014 Institut Pasteur. Published by Elsevier Masson SAS. All rights reserved.

Titanium oxidation state and coordination in the lunar high-titanium glass source mantle

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

Krawczynski, M.J.; Sutton, S.R.; Grove, T.L.

2009-03-20

XANES and EXAFS spectra from synthetic HiTi lunar glasses determine coordination of Ti in the HiTi source region. The amount of Ti{sup 3+} present affects the olivine-opx equilibrium, and the total amount of Ti{sup 3+} present requires a pyx bearing source. Lunar high-titanium (HiTi) ultramafic glasses provide us with evidence of the mantle processes that led to the melting of the lunar magma ocean cumulates nearly one billion years after the magma ocean solidified. Constraints on the depth, temperature and melting processes that formed the HiTi glasses are crucial for understanding the melting history of LMO products. The Apollo 17more » orange glass (A17O) and Apollo 15 red glass (A15R) represent two of the HiTi compositions in the spectrum of pristine ultramafic glasses returned from the moon. The difference between these two compositions is that the A15R contains {approx}40% more TiO{sub 2} than the A17O. The low f{sub O2} of the ultramafic glass source regions allows for a certain amount of Ti{sup 3+} in the source mineralogy; however the amount of Ti{sup 3+} in the source and the host mineral for this element remain relatively unconstrained. In addition to the unknown mineralogy of the source region, the high amount of TiO*{sub 2} and FeO* in the HiTi magmas makes the phase relations extremely sensitive to changes in the oxidation state of the source region. We have previously investigated the oxidation state effect on the olivine-orthopyroxene multiple saturations points of the A15R and A17O and shown that the magnitude of the effect is proportional to the amount of Ti in the system. X-ray absorption near-edge spectroscopy (XANES) and extended X-ray absorption fine-structure (EXAFS) measurements have been made on minerals and glasses in experiments on synthetic analogues to the A17O and A15R. Our results show that Ti{sup 3+} concentration does indeed affect the multiple saturation points, and is an important constituent in the lunar interior.« less

XAFS STUDIES OF NICKEL AND SULFUR SPECIATION IN RESIDENTIAL OIL FLY-ASH PARTICULATE MATTERS (ROFA PM)

EPA Science Inventory

XAFS spectroscopy has been employed to evaluate the effect of fuel compositions and combustion conditions on the amount, form, and distribution of sulfur and nickel in size-fractionated ROFA PM. Analysis of S K-edge XANES establish that sulfate is abundant in all PM. However, dep...

Removal of Ca 2+ from the Oxygen-Evolving Complex in Photosystem II Has Minimal Effect on the Mn 4O 5 Core Structure: A Polarized Mn X-ray Absorption Spectroscopy Study

DOE PAGES

Lohmiller, Thomas; Shelby, Megan L.; Long, Xi; ...

2015-05-19

We studied Ca 2+ -depleted and Ca 2+ -reconstituted spinach photosystem II using polarized X-ray absorption spectroscopy of oriented PS II preparations to investigate the structural and functional role of the Ca 2+ ion in the Mn 4O 5Ca cluster of the oxygen-evolving complex (OEC). Samples were prepared by low pH/citrate treatment as one-dimensionally ordered membrane layers and poised in the Ca 2+ -depleted S 1 (S 1') and S 2 (S 2') states, the S 2'Y Z• state, at which point the catalytic cycle of water oxidation is inhibited, and the Ca 2+ -reconstituted S 1 state. Polarized Mnmore » K-edge XANES and EXAFS spectra exhibit pronounced dichroism. Polarized EXAFS data of all states of Ca 2+ -depleted PS II investigated show only minor changes in distances and orientations of the Mn-Mn vectors compared to the Ca 2+ -containing OEC, which may be attributed to some loss of rigidity of the core structure. Thus, removal of the Ca 2+ ion does not lead to fundamental distortion or rearrangement of the tetranuclear Mn cluster, which indicates that the Ca 2+ ion in the OEC is not critical for structural maintenance of the cluster, at least in the S 1 and S 2 states, but fulfills a crucial catalytic function in the mechanism of the water oxidation reaction. On the basis of this structural information, reasons for the inhibitory effect of Ca 2+ removal are discussed, attributing to the Ca 2+ ion a fundamental role in organizing the surrounding (substrate) water framework and in proton-coupled electron transfer to Y Z• (D1-Tyr161).« less

Formation of ferric oxides from aqueous solutions: A polyhedral approach by X-ray absorption spectroscopy. I. Hydrolysis and formation of ferric gels

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

Combes, J.M.; Manceau, A.; Calas, G.

1989-03-01

X-ray absorption spectroscopy (XAS) was used to follow the evolution of local structural environments around ferric ions during the formation of ferric hydrous oxide gels from 1 M chloride and 0.1 M nitrate solutions. Fe K-XANES and EXAFS confirm that ferric ions remain 6-fold coordinated during this evolution. With increasing OH availability in the solution, Cl{sup {minus}} anions tend gradually to be exchanged for (O, OH, OH{sub 2}) ligands. Below OH/Fe = 1, no structural order is detected beyond the first coordination sphere. Above this ratio, two Fe-Fe distances at 3.05 {angstrom} and 3.44 {angstrom} are observed and correspond tomore » the presence of edge- and vertex-sharing Fe-octahedra. XAS results show that ferric gels and highly polymerized aqueous species are short-range ordered. The main contribution to disorder in the gels arises from the small size of coherently scattering domains also responsible for their X-ray amorphous character. From the initial to the final stage of hydrolysis, particles possess a nearly spherical shape with a minimum average diameter ranging from 10-30 {angstrom} for polymers formed from chloride and nitrate solutions. As polymerization proceeds, the local order extends to several tens of angstroms and the particle structures becomes progressively closer to that of akaganeite ({beta}-FeOOH) or goethite ({alpha}-FeOOH). This local structure is distinct from that of the lepidocrocite ({gamma}-FeOOH)-like structure of ferric gels precipitated after oxidation of divalent Fe solutions. The growth of the crystalline Fe-oxyhydroxides from gels takes place by the progressive long-range ordering in the ferric polymers without modifying the short-range order around Fe.« less

Removal of Ca(2+) from the Oxygen-Evolving Complex in Photosystem II Has Minimal Effect on the Mn4O5 Core Structure: A Polarized Mn X-ray Absorption Spectroscopy Study.

PubMed

Lohmiller, Thomas; Shelby, Megan L; Long, Xi; Yachandra, Vittal K; Yano, Junko

2015-10-29

Ca(2+)-depleted and Ca(2+)-reconstituted spinach photosystem II was studied using polarized X-ray absorption spectroscopy of oriented PS II preparations to investigate the structural and functional role of the Ca(2+) ion in the Mn4O5Ca cluster of the oxygen-evolving complex (OEC). Samples were prepared by low pH/citrate treatment as one-dimensionally ordered membrane layers and poised in the Ca(2+)-depleted S1 (S1') and S2 (S2') states, the S2'YZ(•) state, at which point the catalytic cycle of water oxidation is inhibited, and the Ca(2+)-reconstituted S1 state. Polarized Mn K-edge XANES and EXAFS spectra exhibit pronounced dichroism. Polarized EXAFS data of all states of Ca(2+)-depleted PS II investigated show only minor changes in distances and orientations of the Mn-Mn vectors compared to the Ca(2+)-containing OEC, which may be attributed to some loss of rigidity of the core structure. Thus, removal of the Ca(2+) ion does not lead to fundamental distortion or rearrangement of the tetranuclear Mn cluster, which indicates that the Ca(2+) ion in the OEC is not critical for structural maintenance of the cluster, at least in the S1 and S2 states, but fulfills a crucial catalytic function in the mechanism of the water oxidation reaction. On the basis of this structural information, reasons for the inhibitory effect of Ca(2+) removal are discussed, attributing to the Ca(2+) ion a fundamental role in organizing the surrounding (substrate) water framework and in proton-coupled electron transfer to YZ(•) (D1-Tyr161).

Vertical changes of the Co and Mn speciation along a lateritic regolith developed on peridotites (New Caledonia)

DOE PAGES

Dublet, Gabrielle; Juillot, Farid; Brest, Jessica; ...

2017-07-21

Because they can host significant amounts of Co, the Mn-oxides are commonly considered as the major Co-bearing mineral species in lateritic environments. However, little is known about the process leading to the formation and/or the weathering of these Co-rich Mn-oxides. This lack of knowledge is mainly due to the fact that Co concentrations are too low in primary silicates for classical speciation analysis. In this study, we investigated both Co and Mn speciation in a 64 m thick lateritic regolith developed upon peridotites in New Caledonia, by combining High Energy Resolution Fluorescence Detection X-ray absorption Near Edge Structure (HERFD-XANES) spectroscopymore » at the Co K-edge with classical XANES spectroscopy at the Mn K-edge, bulk chemistry (ICP) and mineralogy (XRD). The results obtained provide new insights into the evolution of Co and Mn speciation as a function of the weathering stages. Co and Mn primarily occur as Co(II) and Mn(II,III) in olivine and serpentine in the bedrock. During the first weathering stage, these forms of Co and Mn are progressively oxidized toward Co(III) and Mn(III,IV), which occur mainly as Co(III)-bearing Mn(III/IV)-oxides in the transition between the saprolite and the laterite. In the uppermost lateritic horizons, long-time weathering resulted in a strong leaching of Co and Mn, and the remaining of these elements occurs as Co(II) and Mn(III) substituting for Fe(III) in goethite. Finally, this latter scavenging process emphasizes the importance of Fe-oxides for the long-term stabilization of Co and Mn in such deeply weathered laterites.« less

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

NASA Astrophysics Data System (ADS)

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

2013-10-01

Ti valence measurements in MgAl2O4 spinel from calcium-aluminum-rich inclusions (CAIs) by X-ray absorption near-edge structure (XANES) spectroscopy show that many spinels have predominantly tetravalent Ti, regardless of host phases. The average spinel in Allende type B1 inclusion TS34 has 87% Ti+4. Most spinels in fluffy type A (FTA) inclusions also have high Ti valence. In contrast, the rims of some spinels in TS34 and spinel grain cores in two Vigarano type B inclusions have larger amounts of trivalent titanium. Spinels from TS34 have approximately equal amounts of divalent and trivalent vanadium. Based on experiments conducted on CAI-like compositions over a range of redox conditions, both clinopyroxene and spinel should be Ti+3-rich if they equilibrated with CAI liquids under near-solar oxygen fugacities. In igneous inclusions, the seeming paradox of high-valence spinels coexisting with low-valence clinopyroxene can be explained either by transient oxidizing conditions accompanying low-pressure evaporation or by equilibration of spinel with relict Ti+4-rich phases (e.g., perovskite) prior to or during melting. Ion probe analyses of large spinel grains in TS34 show that they are enriched in heavy Mg, with an average Δ25Mg of 4.25 ± 0.028‰, consistent with formation of the spinel from an evaporating liquid. Δ25Mg shows small, but significant, variation, both within individual spinels and between spinel and adjacent melilite hosts. The Δ25Mg data are most simply explained by the low-pressure evaporation model, but this model has difficulty explaining the high Ti+4 concentrations in spinel.

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

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

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

2008-01-01

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

Multiscale correlations of iron phases and heavy metals in technogenic magnetic particles from contaminated soils.

PubMed

Yu, Xiuling; Lu, Shenggao

2016-12-01

Technogenic magnetic particles (TMPs) are carriers of heavy metals and organic contaminants, which derived from anthropogenic activities. However, little information on the relationship between heavy metals and TMP carrier phases at the micrometer scale is available. This study determined the distribution and association of heavy metals and magnetic phases in TMPs in three contaminated soils at the micrometer scale using micro-X-ray fluorescence (μ-XRF) and micro-X-ray absorption near-edge structure (μ-XANES) spectroscopy. Multiscale correlations of heavy metals in TMPs were elucidated using wavelet transform analysis. μ-XRF mapping showed that Fe was enriched and closely correlated with Co, Cr, and Pb in TMPs from steel industrial areas. Fluorescence mapping and wavelet analysis showed that ferroalloy was a major magnetic signature and heavy metal carrier in TMPs, because most heavy metals were highly associated with ferroalloy at all size scales. Multiscale analysis revealed that heavy metals in the TMPs were from multiple sources. Iron K-edge μ-XANES spectra revealed that metallic iron, ferroalloy, and magnetite were the main iron magnetic phases in the TMPs. The relative percentage of these magnetic phases depended on their emission sources. Heatmap analysis revealed that Co, Pb, Cu, Cr, and Ni were mainly derived from ferroalloy particles, while As was derived from both ferroalloy and metallic iron phases. Our results indicated the scale-dependent correlations of magnetic phases and heavy metals in TMPs. The combination of synchrotron based X-ray microprobe techniques and multiscale analysis provides a powerful tool for identifying the magnetic phases from different sources and quantifying the association of iron phases and heavy metals at micrometer scale. Copyright © 2016 Elsevier Ltd. All rights reserved.

The effect of synthetic method and annealing temperature on metal site preference in Al(1-x)Ga(x)FeO3.

PubMed

Walker, James D S; Grosvenor, Andrew P

2013-08-05

Magnetoelectric materials couple both magnetic and electronic properties, making them attractive for use in multifunctional devices. The magnetoelectric AFeO3 compounds (Pna2(1); A = Al, Ga) have received attention as the properties of the system depend on composition as well as the synthetic method used. Al(1-x)Ga(x)FeO3. (0 ≤ x ≤ 1) was synthesized by the sol-gel and coprecipitation methods and studied by X-ray absorption near-edge spectroscopy (XANES). Al L(2,3-), Ga K-, and Fe K-edge XANES spectra were collected to examine how the average metal coordination number (CN) changes with the synthetic method. Al and Fe were found to prefer octahedral sites, while Ga prefers the tetrahedral site. It was found that composition played a larger role in determining site occupancies than synthetic method. Samples made by the sol-gel or ceramic methods (reported previously; Walker, J. D. S.; Grosvenor, A. P. J. Solid State Chem. 2013, 197, 147-153) showed smaller spectral changes than samples made via the coprecipitation method. This is attributed to greater ion mobility in samples synthesized via coprecipitation as the reactants do not have a long-range polymeric or oxide network during synthesis like samples synthesized via the sol-gel or ceramic method. Increasing annealing temperature increases the average coordination number of Al, and to a lesser extent Ga, while the average coordination number of Fe decreases. This study indicates that greater disorder is observed when the Al(1-x)Ga(x)FeO3. compounds have high Al content, and when annealed at higher temperatures.

Investigating redox processes under diffusive and advective flow conditions using a coupled omics and synchrotron approach

NASA Astrophysics Data System (ADS)

Kemner, K. M.; Boyanov, M.; Flynn, T. M.; O'Loughlin, E. J.; Antonopoulos, D. A.; Kelly, S.; Skinner, K.; Mishra, B.; Brooks, S. C.; Watson, D. B.; Wu, W. M.

2015-12-01

FeIII- and SO42--reducing microorganisms and the mineral phases they produce have profound implications for many processes in aquatic and terrestrial systems. In addition, many of these microbially-catalysed geochemical transformations are highly dependent upon introduction of reactants via advective and diffusive hydrological transport. We have characterized microbial communities from a set of static microcosms to test the effect of ethanol diffusion and sulfate concentration on UVI-contaminated sediment. The spatial distribution, valence states, and speciation of both U and Fe were monitored in situ throughout the experiment by synchrotron x-ray absorption spectroscopy, in parallel with solution measurements of pH and the concentrations of sulfate, ethanol, and organic acids. After reaction initiation, a ~1-cm thick layer of sediment near the sediment-water (S-W) interface became visibly dark. Fe XANES spectra of the layer were consistent with the formation of FeS. Over the 4 year duration of the experiment, U LIII-edge XANES indicated reduction of U, first in the dark layer and then throughout the sediment. Next, the microcosms were disassembled and samples were taken from the overlying water and different sediment regions. We extracted DNA and characterized the microbial community by sequencing 16S rRNA gene amplicons with the Illumina MiSeq platform and found that the community evolved from its originally homogeneous composition, becoming significantly spatially heterogeneous. We have also developed an x-ray accessible column to probe elemental transformations as they occur along the flow path in a porous medium with the purpose of refining reactive transport models (RTMs) that describe coupled physical and biogeochemical processes in environmental systems. The elemental distribution dynamics and the RTMs of the redox driven processes within them will be presented.

Arsenic speciation and reactivity in poultry litter

USGS Publications Warehouse

Arai, Y.; Lanzirotti, A.; Sutton, S.; Davis, J.A.; Sparks, D.L.

2003-01-01

Recent U.S. government action to lower the maximum concentration levels (MCL) of total arsenic (As) (10 ppb) in drinking water has raised serious concerns about the agricultural use of As-containing biosolids such as poultry litter (PL). In this study, solid-state chemical speciation, desorbability, and total levels of As in PL and long-term amended soils were investigated using novel synchrotronbased probing techniques (microfocused (??) synchrotron X-ray fluorescence (SXRF) and ??-X-ray absorption near-edge structure (XANES) spectroscopies) coupled with chemical digestion and batch experiments. The total As levels in the PL were as high as ???50 mg kg-1, and As(II/III and V) was always concentrated in abundant needle-shaped microscopic particles (???20/ ??m x 850 ??m) associated with Ca, Cu, and Fe and to a lesser extent with S, CI, and Zn. Postedge XANES features of litter particles are dissimilar to those of the organo-As(V) compound in poultry feed (i.e., roxarsone), suggesting possible degradation/transformation of roxarsone in the litter and/or in poultry digestive tracts. The extent of As desorption from the litter increased with increasing time and pH from 4.5 to 7, but at most 15% of the total As was released after 5 d at pH 7, indicating the presence of insoluble phases and/or strongly retained soluble compounds. No significant As accumulation (< 15 mg kg-1) was found in long-term PL-a mended agricultural surface soils. This suggests that As in the PL may have undergone surface and subsurface transport processes. Our research results raise concerns about long-term PL amendment effects on As contamination in surrounding soilwater environments.

Crystal structure and properties of tetragonal EuAg{sub 4}In{sub 8} grown by metal flux technique

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

Subbarao, Udumula; Sarkar, Sumanta; Peter, Sebastian C., E-mail: sebastiancp@jncasr.ac.in

The compound EuAg{sub 4}In{sub 8} has been obtained as single crystals in high yield from reactions run in liquid indium. X-ray diffraction on single crystals suggests that EuAg{sub 4}In{sub 8} crystallizes in the CeMn{sub 4}Al{sub 8} structure type, tetragonal space group I4/mmm with lattice constants a=b=9.7937(2) Å and c=5.7492(2) Å. Crystal structure of EuAg{sub 4}In{sub 8} is composed of pseudo Frank–Kasper cages occupied by one europium atom in each ring, which are shared through the corner along the ab plane resulting in a three dimensional network. The magnetic susceptibility of EuAg{sub 4}In{sub 8} was measured in the temperature range 2–300more » K, which obeyed Curie–Weiss law above 50 K. Magnetic moment value calculated from the fitting indicates the presence of divalent europium, which was confirmed by X-ray absorption near edge spectroscopy. Electrical resistivity measurements suggest that EuAg{sub 4}In{sub 8} is metallic in nature with a probable Fermi liquid behavior at low temperature. - Graphical abstract: The tetragonal EuAg{sub 4}In{sub 8} has been grown as single crystals from reactions run in liquid indium. Magnetic and XANES measurements suggest divalent nature of Eu and resistivity measurements suggest metallic nature. - Highlights: • EuAg{sub 4}In{sub 8} phase having tetragonal phase is grown by metal flux technique. • Magnetic and XANES measurements exhibit divalent nature of Eu in EuAg{sub 4}In{sub 8}. • Resistivity measurement suggests metallic nature and probable Fermi liquid behavior.« less

Systematic XAS study on the reduction and uptake of Tc by magnetite and mackinawite.

PubMed

Yalçıntaş, Ezgi; Scheinost, Andreas C; Gaona, Xavier; Altmaier, Marcus

2016-11-28

The mechanisms for the reduction and uptake of Tc by magnetite (Fe 3 O 4 ) and mackinawite (FeS) are investigated using X-ray absorption spectroscopy (XANES and EXAFS), in combination with thermodynamic calculations of the Tc/Fe systems and accurate characterization of the solution properties (pH m , pe, [Tc]). Batch sorption experiments were performed under strictly anoxic conditions using freshly prepared magnetite and mackinawite in 0.1 M NaCl solutions with varying initial Tc(vii) concentrations (2 × 10 -5 and 2 × 10 -4 M) and Tc loadings (400-900 ppm). XANES confirms the complete reduction of Tc(vii) to Tc(iv) in all investigated systems, as predicted from experimental (pH m + pe) measurements and thermodynamic calculations. Two Tc endmember species are identified by EXAFS in the magnetite system, Tc substituting for Fe in the magnetite structure and Tc-Tc dimers sorbed to the magnetite {111} faces through a triple bond. The sorption endmember is favoured at higher [Tc], whereas incorporation prevails at low [Tc] and less alkaline pH conditions. The key role of pH in the uptake mechanism is interpreted in terms of magnetite solubility, with higher [Fe] and greater recrystallization rates occurring at lower pH values. A TcS x -like phase is predominant in all investigated mackinawite systems, although the contribution of up to 20% of TcO 2 ·xH 2 O(s) (likely as surface precipitate) is observed for the highest investigated loadings (900 ppm). These results provide key inputs for an accurate mechanistic interpretation of the Tc uptake by magnetite and mackinawite, so far controversially discussed in the literature, and represent a highly relevant contribution to the investigation of Tc retention processes in the context of nuclear waste disposal.

Nitrogen incorporation in carbon nitride films produced by direct and dual ion-beam sputtering

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

Abrasonis, G.; Gago, R.; Jimenez, I.

2005-10-01

Carbon (C) and carbon nitride (CN{sub x}) films were grown on Si(100) substrates by direct ion-beam sputtering (IBS) of a carbon target at different substrate temperatures (room temperature-450 deg. C) and Ar/N{sub 2} sputtering gas mixtures. Additionally, the effect of concurrent nitrogen-ion assistance during the growth of CN{sub x} films by IBS was also investigated. The samples were analyzed by elastic recoil detection analysis (ERDA) and x-ray absorption near-edge spectroscopy (XANES). The ERDA results showed that significant nitrogen amount (up to 20 at. %) was incorporated in the films, without any other nitrogen source but the N{sub 2}-containing sputtering gas.more » The nitrogen concentration is proportional to the N{sub 2} content in the sputtering beam and no saturation limit is reached under the present working conditions. The film areal density derived from ERDA revealed a decrease in the amount of deposited material at increasing growth temperature, with a correlation between the C and N losses. The XANES results indicate that N atoms are efficiently incorporated into the carbon network and can be found in different bonding environments, such as pyridinelike, nitrilelike, graphitelike, and embedded N{sub 2} molecules. The contribution of molecular and pyridinelike nitrogen decreases when the temperature increases while the contribution of the nitrilelike nitrogen increases. The concurrent nitrogen ion assistance resulted in the significant increase of the nitrogen content in the film but it induced a further reduction of the deposited material. Additionally, the assisting ions inhibited the formation of the nitrilelike configurations while promoting nitrogen environments in graphitelike positions. The nitrogen incorporation and release mechanisms are discussed in terms of film growth precursors, ion bombardment effects, and chemical sputtering.« less

Adsorption of enrofloxacin in presence of Zn(II) on a calcareous soil.

PubMed

Graouer-Bacart, Mareen; Sayen, Stéphanie; Guillon, Emmanuel

2015-12-01

As a result of their consumption, excretion, disposal and persistence, antibiotics enter the soil environment and may be transported to surface and ground waters. During their transfer through soils, retention processes play a key role in their mobility. Antibiotics often coexist with heavy metals in soils due to agricultural practices and other sources of inputs. In this context, this study deals with the co-adsorption of Zn(II) and enrofloxacin (ENR), a widely-used veterinary antibiotic, on a calcareous soil using batch retention experiments and X-ray Absorption Near Edge Structure (XANES) spectroscopy. To improve our understanding of the interaction of this emerging organic contaminant with metal cations at the water-soil interface, the ternary system containing ENR, Zn(II) and a selected calcareous soil was investigated over a pH range between 7 and 10, at different solid-solution contact times and ENR concentrations. The presence of Zn(II) slightly influenced the retention of the antibiotic, leading to an increase of the adsorbed ENR amounts. The distribution coefficient Kd value increased from 0.66 Lg(-1) for single ENR adsorption to 1.04 Lg(-1) in presence of Zn(II) at a 1/2 ENR/Zn(II) ratio. The combination of adsorption isotherm data, solution speciation diagrams and XANES spectra evidenced a small proportion of Zn(II)-ENR complexes at soil pH leading to the slight increase of ENR adsorption in presence of zinc. These results suggest that it is necessary to consider the interaction between ENR and metal cations when assessing the mobility of ENR in soils. Copyright © 2015 Elsevier Inc. All rights reserved.

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

NASA Astrophysics Data System (ADS)

Tamura, Tomoyuki; Kohyama, Masanori; Ogata, Shuji

2017-07-01

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

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

NASA Astrophysics Data System (ADS)

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

2009-05-01

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

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

NASA Technical Reports Server (NTRS)

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.

Evidence for an unorthodox firing sequence employed by the Berlin Painter. Deciphering ancient ceramic firing conditions through high-resolution material characterization and replication

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

Cianchetta, I.; Trentelman, K.; Maish, J.

XANES spectroscopy was used to complement the results previously obtained with Raman spectroscopy by the same group to determine the firing conditions used in the production of a single vessel painted by the Berlin Painter in the 5th century B.C. The vessel, part of the collection of the J. Paul Getty Museum, presents a complicated layered architecture of black and red gloss, with different stratigraphies present on the interior and exterior surfaces. The study of two samples, one each from the interior and exterior surface of the vessel, was performed with the complementary analytical techniques of X-ray nano- and micro-spectroscopymore » (X-ray fluorescence spectroscopy (XRF) and full-field transmission X-ray micro-spectroscopy (FF-XANES) across the Fe K edge), and supported by a replication study. The replicates, made in a laboratory furnace providing complete control over the firing temperature and oxygen partial pressure, provided a paradigm for the comparison of the mineralogical phases observed in the ancient samples, which led to a deeper understanding of the firing conditions necessary for the production of the Berlin Painter's vessel. Our results confirm the necessity of multiple firings and painting applications to obtain the Berlin Painter's architecture and provide a further example of the multiplicity of techniques and practices employed by the potters of the Kerameikos in ancient Athens.« less

Evidence for an unorthodox firing sequence employed by the Berlin Painter. Deciphering ancient ceramic firing conditions through high-resolution material characterization and replication

DOE PAGES

Cianchetta, I.; Trentelman, K.; Maish, J.; ...

2014-12-10

XANES spectroscopy was used to complement the results previously obtained with Raman spectroscopy by the same group to determine the firing conditions used in the production of a single vessel painted by the Berlin Painter in the 5th century B.C. The vessel, part of the collection of the J. Paul Getty Museum, presents a complicated layered architecture of black and red gloss, with different stratigraphies present on the interior and exterior surfaces. The study of two samples, one each from the interior and exterior surface of the vessel, was performed with the complementary analytical techniques of X-ray nano- and micro-spectroscopymore » (X-ray fluorescence spectroscopy (XRF) and full-field transmission X-ray micro-spectroscopy (FF-XANES) across the Fe K edge), and supported by a replication study. The replicates, made in a laboratory furnace providing complete control over the firing temperature and oxygen partial pressure, provided a paradigm for the comparison of the mineralogical phases observed in the ancient samples, which led to a deeper understanding of the firing conditions necessary for the production of the Berlin Painter's vessel. Our results confirm the necessity of multiple firings and painting applications to obtain the Berlin Painter's architecture and provide a further example of the multiplicity of techniques and practices employed by the potters of the Kerameikos in ancient Athens.« less

Synchrotron-Based In Situ Characterization of Carbon-Supported Platinum and Platinum Monolayer Electrocatalysts

DOE PAGES

Sasaki, Kotaro; Marinkovic, Nebojsa; Isaacs, Hugh S.; ...

2015-11-17

Understanding oxidation/dissolution mechanisms of Pt is critical in designing durable catalysts for the oxygen reduction reaction (ORR), but exact mechanisms remain unclear. Our present work explores the oxidation/dissolution of Pt and Pt monolayer (ML) electrocatalysts over a wide range of applied potentials using cells that facilitate in situ measurements by combining X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD) measurements. Furthermore, the X-ray absorption near edge structure (XANES) measurement demonstrated that Pt nanoparticle surfaces were oxidized from metallic Pt to α-PtO 2-type oxide during the potential sweep from 0.41 to 1.5 V, and the transition state of O or OHmore » adsorption on Pt and the onset of the place exchange process were revealed by the delta mu (Δμ) method. Only the top layers of Pt nanoparticles were oxidized, while the inner Pt atoms remained intact. At a higher potential over 1.9 V, α-PtO 2-type surface oxides dissolve due to local acidification caused by the oxygen evolution reaction and carbon corrosion. Pt oxidation of Pt ML on the Pd nanoparticle electrocatalyst is considerably hampered compared with the Pt/C catalyst, presumably because preferential Pd oxidation proceeds at the defects in Pt MLs up to 0.91 V and through O penetrated through the Pt MLs by the place exchange process above 1.11 V.« less

Composition and hydrophilicity control of Mn-doped ferrite (MnxFe3-xO4) nanoparticles induced by polyol differentiation.

PubMed

Vamvakidis, Kosmas; Katsikini, Maria; Vourlias, George; Angelakeris, Mavroeidis; Paloura, Eleni C; Dendrinou-Samara, Catherine

2015-03-28

Manganese doped ferrite (MnxFe3-xO4) nanoparticles with x = 0.29-0.77 were prepared under solvothermal conditions in the presence solely of a polyol using the trivalent manganese and iron acetylacetonates as precursors. In this facile approach, a variety of polyols such as polyethylene glycol (PEG 8000), tetraethylene glycol (TEG), propylene glycol (PG) and a mixture of TEG and PG (1 : 1) were utilized in a triple role as a solvent, a reducing agent and a surface-functionalizing agent. The composition of the fine cubic-spinel structures was found to be related to the reductive ability of each polyol, while determination of structural characteristics plus the inversion parameter (i = 0.18-0.38) were provided by X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy at both the Fe and Mn K-edges. The saturation magnetization increased up to 80 emu g(-1) when x = 0.35 and i = 0.22. In addition, the as-prepared nanocrystals coated with PEG, PG and PG&TEG showed excellent colloidal stability in water, while the TEG-coated particles were not water dispersible and converted to hydrophilic when were extra PEGylated. Measurements of the (1)H NMR relaxation in water were carried out and the nanoprobes were evaluated as potential contrast agents.

X-ray K-edge absorption spectra of Fe minerals and model compounds: II. EXAFS

NASA Astrophysics Data System (ADS)

Waychunas, Glenn A.; Brown, Gordon E.; Apted, Michael J.

1986-01-01

K-edge extended X-ray absorption fine structure (EXAFS) spectra of Fe in varying environments in a suite of well-characterized silicate and oxide minerals were collected using synchrotron radiation and analyzed using single scattering approximation theory to yield nearest neighbor Fe-O distances and coordination numbers. The partial inverse character of synthetic hercynite spinal was verified in this way. Comparison of the results from all samples with structural data from X-ray diffraction crystal structure refinements indicates that EXAFS-derived first neighbor distances are generally accurate to ±0.02 Å using only theoretically generated phase information, and may be improved over this if similar model compounds are used to determine EXAFS phase functions. Coordination numbers are accurate to ±20 percent and can be similarly improved using model compound EXAFS amplitude information. However, in particular cases the EXAFS-derived distances may be shortened, and the coordination number reduced, by the effects of static and thermal disorder or by partial overlap of the longer Fe-O first neighbor distances with second neighbor distances in the EXAFS structure function. In the former case the total information available in the EXAFS is limited by the disorder, while in the latter case more accurate results can in principle be obtained by multiple neighbor EXAFS analysis. The EXAFS and XANES spectra of Fe in Nain, Labrador osumulite and Lakeview, Oregon plagioclase are also analyzed as an example of the application of X-ray absorption spectroscopy to metal ion site occupation determination in minerals.

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

NASA Astrophysics Data System (ADS)

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

2009-11-01

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

Identifying Different Types of Catalysts for CO2 Reduction by Ethane through Dry Reforming and Oxidative Dehydrogenation.

PubMed

Porosoff, Marc D; Myint, Myat Noe Zin; Kattel, Shyam; Xie, Zhenhua; Gomez, Elaine; Liu, Ping; Chen, Jingguang G

2015-12-14

The recent shale gas boom combined with the requirement to reduce atmospheric CO2 have created an opportunity for using both raw materials (shale gas and CO2 ) in a single process. Shale gas is primarily made up of methane, but ethane comprises about 10 % and reserves are underutilized. Two routes have been investigated by combining ethane decomposition with CO2 reduction to produce products of higher value. The first reaction is ethane dry reforming which produces synthesis gas (CO+H2 ). The second route is oxidative dehydrogenation which produces ethylene using CO2 as a soft oxidant. The results of this study indicate that the Pt/CeO2 catalyst shows promise for the production of synthesis gas, while Mo2 C-based materials preserve the CC bond of ethane to produce ethylene. These findings are supported by density functional theory (DFT) calculations and X-ray absorption near-edge spectroscopy (XANES) characterization of the catalysts under in situ reaction conditions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

NASA Astrophysics Data System (ADS)

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

2014-02-01

Prion-related protein (PrP), a cell-surface copper-binding glycoprotein, is considered to be responsible for a number of transmissible spongiform encephalopathies (TSEs). The structural conversion of PrP from the normal cellular isoform (PrPC) to the post-translationally modified form (PrPSc) is thought to be relevant to Cu2+ binding to histidine residues. Rabbits are one of the few mammalian species that appear to be resistant to TSEs, because of the structural characteristics of the rabbit prion protein (RaPrPC) itself. Here we determined the three-dimensional local structure around the C-terminal high-affinity copper-binding sites using X-ray absorption near-edge structure combined with ab initio calculations in the framework of the multiple-scattering (MS) theory. Result shows that two amino acid resides, Gln97 and Met108, and two histidine residues, His95 and His110, are involved in binding this copper(II) ion. It might help us understand the roles of copper in prion conformation conversions, and the molecular mechanisms of prion-involved diseases.

Investigation of lead bioimmobilization and transformation by Penicillium oxalicum SL2.

PubMed

Ye, Binhui; Luo, Yating; He, Junyu; Sun, Lijuan; Long, Bibo; Liu, Qinglin; Yuan, Xiaofeng; Dai, Peibin; Shi, Jiyan

2018-05-18

Fungi Penicillium oxalicum SL2 was applied for Pb 2+ bioremediation in aqueous solution in this study. After 7 days of incubation at different initial concentrations of Pb 2+ (0, 100, 500 and 2500 mg L -1 ), most of Pb 2+ were removed (90, 98.3, and 86.2%), the maximum Pb content in mycelium reached about 155.6 mg g -1  dw. Meanwhile, the formation of extracellular secondary minerals and intracellular Pb-complex were observed and identified, the speciation of Pb in mycelium was also detected by X-ray absorption near-edge structure (XANES) spectroscopy, i.e., Pb-oxalate, Pb-citrate, Pb-hydrogen phosphate and Pb-glutathione analogues. In addition, content of glutathione and oxidized glutathione was increased under the exposure of Pb 2+ , which implied that glutathione might play a key role in Pb immobilization and detoxification in P. oxalicum SL2. This study elucidated partial mechanisms of Pb immobilization and speciation transformation of this strain, providing an alternative biomaterial in the bioremediation of Pb-contaminated wastewater. Copyright © 2018 Elsevier Ltd. All rights reserved.

Identifying different types of catalysts for CO 2 reduction by ethane through dry reforming and oxidative dehydrogenation

DOE PAGES

Marc D. Porosoff; Chen, Jingguang G.; Myint, Myat Noe Zin; ...

2015-11-10

In this study, the recent shale gas boom combined with the requirement to reduce atmospheric CO 2 have created an opportunity for using both raw materials (shale gas and CO 2) in a single process. Shale gas is primarily made up of methane, but ethane comprises about 10 % and reserves are underutilized. Two routes have been investigated by combining ethane decomposition with CO 2 reduction to produce products of higher value. The first reaction is ethane dry reforming which produces synthesis gas (CO+H 2). The second route is oxidative dehydrogenation which produces ethylene using CO 2 as a softmore » oxidant. The results of this study indicate that the Pt/CeO 2 catalyst shows promise for the production of synthesis gas, while Mo 2C-based materials preserve the C—C bond of ethane to produce ethylene. These findings are supported by density functional theory (DFT) calculations and X-ray absorption near-edge spectroscopy (XANES) characterization of the catalysts under in situ reaction conditions.« less

Electron and ion dynamics study of iron in warm dense matter regime by time-resolved XAS measurements and from first-principles

NASA Astrophysics Data System (ADS)

Ogitsu, T.; Fernandez-Paãella, A.; Correa, A.; Engelhorn, K.; Barbrel, B.; Prendergast, D. G.; Pemmaraju, D.; Beckwith, M.; Kraus, D.; Hamel, S.; Cho, B. I.; Jin, L.; Wong, J.; Heinman, P.; Collins, G. W.; Falcone, R.; Ping, Y.

2016-10-01

We present a study of the electron-phonon coupling of warm dense iron upon femtosecond laser excitation by time-resolved x-ray absorption near edge spectroscopy (XANES). The dynamics of iron in electron-ion non-equilibrium conditions was studied using ab-initio density-functional-theory (DFT) simulations combined with the Two Temperature Model (TTM) where spatial inhomogeneity of electron (and ion) temperature(s) due to short ballistic electron transport length in iron was explicitly taken into consideration. Detailed comparison between our simulation results and experiments indicates that the ion temperature dependence on specific heat and on electron-phonon coupling also plays a relevant role in modeling the relaxation dynamics of electrons and ions. These results are the first experimental evidence of the suppression of the electron-phonon coupling factor of a transition metal at electron temperatures ranging 5000- 10000 K. This work was performed under DOE contract DE-AC52-07NA27344 with support from OFES Early Career program and LLNL LDRD program.

Development and exploration of a new methodology for the fitting and analysis of XAS data.

PubMed

Delgado-Jaime, Mario Ulises; Kennepohl, Pierre

2010-01-01

A new data analysis methodology for X-ray absorption near-edge spectroscopy (XANES) is introduced and tested using several examples. The methodology has been implemented within the context of a new Matlab-based program discussed in a companion related article [Delgado-Jaime et al. (2010), J. Synchrotron Rad. 17, 132-137]. The approach makes use of a Monte Carlo search method to seek appropriate starting points for a fit model, allowing for the generation of a large number of independent fits with minimal user-induced bias. The applicability of this methodology is tested using various data sets on the Cl K-edge XAS data for tetragonal CuCl(4)(2-), a common reference compound used for calibration and covalency estimation in M-Cl bonds. A new background model function that effectively blends together background profiles with spectral features is an important component of the discussed methodology. The development of a robust evaluation function to fit multiple-edge data is discussed and the implications regarding standard approaches to data analysis are discussed and explored within these examples.

Development and exploration of a new methodology for the fitting and analysis of XAS data

PubMed Central

Delgado-Jaime, Mario Ulises; Kennepohl, Pierre

2010-01-01

A new data analysis methodology for X-ray absorption near-edge spectroscopy (XANES) is introduced and tested using several examples. The methodology has been implemented within the context of a new Matlab-based program discussed in a companion related article [Delgado-Jaime et al. (2010 ▶), J. Synchrotron Rad. 17, 132–137]. The approach makes use of a Monte Carlo search method to seek appropriate starting points for a fit model, allowing for the generation of a large number of independent fits with minimal user-induced bias. The applicability of this methodology is tested using various data sets on the Cl K-edge XAS data for tetragonal CuCl4 2−, a common reference compound used for calibration and covalency estimation in M—Cl bonds. A new background model function that effectively blends together background profiles with spectral features is an important component of the discussed methodology. The development of a robust evaluation function to fit multiple-edge data is discussed and the implications regarding standard approaches to data analysis are discussed and explored within these examples. PMID:20029120

Yb7Ni4InGe12: a quaternary compound having mixed valent Yb atoms grown from indium flux.

PubMed

Subbarao, Udumula; Jana, Rajkumar; Chondroudi, Maria; Balasubramanian, Mahalingam; Kanatzidis, Mercouri G; Peter, Sebastian C

2015-03-28

The new intermetallic compound Yb7Ni4InGe12 was obtained as large silver needle shaped single crystals from reactive indium flux. Single crystal X-ray diffraction suggests that Yb7Ni4InGe12 crystallizes in the Yb7Co4InGe12 structure type, and tetragonal space group P4/m and lattice constants are a = b = 10.291(2) Å and c = 4.1460(8) Å. The crystal structure of Yb7Ni4InGe12 consists of columnar units of three different types of channels filled with the Yb atoms. The crystal structure of Yb7Ni4InGe12 is closely related to Yb5Ni4Ge10. The effective magnetic moment obtained from the magnetic susceptibility measurements in the temperature range 200-300 K is 3.66μB/Yb suggests mixed/intermediate valence behavior of ytterbium atoms. X-ray absorption near edge spectroscopy (XANES) confirms that Yb7Ni4InGe12 exhibits mixed valence.

Removal of trichloroethylene by zerovalent iron/activated carbon derived from agricultural wastes.

PubMed

Su, Yuh-fan; Cheng, Yu-ling; Shih, Yang-hsin

2013-11-15

Activated carbon (AC) and zerovalent iron (ZVI) have been widely used in the adsorption and dehalogenation process, respectively, for the removal of organic compounds in environmental treatments. This study aims to prepare ZVI/AC derived from an agricultural waste, coir pith, through simple one-step pyrolysis. The effect of activation temperature and time on the surface area, iron content, and zerovalent iron ratio of ZVI/AC was systemically investigated. The results indicated that the activation of AC by FeSO4 significantly increased surface area of AC and distributed elemental iron over the AC. The X-ray diffraction (XRD), electron spectroscopy for chemical analysis (ESCA), and X-ray absorption near edge structure (XANES) spectra of ZVI/AC revealed that zerovalent iron was present. As compared to AC without FeSO4 activation, ZVI/AC increased the trichloroethylene removal rate constant by 7 times. The dechlorination ability of ZVI/AC was dominated by the zerovalent iron content. We have shown that lab-made ZVI/AC from coir pith can effectively adsorb and dehalogenate the chlorinated compounds in water. Copyright © 2013 Elsevier Ltd. All rights reserved.

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

PubMed

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

2008-10-16

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

Mercury speciation in the Mt. Amiata mining district (Italy): interplay between urban activities and mercury contamination

USGS Publications Warehouse

Rimondi, Valentina; Bardelli, Fabrizio; Benvenuti, Marco; Costagliola, Pilario; Gray, John E.; Lattanzi, Pierfranco

2014-01-01

A fundamental step to evaluate the biogeochemical and eco-toxicological significance of Hg dispersion in the environment is to determine speciation of Hg in solid matrices. In this study, several analytical techniques such as scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS), sequential chemical extractions (SCEs), and X-ray absorption spectroscopy (XANES) were used to identify Hg compounds and Hg speciation in samples collected from the Mt. Amiata Hg mining district, southern Tuscany, Italy. Different geological materials, such as mine waste calcine (retorted ore), soil, stream sediment, and stream water suspended particulate matter were analyzed. Results show that the samples were generally composed of highly insoluble Hg compounds such as sulphides (HgS, cinnabar and metacinnabar), and more soluble Hg halides such as those associated with the mosesite group. Other moderately soluble Hg compounds, HgCl2, HgO and Hg0, were also identified in stream sediments draining the mining area. The presence of these minerals suggests active and continuous runoff of soluble Hg compounds from calcines, where such Hg compounds form during retorting, or later in secondary processes. Specifically, we suggest that, due to the proximity of Hg mines to the urban center of Abbadia San Salvatore, the influence of other anthropogenic activities was a key factor for Hg speciation, resulting in the formation of unusual Hg-minerals such as mosesite.

Oxidative degradation of nalidixic acid by nano-magnetite via Fe2+/O2-mediated reactions.

PubMed

Ardo, Sandy G; Nélieu, Sylvie; Ona-Nguema, Georges; Delarue, Ghislaine; Brest, Jessica; Pironin, Elsa; Morin, Guillaume

2015-04-07

Organic pollution has become a critical issue worldwide due to the increasing input and persistence of organic compounds in the environment. Iron minerals are potentially able to degrade efficiently organic pollutants sorbed to their surfaces via oxidative or reductive transformation processes. Here, we explored the oxidative capacity of nano-magnetite (Fe3O4) having ∼ 12 nm particle size, to promote heterogeneous Fenton-like reactions for the removal of nalidixic acid (NAL), a recalcitrant quinolone antibacterial agent. Results show that NAL was adsorbed at the surface of magnetite and was efficiently degraded under oxic conditions. Nearly 60% of this organic contaminant was eliminated after 30 min exposure to air bubbling in solution in the presence of an excess of nano-magnetite. X-ray diffraction (XRD) and Fe K-edge X-ray absorption spectroscopy (XANES and EXAFS) showed a partial oxidation of magnetite to maghemite during the reaction, and four byproducts of NAL were identified by liquid chromatography-mass spectroscopy (UHPLC-MS/MS). We also provide evidence that hydroxyl radicals (HO(•)) were involved in the oxidative degradation of NAL, as indicated by the quenching of the degradation reaction in the presence of ethanol. This study points out the promising potentialities of mixed valence iron oxides for the treatment of soils and wastewater contaminated by organic pollutants.

Micro- to nanostructure and geochemistry of extant crinoidal echinoderm skeletons.

PubMed

Gorzelak, P; Stolarski, J; Mazur, M; Meibom, A

2013-01-01

This paper reports the results of micro- to nanostructural and geochemical analyses of calcitic skeletons from extant deep-sea stalked crinoids. Fine-scale (SEM, FESEM, AFM) observations show that the crinoid skeleton is composed of carbonate nanograins, about 20-100 nm in diameter, which are partly separated by what appears to be a few nm thick organic layers. Sub-micrometre-scale geochemical mapping of crinoid ossicles using a NanoSIMS ion microprobe, combined with synchrotron high-spatial-resolution X-ray micro-fluorescence (μ-XRF) maps and X-ray absorption near-edge structure spectroscopy (XANES) show that high Mg concentration in the central region of the stereom bars correlates with the distribution of S-sulphate, which is often associated with sulphated polysaccharides in biocarbonates. These data are consistent with biomineralization models suggesting a close association between organic components (including sulphated polysaccharides) and Mg ions. Additionally, geochemical analyses (NanoSIMS, energy dispersive spectroscopy) reveal that significant variations in Mg occur at many levels: within a single stereom trabecula, within a single ossicle and within a skeleton of a single animal. Together, these data suggest that physiological factors play an important role in controlling Mg content in crinoid skeletons and that great care should be taken when using their skeletons to reconstruct, for example, palaeotemperatures and Mg/Ca palaeo-variations of the ocean. © 2012 Blackwell Publishing Ltd.

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

PubMed

Shen, Ya-Ting

2014-03-01

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

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

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

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

2015-07-23

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

X-Ray Absorption Spectroscopy Studies of the Atomic Structure of Zirconium-Doped Lithium Silicate Glasses and Glass-Ceramics, Zirconium-Doped Lithium Borate Glasses, and Vitreous Rare-Earth Phosphates

NASA Astrophysics Data System (ADS)

Yoo, Changhyeon

In the first part of this work, the atomic-scale structure around rare-earth (RE = Pr, Nd, Eu, Dy, and Er) cations (RE3+) in rare-earth sodium ultraphosphate (REUP) glasses were investigated using RE LIII -edge (RE = Nd, Er, Dy, and Eu) and K-edge (RE = Pr and Dy) Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy. (RE2O 3)x(Na2O)y(P2O5) 1-x-y glasses in the compositional range 0 ≤ x ≤ 0.14 and 0.3 ≤ x + y ≤ 0.4 were studied. For the nearest oxygen shell, the RE-oxygen (RE-O) coordination number decreases from 10.8 to 6.5 with increasing RE content for Pr-, Nd-, Dy-, and Er-doped sodium ultraphosphate glasses. For Eu-doped samples, the Eu-O coordination number was between 7.5 and 8.8. Also, the RE-O mean distance ranges were between 2.43-2.45 A, 2.40-2.43 A, 2.36-2.38 A, 2.30-2.35 A, and 2.28-2.30 A for Pr-, Nd-, Eu-, Dy-, and Er-doped samples, respectively. In the second part, a series of Zr-doped (3-10 mol%) lithium silicate (ZRLS) glass-ceramics and their parent glasses and a series of Zr-doped (2-6 mol% ZrO2) lithium borate (ZRLB) glasses were investigated using Zr K-edge EXAFS and X-ray Absorption Near Edge Structure (XANES) spectroscopy. Immediate coordination environments of all ZRLS glasses are remarkably similar for different compositions. For the nearest oxygen shell, the Zr-O coordination number ranges were between 6.1 and 6.3 for nucleated and crystallized samples, respectively. Also, the Zr-O mean distance remains similar around 2.10 A. For these glasses, the composition dependence of structural parameters was small. Small changes in the coordination environment were observed for ZRLS glass-ceramics after thermal treatments. In contrast, Zr coordination environment in ZRLB glasses appear to depend appreciably on the Zr concentration. For the nearest oxygen shell, the Zr-O coordination number increased from 6.1 to 6.8 and the Zr-O distance decreased from 2.18 A to 2.14 A with decreasing ZrO2 content.

Development of high resolution x-ray spectrometers for the investigation of bioinorganic chemistry in metalloproteins

NASA Astrophysics Data System (ADS)

Drury, Owen Byron

We have built an X-ray spectrometer for synchrotron-based high-resolution soft X-ray spectroscopy. The spectrometer uses four 9-pixel arrays of superconducting tunnel junctions (STJs) as sensors. They infer the energy of an absorbed X-ray from a temporary increase in tunneling current. The STJs are operated in a two-stage adiabatic demagnetization refrigerator (ADR) that uses liquid nitrogen and helium for precooling to 77 K and 4.2 K, and gallium gadolinium garnet and iron ammonium sulfate to attain a base temperature below 0.1 K. The sensors are held at the end of a 40-cm-long cold finger within ˜1 cm of a sample located inside the vacuum chamber of a synchrotron beam line end station. The spectrometer has an energy resolution between 10 eV and 20 eV FWHM below 1 keV, can be operated at rates up to ˜106 counts/s. STJ spectrometers are suited for chemical analysis of dilute samples by fluorescence-detected X-ray absorption spectroscopy (XAS) in cases where conventional germanium detectors do not have enough energy resolution. We have used this STJ spectrometer at the Advanced Light Source synchrotron for spectroscopy on the lower energy X-ray absorption edges of the elements Mo, S, Fe and N. These elements play an important role in biological nitrogen fixation at the metalloprotein nitrogenase, and we have examined if STJ spectrometers can be used to provide new insights into some of the open questions regarding the reaction mechanism of this protein. We have taken X-ray absorption near-edge spectra (XANES) and extended fine structure spectra (EXAFS) of an Fe 6N(CO)15-compound containing a single N atom inside a cluster of six Fe atoms, as postulated to exist inside the Fe-S cluster of the FeMo-cofactor (FeMo-co) in nitrogenase. The STJ detector has enabled the first-ever extended range EXAFS scans on nitrogen through the oxygen K-edge, enabling a comparison with N EXAFS on FeMo-co. We have taken iron L23-edge spectra of the Fe-S cluster in FeMo-co, which can be used to measure its oxidation state despite the very small chemical shifts. We also have taken spectra on the molybdenum M-edges and on the sulfur L-edges of inorganic model compounds.

Combining Sequential Extractions and X-ray Absorption Spectroscopy for Quantitative and Qualitative Zinc Speciation in Soil

NASA Astrophysics Data System (ADS)

Bauer, Tatiana; Minkina, Tatiana; Batukaev, Abdulmalik; Nevidomskaya, Dina; Burachevskaya, Marina; Tsitsuashvili, Viktoriya; Urazgildieva, Kamilya

2017-04-01

The combined use of X-ray absorption spectrometry and extractive fractionation is an effective approach for studying the interaction of metal ions with soil compounds and identifying the phases-carriers of metals in soil and their stable fixation. These studies were carried out using the technique of X-ray absorption spectroscopy and chemical extractive fractionation. In a model experiment the samples taken in Calcic Chernozem were artificially contaminated with higher portion of Zn(NO3)2 (2000 mg/kg). The metal were incubated in soil samples for 2 year. The samples of soil mineral and organic phases (calcite, kaolinite, bentonite, humic acids) were saturated with Zn2+ from a solution of nitrate salts of metal. The total content of Zn in soil and soil various phases was determined using the X-ray fluorescence method. Extended X-ray absorption fine structure (EXAFS) Zn was measured at the Structural Materials Science beamline of the Kurchatov Center for Synchrotron Radiation. Sequential fractionation of Zn in soil conducted by Tessier method (Tessier et al., 1979) which determining 5 fractions of metals in soil: exchangeable, bound to Fe-Mn oxide, bound to carbonate, bound to the organic matter, and bound to silicate (residual). This methodology has so far more than 4000 citations (Web of Science), which demonstrates the popularity of this approach. Much Zn compounds are contained in uncontaminated soils in stable primary and secondary silicates inherited from the parental rocks (67% of the total concentrations in all fractions), which is a regional trait of soils in the fore-Caucasian plain. Extracted fractionation of metal compounds in soil samples, artificially contaminated with Zn salts, indicates the priority holding of Zn2+ ions by silicates, carbonates and Fe-Mn oxides. The Zn content significantly increases in the exchangeable fraction. Atomic structure study of the soil various phases saturated with Zn2+ ion by using (XANES) X-ray absorption spectroscopy allowed the determination of mechanism of metal ions interaction with soil phases and the resulting types of chemical bonds. Interaction with soil components modifies the electron structure of the metal ions themselves. The soil contamination with Zn is accompanied by decreasing the stable connection between metal and soil components. Interacting with humic acids in chernozem, the Zn2+ ion is coordinated by functional groups and ligands and forms unstable outer-sphere complexes. Zinc included into octahedral structures of layered minerals and hydro(oxides) can be inner-and outer-sphere adsorbed. The Zn2+ ions enable to replace Ca2+ ions in octahedral positions being coordinated with carbonate ions as ligands, thus forming absorbed complexes at the surface of mineral calcite. This work was supported by grant of the Russian Scientific Foundation № 16-14-10217.

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

NASA Technical Reports Server (NTRS)

Ruckman, Mark W.; Hepp, Aloysius F.

1991-01-01

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

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

NASA Technical Reports Server (NTRS)

Ruckman, Mark W.; Hepp, Aloysius F.

1991-01-01

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

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

PubMed

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

2001-03-01

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

First Ti-XANES analyses of refractory inclusions from Murchison

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

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

2009-03-23

Ti valence in refractory phases is an important recorder of redox conditions in the early solar nebula. We report the valence of Ti in pyroxene, spinel and hibonite in spinel-hibonite and spinel-pyroxene inclusions and in a coarse hibonite grain. A system of solar composition is so reducing that Ti{sup 3+} and Ti{sup 4+} can coexist, making the valence of Ti a valuable indicator of f{sub O2} conditions during formation of nebular materials. The Ti{sup 3+}/Ti{sup 4+} ratios observed in the Ti-rich phases fassaite and rhoenite in coarse-grained refractory inclusions from CV3 chondrites have been shown to be quantitatively consistent withmore » formation in a gas of solar composition (log f{sub O2} = IW-6.8), but these are the only objects in chondrites for which this is the case. Here, we report the valence of Ti in various phases in refractory inclusions from the Murchison CM2 chondrite. The second-highest temperature, major-element-bearing phase predicted to condense from a gas of solar composition, hibonite (ideally CaAl{sub 12}O{sub 19}), can contain significant amounts of Ti, but the hibonite structure can have oxygen vacancies, so calculation of Ti valence from stoichiometry of electron probe analyses is not recommended for hibonite. To date, the only reported measurement of Ti valence in meteoritic hibonite was done by electron spin resonance, on coarse crystals from a Murchison hibonite-perovskite-melilite inclusion. Spinel and most of the pyroxene in CM inclusions contain too little Ti for derivation of Ti{sup 3+}/Ti{sup 4+} ratios from electron probe analyses. X-ray absorption near edge spectroscopy (XANES), however, allows determination of Ti valence in relatively Ti-poor phases. In the present work, we apply synchrotron microXANES to a large hibonite grain from Murchison and to spinel-hibonite (sp-hib) and spinel-pyroxene (sp-pyx) inclusions from Murchison, refractory materials whose Ti{sup 3+}/Ti{sup 4+} ratios have not been previously measured. Analysis of these samples allows comparison of Ti valence of (1) pyroxene in sp-pyx inclusions with that of fassaite; (2) spinel in hibonite-bearing with that of hibonite-free inclusions; and (3) hibonite in sp-hib inclusions with that of large, single grains and the previously analyzed sample.« less

Determination of Arsenic Poisoning and Metabolism in Hair by Synchrotron Radiation: The Case of Phar Lap

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

Kempson, Ivan M.; Henry, Dermot A.; U. South Australia)

2010-08-26

Fresh physical evidence about the demise of the racehorse Phar Lap (see photograph) has been gathered from the study of mane hair samples by synchrotron radiation analysis with high resolution X-ray fluorescence (XRF) and X-ray absorption near edge structure (XANES) analyses. The results are indicative of arsenic ingestion and metabolism, and show that the racing champion died from arsenic poisoning.

Elemental and Molecular Segregation in Oil Paintings due to Lead Soap Degradation.

PubMed

Chen-Wiegart, Yu-Chen Karen; Catalano, Jaclyn; Williams, Garth J; Murphy, Anna; Yao, Yao; Zumbulyadis, Nicholas; Centeno, Silvia A; Dybowski, Cecil; Thieme, Juergen

2017-09-14

The formation of Pb, Zn, and Cu carboxylates (soaps) has caused visible deterioration in hundreds of oil paintings dating from the 15th century to the present. Through transport phenomena not yet understood, free fatty acids in the oil binding medium migrate through the paint and react with pigments containing heavy metals to form soaps. To investigate the complex correlation among the elemental segregation, types of chemical compounds formed, and possible mechanisms of the reactions, a paint sample cross-section from a 15th century oil painting was examined by synchrotron X-ray techniques. X-ray fluorescence (XRF) microscopy, quantified with elemental correlation density distribution, showed Pb and Sn segregation in the soap-affected areas. X-ray absorption near edge structure (XANES) around the Pb-L3 absorption edge showed that Pb pigments and Pb soaps can be distinguished while micro-XANES gave further information on the chemical heterogeneity in the paint film. The advantages and limitations of these synchrotron-based techniques are discussed and compared to those of methods routinely used to analyze paint samples. The results presented set the stage for improving the information extracted from samples removed from works of art and for correlating observations in model paint samples to those in the naturally aged samples, to shed light onto the mechanism of soap formation.

Papers from U.S. Department of Energy Science Undergraduate Laboratory Internship Program (SULI) 2010

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

Not Available

2011-06-22

The solvation sphere of halides in water has been investigated using a combination of extended x-ray absorption fine structure (EXAFS) and x-ray absorption near-edge structure (XANES) analysis techniques. The results have indicated that I{sup -} and Br{sup -} both have an asymmetric, 8 water molecule primary solvation spheres. These spheres are identical, with the Br{sup -} sphere about .3 {angstrom} smaller than the I{sup -} sphere. This study utilized near-edge analysis to supplement EXAFS analysis which suffers from signal dampening/broadening due to thermal noise. This paper has reported on the solvation first sphere of I{sup -} and Br{sup -} inmore » water. Using EXAFS and XANES analysis, strong models which describe the geometric configuration of water molecules coordinated to a central anion have been developed. The combination of these techniques has provided us with a more substantiated argument than relying solely on one or the other. An important finding of this study is that the size of the anion plays a smaller role than previously assumed in determining the number of coordinating water molecules. Further experimental and theoretical investigation is required to understand why the size of the anion plays a minor role in determining the number of water molecules bound.« less

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

NASA Astrophysics Data System (ADS)

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

2013-04-01

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

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

DOE PAGES

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

2016-06-30

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

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

PubMed

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

2016-03-01

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

The Development of Molybdenum Speciation as a Paleoredox Tool

NASA Astrophysics Data System (ADS)

Rodley, J.; Peacock, C.; Mosselmans, J. F. W.; Poulton, S.

2017-12-01

The redox state of the oceans has changed throughout geological time and an understanding of these changes is essential to elucidate links between ocean chemistry, climate and life. Due to its abundance in seawater and redox-sensitive nature, molybdenum has enormous potential as a paleoredox proxy. Although a significant amount of research has been done on molybdenum in ancient and modern sediments in terms of its concentrations and isotopic ratios there remains a limited understanding of the drawdown mechanisms of molybdenum under different redox conditions restricting its use in identifying a range of redox states. In order to address these uncertainties, we have developed a novel sequential extraction technique to examine molybdenum concentrations in six sediment fractions from modern samples that represent oxic, nitrogenous, ferruginous and euxinic environments. In addition we use µ-XRF and µ-XANES synchrotron spectroscopy to examine the molybdenum speciation within these fractions and environments. To interpret our µ-XANES data we have developed an extensive library of molybdenum XANES standards that represent molybdenum sequestration by the sediment fractions identified from the sequential extraction. To further verify our synchrotron results we developed a series of µ-XANES micro-column experiments to examine preferential uptake pathways of molybdenum to different sediment phases under a euxinic water column. The initial data from both the sequential extraction and µ-XANES methods indicate that molybdenum is not limited to a single burial pathway in any of the redox environments. We find that each of the redox environments can be characterised by a limited set of molybdenum phase associations, with molybdenum adsorption to pyrite likely the dominant burial pathway. These findings agree with existing research for molybdenum speciation in euxinic environments suggesting that both pyrite and sulphidised organic matter act as important molybdenum sinks. Our new research shows that pyrite is also an important sink for molybdenum in other redox environments.

High-Iron Biosolids Compost-Induced Changes in Lead and Arsenic Speciation and Bioaccessibility in Co-contaminated Soils

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

Brown, Sally L; Clausen, Ingrid; Chappell, Mark A

2012-10-23

The safety of urban farming has been questioned due to the potential for contamination in urban soils. A laboratory incubation, a field trial, and a second laboratory incubation were conducted to test the ability of high-Fe biosolids–based composts to reduce the bioaccessibility of soil Pb and As in situ. Lead and As bioaccessibility were evaluated using an in vitro assay. Changes in Pb, As, and Fe speciation were determined on select samples after the second laboratory incubation using μ–X-ray fluorescence mapping followed by μ–X-ray absorption near-edge structure (XANES). A compost with Fe added to wastewater treatment residuals (Fe WTR compost)more » added to soils at 100 g kg -1 decreased Pb bioaccessibility in both laboratory incubations. Mixed results were observed for As. Composts tested in the field trial (Fe added as Fe powder or FeCl 2) did not reduce bioaccessible Pb, and limited reductions were observed in bioaccessible As. These composts had no effect on Pb bioaccessibility during the second laboratory incubation. Bulk XANES showed association of Pb with sulfates and carbonates in the control soil. μ-XANES for three points in the Fe WTR amended soil showed Pb present as Fe-sorbed Pb (88 and 100% of two points) and pyromorphite (12 and 53% of two points). Bulk XANES of the Fe WTR compost showed 97% of total Fe present as Fe 3+. The results of this study indicate that addition of high-Fe biosolids compost is an effective means to reduce Pb accessibility only for certain types of Fe-rich materials.« less

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

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

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

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

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

PubMed

Xiong, Wenhui; Peng, Jian; Hu, Yongfeng

2012-02-15

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

Tetra- and hexavalent uranium forms bidentate-mononuclear complexes with particulate organic matter in a naturally uranium-enriched peatland

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

Mikutta, Christian; Langner, Peggy; Bargar, John R.

Peatlands frequently serve as efficient biogeochemical traps for U. Mechanisms of U immobilization in these organic matter-dominated environments may encompass the precipitation of U-bearing mineral(oid)s and the complexation of U by a vast range of (in)organic surfaces. The objective of this work was to investigate the spatial distribution and molecular binding mechanisms of U in soils of an alpine minerotrophic peatland (pH 4.7–6.6, E h = –127 to 463 mV) using microfocused X-ray fluorescence spectrometry and bulk and microfocused U L 3-edge X-ray absorption spectroscopy. The soils contained 2.3–47.4 wt % organic C, 4.1–58.6 g/kg Fe, and up to 335 mg/kg geogenic U. Uranium was found to be heterogeneously distributed at the micrometer scale and enriched as both U(IV) and U(VI) on fibrous and woody plant debris (48 ± 10% U(IV),more » $$\\bar{x}$$ ± σ, n = 22). Bulk U X-ray absorption near edge structure (XANES) spectroscopy revealed that in all samples U(IV) comprised 35–68% of total U ($$\\bar{x}$$ = 50%, n = 15). Shell-fit analyses of bulk U L 3-edge extended X-ray absorption fine structure (EXAFS) spectra showed that U was coordinated to 1.3 ± 0.2 C atoms at a distance of 2.91 ± 0.01 Å ($$\\bar{x}$$ ± σ), which implies the formation of bidentate-mononuclear U(IV/VI) complexes with carboxyl groups. We neither found evidence for U shells at ~3.9 Å, indicative of mineral-associated U or multinuclear U(IV) species, nor for a substantial P/Fe coordination of U. As a result, our data indicates that U(IV/VI) complexation by natural organic matter prevents the precipitation of U minerals as well as U complexation by Fe/Mn phases at our field site, and suggests that organically complexed U(IV) is formed via reduction of organic matter-bound U(VI).« less

Tetra- and hexavalent uranium forms bidentate-mononuclear complexes with particulate organic matter in a naturally uranium-enriched peatland

DOE PAGES

Mikutta, Christian; Langner, Peggy; Bargar, John R.; ...

2016-09-16

Peatlands frequently serve as efficient biogeochemical traps for U. Mechanisms of U immobilization in these organic matter-dominated environments may encompass the precipitation of U-bearing mineral(oid)s and the complexation of U by a vast range of (in)organic surfaces. The objective of this work was to investigate the spatial distribution and molecular binding mechanisms of U in soils of an alpine minerotrophic peatland (pH 4.7–6.6, E h = –127 to 463 mV) using microfocused X-ray fluorescence spectrometry and bulk and microfocused U L 3-edge X-ray absorption spectroscopy. The soils contained 2.3–47.4 wt % organic C, 4.1–58.6 g/kg Fe, and up to 335 mg/kg geogenic U. Uranium was found to be heterogeneously distributed at the micrometer scale and enriched as both U(IV) and U(VI) on fibrous and woody plant debris (48 ± 10% U(IV),more » $$\\bar{x}$$ ± σ, n = 22). Bulk U X-ray absorption near edge structure (XANES) spectroscopy revealed that in all samples U(IV) comprised 35–68% of total U ($$\\bar{x}$$ = 50%, n = 15). Shell-fit analyses of bulk U L 3-edge extended X-ray absorption fine structure (EXAFS) spectra showed that U was coordinated to 1.3 ± 0.2 C atoms at a distance of 2.91 ± 0.01 Å ($$\\bar{x}$$ ± σ), which implies the formation of bidentate-mononuclear U(IV/VI) complexes with carboxyl groups. We neither found evidence for U shells at ~3.9 Å, indicative of mineral-associated U or multinuclear U(IV) species, nor for a substantial P/Fe coordination of U. As a result, our data indicates that U(IV/VI) complexation by natural organic matter prevents the precipitation of U minerals as well as U complexation by Fe/Mn phases at our field site, and suggests that organically complexed U(IV) is formed via reduction of organic matter-bound U(VI).« less

Selenium inhibits the phytotoxicity of mercury in garlic (Allium sativum).

PubMed

Zhao, Jiating; Gao, Yuxi; Li, Yu-Feng; Hu, Yi; Peng, Xiaomin; Dong, Yuanxing; Li, Bai; Chen, Chunying; Chai, Zhifang

2013-08-01

To investigate the influence of selenium on mercury phytotoxicity, the levels of selenium and mercury were analyzed with inductively coupled plasma-mass spectrometry (ICP-MS) in garlic tissues upon exposure to different dosages of inorganic mercury (Hg(2+)) and selenite (SeO3(2-)) or selenate (SeO4(2-)). The distributions of selenium and mercury were examined with micro-synchrotron radiation X-ray fluorescence (μ-SRXRF), and the mercury speciation was investigated with micro-X-ray absorption near edge structure (μ-XANES). The results show that Se at higher exposure levels (>1mg/L of SeO3(2-) or SeO4(2-)) would significantly inhibit the absorption and transportation of Hg when Hg(2+) levels are higher than 1mg/L in culture media. SeO3(2-) and SeO4(2-) were found to be equally effective in reducing Hg accumulation in garlic. The inhibition of Hg uptake by Se correlates well with the influence of Se on Hg phytotoxicity as indicated by the growth inhibition factor. Elemental imaging using μ-SRXRF also shows that Se could inhibit the accumulation and translocation of Hg in garlic. μ-XANES analysis shows that Hg is mainly present in the forms of Hg-S bonding as Hg(GSH)2 and Hg(Met)2. Se exposure elicited decrease of Hg-S bonding in the form of Hg(GSH)2, together with Se-mediated alteration of Hg absorption, transportation and accumulation, may account for attenuated Hg phytotoxicity by Se in garlic. Copyright © 2013 Elsevier Inc. All rights reserved.