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Sample records for absorption xas spectroscopies

  1. Status of the X-Ray Absorption Spectroscopy (XAS) Beamline at the Australian Synchrotron

    NASA Astrophysics Data System (ADS)

    Glover, C.; McKinlay, J.; Clift, M.; Barg, B.; Boldeman, J.; Ridgway, M.; Foran, G.; Garret, R.; Lay, P.; Broadbent, A.

    2007-02-01

    We present herein the current status of the X-ray Absorption Spectroscopy (XAS) Beamline at the 3 GeV Australian Synchrotron. The optical design and performance, details of the insertion device (Wiggler), end station capabilities and construction and commissioning timeline are given.

  2. X-ray absorption spectroscopy (XAS) of toxic metal mineral transformations by fungi.

    PubMed

    Fomina, Marina; Charnock, John; Bowen, Andrew D; Gadd, Geoffrey M

    2007-02-01

    Fungi can be highly efficient biogeochemical agents and accumulators of soluble and particulate forms of metals. This work aims to understand some of the physico-chemical mechanisms involved in toxic metal transformations focusing on the speciation of metals accumulated by fungi and mycorrhizal associations. The amorphous state or poor crystallinity of metal complexes within biomass and relatively low metal concentrations make the determination of metal speciation in biological systems a challenging problem but this can be overcome by using synchrotron-based element-specific X-ray absorption spectroscopy (XAS) techniques. In this research, we have exposed fungi and ectomycorrhizas to a variety of copper-, zinc- and lead-containing minerals. X-ray absorption spectroscopy studies revealed that oxygen ligands (phosphate, carboxylate) played a major role in toxic metal coordination within the fungal and ectomycorrhizal biomass during the accumulation of mobilized toxic metals. Coordination of toxic metals within biomass depended on the fungal species, initial mineral composition, the nitrogen source, and the physiological state/age of the fungal mycelium.

  3. Quantification of rapid environmental redox processes with quick-scanning x-ray absorption spectroscopy (Q-XAS).

    PubMed

    Ginder-Vogel, Matthew; Landrot, Gautier; Fischel, Jason S; Sparks, Donald L

    2009-09-22

    Quantification of the initial rates of environmental reactions at the mineral/water interface is a fundamental prerequisite to determining reaction mechanisms and contaminant transport modeling and predicting environmental risk. Until recently, experimental techniques with adequate time resolution and elemental sensitivity to measure initial rates of the wide variety of environmental reactions were quite limited. Techniques such as electron paramagnetic resonance and Fourier transform infrared spectroscopies suffer from limited elemental specificity and poor sensitivity to inorganic elements, respectively. Ex situ analysis of batch and stirred-flow systems provides high elemental sensitivity; however, their time resolution is inadequate to characterize rapid environmental reactions. Here we apply quick-scanning x-ray absorption spectroscopy (Q-XAS), at sub-second time-scales, to measure the initial oxidation rate of As(III) to As(V) by hydrous manganese(IV) oxide. Using Q-XAS, As(III) and As(V) concentrations were determined every 0.98 s in batch reactions. The initial apparent As(III) depletion rate constants (t < 30 s) measured with Q-XAS are nearly twice as large as rate constants measured with traditional analytical techniques. Our results demonstrate the importance of developing analytical techniques capable of analyzing environmental reactions on the same time scale as they occur. Given the high sensitivity, elemental specificity, and time resolution of Q-XAS, it has many potential applications. They could include measuring not only redox reactions but also dissolution/precipitation reactions, such as the formation and/or reductive dissolution of Fe(III) (hydr)oxides, solid-phase transformations (i.e., formation of layered-double hydroxide minerals), or almost any other reaction occurring in aqueous media that can be measured using x-ray absorption spectroscopy.

  4. X-Ray absorption in homogeneous catalysis research: the iron-catalyzed Michael addition reaction by XAS, RIXS and multi-dimensional spectroscopy.

    PubMed

    Bauer, Matthias; Gastl, Christoph

    2010-06-07

    A survey over X-ray absorption methods in homogeneous catalysis research is given with the example of the iron-catalyzed Michael addition reaction. A thorough investigation of the catalytic cycle was possible by combination of conventional X-ray absorption spectroscopy (XAS), resonant inelastic X-ray scattering (RIXS) and multi-dimensional spectroscopy. The catalytically active compound formed in the first step of the Michael reaction of methyl vinyl ketone with 2-oxocyclopentanecarboxylate (1) could be elucidated in situ by RIXS spectroscopy, and the reduced catalytic activity of FeCl(3) x 6 H(2)O (2) compared to Fe(ClO(4))(3) x 9 H(2)O (3) could be further explained by the formation of a [Fe(III)Cl(4)(-)](3)[Fe(III)(1-H)(2)(H(2)O)(2)(+)][H(+)](2) complex. Chloride was identified as catalyst poison with a combined XAS-UV/vis study, which revealed that Cl(-) binds quantitatively to the available iron centers that are deactivated by formation of [FeCl(4)(-)]. Operando studies in the course of the reaction of methyl vinyl ketone with 1 by combined XAS-Raman spectroscopy allowed the exclusion of changes in the oxidation state and the octahedral geometry at the iron site; a reaction order of two with respect to methyl vinyl ketone and a rate constant of k = 1.413 min(-2) were determined by analysis of the C=C and C=O vibration band. Finally, a dedicated experimental set-up for three-dimensional spectroscopic studies (XAS, UV/vis and Raman) of homogeneous catalytic reactions under laboratory conditions, which emerged from the discussed investigations, is presented.

  5. Quick-EXAFS setup at the SuperXAS beamline for in situ X-ray absorption spectroscopy with 10 ms time resolution

    PubMed Central

    Müller, Oliver; Nachtegaal, Maarten; Just, Justus; Lützenkirchen-Hecht, Dirk; Frahm, Ronald

    2016-01-01

    The quick-EXAFS (QEXAFS) method adds time resolution to X-ray absorption spectroscopy (XAS) and allows dynamic structural changes to be followed. A completely new QEXAFS setup consisting of monochromator, detectors and data acquisition system is presented, as installed at the SuperXAS bending-magnet beamline at the Swiss Light Source (Paul Scherrer Institute, Switzerland). The monochromator uses Si(111) and Si(311) channel-cut crystals mounted on one crystal stage, and remote exchange allows an energy range from 4.0 keV to 32 keV to be covered. The spectral scan range can be electronically adjusted up to several keV to cover multiple absorption edges in one scan. The determination of the Bragg angle close to the position of the crystals allows high-accuracy measurements. Absorption spectra can be acquired with fast gridded ionization chambers at oscillation frequencies of up to 50 Hz resulting in a time resolution of 10 ms, using both scan directions of each oscillation period. The carefully developed low-noise detector system yields high-quality absorption data. The unique setup allows both state-of-the-art QEXAFS and stable step-scan operation without the need to exchange whole monochromators. The long-term stability of the Bragg angle was investigated and absorption spectra of reference materials as well as of a fast chemical reaction demonstrate the overall capabilities of the new setup. PMID:26698072

  6. Use of X-Ray Absorption Spectroscopy (XAS) to Speciate Manganese in Airborne Particulate Matter from 5 Counties Across the US

    PubMed Central

    Datta, Saugata; Rule, Ana M; Mihalic, Jana N; Chillrud, Steve N; Bostick, Benjamin C.; Ramos-Bonilla, Juan P; Han, Inkyu; Polyak, Lisa M; Geyh, Alison S; Breysse, Patrick N

    2012-01-01

    The purpose of this study is to characterize manganese oxidation states and speciation in airborne particulate matter (PM), and describe how these potentially important determinants of PM toxicity vary by location. Ambient PM samples were collected from five counties across the US using a high volume sequential cyclone system that collects PM in dry bulk form segregated into “coarse” and “fine” size fractions. The fine fraction was analyzed for this study. Analyses included total Mn using ICP-MS, and characterization of oxidation states and speciation using X-ray Absorption Spectroscopy (XAS). XAS spectra of all samples and ten standard compounds of Mn were obtained at the National Synchrotron Light Source. XAS data was analyzed using Linear Combination Fitting (LCF). Results of the LCF analysis describe differences in composition between samples. Mn(II) acetate and Mn(II) oxide are present in all samples, while Mn(II) carbonate and Mn(IV) oxide are absent. To the best of our knowledge, this is the first paper to characterize Mn composition of ambient PM and examine differences between urban sites in the US. Differences in oxidation state and composition indicate regional variations in sources and atmospheric chemistry that may help explain differences in health effects identified in epidemiological studies. PMID:22309075

  7. 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

  8. Chemical Phase and Valence Studies of Plasma Sprayed Coatings: EDXRD and X-ray Absorption Spectroscopy (XAS) Results

    DTIC Science & Technology

    2010-06-01

    Versatile XAS micro-(NSLS)/nano(NSLS-II)- probe: local mapping of structure chemistry Rare Earth (RE) 4f -localized atomic, core states** Ce Problem and Ce-L3...powder • Ce3+ n-PS coating Ce4+O2 Ce 3+ !!!!!! PS Plasma Spray Chemical reduction of Ce Average Ce-O distance estimate Rare Earth continuum...local ligand coordination - structure EDXRD: plasma sprayed alumina-titania coatings (on Ti-6-4) • nATCZ → nano composite alumina-titania coating

  9. Chemical shifts of K-X-ray absorption edges on copper in different compounds by X-ray absorption spectroscopy (XAS) with Synchrotron radiation

    NASA Astrophysics Data System (ADS)

    Joseph, D.; Basu, S.; Jha, S. N.; Bhattacharyya, D.

    2012-03-01

    Cu K X-ray absorption edges were measured in compounds such as CuO, Cu(CH3CO2)2, Cu(CO3)2, and CuSO4 where Cu is present in oxidation state of 2+, using the energy dispersive EXAFS beamline at INDUS-2 Synchrotron radiation source at RRCAT, Indore. Energy shifts of ˜4-7 eV were observed for Cu K X-ray absorption edge in the above compounds compared to its value in elemental copper. The difference in the Cu K edge energy shifts in the different compounds having same oxidation state of Cu shows the effect of different chemical environments surrounding the cation in the above compounds. The above chemical effect has been quantitatively described by determining the effective charges on Cu cations in the above compounds.

  10. The Time-resolved and Extreme-conditions XAS (TEXAS) facility at the European Synchrotron Radiation Facility: the energy-dispersive X-ray absorption spectroscopy beamline ID24

    PubMed Central

    Pascarelli, S.; Mathon, O.; Mairs, T.; Kantor, I.; Agostini, G.; Strohm, C.; Pasternak, S.; Perrin, F.; Berruyer, G.; Chappelet, P.; Clavel, C.; Dominguez, M. C.

    2016-01-01

    The European Synchrotron Radiation Facility has recently made available to the user community a facility totally dedicated to Time-resolved and Extreme-conditions X-ray Absorption Spectroscopy – TEXAS. Based on an upgrade of the former energy-dispersive XAS beamline ID24, it provides a unique experimental tool combining unprecedented brilliance (up to 1014 photons s−1 on a 4 µm × 4 µm FWHM spot) and detection speed for a full EXAFS spectrum (100 ps per spectrum). The science mission includes studies of processes down to the nanosecond timescale, and investigations of matter at extreme pressure (500 GPa), temperature (10000 K) and magnetic field (30 T). The core activities of the beamline are centered on new experiments dedicated to the investigation of extreme states of matter that can be maintained only for very short periods of time. Here the infrastructure, optical scheme, detection systems and sample environments used to enable the mission-critical performance are described, and examples of first results on the investigation of the electronic and local structure in melts at pressure and temperature conditions relevant to the Earth’s interior and in laser-shocked matter are given. PMID:26698085

  11. Study of Ga(3+)-induced hydrothermal crystallization of an α-quartz type Ga(1-x)Fe(x)PO4 single crystal by in situ X-ray absorption spectroscopy (XAS).

    PubMed

    Souleiman, Manhal; Cambon, Olivier; Haidoux, Abel; Haines, Julien; Levelut, Claire; Ranieri, Vincent; Hazemann, Jean-Louis

    2012-11-05

    The dissolution of α-FePO(4) and the α-Ga(0.75)Fe(0.25)PO(4) solid solution with α-quartz-type structures under hydrothermal conditions in 1 M HNO(3) aqueous solution was investigated by in situ X-ray absorption spectroscopy (XAS) at the Fe K-edge. The solubility of α-FePO(4) increases with temperature and is higher at 25 MPa than at 50 MPa. The Fe(3+) cation in solution is 6-fold coordinated with an average Fe-O distance close to 2.0 Å. A similar experiment was performed with a solid solution of α-quartz-type Ga(0.75)Fe(0.25)PO(4) as the starting phase under a pressure of 25 MPa. By varying the temperature from 303 K up to 573 K a single crystal was grown with 23% Fe(3+) with the α-quartz-type structure. These results show that the crystallization of pure α-quartz-type FePO(4) by the hydrothermal method is not possible due to the formation of very stable Fe(3+) hexa-aquo complexes [Fe(H(2)O)(6)](3+) and to the absence of FeO(4) tetrahedra in solution. Ga(3+) cations in solution induce the formation of gallophosphate complexes at the solid-liquid interface, which are at the origin of the nuclei for crystallization. We propose a crystallization mechanism in which the Fe(3+) substitutes Ga(3+) with a 4-fold coordination in mixed (iron/gallo)-phosphate complexes that leads to the growth of an α-quartz-type Ga(0.77)Fe(0.23)PO(4) single crystal.

  12. XAS spectroscopy, sulfur, and the brew within blood cells from Ascidia ceratodes.

    PubMed

    Frank, Patrick; Hedman, Britt; Hodgson, Keith O

    2014-02-01

    We report the first use of K-edge X-ray absorption spectroscopy (XAS) as a direct spectroscopic probe of pH and cytosolic emf within living cells. A new accuracy metric of model-based fits to K-edge spectra is further developed. Sulfur functional groups in three collections of living blood cells and one sample of cleared blood plasma from the tunicate Ascidia ceratodes were speciated using K-edge XAS. Cysteine and cystine, the preferred thiol-disulfide model, averaged about 12% of total sulfur. Sulfate monoesters and cyclic diesters unexpectedly constituted 36% of blood cell sulfur. Soluble sulfate averaged about 25% across the three blood cell samples, while the ratio of SO4(2-) to HSO4(-) implied average signet ring vacuolar pH values of 0.85, 1.4, or 3.1. Intracellular (VSO4)(+) was unobserved, while [V(RSO3)n]((3-n)+) was detected in the two lowest pH blood cell samples. About 5% of sulfur was distributed as mono- or dibenzothiophene or ethylene-epi-sulfide, or as a thiadiazole reminiscent of the polycarpathiamines. Blood plasma was dominated by sulfate (83%), but with 15% of an alkylsulfate ester and about 2% of low-valent sulfur. Gravimetric analysis of soluble sulfate yielded average concentrations of blood cell sulfur. Average [cysteine] and [cystine] (ranging ~10-30 mM and ~20-90 mM, respectively) implied blood-cell cytosolic emf values of approximately -0.20 V. High cellular [cysteine] is consistent with the proposed model for enzymatic reduction of vanadate by endogenous thiol, wherein the trajectory of metal site-symmetry is controlled and directed through to a thermodynamically favored 7-coordinate V(III) product.

  13. XAS Spectroscopy, Sulfur, and the Brew Within Blood Cells from Ascidia ceratodes

    PubMed Central

    Frank, Patrick; Hedman, Britt; Hodgson, Keith O.

    2014-01-01

    We report the first use of K-edge x-ray absorption spectroscopy (XAS) as a direct spectroscopic probe of pH and cytosolic emf within living cells. A new accuracy metric of model-based fits to K-edge spectra is further developed. Sulfur functional groups in three collections of living blood cells and one sample of cleared blood plasma from the tunicate Ascidia ceratodes were speciated using K-edge XAS. Cysteine and cystine, the preferred thiol-disulfide model, averaged about 12% of total sulfur. Sulfate monoesters and cyclic diesters unexpectedly constituted 36% of blood cell sulfur. Soluble sulfate averaged about 25% across the three blood cell samples, while the ratio of SO42− to HSO4− implied average signet ring vacuolar pH values of 0.85, 1.4, or 3.1. Intracellular (VSO4)+ was unobserved, while [V(RSO3)n](3−n)+ was detected in the two lowest pH blood cell samples. About 5% of sulfur was distributed as mono- or dibenzothiophene or ethylene-epi-sulfide, or as a thiadiazole reminiscent of the polycarpathiamines. Blood plasma was dominated by sulfate (83%), but with 15% of an alkylsulfate ester and about 2% of low-valent sulfur. Gravimetric analysis of soluble sulfate yielded average concentrations of blood cell sulfur. Average [cysteine] and [cystine] (ranging ~10–30 mM and ~20–90 mM, respectively) implied a blood-cell cytosolic emf values of approximately −0.20 V. High cellular [cysteine] is consistent with the proposed model for enzymatic reduction of vanadate by endogenous thiol, wherein the trajectory of metal site-symmetry is controlled and directed through to a thermodynamically favored 7-coordinate V(III) product. PMID:24333825

  14. Time-dependent X-ray absorption spectroscopic (XAS) study on the transformation of zinc basic salt into bis(N-oxopyridine-2-thionato) zinc (II).

    PubMed

    Paek, Seung-Min; Jo, Won-Young; Park, Man; Choy, Jin-Ho

    2007-11-01

    Solid transchelation reaction was established for the synthesis of bis(N-oxopyridine-2-thionato) zinc (II), commonly known as zinc pyrithione (ZPT), to control particle size using zinc basic salt (ZBS) and aqueous sodium pyrithione solution. Distinguished from ZPT particles prepared by usual precipitation reaction, the obtained ZPT nanoparticles exhibited very narrow size distribution. X-ray absorption spectroscopy (XAS) at Zn K-edge was systematically examined to elucidate time-dependent local structural evolution during solid transchelation reaction. X-ray absorption near edge structure (XANES) analysis clearly revealed that local environment around zinc atoms transformed into pentahedron as reaction proceeded. Based on quantitative X-ray diffraction and XANES analysis, we made structural models. Theoretical XAS spectrum calculated with FEFF code could reproduce experimental one, suggesting that XAS analysis could be very powerful tool to probe phase transformation. Furthermore, according to extended X-ray absorption fine structure (EXAFS) fitting results, Zn-O distance in reaction products gradually increased from 1.96 to 2.07 angstroms, suggesting that zinc atoms bounded with oxygen ones in ZBS were transchelated with pyrithione ligands. This study could be a strong evidence for the usefulness of XAS to study time-dependent structural transformation of nanocrystalline materials.

  15. Simultaneous surface plasmon resonance and x-ray absorption spectroscopy

    SciTech Connect

    Serrano, A.; Rodriguez de la Fuente, O.; Collado, V.; Rubio-Zuazo, J.; Castro, G. R.; Monton, C.; Garcia, M. A.

    2012-08-15

    We present an experimental setup for the simultaneous measurement of surface plasmon resonance (SPR) and x-ray absorption spectroscopy (XAS) on metallic thin films at a synchrotron beamline. The system allows measuring in situ and in real time the effect of x-ray irradiation on the SPR curves to explore the interaction of x-rays with matter. It is also possible to record XAS spectra while exciting SPR in order to study changes in the films induced by the excitation of surface plasmons. Combined experiments recording simultaneously SPR and XAS curves while scanning different parameters can be also carried out. The relative variations in the SPR and XAS spectra that can be detected with this setup range from 10{sup -3} to 10{sup -5}, depending on the particular experiment.

  16. XAS and TRLIF spectroscopy of uranium and neptunium in seawater.

    PubMed

    Maloubier, Melody; Solari, Pier Lorenzo; Moisy, Philippe; Monfort, Marguerite; Den Auwer, Christophe; Moulin, Christophe

    2015-03-28

    Seawater contains radionuclides at environmental levels; some are naturally present and others come from anthropogenic nuclear activity. In this report, the molecular speciation in seawater of uranium(VI) and neptunium(V) at a concentration of 5 × 10(-5) M has been investigated for the first time using a combination of two spectroscopic techniques: Time-resolved laser-induced fluorescence (TRLIF) for U and extended X-ray absorption fine structure (EXAFS) for U and Np at the LIII edge. In parallel, the theoretical speciation of uranium and neptunium in seawater at the same concentration is also discussed and compared to spectroscopic data. The uranium complex was identified as the neutral carbonato calcic complex UO2(CO3)3Ca2, which has been previously described in other natural systems. In the case of neptunium, the complex identified is mainly a carbonato complex whose exact stoichiometry is more difficult to assess. The knowledge of the actinide molecular speciation and reactivity in seawater is of fundamental interest in the particular case of uranium recovery and more generally regarding the actinide life cycle within the biosphere in the case of accidental release. This is the first report of actinide direct speciation in seawater medium that can complement inventory data.

  17. Soliton absorption spectroscopy

    PubMed Central

    Kalashnikov, V. L.; Sorokin, E.

    2010-01-01

    We analyze optical soliton propagation in the presence of weak absorption lines with much narrower linewidths as compared to the soliton spectrum width using the novel perturbation analysis technique based on an integral representation in the spectral domain. The stable soliton acquires spectral modulation that follows the associated index of refraction of the absorber. The model can be applied to ordinary soliton propagation and to an absorber inside a passively modelocked laser. In the latter case, a comparison with water vapor absorption in a femtosecond Cr:ZnSe laser yields a very good agreement with experiment. Compared to the conventional absorption measurement in a cell of the same length, the signal is increased by an order of magnitude. The obtained analytical expressions allow further improving of the sensitivity and spectroscopic accuracy making the soliton absorption spectroscopy a promising novel measurement technique. PMID:21151755

  18. Atomic structure of machined semiconducting chips: An x-ray absorption spectroscopy study

    SciTech Connect

    Paesler, M.; Sayers, D.

    1988-12-01

    X-ray absorption spectroscopy (XAS) has been used to examine the atomic structure of chips of germanium that were produced by single point diamond machining. It is demonstrated that although the local (nearest neighbor) atomic structure is experimentally quite similar to that of single crystal specimens information from more distant atoms indicates the presence of considerable stress. An outline of the technique is given and the strength of XAS in studying the machining process is demonstrated.

  19. Relic Neutrino Absorption Spectroscopy

    SciTech Connect

    Eberle, b

    2004-01-28

    Resonant annihilation of extremely high-energy cosmic neutrinos on big-bang relic anti-neutrinos (and vice versa) into Z-bosons leads to sizable absorption dips in the neutrino flux to be observed at Earth. The high-energy edges of these dips are fixed, via the resonance energies, by the neutrino masses alone. Their depths are determined by the cosmic neutrino background density, by the cosmological parameters determining the expansion rate of the universe, and by the large redshift history of the cosmic neutrino sources. We investigate the possibility of determining the existence of the cosmic neutrino background within the next decade from a measurement of these absorption dips in the neutrino flux. As a by-product, we study the prospects to infer the absolute neutrino mass scale. We find that, with the presently planned neutrino detectors (ANITA, Auger, EUSO, OWL, RICE, and SalSA) operating in the relevant energy regime above 10{sup 21} eV, relic neutrino absorption spectroscopy becomes a realistic possibility. It requires, however, the existence of extremely powerful neutrino sources, which should be opaque to nucleons and high-energy photons to evade present constraints. Furthermore, the neutrino mass spectrum must be quasi-degenerate to optimize the dip, which implies m{sub {nu}} 0.1 eV for the lightest neutrino. With a second generation of neutrino detectors, these demanding requirements can be relaxed considerably.

  20. X-ray Absorption Spectroscopy of the Rare Earth orthophosphates

    SciTech Connect

    Shuh, D.K.; Terminello, L.J.; Boatner, L.A.; Abraham, M.M.

    1993-06-01

    X-ray Absorption Spectroscopy (XAS) of the Rare Earth (RE) 3d levels yields sharp peaks near the edges as a result of strong, quasi-atomic 3d{sup 10}4f{sup n} {yields} 3d-{sup 9}4f{sup n+1} transitions and these transitions exhibit a wealth of spectroscopic features. The XAS measurements of single crystal REPO{sub 4} (RE = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Er) at the 3d edge were performed in the total yield mode at beam line 8-2 at the Stanford Synchrotron Radiation Laboratory (SSRL). The XAS spectra of the RE ions in the orthophosphate matrix generally resemble the XAS of the corresponding RE metal. This is not unexpected and emphasizes the major contribution of the trivalent state to the electronic transitions at the RE 3d edges. These spectra unequivocally identify the transitions originating from well-characterized RE cores and correlate well with previous theoretical investigations.

  1. X-Ray absorption spectroscopy investigation of 1-alkyl-3-methylimidazolium bromide salts

    SciTech Connect

    D'Angelo, Paola; Zitolo, Andrea; Migliorati, Valentina; Bodo, Enrico; Caminiti, Ruggero; Aquilanti, Giuliana; Hazemann, Jean Louis; Testemale, Denis; Mancini, Giordano

    2011-08-21

    X-ray absorption spectroscopy (XAS) has been used to unveil the bromide ion local coordination structure in 1-alkyl-3-methylimidazolium bromide [C{sub n}mim]Br ionic liquids (ILs) with different alkyl chains. The XAS spectrum of 1-ethyl-3-methylimidazolium bromide has been found to be different from those of the other members of the series, from the butyl to the decyl derivatives, that have all identical XAS spectra. This result indicates that starting from 1-buthyl-3-methylimidazolium bromide the local molecular arrangement around the bromide anion is the same independently from the length of the alkyl chain, and that the imidazolium head groups in the liquid ILs with long alkyl chains assume locally the same orientation as in the [C{sub 4}mim]Br crystal. With this study we show that the XAS technique is an effective direct tool for unveiling the local structural arrangements around selected atoms in ILs.

  2. X-ray Absorption Spectroscopy

    SciTech Connect

    Yano, Junko; Yachandra, Vittal K.

    2009-07-09

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

  3. X-Ray Absorption Spectroscopy of Cuprous-Thiolate Clusters in Saccharomyces Cerevisiae Metallothionein

    SciTech Connect

    Zhang, L.; Pickering, I.J.; Winge, D.R.; George, G.N.

    2009-05-28

    Copper (Cu) metallothioneins are cuprous-thiolate proteins that contain multimetallic clusters, and are thought to have dual functions of Cu storage and Cu detoxification. We have used a combination of X-ray absorption spectroscopy (XAS) and density-functional theory (DFT) to investigate the nature of Cu binding to Saccharomyces cerevisiae metallothionein. We found that the XAS of metallothionein prepared, containing a full complement of Cu, was quantitatively consistent with the crystal structure, and that reconstitution of the apo-metallothionein with stoichiometric Cu results in the formation of a tetracopper cluster, indicating cooperative binding of the Cu ions by the metallothionein.

  4. An x-ray absorption spectroscopy study of Cd binding onto a halophilic archaeon

    NASA Astrophysics Data System (ADS)

    Showalter, Allison R.; Szymanowski, Jennifer E. S.; Fein, Jeremy B.; Bunker, Bruce A.

    2016-05-01

    X-ray absorption spectroscopy (XAS) and cadmium (Cd) isotherm experiments determine how Cd adsorbs to the surface of halophilic archaeon Halobacterium noricense. This archaeon, isolated from the Waste Isolation Pilot Plant (WIPP) near Carlsbad, New Mexico could be involved with the transport of toxic metals stored in the transuranic waste in the salt mine. The isotherm experiments show that adsorption is relatively constant across the tolerable pH range for H. noricense. The XAS results indicate that Cd adsorption occurs predominately via a sulfur site, most likely sulfhydryl, with the same site dominating all measured pH values.

  5. Bioacoustic Absorption Spectroscopy

    DTIC Science & Technology

    2016-06-07

    seas in co-operation with fisheries biologists. The first planned experiment will be in the seas off California in co-operation with the Southwest... Fisheries Science Center of NOAA’s National Marine Fisheries Service. These experiments will be designed to investigate the “signatures” of the two major...formulating environmental adaptation strategies for tactical sonars. Fisheries applications: These results suggest that bioacoustic absorptivity can be used to

  6. Note: Sample chamber for in situ x-ray absorption spectroscopy studies of battery materials

    SciTech Connect

    Pelliccione, CJ; Timofeeva, EV; Katsoudas, JP; Segre, CU

    2014-12-01

    In situ x-ray absorption spectroscopy (XAS) provides element-specific characterization of both crystalline and amorphous phases and enables direct correlations between electrochemical performance and structural characteristics of cathode and anode materials. In situ XAS measurements are very demanding to the design of the experimental setup. We have developed a sample chamber that provides electrical connectivity and inert atmosphere for operating electrochemical cells and also accounts for x-ray interactions with the chamber and cell materials. The design of the sample chamber for in situ measurements is presented along with example XAS spectra from anode materials in operating pouch cells at the Zn and Sn K-edges measured in fluorescence and transmission modes, respectively. (C) 2014 AIP Publishing LLC.

  7. High-resolution molybdenum K-edge X-ray absorption spectroscopy analyzed with time-dependent density functional theory.

    PubMed

    Lima, Frederico A; Bjornsson, Ragnar; Weyhermüller, Thomas; Chandrasekaran, Perumalreddy; Glatzel, Pieter; Neese, Frank; DeBeer, Serena

    2013-12-28

    X-ray absorption spectroscopy (XAS) is a widely used experimental technique capable of selectively probing the local structure around an absorbing atomic species in molecules and materials. When applied to heavy elements, however, the quantitative interpretation can be challenging due to the intrinsic spectral broadening arising from the decrease in the core-hole lifetime. In this work we have used high-energy resolution fluorescence detected XAS (HERFD-XAS) to investigate a series of molybdenum complexes. The sharper spectral features obtained by HERFD-XAS measurements enable a clear assignment of the features present in the pre-edge region. Time-dependent density functional theory (TDDFT) has been previously shown to predict K-pre-edge XAS spectra of first row transition metal compounds with a reasonable degree of accuracy. Here we extend this approach to molybdenum K-edge HERFD-XAS and present the necessary calibration. Modern pure and hybrid functionals are utilized and relativistic effects are accounted for using either the Zeroth Order Regular Approximation (ZORA) or the second order Douglas-Kroll-Hess (DKH2) scalar relativistic approximations. We have found that both the predicted energies and intensities are in excellent agreement with experiment, independent of the functional used. The model chosen to account for relativistic effects also has little impact on the calculated spectra. This study provides an important calibration set for future applications of molybdenum HERFD-XAS to complex catalytic systems.

  8. Quantitative investigation of two metallohydrolases by X-ray absorption spectroscopy near-edge spectroscopy

    NASA Astrophysics Data System (ADS)

    Zhao, W.; Chu, W. S.; Yang, F. F.; Yu, M. J.; Chen, D. L.; Guo, X. Y.; Zhou, D. W.; Shi, N.; Marcelli, A.; Niu, L. W.; Teng, M. K.; Gong, W. M.; Benfatto, M.; Wu, Z. Y.

    2007-09-01

    The last several years have witnessed a tremendous increase in biological applications using X-ray absorption spectroscopy (BioXAS), thanks to continuous advancements in synchrotron radiation (SR) sources and detector technology. However, XAS applications in many biological systems have been limited by the intrinsic limitations of the Extended X-ray Absorption Fine Structure (EXAFS) technique e.g., the lack of sensitivity to bond angles. As a consequence, the application of the X-ray absorption near-edge structure (XANES) spectroscopy changed this scenario that is now continuously changing with the introduction of the first quantitative XANES packages such as Minut XANES (MXAN). Here we present and discuss the XANES code MXAN, a novel XANES-fitting package that allows a quantitative analysis of experimental data applied to Zn K-edge spectra of two metalloproteins: Leptospira interrogans Peptide deformylase ( LiPDF) and acutolysin-C, a representative of snake venom metalloproteinases (SVMPs) from Agkistrodon acutus venom. The analysis on these two metallohydrolases reveals that proteolytic activities are correlated to subtle conformation changes around the zinc ion. In particular, this quantitative study clarifies the occurrence of the LiPDF catalytic mechanism via a two-water-molecules model, whereas in the acutolysin-C we have observed a different proteolytic activity correlated to structural changes around the zinc ion induced by pH variations.

  9. X-ray absorption and photoelectron spectroscopy studies on graphite and single-walled carbon nanotubes: Oxygen effect

    NASA Astrophysics Data System (ADS)

    Abbas, M.; Wu, Z. Y.; Zhong, J.; Ibrahim, K.; Fiori, A.; Orlanducci, S.; Sessa, V.; Terranova, M. L.; Davoli, Ivan

    2005-08-01

    We have investigated the electronic states of highly oriented pyrolitic graphite and single-walled carbon nanotubes using x-ray absorption spectroscopy (XAS) before and after annealing treatment in ultrahigh vacuum, and observed that the small peak between π* and σ* features, which has been previously assigned to free-electron-like interlayer states, disappears after in situ annealing treatment, suggesting that the signal may be assigned to a surface contamination, especially oxygen contamination introduced by chemical processing or gas adsorption. Additional experiments by photoelectron spectroscopy as well as XAS methods, performed after aging in air, fully support this interpretation.

  10. Growth of block copolymer stabilized metal nanoparticles probed simultaneously by in situ XAS and UV-Vis spectroscopy.

    PubMed

    Nayak, C; Bhattacharyya, D; Jha, S N; Sahoo, N K

    2016-01-01

    The growth of Au and Pt nanoparticles from their respective chloride precursors using block copolymer-based reducers has been studied by simultaneous in situ measurement of XAS and UV-Vis spectroscopy at the energy-dispersive EXAFS beamline (BL-08) at INDUS-2 SRS at RRCAT, Indore, India. While the XANES spectra of the precursor give real-time information on the reduction process, the EXAFS spectra reveal the structure of the clusters formed at the intermediate stages of growth. The growth kinetics of both types of nanoparticles are found to be almost similar and are found to follow three stages, though the first stage of nucleation takes place earlier in the case of Au than in the case of Pt nanoparticles due to the difference in the reduction potential of the respective precursors. The first two stages of the growth of Au and Pt nanoparticles as obtained by in situ XAS measurements could be corroborated by simultaneous in situ measurement of UV-Vis spectroscopy also.

  11. A Complete Overhaul of the Electron Energy-Loss Spectroscopy and X-Ray Absorption Spectroscopy Database: eelsdb.eu.

    PubMed

    Ewels, Philip; Sikora, Thierry; Serin, Virginie; Ewels, Chris P; Lajaunie, Luc

    2016-06-01

    The electron energy-loss spectroscopy (EELS) and X-ray absorption spectroscopy (XAS) database has been completely rewritten, with an improved design, user interface, and a number of new tools. The database is accessible at https://eelsdb.eu/ and can now be used without registration. The submission process has been streamlined to encourage spectrum submissions and the new design gives greater emphasis on contributors' original work by highlighting their papers. With numerous new filters and a powerful search function, it is now simple to explore the database of several hundred EELS and XAS spectra. Interactive plots allow spectra to be overlaid, facilitating online comparison. An application-programming interface has been created, allowing external tools and software to easily access the information held within the database. In addition to the database itself, users can post and manage job adverts and read the latest news and events regarding the EELS and XAS communities. In accordance with the ongoing drive toward open access data increasingly demanded by funding bodies, the database will facilitate open access data sharing of EELS and XAS spectra.

  12. The apparent absence of chemical sensitivity in the 4d and 5d X-ray absorption spectroscopy of uranium compounds

    SciTech Connect

    Tobin, J. G.

    2013-05-03

    X-ray absorption spectroscopy (XAS) and related derivative measurements have been used to demonstrate that the Pu 5f states are strongly relativistic and have a 5f occupation number near 5. Owing to the success in this regime, it has been argued that the XAS measurements should be a powerful tool to probe 5f occupation variation, both as a function of elemental nature (actinide atomic number) and as a function of physical and chemical perturbation, e.g., oxidation state. We show that XAS and its related measurements fail in this latter aspect for a wide variety of uranium compounds and materials. Possible causes will be discussed.

  13. Capturing Transient Electronic and Molecular Structures in Liquids by Picosecond X-Ray Absorption Spectroscopy

    SciTech Connect

    Gawelda, W.; Pham, V. T.; El Nahhas, A.; Kaiser, M.; Zaushitsyn, Y.; Bressler, C.; Chergui, M.; Johnson, S. L.; Grolimund, D.; Abela, R.; Hauser, A.

    2007-02-02

    We describe an advanced setup for time-resolved x-ray absorption fine structure (XAFS) Spectroscopy with picosecond temporal resolution. It combines an intense femtosecond laser source synchronized to the x-ray pulses delivered into the microXAS beamline of the Swiss Light Source (SLS). The setup is applied to measure the short-lived high-spin geometric structure of photoexcited aqueous Fe(bpy)3 at room temperature.

  14. X-Ray Absorption Spectroscopy of Uranium Dioxide

    SciTech Connect

    Tobin, J G

    2010-12-10

    After the CMMD Seminar by Sung Woo Yu on the subject of the x-ray spectroscopy of UO2, there arose some questions concerning the XAS of UO2. These questions can be distilled down to these three issues: (1) The validity of the data; (2) The monchromator energy calibration; and (3) The validity of XAS component of the figure shown. The following will be shown: (1) The data is valid; (2) It is possible to calibrate the monchromator; and (3) The XAS component of the above picture is correct. The remainder of this document is in three sections, corresponding to these three issues.

  15. Material/element-dependent fluorescence-yield modes on soft X-ray absorption spectroscopy of cathode materials for Li-ion batteries

    DOE PAGES

    Asakura, Daisuke; Hosono, Eiji; Nanba, Yusuke; ...

    2016-03-07

    Here, we evaluate the utilities of fluorescence-yield (FY) modes in soft X-ray absorption spectroscopy (XAS) of several cathodematerials for Li-ion batteries. In the case of total-FY (TFY) XAS for LiNi0.5Mn1.5O4, the line shape of the Mn L3-edge XAS was largely distorted by the self-absorption and saturation effects, while the distortions were less pronounced at the NiL3 edge. The distortions were suppressed for the inverse-partial-FY (IPFY) spectra. We found that, in the cathodematerials, the IPFY XAS is highly effective for the Cr, Mn, and Fe L edges and the TFY and PFY modes are useful enough for the NiL edge whichmore » is far from the O K edge.« less

  16. Material/element-dependent fluorescence-yield modes on soft X-ray absorption spectroscopy of cathode materials for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Asakura, Daisuke; Hosono, Eiji; Nanba, Yusuke; Zhou, Haoshen; Okabayashi, Jun; Ban, Chunmei; Glans, Per-Anders; Guo, Jinghua; Mizokawa, Takashi; Chen, Gang; Achkar, Andrew J.; Hawthron, David G.; Regier, Thomas Z.; Wadati, Hiroki

    2016-03-01

    We evaluate the utilities of fluorescence-yield (FY) modes in soft X-ray absorption spectroscopy (XAS) of several cathode materials for Li-ion batteries. In the case of total-FY (TFY) XAS for LiNi0.5Mn1.5O4, the line shape of the Mn L3-edge XAS was largely distorted by the self-absorption and saturation effects, while the distortions were less pronounced at the Ni L3 edge. The distortions were suppressed for the inverse-partial-FY (IPFY) spectra. We found that, in the cathode materials, the IPFY XAS is highly effective for the Cr, Mn, and Fe L edges and the TFY and PFY modes are useful enough for the Ni L edge which is far from the O K edge.

  17. Low absorption vitreous carbon reactors for operando XAS: a case study on Cu/Zeolites for selective catalytic reduction of NO(x) by NH3.

    PubMed

    Kispersky, Vincent F; Kropf, A Jeremy; Ribeiro, Fabio H; Miller, Jeffrey T

    2012-02-21

    We describe the use of vitreous carbon as an improved reactor material for an operando X-ray absorption spectroscopy (XAS) plug-flow reactor. These tubes significantly broaden the operating range for operando experiments. Using selective catalytic reduction (SCR) of NO(x) by NH(3) on Cu/Zeolites (SSZ-13, SAPO-34 and ZSM-5) as an example reaction, we illustrate the high-quality XAS data achievable with these reactors. The operando experiments showed that in Standard SCR conditions of 300 ppm NO, 300 ppm NH(3), 5% O(2), 5% H(2)O, 5% CO(2) and balance He at 200 °C, the Cu was a mixture of Cu(I) and Cu(II) oxidation states. XANES and EXAFS fitting found the percent of Cu(I) to be 15%, 45% and 65% for SSZ-13, SAPO-34 and ZSM-5, respectively. For Standard SCR, the catalytic rates per mole of Cu for Cu/SSZ-13 and Cu/SAPO-34 were about one third of the rate per mole of Cu on Cu/ZSM-5. Based on the apparent lack of correlation of rate with the presence of Cu(I), we propose that the reaction occurs via a redox cycle of Cu(I) and Cu(II). Cu(I) was not found in in situ SCR experiments on Cu/Zeolites under the same conditions, demonstrating a possible pitfall of in situ measurements. A Cu/SiO(2) catalyst, reduced in H(2) at 300 °C, was also used to demonstrate the reactor's operando capabilities using a bending magnet beamline. Analysis of the EXAFS data showed the Cu/SiO(2) catalyst to be in a partially reduced Cu metal-Cu(I) state. In addition to improvements in data quality, the reactors are superior in temperature, stability, strength and ease of use compared to previously proposed borosilicate glass, polyimide tubing, beryllium and capillary reactors. The solid carbon tubes are non-porous, machinable, can be operated at high pressure (tested at 25 bar), are inert, have high material purity and high X-ray transmittance.

  18. Time-resolved x-ray absorption spectroscopy with a water window high-harmonic source

    NASA Astrophysics Data System (ADS)

    Pertot, Yoann; Schmidt, Cédric; Matthews, Mary; Chauvet, Adrien; Huppert, Martin; Svoboda, Vit; von Conta, Aaron; Tehlar, Andres; Baykusheva, Denitsa; Wolf, Jean-Pierre; Wörner, Hans Jakob

    2017-01-01

    Time-resolved x-ray absorption spectroscopy (TR-XAS) has so far practically been limited to large-scale facilities, to subpicosecond temporal resolution, and to the condensed phase. We report the realization of TR-XAS with a temporal resolution in the low femtosecond range by developing a tabletop high-harmonic source reaching up to 350 electron volts, thus partially covering the spectral region of 280 to 530 electron volts, where water is transmissive. We used this source to follow previously unexamined light-induced chemical reactions in the lowest electronic states of isolated CF4+ and SF6+ molecules in the gas phase. By probing element-specific core-to-valence transitions at the carbon K-edge or the sulfur L-edges, we characterized their reaction paths and observed the effect of symmetry breaking through the splitting of absorption bands and Rydberg-valence mixing induced by the geometry changes.

  19. X-Ray Absorption Spectroscopy and Computer Modelling Study of Nanocrystalline Binary Alkaline Earth Fluorides

    NASA Astrophysics Data System (ADS)

    Chadwick, A. V.; Düvel, A.; Heitjans, P.; Pickup, D. M.; Ramos, S.; Sayle, D. C.; Sayle, T. X. T.

    2015-04-01

    Nanocrystalline samples of Ba1-xCaxF2 prepared by high-energy milling show an unusually high F- ion conductivity, which exhibit a maximum in the magnitude and a minimum in the activation energy at x = 0.5. Here, we report an X-ray absorption spectroscopy (XAS) at the Ca and Sr K edges and the Ba L3 edge and a molecular dynamics (MD) simulation study of the pure and mixed fluorides. The XAS measurements on the pure binary fluorides, CaF2, SrF2 and BaF2 show that high-energy ball-milling produces very little amorphous material, in contrast to the results for ball milled oxides. XAS measurements of Ba1-xCaxF2 reveal that for 0 < x <1 there is considerable disorder in the local environments of the cations which is highest for x = 0.5. Hence the maximum in the conductivity corresponds to the composition with the maximum level of local disorder. The MD calculations also show a highly disordered structure consistent with the XAS results and similarly showing maximum disorder at x = 0.5.

  20. Absorption Spectroscopy in Homogeneous and Micellar Solutions.

    ERIC Educational Resources Information Center

    Shah, S. Sadiq; Henscheid, Leonard G.

    1983-01-01

    Describes an experiment which has helped physical chemistry students learn principles of absorption spectroscopy, the effect of solvent polarity on absorption spectra, and some micellar chemistry. Background information and experimental procedures are provided. (JN)

  1. Atomic absorption spectroscopy in ion channel screening.

    PubMed

    Stankovich, Larisa; Wicks, David; Despotovski, Sasko; Liang, Dong

    2004-10-01

    This article examines the utility of atomic absorption spectroscopy, in conjunction with cold flux assays, to ion channel screening. The multiplicity of ion channels that can be interrogated using cold flux assays and atomic absorption spectroscopy is summarized. The importance of atomic absorption spectroscopy as a screening tool is further elaborated upon by providing examples of the relevance of ion channels to various physiological processes and targeted diseases.

  2. Adsorption of mercury on lignin: combined surface complexation modeling and X-ray absorption spectroscopy studies.

    PubMed

    Lv, Jitao; Luo, Lei; Zhang, Jing; Christie, Peter; Zhang, Shuzhen

    2012-03-01

    Adsorption of mercury (Hg) on lignin was studied at a range of pH values using a combination of batch adsorption experiments, a surface complexation model (SCM) and synchrotron X-ray absorption spectroscopy (XAS). Surface complexation modeling indicates that three types of acid sites on lignin surfaces, namely aliphatic carboxylic-, aromatic carboxylic- and phenolic-type surface groups, contributed to Hg(II) adsorption. The bond distance and coordination number of Hg(II) adsorption samples at pH 3.0, 4.0 and 5.5 were obtained from extended X-ray absorption fine structure (EXAFS) spectroscopy analysis. The results of SCM and XAS combined reveal that the predominant adsorption species of Hg(II) on lignin changes from HgCl(2)(0) to monodentate complex -C-O-HgCl and then bidentate complex -C-O-Hg-O-C- with increasing pH value from 2.0 to 6.0. The good agreement between SCM and XAS results provides new insight into understanding the mechanisms of Hg(II) adsorption on lignin.

  3. 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.

  4. The use of (micro)-X-ray absorption spectroscopy in cement research.

    PubMed

    Scheidegger, A M; Vespa, M; Grolimund, D; Wieland, E; Harfouche, M; Bonhoure, I; Dähn, R

    2006-01-01

    Long-term predictions on the mobility and the fate of radionuclides and contaminants in cementitious waste repositories require a molecular-level understanding of the geochemical immobilization processes involved. In this study, the use of X-ray absorption spectroscopy (XAS) for chemical speciation of trace elements in cementitious materials will be outlined presenting two examples relevant for nuclear waste management. The first example addresses the use of XAS on powdered cementitious materials to determine the local coordination environment of Sn(IV) bound to calcium silicate hydrates (C-S-H). Sn K-edge XAS data of Sn(IV) doped C-S-H can be rationalized by corner sharing binding of Sn octahedra to Si tetrahedra of the C-S-H structure. XAS was further applied to determine the binding mechanism of Sn(IV) in the complex cement matrix. The second example illustrates the potential of emerging synchrotron-based X-ray micro-probe techniques for elucidating the spatial distribution and the speciation of contaminants in highly heterogeneous cementitious materials at the micro-scale. Micro X-ray fluorescence (XRF) and micro-XAS investigations were carried out on Co(II) doped hardened cement paste. These preliminary investigations reveal a highly heterogeneous spatial Co distribution. The presence of a Co(II)-hydroxide-like phase Co(OH)2 and/or Co-Al layered double hydroxide (Co-Al LDH) or Co-phyllosilicate was observed. Surprisingly, some of the initial Co(II) was partially oxidized and incorporated into a Co(III)O(OH)-like phase or a Co-phyllomanganate.

  5. Low-dimensional systems investigated by x-ray absorption spectroscopy: a selection of 2D, 1D and 0D cases

    NASA Astrophysics Data System (ADS)

    Mino, Lorenzo; Agostini, Giovanni; Borfecchia, Elisa; Gianolio, Diego; Piovano, Andrea; Gallo, Erik; Lamberti, Carlo

    2013-10-01

    Over the last three decades low-dimensional systems have attracted increasing interest both from the fundamental and technological points of view due to their unique physical and chemical properties. X-ray absorption spectroscopy (XAS) is a powerful tool for the characterization of such kinds of systems, owing to its chemical selectivity and high sensitivity in interatomic distance determination. Moreover, XAS does not require long-range ordering, that is usually absent in low-dimensional systems. Finally, this technique can simultaneously provide information on electronic and local structural properties of the nanomaterials, significantly contributing to clarify the relation between their atomic structure and their peculiar physical properties. This review provides a general introduction to XAS, discussing the basic theory of the technique, the most used detection modes, the related experimental setups and some complementary relevant characterization techniques (diffraction anomalous fine structure, extended energy-loss fine structure, pair distribution function, x-ray emission spectroscopy, high-energy resolution fluorescence detected XAS and x-ray Raman scattering). Subsequently, a selection of significant applications of XAS to two-, one- and zero-dimensional systems will be presented. The selected low-dimensional systems include IV and III-V semiconductor films, quantum wells, quantum wires and quantum dots; carbon-based nanomaterials (epitaxial graphene and carbon nanotubes); metal oxide films, nanowires, nanorods and nanocrystals; metal nanoparticles. Finally, the future perspectives for the application of XAS to nanostructures are discussed.

  6. Millisecond Kinetics of Nanocrystal Cation Exchange UsingMicrofluidic X-ray Absorption Spectroscopy

    SciTech Connect

    Chan, Emory M.; Marcus, Matthew A.; Fakra, Sirine; Elnaggar,Mariam S.; Mathies, Richard A.; Alivisatos, A. Paul

    2007-05-07

    We describe the use of a flow-focusing microfluidic reactorto measure the kinetics of theCdSe-to-Ag2Se nanocrystal cation exchangereaction using micro-X-ray absorption spectroscopy (mu XAS). The smallmicroreactor dimensions facilitate the millisecond mixing of CdSenanocrystal and Ag+ reactant solutions, and the transposition of thereaction time onto spatial coordinates enables the in situ observation ofthe millisecond reaction with mu XAS. XAS spectra show the progression ofCdSe nanocrystals to Ag2Se over the course of 100 ms without the presenceof long-lived intermediates. These results, along with supporting stoppedflow absorption experiments, suggest that this nanocrystal cationexchange reaction is highly efficient and provide insight into how thereaction progresses in individual particles. This experiment illustratesthe value and potential of in situ microfluidic X-ray synchrotrontechniques for detailed studies of the millisecond structuraltransformations of nanoparticles and other solution-phase reactions inwhich diffusive mixing initiates changes in local bond structures oroxidation states.

  7. X-RAY ABSORPTION SPECTROSCOPY OF YB3+-DOPED OPTICAL FIBERS

    SciTech Connect

    Citron, Robert; Kropf, A.J.

    2008-01-01

    Optical fibers doped with Ytterbium-3+ have become increasingly common in fiber lasers and amplifiers. Yb-doped fibers provide the capability to produce high power and short pulses at specific wavelengths, resulting in highly effective gain media. However, little is known about the local structure, distribution, and chemical coordination of Yb3+ in the fibers. This information is necessary to improve the manufacturing process and optical qualities of the fibers. Five fibers doped with Yb3+ were studied using Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy and X-ray Absorption Near Edge Spectroscopy (XANES), in addition to Yb3+ mapping. The Yb3+ distribution in each fiber core was mapped with 2D and 1D intensity scans, which measured X-ray fluorescence over the scan areas. Two of the five fibers examined showed highly irregular Yb3+ distributions in the core center. In four of the five fibers Yb3+ was detected outside of the given fiber core dimensions, suggesting possible Yb3+ diffusion from the core, manufacturing error, or both. X-ray absorption spectroscopy (XAS) analysis has so far proven inconclusive, but did show that the fibers had differing EXAFS spectra. The Yb3+ distribution mapping proved highly useful, but additional modeling and examination of fiber preforms must be conducted to improve XAS analysis, which has been shown to have great potential for the study of similar optical fi bers.

  8. Redox State of Iron in Lunar Glasses using X-ray Absorption Spectroscopy and Multivariate Analysis

    NASA Astrophysics Data System (ADS)

    Dyar, M. D.; McCanta, M. C.; Lanzirotti, A.; Sutton, S. R.; Carey, C. J.; Mahadevan, S.; Rutherford, M. J.

    2014-12-01

    The oxidation state of igneous materials on a planet is a critically-important variable in understanding magma evolution on bodies in our solar system. However, direct and indirect methods for quantifying redox states are challenging, especially across the broad spectrum of silicate glass compositions found on airless bodies. On the Moon, early Mössbauer studies of bulk samples suggested the presence of significant Fe3+ (>10%) in lunar glasses (green, orange, brown); lunar analog glasses synthesized at fO2 <10-11 have similar Fe3+. All these Mössbauer spectra are challenging to interpret due to the presence of multiple coordination environments in the glasses. X-ray absorption spectroscopy (XAS) allows pico- and nano-scale interrogation of primitive planetary materials using the pre-edge, main edge, and EXAFS regions of absorption edge spectra. Current uses of XAS require availability of standards with compositions similar to those of unknowns and complex procedures for curve-fitting of pre-edge features that produce results with poorly constrained accuracy. A new approach to accurate and quantitative redox measurements with XAS is to couple use of spectra from synthetic glass standards covering a broad compositional range with multivariate analysis (MVA) techniques. Mössbauer and XAS spectra from a suite of 33 synthetic glass standards covering a wide range of compositions and fO2(Dyar et al., this meeting) were used to develop a MVA model that utilizes valuable predictive information not only in the major spectral peaks/features, but in all channels of the XAS region. Algorithms for multivariate analysis t were used to "learn" the characteristics of a data set as a function of varying spectral characteristics. These models were applied to the study of lunar glasses, which provide a challenging test case for these newly-developed techniques due to their very low fO2. Application of the new XAS calibration model to Apollo 15 green (15426, 15427 and 15425

  9. Ce electronic states in Nd(0.45-x)Ce(x)Sr0.55MnO3 probed by x-ray absorption spectroscopy and photoemission.

    PubMed

    Shirai, T; Imada, S; Higashiya, A; Sekiyama, A; Suga, S; Muro, T; Tanaka, Y; Tamasaku, K; Yabashi, M; Ishikawa, T; Miyasaka, S; Tokura, Y

    2013-10-16

    We have investigated the Ce 4f electronic states in the Ce-doped manganites Nd(0.45-x)Ce(x)Sr0.55MnO3 (NCSMO) by means of x-ray absorption spectroscopy (XAS) and hard x-ray photoelectron spectroscopy (HAXPES). The Ce 3d XAS shows that the Ce ions exist in the form of the Ce(3+) and Ce(4+) mixed-valent states, and we have found that the XAS spectral features change with temperature. The Ce 3d XAS and HAXPES spectra for NCSMO agree reasonably well with calculated results based on the single-impurity Anderson model, which takes into account the atomic multiplets and two valence bands. The estimated Ce bulk valence of Nd0.15Ce0.3Sr0.55MnO3 decreases from 3.44 to 3.30 with cooling.

  10. Incorporation of Trace Elements in Ancient and Modern Human Bone: An X-Ray Absorption Spectroscopy Study

    NASA Astrophysics Data System (ADS)

    Pingitore, N. E.; Cruz-Jimenez, G.; Price, T. D.

    2001-12-01

    X-ray absorption spectroscopy (XAS) affords the opportunity to probe the atomic environment of trace elements in human bone. We are using XAS to investigate the mode(s) of incorporation of Sr, Zn, Pb, and Ba in both modern and ancient (and thus possibly altered) human and animal bone. Because burial and diagenesis may add trace elements to bone, we performed XAS analysis on samples of pristine contemporary and ancient, buried human and animal bone. We assume that deposition of these elements during burial occurs by processes distinct from those in vivo, and this will be reflected in their atomic environments. Archaeologists measure strontium in human and animal bone as a guide to diet. Carnivores show lower Sr/Ca ratios than their herbivore prey due to discrimination against Sr relative to Ca up the food chain. In an initial sample suite no difference was observed between modern and buried bone. Analysis of additional buried samples, using a more sensitive detector, revealed significant differences in the distance to the second and third neighbors of the Sr in some of the buried samples. Distances to the first neighbor, oxygen, were similar in all samples. Zinc is also used in paleo-diet studies. Initial x-ray absorption spectroscopy of a limited suite of bones did not reveal any differences between modern and buried samples. This may reflect the limited number of samples examined or the low levels of Zn in typical aqueous solutions in soils. Signals from barium and lead were too low to record useful XAS spectra. Additional samples will be studied for Zn, Ba, and Pb. We conducted our XAS experiments on beam lines 4-1 and 4-3 at the Stanford Synchrotron Radiation Laboratory. Data were collected in the fluorescence mode, using a Lytle detector and appropriate filter, and a solid state, 13-element Ge-detector.

  11. Atomic-scale roughness of Li metal surface evident in soft X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Prendergast, David; Wan, Liwen; Liang, Yufeng; Chuang, Yi-De; Qiao, Ruimin; Yan, Shishen; Yang, Wanli

    2015-03-01

    Realizing Li metal electrodes depends on fundamental understanding and efficient control of surface properties, which requires reliable characterization of the Li metal surface. Controlled experiments of Li K-edge soft X-ray absorption spectroscopy (XAS) reveal evidence of steady oxidation of the Li metal surface even under ultrahigh vacuum (UHV) conditions. The XAS of the short-lived Li metal surface, prepared by in-situ scratching, exhibits a prominent peak at 55.6 eV, more intense and at a slightly higher energy than the first peak expected for bulk Li metal at 55 eV. First-principles XAS calculations explain the origin of both the increased intensity and energy shift. This required the use of surface structural models with under-coordinated Li atoms and an estimated 4 Åinelastic mean-free-path for Auger electrons, implying extreme surface sensitivity of the measurements to the first 2-3 atomic layers. This work provides a benchmark on both experiment and theory for further studies of Li and other reactive metal surfaces, which are currently under scrutiny for next-generation energy storage devices. DP, LW, and YL acknowledge support from the Joint Center for Energy Storage Research, an Energy Innovation Hub funded by the US Dept. of Energy, Office of Science, Basic Energy Sciences.

  12. X-ray absorption spectroscopy of lithium sulfur battery reaction intermediates

    NASA Astrophysics Data System (ADS)

    Wujcik, Kevin; Pascal, Tod; Prendergast, David; Balsara, Nitash

    2015-03-01

    Lithium sulfur batteries have a theoretical energy density nearly five times greater than current lithium ion battery standards, but questions still remain regarding the reaction pathways through which soluble lithium polysulfide (Li2Sx, ``x'' ranging from 2 to 8) reaction intermediates are formed. Complicating spectroelectrochemical approaches to elucidate redox pathways is the challenge of obtaining spectral standards for individual Li2Sx species. Lithium polysulfides cannot be isolated as individual component and exist only in solution as a distribution of different Li2Sx molecules formed via disproportionation reactions (e.g. 2Li2S4 goes to Li2S3 + Li2S5). X-ray absorption spectroscopy (XAS) at the sulfur K-edge has recently been employed as a technique to study Li-S chemistry. We have recently obtained XAS standards for individual Li2Sx species via first principles DFT simulations and the excited electron and core hole approach. Here, experimental sulfur K-edge XAS of Li2Sx species dissolved in poly(ethylene oxide) are compared to spectra obtained from analogous theoretical calculations. The impact that polysulfide solution concentration and the presence of other lithium salts (e.g. LiNO3) have on X-ray spectra of Li2Sx species is explored via experiment and theory.

  13. High energy resolution five-crystal spectrometer for high quality fluorescence and absorption measurements on an x-ray absorption spectroscopy beamline

    SciTech Connect

    Llorens, Isabelle; Lahera, Eric; Delnet, William; Proux, Olivier; Dermigny, Quentin; Gelebart, Frederic; Morand, Marc; Shukla, Abhay; Bardou, Nathalie; Ulrich, Olivier; and others

    2012-06-15

    Fluorescence detection is classically achieved with a solid state detector (SSD) on x-ray absorption spectroscopy (XAS) beamlines. This kind of detection however presents some limitations related to the limited energy resolution and saturation. Crystal analyzer spectrometers (CAS) based on a Johann-type geometry have been developed to overcome these limitations. We have tested and installed such a system on the BM30B/CRG-FAME XAS beamline at the ESRF dedicated to the structural investigation of very dilute systems in environmental, material and biological sciences. The spectrometer has been designed to be a mobile device for easy integration in multi-purpose hard x-ray synchrotron beamlines or even with a laboratory x-ray source. The CAS allows to collect x-ray photons from a large solid angle with five spherically bent crystals. It will cover a large energy range allowing to probe fluorescence lines characteristic of all the elements from Ca (Z = 20) to U (Z = 92). It provides an energy resolution of 1-2 eV. XAS spectroscopy is the main application of this device even if other spectroscopic techniques (RIXS, XES, XRS, etc.) can be also achieved with it. The performances of the CAS are illustrated by two experiments that are difficult or impossible to perform with SSD and the complementarity of the CAS vs SSD detectors is discussed.

  14. The apparent absence of chemical sensitivity in the 4d and 5d X-ray absorption spectroscopy of uranium compounds

    DOE PAGES

    Tobin, J. G.

    2013-05-03

    X-ray absorption spectroscopy (XAS) and related derivative measurements have been used to demonstrate that the Pu 5f states are strongly relativistic and have a 5f occupation number near 5. Owing to the success in this regime, it has been argued that the XAS measurements should be a powerful tool to probe 5f occupation variation, both as a function of elemental nature (actinide atomic number) and as a function of physical and chemical perturbation, e.g., oxidation state. We show that XAS and its related measurements fail in this latter aspect for a wide variety of uranium compounds and materials. Possible causesmore » will be discussed.« less

  15. Cavity Enhanced Ultrafast Transient Absorption Spectroscopy

    NASA Astrophysics Data System (ADS)

    Allison, Thomas K.; Reber, Melanie Roberts; Chen, Yuning

    2015-06-01

    Ultrafast spectroscopy on gas phase systems is typically restricted to techniques involving photoionization, whereas solution phase experiments utilize the detection of light. At Stony Brook, we are developing new techniques for performing femtosecond time-resolved spectroscopy using frequency combs and high-finesse optical resonators. A large detection sensitivity enhancement over traditional methods enables the extension of all-optical ultrafast spectroscopies, such as broad-band transient absorption spectroscopy (TAS) and 2D spectroscopy, to dilute gas phase samples produced in molecular beams. Here, gas phase data can be directly compared to solution phase data. Initial demonstration experiments are focusing on the photodissociation of iodine in small neutral argon clusters, where cluster size strongly influences the effects solvent-caging and geminate recombination. I will discuss these initial results, our high power home-built Yb:fiber laser systems, and also extensions of the methods to the mid-IR to study the vibrational dynamics of hydrogen bonded clusters.

  16. Electrochemical discharge of nanocrystalline magnetite: structure analysis using X-ray diffraction and X-ray absorption spectroscopy.

    PubMed

    Menard, Melissa C; Takeuchi, Kenneth J; Marschilok, Amy C; Takeuchi, Esther S

    2013-11-14

    Magnetite (Fe3O4) is an abundant, low cost, environmentally benign material with potential application in batteries. Recently, low temperature coprecipitation methods have enabled preparation of a series of nanocrystalline magnetite samples with a range of crystallite sizes. Electrochemical cells based on Li/Fe3O4 show a linear increase in capacity with decreasing crystallite size at voltages ≥1.2 V where a 2× capacity improvement relative to commercial (26.2 nm) magnetite is observed. In this report, a combination of X-ray powder diffraction (XRD) and X-ray absorption spectroscopy (XAS) is used to measure magnetite structural changes occurring upon electrochemical reduction, with parent Fe3O4 crystallite size as a variable. Notably, XAS provides evidence of metallic iron formation at high levels of electrochemical reduction.

  17. Speciation and Lability of Ag-, AgCl- and Ag2S-Nanoparticles in Soil Determined by X-ray Absorption Spectroscopy and Diffusive Gradients in Thin Films

    EPA Science Inventory

    Long-term speciation and lability of silver (Ag-), silver chloride (AgCl-) and silver sulfide nanoparticles (Ag2S-NPs) in soil were studied by X-ray absorption spectroscopy (XAS), and newly developed "nano" Diffusive Gradients in Thin Films (DGT) devices. These nano-D...

  18. X-ray absorption spectroscopy and EPR studies of oriented spinach thylakoid preparations

    SciTech Connect

    Andrews, J.C. |

    1995-08-01

    In this study, oriented Photosystem II (PS II) particles from spinach chloroplasts are studied with electron paramagnetic resonance (EPR) and x-ray absorption spectroscopy (XAS) to determine more details of the structure of the oxygen evolving complex (OEC). The nature of halide binding to Mn is also studied with Cl K-edge and Mn EXAFS (extended x-ray absorption fine structure) of Mn-Cl model compounds, and with Mn EXAFS of oriented PS II in which Br has replaced Cl. Attention is focused on the following: photosynthesis and the oxygen evolving complex; determination of mosaic spread in oriented photosystem II particles from signal II EPR measurement; oriented EXAFS--studies of PS II in the S{sub 2} state; structural changes in PS II as a result of treatment with ammonia: EPR and XAS studies; studies of halide binding to Mn: Cl K-edge and Mn EXAFS of Mn-Cl model compounds and Mn EXAFS of oriented Br-treated photosystem II.

  19. X-ray absorption spectroscopy as a probe of dissolved polysulfides in lithium sulfur batteries

    NASA Astrophysics Data System (ADS)

    Pascal, Tod; Prendergast, David

    2015-03-01

    There has been enormous interest lately in lithium sulfur batteries, since they have 5 times the theoretical capacity of lithium ion batteries. Large-scale adoption of this technology has been hampered by numerous shortcomings, chiefly the poor utilization of the active cathode material and rapid capacity fading during cycling. Overcoming these limitations requires methods capable of identifying and quantifying the products of the poorly understood electrochemical reactions. One recent advance has been the use of X-ray absorption spectroscopy (XAS), an element-specific probe of the unoccupied energy levels around an excited atom upon absorption of an X-ray photon, to identify the reaction products and intermediates. In this talk, we'll present first principles molecular dynamics and spectral simulations of dissolved lithium polysulfide species, showing how finite temperature dynamics, molecular geometry, molecular charge state and solvent environment conspire to determine the peak positions and intensity of the XAS. We'll present a spectral analysis of the radical (-1e charge) species, and reveal a unique low energy feature that can be used to identify these species from their more common dianion (-2e charge) counterparts.

  20. Resonant photoemission and X-ray absorption spectroscopies of lithiated magnetite thin film

    NASA Astrophysics Data System (ADS)

    Tsuchiya, Takashi; Kawamura, Kinya; Namiki, Wataru; Furuichi, Shoto; Takayanagi, Makoto; Minohara, Makoto; Kobayashi, Masaki; Horiba, Koji; Kumigashira, Hiroshi; Terabe, Kazuya; Higuchi, Tohru

    2017-04-01

    Resonant photoemission spectroscopy (RPES) and X-ray absorption spectroscopy (XAS) were used to investigate the effect of lithiation on the electronic structure of Fe3O4 thin film relevant to the operation mechanism of nanoionic devices to enable magnetic property tuning. Comparison of the Fe 2p XAS spectrum for lithiated Fe3O4 (Li-Fe3O4) with that for pristine Fe3O4 clearly demonstrated that the number of Fe2+ ions at octahedral B sites is increased by lithiation. The valence band RPES spectra of Li-Fe3O4 further showed that lithiation increases the density of states near the Fermi level originating Fe2+ ions at octahedral B sites. These findings agree well with the observed decrease in the saturation magnetization in the magnetization-magnetic field (M-H) loop of Li-Fe3O4 thin film, indicating that minority spins (down spins) increase (i.e., total spins decrease) due to lithiation. The variation in the number of Fe2+ ions at B sites is suggested to be an underlying operating mechanism of a nanoionics-based magnetic property tuning device.

  1. Examination of arsenic speciation in sulfidic solutions using X-ray absorption spectroscopy.

    PubMed

    Beak, Douglas G; Wilkin, Richard T; Ford, Robert G; Kelly, Shelly D

    2008-03-01

    Both thioarsenites and thioarsenates have been demonstrated to exist in sulfidic waters, yet there is uncertainty regarding the geochemical conditions that govern the formation of these arsenic species. The purpose of this research was to use advanced spectroscopy techniques, speciation modeling, and chromatography to elucidate the chemical speciation of arsenic in sulfidic solutions initially containing arsenite and sulfide. Results of X-ray absorption spectroscopy (XAS) show that experimental solutions contained mixtures of arsenite and thioarsenites with increasing substitution of sulfur for oxygen on arsenic as the sulfide concentration increased. Experimental samples showed no evidence of polymeric arsenic species, or transformation of thioarsenites to thioarsenates. The arsenic speciation measured using XAS was similar to predictions obtained from a thermodynamic model for arsenic speciation, excluding thioarsenate species in sulfidic systems. Our data cast some doubt on the application of chromatographic methods for determining thioarsenates and thioarsenites (or mixtures) in natural waters in cases where the arsenic oxidation state cannot be independently verified. The same chromatographic peak positions proposed for thioarsenates can be explained bythioarsenite species. Furthermore, sample dilution was shown to change the species distribution and care should be taken to avoid sample dilution prior to chromatographic analysis.

  2. Examination of arsenic speciation in sulfidic solutions using x-ray absorption spectroscopy.

    SciTech Connect

    Beak, D. G.; Wilkin, R. T.; Ford, R. G.; Kelly, S. D.; Biosciences Division; EPA

    2008-03-01

    Both thioarsenites and thioarsenates have been demonstrated to exist in sulfidic waters, yet there is uncertainty regarding the geochemical conditions that govern the formation of these arsenic species. The purpose of this research was to use advanced spectroscopy techniques, speciation modeling, and chromatography to elucidate the chemical speciation of arsenic in sulfidic solutions initially containing arsenite and sulfide. Results of X-ray absorption spectroscopy (XAS) show that experimental solutions contained mixtures of arsenite and thioarsenites with increasing substitution of sulfur for oxygen on arsenic as the sulfide concentration increased. Experimental samples showed no evidence of polymeric arsenic species, or transformation of thioarsenites to thioarsenates. The arsenic speciation measured using XAS was similar to predictions obtained from a thermodynamic model for arsenic speciation, excluding thioarsenate species in sulfidic systems. Our data cast some doubt on the application of chromatographic methods for determining thioarsenates and thioarsenites (or mixtures) in natural waters in cases where the arsenic oxidation state cannot be independently verified. The same chromatographic peak positions proposed for thioarsenates can be explained by thioarsenite species. Furthermore, sample dilution was shown to change the species distribution and care should be taken to avoid sample dilution prior to chromatographic analysis.

  3. Application of X-ray Absorption Spectroscopy to the study of nuclear structural materials

    NASA Astrophysics Data System (ADS)

    Liu, Shanshan

    One of key technologies for the next generation nuclear systems are advanced materials, including high temperature structural materials, fast neutron resistance core materials and so on. Local structure determination in these systems, which often are crystallographically intractable, is critical to gaining an understanding of their properties. In this thesis, X-ray Absorption Spectroscopy (XAS), including Extended X-ray Absorption Fine Structure (EXAFS) and X-ray Absorption Near Edge Structure (XANES), is used to examine the geometric and electronic structure of nuclear structural materials under varying conditions. The thesis is divided into two main sections. The first examines the structural analysis of nanostructured ferritic alloys (NFA) which are dispersion strengthened by an ultra high density of Y-Ti-O enriched nano-features, resulting in remarkable high temperature creep strength and radiation damage resistance. Titanium and Yttrium K-edge XAS shows commercial alloys MA957 and J12YWT more closely resemble the as received Fe-14Cr-3W-0.4Ti (wt. %) powders, and mechanically alloyed (MA) powders with 0.25Y2O3 (wt. %). It shows that a significant fraction of substitutional Ti remains dissolved in the (BCC) ferrite matrix. In contrast, annealed powders and hot isostatic press (HIP) consolidated alloys show high temperature heat treatments shift the Y and Ti to more oxidized states that are consistent with combinations of Y2Ti2O7 and, especially, TiO. The second section describes corrosion studies of Pb with 316L stainless steel, molybdenum and spinet (MgAl2O4) at high temperature by XAS. The corrosion of fuel cladding and structural materials by liquid lead at elevated temperatures is an issue that must be considered when designing advanced nuclear systems and high-power spallation neutron targets. The results of ex-situ studies show that a Mo substrate retained a smooth and less corroded surface than 316L stainless steel sample at elevated temperature. In

  4. Triplet absorption spectroscopy and electromagnetically induced transparency

    NASA Astrophysics Data System (ADS)

    Ghafoor, F.; Nazmitdinov, R. G.

    2016-09-01

    Coherence phenomena in a four-level atomic system, cyclically driven by three coherent fields, are investigated thoroughly at zero and weak magnetic fields. Each strongly interacting atomic state is converted to a triplet due to a dynamical Stark effect. Two dark lines with a Fano-like profile arise in the triplet absorption spectrum with anomalous dispersions. We provide conditions to control the widths of the transparency windows by means of the relative phase of the driving fields and the intensity of the microwave field, which closes the optical system loop. The effect of Doppler broadening on the results of the triplet absorption spectroscopy is analysed in detail.

  5. Soft X-ray absorption spectroscopy investigation of the surface chemistry and treatments of copper indium gallium diselenide (CIGS)

    SciTech Connect

    Schwartz, Craig; Nordlund, Dennis; Sokaras, Dimosthenis; Contreras, Miguel; Weng, Tsu -Chien; Mansfield, Lorelle; Hurst, Katherine E.; Dameron, Arrelaine; Ramanathan, Kannan; Prendergast, David; Christensen, Steven T.

    2016-11-10

    The surface and near surface structure of the copper-indium-gallium-selenide (CIGS) absorber layer is integral to producing of a high-quality photovoltaic junction. By using X-ray absorption spectroscopy (XAS) and monitoring multiple elemental absorption edges with both theory and experiment, we are able to identify several features of the surface of CIGS as a function of composition and surface treatments. The XAS data shows trends in the near surface region of oxygen, copper, indium and gallium species as the copper content is varied in the films. The oxygen surface species are also monitored through a series of experiments that systematically investigate the effects of water and various solutions of: ammonium hydroxide, cadmium sulfate, and thiourea. These being components of cadmium sulfide chemical bath deposition (CBD). Characteristics of the CBD are correlated with a restorative effect that produces a normalized, uniform surface chemistry as measured by XAS. This surface chemistry is found in CIGS solar cells with excellent power conversion efficiency (~19%). Finally, the results provide new insight for CIGS processing strategies that seek to replace CBD and/or cadmium sulfide.

  6. Soft X-ray absorption spectroscopy investigation of the surface chemistry and treatments of copper indium gallium diselenide (CIGS)

    DOE PAGES

    Schwartz, Craig; Nordlund, Dennis; Sokaras, Dimosthenis; ...

    2016-11-10

    The surface and near surface structure of the copper-indium-gallium-selenide (CIGS) absorber layer is integral to producing of a high-quality photovoltaic junction. By using X-ray absorption spectroscopy (XAS) and monitoring multiple elemental absorption edges with both theory and experiment, we are able to identify several features of the surface of CIGS as a function of composition and surface treatments. The XAS data shows trends in the near surface region of oxygen, copper, indium and gallium species as the copper content is varied in the films. The oxygen surface species are also monitored through a series of experiments that systematically investigate themore » effects of water and various solutions of: ammonium hydroxide, cadmium sulfate, and thiourea. These being components of cadmium sulfide chemical bath deposition (CBD). Characteristics of the CBD are correlated with a restorative effect that produces a normalized, uniform surface chemistry as measured by XAS. This surface chemistry is found in CIGS solar cells with excellent power conversion efficiency (~19%). Finally, the results provide new insight for CIGS processing strategies that seek to replace CBD and/or cadmium sulfide.« less

  7. Methane overtone absorption by intracavity laser spectroscopy

    NASA Technical Reports Server (NTRS)

    Obrien, James J.

    1990-01-01

    Interpretation of planetary methane (CH4) visible-near IR spectra, used to develop models of planetary atmospheres, has been hampered by a lack of suitable laboratory spectroscopic data. The particular CH4 spectral bands are due to intrinsically weak, high overtone-combination transitions too complex for classical spectroscopic analysis. The traditional multipass cell approach to measuring spectra of weakly absorbing species is insufficiently sensitive to yield reliable results for some of the weakest CH4 absorption features and is difficult to apply at the temperatures of the planetary environments. A time modulated form of intracavity laser spectroscopy (ILS), has been shown to provide effective absorption pathlengths of 100 to 200 km with sample cells less than 1 m long. The optical physics governing this technique and the experimental parameters important for obtaining reliable, quantitative results are now well understood. Quantitative data for CH4 absorption obtained by ILS have been reported recently. Illustrative ILS data for CH4 absorption in the 619.7 nm and 681.9 nm bands are presented. New ILS facilities at UM-St. Louis will be used to measure CH4 absorption in the 700 to 1000 nm region under conditions appropriate to the planetary atmospheres.

  8. Cadmium Chemical Form in Mine Waste Materials by X-ray Absorption Spectroscopy

    NASA Astrophysics Data System (ADS)

    Diacomanolis, V.; Ng, J. C.; Sadler, R.; Harris, H. H.; Nomura, M.; Noller, B. N.

    2010-06-01

    This study examines the molecular form of cadmium (Cd) present in mine wastes by X-ray Absorption Spectroscopy (XAS; Cd>20 mg/kg) using the K-edge of Cd at the Photon Factory Advanced Ring (PF-AR), NW10A beam line at KEK-Tsukuba-Japan. Mine waste materials and zinc concentrate were analyzed for Cd by ICPMS prior to undertaking XAS (range 21-452 mg/kg). Model compounds (CdO, Cd(OH)2, CdCO3, Cdacetate, CdS, Cdstearate, CdDEDTC) and samples were examined in solid form at 20 K. The XANES spectra showed similar E max values for both model compounds and samples. The EXAFS showed that Cd-S in CdS, gives a flatter spectrum in the extended region compared to Cd-O found with CdCO3, CdO and Cd Stearate. Linear combination fitting with model Cd compounds did not give clear assignments of composition, indicating that more detailed EXAFS spectra is required as mineral forms containing Cd were present rather than simple Cd compounds such as CdCO3. The Cd bond for a single shell model in mine waste sample matrices appears to be either Cd-O or Cd-S, or a combination of both. Comparison of molecular data from the XAS studies with bioaccessibility data giving a prediction of bioavailability for mine waste materials provides useful information about the significance of the cadmium form as a contaminant for health risk assessment purposes.

  9. Undistorted X-ray Absorption Spectroscopy Using s-Core-Orbital Emissions.

    PubMed

    Golnak, Ronny; Xiao, Jie; Atak, Kaan; Unger, Isaak; Seidel, Robert; Winter, Bernd; Aziz, Emad F

    2016-05-12

    Detection of secondary emissions, fluorescence yield (FY), or electron yield (EY), originating from the relaxation processes upon X-ray resonant absorption has been widely adopted for X-ray absorption spectroscopy (XAS) measurements when the primary absorption process cannot be probed directly in transmission mode. Various spectral distortion effects inherent in the relaxation processes and in the subsequent transportation of emitted particles (electron or photon) through the sample, however, undermine the proportionality of the emission signals to the X-ray absorption coefficient. In the present study, multiple radiative (FY) and nonradiative (EY) decay channels have been experimentally investigated on a model system, FeCl3 aqueous solution, at the excitation energy of the Fe L-edge. The systematic comparisons between the experimental spectra taken from various decay channels, as well as the comparison with the theoretically simulated Fe L-edge XA spectrum that involves only the absorption process, indicate that the detection of the Fe 3s → 2p partial fluorescence yield (PFY) gives rise to the true Fe L-edge XA spectrum. The two key characteristics generalized from this particular decay channel-zero orbital angular momentum (i.e., s orbital) and core-level emission-set a guideline for obtaining undistorted X-ray absorption spectra in the future.

  10. Material/element-dependent fluorescence-yield modes on soft X-ray absorption spectroscopy of cathode materials for Li-ion batteries

    SciTech Connect

    Asakura, Daisuke; Hosono, Eiji; Nanba, Yusuke; Zhou, Haoshen; Okabayashi, Jun; Ban, Chunmei; Glans, Per -Anders; Guo, Jinghua; Mizokawa, Takashi; Chen, Gang; Achkar, Andrew J.; Hawthron, David G.; Regier, Thomas Z.; Wadati, Hiroki

    2016-03-07

    Here, we evaluate the utilities of fluorescence-yield (FY) modes in soft X-ray absorption spectroscopy (XAS) of several cathodematerials for Li-ion batteries. In the case of total-FY (TFY) XAS for LiNi0.5Mn1.5O4, the line shape of the Mn L3-edge XAS was largely distorted by the self-absorption and saturation effects, while the distortions were less pronounced at the NiL3 edge. The distortions were suppressed for the inverse-partial-FY (IPFY) spectra. We found that, in the cathodematerials, the IPFY XAS is highly effective for the Cr, Mn, and Fe L edges and the TFY and PFY modes are useful enough for the NiL edge which is far from the O K edge.

  11. 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.

  12. Identification of lead chemical form in mine waste materials by X-ray absorption spectroscopy

    SciTech Connect

    Taga, Raijeli L.; Ng, Jack; Zheng Jiajia; Huynh, Trang; Noller, Barry; Harris, Hugh H.

    2010-06-23

    X-ray absorption spectroscopy (XAS) provides a direct means for measuring lead chemical forms in complex samples. In this study, XAS was used to identify the presence of plumbojarosite (PbFe{sub 6}(SO{sub 4}){sub 4}(OH){sub 12}) by lead L{sub 3}-edge XANES spectra in mine waste from a small gold mining operation in Fiji. The presence of plumbojarosite in tailings was confirmed by XRD but XANES gave better resolution. The potential for human uptake of Pb from tailings was measured using a physiologically based extract test (PBET), an in-vitro bioaccessibility (BAc) method. The BAc of Pb was 55%. Particle size distribution of tailings indicated that 40% of PM{sub 10} particulates exist which could be a potential risk for respiratory effects via the inhalation route. Food items collected in the proximity of the mine site had lead concentrations which exceed food standard guidelines. Lead within the mining lease exceeded sediment guidelines. The results from this study are used to investigate exposure pathways via ingestion and inhalation for potential risk exposure pathways of Pb in that locality. The highest Pb concentration in soil and tailings was 25,839 mg/kg, exceeding the Australian National Environment Protection Measure (NEPM) soil health investigation levels.

  13. Identification of lead chemical form in mine waste materials by X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Taga, Raijeli L.; Zheng, Jiajia; Huynh, Trang; Ng, Jack; Harris, Hugh H.; Noller, Barry

    2010-06-01

    X-ray absorption spectroscopy (XAS) provides a direct means for measuring lead chemical forms in complex samples. In this study, XAS was used to identify the presence of plumbojarosite (PbFe6(SO4)4(OH)12) by lead L3-edge XANES spectra in mine waste from a small gold mining operation in Fiji. The presence of plumbojarosite in tailings was confirmed by XRD but XANES gave better resolution. The potential for human uptake of Pb from tailings was measured using a physiologically based extract test (PBET), an in-vitro bioaccessibility (BAc) method. The BAc of Pb was 55%. Particle size distribution of tailings indicated that 40% of PM10 particulates exist which could be a potential risk for respiratory effects via the inhalation route. Food items collected in the proximity of the mine site had lead concentrations which exceed food standard guidelines. Lead within the mining lease exceeded sediment guidelines. The results from this study are used to investigate exposure pathways via ingestion and inhalation for potential risk exposure pathways of Pb in that locality. The highest Pb concentration in soil and tailings was 25,839 mg/kg, exceeding the Australian National Environment Protection Measure (NEPM) soil health investigation levels.

  14. An X-ray diffraction and X-ray absorption spectroscopy joint study of neuroglobin.

    PubMed

    Arcovito, Alessandro; Moschetti, Tommaso; D'Angelo, Paola; Mancini, Giordano; Vallone, Beatrice; Brunori, Maurizio; Della Longa, Stefano

    2008-07-01

    Neuroglobin (Ngb) is a member of the globin family expressed in the vertebrate brain, involved in neuroprotection. A combined approach of X-ray diffraction (XRD) on single crystal and X-ray absorption spectroscopy (XAS) in solution, allows to determine the oxidation state and the structure of the Fe-heme both in the bis-histidine and the CO-bound (NgbCO) states. The overall data demonstrate that under X-ray the iron is photoreduced fairly rapidly, and that the previously reported X-ray structure of ferric Ngb [B. Vallone, K. Nienhaus, M. Brunori, G.U. Nienhaus, Proteins 56 (2004) 85-92] very likely refers to a photoreduced species indistinguishable from the dithionite reduced protein. Results from the XAS analysis of NgbCO in solution are in good agreement with XRD data on the crystal. However prolonged X-ray exposure at 15K determines CO release. This preliminary result paves the way to experiments aimed at the characterization of pentacoordinate ferrous Ngb, the only species competent in binding external ligands such as O2, CO or NO.

  15. X-ray absorption spectroscopy study of a copper-containing material after thermal treatment.

    PubMed

    Wei, Y-L; Huang, M-Y; Wang, H-C; Huang, H-C; Lee, J-F

    2006-04-17

    Thermal immobilization of copper contaminant in a copper-containing solid material collected from local copper smelting and foundry area is investigated in the present work. X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD) are employed for copper speciation. XAS results indicate that cupric hydroxide is the major copper species in the solid material dried at 105 degrees C. After being subjected to a 500 degrees C thermal process, cupric hydroxide still remains as the main copper species, but some Cu(II) is chemically reduced to Cu(I). More cupric hydroxide is progressively converted to Cu(I) as the sample was heated at 1100 degrees C than that heated at 500 degrees C. The sample heated at 500 degrees C is in its original powder form. However, thermal treatment at 1100 degrees C transforms the powder into a hardened granule-like form that is much bigger in size and difficult to be ground into powders. The sample is sintered with the sparingly soluble cuprous oxide and elemental copper being encapsulated inside. Toxicity characteristic leaching procedure (TCLP) results depict that amount of copper leached from the sample (containing 133,000 mg copper kg-1) heated at 1100 degrees C for 2 h is considerably minor, being 367 mg copper kg-1.

  16. Atomic Structure of Pt3Ni Nanoframe Electrocatalysts by in Situ X-ray Absorption Spectroscopy.

    PubMed

    Becknell, Nigel; Kang, Yijin; Chen, Chen; Resasco, Joaquin; Kornienko, Nikolay; Guo, Jinghua; Markovic, Nenad M; Somorjai, Gabor A; Stamenkovic, Vojislav R; Yang, Peidong

    2015-12-23

    Understanding the atomic structure of a catalyst is crucial to exposing the source of its performance characteristics. It is highly unlikely that a catalyst remains the same under reaction conditions when compared to as-synthesized. Hence, the ideal experiment to study the catalyst structure should be performed in situ. Here, we use X-ray absorption spectroscopy (XAS) as an in situ technique to study Pt3Ni nanoframe particles which have been proven to be an excellent electrocatalyst for the oxygen reduction reaction (ORR). The surface characteristics of the nanoframes were probed through electrochemical hydrogen underpotential deposition and carbon monoxide electrooxidation, which showed that nanoframe surfaces with different structure exhibit varying levels of binding strength to adsorbate molecules. It is well-known that Pt-skin formation on Pt-Ni catalysts will enhance ORR activity by weakening the binding energy between the surface and adsorbates. Ex situ and in situ XAS results reveal that nanoframes which bind adsorbates more strongly have a rougher Pt surface caused by insufficient segregation of Pt to the surface and consequent Ni dissolution. In contrast, nanoframes which exhibit extremely high ORR activity simultaneously demonstrate more significant segregation of Pt over Ni-rich subsurface layers, allowing better formation of the critical Pt-skin. This work demonstrates that the high ORR activity of the Pt3Ni hollow nanoframes depends on successful formation of the Pt-skin surface structure.

  17. Speciation of Selenium in Stream Insects Using X-Ray Absorption Spectroscopy

    SciTech Connect

    Andrahennadi, R.; Wayland, M.; Pickering, I.J.

    2009-05-28

    Selenium contamination in the environment is a widespread problem affecting insects and other wildlife. Insects occupy a critical middle link and aid in trophic transfer of selenium in many terrestrial and freshwater food chains, but the mechanisms of selenium uptake through the food chain are poorly understood. In particular, biotransformation of selenium by insects into different chemical forms will greatly influence how toxic or benign the selenium is to that organism or to its predators. We have used X-ray absorption spectroscopy (XAS) to identify the chemical form of selenium in insects inhabiting selenium contaminated streams near Hinton, Alberta (Canada). Selenium K near-edge spectra indicate a variability of selenium speciation among the insects that included mayflies (Ephemeroptera), stoneflies (Plecoptera), caddisflies (Trichoptera), and craneflies (Diptera). Higher percentages of inorganic selenium were observed in primary consumers, detritivores, and filter feeders than in predatory insects. Among the organic forms of selenium, organic selenides constituted a major fraction in most organisms. A species modeled as trimethylselenonium was observed during the pupal stage of caddisflies. These results provide insights into how the insects cope with their toxic cargo, including how the selenium is biotransformed into less toxic forms and how it can be eliminated from the insects. More broadly, this study demonstrates the strengths of XAS to probe the effects of heavy elements at trace levels in insects from the field.

  18. Speciation of selenium in stream insects using X-ray absorption spectroscopy

    SciTech Connect

    Ruwandi Andrahennadi; Mark Wayland; Ingrid J. Pickering

    2007-11-15

    Selenium contamination in the environment is a widespread problem affecting insects and other wildlife. Insects occupy a critical middle link and aid in trophic transfer of selenium in many terrestrial and freshwater food chains, but the mechanisms of selenium uptake through the food chain are poorly understood. In particular, biotransformation of selenium by insects into different chemical forms will greatly influence how toxic or benign the selenium is to that organism or to its predators. We have used X-ray absorption spectroscopy (XAS) to identify the chemical form of selenium in insects inhabiting selenium contaminated streams near Hinton, Alberta (Canada). Selenium K near-edge spectra indicate a variability of selenium speciation among the insects that included mayflies (Ephemeroptera), stoneflies (Plecoptera), caddisflies (Trichoptera), and craneflies (Diptera). Higher percentages of inorganic selenium were observed in primary consumers, detritivores, and filter feeders than in predatory insects. Among the organic forms of selenium, organic selenides constituted a major fraction in most organisms. A species modeled as trimethylselenonium was observed during the pupal stage of caddisflies. These results provide insights into how the insects cope with their toxic cargo, including how the selenium is biotransformed into less toxic forms and how it can be eliminated from the insects. More broadly, this study demonstrates the strengths of XAS to probe the effects of heavy elements at trace levels in insects from the field.

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

    PubMed Central

    2014-01-01

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

  20. UV laser long-path absorption spectroscopy

    NASA Technical Reports Server (NTRS)

    Dorn, Hans-Peter; Brauers, Theo; Neuroth, Rudolf

    1994-01-01

    Long path Differential Optical Absorption Spectroscopy (DOAS) using a picosecond UV laser as a light source was developed in our institute. Tropospheric OH radicals are measured by their rotational absorption lines around 308 nm. The spectra are obtained using a high resolution spectrograph. The detection system has been improved over the formerly used optomechanical scanning device by application of a photodiode array which increased the observed spectral range by a factor of 6 and which utilizes the light much more effectively leading to a considerable reduction of the measurement time. This technique provides direct measurements of OH because the signal is given by the product of the absorption coefficient and the OH concentration along the light path according to Lambert-Beers law. No calibration is needed. Since the integrated absorption coefficient is well known the accuracy of the measurement essentially depends on the extent to which the OH absorption pattern can be detected in the spectra. No interference by self generated OH radicals in the detection lightpath has been observed. The large bandwidth (greater than 0.15 nm) and the high spectral resolution (1.5 pm) allows absolute determination of interferences by other trace gas absorptions. The measurement error is directly accessible from the absorption-signal to baseline-noise ratio in the spectra. The applicability of the method strongly depends on visibility. Elevated concentrations of aerosols lead to considerable attenuation of the laser light which reduces the S/N-ratio. In the moderately polluted air of Julich, where we performed a number of OH measurement spectra. In addition absorption features of unidentified species were frequently detected. A quantitative deconvolution even of the known species is not easy to achieve and can leave residual structures in the spectra. Thus interferences usually increase the noise and deteriorate the OH detection sensitivity. Using diode arrays for sensitive

  1. Zinc ligands in the metal hyperaccumulator Thlaspi caerulescens as determined using X-ray absorption spectroscopy

    SciTech Connect

    Salt, D.E.; Prince, R.C.; Baker, A.J.M.; Raskin, I.; Pickering, I.J.

    1999-03-01

    Using the noninvasive technique of X-ray absorption spectroscopy (XAS), the authors have been able to determine the ligand environment of Zn in different tissues of the Zn-hyperaccumulator Thlaspi caerulescens. The majority of intracellular Zn in roots of T. caerulescens was found to be coordinated with histidine. In the xylem sap Zn was found to be transported mainly as the free hydrated Zn{sup 2+} cation with a smaller proportion coordinated with organic acids. In the shoots, Zn coordination occurred mainly via organic acids, with a smaller proportion present as the hydrated cation and coordinated with histidine and the cell wall. Their data suggest that histidine plays an important role in Zn homeostasis in the roots, whereas organic acids are involved in xylem transport and Zn storage in shoots.

  2. Remote laser evaporative molecular absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Hughes, Gary B.; Lubin, Philip; Cohen, Alexander; Madajian, Jonathan; Kulkarni, Neeraj; Zhang, Qicheng; Griswold, Janelle; Brashears, Travis

    2016-09-01

    We describe a novel method for probing bulk molecular and atomic composition of solid targets from a distant vantage. A laser is used to melt and vaporize a spot on the target. With sufficient flux, the spot temperature rises rapidly, and evaporation of surface materials occurs. The melted spot creates a high-temperature blackbody source, and ejected material creates a plume of surface materials in front of the spot. Molecular and atomic absorption occurs as the blackbody radiation passes through the ejected plume. Bulk molecular and atomic composition of the surface material is investigated by using a spectrometer to view the heated spot through the ejected plume. The proposed method is distinct from current stand-off approaches to composition analysis, such as Laser-Induced Breakdown Spectroscopy (LIBS), which atomizes and ionizes target material and observes emission spectra to determine bulk atomic composition. Initial simulations of absorption profiles with laser heating show great promise for Remote Laser-Evaporative Molecular Absorption (R-LEMA) spectroscopy. The method is well-suited for exploration of cold solar system targets—asteroids, comets, planets, moons—such as from a spacecraft orbiting the target. Spatial composition maps could be created by scanning the surface. Applying the beam to a single spot continuously produces a borehole or trench, and shallow subsurface composition profiling is possible. This paper describes system concepts for implementing the proposed method to probe the bulk molecular composition of an asteroid from an orbiting spacecraft, including laser array, photovoltaic power, heating and ablation, plume characteristics, absorption, spectrometry and data management.

  3. In vivo absorption spectroscopy for absolute measurement.

    PubMed

    Furukawa, Hiromitsu; Fukuda, Takashi

    2012-10-01

    In in vivo spectroscopy, there are differences between individual subjects in parameters such as tissue scattering and sample concentration. We propose a method that can provide the absolute value of a particular substance concentration, independent of these individual differences. Thus, it is not necessary to use the typical statistical calibration curve, which assumes an average level of scattering and an averaged concentration over individual subjects. This method is expected to greatly reduce the difficulties encountered during in vivo measurements. As an example, for in vivo absorption spectroscopy, the method was applied to the reflectance measurement in retinal vessels to monitor their oxygen saturation levels. This method was then validated by applying it to the tissue phantom under a variety of absorbance values and scattering efficiencies.

  4. Probing local structure of pyrochlore lead zinc niobate with synchrotron x-ray absorption spectroscopy technique

    NASA Astrophysics Data System (ADS)

    Kanchiang, Kanokwan; Pramchu, Sittichain; Yimnirun, Rattikorn; Pakawanit, Phakkhananan; Ananta, Supon; Laosiritaworn, Yongyut

    2013-08-01

    Local structure of lead zinc niobate (PZN) ceramic, synthesized via B-site oxide precursor route in atmospheric pressure, was investigated using synchrotron x-ray absorption spectroscopy (XAS) technique. The x-ray absorption near-edge structure (XANES) simulation was first carried out. The XANES simulation results indicate that the PZN ceramic is in pyrochlore phase having Zn2+ substituted on Nb5+ site. Afterwards, the extended x-ray absorption fine structure (EXAFS) analysis was performed to extract the bond length information between Zn2+ and its neighboring atoms. From the EXAFS fitting, the bond length between Zn2+ and Pb2+ in the pyrochlore phase was found to be longer than the previously reported bond length in the perovskite phase. Further, with the radial distribution information of Zn2+'s neighboring atoms, the formation energies along the precursor-to-pyrochlore and precursor-to-perovskite reaction paths were calculated using the density functional theory (DFT). The calculated results show that the formation energy of the perovskite phase is noticeably higher than that of the pyrochlore phase, which is influenced by the presence of energetic Pb2+ lone pair, as the perovskite phase has shorter Zn2+ to Pb2+ bonding. This therefore suggests the steric hindrance of Pb2+ lone pair and the mutual interactions between Pb2+ lone pair and Zn2+ are main causes of the instability of lead zinc niobate in the perovskite structure and confirm the efficacy of XAS and DFT analysis in revealing local structural details of complex pyrochlore materials.

  5. Catalysts at work: From integral to spatially resolved X-ray absorption spectroscopy

    SciTech Connect

    Grunwaldt, Jan-Dierk; Kimmerle, Bertram; Baiker, Alfons; Boye, Pit; Schroer, Christian G.; Glatzel, Pieter; Borca, Camelia N.; Beckmann, Felix

    2009-09-25

    Spectroscopic studies on heterogeneous catalysts have mostly been done in an integral mode. However, in many cases spatial variations in catalyst structure can occur, e.g. during impregnation of pre-shaped particles, during reaction in a catalytic reactor, or in microstructured reactors as the present overview shows. Therefore, spatially resolved molecular information on a microscale is required for a comprehensive understanding of theses systems, partly in ex situ studies, partly under stationary reaction conditions and in some cases even under dynamic reaction conditions. Among the different available techniques, X-ray absorption spectroscopy (XAS) is a well-suited tool for this purpose as the different selected examples highlight. Two different techniques, scanning and full-field X-ray microscopy/tomography, are described and compared. At first, the tomographic structure of impregnated alumina pellets is presented using full-field transmission microtomography and compared to the results obtained with a scanning X-ray microbeam technique to analyse the catalyst bed inside a catalytic quartz glass reactor. On the other hand, by using XAS in scanning microtomography, the structure and the distribution of Cu(0), Cu(I), Cu(II) species in a Cu/ZnO catalyst loaded in a quartz capillary microreactor could be reconstructed quantitatively on a virtual section through the reactor. An illustrating example for spatially resolved XAS under reaction conditions is the partial oxidation of methane over noble metal-based catalysts. In order to obtain spectroscopic information on the spatial variation of the oxidation state of the catalyst inside the reactor XAS spectra were recorded by scanning with a micro-focussed beam along the catalyst bed. Alternatively, full-field transmission imaging was used to efficiently determine the distribution of the oxidation state of a catalyst inside a reactor under reaction conditions. The new technical approaches together with quantitative data

  6. Soft X-ray absorption spectroscopy and resonant inelastic X-ray scattering spectroscopy below 100 eV: probing first-row transition-metal M-edges in chemical complexes.

    PubMed

    Wang, Hongxin; Young, Anthony T; Guo, Jinghua; Cramer, Stephen P; Friedrich, Stephan; Braun, Artur; Gu, Weiwei

    2013-07-01

    X-ray absorption and scattering spectroscopies involving the 3d transition-metal K- and L-edges have a long history in studying inorganic and bioinorganic molecules. However, there have been very few studies using the M-edges, which are below 100 eV. Synchrotron-based X-ray sources can have higher energy resolution at M-edges. M-edge X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) could therefore provide complementary information to K- and L-edge spectroscopies. In this study, M2,3-edge XAS on several Co, Ni and Cu complexes are measured and their spectral information, such as chemical shifts and covalency effects, are analyzed and discussed. In addition, M2,3-edge RIXS on NiO, NiF2 and two other covalent complexes have been performed and different d-d transition patterns have been observed. Although still preliminary, this work on 3d metal complexes demonstrates the potential to use M-edge XAS and RIXS on more complicated 3d metal complexes in the future. The potential for using high-sensitivity and high-resolution superconducting tunnel junction X-ray detectors below 100 eV is also illustrated and discussed.

  7. Surface arsenic speciation of a drinking-water treatment residual using X-ray absorption spectroscopy.

    PubMed

    Makris, Konstantinos C; Sarkar, Dibyendu; Parsons, Jason G; Datta, Rupali; Gardea-Torresdey, Jorge L

    2007-07-15

    Drinking-water treatment residuals (WTRs) present a low-cost geosorbent for As-contaminated waters and soils. Previous work has demonstrated the high affinity of WTRs for As, but data pertaining to the stability of sorbed As is missing. Sorption/desorption and X-ray absorption spectroscopy (XAS), both XANES (X-ray absorption near edge structure) and EXAFS (extended X-ray absorption fine structure) studies, were combined to determine the stability of As sorbed by an Fe-based WTR. Arsenic(V) and As(III) sorption kinetics were biphasic in nature, sorbing >90% of the initial added As (15,000 mg kg(-1)) after 48 h of reaction. Subsequent desorption experiments with a high P load (7500 mg kg(-1)) showed negligible As desorption for both As species, approximately <3.5% of sorbed As; the small amount of desorbed As was attributed to the abundance of sorption sites. XANES data showed that sorption kinetics for either As(III) or As(V) initially added to solution had no effect on the sorbed As oxidation state. EXAFS spectroscopy suggested that As added either as As(III) or as As(V) formed inner-sphere mononuclear, bidentate complexes, suggesting the stability of the sorbed As, which was further corroborated by the minimum As desorption from the Fe-WTR.

  8. An investigation of arsenic compounds in fur and feathers using X-ray absorption spectroscopy speciation and imaging.

    PubMed

    Smith, Paula G; Koch, Iris; Reimer, Kenneth J

    2008-02-01

    The accumulation of arsenic in fur and feathers has been used as an indicator of environmental quality and animal health. However, difficulties remain in distinguishing between arsenic present from external sources versus ingestion. In addition, low extraction efficiencies limit the complete characterization of arsenic compounds in such tissues by conventional analytical techniques (e.g. high performance liquid chromatography inductively coupled plasma mass spectrometry, HPLC-ICP-MS). X-ray absorption spectroscopy (XAS) provides an alternative method for determining the speciation of arsenic compounds directly. Inorganic arsenic is hypothesized to bind to thiol groups present in keratin-rich fur and feathers; however, arsenic-sulphur compounds are rarely reported in extracts of these tissues. Here we report that 5-58% of the total detected arsenic in rodent fur (vole, deer mouse, red squirrel) and bird feathers (gray jay, American tree sparrow, dark-eyed junco) from animals living in areas of elevated arsenic best resembled an arsenic(III)-sulphur compound as determined using XAS. In addition, fur and feathers with non-detectable levels of arsenic by XAS, were able to reduce pentavalent arsenic applied as either contaminated soil or an arsenate solution. XAS-imaging was used to localize dominant trivalent (AsIII) and pentavalent (AsV) arsenic compounds, and results were used to produce a "map" of arsenic in the sample. It is believed that the some of the reduced arsenic was absorbed, while external AsV compounds associated with soil/dust particles were easily distinguished on goose feathers. However, distinguishing whether internal arsenic arose from exogenous (from the environment) or endogenous (from the body) sources proved difficult with this technique.

  9. High-resolution X-ray absorption spectroscopy as a probe of crystal-field and covalency effects in actinide compounds.

    PubMed

    Butorin, Sergei M; Kvashnina, Kristina O; Vegelius, Johan R; Meyer, Daniel; Shuh, David K

    2016-07-19

    Applying the high-energy resolution fluorescence-detection (HERFD) mode of X-ray absorption spectroscopy (XAS), we were able to probe, for the first time to our knowledge, the crystalline electric field (CEF) splittings of the [Formula: see text] shell directly in the HERFD-XAS spectra of actinides. Using ThO2 as an example, data measured at the Th 3d edge were interpreted within the framework of the Anderson impurity model. Because the charge-transfer satellites were also resolved in the HERFD-XAS spectra, the analysis of these satellites revealed that ThO2 is not an ionic compound as previously believed. The Th [Formula: see text] occupancy in the ground state was estimated to be twice that of the Th [Formula: see text] states. We demonstrate that HERFD-XAS allows for characterization of the CEF interaction and degree of covalency in the ground state of actinide compounds as it is extensively done for 3d transition metal systems.

  10. High-resolution X-ray absorption spectroscopy as a probe of crystal-field and covalency effects in actinide compounds

    PubMed Central

    Butorin, Sergei M.; Kvashnina, Kristina O.; Vegelius, Johan R.; Meyer, Daniel; Shuh, David K.

    2016-01-01

    Applying the high-energy resolution fluorescence-detection (HERFD) mode of X-ray absorption spectroscopy (XAS), we were able to probe, for the first time to our knowledge, the crystalline electric field (CEF) splittings of the 5f shell directly in the HERFD-XAS spectra of actinides. Using ThO2 as an example, data measured at the Th 3d edge were interpreted within the framework of the Anderson impurity model. Because the charge-transfer satellites were also resolved in the HERFD-XAS spectra, the analysis of these satellites revealed that ThO2 is not an ionic compound as previously believed. The Th 6d occupancy in the ground state was estimated to be twice that of the Th 5f states. We demonstrate that HERFD-XAS allows for characterization of the CEF interaction and degree of covalency in the ground state of actinide compounds as it is extensively done for 3d transition metal systems. PMID:27370799

  11. Atmospheric Measurements by Cavity Enhanced Absorption Spectroscopy

    NASA Astrophysics Data System (ADS)

    Yi, Hongming; Wu, Tao; Coeur-Tourneur, Cécile; Fertein, Eric; Gao, Xiaoming; Zhao, Weixiong; Zhang, Weijun; Chen, Weidong

    2015-04-01

    Since the last decade, atmospheric environmental monitoring has benefited from the development of novel spectroscopic measurement techniques owing to the significant breakthroughs in photonic technology from the UV to the infrared spectral domain [1]. In this presentation, we will overview our recent development and applications of cavity enhanced absorption spectroscopy techniques for in situ optical monitoring of chemically reactive atmospheric species (such as HONO, NO3, NO2, N2O5) in intensive campaigns [2] and/or in smog chamber studies [3]. These field deployments demonstrated that modern photonic technologies (newly emergent light sources combined with high sensitivity spectroscopic techniques) can provide a useful tool to improve our understanding of tropospheric chemical processes which affect climate, air quality, and the spread of pollution. Experimental detail and preliminary results will be presented. Acknowledgements. The financial support from the French Agence Nationale de la Recherche (ANR) under the NexCILAS (ANR-11-NS09-0002) and the CaPPA (ANR-10-LABX-005) contracts is acknowledged. References [1] X. Cui, C. Lengignon, T. Wu, W. Zhao, G. Wysocki, E. Fertein, C. Coeur, A. Cassez,L. Croisé, W. Chen, et al., "Photonic Sensing of the Atmosphere by absorption spectroscopy", J. Quant. Spectrosc. Rad. Transfer 113 (2012) 1300-1316 [2] T. Wu, Q. Zha, W. Chen, Z. XU, T. Wang, X. He, "Development and deployment of a cavity enhanced UV-LED spectrometer for measurements of atmospheric HONO and NO2 in Hong Kong", Atmos. Environ. 95 (2014) 544-551 [3] T. Wu, C. Coeur-Tourneur, G. Dhont,A. Cassez, E. Fertein, X. He, W. Chen,"Application of IBBCEAS to kinetic study of NO3 radical formation from O3 + NO2 reaction in an atmospheric simulation chamber", J. Quant. Spectrosc. Rad. Transfer 133 (2014)199-205

  12. Highly sensitive detection using Herriott cell for laser absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Zhao, Chongyi; Song, Guangming; Du, Yang; Zhao, Xiaojun; Wang, Wenju; Zhong, Liujun; Hu, Mai

    2016-11-01

    The tunable diode laser absorption spectroscopy combined with the long absorption path technique is a significant method to detect harmful gas. The long optical path could come true by Herriott cell reducing the size of the spectrometers. A 15 cm long Herriott cell with 28.8 m optical absorption path after 96 times reflection was designed that enhanced detection sensitivity of absorption spectroscopy. According to the theory data of calculation, Herriott cell is analyzed and simulated by softwares Matlab and Lighttools.

  13. Double point contact single molecule absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Howard, John Brooks

    Our primary objective with the presentation of this thesis is to utilize superconducting transport through microscopic objects to both excite and analyze the vibrational degrees of freedom of various molecules of a biological nature. The technique stems from a Josephson junction's ability to generate radiation that falls in the terahertz gap (≈ 10 THz) and consequently can be used to excite vibrational modes of simple and complex molecules. Analysis of the change in IV characteristics coupled with the differential conductance dIdV allows determination of both the absorption spectra and the vibrational modes of biological molecules. Presented here are both the theoretical foundations of superconductivity relevant to our experimental technique and the fabrication process of our samples. Comparisons between our technique and that of other absorption spectroscopy techniques are included as a means of providing a reference upon which to judge the merits of our novel procedure. This technique is meant to improve not only our understanding of the vibrational degrees of freedom of useful biological molecules, but also these molecule's structural, electronic and mechanical properties.

  14. X-ray-absorption spectroscopy and n-body distribution functions in condensed matter. I. Theory

    NASA Astrophysics Data System (ADS)

    Filipponi, Adriano; di Cicco, Andrea; Natoli, Calogero Renzo

    1995-12-01

    The general theoretical framework underlying the GNXAS multiple-scattering (MS) data-analysis method for x-ray absorption spectroscopy (XAS) is presented. The main approximations leading to the reduction of the many-body process in that of a photoelectron scattering in an effective potential are summarized. The methods available to expand the extended x-ray-absorption fine-structure χ(k) into physically meaningful terms are described. In particular, emphasis is given to the definition of the irreducible n-body signals γ(n) that can be calculated directly by means of linear combinations of continued fractions, or by using their respective multiple-scattering series. It is found that even for an infinite system the expansion of the χ(k) signal in terms of γ(n) has a better convergence rate than the MS series. Simple expressions for performing the configurational averages of the structural signals in the presence of thermal and structural disorder are derived. These can be used for the structural analysis of molecular, crystalline, or moderately disordered systems. It is shown that in the case of highly disordered systems the expansion in terms of the γ(n) signals is the natural framework for the interpretation of the XAS signal. General equations for the ensemble-averaged χ(k) signal as a function of a series of integrals over the n-body n>~2 distribution functions gn are provided and the possible use of advanced strategies for the inversion of the structural information is suggested.

  15. Characterization and speciation of mercury-bearing mine wastes using X-ray absorption spectroscopy

    USGS Publications Warehouse

    Kim, C.S.; Brown, Gordon E.; Rytuba, J.J.

    2000-01-01

    Mining of mercury deposits located in the California Coast Range has resulted in the release of mercury to the local environment and water supplies. The solubility, transport, and potential bioavailability of mercury are controlled by its chemical speciation, which can be directly determined for samples with total mercury concentrations greater than 100 mg kg-1 (ppm) using X-ray absorption spectroscopy (XAS). This technique has the additional benefits of being non-destructive to the sample, element-specific, relatively sensitive at low concentrations, and requiring minimal sample preparation. In this study, Hg L(III)-edge extended X-ray absorption fine structure (EXAFS) spectra were collected for several mercury mine tailings (calcines) in the California Coast Range. Total mercury concentrations of samples analyzed ranged from 230 to 1060 ppm. Speciation data (mercury phases present and relative abundances) were obtained by comparing the spectra from heterogeneous, roasted (calcined) mine tailings samples with a spectral database of mercury minerals and sorbed mercury complexes. Speciation analyses were also conducted on known mixtures of pure mercury minerals in order to assess the quantitative accuracy of the technique. While some calcine samples were found to consist exclusively of mercuric sulfide, others contain additional, more soluble mercury phases, indicating a greater potential for the release of mercury into solution. Also, a correlation was observed between samples from hot-spring mercury deposits, in which chloride levels are elevated, and the presence of mercury-chloride species as detected by the speciation analysis. The speciation results demonstrate the ability of XAS to identify multiple mercury phases in a heterogeneous sample, with a quantitative accuracy of ??25% for the mercury-containing phases considered. Use of this technique, in conjunction with standard microanalytical techniques such as X-ray diffraction and electron probe microanalysis

  16. Precision Saturated Absorption Spectroscopy of H3+

    NASA Astrophysics Data System (ADS)

    Guan, Yu-chan; Liao, Yi-Chieh; Chang, Yung-Hsiang; Peng, Jin-Long; Shy, Jow-Tsong

    2016-06-01

    In our previous work on the Lamb dips of the νb{2} fundamental band of H3+, the saturated absorption spectrum was obtained by the third-derivative spectroscopy using frequency modulation [1]. However, the frequency modulation also causes error in absolute frequency determination. To solve this problem, we have built an offset-locking system to lock the OPO pump frequency to an iodine-stabilized Nd:YAG laser. With this modification, we are able to scan the OPO idler frequency precisely and obtain the profile of the Lamb dips. Double modulation (amplitude modulation of the idler power and concentration modulation of the ion) is employed to subtract the interference fringes of the signal and increase the signal-to-noise ratio effectively. To Determine the absolute frequency of the idler wave, the pump wave is offset locked on the R(56) 32-0 a10 hyperfine component of 127I2, and the signal wave is locked on a GPS disciplined fiber optical frequency comb (OFC). All references and lock systems have absolute frequency accuracy better than 10 kHz. Here, we demonstrate its performance by measuring one transition of methane and sixteen transitions of H3+. This instrument could pave the way for the high-resolution spectroscopy of a variety of molecular ions. [1] H.-C. Chen, C.-Y. Hsiao, J.-L. Peng, T. Amano, and J.-T. Shy, Phys. Rev. Lett. 109, 263002 (2012).

  17. Investigating the speciation of copper in secondary fly ash by X-ray absorption spectroscopy.

    PubMed

    Tian, Shulei; Yu, Meijuan; Wang, Wei; Wang, Qi; Wu, Ziyu

    2009-12-15

    Although some researchers have reported that chlorides may play an important part in the evaporation of copper during heat treatment of municipal solid waste incinerators (MSWI) fly ash (1, 2) , details on the copper speciation in volatile matters (secondary fly ash, SFA) are still lacking. In this work, we used in situ X-ray absorption spectroscopy (XAS) experiments involving three types of SFA, which was collected from a high-temperature tubular electric furnace by thermal treatment of municipal solid waste incinerator (MSWI) fly ash at 1000, 1150, and 1250 degrees C. The results obtained by a linear combination fit (LCF) of X-ray absorption near edge structure (XANES) spectra revealed that in MSWI fly ash copper mainly exists as CuO and CuSO(4).5H(2)O while chloride almost dominated all the content of the SFA conformation, which was more than 80%. Extended X-ray absorption fine structure (EXAFS) data analysis indicated the presence of both Cu-O and Cu-Cl bonds in the first coordination shell of Cu ions in all SFA, while only Cu-O bonds occur in the MSWI fly ash. Consequently, in the MSWI fly ash during heat treatment copper evaporated as chloride, and the latter plays an important role in the formation of copper chloride.

  18. Transient absorption spectroscopy of laser shocked explosives

    SciTech Connect

    Mcgrane, Shawn D; Dang, Nhan C; Whitley, Von H; Bolome, Cindy A; Moore, D S

    2010-01-01

    Transient absorption spectra from 390-890 nm of laser shocked RDX, PETN, sapphire, and polyvinylnitrate (PVN) at sub-nanosecond time scales are reported. RDX shows a nearly linear increase in absorption with time after shock at {approx}23 GPa. PETN is similar, but with smaller total absorption. A broad visible absorption in sapphire begins nearly immediately upon shock loading but does not build over time. PVN exhibits thin film interference in the absorption spectra along with increased absorption with time. The absorptions in RDX and PETN are suggested to originate in chemical reactions happening on picosecond time scales at these shock stresses, although further diagnostics are required to prove this interpretation.

  19. Applications of absorption spectroscopy using quantum cascade lasers.

    PubMed

    Zhang, Lizhu; Tian, Guang; Li, Jingsong; Yu, Benli

    2014-01-01

    Infrared laser absorption spectroscopy (LAS) is a promising modern technique for sensing trace gases with high sensitivity, selectivity, and high time resolution. Mid-infrared quantum cascade lasers, operating in a pulsed or continuous wave mode, have potential as spectroscopic sources because of their narrow linewidths, single mode operation, tunability, high output power, reliability, low power consumption, and compactness. This paper reviews some important developments in modern laser absorption spectroscopy based on the use of quantum cascade laser (QCL) sources. Among the various laser spectroscopic methods, this review is focused on selected absorption spectroscopy applications of QCLs, with particular emphasis on molecular spectroscopy, industrial process control, combustion diagnostics, and medical breath analysis.

  20. X-ray Absorption Spectroscopy Study of the Effect of Rh doping in Sr2IrO4

    PubMed Central

    Sohn, C. H.; Cho, Deok-Yong; Kuo, C.-T.; Sandilands, L. J.; Qi, T. F.; Cao, G.; Noh, T. W.

    2016-01-01

    We investigate the effect of Rh doping in Sr2IrO4 using X-ray absorption spectroscopy (XAS). We observed appearance of new electron-addition states with increasing Rh concentration (x in Sr2Ir1−xRhxO4) in accordance with the concept of hole doping. The intensity of the hole-induced state is however weak, suggesting weakness of charge transfer (CT) effect and Mott insulating ground states. Also, Ir Jeff = 1/2 upper Hubbard band shifts to lower energy as x increases up to x = 0.23. Combined with optical spectroscopy, these results suggest a hybridisation-related mechanism, in which Rh doping can weaken the (Ir Jeff = 1/2)–(O 2p) orbital hybridisation in the in-planar Rh-O-Ir bond networks. PMID:27025538

  1. Novel spectro-electrochemical cell for in situ/operando observation of common composite electrode with liquid electrolyte by X-ray absorption spectroscopy in the tender X-ray region

    PubMed Central

    Nakanishi, Koji; Kato, Daisuke; Arai, Hajime; Tanida, Hajime; Mori, Takuya; Orikasa, Yuki; Uchimoto, Yoshiharu; Ohta, Toshiaki; Ogumi, Zempachi

    2014-01-01

    A novel spectro-electochemical cell for X-ray absorption spectroscopy in the tender X-ray region (TX-XAS) was designed and fabricated to investigate the electrochemical behavior of common battery materials with liquid electrolytes under in situ/operando conditions. The cell has several unique features, such as high X-ray transmittance, high signal to noise ratio, and high vacuum tightness. These features enable us quick and reliable XAS measurements. Operando P K-edge XAS measurements of an olivine-type LiFePO4 composite positive electrode were carried out to clarify its phosphorus environment during the electrochemical charging process. Results of spectral analysis show that there is no significant change in the oxidation state of phosphorus and in the coordination of the phosphate anions in the charging process, but a closer look of the consecutive XAS spectra suggests the shrinkage of the PO4 cage during the charging process, and the structural changes in a biphasic manner. These results demonstrate the usefulness of the cell for in situ/operando TX-XAS observations of light elements in practical batteries. PMID:25173283

  2. 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

  3. Depth-Resolved X-ray Absorption Spectroscopy by Means of Grazing Emission X-ray Fluorescence.

    PubMed

    Kayser, Yves; Sá, Jacinto; Szlachetko, Jakub

    2015-11-03

    Grazing emission X-ray fluorescence (GEXRF) is well suited for nondestructive elemental-sensitive depth-profiling measurements on samples with nanometer-sized features. By varying the grazing emission angle under which the X-ray fluorescence signal is detected, the probed depth range can be tuned from a few to several hundred nanometers. The dependence of the XRF intensity on the grazing emission angle can be assessed in a sequence of measurements or in a scanning-free approach using a position-sensitive area detector. Hereafter, we will show that the combination of scanning-free GEXRF and fluorescence detected X-ray absorption spectroscopy (XAS) allows for depth-resolved chemical speciation measurements with nanometer-scale accuracy. While the conventional grazing emission geometry is advantageous to minimize self-absorption effects, the use of a scanning-free setup makes the sequential scanning of the grazing emission angles obsolete and paves the way toward time-resolved depth-sensitive XAS measurements. The presented experimental approach was applied to study the surface oxidation of an Fe layer on the top of bulk Si and of a Ge bulk sample. Thanks to the penetrating properties and the insensitivity toward the electric conduction properties of the incident and emitted X-rays, the presented experimental approach is well suited for in situ sample surface studies in the nanometer regime.

  4. 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.

  5. [Digestion-flame atomic absorption spectroscopy].

    PubMed

    Xu, Liang; Hu, Jian-Guo; Liu, Rui-Ping; Wang, Zhi-Min; Narenhua

    2008-01-01

    A microwave digestion-flame atomic absorption spectroscopy (FAAS) method was developed for the determination of metal elements Na, Zn, Cu, Fe, Mn, Ca and Mg in Mongolian patents. The instrument parameters for the determination were optimized, and the appropriate digestion solvent was selected. The recovery of the method was between 95.8% and 104.3%, and the RSD was between 1.6% and 4.2%. The accuracy and precision of the method was tested by comparing the values obtained from the determination of the standard sample, bush twigs and leaves (GSV-1) by this method with the reference values of GSV-1. The determination results were found to be basically consistent with the reference values. The microwave digestion technique was applied to process the samples, and the experimental results showed that compared to the traditional wet method, the present method has the merits of simplicity, saving agents, rapidness, and non-polluting. The method was accurate and reliable, and could be used to determine the contents of seven kinds of metal elements in mongolian patents.

  6. Spatial distribution and speciation of arsenic in peat studied with Microfocused X-ray fluorescence spectrometry and X-ray absorption spectroscopy.

    PubMed

    Langner, Peggy; Mikutta, Christian; Suess, Elke; Marcus, Matthew A; Kretzschmar, Ruben

    2013-09-03

    Arsenic binding by sulfhydryl groups of natural organic matter (NOM) was recently identified as an important As sequestration pathway in the naturally As-enriched minerotrophic peatland Gola di Lago, Switzerland. Here, we explore the microscale distribution, elemental correlations, and chemical speciation of As in the Gola di Lago peat. Thin sections of undisturbed peat samples from 0-37 cm and 200-249 cm depth were analyzed by synchrotron microfocused X-ray fluorescence (μ-XRF) spectrometry and X-ray absorption spectroscopy (μ-XAS). Additionally, peat samples were studied by bulk As, Fe, and S K-edge XAS. Micro-XRF analyses showed that As in the near-surface peat was mainly concentrated in 10-50 μm sized hotspots, identified by μ-XAS as realgar (α-As4S4). In the deep peat layer samples, however, As was more diffusely distributed and mostly associated with particulate NOM of varying decomposition stages. The NOM-associated As was present as trivalent As bound by sulfhydryl groups. Arsenopyrite (FeAsS) and arsenian pyrite (FeAsxS2-x) of <25 μm size, which have escaped detection by bulk As and Fe K-edge XAS, were found as minor As species in the peat. Bulk S K-edge XAS revealed that the deep peat layers were significantly enriched in reduced organic S species. Our findings suggest an authigenic formation of realgar and arsenopyrite in strongly reducing microenvironments of the peat and indicate that As(III)-NOM complexes are formed by the passive sorption of As(III) to NOM. This reaction appears to be favored by a combination of abundant reduced organic S and comparatively low As solution concentrations preventing the formation of secondary As-bearing sulfides.

  7. UV-VIS absorption spectroscopy: Lambert-Beer reloaded.

    PubMed

    Mäntele, Werner; Deniz, Erhan

    2017-02-15

    UV-VIS absorption spectroscopy is used in almost every spectroscopy laboratory for routine analysis or research. All spectroscopists rely on the Lambert-Beer Law but many of them are less aware of its limitations. This tutorial discusses typical problems in routine spectroscopy that come along with technical limitations or careless selection of experimental parameters. Simple rules are provided to avoid these problems.

  8. UV-VIS absorption spectroscopy: Lambert-Beer reloaded

    NASA Astrophysics Data System (ADS)

    Mäntele, Werner; Deniz, Erhan

    2017-02-01

    UV-VIS absorption spectroscopy is used in almost every spectroscopy laboratory for routine analysis or research. All spectroscopists rely on the Lambert-Beer Law but many of them are less aware of its limitations. This tutorial discusses typical problems in routine spectroscopy that come along with technical limitations or careless selection of experimental parameters. Simple rules are provided to avoid these problems.

  9. Note: application of a pixel-array area detector to simultaneous single crystal X-ray diffraction and X-ray absorption spectroscopy measurements.

    PubMed

    Sun, Cheng-Jun; Zhang, Bangmin; Brewe, Dale L; Chen, Jing-Sheng; Chow, G M; Venkatesan, T; Heald, Steve M

    2014-04-01

    X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) are two main x-ray techniques in synchrotron radiation facilities. In this Note, we present an experimental setup capable of performing simultaneous XRD and XAS measurements by the application of a pixel-array area detector. For XRD, the momentum transfer in specular diffraction was measured by scanning the X-ray energy with fixed incoming and outgoing x-ray angles. By selecting a small fixed region of the detector to collect the XRD signal, the rest of the area was available for collecting the x-ray fluorescence for XAS measurements. The simultaneous measurement of XRD and X-ray absorption near edge structure for Pr0.67Sr0.33MnO3 film was demonstrated as a proof of principle for future time-resolved pump-probe measurements. A static sample makes it easy to maintain an accurate overlap of the X-ray spot and laser pump beam.

  10. Note: Application of a pixel-array area detector to simultaneous single crystal x-ray diffraction and x-ray absorption spectroscopy measurements

    SciTech Connect

    Sun, Cheng-Jun Brewe, Dale L.; Heald, Steve M.; Zhang, Bangmin; Chen, Jing-Sheng; Chow, G. M.; Venkatesan, T.

    2014-04-15

    X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) are two main x-ray techniques in synchrotron radiation facilities. In this Note, we present an experimental setup capable of performing simultaneous XRD and XAS measurements by the application of a pixel-array area detector. For XRD, the momentum transfer in specular diffraction was measured by scanning the X-ray energy with fixed incoming and outgoing x-ray angles. By selecting a small fixed region of the detector to collect the XRD signal, the rest of the area was available for collecting the x-ray fluorescence for XAS measurements. The simultaneous measurement of XRD and X-ray absorption near edge structure for Pr{sub 0.67}Sr{sub 0.33}MnO{sub 3} film was demonstrated as a proof of principle for future time-resolved pump-probe measurements. A static sample makes it easy to maintain an accurate overlap of the X-ray spot and laser pump beam.

  11. Interaction of vanadium and sulfate in blood cells from the tunicate Ascidia ceratodes: Observations using x-ray absorption edge structure and EPR spectroscopies

    SciTech Connect

    Frank, P.; Hedman, B.; Hodgson, K.O.; Carlson, R.M.K.

    1994-08-17

    Sulfur K-edge X-ray absorption spectroscopy (S-K XAS) and EPR spectroscopy have been used to investigate the inorganic solution chemistry of vanadium, sulfate, and methanesulfonate, with application to blood cells from the tunicate Ascidia ceratodes. Three independent whole blood cell preparations (S85, S86, W87) collected over a period of 18 months were examined. Average blood cell vanadium concentrations were determined to be 0.099, 0.079, and 0.062 M, respectively. All three collections gave sulfur XAS spectra consistent with significant intracellular concentrations of low-valent sulfur, an alkanesulfonic acid, and sulfate. In model studies, the line width of the sulfate K-edge XAS spectrum was found to titrate with both pH and [V(III)]. Application of this finding to A. ceratodes blood cell sulfur XAS spectra provided evidence for direct interactions between endogenous dissolved sulfate and V(III) in two of the three collections. All three collections yielded sulfate XAS edge spectra consistent with low pH. Curve-fitting analysis of the S-K edge XAS spectra for the three whole blood cell collections yielded the ratios of intracellular sulfate:alkane sulfonate:low-valent sulfur to be as follows: S85, 1.0:0.9:0.36;S86, 1.0;0.5;1.5;W87,1.0;0.44:0.24. Comparisons with models indicated that the low-valent blood cell sulfur included various disulfide-like compounds unlike cystine. This all implies a surprisingly rich and variable sulfur biochemistry in these marine organisms. EPR spectroscopy of whole blood cells from one animal from the W87 collection revealed an endogenous VO{sup 2+}-sulfate interaction. Thus both V(III) and VO{sup 2+} can sense an intracellular pool of sulfate, implying the biological colocation of these two metal ions. The variations in blood chemistry observed over time as described herein caution against definitive application of single point experiments.

  12. Excited-state molecular structures captured by X-ray transient absorption spectroscopy: a decade and beyond.

    PubMed

    Chen, Lin X; Zhang, Xiaoyi; Lockard, Jenny V; Stickrath, Andrew B; Attenkofer, Klaus; Jennings, Guy; Liu, Di-Jia

    2010-03-01

    Transient molecular structures along chemical reaction pathways are important for predicting molecular reactivity, understanding reaction mechanisms, as well as controlling reaction pathways. During the past decade, X-ray transient absorption spectroscopy (XTA, or LITR-XAS, laser-initiated X-ray absorption spectroscopy), analogous to the commonly used optical transient absorption spectroscopy, has been developed. XTA uses a laser pulse to trigger a fundamental chemical process, and an X-ray pulse(s) to probe transient structures as a function of the time delay between the pump and probe pulses. Using X-ray pulses with high photon flux from synchrotron sources, transient electronic and molecular structures of metal complexes have been studied in disordered media from homogeneous solutions to heterogeneous solution-solid interfaces. Several examples from the studies at the Advanced Photon Source in Argonne National Laboratory are summarized, including excited-state metalloporphyrins, metal-to-ligand charge transfer (MLCT) states of transition metal complexes, and charge transfer states of metal complexes at the interface with semiconductor nanoparticles. Recent developments of the method are briefly described followed by a future prospective of XTA. It is envisioned that concurrent developments in X-ray free-electron lasers and synchrotron X-ray facilities as well as other table-top laser-driven femtosecond X-ray sources will make many breakthroughs and realise dreams of visualizing molecular movies and snapshots, which ultimately enable chemical reaction pathways to be controlled.

  13. Excited-state molecular structures captured by x-ray transient absorption spectroscopy : a decade and beyond.

    SciTech Connect

    Chen, L. X.; Zhang, X.; Lockard, J. V.; Stickrath, A. B.; Attenkofer, K.; Jennings, G.; Liu, D.-J.; Northwestern Univ.

    2010-03-02

    Transient molecular structures along chemical reaction pathways are important for predicting molecular reactivity, understanding reaction mechanisms, as well as controlling reaction pathways. During the past decade, X-ray transient absorption spectroscopy (XTA, or LITR-XAS, laser-initiated X-ray absorption spectroscopy), analogous to the commonly used optical transient absorption spectroscopy, has been developed. XTA uses a laser pulse to trigger a fundamental chemical process, and an X-ray pulse(s) to probe transient structures as a function of the time delay between the pump and probe pulses. Using X-ray pulses with high photon flux from synchrotron sources, transient electronic and molecular structures of metal complexes have been studied in disordered media from homogeneous solutions to heterogeneous solution-solid interfaces. Several examples from the studies at the Advanced Photon Source in Argonne National Laboratory are summarized, including excited-state metalloporphyrins, metal-to-ligand charge transfer (MLCT) states of transition metal complexes, and charge transfer states of metal complexes at the interface with semiconductor nanoparticles. Recent developments of the method are briefly described followed by a future prospective of XTA. It is envisioned that concurrent developments in X-ray free-electron lasers and synchrotron X-ray facilities as well as other table-top laser-driven femtosecond X-ray sources will make many breakthroughs and realise dreams of visualizing molecular movies and snapshots, which ultimately enable chemical reaction pathways to be controlled.

  14. XAS and RIXS study of acetic acid and methyl formate in liquid

    NASA Astrophysics Data System (ADS)

    Takahashi, O.; Nishida, N.; Kanai, S.; Horikawa, Y.; Tokushima, T.

    2016-05-01

    Structure of acetic acid (AA) and methyl formate (MF) in the liquid phase is studied using X-ray absorption spectroscopy (XAS) and X-ray emission spectroscopy (XES) experimentally and theoretically. Two distinct XES spectra are observed by tuning photon energy for both molecules. Model structure in the liquid phase is constructed using the classical and first principle molecular dynamics simulations, and XES spectra are calculated using density functional theory. Calculated XES spectra are consistent with experimental ones. The effect of core-hole induced excited state molecular dynamics are discussed.

  15. X-ray absorption spectroscopy and magnetic circular dichroism studies of L10-Mn-Ga thin films

    NASA Astrophysics Data System (ADS)

    Glas, M.; Sterwerf, C.; Schmalhorst, J. M.; Ebke, D.; Jenkins, C.; Arenholz, E.; Reiss, G.

    2013-11-01

    Tetragonally distorted Mn3-xGax thin films with 0.1absorption spectroscopy (XAS) and magnetic circular dichroism (XMCD). A highly textured L10 crystal structure of the Mn-Ga films was verified by X-ray diffraction measurements. For samples with e-beam evaporated MgO barrier no evidence for Mn-O was found whereas in samples with magnetron sputtered MgO, Mn-O was detected, even for the thickest interlayer thickness. Both XAS and XMCD measurements showed an increasing interfacial Mn-O amount with decreasing CoFeB interlayer thickness. Additional element specific full hysteresis loops determined an out-of-plane magnetization axis for the Mn and Co, respectively.

  16. X-ray absorption spectroscopy and magnetic circular dichroism studies of L1{sub 0}-Mn-Ga thin films

    SciTech Connect

    Glas, M. Sterwerf, C.; Schmalhorst, J. M.; Reiss, G.; Ebke, D.; Jenkins, C.; Arenholz, E.

    2013-11-14

    Tetragonally distorted Mn{sub 3−x}Ga{sub x} thin films with 0.1absorption spectroscopy (XAS) and magnetic circular dichroism (XMCD). A highly textured L1{sub 0} crystal structure of the Mn-Ga films was verified by X-ray diffraction measurements. For samples with e-beam evaporated MgO barrier no evidence for Mn-O was found whereas in samples with magnetron sputtered MgO, Mn-O was detected, even for the thickest interlayer thickness. Both XAS and XMCD measurements showed an increasing interfacial Mn-O amount with decreasing CoFeB interlayer thickness. Additional element specific full hysteresis loops determined an out-of-plane magnetization axis for the Mn and Co, respectively.

  17. Ultrafast transient absorption spectroscopy: principles and application to photosynthetic systems.

    PubMed

    Berera, Rudi; van Grondelle, Rienk; Kennis, John T M

    2009-01-01

    The photophysical and photochemical reactions, after light absorption by a photosynthetic pigment-protein complex, are among the fastest events in biology, taking place on timescales ranging from tens of femtoseconds to a few nanoseconds. The advent of ultrafast laser systems that produce pulses with femtosecond duration opened up a new area of research and enabled investigation of these photophysical and photochemical reactions in real time. Here, we provide a basic description of the ultrafast transient absorption technique, the laser and wavelength-conversion equipment, the transient absorption setup, and the collection of transient absorption data. Recent applications of ultrafast transient absorption spectroscopy on systems with increasing degree of complexity, from biomimetic light-harvesting systems to natural light-harvesting antennas, are presented. In particular, we will discuss, in this educational review, how a molecular understanding of the light-harvesting and photoprotective functions of carotenoids in photosynthesis is accomplished through the application of ultrafast transient absorption spectroscopy.

  18. Sulfur K-edge X-ray absorption spectroscopy as an experimental probe for S-nitroso proteins

    SciTech Connect

    Szilagyi, Robert K. . E-mail: Szilagyi@Montana.EDU; Schwab, David E.

    2005-04-29

    X-ray absorption spectroscopy at the sulfur K-edge (2.4-2.6 keV) provides a sensitive and specific technique to identify S-nitroso compounds, which have significance in nitric oxide-based cell signaling. Unique spectral features clearly distinguish the S-nitroso-form of a cysteine residue from the sulfhydryl-form or from a methionine thioether. Comparison of the sulfur K-edge spectra of thiolate, thiol, thioether, and S-nitroso thiolate compounds indicates high sensitivity of energy positions and intensities of XAS pre-edge features as determined by the electronic environment of the sulfur absorber. A new experimental setup is being developed for reaching the in vivo concentration range of S-nitroso thiol levels in biological samples.

  19. Fe-heme structure in Cu, Zn superoxide dismutase from Haemophilus ducreyi by X-ray absorption spectroscopy.

    PubMed

    D'Angelo, Paola; Zitolo, Andrea; Pacello, Francesca; Mancini, Giordano; Proux, Olivier; Hazemann, Jean Louis; Desideri, Alessandro; Battistoni, Andrea

    2010-06-01

    We have carried out an X-ray Absorption Spectroscopy (XAS) study of ferric, ferrous, CO- and NO-bound Haemophilus ducreyi Cu,ZnSOD (HdSOD) in solution to investigate the structural modifications induced by the binding of small gaseous ligands to heme in this enzyme. The combined analysis of EXAFS and XANES data has allowed us to characterize the local structure around the Fe-heme with 0.02A accuracy, revealing a heterogeneity in the distances between iron and the two histidine ligands which was not evident in the X-ray crystal structure. In addition, we have shown that the metal oxidation state does not influence the Fe-heme coordination environment, whereas the presence of the CO and NO ligands induces local structural rearrangements in the enzyme which are very similar to those already observed in other hexa-coordinated heme proteins, such as neuroglobin.

  20. An X-Ray Absorption Spectroscopy Study of Ball-Milled Lithium Tantalate and Lithium Titanate Nanocrystals

    NASA Astrophysics Data System (ADS)

    Chadwick, A. V.; Pickup, D. M.; Ramos, S.; Cibin, G.; Tapia-Ruiz, N.; Breuer, S.; Wohlmuth, D.; Wilkening, M.

    2017-02-01

    Previous work has shown that nanocrystalline samples of lithium tantalate and titanate prepared by high-energy milling show unusually high lithium ion conductivity. Here, we report an X-ray absorption spectroscopy (XAS) study at the Ti K-edge and the Ta L3 edge of samples that have been milled for various lengths of time. For both systems the results show that milling creates amorphous material whose quantity increases with the milling time. The more extensive data for the tantalate shows that milling for only 30 minutes generates ∼25% amorphous content in the sample. The content rises to ∼60% after 16 hours. It is suggested that it is the motion of the lithium ions through the amorphous content that provides the mechanism for the high ionic conductivity.

  1. 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.

  2. Arsenic speciation in solids using X-ray absorption spectroscopy

    USGS Publications Warehouse

    Foster, Andrea L.; Kim, Chris S.

    2014-01-01

    One of the most important aims of this review is to clarify the different types of analysis that are performed on As-XAS spectra, and to describe the benefits, drawbacks, and limitations of each. Arsenic XAS spectra are analyzed to obtain one or more of the following types of information (in increasing order of sophistication):

  3. X-ray absorption spectroscopy proves the trigonal-planar sulfur-only coordination of copper(I) with high-affinity tripodal pseudopeptides.

    PubMed

    Jullien, Anne-Solène; Gateau, Christelle; Kieffer, Isabelle; Testemale, Denis; Delangle, Pascale

    2013-09-03

    A series of tripodal ligands L derived from nitrilotriacetic acid (NTA) and extended by three converging metal-binding cysteine chains were previously found to bind selectively copper(I) both in vitro and in vivo. The ligands L(1) (ester) and L(2) (amide) were demonstrated to form copper(I) species with very high affinities, close to that reported for the metal-sequestering metallothioneins (MTs; log K(Cu-MT) ≈ 19). Here, an in-depth study by Cu K-edge X-ray absorption spectroscopy (XAS) was performed to completely characterize the copper(I) coordination sphere in the complexes, previously evidenced by other physicochemical analyses. The X-ray absorption near-edge structure (XANES) spectra shed light on the equilibrium between a mononuclear complex and a cluster for both L(1) (ester) and L(2) (amide). The exclusive symmetric CuS3 geometry adopted in the mononuclear complexes (Cu-S ≈ 2.23 Å) was clearly demonstrated by extended X-ray absorption fine structure (EXAFS) analyses. The EXAFS analyses also proved that the clusters are organized on a symmetric CuS3 core (Cu-S ≈ 2.26 Å) and interact with three nearby copper atoms (Cu---Cu ≈ 2.7 Å), consistent with the Cu6S9-type clusters previously characterized by pulsed gradient spin echo NMR spectroscopy. XAS data obtained for other architectures based on the NTA template (L(3) acid, L(4) without a functionalized carbonyl group, etc.) demonstrated the formation of polymetallic species only, which evidence the necessity of the proximal ester or amide group to stabilize the CuS3 mononuclear species. Finally, XAS was demonstrated to be a powerful method to quantify the equilibrium between the two copper(I) environments evidenced with L(1) and L(2) at different copper concentrations and to determine the equilibrium constants between these two complexes.

  4. Photoelectron and X-ray Absorption Spectroscopy Of Pu

    SciTech Connect

    Tobin, J; Chung, B; Schulze, R; Farr, J; Shuh, D

    2003-11-12

    We have performed Photoelectron Spectroscopy and X-Ray Absorption Spectroscopy upon highly radioactive samples of Plutonium at the Advanced Light Source in Berkeley, CA, USA. First results from alpha and delta Plutonium are reported as well as plans for future studies of actinide studies.

  5. Local electronic states of Fe4N films revealed by x-ray absorption spectroscopy and x-ray magnetic circular dichroism

    NASA Astrophysics Data System (ADS)

    Ito, Keita; Toko, Kaoru; Takeda, Yukiharu; Saitoh, Yuji; Oguchi, Tamio; Suemasu, Takashi; Kimura, Akio

    2015-05-01

    We performed x-ray absorption spectroscopy (XAS) and x-ray magnetic circular dichroism (XMCD) measurements at Fe L2,3 and N K-edges for Fe4N epitaxial films grown by molecular beam epitaxy. In order to clarify the element specific local electronic structure of Fe4N, we compared experimentally obtained XAS and XMCD spectra with those simulated by a combination of a first-principles calculation and Fermi's golden rule. We revealed that the shoulders observed at Fe L2,3-edges in the XAS and XMCD spectra were due to the electric dipole transition from the Fe 2p core-level to the hybridization state generated by σ* anti-bonding between the orbitals of N 2p at the body-centered site and Fe 3d on the face-centered (II) sites. Thus, the observed shoulders were attributed to the local electronic structure of Fe atoms at II sites. As to the N K-edge, the line shape of the obtained spectra was explained by the dipole transition from the N 1s core-level to the hybridization state formed by π* and σ* anti-bondings between the Fe 3d and N 2p orbitals. This hybridization plays an important role in featuring the electronic structures and physical properties of Fe4N.

  6. Local electronic states of Fe{sub 4}N films revealed by x-ray absorption spectroscopy and x-ray magnetic circular dichroism

    SciTech Connect

    Ito, Keita; Toko, Kaoru; Suemasu, Takashi; Takeda, Yukiharu; Saitoh, Yuji; Oguchi, Tamio; Kimura, Akio

    2015-05-21

    We performed x-ray absorption spectroscopy (XAS) and x-ray magnetic circular dichroism (XMCD) measurements at Fe L{sub 2,3} and N K-edges for Fe{sub 4}N epitaxial films grown by molecular beam epitaxy. In order to clarify the element specific local electronic structure of Fe{sub 4}N, we compared experimentally obtained XAS and XMCD spectra with those simulated by a combination of a first-principles calculation and Fermi's golden rule. We revealed that the shoulders observed at Fe L{sub 2,3}-edges in the XAS and XMCD spectra were due to the electric dipole transition from the Fe 2p core-level to the hybridization state generated by σ* anti-bonding between the orbitals of N 2p at the body-centered site and Fe 3d on the face-centered (II) sites. Thus, the observed shoulders were attributed to the local electronic structure of Fe atoms at II sites. As to the N K-edge, the line shape of the obtained spectra was explained by the dipole transition from the N 1s core-level to the hybridization state formed by π* and σ* anti-bondings between the Fe 3d and N 2p orbitals. This hybridization plays an important role in featuring the electronic structures and physical properties of Fe{sub 4}N.

  7. Site- and phase-selective x-ray absorption spectroscopy based on phase-retrieval calculation

    NASA Astrophysics Data System (ADS)

    Kawaguchi, Tomoya; Fukuda, Katsutoshi; Matsubara, Eiichiro

    2017-03-01

    Understanding the chemical state of a particular element with multiple crystallographic sites and/or phases is essential to unlocking the origin of material properties. To this end, resonant x-ray diffraction spectroscopy (RXDS) achieved through a combination of x-ray diffraction (XRD) and x-ray absorption spectroscopy (XAS) techniques can allow for the measurement of diffraction anomalous fine structure (DAFS). This is expected to provide a peerless tool for electronic/local structural analyses of materials with complicated structures thanks to its capability to extract spectroscopic information about a given element at each crystallographic site and/or phase. At present, one of the major challenges for the practical application of RXDS is the rigorous determination of resonant terms from observed DAFS, as this requires somehow determining the phase change in the elastic scattering around the absorption edge from the scattering intensity. This is widely known in the field of XRD as the phase problem. The present review describes the basics of this problem, including the relevant background and theory for DAFS and a guide to a newly-developed phase-retrieval method based on the logarithmic dispersion relation that makes it possible to analyze DAFS without suffering from the intrinsic ambiguities of conventional iterative-fitting. Several matters relating to data collection and correction of RXDS are also covered, with a final emphasis on the great potential of powder-sample-based RXDS (P-RXDS) to be used in various applications relevant to practical materials, including antisite-defect-type electrode materials for lithium-ion batteries.

  8. Site- and phase-selective x-ray absorption spectroscopy based on phase-retrieval calculation.

    PubMed

    Kawaguchi, Tomoya; Fukuda, Katsutoshi; Matsubara, Eiichiro

    2017-03-22

    Understanding the chemical state of a particular element with multiple crystallographic sites and/or phases is essential to unlocking the origin of material properties. To this end, resonant x-ray diffraction spectroscopy (RXDS) achieved through a combination of x-ray diffraction (XRD) and x-ray absorption spectroscopy (XAS) techniques can allow for the measurement of diffraction anomalous fine structure (DAFS). This is expected to provide a peerless tool for electronic/local structural analyses of materials with complicated structures thanks to its capability to extract spectroscopic information about a given element at each crystallographic site and/or phase. At present, one of the major challenges for the practical application of RXDS is the rigorous determination of resonant terms from observed DAFS, as this requires somehow determining the phase change in the elastic scattering around the absorption edge from the scattering intensity. This is widely known in the field of XRD as the phase problem. The present review describes the basics of this problem, including the relevant background and theory for DAFS and a guide to a newly-developed phase-retrieval method based on the logarithmic dispersion relation that makes it possible to analyze DAFS without suffering from the intrinsic ambiguities of conventional iterative-fitting. Several matters relating to data collection and correction of RXDS are also covered, with a final emphasis on the great potential of powder-sample-based RXDS (P-RXDS) to be used in various applications relevant to practical materials, including antisite-defect-type electrode materials for lithium-ion batteries.

  9. Evidence for core-shell nanoclusters in oxygen dispersion strengthened steels measured using X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Liu, S.; Odette, G. R.; Segre, C. U.

    2014-02-01

    Nanostructured ferritic alloys (NFA) dispersion strengthened by an ultra high density of Y-Ti-O enriched nano-features (NF) exhibit superior creep strength and the potential for high resistance to radiation damage. However, the detailed character of the NF, that precipitate from solid solution during hot consolidation of metallic powders mechanically alloyed with Y2O3, are not well understood. In order to clarify the nature of the NF, X-ray absorption spectroscopy (XAS) technique, including X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) were used to characterize the local structure of the Ti and Y atoms in both NFA powders and consolidated alloys. The powders were characterized in the as-received, as-milled and after annealing milled powders at 850, 1000 and 1150 °C. The consolidated alloys included powders hot isostatic pressed (HIPed) at 1150 °C and commercial vendor alloys, MA957 and J12YWT. The NFA XAS data were compared various Ti and Y-oxide standards. The XANES and EXAFS spectra for the annealed and HIPed powders are similar and show high temperature heat treatments shift the Y and Ti to more oxidized states that are consistent with combinations of Y2Ti2O7 and, especially, TiO. However, the MA957 and J12YWT and annealed-consolidated powder data differ. The commercial vendor alloys results more closely resemble the as-milled powder data and all show that a significant fraction of substitutional Ti remains dissolved in the (BCC) ferrite matrix.

  10. Evidence for core–shell nanoclusters in oxygen dispersion strengthened steels measured using X-ray absorption spectroscopy

    SciTech Connect

    Liu, S.; Odette, G. R.; Segre, C. U.

    2014-02-01

    Nanostructured ferritic alloys (NFA) dispersion strengthened by an ultra high density of Y–Ti–O enriched nano-features (NF) exhibit superior creep strength and the potential for high resistance to radiation damage. However, the detailed character of the NF, that precipitate from solid solution during hot consolidation of metallic powders mechanically alloyed with Y₂O₃, are not well understood. In order to clarify the nature of the NF, X-ray absorption spectroscopy (XAS) technique, including X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) were used to characterize the local structure of the Ti and Y atoms in both NFA powders and consolidated alloys. The powders were characterized in the as-received, as-milled and after annealing milled powders at 850, 1000 and 1150 °C. The consolidated alloys included powders hot isostatic pressed (HIPed) at 1150 °C and commercial vendor alloys, MA957 and J12YWT. The NFA XAS data were compared various Ti and Y-oxide standards. The XANES and EXAFS spectra for the annealed and HIPed powders are similar and show high temperature heat treatments shift the Y and Ti to more oxidized states that are consistent with combinations of Y₂Ti₂O₇ and, especially, TiO. However, the MA957 and J12YWT and annealed–consolidated powder data differ. The commercial vendor alloys results more closely resemble the as-milled powder data and all show that a significant fraction of substitutional Ti remains dissolved in the (BCC) ferrite matrix.

  11. X-ray absorption spectroscopy systematics at the tungsten L-edge.

    PubMed

    Jayarathne, Upul; Chandrasekaran, Perumalreddy; Greene, Angelique F; Mague, Joel T; DeBeer, Serena; Lancaster, Kyle M; Sproules, Stephen; Donahue, James P

    2014-08-18

    A series of mononuclear six-coordinate tungsten compounds spanning formal oxidation states from 0 to +VI, largely in a ligand environment of inert chloride and/or phosphine, was interrogated by tungsten L-edge X-ray absorption spectroscopy. The L-edge spectra of this compound set, comprised of [W(0)(PMe3)6], [W(II)Cl2(PMePh2)4], [W(III)Cl2(dppe)2][PF6] (dppe = 1,2-bis(diphenylphosphino)ethane), [W(IV)Cl4(PMePh2)2], [W(V)(NPh)Cl3(PMe3)2], and [W(VI)Cl6], correlate with formal oxidation state and have usefulness as references for the interpretation of the L-edge spectra of tungsten compounds with redox-active ligands and ambiguous electronic structure descriptions. The utility of these spectra arises from the combined correlation of the estimated branching ratio of the L3,2-edges and the L1 rising-edge energy with metal Zeff, thereby permitting an assessment of effective metal oxidation state. An application of these reference spectra is illustrated by their use as backdrop for the L-edge X-ray absorption spectra of [W(IV)(mdt)2(CO)2] and [W(IV)(mdt)2(CN)2](2-) (mdt(2-) = 1,2-dimethylethene-1,2-dithiolate), which shows that both compounds are effectively W(IV) species even though the mdt ligands exist at different redox levels in the two compounds. Use of metal L-edge XAS to assess a compound of uncertain formulation requires: (1) Placement of that data within the context of spectra offered by unambiguous calibrant compounds, preferably with the same coordination number and similar metal ligand distances. Such spectra assist in defining upper and/or lower limits for metal Zeff in the species of interest. (2) Evaluation of that data in conjunction with information from other physical methods, especially ligand K-edge XAS. (3) Increased care in interpretation if strong π-acceptor ligands, particularly CO, or π-donor ligands are present. The electron-withdrawing/donating nature of these ligand types, combined with relatively short metal-ligand distances, exaggerate

  12. X-ray Absorption Spectroscopy Systematics at the Tungsten L-Edge

    PubMed Central

    2015-01-01

    A series of mononuclear six-coordinate tungsten compounds spanning formal oxidation states from 0 to +VI, largely in a ligand environment of inert chloride and/or phosphine, was interrogated by tungsten L-edge X-ray absorption spectroscopy. The L-edge spectra of this compound set, comprised of [W0(PMe3)6], [WIICl2(PMePh2)4], [WIIICl2(dppe)2][PF6] (dppe = 1,2-bis(diphenylphosphino)ethane), [WIVCl4(PMePh2)2], [WV(NPh)Cl3(PMe3)2], and [WVICl6], correlate with formal oxidation state and have usefulness as references for the interpretation of the L-edge spectra of tungsten compounds with redox-active ligands and ambiguous electronic structure descriptions. The utility of these spectra arises from the combined correlation of the estimated branching ratio of the L3,2-edges and the L1 rising-edge energy with metal Zeff, thereby permitting an assessment of effective metal oxidation state. An application of these reference spectra is illustrated by their use as backdrop for the L-edge X-ray absorption spectra of [WIV(mdt)2(CO)2] and [WIV(mdt)2(CN)2]2– (mdt2– = 1,2-dimethylethene-1,2-dithiolate), which shows that both compounds are effectively WIV species even though the mdt ligands exist at different redox levels in the two compounds. Use of metal L-edge XAS to assess a compound of uncertain formulation requires: (1) Placement of that data within the context of spectra offered by unambiguous calibrant compounds, preferably with the same coordination number and similar metal ligand distances. Such spectra assist in defining upper and/or lower limits for metal Zeff in the species of interest. (2) Evaluation of that data in conjunction with information from other physical methods, especially ligand K-edge XAS. (3) Increased care in interpretation if strong π-acceptor ligands, particularly CO, or π-donor ligands are present. The electron-withdrawing/donating nature of these ligand types, combined with relatively short metal–ligand distances, exaggerate the difference

  13. Synchrotron X-ray Powder Diffraction and Absorption Spectroscopy in Pulsed Magnetic Fields with Milliseconds Duration

    NASA Astrophysics Data System (ADS)

    Vanacken, J.; Detlefs, C.; Mathon, O.; Frings, P.; Duc, F.; Lorenzo, J. E.; Nardone, M.; Billette, J.; Zitouni, A.; Dominguez, M.-C.; Herczeg, J.; Bras, W.; Moshchalkov, V. V.; Rikken, G.

    2007-03-01

    X-ray Powder Diffraction and X-ray Absorption Spectroscopy experiments (WAS) and X-ray magnetic circular dichroism (XMCD) experiments were carried out at the ESRF DUBBLE beam line (BM26) and at the energy dispersive beam line (ID24), respectively. A mobile pulse generator, developed at the LNCMP, delivered 110kJ to the load coil, which was sufficient to generate peak fields of 30T with a rise time of about 5 ms. A liquid He flow cryostat allowed us to vary the sample temperature accurately between 4.2K and 300K. Powder diffraction patterns of TbVO4 were recorded in a broad temperature range using 21 keV monochromatic X-rays and using an on-line image plate detector. We observed the suppression of the Jahn-Teller structural distortion in TbVO4 due to the high magnetic pulsed field. XAS spectra could be measured and finite XMCD signals, directly proportional to the magnetic moment on the Gd absorber atom, were measured in thin Gd foils. Thanks to its element and orbital selectivity, XMCD proofs to be very useful in probing the magnetic properties and due to the strong brilliance of the synchrotron beam, the signals can be measured even in the ms range.

  14. Properties of aqueous nitrate and nitrite from x-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Smith, Jacob W.; Lam, Royce K.; Shih, Orion; Rizzuto, Anthony M.; Prendergast, David; Saykally, Richard J.

    2015-08-01

    Nitrate and nitrite ions are of considerable interest, both for their widespread use in commercial and research contexts and because of their central role in the global nitrogen cycle. The chemistry of atmospheric aerosols, wherein nitrate is abundant, has been found to depend on the interfacial behavior of ionic species. The interfacial behavior of ions is determined largely by their hydration properties; consequently, the study of the hydration and interfacial behavior of nitrate and nitrite comprises a significant field of study. In this work, we describe the study of aqueous solutions of sodium nitrate and nitrite via X-ray absorption spectroscopy (XAS), interpreted in light of first-principles density functional theory electronic structure calculations. Experimental and calculated spectra of the nitrogen K-edge XA spectra of bulk solutions exhibit a large 3.7 eV shift between the XA spectra of nitrate and nitrite resulting from greater stabilization of the nitrogen 1s energy level in nitrate. A similar shift is not observed in the oxygen K-edge XA spectra of NO3- and NO2-. The hydration properties of nitrate and nitrite are found to be similar, with both anions exhibiting a similar propensity towards ion pairing.

  15. Properties of aqueous nitrate and nitrite from x-ray absorption spectroscopy

    SciTech Connect

    Smith, Jacob W.; Lam, Royce K.; Saykally, Richard J.; Shih, Orion; Rizzuto, Anthony M.; Prendergast, David

    2015-08-28

    Nitrate and nitrite ions are of considerable interest, both for their widespread use in commercial and research contexts and because of their central role in the global nitrogen cycle. The chemistry of atmospheric aerosols, wherein nitrate is abundant, has been found to depend on the interfacial behavior of ionic species. The interfacial behavior of ions is determined largely by their hydration properties; consequently, the study of the hydration and interfacial behavior of nitrate and nitrite comprises a significant field of study. In this work, we describe the study of aqueous solutions of sodium nitrate and nitrite via X-ray absorption spectroscopy (XAS), interpreted in light of first-principles density functional theory electronic structure calculations. Experimental and calculated spectra of the nitrogen K-edge XA spectra of bulk solutions exhibit a large 3.7 eV shift between the XA spectra of nitrate and nitrite resulting from greater stabilization of the nitrogen 1s energy level in nitrate. A similar shift is not observed in the oxygen K-edge XA spectra of NO{sub 3}{sup −} and NO{sub 2}{sup −}. The hydration properties of nitrate and nitrite are found to be similar, with both anions exhibiting a similar propensity towards ion pairing.

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

    SciTech Connect

    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 spectroscopy (XAS) is a short-range order, element specific technique that can be utilized to probe the processes occurring at operating electrode surfaces, as well for studying the amorphous materials and nano-particles making up the electrodes. It has been increasingly used in recent years to study fuel cell catalysts through application of the and #916; and mgr; XANES technique, in combination with the more traditional X-ray Absorption Near Edge Structure (XANES) and Extended X-ray Absorption Fine Structure (EXAFS) techniques. The and #916; and mgr; XANES data analysis technique, previously developed and applied to heterogeneous catalysts and fuel cell electrocatalysts by the GWU group, was extended in this work to provide for the first time space resolved adsorbate coverages on both electrodes of a direct methanol fuel cell. Even more importantly, the and #916; and mgr; technique was applied for the first time to battery relevant materials, where bulk properties such as the oxidation state and local geometry of a cathode are followed.

  17. The structures of T6, T3R3 and R6 bovine insulin: combining X-ray diffraction and absorption spectroscopy.

    PubMed

    Frankær, Christian Grundahl; Knudsen, Marianne Vad; Norén, Katarina; Nazarenko, Elena; Ståhl, Kenny; Harris, Pernille

    2012-10-01

    The crystal structures of three conformations, T(6), T(3)R(3) and R(6), of bovine insulin were solved at 1.40, 1.30 and 1.80 Å resolution, respectively. All conformations crystallized in space group R3. In contrast to the T(6) and T(3)R(3) structures, different conformations of the N-terminal B-chain residue PheB1 were observed in the R(6) insulin structure, resulting in an eightfold doubling of the unit-cell volume upon cooling. The zinc coordination in each conformation was studied by X-ray absorption spectroscopy (XAS), including both EXAFS and XANES. Zinc adopts a tetrahedral coordination in all R(3) sites and an octahedral coordination in T(3) sites. The coordination distances were refined from XAS with a standard deviation of <0.01 Å. In contrast to the distances determined from the medium-resolution crystal structures, the XAS results were in good agreement with similar coordination geometries found in small molecules, as well as in other high-resolution insulin structures. As the radiation dose for XRD experiments is two orders of magnitude higher compared with that of XAS experiments, the single crystals were exposed to a higher degree of radiation damage that affected the zinc coordination in the T(3) sites in particular. Furthermore, XANES spectra for the zinc sites in T(6) and R(6) insulin were successfully calculated using finite difference methods and the bond distances and angles were optimized from a quantitative XANES analysis.

  18. Conduction-band electronic states of YbInCu{sub 4} studied by photoemission and soft x-ray absorption spectroscopies

    SciTech Connect

    Utsumi, Yuki; Kurihara, Hidenao; Maso, Hiroyuki; Tobimatsu, Komei; Sato, Hitoshi; Shimada, Kenya; Namatame, Hirofumi; Hiraoka, Koichi; Kojima, Kenichi; Ohkochi, Takuo; Fujimori, Shin-ichi; Takeda, Yukiharu; Saitoh, Yuji; Mimura, Kojiro; Ueda, Shigenori; Yamashita, Yoshiyuki; Yoshikawa, Hideki; Kobayashi, Keisuke; Oguchi, Tamio; Taniguchi, Masaki

    2011-09-15

    We have studied conduction-band (CB) electronic states of a typical valence-transition compound YbInCu{sub 4} by means of temperature-dependent hard x-ray photoemission spectroscopy (HX-PES) of the Cu 2p{sub 3/2} and In 3d{sub 5/2} core states taken at h{nu}=5.95 keV, soft x-ray absorption spectroscopy (XAS) of the Cu 2p{sub 3/2} core absorption region around h{nu}{approx}935 eV, and soft x-ray photoemission spectroscopy (SX-PES) of the valence band at the Cu 2p{sub 3/2} absorption edge of h{nu}=933.0 eV. With decreasing temperature below the valence transition at T{sub V}=42 K, we have found that (1) the Cu 2p{sub 3/2} and In 3d{sub 5/2} peaks in the HX-PES spectra exhibit the energy shift toward the lower binding-energy side by {approx}40 and {approx}30 meV, respectively, (2) an energy position of the Cu 2p{sub 3/2} main absorption peak in the XAS spectrum is shifted toward higher photon-energy side by {approx}100 meV, with an appearance of a shoulder structure below the Cu 2p{sub 3/2} main absorption peak, and (3) an intensity of the Cu L{sub 3}VV Auger spectrum is abruptly enhanced. These experimental results suggest that the Fermi level of the CB-derived density of states is shifted toward the lower binding-energy side. We have described the valence transition in YbInCu{sub 4} in terms of the charge transfer from the CB to Yb 4f states.

  19. Nearedge Absorption Spectroscopy of Interplanetary Dust Particles

    SciTech Connect

    Brennan, S.; Luening, K.; Pianetta, P.; Bradley, J.; Graham, G.; Westphal, A.; Snead, C.; Dominguez, G.; /SLAC, SSRL

    2006-10-25

    Interplanetary Dust Particles (IDPs) are derived from primitive Solar System bodies like asteroids and comets. Studies of IDPs provide a window onto the origins of the solar system and presolar interstellar environments. We are using Total Reflection X-ray Fluorescence (TXRF) techniques developed for the measurement of the cleanliness of silicon wafer surfaces to analyze these particles with high detection sensitivity. In addition to elemental analysis of the particles, we have collected X-ray Absorption Near-Edge spectra in a grazing incidence geometry at the Fe and Ni absorption edges for particles placed on a silicon wafer substrate. We find that the iron is dominated by Fe{sub 2}O{sub 3}.

  20. An in situ sample environment reaction cell for spatially resolved x-ray absorption spectroscopy studies of powders and small structured reactors

    SciTech Connect

    Zhang, Chu; Gustafson, Johan; Merte, Lindsay R.; Evertsson, Jonas; Norén, Katarina; Carlson, Stefan; Svensson, Håkan; Carlsson, Per-Anders

    2015-03-15

    An easy-to-use sample environment reaction cell for X-ray based in situ studies of powders and small structured samples, e.g., powder, pellet, and monolith catalysts, is described. The design of the cell allows for flexible use of appropriate X-ray transparent windows, shielding the sample from ambient conditions, such that incident X-ray energies as low as 3 keV can be used. Thus, in situ X-ray absorption spectroscopy (XAS) measurements in either transmission or fluorescence mode are facilitated. Total gas flows up to about 500 ml{sub n}/min can be fed while the sample temperature is accurately controlled (at least) in the range of 25–500 °C. The gas feed is composed by a versatile gas-mixing system and the effluent gas flow composition is monitored with mass spectrometry (MS). These systems are described briefly. Results from simultaneous XAS/MS measurements during oxidation of carbon monoxide over a 4% Pt/Al{sub 2}O{sub 3} powder catalyst are used to illustrate the system performance in terms of transmission XAS. Also, 2.2% Pd/Al{sub 2}O{sub 3} and 2% Ag − Al{sub 2}O{sub 3} powder catalysts have been used to demonstrate X-ray absorption near-edge structure (XANES) spectroscopy in fluorescence mode. Further, a 2% Pt/Al{sub 2}O{sub 3} monolith catalyst was used ex situ for transmission XANES. The reaction cell opens for facile studies of structure-function relationships for model as well as realistic catalysts both in the form of powders, small pellets, and coated or extruded monoliths at near realistic conditions. The applicability of the cell for X-ray diffraction measurements is discussed.

  1. Analysis of the effects of surface chemistry on the XAS spectra of CdSe nanomaterials

    NASA Astrophysics Data System (ADS)

    Whitley, Heather; Prendergast, David; Ogitsu, Tadashi; Schwegler, Eric

    2010-03-01

    X-ray absorption spectroscopy (XAS) is an element-specific probe of local electronic structure, and is an ideal method to analyze chemical bonding. We investigate the consistency of theoretically predicted structures of CdSe nanomaterials with recently measured XAS via ab initio calculations. Using plane-wave DFT, the x-ray absorption cross-section for the Cd L3-edge of small CdSe clusters with a variety of surface ligands is calculated. We also highlight the importance of including excitonic effects in our simulations of core excitation spectra. We compare our simulations to existing experimental data on the ligand dependence of XAS for ligated quantum dots up to ˜3nm in diameter. Based on the favorable comparison of our theoretical spectra with experimental measurements, we infer the validity of our DFT-derived structure and surface passivation for these quantum dots and its relevance to understanding optoelectronic properties of solution-synthesized CdSe nanocrystals. Prepared by LLNL under Contract DE-AC52-07NA27344.

  2. Optoacoustic spectroscopy and its application to molecular and particle absorption

    NASA Astrophysics Data System (ADS)

    Trees, Charles C.; Voss, Kenneth J.

    1990-09-01

    Light absorption in the ocean has been the least studied optical property because of the difficulties in making accurate measurements. With the previously used techniques, large differences have been reported for the specific absorption coefficient of phytoplankton (cultures and natural assemblages). It is difficult to determine if the diversity in these values are methodological or a function of actual variations in absorption. With the renewed interest and activity in optoacoustic spectroscopy (OAS), which accurately measures absorption, some of these discrepancies should be resolved. In this method, as molecules and particles absorb light from a modulated source, they thermally expand and contract, thereby generating acoustic waves, at the modulation frequency, which are detected by a hydrophone. Optoacoustic spectroscopy is ideally suited for measuring dissolved organic material and particle absorptions because of its high sensitivity (105m1) and the egligible effect of scattered light. In this paper the instrumental design for an optoacoustic spectrophotometer (OAS), which pecifically measures phytoplankton absorption (420-S5Onm), is described. The spectral absorption of dissolved organic material and a phytoplankton culture is presented. OAS holds promise in being able to measure absorption without use of either filtration or concentration techniques.

  3. In situ soft X-ray absorption spectroscopy of flames

    NASA Astrophysics Data System (ADS)

    Frank, Jonathan H.; Shavorskiy, Andrey; Bluhm, Hendrik; Coriton, Bruno; Huang, Erxiong; Osborn, David L.

    2014-10-01

    The feasibility of in situ soft X-ray absorption spectroscopy for imaging carbonaceous species in hydrocarbon flames is demonstrated using synchrotron radiation. Soft X-rays are absorbed by core level electrons in all carbon atoms regardless of their molecular structure. Core electron spectroscopy affords distinct advantages over valence spectroscopy, which forms the basis of traditional laser diagnostic techniques for combustion. In core level spectroscopy, the transition linewidths are predominantly determined by the instrument response function and the decay time of the core-hole, which is on the order of a femtosecond. As a result, soft X-ray absorption measurements can be performed in flames with negligible Doppler and collisional broadening. Core level spectroscopy has the further advantage of measuring all carbonaceous species regardless of molecular structure in the far-edge region, whereas near-edge features are molecule specific. Interferences from non-carbon flame species are unstructured and can be subtracted. In the present study, absorption measurements in the carbon K-edge region are demonstrated in low-pressure ( P total = 20-30 Torr) methane jet flames. Two-dimensional imaging of the major carbonaceous species, CH4, CO2, and CO, is accomplished by tuning the synchrotron radiation to the respective carbon K-edge, near-edge X-ray absorption fine structure (NEXAFS) transitions and scanning the burner.

  4. Molecular shock response of explosives: electronic absorption spectroscopy

    SciTech Connect

    Mcgrne, Shawn D; Moore, David S; Whitley, Von H; Bolme, Cindy A; Eakins, Daniel E

    2009-01-01

    Electronic absorption spectroscopy in the range 400-800 nm was coupled to ultrafast laser generated shocks to begin addressing the question of the extent to which electronic excitations are involved in shock induced reactions. Data are presented on shocked polymethylmethacrylate (PMMA) thin films and single crystal pentaerythritol tetranitrate (PETN). Shocked PMMA exhibited thin film interference effects from the shock front. Shocked PETN exhibited interference from the shock front as well as broadband increased absorption. Relation to shock initiation hypotheses and the need for time dependent absorption data (future experiments) is briefly discussed.

  5. Molecular Shock Response of Explosives: Electronic Absorption Spectroscopy

    NASA Astrophysics Data System (ADS)

    McGrane, S. D.; Moore, D. S.; Whitley, V. H.; Bolme, C. A.; Eakins, D. E.

    2009-12-01

    Electronic absorption spectroscopy in the range 400-800 nm was coupled to ultrafast laser generated shocks to begin addressing the extent to which electronic excitations are involved in shock induced reactions. Data are presented on shocked polymethylmethacrylate (PMMA) thin films and single crystal pentaerythritol tetranitrate (PETN). Shocked PMMA exhibited thin film interference effects from the shock front. Shocked PETN exhibited interference as well as broadband increased absorption. Relation to shock initiation and the need for time dependent absorption (future experiments) is briefly discussed.

  6. Characterization of Metalloproteins by High-throughput X-ray Absorption Spectroscopy

    SciTech Connect

    W Shi; M Punta; J Bohon; J Sauder; R DMello; M Sullivan; J Toomey; D Abel; M Lippi; et al.

    2011-12-31

    High-throughput X-ray absorption spectroscopy was used to measure transition metal content based on quantitative detection of X-ray fluorescence signals for 3879 purified proteins from several hundred different protein families generated by the New York SGX Research Center for Structural Genomics. Approximately 9% of the proteins analyzed showed the presence of transition metal atoms (Zn, Cu, Ni, Co, Fe, or Mn) in stoichiometric amounts. The method is highly automated and highly reliable based on comparison of the results to crystal structure data derived from the same protein set. To leverage the experimental metalloprotein annotations, we used a sequence-based de novo prediction method, MetalDetector, to identify Cys and His residues that bind to transition metals for the redundancy reduced subset of 2411 sequences sharing <70% sequence identity and having at least one His or Cys. As the HT-XAS identifies metal type and protein binding, while the bioinformatics analysis identifies metal-binding residues, the results were combined to identify putative metal-binding sites in the proteins and their associated families. We explored the combination of this data with homology models to generate detailed structure models of metal-binding sites for representative proteins. Finally, we used extended X-ray absorption fine structure data from two of the purified Zn metalloproteins to validate predicted metalloprotein binding site structures. This combination of experimental and bioinformatics approaches provides comprehensive active site analysis on the genome scale for metalloproteins as a class, revealing new insights into metalloprotein structure and function.

  7. Design and Operation of a High Pressure Reaction Cell for in situ X-ray Absorption Spectroscopy

    SciTech Connect

    Bare,S.; Yang, N.; Kelly, S.; Mickelson, G.; Modica, F.

    2007-01-01

    X-ray absorption spectroscopy measurements of catalytic reactions have been instrumental in advancing the understanding of catalytic processes. These measurements require an in situ catalysis reaction cell with unique properties. Here we describe the design and initial operation of an in situ/operando catalysis reaction cell for transmission X-ray absorption spectroscopy measurements. The cell is designed: to be an ideal catalytic reactor with no mass transfer effects; to give the same conversion and selectivity under similar space velocities as standard laboratory micro-reactors; to be operational temperatures up to 600 {sup o}C and pressures up to 14 bar; to be X-ray transparent allowing XAS measurement to be collected in transmission for all elements with Z {>=} 23 (vanadium K-edge at 5.5 keV); to measure the actual catalyst bed temperature; to not use o-ring seals, or water cooling; to be robust, compact, easy to assemble, and use, and relatively low cost to produce. The heart of the cell is fabricated from an X-ray transparent beryllium tube that forms a plug flow reactor. XAFS data recorded during the reduction of a Re/{gamma}-A{sub 2}O{sub 3} catalyst as a function of hydrogen pressure from 0.05 to 8 bar, and from a Pt-Sn/{gamma}-A{sub 2}O{sub 3} catalyst during n-heptane reforming are given as initial examples of the versatility of the reactor.

  8. Intermediate coupling for core-level excited states: Consequences for X-Ray absorption spectroscopy

    SciTech Connect

    Bagus, Paul S.; Sassi, Michel J.; Rosso, Kevin M.

    2015-04-01

    The origin of the complex NEXAFS features of X-Ray Absorption, XAS, spectra in transition metal complexes is analyzed and interpreted in terms of the angular momentum coupling of the open shell electrons. Especially for excited configurations where a core-electron is promoted to an open valence shell, the angular momentum coupling is intermediate between the two limits of Russell- Saunders, RS, coupling where spin-orbit splitting of the electron shells is neglected and j-j coupling where this splitting is taken as dominant. The XAS intensities can be understood in terms of two factors: (1) The dipole selection rules that give the allowed excited RS multiplets and (2) The contributions of these allowed multiplets to the wavefunctions of the intermediate coupled levels. It is shown that the origin of the complex XAS spectra is due to the distribution of the RS allowed multiplets over several different intermediate coupled excited levels. The specific case that is analyzed is the L2,3 edge XAS of an Fe3+ cation, because this cation allows a focus on the angular momentum coupling to the exclusion of other effects; e.g., chemical bonding. Arguments are made that the properties identified for this atomic case are relevant for more complex materials. The analysis is based on the properties of fully relativistic, ab initio, many-body wavefunctions for the initial and final states of the XAS process. The wavefunction properties considered include the composition of the wavefunctions in terms of RS multiplets and the occupations of the spin-orbit split open shells; the latter vividly show whether the coupling is j-j or not.

  9. Absorption and Emission Spectroscopy of a Lasing Material: Ruby

    ERIC Educational Resources Information Center

    Esposti, C. Degli; Bizzocchi, L.

    2007-01-01

    Ruby is a crystalline material, which comes very expensive and is of great significance, as it helped in the creation of first laser. An experiment to determine the absorption and emission spectroscopy, in addition to the determination of the room-temperature lifetime of the substance is being described.

  10. Atomic Absorption Spectroscopy. The Present and the Future.

    ERIC Educational Resources Information Center

    Slavin, Walter

    1982-01-01

    The status of current techniques and methods of atomic absorption (AA) spectroscopy (flame, hybrid, and furnace AA) is discussed, including limitations. Technological opportunities and how they may be used in AA are also discussed, focusing on automation, microprocessors, continuum AA, hybrid analyses, and others. (Author/JN)

  11. Visualizing the Solute Vaporization Interference in Flame Atomic Absorption Spectroscopy

    ERIC Educational Resources Information Center

    Dockery, Christopher R.; Blew, Michael J.; Goode, Scott R.

    2008-01-01

    Every day, tens of thousands of chemists use analytical atomic spectroscopy in their work, often without knowledge of possible interferences. We present a unique approach to study these interferences by using modern response surface methods to visualize an interference in which aluminum depresses the calcium atomic absorption signal. Calcium…

  12. [Burner head with high sensitivity in atomic absorption spectroscopy].

    PubMed

    Feng, X; Yang, Y

    1998-12-01

    This paper presents a burner head with gas-sample separate entrance and double access, which is used for atomic absorption spectroscopy. According to comparison and detection, the device can improve sensitivity by a factor of 1 to 5. In the meantime it has properties of high stability and resistance to interference.

  13. Developing a Transdisciplinary Teaching Implement for Atomic Absorption Spectroscopy

    ERIC Educational Resources Information Center

    Drew, John

    2008-01-01

    In this article I explain why I wrote the set of teaching notes on Atomic Absorption Spectroscopy (AAS) and why they look the way they do. The notes were intended as a student reference to question, highlight and write over as much as they wish during an initial practical demonstration of the threshold concept being introduced, in this case…

  14. Peculiar Behavior of (U,Am)O(2-δ) Compounds for High Americium Contents Evidenced by XRD, XAS, and Raman Spectroscopy.

    PubMed

    Lebreton, Florent; Horlait, Denis; Caraballo, Richard; Martin, Philippe M; Scheinost, Andreas C; Rossberg, Andre; Jégou, Christophe; Delahaye, Thibaud

    2015-10-19

    In U(1-x)Am(x)O(2±δ) compounds with low americium content (x ≤ 20 atom %) and oxygen-to-metal (O/M) ratios close to 2.0, Am(III+) cations are charge-balanced by an equivalent amount of U(V+) cations while the fluorite structure of pure U(IV+)O2 is maintained. Up to now, it is unknown whether this observation also holds for higher americium contents. In this study, we combined X-ray diffraction with Raman and X-ray absorption spectroscopies to investigate a U(0.5)Am(0.5)O(2±δ) compound. Our results indicate that americium is again only present as Am(III+), while U(V+) remains below the amount required for charge balance. Unlike lower americium contents, this leads to an overall oxygen hypostoichiometry with an average O/M ratio of 1.92(2). The cationic sublattice is only slightly affected by the coexistence of large amounts of reduced (Am(III+)) and oxidized (U(V+)) cations, whereas significant deviations from the fluorite structure are evidenced by both extended X-ray absorption fine structure and Raman spectroscopies in the oxygen sublattice, with the observation of both vacancies and interstitials, the latter being apparently consistent with the insertion of U6O12 cuboctahedral-type clusters (as observed in the U4O9 or U3O7 phases). These results thus highlight the specificities of uranium-americium mixed oxides, which behave more like trivalent lanthanide-doped UO2 than U(1-x)Pu(x)O(2±δ) MOX fuels.

  15. Combined surface plasmon resonance and X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Garcia, Miguel Angel; Serrano, Aida; Rodriguez de La Fuente, Oscar; Castro, German R.

    2012-02-01

    We present a system for the excitation and measurement of surface plasmons in metallic films based on the Kretschmann-Raether configuration that can be installed in a synchrotron beamline. The device was mounted an tested in a hard X-ray Absorption beamline, BM25 Spline at ESRF. Whit this device it is possible to carry on experiments combining surface plasmon and X-ray absorption spectroscopies. The surface plasmons can be use to monitor in situ changes induced by the X-rays in the metallic films or the dielectric overlayer. Similarly, the changes in the electronic configuration of the material when surface plasmons are excited can be measured by X-ray absorption spectroscopy. The resolution of the system allows to observe changes in the signals of the order of 10-3 to 10-5 depending on the particular experiment and used configuration. The system is available for experiments at the beamline.

  16. Li deinsertion mechanism and Jahn–Teller distortion in LiFe0.75Mn0.25PO4: an operando x-ray absorption spectroscopy investigation

    NASA Astrophysics Data System (ADS)

    Iadecola, Antonella; Perea, Alexis; Aldon, Laurent; Aquilanti, Giuliana; Stievano, Lorenzo

    2017-04-01

    The electrochemical lithiation of the mixed metal olivine LiFe0.75Mn0.25PO4 was followed by operando x-ray absorption spectroscopy (XAS) at both Fe and Mn K edges. XAS data were interpreted using an innovating chemometric approach, allowing the detailed reconstruction of the rather complicated reaction mechanism involving two different metal centres. In this way it was possible to precisely describe the Jahn–Teller effect occurring upon oxidation of the manganese centres. The thorough comprehension of the electrochemical mechanism is of high interest for studying the effect of lithium extraction in the olivine structure in the presence of Mn, which is known to partially hamper the complete lithiation of such mixed metal systems.

  17. Polarization-enhanced absorption spectroscopy for laser stabilization.

    PubMed

    Kunz, Paul D; Heavner, Thomas P; Jefferts, Steven R

    2013-11-20

    We demonstrate a variation of pump-probe spectroscopy that is particularly useful for laser frequency stabilization. The polarization-enhanced absorption spectroscopy (POLEAS) signal provides a significant improvement in signal-to-noise ratio over saturated absorption spectroscopy (SAS) for the important and commonly used atomic cycling transitions. The improvements can directly increase the short-term stability of a laser frequency lock, given sufficient servo loop bandwidth. The long-term stability of the POLEAS method, which is limited by environmental sensitivities, is comparable to that of SAS. The POLEAS signal is automatically Doppler-free, without requiring a separate Doppler subtraction beam, and lends itself to straightforward compact packaging. Finally, by increasing the amplitude of the desired (cycling) peak, while reducing the amplitude of all other peaks in the manifold, the POLEAS method eases the implementation of laser auto-locking schemes.

  18. Analyte-induced spectral filtering in femtosecond transient absorption spectroscopy

    DOE PAGES

    Abraham, Baxter; Nieto-Pescador, Jesus; Gundlach, Lars

    2017-03-06

    Here, we discuss the influence of spectral filtering by samples in femtosecond transient absorption measurements. Commercial instruments for transient absorption spectroscopy (TA) have become increasingly available to scientists in recent years and TA is becoming an established technique to measure the dynamics of photoexcited systems. Furthermore, we show that absorption of the excitation pulse by the sample can severely alter the spectrum and consequently the temporal pulse shape. This “spectral self-filtering” effect can lead to systematic errors and misinterpretation of data, most notably in concentration dependent measurements. Finally, the combination of narrow absorption peaks in the sample with ultrafast broadbandmore » excitation pulses is especially prone to this effect.« less

  19. Communication: XUV transient absorption spectroscopy of iodomethane and iodobenzene photodissociation.

    PubMed

    Drescher, L; Galbraith, M C E; Reitsma, G; Dura, J; Zhavoronkov, N; Patchkovskii, S; Vrakking, M J J; Mikosch, J

    2016-07-07

    Time-resolved extreme ultraviolet (XUV) transient absorption spectroscopy of iodomethane and iodobenzene photodissociation at the iodine pre-N4,5 edge is presented, using femtosecond UV pump pulses and XUV probe pulses from high harmonic generation. For both molecules the molecular core-to-valence absorption lines fade immediately, within the pump-probe time-resolution. Absorption lines converging to the atomic iodine product emerge promptly in CH3I but are time-delayed in C6H5I. We attribute this delay to the initial π → σ(*) excitation in iodobenzene, which is distant from the iodine reporter atom. We measure a continuous shift in energy of the emerging atomic absorption lines in CH3I, attributed to relaxation of the excited valence shell. An independent particle model is used to rationalize the observed experimental findings.

  20. Communication: XUV transient absorption spectroscopy of iodomethane and iodobenzene photodissociation

    NASA Astrophysics Data System (ADS)

    Drescher, L.; Galbraith, M. C. E.; Reitsma, G.; Dura, J.; Zhavoronkov, N.; Patchkovskii, S.; Vrakking, M. J. J.; Mikosch, J.

    2016-07-01

    Time-resolved extreme ultraviolet (XUV) transient absorption spectroscopy of iodomethane and iodobenzene photodissociation at the iodine pre-N4,5 edge is presented, using femtosecond UV pump pulses and XUV probe pulses from high harmonic generation. For both molecules the molecular core-to-valence absorption lines fade immediately, within the pump-probe time-resolution. Absorption lines converging to the atomic iodine product emerge promptly in CH3I but are time-delayed in C6H5I. We attribute this delay to the initial π → σ* excitation in iodobenzene, which is distant from the iodine reporter atom. We measure a continuous shift in energy of the emerging atomic absorption lines in CH3I, attributed to relaxation of the excited valence shell. An independent particle model is used to rationalize the observed experimental findings.

  1. In-plane polarization dependence of (Bi,Pb)2Sr2CaCu2O8+δ single crystals studied by X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Ghafari, A.; Ariffin, A. K.; Janowitz, C.; Dwelk, H.; Krapf, A.; Manzke, R.

    2014-06-01

    The effects of in-plane polarization change on the determination of the hole density of weakly under-doped (Bi, Pb)-2212 single crystals has been studied by x-ray absorption spectroscopy (XAS). The XAS signal at the CuL3 edge (925-940 eV) and O K edge (525 eV to 539 eV) were recorded under continuous rotation of the CuO2 plane from 0° to 180° with a minimum increment of 1.8°, yielding experimentally an in-plane polarization dependence for the absorption signals at the respective threshold. From that the in-plane angular dependence of the hole density (nH(φ) could be determined. Fermi's golden rule was then used for the evaluation of the in-plane polarization dependence showing the expected polarization independence in disaccord to the experimental observations. Possible scenarios to solve this issue are discussed. Our results propose that polarization dependence could be due to inhomogeneous distribution of holes in the CuO2 planes which is also supported by models. Second, the role of out of plane orbitals has to be taken into account for interpretation.

  2. Estimation of molar absorptivities and pigment sizes for eumelanin and pheomelanin using femtosecond transient absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Piletic, Ivan R.; Matthews, Thomas E.; Warren, Warren S.

    2009-11-01

    Fundamental optical and structural properties of melanins are not well understood due to their poor solubility characteristics and the chemical disorder present during biomolecular synthesis. We apply nonlinear transient absorption spectroscopy to quantify molar absorptivities for eumelanin and pheomelanin and thereby get an estimate for their average pigment sizes. We determine that pheomelanin exhibits a larger molar absorptivity at near IR wavelengths (750nm), which may be extended to shorter wavelengths. Using the molar absorptivities, we estimate that melanin pigments contain ˜46 and 28 monomer units for eumelanin and pheomelanin, respectively. This is considerably larger than the oligomeric species that have been recently proposed to account for the absorption spectrum of eumelanin and illustrates that larger pigments comprise a significant fraction of the pigment distribution.

  3. Estimation of molar absorptivities and pigment sizes for eumelanin and pheomelanin using femtosecond transient absorption spectroscopy.

    PubMed

    Piletic, Ivan R; Matthews, Thomas E; Warren, Warren S

    2009-11-14

    Fundamental optical and structural properties of melanins are not well understood due to their poor solubility characteristics and the chemical disorder present during biomolecular synthesis. We apply nonlinear transient absorption spectroscopy to quantify molar absorptivities for eumelanin and pheomelanin and thereby get an estimate for their average pigment sizes. We determine that pheomelanin exhibits a larger molar absorptivity at near IR wavelengths (750 nm), which may be extended to shorter wavelengths. Using the molar absorptivities, we estimate that melanin pigments contain approximately 46 and 28 monomer units for eumelanin and pheomelanin, respectively. This is considerably larger than the oligomeric species that have been recently proposed to account for the absorption spectrum of eumelanin and illustrates that larger pigments comprise a significant fraction of the pigment distribution.

  4. Electronic structure of self-doped layered Eu3F4Bi2S4 material revealed by x-ray absorption spectroscopy and photoelectron spectromicroscopy

    NASA Astrophysics Data System (ADS)

    Paris, E.; Sugimoto, T.; Wakita, T.; Barinov, A.; Terashima, K.; Kandyba, V.; Proux, O.; Kajitani, J.; Higashinaka, R.; Matsuda, T. D.; Aoki, Y.; Yokoya, T.; Mizokawa, T.; Saini, N. L.

    2017-01-01

    We have studied the electronic structure of Eu3F4Bi2S4 using a combination of Eu L3-edge x-ray absorption spectroscopy (XAS) and space-resolved angle-resolved photoemission spectroscopy (ARPES). From the Eu L3-edge XAS, we have found that the Eu in this system is in mixed valence state with coexistence of Eu2 +/Eu3 + . The bulk charge doping was estimated to be ˜0.3 per Bi site in Eu3F4Bi2S4 , which corresponds to the nominal x in a typical REO1 -xFxBiS2 system (RE: rare-earth elements). From the space-resolved ARPES, we have ruled out the possibility of any microscale phase separation of Eu valence in the system. Using a microfocused beam we have observed the band structure as well as the Fermi surface that appeared similar to other compounds of this family with disconnected rectangular electronlike pockets around the X point. The Luttinger volume analysis gives the effective carrier to be 0.23 electrons per Bi site in Eu3F4Bi2S4 , indicating that the system is likely to be in the underdoped region of its superconducting phase diagram.

  5. Using combined XAS/DRIFTS to study CO/NO Oxidation over Pt/Al2O3 catalysts

    NASA Astrophysics Data System (ADS)

    Gänzler, A. M.; Lichtenberg, H.; Frenkel, A. I.; Casapu, M.; Boubnov, A.; Wang, D.; Grunwaldt, J.-D.

    2016-05-01

    Combined X-ray absorption spectroscopy (XAS) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) were applied to investigate the interaction between reaction atmosphere, adsorbates and Pt oxidation state of Pt/Al2O3 model diesel oxidation catalysts under CO/NO oxidation conditions. The Pt oxidation state was correlated to the adsorbates on the catalyst's surface. Even at low temperature the reaction atmosphere had a strong impact on the oxidation state of the catalyst, and the oxidation state in turn strongly affected CO adsorption on the Pt particles.

  6. Speciation of zinc in municipal solid waste incineration fly ash after heat treatment: an X-ray absorption spectroscopy study.

    PubMed

    Struis, Rudolf P W J; Ludwig, Christian; Lutz, Harald; Scheidegger, André M

    2004-07-01

    Fly ash is commonly deposited in special landfills as it contains toxic concentrations of heavy metals, such as Zn, Pb, Cd, and Cu. This study was inspired by our efforts to detoxify fly ash from municipal solid waste incineration by thermal treatment to produce secondary raw materials suited for reprocessing. The potential of the thermal treatment was studied by monitoring the evaporation rate of zinc from a certified fly ash (BCR176) during heating between 300 and 950 degrees C under different carrier gas compositions. Samples were quenched at different temperatures for subsequent investigation with X-ray absorption spectroscopy (XAS). The XAS spectra were analyzed using principal component analysis (PCA), target transformation (TT), and linear combination fitting (LCF) to analyze the major Zn compounds in the fly ash as a function of the temperature. The original fly ash comprised about 60% zinc oxides mainly in the form of hydrozincite (Zn5(OH)6(CO3)2) and 40% inerts like willemite (Zn2SiO4) and gahnite (ZnAl2O4) in a weight ratio of about 3:1. At intermediate temperatures (550-750 degrees C) the speciation underlines the competition between indigenous S and Cl with solid zinc oxides to form either volatile ZnCl2 or solid ZnS. ZnS then transformed into volatile species at about 200 degrees C higher temperatures. The inhibiting influence of S was found absent when oxygen was introduced to the inert carrier gas stream or chloride-donating alkali salt was added to the fly ash.

  7. Infrared absorption spectroscopy and chemical kinetics of free radicals

    SciTech Connect

    Curl, R.F.; Glass, G.P.

    1993-12-01

    This research is directed at the detection, monitoring, and study of chemical kinetic behavior by infrared absorption spectroscopy of small free radical species thought to be important intermediates in combustion. During the last year, infrared kinetic spectroscopy using excimer laser flash photolysis and color-center laser probing has been employed to study the high resolution spectrum of HCCN, the rate constant of the reaction between ethynyl (C{sub 2}H) radical and H{sub 2} in the temperature region between 295 and 875 K, and the recombination rate of propargyl (CH{sub 2}CCH) at room temperature.

  8. Soft X-ray absorption and photoemission spectroscopy study of semiconductor oxide nanoparticles for dye-sensitized solar cell: ZnSnO3 and Zn2SnO4

    NASA Astrophysics Data System (ADS)

    Kim, Hyun Woo; Lee, Eunsook; Kim, D. H.; Seong, Seungho; Moon, Soo Yeon; Shin, Yu-Ju; Baik, J.; Shin, H. J.; Kang, J.-S.

    2016-06-01

    The electronic structures of the Zn-stannate nanoparticles of ZnSnO3 and Zn2SnO4, which are the potential nano-structured semiconductor oxides for a dye sensitized solar cell (DSSC), have been investigated by employing photoemission spectroscopy (PES) and soft X-ray absorption spectroscopy (XAS), and compared to those of reference materials. The divalent and tetravalent valence states of Zn2+ and Sn4+ ions are confirmed experimentally. The energy levels of both the valence-band and conduction-band edges are determined experimentally. The top of the valence band in PES is slightly higher in Zn2SnO4 than in ZnSnO3. The onset energies of the O 1s XAS spectra of the Zn-stannates are found to be similar to each other, but higher than that of TiO2. The O 1 s XAS spectrum of ZnSnO3 exhibits the higher unoccupied density of states near the bottom of the conduction band than those of Zn2SnO4, SnO2 and ZnO, reflecting the larger number of holes in the Zn 3 d bands of ZnSnO3. Hence, the easier electron transfer is expected from the LUMO (lowest unoccupied molecular orbital) of a dye molecule to the conduction band of ZnSnO3 nanoparticles on the transparent conductive electrode of a DSSC.

  9. Absorption/emission spectroscopy and applications using shock tubes

    NASA Astrophysics Data System (ADS)

    Sulzmann, K. G. P.

    1988-09-01

    A historical overview is presented about the important contributions made by Penner, his co-workers, and his students to the application of shock-tube techniques for quantitative emission and absorption spectroscopy and its applications to chemical kinetics studies in high-temperature gases. The discussions address critical aspects related to valid determinations of quantitative spectroscopic data and chemical rate parameters and stress the requirements for uniformly heated gas samples, temperature determinations, gas-mixture preparations, selection of useful spectral intervals, verification of LTE conditions, time resolutions for concentration histories, uniqueness of kinetic measurements, as well as accuracies and reproducibilities of measurement results.The potential of absorption spectroscopy by molecule and/or radical resonance radiation and by laser transmission techniques is highlighted for kinetic studies in mixtures with very small reactant concentrations.Besides the work by the honoree and his school, the references include books, monographs and key articles related to the subjects discussed.

  10. Americium characterization by X-ray fluorescence and absorption spectroscopy in plutonium uranium mixed oxide

    SciTech Connect

    Degueldre, Claude Cozzo, Cedric; Martin, Matthias; Grolimund, Daniel; Mieszczynski, Cyprian

    2013-06-01

    Plutonium uranium mixed oxide (MOX) fuels are currently used in nuclear reactors. The actinides in these fuels need to be analyzed after irradiation for assessing their behaviour with regard to their environment and the coolant. In this work the study of the atomic structure and next-neighbour environment of Am in the (Pu,U)O₂ lattice in an irradiated (60 MW d kg⁻¹) MOX sample was performed employing micro-X-ray fluorescence (µ-XRF) and micro-X-ray absorption fine structure (µ-XAFS) spectroscopy. The chemical bonds, valences and stoichiometry of Am (~0.66 wt%) are determined from the experimental data gained for the irradiated fuel material examined in its peripheral zone (rim) of the fuel. In the irradiated sample Am builds up as Am³⁺ species within an [AmO₈]¹³⁻ coordination environment (e.g. >90%) and no (<10%) Am(IV) or (V) can be detected in the rim zone. The occurrence of americium dioxide is avoided by the redox buffering activity of the uranium dioxide matrix. - Graphical abstract: Americium LIII XAFS spectra recorded for the irradiated MOX sub-sample in the rim zone for a 300 μm×300 μm beam size area investigated over six scans of 4 h. The records remain constant during multi-scan. The analysis of the XAFS signal shows that Am is found as trivalent in the UO₂ matrix. This analytical work shall open the door of very challenging analysis (speciation of fission product and actinides) in irradiated nuclear fuels. - Highlights: • Americium was characterized by microX-ray absorption spectroscopy in irradiated MOX fuel. • The americium redox state as determined from XAS data of irradiated fuel material was Am(III). • In the sample, the Am³⁺ face an AmO₈¹³⁻coordination environment in the (Pu,U)O₂ matrix. • The americium dioxide is reduced by the uranium dioxide matrix.

  11. Label free detection of phospholipids by infrared absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Ahmed, Tahsin; Foster, Erick; Vigil, Genevieve; Khan, Aamir A.; Bohn, Paul; Howard, Scott S.

    2014-08-01

    We present our study on compact, label-free dissolved lipid sensing by combining capillary electrophoresis separation in a PDMS microfluidic chip online with mid-infrared (MIR) absorption spectroscopy for biomarker detection. On-chip capillary electrophoresis is used to separate the biomarkers without introducing any extrinsic contrast agent, which reduces both cost and complexity. The label free biomarker detection could be done by interrogating separated biomarkers in the channel by MIR absorption spectroscopy. Phospholipids biomarkers of degenerative neurological, kidney, and bone diseases are detectable using this label free technique. These phospholipids exhibit strong absorption resonances in the MIR and are present in biofluids including urine, blood plasma, and cerebrospinal fluid. MIR spectroscopy of a 12-carbon chain phosphatidic acid (PA) (1,2-dilauroyl-snglycero- 3-phosphate (sodium salt)) dissolved in N-methylformamide, exhibits a strong amide peak near wavenumber 1660 cm-1 (wavelength 6 μm), arising from the phosphate headgroup vibrations within a low-loss window of the solvent. PA has a similar structure to many important phospholipids molecules like phosphatidylcholine (PC), phosphatidylinositol (PI), phosphatidylethanolamine (PE), phosphatidylglycerol (PG), and phosphatidylserine (PS), making it an ideal molecule for initial proof-of-concept studies. This newly proposed detection technique can lead us to minimal sample preparation and is capable of identifying several biomarkers from the same sample simultaneously.

  12. Temperature dependent soft x-ray absorption spectroscopy of liquids.

    PubMed

    Meibohm, Jan; Schreck, Simon; Wernet, Philippe

    2014-10-01

    A novel sample holder is introduced which allows for temperature dependent soft x-ray absorption spectroscopy of liquids in transmission mode. The setup is based on sample cells with x-ray transmissive silicon nitride windows. A cooling circuit allows for temperature regulation of the sample liquid between -10 °C and +50 °C. The setup enables to record soft x-ray absorption spectra of liquids in transmission mode with a temperature resolution of 0.5 K and better. Reliability and reproducibility of the spectra are demonstrated by investigating the characteristic temperature-induced changes in the oxygen K-edge x-ray absorption spectrum of liquid water. These are compared to the corresponding changes in the oxygen K-edge spectra from x-ray Raman scattering.

  13. In-situ X-ray absorption spectroscopy analysis of capacity fade in nanoscale-LiCoO2

    NASA Astrophysics Data System (ADS)

    Patridge, Christopher J.; Love, Corey T.; Swider-Lyons, Karen E.; Twigg, Mark E.; Ramaker, David E.

    2013-07-01

    The local structure of nanoscale (∼10-40 nm) LiCoO2 is monitored during electrochemical cycling utilizing in-situ X-ray absorption spectroscopy (XAS). The high surface area of the LiCoO2 nanoparticles not only enhances capacity fade, but also provides a large signal from the particle surface relative to the bulk. Changes in the nanoscale LiCoO2 metal-oxide bond lengths, structural disorder, and chemical state are tracked during cycling by adapting the delta mu (Δμ) technique in complement with comprehensive extended X-ray absorption fine structure (EXAFS) modeling. For the first time, we use a Δμ EXAFS method, and by comparison of the difference EXAFS spectra, extrapolate significant coordination changes and reduction of cobalt species with cycling. This combined approach suggests Li-Co site exchange at the surface of the nanoscale LiCoO2 as a likely factor in the capacity fade and irreversible losses in practical, microscale LiCoO2.

  14. Pump-Flow-Probe X-Ray Absorption Spectroscopy as a Tool for Studying Intermediate States of Photocatalytic Systems

    PubMed Central

    Smolentsev, Grigory; Guda, Alexander; Zhang, XIaoyi; Haldrup, Kristoffer; Andreiadis, Eugen; Chavarot-Kerlidou, Murielle; Canton, Sophie E.; Nachtegaal, Maarten; Artero, Vincent; Sundstrom, Villy

    2014-01-01

    A new setup for pump-flow-probe X-ray absorption spectroscopy has been implemented at the SuperXAS beamline of the Swiss Light Source. It allows recording X-ray absorption spectra with a time resolution of tens of microseconds and high detection efficiency for samples with sub-mM concentrations. A continuous wave laser is used for the photoexcitation, with the distance between laser and X-ray beams and velocity of liquid flow determining the time delay, while the focusing of both beams and the flow speed define the time resolution. This method is compared with the alternative measurement technique that utilizes a 1 kHz repetition rate laser and multiple X-ray probe pulses. Such an experiment was performed at beamline 11ID-D of the Advanced Photon Source. Advantages, limitations and potential for improvement of the pump-flow-probe setup are discussed by analyzing the photon statistics. Both methods, with Co K-edge probing were applied to the investigation of a cobaloxime-based photo-catalytic reaction. The interplay between optimizing for efficient photoexcitation and time resolution as well as the effect of sample degradation for these two setups are discussed. PMID:24443663

  15. Atmospheric and environmental sensing by photonic absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Chen, W.; Wu, T.; Zhao, W.; Wysocki, G.; Cui, X.; Lengignon, C.; Maamary, R.; Fertein, E.; Coeur, C.; Cassez, A.; Wang, Y.; Zhang, W.; Gao, X.; Liu, W.; Dong, F.; Zha, G.; Zheng, Xu; Wang, T.

    2013-01-01

    Chemically reactive short-lived species play a crucial role in tropospheric processes affecting regional air quality and global climate change. Contrary to long-lived species (such as greenhouse gases), fast, accurate and precise monitoring changes in concentration of atmospheric short-lived species represents a real challenge due to their short life time (~1 s for OH radical) and very low concentration in the atmosphere (down to 106 molecules/cm3, corresponding to 0.1 pptv at standard temperature and pressure). We report on our recent progress in instrumentation developments for spectroscopic sensing of trace reactive species. Modern photonic sources such as quantum cascade laser (QCL), distributed feedback (DFB) diode laser, light emitting diode (LED), difference-frequency generation (DFG) parametric source are implemented in conjunction with highsensitivity spectroscopic measurement techniques for : (1) nitrous acid (HONO) monitoring by QCL-based long optical pathlength absorption spectroscopy and LED-based IBBCEAS (incoherent broadband cavity-enhanced absorption spectroscopy); (2) DFB laser-based hydroxyl free radical (OH) detection using WM-OA-ICOS (wavelength modulation off-axis integrated cavity output spectroscopy) and FRS (Faraday rotation spectroscopy), respectively; (3) nitrate radical (NO3) and nitrogen dioxide (NO2) simultaneous measurements with IBBCEAS approach. Applications in field observation and in smog chamber study will be presented.

  16. Use of absorption spectroscopy for refined petroleum product discrimination

    NASA Astrophysics Data System (ADS)

    Short, Michael

    1991-07-01

    On-line discrimination between arbitrary petroleum products is necessary for optimal control of petroleum refinery and pipeline operation and process control involving petroleum distillates. There are a number of techniques by which petroleum products can be distinguished from one another. Among these, optical measurements offer fast, non-intrusive, real-time characterization. The application examined here involves optically monitoring the interface between dissimilar batches of fluids in a gasoline pipeline. After examination of near- infrared and mid-infrared absorption spectroscopy and Raman spectroscopy, Fourier transform mid-infrared (FTIR) spectroscopy was chosen as the best candidate for implementation. On- line FTIR data is presented, verifying the applicability of the technique for batch interface detection.

  17. Mn l3,2 x-ray absorption spectroscopy and magnetic circulardichroism in ferromagnetic ga1-xmnxp

    SciTech Connect

    Stone, P.R.; Scarpulla, M.A.; Farshchi, R.; Sharp, I.D.; Beeman,J.W.; Yu, K.M.; Arenholz, E.; Denlinger, J.; Haller, E.E.; Dubon, O.D.

    2007-07-26

    We have measured the X-ray absorption (XAS) and X-ray magnetic circular dichroism (XMCD) at the Mn L{sub 3,2} edges in ferromagnetic Ga{sub 1-x}Mn{sub x}P films for 0.018 {le} x {le} 0.042. Large XMCD asymmetries at the L{sub 3} edge indicate significant spin-polarization of the density of states at the Fermi energy. The spectral shapes of the XAS and XMCD are nearly identical with those for Ga{sub 1-x}Mn{sub x}As indicating that the hybridization of Mn d states and anion p states is similar in the two materials. Finally, compensation with sulfur donors not only lowers the ferromagnetic Curie temperature but also reduces the spin polarization of the hole states.

  18. Association of Copper to Riboflavin Binding Protein; Characterization by EPR and XAS

    SciTech Connect

    Smith,S.; Bencze, K.; Wasiukanis, K.; Stemmler, T.; Benore-Parsons, M.

    2008-01-01

    The association of copper to Riboflavin Binding Protein (RBP) from egg white has been studied by electron paramagnetic resonance (EPR) and X-ray absorption (XAS) spectroscopies. The type II site contains a mix of copper I and II in an oxygen rich environment. The association of copper to Riboflavin Binding Protein (RBP) from egg white has been studied by electron paramagnetic resonance (EPR) and X-ray absorption (XAS) spectroscopies in order to provide insight into how this essential protein may transport and store copper in avian embryos. Riboflavin Binding Protein, RBP, purified from avian egg white, has been shown to bind copper in a 1:1 molar ratio when dialyzed against copper(II) [1]. While the egg is a unique environment and quite rich in copper, the mechanisms by which this copper is delivered during development and stored for eventual use remain unclear [2]. Since RBP is already identified in the active transport of the cofactor riboflavin to the egg, evidence of its copper binding ability may suggest an additional role for RBP in the transport and storage of copper.

  19. A dispenser-reactor apparatus applied for in situ XAS monitoring of Pt nanoparticle formation.

    PubMed

    Boita, Jocenir; Castegnaro, Marcus Vinicius; Alves, Maria do Carmo Martins; Morais, Jonder

    2015-05-01

    In situ time-resolved X-ray absorption spectroscopy (XAS) measurements collected at the Pt L3-edge during the synthesis of Pt nanoparticles (NPs) in aqueous solution are reported. A specially designed dispenser-reactor apparatus allowed for monitoring changes in the XAS spectra from the earliest moments of Pt ions in solution until the formation of metallic nanoparticles with a mean diameter of 4.9 ± 1.1 nm. By monitoring the changes in the local chemical environment of the Pt atoms in real time, it was possible to observe that the NPs formation kinetics involved two stages: a reduction-nucleation burst followed by a slow growth and stabilization of NPs. Subsequently, the synthesized Pt NPs were supported on activated carbon and characterized by synchrotron-radiation-excited X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and extended X-ray absorption fine structure (EXAFS). The supported Pt NPs remained in the metallic chemical state and with a reduced size, presenting slight lattice parameter contraction in comparison with the bulk Pt values.

  20. Speciation of organotins in polyvinyl chloride pipe via X-ray absorption spectroscopy and in leachates using GC-PFPD after derivatisation.

    PubMed

    Impellitteri, Christopher A; Evans, Otis; Ravel, Bruce

    2007-04-01

    Three different polyvinyl chloride (PVC) pipe types were subjected to de-ionized water exposures over the course of at least 180 days. Water exposed to the pipe was analyzed for organotin speciation and concentration. Organotin concentrations were the highest during the first 1-5 days. The species and concentrations of organotins leached varied by pipe type. Data were normalized by surface area in order to compare laboratory results with results from a residential pipe system. For one pipe type, the lowest non-zero concentrations from the laboratory tests overestimated organotin concentrations in solution when compared with water samples from the same pipe type in a residence. For organotin exposure estimates, a range of 0.1 ng m(-2) to 10 ng m(-2) could be used for mature pipes (e.g. in use for 1 year). These estimates should be refined with more field study, however, due to the high variation in organotin species and concentrations leached as a function of pipe type, accuracy within an order of magnitude may be optimal as, in many instances, the type of pipe installed or buried may be unknown. X-ray absorption spectroscopy (XAS) was used to identify organic and inorganic tin species in reference materials and the PVC samples. Monobutyl tin was identified as the primary organotin species in the pipes. Results from the XAS analyses also indicate that the technique shows promise for distinguishing between inorganic tin and organotins. Furthermore, organotins may be distinguished between mono-, di-, and tri-ligand species using XAS.

  1. Structural differences of oxidized iron-sulfur and nickel-iron cofactors in O2-tolerant and O2-sensitive hydrogenases studied by X-ray absorption spectroscopy.

    PubMed

    Sigfridsson, Kajsa G V; Leidel, Nils; Sanganas, Oliver; Chernev, Petko; Lenz, Oliver; Yoon, Ki-Seok; Nishihara, Hirofumi; Parkin, Alison; Armstrong, Fraser A; Dementin, Sébastien; Rousset, Marc; De Lacey, Antonio L; Haumann, Michael

    2015-02-01

    The class of [NiFe]-hydrogenases comprises oxygen-sensitive periplasmic (PH) and oxygen-tolerant membrane-bound (MBH) enzymes. For three PHs and four MBHs from six bacterial species, structural features of the nickel-iron active site of hydrogen turnover and of the iron-sulfur clusters functioning in electron transfer were determined using X-ray absorption spectroscopy (XAS). Fe-XAS indicated surplus oxidized iron and a lower number of ~2.7 Å Fe-Fe distances plus additional shorter and longer distances in the oxidized MBHs compared to the oxidized PHs. This supported a double-oxidized and modified proximal FeS cluster in all MBHs with an apparent trimer-plus-monomer arrangement of its four iron atoms, in agreement with crystal data showing a [4Fe3S] cluster instead of a [4Fe4S] cubane as in the PHs. Ni-XAS indicated coordination of the nickel by the thiol group sulfurs of four conserved cysteines and at least one iron-oxygen bond in both MBH and PH proteins. Structural differences of the oxidized inactive [NiFe] cofactor of MBHs in the Ni-B state compared to PHs in the Ni-A state included a ~0.05 Å longer Ni-O bond, a two times larger spread of the Ni-S bond lengths, and a ~0.1 Å shorter Ni-Fe distance. The modified proximal [4Fe3S] cluster, weaker binding of the Ni-Fe bridging oxygen species, and an altered localization of reduced oxygen species at the active site may each contribute to O2 tolerance.

  2. Combining single-particle inductively coupled plasma mass spectrometry and X-ray absorption spectroscopy to evaluate the release of colloidal arsenic from environmental samples.

    PubMed

    Gomez-Gonzalez, Miguel Angel; Bolea, Eduardo; O'Day, Peggy A; Garcia-Guinea, Javier; Garrido, Fernando; Laborda, Francisco

    2016-07-01

    Detection and sizing of natural colloids involved in the release and transport of toxic metals and metalloids is essential to understand and model their environmental effects. Single-particle inductively coupled plasma mass spectrometry (SP-ICP-MS) was applied for the detection of arsenic-bearing particles released from mine wastes. Arsenic-bearing particles were detected in leachates from mine wastes, with a mass-per-particle detection limit of 0.64 ng of arsenic. Conversion of the mass-per-particle information provided by SP-ICP-MS into size information requires knowledge of the nature of the particles; therefore, synchrotron-based X-ray absorption spectroscopy (XAS) was used to identify scorodite (FeAsO4·2H2O) as the main species in the colloidal particles isolated by ultrafiltration. The size of the scorodite particles detected in the leachates was below 300-350 nm, in good agreement with the values obtained by TEM. The size of the particles detected by SP-ICP-MS was determined as the average edge of scorodite crystals, which show a rhombic dipyramidal form, achieving a size detection limit of 117 nm. The combined use of SP-ICP-MS and XAS allowed detection, identification, and size determination of scorodite particles released from mine wastes, suggesting their potential to transport arsenic. Graphical abstract Analytical approach for the detection and size characterization of As-bearing particles by SP-ICP-MS and XAS in environmental samples.

  3. New Homogeneous Standards by Atomic Layer Deposition for Synchrotron X-ray Fluorescence and Absorption Spectroscopies.

    SciTech Connect

    Butterworth, A.L.; Becker, N.; Gainsforth, Z.; Lanzirotti, A.; Newville, M.; Proslier, T.; Stodolna, J.; Sutton, S.; Tyliszczak, T.; Westphal, A.J.; Zasadzinski, J.

    2012-03-13

    Quantification of synchrotron XRF analyses is typically done through comparisons with measurements on the NIST SRM 1832/1833 thin film standards. Unfortunately, these standards are inhomogeneous on small scales at the tens of percent level. We are synthesizing new homogeneous multilayer standards using the Atomic Layer Deposition technique and characterizing them using multiple analytical methods, including ellipsometry, Rutherford Back Scattering at Evans Analytical, Synchrotron X-ray Fluorescence (SXRF) at Advanced Photon Source (APS) Beamline 13-ID, Synchrotron X-ray Absorption Spectroscopy (XAS) at Advanced Light Source (ALS) Beamlines 11.0.2 and 5.3.2.1 and by electron microscopy techniques. Our motivation for developing much-needed cross-calibration of synchrotron techniques is borne from coordinated analyses of particles captured in the aerogel of the NASA Stardust Interstellar Dust Collector (SIDC). The Stardust Interstellar Dust Preliminary Examination (ISPE) team have characterized three sub-nanogram, {approx}1{micro}m-sized fragments considered as candidates to be the first contemporary interstellar dust ever collected, based on their chemistries and trajectories. The candidates were analyzed in small wedges of aerogel in which they were extracted from the larger collector, using high sensitivity, high spatial resolution >3 keV synchrotron x-ray fluorescence spectroscopy (SXRF) and <2 keV synchrotron x-ray transmission microscopy (STXM) during Stardust ISPE. The ISPE synchrotron techniques have complementary capabilities. Hard X-ray SXRF is sensitive to sub-fg mass of elements Z {ge} 20 (calcium) and has a spatial resolution as low as 90nm. X-ray Diffraction data were collected simultaneously with SXRF data. Soft X-ray STXM at ALS beamline 11.0.2 can detect fg-mass of most elements, including cosmochemically important oxygen, magnesium, aluminum and silicon, which are invisible to SXRF in this application. ALS beamline 11.0.2 has spatial resolution

  4. Chloride ligation in inorganic manganese model compounds relevant to Photosystem II studied using X-ray absorption spectroscopy

    PubMed Central

    Pizarro, Shelly A.; Visser, Hendrik; Cinco, Roehl M.; Robblee, John H.; Pal, Samudranil; Mukhopadhyay, Sumitra; Mok, Henry J.; Sauer, Kenneth; Wieghardt, Karl; Armstrong, William H.

    2014-01-01

    Chloride ions are essential for proper function of the photosynthetic oxygen-evolving complex (OEC) of Photosystem II (PS II). Although proposed to be directly ligated to the Mn cluster of the OEC, the specific structural and mechanistic roles of chloride remain unresolved. This study utilizes X-ray absorption spectroscopy (XAS) to characterize the Mn–Cl interaction in inorganic compounds that contain structural motifs similar to those proposed for the OEC. Three sets of model compounds are examined; they possess core structures MnIV3O4X (X = Cl, F, or OH) that contain a di-μ-oxo and two mono-μ-oxo bridges or MnIV2O2X (X = Cl, F, OH, OAc) that contain a di-μ-oxo bridge. Each set of compounds is examined for changes in the XAS spectra that are attributable to the replacement of a terminal OH or F ligand, or bridging OAc ligand, by a terminal Cl ligand. The X-ray absorption near edge structure (XANES) shows changes in the spectra on replacement of OH, OAc, or F by Cl ligands that are indicative of the overall charge of the metal atom and are consistent with the electronegativity of the ligand atom. Fourier transforms (FTs) of the extended X-ray absorption fine structure (EXAFS) spectra reveal a feature that is present only in compounds where chloride is directly ligated to Mn. These FT features were simulated using various calculated Mn–X interactions (X = O, N, Cl, F), and the best fits were found when a Mn–Cl interaction at a 2.2–2.3 Å bond distance was included. There are very few high-valent Mn halide complexes that have been synthesized, and it is important to make such a comparative study of the XANES and EXAFS spectra because they have the potential for providing information about the possible presence or absence of halide ligation to the Mn cluster in PS II. PMID:14758524

  5. X-ray absorption spectroscopy study of the local environment around tungsten and molybdenum ions in tungsten-phosphate and molybdenum-phosphate glasses

    NASA Astrophysics Data System (ADS)

    Kuzmin, A.; Purans, J.

    1997-02-01

    X-ray absorption spectroscopy (XAS) was used to study the local environment around tungsten and molybdenum ions in BaO-P2O5-WO3 and CaO-P2O5-MoO3 glasses having different composition of WO3 and MoO3 oxides. The W L1,3 and Mo K edges x-ray absorption spectra were measured in transmission mode at room temperature using the synchrotron radiation emitted by the ADONE and LURE DCI storage rings, respectively. The analysis of x-ray absorption near edge structure (XANES) and extended x-ray absorption fine structure (EXAFS) in glasses was performed in comparison with the results for a number of crystalline WO3, CaWO4, Na0.66WO3 alpha- MoO3, beta-MoO3 and amorphous a-WO3, a-MoO3 compounds. The results of the EXAFS modeling by two different methods [(1) multi-shell best-fit procedure within harmonic approximation and (2) model-independent radial distribution function approach] allowed us to extract detailed structural information on the first coordination shell of metal (W or Mo) ions. Using the obtained data together with the information given by XRD, EPR and optical spectroscopies, we propose the model of incorporation of W and Mo ions within the glass network.

  6. APPLICATION OF ABSORPTION SPECTROSCOPY TO ACTINIDE PROCESS ANALYSIS AND MONITORING

    SciTech Connect

    Lascola, R.; Sharma, V.

    2010-06-03

    The characteristic strong colors of aqueous actinide solutions form the basis of analytical techniques for actinides based on absorption spectroscopy. Colorimetric measurements of samples from processing activities have been used for at least half a century. This seemingly mature technology has been recently revitalized by developments in chemometric data analysis. Where reliable measurements could formerly only be obtained under well-defined conditions, modern methods are robust with respect to variations in acidity, concentration of complexants and spectral interferents, and temperature. This paper describes two examples of the use of process absorption spectroscopy for Pu analysis at the Savannah River Site, in Aiken, SC. In one example, custom optical filters allow accurate colorimetric measurements of Pu in a stream with rapid nitric acid variation. The second example demonstrates simultaneous measurement of Pu and U by chemometric treatment of absorption spectra. The paper concludes with a description of the use of these analyzers to supplement existing technologies in nuclear materials monitoring in processing, reprocessing, and storage facilities.

  7. Polarization-controlled optimal scatter suppression in transient absorption spectroscopy

    PubMed Central

    Malý, Pavel; Ravensbergen, Janneke; Kennis, John T. M.; van Grondelle, Rienk; Croce, Roberta; Mančal, Tomáš; van Oort, Bart

    2017-01-01

    Ultrafast transient absorption spectroscopy is a powerful technique to study fast photo-induced processes, such as electron, proton and energy transfer, isomerization and molecular dynamics, in a diverse range of samples, including solid state materials and proteins. Many such experiments suffer from signal distortion by scattered excitation light, in particular close to the excitation (pump) frequency. Scattered light can be effectively suppressed by a polarizer oriented perpendicular to the excitation polarization and positioned behind the sample in the optical path of the probe beam. However, this introduces anisotropic polarization contributions into the recorded signal. We present an approach based on setting specific polarizations of the pump and probe pulses, combined with a polarizer behind the sample. Together, this controls the signal-to-scatter ratio (SSR), while maintaining isotropic signal. We present SSR for the full range of polarizations and analytically derive the optimal configuration at angles of 40.5° between probe and pump and of 66.9° between polarizer and pump polarizations. This improves SSR by (or compared to polarizer parallel to probe). The calculations are validated by transient absorption experiments on the common fluorescent dye Rhodamine B. This approach provides a simple method to considerably improve the SSR in transient absorption spectroscopy. PMID:28262765

  8. Polarization-controlled optimal scatter suppression in transient absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Malý, Pavel; Ravensbergen, Janneke; Kennis, John T. M.; van Grondelle, Rienk; Croce, Roberta; Mančal, Tomáš; van Oort, Bart

    2017-03-01

    Ultrafast transient absorption spectroscopy is a powerful technique to study fast photo-induced processes, such as electron, proton and energy transfer, isomerization and molecular dynamics, in a diverse range of samples, including solid state materials and proteins. Many such experiments suffer from signal distortion by scattered excitation light, in particular close to the excitation (pump) frequency. Scattered light can be effectively suppressed by a polarizer oriented perpendicular to the excitation polarization and positioned behind the sample in the optical path of the probe beam. However, this introduces anisotropic polarization contributions into the recorded signal. We present an approach based on setting specific polarizations of the pump and probe pulses, combined with a polarizer behind the sample. Together, this controls the signal-to-scatter ratio (SSR), while maintaining isotropic signal. We present SSR for the full range of polarizations and analytically derive the optimal configuration at angles of 40.5° between probe and pump and of 66.9° between polarizer and pump polarizations. This improves SSR by (or compared to polarizer parallel to probe). The calculations are validated by transient absorption experiments on the common fluorescent dye Rhodamine B. This approach provides a simple method to considerably improve the SSR in transient absorption spectroscopy.

  9. Pathlength Determination for Gas in Scattering Media Absorption Spectroscopy

    PubMed Central

    Mei, Liang; Somesfalean, Gabriel; Svanberg, Sune

    2014-01-01

    Gas in scattering media absorption spectroscopy (GASMAS) has been extensively studied and applied during recent years in, e.g., food packaging, human sinus monitoring, gas diffusion studies, and pharmaceutical tablet characterization. The focus has been on the evaluation of the gas absorption pathlength in porous media, which a priori is unknown due to heavy light scattering. In this paper, three different approaches are summarized. One possibility is to simultaneously monitor another gas with known concentration (e.g., water vapor), the pathlength of which can then be obtained and used for the target gas (e.g., oxygen) to retrieve its concentration. The second approach is to measure the mean optical pathlength or physical pathlength with other methods, including time-of-flight spectroscopy, frequency-modulated light scattering interferometry and the frequency domain photon migration method. By utilizing these methods, an average concentration can be obtained and the porosities of the material are studied. The last method retrieves the gas concentration without knowing its pathlength by analyzing the gas absorption line shape, which depends upon the concentration of buffer gases due to intermolecular collisions. The pathlength enhancement effect due to multiple scattering enables also the use of porous media as multipass gas cells for trace gas monitoring. All these efforts open up a multitude of different applications for the GASMAS technique. PMID:24573311

  10. Observation of charge transfer cascades in α-Fe2O3/IrOx photoanodes by operando X-ray absorption spectroscopy.

    PubMed

    Minguzzi, Alessandro; Naldoni, Alberto; Lugaresi, Ottavio; Achilli, Elisabetta; D'Acapito, Francesco; Malara, Francesco; Locatelli, Cristina; Vertova, Alberto; Rondinini, Sandra; Ghigna, Paolo

    2017-02-22

    Electrochemical devices for energy conversion and storage are central for a sustainable economy. The performance of electrodes is driven by charge transfer across different layer materials and an understanding of the mechanistics is pivotal to gain improved efficiency. Here, we directly observe the transfer of photogenerated charge carriers in a photoanode made of hematite (α-Fe2O3) and a hydrous iridium oxide (IrOx) overlayer, which plays a key role in photoelectrochemical water oxidation. Through the use of operando X-ray absorption spectroscopy (XAS), we probe the change in occupancy of the Ir 5d levels during optical band gap excitation of α-Fe2O3. At potentials where no photocurrent is observed, electrons flow from the α-Fe2O3 photoanode to the IrOx overlayer. In contrast, when the composite electrode produces a sustained photocurrent (i.e., 1.4 V vs. RHE), a significant transfer of holes from the illuminated α-Fe2O3 to the IrOx layer is clearly demonstrated. The analysis of the operando XAS spectra further suggests that oxygen evolution actually occurs both at the α-Fe2O3/electrolyte and α-Fe2O3/IrOx interfaces. These findings represent an important outcome for a better understanding of composite photoelectrodes and their use in photoelectrochemical systems, such as hydrogen generation or CO2 reduction from sunlight.

  11. Dopant activation in Sn-doped Ga{sub 2}O{sub 3} investigated by X-ray absorption spectroscopy

    SciTech Connect

    Siah, S. C. Brandt, R. E.; Jaramillo, R.; Buonassisi, T.; Lim, K.; Schelhas, L. T.; Toney, M. F.; Heinemann, M. D.; Chua, D.; Gordon, R. G.; Wright, J.; Segre, C. U.; Perkins, J. D.

    2015-12-21

    Doping activity in both beta-phase (β-) and amorphous (a-) Sn-doped gallium oxide (Ga{sub 2}O{sub 3}:Sn) is investigated by X-ray absorption spectroscopy (XAS). A single crystal of β-Ga{sub 2}O{sub 3}:Sn grown using edge-defined film-fed growth at 1725 °C is compared with amorphous Ga{sub 2}O{sub 3}:Sn films deposited at low temperature (<300 °C). Our XAS analyses indicate that activated Sn dopant atoms in conductive single crystal β-Ga{sub 2}O{sub 3}:Sn are present as Sn{sup 4+}, preferentially substituting for Ga at the octahedral site, as predicted by theoretical calculations. In contrast, inactive Sn atoms in resistive a-Ga{sub 2}O{sub 3}:Sn are present in either +2 or +4 charge states depending on growth conditions. These observations suggest the importance of growing Ga{sub 2}O{sub 3}:Sn at high temperature to obtain a crystalline phase and controlling the oxidation state of Sn during growth to achieve dopant activation.

  12. Dynamic transformation of small Ni particles during methanation of CO2 under fluctuating reaction conditions monitored by operando X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Mutz, B.; Carvalho, H. W. P.; Kleist, W.; Grunwaldt, J.-D.

    2016-05-01

    A 10 wt.-% Ni/Al2O3 catalyst with Ni particles of about 4 nm was prepared and applied in the methanation of CO2 under dynamic reaction conditions. Fast phase transformations between metallic Ni, NiO and NiCO3 were observed under changing reaction atmospheres using operando X-ray absorption spectroscopy (XAS). Removing H2 from the feed gas and, thus, simulating a H2 dropout during the methanation reaction led to oxidation of the active sites. The initial reduced state of the Ni particles could not be recovered under methanation atmosphere (H2/CO2 = 4); this was only possible with an effective reactivation step applying H2 at increased temperatures. Furthermore, the cycling of the gas atmospheres resulted in a steady deactivation of the catalyst. Operando XAS is a powerful tool to monitor these changes and the behavior of the catalyst under working conditions to improve the understanding of the catalytic processes and deactivation phenomena.

  13. Local atomic structure of chromium bearing precipitates in chromia doped uranium dioxide investigated by combined micro-beam X-ray diffraction and absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Kuri, G.; Mieszczynski, C.; Martin, M.; Bertsch, J.; Borca, C. N.; Delafoy, Ch.

    2014-06-01

    Experimental studies have evidenced the presence of some chromium oxide precipitates in chromia (Cr2O3) doped UO2 fuels, currently being used in many light water reactors. The main objective of this study was to analyze the atomic scale microstructure of these precipitates in a non-destructive way employing modern synchrotron-based X-ray radiation. To investigate UO2 microstructures and chemical compositions of the precipitates an industrial grade fresh Cr2O3-doped UO2 pellet (produced with an initial amount of 0.16 wt.% Cr2O3 powder) was examined using scanning electron microscopy (SEM) and electron probe micro analysis (EPMA). Average grain diameter of the UO2 matrix was measured by SEM image analysis method. Precipitates were detected by EPMA. For all precipitates of micrometer scale analyzed by EPMA the composition was determined to be very close to Cr2O3. The structural property and the next neighbor Cr atomic environment in these precipitates were studied by a combination of more sensitive tools such as micro-focused X-ray diffraction (μ-XRD) and absorption spectroscopy (μ-XAS). According to the XRD data, the chromia precipitates contain structural disorder and have a somewhat distorted lattice structure as compared to that of standard and crystalline α-Cr2O3 hexagonal crystal unit cell. The μ-XAS results provide insight into the local atomic environment of chromium including the oxidation state assignment.

  14. The Ancient Wood of the Acqualadrone Rostrum: A Materials History Through GC-MS and Sulfur X-ray Absorption Spectroscopy

    PubMed Central

    Frank, Patrick; Caruso, Francesco; Caponetti, Eugenio

    2012-01-01

    In 2008 the rostrum from an ancient warship was recovered from the Mediterranean near Acqualadrone, Sicily. To establish its provenance and condition, samples of black and brown rostrum wood were examined using sulfur K-edge x-ray absorption spectroscopy (XAS) and GC-MS. GC-MS of pyrolytic volatiles yielded only guaiacyl derivatives, indicating construction from pinewood. A derivatized extract of black wood yielded forms of abietic acid and sandaracopimaric acid consistent with pine pitch waterproofing. Numerical fits to the sulfur K-edge XAS spectra showed that about 65% of the endogenous sulfur consisted of thiols and disulfides. Elemental sulfur was about 2% and 7% in black and brown wood, respectively, while pyritic sulfur was about 12% and 6%. About 2% of the sulfur in both wood types was modeled as trimethylsulfonium, possibly reflecting biogenic dimethylsulfonio-propionate. High valent sulfur was exclusively represented by sulfate esters, consistent with bacterial sulfotransferase activity. Traces of chloride were detected, but no free sulfate ion. In summary, the rostrum was manufactured of pine wood and subsequently waterproofed with pine pitch. The subsequent 2300 years included battle, foundering, and marine burial followed by anoxia, bacterial colonization, sulfate reduction, and mobilization of transition metals, which produced pyrite and copious appended sulfur functionality. PMID:22545724

  15. Trivalent atom contribution on solid-solid transformation of Ga13 polycation intercalated clay into sodalite investigated by X-ray absorption spectroscopy.

    PubMed

    Lee, Sung-Reol; Park, Man; Han, Yang-Su; Hwang, Sung-Ho; Choy, Jin-Ho

    2005-05-19

    Solid-solid transformation mechanism of Ga Keggin-type ion intercalated clay into sodalite has been clarified by X-ray diffraction (XRD), FT-IR spectroscopy, and X-rayabsorption spectroscopy (XAS). To follow the structural evolution precisely by XANES and EXAFS, the XAS active element containing polycation [Ga13O4(OH)24(H2O)12]7+ was intercalated into montmorillonite (MMT). FT-IR and XAS spectra confirm that the formation of sodalite framework is initiated by the delocalized rearrangement between silicate networks and collapsed interlayered Ga species, and is followed by the incorporation of Al in the octahedral sheet of clay (MMT). According to the XAS studies, it is found that the formation of Ga(Al)-O-Si species is strongly influenced by the trivalent cations, which are rapidly changed in the environment, followed by reaction with the silicate network of clay during the solid-solid transformation.

  16. Diagnostic potential of cosmic-neutrino absorption spectroscopy

    SciTech Connect

    Barenboim, Gabriela; Requejo, Olga Mena; Quigg, Chris

    2005-04-15

    Annihilation of extremely energetic cosmic neutrinos on the relic-neutrino background can give rise to absorption lines at energies corresponding to formation of the electroweak gauge boson Z{sup 0}. The positions of the absorption dips are set by the masses of the relic neutrinos. Suitably intense sources of extremely energetic (10{sup 21}-10{sup 25}-eV) cosmic neutrinos might therefore enable the determination of the absolute neutrino masses and the flavor composition of the mass eigenstates. Several factors--other than neutrino mass and composition--distort the absorption lines, however. We analyze the influence of the time evolution of the relic-neutrino density and the consequences of neutrino decay. We consider the sensitivity of the line shape to the age and character of extremely energetic neutrino sources, and to the thermal history of the Universe, reflected in the expansion rate. We take into account Fermi motion arising from the thermal distribution of the relic-neutrino gas. We also note the implications of Dirac vs. Majorana relics, and briefly consider unconventional neutrino histories. We ask what kinds of external information would enhance the potential of cosmic-neutrino absorption spectroscopy, and estimate the sensitivity required to make the technique a reality.

  17. Diagnostic potential of cosmic-neutrino absorption spectroscopy

    SciTech Connect

    Barenboim, Gabriela; Mena Requejo, Olga; Quigg, Chris; /Fermilab

    2004-12-01

    Annihilation of extremely energetic cosmic neutrinos on the relic-neutrino background can give rise to absorption lines at energies corresponding to formation of the electroweak gauge boson Z{sup 0}. The positions of the absorption dips are set by the masses of the relic neutrinos. Suitably intense sources of extremely energetic (10{sup 21} - 10{sup 25}-eV) cosmic neutrinos might therefore enable the determination of the absolute neutrino masses and the flavor composition of the mass eigenstates. Several factors--other than neutrino mass and composition--distort the absorption lines, however. We analyze the influence of the time-evolution of the relic-neutrino density and the consequences of neutrino decay. We consider the sensitivity of the lineshape to the age and character of extremely energetic neutrino sources, and to the thermal history of the Universe, reflected in the expansion rate. We take into account Fermi motion arising from the thermal distribution of the relic-neutrino gas. We also note the implications of Dirac vs. Majorana relics, and briefly consider unconventional neutrino histories. We ask what kinds of external information would enhance the potential of cosmic-neutrino absorption spectroscopy, and estimate the sensitivity required to make the technique a reality.

  18. Principles and calibration of collinear photofragmentation and atomic absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Sorvajärvi, Tapio; Toivonen, Juha

    2014-06-01

    The kinetics of signal formation in collinear photofragmentation and atomic absorption spectroscopy (CPFAAS) are discussed, and theoretical equations describing the relation between the concentration of the target molecule and the detected atomic absorption in case of pure and impure samples are derived. The validity of the equation for pure samples is studied experimentally by comparing measured target molecule concentrations to concentrations determined using two other independent techniques. Our study shows that CPFAAS is capable of measuring target molecule concentrations from parts per billion (ppb) to hundreds of parts per million (ppm) in microsecond timescale. Moreover, the possibility to extend the dynamic range to cover eight orders of magnitude with a proper selection of fragmentation light source is discussed. The maximum deviation between the CPFAAS technique and a reference measurement technique is found to be less than 5 %. In this study, potassium chloride vapor and atomic potassium are used as a target molecule and a probed atom, respectively.

  19. The determination of vanadium in brines by atomic absorption spectroscopy

    USGS Publications Warehouse

    Crump-Wiesner, Hans J.; Feltz, H.R.; Purdy, W.C.

    1971-01-01

    A standard addition method is described for the determination of vanadium in brines by atomic absorption spectroscopy with a nitrous oxide-acetylene flame. Sample pH is adjusted to 1.0 with concentrated hydrochloric acid and the vanadium is directly extracted with 5% cupferron in methyl isobutyl ketone (MIBK). The ketone layer is then aspirated into the flame and the recorded absorption values are plotted as a function of the concentration of the added metal. As little as 2.5 ??g l-1 of vanadium can be detected under the conditions of the procedure. Tungsten and tin interfere when present in excess of 5 and 10 ??g ml-1, respectively. The concentrations of the two interfering ions normally found in brines are well below interference levels. ?? 1971.

  20. Imide photodissociation investigated by X-ray absorption spectroscopy.

    PubMed

    Johnson, Phillip S; Cook, Peter L; Liu, Xiaosong; Yang, Wanli; Bai, Yiqun; Abbott, Nicholas L; Himpsel, F J

    2012-06-21

    X-ray absorption spectroscopy is used to investigate the photodissociation of the imides PMDI (pyromellitic diimide) and SSMCC (sulfosuccinimidyl 4-(N-maleimidomethyl) cyclohexane-1-carboxylate). PMDI contains only one type of imide, and its photodissociation can be explained by a simple conversion from imide to a mix of imine and nitrile after desorption of the oxygens from the imide. SSMCC contains two different imides. One reacts like PMDI, the other in a more complex multistep process. Eventually, N(2) is formed in the bulk of the sample at high radiation density. The sequence of reactions is inferred from the π* peaks in total electron yield and fluorescence yield absorption spectra at the N 1s and O 1s edges. First-order rate equations are used to model the evolution of the peak areas versus radiation dose.

  1. Quantitative analysis of immobilized metalloenzymes by atomic absorption spectroscopy.

    PubMed

    Opwis, Klaus; Knittel, Dierk; Schollmeyer, Eckhard

    2004-12-01

    A new, sensitive assay for the quantitative determination of immobilized metal containing enzymes has been developed using atomic absorption spectroscopy (AAS). In contrast with conventionally used indirect methods the described quantitative AAS assay for metalloenzymes allows more exact analyses, because the carrier material with the enzyme is investigated directly. As an example, the validity and reliability of the method was examined by fixing the iron-containing enzyme catalase on cotton fabrics using different immobilization techniques. Sample preparation was carried out by dissolving the loaded fabrics in sulfuric acid before oxidising the residues with hydrogen peroxide. The iron concentrations were determined by flame atomic absorption spectrometry after calibration of the spectrometer with solutions of the free enzyme at different concentrations.

  2. Characteristics of Organobentonite and Study of Iodide Adsorption on Organobentonite using X-ray Absorption Spectroscopy

    NASA Astrophysics Data System (ADS)

    Yoon, J.; Ha, J.; Hwang, B.; Hwang, J.; Brown, G. E.

    2008-12-01

    The adsorption of iodide on untreated bentonite and bentonites modified with organic cation (i.e., hexadecylpyridinium chloride monohydrate (HDP+)) was investigated, and the organobentonites were characterized using uptake measurements, micro X-ray diffraction (micro-XRD), and electrophoretic mobility measurements prior to reaction with KI solutions. Uptake measurements indicate that bentonite has a high affinity for HDP+. Increasing [HDP+](aq) results in an increase in HDP+ uptake on bentonite by up to 280% of the CEC equivalents of bentonite, and causes a concomitant increase in Na released as a result of the replacement of exchangeable inorganic cations in bentonite interlayers. Based micro-XRD, the d001 spacing of untreated bentonite was 1.22 nm whereas organobentonites modified with HDP+ at different equivalent amounts, corresponding to 100%, 200%, and 400% of the cation exchange capacity (CEC) of bentonite, showed d001 spacings of 1.96 nm, 3.77 nm, and 3.77 nm, respectively. Our micro-XRD study indicates that organobentonites significantly expanded in basal spacing and organic cations were substantially intercalated into the interlayer spaces of montmorillonite. The electrophoretic mobility indicates that the untreated bentonite had a negative surface charge over the entire pH range examined (pH 2-12) whereas the organobentonite at an equivalent amount corresponding to 200% of the CEC had a positive surface charge over this pH range. We found significant differences in adsorption capacities of iodide depending on the bentonite properties as follows: iodide adsorption capacities were 439 mmol/kg for the bentonite modified with HDP+ at an equivalent amount corresponding to 200% of the CEC of bentonite whereas no adsorption of iodide was observed for the untreated bentonite. The molecular environments of iodine adsorbed on organobentonites were further studied using I K-edge and LIII-edge x-ray absorption spectroscopy (XAS). The X-ray absorption near

  3. Fingerprints of polycyclic aromatic hydrocarbons (PAHs) in infrared absorption spectroscopy.

    PubMed

    Tommasini, Matteo; Lucotti, Andrea; Alfè, Michela; Ciajolo, Anna; Zerbi, Giuseppe

    2016-01-05

    We have analyzed a set of 51 PAHs whose structures have been hypothesized from mass spectrometry data collected on samples extracted from carbon particles of combustion origin. We have obtained relationships between infrared absorption signals in the fingerprint region (mid-IR) and the chemical structures of PAHs, thus proving the potential of IR spectroscopy for the characterization of the molecular structure of aromatic combustion products. The results obtained here for the spectroscopic characterization of PAHs can be also of interest in Materials Science and Astrophysics.

  4. Monitoring PVD metal vapors using laser absorption spectroscopy

    SciTech Connect

    Braun, D.G.; Anklam, T.M.; Berzins, L.V.; Hagans, K.G.

    1994-04-01

    Laser absorption spectroscopy (LAS) has been used by the Atomic Vapor Laser Isotope Separation (AVLIS) program for over 10 years to monitor the co-vaporization of uranium and iron in its separators. During that time, LAS has proven to be an accurate and reliable method to monitor both the density and composition of the vapor. It has distinct advantages over other rate monitors, in that it is completely non-obtrusive to the vaporization process and its accuracy is unaffected by the duration of the run. Additionally, the LAS diagnostic has been incorporated into a very successful process control system. LAS requires only a line of sight through the vacuum chamber, as all hardware is external to the vessel. The laser is swept in frequency through an absorption line of interest. In the process a baseline is established, and the line integrated density is determined from the absorption profile. The measurement requires no hardware calibration. Through a proper choice of the atomic transition, a wide range of elements and densities have been monitored (e.g. nickel, iron, cerium and gadolinium). A great deal of information about the vapor plume can be obtained from the measured absorption profiles. By monitoring different species at the same location, the composition of the vapor is measured in real time. By measuring the same density at different locations, the spatial profile of the vapor plume is determined. The shape of the absorption profile is used to obtain the flow speed of the vapor. Finally, all of the above information is used evaluate the total vaporization rate.

  5. Mid-infrared absorption spectroscopy using quantum cascade lasers

    NASA Astrophysics Data System (ADS)

    Haibach, Fred; Erlich, Adam; Deutsch, Erik

    2011-06-01

    Block Engineering has developed an absorption spectroscopy system based on widely tunable Quantum Cascade Lasers (QCL). The QCL spectrometer rapidly cycles through a user-selected range in the mid-infrared spectrum, between 6 to 12 μm (1667 to 833 cm-1), to detect and identify substances on surfaces based on their absorption characteristics from a standoff distance of up to 2 feet with an eye-safe laser. It can also analyze vapors and liquids in a single device. For military applications, the QCL spectrometer has demonstrated trace explosive, chemical warfare agent (CWA), and toxic industrial chemical (TIC) detection and analysis. The QCL's higher power density enables measurements from diffuse and highly absorbing materials and substrates. Other advantages over Fourier Transform Infrared (FTIR) spectroscopy include portability, ruggedness, rapid analysis, and the ability to function from a distance through free space or a fiber optic probe. This paper will discuss the basic technology behind the system and the empirical data on various safety and security applications.

  6. In situ XAS studies of Pt{sub x}Pd{sub 1-x} nanoparticles under thermal annealing

    SciTech Connect

    Bernardi, F.; Morais, J.; Alves, M. C. M.

    2009-01-29

    In this work, we have studied Pt{sub x}Pd{sub 1-x}(x = 1, 0.7 or 0.5) nanoparticles subjected to H{sub 2} reduction and sulfidation under H{sub 2}S atmosphere, both at 300 deg. C. The system was studied by in-situ x-ray absorption spectroscopy (in-situ XAS). We observed that the efficiency of sulfidation is directly proportional to the quantity of Pd atoms in the nanoparticle, provided the reduction process has been achieved.

  7. Sulfur allocation and vanadium-sulfate interactions in whole blood cells from the tunicate Ascidia ceratodes, investigated using X-ray absorption spectroscopy

    SciTech Connect

    Frank, P.; Hedman, B.; Hodgson, K.O.

    1999-01-25

    Sulfur K-edge X-ray absorption spectroscopy (XAS) has been used to investigate the distribution of sulfur types in two whole blood cell samples, in selected subcellular blood fractions, and in cell-free plasma from the tunicate Ascidia ceratodes. Whole blood cells are rich in sulfate, aliphatic sulfonate, and l0w-valent sulfur. The sulfur K-edge XAS spectrum of washed blood cell membranes revealed traces of sulfate and low-valent sulfur, but no sulfate ester or sulfonate. Sulfonate is thus exclusively cytosolic. Cell-free blood plasma contains primarily sulfate sulfur. Gaussian fitting and sulfate quantitation for two whole blood cell samples, each representing dozens of individuals from separate collections taken per annum, yielded average sulfur type concentrations for the two populations: (first year, second year): [sulfate], 110 mM, 150 mM; [sulfonate], 99 mM, 70 mM, and; [low-valent sulfur], 41 mM, 220 mM. On titration of sulfate with acid or V(III) in aqueous solution, the strong 2,482.4 eV 1s {r_arrow} (valence t{sub 2}) sulfur K-edge XAS transition of tetrahedral SO{sub 4}{sup 2{minus}} splits into 1s {r_arrow} a{sub 1} and 1s {r_arrow} e transitions, because HSO{sub 4}{sup {minus}} and VSO{sub 4}{sup +} are of C{sub 3v} symmetry. Gaussian fits and appropriate comparisons allow the following assignments: (compound/complex, 1s {r_arrow}a{sub 1} (eV), 1s {r_arrow} e (eV)): myo-inositol hexasulfate, 2,480.8, 2,482.8; HSO{sub 4}{sup {minus}}, 2,481.4, 2,482.7; VSO{sub 4}{sup +}, 2,481.2, 2,482.9. The energy separating the a{sub 1} and e states of complexed sulfate appears to be solvation dependent. From these studies is derived an explicit inorganic spectrochemical model for biological V(III) and sulfate. The average endogenous equilomer concentrations of sulfate complexed with V(III) and/or H{sup +} within the two blood cell samples are calculated from this model. The results provide a natural explanation for the observed biological broadening of A. ceratodes

  8. Silver in geological fluids from in situ X-ray absorption spectroscopy and first-principles molecular dynamics

    NASA Astrophysics Data System (ADS)

    Pokrovski, Gleb S.; Roux, Jacques; Ferlat, Guillaume; Jonchiere, Romain; Seitsonen, Ari P.; Vuilleumier, Rodolphe; Hazemann, Jean-Louis

    2013-04-01

    The molecular structure and stability of species formed by silver in aqueous saline solutions typical of hydrothermal settings were quantified using in situ X-ray absorption spectroscopy (XAS) measurements, quantum-chemical modeling of near-edge absorption spectra (XANES) and extended fine structure spectra (EXAFS), and first-principles molecular dynamics (FPMD). Results show that in nitrate-bearing acidic solutions to at least 200 °C, silver speciation is dominated by the hydrated Ag+ cation surrounded by 4-6 water molecules in its nearest coordination shell with mean Ag-O distances of 2.32 ± 0.02 Å. In NaCl-bearing acidic aqueous solutions of total Cl concentration from 0.7 to 5.9 mol/kg H2O (m) at temperatures from 200 to 450 °C and pressures to 750 bar, the dominant species are the di-chloride complex AgCl2- with Ag-Cl distances of 2.40 ± 0.02 Å and Cl-Ag-Cl angle of 160 ± 10°, and the tri-chloride complex AgCl32- of a triangular structure and mean Ag-Cl distances of 2.60 ± 0.05 Å. With increasing temperature, the contribution of the tri-chloride species decreases from ˜50% of total dissolved Ag in the most concentrated solution (5.9m Cl) at 200 °C to less than 10-20% at supercritical temperatures for all investigated solutions, so that AgCl2- becomes by far the dominant Ag-bearing species at conditions typical of hydrothermal-magmatic fluids. Both di- and tri-chloride species exhibit outer-sphere interactions with the solvent as shown by the detection, using FPMD modeling, of H2O, Cl-, and Na+ at distances of 3-4 Å from the silver atom. The species fractions derived from XAS and FPMD analyses, and total AgCl(s) solubilities, measured in situ in this work from the absorption edge height of XAS spectra, are in accord with thermodynamic predictions using the stability constants of AgCl2- and AgCl32- from Akinfiev and Zotov (2001) and Zotov et al. (1995), respectively, which are based on extensive previous AgCl(s) solubility measurements. These data

  9. Azimuthal Doppler shift of absorption spectrum in optical vortex laser absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Yoshimura, Shinji; Aramaki, Mitsutoshi; Ozawa, Naoya; Terasaka, Kenichiro; Tanaka, Masayoshi; Nagaoka, Kenichi; Morisaki, Tomohiro

    2016-10-01

    Laser spectroscopy is a powerful diagnostic tool for measuring the mean flow velocity of plasma particles. We have been developing a new laser spectroscopy method utilizing an optical vortex beam, which has helical phase fronts corresponding to the phase change in the azimuthal direction. Because of this phase change, a Doppler effect is experienced even by an atom crossing the beam vertically. The additional azimuthal Doppler shift is proportional to the topological charge of optical vortex and is inversely proportional to the distance from the beam axis in which the beam intensity is vanished by destructive interference or the phase singularity. In order to detect the azimuthal Doppler shift, we have performed a laser absorption spectroscopy experiment with the linear ECR plasma device HYPER-I. Since the azimuthal Doppler shift depends on a position in the beam cross section, the absorption spectra at various positions were reconstructed from the transmitted beam intensity measured by a beam profiler. We have observed a clear spatial dependence of the Doppler shift, which qualitatively agreed with theory. Detailed experimental results, as well as remaining issues and future prospect, will be discussed at the meeting. This study was partially supported by JAPS KAKENHI Grand Numbers 15K05365 and 25287152.

  10. An X-ray absorption spectroscopy study of neptunium(V) reactions with Mackinawite (FeS).

    PubMed

    Moyes, Lesley N; Jones, Mark J; Reed, Wendy A; Livens, Francis R; Charnock, John M; Mosselmans, J Frederick W; Hennig, Christoph; Vaughan, David J; Pattrick, Richard A D

    2002-01-15

    Neptunium is a transuranium element, produced in tonne quantities in nuclear reactors. Because it has access to a range of oxidation states, neptunium may undergo redox transformations in the environment and these can have far-reaching effects on its environmental mobility. Here, the reaction of NpO2+ (the soluble and thermodynamically stable neptunium species in oxic systems) with microcrystalline mackinawite is studied. Uptake of neptunium from solution is relatively low (approximately 10% of the total initially present in solution) and independent of initial solution concentration over the range 0.27-2.74 mM and of equilibration time. X-ray absorption spectroscopy (XAS) of the solid sulfide samples indicates nearest neighbor oxygen atoms at distances around 2.25-2.26 A, sulfur atoms at around 2.61-2.64 A, and two more distant shells fitted with iron, at 3.91-3.95 A and 4.15-4.16 A. These observations suggest that on interaction with the sulfide surface reduction of Np(V) to Np(IV) occurs, accompanied by loss of axial oxygen atoms. Neptunium coordinates directly to surface sulfide atoms, in contrast to the behavior previously observed for uranium under similar conditions. These results demonstrate the importance and variability of the speciation of redox sensitive actinides under anoxic conditions.

  11. Role of Bi promotion and solvent in platinum-catalyzed alcohol oxidation probed by in situ X-ray absorption and ATR-IR spectroscopy.

    PubMed

    Mondelli, Cecilia; Grunwaldt, Jan-Dierk; Ferri, Davide; Baiker, Alfons

    2010-01-01

    Modification of 5 wt% Pt/Al(2)O(3) by Bi (0.9 wt%) affords a drastic improvement of catalytic activity in the liquid phase aerobic oxidation of benzyl alcohol. The nature of the solvent employed, cyclohexane or toluene, seems to influence the catalytic activity as well. We have investigated the catalysts under working conditions using in situ X-ray absorption spectroscopy (XAS) and attenuated total reflection infrared spectroscopy (ATR-IR), aiming at uncovering the roles of the metal promoter and the reaction medium. XAS confirms that Bi is oxidized more easily than Pt, maintaining the catalytic activity of the metallic Pt sites for a longer period of time. Interestingly, toluene contrary to cyclohexane reduced Pt to a large extent. The freshly reduced noble metal sites seem to directly interact with the solvent, inducing an immediate poisoning of the material and limiting its performance. This behaviour is not observed in the presence of Bi, whose geometric effect (site blocking) is interpreted as additionally limiting the adsorption of toluene and the premature deactivation of Pt. ATR-IR spectroscopy during CO adsorption on Pt and during reaction indicates that Bi is located rather on extended surfaces than on step or kink sites. Side products, CO and benzoate species, appearing during the reaction reveal that the geometric suppression of undesired reactions does not occur to the same extent on Pt-based catalysts as on Pd, suggesting that decarbonylation of the produced aldehyde on Pt may occur also on sites other than the (111) terraces.

  12. Femtosecond transient absorption spectroscopy of silanized silicon quantum dots

    NASA Astrophysics Data System (ADS)

    Kuntermann, Volker; Cimpean, Carla; Brehm, Georg; Sauer, Guido; Kryschi, Carola; Wiggers, Hartmut

    2008-03-01

    Excitonic properties of colloidal silicon quantum dots (Si qdots) with mean sizes of 4nm were examined using stationary and time-resolved optical spectroscopy. Chemically stable silicon oxide shells were prepared by controlled surface oxidation and silanization of HF-etched Si qdots. The ultrafast relaxation dynamics of photogenerated excitons in Si qdot colloids were studied on the picosecond time scale from 0.3psto2.3ns using femtosecond-resolved transient absorption spectroscopy. The time evolution of the transient absorption spectra of the Si qdots excited with a 150fs pump pulse at 390nm was observed to consist of decays of various absorption transitions of photoexcited electrons in the conduction band which overlap with both the photoluminescence and the photobleaching of the valence band population density. Gaussian deconvolution of the spectroscopic data allowed for disentangling various carrier relaxation processes involving electron-phonon and phonon-phonon scatterings or arising from surface-state trapping. The initial energy and momentum relaxation of hot carriers was observed to take place via scattering by optical phonons within 0.6ps . Exciton capturing by surface states forming shallow traps in the amorphous SiOx shell was found to occur with a time constant of 4ps , whereas deeper traps presumably localized in the Si-SiOx interface gave rise to exciton trapping processes with time constants of 110 and 180ps . Electron transfer from initially populated, higher-lying surface states to the conduction band of Si qdots (>2nm) was observed to take place within 400 or 700fs .

  13. Precision atomic beam density characterization by diode laser absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Oxley, Paul; Wihbey, Joseph

    2016-09-01

    We provide experimental and theoretical details of a simple technique to determine absolute line-of-sight integrated atomic beam densities based on resonant laser absorption. In our experiments, a thermal lithium beam is chopped on and off while the frequency of a laser crossing the beam at right angles is scanned slowly across the resonance transition. A lock-in amplifier detects the laser absorption signal at the chop frequency from which the atomic density is determined. The accuracy of our experimental method is confirmed using the related technique of wavelength modulation spectroscopy. For beams which absorb of order 1% of the incident laser light, our measurements allow the beam density to be determined to an accuracy better than 5% and with a precision of 3% on a time scale of order 1 s. Fractional absorptions of order 10-5 are detectable on a one-minute time scale when we employ a double laser beam technique which limits laser intensity noise. For a lithium beam with a thickness of 9 mm, we have measured atomic densities as low as 5 × 104 atoms cm-3. The simplicity of our technique and the details we provide should allow our method to be easily implemented in most atomic or molecular beam apparatuses.

  14. Optical re-injection in cavity-enhanced absorption spectroscopy

    PubMed Central

    Leen, J. Brian; O’Keefe, Anthony

    2014-01-01

    Non-mode-matched cavity-enhanced absorption spectrometry (e.g., cavity ringdown spectroscopy and integrated cavity output spectroscopy) is commonly used for the ultrasensitive detection of trace gases. These techniques are attractive for their simplicity and robustness, but their performance may be limited by the reflection of light from the front mirror and the resulting low optical transmission. Although this low transmitted power can sometimes be overcome with higher power lasers and lower noise detectors (e.g., in the near-infrared), many regimes exist where the available light intensity or photodetector sensitivity limits instrument performance (e.g., in the mid-infrared). In this article, we describe a method of repeatedly re-injecting light reflected off the front mirror of the optical cavity to boost the cavity's circulating power and deliver more light to the photodetector and thus increase the signal-to-noise ratio of the absorption measurement. We model and experimentally demonstrate the method's performance using off-axis cavity ringdown spectroscopy (OA-CRDS) with a broadly tunable external cavity quantum cascade laser. The power coupled through the cavity to the detector is increased by a factor of 22.5. The cavity loss is measured with a precision of 2 × 10−10 cm−1/\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{upgreek} \\usepackage{mathrsfs} \\setlength{\\oddsidemargin}{-69pt} \\begin{document} }{}$\\sqrt {{\\rm Hz;}}$\\end{document} Hz ; an increase of 12 times over the standard off-axis configuration without reinjection and comparable to the best reported sensitivities in the mid-infrared. Finally, the re-injected CRDS system is used to measure the spectrum of several volatile organic compounds, demonstrating the improved ability to resolve weakly absorbing spectroscopic features. PMID:25273701

  15. Optical re-injection in cavity-enhanced absorption spectroscopy

    SciTech Connect

    Leen, J. Brian O’Keefe, Anthony

    2014-09-15

    Non-mode-matched cavity-enhanced absorption spectrometry (e.g., cavity ringdown spectroscopy and integrated cavity output spectroscopy) is commonly used for the ultrasensitive detection of trace gases. These techniques are attractive for their simplicity and robustness, but their performance may be limited by the reflection of light from the front mirror and the resulting low optical transmission. Although this low transmitted power can sometimes be overcome with higher power lasers and lower noise detectors (e.g., in the near-infrared), many regimes exist where the available light intensity or photodetector sensitivity limits instrument performance (e.g., in the mid-infrared). In this article, we describe a method of repeatedly re-injecting light reflected off the front mirror of the optical cavity to boost the cavity's circulating power and deliver more light to the photodetector and thus increase the signal-to-noise ratio of the absorption measurement. We model and experimentally demonstrate the method's performance using off-axis cavity ringdown spectroscopy (OA-CRDS) with a broadly tunable external cavity quantum cascade laser. The power coupled through the cavity to the detector is increased by a factor of 22.5. The cavity loss is measured with a precision of 2 × 10{sup −10} cm{sup −1}/√(Hz;) an increase of 12 times over the standard off-axis configuration without reinjection and comparable to the best reported sensitivities in the mid-infrared. Finally, the re-injected CRDS system is used to measure the spectrum of several volatile organic compounds, demonstrating the improved ability to resolve weakly absorbing spectroscopic features.

  16. Optical re-injection in cavity-enhanced absorption spectroscopy.

    PubMed

    Leen, J Brian; O'Keefe, Anthony

    2014-09-01

    Non-mode-matched cavity-enhanced absorption spectrometry (e.g., cavity ringdown spectroscopy and integrated cavity output spectroscopy) is commonly used for the ultrasensitive detection of trace gases. These techniques are attractive for their simplicity and robustness, but their performance may be limited by the reflection of light from the front mirror and the resulting low optical transmission. Although this low transmitted power can sometimes be overcome with higher power lasers and lower noise detectors (e.g., in the near-infrared), many regimes exist where the available light intensity or photodetector sensitivity limits instrument performance (e.g., in the mid-infrared). In this article, we describe a method of repeatedly re-injecting light reflected off the front mirror of the optical cavity to boost the cavity's circulating power and deliver more light to the photodetector and thus increase the signal-to-noise ratio of the absorption measurement. We model and experimentally demonstrate the method's performance using off-axis cavity ringdown spectroscopy (OA-CRDS) with a broadly tunable external cavity quantum cascade laser. The power coupled through the cavity to the detector is increased by a factor of 22.5. The cavity loss is measured with a precision of 2 × 10(-10) cm(-1)/√Hz; an increase of 12 times over the standard off-axis configuration without reinjection and comparable to the best reported sensitivities in the mid-infrared. Finally, the re-injected CRDS system is used to measure the spectrum of several volatile organic compounds, demonstrating the improved ability to resolve weakly absorbing spectroscopic features.

  17. Combined non-destructive XRF and SR-XAS study of archaeological artefacts.

    PubMed

    Bardelli, Fabrizio; Barone, Germana; Crupi, Vincenza; Longo, Francesca; Majolino, Domenico; Mazzoleni, Paolo; Venuti, Valentina

    2011-03-01

    We report on a non-destructive study of Sicilian ceramic fragments of cultural heritage interest, classified as "proto-majolica" pottery and dating back to the twelfth to thirteen centuries AD. The analytical approach used is based on the employment of two totally non-invasive spectroscopic techniques: X-ray fluorescence (XRF), using a portable energy-dispersive XRF analyser, and X-ray absorption spectroscopy, using synchrotron radiation as a probe (SR-XAS). XRF measurements allowed us to collect elemental and spatially resolved information on major and minor constituents of the decorated coating of archaeological pottery fragments, so providing preliminary results on the main components characterizing the surface. In particular, we assigned to Fe and Mn the role of key elements of the colouring agent. With the aim of obtaining more detailed information, we performed SR-XAS measurements at the Fe and Mn K-edges at the Italian BM08 beamline at the European Synchrotron Radiation Facility (Grenoble, France). The experimental data were analysed by applying principal component analysis and least-squares fitting to the near-edge part of the spectra (X-ray absorption near-edge structure) to determine the samples' speciation. From the overall results, umber, a class of brownish pigments characterized by a mixture of hydrated iron and manganese oxides, has been ascribed as a pigmenting agent.

  18. Optical absorption and scattering spectroscopies of single nano-objects.

    PubMed

    Crut, Aurélien; Maioli, Paolo; Del Fatti, Natalia; Vallée, Fabrice

    2014-06-07

    Developments of optical detection and spectroscopy methods for single nano-objects are key advances for applications and fundamental understanding of the novel properties exhibited by nanosize systems. These methods are reviewed, focusing on far-field optical approaches based on light absorption and elastic scattering. The principles of the main linear and nonlinear methods are described and experimental results are illustrated in the case of metal nanoparticles, stressing the key role played by the object environment, such as the presence of a substrate, bound surface molecules or other nano-objects. Special attention is devoted to quantitative methods and correlation of the measured optical spectra of a nano-object with its morphology, characterized either optically or by electron microscopy, as this permits precise comparison with theoretical models. Application of these methods to optical detection and spectroscopy for single semiconductor nanowires and carbon nanotubes is also presented. Extension to ultrafast nonlinear extinction or scattering spectroscopies of single nano-objects is finally discussed in the context of investigation of their nonlinear optical response and their electronic, acoustic and thermal properties.

  19. Soft X-Ray Studies of Pu Electronic Structure: Past Lessons From XAS and Future Direction With BIS

    SciTech Connect

    Tobin, J G; Yu, S W; Chung, B W; Waddill, G D; Kutepov, A L

    2008-12-10

    Synchrotron-radiation-based spectroscopies such as X-ray Absorption Spectroscopy (XAS) have contributed greatly to our improved understanding of Pu electronic structure. However, significant questions remain concerning the nature of Pu electronic structure. Perhaps the missing piece of the puzzle is the direct experimental determination of the unoccupied electronic structure using high energy inverse photoelectron spectroscopy (IPES) or Bremstrahlung Isochromat Spectroscopy (BIS). Past BIS studies of Th and U indicate the feasibility and utility of Pu studies. To this end, a new BIS capability has been developed in our laboratory. Electron stimulated emission of photons has been carried out using the XES-350 monochromator and detector system. Our preliminary results and future plans will be presented.

  20. Atomic Absorption Spectroscopy, Atomic Emission Spectroscopy, and Inductively Coupled Plasma-Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Miller, Dennis D.; Rutzke, Michael A.

    Atomic spectroscopy has played a major role in the development of our current database for mineral nutrients and toxicants in foods. When atomic absorption spectrometers became widely available in the 1960s, the development of atomic absorption spectroscopy (AAS) methods for accurately measuring trace amounts of mineral elements in biological samples paved the way for unprecedented advances in fields as diverse as food analysis, nutrition, biochemistry, and toxicology (1). The application of plasmas as excitation sources for atomic emission spectroscopy (AES) led to the commercial availability of instruments for inductively coupled plasma - atomic emission spectroscopy (ICP-AES) beginning in the late 1970s. This instrument has further enhanced our ability to measure the mineral composition of foods and other materials rapidly, accurately, and precisely. More recently, plasmas have been joined with mass spectrometers (MS) to form inductively coupled plasma-mass spectrometer ICP-MS instruments that are capable of measuring mineral elements with extremely low detection limits. These three instrumental methods have largely replaced traditional wet chemistry methods for mineral analysis of foods, although traditional methods for calcium, chloride, iron, and phosphorus remain in use today (see Chap. 12).

  1. Investigating Actinide Molecular Adducts From Absorption Edge Spectroscopy

    SciTech Connect

    Den Auwer, C.; Conradson, S.D.; Guilbaud, P.; Moisy, P.; Mustre de Leon, J.; Simoni, E.; /SLAC, SSRL

    2006-10-27

    Although Absorption Edge Spectroscopy has been widely applied to the speciation of actinide elements, specifically at the L{sub III} edge, understanding and interpretation of actinide edge spectra are not complete. In that sense, semi-quantitative analysis is scarce. In this paper, different aspects of edge simulation are presented, including semi-quantitative approaches. Comparison is made between various actinyl (U, Np) aquo or hydroxy compounds. An excursion into transition metal osmium chemistry allows us to compare the structurally related osmyl and uranyl hydroxides. The edge shape and characteristic features are discussed within the multiple scattering picture and the role of the first coordination sphere as well as contributions from the water solvent are described.

  2. Terahertz absorption spectroscopy of protein-containing reverse micellar solution

    NASA Astrophysics Data System (ADS)

    Murakami, H.; Toyota, Y.; Nishi, T.; Nashima, S.

    2012-01-01

    Terahertz time-domain spectroscopy has been carried out for AOT/isooctane reverse micellar solution with myoglobin at the water-to-surfactant molar ratios ( w0) of 0.2 and 4.4. The amplitude of the absorption spectrum increases with increasing the protein concentration at w0 = 0.2, whereas it decreases at w0 = 4.4. The molar extinction coefficients of the protein-filled reverse micelle, and the constituents, i.e., myoglobin, water, and AOT, have been derived by use of the structural parameters of the micellar solution. The experimental results are interpreted in terms of hydration onto the protein and surfactant in the reverse micelle.

  3. High Resolution Absorption Spectroscopy using Externally Dispersed Interferometry

    SciTech Connect

    Edelstein, J; Erskine, D J

    2005-07-06

    We describe the use of Externally Dispersed Interferometry (EDI) for high-resolution absorption spectroscopy. By adding a small fixed-delay interferometer to a dispersive spectrograph, a precise fiducial grid in wavelength is created over the entire spectrograph bandwidth. The fiducial grid interacts with narrow spectral features in the input spectrum to create a moire pattern. EDI uses the moire pattern to obtain new information about the spectra that is otherwise unavailable, thereby improving spectrograph performance. We describe the theory and practice of EDI instruments and demonstrate improvements in the spectral resolution of conventional spectrographs by a factor of 2 to 6. The improvement of spectral resolution offered by EDI can benefit space instruments by reducing spectrograph size or increasing instantaneous bandwidth.

  4. Investigating DNA Radiation Damage Using X-Ray Absorption Spectroscopy

    PubMed Central

    Czapla-Masztafiak, Joanna; Szlachetko, Jakub; Milne, Christopher J.; Lipiec, Ewelina; Sá, Jacinto; Penfold, Thomas J.; Huthwelker, Thomas; Borca, Camelia; Abela, Rafael; Kwiatek, Wojciech M.

    2016-01-01

    The biological influence of radiation on living matter has been studied for years; however, several questions about the detailed mechanism of radiation damage formation remain largely unanswered. Among all biomolecules exposed to radiation, DNA plays an important role because any damage to its molecular structure can affect the whole cell and may lead to chromosomal rearrangements resulting in genomic instability or cell death. To identify and characterize damage induced in the DNA sugar-phosphate backbone, in this work we performed x-ray absorption spectroscopy at the P K-edge on DNA irradiated with either UVA light or protons. By combining the experimental results with theoretical calculations, we were able to establish the types and relative ratio of lesions produced by both UVA and protons around the phosphorus atoms in DNA. PMID:27028640

  5. La Saturated Absorption Spectroscopy for Applications in Quantum Information

    NASA Astrophysics Data System (ADS)

    Becker, Patrick; Donoghue, Liz; Dungan, Kristina; Liu, Jackie; Olmschenk, Steven

    2015-05-01

    Quantum information may revolutionize computation and communication by utilizing quantum systems based on matter quantum bits and entangled light. Ions are excellent candidates for quantum bits as they can be well-isolated from unwanted external influences by trapping and laser cooling. Doubly-ionized lanthanum in particular shows promise for use in quantum information as it has infrared transitions in the telecom band, with low attenuation in standard optical fiber, potentially allowing for long distance information transfer. However, the hyperfine splittings of the lowest energy levels, required for laser cooling, have not been measured. We present progress and recent results towards measuring the hyperfine splittings of these levels in lanthanum by saturated absorption spectroscopy with a hollow cathode lamp. This research is supported by the Army Research Office, Research Corporation for Science Advancement, and Denison University.

  6. Antimony quantification in Leishmania by electrothermal atomic absorption spectroscopy.

    PubMed

    Roberts, W L; Rainey, P M

    1993-05-15

    Tri- and pentavalent antimony were quantified in Leishmania mexicana pifanoi amastigotes and promastigotes by atomic absorption spectroscopy with electrothermal atomization. Leishmania grown in axenic culture were treated with either potassium antimony tartrate [Sb(III)] or sodium stibogluconate [Sb(V)]. The parasites were collected, digested with nitric acid, and subjected to atomic absorption spectroscopy. The method was linear from 0 to 7 ng of antimony. The interassay coefficients of variation were 9.6 and 5.7% (N = 5) for 0.52 and 3.7-ng samples of leishmanial antimony, respectively. The limit of detection was 95 pg of antimony. The assay was used to characterize Sb(III) and Sb(V) influx and efflux kinetics. Influx rates were determined at antimony concentrations that produced a 50% inhibition of growth (IC50). The influx rates of Sb(V) into amastigotes and promastigotes were 4.8 and 12 pg/million cells/h, respectively, at 200 micrograms antimony/ml. The influx rate of Sb(III) into amastigotes was 41 pg/million cells/h at 20 micrograms antimony/ml. Influx of Sb(III) into promastigotes at 1 microgram antimony/ml was rapid and reached a plateau of 175 pg/million cells in 2 h. Efflux of Sb(III) and Sb(V) from amastigotes and promastigotes exhibited biphasic kinetics. The initial (alpha) half-life of Sb(V) efflux was less than 4 min and that of Sb(III) was 1-2 h. The apparent terminal (beta) half-lives ranged from 7 to 14 h.

  7. Absorption and emission spectroscopy in natural and synthetic corundum

    NASA Astrophysics Data System (ADS)

    Spinolo, G.; Palanza, V.; Ledonne, A.; Paleari, A.

    2009-04-01

    sapphires absorption spectra. In conclusion, both for metamorphic, synthetic and magmatic sapphires we reached a quite complete interpretation of the spectroscopic data in terms of "non interacting impurity ions". Orange, purple and green sapphires absorption spectra may also be discussed in terms of such interpretative approach. References Fontana I, LeDonne A, Palanza V, Binetti S and Spinolo G (2008) Optical spectroscopy study of type 1 natural and synthetic sapphires. J. Phys:Condens.Matter 20:125228-125232

  8. Non-destructive plant health sensing using absorption spectroscopy

    NASA Technical Reports Server (NTRS)

    Bledsoe, Jim; Manukian, Ara; Pearce, Michael; Weiss, Lee

    1988-01-01

    The sensor group of the 1988 EGM 4001 class, working on NASA's Controlled Ecological Life Support Systems (CELSS) project, investigated many different plant health indicators and the technologies used to test them. The project selected by the group was to measure chlorophyll levels using absorption spectroscopy. The spectrometer measures the amount of chlorophyll in a leaf by measuring the intensity of light of a specific wavelength that is passed through a leaf. The three wavelengths of light being used corresponded to the near-IR absorption peaks of chlorophyll a, chlorophyll b, and chlorophyll-free structures. Experimentation showed that the sensor is indeed measuring levels of chlorophyll a and b and their changes before the human eye can see any changes. The detector clamp causes little damage to the leaf and will give fairly accurate readings on similar locations on a leaf, freeing the clamp from having to remain on the same spot of a leaf for all measurements. External light affects the readings only slightly so that measurements may be taken in light or dark environments. Future designs and experimentation will concentrate on reducing the size of the sensor and adapting it to a wider range of plants.

  9. Laser absorption spectroscopy system for vaporization process characterization and control

    SciTech Connect

    Galkowski, J.; Hagans, K.

    1993-09-07

    In support of the Lawrence Livermore National Laboratory`s (LLNL`s) Uranium Atomic Vapor Laser Isotope Separation (U-AVLIS) Program, a laser atomic absorption spectroscopy (LAS) system has been developed. This multi-laser system is capable of simultaneously measuring the line densities of {sup 238}U ground and metastable states, {sup 235}U ground and metastable states, iron, and ions at up to nine locations within the separator vessel. Supporting enrichment experiments that last over one hundred hours, this laser spectroscopy system is employed to diagnose and optimize separator system performance, control the electron beam vaporizer and metal feed systems, and provide physics data for the validation of computer models. As a tool for spectroscopic research, vapor plume characterization, vapor deposition monitoring, and vaporizer development, LLNL`s LAS laboratory with its six argon-ion-pumped ring dye lasers and recently added Ti:Sapphire and external-cavity diode-lasers has capabilities far beyond the requirements of its primary mission.

  10. Lifetime-Broadening-Suppressed X-ray Absorption Spectrum of β-YbAlB4 Deduced from Yb 3d → 2p Resonant X-ray Emission Spectroscopy

    NASA Astrophysics Data System (ADS)

    Kawamura, Naomi; Kanai, Noriko; Hayashi, Hisashi; Matsuda, Yasuhiro H.; Mizumaki, Masaichiro; Kuga, Kentaro; Nakatsuji, Satoru; Watanabe, Shinji

    2017-01-01

    In this work, the Yb 3d → 2p (Yb Lα1,2) resonant X-ray emission spectrum of β-YbAlB4 was acquired using excitation energies around the Yb L3-edge, at 2 K. Subsequently, the lifetime-broadening-suppressed (LBS) X-ray absorption structure (XAS) spectrum was obtained using the SIM-RIXS program. This spectrum was found to exhibit clearly resolved pre-edge and shoulder structures. Resonant Lα1 emission spectra were well reproduced from LBS-XAS profiles over wide ranges of excitation and emission energies. In contrast, noticeable discrepancies appeared between the experimental and simulated Lα2 emission spectra, suggesting an effect resulting from M4M5O1 Coster-Kronig transitions. LBS-XAS, in conjunction with partial fluorescence yield (PFY) XAS and transmission XAS, determined a value for the Yb valence (v) in β-YbAlB4 of 2.76 ± 0.08 at 2 K. Despite this relatively large uncertainty in v, each method provided a consistent variation in valence (δv) as the temperature was raised from 2 to 280 K: 0.060 ± 0.004 (LBS-XAS), 0.061 ± 0.005 (PFY-XAS) and 0.058 ± 0.007 (transmission XAS). The smaller δv associated with LBS-XAS demonstrates the greater precision of this method.

  11. Performance and characteristics of a high pressure, high temperature capillary cell with facile construction for operando x-ray absorption spectroscopy

    SciTech Connect

    Bansode, Atul; Urakawa, Atsushi; Guilera, Gemma; Simonelli, Laura; Avila, Marta; Cuartero, Vera

    2014-08-15

    We demonstrate the use of commercially available fused silica capillary and fittings to construct a cell for operando X-ray absorption spectroscopy (XAS) for the study of heterogeneously catalyzed reactions under high pressure (up to 200 bars) and high temperature (up to 280 °C) conditions. As the first demonstration, the cell was used for CO{sub 2} hydrogenation reaction to examine the state of copper in a conventional Cu/ZnO/Al{sub 2}O{sub 3} methanol synthesis catalyst. The active copper component of the catalyst was shown to remain in the metallic state under supercritical reaction conditions, at 200 bars and up to 260 °C. With the coiled heating system around the capillary, one can easily change the length of the capillary and control the amount of catalyst under investigation. With precise control of reactant(s) flow, the cell can mimic and serve as a conventional fixed-bed micro-reactor system to obtain reliable catalytic data. This high comparability of the reaction performance of the cell and laboratory reactors is crucial to gain insights into the nature of actual active sites under technologically relevant reaction conditions. The large length of the capillary can cause its bending upon heating when it is only fixed at both ends because of the thermal expansion. The degree of the bending can vary depending on the heating mode, and solutions to this problem are also presented. Furthermore, the cell is suitable for Raman studies, nowadays available at several beamlines for combined measurements. A concise study of CO{sub 2} phase behavior by Raman spectroscopy is presented to demonstrate a potential of the cell for combined XAS-Raman studies.

  12. Comparison of absorption, fluorescence, and polarization spectroscopy of atomic rubidium

    NASA Astrophysics Data System (ADS)

    Ashman, Seth; Stifler, Cayla; Romero, Joaquin

    2015-05-01

    An ongoing spectroscopic investigation of atomic rubidium utilizes a two-photon, single-laser excitation process. Transitions accessible with our tunable laser include 5P1 / 2F' <-- 5S1 / 2 F and 5P3 / 2F' <-- 5S1 / 2 F . The laser is split into a pump and probe beam to allow for Doppler-free measurements of transitions between hyperfine levels. The pump and probe beams are overlapped in a counter-propagating geometry and the laser frequency scans over a transition. Absorption, fluorescence and polarization spectroscopy techniques are applied to this basic experimental setup. The temperature of the vapor cell and the power of the pump and probe beams have been varied to explore line broadening effects and signal-to-noise of each technique. This humble setup will hopefully grow into a more robust experimental arrangement in which double resonance, two-laser excitations are used to explore hyperfine state changing collisions between rubidium atoms and noble gas atoms. Rb-noble gas collisions can transfer population between hyperfine levels, such as 5P3 / 2 (F' = 3) <-- Collision 5P3 / 2 (F ' = 2) , and the probe beam couples 7S1 / 2 (F'' = 2) <-- 5P3 / 2 (F' = 3) . Polarization spectroscopy signal depends on the rate of population transfer due to the collision as well as maintaining the orientation created by the pump laser. Fluorescence spectroscopy relies only on transfer of population due to the collision. Comparison of these techniques yields information regarding the change of the magnetic sublevels, mF, during hyperfine state changing collisions.

  13. In situ x-ray absorption spectroscopy study of tin anode nanomaterials for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Pelliccione, Christopher J.

    Tin is an attractive alternative to replace traditional carbon based anodes in lithium-ion batteries (LIBs) due to the nearly three-fold increase in theoretical capacity over carbon. However, metallic tin suffers from volumetric expansion of the crystal structure during initial lithium insertion that quickly degrades the material and reduces the performance of the battery. Various techniques have been previously investigated with the goal of suppressing this destructive expansion by incorporating oxygen or a lithium-inactive metal into the tin to provide structural support and mitigate volumetric expansion. These materials show increased capacity retention compared to metallic tin, but still suffer from capacity fading. The nature of these structural degradations must be fully understood to permit engineering of materials that avoid these destructive tendencies and can be considered as viable options for LIBs. In situ X-ray absorption spectroscopy (XAS) measurements were acquired on Sn, SnO2, Sn3O2(OH) 2, Cu6Sn5 and Ni3Sn4 nanoparticle anodes for LIBs. Accompanying the electrochemical characterization conducted on each material, the local atomic structure was modeled as a function of potential during the first charge and also as a function of charged/discharged states for several cycles. The extended X-ray absorption fine structure (EXAFS) theoretical modeling included the first unambiguous observation of Sn-Li coordination numbers and atomic distances in tin-based anode materials. From correlating the electrochemical performance to the EXAFS analysis, the long-term capacity retention of tin-based anodes is dependent on the structural deformations that occur during the first charge. The conversion of oxygen to amorphous Li2O, and the network that it forms, has a dramatic effect on the kinetics of the system and the stability of the local metallic tin structure.

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

    SciTech Connect

    Marcos, E. Sanchez; Beret, E. C.; Martinez, J. M.; Pappalardo, R. R.; Ayala, R.; Munoz-Paez, A.

    2007-11-29

    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 Cr{sup 3+}, Rh{sup 3+}, Ir{sup 3+}, (b) the invisibility by XAS of certain structures characterized by Computer Simulations but exhibiting high dynamical behavior and (c) the solvation of Br{sup -} in acetonitrile.

  15. Self-calibration wavelength modulation spectroscopy for acetylene detection based on tunable diode laser absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Huang, Qin-Bin; Xu, Xue-Mei; Li, Chen-Jing; Ding, Yi-Peng; Cao, Can; Yin, Lin-Zi; Ding, Jia-Feng

    2016-11-01

    The expressions of the second harmonic (2f) signal are derived on the basis of absorption spectral and lock-in theories. A parametric study indicates that the phase shift between the intensity and wavelength modulation makes a great contribution to the 2f signal. A self-calibration wavelength modulation spectroscopy (WMS) method based on tunable diode laser absorption spectroscopy (TDLAS) is applied, combining the advantages of ambient pressure, temperature suppression, and phase-shift influences elimination. Species concentration is retrieved simultaneously from selected 2f signal pairs of measured and reference WMS-2f spectra. The absorption line of acetylene (C2H2) at 1530.36 nm near-infrared is selected to detect C2H2 concentrations in the range of 0-400 ppmv. System sensitivity, detection precision and limit are markedly improved, demonstrating that the self-calibration method has better detecting performance than the conventional WMS. Project supported by the National Natural Science Foundation of China (Grant Nos. 61172047, 61502538, and 61501525).

  16. Oxidation of In xGa 1- xAs yP 1- y by NO 2 studied with Auger electron spectroscopy

    NASA Astrophysics Data System (ADS)

    Bahr, C. C.; Paparazzo, E.; Moretto, L.; Lama, F.; Zema, N.

    1994-09-01

    We have studied the oxidation of quaternary InGaAsP materials by NO 2, using Auger electron spectroscopy for both elemental and chemical analysis of the surface. We report that NO 2 induces a preferential oxidation, forming oxides of Ga, In, and P. The As remains unoxidized. From Ar + ion milling we find that the oxide layers are fairly thin (less than 10 Å), even at high exposures (greater than 1000 L) of NO 2, where we obtain a saturation coverage of approximately 0.3 ML (monolayers). We have also measured electron energy loss spectra (EELS) and observe the disappearance of the surface plasmon loss feature upon oxide formation.

  17. Determination of Aluminum Concentration in Seawater by Colorimetry and Atomic Absorption Spectroscopy.

    DTIC Science & Technology

    1972-11-30

    this was also high. 5 . ,Irj ~ - • lri*; llo. TALLE 2 ATOMIC ABSORPTION SPECTROSCOPY DETEPIJINATION OF ALUMINU1 CONCENTRATIO11 OF SEAWATER OCEAN...Concentration in Seawater by Colorimetr-y and Atomic Absorption Spectroscopy Charles A. Greene, Jr. and Everett N. Jones Ocean Science Department T14

  18. Absorption and emission spectroscopy of individual semiconductor nanostructures

    NASA Astrophysics Data System (ADS)

    McDonald, Matthew P.

    The advent of controllable synthetic methods for the production of semiconductor nanostructures has led to their use in a host of applications, including light-emitting diodes, field effect transistors, sensors, and even television displays. This is, in part, due to the size, shape, and morphologically dependent optical and electrical properties that make this class of materials extremely customizable; wire-, rod- and sphere-shaped nanocrystals are readily synthesized through common wet chemical methods. Most notably, confining the physical dimension of the nanostructure to a size below its Bohr radius (aB) results in quantum confinement effects that increase its optical energy gap. Not only the size, but the shape of a particle can be exploited to tailor its optical and electrical properties. For example, confined CdSe quantum dots (QDs) and nanowires (NWs) of equivalent diameter possess significantly different optical gaps. This phenomenon has been ascribed to electrostatic contributions arising from dielectric screening effects that are more pronounced in an elongated (wire-like) morphology. Semiconducting nanostructures have thus received significant attention over the past two decades. However, surprisingly little work has been done to elucidate their basic photophysics on a single particle basis. What has been done has generally been accomplished through emission-based measurements, and thus does not fully capture the full breadth of these intriguing systems. What is therefore needed then are absorption-based studies that probe the size and shape dependent evolution of nanostructure photophysics. This thesis summarizes the single particle absorption spectroscopy that we have carried out to fill this knowledge gap. Specifically, the diameter-dependent progression of one-dimensional (1D) excitonic states in CdSe NWs has been revealed. This is followed by a study that focuses on the polarization selection rules of 1D excitons within single CdSe NWs. Finally

  19. In-situ X-ray absorption spectroscopy analysis of capacity fade in nanoscale-LiCoO{sub 2}

    SciTech Connect

    Patridge, Christopher J.; Swider-Lyons, Karen E.; Twigg, Mark E.; Ramaker, David E.

    2013-07-15

    The local structure of nanoscale (∼10–40 nm) LiCoO{sub 2} is monitored during electrochemical cycling utilizing in-situ X-ray absorption spectroscopy (XAS). The high surface area of the LiCoO{sub 2} nanoparticles not only enhances capacity fade, but also provides a large signal from the particle surface relative to the bulk. Changes in the nanoscale LiCoO{sub 2} metal-oxide bond lengths, structural disorder, and chemical state are tracked during cycling by adapting the delta mu (Δμ) technique in complement with comprehensive extended X-ray absorption fine structure (EXAFS) modeling. For the first time, we use a Δμ EXAFS method, and by comparison of the difference EXAFS spectra, extrapolate significant coordination changes and reduction of cobalt species with cycling. This combined approach suggests Li–Co site exchange at the surface of the nanoscale LiCoO{sub 2} as a likely factor in the capacity fade and irreversible losses in practical, microscale LiCoO{sub 2}. - Graphical abstract: Electrochemical cycling of Li-ion batteries has strong impact on the structure and integrity of the cathode active material particularly near the surface/electrolyte interface. In developing a new method, we have used in-situ X-ray absorption spectroscopy during electrochemical cycling of nanoscale LiCoO{sub 2} to track changes during charge and discharge and between subsequent cycles. Using difference spectra, several small changes in Co-O bond length, Co-O and Co-Co coordination, and site exchange between Co and Li sites can be tracked. These methods show promise as a new technique to better understand processes which lead to capacity fade and loss in Li-ion batteries. - Highlights: • A new method is developed to understand capacity fade in Li-ion battery cathodes. • Structural changes are tracked during Li intercalation/deintercalation of LiCoO{sub 2}. • Surface structural changes are emphasized using nanoscale-LiCoO{sub 2} and difference spectra. • Full multiple

  20. Relationship between ferroelectric properties and local structure of Pb1-xBaxZr0.40Ti0.60O3 ceramic materials studied by X-ray absorption and Raman spectroscopies

    NASA Astrophysics Data System (ADS)

    Mesquita, Alexandre; Michalowicz, Alain; Moscovici, Jacques; Pizani, Paulo Sergio; Mastelaro, Valmor Roberto

    2016-08-01

    This paper reports on the structural characterization of Pb1-xBaxZr0.40Ti0.60O3 (PBZT) ferroelectric ceramic compositions prepared by the conventional solid state reaction method. X-ray absorption spectroscopy (XAS) and Raman spectroscopy were used in the probing of the local structure of PBZT samples that exhibit a normal or relaxor ferroelectric behavior. They showed a considerable local disorder around Zr and Pb atoms in the samples of tetragonal or cubic long-range order symmetry. The intensity of the E(TO3) mode in the Raman spectra of PBZT relaxor samples remains constant at temperatures lower than Tm, which has proven the stabilization of the correlation process between nanodomains.

  1. Decay Heat Measurements Using Total Absorption Gamma-ray Spectroscopy

    NASA Astrophysics Data System (ADS)

    Rice, S.; Valencia, E.; Algora, A.; Taín, J. L.; Regan, P. H.; Podolyák, Z.; Agramunt, J.; Gelletly, W.; Nichols, A. L.

    2012-09-01

    A knowledge of the decay heat emitted by thermal neutron-irradiated nuclear fuel is an important factor in ensuring safe reactor design and operation, spent fuel removal from the core, and subsequent storage prior to and after reprocessing, and waste disposal. Decay heat can be readily calculated from the nuclear decay properties of the fission products, actinides and their decay products as generated within the irradiated fuel. Much of the information comes from experiments performed with HPGe detectors, which often underestimate the beta feeding to states at high excitation energies. This inability to detect high-energy gamma emissions effectively results in the derivation of decay schemes that suffer from the pandemonium effect, although such a serious problem can be avoided through application of total absorption γ-ray spectroscopy (TAS). The beta decay of key radionuclei produced as a consequence of the neutron-induced fission of 235U and 239Pu are being re-assessed by means of this spectroscopic technique. A brief synopsis is given of the Valencia-Surrey (BaF2) TAS detector, and their method of operation, calibration and spectral analysis.

  2. Femtosecond XUV transient absorption spectroscopy of small organic molecules

    NASA Astrophysics Data System (ADS)

    Lackner, Florian; Chatterley, Adam S.; Neumark, Daniel M.; Leone, Stephen R.; Gessner, Oliver

    2015-05-01

    High-order harmonic generation has evolved as a powerful method for the generation of femtosecond XUV pulses with table-top laser systems. Femtosecond XUV transient absorption spectroscopy is an emerging application of these novel light sources for the investigation of molecular dynamics. Recording time-dependent XUV induced core-to-valence transitions traces a molecular response to an initial perturbation with IR, VIS or UV laser pulses from the perspective of distinct atomic sites. Preliminary results for sulfur and selenium containing organic molecules, such as thiophene (C4H4S) and selenophene(C4H4Se), are presented. While molecular orbital dynamics in thiophene will be monitored at the sulfur 2p edge around 165 eV, experiments at the Se 3d (57 eV) and Se 3p (163 eV) edges of selenophene will provide insight about the impact of specific inner-shell transitions within the same atom on the spectroscopic fingerprint of similar dynamics. The method's element-specificity and sensitivity to local valance electronic structures will be exploited to monitor the photo-induced opening of the aromatic rings at the S-C and Se-C bonds, thereby shining new light on the primary steps of photochemical reaction pathways in organic compounds.

  3. In situ measurement of ferric iron in lunar glass beads using Fe-XAS

    NASA Astrophysics Data System (ADS)

    McCanta, Molly C.; Dyar, M. Darby; Rutherford, Malcolm J.; Lanzirotti, Antonio; Sutton, Stephen R.; Thomson, Bradley J.

    2017-03-01

    Through use of a new X-ray Absorption Spectroscopy (XAS) calibration for Fe3+ analysis in silicate glasses, the first direct measurements of ferric iron in natural lunar picritic glasses are presented. Lunar glass beads from the Apollo sample collection contain up to 60.0% Fe3+. No correlation with melt chemical properties, such as Mg# or weight % TiO2, or physical properties, such as bead diameter, was observed. Fe3+/ΣFe is negatively correlated with NBO/T. These elevated Fe3+/ΣFe values reflect eruption and post-eruption oxidation due to magmatic degassing of H or OH. Glass beads observed to be zoned to lower Fe3+/ΣFe rims may represent a subsequent reduction in the lunar vacuum prior to cooling through the glass transition temperature.

  4. A new metal exchanged zeolite for a present environmental problem. An in-situ XAS study

    NASA Astrophysics Data System (ADS)

    Alonso-Escobar, C.; Franch-Martí, C.; Palomares, A. E.; Rey, F.; Guilera, G.

    2013-04-01

    The medium pore zeolite, TNU-9, is prepared and studied for the selective catalytic reduction (SCR) of NO using C3H8 as the reducing agent. The catalytic activity of TNU-9 zeolites for the SCR is comparable to other known highly active zeolites but with the advantage of TNU-9 of having almost the same catalytic performance in the presence of H2O during reaction. The nature and behaviour of Cu and Co active sites contained in the TNU-9 catalysts have been studied under operation conditions using X-ray Absorption Spectroscopy (XAS) to understand the key parameters controlling the performance of this reaction.1 It was found that the well dispersed Cu and Co centres need to be in a mixed valence state to obtain good catalytic results for the SCR and that the catalytic performance is related to the topology of the TNU-9 itself.

  5. Intracavity Dye-Laser Absorption Spectroscopy (IDLAS) for application to planetary molecules

    NASA Technical Reports Server (NTRS)

    Lang, Todd M.; Allen, John E., Jr.

    1990-01-01

    Time-resolved, quasi-continuous wave, intracavity dye-laser absorption spectroscopy is applied to the investigation of absolute absorption coefficients for vibrational-rotational overtone bands of water at visible wavelengths. Emphasis is placed on critical factors affecting detection sensitivity and data analysis. Typical generation-time dependent absorption spectra are given.

  6. Adding diffuse reflectance infrared Fourier transform spectroscopy capability to extended x-ray-absorption fine structure in a new cell to study solid catalysts in combination with a modulation approach

    NASA Astrophysics Data System (ADS)

    Chiarello, Gian Luca; Nachtegaal, Maarten; Marchionni, Valentina; Quaroni, Luca; Ferri, Davide

    2014-07-01

    We describe a novel cell used to combine in situ transmission X-ray absorption spectroscopy (XAS) with diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) in a single experiment. The novelty of the cell design compared to current examples is that both radiations are passed through an X-ray and IR transparent window in direct contact with the sample. This innovative geometry also offers a wide surface for IR collection. In order to avoid interference from the crystalline IR transparent materials (e.g., CaF2, MgF2, diamond) a 500 μm carbon filled hole is laser drilled in the center of a CaF2 window. The cell is designed to represent a plug flow reactor, has reduced dead volume in order to allow for fast exchange of gases and is therefore suitable for experiments under fast transients, e.g., according to the concentration modulation approach. High quality time-resolved XAS and DRIFTS data of a 2 wt.% Pt/Al2O3 catalyst are obtained in concentration modulation experiments where CO (or H2) pulses are alternated to O2 pulses at 150 °C. We show that additional information can be obtained on the Pt redox dynamic under working conditions thanks to the improved sensitivity given by the modulation approach followed by Phase Sensitive Detection (PSD) analysis. It is anticipated that the design of the novel cell is likely suitable for a number of other in situ spectroscopic and diffraction methods.

  7. Room temperature redox reaction by oxide ion migration at carbon/Gd-doped CeO2 heterointerface probed by an in situ hard x-ray photoemission and soft x-ray absorption spectroscopies

    PubMed Central

    Tsuchiya, Takashi; Miyoshi, Shogo; Yamashita, Yoshiyuki; Yoshikawa, Hideki; Terabe, Kazuya; Kobayashi, Keisuke; Yamaguchi, Shu

    2013-01-01

    In situ hard x-ray photoemission spectroscopy (HX-PES) and soft x-ray absorption spectroscopy (SX-XAS) have been employed to investigate a local redox reaction at the carbon/Gd-doped CeO2 (GDC) thin film heterointerface under applied dc bias. In HX-PES, Ce3d and O1s core levels show a parallel chemical shift as large as 3.2 eV, corresponding to the redox window where ionic conductivity is predominant. The window width is equal to the energy gap between donor and acceptor levels of the GDC electrolyte. The Ce M-edge SX-XAS spectra also show a considerable increase of Ce3+ satellite peak intensity, corresponding to electrochemical reduction by oxide ion migration. In addition to the reversible redox reaction, two distinct phenomena by the electrochemical transport of oxide ions are observed as an irreversible reduction of the entire oxide film by O2 evolution from the GDC film to the gas phase, as well as a vigorous precipitation of oxygen gas at the bottom electrode to lift off the GDC film. These in situ spectroscopic observations describe well the electrochemical polarization behavior of a metal/GDC/metal capacitor-like two-electrode cell at room temperature. PMID:27877594

  8. X-ray absorption studies of battery materials

    SciTech Connect

    McBreen, J.

    1996-10-01

    X-ray absorption spectroscopy (XAS) is ideal for {ital in}{ital situ} studies of battery materials because both the probe and signal are penetrating x rays. The advantage of XAS being element specific permits investigation of the environment of a constituent element in a composite material. This makes it very powerful for studying electrode additives and corrosion of individual components of complex metal hydride alloys. The near edge part of the spectrum (XANES) provides information on oxidation state and site symmetry of the excited atom. This is particularly useful in study of corrosion and oxidation changes in cathode materials during charge/discharge cycle. Extended fine structure (EXAFS) gives structural information. Thus the technique provides both chemical and structural information. Since XAS probes only short range order, it can be applied to study of amorphous electrode materials and electrolytes. This paper discusses advantages and limitations of the method, as well as some experimental aspects.

  9. Degradation of Bimetallic Model Electrocatalysts ___ an in situ XAS Study

    SciTech Connect

    Friebel, Daniel

    2011-06-22

    One of the major challenges in the development of clean energy fuel cells is the performance degradation of the electrocatalyst, which, apart from poisoning effects, can suffer from corrosion due to its exposure to a harsh environment under high potentials. In this communication, we demonstrate how interactions of Pt with a transition metal support affect not only, as commonly intended, the catalytic activity, but also the reactivity of Pt towards oxide formation or dissolution. We use two well-defined single-crystal model systems, Pt/Rh(111) and Pt/Au(111) and a unique x-ray spectroscopy technique with enhanced energy resolution to monitor the potential-dependent oxidation state of Pt, and find two markedly different oxidation mechanisms on the two different substrates. This information can be of great significance for future design of more active and more stable catalysts. We have studied the potential-induced degradation of Pt monolayer model electrocatalysts on Rh(111) and Au(111) single-crystal substrates. The anodic formation of Pt oxides was monitored using in situ high energy resolution fluorescence detection x-ray absorption spectroscopy (HERFD XAS). Although Pt was deposited on both substrates in a three-dimensional island growth mode, we observed remarkable differences during oxide formation that can only be understood in terms of strong Pt-substrate interactions throughout the Pt islands. Anodic polarization of Pt/Rh(111) up to +1.6 V vs. RHE (reversible hydrogen electrode) leads to formation an incompletely oxidized passive layer, whereas formation of PtO2 and partial Pt dissolution is observed for Pt/Au(111).

  10. Characterization of interfacially electronic structures of gold-magnetite heterostructures using X-ray absorption spectroscopy.

    PubMed

    Lin, Fang-hsin; Doong, Ruey-an

    2014-03-01

    Gold-magnetite heterostructures are novel nanomaterials which can rapidly catalyze the reduction reaction of nitroaromatics. In this study, the interfacially structural and electronic properties of various morphologies of Au-Fe3O4 heterostructures were systematically investigated using X-ray absorbance spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS). The effect of change in electronic structure and charge transfer on electrochemically catalytic activity of Au-Fe3O4 heterostructures was further evaluated by oxygen reduction reaction (ORR). The shifts in binding energy of Au4f and Fe2p peaks in XPS spectra indicate the charge transfer between the Au and Fe3O4 nanoparticles. The increase in d-hole population of Au seeds after the conjugation with iron oxides follows the order flower-like Au-Fe3O4 (FLNPs)>dumbbell-like Au-Fe3O4 (DBNPs)>Au seeds. In addition, the Fe(2+) valence state increases in Au-Fe3O4 heterostructures, which provides evidence to support the hypothesis of charge transfer between Au and Fe3O4 nanoparticles. The theoretical simulation of Au L3-edge XAS further confirms the production of Au-Fe and Au-O bonds at the interface of Au/Fe3O4 and the epitaxial linkage relationship between Au and Fe3O4 nanoparticles. In addition, the electron deficient of Au seeds increases upon increasing Fe3O4 nanoparticles on a single Au seed, and subsequently decreases the catalytic activity of Au in the Au-Fe3O4 heterostructures. The catalytic activity of Au-Fe3O4 toward ORR follows the order Au seeds>Au-Fe3O4 DBNPs>Au-Fe3O4 FLNPs, which is positively correlated to the extent of electronic deficiency of Au in Au-Fe3O4 heterostructures.

  11. Use of L-edge X-ray absorption spectroscopy to characterize multiple valence states of 3 d transition metals; a new probe for mineralogical and geochemical research

    NASA Astrophysics Data System (ADS)

    Cressey, G.; Henderson, C. M. B.; van der Laan, G.

    1993-07-01

    2 p ( L 2,3) X-ray absorption spectra are presented for a range of minerals to demonstrate the usefulness of L-edge spectroscopy as a symmetry- and valenceselective probe. 2 p XAS provides a sensitive fingerprint of the electronic states of 3 d transition metals and can be applied to phases containing mixtures of such elements. Calculated spectra for 3 d n → 2 p 5 3 d n+1 transitions provide a basis for the interpretation of the measured spectra. Thus, in principle, multiple valence states of a particular 3 d metal can be precisely characterized from a single L-edge spectrum. Examples of vanadium L-edge spectra are presented for a range of minerals; these complex spectra hold information concerning the presence of vanadium in multiple valence states. The Cu L-edge spectrum of sulvanite (Cu3 VS4) indicates the presence of both Cu+ and Cu2+; the V L-edge spectrum of the same sample shows that both V2+ and V5+ are present. Spectral simulations representing mixtures of Fe d 5 and Fe d 6 states are used to quantify Fe3+/ ∑Fe in a spinel, a glass, and an amphibole, all of which contain Fe as a major component. To illustrate the sensitivity of 2 p XAS in a dilute system, the Fe L-edge spectrum of amethyst ( α-SiO2: Fe) has been recorded; this spectrum shows that ˜68% of the Fe in amethyst is Fe2+, and ˜32% is Fe3+. Although previous studies on amethyst using other spectroscopic methods cite evidence for Fe4+, there is no indication in the L-edge spectrum for Fe4+ in amethyst. Comparison of theoretical and experimental spectra not only allows the valence states of 3 d ions to be recognised, but also provides site-symmetry information and crystal field parameters for each ion site.

  12. The nature of chemical bonding in actinide and lanthanide ferrocyanides determined by X-ray absorption spectroscopy and density functional theory.

    PubMed

    Dumas, Thomas; Guillaumont, Dominique; Fillaux, Clara; Scheinost, Andreas; Moisy, Philippe; Petit, Sébastien; Shuh, David K; Tyliszczak, Tolek; Den Auwer, Christophe

    2016-01-28

    The electronic properties of actinide cations are of fundamental interest to describe intramolecular interactions and chemical bonding in the context of nuclear waste reprocessing or direct storage. The 5f and 6d orbitals are the first partially or totally vacant states in these elements, and the nature of the actinide ligand bonds is related to their ability to overlap with ligand orbitals. Because of its chemical and orbital selectivities, X-ray absorption spectroscopy (XAS) is an effective probe of actinide species frontier orbitals and for understanding actinide cation reactivity toward chelating ligands. The soft X-ray probes of the light elements provide better resolution than actinide L3-edges to obtain electronic information from the ligand. Thus coupling simulations to experimental soft X-ray spectral measurements and complementary quantum chemical calculations yields quantitative information on chemical bonding. In this study, soft X-ray XAS at the K-edges of C and N, and the L2,3-edges of Fe was used to investigate the electronic structures of the well-known ferrocyanide complexes K4Fe(II)(CN)6, thorium hexacyanoferrate Th(IV)Fe(II)(CN)6, and neodymium hexacyanoferrate KNd(III)Fe(II)(CN)6. The soft X-ray spectra were simulated based on quantum chemical calculations. Our results highlight the orbital overlapping effects and atomic effective charges in the Fe(II)(CN)6 building block. In addition to providing a detailed description of the electronic structure of the ferrocyanide complex (K4Fe(II)(CN)6), the results strongly contribute to confirming the actinide 5f and 6d orbital oddity in comparison to lanthanide 4f and 5d.

  13. Formation mechanism of LiFePO 4/C composite powders investigated by X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Hsu, Kuei-Feng; Hu, Shao-Kang; Chen, Chinh-Hsiang; Cheng, Ming-Yao; Tsay, Sun-Yuan; Chou, Tse-Chuan; Sheu, Hwo-Shuenn; Lee, Jyh-Fu; Hwang, Bing-Joe

    The local structure and oxidation states for both the precursors and the LiFePO 4/C composite powders were investigated by X-ray absorption spectroscopy (XAS) to provide a deep insight into their formation mechanism. It was found that the local structure and oxidation states of the precursors and the synthesized LiFePO 4/C powders as well as the electrochemical properties of the synthesized powders were strongly influenced by the R ratio (R: molar ratio of citric acid to total metal ions). The oxidation states of iron ions of the precursors for R = 1 and 0.75 consist mainly of Fe(II) and traces of Fe(III). However, the oxidation state of iron ions of the precursor for R = 0.5 comprises mainly of Fe(III). The oxidation state of iron ions of all the synthesized powders is Fe(II). The structure of the precursors and the synthesized powders for R = 1 and 0.75 is more ordering than that for R = 0.5. It is in good agreement with the observation of the cation mixing obtained from the Riteveld analysis of the XRD data. The better the electrochemical performance is, the more ordering the structure or the less the cation mixing. However, the effect of the R values on the carbon content is also essential for the electrochemical properties of the synthesized LiFePO 4/C composite powders. Increasing the carbon content leads to the increase in the electronic conductivity but impedes the Li + ion diffusion of the composite materials. Consequently, the powders synthesized at the optimal R ratio of 0.75 exhibited the highest initial capacity, about 150 mAh g -1 when cycled at 1/40 C rate at room temperature. The structural scheme of the precursors and the synthesized powders and the formation mechanism of the LiFePO 4/C composite powders are also addressed in this work.

  14. Methanogenic activity tests by Infrared Tunable Diode Laser Absorption Spectroscopy.

    PubMed

    Martinez-Cruz, Karla; Sepulveda-Jauregui, Armando; Escobar-Orozco, Nayeli; Thalasso, Frederic

    2012-10-01

    Methanogenic activity (MA) tests are commonly carried out to estimate the capability of anaerobic biomass to treat effluents, to evaluate anaerobic activity in bioreactors or natural ecosystems, or to quantify inhibitory effects on methanogenic activity. These activity tests are usually based on the measurement of the volume of biogas produced by volumetric, pressure increase or gas chromatography (GC) methods. In this study, we present an alternative method for non-invasive measurement of methane produced during activity tests in closed vials, based on Infrared Tunable Diode Laser Absorption Spectroscopy (MA-TDLAS). This new method was tested during model acetoclastic and hydrogenotrophic methanogenic activity tests and was compared to a more traditional method based on gas chromatography. From the results obtained, the CH(4) detection limit of the method was estimated to 60 ppm and the minimum measurable methane production rate was estimated to 1.09(.)10(-3) mg l(-1) h(-1), which is below CH(4) production rate usually reported in both anaerobic reactors and natural ecosystems. Additionally to sensitivity, the method has several potential interests compared to more traditional methods among which short measurements time allowing the measurement of a large number of MA test vials, non-invasive measurements avoiding leakage or external interferences and similar cost to GC based methods. It is concluded that MA-TDLAS is a promising method that could be of interest not only in the field of anaerobic digestion but also, in the field of environmental ecology where CH(4) production rates are usually very low.

  15. Local structure of Fe in Fe-doped misfit-layered calcium cobaltite: An X-ray absorption spectroscopy study

    SciTech Connect

    Prasoetsopha, Natkrita; Pinitsoontorn, Supree; Bootchanont, Atipong; Kidkhunthod, Pinit; Srepusharawoot, Pornjuk; Kamwanna, Teerasak; Amornkitbamrung, Vittaya; Kurosaki, Ken; Yamanaka, Shinsuke

    2013-08-15

    Polycrystalline Ca{sub 3}Co{sub 4−x}Fe{sub x}O{sub 9+δ} ceramics (x=0, 0.01, 0.03, 0.05) were fabricated using a simple thermal hydro-decomposition method and a spark plasma sintering technique. Thermoelectric property measurements showed that increasing Fe concentration resulted in a decrease in electrical resistivity, thermopower and thermal conductivity, leading to an improvement in the dimensionless figure-of-merit, >35% for x=0.05 at 1073 K. An X-ray absorption spectroscopy technique was used to investigate the local structure of Fe ions in the Ca{sub 3}Co{sub 4−x}Fe{sub x}O{sub 9+δ} structure for the first time. By fitting data from the extended X-ray absorption fine structure (EXAFS) spectra and analyzing the X-ray absorption near-edge structure (XANES) spectra incorporated with first principle simulation, it was shown that Fe was substituted for Co in the the Ca{sub 2}CoO{sub 3} (rocksalt, RS) layer rather than in the CoO{sub 2} layer. Variation in the thermoelectric properties as a function of Fe concentration was attributed to charge transfer between the CoO{sub 2} and the RS layers. The origin of the preferential Fe substitution site was investigated considering the ionic radii of Co and Fe and the total energy of the system. - Graphical abstract: The Fe K-edge XANES spectra of: (a) experimental result in comparison to the simulated spectra when Fe atoms were substituted in the RS layer; (b) with magnetic moment; (c) without magnetic moment, and in the CoO{sub 2} layer; (d) with magnetic moment and (e) without magnetic moment. Highlights: • Synthesis, structural studies, and thermoelectric properties of Ca{sub 3}Co{sub 4−x}Fe{sub x}O{sub 9+δ}. • Direct evidence for the local structure of the Fe ions in the Ca{sub 3}Co{sub 4−x}Fe{sub x}O{sub 9+δ} using XAS analysis. • EXAFS and XANES analysis showed that Fe was likely to be situated in the RS layer structure. • Changes in TE property with Fe content was due to charge transfer between

  16. Examination of arsenic(III) and (V) uptake by the desert plant species mesquite (Prosopis spp.) using X-ray absorption spectroscopy.

    PubMed

    Aldrich, M V; Peralta-Videa, J R; Parsons, J G; Gardea-Torresdey, J L

    2007-07-01

    This study describes the effects of Arsenic(III) and (V) on the growth and their uptake by the desert plant mesquite (Prosopis spp.). Seedlings were sown in agar-based medium containing a modified Hoagland's nutrient solution. After 1 week, the seedlings were transplanted to arsenic (As) treated agar media that contained 5 mgL(-1) of As either As(III) (As(2)O(3)) or As(V) (As(2)O(5)). The plants were harvested after 14 days of growth and sectioned into roots, stems, and leaves. After digestion, As concentrations in the roots, stems, and leaves were determined using inductively coupled plasma-optical emission spectroscopy (ICP-OES). Our results showed that the As concentrations from As(V) were significantly higher than the As concentrations from As(III) in all portions of the plant. Plants exposed to As(V) concentrated (mg As kg(-1) d wt) about 770+/-191, 326+/-94, and 119+/-18 in roots, stems, and leaves, respectively. X-ray absorption spectroscopy (XAS) showed that As(V) was reduced to As(III) inside the mesquite plant. In addition, greater than 90% of the As(III) found in the mesquite plants was bound to sulfur ligands in the roots, stems and leaves.

  17. Monitoring spacecraft atmosphere contaminants by laser absorption spectroscopy

    NASA Technical Reports Server (NTRS)

    Steinfeld, J. I.

    1975-01-01

    Data were obtained which will provide a test of the accuracy of the differential absorption method for trace contaminant detection in many-component gas mixtures. The necessary accurate absorption coefficient determinations were carried out for several gases; acetonitrile, 1,2-dichloroethane, Freon-113, furan, methyl ethyl ketone, and t-butyl alcohol. The absorption coefficients are displayed graphically. An opto-acoustic method was tested for measuring absorbance, similar to the system described by Dewey.

  18. Studies of cavity enhanced absorption spectroscopy for weak absorption gas measurements

    NASA Astrophysics Data System (ADS)

    Li, Liucheng; Duo, Liping; Gong, Deyu; Ma, Yanhua; Zhang, Zhiguo; Wang, Yuanhu; Zhou, Dongjian; Jin, Yuqi

    2017-01-01

    In order to determine the concentrations of trace amount metastable species in chemical lasers, an off-axis cavity enhanced absorption spectrometer for the detection of weak absorption gases has been built with a noise equivalent absorption sensitivity of 1.6x10-8 cm-1. The absorption spectrum of trace amount gaseous ammonia and water vapor was obtained with a spectral resolution of about 78 MHz. A multiple-line absorption spectroscopic method to determine the temperature of gaseous ammonia has been developed by use of multiple lines of ammonia molecule absorption spectrum.

  19. Local structure study of (In{sub 0.95−x}Fe{sub x}Cu{sub 0.05}){sub 2}O{sub 3} thin films using x-ray absorption spectroscopy

    SciTech Connect

    Ren, Yuan; Xing, Yaya; Ma, Guanxiong; Wang, Shiqi; An, Yukai Liu, Jiwen; Zhao, Xingliang

    2015-07-15

    The (In{sub 0.95−x}Fe{sub x}Cu{sub 0.05}){sub 2}O{sub 3} (x = 0.06, 0.08, 0.15, and 0.20) films prepared by RF-magnetron sputtering were investigated by the combination of x-ray absorption spectroscopy (XAS) at Fe, Cu, and O K-edge. Although the Fe and O K-edge XAS spectra show that the Fe atoms substitute for the In sites of In{sub 2}O{sub 3} lattice for all the films, the Cu K-edge XAS spectra reveal that the codoped Cu atoms are separated to form the Cu metal clusters. After being annealed in air, the Fe atoms are still substitutionally incorporated into the In{sub 2}O{sub 3} lattice, while the Cu atoms form the CuO secondary phases. With the increase of Fe concentration, the bond length R{sub Fe-O} shortens and the Debye–Waller factor σ{sup 2}{sub Fe-O} increases in the first coordination shell of Fe, which are attributed to the relaxation of oxygen environment around the substitutional Fe ions. The forming of Cu relating secondary phases in the films is due to high ionization energy of Cu atoms, leading that the Cu atoms are energetically much harder to be oxidized to substitute for the In sites of In{sub 2}O{sub 3} lattice than Fe atoms. These results provide new experimental guidance in the preparation of the codoped In{sub 2}O{sub 3} based dilute magnetic oxides.

  20. Aerosol particle absorption spectroscopy by photothermal modulation of Mie scattered light

    SciTech Connect

    Campillo, A.J.; Dodge, C.J.; Lin, H.B.

    1981-09-15

    Absorption spectroscopy of suspended submicron-sized aqueous ammonium-sulfate aerosol droplets has been performed by employing a CO/sub 2/ laser to photothermally modulate visible Mie scattered light. (AIP)

  1. Determination of tin in poly(vinyl chloride) by atomic-absorption spectroscopy.

    PubMed

    Anwar, J; Marr, I L

    1982-10-01

    A simple procedure is described for the determination of tin in PVC by atomic-absorption spectroscopy with an air-hydrogen flame, after wet digestion of the sample with sulphuric acid and hydrogen peroxide.

  2. X-ray Absorption Spectroscopy of Zinc in Airborne Particulate Matter Shows Tire Debris Concentrated in > 0.5 μm Fraction

    NASA Astrophysics Data System (ADS)

    Pingitore, N. E.; Clague, J. W.; Gill, T. E.; Amaya, M. A.; Cahill, T. A.

    2009-12-01

    Using X-ray absorption spectroscopy (XAS), we speciated Zn in size-resolved fractions of particulate matter (PM) from El Paso, Texas. Spectral patterns indicated that Zn in tire debris is the dominant form of Zn in PM coarser than 0.5 μm in aerodynamic diameter. Although concentrated in the > 0.5 μm fraction, a large portion of the tire debris in PM is small enough to penetrate and deposit in the lower respiratory tract. We collected 3 sets of size-resolved samples of airborne particulate matter (PM) over periods of several days to several weeks in November 2008, and April and May 2009. Local PM compositions typically are dominated by anthropogenic input in November and geologic sources in April, and a mixture in May. The collection site is in the urban core of El Paso, TX, contiguous to the University of Texas at El Paso, 0.6 km from Interstate Highway 10, 0.4 km from State Highway 20, and 1 km from Cd. Juarez, Chihuahua, Mexico. The DRUM sampler (Davis Rotating Uniform size-cut Monitor) employs a rotating Lundgren-type impactor, draws 10 l per minute, and deposits PM on plastic strips mounted on rotating drums. The sampler collected and segregated ambient PM into 8 size cuts: 12-5 μm, 5-2.5, 2.5-1.15, 1.15-0.75, 0.75-0.56, 0.56-0.34, 0.34-0.26, and 0.26-0.09. We conducted the X-ray absorption spectroscopy (XAS) experiments at the Stanford Synchrotron Radiation Lightsource on beam line 7-3. Spectra of the 24 samples of PM and numerous model compounds were collected at the Zn K absorption edge in fluorescence mode using a 30-element Ge solid-state detector. The overall spectral patterns from the 3 seasons were similar to one another. But strikingly, each set of 8 XAS spectra displayed an obvious change in the Zn speciation at the 0.56-0.75 μm size cut. We compared the PM spectra to those of our suite of known model compounds and materials. The spectral pattern of the coarser size cuts was quite similar to those of the tires we tested. The Zn in the tires

  3. Comparison of Lead Species in Household Dust Wipes, Soil, and Airborne Particulate Matter in El Paso, Texas, by X-Ray Absorption Spectroscopy

    NASA Astrophysics Data System (ADS)

    Pingitore, N. E.; Clague, J.; Amaya, M. A.

    2006-12-01

    Understanding the interplay of indoor and outdoor sources of lead in an urban setting is one foundation in establishing risk for lead exposure in children in our cities. A household may be the source for lead contamination due to the deterioration of interior lead-based paint, or a sink if lead particles are tracked or blown into the home from such potential ambient sources as yard soil or urban street dust. In addressing this issue, X-Ray Absorption Spectroscopy (XAS) presents the opportunity to directly and quantitatively speciate lead at low concentrations in bulk samples. We performed XAS analyses on dust wipes from window sills or floors from 8 houses that exceeded Federal standards for lead in dust. We entered these data into a Principal Components Analysis (PCA) that also included El Paso environmental samples: lead-based paints, soils, and airborne particulate matter. A simple two-component mixing system accounted for more than 95% of the variance of this data set. Paint and lead oxide appear to be the principal components, with all the samples falling in a compositional range from pure paint to 75% paint, 25% lead oxide. Note that several different lead compounds are possible constituents of a given lead-based paint. The paints spread from one end out along perhaps a fifth of the range of the compositional axis, followed closely, but not overlapped, by the soil samples, which covered the remainder of the compositional range. Two of the dust wipes plotted within the paint range, and the remaining 6 dust wipes plotted randomly through the soil range. Samples of airborne particulate matter plotted in both the paint and soil ranges. These observations suggest that the lead on most of the dust wipes originated outside the house, probably from deteriorated exterior lead-based paint deposited in adjacent yards. This paint mixed with lead oxide present in the soil and entered the houses by the airborne route. The probable source of the oxide in the soil is former

  4. XAS Studies of Arsenic in the Environment

    SciTech Connect

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

    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.

  5. Reaction cell for in situ soft x-ray absorption spectroscopy and resonant inelastic x-ray scattering measurements of heterogeneous catalysis up to 1 atm and 250 °C

    SciTech Connect

    Kristiansen, P. T.; Rocha, T. C. R.; Knop-Gericke, A.; Guo, J. H.; Duda, L. C.

    2013-11-15

    We present a novel in situ reaction cell for heterogeneous catalysis monitored in situ by x-ray absorption spectroscopy (XAS) and resonant inelastic x-ray scattering (RIXS). The reaction can be carried out at a total pressure up to 1 atm, a regime that has not been accessible to comparable in situ techniques and thus closes the pressure gap to many industrial standard conditions. Two alternate catalyst geometries were tested: (A) a thin film evaporated directly onto an x-ray transparent membrane with a flowing reaction gas mixture behind it or (B) a powder placed behind both the membrane and a gap of flowing reaction gas mixture. To illustrate the working principle and feasibility of our reaction cell setup we have chosen ethylene epoxidation over a silver catalyst as a test case. The evolution of incorporated oxygen species was monitored by total electron/fluorescence yield O K-XAS as well as O K-RIXS, which is a powerful method to separate contributions from inequivalent sites. We find that our method can reliably detect transient species that exist during catalytic reaction conditions that are hardly accessible using other spectroscopic methods.

  6. Reaction cell for in situ soft x-ray absorption spectroscopy and resonant inelastic x-ray scattering measurements of heterogeneous catalysis up to 1 atm and 250 °C.

    PubMed

    Kristiansen, P T; Rocha, T C R; Knop-Gericke, A; Guo, J H; Duda, L C

    2013-11-01

    We present a novel in situ reaction cell for heterogeneous catalysis monitored in situ by x-ray absorption spectroscopy (XAS) and resonant inelastic x-ray scattering (RIXS). The reaction can be carried out at a total pressure up to 1 atm, a regime that has not been accessible to comparable in situ techniques and thus closes the pressure gap to many industrial standard conditions. Two alternate catalyst geometries were tested: (A) a thin film evaporated directly onto an x-ray transparent membrane with a flowing reaction gas mixture behind it or (B) a powder placed behind both the membrane and a gap of flowing reaction gas mixture. To illustrate the working principle and feasibility of our reaction cell setup we have chosen ethylene epoxidation over a silver catalyst as a test case. The evolution of incorporated oxygen species was monitored by total electron/fluorescence yield O K-XAS as well as O K-RIXS, which is a powerful method to separate contributions from inequivalent sites. We find that our method can reliably detect transient species that exist during catalytic reaction conditions that are hardly accessible using other spectroscopic methods.

  7. Direct and quantitative photothermal absorption spectroscopy of individual particulates

    SciTech Connect

    Tong, Jonathan K.; Hsu, Wei-Chun; Eon Han, Sang; Burg, Brian R.; Chen, Gang; Zheng, Ruiting; Shen, Sheng

    2013-12-23

    Photonic structures can exhibit significant absorption enhancement when an object's length scale is comparable to or smaller than the wavelength of light. This property has enabled photonic structures to be an integral component in many applications such as solar cells, light emitting diodes, and photothermal therapy. To characterize this enhancement at the single particulate level, conventional methods have consisted of indirect or qualitative approaches which are often limited to certain sample types. To overcome these limitations, we used a bilayer cantilever to directly and quantitatively measure the spectral absorption efficiency of a single silicon microwire in the visible wavelength range. We demonstrate an absorption enhancement on a per unit volume basis compared to a thin film, which shows good agreement with Mie theory calculations. This approach offers a quantitative approach for broadband absorption measurements on a wide range of photonic structures of different geometric and material compositions.

  8. VUV absorption spectroscopy of bacterial spores and DNA components

    NASA Astrophysics Data System (ADS)

    Fiebrandt, Marcel; Lackmann, Jan-Wilm; Raguse, Marina; Moeller, Ralf; Awakowicz, Peter; Stapelmann, Katharina

    2017-01-01

    Low-pressure plasmas can be used to inactivate bacterial spores and sterilize goods for medical and pharmaceutical applications. A crucial factor are damages induced by UV and VUV radiation emitted by the plasma. To analyze inactivation processes and protection strategies of spores, absorption spectra of two B. subtilis strains are measured. The results indicate, that the inner and outer coat of the spore significantly contribute to the absorption of UV-C and also of the VUV, protecting the spore against radiation based damages. As the sample preparation can significantly influence the absorption spectra due to salt residues, the cleaning procedure and sample deposition is tested for its reproducibility by measuring DNA oligomers and pUC18 plasmid DNA. The measurements are compared and discussed with results from the literature, showing a strong decrease of the salt content enabling the detection of absorption structures in the samples.

  9. In situ Gas Temperature Measurements by UV-Absorption Spectroscopy

    NASA Astrophysics Data System (ADS)

    Fateev, A.; Clausen, S.

    2009-02-01

    The absorption spectrum of the NO A2Σ+ ← X2Πγ-system can be used for in situ evaluation of gas temperature. Experiments were performed with a newly developed atmospheric-pressure high-temperature flow gas cell at highly uniform and stable gas temperatures over a 0.533 m path in the range from 23 °C to 1,500 °C. The gas temperature was evaluated (1) from the analysis of the structure of selected NO high-resolution γ-absorption bands and (2) from the analysis of vibrational distribution in the NO γ-absorption system in the (211-238) nm spectral range. The accuracy of both methods is discussed. Validation of the classical Lambert-Beer law has been demonstrated at NO concentrations up to 500 ppm and gas temperatures up to 1,500 °C over an optical absorption path length of 0.533 m.

  10. The use of CNDO in spectroscopy. XV. Two photon absorption

    NASA Astrophysics Data System (ADS)

    Marchese, Francis T.; Seliskar, C. J.; Jaffé, H. H.

    1980-04-01

    Two-photon absorptivities have been calculated within the CNDO/S-CI molecular orbital framework of Del Bene and Jaffé utilizing the second order time dependent perturbation equations of Göppert-Mayer and polarization methods of McClain. Good agreement is found between this theory and experiment for transition energies, symmetries, and two-photon absorptivities for the following molecules: biphenyl, terphenyl, 2,2'-difluorobiphenyl, 2,2'-bipyridyl, phenanthrene, and the isoelectronic series: fluorene, carbazole, dibenzofuran.

  11. Trace gas absorption spectroscopy using laser difference-frequency spectrometer for environmental application

    NASA Technical Reports Server (NTRS)

    Chen, W.; Cazier, F.; Boucher, D.; Tittel, F. K.; Davies, P. B.

    2001-01-01

    A widely tunable infrared spectrometer based on difference frequency generation (DFG) has been developed for organic trace gas detection by laser absorption spectroscopy. On-line measurements of concentration of various hydrocarbons, such as acetylene, benzene, and ethylene, were investigated using high-resolution DFG trace gas spectroscopy for highly sensitive detection.

  12. High-Resolution Absorption Spectroscopy of NO2

    DTIC Science & Technology

    1987-08-31

    identify by block number) FIELD GROUP SUB-GROUP Atmospheric propagation, Laser spectroscopy, Nitrogen dioxide , Spectroscopy 19. RACT (Continue on reverse if...pulsed dye laser having a 0.05-A"-bandwidth (FWHM). This represents an improvement of at least a factor of three over the resolution employed in...concise interpretation of the observed features has yet to be made. Actual state-to-state assignments in the visible and near UV have been possible only

  13. Method and apparatus for aerosol particle absorption spectroscopy

    DOEpatents

    Campillo, Anthony J.; Lin, Horn-Bond

    1983-11-15

    A method and apparatus for determining the absorption spectra, and other properties, of aerosol particles. A heating beam source provides a beam of electromagnetic energy which is scanned through the region of the spectrum which is of interest. Particles exposed to the heating beam which have absorption bands within the band width of the heating beam absorb energy from the beam. The particles are also illuminated by light of a wave length such that the light is scattered by the particles. The absorption spectra of the particles can thus be determined from an analysis of the scattered light since the absorption of energy by the particles will affect the way the light is scattered. Preferably the heating beam is modulated to simplify the analysis of the scattered light. In one embodiment the heating beam is intensity modulated so that the scattered light will also be intensity modulated when the particles absorb energy. In another embodiment the heating beam passes through an interferometer and the scattered light reflects the Fourier Transform of the absorption spectra.

  14. HERFD-XAS and valence-to-core-XES: new tools to push the limits in research with hard X-rays?

    PubMed

    Bauer, Matthias

    2014-07-21

    In this perspective, the HERFD-XANES (high energy resolution fluorescence detected X-ray absorption near edge structure) and Kβ2,5- or V2C-XES (valence-to-core X-ray emission spectroscopy) methods are discussed as new and powerful tools for chemical research with hard X-rays. This includes a brief survey of the underlying physical processes and the introduction of experimental issues. The potential of both methods to overcome limitations of conventional XAS (X-ray absorption spectroscopy) and to push the limits for obtaining new information about the electronic and geometric structures of metal centers, in the solid state structure or heterogeneous catalysts, but also in metal complexes and homogeneous catalysts, is discussed by presenting a survey of representative references and recent own studies, rounded off by a conclusion and outlook.

  15. Review on VUV to MIR absorption spectroscopy of atmospheric pressure plasma jets

    NASA Astrophysics Data System (ADS)

    Reuter, Stephan; Santos Sousa, Joao; Stancu, Gabi Daniel; Hubertus van Helden, Jean-Pierre

    2015-10-01

    Absorption spectroscopy (AS) represents a reliable method for the characterization of cold atmospheric pressure plasma jets. The method’s simplicity stands out in comparison to competing diagnostic techniques. AS is an in situ, non-invasive technique giving absolute densities, free of calibration procedures, which other diagnostics, such as laser-induced fluorescence or optical emission spectroscopy, have to rely on. Ground state densities can be determined without the knowledge of the influence of collisional quenching. Therefore, absolute densities determined by absorption spectroscopy can be taken as calibration for other methods. In this paper, fundamentals of absorption spectroscopy are presented as an entrance to the topic. In the second part of the manuscript, a review of AS performed on cold atmospheric pressure plasma jets, as they are used e.g. in the field of plasma medicine, is presented. The focus is set on special techniques overcoming not only the drawback of spectrally overlapping absorbing species, but also the line-of-sight densities that AS usually provides or the necessity of sufficiently long absorption lengths. Where references are not available for measurements on cold atmospheric pressure plasma jets, other plasma sources including low-pressure plasmas are taken as an example to give suggestions for possible approaches. The final part is a table summarizing examples of absorption spectroscopic measurements on cold atmospheric pressure plasma jets. With this, the paper provides a ‘best practice’ guideline and gives a compendium of works by groups performing absorption spectroscopy on cold atmospheric pressure plasma jets.

  16. Direct and quantitative broadband absorptance spectroscopy with multilayer cantilever probes

    DOEpatents

    Hsu, Wei-Chun; Tong, Jonathan Kien-Kwok; Liao, Bolin; Chen, Gang

    2015-04-21

    A system for measuring the absorption spectrum of a sample is provided that includes a broadband light source that produces broadband light defined within a range of an absorptance spectrum. An interferometer modulates the intensity of the broadband light source for a range of modulation frequencies. A bi-layer cantilever probe arm is thermally connected to a sample arm having at most two layers of materials. The broadband light modulated by the interferometer is directed towards the sample and absorbed by the sample and converted into heat, which causes a temperature rise and bending of the bi-layer cantilever probe arm. A detector mechanism measures and records the deflection of the probe arm so as to obtain the absorptance spectrum of the sample.

  17. [The Research for Trace Ammonia Escape Monitoring System Based on Tunable Diode Laser Absorption Spectroscopy].

    PubMed

    Zhang, Li-fang; Wang, Fei; Yu, Li-bin; Yan, Jian-hua; Cen, Ke-fa

    2015-06-01

    In order to on-line measure the trace ammonia slip of the commercial power plant in the future, this research seeks to measure the trace ammonia by using tunable diode laser absorption spectroscopy under ambient temperature and pressure, and at different temperatures, and the measuring temperature is about 650 K in the power plant. In recent years lasers have become commercially available in the near-infrared where the transitions are much stronger, and ammonia's spectroscopy is pretty complicated and the overlapping lines are difficult to resolve. A group of ammonia transitions near 4 433.5 cm(-1) in the v2 +v3 combination band have been thoroughly selected for detecting lower concentration by analyzing its absorption characteristic and considering other absorption interference in combustion gases where H2O and CO2 mole fraction are very large. To illustrate the potential for NH3 concentration measurements, predictions for NH3, H2O and CO2 are simultaneously simulated, NH3 absorption lines near 4 433.5 cm(-1) wavelength meet weaker H2O absorption than the commercial NH3 lines, and there is almost no CO2 absorption, all the parameters are based on the HITRAN database, and an improved detection limit was obtained for interference-free NH3 monitoring, this 2.25 μm band has line strengths several times larger than absorption lines in the 1.53 μm band which was often used by NH3 sensors for emission monitoring and analyzing. The measurement system was developed with a new Herriott cell and a heated gas cell realizing fast absorption measurements of high resolution, and combined with direct absorption and wavelenguh modulation based on tunable diode laser absorption spectroscopy at different temperatures. The lorentzian line shape is dominant at ambient temperature and pressure, and the estimated detectivity is approximately 0.225 x 10(-6) (SNR = 1) for the directed absorption spectroscopy, assuming a noise-equivalent absorbance of 1 x 10(-4). The heated cell

  18. Time-resolved pump-probe spectroscopy of intraband absorption by a semiconductor nanorod

    NASA Astrophysics Data System (ADS)

    Leonov, Mikhail Y.; Rukhlenko, Ivan D.; Baranov, Alexander V.; Fedorov, Anatoly V.

    2013-09-01

    We develop a theory of time-resolved pump-probe optical spectroscopy of intraband absorption of a probe pulse inside an anisotropic semiconductor nanorod. The absorption is preceded by the absorption of the pump pulse resonant to an interband transition. It is assumed that the resonantly exited states of the nanorod are interrelated via the relaxation induced by their interaction with a bath. We reveal the conditions for which the absorption of the probe's pulse is governed by a simple formula regardless of the pulse's shape. This formula is useful for the analysis of the experimental data containing information on the relaxation parameters of the nanorod's electronic subsystem.

  19. Studies of Arctic Middle Atmosphere Chemistry using Infrared Absorption Spectroscopy

    NASA Astrophysics Data System (ADS)

    Lindenmaier, Rodica

    The objective of this Ph.D. project is to investigate Arctic middle atmosphere chemistry using solar infrared absorption spectroscopy. These measurements were made at the Polar Environment Atmospheric Research Laboratory (PEARL) at Eureka, Nunavut, which is operated by the Canadian Network for the Detection of Atmospheric Change (CANDAC). This research is part of the CANDAC/PEARL Arctic Middle Atmosphere Chemistry theme and aims to improve our understanding of the processes controlling the stratospheric ozone budget using measurements of the concentrations of stratospheric constituents. The instrument, a Bruker IFS 125HR Fourier transform infrared (FTIR) spectrometer, has been specifically designed for high-resolution measurements over a broad spectral range and has been used to measure reactive species, source gases, reservoirs, and dynamical tracers at PEARL since August 2006. The first part of this research focuses on the optimization of ozone retrievals, for which 22 microwindows were studied and compared. The spectral region from 1000 to 1005 cm-1 was found to be the most sensitive in both the stratosphere and troposphere, giving the highest number of independent pieces of information and the smallest total error for retrievals at Eureka. Similar studies were performed in coordination with the Network for the Detection of Atmospheric Composition Change for nine other species, with the goal of improving and harmonizing the retrieval parameters among all Infrared Working Group sites. Previous satellite validation exercises have identified the highly variable polar conditions of the spring period to be a challenge. In this work, comparisons between the 125HR and ACE-FTS (Atmospheric Chemistry Experiment-Fourier transform spectrometer) from 2007 to 2010 have been used to develop strict criteria that allow the ground and satellite-based instruments to be confidently compared. After applying these criteria, the differences between the two instruments were generally

  20. X-ray emission spectroscopy.

    PubMed

    Bergmann, Uwe; Glatzel, Pieter

    2009-01-01

    We describe the chemical information that can be obtained by means of hard X-ray emission spectroscopy (XES). XES is presented as a technique that is complementary to X-ray absorption spectroscopy (XAS) and that provides valuable information with respect to the electronic structure (local charge- and spin-density) as well as the ligand environment of a 3d transition metal. We address non-resonant and resonant XES and present results that were recorded on Mn model systems and the Mn(4)Ca-cluster in the oxygen evolving complex of photosystem II. A brief description of the instrumentation is given with an outlook toward future developments.

  1. Ultrafast Extreme Ultraviolet Absorption Spectroscopy of Methylammonium Lead Iodide Perovskite

    NASA Astrophysics Data System (ADS)

    Verkamp, Max A.; Lin, Ming-Fu; Ryland, Elizabeth S.; Vura-Weis, Josh

    2016-06-01

    Methylammonium lead iodide (perovskite) is a leading candidate for use in next-generation solar cell devices. However, the photophysics responsible for its strong photovoltaic qualities are not fully understood. Ultrafast extreme ultraviolet (XUV) absorption was used to investigate electron and hole dynamics in perovskite by observing transitions from a common inner-shell level (I 4d) to the valence and conduction bands. Ultrashort (30 fs) pulses of XUV radiation with a broad spectrum (40-70 eV) were generated via high-harmonic generation using a tabletop instrument. Transient absorption measurements with visible pump and XUV probe directly observed the relaxation of charge carriers in perovskite after above-band excitation in the femtosecond and picosecond time ranges.

  2. Mapping of the Local Interstellar Medium using Absorption Line Spectroscopy

    NASA Astrophysics Data System (ADS)

    Penprase, Bryan Edward

    2017-01-01

    Using the Yale SMARTS 1.5-meter telescope at CTIO and the CHIRON spectrograph, we have developed a program for mapping the local interstellar medium using a sample of over 200 newly observed B stars previously unobserved using Na I absorption lines. This sample includes stars that extend out to map beyond the local bubble to 500 pc. The sample has been observed using high resolution absorption lines, and when combined with previously observed stars with Na I and Ca II data provides a more complete picture of the local ISM than previous surveys. The distances to the stars using the new GAIA database also allows for more accurate determination of distances to features in the lcoal ISM, and new maps of the structure of the ISM hav been prepared with the data.

  3. Direct and Quantitative Photothermal Absorption Spectroscopy of Individual Particulates

    DTIC Science & Technology

    2013-01-01

    photovoltaics and photo detectors.17,22,23 To predict the absorptive properties of an individual silicon microwire, the well-established Mie theory was... silicon microwire is frequency limiting .43 It was also observed that vibration, thermal drift, and electrical noise were significant below 100 Hz. In...NOTES 14. ABSTRACT 15. SUBJECT TERMS 16. SECURITY CLASSIFICATION OF: 17. LIMITATION OF ABSTRACT Same as Report (SAR) 18. NUMBER OF PAGES 7

  4. Aerosol particle microphotography and glare-spot absorption spectroscopy.

    PubMed

    Arnold, S; Holler, S; Li, J H; Serpengüzel, A; Auffermann, W F; Hill, S C

    1995-04-01

    The relative intensities of glare spots in the image of an electrodynamically trapped aerosol droplet are measured experimentally with an aerosol particle microscope and calculated theoretically. The theoretical calculations are in good agreement with these experiments and indicate that the intensities of these spots are extremely sensitive to the imaginary part of the refractive index. Experimentally, we obtain the molecular absorption spectrum of an impurity within a droplet by recording the spectrum of an individual glare spot produced by broadband illumination.

  5. Potential of Chilopsis Linearis for Gold Phytomining: Using XAS to Determine Gold Reduction And Nanoparticle Formation Within Plant Tissues

    SciTech Connect

    E, Rodriguez; Parsons, J.G.; Peralta-Videa, J.R.; Cruz-Jiminez, G.; Romera-Gonzalez, J.; Sanchez-Salcido, B.E.; Saupe, G.B.; Duarte-Gardea, M.; Gardea-Torresdey, J.L.

    2009-06-04

    This study reports on the capability of the desert plant Chilopsis linearis (Cav.) Sweet (desert willow) to uptake gold (Au) from gold-enriched media at different plant-growth stages. Plants were exposed to 20, 40, 80, 160, and 320 mg Au L{sup -1} in agar-based growing media for 13, 18, 23, and 35 d. The Au content and oxidation state of Au in the plants were determined using an inductively coupled plasma/optical emission spectrometer (ICP/OES) and X-ray absorption spectroscopy (XAS), respectively. Gold concentrations ranging from 20 to 80 mg Au L{sup -1} did not significantly affect Chilopsis linearis plant growth. The concentration of gold in the plants increased as the age of the plant increased. The Au concentrations in leaves for the 20, 40, 80, and 160 mg Au L{sup -1} treatments were 32, 60, 62, and 179 mg Au kg{sup -1} dry weight mass, respectively, demonstrating the gold uptake capability of desert willow. The XAS data indicated that desert willow produced gold nanoparticles within plant tissues. Plants exposed to 160 mg Au L{sup -1} formed nanoparticles that averaged approximately 8, 35, and 18 in root, stem, and leaves, respectively. It was observed that the average size of the Au nanoparticles formed by the plants is related to the total Au concentration in tissues and their location in the plant.

  6. X-Ray Absorption Spectroscopy Of Thin Foils Irradiated By An Ultra-short Laser Pulse

    SciTech Connect

    Renaudin, P.; Blancard, C.; Cosse, P.; Faussurier, G.; Lecherbourg, L.; Audebert, P.; Bastiani-Ceccotti, S.; Geindre, J.-P.; Shepherd, R.

    2007-08-02

    Point-projection K-shell absorption spectroscopy has been used to measure absorption spectra of transient plasma created by an ultra-short laser pulse. The 1s-2p and 1s-3p absorption lines of weakly ionized aluminum and the 2p-3d absorption lines of bromine were measured over an extended range of densities in a low-temperature regime. Independent plasma characterization was obtained using frequency domain interferometry diagnostic (FDI) that allows the interpretation of the absorption spectra in terms of spectral opacities. Assuming local thermodynamic equilibrium, spectral opacity calculations have been performed using the density and temperature inferred from the FDI diagnostic to compare to the measured absorption spectra. A good agreement is obtained when non-equilibrium effects due to non-stationary atomic physics are negligible at the x-ray probe time.

  7. X-Ray Absorption Spectroscopy Of Thin Foils Irradiated By An Ultra-short Laser Pulse

    NASA Astrophysics Data System (ADS)

    Renaudin, P.; Lecherbourg, L.; Blancard, C.; Cossé, P.; Faussurier, G.; Audebert, P.; Bastiani-Ceccotti, S.; Geindre, J.-P.; Shepherd, R.

    2007-08-01

    Point-projection K-shell absorption spectroscopy has been used to measure absorption spectra of transient plasma created by an ultra-short laser pulse. The 1s-2p and 1s-3p absorption lines of weakly ionized aluminum and the 2p-3d absorption lines of bromine were measured over an extended range of densities in a low-temperature regime. Independent plasma characterization was obtained using frequency domain interferometry diagnostic (FDI) that allows the interpretation of the absorption spectra in terms of spectral opacities. Assuming local thermodynamic equilibrium, spectral opacity calculations have been performed using the density and temperature inferred from the FDI diagnostic to compare to the measured absorption spectra. A good agreement is obtained when non-equilibrium effects due to non-stationary atomic physics are negligible at the x-ray probe time.

  8. Non-coincident multi-wavelength emission absorption spectroscopy

    SciTech Connect

    Baumann, L.E.

    1995-02-01

    An analysis is presented of the effect of noncoincident sampling on the measurement of atomic number density and temperature by multiwavelength emission absorption. The assumption is made that the two signals, emission and transmitted lamp, are time resolved but not coincident. The analysis demonstrates the validity of averages of such measurements despite fluctuations in temperature and optical depth. At potassium-seeded MHD conditions, the fluctuations introduce additional uncertainty into measurements of potassium atom number density and temperature but do not significantly bias the average results. Experimental measurements in the CFFF aerodynamic duct with coincident and noncoincident sampling support the analysis.

  9. Absorption spectroscopy of a laboratory photoionized plasma experiment at Z

    SciTech Connect

    Hall, I. M.; Durmaz, T.; Mancini, R. C.; Bailey, J. E.; Rochau, G. A.; Golovkin, I. E.; MacFarlane, J. J.

    2014-03-15

    The Z facility at the Sandia National Laboratories is the most energetic terrestrial source of X-rays and provides an opportunity to produce photoionized plasmas in a relatively well characterised radiation environment. We use detailed atomic-kinetic and spectral simulations to analyze the absorption spectra of a photoionized neon plasma driven by the x-ray flux from a z-pinch. The broadband x-ray flux both photoionizes and backlights the plasma. In particular, we focus on extracting the charge state distribution of the plasma and the characteristics of the radiation field driving the plasma in order to estimate the ionisation parameter.

  10. A GAS TEMPERATURE PROFILE BY INFRARED EMISSION-ABSORPTION SPECTROSCOPY

    NASA Technical Reports Server (NTRS)

    Buchele, D. R.

    1994-01-01

    This computer program calculates the temperature profile of a flame or hot gas. Emphasis is on profiles found in jet engine or rocket engine exhaust streams containing water vapor or carbon dioxide as radiating gases. The temperature profile is assumed to be axisymmetric with a functional form controlled by two variable parameters. The parameters are calculated using measurements of gas radiation at two wavelengths in the infrared spectrum. Infrared emission and absorption measurements at two or more wavelengths provide a method of determining a gas temperature profile along a path through the gas by using a radiation source and receiver located outside the gas stream being measured. This permits simplified spectral scanning of a jet or rocket engine exhaust stream with the instrumentation outside the exhaust gas stream. This program provides an iterative-cyclic computation in which an initial assumed temperature profile is altered in shape until the computed emission and absorption agree, within specified limits, with the actual instrument measurements of emission and absorption. Temperature determination by experimental measurements of emission and absorption at two or more wavelengths is also provided by this program. Additionally, the program provides a technique for selecting the wavelengths to be used for determining the temperature profiles prior to the beginning of the experiment. By using this program feature, the experimenter has a higher probability of selecting wavelengths which will result in accurate temperature profile measurements. This program provides the user with a technique for determining whether this program will be sufficiently accurate for his particular application, as well as providing a means of finding the solution. The input to the program consists of four types of data: (1) computer program control constants, (2) measurements of gas radiance and transmittance at selected wavelengths, (3) tabulations from the literature of gas

  11. XAS/EXAFS studies of Ge nanoparticles produced by reaction between Mg 2 Ge and GeCl 4

    NASA Astrophysics Data System (ADS)

    Pugsley, Andrew J.; Bull, Craig L.; Sella, Andrea; Sankar, Gopinathan; McMillan, Paul F.

    2011-09-01

    We present results of an XAS and EXAFS study of the synthesis of Ge nanoparticles formed by a metathesis reaction between Mg 2Ge and GeCl 4 in diglyme (diethylene glycol dimethyl ether). The progress of the formation reaction and the products formed at various stages in the processing was characterised by TEM and optical spectroscopy as well as in situ XAS/EXAFS studies using specially designed reaction cells.

  12. Quasi zero-background tunable diode laser absorption spectroscopy employing a balanced Michelson interferometer.

    PubMed

    Guan, Zuguang; Lewander, Märta; Svanberg, Sune

    2008-12-22

    Tunable diode laser spectroscopy (TDLS) normally observes small fractional absorptive reductions in the light flux. We show, that instead a signal increase on a zero background can be obtained. A Michelson interferometer, which is initially balanced out in destructive interference, is perturbed by gas absorption in one of its arms. Both theoretical analysis and experimental demonstration show that the proposed zero-background TDLS can improve the achievable signal-to-noise ratio.

  13. Calibration of effective optical path length for hollow-waveguide based gas cell using absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Liu, Lin; Du, Zhenhui; Li, Jinyi

    2016-10-01

    The Hollow Waveguide (HWG) has emerged as a novel tool to transmit laser power. Owing to its long Effective Optical Path Length (EOPL) within a relatively small volume, it is suitable for the application as a gas cell in concentration measurement by using laser spectroscopy. The measurement of effective optical path length for a hollow waveguide, which possesses the physical length of 284.0 cm, by using Tunable Diode Laser Absorption Spectroscopy (TDLAS) was demonstrated. Carbon dioxide was used as a sample gas for a hollow waveguide calibration. A 2004 nm Distributed Feed-Back (DFB) laser was used as the light source to cover a CO2 line near 2003 nm, which was selected as the target line in the measurement. The reference direct absorption spectroscopy signal was obtained by delivering CO2 into a reference cell possessing a length of 29.4 cm. Then the effective optical path length of HWG was calculated by least-squares fitting the measured absorption signal to the reference absorption signal. The measured EOPL of HWG was 282.8 cm and the repeatability error of effective optical path length was calculated as 0.08 cm. A detection limit of 0.057 cm (with integral time 5 s) characterized by the Allan variance, was derived. The effective optical path length is obtained as the significant parameter to calculate the concentration of gases and it is of great importance to precise measurement of absorption spectroscopy.

  14. Analysis of the absorption layer of CIGS solar cell by laser-induced breakdown spectroscopy.

    PubMed

    Lee, Seok H; Shim, Hee S; Kim, Chan K; Yoo, Jong H; Russo, Richard E; Jeong, Sungho

    2012-03-01

    Laser induced breakdown spectroscopy (LIBS) was applied for the elemental analysis of the thin copper indium gallium diselenide (CuIn(1-x)Ga(x)Se(2) [CIGS]) absorption layer deposited on Mo-coated soda-lime glass by the co-evaporation technique. The optimal laser and detection parameters for LIBS measurement of the CIGS absorption layer (1.23 μm) were investigated. The calibration results of Ga/In ratio with respect to the concentration ratios measured by x-ray fluorescence and inductively coupled plasma optical emission spectroscopy showed good linearity.

  15. Near-infrared absorption spectroscopy of interstellar hydrocarbon grains

    NASA Technical Reports Server (NTRS)

    Pendleton, Y. J.; Sandford, S. A.; Allamandola, L. J.; Tielens, A. G. G. M.; Sellgren, K.

    1994-01-01

    We present new 3600 - 2700/cm (2.8 - 3.7 micrometer) spectra of objects whose extinction is dominated by dust in the diffuse interstellar medium. The observations presented here augment an ongoing study of the organic component of the diffuse interstellar medium. These spectra contain a broad feature centered near 3300/cm (3.0 micrometers) and/or a feature with a more complex profile near 2950/cm (3.4 micrometers), the latter of which is attributed to saturated aliphatic hydrocarbons in interstellar grains and is the primary interest of this paper. As in our earlier work, the similarity of the absorption bands near 2950/cm (3.4 micrometers) along different lines of sight and the correlation of these features with interstellar extinction reveal that the carrier of this band lies in the dust in the diffuse interstellar medium (DISM). At least 2.5% of the cosmic carbon in the local interstellar medium and 4% toward the Galactic center is tied up in the carrier of the 2950/cm (3.4 micrometer) band. The spectral structure of the diffuse dust hydrocarbon C-H stretch absorption features is reasonably similar to UV photolyzed laboratory ice residues and is quite similar to the carbonaceous component of the Murchison meteorite. The similarity between the DISM and the meteoritic spectrum suggests that some of the interstellar material originally incorporated into the solar nebula may have survived relatively untouched in primitive solar system bodies. Comparisons of the DISM spectrum to hydrogenated amorphous carbon and quenched carbonaceous composite are also presented. The A(sub V)/tau ratio for the 2950/cm (3.4 micrometer) feature is lower toward the Galactic center than toward sources in the local solar neighborhood (approximately 150 for the Galactic center sources vs. approximately 250 for the local ISM sources). A similar trend has been observed previously for silicates in the diffuse medium by Roche & Aitken, suggesting that (1) the silicate and carbonaceous

  16. Spin-Polarization-Induced Preedge Transitions in the Sulfur K-Edge XAS Spectra of Open-Shell Transition-Metal Sulfates: Spectroscopic Validation of σ-Bond Electron Transfer.

    PubMed

    Frank, Patrick; Szilagyi, Robert K; Gramlich, Volker; Hsu, Hua-Fen; Hedman, Britt; Hodgson, Keith O

    2017-02-06

    Sulfur K-edge X-ray absorption spectroscopy (XAS) spectra of the monodentate sulfate complexes [M(II)(itao)(SO4)(H2O)0,1] (M = Co, Ni, Cu) and [Cu(Me6tren)(SO4)] exhibit well-defined preedge transitions at 2479.4, 2479.9, 2478.4, and 2477.7 eV, respectively, despite having no direct metal-sulfur bond, while the XAS preedge of [Zn(itao)(SO4)] is featureless. The sulfur K-edge XAS of [Cu(itao)(SO4)] but not of [Cu(Me6tren)(SO4)] uniquely exhibits a weak transition at 2472.1 eV, an extraordinary 8.7 eV below the first inflection of the rising K-edge. Preedge transitions also appear in the sulfur K-edge XAS of crystalline [M(II)(SO4)(H2O)] (M = Fe, Co, Ni, and Cu, but not Zn) and in sulfates of higher-valent early transition metals. Ground-state density functional theory (DFT) and time-dependent DFT (TDDFT) calculations show that charge transfer from coordinated sulfate to paramagnetic late transition metals produces spin polarization that differentially mixes the spin-up (α) and spin-down (β) spin orbitals of the sulfate ligand, inducing negative spin density at the sulfate sulfur. Ground-state DFT calculations show that sulfur 3p character then mixes into metal 4s and 4p valence orbitals and various combinations of ligand antibonding orbitals, producing measurable sulfur XAS transitions. TDDFT calculations confirm the presence of XAS preedge features 0.5-2 eV below the rising sulfur K-edge energy. The 2472.1 eV feature arises when orbitals at lower energy than the frontier occupied orbitals with S 3p character mix with the copper(II) electron hole. Transmission of spin polarization and thus of radical character through several bonds between the sulfur and electron hole provides a new mechanism for the counterintuitive appearance of preedge transitions in the XAS spectra of transition-metal oxoanion ligands in the absence of any direct metal-absorber bond. The 2472.1 eV transition is evidence for further radicalization from copper(II), which extends across a

  17. Total absorption spectroscopy of N = 51 nucleus 85Se

    NASA Astrophysics Data System (ADS)

    Goetz, K. C.; Grzywacz, R. K.; Rykaczewski, K. P.; Karny, M.; Fialkowska, A.; Wolinska-Cichocka, M.; Rasco, B. C.; Zganjar, E. F.; Johnson, J. W.; Gross, C. J.

    2014-09-01

    An experimental campaign utilizing the Modular Total Absorption Spectrometer (MTAS) was conducted at the HRIBF facility in January of 2012. The campaign studied 22 isotopes, many of which were identified as the highest priority for decay heat analysis during a nuclear fuel cycle, see the report by the OECD-IAEA Nuclear Energy Agency in 2007. The case of 85Se will be discussed. 85Se is a Z = 34, N = 51 nucleus with the valence neutron located in the positive parity sd single particle state. Therefore, its decay properties are determined by interplay between first forbidden decays of the valence neutron and Gamow-Teller decay of a 78Ni core. Analysis of the data obtained during the January 2012 run indicates a significant increase of the beta strength function when compared with previous measurements, see Ref..

  18. Monitoring spacecraft atmosphere contaminants by laser absorption spectroscopy

    NASA Technical Reports Server (NTRS)

    Steinfeld, J. I.

    1976-01-01

    Laser-based spectrophotometric methods which have been proposed for the detection of trace concentrations of gaseous contaminants include Raman backscattering (LIDAR) and passive radiometry (LOPAIR). Remote sensing techniques using laser spectrometry are presented and in particular a simple long-path laser absorption method (LOLA), which is capable of resolving complex mixtures of closely related trace contaminants at ppm levels is discussed. A number of species were selected for study which are representative of those most likely to accumulate in closed environments, such as submarines or long-duration manned space flights. Computer programs were developed which will permit a real-time analysis of the monitored atmosphere. Estimates of the dynamic range of this monitoring technique for various system configurations, and comparison with other methods of analysis, are given.

  19. VUV Absorption Spectroscopy of Planetary Molecules at Low Temperature

    NASA Astrophysics Data System (ADS)

    Jolly, A.; Benilan, Y.; Ferradaz, T.; Fray, N.; Schwell, M.

    2005-08-01

    A critical review of the available absorption coefficient in the vacuum ultraviolet domain (100-200 nm) has lead us to undertake new measurements at the Berlin synchrotron facility (BESSY). Many of the molecules detected in planetary atmospheres and in particular those which need to be synthesized in the laboratory, have never been measured at low temperature. The first molecules that we have studied are HCN, HC3N and C2N2. New absorption coefficients have been obtained including first spectra at low temperature (220 K). The effect of the temperature on the spectra can then be discussed in view of the application to the much colder atmosphere of Titan. The nitriles studied here play an important role in the chemistry taking place in Titan's atmosphere and are believed to be responsible for the formation of Titan's aerosols. From our measurements, we have calculated the photodissociation rates for each molecule which are essential to include in any photochemical model. This is true for Titan but also for cometary and interstellar medium models. To describe the formation of a solid phase, the models also need to include photodissociation rates for larger molecules which have not been detected yet. This will now be possible for HC5N since the first spectra of this molecule has been obtained by our team. Furthermore, the first stellar occultation measurement of Titan's atmosphere by the UV spectrometer (UVIS) on board the CASSINI spacecraft has permitted the detection of species not observed before in this wavelength domain. But it has also shown a lack of experimental data in this domain. So far, the model is not able to reproduce the observed spectral feature. C4H2 is the molecule that should explain some of the observed feature but absolute cross sections are missing. We will present our latest experimental measurements on this molecule.

  20. Gold nanoparticles with different capping systems: an electronic and structural XAS analysis.

    PubMed

    López-Cartes, C; Rojas, T C; Litrán, R; Martínez-Martínez, D; de la Fuente, J M; Penadés, S; Fernández, A

    2005-05-12

    Gold nanoparticles (NPs) have been prepared with three different capping systems: a tetralkylammonium salt, an alkanethiol, and a thiol-derivatized neoglycoconjugate. Also gold NPs supported on a porous TiO(2) substrate have been investigated. X-ray absorption spectroscopy (XAS) has been used to determine the electronic behavior of the different capped/supported systems regarding the electron/hole density of d states. Surface and size effects, as well as the role of the microstructure, have been also studied through an exhaustive analysis of the EXAFS (extended X-ray absorption fine structure) data. Very small gold NPs functionalized with thiol-derivatized molecules show an increase in d-hole density at the gold site due to Au-S charge transfer. This effect is overcoming size effects (which lead to a slightly increase of the d-electron density) for high S:Au atomic ratios and core-shell microstructures where an atomically abrupt Au-S interface likely does not exist. It has been also shown that thiol functionalization of very small gold NPs is introducing a strong distortion as compared to fcc order. To the contrary, electron transfer from reduced support oxides to gold NPs can produce a higher increase in d-electron density at the gold site, as compared to naked gold clusters.

  1. Difference Between Far-Infrared Photoconductivity Spectroscopy and Absorption Spectroscopy: Theoretical Evidence of the Electron Reservoir Mechanism

    NASA Astrophysics Data System (ADS)

    Toyoda, Tadashi; Fujita, Maho; Uchida, Tomohisa; Hiraiwa, Nobuyoshi; Fukuda, Taturo; Koizumi, Hideki; Zhang, Chao

    2013-08-01

    The intriguing difference between far-infrared photoconductivity spectroscopy and absorption spectroscopy in the measurement of the magnetoplasmon frequency in GaAs quantum wells reported by Holland et al. [Phys. Rev. Lett. 93, 186804 (2004)] remains unexplained to date. This Letter provides a consistent mechanism to solve this puzzle. The mechanism is based on the electron reservoir model for the integer quantum Hall effect in graphene [Phys. Lett. A 376, 616 (2012)]. We predict sharp kinks to appear in the magnetic induction dependence of the magnetoplasmon frequency at very low temperatures such as 14 mK in the same GaAs quantum well sample used by Holland et al..

  2. X-ray absorption and emission spectroscopy study of Mn and Co valence and spin states in TbM n1 -xC oxO3

    NASA Astrophysics Data System (ADS)

    Cuartero, V.; Lafuerza, S.; Rovezzi, M.; García, J.; Blasco, J.; Subías, G.; Jiménez, E.

    2016-10-01

    The valence and spin state evolution of Mn and Co on TbM n1 -xC oxO3 series is precisely determined by means of soft and hard x-ray absorption spectroscopy (XAS) and K β x-ray emission spectroscopy (XES). Our results show the change from M n3 + to M n4 + both high-spin (HS) together with the evolution from C o2 + HS to C o3 + low-spin (LS) with increasing x . In addition, high energy resolution XAS spectra on the K pre-edge region are interpreted in terms of the strong charge transfer and hybridization effects along the series. These results correlate well with the spin values of Mn and Co atoms obtained from the K β XES data. In this paper, we determine that Co enters into the transition metal sublattice of TbMn O3 as a divalent ion in HS state, destabilizing the Mn long-range magnetic order since very low doping compositions (x ≤0.1 ). Samples in the intermediate composition range (0.4 ≤x ≤0.6 ) adopt the crystal structure of a double perovskite with long-range ferromagnetic ordering which is due to M n4 + -O-C o2 + superexchange interactions with both cations in HS configuration. Ferromagnetism vanishes for x ≥0.7 due to the structural disorder that collapses the double perovskite structure. The spectroscopic techniques reveal the occurrence of M n4 + HS and a fluctuating valence state C o2 + HS/C o3 + LS in this composition range. Disorder and competitive interactions lead to a magnetic glassy behavior in these samples.

  3. Speciation and thermodynamic properties of zinc in sulfur-rich hydrothermal fluids: Insights from ab initio molecular dynamics simulations and X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Mei, Yuan; Etschmann, Barbara; Liu, Weihua; Sherman, David M.; Testemale, Denis; Brugger, Joël

    2016-04-01

    Chlorine and sulfur are the main elements involved in the complexing of metals in ore-forming fluids. The nature and thermodynamic properties of the Zn(II)-Cl complexes have been investigated by previous experimental and theoretical studies and are now well established up to high temperatures (600 °C). In contrast, the role of bisulfide complexes for zinc speciation in sulfur-bearing fluids remains poorly known, and a better understanding of Zn(II)-HS complexation is required for modeling zinc transport in magmatic and metamorphic fluids and for optimizing the hydrometallurgical processing of sulfide ores. We have conducted ab initio molecular dynamics (MD) simulations to calculate the speciation of Zn(II)-HS complexes from ambient to hydrothermal-magmatic conditions (25-600 °C, up to 2000 bar). These theoretical calculations were complemented by X-ray absorption spectroscopy (XAS) measurements of Zn(II) in HS--rich solutions at 200-500 °C and 600-1000 bar. The speciation and geometrical properties predicted by the ab initio MD simulations and the in situ XAS data are in excellent agreement. Upon heating from room temperature to 250 °C, Zn(II) speciation in HS--rich solutions shows a transition from the sixfold octahedral hexaaquo complex [Zn(H2O)6]2+ to fourfold tetrahedral [Zn(HS)n(H2O)4-n]2-n complexes (n = 1-4). Ab initio MD simulations also show that at temperatures > 250 °C, the threefold trigonal-planar [Zn(HS)3]- complex becomes increasingly stable, and predominates in S-rich solutions; in contrast, chloro-complexes display a tetrahedral geometry at 25-500 °C, while trigonal planar ZnCl3- predominates at temperatures > 500 °C. The stability constants of Zn(II)-HS complexes were calculated by thermodynamic integration of constrained ab initio MD simulations at 200, 350 and 600 °C. The stability constants generated from this study predict that zinc can be transported by HS- at high temperature in reduced, neutral to alkaline solutions, while Zn

  4. Predicting X-ray absorption spectra of semiconducting polymers for electronic structure and morphology characterization

    NASA Astrophysics Data System (ADS)

    Su, Gregory; Patel, Shrayesh; Pemmaraju, C. Das; Kramer, Edward; Prendergast, David; Chabinyc, Michael

    2015-03-01

    Core-level X-ray absorption spectroscopy (XAS) reveals important information on the electronic structure of materials and plays a key role in morphology characterization. Semiconducting polymers are the active component in many organic electronics. Their electronic properties are critically linked to device performance, and a proper understanding of semiconducting polymer XAS is crucial. Techniques such as resonant X-ray scattering rely on core-level transitions to gain materials contrast and probe orientational order. However, it is difficult to identify these transitions based on experiments alone, and complementary simulations are required. We show that first-principles calculations can capture the essential features of experimental XAS of semiconducting polymers, and provide insight into which molecular model, such as oligomers or periodic boundary conditions, are best suited for XAS calculations. Simulated XAS can reveal contributions from individual atoms and be used to visualize molecular orbitals. This allows for improved characterization of molecular orientation and scattering analysis. These predictions lay the groundwork for understanding how chemical makeup is linked to electronic structure, and to properly utilize experiments to characterize semiconducting polymers.

  5. Distribution and speciation of bromine in mammalian tissue and fluids by X-ray fluorescence imaging and X-ray absorption spectroscopy.

    PubMed

    Ceko, Melanie J; Hummitzsch, Katja; Hatzirodos, Nicholas; Bonner, Wendy; James, Simon A; Kirby, Jason K; Rodgers, Raymond J; Harris, Hugh H

    2015-05-01

    Bromine is one of the most abundant and ubiquitous trace elements in the biosphere and until recently had not been shown to perform any essential biological function in animals. A recent study demonstrated that bromine is required as a cofactor for peroxidasin-catalysed formation of sulfilimine crosslinks in Drosophila. In addition, bromine dietary deficiency is lethal in Drosophila, whereas bromine replenishment restores viability. The aim of this study was to examine the distribution and speciation of bromine in mammalian tissues and fluids to provide further insights into the role and function of this element in biological systems. In this study we used X-ray fluorescence (XRF) imaging and inductively coupled plasma-mass spectrometry (ICP-MS) to examine the distribution of bromine in bovine ovarian tissue samples, follicular fluid and aortic serum, as well as human whole blood and serum and X-ray absorption spectroscopy (XAS) to identify the chemical species of bromine in a range of mammalian tissue (bovine, ovine, porcine and murine), whole blood and serum samples (bovine, ovine, porcine, murine and human), and marine samples (salmon (Salmo salar), kingfish (Seriola lalandi) and Scleractinian coral). Bromine was found to be widely distributed across all tissues and fluids examined. In the bovine ovary in particular it was more concentrated in the sub-endothelial regions of arterioles. Statistical comparison of the near-edge region of the X-ray absorption spectra with a library of bromine standards led to the conclusion that the major form of bromine in all samples analysed was bromide.

  6. Time-Resolved Broadband Cavity-Enhanced Absorption Spectroscopy behind Shock Waves.

    PubMed

    Matsugi, Akira; Shiina, Hiroumi; Oguchi, Tatsuo; Takahashi, Kazuo

    2016-04-07

    A fast and sensitive broadband absorption technique for measurements of high-temperature chemical kinetics and spectroscopy has been developed by applying broadband cavity-enhanced absorption spectroscopy (BBCEAS) in a shock tube. The developed method has effective absorption path lengths of 60-200 cm, or cavity enhancement factors of 12-40, over a wavelength range of 280-420 nm, and is capable of simultaneously recording absorption time profiles over an ∼32 nm spectral bandpass in a single experiment with temporal and spectral resolutions of 5 μs and 2 nm, respectively. The accuracy of the kinetic and spectroscopic measurements was examined by investigating high-temperature reactions and absorption spectra of formaldehyde behind reflected shock waves using 1,3,5-trioxane as a precursor. The rate constants obtained for the thermal decomposition reactions of 1,3,5-trioxane (to three formaldehyde molecules) and formaldehyde (to HCO + H) agreed well with the literature data. High-temperature absorption cross sections of formaldehyde between 280 and 410 nm have been determined at the post-reflected-shock temperatures of 955, 1265, and 1708 K. The results demonstrate the applicability of the BBCEAS technique to time- and wavelength-resolved sensitive absorption measurements at high temperatures.

  7. [High-order derivative spectroscopy of infrared absorption spectra of the reaction centers from Rhodobacter sphaeroides].

    PubMed

    2005-01-01

    The infrared absorption spectra of reduced and chemically oxidized reaction center preparations from the purple bacterium Rhodobacter sphaeroides were investigated by means of high-order derivative spectroscopy. The model Gaussian band with a maximum at 810 nm and a half-band of 15 nm found in the absorption spectrum of the reduced reaction center preparation is eliminated after the oxidation of photoactive bacteriochlorophyll dimer (P). This band was related to the absorption of the P(+)y excitonic band of P. On the basis of experimental results, it was concluded that the bleaching of the P(+)y absorption band at 810 nm in the oxidized reaction center preparations gives the main contribution to the blue shift of the 800 nm absorption band of Rb. sphaeroides reaction centers.

  8. [Near infrared Cavity enhanced absorption spectroscopy study of NO2O].

    PubMed

    Wu, Zhi-wei; Dong, Yan-ting; Zhou, Wei-dong

    2014-08-01

    Using a tunable near infrared external cavity diode laser and a 650 mm long high finesse optical cavity consisting of two highly reflective (R=99.97% at 6561.39 cm(-1)) plan-concave mirrors of curvature radius approximately 1000 mm, a cavity enhanced absorption spectroscopy (CEAS) system was made. The absorption spectra centered at 6561.39 cm(-1) of pure N2O gas and gas mixtures of N2O and N2 were recorded. According to the absorption of N2O at 6561.39 cm(-1) in the cavity, the measured effective absorption path was about 1460 km. The spectra line intensity and line-width of N2O centered at 6561.39 cm(-1) were carefully studied. The relationship between the line-width of absorption spectra and the gas pressure was derived. The pressure broadening parameter of N2 gas for NO2O line centered at 6 561. 39 cm(-1) was deduced and given a value of approximately (0.114 +/- 0.004) cm(-1) x atm(-1). The possibility to detect trace N2O gas in mixture using this CEAS system was investigated. By recording the ab- sorption spectra of N2O gas mixtures at different concentration, the relationship between the line intensity and gas concentration was derived. The minimum detectable absorption was found to be 2.34 x 10(-7) cm(-1) using this cavity enhanced absorption spectroscopy system. And te measurement precision in terms of relative standard deviation (RSD) for N2O is approximately 1.73%, indicating the possibility of using the cavity enhanced absorption spectroscopy system for micro gas N2O analysis in the future.

  9. Mechanistic Study of CO 2 Photoreduction with H 2 O on Cu/TiO 2 Nanocomposites by in Situ X-ray Absorption and Infrared Spectroscopies

    SciTech Connect

    Liu, Lianjun; Zhao, Cunyu; Miller, Jeffrey T.; Li, Ying

    2016-12-15

    Cu/TiO2 composites are extensively studied for photocatalytic reduction of CO2 with H2O, but the roles of Cu species (Cu2+, Cu+, or Cu0) is not well understood, and the photocatalyst deactivation mechanism is seldom addressed. In this work, we have employed in situ techniques, i.e., X-ray absorption spectroscopy (XAS) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), to explore the surface chemistry of Cu/TiO2 composites under CO2 photoreduction environment. We found that the air-calcined Cu/TiO2 (Cu/Ti(air)) surface was dominated by isolated Cu2+ sites, while the one post-treated with H2 at 200 °C (Cu/Ti(H2)) was rich in Cu+ and oxygen vacancy (VO). Cu/Ti(H2) showed more than 50% higher activity than Cu/Ti(air) for CO2 photoreduction to CO, mainly resulting from the synergy of Cu+, OH groups, and VO that could scavenge holes to enhance electron transfer, provide CO2 adsorption sites, and facilitate the activation and conversion of the adsorbed CO2 (HCO3– and CO2–). Meanwhile, the consumption of OH groups and Cu+ active sites by holes may result in the deactivation of Cu/Ti(H2). Moreover, in situ XAS results directly demonstrated that (1) the photoinduced oxidation of Cu+ to Cu2+ changed the surrounding environments of Cu by increasing the coordination number; (2) thermal treatment by H2 could not fully recover the OH and Cu+ sites to their original states; and (3) adding hole scavengers (e.g., methanol) maintained or even increased the more active Cu+ species from the photoreduction of Cu2+, thus leading to a higher and more stable CO2 reduction activity. Findings in this work and the application of in situ XAS technique will help develop a more efficient photocatalyst for CO2 photoreduction and advance the understanding of the reaction mechanism and surface chemistry.

  10. Synchrotron radiation based Mössbauer absorption spectroscopy of various nuclides

    NASA Astrophysics Data System (ADS)

    Masuda, Ryo; Kobayashi, Yasuhiro; Kitao, Shinji; Kurokuzu, Masayuki; Saito, Makina; Yoda, Yoshitaka; Mitsui, Takaya; Seto, Makoto

    2016-12-01

    Synchrotron-radiation (SR) based Mössbauer absorption spectroscopy of various nuclides is reviewed. The details of the measuring system and analysis method are described. Especially, the following two advantages of the current system are described: the detection of internal conversion electrons and the close distance between the energy standard scatterer and the detector. Both of these advantages yield the enhancement of the counting rate and reduction of the measuring time. Furthermore, SR-based Mössbauer absorption spectroscopy of 40K, 151Eu, and 174Yb is introduced to show the wide applicability of this method. In addition to these three nuclides, SR-based Mössbauer absorption spectroscopy of 61Ni, 73Ge, 119Sn, 125Te, 127I, 149Sm, and 189Os has been performed. We continue to develop the method to increase available nuclides and to increase its ease of use. The complementary relation between the time-domain method using SR, such as nuclear forward scattering and the energy-domain methods such as SR-based Mössbauer absorption spectroscopy is also noted.

  11. Circuit Board Analysis for Lead by Atomic Absorption Spectroscopy in a Course for Nonscience Majors

    ERIC Educational Resources Information Center

    Weidenhammer, Jeffrey D.

    2007-01-01

    A circuit board analysis of the atomic absorption spectroscopy, which is used to measure lead content in a course for nonscience majors, is being presented. The experiment can also be used to explain the potential environmental hazards of unsafe disposal of various used electronic equipments.

  12. DETERMINING BERYLLIUM IN DRINKING WATER BY GRAPHITE FURNACE ATOMIC ABSORPTION SPECTROSCOPY

    EPA Science Inventory

    A direct graphite furnace atomic absorption spectroscopy method for the analysis of beryllium in drinking water has been derived from a method for determining beryllium in urine. Ammonium phosphomolybdate and ascorbic acid were employed as matrix modifiers. The matrix modifiers s...

  13. Attosecond Transient Absorption Spectroscopy of doubly-excited states in helium

    NASA Astrophysics Data System (ADS)

    Argenti, Luca; Ott, Christian; Pfeifer, Thomas; Martín, Fernando

    2014-04-01

    Theoretical calculations of the XUV attosecond transient absorption spectrum (ATAS) of helium in the doubly-excited state region reproduce recent high-precision measurements, reveal novel means of controlling the dynamics of transiently-bound electronic wavepackets in intense laser fields, and indicates a possible extension of 2D-spectroscopies to the XUV range.

  14. Determination of sub microgram amounts of selenium in rocks by atomic-absorption spectroscopy.

    PubMed

    Golembeski, T

    1975-06-01

    Atomic-absorption spectroscopy was used to determine trace amounts of selenium accurately in U.S. Geological Survey standard rocks, GSP-1, W-1 and BCR-1. The results obtained were compared with those obtained by neutron-activation analysis and excellent agreement was found; in addition, the selenium:sulphur ratio was calculated and agreed with results obtained by other workers.

  15. Absorption and Scattering Coefficients: A Biophysical-Chemistry Experiment Using Reflectance Spectroscopy

    ERIC Educational Resources Information Center

    Cordon, Gabriela B.; Lagorio, M. Gabriela

    2007-01-01

    A biophysical-chemistry experiment, based on the reflectance spectroscopy for calculating the absorption and scattering coefficients of leaves is described. The results show that different plants species exhibit different values for both the coefficients because of their different pigment composition.

  16. LISA: the Italian CRG beamline for x-ray Absorption Spectroscopy at ESRF

    NASA Astrophysics Data System (ADS)

    d'Acapito, F.; Trapananti, A.; Puri, A.

    2016-05-01

    LISA is the acronym of Linea Italiana per la Spettroscopia di Assorbimento di raggi X (Italian beamline for X-ray Absorption Spectroscopy) and is the upgrade of the former GILDA beamline installed on the BM08 bending magnet port of European Synchrotron Radiation Facility (ESRF). Within this contribution a full description of the project is provided.

  17. X-ray absorption spectroscopy on the basis of hybrid X-pinch radiation

    SciTech Connect

    Tilikin, I. N. Shelkovenko, T. A.; Pikuz, S. A.; Knapp, P. F.; Hammer, D. A.

    2015-07-15

    Results of experiments on X-ray absorption spectroscopy carried out at the BIN (270 kA, 100 ns) and XP (450 kA, 45 ns) facilities are presented. Continuum radiation of a Mo hybrid X-pinch was used as probing radiation, against which absorption lines of the plasma of exploded Al wires placed in the return current circuit of a hybrid X-pinch, as well as in a two- and four-wire array, were observed. The experiments have demonstrated that the radiation of a hybrid X-pinch hot spot can be used as probing radiation for X-ray absorption spectroscopy and that, in many parameters, such a source surpasses those on the basis of laser-produced plasma. The plasma parameters in arrays made of two and four Al wires were studied experimentally.

  18. Spectrum sensing of trace C(2)H(2) detection in differential optical absorption spectroscopy technique.

    PubMed

    Chen, Xi; Dong, Xiaopeng

    2014-09-10

    An improved algorithm for trace C(2)H(2) detection is presented in this paper. The trace concentration is accurately calculated by focusing on the absorption spectrum from the frequency domain perspective. The advantage of the absorption spectroscopy frequency domain algorithm is its anti-interference capability. First, the influence of the background noise on the minimum detectable concentration is greatly reduced. Second, the time-consuming preprocess of spectra calibration in the differential optical absorption spectroscopy technique is skipped. Experimental results showed the detection limit of 50 ppm is achieved at a lightpath length of 0.2 m. This algorithm can be used in real-time spectrum analysis with high accuracy.

  19. X-ray absorption spectroscopy on the basis of hybrid X-pinch radiation

    NASA Astrophysics Data System (ADS)

    Tilikin, I. N.; Shelkovenko, T. A.; Pikuz, S. A.; Knapp, P. F.; Hammer, D. A.

    2015-07-01

    Results of experiments on X-ray absorption spectroscopy carried out at the BIN (270 kA, 100 ns) and XP (450 kA, 45 ns) facilities are presented. Continuum radiation of a Mo hybrid X-pinch was used as probing radiation, against which absorption lines of the plasma of exploded Al wires placed in the return current circuit of a hybrid X-pinch, as well as in a two- and four-wire array, were observed. The experiments have demonstrated that the radiation of a hybrid X-pinch hot spot can be used as probing radiation for X-ray absorption spectroscopy and that, in many parameters, such a source surpasses those on the basis of laser-produced plasma. The plasma parameters in arrays made of two and four Al wires were studied experimentally.

  20. Solving the Structure of Reaction Intermediates by Time-Resolved Synchrotron X-ray Absorption Spectroscopy

    SciTech Connect

    Wang, Q.; Hanson, J; Frenkel, A

    2008-01-01

    We present a robust data analysis method of time-resolved x-ray absorption spectroscopy experiments suitable for chemical speciation and structure determination of reaction intermediates. Chemical speciation is done by principal component analysis (PCA) of the time-resolved x-ray absorption near-edge structure data. Structural analysis of intermediate phases is done by theoretical modeling of their extended x-ray absorption fine-structure data isolated by PCA. The method is demonstrated using reduction and reoxidation of Cu-doped ceria catalysts where we detected reaction intermediates and measured fine details of the reaction kinetics. This approach can be directly adapted to many time-resolved x-ray spectroscopy experiments where new rapid throughput data collection and analysis methods are needed.

  1. The Five-To-Six-Coordination Transition of Ferric Human Serum Heme-Albumin Is Allosterically-Modulated by Ibuprofen and Warfarin: A Combined XAS and MD Study

    PubMed Central

    Bionducci, Monica; Fanali, Gabriella; Meli, Massimiliano; Colombo, Giorgio; Fasano, Mauro; Ascenzi, Paolo; Mobilio, Settimio

    2014-01-01

    Human serum albumin (HSA) is involved physiologically in heme scavenging; in turn, heme-albumin (HSA-heme-Fe) displays globin-like properties. Here, the allosteric effect of ibuprofen and warfarin on the local atomic structure around the ferric heme-Fe (heme-Fe(III)) atom of HSA-heme-Fe (HSA-heme-Fe(III)) has been probed by Fe-K edge X-ray absorption spectroscopy (XAS). The quantitative analysis of the Fe-K edge extended X-ray absorption fine structure (EXAFS) signals and modeling of the near edge (XANES) spectral features demonstrated that warfarin and ibuprofen binding modify the local structure of the heme-Fe(III). Combined XAS data analysis and targeted molecular dynamics (MD) simulations provided atomic resolution insights of protein structural rearrangements required to accommodate the heme-Fe(III) upon ibuprofen and warfarin binding. In the absence of drugs, the heme-Fe(III) atom is penta-coordinated having distorted 4+1 configuration made by the nitrogen atoms of the porphyrin ring and the oxygen phenoxy atom of the Tyr161 residue. MD simulations show that ibuprofen and warfarin association to the secondary fatty acid (FA) binding site 2 (FA2) induces a reorientation of domain I of HSA-heme-Fe(III), this leads to the redirection of the His146 residue providing an additional bond to the heme-Fe(III) atom, providing the 5+1 configuration. The comparison of Fe-K edge XANES spectra calculated using MD structures with those obtained experimentally confirms the reliability of the proposed structural model. As a whole, combining XAS and MD simulations it has been possible to provide a reliable model of the heme-Fe(III) atom coordination state and to understand the complex allosteric transition occurring in HSA-heme-Fe(III) upon ibuprofen and warfarin binding. PMID:25153171

  2. [Influence of silver/silicon dioxide on infrared absorption spectroscopy of sodium nitrate].

    PubMed

    Yang, Shi-Ling; Yue, Li; Jia, Zhi-Jun

    2014-09-01

    Quickly detecting of ocean nutrient was one important task in marine pollution monitoring. We discovered the application of surface-enhanced infrared absorption spectroscopy in the detection of ocean nutrient through researching the evaporation of sodium nitrate solution. The silicon dioxide (SiO2) with highly dispersion was prepared by Stober method, The silver/silica (Ag/SiO2) composite materials were prepared by mixing ammonia solution and silicon dioxide aqueous solution. Three kinds of composite materials with different surface morphology were fabricated through optimizing the experimental parameter and changing the experimental process. The surface morphology, crystal orientation and surface plasmon resonance were investigated by means of the scanning electronic microscope (SEM), X-ray diffraction (XRD), UV-Visible absorption spectrum and infrared ab- sorption spectroscopy. The SEM images showed that the sample A was purified SiO2, sample B and sample C were mixture of silver nanoparticle and silicon dioxide, while sample D was completed nanoshell structure. The absorption spectroscopy showed that there was surface plasmon resonance in the UV-visible region, while there was possibility of surface plasmon resonance in the Infrared absorption region. The effect of Ag/SiO2 composite material on the infrared absorption spectra of sodium nitrite solution was investigated through systematically analyzing the infrared absorption spectroscopy of sodium nitrate solution during its evaporation, i. e. the peak integration area of nitrate and the peak integration area of water molecule. The experimental results show that the integration area of nitrate was enhanced greatly during the evaporation process while the integration area of water molecule decreased continuously. The integration area of nitrate comes from the anti-symmetric stretch vibration and the enhancement of the vibration is attributed to the interface effect of Ag/SiO2 which is consistent with Jensen T

  3. Pharmaceutical applications of separation of absorption and scattering in near-infrared spectroscopy (NIRS).

    PubMed

    Shi, Zhenqi; Anderson, Carl A

    2010-12-01

    The number of near-infrared (NIR) spectroscopic applications in the pharmaceutical sciences has grown significantly in the last decade. Despite its widespread application, the fundamental interaction between NIR radiation and pharmaceutical materials is often not mechanistically well understood. Separation of absorption and scattering in near-infrared spectroscopy (NIRS) is intended to extract absorption and scattering spectra (i.e., absorption and reduced scattering coefficients) from reflectance/transmittance NIR measurements. The purpose of the separation is twofold: (1) to enhance the understanding of the individual roles played by absorption and scattering in NIRS and (2) to apply the separated absorption and scattering spectra for practical spectroscopic analyses. This review paper surveys the multiple techniques reported to date on the separation of NIR absorption and scattering within pharmaceutical applications, focusing on the instrumentations, mathematical approaches used to separate absorption and scattering and related pharmaceutical applications. This literature review is expected to enhance the understanding and thereby the utility of NIRS in pharmaceutical science. Further, the measurement and subsequent understanding of the separation of absorption and scattering is expected to increase not only the number of NIRS applications, but also their robustness.

  4. Determination of Calcium in Cereal with Flame Atomic Absorption Spectroscopy: An Experiment for a Quantitative Methods of Analysis Course

    ERIC Educational Resources Information Center

    Bazzi, Ali; Kreuz, Bette; Fischer, Jeffrey

    2004-01-01

    An experiment for determination of calcium in cereal using two-increment standard addition method in conjunction with flame atomic absorption spectroscopy (FAAS) is demonstrated. The experiment is intended to introduce students to the principles of atomic absorption spectroscopy giving them hands on experience using quantitative methods of…

  5. ED-XAS Data Reveal In-situ Time-Resolved Adsorbate Coverage on Supported Molybdenum Oxide Catalysts during Propane Dehydrogenation

    NASA Astrophysics Data System (ADS)

    Ramaker, David; Gatewood, Daniel; Beale, Andrew M.; Weckhuysen, Bert M.

    2007-02-01

    Energy-Dispersive X-ray Absorption Spectroscopy (ED-XAS) data combined with UV/Vis, Raman, and mass spectrometry data on alumina- and silica-supported molybdenum oxide catalysts under propane dehydrogenation conditions have been previously reported. A novel Δμ adsorbate isolation technique was applied here to the time-resolved (0.1 min) Mo K-edge ED-XAS data by taking the difference of absorption, μ, at t>1 against the initial time, t=0. Further, full multiple scattering calculations using the FEFF 8.0 code are performed to interpret the Δμ signatures. The resulting difference spectra and interpretation provide real time propane coverage and O depletion at the MoOn surface. The propane coverage is seen to correlate with the propene and/or coke production, with the maximum coke formation occurring when the propane coverage is the largest. Combined, these data give unprecedented insight into the complicated dynamics for propane dehydrogenation.

  6. ED-XAS Data Reveal In-situ Time-Resolved Adsorbate Coverage on Supported Molybdenum Oxide Catalysts during Propane Dehydrogenation

    SciTech Connect

    Ramaker, David; Gatewood, Daniel; Beale, Andrew M.; Weckhuysen, Bert M.

    2007-02-02

    Energy-Dispersive X-ray Absorption Spectroscopy (ED-XAS) data combined with UV/Vis, Raman, and mass spectrometry data on alumina- and silica-supported molybdenum oxide catalysts under propane dehydrogenation conditions have been previously reported. A novel {delta}{mu} adsorbate isolation technique was applied here to the time-resolved (0.1 min) Mo K-edge ED-XAS data by taking the difference of absorption, {mu}, at t>1 against the initial time, t=0. Further, full multiple scattering calculations using the FEFF 8.0 code are performed to interpret the {delta}{mu} signatures. The resulting difference spectra and interpretation provide real time propane coverage and O depletion at the MoOn surface. The propane coverage is seen to correlate with the propene and/or coke production, with the maximum coke formation occurring when the propane coverage is the largest. Combined, these data give unprecedented insight into the complicated dynamics for propane dehydrogenation.

  7. Skeletal Ru/Cu catalysts prepared from crystalline and quasicrystalline ternary alloy precursors: characterization by X-ray absorption spectroscopy and CO oxidation.

    PubMed

    Highfield, James; Liu, Tao; Loo, Yook Si; Grushko, Benjamin; Borgna, Armando

    2009-02-28

    The Ru/Cu system is of historical significance in catalysis. The early development and application of X-ray absorption spectroscopy (XAS) led to the original 'bimetallic cluster" concept for highly-immiscible systems. This work explores alkali leaching of Al-based ternary crystalline and quasicrystalline precursors as a potential route to bulk Ru/Cu alloys. Single-phase ternary alloys at 3 trial compositions; Al(71)Ru(22)Cu(7), Al(70.5)Ru(17)Cu(12.5), and Al(70)Ru(10)Cu(20), were prepared by arc melting of the pure metal components. After leaching, the bimetallic residues were characterized principally by transmission XAS, "as-leached" and after annealing in H(2) (and passivation) in a thermobalance. XRD and BET revealed a nanocrystalline product with a native structure of hexagonal Ru. XPS surface analysis of Ru(22)Cu(7) and Ru(17)Cu(12.5) found only slight enrichment by Cu in the as-leached forms, with little change upon annealing. Ru(10)Cu(20) was highly segregated as-leached. XANES data showed preferential oxidation of Cu in Ru(22)Cu(7), implying that it exists as an encapsulating layer. TG data supports this view since it does not show the distinct two-stage O(2) uptake characteristic of skeletal Ru. Cu K-edge EXAFS data for Ru(22)Cu(7) were unique in showing a high proportion of Ru neighbours. The spacing, d(CuRu) = 2.65 A, was that expected from a hypothetical (ideal) solid solution at this composition, but this is unlikely in such a bulk-immiscible system and Ru K-edge EXAFS failed to confirm bulk alloying. Furthermore its invariance under annealing was more indicative of an interfacial bond between bulk components, although partial alloying with retention of local order cannot entirely be ruled out. The XAS and XPS data were reconciled in a model involving surface and bulk segregation, Cu being present at both the grain exterior and in ultra-fine internal pores. This structure can be considered as the 3-dimensional analogue of the classical type

  8. Recovery of acetylene absorption line profile basing on tunable diode laser spectroscopy with intensity modulation and photoacoustic spectroscopy

    NASA Astrophysics Data System (ADS)

    Li, Li; Thursby, Graham; Stewart, George; Arsad, Norhana; Uttamchandani, Deepak; Culshaw, Brian; Wang, Yiding

    2010-04-01

    A novel and direct absorption line recovery technique based on tunable diode laser spectroscopy with intensity modulation is presented. Photoacoustic spectroscopy is applied for high sensitivity, zero background and efficient acoustic enhancement at a low modulation frequency. A micro-electromechanical systems (MEMS) mirror driven by an electrothermal actuator is used for generating laser intensity modulation (without wavelength modulation) through the external reflection. The MEMS mirror with 10μm thick structure material layer and 100nm thick gold coating is formed as a circular mirror of 2mm diameter attached to an electrothermal actuator and is fabricated on a chip that is wire-bonded and placed on a PCB holder. Low modulation frequency is adopted (since the resonant frequencies of the photoacoustic gas cell and the electrothermal actuator are different) and intrinsic high signal amplitude characteristics in low frequency region achieved from measured frequency responses for the MEMS mirror and the gas cell. Based on the property of photoacoustic spectroscopy and Beer's law that detectable sensitivity is a function of input laser intensity in the case of constant gas concentration and laser path length, a Keopsys erbium doped fibre amplifier (EDFA) with opto-communication C band and high output power up to 1W is chosen to increase the laser power. High modulation depth is achieved through adjusting the MEMS mirror's reflection position and driving voltage. In order to scan through the target gas absorption line, the temperature swept method is adopted for the tunable distributed feed-back (DFB) diode laser working at 1535nm that accesses the near-infrared vibration-rotation spectrum of acetylene. The profile of acetylene P17 absorption line at 1535.39nm is recovered ideally for ~100 parts-per-million (ppm) acetylene balanced by nitrogen. The experimental signal to noise ratio (SNR) of absorption line recovery for 500mW laser power was ~80 and hence the

  9. Photocarrier dynamics in anatase TiO{sub 2} investigated by pump-probe absorption spectroscopy

    SciTech Connect

    Matsuzaki, H. E-mail: okamotoh@k.u-tokyo.ac.jp; Matsui, Y.; Uchida, R.; Yada, H.; Terashige, T.; Li, B.-S.; Sawa, A.; Kawasaki, M.; Tokura, Y.; Okamoto, H. E-mail: okamotoh@k.u-tokyo.ac.jp

    2014-02-07

    The dynamics of photogenerated electrons and holes in undoped anatase TiO{sub 2} were studied by femtosecond absorption spectroscopy from the visible to mid-infrared region (0.1–2.0 eV). The transient absorption spectra exhibited clear metallic responses, which were well reproduced by a simple Drude model. No mid-gap absorptions originating from photocarrier localization were observed. The reduced optical mass of the photocarriers obtained from the Drude-model analysis is comparable to theoretically expected one. These results demonstrate that both photogenerated holes and electrons act as mobile carriers in anatase TiO{sub 2}. We also discuss scattering and recombination dynamics of photogenerated electrons and holes on the basis of the time dependence of absorption changes.

  10. Ultrafast carrier dynamics of titanic acid nanotubes investigated by transient absorption spectroscopy.

    PubMed

    Wang, Li; Zhao, Hui; Pan, Lin Yun; Weng, Yu Xiang; Nakato, Yoshihiro; Tamai, Naoto

    2010-12-01

    Carrier dynamics of titanic acid nanotubes (phase of H2Ti2O5.H2O) deposited on a quartz plate was examined by visible/near-IR transient absorption spectroscopy with an ultraviolet excitation. The carrier dynamics of titanic acid nanotubes follows the fast trapping process which attributed to the intrinsic tubular structure, the relaxation of shallow trapped carriers and the recombination as a second-order kinetic process. Transient absorption of titanic acid nanotubes was dominated by the absorption of surface-trapped holes in visible region around 500 nm, which was proved by the faster decay dynamics in the presence of polyvinyl alcohol as a hole-scavenger. However, the slow relaxation of free carriers was much more pronounced in the TiO2 single crystals, as compared with the transient absorption spectra of titanic acid nanotubes under the similar excitation.

  11. Characterization of selective binding of alkali cations with carboxylate by x-ray absorption spectroscopy of liquid microjets

    SciTech Connect

    Saykally, Richard J; Uejio, Janel S.; Schwartz, Craig P.; Duffin, Andrew M.; Drisdell, Walter S.; Cohen, Ronald C.; Saykally, Richard J.

    2008-01-08

    We describe an approach for characterizing selective binding between oppositely charged ionic functional groups under biologically relevant conditions. Relative shifts in K-shell x-ray absorption spectra of aqueous cations and carboxylate anions indicate the corresponding binding strengths via perturbations of carbonyl antibonding orbitals. XAS spectra measured for aqueous formate and acetate solutions containing lithium, sodium, and potassium cations reveal monotonically stronger binding of the lighter metals, supporting recent results from simulations and other experiments. The carbon K-edge spectra of the acetate carbonyl feature centered near 290 eV clearly indicate a preferential interaction of sodium versus potassium, which was less apparent with formate. These results are in accord with the Law of Matching Water Affinities, relating relative hydration strengths of ions to their respective tendencies to form contact ion pairs. Density functional theory calculations of K-shell spectra support the experimental findings.

  12. Minute Concentration Measurements of Simple Hydrocarbon Species Using Supercontinuum Laser Absorption Spectroscopy.

    PubMed

    Yoo, Jihyung; Traina, Nicholas; Halloran, Michael; Lee, Tonghun

    2016-06-01

    Minute concentration measurements of simple hydrocarbon gases are demonstrated using near-infrared supercontinuum laser absorption spectroscopy. Absorption-based gas sensors, particularly when combined with optical fiber components, can significantly enhance diagnostic capabilities to unprecedented levels. However, these diagnostic techniques are subject to limitations under certain gas sensing applications where interference and harsh conditions dominate. Supercontinuum laser absorption spectroscopy is a novel laser-based diagnostic technique that can exceed the above-mentioned limitations and provide accurate and quantitative concentration measurement of simple hydrocarbon species while maintaining compatibility with telecommunications-grade optical fiber components. Supercontinuum radiation generated using a highly nonlinear photonic crystal fiber is used to probe rovibrational absorption bands of four hydrocarbon species using full-spectral absorption diagnostics. Absorption spectra of methane (CH4), acetylene (C2H2), and ethylene (C2H4) were measured in the near-infrared spectrum at various pressures and concentrations to determine the accuracy and feasibility of the diagnostic strategy. Absorption spectra of propane (C3H8) were subsequently probed between 1650 nm and 1700 nm, to demonstrate the applicability of the strategy. Measurements agreed very well with simulated spectra generated using the HITRAN database as well as with previous experimental results. Absorption spectra of CH4, C2H2, and C2H4 were then analyzed to determine their respective measurement accuracy and detection limit. Concentration measurements integrated from experimental results were in very good agreement with independent concentration measurements. Calculated detection limits of CH4, C2H2, and C2H4 at room temperature and atmospheric pressure are 0.1%, 0.09%, and 0.17%, respectively.

  13. Determining Concentrations and Temperatures in Semiconductor Manufacturing Plasmas via Submillimeter Absorption Spectroscopy

    NASA Astrophysics Data System (ADS)

    Helal, Yaser H.; Neese, Christopher F.; De Lucia, Frank C.; Ewing, Paul R.; Agarwal, Ankur; Craver, Barry; Stout, Phillip J.; Armacost, Michael D.

    2016-06-01

    Plasmas used in the manufacturing processes of semiconductors are similar in pressure and temperature to plasmas used in studying the spectroscopy of astrophysical species. Likewise, the developed technology in submillimeter absorption spectroscopy can be used for the study of industrial plasmas and for monitoring manufacturing processes. An advantage of submillimeter absorption spectroscopy is that it can be used to determine absolute concentrations and temperatures of plasma species without the need for intrusive probes. A continuous wave, 500 - 750 GHz absorption spectrometer was developed for the purpose of being used as a remote sensor of gas and plasma species. An important part of this work was the optical design to match the geometry of existing plasma reactors in the manufacturing industry. A software fitting routine was developed to simultaneously fit for the background and absorption signal, solving for concentration, rotational temperature, and translational temperature. Examples of measurements made on inductively coupled plasmas will be demonstrated. We would like to thank the Texas Analog Center of Excellence/Semiconductor Research Corporation (TxACE/SRC) and Applied Materials for their support of this work.

  14. Absorption spectroscopy at the ultimate quantum limit from single-photon states

    NASA Astrophysics Data System (ADS)

    Whittaker, R.; Erven, C.; Neville, A.; Berry, M.; O’Brien, J. L.; Cable, H.; Matthews, J. C. F.

    2017-02-01

    Absorption spectroscopy is routinely used to characterise chemical and biological samples. For the state-of-the-art in laser absorption spectroscopy, precision is theoretically limited by shot-noise due to the fundamental Poisson-distribution of photon number in laser radiation. In practice, the shot-noise limit can only be achieved when all other sources of noise are eliminated. Here, we use wavelength-correlated and tuneable photon pairs to demonstrate how absorption spectroscopy can be performed with precision beyond the shot-noise limit and near the ultimate quantum limit by using the optimal probe for absorption measurement—single photons. We present a practically realisable scheme, which we characterise both the precision and accuracy of by measuring the response of a control feature. We demonstrate that the technique can successfully probe liquid samples and using two spectrally similar types of haemoglobin we show that obtaining a given precision in resolution requires fewer heralded single probe photons compared to using an idealised laser.

  15. Rapid, Time-Division Multiplexed, Direct Absorption- and Wavelength Modulation-Spectroscopy

    PubMed Central

    Klein, Alexander; Witzel, Oliver; Ebert, Volker

    2014-01-01

    We present a tunable diode laser spectrometer with a novel, rapid time multiplexed direct absorption- and wavelength modulation-spectroscopy operation mode. The new technique allows enhancing the precision and dynamic range of a tunable diode laser absorption spectrometer without sacrificing accuracy. The spectroscopic technique combines the benefits of absolute concentration measurements using calibration-free direct tunable diode laser absorption spectroscopy (dTDLAS) with the enhanced noise rejection of wavelength modulation spectroscopy (WMS). In this work we demonstrate for the first time a 125 Hz time division multiplexed (TDM-dTDLAS-WMS) spectroscopic scheme by alternating the modulation of a DFB-laser between a triangle-ramp (dTDLAS) and an additional 20 kHz sinusoidal modulation (WMS). The absolute concentration measurement via the dTDLAS-technique allows one to simultaneously calibrate the normalized 2f/1f-signal of the WMS-technique. A dTDLAS/WMS-spectrometer at 1.37 μm for H2O detection was built for experimental validation of the multiplexing scheme over a concentration range from 50 to 3000 ppmV (0.1 MPa, 293 K). A precision of 190 ppbV was achieved with an absorption length of 12.7 cm and an averaging time of two seconds. Our results show a five-fold improvement in precision over the entire concentration range and a significantly decreased averaging time of the spectrometer. PMID:25405508

  16. High sensitivity ultra-broad-band absorption spectroscopy of inductively coupled chlorine plasma

    NASA Astrophysics Data System (ADS)

    Marinov, Daniil; Foucher, Mickaël; Campbell, Ewen; Brouard, Mark; Chabert, Pascal; Booth, Jean-Paul

    2016-06-01

    We propose a method to measure the densities of vibrationally excited Cl2(v) molecules in levels up to v  =  3 in pure chlorine inductively coupled plasmas (ICPs). The absorption continuum of Cl2 in the 250-450 nm spectral range is deconvoluted into the individual components originating from the different vibrational levels of the ground state, using a set of ab initio absorption cross sections. It is shown that gas heating at constant pressure is the major depletion mechanism of the Cl2 feedstock in the plasma. In these line-integrated absorption measurements, the absorption by the hot (and therefore rarefied) Cl2 gas in the reactor centre is masked by the cooler (and therefore denser) Cl2 near the walls. These radial gradients in temperature and density make it difficult to assess the degree of vibrational excitation in the centre of the reactor. The observed line-averaged vibrational distributions, when analyzed taking into account the radial temperature gradient, suggest that vibrational and translational degrees of freedom in the plasma are close to local equilibrium. This can be explained by efficient vibrational-translational (VT) relaxation between Cl2 and Cl atoms. Besides the Cl2(v) absorption band, a weak continuum absorption is observed at shorter wavelengths, and is attributed to photodetachment of Cl- negative ions. Thus, line-integrated densities of negative ions in chlorine plasmas can be directly measured using broad-band absorption spectroscopy.

  17. Evaluation of ammonia absorption coefficients by photoacoustic spectroscopy for detection of ammonia levels in human breath

    NASA Astrophysics Data System (ADS)

    Dumitras, D. C.; Dutu, D. C.; Matei, C.; Cernat, R.; Banita, S.; Patachia, M.; Bratu, A. M.; Petrus, M.; Popa, C.

    2011-04-01

    Photoacoustic spectroscopy represents a powerful technique for measuring extremely low absorptions independent of the path length and offers a degree of parameter control that cannot be attained by other methods. We report precise measurements of the ammonia absorption coefficients at the CO2 laser wavelengths by using a photoacoustic (PA) cell in an extracavity configuration and we compare our results with other values reported in the literature. Ammonia presents a clear fingerprint spectrum and high absorption strengths in the CO2 wavelengths region. Because more than 250 molecular gases of environmental concern for atmospheric, industrial, medical, military, and scientific spheres exhibit strong absorption bands in the region 9.2-10.8 μm, we have chosen a frequency tunable CO2 laser. In the present work, ammonia absorption coefficients were measured at both branches of the CO2 laser lines by using a calibrated mixture of 10 ppm NH3 in N2. We found the maximum absorption in the 9 μm region, at 9R(30) line of the CO2 laser. One of the applications based on the ammonia absorption coefficients is used to measure the ammonia levels in exhaled human breath. This can be used to determine the exact time necessary at every session for an optimal degree of dialysis at patients with end-stage renal disease.

  18. Influence of temperature and turbidity on water COD detection by UV absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Zhou, Kun-peng; Bi, Wei-hong; Zhang, Qi-hang; Fu, Xing-hu; Wu, Guo-qing

    2016-11-01

    Ultraviolet (UV) absorption spectroscopy is used to detect the concentration of water chemical oxygen demand (COD). The UV absorption spectra of COD solutions are analyzed qualitatively and quantitatively. The partial least square (PLS) algorithm is used to model COD solution and the modeling results are compared. The influence of environmental temperature and turbidity is analyzed. These results show that the influence of temperature on the predicted value can be ignored. However, the change of turbidity can affect the detection results of UV spectra, and the COD detection error can be effectively compensated by establishing the single-element regression model.

  19. Thin-film absorption coefficients by attenuated-total-reflection spectroscopy.

    PubMed

    Holm, R T; Palik, E D

    1978-02-01

    The application of attenuated-total-reflection spectroscopy to the measurement of the absorption coefficient of thin films is presented. For low absorption the sensitivity of ATR is discussed in terms of the concept of an effective thickness. Both the case in which the refractive index of the film is higher and the case in which it is lower than that of the ATR trapezoid are considered. Experimental ATR data for antireflection-coating materials for laser windows is analyzed and compared with calorimetric data.

  20. Assignment of benzodiazepine UV absorption spectra by the use of photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Khvostenko, O. G.; Tzeplin, E. E.; Lomakin, G. S.

    2002-04-01

    Correlations between singlet transition energies and energy gaps of corresponding pairs of occupied and unoccupied molecular orbitals were revealed in a series of benzodiazepines. The occupied orbital energies were taken from the photoelectron spectra of the compound investigated, the unoccupied ones were obtained from MNDO/d calculations, and the singlet energies were taken from the UV absorption spectra. The correspondence of the singlet transitions to certain molecular orbitals was established using MNDO/d calculations and comparing between UV and photoelectron spectra. It has been concluded that photoelectron spectroscopy can be applied for interpretation of UV absorption spectra of various compounds on the basis of similar correlations.

  1. Interactions of hypericin with a model mutagen - Acridine orange analyzed by light absorption and fluorescence spectroscopy

    NASA Astrophysics Data System (ADS)

    Pietrzak, Monika; Szabelski, Mariusz; Kasparek, Adam; Wieczorek, Zbigniew

    2017-02-01

    The present study was designed to estimate the ability of hypericin to interact with a model mutagen - acridine orange. The hetero-association of hypericin and acridine orange was investigated with absorption and fluorescence spectroscopy methods in aqueous solution of DMSO. The data indicate that hypericin forms complexes with acridine orange and that the association constants are relatively high and depend on DMSO concentration. The absorption spectra of the hypericin - acridine orange complexes were examined as well. Owing to its ability to interact with flat aromatic compounds, hypericin may potentially be used as an interceptor molecule.

  2. 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, CuFe2 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 CuFe2 O 4. A phase pure tetragonal CuFe2 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 structure (XANES), extended X-raymore » 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

  3. 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

    SciTech Connect

    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.

    2016-06-06

    Copper ferrite, CuFe2 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 CuFe2 O 4. A phase pure tetragonal CuFe2 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 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). 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.

  4. Practical review on the use of synchrotron based micro- and nano- X-ray fluorescence mapping and X-ray absorption spectroscopy to investigate the interactions between plants and engineered nanomaterials.

    PubMed

    Castillo-Michel, Hiram A; Larue, Camille; Pradas Del Real, Ana E; Cotte, Marine; Sarret, Geraldine

    2017-01-01

    The increased use of engineered nanomaterials (ENMs) in commercial products and the continuous development of novel applications, is leading to increased intentional and unintentional release of ENMs into the environment with potential negative impacts. Particularly, the partition of nanoparticles (NPs) to waste water treatment plant (WWTP) sludge represents a potential threat to agricultural ecosystems where these biosolids are being applied as fertilizers. Moreover, several applications of ENMs in agriculture and soil remediation are suggested. Therefore, detailed risk assessment should be done to evaluate possible secondary negative impacts. The impact of ENMS on plants as central component of ecosystems and worldwide food supply is of primary relevance. Understanding the fate and physical and chemical modifications of NPs in plants and their possible transfer into food chains requires specialized analytical techniques. Due to the importance of both chemical and physical factors to consider for a better understanding of ENMs behavior in complex matrices, these materials can be considered a new type of analyte. An ideal technique should require minimal sample preparation, be non-destructive, and offer the best balance between sensitivity, chemical specificity, and spatial resolution. Synchrotron radiation (SR) techniques are particularly adapted to investigate localization and speciation of ENMs in plants. SR X-ray fluorescence mapping (SR-XFM) offers multi-elemental detection with lateral resolution down to the tens of nm, in combination with spatially resolved X-ray absorption spectroscopy (XAS) speciation. This review will focus on important methodological aspects regarding sample preparation, data acquisition and data analysis of SR-XFM/XAS to investigate interactions between plants and ENMs.

  5. Abrupt versus Gradual Spin-Crossover in Fe(II)(phen)2(NCS)2 and Fe(III)(dedtc)3 Compared by X-ray Absorption and Emission Spectroscopy and Quantum-Chemical Calculations.

    PubMed

    Mebs, Stefan; Braun, Beatrice; Kositzki, Ramona; Limberg, Christian; Haumann, Michael

    2015-12-21

    Molecular spin-crossover (SCO) compounds are attractive for information storage and photovoltaic technologies. We compared two prototypic SCO compounds with Fe(II)N6 (1, [Fe(phen)2(NCS)2], with phen = 1,10-phenanthroline) or Fe(III)S6 (2, [Fe(dedtc)3], with dedtc = N,N'-diethyldithiocarbamate) centers, which show abrupt (1) or gradual (2) thermally induced SCO, using K-edge X-ray absorption and Kβ emission spectroscopy (XAS/XES) in a 8-315 K temperature range, single-crystal X-ray diffraction (XRD), and density functional theory (DFT). Core-to-valence and valence-to-core electronic transitions in the XAS/XES spectra and bond lengths change from XRD provided benchmark data, verifying the adequacy of the TPSSh/TZVP DFT approach for the description of low-spin (LS) and high-spin (HS) species. Determination of the spin densities, charge distributions, bonding descriptors, and valence-level configurations, as well as similar experimental and calculated enthalpy changes (ΔH), suggested that the varying metal-ligand bonding properties and deviating electronic structures converge to similar enthalpic contributions to the free-energy change (ΔG) and thus presumably are not decisive for the differing SCO behavior of 1 and 2. Rather, SCO seems to be governed by vibrational contributions to the entropy changes (ΔS) in both complexes. Intra- and intermolecular interactions in crystals of 1 and 2 were identified by atoms-in-molecules analysis. Thermal excitation of individual dedtc ligand vibrations accompanies the gradual SCO in 2. In contrast, extensive inter- and intramolecular phen/NCS vibrational mode coupling may be an important factor in the cooperative SCO behavior of 1.

  6. Molecular scale shock response: electronic absorption spectroscopy of laser shocked explosives

    NASA Astrophysics Data System (ADS)

    McGrane, Shawn; Whitley, Von; Moore, David; Bolme, Cindy; Eakins, Daniel

    2009-06-01

    Single shot spectroscopies are being employed to answer questions fundamental to shock initiation of explosives. The goals are to: 1) determine the extent to which electronic excitations are, or are not, involved in shock induced reactions, 2) test the multiphonon up-pumping hypothesis in explosives, and 3) provide data on the initial evolution of temperature and chemistry following the shock loading of explosives on scales amenable to comparison to molecular dynamics simulations. The data presented in this talk are focused on answering the first question. Recent experimental results measuring the time history of ultraviolet/visible absorption spectroscopy of laser shocked explosive thin films and single crystals will be discussed.

  7. Os layers spontaneously deposited on the Pt(111) electrode : XPS, STM and GIF-XAS study.

    SciTech Connect

    Rhee, C. K.; Wakisaka, M.; Tolmachev, Y.; Johnston, C.; Haasch, R.; Attenkofer, K.; Lu, G. Q.; You, H.; Wieckowski, A.; Univ. of Illinois Champaigh-Urbana

    2003-01-01

    Scanning tunneling microscopy (STM) characterized adlayers of spontaneously deposited osmium on a Pt(111) electrode were investigated using ex-situ X-ray photoemission spectroscopy (XPS) and in-situ grazing incidence fluorescence X-ray absorption spectroscopy (GIF-XAS). After a single spontaneous deposition, monoatomic (or nearly monoatomic) nanoislands of osmium are formed. The island diameter varies from 2 to 5 nm depending on the Os coverage, which in turn is adjusted by varying the concentration of the Os precursor salt (OsCl3) in the deposition bath and/or by the deposition time. XPS reveals three oxidation states: a metallic Os (the 4f7/2 core level binding energy of 50.8 eV), Os(IV) (51.5 eV) and Os(VIII) (52.4 eV). The metallic osmium exists at potentials below 500 mV (vs. RHE) while above 500 mV osmium is oxidized to Os(IV). Electrodissolution of osmium begins above 900 mV and occurs simultaneously with platinum oxidation. At ca. 1200 mV V versus the RHE reference, the oxidation state of some small amounts of osmium that survive dissolution is the Os(VIII). We demonstrate, for the first time, that mixed or odd valencies of osmium exist on the platinum surface at potentials higher that 800 mV. In-situ GIF-XAS measurements of an Os LIII edge also reveal the presence of three Os oxidation states. Namely, below the electrode potential of 400 mV, the X-ray fluorescent energy at maximum absorption is 10.8765 keV, and is characteristic of the metallic Os. In the potential range between 500 and 1000 mV this energy is gradually shifted to higher values, assignable to higher valencies of osmium, like Os(IV). This tendency continues to higher potentials consistent with the third, highly oxidized osmium form present, most likely Os(VIII). The variation of the 'raw edge jump height' of Os with the electrode potential, which is equivalent to a drop in osmium surface concentration, demonstrates that the electrochemical stripping of Os begins below 1.0 V versus RHE, as

  8. A quantitative description of the ground-state wave function of Cu(A) by X-ray absorption spectroscopy: comparison to plastocyanin and relevance to electron transfer.

    PubMed

    DeBeer George, S; Metz, M; Szilagyi, R K; Wang, H; Cramer, S P; Lu, Y; Tolman, W B; Hedman, B; Hodgson, K O; Solomon, E I

    2001-06-20

    To evaluate the importance of the electronic structure of Cu(A) to its electron-transfer (ET) function, a quantitative description of the ground-state wave function of the mixed-valence (MV) binuclear Cu(A) center engineered into Pseudomonas aeruginosa azurin has been developed, using a combination of S K-edge and Cu L-edge X-ray absorption spectroscopies (XAS). Parallel descriptions have been developed for a binuclear thiolate-bridged MV reference model complex ([(L(i)(PrdacoS)Cu)(2)](+)) and a homovalent (II,II) analogue ([L(i)(Pr2tacnS)Cu)(2)](2+), where L(i)(PrdacoS) and L(i)(Pr2tacnS) are macrocyclic ligands with attached thiolates that bridge the Cu ions. Previous studies have qualitatively defined the ground-state wave function of Cu(A) in terms of ligand field effects on the orbital orientation and the presence of a metal--metal bond. The studies presented here provide further evidence for a direct Cu--Cu interaction and, importantly, experimentally quantify the covalency of the ground-state wave function. The experimental results are further supported by DFT calculations. The nature of the ground-state wave function of Cu(A) is compared to that of the well-defined blue copper site in plastocyanin, and the importance of this wave function to the lower reorganization energy and ET function of Cu(A) is discussed. This wave function incorporates anisotropic covalency into the intra- and intermolecular ET pathways in cytochrome c oxidase. Thus, the high covalency of the Cys--Cu bond allows a path through this ligand to become competitive with a shorter His path in the intramolecular ET from Cu(A) to heme a and is particularly important for activating the intermolecular ET path from heme c to Cu(A).

  9. Submillimeter Absorption Spectroscopy in Semiconductor Manufacturing Plasmas and Comparison to Theoretical Models

    NASA Astrophysics Data System (ADS)

    Helal, Yaser H.; Neese, Christopher F.; De Lucia, Frank C.; Ewing, Paul R.; Agarwal, Ankur; Craver, Barry; Stout, Phillip J.; Armacost, Michael D.

    2015-06-01

    Plasmas used in the semiconductor manufacturing industry are of a similar nature to the environments often created for submillimeter spectroscopic study of astrophysical species. At the low operating pressures of these plasmas, submillimeter absorption spectroscopy is a method capable of measuring the abundances and temperatures of molecules, radicals, and ions without disturbing any of the properties of the plasma. These measurements provide details and insight into the interactions and reactions occurring within the plasma and their implications for semiconductor manufacturing processes. A continuous wave, 500 to 750 GHz, absorption spectrometer was designed and used to make measurements of species in semiconductor processing plasmas. Comparisons with expectations from theoretical plasma models provide a basis for validating and improving these models, which is a complex and difficult science itself. Furthermore, these comparisons are an evaluation for the use of submillimeter spectroscopy as a diagnostic tool in manufacturing processes.

  10. Electrochemical flowcell for in-situ investigations by soft x-ray absorption and emission spectroscopy

    SciTech Connect

    Schwanke, C.; Lange, K. M.; Golnak, R.; Xiao, J.

    2014-10-15

    A new liquid flow-cell designed for electronic structure investigations at the liquid-solid interface by soft X-ray absorption and emission spectroscopy is presented. A thin membrane serves simultaneously as a substrate for the working electrode and solid state samples as well as for separating the liquid from the surrounding vacuum conditions. In combination with counter and reference electrodes this approach allows in-situ studies of electrochemical deposition processes and catalytic reactions at the liquid-solid interface in combination with potentiostatic measurements. As model system in-situ monitoring of the deposition process of Co metal from a 10 mM CoCl{sub 2} aqueous solution by X-ray absorption and emission spectroscopy is presented.

  11. Electrochemical flowcell for in-situ investigations by soft x-ray absorption and emission spectroscopy.

    PubMed

    Schwanke, C; Golnak, R; Xiao, J; Lange, K M

    2014-10-01

    A new liquid flow-cell designed for electronic structure investigations at the liquid-solid interface by soft X-ray absorption and emission spectroscopy is presented. A thin membrane serves simultaneously as a substrate for the working electrode and solid state samples as well as for separating the liquid from the surrounding vacuum conditions. In combination with counter and reference electrodes this approach allows in-situ studies of electrochemical deposition processes and catalytic reactions at the liquid-solid interface in combination with potentiostatic measurements. As model system in-situ monitoring of the deposition process of Co metal from a 10 mM CoCl2 aqueous solution by X-ray absorption and emission spectroscopy is presented.

  12. Determination of copper, zinc and iron in broncho-alveolar lavages by atomic absorption spectroscopy.

    PubMed

    Harlyk, C; Mccourt, J; Bordin, G; Rodriguez, A R; van der Eeckhout, A

    1997-11-01

    Concentrations of Zn, Cu and Fe were measured in 157 broncho-alveolar lavages (BAL), before and after centrifugation, collected at the Leuven University Hospital (Belgium). Zn was measured by flame-atomic absorption spectroscopy, using direct calibration, while Cu and Fe were determined by electrothermal atomic absorption spectroscopy, using the method of standard additions. For Fe only 56 samples were measured. Most of the studied elements are present in the liquid phase (supernatant). About 90% of Cu concentrations lie between 0 and 15 micrograms/kg, while 90% of Zn concentrations are lower than 230 micrograms/kg, with 30% between 30 and 70 micrograms/kg, and 50% between 100 and 200 micrograms/kg. There seems to be a reverse relationship between Cu and Zn levels with high Cu going along with low Zn and vice versa.

  13. Development of Ta-based Superconducting Tunnel Junction X-ray Detectors for Fluorescence XAS

    SciTech Connect

    Friedrich, S; Drury, O; Hall, J; Cantor, R

    2009-09-23

    We are developing superconducting tunnel junction (STJ) soft X-ray detectors for chemical analysis of dilute samples by fluorescence-detected X-ray absorption spectroscopy (XAS). Our 36-pixel Nb-based STJ spectrometer covers a solid angle {Omega}/4{pi} {approx} 10{sup -3}, offers an energy resolution of {approx}10-20 eV FWHM for energies up to {approx}1 keV, and can be operated at total count rates of {approx}10{sup 6} counts/s. For increased quantum efficiency and cleaner response function, we have now started the development of Ta-based STJ detector arrays. Initial devices modeled after our Nb-based STJs have an energy resolution below 10 eV FWHM for X-ray energies below 1 keV, and pulse rise time discrimination can be used to improve their response function for energies up to several keV. We discuss the performance of the Ta-STJs and outline steps towards the next-generation of large STJ detector arrays with higher sensitivity.

  14. 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

  15. Development of Ta-based Superconducting Tunnel Junction X-ray Detectors for Fluorescence XAS

    SciTech Connect

    Friedrich, Stephan; Drury, Owen B.; Hall, John; Cantor, Robin

    2010-06-23

    We are developing superconducting tunnel junction (STJ) soft X-ray detectors for chemical analysis of dilute samples by fluorescence-detected X-ray absorption spectroscopy (XAS). Our 36-pixel Nb-based STJ spectrometer covers a solid angle {Omega}/4{pi}{approx_equal}10{sup -3}, offers an energy resolution of {approx}10-20 eV FWHM for energies up to {approx}1 keV, and can be operated at total count rates of {approx}10{sup 6} counts/s. For increased quantum efficiency and cleaner response function, we have now started the development of Ta-based STJ detector arrays. Initial devices modeled after our Nb-based STJs have an energy resolution below 10 eV FWHM for X-ray energies below 1 keV, and pulse rise time discrimination can be used to improve their response function for energies up to several keV. We discuss the performance of the Ta-STJs and outline steps towards the next-generation of large STJ detector arrays with higher sensitivity.

  16. Progress in Applying Tunable Diode Laser Absorption Spectroscopy to Scramjet Isolators and Combustors

    DTIC Science & Technology

    2010-05-01

    AFRL-RZ-WP-TP-2010-2146 PROGRESS IN APPLYING TUNABLE DIODE LASER ABSORPTION SPECTROSCOPY TO SCRAMJET ISOLATORS AND COMBUSTORS Michael S... COMBUSTORS 5a. CONTRACT NUMBER IN HOUSE 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 61102F 6. AUTHOR(S) Michael S. Brown, Skip Williams...paths -- scramjet engines in particular. In this report we summarize our progress in applying TDLAS to scramjet isolators and combustors . 15

  17. X-ray absorption spectroscopy beyond the core-hole lifetime

    SciTech Connect

    Haemaelaeinen, K.; Hastings, J.B.; Siddons, D.P.; Berman, L.

    1992-01-01

    A new technique to overcome the core-hole lifetime broadening in x-ray absorption spectroscopy is presented. It utilizes a high resolution fluorescence spectrometer which can be used to analyze the fluorescence photon energy with better resolution than the natural lifetime width. Furthermore, the high resolution spectrometer can also be used to select the final state in the fluorescence process which can offer spin selectivity even without long range magnetic order in the sample.

  18. X-ray absorption spectroscopy beyond the core-hole lifetime

    SciTech Connect

    Haemaelaeinen, K.; Hastings, J.B.; Siddons, D.P.; Berman, L.

    1992-10-01

    A new technique to overcome the core-hole lifetime broadening in x-ray absorption spectroscopy is presented. It utilizes a high resolution fluorescence spectrometer which can be used to analyze the fluorescence photon energy with better resolution than the natural lifetime width. Furthermore, the high resolution spectrometer can also be used to select the final state in the fluorescence process which can offer spin selectivity even without long range magnetic order in the sample.

  19. Conformational study of the chromophore of C-phycocyanin by resonance raman and electronic absorption spectroscopy.

    NASA Astrophysics Data System (ADS)

    Margulies, L.; Toporowicz, M.

    1988-05-01

    The conformation of the chromophore of C-phycocyanin (PC) was investigated by using electronic absorption and resonance Raman spectroscopy, and theoretical calculations. Using an A-dihydrobilindione as model compound, the syn, syn, syn conformation was established for the isolated chromophore in solution. For the native PC, the best results were obtained by considering the syn, syn, anti conformation, although the possibility of having a syn, anti, anti conformation could not be excluded.

  20. Intracavity Laser Absorption Spectroscopy of Platinum Nitride in the Near Infrared

    NASA Astrophysics Data System (ADS)

    O'Brien, Leah C.; Womack, Kaitlin A.; O'Brien, James J.; Whittemore, Sean

    2013-06-01

    The (2,0) band of the A^{2}Σ^{-} - X^{2}Π_{1/2} electronic transition of PtN has been recorded using intracavity laser absorption spectroscopy. Transitions from ^{194}PtN, ^{195}PtN, and ^{196}PtN isotopologues are observed, as well as the nuclear hyperfine splitting due to ^{195}Pt with I=1/2. The results of the analysis will be presented and compared with ab initio calculations.

  1. Application of microemulsions in determination of chromium naphthenate in gasoline by flame atomic absorption spectroscopy.

    PubMed

    Du, B; Wei, Q; Wang, S; Yu, W

    1997-10-01

    A new method using microemulsified samples is presented. It is for the determination of chromium naphthenate in gasoline by flame absorption spectroscopy. The method has the advantage of simplicity, speed and the use of aqueous standards for calibration instead of organic standards. Coexistent elements do not disturb the determination. Results obtained by this method were better than those obtained by other methods for the same samples.

  2. Nile blue shows its true colors in gas-phase absorption and luminescence ion spectroscopy

    NASA Astrophysics Data System (ADS)

    Stockett, M. H.; Houmøller, J.; Brøndsted Nielsen, S.

    2016-09-01

    Nile blue is used extensively in biology as a histological stain and fluorescent probe. Its absorption and emission spectra are strongly solvent dependent, with variations larger than 100 nm. The molecule is charged due to an iminium group, and it is therefore an obvious target for gas-phase ion spectroscopy. Here we report the absorption and emission spectra of the mass-selected bare ions isolated in vacuo, and based on our results we revisit the interpretation of solution-phase spectra. An accelerator mass spectrometer was used for absorption spectroscopy where the absorption is represented by the yield of photofragment ions versus excitation wavelength (action spectroscopy). The luminescence experiments were done with a newly built ion trap setup equipped with an electrospray ion source, and some details on the mass selection technique will be given which have not been described before. In vacuo, the absorption and emission maxima are at 580 ± 10 nm and 628 ± 1 nm. These values are somewhat blue-shifted relative to those obtained in most solvents; however, they are much further to the red than those in some of the most non-polar solvents. Furthermore, the Stokes shift in the gas phase (1300 cm-1) is much smaller than that in these non-polar solvents but similar to that in polar ones. An explanation based on charge localization by solvent dipoles, or by counterions in some non-polar solvents, can fully account for these findings. Hence in the case of ions, it is nontrivial to establish intrinsic electronic transition energies from solvatochromic shifts alone.

  3. Supercontinuum high-speed cavity-enhanced absorption spectroscopy for sensitive multispecies detection.

    PubMed

    Werblinski, Thomas; Lämmlein, Bastian; Huber, Franz J T; Zigan, Lars; Will, Stefan

    2016-05-15

    Cavity-enhanced absorption spectroscopy is promising for many applications requiring a very high concentration sensitivity but often accompanied by low temporal resolution. In this Letter, we demonstrate a broadband cavity-enhanced absorption spectrometer capable of detection rates of up to 50 kHz, based on a spatially coherent supercontinuum (SC) light source and an in-house-built, high-speed near-infrared spectrograph. The SC spectrometer allows for the simultaneous quantitative detection of CO2, C2H2, and H2O within a spectral range from 1420 to 1570 nm. Using cavity mirrors with a specified reflectivity of R=98.0±0.3% a minimal spectrally averaged absorption coefficient of αmin=1·10-5  cm-1 can be detected at a repetition rate of 50 kHz.

  4. Gas trace detection with cavity enhanced absorption spectroscopy: a review of its process in the field

    NASA Astrophysics Data System (ADS)

    Liu, Siqi; Luo, Zhifu; Tan, Zhongqi; Long, Xingwu

    2016-11-01

    Cavity-enhanced absorption spectroscopy (CEAS) is a technology in which the intracavity absorption is deduced from the intensity of light transmitted by the high finesse optical cavity. Then the samples' parameters, such as their species, concentration and absorption cross section, would be detection. It was first proposed and demonstrated by Engeln R. [1] and O'Keefe[2] in 1998. This technology has extraordinary detection sensitivity, high resolution and good practicability, so it is used in many fields , such as clinical medicine, gas detection and basic physics research. In this paper, we focus on the use of gas trace detection, including the advance of CEAS over the past twenty years, the newest research progresses, and the prediction of this technology's development direction in the future.

  5. Photodissociation Structural Dynamics of TrirutheniumDodecacarbonyl Investigated by X-ray Transient Absorption Spectroscopy

    NASA Astrophysics Data System (ADS)

    Harpham, Michael R.; Stickrath, Andrew, B.; Zhang, Xiaoyi,; Huang, Jier; Mara, Michael W.; Chen, Lin X.; Liu, Di-Jia

    2013-10-01

    The molecular and electronic structures of the transient intermediates generated from the photolysis of trirutheniumdodecacarbonyl, Ru3(CO)12, by ultrafast UV (351 nm) laser excitation were investigated using X-ray transient absorption (XTA) spectroscopy. The electronic configuration change and nuclear rearrangement after the dissociation of carbonyls were observed at ruthenium K-edge X-ray absorption near edge structure and X-ray absorption fine structure spectra. Analysis of XTA data, acquired after 100, 200, and 400 ps and 300 ns time delay following the photoexcitation, identified the presence of three intermediate species with Ru3(CO)10 being the most dominating one. The results set an example of applying XTA in capturing both transient electronic and nuclear configurations in metal clusters simulating catalysts in chemical reactions.

  6. Absorption spectroscopy setup for determination of whole human blood and blood-derived materials spectral characteristics

    NASA Astrophysics Data System (ADS)

    Wróbel, M. S.; Gnyba, M.; Milewska, D.; Mitura, K.; Karpienko, K.

    2015-09-01

    A dedicated absorption spectroscopy system was set up using tungsten-halogen broadband source, optical fibers, sample holder, and a commercial spectrometer with CCD array. Analysis of noise present in the setup was carried out. Data processing was applied to the absorption spectra to reduce spectral noise, and improve the quality of the spectra and to remove the baseline level. The absorption spectra were measured for whole blood samples, separated components: plasma, saline, washed erythrocytes in saline and human whole blood with biomarkers - biocompatible nanodiamonds (ND). Blood samples had been derived from a number of healthy donors. The results prove a correct setup arrangement, with adequate preprocessing of the data. The results of blood-ND mixtures measurements show no toxic effect on blood cells, which proves the NDs as a potential biocompatible biomarkers.

  7. Electronic structure of warm dense copper studied by ultrafast x-ray absorption spectroscopy.

    PubMed

    Cho, B I; Engelhorn, K; Correa, A A; Ogitsu, T; Weber, C P; Lee, H J; Feng, J; Ni, P A; Ping, Y; Nelson, A J; Prendergast, D; Lee, R W; Falcone, R W; Heimann, P A

    2011-04-22

    We use time-resolved x-ray absorption spectroscopy to investigate the unoccupied electronic density of states of warm dense copper that is produced isochorically through the absorption of an ultrafast optical pulse. The temperature of the superheated electron-hole plasma, which ranges from 4000 to 10 000 K, was determined by comparing the measured x-ray absorption spectrum with a simulation. The electronic structure of warm dense copper is adequately described with the high temperature electronic density of state calculated by the density functional theory. The dynamics of the electron temperature is consistent with a two-temperature model, while a temperature-dependent electron-phonon coupling parameter is necessary.

  8. Deep ultraviolet Raman spectroscopy: A resonance-absorption trade-off illustrated by diluted liquid benzene

    NASA Astrophysics Data System (ADS)

    Chadwick, C. T.; Willitsford, A. H.; Philbrick, C. R.; Hallen, H. D.

    2015-12-01

    The magnitude of resonance Raman intensity, in terms of the real signal level measured on-resonance compared to the signal level measured off-resonance for the same sample, is investigated using a tunable laser source. Resonance Raman enhancements, occurring as the excitation energy is tuned through ultraviolet absorption lines, are used to examine the 1332 cm-1 vibrational mode of diamond and the 992 cm-1 ring-breathing mode of benzene. Competition between the wavelength dependent optical absorption and the magnitude of the resonance enhancement is studied using measured signal levels as a function of wavelength. Two system applications are identified where the resonance Raman significantly increases the real signal levels despite the presence of strong absorption: characterization of trace species in laser remote sensing and spectroscopy of the few molecules in the tiny working volumes of near-field optical microscopy.

  9. A sample holder for soft x-ray absorption spectroscopy of liquids in transmission mode.

    PubMed

    Schreck, Simon; Gavrila, Gianina; Weniger, Christian; Wernet, Philippe

    2011-10-01

    A novel sample holder for soft x-ray absorption spectroscopy of liquids in transmission mode based on sample cells with x-ray transparent silicon nitride membranes is introduced. The sample holder allows for a reliable preparation of ultrathin liquid films with an adjustable thickness in the nm-μm range. This enables measurements of high quality x-ray absorption spectra of liquids in transmission mode, as will be shown for the example of liquid H(2)O, aqueous solutions of 3d-transition metal ions and alcohol-water mixtures. The fine structure of the x-ray absorption spectra is not affected by the sample thickness. No effects of the silicon nitride membranes were observed in the spectra. It is shown how an inhomogeneous thickness of the sample affects the spectra and how this can be avoided.

  10. Sensitive and rapid laser diagnostic for shock tube kinetics studies using cavity-enhanced absorption spectroscopy.

    PubMed

    Sun, Kai; Wang, Shengkai; Sur, Ritobrata; Chao, Xing; Jeffries, Jay B; Hanson, Ronald K

    2014-04-21

    We report the first application of cavity-enhanced absorption spectroscopy (CEAS) using a coherent light source for sensitive and rapid gaseous species time-history measurements in a shock tube. Off-axis alignment and fast scanning of the laser wavelength were used to minimize coupling noise in a low-finesse cavity. An absorption gain factor of 83 with a measurement time resolution of 20 µs was demonstrated for C2H2 detection using a near-infrared transition near 1537 nm, corresponding to a noise-equivalent detection limit of 20 ppm at 296 K and 76 ppm at 906 K at 50 kHz. This substantial gain in signal, relative to conventional single-pass absorption, will enable ultra-sensitive species detection in shock tube kinetics studies, particularly useful for measurements of minor species and for studies of dilute reactive systems.

  11. Spectroscopy of CuN in the Near Infrared by Intracavity Laser Absorption Spectroscopy

    NASA Astrophysics Data System (ADS)

    O'Brien, Leah C.; Womack, Kaitlin A.; O'Brien, James J.

    2012-06-01

    Transitions with red-degraded bandheads have been identified at 13005, 12963, 12957, and 12948 cm-1. One P and one R branch are identified in each transition. We have tentatively assigned these transitions as absorption from the X 3Σ- ground state of CuN. Rotational analyses of these bands are in progress, and results will be presented. A strong perturbation is observed in one of the excited states. The electronic structure of CuN will be discussed and compared with predicted electronic states from theoretical calculations. The gas phase CuN molecules were produced using a copper hollow cathode in a plasma discharge.

  12. Picosecond and femtosecond X-ray absorption spectroscopy of molecular systems.

    PubMed

    Chergui, Majed

    2010-03-01

    The need to visualize molecular structure in the course of a chemical reaction, a phase transformation or a biological function has been a dream of scientists for decades. The development of time-resolved X-ray and electron-based methods is making this true. X-ray absorption spectroscopy is ideal for the study of structural dynamics in liquids, because it can be implemented in amorphous media. Furthermore, it is chemically selective. Using X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) in laser pump/X-ray probe experiments allows the retrieval of the local geometric structure of the system under study, but also the underlying photoinduced electronic structure changes that drive the structural dynamics. Recent developments in picosecond and femtosecond X-ray absorption spectroscopy applied to molecular systems in solution are reviewed: examples on ultrafast photoinduced processes such as intramolecular electron transfer, low-to-high spin change, and bond formation are presented.

  13. Mid-infrared laser absorption spectroscopy of NO2 at elevated temperatures

    NASA Astrophysics Data System (ADS)

    Sur, Ritobrata; Peng, Wen Yu; Strand, Christopher; Mitchell Spearrin, R.; Jeffries, Jay B.; Hanson, Ronald K.; Bekal, Anish; Halder, Purbasha; Poonacha, Samhitha P.; Vartak, Sameer; Sridharan, Arun K.

    2017-01-01

    A mid-infrared quantum cascade laser absorption sensor was developed for in-situ detection of NO2 in high-temperature gas environments. A cluster of spin-split transitions near 1599.9 cm-1 from the ν3 absorption band of NO2 was selected due to the strength of these transitions and the low spectral interference from water vapor within this region. Temperature- and species-dependent collisional broadening parameters of ten neighboring NO2 transitions with Ar, O2, N2, CO2 and H2O were measured and reported. The spectral model was validated through comparisons with direct absorption spectroscopy measurements of NO2 seeded in various bath gases. The performance of the scanned wavelength modulation spectroscopy (WMS)-based sensor was demonstrated in a combustion exhaust stream seeded with varying flow rates of NO2, achieving reliable detection of 1.45 and 1.6 ppm NO2 by mole at 600 K and 800 K, respectively, with a measurement uncertainty of ±11%. 2σ noise levels of 360 ppb and 760 ppb were observed at 600 K and 800 K, respectively, in an absorption path length of 1.79 m.

  14. Wafer-scale metasurface for total power absorption, local field enhancement and single molecule Raman spectroscopy.

    PubMed

    Wang, Dongxing; Zhu, Wenqi; Best, Michael D; Camden, Jon P; Crozier, Kenneth B

    2013-10-04

    The ability to detect molecules at low concentrations is highly desired for applications that range from basic science to healthcare. Considerable interest also exists for ultrathin materials with high optical absorption, e.g. for microbolometers and thermal emitters. Metal nanostructures present opportunities to achieve both purposes. Metal nanoparticles can generate gigantic field enhancements, sufficient for the Raman spectroscopy of single molecules. Thin layers containing metal nanostructures ("metasurfaces") can achieve near-total power absorption at visible and near-infrared wavelengths. Thus far, however, both aims (i.e. single molecule Raman and total power absorption) have only been achieved using metal nanostructures produced by techniques (high resolution lithography or colloidal synthesis) that are complex and/or difficult to implement over large areas. Here, we demonstrate a metasurface that achieves the near-perfect absorption of visible-wavelength light and enables the Raman spectroscopy of single molecules. Our metasurface is fabricated using thin film depositions, and is of unprecedented (wafer-scale) extent.

  15. Nanoscale infrared absorption spectroscopy of individual nanoparticles enabled by scattering-type near-field microscopy.

    PubMed

    Stiegler, Johannes M; Abate, Yohannes; Cvitkovic, Antonija; Romanyuk, Yaroslav E; Huber, Andreas J; Leone, Stephen R; Hillenbrand, Rainer

    2011-08-23

    Infrared absorption spectroscopy is a powerful and widely used tool for analyzing the chemical composition and structure of materials. Because of the diffraction limit, however, it cannot be applied for studying individual nanostructures. Here we demonstrate that the phase contrast in substrate-enhanced scattering-type scanning near-field optical microscopy (s-SNOM) provides a map of the infrared absorption spectrum of individual nanoparticles with nanometer-scale spatial resolution. We succeeded in the chemical identification of silicon nitride nanoislands with heights well below 10 nm, by infrared near-field fingerprint spectroscopy of the Si-N stretching bond. Employing a novel theoretical model, we show that the near-field phase spectra of small particles correlate well with their far-field absorption spectra. On the other hand, the spectral near-field contrast does not scale with the volume of the particles. We find a nearly linear scaling law, which we can attribute to the near-field coupling between the near-field probe and the substrate. Our results provide fundamental insights into the spectral near-field contrast of nanoparticles and clearly demonstrate the capability of s-SNOM for nanoscale chemical mapping based on local infrared absorption.

  16. Adsorption of Uranyl ions on Amine-functionalization of MIL-101(Cr) Nanoparticles by a Facile Coordination-based Post-synthetic strategy and X-ray Absorption Spectroscopy Studies

    NASA Astrophysics Data System (ADS)

    Zhang, Jian-Yong; Zhang, Na; Zhang, Linjuan; Fang, Yongzheng; Deng, Wei; Yu, Ming; Wang, Ziqiang; Li, Lina; Liu, Xiyan; Li, Jingye

    2015-09-01

    By a facile coordination-based post-synthetic strategy, the high surface area MIL-101(Cr) nanoparticles was functionallized by grafting amine group of ethylenediamine (ED) on coordinatively unsaturated Cr(III) centers, yielding a series of ED-MIL-101(Cr)-based adsorbents and their application for adsorption of U(VI) from aqueous solution were also studied. The obtained ED-functionallized samples with different ED contents were characterized by powder X-ray diffraction (PXRD), scanning electron microscope (SEM), energy dispersive X-ray spectroscopy (EDX), FTIR, elemental analysis (EA) and N2 adsorption and desorption isothermal. Compared with the pristine MIL-101(Cr) sorbents, the ED-functionallized MIL-101(Cr) exhibits significantly higher adsorption capacity for U(VI) ions from water with maximum adsorption capacities as high as 200 mg/g (corresponding to 100% extraction rate) at pH of 4.5 with ED/Cr ratio of 0.68 and the sorbed U(VI) ions can easily be desorbed at lower pH (pH ≤ 2.0). The adsorption mode of U(VI) ions and effects of grafted ED on the MIL-101(Cr) frameworks were also been studied by X-ray absorption spectroscopy (XAS). We believe that this work establishes a simple and energy efficient route to a novel type of functional materials for U(VI) ions extraction from solution via the post-synthetic modification (PSM) strategy.

  17. Adsorption of Uranyl ions on Amine-functionalization of MIL-101(Cr) Nanoparticles by a Facile Coordination-based Post-synthetic strategy and X-ray Absorption Spectroscopy Studies

    PubMed Central

    Zhang, Jian-Yong; Zhang, Na; Zhang, Linjuan; Fang, Yongzheng; Deng, Wei; Yu, Ming; Wang, Ziqiang; Li, Lina; Liu, Xiyan; Li, Jingye

    2015-01-01

    By a facile coordination-based post-synthetic strategy, the high surface area MIL-101(Cr) nanoparticles was functionallized by grafting amine group of ethylenediamine (ED) on coordinatively unsaturated Cr(III) centers, yielding a series of ED-MIL-101(Cr)-based adsorbents and their application for adsorption of U(VI) from aqueous solution were also studied. The obtained ED-functionallized samples with different ED contents were characterized by powder X-ray diffraction (PXRD), scanning electron microscope (SEM), energy dispersive X-ray spectroscopy (EDX), FTIR, elemental analysis (EA) and N2 adsorption and desorption isothermal. Compared with the pristine MIL-101(Cr) sorbents, the ED-functionallized MIL-101(Cr) exhibits significantly higher adsorption capacity for U(VI) ions from water with maximum adsorption capacities as high as 200 mg/g (corresponding to 100% extraction rate) at pH of 4.5 with ED/Cr ratio of 0.68 and the sorbed U(VI) ions can easily be desorbed at lower pH (pH ≤ 2.0). The adsorption mode of U(VI) ions and effects of grafted ED on the MIL-101(Cr) frameworks were also been studied by X-ray absorption spectroscopy (XAS). We believe that this work establishes a simple and energy efficient route to a novel type of functional materials for U(VI) ions extraction from solution via the post-synthetic modification (PSM) strategy. PMID:26354407

  18. Titanium-silicon oxide film structures for polarization-modulated infrared reflection absorption spectroscopy

    PubMed Central

    Dunlop, Iain E.; Zorn, Stefan; Richter, Gunther; Srot, Vesna; Kelsch, Marion; van Aken, Peter A.; Skoda, Maximilian; Gerlach, Alexander; Spatz, Joachim P.; Schreiber, Frank

    2010-01-01

    We present a titanium-silicon oxide film structure that permits polarization modulated infrared reflection absorption spectroscopy on silicon oxide surfaces. The structure consists of a ~6 nm sputtered silicon oxide film on a ~200 nm sputtered titanium film. Characterization using conventional and scanning transmission electron microscopy, electron energy loss spectroscopy, X-ray photoelectron spectroscopy and X-ray reflectometry is presented. We demonstrate the use of this structure to investigate a selectively protein-resistant self-assembled monolayer (SAM) consisting of silane-anchored, biotin-terminated poly(ethylene glycol) (PEG). PEG-associated IR bands were observed. Measurements of protein-characteristic band intensities showed that this SAM adsorbed streptavidin whereas it repelled bovine serum albumin, as had been expected from its structure. PMID:20418963

  19. [On using tunable diode laser absorption spectroscopy to determine gas fluxes over cropland].

    PubMed

    Tian, Yong-zhi; Liu, Jian-guo; Zhang, Yu-jun; Lu, Yi-huai; He, Ying

    2012-04-01

    Tunable diode laser absorption spectroscopy (TDLAS) is a compact, automated, high precision technique and fit for in-situ or field measurements. Two spectroscopy measurement systems, TDLAS and NDIR (non-dispersive infrared spectroscopy), were used to monitor trace gas emission over cropland at Fengqiu Agricultural Ecology Experimental Station for one month. The fluxes of carbon dioxide were estimated by flux-gradient and eddy covariance method, respectively. A footprint model was developed during experiment. Based on this model, the source areas of TDLAS and NDIR were investigated. The effects of different factors on the flux measurement were also analyzed. The authors concluded that the source areas for the two techniques are discrepant in most of the cases. The source areas increase with path length and detecting height. This result will help the installation of instruments.

  20. High-resolution X-ray absorption spectroscopy of iron carbonyl complexes.

    PubMed

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

    2015-06-07

    We apply high-energy-resolution fluorescence-detected (HERFD) X-ray absorption near-edge spectroscopy (XANES) to study iron carbonyl complexes. Mono-, bi-, and tri-nuclear carbonyl complexes and pure carbonyl complexes as well as carbonyl complexes containing hydrocarbon ligands are considered. The HERFD-XANES spectra reveal multiple pre-edge peaks with individual signatures for each complex, which could not be detected previously with conventional XANES spectroscopy. These peaks are assigned and analysed with the help of TD-DFT calculations. We demonstrate that the pre-edge peaks can be used to distinguish the different types of iron-iron interactions in carbonyl complexes. This opens up new possibilities for applying HERFD-XANES spectroscopy to probe the electronic structure of iron catalysts.

  1. Core-Hole Effect in the Ce L3 X-Ray Absorption Spectra of CeO2 and CeFe2: New Examination by Using Resonant X-Ray Emission Spectroscopy

    NASA Astrophysics Data System (ADS)

    Kotani, A.

    2013-06-01

    We consider two different resonant X-ray emission spectra for Ce compounds: Ce 3d to 2p X-ray emission (denoted by 3d-RXES) and valence to 2p X-ray emission (v-RXES), both of which follow the Ce 2p to 5d resonant excitation. We propose that the comparison of the 3d- and v-RXES spectra is a new powerful method of directly detecting the core-hole effect in the final state of Ce L3 X-ray absorption spectra (XAS). We applied this method to recent experimental RXES spectra for CeO2 and CeFe2, and showed unambiguously that the core-hole effect should be essential in the XAS of both materials. This result is confirmed by theoretical calculations, which reproduce well the experimental RXES and XAS spectra. We conclude that the ground state of CeO2 is in the mixed state of 4f0 and 4f1_{L} configurations, where _{L} is a ligand hole, instead of a pure 4f0 configuration which was proposed recently by first-principles energy band calculations. Also, we conclude that the double peaks observed in L3 XAS of CeFe2 are caused by the 4f0 and 4f1 configurations, which are mixed in the ground state but separated in energy by the large core-hole potential in the final state of XAS.

  2. Determination of zinc in serum, blood, and ultrafiltrate fluid from patients on hemofiltration by graphite furnace/atomic absorption spectroscopy or flow injection analysis/atomic absorption spectroscopy.

    PubMed

    de Blas, O J; Rodriguez, R S; Mendez, J H; Tomero, J A; Gomez, B de L; Gonzalez, S V

    1994-01-01

    Two methods were optimized for the determination of zinc in samples of blood, serum, and ultrafiltrate fluid from patients with chronic renal impairment undergoing hemofiltration. In the first procedure, after acid digestion of the samples, Zn in blood and serum is determined by a system coupled to flow injection analysis and atomic absorption spectroscopy. The method is rapid, automated, simple, needs small amounts of sample, and has acceptable analytical characteristics. The analytical characteristics obtained were as follows: determination range of method, 0.05-2.0 ppm of Zn; precision as coefficient of variation (CV), 5.3%; recovery, 95-105%; and detection limit (DL), 0.02 ppm. The second method is optimized for ultrafiltrate fluid because the sensitivity of the first procedure is not suitable for the levels of Zn (ppb or ng/mL) in these samples. The technique chosen was atomic absorption spectroscopy with electrothermal atomization in a graphite furnace. The analytical characteristics obtained were as follows: determination range of method, 0.3-2.0 ppb Zn; CV, 5.7%; recovery, 93-107%; and DL, 0.12 ppb. The methods were used to determine zinc in samples of blood, serum, and ultrafiltrate fluid from 5 patients with chronic renal impairment undergoing hemofiltration to discover whether there were significant differences in the zinc contents of blood, serum, and ultrafiltrate fluid after the hemofiltration process. An analysis of variance of the experimental data obtained from a randomly selected group of 5 patients showed that zinc concentrations in the ultrafiltrate fluid, venous blood, and venous serum do not vary during hemofiltration (p < 0.05), whereas in arterial blood and serum, the time factor has a significant effect.

  3. Cavity enhanced ultra-thin aluminum plasmonic resonator for surface enhanced infrared absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Wei, Wei; Jiang, Xiao; Nong, Jinpeng; Chen, Na; Lan, Guilian; Tang, Linlong

    2016-11-01

    Owing to the advantages of natural abundance, low cost, and amenability to manufacturing processes, aluminum has recently been recognized as a highly promising plasmonic material that attracts extensive research interest. Here, we propose a cavity-enhanced ultra-thin plasmonic resonator for surface enhanced infrared absorption spectroscopy. The considered resonator consists of a patterned ultra-thin aluminum grating strips, a dielectric spacer layer and a reflective layer. In such structure, the resonance absorption is enhanced by the cavity formed between the patterned aluminum strips and the reflective layer. It is demonstrated that the spectral features of the resonator can be tuned by adjusting the structural parameters. Furthermore, in order to achieve a deep and broad spectral line shape, the spacer layer thickness should be properly designed to realize the simultaneous resonances for the electric and the magnetic excitations. The enhanced infrared absorption characteristics can be used for infrared sensing of the environment. When the resonator is covered with a molecular layer, the resonator can be used as a surface enhanced infrared absorption substrate to enhance the absorption signal of the molecules. A high enhanced factor of 1.15×105 can be achieved when the resonance wavelength of resonator is adjusted to match the desired vibrational mode of the molecules. Such a cavity-enhanced plasmonic resonator, which is easy for practical fabrication, is expected to have potential applications for infrared sensing with high-performance.

  4. Infrared intracavity laser absorption spectroscopy with a continuous-scan Fourier-transform interferometer.

    PubMed

    Cheng, J; Lin, H; Hu, S; He, S; Zhu, Q; Kachanov, A

    2000-05-01

    High-quality broadband infrared high-resolution spectra were obtained by use of the intracavity laser absorption spectroscopy technique with a Ti:sapphire laser in combination with a continuous-scan Fourier-transform (FT) interferometer. With electronic filtering used to smooth out the fluctuations of the laser power, the absorption of atmospheric water vapor in the range of 12,450-12,700 cm(-1) was recorded at a resolution of 0.05 cm(-1). A signal-to-noise ratio of greater than 300 was observed in this spectrum, corresponding to a minimum detectable absorption of approximately 2 x 10(-9) cm(-1). Comparison with previous measurements by use of a conventional FT technique shows that this method gives absorption spectra with highly accurate line positions along with reasonable line intensities. Investigation of the evolution of intracavity laser absorption spectra with the generation time is also shown to be possible with a continuous-scan FT spectrometer by use of the interleave rapid-scan method.

  5. [Study on removing the lamp spectrum structure in differential optical absorption spectroscopy].

    PubMed

    Qu, Xiao-ying; Li, Yu-jin

    2010-11-01

    Differential optical absorption spectroscopy (DOAS) technique has been used to measure trace gases in the atmosphere by their strongly structured absorption of radiation in the UV and visible spectral range, and nowadays this technique has been widely utilized to measure trace polluted gases in the atmosphere e.g. SO2, NO2, O3, HCHO, etc. However, there exists lamp (xenon lamp or deuteriumlamp) spectrum structure in the measured band (300-700 nm) of the absorption spectra of atmosphere, which badly impacts on precision of retrieving the concentration of trace gases in the atmosphere. People home and abroad generally employ two ways to handle this problem, one is segmenting band retrieving method, another is remedial retrieving method. In the present paper, a new retrieving method to deal with this trouble is introduced. The authors used moving-window average smoothing method to obtain the slow part of the absorption spectra of atmosphere, then achieved the lamp (xenon lamp in the paper) spectrum structure in the measured band of the absorption spectra of atmosphere. The authors analyzed and retrieved the measured spectrum of the atmosphere, and the result is better than the forenamed ways. Chi-square of residuum is 2.995 x 10(-4), and this method was proved to be able to avoid shortcoming of choosing narrowband and disadvantage of discovering the new component of atmosphere in retrieving the concentration of air pollutants and measuring the air pollutants.

  6. A split imaging spectrometer for temporally and spatially resolved titanium absorption spectroscopy

    SciTech Connect

    Hager, J. D. Lanier, N. E.; Kline, J. L.; Flippo, K. A.; Bruns, H. C.; Schneider, M.; Saculla, M.; McCarville, T.

    2014-11-15

    We present a temporally and a spatially resolved spectrometer for titanium x-ray absorption spectroscopy along 2 axial symmetric lines-of-sight. Each line-of-sight of the instrument uses an elliptical crystal to acquire both the 2p and 3p Ti absorption lines on a single, time gated channel of the instrument. The 2 axial symmetric lines-of-sight allow the 2p and 3p absorption features to be measured through the same point in space using both channels of the instrument. The spatially dependent material temperature can be inferred by observing the 2p and the 3p Ti absorption features. The data are recorded on a two strip framing camera with each strip collecting data from a single line-of-sight. The design is compatible for use at both the OMEGA laser and the National Ignition Facility. The spectrometer is intended to measure the material temperature behind a Marshak wave in a radiatively driven SiO{sub 2} foam with a Ti foam tracer. In this configuration, a broad band CsI backlighter will be used for a source and the Ti absorption spectrum measured.

  7. New advances in the use of infrared absorption spectroscopy for the characterization of heterogeneous catalytic reactions.

    PubMed

    Zaera, Francisco

    2014-11-21

    Infrared absorption spectroscopy has proven to be one of the most powerful spectroscopic techniques available for the characterization of catalytic systems. Although the history of IR absorption spectroscopy in catalysis is long, the technique continues to provide key fundamental information about a variety of catalysts and catalytic reactions, and to also offer novel options for the acquisition of new information on both reaction mechanisms and the nature of the solids used as catalysts. In this review, an overview is provided of the main contributions that have been derived from IR absorption spectroscopy studies of catalytic systems, and a discussion is included on new trends and new potential directions of research involving IR in catalysis. We start by briefly describing the power of Fourier-transform IR (FTIR) instruments and the main experimental IR setups available, namely, transmission (TIR), diffuse reflectance (DRIFTS), attenuated total reflection (ATR-IR), and reflection-absorption (RAIRS), for advancing research in catalysis. We then discuss the different environments under which IR characterization of catalysts is carried out, including in situ and operando studies of typical catalytic processes in gas-phase, research with model catalysts in ultrahigh vacuum (UHV) and so-called high-pressure cell instruments, and work involving liquid/solid interfaces. A presentation of the type of information extracted from IR data follows in terms of the identification of adsorbed intermediates, the characterization of the surfaces of the catalysts themselves, the quantitation of IR intensities to extract surface coverages, and the use of probe molecules to identify and titrate specific catalytic sites. Finally, the different options for carrying out kinetic studies with temporal resolution such as rapid-scan FTIR, step-scan FTIR, and the use of tunable lasers or synchrotron sources, and to obtain spatially resolved spectra, by sample rastering or by 2D imaging, are

  8. Cavity ring-down spectroscopy (CRDS) system for measuring atmospheric mercury using differential absorption

    NASA Astrophysics Data System (ADS)

    Pierce, A.; Obrist, D.; Moosmuller, H.; Moore, C.

    2012-04-01

    Atmospheric elemental mercury (Hg0) is a globally pervasive element that can be transported and deposited to remote ecosystems where it poses — particularly in its methylated form — harm to many organisms including humans. Current techniques for measurement of atmospheric Hg0 require several liters of sample air and several minutes for each analysis. Fast-response (i.e., 1 second or faster) measurements would improve our ability to understand and track chemical cycling of mercury in the atmosphere, including high frequency Hg0 fluctuations, sources and sinks, and chemical transformation processes. We present theory, design, challenges, and current results of our new prototype sensor based on cavity ring-down spectroscopy (CRDS) for fast-response measurement of Hg0 mass concentrations. CRDS is a direct absorption technique that implements path-lengths of multiple kilometers in a compact absorption cell using high-reflectivity mirrors, thereby improving sensitivity and reducing sample volume compared to conventional absorption spectroscopy. Our sensor includes a frequency-doubled, dye-laser emitting laser pulses tunable from 215 to 280 nm, pumped by a Q-switched, frequency tripled Nd:YAG laser with a pulse repetition rate of 50 Hz. We present how we successfully perform automated wavelength locking and stabilization of the laser to the peak Hg0 absorption line at 253.65 nm using an external isotopically-enriched mercury (202Hg0) cell. An emphasis of this presentation will be on the implementation of differential absorption measurement whereby measurements are alternated between the peak Hg0 absorption wavelength and a nearby wavelength "off" the absorption line. This can be achieved using a piezo electric tuning element that allows for pulse-by-pulse tuning and detuning of the laser "online" and "offline" of the Hg absorption line, and thereby allows for continuous correction of baseline extinction losses. Unexpected challenges with this approach included

  9. [Second-harmonic detection with tunable diode laser absorption spectroscopy of CO and CO2 at 1.58 microm].

    PubMed

    Tu, Xing-Hua; Liu, Wen-Qing; Zhang, Yu-Jun; Dong, Feng-Zhong; Wang, Min; Wang, Tie-Dong; Wang, Xiao-Mei; Liu, Jian-Guo

    2006-07-01

    Tunable diode laser absorption spectroscopy has been applied in the fields of atmospheric chemistry and monitoring pollutant gases as a new method of measuring trace gases. The technique of remote sensing of CO and CO2 at 760 mm Hg pressure with tunable diode laser absorption spectroscopy in the near-infrared region is introduced. And the relationship between the second-harmonic spectrum of CO2 in Lorentzian line shape and the modulation amplitude is also presented.

  10. Excited state X-ray absorption spectroscopy: Probing both electronic and structural dynamics

    NASA Astrophysics Data System (ADS)

    Neville, Simon P.; Averbukh, Vitali; Ruberti, Marco; Yun, Renjie; Patchkovskii, Serguei; Chergui, Majed; Stolow, Albert; Schuurman, Michael S.

    2016-10-01

    We investigate the sensitivity of X-ray absorption spectra, simulated using a general method, to properties of molecular excited states. Recently, Averbukh and co-workers [M. Ruberti et al., J. Chem. Phys. 140, 184107 (2014)] introduced an efficient and accurate L 2 method for the calculation of excited state valence photoionization cross-sections based on the application of Stieltjes imaging to the Lanczos pseudo-spectrum of the algebraic diagrammatic construction (ADC) representation of the electronic Hamiltonian. In this paper, we report an extension of this method to the calculation of excited state core photoionization cross-sections. We demonstrate that, at the ADC(2)x level of theory, ground state X-ray absorption spectra may be accurately reproduced, validating the method. Significantly, the calculated X-ray absorption spectra of the excited states are found to be sensitive to both geometric distortions (structural dynamics) and the electronic character (electronic dynamics) of the initial state, suggesting that core excitation spectroscopies will be useful probes of excited state non-adiabatic dynamics. We anticipate that the method presented here can be combined with ab initio molecular dynamics calculations to simulate the time-resolved X-ray spectroscopy of excited state molecular wavepacket dynamics.

  11. UV-Vis Reflection-Absorption Spectroscopy at air-liquid interfaces.

    PubMed

    Rubia-Payá, Carlos; de Miguel, Gustavo; Martín-Romero, María T; Giner-Casares, Juan J; Camacho, Luis

    2015-11-01

    UV-Visible Reflection-Absorption Spectroscopy (UVRAS) technique is reviewed with a general perspective on fundamental and applications. UVRAS is formally identical to IR Reflection-Absorption Spectroscopy (IRRAS), and therefore, the methodology developed for this IR technique can be applied in the UV-visible region. UVRAS can be applied to air-solid, air-liquid or liquid-liquid interfaces. This review focuses on the use of UVRAS for studying Langmuir monolayers. We introduce the theoretical framework for a successful understanding of the UVRAS data, and we illustrate the usage of this data treatment to a previous study from our group comprising an amphiphilic porphyrin. For ultrathin films with a thickness of few nm, UVRAS produces positive or negative bands when p-polarized radiation is used, depending on the incidence angle and the orientation of dipole absorption. UVRAS technique provides highly valuable information on tilt of chromophores at the air-liquid interface, and moreover allows the determination of optical parameters. We propose UVRAS as a powerful technique to investigate the in situ optical properties of Langmuir monolayers.

  12. High-performance dispersive Raman and absorption spectroscopy as tools for drug identification

    NASA Astrophysics Data System (ADS)

    Pawluczyk, Olga; Andrey, Sam; Nogas, Paul; Roy, Andrew; Pawluczyk, Romuald

    2009-02-01

    Due to increasing availability of pharmaceuticals from many sources, a need is growing to quickly and efficiently analyze substances in terms of the consistency and accuracy of their chemical composition. Differences in chemical composition occur at very low concentrations, so that highly sensitive analytical methods become crucial. Recent progress in dispersive spectroscopy with the use of 2-dimensional detector arrays, permits for signal integration along a long (up to 12 mm long) entrance slit of a spectrometer, thereby increasing signal to noise ratio and improving the ability to detect small concentration changes. This is achieved with a non-scanning, non-destructive system. Two different methods using P&P Optica high performance spectrometers were used. High performance optical dispersion Raman and high performance optical absorption spectroscopy were employed to differentiate various acetaminophen-containing drugs, such as Tylenol and other generic brands, which differ in their ingredients. A 785 nm excitation wavelength was used in Raman measurements and strong Raman signals were observed in the spectral range 300-1800 cm-1. Measurements with the absorption spectrometer were performed in the wavelength range 620-1020 nm. Both Raman and absorption techniques used transmission light spectrometers with volume phase holographic gratings and provided sufficient spectral differences, often structural, allowing for drug differentiation.

  13. Time resolved metal line profile by near-ultraviolet tunable diode laser absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Vitelaru, C.; de Poucques, L.; Minea, T. M.; Popa, G.

    2011-03-01

    Pulsed systems are extensively used to produce active species such as atoms, radicals, excited states, etc. The tunable diode laser absorption spectroscopy (TD-LAS) is successfully used to quantify the density of absorbing species, but especially for stationary or slow changing systems. The time resolved-direct absorption profile (TR-DAP) measurement method by TD-LAS, with time resolution of μs is proposed here as an extension of the regular use of diode laser absorption spectroscopy. The spectral narrowness of laser diodes, especially in the blue range (˜0.01 pm), combined with the nanosecond fast trigger of the magnetron pulsed plasma and long trace recording on the oscilloscope (period of second scale) permit the detection of the sputtered titanium metal evolution in the afterglow (˜ms). TR-DAP method can follow the time-dependence of the temperature (Doppler profile) and the density (deduced from the absorbance) of any medium and heavy species in a pulsed system.

  14. [Signal analysis and spectrum distortion correction for tunable diode laser absorption spectroscopy system].

    PubMed

    Bao, Wei-Yi; Zhu, Yong; Chen, Jun; Chen, Jun-Qing; Liang, Bo

    2011-04-01

    In the present paper, the signal of a tunable diode laser absorption spectroscopy (TDLAS) trace gas sensing system, which has a wavelength modulation with a wide range of modulation amplitudes, is studied based on Fourier analysis method. Theory explanation of spectrum distortion induced by laser intensity amplitude modulation is given. In order to rectify the spectrum distortion, a method of synchronous amplitude modulation suppression by a variable optical attenuator is proposed. To validate the method, an experimental setup is designed. Absorption spectrum measurement experiments on CO2 gas were carried out. The results show that the residual laser intensity modulation amplitude of the experimental system is reduced to -0.1% of its original value and the spectrum distortion improvement is 92% with the synchronous amplitude modulation suppression. The modulation amplitude of laser intensity can be effectively reduced and the spectrum distortion can be well corrected by using the given correction method and system. By using a variable optical attenuator in the TDLAS (tunable diode laser absorption spectroscopy) system, the dynamic range requirements of photoelectric detector, digital to analog converter, filters and other aspects of the TDLAS system are reduced. This spectrum distortion correction method can be used for online trace gas analyzing in process industry.

  15. Excited state X-ray absorption spectroscopy: Probing both electronic and structural dynamics.

    PubMed

    Neville, Simon P; Averbukh, Vitali; Ruberti, Marco; Yun, Renjie; Patchkovskii, Serguei; Chergui, Majed; Stolow, Albert; Schuurman, Michael S

    2016-10-14

    We investigate the sensitivity of X-ray absorption spectra, simulated using a general method, to properties of molecular excited states. Recently, Averbukh and co-workers [M. Ruberti et al., J. Chem. Phys. 140, 184107 (2014)] introduced an efficient and accurate L(2) method for the calculation of excited state valence photoionization cross-sections based on the application of Stieltjes imaging to the Lanczos pseudo-spectrum of the algebraic diagrammatic construction (ADC) representation of the electronic Hamiltonian. In this paper, we report an extension of this method to the calculation of excited state core photoionization cross-sections. We demonstrate that, at the ADC(2)x level of theory, ground state X-ray absorption spectra may be accurately reproduced, validating the method. Significantly, the calculated X-ray absorption spectra of the excited states are found to be sensitive to both geometric distortions (structural dynamics) and the electronic character (electronic dynamics) of the initial state, suggesting that core excitation spectroscopies will be useful probes of excited state non-adiabatic dynamics. We anticipate that the method presented here can be combined with ab initio molecular dynamics calculations to simulate the time-resolved X-ray spectroscopy of excited state molecular wavepacket dynamics.

  16. Angle-tunable enhanced infrared reflection absorption spectroscopy via grating-coupled surface plasmon resonance.

    PubMed

    Petefish, Joseph W; Hillier, Andrew C

    2014-03-04

    Surface enhanced infrared absorption (SEIRA) spectroscopy is an attractive method for increasing the prominence of vibrational modes in infrared spectroscopy. To date, the majority of reports associated with SEIRA utilize localized surface plasmon resonance from metal nanoparticles to enhance electromagnetic fields in the region of analytes. Limited work has been performed using propagating surface plasmons as a method for SEIRA excitation. In this report, we demonstrate angle-tunable enhancement of vibrational stretching modes associated with a thin poly(methyl methacrylate) (PMMA) film that is coupled to a silver-coated diffraction grating. Gratings are fabricated using laser interference lithography to achieve precise surface periodicities, which can be used to generate surface plasmons that overlap with specific vibrational modes in the polymer film. Infrared reflection absorption spectra are presented for both bare silver and PMMA-coated silver gratings at a range of angles and polarization states. In addition, spectra were obtained with the grating direction oriented perpendicular and parallel to the infrared source in order to isolate plasmon enhancement effects. Optical simulations using the rigorous coupled-wave analysis method were used to identify the origin of the plasmon-induced enhancement. Angle-dependent absorption measurements achieved signal enhancements of more than 10-times the signal in the absence of the plasmon.

  17. The role of X-ray spectroscopy in understanding the geometric and electronic structure of nitrogenase.

    PubMed

    Kowalska, Joanna; DeBeer, Serena

    2015-06-01

    X-ray absorption (XAS) and X-ray emission spectroscopy (XES) provide element specific probes of the geometric and electronic structures of metalloprotein active sites. As such, these methods have played an integral role in nitrogenase research beginning with the first EXAFS studies on nitrogenase in the late 1970s. Herein, we briefly explain the information that can be extracted from XAS and XES. We then highlight the recent applications of these methods in nitrogenase research. The influence of X-ray spectroscopy on our current understanding of the atomic structure and electronic structure of iron molybdenum cofactor (FeMoco) is emphasized. Contributions of X-ray spectroscopy to understanding substrate interactions and cluster biosynthesis are also discussed. This article is part of a Special Issue entitled: Fe/S proteins: Analysis, structure, function, biogenesis and diseases.

  18. Broadband spectroscopy with external cavity quantum cascade lasers beyond conventional absorption measurements.

    PubMed

    Lambrecht, Armin; Pfeifer, Marcel; Konz, Werner; Herbst, Johannes; Axtmann, Felix

    2014-05-07

    Laser spectroscopy is a powerful tool for analyzing small molecules, i.e. in the gas phase. In the mid-infrared spectral region quantum cascade lasers (QCLs) have been established as the most frequently used laser radiation source. Spectroscopy of larger molecules in the gas phase, of complex mixtures, and analysis in the liquid phase requires a broader tuning range and is thus still the domain of Fourier transform infrared (FTIR) spectroscopy. However, the development of tunable external cavity (EC) QCLs is starting to change this situation. The main advantage of QCLs is their high spectral emission power that is enhanced by a factor of 10(4) compared with thermal light sources. Obviously, transmission measurements with EC-QCLs in strongly absorbing samples are feasible, which can hardly be measured by FTIR due to detector noise limitations. We show that the high power of EC-QCLs facilitates spectroscopy beyond simple absorption measurements. Starting from QCL experiments with liquid samples, we show results of fiber evanescent field analysis (FEFA) to detect pesticides in drinking water. FEFA is a special case of attenuated total reflection spectroscopy. Furthermore, powerful CW EC-QCLs enable fast vibrational circular dichroism (VCD) spectroscopy of chiral molecules in the liquid phase - a technique which is very time consuming with standard FTIR equipment. We present results obtained for the chiral compound 1,1'-bi-2-naphthol (BINOL). Finally, powerful CW EC-QCLs enable the application of laser photothermal emission spectroscopy (LPTES). We demonstrate this for a narrowband and broadband absorber in the gas phase. All three techniques have great potential for MIR process analytical applications.

  19. A new structural motif for biological iron: iron K-edge XAS reveals a [Fe4-mu-(OR)5(OR)(9-10)] cluster in the ascidian Perophora annectens.

    PubMed

    Frank, Patrick; DeTomaso, Anthony; Hedman, Britt; Hodgson, Keith O

    2006-05-15

    The Phlebobranch ascidian Perophora annectens surprisingly exhibited a biological Fe/V ratio of approximately 15:1 on multichannel X-ray fluorescence analysis of two independent collections of organisms. Iron K-edge X-ray absorption spectroscopy (XAS) indicated a single form of iron. The XAS K-edge of the first collection of blood cells was shifted approximately +1 eV relative to that of the second, indicating redox activity with average iron oxidation states of 2.67+ and 2.60+. The first-derivative iron XAS K-edge features at 7120.5, 7124, and 7128 eV resembled the XAS of magnetite but not of ferritin or of dissolved Fe(II) or Fe(III). Pseudo-Voigt fits to blood-cell iron K-edge XAS spectra yielded 12.4 integrated units of preedge intensity, indicating a noncentrosymmetric environment. The non-phase-corrected extended X-ray absorption fine structure (EXAFS) Fourier transform spectrum showed a first-shell O/N peak at 1.55 angstroms and an intense Fe-Fe feature at 2.65 angstroms. Fits to the EXAFS required a split first shell with two O at 1.93 angstroms and three O at 2.07 angstroms, consistent with terminal and bridging alkoxide ligands, respectively. More distant shells included three C at 2.87 angstroms, two Fe at 3.08 angstroms, three O at 3.29 angstroms, and one Fe at 3.8 angstroms. Structural models consistent with these findings include a [Fe4(OR)13](2-/3-) broken-edged Fe4O5 cuboid or a [Fe4(OR)14](3-/4-) "Jacob's ladder" with three edge-fused Fe2(OR)2 rhombs. Either of these models represents an entirely new structural motif for biological iron. Vanadium domination of blood-cell metals cannot be a defining trait of Phlebobranch tunicates so long as P. annectens is included among them.

  20. Contributions of Paint and Soil to Pb in Household Dust Wipes: An XAS Study

    NASA Astrophysics Data System (ADS)

    Pingitore, N. E.; Clague, J. W.; Amaya, M. A.

    2010-12-01

    Speciation of Pb by X-ray absorption spectroscopy (XAS) indicated that Pb compounds associated with lead-based paint accounted for perhaps half of the Pb in 24 household dust wipes collected in El Paso, Texas. Soil-derived, sorbed Pb, likely Pb-humate, was also a major Pb species in many of the dust wipes. Household dust wipes are a standard technique for evaluating health risks of Pb to children, particularly toddlers, in public and private housing. The level of Pb in the wipes does not, however, indicate whether the source of the Pb is the house itself (peeling or powdering interior or exterior paint) or external, from contaminated soil or airborne particulate matter brought into the house by wind or foot traction. Understanding the origin of Pb in household dust is important in remediation: cover the old paint or remove the yard soil. XAS speciation can assist in understanding the source of Pb in household dust. The presence of significant Pb-humate requires a soil source, and suggests the need for soil remediation. Such species of Pb as hydrocerussite, lead sulfate, lead silicate, and lead chromate can be presumed to be components of lead-based paint. These may represent interior and/or exterior paint and thus do not uniquely identify the locus of the Pb source(s). Pb L-III edge XAFS data were collected on beam lines 7-3, 10-2, and 11-2 at SSRL at typical conditions of 3 GeV field and 80-200 mA current, using Si(220) water- or liquid-nitrogen-cooled monochromator crystals. Data were collected at ambient temperature in fluorescence mode using a 13- or 30-element Ge detector with a Se 3 or 6 filter and Soller slits to reduce scattered radiation. This publication was made possible by grant numbers 1RO1-ES11367 and 1 S11 ES013339-01A1 from the National Institute of Environmental Health Sciences (NIEHS), NIH. Its contents are solely the responsibility of the authors and do not necessarily represent the official views of the NIEHS, NIH. Portions of this research were

  1. Temperature and multi-species measurements by supercontinuum absorption spectroscopy for IC engine applications.

    PubMed

    Werblinski, Thomas; Engel, Sascha R; Engelbrecht, Rainer; Zigan, Lars; Will, Stefan

    2013-06-03

    The first supercontinuum (SC) absorption spectroscopy measurements showing the feasibility of quantitative temperature evaluation are presented to the best of the authors' knowledge. Temperature and multi-species measurements were carried out at a detection rate of ~2 MHz in a high-temperature flow cell within a temperature range from 450 K to 750 K at 0.22 MPa, representing conditions during the suction and compression stroke in an internal combustion (IC) engine. The broadband SC pulses were temporally dispersed into fast wavelength sweeps, covering the overtone absorption bands 2ν(1), 2ν(3), ν(1) + ν(3) of H2O and 3ν(3) of CO2 in the near-infrared region from 1330 nm to 1500 nm. The temperature information is inferred from the peak ratio of a temperature sensitive (1362.42 nm) and insensitive (1418.91 nm) absorption feature in the ν(1) + ν(3) overtone bands of water. The experimental results are in very good agreement with theoretical intensity ratios calculated from absorption spectra based on HiTran data.

  2. Tunable Diode Laser Atomic Absorption Spectroscopy for Detection of Potassium under Optically Thick Conditions.

    PubMed

    Qu, Zhechao; Steinvall, Erik; Ghorbani, Ramin; Schmidt, Florian M

    2016-04-05

    Potassium (K) is an important element related to ash and fine-particle formation in biomass combustion processes. In situ measurements of gaseous atomic potassium, K(g), using robust optical absorption techniques can provide valuable insight into the K chemistry. However, for typical parts per billion K(g) concentrations in biomass flames and reactor gases, the product of atomic line strength and absorption path length can give rise to such high absorbance that the sample becomes opaque around the transition line center. We present a tunable diode laser atomic absorption spectroscopy (TDLAAS) methodology that enables accurate, calibration-free species quantification even under optically thick conditions, given that Beer-Lambert's law is valid. Analyte concentration and collisional line shape broadening are simultaneously determined by a least-squares fit of simulated to measured absorption profiles. Method validation measurements of K(g) concentrations in saturated potassium hydroxide vapor in the temperature range 950-1200 K showed excellent agreement with equilibrium calculations, and a dynamic range from 40 pptv cm to 40 ppmv cm. The applicability of the compact TDLAAS sensor is demonstrated by real-time detection of K(g) concentrations close to biomass pellets during atmospheric combustion in a laboratory reactor.

  3. Determining crystal phase purity in c-BP through X-ray absorption spectroscopy.

    PubMed

    Huber, S P; Medvedev, V V; Gullikson, E; Padavala, B; Edgar, J H; van de Kruijs, R W E; Bijkerk, F; Prendergast, D

    2017-02-02

    We employ X-ray absorption near-edge spectroscopy at the boron K-edge and the phosphorus L2,3-edge to study the structural properties of cubic boron phosphide (c-BP) samples. The X-ray absorption spectra are modeled from first-principles within the density functional theory framework using the excited electron core-hole (XCH) approach. A simple structural model of a perfect c-BP crystal accurately reproduces the P L2,3-edge, however it fails to describe the broad and gradual onset of the B K-edge. Simulations of the spectroscopic signatures in boron 1s excitations of intrinsic point defects and the hexagonal BP crystal phase show that these additions to the structural model cannot reproduce the broad pre-edge of the experimental spectrum. Calculated formation enthalpies show that, during the growth of c-BP, it is possible that amorphous boron phases can be grown in conjunction with the desired boron phosphide crystalline phase. In combination with experimental and theoretically obtained X-ray absorption spectra of an amorphous boron structure, which have a similar broad absorption onset in the B K-edge spectrum as the cubic boron phosphide samples, we provide evidence for the presence of amorphous boron clusters in the synthesized c-BP samples.

  4. [Concentration retrieving method of SO2 using differential optical absorption spectroscopy based on statistics].

    PubMed

    Liu, Bin; Sun, Chang-Ku; Zhang, Chi; Zhao, Yu-Mei; Liu, Jun-Ping

    2011-01-01

    A concentration retrieving method using statistics is presented, which is applied in differential optical absorption spectroscopy (DOAS) for measuring the concentration of SO2. The method uses the standard deviation of the differential absorption to represents the gas concentration. Principle component analysis (PCA) method is used to process the differential absorption spectrum. In the method, the basis data for the concentration retrieval of SO2 is the combination of the PCA processing result, the correlation coefficient, and the standard deviation of the differential absorption. The method is applied to a continuous emission monitoring system (CEMS) with optical path length of 0.3 m. Its measuring range for SO2 concentration is 0-5 800 mg x m(-3). The nonlinear calibration and the temperature compensation for the system were executed. The full scale error of the retrieving concentration is less than 0.7% FS. And the measuring result is -4.54 mg x m(-3) when the concentration of SO2 is zero.

  5. Diffuse reflectance spectroscopy as a tool to measure the absorption coefficient in skin: system calibration.

    PubMed

    Karsten, A E; Singh, A; Karsten, P A; Braun, M W H

    2013-02-01

    An individualised laser skin treatment may enhance the treatment and reduces risks and side-effects. The optical properties (absorption and scattering coefficients) are important parameters in the propagation of laser light in skin tissue. The differences in the melanin content of different skin phototypes influence the absorption of the light. The absorption coefficient at the treatment wavelength for an individual can be determined by diffuse reflectance spectroscopy, using a probe containing seven fibres. Six of the fibres deliver the light to the measurement site and the central fibre collects the diffused reflected light. This is an in vivo technique, offering benefits for near-real-time results. Such a probe, with an effective wavelength band from 450 to 800 nm, was used to calibrate skin-simulating phantoms consisting of intralipid and ink. The calibration constants were used to calculate the absorption coefficients from the diffuse reflectance measurements of three volunteers (skin phototypes, II, IV and V) for sun-exposed and non-exposed areas on the arm.

  6. An x-ray absorption spectroscopy study of Mo oxidation in Pb at elevated temperatures

    SciTech Connect

    Liu, Shanshan; Olive, Daniel; Terry, Jeff; Segre, Carlo U.

    2009-06-30

    The corrosion of fuel cladding and structural materials by lead and lead-bismuth eutectic in the liquid state at elevated temperatures is an issue that must be considered when designing advanced nuclear systems and high-power spallation neutron targets. In this work, lead corrosion studies of molybdenum were performed to investigate the interaction layer as a function of temperature by X-ray absorption spectroscopy. In situ X-ray absorption measurements on a Mo substrate with a 3-6 {micro}m layer of Pb deposited by thermal evaporation were performed at temperatures up to 900 C and at a 15{sup o} angle to the incident X-rays. The changes in the local atomic structure of the corrosion layer are visible in the difference extended X-ray absorption fine structure and the linear combination fitting of the X-ray absorption near-edge structure to as-deposited molybdenum sample and molybdenum oxide (MoO{sub 2} and MoO{sub 3}) standards. The data are consistent with the appearance of MoO{sub 3} in an intermediate temperature range (650-800 C) and the more stable MoO{sub 2} phase dominating at high and low temperatures.

  7. The analysis of time-resolved optical waveguide absorption spectroscopy based on positive matrix factorization.

    PubMed

    Liu, Ping; Li, Zhu; Li, Bo; Shi, Guolong; Li, Minqiang; Yu, Daoyang; Liu, Jinhuai

    2013-08-01

    Time-resolved optical waveguide absorption spectroscopy (OWAS) makes use of an evanescent field to detect the polarized absorption spectra of sub-monomolecular adlayers. This technique is suitable for the investigation of kinetics at the solid/liquid interface of dyes, pigments, fluorescent molecules, quantum dots, metallic nanoparticles, and proteins with chromophores. In this work, we demonstrate the application of positive matrix factorization (PMF) to analyze time-resolved OWAS for the first time. Meanwhile, PCA is researched to compare with PMF. The absorption/desorption kinetics of Rhodamine 6G (R6G) onto a hydrophilic glass surface and the dynamic process of Meisenheimer complex between Cysteine and TNT are selected as samples to verify experimental system and analytical methods. The results are shown that time-resolved OWAS can well record the absorption/desorption of R6G onto a hydrophilic glass surface and the dynamic formation process of Meisenheimer complexes. The feature of OWAS extracted by PMF is dynamic and consistent with the results analyzed by the traditional function of time/wavelength-absorbance. Moreover, PMF prevents the negative factors from occurring, avoids contradicting physical reality, and makes factors more easily interpretable. Therefore, we believe that PMF will provide a valuable analysis route to allow processing of increasingly large and complex data sets.

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

    SciTech Connect

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

    2017-01-01

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

  9. Measurement of temperature profiles in flames by emission-absorption spectroscopy

    NASA Technical Reports Server (NTRS)

    Simmons, F. S.; Arnold, C. B.; Lindquist, G. H.

    1972-01-01

    An investigation was conducted to explore the use of infrared and ultraviolet emission-absorption spectroscopy for determination of temperature profiles in flames. Spectral radiances and absorptances were measured in the 2.7-micron H2O band and the 3064-A OH band in H2/O2 flames for several temperature profiles which were directly measured by a sodium line-reversal technique. The temperature profiles, determined by inversion of the infrared and ultraviolet spectra, showed an average disagreement with line-reversal measurements of 50 K for the infrared and 200 K for the ultraviolet at a temperature of 2600 K. The reasons for these discrepancies are discussed in some detail.

  10. The nature of arsenic in uranium mill tailings by X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Cutler, J. N.; Chen, N.; Jiang, D. T.; Demopoulos, G. P.; Jia, Y.; Rowson, J. W.

    2003-05-01

    In order to understand the evolving world of environmental issues, the ability to characterize and predict the stability and bioavailability of heavy métal contaminants in mine waste is becoming increasingly more important. X-ray Absorption Near Edge Structure (XANES) and Extended X-ray Absorption Fine Structure (EXAFS) spectroscopies were used to characterize a series of synthetic and natural samples associated with mine tailings processing. XANES was shown to be excellent as a tool to rapidly differentiate oxidation states of arsenic within the samples. The EXAFS spectra provided information on the mineralogy of the precipitated raffinate and tailings and showed that these samples are composed of a mixture of amorphous ferric arsenates, adsorbed arsenates and a mixture of other poorly ordered arsenates.

  11. Ablation-initiated Isotope-selective Atomic Absorption Spectroscopy of Lanthanide Elements

    SciTech Connect

    Miyabe, M.; Oba, M.; Iimura, H.; Akaoka, K.; Maruyama, Y.; Wakaida, I.; Watanabe, K.

    2009-03-17

    For remote isotope analysis of low-decontaminated trans-uranium (TRU) fuel, absorption spectroscopy has been applied to a laser-ablated plume of lanthanide elements. To improve isotopic selectivity and detection sensitivity of the ablated species, various experimental conditions were optimized. Isotope-selective absorption spectra were measured by observing the slow component of the plume produced under low-pressure rare-gas ambient. The measured minimum line width of about 0.9 GHz was close to the Doppler width of the Gd atomic transition at room temperature. The relaxation rate of high-lying metastable state was found to be higher than that of the ground state, which suggests that higher analytical sensitivity can be obtained using low-lying state transition. Under helium gas environment, Doppler splitting was caused from particle motion. This effect was considered for optimization for isotope selection and analysis. Some analytical performances of this method were determined under optimum conditions and were discussed.

  12. Differential Optical Absorption Spectroscopy (DOAS) using Targets: SO2 and NO2 Measurements in Montevideo City

    NASA Astrophysics Data System (ADS)

    Louban, Ilia; Píriz, Gustavo; Platt, Ulrich; Frins, Erna

    2008-04-01

    SO2 and NO2 were remotely measured in a main street of Montevideo city using Multiaxis-Differential Optical Absorption Spectroscopy (MAX-DOAS) combined with on-field selected targets. Target-based measurements are the basis of a new experimental procedure called Topographic Target Light scattering-DOAS (TOTAL-DOAS) that provides a well define absorption path to measure the near surface distribution of trace gases in the boundary layer. It combines the measurement principles of the long-path DOAS and zenith-scattered sunlight DOAS, within the near UV and VIS spectral range. We give a general description of the procedure and present first results of the 2006 campaign at Montevideo.

  13. Reflection-absorption infrared spectroscopy of thin films using an external cavity quantum cascade laser

    NASA Astrophysics Data System (ADS)

    Phillips, Mark C.; Craig, Ian M.; Blake, Thomas A.

    2013-01-01

    We present experimental demonstrations using a broadly tunable external cavity quantum cascade laser (ECQCL) to perform Reflection-Absorption InfraRed Spectroscopy (RAIRS) of thin layers and residues on surfaces. The ECQCL compliance voltage was used to measure fluctuations in the ECQCL output power and improve the performance of the RAIRS measurements. Absorption spectra from self-assembled monolayers of a fluorinated alkane thiol and a thiol carboxylic acid were measured and compared with FTIR measurements. RAIRS spectra of the explosive compounds PETN, RDX, and tetryl deposited on gold substrates were also measured. Rapid measurement times and low noise were demonstrated, with <1E-3 absorbance noise for a 10 second measurement time.

  14. Quantifying the effect of finite spectral bandwidth on extinction coefficient of species in laser absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Singh, Manjeet; Singh, Jaswant; Singh, Baljit; Ghanshyam, C.

    2016-11-01

    The aim of this study is to quantify the finite spectral bandwidth effect on laser absorption spectroscopy for a wide-band laser source. Experimental analysis reveals that the extinction coefficient of an analyte is affected by the bandwidth of the spectral source, which may result in the erroneous conclusions. An approximate mathematical model has been developed for optical intensities having Gaussian line shape, which includes the impact of source's spectral bandwidth in the equation for spectroscopic absorption. This is done by introducing a suitable first order and second order bandwidth approximation in the Beer-Lambert law equation for finite bandwidth case. The derived expressions were validated using spectroscopic analysis with higher SBW on a test sample, Rhodamine B. The concentrations calculated using proposed approximation, were in significant agreement with the true values when compared with those calculated with conventional approach.

  15. Space Launch System Base Heating Test: Tunable Diode Laser Absorption Spectroscopy

    NASA Technical Reports Server (NTRS)

    Parker, Ron; Carr, Zak; MacLean, Mathew; Dufrene, Aaron; Mehta, Manish

    2016-01-01

    This paper describes the Tunable Diode Laser Absorption Spectroscopy (TDLAS) measurement of several water transitions that were interrogated during a hot-fire testing of the Space Launch Systems (SLS) sub-scale vehicle installed in LENS II. The temperature of the recirculating gas flow over the base plate was found to increase with altitude and is consistent with CFD results. It was also observed that the gas above the base plate has significant velocity along the optical path of the sensor at the higher altitudes. The line-by-line analysis of the H2O absorption features must include the effects of the Doppler shift phenomena particularly at high altitude. The TDLAS experimental measurements and the analysis procedure which incorporates the velocity dependent flow will be described.

  16. Reconstruction of an excited-state molecular wave packet with attosecond transient absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Cheng, Yan; Chini, Michael; Wang, Xiaowei; González-Castrillo, Alberto; Palacios, Alicia; Argenti, Luca; Martín, Fernando; Chang, Zenghu

    2016-08-01

    Attosecond science promises to allow new forms of quantum control in which a broadband isolated attosecond pulse excites a molecular wave packet consisting of a coherent superposition of multiple excited electronic states. This electronic excitation triggers nuclear motion on the molecular manifold of potential energy surfaces and can result in permanent rearrangement of the constituent atoms. Here, we demonstrate attosecond transient absorption spectroscopy (ATAS) as a viable probe of the electronic and nuclear dynamics initiated in excited states of a neutral molecule by a broadband vacuum ultraviolet pulse. Owing to the high spectral and temporal resolution of ATAS, we are able to reconstruct the time evolution of a vibrational wave packet within the excited B'Σ1u+ electronic state of H2 via the laser-perturbed transient absorption spectrum.

  17. Absorption spectroscopy of wire-array plasma at the non-radiative stage

    NASA Astrophysics Data System (ADS)

    Ivanov, V. V.; Hakel, P.; Mancini, R. C.; Wiewior, P.; Durmaz, T.; Anderson, A.; Astanovitskiy, A.; Chalyy, O.; Altemara, S. D.; Papp, D.; McKee, E.; Chittenden, J. P.; Niasse, N.; Shevelko, A. P.

    2010-11-01

    Absorption spectroscopy was applied to 1 MA wire-array Z-pinches. The 50 TW Leopard laser was coupled with the Zebra generator for x-ray backlighting of wire arrays. Wire-array plasmas were investigated at the ablation and implosion stages. Broadband x-ray radiation from a laser produced Sm plasma was used to backlight Al star wire arrays in the range of 7-9 å. Two time-integrated x-ray conical spectrometers recorded reference and main spectra. The backlighting radiation was separated from the powerful Z-pinch x-ray burst by collimators. A comparison of the backlighting radiation spectra that passed through the plasma with reference spectra indicates absorption lines in the range of 8.2-8.4 å. A plasma density profile was simulated with a 3D resistive MHD code. Simulations with atomic kinetics models derived an electron temperature of Al wire-array plasma.

  18. Infrared and near infrared transient absorption spectroscopy of molecular free radicals

    SciTech Connect

    Sears, T.J.; Wu, M.; Hall, G.E.; Chang, B.C.; Hansford, G.; Bloch, J.C.; Field, R.W.

    1993-12-31

    The advantages of absorption spectroscopy at low absorbances include a linear relationship between signal size and number of absorbing molecules, line of sight measurement, and easily interpretable lineshape functions. The main disadvantage is due to the necessity of measuring a small change in light intensity, usually in the presence of a strong background, which limits the sensitivity. In this work, recent results obtained using absorption techniques with continuous wave lasers to measure vibrational and electronic spectra in the mid- and near-infrared of small free radicals are reported. The radical of interest was generated by excimer laser photolysis of a chemically stable precursor molecule and detected by measuring the transient decrease in power of a continuous wave probe laser that traversed the photolyzed volume before being imaged onto a detector.

  19. Melting of iron determined by X-ray absorption spectroscopy to 100 GPa

    PubMed Central

    Aquilanti, Giuliana; Trapananti, Angela; Karandikar, Amol; Kantor, Innokenty; Marini, Carlo; Mathon, Olivier; Pascarelli, Sakura; Boehler, Reinhard

    2015-01-01

    Temperature, thermal history, and dynamics of Earth rely critically on the knowledge of the melting temperature of iron at the pressure conditions of the inner core boundary (ICB) where the geotherm crosses the melting curve. The literature on this subject is overwhelming, and no consensus has been reached, with a very large disagreement of the order of 2,000 K for the ICB temperature. Here we report new data on the melting temperature of iron in a laser-heated diamond anvil cell to 103 GPa obtained by X-ray absorption spectroscopy, a technique rarely used at such conditions. The modifications of the onset of the absorption spectra are used as a reliable melting criterion regardless of the solid phase from which the solid to liquid transition takes place. Our results show a melting temperature of iron in agreement with most previous studies up to 100 GPa, namely of 3,090 K at 103 GPa. PMID:26371317

  20. Reflection-Absorption Infrared Spectroscopy of Thin Films Using an External Cavity Quantum Cascade Laser

    SciTech Connect

    Phillips, Mark C.; Craig, Ian M.; Blake, Thomas A.

    2013-02-04

    We present experimental demonstrations using a broadly tunable external cavity quantum cascade laser (ECQCL) to perform Reflection-Absorption InfraRed Spectroscopy (RAIRS) of thin layers and residues on surfaces. The ECQCL compliance voltage was used to measure fluctuations in the ECQCL output power and improve the performance of the RAIRS measurements. Absorption spectra from self-assembled monolayers of a fluorinated alkane thiol and a thiol carboxylic acid were measured and compared with FTIR measurements. RAIRS spectra of the explosive compounds PETN, RDX, and tetryl deposited on gold substrates were also measured. Rapid measurement times and low noise were demonstrated, with < 1E-3 absorbance noise for a 10 second measurement time.

  1. Quantitative Determination of Absolute Organohalogen Concentrations in Environmental Samples by X-ray Absorption Spectroscopy

    SciTech Connect

    Leri,A.; Hay, M.; Lanzirotti, A.; Rao, W.; Myneni, S.

    2006-01-01

    An in situ procedure for quantifying total organic and inorganic Cl concentrations in environmental samples based on X-ray absorption near-edge structure (XANES) spectroscopy has been developed. Cl 1s XANES spectra reflect contributions from all Cl species present in a sample, providing a definitive measure of total Cl concentration in chemically heterogeneous samples. Spectral features near the Cl K-absorption edge provide detailed information about the bonding state of Cl, whereas the absolute fluorescence intensity of the spectra is directly proportional to total Cl concentration, allowing for simultaneous determination of Cl speciation and concentration in plant, soil, and natural water samples. Absolute Cl concentrations are obtained from Cl 1s XANES spectra using a series of Cl standards in a matrix of uniform bulk density. With the high sensitivity of synchrotron-based X-ray absorption spectroscopy, Cl concentration can be reliably measured down to the 5-10 ppm range in solid and liquid samples. Referencing the characteristic near-edge features of Cl in various model compounds, we can distinguish between inorganic chloride (Cl{sub inorg}) and organochlorine (Cl{sub org}), as well as between aliphatic Cl{sub org} and aromatic Cl{sub org}, with uncertainties in the range of {approx}6%. In addition, total organic and inorganic Br concentrations in sediment samples are quantified using a combination of Br 1s XANES and X-ray fluorescence (XRF) spectroscopy. Br concentration is detected down to {approx}1 ppm by XRF, and Br 1s XANES spectra allow quantification of the Br{sub inorg} and Br{sub org} fractions. These procedures provide nondestructive, element-specific techniques for quantification of Cl and Br concentrations that preclude extensive sample preparation.

  2. Laser plasma x-ray source for ultrafast time-resolved x-ray absorption spectroscopy

    DOE PAGES

    Miaja-Avila, L.; O'Neil, G. C.; Uhlig, J.; ...

    2015-03-02

    We describe a laser-driven x-ray plasma source designed for ultrafast x-ray absorption spectroscopy. The source is comprised of a 1 kHz, 20 W, femtosecond pulsed infrared laser and a water target. We present the x-ray spectra as a function of laser energy and pulse duration. Additionally, we investigate the plasma temperature and photon flux as we vary the laser energy. We obtain a 75 μm FWHM x-ray spot size, containing ~106 photons/s, by focusing the produced x-rays with a polycapillary optic. Since the acquisition of x-ray absorption spectra requires the averaging of measurements from >107 laser pulses, we also presentmore » data on the source stability, including single pulse measurements of the x-ray yield and the x-ray spectral shape. In single pulse measurements, the x-ray flux has a measured standard deviation of 8%, where the laser pointing is the main cause of variability. Further, we show that the variability in x-ray spectral shape from single pulses is low, thus justifying the combining of x-rays obtained from different laser pulses into a single spectrum. Finally, we show a static x-ray absorption spectrum of a ferrioxalate solution as detected by a microcalorimeter array. Altogether, our results demonstrate that this water-jet based plasma source is a suitable candidate for laboratory-based time-resolved x-ray absorption spectroscopy experiments.« less

  3. Laser plasma x-ray source for ultrafast time-resolved x-ray absorption spectroscopy

    PubMed Central

    Miaja-Avila, L.; O'Neil, G. C.; Uhlig, J.; Cromer, C. L.; Dowell, M. L.; Jimenez, R.; Hoover, A. S.; Silverman, K. L.; Ullom, J. N.

    2015-01-01

    We describe a laser-driven x-ray plasma source designed for ultrafast x-ray absorption spectroscopy. The source is comprised of a 1 kHz, 20 W, femtosecond pulsed infrared laser and a water target. We present the x-ray spectra as a function of laser energy and pulse duration. Additionally, we investigate the plasma temperature and photon flux as we vary the laser energy. We obtain a 75 μm FWHM x-ray spot size, containing ∼106 photons/s, by focusing the produced x-rays with a polycapillary optic. Since the acquisition of x-ray absorption spectra requires the averaging of measurements from >107 laser pulses, we also present data on the source stability, including single pulse measurements of the x-ray yield and the x-ray spectral shape. In single pulse measurements, the x-ray flux has a measured standard deviation of 8%, where the laser pointing is the main cause of variability. Further, we show that the variability in x-ray spectral shape from single pulses is low, thus justifying the combining of x-rays obtained from different laser pulses into a single spectrum. Finally, we show a static x-ray absorption spectrum of a ferrioxalate solution as detected by a microcalorimeter array. Altogether, our results demonstrate that this water-jet based plasma source is a suitable candidate for laboratory-based time-resolved x-ray absorption spectroscopy experiments. PMID:26798792

  4. Laser plasma x-ray source for ultrafast time-resolved x-ray absorption spectroscopy

    SciTech Connect

    Miaja-Avila, L.; O'Neil, G. C.; Uhlig, J.; Cromer, C. L.; Dowell, M. L.; Jimenez, R.; Hoover, A. S.; Silverman, K. L.; Ullom, J. N.

    2015-03-02

    We describe a laser-driven x-ray plasma source designed for ultrafast x-ray absorption spectroscopy. The source is comprised of a 1 kHz, 20 W, femtosecond pulsed infrared laser and a water target. We present the x-ray spectra as a function of laser energy and pulse duration. Additionally, we investigate the plasma temperature and photon flux as we vary the laser energy. We obtain a 75 μm FWHM x-ray spot size, containing ~106 photons/s, by focusing the produced x-rays with a polycapillary optic. Since the acquisition of x-ray absorption spectra requires the averaging of measurements from >107 laser pulses, we also present data on the source stability, including single pulse measurements of the x-ray yield and the x-ray spectral shape. In single pulse measurements, the x-ray flux has a measured standard deviation of 8%, where the laser pointing is the main cause of variability. Further, we show that the variability in x-ray spectral shape from single pulses is low, thus justifying the combining of x-rays obtained from different laser pulses into a single spectrum. Finally, we show a static x-ray absorption spectrum of a ferrioxalate solution as detected by a microcalorimeter array. Altogether, our results demonstrate that this water-jet based plasma source is a suitable candidate for laboratory-based time-resolved x-ray absorption spectroscopy experiments.

  5. Laser plasma x-ray source for ultrafast time-resolved x-ray absorption spectroscopy.

    PubMed

    Miaja-Avila, L; O'Neil, G C; Uhlig, J; Cromer, C L; Dowell, M L; Jimenez, R; Hoover, A S; Silverman, K L; Ullom, J N

    2015-03-01

    We describe a laser-driven x-ray plasma source designed for ultrafast x-ray absorption spectroscopy. The source is comprised of a 1 kHz, 20 W, femtosecond pulsed infrared laser and a water target. We present the x-ray spectra as a function of laser energy and pulse duration. Additionally, we investigate the plasma temperature and photon flux as we vary the laser energy. We obtain a 75 μm FWHM x-ray spot size, containing ∼10(6) photons/s, by focusing the produced x-rays with a polycapillary optic. Since the acquisition of x-ray absorption spectra requires the averaging of measurements from >10(7) laser pulses, we also present data on the source stability, including single pulse measurements of the x-ray yield and the x-ray spectral shape. In single pulse measurements, the x-ray flux has a measured standard deviation of 8%, where the laser pointing is the main cause of variability. Further, we show that the variability in x-ray spectral shape from single pulses is low, thus justifying the combining of x-rays obtained from different laser pulses into a single spectrum. Finally, we show a static x-ray absorption spectrum of a ferrioxalate solution as detected by a microcalorimeter array. Altogether, our results demonstrate that this water-jet based plasma source is a suitable candidate for laboratory-based time-resolved x-ray absorption spectroscopy experiments.

  6. Tunable Diode Laser Absorption Spectroscopy of Metastable Atoms in Dusty Plasmas

    SciTech Connect

    Hoang Tung Do; Hippler, Rainer

    2008-09-07

    Spatial density profile of neon metastable produced in dusty plasma was investigated by means of tunable diode laser absorption spectroscopy. The line averaged measured density drops about 30% with the presence of dust particles. The observations provide evidence for a significant interaction between atoms and powder particles which are important for energy transfer from plasma to particles. The power per unit area absorbed by dust particles due to the collision of metastable atoms with dust particle surface is about some tens of mW/m{sup 2}.

  7. Metal release in metallothioneins induced by nitric oxide: X-ray absorption spectroscopy study.

    PubMed

    Casero, Elena; Martín-Gago, José A; Pariente, Félix; Lorenzo, Encarnación

    2004-12-01

    Metallothioneins (MTs) are low molecular weight proteins that include metal ions in thiolate clusters. The capability of metallothioneins to bind different metals has suggested their use as biosensors for different elements. We study here the interaction of nitric oxide with rat liver MTs by using in situ X-ray absorption spectroscopy techniques. We univocally show that the presence of NO induces the release of Zn atoms from the MT structure to the solution. Zn ions transform in the presence of NO from a tetrahedral four-fold coordinated environment in the MT into a regular octahedral six-fold coordinated state, with interatomic distances compatible with those of Zn solvated in water.

  8. Determination of the melting temperature of palladium nanoparticles by X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Vlasenko, V. G.; Podsukhina, S. S.; Kozinkin, A. V.; Zubavichus, Ya. V.

    2016-02-01

    The anharmonicity parameters of the interatomic potential in ~4-nm palladium nanoparticles deposited on poly(tetra)fluoroethylene microgranules 0.2-0.5 μm in average size were studied by X-ray absorption spectroscopy from an analysis of temperature-dependent EXAFS Pd K edges. The parameters of the interatomic potential obtained were used to calculate melting temperature T melt = 1591 K and Debye temperature ΘD = 257 K of palladium nanoparticles; these temperatures are significantly lower than those in metallic palladium: 277 K and 1825 K, respectively.

  9. Determination of heavy metals in solid emission and immission samples using atomic absorption spectroscopy

    SciTech Connect

    Fara, M.; Novak, F.

    1995-12-01

    Both flame and electrothermal methods of atomic absorption spectroscopy (AAS) have been applied to the determination of Al, As, Be, Ca, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, TI, Se, V and Zn in emission and emission (deposition) samples decomposed in open PTFE test-tubes by individual fuming-off hydrofluoric, perchloroic and nitric acid. An alternative hydride technique was also used for As and Se determination and Hg was determined using a self-contained AAS analyzer. A graphite platform proved good to overcome non-spectral interferences in AAS-ETA. Methods developed were verified by reference materials (inc. NBS 1633a).

  10. Wavelength modulation spectroscopy--digital detection of gas absorption harmonics based on Fourier analysis.

    PubMed

    Mei, Liang; Svanberg, Sune

    2015-03-20

    This work presents a detailed study of the theoretical aspects of the Fourier analysis method, which has been utilized for gas absorption harmonic detection in wavelength modulation spectroscopy (WMS). The lock-in detection of the harmonic signal is accomplished by studying the phase term of the inverse Fourier transform of the Fourier spectrum that corresponds to the harmonic signal. The mathematics and the corresponding simulation results are given for each procedure when applying the Fourier analysis method. The present work provides a detailed view of the WMS technique when applying the Fourier analysis method.

  11. Infrared reflection absorption spectroscopy investigation of carbon nanotube growth on cobalt catalyst surfaces

    NASA Astrophysics Data System (ADS)

    Kimura, Yasuo; Numasawa, Takeru; Nihei, Mizuhisa; Niwano, Michio

    2007-02-01

    To clarify the effect the oxygen has on the carbon nanotube (CNT) growth mechanisms, the authors use infrared absorption spectroscopy for the monitoring of CNT growth on cobalt catalyst surfaces. CNT grew when methanol was used as a reaction gas, while they did not grow when methane was used. The authors observed spectral changes due to the formation of cobalt oxides and methoxides on the cobalt catalyst surfaces only during the growth of CNT. The results indicate that partial oxidation of the cobalt catalyst surface increases the adsorption probability of the reaction gas and ultimately induces growth of CNT.

  12. The determination of aluminum, copper, iron, and lead in glycol formulations by atomic absorption spectroscopy

    NASA Technical Reports Server (NTRS)

    1977-01-01

    Initial screening tests and the results obtained in developing procedures to determine Al, Cu, Fe, and Pb in glycol formulations are described. Atomic absorption completion was selected for Cu, Fe and Pb, and after comparison with emission spectroscopy, was selected for Al also. Before completion, carbon, iron, and lead are extracted with diethyl dithio carbamate (DDC) into methyl isobutyl ketone (MIBK). Aluminum was also extracted into MIBK using 8-hydroxyquinoline as a chelating agent. As little as 0.02 mg/l carbon and 0.06 mg/l lead or iron may be determined in glycol formulations. As little as 0.3 mg/l aluminum may be determined.

  13. Intracavity Laser Absorption Spectroscopy of Zirconium Fluoride in the Near Infrared

    NASA Astrophysics Data System (ADS)

    O'Brien, Leah C.; Harms, Jack C.; O'Brien, James J.

    2013-06-01

    A new band of ZrF has been recorded in the near-infrared with rotational resolution using intracavity laser absorption spectroscopy. A red-degraded bandhead is observed at 12527wn, and 2 R-branches and 2 P-branches have been identified. The results of the analysis will be presented. The gas phase ZrF molecules were produced using a zirconium-lined hollow cathode in an argon-based electric discharge with a small amount of SF_{6}.

  14. Quantum Cascade Laser Absorption Spectroscopy as a Plasma Diagnostic Tool: An Overview

    PubMed Central

    Welzel, Stefan; Hempel, Frank; Hübner, Marko; Lang, Norbert; Davies, Paul B.; Röpcke, Jürgen

    2010-01-01

    The recent availability of thermoelectrically cooled pulsed and continuous wave quantum and inter-band cascade lasers in the mid-infrared spectral region has led to significant improvements and new developments in chemical sensing techniques using in-situ laser absorption spectroscopy for plasma diagnostic purposes. The aim of this article is therefore two-fold: (i) to summarize the challenges which arise in the application of quantum cascade lasers in such environments, and, (ii) to provide an overview of recent spectroscopic results (encompassing cavity enhanced methods) obtained in different kinds of plasma used in both research and industry. PMID:22163581

  15. Total Absorption Spectroscopy Study of (92)Rb Decay: A Major Contributor to Reactor Antineutrino Spectrum Shape.

    PubMed

    Zakari-Issoufou, A-A; Fallot, M; Porta, A; Algora, A; Tain, J L; Valencia, E; Rice, S; Bui, V M; Cormon, S; Estienne, M; Agramunt, J; Äystö, J; Bowry, M; Briz, J A; Caballero-Folch, R; Cano-Ott, D; Cucoanes, A; Elomaa, V-V; Eronen, T; Estévez, E; Farrelly, G F; Garcia, A R; Gelletly, W; Gomez-Hornillos, M B; Gorlychev, V; Hakala, J; Jokinen, A; Jordan, M D; Kankainen, A; Karvonen, P; Kolhinen, V S; Kondev, F G; Martinez, T; Mendoza, E; Molina, F; Moore, I; Perez-Cerdán, A B; Podolyák, Zs; Penttilä, H; Regan, P H; Reponen, M; Rissanen, J; Rubio, B; Shiba, T; Sonzogni, A A; Weber, C

    2015-09-04

    The antineutrino spectra measured in recent experiments at reactors are inconsistent with calculations based on the conversion of integral beta spectra recorded at the ILL reactor. (92)Rb makes the dominant contribution to the reactor antineutrino spectrum in the 5-8 MeV range but its decay properties are in question. We have studied (92)Rb decay with total absorption spectroscopy. Previously unobserved beta feeding was seen in the 4.5-5.5 region and the GS to GS feeding was found to be 87.5(25)%. The impact on the reactor antineutrino spectra calculated with the summation method is shown and discussed.

  16. A quality control technique based on UV-VIS absorption spectroscopy for tequila distillery factories

    NASA Astrophysics Data System (ADS)

    Barbosa Garcia, O.; Ramos Ortiz, G.; Maldonado, J. L.; Pichardo Molina, J.; Meneses Nava, M. A.; Landgrave, Enrique; Cervantes, M. J.

    2006-02-01

    A low cost technique based on the UV-VIS absorption spectroscopy is presented for the quality control of the spirit drink known as tequila. It is shown that such spectra offer enough information to discriminate a given spirit drink from a group of bottled commercial tequilas. The technique was applied to white tequilas. Contrary to the reference analytic methods, such as chromatography, for this technique neither special personal training nor sophisticated instrumentations is required. By using hand-held instrumentation this technique can be applied in situ during the production process.

  17. Diffuse-light absorption spectroscopy for beer classification and prediction of alcoholic content

    NASA Astrophysics Data System (ADS)

    Ciaccheri, L.; Samano Baca, E. E.; Russo, M. T.; Ottevaere, H.; Thienpont, H.; Mignani, A. G.

    2012-04-01

    A miscellaneous of 86 beers was characterized by non-destructive, fast and reagent-free optical measurements. Diffuselight absorption spectroscopy performed in the visible and near-infrared bands was used to gather a turbidity-free spectroscopic information. Also, conventional turbidity and refractive index measurements were added for completing the optical characterization. The near-infrared spectra provided a straightforward turbidity-free assessment of the alcoholic strength. Then, the entire optical data set was processed by means of multivariate analysis looking for a beer clustering according to the own character and identity. Good results were achieved, indicating that optical methods can be successfully used for beer authentication.

  18. [Measurement of trace elements in blood serum by atomic absorption spectroscopy with electrothermal atomization].

    PubMed

    Rogul'skiĭ, Iu V; Danil'chenko, S N; Lushpa, A P; Sukhodub, L F

    1997-09-01

    Describes a method for measuring trace elements Cr, Mn, Co, Fe, Cu, Zn, and Mo in the blood serum using non-flame atomization (KAC 120.1 complex). Optimal conditions for preparing the samples were defined, temperature regimens for analysis of each element selected, and original software permitting automated assays created. The method permits analysis making use of the minimal samples: 0.1 ml per 10 parallel measurements, which is 100 times less than needed for atomic absorption spectroscopy with flame atomization of liquid samples. Metrological characteristics of the method are assessed.

  19. Multiplexed detection of xylene and trichloroethylene in water by photonic crystal absorption spectroscopy.

    PubMed

    Lai, Wei-Cheng; Chakravarty, Swapnajit; Zou, Yi; Chen, Ray T

    2013-10-01

    We experimentally demonstrate simultaneous selective detection of xylene and trichloroethylene (TCE) using multiplexed photonic crystal waveguides (PCWs) by near-infrared optical absorption spectroscopy on a chip. Based on the slow light effect of photonic crystal structure, the sensitivity of our device is enhanced to 1 ppb (v/v) for xylene and 10 ppb (v/v) for TCE in water. Multiplexing is enabled by multimode interference power splitters and Y-combiners that integrate multiple PCWs on a silicon chip in a silicon-on-insulator platform.

  20. Solvation and Deprotonation Dynamics in Reverse Micelles via Broadband Femtoseond Transient Absorption (BFTA) Spectroscopy

    NASA Astrophysics Data System (ADS)

    Cole, Richard

    2009-10-01

    Broadband femtosecond transient absorption (BFTA) spectroscopy is a useful tool in characterizing femtosecond and picosecond physical and chemical dynamics such as solvation, electron transfer, and deprotonation dynamics. This presentation will focus on our most recent results, which utilize BFTA spectroscopy in the ultraviolet-visible (UV-vis) spectral range to probe deprotonation and solvation dynamics in the nanoscopic confinement of reverse micelles. In these studies, pyranine, a `photo-acid', probes both solvation and deprotonation dynamics in reverse micelles formed from cationic (cetyl trimethylammonium bromide, CTAB), anionic (sodium dioctyl sulfosuccinate, AOT), and neutral (polyoxyethylene nonylphenylether, Igepal) surfactants. Dynamic behavior will be discussed in terms of the degree of nanoscopic confinement (micellar size) and the impact of varying interfacial environments.

  1. XAS on Rh and Ir metal sites in post synthetically functionalized UiO-67 Zirconium MOFs

    NASA Astrophysics Data System (ADS)

    Braglia, L.; Borfecchia, E.; Lomachenko, K. A.; Øien, S.; Lillerud, K. P.; Lamberti, C.

    2016-05-01

    We synthesized UiO-67 metal-organic-frameworks (MOFs) functionalized with different transition metals (Rh, Ir). Using EXAFS we verified that the synthesis has been successful. Furthermore, we observed the change of local environment while varying of metal site. XAS spectroscopy is the most informative technique to characterize these kind of materials and to study the local environment around the metal site.

  2. Structural changes in a polyelectrolyte multilayer assembly investigated by reflection absorption infrared spectroscopy and sum frequency generation spectroscopy.

    PubMed

    Kett, Peter J N; Casford, Michael T L; Yang, Amanda Y; Lane, Thomas J; Johal, Malkiat S; Davies, Paul B

    2009-02-12

    The structure of polyelectrolyte multilayer films adsorbed onto either a per-protonated or per-deuterated 11-mercaptoundecanoic acid (h-MUA/d-MUA) self assembled monolayer (SAM) on gold was investigated in air using two surface vibrational spectroscopy techniques, namely, reflection absorption infrared spectroscopy (RAIRS) and sum frequency generation (SFG) spectroscopy. Determination of film masses and dissipation values were made using a quartz crystal microbalance with dissipation monitoring (QCM-D). The films, containing alternating layers of the polyanion poly[1-[4-(3-carboxy-4-hydroxyphenylazo) benzenesulfonamido]-1,2-ethanediyl, sodium salt] (PAZO) and the polycation poly(ethylenimine) (PEI) built on the MUA SAM, were formed using the layer-by-layer electrostatic self-assembly method. The SFG spectrum of the SAM itself comprised strong methylene resonances, indicating the presence of gauche defects in the alkyl chains of the acid. The RAIRS spectrum of the SAM also contained strong methylene bands, indicating a degree of orientation of the methylene groups parallel to the surface normal. Changes in the SFG and RAIRS spectra when a PEI layer was adsorbed on the MUA monolayer showed that the expected electrostatic interaction between the polymer and the SAM, probably involving interpenetration of the PEI into the MUA monolayer, caused a straightening of the alkyl chains of the MUA and, consequently, a decrease in the number of gauche defects. When a layer of PAZO was subsequently deposited on the MUA/PEI film, further spectral changes occurred that can be explained by the formation of a complex PEI/PAZO interpenetrated layer. A per-deuterated MUA SAM was used to determine the relative contributions from the adsorbed polyelectrolytes and the MUA monolayer to the RAIRS and SFG spectra. Spectroscopic and adsorbed mass measurements combined showed that as further bilayers were constructed the interpenetration of PAZO into preadsorbed PEI layers was repeated, up to

  3. Evolution of silver nanoparticles in the rat lung investigated by X-ray absorption spectroscopy

    SciTech Connect

    Davidson, R. Andrew; Anderson, Donald S.; Van Winkle, Laura S.; Pinkerton, Kent E.; Guo, T.

    2014-12-16

    Following a 6-h inhalation exposure to aerosolized 20 and 110 nm diameter silver nanoparticles, lung tissues from rats were investigated with X-ray absorption spectroscopy, which can identify the chemical state of silver species. Lung tissues were processed immediately after sacrifice of the animals at 0, 1, 3, and 7 days post exposure and the samples were stored in an inert and low-temperature environment until measured. We found that it is critical to follow a proper processing, storage and measurement protocol; otherwise only silver oxides are detected after inhalation even for the larger nanoparticles. The results of X-ray absorption spectroscopy measurements taken in air at 85 K suggest that the dominating silver species in all the postexposure lung tissues were metallic silver, not silver oxide, or solvated silver cations. The results further indicate that the silver nanoparticles in the tissues were transformed from the original nanoparticles to other forms of metallic silver nanomaterials and the rate of this transformation depended on the size of the original nanoparticles. Furthermore, we found that 20 nm diameter silver nanoparticles were significantly modified after aerosolization and 6-h inhalation/deposition, whereas larger, 110 nm diameter nanoparticles were largely unchanged. Over the seven-day postexposure period the smaller 20 nm silver nanoparticles underwent less change in the lung tissue than the larger 110 nm silver nanoparticles. In contrast, silica-coated gold nanoparticles did not undergo any modification processes and remained as the initial nanoparticles throughout the 7-day study period.

  4. Peroxy radical detection for airborne atmospheric measurements using absorption spectroscopy of NO2

    NASA Astrophysics Data System (ADS)

    Horstjann, M.; Andrés Hernández, M. D.; Nenakhov, V.; Chrobry, A.; Burrows, J. P.

    2014-05-01

    Development of an airborne instrument for the determination of peroxy radicals (PeRCEAS - peroxy radical chemical enhancement and absorption spectroscopy) is reported. Ambient peroxy radicals (HO2 and RO2, R being an organic chain) are converted to NO2 in a reactor using a chain reaction involving NO and CO. Provided that the amplification factor, called effective chain length (eCL), is known, the concentration of NO2 can be used as a proxy for the peroxy radical concentration in the sampled air. The eCL depends on radical surface losses and must thus be determined experimentally for each individual setup. NO2 is detected by continuous-wave cavity ring-down spectroscopy (cw-CRDS) using an extended cavity diode laser (ECDL) at 408.9 nm. Optical feedback from a V-shaped resonator maximizes transmission and allows for a simple detector setup. CRDS directly yields absorption coefficients, thus providing NO2 concentrations without additional calibration. The optimum 1σ detection limit is 0.3 ppbv at an averaging time of 40 s and an inlet pressure of 300 hPa. Effective chain lengths were determined for HO2 and CH3O2 at different inlet pressures. The 1σ detection limit at an inlet pressure of 300 hPa for HO2 is 3 pptv for an averaging time of 120 s.

  5. Combined characterization of bovine polyhemoglobin microcapsules by UV-Vis absorption spectroscopy and cyclic voltammetry.

    PubMed

    Knirsch, Marcos Camargo; Dell'Anno, Filippo; Salerno, Marco; Larosa, Claudio; Polakiewicz, Bronislaw; Eggenhöffner, Roberto; Converti, Attilio

    2017-03-01

    Polyhemoglobin produced from pure bovine hemoglobin by reaction with PEG bis(N-succynimidil succinate) as a cross-linking agent was encapsulated in gelatin and dehydrated by freeze-drying. Free carboxyhemoglobin and polyhemoglobin microcapsules were characterized by UV-Vis spectroscopy in the absorption range 450-650 nm and cyclic voltammetry in the voltage range from -0.8 to 0.6 mV to evaluate the ability to break the bond with carbon monoxide and to study the carrier's affinity for oxygen, respectively. SEM used to observe the shape of cross-linked gelatin-polyhemoglobin microparticles showed a regular distribution of globular shapes, with mean size of ~750 nm, which was ascribed to gelatin. Atomic absorption spectroscopy was also performed to detect iron presence in microparticles. Cyclic voltammetry using an Ag-AgCl electrode highlighted characteristic peaks at around -0.6 mV that were attributed to reversible oxygen bonding with iron in oxy-polyhemoglobin structure. These results suggest this technique as a powerful, direct and alternative method to evaluate the extent of hemoglobin oxygenation.

  6. Total Absorption Spectroscopy of the 137Xe, 137I, and 92Rb β-Decays

    NASA Astrophysics Data System (ADS)

    Rasco, B. C.; Fijałkowska, A.; Karny, M.; Rykaczewski, K. P.; Wolińska-Cichocka, M.; Goetz, K. C.; Grzywacz, R. K.; Gross, C. J.; Miernik, K.; Stracener, D.

    2015-10-01

    The NaI(Tl) based Modular Total Absorption Spectrometer (MTAS) was constructed to measure improved β-decay feeding patterns from neutron-rich nuclei. It is difficult to measure β-decay feeding intensities with high precision γ-ray measurements due to the low efficiency of high precision detectors. There are several important applications of improved measurements of β-decay feeding patterns by total absorption spectroscopy; improve understanding of elemental abundances in the universe, help with stockpile stewardship, contribute to understanding of underlying nuclear structure, and improve β-decay feeding measurements to calculate accurately the νe spectra needed to evaluate precisely reactor neutrino measurements. We present β-decay feeding results for two ``priority one'' measurements, 137Xe and 137I, and for 92Rb, which is a large individual contributor to the νe uncertainty of the reactor anomaly. In addition to β- γ decays, 137I has a β-neutron decay channel which is measurable in MTAS. We will demonstrate techniques for analyzing MTAS γ-decay data. We will also describe β and neutron spectroscopy in MTAS. This work was supported by the US DOE by Award No. DE-FG02- 96ER40978 and by US DOE, Office of Nuclear Physics.

  7. Evolution of Silver Nanoparticles in the Rat Lung Investigated by X-ray Absorption Spectroscopy

    PubMed Central

    2015-01-01

    Following a 6-h inhalation exposure to aerosolized 20 and 110 nm diameter silver nanoparticles, lung tissues from rats were investigated with X-ray absorption spectroscopy, which can identify the chemical state of silver species. Lung tissues were processed immediately after sacrifice of the animals at 0, 1, 3, and 7 days post exposure and the samples were stored in an inert and low-temperature environment until measured. We found that it is critical to follow a proper processing, storage and measurement protocol; otherwise only silver oxides are detected after inhalation even for the larger nanoparticles. The results of X-ray absorption spectroscopy measurements taken in air at 85 K suggest that the dominating silver species in all the postexposure lung tissues were metallic silver, not silver oxide, or solvated silver cations. The results further indicate that the silver nanoparticles in the tissues were transformed from the original nanoparticles to other forms of metallic silver nanomaterials and the rate of this transformation depended on the size of the original nanoparticles. We found that 20 nm diameter silver nanoparticles were significantly modified after aerosolization and 6-h inhalation/deposition, whereas larger, 110 nm diameter nanoparticles were largely unchanged. Over the seven-day postexposure period the smaller 20 nm silver nanoparticles underwent less change in the lung tissue than the larger 110 nm silver nanoparticles. In contrast, silica-coated gold nanoparticles did not undergo any modification processes and remained as the initial nanoparticles throughout the 7-day study period. PMID:25517690

  8. Time-resolved postdischarge absolute silicon monoxide density measurement by resonant absorption spectroscopy in a nonthermal atmospheric plasma

    SciTech Connect

    Motret, Olivier; Coursimault, Fabien; Pouvesle, Jean-Michel

    2006-11-01

    In this study we present the technique of resonant absorption spectroscopy diagnostic developed to estimate the density of silicon monoxide (SiO) molecules during the postdischarge of an atmospheric dielectric barrier discharge plasma. The ultraviolet (0,0) rovibrational band of the SiO(A {sup 1}{pi}-X {sup 1}{sigma}{sup +}) electronic transition was investigated. Effective values of absorption coefficient and absorption cross section for the rotational transitions under consideration were calculated. The SiO concentration was estimated by comparison between experimental and computed spectra. The self-absorption in the probe reactor was taken into account in the computed spectra.

  9. Electronic structure measurements of metal-organic solar cell dyes using x-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Johnson, Phillip S.

    The focus of this thesis is twofold: to report the results of X-ray absorption studies of metal-organic dye molecules for dye-sensitized solar cells and to provide a basic training manual on X-ray absorption spectroscopy techniques and data analysis. The purpose of our research on solar cell dyes is to work toward an understanding of the factors influencing the electronic structure of the dye: the choice of the metal, its oxidation state, ligands, and cage structure. First we study the effect of replacing Ru in several common dye structures by Fe. First-principles calculations and X-ray absorption spectroscopy at the C 1s and N 1s edges are combined to investigate transition metal dyes in octahedral and square planar N cages. Octahedral molecules are found to have a downward shift in the N 1s-to-pi* transition energy and an upward shift in C 1s-to-pi* transition energy when Ru is replaced by Fe, explained by an extra transfer of negative charge from Fe to the N ligands compared to Ru. For the square planar molecules, the behavior is more complex because of the influence of axial ligands and oxidation state. Next the crystal field parameters for a series of phthalocyanine and porphyrins dyes are systematically determined using density functional calculations and atomic multiplet calculations with polarization-dependent X-ray absorption spectra. The polarization dependence of the spectra provides information on orbital symmetries which ensures the determination of the crystal field parameters is unique. A uniform downward scaling of the calculated crystal field parameters by 5-30% is found to be necessary to best fit the spectra. This work is a part of the ongoing effort to design and test new solar cell dyes. Replacing the rare metal Ru with abundant metals like Fe would be a significant advance for dye-sensitized solar cells. Understanding the effects of changing the metal centers in these dyes in terms of optical absorption, charge transfer, and electronic

  10. Impact of atmospheric state uncertainties on retrieved XCO2 columns from laser differential absorption spectroscopy measurements

    NASA Astrophysics Data System (ADS)

    Zaccheo, T. Scott; Pernini, Timothy; Snell, Hilary E.; Browell, Edward V.

    2014-01-01

    This work assesses the impact of uncertainties in atmospheric state knowledge on retrievals of carbon dioxide column amounts (XCO2) from laser differential absorption spectroscopy (LAS) measurements. LAS estimates of XCO2 columns are normally derived not only from differential absorption observations but also from measured or prior knowledge of atmospheric state that includes temperature, moisture, and pressure along the viewing path. In the case of global space-based monitoring systems, it is often difficult if not impossible to provide collocated in situ measurements of atmospheric state for all observations, so retrievals often rely on collocated remote-sensed data or values derived from numerical weather prediction (NWP) models to describe the atmospheric state. A radiative transfer-based simulation framework, combined with representative global upper-air observations and matched NWP profiles, was used to assess the impact of model differences on estimates of column CO2 and O2 concentrations. These analyses focus on characterizing these errors for LAS measurements of CO2 in the 1.57-μm region and of O2 in the 1.27-μm region. The results provide a set of signal-to-noise metrics that characterize the errors in retrieved values associated with uncertainties in atmospheric state and provide a method for selecting optimal differential absorption line pairs to minimize the impact of these noise terms.

  11. Initial Results of Optical Vortex Laser Absorption Spectroscopy in the HYPER-I Device

    NASA Astrophysics Data System (ADS)

    Yoshimura, Shinji; Asai, Shoma; Aramaki, Mitsutoshi; Terasaka, Kenichiro; Ozawa, Naoya; Tanaka, Masayoshi; Morisaki, Tomohiro

    2015-11-01

    Optical vortex beams have a potential to make a new Doppler measurement, because not only parallel but perpendicular movement of atoms against the beam axis causes the Doppler shift of their resonant absorption frequency. As the first step of a proof-of-principle experiment, we have performed the optical vortex laser absorption spectroscopy for metastable argon neutrals in an ECR plasma produced in the HYPER-I device at the National Institute for Fusion Science, Japan. An external cavity diode laser (TOPTICA, DL100) of which center wavelength was 696.735 nm in vacuum was used for the light source. The Hermite-Gaussian (HG) beam was converted into the Laguerre-Gaussian (LG) beam (optical vortex) by a computer-generated hologram displayed on the spatial light modulator (Hamamatsu, LCOS-SLM X10468-07). In order to make fast neutral flow across the LG beam, a high speed solenoid valve system was installed on the HYPER-I device. Initial results including the comparison of absorption spectra for HG and LG beams will be presented. This study was supported by NINS young scientists collaboration program for cross-disciplinary study, NIFS collaboration research program (NIFS13KOAP026), and JSPS KAKENHI grant number 15K05365.

  12. Study of acyl group migration by femtosecond transient absorption spectroscopy and computational chemistry.

    PubMed

    Pritchina, Elena A; Gritsan, Nina P; Burdzinski, Gotard T; Platz, Matthew S

    2007-10-25

    The primary photophysical and photochemical processes in the photochemistry of 1-acetoxy-2-methoxyanthraquinone (1a) were studied using femtosecond transient absorption spectroscopy. Excitation of 1a at 270 nm results in the population of a set of highly excited singlet states. Internal conversion to the lowest singlet npi* excited state, followed by an intramolecular vibrational energy redistribution (IVR) process, proceeds with a time constant of 150 +/- 90 fs. The 1npi* excited state undergoes very fast intersystem crossing (ISC, 11 +/- 1 ps) to form the lowest triplet pipi* excited state which contains excess vibrational energy. The vibrational cooling occurs somewhat faster (4 +/- 1 ps) than ISC. The primary photochemical process, migration of acetoxy group, proceeds on the triplet potential energy surface with a time constant of 220 +/- 30 ps. The transient absorption spectra of the lowest singlet and triplet excited states of 1a, as well as the triplet excited state of the product, 9-acetoxy-2-methoxy-1,10-anthraquinone (2a), were detected. The assignments of the transient absorption spectra were supported by time-dependent DFT calculations of the UV-vis spectra of the proposed intermediates. All of the stationary points for acyl group migration on the triplet and ground state singlet potential energy surfaces were localized, and the influence of the acyl group substitution on the rate constants of the photochemical and thermal processes was analyzed.

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

    SciTech Connect

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

    2016-03-01

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

  14. Sedimentation field flow fractionation and optical absorption spectroscopy for a quantitative size characterization of silver nanoparticles.

    PubMed

    Contado, Catia; Argazzi, Roberto; Amendola, Vincenzo

    2016-11-04

    Many advanced industrial and biomedical applications that use silver nanoparticles (AgNPs), require that particles are not only nano-sized, but also well dispersed, not aggregated and not agglomerated. This study presents two methods able to give rapidly sizes of monodispersed AgNPs suspensions in the dimensional range of 20-100nm. The first method, based on the application of Mie's theory, determines the particle sizes from the values of the surface plasmon resonance wavelength (SPRMAX), read from the optical absorption spectra, recorded between 190nm and 800nm. The computed sizes were compared with those determined by transmission electron microscopy (TEM) and dynamic light scattering (DLS) and resulted in agreement with the nominal values in a range between 13% (for 20nm NPs) and 1% (for 100nm NPs), The second method is based on the masterly combination of the Sedimentation Field Flow Fractionation (SdFFF - now sold as Centrifugal FFF-CFFF) and the Optical Absorption Spectroscopy (OAS) techniques to accomplish sizes and quantitative particle size distributions for monodispersed, non-aggregated AgNPs suspensions. The SdFFF separation abilities, well exploited to size NPs, greatly benefits from the application of Mie's theory to the UV-vis signal elaboration, producing quantitative mass-based particle size distributions, from which trusted number-sized particle size distributions can be derived. The silver mass distributions were verified and supported by detecting off-line the Ag concentration with the graphite furnace atomic absorption spectrometry (GF-AAS).

  15. The Optical Absorption Coefficient of Bean Seeds Investigated Using Photoacoustic Spectroscopy

    NASA Astrophysics Data System (ADS)

    Sanchez-Hernandez, G.; Hernandez-Aguilar, C.; Dominguez-Pacheco, A.; Cruz-Orea, A.; Perez-Reyes, M. C. J.; Martinez, E. Moreno

    2015-06-01

    A knowledge about seed optical parameters is of great relevance in seed technology practice. Such parameters provide information about its absorption and reflectance, which could be useful for biostimulation processes, by light sources, in early stages of seed germination. In the present research photoacoustic spectroscopy (PAS) and the Rosencwaig and Gersho model were used to determine the optical absorption coefficient () of five varieties of bean seeds ( Phaseolus vulgaris L.), of different productive cycles; the seeds were biostimulated by laser treatment to evaluate the effects of biostimulation pre-sowing. It was found that the bean varieties V1, V2, V4, and V5 were optically opaque in the visible spectrum; in the case of the V3 variety, this sample was optically transparent from 680 nm. The varieties of the studied bean seeds showed significant statistical differences in sizes and also in their optical absorption spectra. The biostimulation effects showed that the seed samples with a higher optical penetration length had a positive biostimulation, in the percentage of germination, obtaining an enhancement of 47 % compared to the control sample. The utility of PAS for the optical characterization of seeds has been demonstrated in this study of the laser biostimulation process of this kind of samples.

  16. ODS steel raw material local structure analysis using X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Cintins, A.; Anspoks, A.; Purans, J.; Kuzmin, A.; Timoshenko, J.; Vladimirov, P.; Gräning, T.; Hoffmann, J.

    2015-03-01

    Oxide dispersion strengthened (ODS) steels are promising materials for fusion power reactors, concentrated solar power plants, jet engines, chemical reactors as well as for hydrogen production from thermolysis of water. In this study we used X-ray absorption spectroscopy at the Fe and Cr K-edges as a tool to get insight into the local structure of ferritic and austenitic ODS steels around Fe and Cr atoms and its transformation during mechanical alloying process. Using the analysis of X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) we found that for austenitic samples a transformation of ferritic steel to austenitic steel is detectable after 10 hours of milling and proceeds till 40 hours of milling; only small amount of a-phase remains after 80 hours of milling. We found that the Cr K-edge EXAFS can be used to observe distortions inside the material and to get an impression on the formation of chromium clusters. In-situ EXAFS experiments offer a reliable method to investigate the ferritic to austenitic transformation.

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

    PubMed Central

    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

    2017-01-01

    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. PMID:28186190

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

    PubMed

    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

    2017-02-10

    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 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:Nx. The well-ordered chemical environments induced by nitrogen dopant are revealed by XANES and RIXS measurements.

  19. Doppler-Free Two-Photon Absorption Spectroscopy of Naphthalene Assisted by AN Optical Frequency Comb

    NASA Astrophysics Data System (ADS)

    Nishiyama, Akiko; Matsuba, Ayumi; Misono, Masatoshi

    2014-06-01

    Optical frequency combs are powerful tools for precise frequency measurements in various wavelength regions. The combs have been applied not only to metrology, but also to molecular spectroscopy. Recently, we studied high resolution spectroscopy of iodine molecule assisted by an optical frequency comb. In the study, the comb was used for frequency calibration of a scanning dye laser. In this study, we developed a frequency calibration scheme with a comb and an acousto-optic modulator to realize more precise frequency measurement in a wide frequency range. And the frequency calibration scheme was applied to Doppler-free two-photon absorption (DFTPA) spectroscopy of naphthalene. Naphthalene is one of the prototypical aromatic molecules, and its detailed structure and dynamics in excited states have been reported. We measured DFTPA spectra of A^1B1u(v4=1) ← X^1A_g(v=0) transition around 298 nm. A part of obtained spectra is shown in the figure. The spectral lines are rotationally resolved and the resolution is about 100 kHz. The horizontal axis was calibrated by the developed frequency calibration system employing the comb. The uncertainties of the calibrated frequencies were determined by the fluctuations of the comb modes which were stabilized to a GPS-disciplined clock. A. Nishiyama, D. Ishikawa, and M. Misono, J. Opt. Soc. Am. B 30, 2107 (2013).

  20. 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.

  1. Absorption spectroscopy characterization measurements of a laser-produced Na atomic beam

    SciTech Connect

    Ching, C.H.; Bailey, J.E.; Lake, P.W.; Filuk, A.B.; Adams, R.G.; McKenney, J.

    1997-01-01

    A pulsed Na atomic beam source developed for spectroscopic diagnosis of a high-power ion diode is described. The goal is to produce a {approximately}10{sup 12}-cm{sup {minus}3}-density Na atomic beam that can be injected into the diode acceleration gap to measure electric and magnetic fields from the Stark and Zeeman effects through laser-induced fluorescence or absorption spectroscopy. A {approximately}10 ns full width at half-maximum (FWHM), 1.06 {mu}m, 0.6 J/cm{sup 2} laser incident through a glass slide heats a Na-bearing thin film, creating a plasma that generates a sodium vapor plume. A {approximately}1 {mu}s FWHM dye laser beam tuned to 5890 {Angstrom} is used for absorption measurement of the NaI resonant doublet by viewing parallel to the film surface. The dye laser light is coupled through a fiber to a spectrograph with a time-integrated charge-coupled-device camera. A two-dimensional mapping of the Na vapor density is obtained through absorption measurements at different spatial locations. Time-of-flight and Doppler broadening of the absorption with {approximately}0.1 {Angstrom} spectral resolution indicate that the Na neutral vapor temperature is about 0.5{endash}2 eV. Laser-induced fluorescence from {approximately}1{times}10{sup 12} cm{sup {minus}3} NaI 3s-3p lines observed with a streaked spectrograph provides a signal level sufficient for {approximately}{plus_minus}0.06 {Angstrom} wavelength shift measurements in a mock-up of an ion diode experiment. {copyright} {ital 1997 American Institute of Physics.}

  2. Absorption spectroscopy characterization measurements of a laser-produced Na atomic beam

    SciTech Connect

    Ching, C.H.; Bailey, J.E.; Lake, P.W.; Filuk, A.B.; Adams, R.G.; McKenney, J.

    1996-06-01

    This work describes a pulsed Na atomic beam source developed for spectroscopic diagnosis of a high-power ion diode on the Particle Beam Fusion Accelerator II. The goal is to produce a {approximately} 10{sup 12}-cm{sup {minus}3}-density Na atomic beam that can be injected into the diode acceleration gap to measure electric and magnetic fields from the Stark and Zeeman effects through laser-induced-fluorescence or absorption spectroscopy. A {approximately} 10 ns fwhm, 1.06 {micro}m, 0.6 J/cm{sup 2} laser incident through a glass slide heats a Na-bearing thin film, creating a plasma that generates a sodium vapor plume. A {approximately} 1 {micro}sec fwhm dye laser beam tuned to 5,890 {angstrom} is used for absorption measurement of the Na I resonant doublet by viewing parallel to the film surface. The dye laser light is coupled through a fiber to a spectrograph with a time-integrated CCD camera. A two-dimensional mapping of the Na vapor density is obtained through absorption measurements at different spatial locations. Time-of-flight and Doppler broadening of the absorption with {approximately} 0.1 {angstrom} spectral resolution indicate that the Na neutral vapor temperature is about 0.5 to 2 eV. Laser-induced-fluorescence from {approximately} 1 {times} 10{sup 12}-cm{sup {minus}3} Na I 3s-3p lines observed with a streaked spectrograph provides a signal level sufficient for {approximately} 0.06 {angstrom} wavelength shift measurements in a mock-up of an ion diode experiment.

  3. INTEGRAL FIELD SPECTROSCOPY OF AGN ABSORPTION OUTFLOWS: MRK 509 AND IRAS F04250–5718

    SciTech Connect

    Liu, Guilin; Arav, Nahum; Rupke, David S. N.

    2015-11-15

    Ultraviolet (UV) absorption lines provide abundant spectroscopic information enabling the probe of the physical conditions in active galactic nucleus (AGN) outflows, but the outflow radii (and the energetics consequently) can only be determined indirectly. We present the first direct test of these determinations using integral field unit (IFU) spectroscopy. We have conducted Gemini IFU mapping of the ionized gas nebulae surrounding two AGNs, whose outflow radii have been constrained by UV absorption line analyses. In Mrk 509, we find a quasi-spherical outflow with a radius of 1.2 kpc and a velocity of ∼290 km s{sup −1}, while IRAS F04250–5718 is driving a biconical outflow extending out to 2.9 kpc, with a velocity of ∼580 km s{sup −1} and an opening angle of ∼70°. The derived mass flow rate ∼5 and >1 M{sub ⊙} yr{sup −1}, respectively, and the kinetic luminosity ≳1 × 10{sup 41} erg s{sup −1} for both. Adopting the outflow radii and geometric parameters measured from IFU, absorption line analyses would yield mass flow rates and kinetic luminosities in agreement with the above results within a factor of ∼2. We conclude that the spatial locations, kinematics, and energetics revealed by this IFU emission-line study are consistent with pre-existing UV absorption line analyses, providing a long-awaited direct confirmation of the latter as an effective approach for characterizing outflow properties.

  4. Laser absorption spectroscopy using lead salt and quantum cascade tunable lasers

    NASA Astrophysics Data System (ADS)

    Namjou-Khales, Khosrow

    A new class of analytic instruments based on the detection of chemical species through their spectroscopic absorption 'fingerprint' is emerging based on the use of tunable semiconductor lasers as the excitation source. Advantages of this approach include compact device size, in-line measurement capability, and large signal-bandwidth product. To realize these advantages will require the marriage of laser devices with broad tunability in the infrared spectral range with sophisticated signal processing techniques. Currently, commercial devices based on short wavelength telecommunications type lasers exist but there is potential for much more versatile instruments based on longer wavelength operation. This thesis is divided into two parts. In the first part I present a theoretical analysis and experimental characterization of frequency and wavelength modulation spectroscopy using long wavelength infrared tunable lasers. The experimental measurements were carried out using commercially available lead salt lasers and excellent agreement is found between theoretically predicted performance and experimental verification. The lead salt laser has several important drawbacks as a source in practical instrumentation. In the second part of the thesis I report on the use of the quantum cascade (QC) laser for use in sensitive absorption spectroscopy. The QC laser is a new type of tunable device developed at Bell Laboratories. It features broad infrared tunability, single mode distributed feedback operation, and near room temperature lasing. Using the modulation techniques developed originally for the lead salt lasers, the QC laser was used to detect Nsb2O and other small molecules with absorption features near 8 mum wavelength. The noise equivalent absorption for our measurements was 5× 10sp{-5}/sqrt{Hz} which corresponds to a detection limit of ˜0.25 ppm-m/sqrt{Hz} for Nsb2O. The QC laser sensitivity was found to be limited by excess amplitude modulation in the detection

  5. In-situ ultra-sensitive infrared absorption spectroscopy of biomolecule interactions in real time with plasmonic nanoantennas

    PubMed Central

    Adato, Ronen; Altug, Hatice

    2013-01-01

    Infrared absorption spectroscopy is a powerful biochemical analysis tool as it extracts detailed molecular structural information in a label-free fashion. Its molecular specificity renders the technique sensitive to the subtle conformational changes exhibited by proteins in response to a variety of stimuli. Yet, sensitivity limitations and the extremely strong absorption bands of liquid water severely limit infrared spectroscopy in performing kinetic measurements in biomolecules’ native, aqueous environments. Here we demonstrate a plasmonic chip-based technology that overcomes these challenges, enabling the in-situ monitoring of protein and nanoparticle interactions at high sensitivity in real time, even allowing the observation of minute volumes of water displacement during binding events. Our approach leverages the plasmonic enhancement of absorption bands in conjunction with a non-classical form of internal reflection. These features not only expand the reach of infrared spectroscopy to a new class of biological interactions but also additionally enable a unique chip-based technology. PMID:23877168

  6. In-situ ultra-sensitive infrared absorption spectroscopy of biomolecule interactions in real time with plasmonic nanoantennas.

    PubMed

    Adato, Ronen; Altug, Hatice

    2013-01-01

    Infrared absorption spectroscopy is a powerful biochemical analysis tool as it extracts detailed molecular structural information in a label-free fashion. Its molecular specificity renders the technique sensitive to the subtle conformational changes exhibited by proteins in response to a variety of stimuli. Yet, sensitivity limitations and the extremely strong absorption bands of liquid water severely limit infrared spectroscopy in performing kinetic measurements in biomolecules' native, aqueous environments. Here we demonstrate a plasmonic chip-based technology that overcomes these challenges, enabling the in-situ monitoring of protein and nanoparticle interactions at high sensitivity in real time, even allowing the observation of minute volumes of water displacement during binding events. Our approach leverages the plasmonic enhancement of absorption bands in conjunction with a non-classical form of internal reflection. These features not only expand the reach of infrared spectroscopy to a new class of biological interactions but also additionally enable a unique chip-based technology.

  7. Sulfur K-edge X-ray absorption spectroscopy and density functional theory calculations on superoxide reductase: role of the axial thiolate in reactivity.

    PubMed

    Dey, Abhishek; Jenney, Francis E; Adams, Michael W W; Johnson, Michael K; Hodgson, Keith O; Hedman, Britt; Solomon, Edward I

    2007-10-17

    Superoxide reductase (SOR) is a non-heme iron enzyme that reduces superoxide to peroxide at a diffusion-controlled rate. Sulfur K-edge X-ray absorption spectroscopy (XAS) is used to investigate the ground-state electronic structure of the resting high-spin and CN- bound low-spin FeIII forms of the 1Fe SOR from Pyrococcus furiosus. A computational model with constrained imidazole rings (necessary for reproducing spin states), H-bonding interaction to the thiolate (necessary for reproducing Fe-S bond covalency of the high-spin and low-spin forms), and H-bonding to the exchangeable axial ligand (necessary to reproduce the ground state of the low-spin form) was developed and then used to investigate the enzymatic reaction mechanism. Reaction of the resting ferrous site with superoxide and protonation leading to a high-spin FeIII-OOH species and its subsequent protonation resulting in H2O2 release is calculated to be the most energetically favorable reaction pathway. Our results suggest that the thiolate acts as a covalent anionic ligand. Replacing the thiolate with a neutral noncovalent ligand makes protonation very endothermic and greatly raises the reduction potential. The covalent nature of the thiolate weakens the FeIII bond to the proximal oxygen of this hydroperoxo species, which raises its pKa by an additional 5 log units relative to the pKa of a primarily anionic ligand, facilitating its protonation. A comparison with cytochrome P450 indicates that the stronger equatorial ligand field from the porphyrin results in a low-spin FeIII-OOH species that would not be capable of efficient H2O2 release due to a spin-crossing barrier associated with formation of a high-spin 5C FeIII product. Additionally, the presence of the dianionic porphyrin pi ring in cytochrome P450 allows O-O heterolysis, forming an FeIV-oxo porphyrin radical species, which is calculated to be extremely unfavorable for the non-heme SOR ligand environment. Finally, the 5C FeIII site that results

  8. (n,m)-Specific Absorption Cross Sections of Single-Walled Carbon Nanotubes Measured by Variance Spectroscopy.

    PubMed

    Sanchez, Stephen R; Bachilo, Sergei M; Kadria-Vili, Yara; Lin, Ching-Wei; Weisman, R Bruce

    2016-11-09

    A new method based on variance spectroscopy has enabled the determination of absolute absorption cross sections for the first electronic transition of 12 (n,m) structural species of semiconducting single-walled carbon nanotubes (SWCNTs). Spectrally resolved measurements of fluorescence variance in dilute bulk samples provided particle number concentrations of specific SWCNT species. These values were converted to carbon concentrations and correlated with resonant components in the absorbance spectrum to deduce (n,m)-specific absorption cross sections (absorptivities) for nanotubes ranging in diameter from 0.69 to 1.03 nm. The measured cross sections per atom tend to vary inversely with nanotube diameter and are slightly greater for structures of mod 1 type than for mod 2. Directly measured and extrapolated values are now available to support quantitative analysis of SWCNT samples through absorption spectroscopy.

  9. Application of atomic absorption spectroscopy for detection of multimetal traces in low-voltage electrical marks.

    PubMed

    Jakubeniene, Marija; Zakaras, Algirdas; Minkuviene, Zita Nijole; Benoshys, Alvydas

    2006-08-10

    Application of atomic absorption spectroscopy to detect multimetal traces in injured skin is a promising tool for investigation of fatalities caused by electrocution. The present paper is aimed at testing the reliability of this method for metal traces detection in electric current marks and is focused on study of peculiarities of metal penetration into the skin exposed to a current impact. Bare aluminum wire, tin-lead coated copper multistrand wire, and zinc-plated steel rope were used to make electrical marks on pig skin. It is demonstrated that amount of copper, zinc, lead, and iron may serve as statistically reliable indicators for the type of wire, which caused the electrical mark, in spite of the background content of these metals in the skin without injury. Different penetration rates for different metals contained in the wire inflicting an electrical mark were observed.

  10. Visualizing interfacial charge transfer in dye sensitized nanoparticles using x-ray transient absorption spectroscopy.

    SciTech Connect

    Zhang, X. Y.; Smolentsev, G.; Guo, J.; Attenkofer, K.; Kurtz, C.; Jennings, G.; Lockard, J. V.; Stickrath, A. B.; Chen, L. X.

    2011-01-01

    A molecular level understanding of the structural reorganization accompanying interfacial electron transfer is important for rational design of solar cells. Here we have applied XTA (X-ray transient absorption) spectroscopy to study transient structures in a heterogeneous interfacial system mimicking the charge separation process in dye-sensitized solar cell (DSSC) with Ru(dcbpy){sub 2}(NCS){sub 2} (RuN3) dye adsorbed to TiO{sub 2} nanoparticle surfaces. The results show that the average Ru-NCS bond length reduces by 0.06 {angstrom}, whereas the average Ru-N(dcbpy) bond length remains nearly unchanged after the electron injection. The differences in bond-order change and steric hindrance between two types of ligands are attributed to their structural response in the charge separation. This study extends the application of XTA into optically opaque hybrid interfacial systems relevant to the solar energy conversion.

  11. Electronic topological transition in zinc under pressure: An x-ray absorption spectroscopy study

    SciTech Connect

    Aquilanti, G.; Trapananti, A.; Pascarelli, S.; Minicucci, M.; Principi, E.; Liscio, F.; Twarog, A.

    2007-10-01

    Zinc metal has been studied at high pressure using x-ray absorption spectroscopy. In order to investigate the role of the different degrees of hydrostaticity on the occurrence of structural anomalies following the electronic topological transition, two pressure transmitting media have been used. Results show that the electronic topological transition, if it exists, does not induce an anomaly in the local environment of compressed Zn as a function of hydrostatic pressure and any anomaly must be related to a loss of hydrostaticity of the pressure transmitting medium. The near-edge structures of the spectra, sensitive to variations in the electronic density of states above the Fermi level, do not show any evidence of electronic transition whatever pressure transmitting medium is used.

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

    PubMed Central

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

    2015-01-01

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

  13. Studies of Y-Ba-Cu-O single crystals by x-ray absorption spectroscopy

    SciTech Connect

    Krol, A.; Ming, Z.H.; Kao, Y.H.; Nuecker, N.; Roth, G.; Fink, J.; Smith, G.C.; Erband, A.; Mueller-Vogt, G.; Karpinski, J.; Kaldis, E.; Schoenmann, K.

    1992-02-01

    The symmetry and density of unoccupied states of YBa{sub 2}Cu{sub 3}O{sub 7} YBa{sub 2}Cu{sub 4}O{sub 8} have been investigated by orientation dependent x-ray absorption spectroscopy on the O 1s edge using a bulk-sensitive fluorescence-yield-detection method. It has been found that the O 2p holes are distributed equally between the CuO{sub 2} planes and CuO chains and that the partial density of unoccupied O 2p states in the CuO{sub 2} planes are identical in both systems investigated. The upper Hubbard band has been observed in the planes but not in the chains in both systems. 18 refs.

  14. The Optical Absorption Coefficient of Maize Grains Investigated by Photoacoustic Spectroscopy

    NASA Astrophysics Data System (ADS)

    Rodríguez-Páez, C. L.; Carballo-Carballo, A.; Rico-Molina, R.; Hernández-Aguilar, C.; Domínguez-Pacheco, A.; Cruz-Orea, A.; Moreno-Martínez, E.

    2017-01-01

    In the maize and tortilla industry, it is important to characterize the color of maize ( Zea mays L.) grain, as it is one of the attributes that directly affect the quality of the tortillas consumed by the population. For this reason, the availability of alternative techniques for assessing and improving the quality of grain is valued. Photoacoustic spectroscopy has proven to be a useful tool for characterizing maize grain. So, the objective of the present study was to determine the optical absorption coefficient β of the maize grain used to make tortillas from two regions of Mexico: (a) Valles Altos, 2012-2013 production cycle and (b) Guasave, Sinaloa, 2013-2014 production cycle. Traditional reflectance measurements, physical characteristics of the grain and nutrient content were also calculated. The experimental results show different characteristics for maize grains.

  15. Time-resolved broadband cavity-enhanced absorption spectroscopy for chemical kinetics.

    SciTech Connect

    Sheps, Leonid; Chandler, David W.

    2013-04-01

    Experimental measurements of elementary reaction rate coefficients and product branching ratios are essential to our understanding of many fundamentally important processes in Combustion Chemistry. However, such measurements are often impossible because of a lack of adequate detection techniques. Some of the largest gaps in our knowledge concern some of the most important radical species, because their short lifetimes and low steady-state concentrations make them particularly difficult to detect. To address this challenge, we propose a novel general detection method for gas-phase chemical kinetics: time-resolved broadband cavity-enhanced absorption spectroscopy (TR-BB-CEAS). This all-optical, non-intrusive, multiplexed method enables sensitive direct probing of transient reaction intermediates in a simple, inexpensive, and robust experimental package.

  16. Fast transient absorption spectroscopy of the early events in photoexcited chiral benzophenone naphthalene dyads

    NASA Astrophysics Data System (ADS)

    Perez-Ruiz, Raul; Groeneveld, Michiel; van Stokkum, Ivo H. M.; Tormos, Rosa; Williams, René M.; Miranda, Miguel A.

    2006-09-01

    Photoinduced intra-molecular energy transfer in two ketoprofen(KP)-naproxol(NPX) diastereomers proceeds via two pathways. Very fast singlet-triplet energy transfer ( k = 1.2 × 10 11 s -1) from KP to NPX occurs for a small percentage (6%) and the major pathway is triplet-triplet energy transfer ( k ˜ 3 × 10 9 s -1). This was shown with femtosecond transient absorption spectroscopy and global and target analysis. Whereas the NPX triplet decay is strongly stereospecific (ratio of 1.6), the NPX triplet state formation for both dyads is very similar (ratio of 1 for the fast process and 1.2 for the slower process).

  17. The irradiation of ammonia ice studied by near edge x-ray absorption spectroscopy

    SciTech Connect

    Parent, Ph.; Bournel, F.; Lasne, J.; Laffon, C.; Carniato, S.; Lacombe, S.; Strazzulla, G.; Gardonio, S.; Lizzit, S.; Kappler, J.-P.; Joly, L.

    2009-10-21

    A vapor-deposited NH{sub 3} ice film irradiated at 20 K with 150 eV photons has been studied with near-edge x-ray absorption fine structure (NEXAFS) spectroscopy at the nitrogen K-edge. Irradiation leads to the formation of high amounts (12%) of molecular nitrogen N{sub 2}, whose concentration as a function of the absorbed energy has been quantified to 0.13 molecule/eV. The stability of N{sub 2} in solid NH{sub 3} has been also studied, showing that N{sub 2} continuously desorbs between 20 and 95 K from the irradiated ammonia ice film. Weak concentrations (<1%) of other photoproducts are also detected. Our NEXAFS simulations show that these features own to NH{sub 2}, N{sub 2}H{sub 2}, and N{sub 3}{sup -}.

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

    PubMed

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

    2015-10-20

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

  19. Biomimetic environment to study E. coli complex I through surface-enhanced IR absorption spectroscopy.

    PubMed

    Kriegel, Sébastien; Uchida, Taro; Osawa, Masatoshi; Friedrich, Thorsten; Hellwig, Petra

    2014-10-14

    In this study complex I was immobilized in a biomimetic environment on a gold layer deposited on an ATR-crystal in order to functionally probe the enzyme against substrates and inhibitors via surface-enhanced IR absorption spectroscopy (SEIRAS) and cyclic voltammetry (CV). To achieve this immobilization, two methods based on the generation of a high affinity self-assembled monolayer (SAM) were probed. The first made use of the affinity of Ni-NTA toward a hexahistidine tag that was genetically engineered onto complex I and the second exploited the affinity of the enzyme toward its natural substrate NADH. Experiments were also performed with complex I reconstituted in lipids. Both approaches have been found to be successful, and electrochemically induced IR difference spectra of complex I were obtained.

  20. Intracavity laser absorption spectroscopy using mid-IR quantum cascade laser

    NASA Astrophysics Data System (ADS)

    Medhi, G.; Muravjov, A. V.; Saxena, H.; Fredricksen, C. J.; Brusentsova, T.; Peale, R. E.; Edwards, O.

    2011-06-01

    Intracavity Laser Absorption Spectroscopy (ICLAS) at IR wavelengths offers an opportunity for spectral sensing with sufficient sensitivity to detect vapors of low vapor pressure compounds such as explosives. Reported here are key enabling technologies for this approach, including multi-mode external-cavity quantum cascade lasers and a scanning Fabry-Perot spectrometer to analyze the laser mode spectrum in the presence of a molecular intracavity absorber. Reported also is the design of a compact integrated data acquisition and control system. Applications include military and commercial sensing for threat compounds, chemical gases, biological aerosols, drugs, and banned or invasive plants or animals, bio-medical breath analysis, and terrestrial or planetary atmosphere science.

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

    SciTech Connect

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

    2001-03-25

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

  2. Detection, identification and mapping of iron anomalies in brain tissue using X-ray absorption spectroscopy

    SciTech Connect

    Mikhaylova, A.; Davidson, M.; Toastmann, H.; Channell, J.E.T.; Guyodo, Y.; Batich, C.; Dobson, J.

    2008-06-16

    This work describes a novel method for the detection, identification and mapping of anomalous iron compounds in mammalian brain tissue using X-ray absorption spectroscopy. We have located and identified individual iron anomalies in an avian tissue model associated with ferritin, biogenic magnetite and haemoglobin with a pixel resolution of less than 5 {micro}m. This technique represents a breakthrough in the study of both intra- and extra-cellular iron compounds in brain tissue. The potential for high-resolution iron mapping using microfocused X-ray beams has direct application to investigations of the location and structural form of iron compounds associated with human neurodegenerative disorders - a problem which has vexed researchers for 50 years.

  3. Performance improvements in temperature reconstructions of 2-D tunable diode laser absorption spectroscopy (TDLAS)

    NASA Astrophysics Data System (ADS)

    Choi, Doo-Won; Jeon, Min-Gyu; Cho, Gyeong-Rae; Kamimoto, Takahiro; Deguchi, Yoshihiro; Doh, Deog-Hee

    2016-02-01

    Performance improvement was attained in data reconstructions of 2-dimensional tunable diode laser absorption spectroscopy (TDLAS). Multiplicative Algebraic Reconstruction Technique (MART) algorithm was adopted for data reconstruction. The data obtained in an experiment for the measurement of temperature and concentration fields of gas flows were used. The measurement theory is based upon the Beer-Lambert law, and the measurement system consists of a tunable laser, collimators, detectors, and an analyzer. Methane was used as a fuel for combustion with air in the Bunsen-type burner. The data used for the reconstruction are from the optical signals of 8-laser beams passed on a cross-section of the methane flame. The performances of MART algorithm in data reconstruction were validated and compared with those obtained by Algebraic Reconstruction Technique (ART) algorithm.

  4. Structural analysis of sulfur in natural rubber using X-ray absorption near-edge spectroscopy.

    PubMed

    Pattanasiriwisawa, Wanwisa; Siritapetawee, Jaruwan; Patarapaiboolchai, Orasa; Klysubun, Wantana

    2008-09-01

    X-ray absorption near-edge spectroscopy (XANES) has been applied to natural rubber in order to study the local environment of sulfur atoms in sulfur crosslinking structures introduced in the vulcanization process. Different types of chemical accelerators in conventional, semi-efficient and efficient vulcanization systems were investigated. The experimental results show the good sensitivity and reproducibility of XANES to characterize the local geometry and electronic environment of the sulfur K-shell under various conditions of vulcanization and non-vulcanization of natural rubber. Several applications of XANES in this study demonstrate an alternative way of identifying sulfur crosslinks in treated natural rubber based on differences in their spectra and oxidation states.

  5. Elemental characterisation of melanin in feathers via synchrotron X-ray imaging and absorption spectroscopy

    PubMed Central

    Edwards, Nicholas P.; van Veelen, Arjen; Anné, Jennifer; Manning, Phillip L.; Bergmann, Uwe; Sellers, William I.; Egerton, Victoria M.; Sokaras, Dimosthenis; Alonso-Mori, Roberto; Wakamatsu, Kazumasa; Ito, Shosuke; Wogelius, Roy A.

    2016-01-01

    Melanin is a critical component of biological systems, but the exact chemistry of melanin is still imprecisely known. This is partly due to melanin’s complex heterogeneous nature and partly because many studies use synthetic analogues and/or pigments extracted from their natural biological setting, which may display important differences from endogenous pigments. Here we demonstrate how synchrotron X-ray analyses can non-destructively characterise the elements associated with melanin pigment in situ within extant feathers. Elemental imaging shows that the distributions of Ca, Cu and Zn are almost exclusively controlled by melanin pigment distribution. X-ray absorption spectroscopy demonstrates that the atomic coordination of zinc and sulfur is different within eumelanised regions compared to pheomelanised regions. This not only impacts our fundamental understanding of pigmentation in extant organisms but also provides a significant contribution to the evidence-based colour palette available for reconstructing the appearance of fossil organisms. PMID:27658854

  6. Detection of the transient PNO molecule by infrared laser absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Bell, I. S.; Hamilton, P. A.; Davies, P. B.

    The PNO molecule has been observed in the gas phase for the first time. Some 200 vibrationrotation transitions were detected in the 1760cm-1 region using infrared diode laser absorption spectroscopy in a long path cell. Most of the lines can be assigned to the (001)←(000) stretching fundamental and (011)←(010) hot band transitions. The fundamental band exhibits a perturbation at high rotational levels which leads to a unique assignment of the rotational numbering. The effective rotational constants determined are in good agreement with ab initio predictions and the band origin, 1756.64586(24)cm-1, is very close to the matrix value. A tentative rotational assignment of the hot band transitions has been made which gives a band origin of 1748.388cm-1.

  7. [Genetic programming used for the measurement of CO concentration based on nondispersive infrared absorption spectroscopy].

    PubMed

    Chen, Jin; Duan, Fa-jie; Tong, Ying; Gao, Qiang

    2011-07-01

    Nondispersive infrared absorption spectroscopy(NDIR) is an important method to measure CO concentration in the air. In the present study, an open-path measurement system and continuous measuring device was developed, and genetic programming was used to establish the calibration model of subjects' light intensity sampling values. Continuous measurements were carried out in 10 different concentration of CO, and 40 sampled data were acquired and analyzed. For validation set, the correlation coefficient was 0.9997. The biggest relative error of validation was 4.00%, and the average relative error was 1.11%. Results show that genetic programming can be a good method for the modeling of gas concentration measurements equipped with NDIR systems.

  8. [Studies on the remote measurement of the emission of formaldehyde by mobile differential optical absorption spectroscopy].

    PubMed

    Wu, Feng-Cheng; Xie, Pin-Hua; Li, Ang; Si, Fu-Qi; Dou, Ke; Liu, Yu; Xu, Jin; Wang, Jie

    2011-11-01

    Formaldehyde (HCHO) is the most abundant carbonyl compounds that play an important role in atmospheric chemistry and photochemical reactions. Formaldehyde is an important indicator of atmospheric reactivity and urban atmospheric aerosol precursors. In the present paper, the emission of formaldehyde from chemical area was measured using the mobile differential optical absorption spectroscopy (DOAS). This instrument uses the zenith scattered sunlight as the light source with successful sampling in the area loop. Vertical column density was retrieved by this system, combined with the meteorological wind field and car speed information, the emission of formaldehyde in the area was estimated. The authors carried out the measuring experiment in one chemical plant in Beijing using this technology. The result showed that the average value of the flux of formaldehyde in this area was 605 kg x h(-1) during the measuring period.

  9. Instrument for x-ray absorption spectroscopy with in situ electrical control characterizations

    SciTech Connect

    Huang, Chun-Chao; Chang, Shu-Jui; Yang, Chao-Yao; Tseng, Yuan-Chieh; Chou, Hsiung

    2013-12-15

    We report a synchrotron-based setup capable of performing x-ray absorption spectroscopy and x-ray magnetic circular dichroism with simultaneous electrical control characterizations. The setup can enable research concerning electrical transport, element- and orbital-selective magnetization with an in situ fashion. It is a unique approach to the real-time change of spin-polarized electronic state of a material/device exhibiting magneto-electric responses. The performance of the setup was tested by probing the spin-polarized states of cobalt and oxygen of Zn{sub 1-x}Co{sub x}O dilute magnetic semiconductor under applied voltages, both at low (∼20 K) and room temperatures, and signal variations upon the change of applied voltage were clearly detected.

  10. Broadband femtosecond transient absorption spectroscopy for a CVD Mo S2 monolayer

    NASA Astrophysics Data System (ADS)

    Aleithan, Shrouq H.; Livshits, Maksim Y.; Khadka, Sudiksha; Rack, Jeffrey J.; Kordesch, Martin E.; Stinaff, Eric

    2016-07-01

    Carrier dynamics in monolayer Mo S2 have been investigated using broadband femtosecond transient absorption spectroscopy (FTAS). A tunable pump pulse was used while a broadband probe pulse revealed ground and excited state carrier dynamics. Interestingly, for pump wavelengths both resonant and nonresonant with the A and B excitons, we observe a broad ground state bleach around 2.9 eV, with decay components similar to A and B. Associating this bleach with the band nesting region between K and Γ in the band structure indicates significant k-space delocalization and overlap among excitonic wave functions identified as A, B, C, and D. Comparison of time dynamics for all features in resonance and nonresonance excitation is consistent with this finding.

  11. Uranium and thorium sorption on minerals studied by x-ray absorption spectroscopy

    SciTech Connect

    Hudson, E.A.; Terminello, L.J.; Viani, B.E.

    1995-12-01

    Several actinide-mineral sorption systems were studied by uranium and thorium L{sub 3}-edge x-ray absorption spectroscopy. A series of layer silicate minerals, including micas, were selected for their systematic variations in surface structure, e.g. degree of permanent negative charge on the basal planes. An expansible layer silicate, vermiculite, was treated to provide several different interlayer spacings, allowing variations in the accessibility of interior cation exchange sites. The finely powdered minerals were exposed to aqueous solutions of uranyl chloride or thorium chloride. Analysis of the EXAFS and XANES spectra indicates the influence of the mineral substrate upon the local structure of the bound actinide species. Trends in the data are interpreted based upon the known variations in mineral structure.

  12. Accurate frequency of the 119 micron methanol laser from tunable far-infrared absorption spectroscopy

    NASA Technical Reports Server (NTRS)

    Inguscio, M.; Zink, L. R.; Evenson, K. M.; Jennings, D. A.

    1990-01-01

    High-accuracy absorption spectroscopy of CH3OH in the far infrared is discussed. In addition to 22 transitions in the ground state, the frequency of the (n, tau, J, K), (0, 1, 16, 8) to (0, 2, 15, 7) transition in the nu5 excited vibrational level, which is responsible for the laser emission at 119 microns, was measured. The measured frequency is 2,522,782.57(10) MHz at zero pressure, with a pressure shift of 6.1(32) kHz/Pa (0.805/420/ MHz/torr). An accurate remeasurement of the laser emission frequency has also been performed, and the results are in good agreement.

  13. Elemental characterisation of melanin in feathers via synchrotron X-ray imaging and absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Edwards, Nicholas P.; van Veelen, Arjen; Anné, Jennifer; Manning, Phillip L.; Bergmann, Uwe; Sellers, William I.; Egerton, Victoria M.; Sokaras, Dimosthenis; Alonso-Mori, Roberto; Wakamatsu, Kazumasa; Ito, Shosuke; Wogelius, Roy A.

    2016-09-01

    Melanin is a critical component of biological systems, but the exact chemistry of melanin is still imprecisely known. This is partly due to melanin’s complex heterogeneous nature and partly because many studies use synthetic analogues and/or pigments extracted from their natural biological setting, which may display important differences from endogenous pigments. Here we demonstrate how synchrotron X-ray analyses can non-destructively characterise the elements associated with melanin pigment in situ within extant feathers. Elemental imaging shows that the distributions of Ca, Cu and Zn are almost exclusively controlled by melanin pigment distribution. X-ray absorption spectroscopy demonstrates that the atomic coordination of zinc and sulfur is different within eumelanised regions compared to pheomelanised regions. This not only impacts our fundamental understanding of pigmentation in extant organisms but also provides a significant contribution to the evidence-based colour palette available for reconstructing the appearance of fossil organisms.

  14. [Determination of trace selenium in edible fungi with graphite furnace atomic absorption spectroscopy].

    PubMed

    Tie, Mei; Zhang, Wei; Li, Jing; Jing, Kui; Zang, Shu-liang; Li, Hua-wei

    2006-01-01

    In the present article, samples were digested by a quartz high-pressure digestion pot, reducing the loss of selenium in digestion. The content of selenium in edible fungi was determined by using graphite furnace atomic absorption spectroscopy, and the results showed that when the content of selenium in edible fungi was determined by using 1% Ni(NO3)2 as a matrix modifier, ashing temperature of 500 degreed C, and atomization temperature of 2 500 degrees C, and rectifying background by deuterium light, the recovery was in the range of 92.1%-115.5%, the relative standard deviation of the method was 1.28%, and the limit of detection was 15.8 microg x L(-1). The method was suitable for the determination of trace selenium in edible fungi with the advantages of being simple, rapid, sensitive, stable and accurate etc., and the results were satisfactory.

  15. Etalon-induced baseline drift and correction in atom flux sensors based on atomic absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Du, Yingge; Chambers, Scott A.

    2014-10-01

    Atom flux sensors based on atomic absorption (AA) spectroscopy are of significant interest in thin film growth as they can provide unobtrusive, element specific real-time flux sensing and control. The ultimate sensitivity and performance of these sensors are strongly affected by baseline drift. Here we demonstrate that an etalon effect resulting from temperature changes in optical viewport housings is a major source of signal instability, which has not been previously considered, and cannot be corrected using existing methods. We show that small temperature variations in the fused silica viewports can introduce intensity modulations of up to 1.5% which in turn significantly deteriorate AA sensor performance. This undesirable effect can be at least partially eliminated by reducing the size of the beam and tilting the incident light beam off the viewport normal.

  16. Determination of tellurium in geochemical materials by flameless atomic-absorption spectroscopy.

    PubMed

    Sighinolfi, G P; Santos, A M; Martinelli, G

    1979-02-01

    A method is described for the determination of tellurium at nanogram levels in rocks and in other complex materials by the use of flameless atomic-absorption spectroscopy. A very selective organic extraction procedure is applied to avoid matrix interference effects during extraction of Te and the atomization stage in the graphite furnace. Prior separation of iron and other interfering elements is achieved by a combined cupferron-ethyl acetate extraction. Tellerium is extracted from 6M hydrochloric acid with MIBK and stripped into aqueous medium. Pipetting of the aqueous extract into the graphite furnace gives fairly good instrumental reproducibility (2-3% error). Detection limits of about 10 ppM Te for a 0.5-g sample have been achieved with the medium-performance apparatus used. Results for Te in some geochemical reference materials are reported. Indications are given for the determination of Sb and Mo in the same solutions.

  17. Determination of palladium by graphite furnace atomic absorption spectroscopy without matrix matching.

    PubMed

    Jia, X; Wang, T; Wu, J

    2001-05-30

    A graphite furnace atomic absorption spectroscopy method for the analysis of the palladium (Pd) content in bulk pharmaceutical drug substances and their intermediates prepared in aqueous solutions is extended to samples prepared in acetonitrile (ACN) and ACN-water mixtures as well to samples prepared in dimethyl sulfoxide (DMSO) and DMSO-water mixtures. The Pd content in samples solubilized in these solvents can be accurately determined with calibration established with standards prepared in aqueous solutions without matrix matching or using the method of standard additions. The validity of this method is demonstrated by spike recovery studies and by the agreement with results for the same samples prepared in these solvents, in concentrated nitric acid, and prepared by a microwave digestion system.

  18. Absolute 1* quantum yields for the ICN A state by diode laser gain versus absorption spectroscopy

    NASA Technical Reports Server (NTRS)

    Hess, Wayne P.; Leone, Stephen R.

    1987-01-01

    Absolute I* quantum yields were measured as a function of wavelength for room temperature photodissociation of the ICN A state continuum. The temperature yields are obtained by the technique of time-resolved diode laser gain-versus-absorption spectroscopy. Quantum yields are evaluated at seven wavelengths from 248 to 284 nm. The yield at 266 nm is 66.0 +/- 2% and it falls off to 53.4 +/- 2% and 44.0 +/- 4% at 284 and 248 respectively. The latter values are significantly higher than those obtained by previous workers using infrared fluorescence. Estimates of I* quantum yields obtained from analysis of CN photofragment rotational distributions, as discussed by other workers, are in good agreement with the I* yields. The results are considered in conjunction with recent theoretical and experimental work on the CN rotational distributions and with previous I* yield results.

  19. Infrared Reflection-Absorption Spectroscopy: Principles and Applications to Lipid-Protein Interaction in Langmuir Films

    PubMed Central

    Mendelsohn, Richard; Mao, Guangru; Flach, Carol R.

    2010-01-01

    Infrared reflection-absorption spectroscopy (IRRAS) of lipid/protein monolayer films in situ at the air/water interface provides unique molecular structure and orientation information from the film constituents. The technique is thus well suited for studies of lipid/protein interaction in a physiologically relevant environment. Initially, the nature of the IRRAS experiment is described and the molecular structure information that may be obtained is recapitulated. Subsequently, several types of applications, including the determination of lipid chain conformation and tilt as well as elucidation of protein secondary structure are reviewed. The current article attempts to provide the reader with an understanding of the current capabilities of IRRAS instrumentation and the type of results that have been achieved to date from IRRAS studies of lipids, proteins and lipid/protein films of progressively increasing complexity. Finally, possible extensions of the technology are briefly considered. PMID:20004639

  20. High resolution laser induced fluorescence Doppler velocimetry utilizing saturated absorption spectroscopy

    SciTech Connect

    Aramaki, Mitsutoshi; Ogiwara, Kohei; Etoh, Shuzo; Yoshimura, Shinji; Tanaka, Masayoshi Y.

    2009-05-15

    A high resolution laser induced fluorescence (LIF) system has been developed to measure the flow velocity field of neutral particles in an electron-cyclotron-resonance argon plasma. The flow velocity has been determined by the Doppler shift of the LIF spectrum, which is proportional to the velocity distribution function. Very high accuracy in velocity determination has been achieved by installing a saturated absorption spectroscopy unit into the LIF system, where the absolute value and scale of laser wavelength are determined by using the Lamb dip and the fringes of a Fabry-Perot interferometer. The minimum detectable flow velocity of a newly developed LIF system is {+-}2 m/s, and this performance remains unchanged in a long-time experiment. From the radial measurements of LIF spectra of argon metastable atoms, it is found that there exists an inward flow of neutral particles associated with neutral depletion.