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Sample records for absorption spectroscopy xanes

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

    PubMed

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

    2012-03-16

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

  2. Probing Warm Dense Matter electronic structure using X-ray absorption Near Edge Spectroscopy (XANES)

    NASA Astrophysics Data System (ADS)

    Benuzzi Mounaix, Alessandra

    2011-06-01

    The behavior and physical properties of warm dense matter, fundamental for various branches of physics including planetology and Inertial Confinement Fusion, are non trivial to simulate either theoretically, numerically or experimentally. Despite important progress obtained in the last decade on macroscopic characterization (e.g. equations of state), microscopic studies are today necessary to investigate finely the WDM structure changes, the phase transitions and to test physical hypothesis and approximations commonly used in calculations. In this work, highly compressed aluminum has been investigated with the aim of bringing information on the evolution of its electronic structure by using K-edge shift and XANES. The experiment was performed at LULI laboratory where we used one long pulse (500 ps, IL ~ 8 1013 W/cm2) to create a uniform shock and a second ps beam (IL ~ 1017 W/cm2) to generate an ultra-short broadband X-ray source near the Al K-edge. The spectra were registered by using two conical KAP Bragg crystals. The main target was designed to probe the Aluminum in reshocked conditions allowing us to probe and to test theories in an extreme regime up to now unexplored (ρ ~ 3 ρ0 and T ~ 8 eV). The hydrodynamical Al conditions were measured by using VISARs interferometers and self-emission diagnostics. By increasing the delay between the two beams, we have been able to observe the modification of absorption spectra for unloading Al conditions (ρ >= 0.5 g/cc), and to put in evidence the relocalization of the 3p valence electrons occurring in the metal-non metal transition. All data have been compared to ab initio and dense plasma calculations.

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

    NASA Astrophysics Data System (ADS)

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

    1997-02-01

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

  4. Identification of sources of lead in the atmosphere by chemical speciation using X-ray absorption near-edge structure (XANES) spectroscopy.

    PubMed

    Sakata, Kohei; Sakaguchi, Aya; Tanimizu, Masaharu; Takaku, Yuichi; Yokoyama, Yuka; Takahashi, Yoshio

    2014-02-01

    Sources of Pb pollution in the local atmosphere together with Pb species, major ions, and heavy metal concentrations in a size-fractionated aerosol sample from Higashi-Hiroshima (Japan) have been determined by X-ray absorption near-edge structure (XANES) spectroscopy, ion chromatography, and ICP-MS/AES, respectively. About 80% of total Pb was concentrated in fine aerosol particles. Lead species in the coarse aerosol particles were PbC2O4, 2PbCO3 Pb(OH)2, and Pb(NO3)2, whereas Pb species in the fine aerosol particles were PbC2O4, PbSO4, and Pb(NO3)2. Chemical speciation and abundance data suggested that the source of Pb in the fine aerosol particles was different from that of the coarse ones. The dominant sources of Pb in the fine aerosol particles were judged to be fly ash from a municipal solid waste incinerator and heavy oil combustion. For the coarse aerosol particles, road dust was considered to be the main Pb source. In addition to Pb species, elemental concentrations in the aerosols were also determined. The results suggested that Pb species in size-fractionated aerosols can be used to identify the origin of aerosol particles in the atmosphere as an alternative to Pb isotope ratio measurement.

  5. 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.

  6. Phosphorus K-edge XANES spectroscopy of mineral standards

    PubMed Central

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

    2011-01-01

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

  7. Phosphorus K-edge XANES Spectroscopy of Mineral Standards

    SciTech Connect

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

    2011-12-31

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

  8. Spatially resolved sulfur K-edge XANES spectroscopy of wheat leaves infected by Puccinia triticina

    NASA Astrophysics Data System (ADS)

    Lichtenberg, H.; Prange, A.; Steiner, U.; Oerke, E.-C.; Hormes, J.

    2009-11-01

    In this study, wheat leaves infected with brown rust, a plant disease of serious economic concern caused by the fungus Puccinia triticina, were investigated using spatially resolved XANES (X-ray Absorption Near Edge Structure) spectroscopy at the sulfur K-absorption edge.

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

    SciTech Connect

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

    2006-01-01

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

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

    NASA Astrophysics Data System (ADS)

    Bovenkamp-Langlois, Lisa; Roy, Amitava

    2016-05-01

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

  11. Reduced chromium in olivine grains from lunar basalt 15555 - X-ray Absorption Near Edge Structure (XANES)

    NASA Technical Reports Server (NTRS)

    Sutton, S. R.; Jones, K. W.; Gordon, B.; Rivers, M. L.; Bajt, S.; Smith, J. V.

    1993-01-01

    The oxidation state of Cr in 200-micron regions within individual lunar olivine and pyroxene grains from lunar basalt 15555 was inferred using X-ray Absorption Near Edge Structure (XANES). Reference materials had previously been studied by optical absorption spectroscopy and included Cr-bearing borosilicate glasses synthesized under controlled oxygen fugacity and Cr-doped olivines. The energy dependence of XANES spectral features defined by these reference materials indicated that Cr is predominantly divalent in the lunar olivine and trivalent in the pyroxene. These results, coupled with the apparent f(02)-independence of partitioning coefficients for Cr into olivine, imply that the source magma was dominated by divalent Cr at the time of olivine crystallization.

  12. Determination of phosphorus speciation in dairy manure using XRD and XANES spectroscopy.

    PubMed

    Güngör, Kerem; Jürgensen, Astrid; Karthikeyan, K G

    2007-01-01

    Intensive manure application is an important source of diffuse phosphorus (P) pollution. Phosphorus availability from animal manure is influenced by its chemical speciation. The major objective of this study was to investigate the P speciation in raw and anaerobically digested dairy manure with an emphasis on the calcium (Ca) and magnesium (Mg) phosphate phases. Influent and effluent from an on-farm digester in Wisconsin were sampled and sieved, and the 25 to 53 microm size fraction was dried for X-ray powder diffraction (XRD) and P K-edge X-ray absorption near edge structure (XANES) analyses. Struvite (MgNH4PO4.6H2O) was identified in both the raw (influent) and anaerobically digested (effluent) manure using XRD. Qualitative analysis of P K-edge XANES spectra indicated that the Ca orthophosphate phases, except dicalcium phosphate anhydrous (DCPA) or monetite (CaHPO4), were not abundant in dairy manure. Linear combination fitting (LCF) of the P standard compounds showed that 57.0 and 43.0% of P was associated with DCPA and struvite, respectively, in the raw manure. In the anaerobically digested sample, 78.2% of P was present as struvite and 21.8% of P was associated with hydroxylapatite (HAp). The P speciation shifted toward Mg orthophosphates and least soluble Ca orthophosphates following anaerobic digestion. Similarity between the aqueous orthophosphate (aq-PO4), newberyite (MgHPO4.3H2O), and struvite spectra can cause inaccurate P speciation determination when dairy manure is analyzed solely using P K-edge XANES spectroscopy; however, XANES can be used in conjunction with XRD to quantify the distribution of inorganic P species in animal manure. PMID:17965388

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2013-04-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

  16. F K-edge X-ray absorption near-edge structure (XANES) of AlF3 polymorphs: combining ab initio calculations with Walsh correlation diagrams.

    PubMed

    Schroeder, Sven L M; Weiher, Norbert

    2006-04-21

    The X-ray absorption near-edge structures (XANES) at the F K-edge of alpha-AlF(3), beta-AlF(3) and a tetragonal AlF(3) phase are analysed by a combination of ab initio calculations with the FEFF8 code and a phenomenological discussion of local molecular orbital (MO) symmetries at the absorbing fluorine atoms. By means of a Walsh correlation diagram it is shown that the two intense absorption bands observed at the F K-edges of the AlF(3) polymorphs can be interpreted as transitions to anti-bonding MOs in [Al-F-Al]-units that have C(2v) and D(infinity h) point group symmetries. The energies of both anti-bonding orbitals are very insensitive to the angle between the Al-F bonds, which explains the close similarity of the XANES signatures from the three polymorphs. The FEFF8 analysis shows that the increased broadening of the XANES structure for beta-AlF(3) and the tetragonal AlF(3) phase is due to the superposition of the individual absorption spectra from the crystallographically distinct F species. The interpretation in terms of local MOs provides for the first time a "chemically intuitive" approach to investigations of solid fluorides by XANES spectroscopy and provides a simple conceptual framework for the discussion of the electronic structure in AlF(3) materials.

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

    SciTech Connect

    Lichtenberg, H.; Hormes, J.; Prange, A.; Modrow, H.

    2007-02-02

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

  18. Structural changes of nucleic acid base in aqueous solution as observed in X-ray absorption near edge structure (XANES)

    NASA Astrophysics Data System (ADS)

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

    2014-01-01

    X-ray absorption near edge structure (XANES) spectra for adenine-containing nucleotides, adenosine 5‧-monophosphate (AMP) and adenosine 5‧-triphosphate (ATP) in aqueous solutions at the nitrogen K-edge region were measured. The two intense peaks in XANES spectra are assigned to transitions of 1s electrons to the π∗ orbitals of different types of N atoms with particular bonding characteristics. The difference between their spectra is ascribed to protonation of a particular N atom. Similarity observed in XANES spectra of guanosine 5‧-monophosphate (GMP) and ATP is also interpreted as similar bonding characters of the N atoms in the nucleobase moiety.

  19. Interlayer Potassium And Its Neighboring Atoms in Micas: Crystal-Chemical Modeling And Xanes Spectroscopy

    SciTech Connect

    Brigatti, M.F.; Malferrari, D.; Poppi, M.; Mottana, A.; Cibin, G.; Marcelli, A.; Cinque, G.

    2009-05-12

    A detailed description of the interlayer site in trioctahedral true micas is presented based on a statistical appraisal of crystal-chemical, structural, and spectroscopic data determined on two sets of trioctahedral micas extensively studied by both X-ray diffraction refinement on single crystals (SC-XRD) and X-ray absorption fine spectroscopy (XAFS) at the potassium K-edge. Spectroscopy was carried out on both random powders and oriented cleavage flakes, the latter setting taking advantage of the polarized character of synchrotron radiation. Such an approach (AXANES) is shown to be complementary to crystal-chemical investigation based on SC-XRD refinement. However, the results are not definitive as they focus on few samples having extreme features only (e.g., end-members, unusual compositions, and samples with extreme and well-identified substitution mechanisms). The experimental absorption K-edge (XANES) for potassium was decomposed by calculation and extrapolated into a full in-plane absorption component ({sigma}{parallel}) and a full out-of-plane absorption component ({sigma}{perpendicular}). These two patterns reflect different structural features: {sigma}{parallel}represents the arrangement of the atoms located in the mica interlayer space and facing tetrahedral sheets; {sigma}{perpendicular} is associated with multiple-scattering interactions entering deep into the mica structure, thus also reflecting interactions with the heavy atoms (essentially Fe) located in the octahedral sheet. The out-of-plane patterns also provide insights into the electronic properties of the octahedral cations, such as their oxidation states (e.g., Fe{sup 2+} and Fe{sup 3+}) and their ordering (e.g., trans- vs. cis-setting). It is also possible to distinguish between F- and OH-rich micas due to peculiar absorption features originating from the F vs. OH occupancy of the O4 octahedral site. Thus, combining crystal-chemical, structural, and spectroscopic information is shown to be a

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

    SciTech Connect

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

    2005-01-01

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

  1. Photothermal absorption correlation spectroscopy.

    PubMed

    Octeau, Vivien; Cognet, Laurent; Duchesne, Laurence; Lasne, David; Schaeffer, Nicolas; Fernig, David G; Lounis, Brahim

    2009-02-24

    Fluorescence correlation spectroscopy (FCS) is a popular technique, complementary to cell imaging for the investigation of dynamic processes in living cells. Based on fluorescence, this single molecule method suffers from artifacts originating from the poor fluorophore photophysics: photobleaching, blinking, and saturation. To circumvent these limitations we present here a new correlation method called photothermal absorption correlation spectroscopy (PhACS) which relies on the absorption properties of tiny nano-objects. PhACS is based on the photothermal heterodyne detection technique and measures akin FCS, the time correlation function of the detected signals. Application of this technique to the precise determination of the hydrodynamic sizes of different functionalized gold nanoparticles are presented, highlighting the potential of this method. PMID:19236070

  2. X-ray absorption spectroscopy of metalloproteins.

    PubMed

    Ward, Jesse; Ollmann, Emily; Maxey, Evan; Finney, Lydia A

    2014-01-01

    Metalloproteins are enormously important in biology. While a variety of techniques exist for studying metals in biology, X-ray absorption spectroscopy is particularly useful in that it can determine the local electronic and physical structure around the metal center, and is one of the few avenues for studying "spectroscopically silent" metal ions like Zn(II) and Cu(I) that have completely filled valence bands. While X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) are useful for studying metalloprotein structure, they suffer the limitation that the detected signal is an average of all the various metal centers in the sample, which limits its usefulness for studying metal centers in situ or in cell lysates. It would be desirable to be able to separate the various proteins in a mixture prior to performing X-ray absorption studies, so that the derived signal is from one species only. Here we describe a method for performing X-ray absorption spectroscopy on protein bands following electrophoretic separation and western blotting.

  3. Sulfur species in Asphaltene, Resin, and Oil Fractions of Crude Oils by XANES and IR Spectroscopy Methods

    NASA Astrophysics Data System (ADS)

    Kirtley, Sudipa

    2002-03-01

    XANES (X-ray Absorption Near-Edge Spectroscopy) method has been employed to elucidate the sulfoxide percentages in the resin and oil fraction of a particular crude oil, which is known to have a high sulfoxide content in the asphaltene fraction. This investigation is performed to determine whether the sulfoxide polar group is also a dominant sulfur form in the resin and the oil fractions of the same crude oil; typically, the oil fractions are non-polar. The asphaltene fraction, as well as the resin and oil fraction of another crude oil are systematically low in sulfoxide content. The IR results confirm the sulfoxide finding. This supports the view that the oxidation process probably took place within the earth formation. These sulfoxide results should be considered when comparing asphaltenes from different studies and samples, as the polar sulfoxides often determine the asphaltene fraction.

  4. Structural investigations of PuIII phosphate by X-ray diffraction, MAS-NMR and XANES spectroscopy

    NASA Astrophysics Data System (ADS)

    Popa, Karin; Raison, Philippe E.; Martel, Laura; Martin, Philippe M.; Prieur, Damien; Solari, Pier L.; Bouëxière, Daniel; Konings, Rudy J. M.; Somers, Joseph

    2015-10-01

    PuPO4 was prepared by a solid state reaction method and its crystal structure at room temperature was solved by powder X-ray diffraction combined with Rietveld refinement. High resolution XANES measurements confirm the +III valence state of plutonium, in agreement with valence bond derivation. The presence of the americium (as β- decay product of plutonium) in the +III oxidation state was determined based on XANES spectroscopy. High resolution solid state 31P NMR agrees with the XANES results and the presence of a solid-solution.

  5. 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.

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

    PubMed

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

    2015-01-01

    Understanding legacy phosphorus (P) build-up and draw-down from long-term fertilization is essential for effective P management. Using replicated plots from Saskatchewan, Canada, with P fertilization from 1967 to 1995 followed by either P fertilization or P cessation (1995-2010), soil P was characterized in surface and subsurface layers using sequential fractionation, P K-edge X-ray absorption near-edge structure (XANES) and solution (31)P nuclear magnetic resonance (P NMR) spectroscopy. Legacy P from a 28-year build-up was sufficient for 15 years of wheat cultivation, resulting in no significant differences in crop yield in 2010. In surface soils, soil test (Olsen) P decreased significantly in unfertilized plots compared with 1995, which was reflected in declining aluminum (hydr)oxide-associated inorganic P by fractionation and XANES. Furthermore, XANES analysis revealed a decrease of calcium-associated P in 2010-unfertilized soils at both depths and an increase of Fe (hydr)oxides-associated P in the 2010-fertilized and -unfertilized surface soils relative to the 1995 soils. Increased total organic P and orthophosphate diesters by P NMR and accumulated inositol hexaphosphate by XANES were observed in surface soils with P fertilization cessation. In subsurface soils, few legacy P transformations were detected. These results provide important information about legacy P to improve agricultural sustainability while mitigating water quality deterioration. PMID:25426546

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

    NASA Astrophysics Data System (ADS)

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

    2007-04-01

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

  8. XANES in Nanobiology

    NASA Astrophysics Data System (ADS)

    Metzler, Rebecca A.; Olabisi, Ronke M.; Abrecht, Mike; Ariosa, Daniel; Johnson, Christopher J.; Gilbert, Benjamin; Frazer, Bradley H.; Coppersmith, Susan N.; Gilbert, P. U. P. A.

    2007-02-01

    The combination of spectroscopy and microscopy enables unprecedented insights into the molecular and crystal structures of organic and inorganic materials, and their interfaces. This is relevant to the field of biomaterials in general and biominerals in particular. In this framework, we extensively analyzed various proteins, minerals and biominerals. Here we present two novel observations: x-ray absorption near-edge structure (XANES) spectroscopy at the carbon K-edge is sensitive to protein misfolding and aggregation into amyloid fibrils, and to the polar and azimuthal rotation of the CaCO3 polymorph aragonite.

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

    NASA Astrophysics Data System (ADS)

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

    2013-10-01

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

  10. Understanding the Zr and Si interdispersion in Zr1-xSixO2 mesoporous thin films by using FTIR and XANES spectroscopy.

    PubMed

    Andrini, Leandro; Angelomé, Paula C; Soler-Illia, Galo J A A; Requejo, Félix G

    2016-06-14

    Zr-Si mixed mesoporous oxides were obtained in a wide range of proportions, from 0 to 30% and from 70 to 100% of Si, using Si(OEt)4 and ZrCl4 as precursors and Pluronic F127 as a template. The oxide mesostructure was characterized by transmission electron microscopy and 2D-small angle X-ray scattering. Fourier transform infrared spectroscopy measurements suggested a local homogeneous interdispersion of both cations. Further selective studies using X-ray Absorption Near Edge Structure (XANES) spectroscopy for separately Zr and Si local environments, allowed for demonstrating that the Zr coordination varies from close to 7 to 6, when its concentration in the mixed oxide is reduced. In addition, it was possible to determine that in mixed oxides with low Zr concentrations, Zr can fit into the spaces occupied by Si in SiO2 pure oxide. An equivalent XANES result was obtained for Si, which is also compatible with the information obtained by FTIR. Furthermore, the Zr-O distance varied from close to 2.2 Å to 1.7 Å when the Zr concentration decreased. Finally, our study also demonstrates the usefulness of XANES to selectively assess the local structure (coordination, symmetry and chemical state) of specific atoms in nanostructured systems.

  11. X-ray absorption spectroscopy in electrical fields: An element-selective probe of atomic polarization

    NASA Astrophysics Data System (ADS)

    Ney, V.; Wilhelm, F.; Ollefs, K.; Rogalev, A.; Ney, A.

    2016-01-01

    We have studied a range of polar and nonpolar materials using x-ray absorption near-edge spectroscopy (XANES) in external electric fields. An energy shift of the XANES by a few meV/kV is found which scales linearly with the applied voltage, thus being reminiscent of the linear Stark effect. This is corroborated by the consistent presence of this energy shift in polar thin films and bulk crystals and its absence in nonpolar materials as well as in conducting films. The observed energy shift of the XANES is different between two atomic species in one specimen and appears to scale linearly with the atomic number of the studied element. Therefore, XANES in electrical fields opens the perspective to study atomic polarization with element specificity in a range of functional materials.

  12. Growth of Au@Pt coreshell nanoparticles: Probed by in-situ XANES and UV-visible spectroscopy

    NASA Astrophysics Data System (ADS)

    Nayak, C.; Bhattacharyya, K.; Tripathi, A. K.; Jha, S. N.; Bhattacharyya, D.; Sahoo, N. K.

    2016-05-01

    Au@Pt core shell nanoparticles have been synthesized by reducing Au and Pt chloride precursors with Block Co-polymer and Ascorbic acid. The growth and nucleation of Au@Pt nanoparticles have been investigated by in-situ time resolved XANES measurement which gives the evolution of the reduction process of the precursors. Linear combination fitting of the XANES spectra has been carried out to find the fraction of Au and Pt cations reduced at a particular reaction time. UV-Visible spectroscopy is used as a complementary technique which gives the changes in the Au SPR peak as Au@Pt core shell nanoparticles are formed.

  13. Structure and Composition of Cu Doped CdSe Nanocrystals Using Soft X-ray Absorption Spectroscopy

    SciTech Connect

    Meulenberg, R W; van Buuren, T; Hanif, K M; Willey, T M; Strouse, G F; Terminello, L J

    2004-06-04

    The local structure and composition of Cu ions dispersed in CdSe nanocrystals is examined using soft x-ray absorption near edge spectroscopy (XANES). Using Cu L-edge XANES and X-ray photoelectron measurements (XPS), we find that the Cu ions exist in the Cu(I) oxidation state. We also find that the observed Cu L-edge XANES signal is directly proportional to the molar percent of Cu present in our final material. Se L-edge XANES indicates changes in the Se density of states with Cu doping, due to a chemical bonding effect, and supports a statistical doping mechanism. Photoluminescence (PL) measurements indicate the Cu ions may act as deep electron traps. We show that XANES, XPS, and PL are a powerful combination of methods to study the electronic and chemical structure of dopants in nanostructured materials.

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

    SciTech Connect

    Popa, Karin; Raison, Philippe E.; Martel, Laura; Martin, Philippe M.; Solari, Pier L.; Bouëxière, Daniel; Konings, Rudy J.M.; Somers, Joseph

    2015-10-15

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

  15. Concentration-modulated absorption spectroscopy.

    PubMed

    Langley, A J; Beaman, R A; Baran, J; Davies, A N; Jones, W J

    1985-07-01

    Concentration modulation is demonstrated to be a technique capable of markedly extending sensitivity limits in absorption spectroscopy. The gain generated relates in such a manner to sample transmittance that for the first reported time direct spectroscopic concentration measurements become possible. When concentration modulation is used with picosecond lasers, state lifetimes can be determined to a limit of approximately 20 psec.

  16. X-ray absorption near-edge structure (XANES) studies on Sb-doped Bi2UO6 at Bi and U edges

    NASA Astrophysics Data System (ADS)

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

    2013-02-01

    X-ray absorption spectroscopy (XAS) measurements at Bi and U LIII edges with synchrotron radiation have been carried out on Bi2-xSbxUO6 samples for x= 0.04, 0.08, 0.12, 0.16 and 0.40 which are possible by-products of Bi based coolant and Uranium based fuels in advanced high temperature nuclear reactors. The chemical shift of the Bi absorption edges in the samples have been determined accurately from the XANES region of the X-ray absorption spectra and have been explained in terms of the difference in electronegativity values of Sb and Bi. The chemical shift of absorption edges show systematic variation only upto x = 0.08 (i.e., 4% Sb doping), which shows that the Sb enter in the matrix properly up to 4% doping concentration. The local structure of U is found to remain unchanged on Sb doping indicating clearly that Sb dopants preferably replace Bi atoms.

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

    NASA Astrophysics Data System (ADS)

    Denoeud, Adrien

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

  18. 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. PMID:18728323

  19. A valence state evaluation of a positive electrode material in an Li-ion battery with first-principles K- and L-edge XANES spectral simulations and resonance photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Kubobuchi, Kei; Mogi, Masato; Matsumoto, Masashi; Baba, Teruhisa; Yogi, Chihiro; Sato, Chikai; Yamamoto, Tomoyuki; Mizoguchi, Teruyasu; Imai, Hideto

    2016-10-01

    X-ray absorption near edge structure (XANES) analysis is an element-specific method for proving electronic state mostly in the field of applied physics, such as battery and catalysis reactions, where the valence change plays an important role. In particular, many results have been reported for the analysis of positive electrode materials of Li-ion batteries, where multiple transition materials contribute to the reactions. However, XANES analysis has been limited to identifying the valence state simply in comparison with reference materials. When the shape of XANES spectra shows complicated changes, we were not able to identify the valence states or estimate the valence quantitatively, resulting in insufficient reaction analysis. To overcome such issues, we propose a valence state evaluation method using K- and L-edge XANES analysis with first-principles simulations. By using this method, we demonstrated that the complicated reaction mechanism of Li(Ni1/3Co1/3Mn1/3)O2 can be successfully analyzed for distinguishing each contribution of Ni, Co, Mn, and O to the redox reactions during charge operation. In addition to the XANES analysis, we applied resonant photoelectron spectroscopy (RPES) and diffraction anomalous fine structure spectroscopy (DAFS) with first-principles calculations to the reaction analysis of Co and Mn, which shows no or very little contribution to the redox. The combination of RPES and first-principles calculations successfully enables us to confirm the contribution of Co at high potential regions by electively observing Co 3d orbitals. Through the DAFS analysis, we deeply analyzed the spectral features of Mn K-edges and concluded that the observed spectral shape change for Mn does not originate from the valence change but from the change in distribution of wave functions around Mn upon Li extraction.

  20. Organic carbon and sulphur compounds in wetland soils: insights on structure and transformation processes using K-edge XANES and NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Jokic, Aleksander; Cutler, Jeffrey N.; Ponomarenko, Elena; van der Kamp, Garth; Anderson, Darwin W.

    2003-07-01

    X-ray absorption near-edge structure (XANES) and nuclear magnetic resonance (NMR) spectroscopy were used in combination to characterize organic carbon structures in a series of wetland soils in Saskatchewan, and XANES spectroscopy was also used to examine sulphur speciation in the soils. The organic C contents of most of the wetland soils are consistently higher by a factor of two to five times compared to adjacent well-drained soils. NMR analyses indicate that the organic matter in the wetland soils consists of predominantly aliphatic structures such as carbohydrates and long chain poly(methylene) units which are refractory structures found in plant waxes. The poly(methylene) structures have a significant capacity to sorb nonpolar organic molecules. The phenolic OH and carboxyl group content of the wetland soils studied is an additional significant factor in their sequestering ability for heavy metals or pesticides. Carbon XANES spectroscopy shows that the surface (˜10 nm) layer of particulate organic matter has a structure dominated by aromatic, carbohydrate and carboxylic acid-like material apparently derived from partially degraded lignin and cellulose polymers which are adsorbed onto clay minerals. The aliphatic structures remaining in this surface layer are probably recalcitrant (poly)methylene units. At a depth of ˜100 nm, the aliphatic content significantly increases suggesting the presence of more labile structures. The presence of these more labile aliphatic compounds may be due to slow decomposition rates in the wet, often cool environments present and to the protective action of the more refractory components in the surface ˜10 nm of the organic matter. Drying of the wetlands, either by draining or as a result of climate change, is likely to result in the rapid decomposition of these labile organic structures releasing carbon dioxide. Our data indicate that the preservation of the organic carbon compounds in these soils is a result of their presence

  1. Characterization of Oxygen Containing Functional Groups on Carbon Materials with Oxygen K-edge X-ray Absorption Near Edge Structure Spectroscopy

    SciTech Connect

    K Kim; P Zhu; L Na; X Ma; Y Chen

    2011-12-31

    Surface functional groups on carbon materials are critical to their surface properties and related applications. Many characterization techniques have been used to identify and quantify the surface functional groups, but none is completely satisfactory especially for quantification. In this work, we used oxygen K-edge X-ray absorption near edge structure (XANES) spectroscopy to identify and quantify the oxygen containing surface functional groups on carbon materials. XANES spectra were collected in fluorescence yield mode to minimize charging effect due to poor sample conductivity which can potentially distort XANES spectra. The surface functional groups are grouped into three types, namely carboxyl-type, carbonyl-type, and hydroxyl-type. XANES spectra of the same type are very similar while spectra of different types are significantly different. Two activated carbon samples were analyzed by XANES. The total oxygen contents of the samples were estimated from the edge step of their XANES spectra, and the identity and abundance of different functional groups were determined by fitting of the sample XANES spectrum to a linear combination of spectra of the reference compounds. It is concluded that oxygen K-edge XANES spectroscopy is a reliable characterization technique for the identification and quantification of surface functional groups on carbon materials.

  2. Phosphorus speciation of forest-soil organic surface layers using P K-edge XANES spectroscopy

    SciTech Connect

    Prietzel, Jörg; Thieme, Jürgen; Paterson, David

    2012-02-07

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

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

    SciTech Connect

    J Prietzel; J Thieme; D Paterson

    2011-12-31

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

  4. The speciation of soluble sulphur compounds in bacterial culture fluids by X-ray absorption near edge structure spectroscopy.

    PubMed

    Franz, Bettina; Lichtenberg, Henning; Hormes, Josef; Dahl, Christiane; Prange, Alexander

    2009-11-01

    Over the last decade X-ray absorption near edge structure (XANES) spectroscopy has been used in an increasing number of microbiological studies. In addition to other applications it has served as a valuable tool for the investigation of the sulphur globules deposited intra- or extracellularly by certain photo- and chemotrophic sulphur-oxidizing (Sox) bacteria. For XANES measurements, these deposits can easily be concentrated by filtration or sedimentation through centrifugation. However, during oxidative metabolism of reduced sulphur compounds, such as sulphide or thiosulphate, sulphur deposits are not the only intermediates formed. Soluble intermediates such as sulphite may also be produced and released into the medium. In this study, we explored the potential of XANES spectroscopy for the detection and speciation of sulphur compounds in culture supernatants of the phototrophic purple sulphur bacterium Allochromatium vinosum. More specifically, we investigated A. vinosum DeltasoxY, a strain with an in frame deletion of the soxY gene. This gene encodes an essential component of the thiosulphate-oxidizing Sox enzyme complex. Improved sample preparation techniques developed for the DeltasoxY strain allowed for the first time not only the qualitative but also the quantitative analysis of bacterial culture supernatants by XANES spectroscopy. The results thus obtained verified and supplemented conventional HPLC analysis of soluble sulphur compounds. Sulphite and also oxidized organic sulphur compounds were shown by XANES spectroscopy to be present, some of which were not seen when standard HPLC protocols were used.

  5. Graphene intracavity spaser absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Lozovik, Yu. E.; Nechepurenko, I. A.; Dorofeenko, A. V.

    2016-09-01

    We propose an intracavity plasmon absorption spectroscopy method based on graphene active plasmonics. It is shown that the plasmonic cavity contribution to the sensitivity is proportional to the quality factor Q of the graphene plasmonic cavity and reaches two orders of magnitude. The addition of gain medium into the cavity increases the sensitivity of method. Maximum sensitivity is reached in the vicinity of the plasmon generation threshold. The gain contribution to the sensitivity is proportional to Q1/2. The giant amplification of sensitivity in the graphene plasmon generator is associated with a huge path length, limited only by the decoherence processes. An analytical estimation of the sensitivity to loss caused by analyzed particles (molecules, nanoparticles, etc.) normalized by the single pass plasmon scheme is derived. Usage of graphene nanoflakes as plasmonic cavity allows a high spatial resolution to be reached, in addition to high sensitivity.

  6. Metallization of warm dense SiO(2) studied by XANES spectroscopy.

    PubMed

    Denoeud, A; Benuzzi-Mounaix, A; Ravasio, A; Dorchies, F; Leguay, P M; Gaudin, J; Guyot, F; Brambrink, E; Koenig, M; Le Pape, S; Mazevet, S

    2014-09-12

    We investigate the evolution of the electronic structure of fused silica in a dense plasma regime using time-resolved x-ray absorption spectroscopy. We use a nanosecond (ns) laser beam to generate a strong uniform shock wave in the sample and a picosecond (ps) pulse to produce a broadband x-ray source near the Si K edge. By varying the delay between the two laser beams and the intensity of the ns beam, we explore a large thermodynamical domain with densities varying from 1 to 5  g/cm^{3} and temperatures up to 5 eV. In contrast to normal conditions where silica is a well-known insulator with a wide band gap of 8.9 eV, we find that shocked silica exhibits a pseudogap as a semimetal throughout this thermodynamical domain. This is in quantitative agreement with density functional theory predictions performed using the generalized gradient approximation. PMID:25259992

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

    NASA Astrophysics Data System (ADS)

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

    2014-07-01

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

  8. Alkali-support interactions on rubidium base catalysts determined by XANES, EXAFS, CO{sub 2} adsorption, and IR spectroscopy

    SciTech Connect

    Doskocil, E.J.; Bordawekar, S.V.; Davis, R.J.

    1997-07-01

    Rubidium was supported on a variety of catalyst supports, including magnesia, titania, alumina, carbon, and silica. Except for Rb/MgO, none of the oxide-based samples contained surface carbonates as detected by IR spectroscopy after pretreatment at 773 K. The XANES and EXAFS associated with the Rb K edge indicated that the local structure around Rb was highly dependent on the support composition. Results from CO{sub 2} stepwise TPD showed that Rb/MgO possessed strongly basic sites that were not present on pure MgO. The basic sites formed by Rb addition to the other supports were weaker than those on Rb/MgO. Decomposition of 2-propanol at 593 K was used to relate catalytic activity to surface basicity. 40 refs., 16 figs., 4 tabs.

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

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

    The distribution of trivalent and tetravalent cerium, Ce(III) and Ce(IV) respectively, in a lateritic profile from Madagascar, has been characterized by X-ray-absorption near-edge structure (XANES) spectroscopy at the Ce LIII-edge on the LUCIA beamline (SOLEIL synchrotron, France). XANES spectra were acquired on bulk-rock samples as well as on specific lateritic minerals or polymineral zones (in-situ measurements) of the tonalite bedrock and the three overlying weathered horizons (C-, B- and A-horizons). Geochemically, the bedrock, and the A- and C-horizons show similar rare earth element content (REE = 363-405 mg/kg). They also display the same positive Ce-anomaly (CeCN/Ce∗ = 1.12-1.45), which is therefore likely to be inherited from the bedrock. In the B-horizon, the higher REE content (REE = 2194 mg/kg) and the larger Ce-anomaly (CeCN/Ce∗ = 4.26) are consistent with an accumulation zone caused by the evaporation of groundwater during the dry season. There is a good agreement between the Ce(III)/Cetotal ratio (XCe(III)) deduced from the positive Ce-anomaly (bulk-rock geochemical data) and that derived from XANES spectroscopy on the same bulk-rock samples (BR-XCe(III)-XANES) in the bedrock, and the C- and B-horizons. In the A-horizon, XANES measurements on bulk rock and minerals revealed a higher BR-XCe(III)-XANES (up to 100%) compared to the XCe(III) deduced from geochemical data (XCe(III) = 79%). The preservation of a positive Ce-anomaly in the A-horizon suggests that the Ce mobilization and redistribution during weathering occurred with no significant Ce fractionation from other trivalent REE. Remarkably, the only investigated sample where cerianite is observed belongs to the B-horizon. Within this horizon, Ce oxidation state varies depending on the microstructural position (porosity, cracks, clay-rich groundmass). The highest Ce(IV) concentrations are measured in cerianite (and aluminophosphates) localized in pores at the vicinity of Mn-rich domains (XCe(III)-XANES

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

    SciTech Connect

    Nemana,S.; Gates, B.

    2006-01-01

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

  11. Measurement of c-axis angular orientation in calcite (CaCO3) nanocrystals using X-ray absorption spectroscopy

    PubMed Central

    Gilbert, P. U. P. A.; Young, Anthony; Coppersmith, Susan N.

    2011-01-01

    We demonstrate that the ability to manipulate the polarization of synchrotron radiation can be exploited to enhance the capabilities of X-ray absorption near-edge structure (XANES) spectroscopy, to include linear dichroism effects. By acquiring spectra at the same photon energies but different polarizations, and using a photoelectron emission spectromicroscope (PEEM), one can quantitatively determine the angular orientation of micro- and nanocrystals with a spatial resolution down to 10 nm. XANES-PEEM instruments are already present at most synchrotrons, hence these methods are readily available. The methods are demonstrated here on geologic calcite (CaCO3) and used to investigate the prismatic layer of a mollusk shell, Pinctada fucata. These XANES-PEEM data reveal multiply oriented nanocrystals within calcite prisms, previously thought to be monocrystalline. The subdivision into multiply oriented nanocrystals, spread by more than 50°, may explain the excellent mechanical properties of the prismatic layer, known for decades but never explained. PMID:21693647

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

    NASA Astrophysics Data System (ADS)

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

    2014-08-01

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

  13. 279 - Xanes Studies on UV-Irradiated Interstellar Ice Analogs: A Comparison to STARDUST Samples

    NASA Technical Reports Server (NTRS)

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

    2010-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-02-01

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

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

    PubMed Central

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

    2016-01-01

    We have developed an X-ray absorption near edge structure spectroscopy method using fluorescence detection for visualizing in vivo coordination environments of metals in biological specimens. This approach, which we term fluorescence imaging XANESXANES), allows us to spatially depict metal-protein associations in a native, hydrated state whilst avoiding intrinsic chemical damage from radiation. This method was validated using iron-challenged Caenorhabditis elegans to observe marked alterations in redox environment. PMID:26861174

  16. XANES Identification of Plutonium Speciation in RFETS Samples

    SciTech Connect

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

    2009-06-03

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

  17. 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.

  18. Surface Arsenic Speciation of a Drinking-Water Treatment Residual Using X-Ray Absorption Spectroscopy

    SciTech Connect

    Makris, K.C.; Sarkar, D.; Parsons, J.G.; Datta, R.; Gardea-Torresdey, J.L.

    2009-06-03

    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{sup -1}) after 48 h of reaction. Subsequent desorption experiments with a high P load (7500 mg kg{sup -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.

  19. Further advancement of differential optical absorption spectroscopy: theory of orthogonal optical absorption spectroscopy.

    PubMed

    Liudchik, Alexander M

    2014-08-10

    A modified version of the differential optical absorption spectroscopy (DOAS) method is presented. The technique is called orthogonal optical absorption spectroscopy (OOAS). A widespread variant of DOAS with smoothing of the registered spectrum and absorption cross sections being made employing a polynomial regression is a particular case of OOAS. The concept of OOAS provides a variety of new possibilities for constructing computational schemes and analyzing the influence of different error sources on calculated concentrations. PMID:25320931

  20. Absorption spectroscopy: technique provides extremely high sensitivity.

    PubMed

    Provencal, R A; Paul, J B; Michael, E; Saykally, R J

    1998-06-01

    Technology associated with cavity ringdown laser absorption spectroscopy is reviewed. The technique is used to study general trace analysis, free radicals in flames and chemical reactors, molecular ions in electrical discharges, biological molecules and water clusters in supersonic jets, and vibrational overtones of stable molecules. Its specific enough to detect about 1-ppm fractional absorption by a gaseous sample in about 10 microseconds. The use of mirrors in ringdown sepctroscopy is explained. Other topics include the generation of pulsed infrared rays and the adaptation of ringdown spectroscopy for use with narrow-bandwidth continuous-wave lasers. PMID:11541906

  1. X-ray absorption spectroscopy of iron at multimegabar pressures in laser shock experiments

    NASA Astrophysics Data System (ADS)

    Harmand, M.; Ravasio, A.; Mazevet, S.; Bouchet, J.; Denoeud, A.; Dorchies, F.; Feng, Y.; Fourment, C.; Galtier, E.; Gaudin, J.; Guyot, F.; Kodama, R.; Koenig, M.; Lee, H. J.; Miyanishi, K.; Morard, G.; Musella, R.; Nagler, B.; Nakatsutsumi, M.; Ozaki, N.; Recoules, V.; Toleikis, S.; Vinci, T.; Zastrau, U.; Zhu, D.; Benuzzi-Mounaix, A.

    2015-07-01

    Taking advantage of the new opportunities provided by x-ray free electron laser (FEL) sources when coupled to a long laser pulse as available at the Linear Coherent Light Source (LCLS), we have performed x-ray absorption near-edge spectroscopy (XANES) of laser shock compressed iron up to 420 GPa (±50 ) and 10 800 K (±1390 ). Visible diagnostics coupled with hydrodynamic simulations were used to infer the thermodynamical conditions along the Hugoniot and the release adiabat. A modification of the pre-edge feature at 7.12 keV in the XANES spectra is observed above pressures of 260 GPa along the Hugoniot. Comparing with ab initio calculations and with previous laser-heated diamond cell data, we propose that such changes in the XANES pre-edge could be a signature of molten iron. This interpretation then suggests that iron is molten at pressures and temperatures higher than 260 GPa (±29 ) and 5680 K (±700 ) along the principal Fe Hugoniot.

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

    SciTech Connect

    Yadav, Ashok Kumar; Jha, S. N.; Bhattacharyya, D.; Haque, Sk Maidul; Shukla, Dinesh; Choudhary, Ram Janay

    2015-11-15

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

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

    NASA Astrophysics Data System (ADS)

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

    2004-07-01

    Sol-gel glass matrices containing lanthanides have numerous technological applications and their formation involves several chemical facets. In the case of cerium, its ability to exist in two different oxidation states or in mixed valence state provides additional complexities for the sol-gel process. The oxidation state of cerium present during different facets of preparation of sol-gel glasses, and also as a function of the starting oxidation state of cerium added, were studied both by optical spectroscopy and X-ray absorption near-edge structures (XANES). The findings acquired by each approach were compared. The primary focus was on the redox chemistries associated with sample preparation, gelation, and thermal treatment. When Ce 3+ is introduced into the starting sols, the trivalent state normally prevails in the wet and room temperature-dried gels. Heating in air at >100 °C can generate a light yellow coloration with partial oxidation to the tetravalent state. Above 200 °C and up to ˜1000 °C, cerium is oxidized to its tetravalent state. In contrast, when tetravalent cerium is introduced into the sol, both the wet and room temperature-dried gels lose the yellow-brown color of the initial ceric ammonium nitrate solution. When the sol-gel is heated to 110 °C it turns yellowish as the cerium tends to be re-oxidized. The yellow color is believed to represent the effect of oxidation and oligomerization of the cerium-silanol units in the matrix. The luminescence properties are also affected by these changes, the details of which are reported herein.

  4. Combined Sulfur K-edge XANES Spectroscopy and Stable Isotope Analysis of Fulvic Acids and Groundwater Sulfate Identify Sulfur Cycling in a Karstic Catchment Area

    SciTech Connect

    Einsiedl,F.; Schafer, T.; Northrup, P.

    2007-01-01

    Chemical and isotope analyses on groundwater sulfate, atmospheric deposition sulfate and fulvic acids (FAs) associated sulfur were used to determine the S cycling in a karstic catchment area of the Franconian Alb, Southern Germany. Sulfur K-edge X-ray absorption near edge structure (XANES) spectroscopy provided information on the oxidation state and the mechanism of the incorporation of sulfur in FAs. During base flow {delta}{sup 34}S values of groundwater sulfate were slightly depleted to those of recent atmospheric sulfate deposition with mean amount-weighted {delta}{sup 34}S values of around + 3{per_thousand}. The {delta}{sup 18}O values of groundwater sulfate shifted to lower values compared to those of atmospheric deposition and indicated steadiness from base flow to peak flow. The reduced sulfur species (S{sub -1}/thiol; S{sub 0}/thiophene, disulfide, S{sub +2}2/sulfoxide) of soil FAs averaged around 49% of the total sulfur and {delta}{sup 34}S value in FAs was found to be 0.5{per_thousand}. The formation of polysulfides and thiols in FAs in concert with a decreasing isotope value of {delta}{sup 34}S in FAs with respect to those of atmospheric deposition sulfate suggests oxidation of H{sub 2}S, enriched in the {sup 32}S isotope, with organic material. The depletion of {delta}{sup 18}O-SO{sub 4}{sup 2-} by several per mil in groundwater sulfate with respect to those of atmospheric deposition is, therefore, consistent with the hypothesis that SO{sub 4}{sup 2-} has been cycled through the organic S pool as well as that groundwater sulfate is formed by oxidation of H{sub 2}S with organic matter in the mineral soil of the catchment area.

  5. Near-edge x-ray absorption spectroscopy of RT/sub 2/Si/sub 2/ and RT/sub 2/Ge/sub 2/ compounds

    SciTech Connect

    Ansari, P.H.; Qi, B.; Liang, G.; Perez, I.; Lu, F.; Croft, M.

    1988-04-15

    X-ray absorption near-edge spectroscopy (XANES) measurements on 1:2:2 compounds of the form RT/sub 2/X/sub 2/ with R = Ce and Eu, T = a transition metal, and X = Si or Ge are presented. XANES measurements on each of the three sublattices are used to elucidate elements of the electronic structure of these compounds. In particular, the evidence for the strongly bonded T-X planes, the coupling of the Ce valence-state stability to the T-X planes, and the response of the X-p orbitals to varying transition-metal components are discussed.

  6. Amorphisation mechanism of a flint aggregate during the alkali-silica reaction: X-ray diffraction and X-ray absorption XANES contributions

    SciTech Connect

    Verstraete, J.; Khouchaf, L.; Bulteel, D.; Garcia-Diaz, E.; Flank, A.M; Tuilier, M.H

    2004-04-01

    Flint samples at different stages of the Alkali-Silica Reaction were prepared and analyzed by X-ray diffraction (XRD) and silicon K-edge X-ray absorption near edge structure techniques (XANES). The results are compared to those of measurements performed on alpha quartz c-SiO{sub 2} and rough flint aggregate. The molar fraction of Q{sub 3} sites is determined as a function of the time of reaction. Up to 14 h of attack, the effect of the reaction seems of little importance. From 30 to 168 h, we showed an acceleration of the effect of the reaction on the crystal structure of the aggregate resulting in an amorphisation of the crystal. During this period, the amorphous fraction increases linearly with the number of Q{sub 3} sites. The results of the XANES confirm the amorphisation of the aggregate during the reaction and show the presence of silicon in a tetrahedral environment of oxygen whatever the time of attack.

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

    SciTech Connect

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

    2014-08-07

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

  8. Sulfur Poisoning Mechanism of Steam Reforming Catalysts: an X-ray Absorption Near Edge Structure (XANES) Spectroscopic Study

    SciTech Connect

    Chen, Y.; Xie, C; Li, Y; Song, C; Bolin, T

    2010-01-01

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

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

    SciTech Connect

    Chen, Y.; Xie, C.; Li, Y.; Song, C.; Bolin, T.; X-Ray Science Division; Pennsylvania State Univ.

    2010-04-29

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

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

    PubMed

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

    2010-06-01

    The present XANES study aims at elucidating the roles of carbon deposits and metal sulfides in the catalyst deactivation in steam reforming reactions with the presence of sulfur. CeO(2)-Al(2)O(3)-supported Ni and Rh-based catalysts were tested in steam reforming of liquid hydrocarbon fuel containing 350 ppm sulfur for H(2) production at 800 degrees C. The Rh catalyst demonstrated much better sulfur tolerance than the Ni catalyst. XANES revealed that there are various sulfur species (metal sulfide, sulfonate, sulfate and organic sulfide) on the used Ni and Rh catalysts. Metal sulfide and organic sulfide are the dominant sulfur species on the Ni catalyst whereas sulfonate and sulfate predominate on the Rh catalyst. Meanwhile organic sulfide and sulfate are also observed on the support alone. Furthermore, there are more carbon deposits formed in the presence of sulfur on both catalysts. More carboxyl groups occur on the carbon deposits formed on the same catalyst when there is no sulfur in the fuel. From correlation analysis of the amounts of nickel sulfide and carbon deposits along with the relative catalytic activity loss, we conclude that sulfur causes the initial deactivation of the Ni catalyst by metal sulfide formation in the first few hours while build-up of carbon deposits contributes mainly to the subsequent deactivation. PMID:20431820

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

    NASA Astrophysics Data System (ADS)

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

    2013-04-01

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

  12. 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.

  13. XANES of Chromium in Sludges Used as Soil Ameliorants

    SciTech Connect

    Naftel, S.J.; Martin, R.R.; Sham, T.K.; Hart, B.; Powell, M.A.

    2010-12-01

    Samples of sewage sludges proposed for use as soil ameliorants in an Indo-Canadian project were tested for chromium content. Standard aqua regia extractions found one sludge to have excessive amounts of Cr. X-ray absorption near-edge structure (XANES) spectroscopy, however, indicated that the Cr was present in the relatively benign Cr(III) oxidation state in all the sludge samples.

  14. Absorption spectroscopy with quantum cascade lasers

    NASA Technical Reports Server (NTRS)

    Kosterev, A. A.; Curl, R. F.; Tittel, F. K.; Gmachl, C.; Capasso, F.; Sivco, D. L.; Baillargeon, J. N.; Hutchinson, A. L.; Cho, A. Y.

    2001-01-01

    Novel pulsed and cw quantum cascade distributed feedback (QC-DFB) lasers operating near lambda=8 micrometers were used for detection and quantification of trace gases in ambient air by means of sensitive absorption spectroscopy. N2O, 12CH4, 13CH4, and different isotopic species of H2O were detected. Also, a highly selective detection of ethanol vapor in air with a sensitivity of 125 parts per billion by volume (ppb) was demonstrated.

  15. OH absorption spectroscopy in a flame using spatial heterodyne spectroscopy

    NASA Astrophysics Data System (ADS)

    Bartula, Renata J.; Ghandhi, Jaal B.; Sanders, Scott T.; Mierkiewicz, Edwin J.; Roesler, Fred L.; Harlander, John M.

    2007-12-01

    We demonstrate measurements of OH absorption spectra in the post-flame zone of a McKenna burner using spatial heterodyne spectroscopy (SHS). SHS permits high-resolution, high-throughput measurements. In this case the spectra span ~308-310 nm with a resolution of 0.03 nm, even though an extended source (extent of ~2×10-7 m2 rad2) was used. The high spectral resolution is important for interpreting spectra when multiple absorbers are present for inferring accurate gas temperatures from measured spectra and for monitoring weak absorbers. The present measurement paves the way for absorption spectroscopy by SHS in practical combustion devices, such as reciprocating and gas-turbine engines.

  16. µ-XANES AND µ-XRF INVESTIGATIONS OF METAL BINDING MECHANISMS IN BIOSOLIDS

    EPA Science Inventory

    Micro-X-ray fluorescence (µ-XRF) microprobe analysis and micro-X-ray absorption near edge spectroscopy (µ-XANES) were employed to identify Fe and Mn phases and their association with selected toxic elements in two biosolids (limed composted and Nu-Earth) containing low ...

  17. Experimental station for laser-based picosecond time-resolved x-ray absorption near-edge spectroscopy

    SciTech Connect

    Dorchies, F. Fedorov, N.; Lecherbourg, L.

    2015-07-15

    We present an experimental station designed for time-resolved X-ray Absorption Near-Edge Spectroscopy (XANES). It is based on ultrashort laser-plasma x-ray pulses generated from a table-top 100 mJ-class laser at 10 Hz repetition rate. A high transmission (10%–20%) x-ray beam line transport using polycapillary optics allows us to set the sample in an independent vacuum chamber, providing high flexibility over a wide spectral range from 0.5 up to 4 keV. Some XANES spectra are presented, demonstrating 1% noise level in only ∼1 mn and ∼100 cumulated laser shots. Time-resolved measurements are reported, indicating that the time resolution of the entire experimental station is 3.3 ± 0.6 ps rms.

  18. Experimental station for laser-based picosecond time-resolved x-ray absorption near-edge spectroscopy.

    PubMed

    Dorchies, F; Fedorov, N; Lecherbourg, L

    2015-07-01

    We present an experimental station designed for time-resolved X-ray Absorption Near-Edge Spectroscopy (XANES). It is based on ultrashort laser-plasma x-ray pulses generated from a table-top 100 mJ-class laser at 10 Hz repetition rate. A high transmission (10%-20%) x-ray beam line transport using polycapillary optics allows us to set the sample in an independent vacuum chamber, providing high flexibility over a wide spectral range from 0.5 up to 4 keV. Some XANES spectra are presented, demonstrating 1% noise level in only ∼1 mn and ∼100 cumulated laser shots. Time-resolved measurements are reported, indicating that the time resolution of the entire experimental station is 3.3 ± 0.6 ps rms.

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

    PubMed

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

    2016-10-01

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

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

    PubMed

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

    2016-10-01

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

  1. Gas in scattering media absorption spectroscopy - GASMAS

    NASA Astrophysics Data System (ADS)

    Svanberg, Sune

    2008-09-01

    An overview of the new field of Gas in Scattering Media Absorption Spectroscopy (GASMAS) is presented. GASMAS combines narrow-band diode-laser spectroscopy with diffuse media optical propagation. While solids and liquids have broad absorption features, free gas in pores and cavities in the material is characterized by sharp spectral signatures, typically 10,000 times sharper than those of the host material. Many applications in materials science, food packaging, pharmaceutics and medicine have been demonstrated. So far molecular oxygen and water vapour have been studied around 760 and 935 nm, respectively. Liquid water, an important constituent in many natural materials, such as tissue, has a low absorption at such wavelengths, allowing propagation. Polystyrene foam, wood, fruits, food-stuffs, pharmaceutical tablets, and human sinus cavities have been studied. Transport of gas in porous media can readily be studied by first immersing the material in, e.g., pure nitrogen, and then observing the rate at which normal air, containing oxygen, reinvades the material. The conductance of the sinus connective passages can be measured in this way by flushing the nasal cavity with nitrogen. Also other dynamic processes such as drying of materials can be studied. The techniques have also been extended to remote-sensing applications (LIDAR-GASMAS).

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  3. Aerosol optical absorption measurements with photoacoustic spectroscopy

    NASA Astrophysics Data System (ADS)

    Liu, Kun; Wang, Lei; Liu, Qiang; Wang, Guishi; Tan, Tu; Zhang, Weijun; Chen, Weidong; Gao, Xiaoming

    2015-04-01

    Many parameters related to radiative forcing in climate research are known only with large uncertainties. And one of the largest uncertainties in global radiative forcing is the contribution from aerosols. Aerosols can scatter or absorb the electromagnetic radiation, thus may have negative or positive effects on the radiative forcing of the atmosphere, respectively [1]. And the magnitude of the effect is directly related to the quantity of light absorbed by aerosols [2,3]. Thus, sensitivity and precision measurement of aerosol optical absorption is crucial for climate research. Photoacoustic spectroscopy (PAS) is commonly recognized as one of the best candidates to measure the light absorption of aerosols [4]. A PAS based sensor for aerosol optical absorption measurement was developed. A 532 nm semiconductor laser with an effective power of 160 mW was used as a light source of the PAS sensor. The PAS sensor was calibrated by using known concentration NO2. The minimum detectable optical absorption coefficient (OAC) of aerosol was determined to be 1 Mm-1. 24 hours continues measurement of OAC of aerosol in the ambient air was carried out. And a novel three wavelength PAS aerosol OAC sensor is in development for analysis of aerosol wavelength-dependent absorption Angstrom coefficient. Reference [1] U. Lohmann and J. Feichter, Global indirect aerosol effects: a review, Atmos. Chem. Phys. 5, 715-737 (2005) [2] M. Z. Jacobson, Strong radiative heating due to the mixing state of black carbon in atmospheric aerosols, Nature 409, 695-697 (2001) [3] V. Ramanathan and G. Carmichae, Global and regional climate changes due to black carbon, nature geoscience 1, 221-227 (2008) [4] W.P Arnott, H. Moosmuller, C. F. Rogers, T. Jin, and R. Bruch, Photoacoustic spectrometer for measuring light absorption by aerosol: instrument description. Atmos. Environ. 33, 2845-2852 (1999).

  4. 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

  5. In Situ X-ray Absorption Near-Edge Structure Spectroscopy of ZnO Nanowire Growth During Chemical Bath Deposition

    SciTech Connect

    McPeak, Kevin M.; Becker, Matthew A.; Britton, Nathan G.; Majidi, Hasti; Bunker, Bruce A.; Baxter, Jason B.

    2010-12-03

    Chemical bath deposition (CBD) offers a simple and inexpensive route to deposit semiconductor nanostructures, but lack of fundamental understanding and control of the underlying chemistry has limited its versatility. Here we report the first use of in situ X-ray absorption spectroscopy during CBD, enabling detailed investigation of both reaction mechanisms and kinetics of ZnO nanowire growth from zinc nitrate and hexamethylenetetramine (HMTA) precursors. Time-resolved X-ray absorption near-edge structure (XANES) spectra were used to quantify Zn(II) speciation in both solution and solid phases. ZnO crystallizes directly from [Zn(H{sub 2}O){sub 6}]{sup 2+} without long-lived intermediates. Using ZnO nanowire deposition as an example, this study establishes in situ XANES spectroscopy as an excellent quantitative tool to understand CBD of nanomaterials.

  6. 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.

  7. The pathogenesis of Randall's plaque: a papilla cartography of Ca compounds through an ex vivo investigation based on XANES spectroscopy.

    PubMed

    Carpentier, Xavier; Bazin, Dominique; Jungers, Paul; Reguer, Solenn; Thiaudière, Dominique; Daudon, Michel

    2010-05-01

    At the surface of attached kidney stones, a particular deposit termed Randall's plaque (RP) serves as a nucleus. This structural particularity as well as other major public health problems such as diabetes type-2 may explain the dramatic increase in urolithiasis now affecting up to 20% of the population in the industrialized countries. Regarding the chemical composition, even if other phosphate phases such as whitlockite or brushite can be found as minor components (less than 5%), calcium phosphate apatite as well as amorphous carbonated calcium phosphate (ACCP) are the major components of most RPs. Through X-ray absorption spectroscopy performed at the Ca K-absorption edge, a technique specific to synchrotron radiation, the presence and crystallinity of the Ca phosphate phases present in RP were determined ex vivo. The sensitivity of the technique was used as well as the fact that the measurements can be performed directly on the papilla. The sample was stored in formol. Moreover, a first mapping of the chemical phase from the top of the papilla to the deep medulla is obtained. Direct structural evidence of the presence of ACCP as a major constituent is given for the first time. This set of data, coherent with previous studies, shows that this chemical phase can be considered as one precursor in the genesis of RP.

  8. Structure, Bonding, and Stability of Mercury Complexes with Thiolate and Thioether Ligands from High-Resolution XANES Spectroscopy and First-Principles Calculations.

    PubMed

    Manceau, Alain; Lemouchi, Cyprien; Rovezzi, Mauro; Lanson, Martine; Glatzel, Pieter; Nagy, Kathryn L; Gautier-Luneau, Isabelle; Joly, Yves; Enescu, Mironel

    2015-12-21

    We present results obtained from high energy-resolution L3-edge XANES spectroscopy and first-principles calculations for the structure, bonding, and stability of mercury(II) complexes with thiolate and thioether ligands in crystalline compounds, aqueous solution, and macromolecular natural organic matter (NOM). Core-to-valence XANES features that vary in intensity differentiate with unprecedented sensitivity the number and identity of Hg ligands and the geometry of the ligand environment. Post-Hartree-Fock XANES calculations, coupled with natural population analysis, performed on MP2-optimized Hg[(SR)2···(RSR)n] complexes show that the shape, position, and number of electronic transitions observed at high energy-resolution are directly correlated to the Hg and S (l,m)-projected empty densities of states and occupations of the hybridized Hg 6s and 5d valence orbitals. Linear two-coordination, the most common coordination geometry in mercury chemistry, yields a sharp 2p to 6s + 5d electronic transition. This transition varies in intensity for Hg bonded to thiol groups in macromolecular NOM. The intensity variation is explained by contributions from next-nearest, low-charge, thioether-type RSR ligands at 3.0-3.3 Å from Hg. Thus, Hg in NOM has two strong bonds to thiol S and k additional weak Hg···S contacts, or 2 + k coordination. The calculated stabilization energy is -5 kcal/mol per RSR ligand. Detection of distant ligands beyond the first coordination shell requires precise measurement of, and comparison to, spectra of reference compounds as well as accurate calculation of spectra for representative molecular models. The combined experimental and theoretical approaches described here for Hg can be applied to other closed-shell atoms, such as Ag(I) and Au(I). To facilitate further calculation of XANES spectra, experimental data, a new crystallographic structure of a key mercury thioether complex, Cartesian coordinates of the computed models, and examples of

  9. 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.

  10. 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.

  11. Understanding Sulfur Poisoning and Regeneration of Nickel Biomass Conditioning Catalysts using X-Ray Absorption Spectroscopy

    SciTech Connect

    Yung, M. M.; Cheah, S.; Kuhn, J. N.

    2013-01-01

    The production of biofuels can proceed via a biomass gasification to produce syngas, which can then undergo catalytic conditioning and reforming reactions prior to being sent to a fuel synthesis reactor. Catalysts used for biomass conditioning are plagued by short lifetimes which are a result of, among other things, poisoning. Syngas produced from biomass gasification may contain between 30-300 ppm H2S, depending on the feedstock and gasification conditions, and H2S is a key catalyst poison. In order to overcome catalyst poisoning, either an H2S-tolerant catalyst or an efficient regeneration protocol should be employed. In this study, sulfur K-edge X-ray absorption near edge spectroscopy (XANES) was used to monitor sulfur species on spent catalyst samples and the transformation of these species from sulfides to sulfates during steam and air regeneration on a Ni/Mg/K/Al2O3 catalyst used to condition biomass-derived syngas. Additionally, nickel K-edge EXAFS and XANES are used to examine the state of nickel species on the catalysts. Post-reaction samples showed the presence of sulfides on the H2S-poisoned nickel catalyst and although some gaseous sulfur species were observed to leave the catalyst bed during regeneration, sulfur remained on the catalyst and a transformation from sulfides to sulfates was observed. The subsequent H2 reduction led to a partial reduction of sulfates back to sulfides. A proposed reaction sequence is presented and recommended regeneration strategies are discussed.

  12. 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

  13. X-ray structure analysis of a metalloprotein with enhanced active-site resolution using in situ x-ray absorption near edge structure spectroscopy.

    PubMed

    Arcovito, Alessandro; Benfatto, Maurizio; Cianci, Michele; Hasnain, S Samar; Nienhaus, Karin; Nienhaus, G Ulrich; Savino, Carmelinda; Strange, Richard W; Vallone, Beatrice; Della Longa, Stefano

    2007-04-10

    X-ray absorption spectroscopy is exquisitely sensitive to the coordination geometry of an absorbing atom and therefore allows bond distances and angles of the surrounding atomic cluster to be measured with atomic resolution. By contrast, the accuracy and resolution of metalloprotein active sites obtainable from x-ray crystallography are often insufficient to analyze the electronic properties of the metals that are essential for their biological functions. Here, we demonstrate that the combination of both methods on the same metalloprotein single crystal yields a structural model of the protein with exceptional active-site resolution. To this end, we have collected an x-ray diffraction data set to 1.4-A resolution and Fe K-edge polarized x-ray absorption near edge structure (XANES) spectra on the same cyanomet sperm whale myoglobin crystal. The XANES spectra were quantitatively analyzed by using a method based on the multiple scattering approach, which yielded Fe-heme structural parameters with +/-(0.02-0.07)-A accuracy on the atomic distances and +/-7 degrees on the Fe-CN angle. These XANES-derived parameters were subsequently used as restraints in the crystal structure refinement. By combining XANES and x-ray diffraction, we have obtained an cyanomet sperm whale myoglobin structural model with a higher precision of the bond lengths and angles at the active site than would have been possible with crystallographic analysis alone.

  14. 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).

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

    SciTech Connect

    Panda, Manas Ranjan Bhowmik, R. N.; Sinha, A. K.

    2015-06-24

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

  16. Zn distribution and speciation in zinc-containing steelmaking wastes by synchrotron radiation induced μ-XRF and μ-XANES spectroscopy

    NASA Astrophysics Data System (ADS)

    Wang, Lihua; Huang, Yuying; Lu, Xiaoming

    2013-04-01

    Zinc is an important element in steelmaking industry not only for its impact on environment but also for its hazardous influence to steel production. Collecting information about the chemical association of zinc in zinc-containing steelmaking wastes is fundamental for monitoring its behavior during further treatment. In the work presented here, the spatial distribution, and chemical forms of zinc in accumulated particles of zinc-containing steelmaking wastes, including electric arc furnace dust (EAFD) and basic oxygen furnace OG sludge (BOF OG), have been investigated using synchrotron radiation induced μ-XRF and μ-XANES spectroscopy. Results of μ-XRF analysis showed that zinc distributed in two ways. One was shared with iron and its distribution showed a positive correlation with that of iron. The other was accumulated in some well-defined hot spots with high amount and its distribution showed negative correlation with that of iron. For EAFD, results of μ-XANES spectroscopy indicated that zinc was mainly present in the form of ZnFe2O4 within the whole particles no matter the spots with high or low zinc content. Whereas for BOF OG, ZnFe2O4 was the main constituent in well-defined hot spots while in other regions zinc was mainly in the form of zinc carbonate. These results indicated that chemical reaction between zinc and other components occurred during the formation of accumulated OG sludge particles. If the above findings could be confirmed by more systematic investigations, it will provide valuable information for treating and utilizing these metallurgical residues.

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

    NASA Technical Reports Server (NTRS)

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

    2013-01-01

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

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

    PubMed

    Nilmoung, Sukunya; Kidkhunthod, Pinit; Maensiri, Santi

    2015-11-01

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

  19. 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

  20. 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.

  1. 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.

  2. Applications of Absorption Spectroscopy Using Quantum Cascade Lasers.

    PubMed

    2014-10-01

    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.

  3. Incorporation of arsenic in mammal bone: X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Kretschmer, X.; Pingitore, N. E.; Cruz-Jimenez, G.

    2002-12-01

    X-ray absorption spectroscopy (XAS) of the distal tibia of a modern deer, Odocoileus virginianus, revealed that the energy position of the As K edge matched that of a reference arsenic(V) model compound. Comparison of the x-ray absorption near edge structure (XANES) of the deer spectrum to the spectra of model As compounds indicated a close match to arsenate(V), e.g., zinc orthoarsenate(5). This indicates that the nearest-neighbor shell of the arsenic in the bone consists of four oxygens in the tetrahedral arrangement typical of arsenic(V) oxysalts. The XANES analysis demonstrates that the arsenic in the deer bone is not associated with an organic compound as a result of methylation. This suggests that the arsenic is associated with the mineral fraction of the bone, most likely with As substituting for P at the latter's structural site in the hydroxyapatite. The XAS data for the deer bone were very noisy due to the low level of arsenic present, just over 1 ppm.. A total of 18 scans, taking nearly a full 8-hour beam shift, were averaged to obtain the spectrum studied. It is not clear that the second neighbor shell can be characterized sufficiently from these data to confirm that As substitutes for P in hydroxyapatite. We conducted our XAS experiments on beam line 4-3 at the Stanford Synchrotron Radiation Laboratory. Data were collected in the fluorescence mode, using a solid state, 13-element Ge-detector. The energy reference was As(0) metal foil run parasitically in transmission mode during collection of the bone spectra. The edge shift seen in the experimental and As(V) model compound relative to the energy position of the arsenic(0) foil is consistent with the additional energy required to photoeject the 1-s electron of As(V), relative to that required for As(0). Arsenic content of the deer bone was determined by inductively coupled plasma mass spectrometry.

  4. Ultrafast Excited State Relaxation of a Metalloporphyrin Revealed by Femtosecond X-ray Absorption Spectroscopy.

    PubMed

    Shelby, Megan L; Lestrange, Patrick J; Jackson, Nicholas E; Haldrup, Kristoffer; Mara, Michael W; Stickrath, Andrew B; Zhu, Diling; Lemke, Henrik T; Chollet, Matthieu; Hoffman, Brian M; Li, Xiaosong; Chen, Lin X

    2016-07-20

    Photoexcited Nickel(II) tetramesitylporphyrin (NiTMP), like many open-shell metalloporphyrins, relaxes rapidly through multiple electronic states following an initial porphyrin-based excitation, some involving metal centered electronic configuration changes that could be harnessed catalytically before excited state relaxation. While a NiTMP excited state present at 100 ps was previously identified by X-ray transient absorption (XTA) spectroscopy at a synchrotron source as a relaxed (d,d) state, the lowest energy excited state (J. Am. Chem. Soc., 2007, 129, 9616 and Chem. Sci., 2010, 1, 642), structural dynamics before thermalization were not resolved due to the ∼100 ps duration of the available X-ray probe pulse. Using the femtosecond (fs) X-ray pulses of the Linac Coherent Light Source (LCLS), the Ni center electronic configuration from the initial excited state to the relaxed (d,d) state has been obtained via ultrafast Ni K-edge XANES (X-ray absorption near edge structure) on a time scale from hundreds of femtoseconds to 100 ps. This enabled the identification of a short-lived Ni(I) species aided by time-dependent density functional theory (TDDFT) methods. Computed electronic and nuclear structure for critical excited electronic states in the relaxation pathway characterize the dependence of the complex's geometry on the electron occupation of the 3d orbitals. Calculated XANES transitions for these excited states assign a short-lived transient signal to the spectroscopic signature of the Ni(I) species, resulting from intramolecular charge transfer on a time scale that has eluded previous synchrotron studies. These combined results enable us to examine the excited state structural dynamics of NiTMP prior to thermal relaxation and to capture intermediates of potential photocatalytic significance.

  5. Use of X-ray absorption spectroscopy in the search for the best LIGO mirror coatings

    NASA Astrophysics Data System (ADS)

    McGuire, Stephen C.

    2008-03-01

    The Laser Interferometer Gravitational-wave Observatory (LIGO) seeks to improve its sensitivity for gravity-wave detection by a factor of ten during its next phase of operation, Advanced LIGO. In order to achieve this goal it is necessary to design and fabricate test mass mirrors that help minimize the noise in the interferometers and in doing so maximize gravity-wave detection capability. In this talk we will present recent results from our program of X-ray absorption spectroscopy measurements to obtain detailed chemical composition and structure of titania (TiO2)-doped tantala (Ta2O5) multilayers fabricated via ion beam sputtering on SiO2 substrates. Our investigations focus on how the microscopic features of the coatings influence their macroscopic mechanical loss properties. Our goal is to obtain correlations between chemical impurities and/or dopants and the optical absorption and mechanical loss characteristics of these multilayer coatings. To examine our samples we use synchrotron-based X-ray absorption Spectroscopy (XAS) techniques including Extended X-ray Absorption Fine Structure (EXAFS), X-ray Absorption Near Edge Structure (XANES) and X-ray Fluorescence (XRF). We present chemical and structural data obtained at the titanium K-edge and tantalum LIII-edge as well as relative elemental distribution information (Ti/Ta, Fe/Ta, and Cr/Ta) obtained via XRF. Following a brief description of the LIGO experiment, our program of research in optical materials for use in advanced versions of the interferometer will be described.

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

    PubMed

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

    2015-09-01

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

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

    PubMed Central

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

    2012-01-01

    This paper focuses on providing new results relating to the impacts of Diurnal variation, Vertical distribution, and Emission source on sulfur K-edge XANES spectrum of aerosol samples. All aerosol samples used in the diurnal variation experiment were preserved using anoxic preservation stainless cylinders (APSCs) and pressure-controlled glove boxes (PCGBs), which were specially designed to prevent oxidation of the sulfur states in PM10. Further investigation of sulfur K-edge XANES spectra revealed that PM10 samples were dominated by S(VI), even when preserved in anoxic conditions. The “Emission source effect” on the sulfur oxidation state of PM10 was examined by comparing sulfur K-edge XANES spectra collected from various emission sources in southern Thailand, while “Vertical distribution effects” on the sulfur oxidation state of PM10 were made with samples collected from three different altitudes from rooftops of the highest buildings in three major cities in Thailand. The analytical results have demonstrated that neither “Emission source” nor “Vertical distribution” appreciably contribute to the characteristic fingerprint of sulfur K-edge XANES spectrum in PM10. PMID:22988545

  8. A XANES study of chromophores in archaeological glass

    NASA Astrophysics Data System (ADS)

    Arletti, Rossella; Quartieri, Simona; Freestone, Ian C.

    2013-04-01

    We applied X-ray absorption near edge spectroscopy (XANES) to obtain information on the origin of glass colour of several archaeological samples and on the oxidation conditions employed during their production. We studied a series of selected glass fragments—mainly from excavated primary and secondary production centres and dated to the first millennium AD—containing iron and manganese in a wide compositional range. In most of the studied samples iron is rather oxidised, while Mn K-edge XANES data show that, in all the studied glasses, Mn is mainly present in its reduced form (predominantly 2+), with the possible subordinate presence of Mn3+. The most oxidised samples are the HIMT (high iron manganese titanium) glasses, while the less oxidised ones belong to the primary natron glass series from the early Islamic tank furnaces at Bet Eliezer (Israel), and to the series coming from a Roman glass workshop excavated in Basinghall Street, London. In these glasses, iron is approximately equally distributed over the 2+ and 3+ oxidation states. The XANES analyses of two glasses which had been deliberately decolourized using Sb- and Mn-based decolourizers demonstrate that Sb is more effective than Mn as oxidant.

  9. X-ray absorption spectroscopy elucidates the impact of structural disorder on electron mobility in amorphous zinc-tin-oxide thin films

    SciTech Connect

    Siah, Sin Cheng E-mail: buonassisi@mit.edu; Lee, Yun Seog; Buonassisi, Tonio E-mail: buonassisi@mit.edu; Lee, Sang Woon; Gordon, Roy G.; Heo, Jaeyeong; Shibata, Tomohiro; Segre, Carlo U.

    2014-06-16

    We investigate the correlation between the atomic structures of amorphous zinc-tin-oxide (a-ZTO) thin films grown by atomic layer deposition (ALD) and their electronic transport properties. We perform synchrotron-based X-ray absorption spectroscopy at the K-edges of Zn and Sn with varying [Zn]/[Sn] compositions in a-ZTO thin films. In extended X-ray absorption fine structure (EXAFS) measurements, signal attenuation from higher-order shells confirms the amorphous structure of a-ZTO thin films. Both quantitative EXAFS modeling and X-ray absorption near edge spectroscopy (XANES) reveal that structural disorder around Zn atoms increases with increasing [Sn]. Field- and Hall-effect mobilities are observed to decrease with increasing structural disorder around Zn atoms, suggesting that the degradation in electron mobility may be correlated with structural changes.

  10. Absorption and fluorescence spectroscopy on a smartphone

    NASA Astrophysics Data System (ADS)

    Hossain, Md. Arafat; Canning, John; Cook, Kevin; Ast, Sandra; Rutledge, Peter J.; Jamalipour, Abbas

    2015-07-01

    A self-powered smartphone-based field-portable "dual" spectrometer has been developed for both absorption and fluorescence measurements. The smartphone's existing flash LED has sufficient optical irradiance to undertake absorption measurements within a 3D-printed case containing a low cost nano-imprinted polymer diffraction grating. A UV (λex ~ 370 nm) and VIS (λex ~ 450 nm) LED are wired into the circuit of the flash LED to provide an excitation source for fluorescence measurements. Using a customized app on the smartphone, measurements of absorption and fluorescence spectra are demonstrated using pH-sensitive and Zn2+-responsive probes. Detection over a 300 nm span with 0.42 nm/pixel spectral resolution is demonstrated. Despite the low cost and small size of the portable spectrometer, the results compare well with bench top instruments.

  11. 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. PMID:25239063

  12. Chemical forms of sulfur in geological and archeological asphaltenes from Middle East, France, and Spain determined by sulfur K- and L-edge X-ray absorption near-edge structure spectroscopy

    NASA Astrophysics Data System (ADS)

    Sarret, Géraldine; Connan, Jacques; Kasrai, Masoud; Bancroft, G. Michael; Charrié-Duhaut, Armelle; Lemoine, Sylvie; Adam, Pierre; Albrecht, Pierre; Eybert-Bérard, Laurent

    1999-11-01

    Asphaltene samples extracted from archeological and geological bitumens from the Middle East, France, and Spain were studied by sulfur K- and L-edge X-ray absorption near-edge structure (XANES) spectroscopy in combination with isotopic analyses (δ 13C and δD). Within each series, the samples were genetically related by their δ 13C values. The gross and elemental composition and the δD values were used to characterize the weathering state of the samples. Sulfur K- and L-edge XANES results show that in all the samples, dibenzothiophenes are the dominant forms of sulfur. In the least oxidized asphaltenes, minor species include disulfides, alkyl and aryl sulfides, and sulfoxides. With increasing alteration the proportion of oxidized sulfur (sulfoxides, sulfones, sulfonates and sulfates) increases, whereas the disulfide and sulfide content decreases. This evolution is observed in all the series, regardless of the origin of the asphaltenes. This work illustrates the advantages of XANES spectroscopy as a selective probe for determining sulfur speciation in natural samples. It also shows that S K- and L-edge XANES spectroscopy are complementary for identifying the oxidized and reduced forms of sulfur, respectively.

  13. Polarized x-ray-absorption spectroscopy of the uranyl ion: Comparison of experiment and theory

    SciTech Connect

    Hudson, E.A.; Allen, P.G.; Terminello, L.J.; Denecke, M.A.; Reich, T.

    1996-07-01

    The x-ray linear dichroism of the uranyl ion (UO{sub 2}{sup 2+}) in uranium {ital L}{sub 3}-edge extended x-ray-absorption fine structure (EXAFS), and {ital L}{sub 1}- and {ital L}{sub 3}-edge x-ray-absorption near-edge structure (XANES), has been investigated both by experiment and theory. A striking polarization dependence is observed in the experimental XANES and EXAFS for an oriented single crystal of uranyl acetate dihydrate [UO{sub 2}(CH{sub 3}CO{sub 2}){sub 2}{center_dot}2H{sub 2}O], with the x-ray polarization vector aligned either parallel or perpendicular to the bond axis of the linear uranyl cation (O-U-O). Single-crystal results are compared to experimental spectra for a polycrystalline uranyl acetate sample and to calculations using the {ital ab} {ital initio} multiple-scattering (MS) code FEFF 6. Theoretical XANES spectra for uranyl fluoride (UO{sub 2}F{sub 2}) reproduce all the features of the measured uranyl acetate spectra. By identifying scattering paths which contribute to individual features in the calculated spectrum, a detailed understanding of the {ital L}{sub 1}-edge XANES is obtained. MS paths within the uranyl cation have a notable influence upon the XANES. The measured {ital L}{sub 3}-edge EXAFS is also influenced by MS, especially when the x-ray polarization is parallel to the uranyl species. These MS contributions are extracted from the total EXAFS and compared to calculations. The best agreement with the isolated MS signal is obtained by using nonoverlapped muffin-tin spheres in the FEFF 6 calculation. This contrasts the {ital L}{sub 1}-edge XANES calculations, in which overlapping was required for the best agreement with experiment. {copyright} {ital 1996 The American Physical Society.}

  14. Micro-X-ray absorption near edge structure spectroscopy investigations of baroque tin-amalgam mirrors at BESSY using a capillary focusing system

    NASA Astrophysics Data System (ADS)

    Bartoll, J.; Röhrs, S.; Erko, A.; Firsov, A.; Bjeoumikhov, A.; Langhoff, N.

    2004-10-01

    An elliptically shaped glass monocapillary with a spatial resolution of 5 μm has been used for the fine focusing of the pre-focused X-ray beam produced by the graded-crystal monochromator beamline, KMC-2. The flux density gain of 50 was experimentally measured. The microprobe has been used in the energy range of 3.5-15 keV. Micro-X-ray fluorescence analysis (μXFA) and micro-X-ray absorption near edge structure spectroscopyXANES) measurements on test samples and investigations of baroque tin-amalgam mirrors were done.

  15. [Study of retrieving formaldehyde with differential optical absorption spectroscopy].

    PubMed

    Li, Yu-Jin; Xie, Pin-Hua; Qin, Min; Qu, Xiao-Ying; Hu, Lin

    2009-01-01

    The present paper introduces the method of retrieving the concentration of HCHO with differential optical absorption spectroscopy (DOAS). The authors measured ambient HCHO in Beijing region with the help of differential optical absorption spectroscopy instrument made by ourself, and discussed numerous factors in retrieving the concentration of HCHO with differential optical absorption spectroscopy (DOAS), especially, the choice of HCHO wave band, how to avoid absorption of ambient SO2, NO2 and O3, and the influence of the Xenon lamp spectrum structure on the absorption of ambient HCHO. The authors achieved the HCHO concentration by simultaneously retrieving the concentrations of HCHO, SO2, NO2 and O3 with non-linear least square fitting method, avoiding the effect of choosing narrow wave of HCHO and the residual of SO2, NO2, O3 and the Xenon lamp spectrum structure in retrieving process to attain the concentration of HCHO, Finally the authors analyzed the origin of error in retrieving the concentration of HCHO with differential optical absorption spectroscopy (DOAS), and the total error is within 13.7% in this method. PMID:19385238

  16. Atomic absorption spectroscopy with high temperature flames.

    PubMed

    Willis, J B

    1968-07-01

    An account is given of the history of the development of high temperature flames for the atomic absorption measurement of metals forming refractory oxides. The principles governing the design of premix burners for such flames, and the relative merits of different types of nebulizer burner systems are described. After a brief account of the structure and emission characteristics of the premixed oxygen-acetylene and nitrous oxide-acetylene flames, the scope and limitations of the latter flame in chemical analysis are discussed.

  17. Diode laser absorption spectroscopy of lithium isotopes

    NASA Astrophysics Data System (ADS)

    Olivares, Ignacio E.; González, Iván A.

    2016-10-01

    We study Doppler-limited laser intensity absorption, in a thermal lithium vapor containing 7Li and 6Li atoms in a 9 to 1 ratio, using a narrow-linewidth single-longitudinal-mode tunable external cavity diode laser at the wavelength of 670.8 nm. The lithium vapor was embedded in helium or argon buffer gas. The spectral lineshapes were rigorously predicted for D_1 and D_2 for the lithium 6 and 7 isotope lines using reduced optical Bloch equations, specifically derived, from a density matrix analysis. Here, a detailed comparison is provided of the predicted lineshapes with the measured 7Li-D_2, 7Li-D_1, 6Li-D_2 and 6Li-D_1 lines, in the case of high vapor density and with intensity above the saturation intensity. To our knowledge, this is the first time that such detailed comparison is reported in the open literature. The calculations were also extended to saturated absorption spectra and compared to measured Doppler-free 7Li-D_2 and 6Li-D_2 hyperfine lines.

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

    NASA Astrophysics Data System (ADS)

    Glazoff, Michael V.

    2016-04-01

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

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

    SciTech Connect

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

    2008-06-16

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

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

    NASA Astrophysics Data System (ADS)

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

    2005-01-01

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

  1. 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.

  2. 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.

  3. Phosphorus speciation in sequentially extracted agro-industrial by-products: evidence from X-ray absorption near edge structure spectroscopy.

    PubMed

    Kruse, Jens; Negassa, Wakene; Appathurai, Narayana; Zuin, Lucia; Leinweber, Peter

    2010-01-01

    The phosphorus (P) in agro-industrial by-products--a potential source of freshwater eutrophication but also a valuable fertilizer--needs to be speciated to evaluate its fate in the environment. We investigated to what extent X-ray absorption near edge structure (XANES) spectroscopy at the P K- and L2.3-edges reflected differences in sequentially extracted filter cakes from sugarcane (Saccharum officinarum L.) (FIC) and niger seed (Guizotia abyssinica Cass.; NIC) processing industry in Ethiopia. The P fractionation removed more labile (54%) and H2SO4-P (28%) from FIC than from NIC (18% labile, 12% H2SO4-P). For the FIC residues after each extraction step, linear combination (LC) fitting of P K-edge spectra provided evidence for the enrichment of Ca-P after the NaOH-extraction and its almost complete removal after the H2SO4-treatment. The LC-fitting was unsuccessful for the NIC samples, likely because of the predominance of organic P compounds. The different proportions of Ca-P compounds between FIC (large) and NIC (small) were more distinctive in L2-than in the K-edge XANES spectra. In conclusion, the added value of complementary P K- and L2.3-edge XANES was clearly demonstrated, and the P fractionation and speciation results together justify using FIC and NIC as soil amendments in the tropics.

  4. 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…

  5. 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)

  6. 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…

  7. Laser photothermal spectroscopy of light-induced absorption

    SciTech Connect

    Skvortsov, L A

    2013-01-31

    Basic methods of laser photothermal spectroscopy, which are used to study photoinduced absorption in various media, are briefly considered. Comparative analysis of these methods is performed and the latest results obtained in this field are discussed. Different schemes and examples of their practical implementation are considered. (review)

  8. 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.

  9. 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

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

    SciTech Connect

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

    1994-03-01

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

  11. 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.

  12. Biological X-ray absorption spectroscopy and metalloproteomics.

    PubMed

    Ascone, Isabella; Strange, Richard

    2009-05-01

    In the past seven years the size of the known protein sequence universe has been rapidly expanding. At present, more then five million entries are included in the UniProtKB/TrEMBL protein database. In this context, a retrospective evaluation of recent X-ray absorption studies is undertaken to assess its potential role in metalloproteomics. Metalloproteomics is the structural and functional characterization of metal-binding proteins. This is a new area of active research which has particular relevance to biology and for which X-ray absorption spectroscopy is ideally suited. In the last three years, biological X-ray absorption spectroscopy (BioXAS) has been included among the techniques used in post-genomics initiatives for metalloprotein characterization. The emphasis of this review is on the progress in BioXAS that has emerged from recent meetings in 2007-2008. Developments required to enable BioXAS studies to better contribute to metalloproteomics throughput are also discussed. Overall, this paper suggests that X-ray absorption spectroscopy could have a higher impact on metalloproteomics, contributing significantly to the understanding of metal site structures and of reaction mechanisms for metalloproteins. PMID:19395808

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

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

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

  14. Electron Wavepacket Interference Observed by Attosecond Transient Absorption Spectroscopy

    NASA Astrophysics Data System (ADS)

    Gallmann, L.; Holler, M.; Schapper, F.; Keller, U.

    Attosecond time-resolved transient absorption spectroscopy is performed in a dense helium target by superimposing an attosecond pulse train (APT) with a moderately strong infrared field. We observe rapid oscillations of the absorption of the individual harmonics as a function of time-delay between the APT and IR field even for harmonic energies well below the ionization threshold. The phase dependence of these modulations on atto-chirp and IR intensity yields direct evidence for the interference of transiently bound electronic wavepackets as the underlying mechanism.

  15. 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.

  16. Multiphoton cascade absorption in single molecule fluorescence saturation spectroscopy.

    PubMed

    Winckler, Pascale; Jaffiol, Rodolphe

    2013-05-01

    Saturation spectroscopy is a relevant method to investigate photophysical parameters of single fluorescent molecules. Nevertheless, the impact of a gradual increase, over a broad range, of the laser excitation on the intramolecular dynamics is not completely understood, particularly concerning their fluorescence emission (the so-called brightness). Thus, we propose a comprehensive theoretical and experimental study to interpret the unexpected evolution of the brightness with the laser power taking into account the cascade absorption of two and three photons. Furthermore, we highlight the key role played by the confocal observation volume in fluorescence saturation spectroscopy of single molecules in solution.

  17. Reference spectra of important adsorbed organic and inorganic phosphate binding forms for soil P speciation using synchrotron-based K-edge XANES spectroscopy.

    PubMed

    Prietzel, Jörg; Harrington, Gertraud; Häusler, Werner; Heister, Katja; Werner, Florian; Klysubun, Wantana

    2016-03-01

    Direct speciation of soil phosphorus (P) by linear combination fitting (LCF) of P K-edge XANES spectra requires a standard set of spectra representing all major P species supposed to be present in the investigated soil. Here, available spectra of free- and cation-bound inositol hexakisphosphate (IHP), representing organic P, and of Fe, Al and Ca phosphate minerals are supplemented with spectra of adsorbed P binding forms. First, various soil constituents assumed to be potentially relevant for P sorption were compared with respect to their retention efficiency for orthophosphate and IHP at P levels typical for soils. Then, P K-edge XANES spectra for orthophosphate and IHP retained by the most relevant constituents were acquired. The spectra were compared with each other as well as with spectra of Ca, Al or Fe orthophosphate and IHP precipitates. Orthophosphate and IHP were retained particularly efficiently by ferrihydrite, boehmite, Al-saturated montmorillonite and Al-saturated soil organic matter (SOM), but far less efficiently by hematite, Ca-saturated montmorillonite and Ca-saturated SOM. P retention by dolomite was negligible. Calcite retained a large portion of the applied IHP, but no orthophosphate. The respective P K-edge XANES spectra of orthophosphate and IHP adsorbed to ferrihydrite, boehmite, Al-saturated montmorillonite and Al-saturated SOM differ from each other. They also are different from the spectra of amorphous FePO4, amorphous or crystalline AlPO4, Ca phosphates and free IHP. Inclusion of reference spectra of orthophosphate as well as IHP adsorbed to P-retaining soil minerals in addition to spectra of free or cation-bound IHP, AlPO4, FePO4 and Ca phosphate minerals in linear combination fitting exercises results in improved fit quality and a more realistic soil P speciation. A standard set of P K-edge XANES spectra of the most relevant adsorbed P binding forms in soils is presented. PMID:26917141

  18. Beta-decay studies using total absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    GSI-TAS Collaboration; LUCRECIA-TAgS Collaboration; Algora, A.; Batist, L.; Borge, M. J. G.; Cano-Ott, D.; Collatz, R.; Courtin, S.; Dessagne, Ph; Fraile, L. M.; Gadea, A.; Gelletly, W.; Hellström, M.; Janas, Z.; Jungclaus, A.; Kirchner, R.; Karny, M.; Le Scornet, G.; Miehé, Ch; Maréchal, F.; Moroz, F.; Nácher, E.; Poirier, E.; Roeckl, E.; Rubio, B.; Rykaczewski, K.; Tain, J. L.; Tengblad, O.; Wittmann, V.

    2003-04-01

    . Beta-decay experiments are a primary source of information for nuclear-structure studies and at the same time complementary to in-beam investigations of nuclei far from stability. Although both types of experiment are mainly based on γ -ray spectroscopy, they face different experimental problems. The so-called Pandemonium effect is a critical problem in β -decay if we are to test theoretically calculated transition probabilities. In this contribution we will present a solution to this problem using total absorption spectroscopy methods. We will also present some examples of experiments carried out with the Total Absorption Spectrometer (TAS) at GSI an describe a new device LUCRECIA recently installed at CERN.

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

    SciTech Connect

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

    2007-02-02

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

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

    PubMed

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

    2001-03-01

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

  1. X-ray absorption spectroscopy of strongly disordered glasses: Local structure around Ag ions in g-Ag{sub 2}O{center_dot}nB{sub 2}O{sub 3}

    SciTech Connect

    Kuzmin, A.; Dalba, G.; Fornasini, P.; Rocca, F.; Sipr, O.

    2006-05-01

    The local structure around Ag ions in silver borate glasses g-Ag{sub 2}O{center_dot}nB{sub 2}O{sub 3} (n=2,4) was studied by x-ray absorption spectroscopy at the Ag K edge for temperatures from 77 to 450 K. Extended x-ray absorption fine structure (EXAFS) analysis based on cumulant expansion or multishell Gaussian model fails for these systems. Therefore, the radial distribution functions (RDFs) around Ag ions were reconstructed using a method based on the direct inversion of the EXAFS expression. The RDFs consist of about eight atoms (oxygens and borons), exhibit a relatively weak temperature dependence, and indicate the presence of strong static disorder. Two main components can be identified in RDFs, located at about 2.3-2.4 A and 2.5-3.4 A, respectively. The chemical types of atoms contributing to the RDF were determined via a simulation of configurationally averaged x-ray absorption near-edge structure (XANES) and EXAFS signals. The immediate neighborhood of Ag contains mostly oxygens while borons dominate at larger distances. The combination of EXAFS and XANES techniques allowed us to determine a more complete structural model than would be possible by relying solely on either EXAFS or XANES alone.

  2. 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.

  3. Terahertz vibrational absorption spectroscopy using microstrip-line waveguides

    NASA Astrophysics Data System (ADS)

    Byrne, M. B.; Cunningham, J.; Tych, K.; Burnett, A. D.; Stringer, M. R.; Wood, C. D.; Dazhang, L.; Lachab, M.; Linfield, E. H.; Davies, A. G.

    2008-11-01

    We demonstrate that terahertz microstrip-line waveguides can be used to measure absorption spectra of polycrystalline materials with a high frequency resolution (˜2 GHz) and with a spatial resolution that is determined by the microstrip-line dimensions, rather than the free-space wavelength. The evanescent terahertz-bandwidth electric field extending above the microstrip line interacts with, and is modified by, overlaid dielectric samples, thus enabling the characteristic vibrational absorption resonances in the sample to be probed. As an example, the terahertz absorption spectrum of polycrystalline lactose monohydrate was investigated; the lowest lying mode was observed at 534(±2) GHz, in excellent agreement with free-space measurements. This microstrip technique offers both a higher spatial and frequency resolution than free-space terahertz time-domain spectroscopy and requires no contact between the waveguide and sample.

  4. 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.

  5. XANES study of Fe-implanted strontium titanate

    SciTech Connect

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

    2014-03-31

    Properties of strontium titanate SrTiO{sub 3} (STO) depend to a great extent on the substitutional dopants and defects of crystal structure. The ion beam implantation method was used for doping STO (001) crystals with Fe at different doses. Implanted samples were then annealed at 350°C in oxygen to induce recrystallization and remove oxygen vacancies produced during ion implantation process. The effect of Fe doping and post-implantation annealing was studied by X-ray Absorption Near Edge Spectroscopy (XANES) method and Superconducting Quantum Interference Device (SQUID). XANES allowed to monitor the change in structure of STO crystals and in the local environment of Fe following the implantation and annealing steps. SQUID measurements revealed correlation between magnetic moment and Fe implantation dose. Ferromagnetic hysteresis was observed on selected Fe-implanted STO at 5 K. The observed magnetic properties can be correlated with the several Fe oxide phases in addition to the presence of O/Ti vacancies.

  6. XANES mapping of organic sulfate in three scleractinian coral skeletons

    NASA Astrophysics Data System (ADS)

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

    2003-01-01

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

  7. Hemeproteins: Recent Advances in Quantitative XANES Analysis

    NASA Astrophysics Data System (ADS)

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

    2007-02-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-11-01

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

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

    PubMed

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

    2014-08-30

    The geochemical behavior and speciation of arsenic (As) in paddy soils is strongly controlled by soil redox conditions and the sequestration by soil iron oxyhydroxides. Hence, the effects of iron oxide reductive dissolution on the adsorption, transformation and precipitation of As(III) and As(V) in soils were investigated using batch experiments and synchrotron based techniques to gain a deeper understanding at both macroscopic and microscopic scales. The results of batch sorption experiments revealed that the sorption capacity of As(V) on anoxic soil was much higher than that on control soil. Synchrotron based X-ray fluorescence (μ-XRF) mapping studies indicated that As was heterogeneously distributed and was mainly associated with iron in the soil. X-ray absorption near edge structure (XANES), micro-X-ray absorption near edge structure (μ-XANES) and X-ray photoelectron spectroscopy (XPS) analyses revealed that the primary speciation of As in the soil is As(V). These results further suggested that, when As(V) was introduced into the anoxic soil, the rapid coprecipitation of As(V) with ferric/ferrous ion prevented its reduction to As(III), and was the main mechanism controlling the immobilization of As. This research could improve the current understanding of soil As chemistry in paddy and wetland soils. PMID:25064258

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

    SciTech Connect

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

    2010-06-23

    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){sub 2}, CdCO{sub 3}, 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 CdCO{sub 3}, 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 CdCO{sub 3}. 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.

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

    NASA Technical Reports Server (NTRS)

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

    2011-01-01

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

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

    NASA Astrophysics Data System (ADS)

    Hsiung, Tung Li; Wang, H. Paul; Wei, Yu-Ling

    2007-02-01

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

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

    SciTech Connect

    Hsiung Tungli; Wang, H. Paul; Wei Yuling

    2007-02-02

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

  14. Arsenic speciation in tissues of the hyperacumulator P. calomelanos var. austroamericana using x-ray absorption spectroscopy.

    SciTech Connect

    Heald, S. M.; Kachenko, A.; Graefe, M.; Singh, B.; X-Ray Science Division; Univ. of Sydney

    2010-06-15

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

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

    PubMed

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

    2009-09-10

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

  16. 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

  17. 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.

  18. EXAFS and XANES analysis of oxides at the nanoscale

    PubMed Central

    Kuzmin, Alexei; Chaboy, Jesús

    2014-01-01

    Worldwide research activity at the nanoscale is triggering the appearance of new, and frequently surprising, materials properties in which the increasing importance of surface and interface effects plays a fundamental role. This opens further possibilities in the development of new multifunctional materials with tuned physical properties that do not arise together at the bulk scale. Unfortunately, the standard methods currently available for solving the atomic structure of bulk crystals fail for nanomaterials due to nanoscale effects (very small crystallite sizes, large surface-to-volume ratio, near-surface relaxation, local lattice distortions etc.). As a consequence, a critical reexamination of the available local-structure characterization methods is needed. This work discusses the real possibilities and limits of X-ray absorption spectroscopy (XAS) analysis at the nanoscale. To this end, the present state of the art for the interpretation of extended X-ray absorption fine structure (EXAFS) is described, including an advanced approach based on the use of classical molecular dynamics and its application to nickel oxide nanoparticles. The limits and possibilities of X-ray absorption near-edge spectroscopy (XANES) to determine several effects associated with the nanocrystalline nature of materials are discussed in connection with the development of ZnO-based dilute magnetic semiconductors (DMSs) and iron oxide nanoparticles. PMID:25485137

  19. Absorption spectroscopy with sub-angstrom beams: ELS in STEM

    NASA Astrophysics Data System (ADS)

    Spence, John C. H.

    2006-03-01

    Electron-energy loss spectroscopy (EELS) performed using a modern transmission scanning electron microscope (STEM) now offers sub-nanometre spatial resolution and an energy resolution down to 200 meV or less, in favourable cases. The absorption spectra, which probe empty states, cover the soft x-ray region and may be obtained under conditions of well-defined momentum transfer (angle-resolved), providing a double projection onto crystallographic site and symmetry within the density of states. By combining the very high brightness of field-emission electron sources (brighter than a synchrotron) with the high cross-section of electron scattering, together with parallel detection (not possible with scanning x-ray absorption spectroscopy), a form of spectroscopy ideally suited to the study of nanostructures, interfacial states and defects in materials is obtained with uniquely high spatial resolution. We review the basic theory, the relationship of EELS to optical properties and the dielectric response function, the removal of multiple scattering artefacts and channelling effects. We consider applications in the light of recent developments in aberration corrector and electron monochromator design. Examples are cited of inner-shell spectra obtained from individual atoms within thin crystals, of the detection of interfacial electronic states in semiconductors, of inner-shell near edge structure mapped with sub-nanometre spatial resolution in glasses and of spectra obtained from individual carbon nanotubes, amongst many others.

  20. 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.

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

    PubMed

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

    2016-02-24

    Since the commercialization of lithium ion batteries (LIBs), layered transition metal oxides (LiMO2, where M = Co, Mn, Ni, or mixtures thereof) have been materials of choice for LIB cathodes. During cycling, the transition metals change their oxidation states, an effect that can be tracked by detecting energy shifts in the X-ray absorption near edge structure (XANES) spectrum. X-ray absorption spectroscopy (XAS) can therefore be used to visualize and quantify lithiation kinetics in transition metal oxide cathodes; however, in-situ measurements are often constrained by temporal resolution and X-ray dose, necessitating compromises in the electrochemistry cycling conditions used or the materials examined. We report a combined approach to reduce measurement time and X-ray exposure for operando XAS studies of lithium ion batteries. A highly discretized energy resolution coupled with advanced post-processing enables rapid yet reliable identification of the oxidation state. A full-field microscopy setup provides sub-particle resolution over a large area of battery electrode, enabling the oxidation state within many transition metal oxide particles to be tracked simultaneously. Here, we apply this approach to gain insights into the lithiation kinetics of a commercial, mixed-metal oxide cathode material, nickel cobalt aluminium oxide (NCA), during (dis)charge and its degradation during overcharge.

  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. X-ray absorption spectroscopy of liquid surface

    NASA Astrophysics Data System (ADS)

    Watanabe, Iwao; Tanida, Hajime; Kawauchi, Sigehiro; Harada, Makoto; Nomura, Masaharu

    1997-09-01

    An apparatus has been constructed for x-ray absorption spectroscopy of elements at air/aqueous solution interface. Its surface sensitivity is gained from glancing incidence of synchrotron radiation under total reflection condition. The absorption is detected by total conversion He ion-yield method. This apparatus was operated at the beam line 7C of Photon Factory, where the incident photon beam comes from a sagittal focus double-crystal monochromator via a 70-cm-long bent mirror. The mirror focuses the beam vertically and changes the beam direction downward by 1 mrad to irradiate solution surface. The essential requirement of this technique, ripple-free liquid surface at accurate position, was attained by introducing a trough on a floating boat, continuous surface level monitoring, and an automatic Z-stage control. The x-ray absorption edge jump demonstrated that surface concentration of bromide ion follows the Langmuir type adsorption for tetraalkylammonuim bromide solution. By comparing the jump values for surface-active and -inactive bromide salt solutions, the detecting depth of the present technique was determined to be 8.8 nm. An extended x-ray absorption fine structure analysis of bromide ion segregated to the surface by stearyltrimethylammonium cation indicated that its solvation structure is different from that of bulk.

  4. 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.

  5. 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.

  6. Spatially resolved concentration measurements based on backscatter absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Wang, Ze; Sanders, Scott T.; Robinson, Michael A.

    2016-06-01

    We demonstrate the feasibility of spatially resolved measurements of gas properties using direct absorption spectroscopy in conjunction with backscattered signals. We report a 1-D distribution of H2O mole fraction with a spatial resolution of 5 mm. The peak and average discrepancy between the measured and expected mole fraction are 21.1 and 8.0 %, respectively. The demonstration experiment is related to a diesel aftertreatment system; a selective catalytic reduction brick made of cordierite is used. The brick causes volume scattering interference; advanced baseline fitting based on a genetic algorithm is used to reduce the effects of this interference by a factor of 2.3.

  7. Atmospheric absorption spectroscopy using Tm: fiber sources around two microns

    NASA Astrophysics Data System (ADS)

    Kadwani, Pankaj; Chia, Jeffrey; Altal, Faleh; Sims, Robert A.; Willis, Christina; Shah, Lawrence; Killinger, Dennis; Richardson, Martin C.

    2011-03-01

    We report on a thulium doped silica fiber ASE source for absorption spectroscopy of CO2. The average spectral power of this source was 2.3-6.1 μW/nm. This low spectral power of this source posed limitation in the sensitivity of the system which was overcome by using an ultrashort pulsed Raman amplifier system with 50-125 μW/nm average spectral power. This system produced CO2 sensitivity better than 300 ppm making measurement of CO2 possible at standard atmospheric concentrations.

  8. Piezo-locking a diode laser with saturated absorption spectroscopy

    SciTech Connect

    Debs, J. E.; Robins, N. P.; Lance, A.; Kruger, M. B.; Close, J. D

    2008-10-01

    We demonstrate modulation-based frequency locking of an external cavity diode laser, utilizing a piezo-electrically actuated mirror, external to the laser cavity, to create an error signal from saturated absorption spectroscopy. With this method, a laser stabilized to a rubidium hyperfine transition has a FWHM of 130 kHz over seconds, making the locked laser suitable for experiments in atomic physics, such as creating and manipulating Bose-Einstein condensates. This technique combines the advantages of low-amplitude modulation, simplicity, performance, and price, factors that are usually considered to be mutually exclusive.

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

    NASA Astrophysics Data System (ADS)

    Galkowski, Joseph J.; Hagans, Karla G.

    1994-03-01

    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 multilaser system is capable of simultaneously measuring the line densities of 238U ground and metastable states, 235U 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. Iron near absorption edge X-ray spectroscopy at aqueous-membrane interfaces

    SciTech Connect

    Wang, Wenjie; Kuzmenko, Ivan; Vaknin, David

    2014-01-01

    Employing synchrotron X-ray scattering, we systematically determine the absorption near-edge spectra (XANES) of iron in its ferrous (Fe2+) and ferric (Fe3+) states both as ions in aqueous solutions and as they bind to form a single layer to anionic templates that consist of carboxyl or phosphate groups at aqueous/vapor interfaces. While the XANES of bulk iron ions show that the electronic state and coordination of iron complexes in the bulk are isotropic, the interfacial bound ions show a signature of a broken inversion-symmetry environment. The XANES of Fe2+ and Fe3+ in the bulk possess distinct profiles however, upon binding they practically exhibit similar patterns. This indicates that both bound ions settle into a stable electronic and coordination configuration with an effective fractional valence (for example, Fe[2+nu]+, 0 < nu < 1) at charged organic templates. Such two dimensional properties may render interfacial iron, abundant in living organisms, a more efficient and versatile catalytic behavior.

  11. 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.

  12. 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.

  13. X-ray absorption spectroscopy on the calcium cofactor to the manganese cluster in photosynthetic oxygen evolution

    SciTech Connect

    Cinco, Roehl M.

    1999-12-16

    Along with Mn, calcium and chloride ions are necessary cofactors for oxygen evolution in Photosystem II (PS II). To further test and verify whether Ca is close to the Mn cluster, the authors substituted strontium for Ca and probed from the Sr point of view for any nearby Mn. The extended X-ray absorption fine structure (EXAFS) of Sr-reactivated PS II indicates major differences between the intact and NH{sub 2}OH-treated samples. In intact samples, the Fourier transform of the Sr EXAFS shows a Fourier peak that is missing in inactive samples. This peak II is best simulated by two Mn neighbors at a distance of 3.5 Angstrom, confirming the proximity of Ca (Sr) cofactor to the Mn cluster. In addition, polarized Sr EXAFS on oriented Sr-reactivated samples shows this peak II is dichroic: large magnitude at 10 degrees (angle between the PS II membrane normal and the x-ray electric field vector) and small at 80 degrees. Analysis of the dichroism yields the relative angle between the Sr-Mn vector and membrane normal (23 degrees {+-} 4 degrees), and the isotropic coordination number for these layered samples. X-ray absorption spectroscopy has also been employed to assess the degree of similarity between the manganese cluster in PS II and a family of synthetic manganese complexes containing the distorted cubane [Mn{sub 4}O{sub 3}X] core (X = benzoate, acetate, methoxide, hydroxide, azide, fluoride, chloride or bromide). In addition, Mn{sub 4}O{sub 3}Cl complexes containing three or six terminal Cl ligands at three of the Mn were included in this study. The EXAFS method detects the small changes in the core structures as X is varied in this series, and serves to exclude these distorted cubanes of C3v symmetry as a topological model for the Mn catalytic cluster. The sulfur K-edge x-ray absorption near-edge structure (XANES) spectra for the amino acids cysteine, methionine, their corresponding oxidized forms cystine and methionine sulfoxide, and glutathione show distinct

  14. Sensitive detection of weak absorption signals in photoacoustic spectroscopy by using derivative spectroscopy and wavelet transform

    NASA Astrophysics Data System (ADS)

    Zheng, Jincun; Tang, Zhilie; He, Yongheng; Guo, Lina

    2008-05-01

    This report presents a practical analytical method of photoacoustic (PA) spectroscopy that is based on wavelet transform (WT) and the first-derivative PA spectrum. An experimental setup is specially designed to obtain the first-derivative spectrum, which aims to identify some unnoticeable absorption peaks in the normal PA spectrum. To enhance the detectability of overlapping spectral bands, the WT is used to decompose the PA spectrum signals into a series of localized contributions (details and approximation) on the basis of the frequency. For the decomposed contributions do not change the absorption peak position of PA spectrum, one can retrieve the weak absorption signals by the decomposed result of WT. Because of the use of derivative spectroscopy and WT, three unnoticeable absorption peaks that are hidden in the PA spectrum of carbon absorption are precisely retrieved, the wavelengths of which are 699.7, 752.7, and 775.5nm, respectively. This analytical method, which has the virtue of using a physical method and using a computer software method, can achieve great sensitivity and accuracy for PA spectral analysis.

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

    NASA Technical Reports Server (NTRS)

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

    2014-01-01

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

  16. 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 .

  17. Rapid Scan Absorption Spectroscopy with Applications for Remote Sensing

    NASA Astrophysics Data System (ADS)

    Douglass, K.; Maxwell, S. E.; Truong, G.; Van Zee, R. D.; Hodges, J. T.; Plusquellic, D.; Long, D.; Whetstone, J. R.

    2013-12-01

    Our objective is to develop accurate and reliable methods for quantifying distributed carbon sources and sinks to support both mitigation efforts and climate change research. The presentation will describe a method for rapid step-scan absorption spectroscopy in the near-infrared wavelength range for the measurement of greenhouse gases. The method utilizes a fiber coupled laser system and a free space confocal cavity to effectively scan the laser system over a bandwidth of 37.5 GHz (1.25 cm-1), with a step size of 300 MHz (0.01 cm-1) and a scan rate of 40 kHz. The laser system is scanned with microwave precision over a full absorption lineshape profile. Measurements have been demonstrated in a 45 m long multipass cell for detection of carbon dioxide near 1602.4 nm (6240.6 cm-1) and for methane near 1645.5 nm (6077.2 cm 1). Ambient level detection is demonstrated using the multipass cell with a signal-to-noise ratio of ~5:1 in a 5 ms integration time. The scan speed, resolution and bandwidth are well suited for remote sensing using integrated path and differential absorption LIDAR techniques.

  18. 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.

  19. 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. PMID:25273701

  20. 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

  1. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

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

    EPA Science Inventory

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

  4. Confocal XANES and the Attic black glaze: the three-stage firing process through modern reproduction.

    PubMed

    Lühl, Lars; Hesse, Bernhard; Mantouvalou, Ioanna; Wilke, Max; Mahlkow, Sammia; Aloupi-Siotis, Eleni; Kanngiesser, Birgit

    2014-07-15

    The decorated black- and red-figured Athenian vases (sixth and fifth century BC) and the plain black-glazed ware represent a milestone in our material culture due to their aesthetic and technological value; the Attic black glaze is of particular interest since it is a highly resistant potash-alumino-silicate glass, colored by magnetite nanocrystals (<200 nm). This study presents a new methodological approach for correlating the iron oxidation state in the black glaze layer with the manufacturing process by means of conventional and confocal X-ray absorption near edge spectroscopy (XANES). The enhanced surface sensitivity of confocal XANES is combined with conventional XANES resulting in higher counting rates to reliably evaluate the iron oxidation state (Fe(3+)/ΣFe) of the surface layer. A detailed description of the new evaluation procedure is presented. The three-stage firing process was retraced by correlating selected attic black-glazed (BG) specimens from different periods (Archaic, Classical, Hellenistic) with laboratory reproductions. The modern BG specimens serving as reference samples were produced by following the three-stage firing process (i.e., under oxidizing-reducing-oxidizing (ORO) conditions) at different top temperatures, using clay suspensions of different particle size produced with treatment of raw illitic clays from Attica. PMID:24905420

  5. Mn k-edge x-ray absorption spectroscopy (XAS) studies of La{sub 1-x}Sr{sub x}MnO{sub 3}.

    SciTech Connect

    Mini, S. M.; Mitchell, J.; Hinks, D. G.; Alatas, A.; Rosenmann, D.; Kimball, C. W.; Montano, P. A.

    1998-03-06

    Systematic Mn K-edge x-ray absorption spectroscopy (XAS) measurements on samples of La{sub 1{minus}x}Sr{sub x}MnO{sub 3}, which are precursors to colossal magnetoresistive (CMR) materials, are reported. Detailed results on the edge or chemical shift as a function of Sr concentration (hole doping) and sample preparation (air vs oxygen annealed), are discussed. For comparison, a systematic XANES study of the Mn K-edge energy shift, denoting valence change in Mn, has been made in standard manganese oxide systems. Contrary to expectations, the variation in near-edge energies for Mn in La{sub 0.725}Sr{sub 0.275}MnO{sub 3} were small when compared to the difference between that for manganese oxide standards of nominal valence of +3 and +4 (Mn{sub 2}O{sub 3} and MnO{sub 2}).

  6. Cation distribution in Ni{sub 1−x}Zn{sub x}Fe{sub 2}O{sub 4} using X-ray absorption spectroscopy

    SciTech Connect

    Yadav, A. K. Jha, S. N.; Bhattacharyya, D.; Sahoo, N. K.; Jadhav, J.; Biswas, S.

    2014-04-24

    Spinel ferrite samples of Ni{sub 1−x}Zn{sub x}Fe{sub 2}O{sub 4} (for x=0.2, 0.4, 0.5, 0.6 and 0.8) nanoparticles prepared by a novel chemical synthesis method have been characterized by X-ray Absorption Spectroscopy (XAS) technique to investigate the distribution of cations in the unit cell. XANES region clearly shows that as Ni concentration increases, the pre-edge feature, which is a characteristic of tetrahedral coordination of Fe, is enhanced. A quantitative determination of the relative occupancy of iron cation in the octahedral and tetrahedral sites of the spinel structure was obtained from EXAFS data analysis. It has been found that as atomic fraction of Ni is increased from 0.2 to 0.8, Fe occupancy at tetrahedral to octahedral sites is increased from 13:87 and to 39:61.

  7. Intracavity laser absorption spectroscopy of platinum fluoride, PtF

    NASA Astrophysics Data System (ADS)

    Handler, Kimberly G.; Harris, Rachel A.; O'Brien, Leah C.; O'Brien, James J.

    2011-01-01

    Two vibrational bands of an electronic transition of PtF occurring at 11 940 cm -1 and 12 496 cm -1 were recorded and analyzed. These transitions are identified as the (0,0) and (1,0) bands of an [11.9] Ω = 3/2 - XΩ = 3/2 electronic transition. Gas phase PtF was produced in a copper hollow cathode lined with platinum foil using a trace amount of SF 6, and the spectrum was recorded at Doppler resolution by intracavity laser absorption spectroscopy. This work represents the first published spectroscopic data on PtF. Molecular constants for the ground and excited electronic states are presented.

  8. 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.

  9. Infrared Absorption Spectroscopy and Chemical Kinetics of Free Radicals

    SciTech Connect

    Curl, Robert F; Glass, Graham

    2004-11-01

    This research was directed at the detection, monitoring, and study of the chemical kinetic behavior by infrared absorption spectroscopy of small free radical species thought to be important intermediates in combustion. Work on the reaction of OH with acetaldehyde has been completed and published and work on the reaction of O({sup 1}D) with CH{sub 4} has been completed and submitted for publication. In the course of our investigation of branching ratios of the reactions of O({sup 1}D) with acetaldehyde and methane, we discovered that hot atom chemistry effects are not negligible at the gas pressures (13 Torr) initially used. Branching ratios of the reaction of O({sup 1}D) with CH{sub 4} have been measured at a tenfold higher He flow and fivefold higher pressure.

  10. 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.

  11. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2012-08-01

    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 10-3 to 10-5, depending on the particular experiment.

  13. 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.

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

    SciTech Connect

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

    2009-01-01

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

  15. Understanding Electrocatalytic Pathways in Low and Medium Temperature Fuel Cells: Synchrotron-based In Situ X-Ray Absorption Spectroscopy

    SciTech Connect

    Mukerjee, S.; Ziegelbauer, J; Arruda, T; Ramaker, D; Shyam, B

    2008-01-01

    Over the last few decades, researchers have made significant developments in producing more advanced electrocatalytic materials for power generation applications. For example, traditional fuel cell catalysts often involve high-priced precious metals such as Pt. However, in order for fuel cells to become commercially viable, there is a need to reduce or completely remove precious metal altogether. As a result, a myriad of novel, unconventional materials have been explored such as chalcogenides, porphyrins, and organic-metal-macrocycles for low/medium temperature fuel cells as well as enzymatic and microbial fuel cells. As these materials increasingly become more complex, researchers often find themselves in search of new characterization methods, especially those which are allow in situ and operando measurements with element specificity. One such method that has received much attention for analysis of electrocatalytic materials is X-ray absorption spectroscopy (XAS). XAS is an element specific, core level absorption technique which yields structural and electronic information. As a core electron method, XAS requires an extremely bright source, hence a synchrotron. The resulting intensity of synchrotron radiation allow for experiments to be conducted in situ, under electrochemically relevant conditions. Although a bulk-averaging technique requiring rigorous mathematical manipulation, XAS has the added benefit that it can probe materials which possess no long range order. This makes it ideal to characterize nano-scale electrocatalysts. XAS experiments are conducted by ramping the X-ray photon energy while measuring absorption of the incident beam the sample or by counting fluorescent photons released from a sample due to subsequent relaxation. Absorption mode XAS follows the Beer-Lambert Law, {mu}x = log(I{sub 0}/I{sub t}) (1) where {mu} is the absorption coefficient, x is the sample thickness and I{sub 0} and I{sub t} are the intensities of the incident and

  16. Polarized X-Ray Absorption Spectroscopy of Single-Crystal Mn(V) Complexes Relevant to the Oxygen-Evolving Complex of Photosystem II

    SciTech Connect

    Yano, J.K.; Robblee, J.; Pushkar, Y.; Marcus, M.A.; Bendix, J.; Workman, J.M.; Collins, T.J.; Solomon, E.I.; George, S.D.; Yachandra, V.K.; /LBL, Berkeley /Copenhagen U. /Stanford U., Chem. Dept. /SLAC, SSRL

    2007-10-16

    High-valent Mn-oxo species have been suggested to have a catalytically important role in the water splitting reaction which occurs in the Photosystem II membrane protein. In this study, five- and six-coordinate mononuclear Mn(V) compounds were investigated by polarized X-ray absorption spectroscopy in order to understand the electronic structure and spectroscopic characteristics of high-valent Mn species. Single crystals of the Mn(V)-nitrido and Mn(V)-oxo compounds were aligned along selected molecular vectors with respect to the X-ray polarization vector using X-ray diffraction. The local electronic structure of the metal site was then studied by measuring the polarization dependence of X-ray absorption near-edge spectroscopy (XANES) pre-edge spectra (1s to 3d transition) and comparing with the results of density functional theory (DFT) calculations. The Mn(V)-nitrido compound, in which the manganese is coordinated in a tetragonally distorted octahedral environment, showed a single dominant pre-edge peak along the MnN axis that can be assigned to a strong 3dz2-4pz mixing mechanism. In the square pyramidal Mn(V)-oxo system, on the other hand, an additional peak was observed at 1 eV below the main pre-edge peak. This component was interpreted as a 1s to 3dxz,yz transition with 4px,y mixing, due to the displacement of the Mn atom out of the equatorial plane. The XANES results have been correlated to DFT calculations, and the spectra have been simulated using a TD (time-dependent)-DFT approach. The relevance of these results to understanding the mechanism of the photosynthetic water oxidation is discussed.

  17. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

    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 mln/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/Al2O3 powder catalyst are used to illustrate the system performance in terms of transmission XAS. Also, 2.2% Pd/Al2O3 and 2% Ag - Al2O3 powder catalysts have been used to demonstrate X-ray absorption near-edge structure (XANES) spectroscopy in fluorescence mode. Further, a 2% Pt/Al2O3 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.

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

    SciTech Connect

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

    2007-01-19

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

  20. 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.

  1. Temperature and pressure measurement based on tunable diode laser absorption spectroscopy with gas absorption linewidth detection

    NASA Astrophysics Data System (ADS)

    Meng, Yunxia; Liu, Tiegen; Liu, Kun; Jiang, Junfeng; Wang, Tao; Wang, Ranran

    2014-11-01

    A gas temperature and pressure measurement method based on Tunable Diode Laser Absorption Spectroscopy (TDLAS) detecting linewidth of gas absorption line was proposed in this paper. Combined with Lambert-Beer Law and ideal gas law, the relationship between temperature, pressure and gas linewidth with Lorentzian line shape was investigated in theory. Taking carbon monoxide (CO) at 1567.32 nm for example, the linewidths of gas absorption line in different temperatures and pressures were obtained by simulation. The relationship between the linewidth of second harmonic and temperature, pressure with the coefficient 0.025 pm/K and 0.0645 pm/kPa respectively. According to the relationship of simulation results and detected linewidth, the undefined temperature and pressure of CO gas were measured. The gas temperature and pressure measurement based on linewidth detection, avoiding the influence of laser intensity, is an effective temperature and pressure measurement method. This method also has the ability to detect temperature and pressure of other gases with Lorentzian line shape.

  2. Determining copper and lead binding in Larrea tridentata through chemical modification and X-ray absorption spectroscopy

    SciTech Connect

    Polette, L.; Gardea-Torresdey, J.L.; Chianelli, R.; Pickering, I.J.; George, G.N.

    1997-12-31

    Metal contamination in soils has become a widespread problem. Emerging technologies, such as phytoremediation, may offer low cost cleanup methods. The authors have identified a desert plant, Larrea tridentata (creosote bush), which naturally grows and uptakes copper and lead from a contaminated area near a smelting operation. They determined, through chemical modification of carboxyl groups with methanol, that these functional groups may be responsible for a portion of copper(II) binding. In contrast, lead binding was minimally affected by modification of carboxyl groups. X-ray absorption spectroscopy studies conducted at Stanford Synchrotron Radiation Laboratory (SSRL) further support copper binding to oxygen-coordinated ligands and also imply that the binding is not solely due to phytochelatins. The EXAFS data indicate the presence of both Cu-O and Cu-S back scatters, no short Cu-Cu interactions, but with significant Cu-Cu back scattering at 3.7 {angstrom} (unlike phytochelatins with predominantly Cu-S coordination and short Cu-Cu interactions at 2.7 {angstrom}). Cu EXAFS of roots and leaves also vary depending on the level of heavy metal contamination in the environment from which the various creosote samples were obtained. In contrast, Pb XANES data of roots and leaves of creosote collected from different contaminated sites indicate no difference in valence states or ligand coordination.

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

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

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

  4. Titanium local structure in tektite probed by X-ray absorption fine structure spectroscopy.

    PubMed

    Wang, Ling; Yoshiasa, Akira; Okube, Maki; Takeda, Takashi

    2011-11-01

    The local structure of titanium in tektites from six strewn fields was studied by Ti K-edge X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) in order to provide quantitative data on Ti-O distance and Ti coordination number. The titanium in tektites possessed different coordination environment types. XANES spectra patterns revealed resemblance to high-temperature TiO(2)-SiO(2) glass and TiO(2) anatase. All samples showed that the valence of Ti is 4+. Based on the Ti-O distances, coordination numbers and radial distribution function determined by EXAFS analyses, the tektites were classified into three types: type I, Ti occupies a four-coordinated tetrahedral site with Ti-O distances of 1.84-1.79 Å; type II, Ti occupies a five-coordinated trigonal bipyramidal or tetragonal pyramidal site with Ti-O distances of 1.92-1.89 Å; type III, Ti occupies a six-coordinated octahedral site with Ti-O distances of 2.00-1.96 Å. Although Ti occupies the TiO(6) octahedral site in most titanium minerals under ambient conditions, some tektites have four- and five-coordinated Ti. This study indicated that the local structure of Ti might change in impact events and the following stages.

  5. Titanium local structure in tektite probed by X-ray absorption fine structure spectroscopy.

    PubMed

    Wang, Ling; Yoshiasa, Akira; Okube, Maki; Takeda, Takashi

    2011-11-01

    The local structure of titanium in tektites from six strewn fields was studied by Ti K-edge X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) in order to provide quantitative data on Ti-O distance and Ti coordination number. The titanium in tektites possessed different coordination environment types. XANES spectra patterns revealed resemblance to high-temperature TiO(2)-SiO(2) glass and TiO(2) anatase. All samples showed that the valence of Ti is 4+. Based on the Ti-O distances, coordination numbers and radial distribution function determined by EXAFS analyses, the tektites were classified into three types: type I, Ti occupies a four-coordinated tetrahedral site with Ti-O distances of 1.84-1.79 Å; type II, Ti occupies a five-coordinated trigonal bipyramidal or tetragonal pyramidal site with Ti-O distances of 1.92-1.89 Å; type III, Ti occupies a six-coordinated octahedral site with Ti-O distances of 2.00-1.96 Å. Although Ti occupies the TiO(6) octahedral site in most titanium minerals under ambient conditions, some tektites have four- and five-coordinated Ti. This study indicated that the local structure of Ti might change in impact events and the following stages. PMID:21997913

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

    USGS Publications Warehouse

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

    2003-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2009-11-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

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

    PubMed Central

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

    2016-01-01

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

  10. New developments in micro-X-ray diffraction and X-ray absorption spectroscopy for high-pressure research at 16-BM-D at the Advanced Photon Source.

    PubMed

    Park, Changyong; Popov, Dmitry; Ikuta, Daijo; Lin, Chuanlong; Kenney-Benson, Curtis; Rod, Eric; Bommannavar, Arunkumar; Shen, Guoyin

    2015-07-01

    The monochromator and focusing mirrors of the 16-BM-D beamline, which is dedicated to high-pressure research with micro-X-ray diffraction (micro-XRD) and X-ray absorption near edge structure (XANES) (6-45 keV) spectroscopy, have been recently upgraded. Monochromatic X-rays are selected by a Si (111) double-crystal monochromator operated in an artificial channel-cut mode and focused to 5 μm × 5 μm (FWHM) by table-top Kirkpatrick-Baez type mirrors located near the sample stage. The typical X-ray flux is ∼5 × 10(8) photons/s at 30 keV. The instrumental resolution, Δq/qmax, reaches to 2 × 10(-3) and is tunable through adjustments of the detector distance and X-ray energy. The setup is stable and reproducible, which allows versatile application to various types of experiments including resistive heating and cryogenic cooling as well as ambient temperature compression. Transmission XANES is readily combined with micro-XRD utilizing the fixed-exit feature of the monochromator, which allows combined XRD-XANES measurements at a given sample condition.

  11. New developments in micro-X-ray diffraction and X-ray absorption spectroscopy for high-pressure research at 16-BM-D at the Advanced Photon Source

    NASA Astrophysics Data System (ADS)

    Park, Changyong; Popov, Dmitry; Ikuta, Daijo; Lin, Chuanlong; Kenney-Benson, Curtis; Rod, Eric; Bommannavar, Arunkumar; Shen, Guoyin

    2015-07-01

    The monochromator and focusing mirrors of the 16-BM-D beamline, which is dedicated to high-pressure research with micro-X-ray diffraction (micro-XRD) and X-ray absorption near edge structure (XANES) (6-45 keV) spectroscopy, have been recently upgraded. Monochromatic X-rays are selected by a Si (111) double-crystal monochromator operated in an artificial channel-cut mode and focused to 5 μm × 5 μm (FWHM) by table-top Kirkpatrick-Baez type mirrors located near the sample stage. The typical X-ray flux is ˜5 × 108 photons/s at 30 keV. The instrumental resolution, Δq/qmax, reaches to 2 × 10-3 and is tunable through adjustments of the detector distance and X-ray energy. The setup is stable and reproducible, which allows versatile application to various types of experiments including resistive heating and cryogenic cooling as well as ambient temperature compression. Transmission XANES is readily combined with micro-XRD utilizing the fixed-exit feature of the monochromator, which allows combined XRD-XANES measurements at a given sample condition.

  12. New developments in micro-X-ray diffraction and X-ray absorption spectroscopy for high-pressure research at 16-BM-D at the Advanced Photon Source

    SciTech Connect

    Park, Changyong Popov, Dmitry; Ikuta, Daijo; Lin, Chuanlong; Kenney-Benson, Curtis; Rod, Eric; Bommannavar, Arunkumar; Shen, Guoyin

    2015-07-15

    The monochromator and focusing mirrors of the 16-BM-D beamline, which is dedicated to high-pressure research with micro-X-ray diffraction (micro-XRD) and X-ray absorption near edge structure (XANES) (6-45 keV) spectroscopy, have been recently upgraded. Monochromatic X-rays are selected by a Si (111) double-crystal monochromator operated in an artificial channel-cut mode and focused to 5 μm × 5 μm (FWHM) by table-top Kirkpatrick-Baez type mirrors located near the sample stage. The typical X-ray flux is ∼5 × 10{sup 8} photons/s at 30 keV. The instrumental resolution, Δq/q{sub max}, reaches to 2 × 10{sup −3} and is tunable through adjustments of the detector distance and X-ray energy. The setup is stable and reproducible, which allows versatile application to various types of experiments including resistive heating and cryogenic cooling as well as ambient temperature compression. Transmission XANES is readily combined with micro-XRD utilizing the fixed-exit feature of the monochromator, which allows combined XRD-XANES measurements at a given sample condition.

  13. Gas in Scattering Media Absorption Spectroscopy -- Laser Spectroscopy in Unconventional Environments

    NASA Astrophysics Data System (ADS)

    Svanberg, Sune

    2010-02-01

    An overview of the new field of Gas in Scattering Media Absorption Spectroscopy (GASMAS) is presented. The GASMAS technique combines narrow-band diode-laser spectroscopy with optical propagation in diffuse media. Whereas solids and liquids have broad absorption features, free gas in pores and cavities in the material is characterized by sharp spectral signatures. These are typically 10,000 times sharper than those of the host material. Many applications in materials science, food packaging, pharmaceutics and medicine have been demonstrated. Molecular oxygen and water vapor have been studied around 760 and 935 nm, respectively. Liquid water, an important constituent in many natural materials, such as tissue, has a low absorption at such wavelengths, allowing propagation. Polystyrene foam, wood, fruits, food-stuffs, pharmaceutical tablets, and human sinus cavities have been studied, demonstrating new possibilities for characterization and diagnostics. Transport of gas in porous media can readily be studied by first immersing the material in, e.g., pure nitrogen gas, and then observing the rate at which normal air, containing oxygen, reinvades the material. The conductance of the human sinus connective passages can be measured in this way by flushing the nasal cavity with nitrogen, while breathing normally through the mouth. A clinical study comprising 40 patients has been concluded.

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

    PubMed

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

    2011-11-01

    Osteoporosis represents a major public health problem and increases patient morbidity through its association with fragility fractures. Among the different treatments proposed, strontium-based drugs have been shown to increase bone mass in postmenopausal osteoporosis patients and to reduce fracture risk. While the localization of Sr(2+) cations in the bone matrix has been extensively studied, little is known regarding the status of Sr(2+) cations in natural biological apatite. In this investigation the local environment of Sr(2+) cations has been investigated through XANES (X-ray absorption near-edge structure) spectroscopy in a set of pathological and physiological apatites. To assess the localization of Sr(2+) cations in these biological apatites, numerical simulations using the ab initio FEFF9 X-ray spectroscopy program have been performed. The complete set of data show that the XANES part of the absorption spectra may be used as a fingerprint to determine the localization of Sr(2+) cations versus the mineral part of calcifications. More precisely, it appears that a relationship exists between some features present in the XANES part and a Sr(2+)/Ca(2+) substitution process in site (I) of crystal apatite. Regarding the data, further experiments are needed to confirm a possible link between the relationship between the preparation mode of the calcification (cellular activity for physiological calcification and precipitation for the pathological one) and the adsorption mode of Sr(2+) cations (simple adsorption or insertion). Is it possible to draw a line between life and chemistry through the localization of Sr in apatite? The question is open for discussion. A better structural description of these physiological and pathological calcifications will help to develop specific therapies targeting the demineralization process in the case of osteoporosis. PMID:21997917

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

    NASA Astrophysics Data System (ADS)

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

    2007-11-01

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

  16. Quantitative analysis of deconvolved X-ray absorption near-edge structure spectra: a tool to push the limits of the X-ray absorption spectroscopy technique.

    PubMed

    D'Angelo, Paola; Migliorati, Valentina; Persson, Ingmar; Mancini, Giordano; Della Longa, Stefano

    2014-09-15

    A deconvolution procedure has been applied to K-edge X-ray absorption near-edge structure (XANES) spectra of lanthanoid-containing solid systems, namely, hexakis(dmpu)praseodymium(III) and -gadolinium(III) iodide. The K-edges of lanthanoids cover the energy range 38 (La)-65 (Lu) keV, and the large widths of the core-hole states lead to broadening of spectral features, reducing the content of structural information that can be extracted from the raw X-ray absorption spectra. Here, we demonstrate that deconvolution procedures allow one to remove most of the instrumental and core-hole lifetime broadening in the K-edge XANES spectra of lanthanoid compounds, highlighting structural features that are lost in the raw data. We show that quantitative analysis of the deconvolved K-edge XANES spectra can be profitably used to gain a complete local structural characterization of lanthanoid-containing systems not only for the nearest neighbor atoms but also for higher-distance coordination shells. PMID:25171598

  17. X-ray absorption spectroscopy of GeO2 glass to 64 GPa.

    PubMed

    Hong, Xinguo; Newville, Matthew; Duffy, Thomas S; Sutton, Stephen R; Rivers, Mark L

    2014-01-22

    The structural behavior of GeO2 glass has been investigated up to 64 GPa using results from x-ray absorption spectroscopy in a diamond anvil cell combined with previously reported density measurements. The difference between the nearest Ge-O distances of glassy and rutile-type GeO2 disappears at the Ge-O distance maximum at 20 GPa, indicating completion of the tetrahedral-octahedral transition in GeO2 glass. The mean-square displacement σ(2) of the Ge-O distance in the first Ge-O shell increases progressively to a maximum at 10 GPa, followed by a substantial reduction at higher pressures. The octahedral glass is, as expected, less dense and has a higher compressibility than the corresponding crystalline phase, but the differences in Ge-O distance and density between the glass and the crystals are gradually eliminated over the 20-40 GPa pressure range. Above 40 GPa, GeO2 forms a dense octahedral glass with a compressibility similar to that of the corresponding crystalline phase (α-PbO2 type). The EXAFS and XANES spectra show evidence for subtle changes in the dense glass continuing to occur at these high pressures. The Ge-O bond distance shows little change between 45-64 GPa, and this may reflect a balance between bond shortening and a gradual coordination number increase with compression. The density of the glass is similar to that of the α-PbO2-type phase, but the Ge-O distance is longer and is close to that in the higher-coordination pyrite-type phase which is stable above ∼60 GPa. The density data provide evidence for a possible discontinuity and change in compressibility at 40-45 GPa, but there are no major changes in the corresponding EXAFS spectra. A pyrite-type local structural model for the glass can provide a reasonable fitting to the XAFS spectra at 64 GPa. PMID:24285424

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

    DOE PAGES

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

    2016-05-23

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

  19. X-Ray Absorption Spectroscopy of Strontium(II) Coordination.

    PubMed

    Sahai; Carroll; Roberts; O'Day

    2000-02-15

    Sorption of dissolved strontium on kaolinite, amorphous silica, and goethite was studied as a function of pH, aqueous strontium concentration, the presence or absence of atmospheric CO(2) or dissolved phosphate, and aging over a 57-day period. Selected sorption samples ([Sr(aq)](i) approximately 0.5-1x10(-3) m) were examined with synchrotron X-ray absorption spectroscopy (XAS) at low (13-23 K) and room temperatures to determine the local molecular coordination around strontium. Quantitative analyses of the extended X-ray absorption fine structure (EXAFS) of kaolinite, amorphous silica, and most goethite sorption samples showed a single first shell of 9-10 (+/-1) oxygen atoms around strontium at an average Sr-O bond-distance of 2.61 (+/-0.02) Å, indicating hydrated surface complexes. The EXAFS spectra were unchanged after reaction for up to 57 days. Likewise, in kaolinite sorption samples prepared in 100% nitrogen atmosphere, the presence of dissolved phosphate (0.5x10(-3) m) in addition to strontium did not change the local coordination around strontium. In two goethite sorption samples reacted in air at pH approximately 8.5, the EXAFS spectra (collected at low and room temperature) clearly showed that the local structure around strontium is that of strontianite (SrCO(3)(s)). We also noted an increase in strontium uptake on goethite in the presence of atmospheric CO(2) in batch experiments, relative to CO(2)-free experiments. These observations suggest that sorption of carbonate may nucleate the precipitation of SrCO(3) in the pH range in which carbonate sorption on goethite is near a maximum. At higher pH, carbonate surface sorption decreases as dissolved CO(2) decreases. For goethite sorption samples above pH 8.6, hydrated surface complexes, rather than a precipitate, were observed in the EXAFS spectra. Copyright 2000 Academic Press.

  20. Indirect absorption spectroscopy using quantum cascade lasers: mid-infrared refractometry and photothermal spectroscopy.

    PubMed

    Pfeifer, Marcel; Ruf, Alexander; Fischer, Peer

    2013-11-01

    We record vibrational spectra with two indirect schemes that depend on the real part of the index of refraction: mid-infrared refractometry and photothermal spectroscopy. In the former, a quantum cascade laser (QCL) spot is imaged to determine the angles of total internal reflection, which yields the absorption line via a beam profile analysis. In the photothermal measurements, a tunable QCL excites vibrational resonances of a molecular monolayer, which heats the surrounding medium and changes its refractive index. This is observed with a probe laser in the visible. Sub-monolayer sensitivities are demonstrated.

  1. Cavity-Enhanced Absorption Spectroscopy and Photoacoustic Spectroscopy for Human Breath Analysis

    NASA Astrophysics Data System (ADS)

    Wojtas, J.; Tittel, F. K.; Stacewicz, T.; Bielecki, Z.; Lewicki, R.; Mikolajczyk, J.; Nowakowski, M.; Szabra, D.; Stefanski, P.; Tarka, J.

    2014-12-01

    This paper describes two different optoelectronic detection techniques: cavity-enhanced absorption spectroscopy and photoacoustic spectroscopy. These techniques are designed to perform a sensitive analysis of trace gas species in exhaled human breath for medical applications. With such systems, the detection of pathogenic changes at the molecular level can be achieved. The presence of certain gases (biomarkers), at increased concentration levels, indicates numerous human diseases. Diagnosis of a disease in its early stage would significantly increase chances for effective therapy. Non-invasive, real-time measurements, and high sensitivity and selectivity, capable of minimum discomfort for patients, are the main advantages of human breath analysis. At present, monitoring of volatile biomarkers in breath is commonly useful for diagnostic screening, treatment for specific conditions, therapy monitoring, control of exogenous gases (such as bacterial and poisonous emissions), as well as for analysis of metabolic gases.

  2. 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

  3. Revised Mossbauer Calibration for Fe3+/FeT of XANES Basalt Standards: Implications for MORB

    NASA Astrophysics Data System (ADS)

    Hirschmann, M. M.; Zhang, H.; Cottrell, E.

    2015-12-01

    Among techniques for determining Fe3+/FeT of natural glasses, XANES affords high precision, spatial resolution, and sample throughput and consequently has become widely used. However, because XANES determinations depend on standardization against materials of known Fe3+/FeT, they are only as accurate as the methods used for calibration. In many cases, calibration is performed with Mossbauer spectroscopy. Accurate determination of Fe3+/FeT by Mossbauer spectroscopy is the subject of a long-standing controversy, in part owing to debate as to the influence of recoilless fraction on the area ratios of room temperature (RT) Mossbauer absorption doublets associated with paramagnetic Fe2+ and Fe3+ in silicate glasses. Recoilless fraction effects for glasses are comparatively subtle, and so characterization efforts have not always produced statistically resolvable effects, in part because glasses produce broadened line shapes that degrade analytical precision, but both theoretical considerations of bond strengths and abundant evidence from minerals demonstrate that RT Mossbauer analyses will overestimate Fe3+/FeTof Fe-bearing silicates. Cottrell & Kelley (2011) used the basalt XANES calibration of Cottrell et al. (2009) to show that the average Fe3+/FeT of MORB glasses is close to 0.16, but this calibration depends chiefly on RT Mossbauer spectra of a suite of standard glasses. New cryogenic (10 K) Mossbauer spectra of these same glasses suggests a correction factor, C, of 1.1, where [Fe3+/FeT(corrected)]=[Fe3+/FeT (RT)]/([Fe3+/FeT (RT)]+C(1-[Fe3+/FeT(RT)]). If this correction is applied to the XANES data, the median of MORB glasses is ~0.15. Because recoilless fractions are not exactly unity even at 10 K, this correction represents a minimum; however the 10 K data are in good agreement with Fe3+/FeT predicted for the Mossbauer standards by the wet-chemistry-based model of Kress and Carmichael (1991) based on the synthesis fO2. The precision of XANES for the determination

  4. Near Edge X-ray Absorption Spectroscopy of Polymers

    NASA Astrophysics Data System (ADS)

    Dhez, Olivier; Ade, Harald; Urquhart, Stephen

    2001-03-01

    Synthetic and natural polymers exhibit a rich carbon, nitrogen and oxygen K-edge Near Edge X-ray Absorption Fine Structure (NEXAFS). The spectroscopic variations with chemical structure and composition are interesting in their own right. In addition, the large spectroscopic variability can be utilized for the compositional analysis of materials. This is particularly useful for high spatial resolution NEXAFS microanalysis at lateral spatial resolutions exceeding that achievable with more traditional compositional analysis tools such as Infrared and NMR spectroscopy. To increase our understanding of NEXAFS spectra and to start a database for microanalysis, we acquired carbon NEXAFS spectra of the following polymers: polycarbonate, poly(oxybenzoate-co-2,6oxynaphthoate), poly (p-phenylene terephtalamide), toluene diisocyanate polyurethane, toluene diisocyanate polyurea, 4,4'-methylene di-p-phenylene isocyanate polyurethane, 4,4'-methylene di-p-phenylene isocyanate polyurea, poly(ether ether ketone), poly(alpha-methylstyrene), poly-styrene, poly bromostyrene, poly(2-vinyl styrene), polyethylene, poly(ethylene oxide), polypropylene, poly(propylene oxide), polyisobutylene, ethylene propylene rubber, poly(methyl -metacrylate). These spectra were obtained in transmission with an energy resolution of 150 meV. The energy scale was carefully calibrated in-situ utilizing C02 gas as a reference. Spectral assignments are made based on model compounds and theoretical calculations.

  5. Urban ozone measurements using differential optical absorption spectroscopy.

    PubMed

    Morales, J A; Treacy, J; Coffey, S

    2004-05-01

    In order to improve the air quality in Europe the European Commission has issued a number of directives with regard to acceptable levels of a range of gaseous pollutants, which includes ozone. Therefore, monitoring of this compound is necessary to comply with EU legislation, to provide improved pollution warnings for those who are sensitive to air pollutants as well as providing valuable data for environmental planning. Open-path spectroscopic techniques, such as differential optical absorption spectroscopy (DOAS), are ideal for monitoring pollutants because of the advantages they offer over classical methods and point-source analysers. A DOAS system has been installed in Dublin city centre to monitor a range of criteria pollutants including ozone. Observations of urban background ozone concentrations are presented. The measurements are compared with those obtained using a UV point-source analyser and are presented in the context of the current EU directive. The influence of trans-boundary pollution from mainland Europe leading to ozone episodes is also discussed. Observations of high ozone during this measurement campaign coincided with the influx of photochemically polluted air masses which originated over continental Europe. For the analysed time interval, the data suggest that the ground ozone level in Dublin might be significantly influenced by long-range transport from the United Kingdom and continental Europe. PMID:14963627

  6. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2014-04-01

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

  8. External Cavity Quantum Cascade Laser for Quartz Tuning Fork Photoacoustic Spectroscopy of Broad Absorption Features

    SciTech Connect

    Phillips, Mark C.; Myers, Tanya L.; Wojcik, Michael D.; Cannon, Bret D.

    2007-05-01

    We demonstrate mid-infrared spectroscopy of large molecules with broad absorption features using a tunable external cavity quantum cascade laser. Absorption spectra for two different Freons are measured over the range 1130-1185 cm-1 with 0.2 cm-1 resolution via laser photoacoustic spectroscopy with quartz tuning forks as acoustic transducers. The measured spectra are in excellent agreement with published reference absorption spectra.

  9. Development of achromatic full-field hard x-ray microscopy and its application to x-ray absorption near edge structure spectromicroscopy

    NASA Astrophysics Data System (ADS)

    Matsuyama, S.; Emi, Y.; Kino, H.; Kohmura, Y.; Yabashi, M.; Ishikawa, T.; Yamauchi, K.

    2014-09-01

    An achromatic and high-resolution hard X-ray microscope was developed, in which advanced Kirkpatrick-Baez mirror optics with four total-reflection mirrors was employed as an objective. A fine test pattern with a 100 nm feature size could successfully be resolved. Full-field imaging, in combination with X-ray absorption near edge structure (XANES) spectroscopy, was used to characterize tungsten particles. XANES spectra were obtained over the entire observation area, showing good agreement with the XANES spectrum of pure tungsten.

  10. Solvation structure of the halides from x-ray absorption spectroscopy.

    PubMed

    Antalek, Matthew; Pace, Elisabetta; Hedman, Britt; Hodgson, Keith O; Chillemi, Giovanni; Benfatto, Maurizio; Sarangi, Ritimukta; Frank, Patrick

    2016-07-28

    Three-dimensional models for the aqueous solvation structures of chloride, bromide, and iodide are reported. K-edge extended X-ray absorption fine structure (EXAFS) and Minuit X-ray absorption near edge (MXAN) analyses found well-defined single shell solvation spheres for bromide and iodide. However, dissolved chloride proved structurally distinct, with two solvation shells needed to explain its strikingly different X-ray absorption near edge structure (XANES) spectrum. Final solvation models were as follows: iodide, 8 water molecules at 3.60 ± 0.13 Å and bromide, 8 water molecules at 3.40 ± 0.14 Å, while chloride solvation included 7 water molecules at 3.15 ± 0.10 Å, and a second shell of 7 water molecules at 4.14 ± 0.30 Å. Each of the three derived solvation shells is approximately uniformly disposed about the halides, with no global asymmetry. Time-dependent density functional theory calculations simulating the chloride XANES spectra following from alternative solvation spheres revealed surprising sensitivity of the electronic state to 6-, 7-, or 8-coordination, implying a strongly bounded phase space for the correct structure during an MXAN fit. MXAN analysis further showed that the asymmetric solvation predicted from molecular dynamics simulations using halide polarization can play no significant part in bulk solvation. Classical molecular dynamics used to explore chloride solvation found a 7-water solvation shell at 3.12 (-0.04/+0.3) Å, supporting the experimental result. These experiments provide the first fully three-dimensional structures presenting to atomic resolution the aqueous solvation spheres of the larger halide ions. PMID:27475372

  11. Solvation structure of the halides from x-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Antalek, Matthew; Pace, Elisabetta; Hedman, Britt; Hodgson, Keith O.; Chillemi, Giovanni; Benfatto, Maurizio; Sarangi, Ritimukta; Frank, Patrick

    2016-07-01

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

  12. Following ORR intermediates adsorbed on a Pt cathode catalyst during break-in of a PEM fuel cell by in operando X-ray absorption spectroscopy.

    PubMed

    Ramaker, D E; Korovina, A; Croze, V; Melke, J; Roth, C

    2014-07-21

    In operando X-ray absorption spectroscopy data using the Δμ X-ray Absorption Near Edge Spectroscopy (XANES) analysis procedure is used to follow the ORR intermediate adsorbate coverage on a working catalyst in a PEMFC during initial activation and break-in. The adsorbate coverage and log i (Tafel) curves reveal a strong correlation, i.e., an increase in adsorbate intermediate coverage poisons Pt sites thereby decreasing the current. A decrease in Pt-O bond strength commensurate with decrease in potential causes a sequence of different dominant adsorbate volcano curves to exist, namely first O, then OH, and then OOH exactly as predicted by the different ORR kinetics mechanisms. During break-in, the incipient O coverage coming from exposure to air during storage and MEA preparation is rather quickly removed, compared to the slower and more subtle nanoparticle morphological changes, such as the rounding of the Pt nanoparticle edges/corners and smoothing of the planar surfaces, driven by the nanoparticle's tendency to lower its surface energy. These morphological changes increase the Pt-Pt average coordination number, decrease the average Pt-O bond strength, and thereby decrease the coverage of ORR intermediates, allowing increase in the current.

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

    PubMed

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

    2015-07-01

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

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

    PubMed

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

    2015-07-01

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

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

    SciTech Connect

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

    2014-03-11

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

  16. Nocturnal Measurements of HONO by Differential Optical Absorption Spectroscopy

    NASA Astrophysics Data System (ADS)

    Wojtal, P.; McLaren, R.

    2011-12-01

    Differential optical absorption spectroscopy (DOAS) was used to quantify the concentration of HONO, NO2 and SO2 in the nocturnal urban atmosphere at York University over a period of one year. These measurements form a comprehensive HONO data set, including a large range of temperatures, relative humidity, surface conditions (snow, water, dry, etc.) and NO2 concentrations. Laboratory studies and observations within the nocturnal boundary layer reported in the literature suggest heterogeneous conversion of NO2 on surface adsorbed water as the major nighttime source of HONO. HONO formation and photolysis is believed to represent a major source term in the hydroxyl radical budget in polluted continental regions. Currently, most air quality models tend to significantly underpredict HONO, caused by the lack of understanding of HONO formation processes and the parameters that affect its concentration. Recently, we reported nocturnal pseudo steady states (PSS) of HONO in an aqueous marine environment and a conceptual model for HONO formation on aqueous surfaces was proposed. The data set collected at York University is being analyzed with a view towards further understanding the nighttime HONO formation mechanism and testing several hypotheses: 1) A HONO PSS can exist during certain times at night in an urban area in which the HONO concentration is independent of NO2, given the surface contains sufficient water coverage and is saturated with nitrogen containing precursors; 2) The concentration of HONO is positively correlated with temperature during periods where a PSS exists; 3) Different conversion efficiencies of NO2 to HONO exist on dry, wet and snow surfaces; 4) HONO formation has a NO2 order dependence between 0 and 2nd order, dependant on NO2 concentration, relative humidity, etc. The data set will be presented along with statistical analysis that sheds new light on the source of HONO in urban areas at night.

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

  19. Silver Valence and Local Environments in Borosilicate and Calcium Aluminoborate Waste Glasses as determined from X-ray Absorption Spectroscopy

    SciTech Connect

    McKeown,D.; Gan, H.; Pegg, I.

    2005-01-01

    Silver K-edge X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) data were collected and analyzed to characterize silver (Ag) environments in borosilicate and Ca-aluminoborate glass formulations developed as potential candidates for the immobilization of certain nuclear wastes. Silver is found in some nuclear waste streams and must be encapsulated in glass during waste vitrification processes. A related concern deals with phase separation within these glasses and whether colloidal silver would be present in the glass melt, which could present processing issues, or in the waste glass product. Characterization of the silver environments provides useful information for optimizing the silver incorporation ability of such glasses. Data were also gathered on four crystalline standards: Ag-foil, Ag{sub 2}O, argentojarosite (AgFe{sub 3}(SO{sub 4}){sub 2}(OH){sub 6}), and AgO. XANES data indicate Ag{sup +} as the dominant species in the glasses. XANES and EXAFS data show that the average Ag environment in the Ca-aluminoborate glass is different compared with those in the two borosilicate glasses investigated. EXAFS analyses show that Ag in the borosilicate glasses is coordinated by two oxygens in a similar environment to that in crystalline Ag{sub 2}O, except that the associated Ag-O distances are approximately 0.10 Angstroms longer in the glass. Silver in the Ca-aluminoborate glass may be within one highly disordered site, or possibly, several different sites, where the average Ag-O distance, coordination number, and Debye-Waller factor are larger than those determined for the borosilicate glasses. Despite their relatively high silver contents, there is no evidence from XANES or EXAFS of colloidal silver in the glasses investigated.

  20. A cavity type absorption cell for double resonance microwave spectroscopy.

    NASA Technical Reports Server (NTRS)

    Lee, M. C.; White, W. F.

    1972-01-01

    Description of an experimental dual resonant cavity absorption cell for observing microwave spectroscopic double-resonance effects. The device is composed of two Fabry-Perot interferometers excited by independent microwave sources and mounted at right angles in a suitable vacuum enclosure. The pumping transition is modulated by one source and the modulation induced on the rf absorption in the orthogonal cavity is detected.

  1. High-energy resolution X-ray absorption and emission spectroscopy reveals insight into unique selectivity of La-based nanoparticles for CO2

    PubMed Central

    Hirsch, Ofer; Kvashnina, Kristina O.; Luo, Li; Süess, Martin J.; Glatzel, Pieter; Koziej, Dorota

    2015-01-01

    The lanthanum-based materials, due to their layered structure and f-electron configuration, are relevant for electrochemical application. Particularly, La2O2CO3 shows a prominent chemoresistive response to CO2. However, surprisingly less is known about its atomic and electronic structure and electrochemically significant sites and therefore, its structure–functions relationships have yet to be established. Here we determine the position of the different constituents within the unit cell of monoclinic La2O2CO3 and use this information to interpret in situ high-energy resolution fluorescence-detected (HERFD) X-ray absorption near-edge structure (XANES) and valence-to-core X-ray emission spectroscopy (vtc XES). Compared with La(OH)3 or previously known hexagonal La2O2CO3 structures, La in the monoclinic unit cell has a much lower number of neighboring oxygen atoms, which is manifested in the whiteline broadening in XANES spectra. Such a superior sensitivity to subtle changes is given by HERFD method, which is essential for in situ studying of the interaction with CO2. Here, we study La2O2CO3-based sensors in real operando conditions at 250 °C in the presence of oxygen and water vapors. We identify that the distribution of unoccupied La d-states and occupied O p- and La d-states changes during CO2 chemoresistive sensing of La2O2CO3. The correlation between these spectroscopic findings with electrical resistance measurements leads to a more comprehensive understanding of the selective adsorption at La site and may enable the design of new materials for CO2 electrochemical applications. PMID:26668362

  2. Characterization of Chromium Bioremediation Products in Flow-Through Column Sediments Using Micro-X-ray Fluorescence and X-ray Absorption Spectroscopy.

    PubMed

    Varadharajan, Charuleka; Han, Ruyang; Beller, Harry R; Yang, Li; Marcus, Matthew A; Michel, Marc; Nico, Peter S

    2015-05-01

    Microbially mediated reductive immobilization of chromium is a possible remediation technique for sites contaminated with Cr(VI). This study is part of a broader effort investigating the biogeochemical mechanisms for Cr(VI) reduction in Hanford 100H aquifer sediments using flow-through laboratory columns. It had previously been shown that reduced chromium in the solid phase was in the form of freshly precipitated mixed-phase Cr(III)-Fe(III) (hydr)oxides, irrespective of the biogeochemical conditions in the columns. In this study, the reduced Cr phases in the columns were investigated further using spectroscopy to understand the structure and mechanisms involved in the formation of the end products. Several samples representing potential processes that could be occurring in the columns were synthesized in the laboratory and characterized using X-ray absorption near edge structure (XANES) and X-ray scattering. The XANES of Cr(III) particles in the columns most closely resembled those from synthetic samples produced by the abiotic reaction of Cr(VI) with microbially reduced Fe(II). Microbially mediated Cr-Fe reduction products were distinct from abiotic Cr-Fe (hydr)oxides [CrFe(OH)] and organically complexed Cr(III) sorbed onto the surface of a mixed ferrihydrite-goethite mineral phase. Furthermore, analyses of the abiotically synthesized samples revealed that even the end products of purely abiotic, iron-mediated reduction of Cr(VI) are affected by factors such as the presence of excess aqueous Fe(II) and cellular matter. These results suggest that CrFe(OH) phases made under realistic subsurface conditions or in biotic cultures are structurally different from pure Cr(OH) or laboratory-synthesized CrFe(OH). The observed structural differences imply that the reactivity and stability of biogenic CrFe(OH) could potentially be different from that of abiotic CrFe(OH).

  3. The use of UV-Vis absorption spectroscopy for studies of natively disordered proteins.

    PubMed

    Permyakov, Eugene A

    2012-01-01

    Absorption spectroscopy can be used to monitor structural changes upon transitions from ordered to disordered state in proteins. Changes in environment of tryptophan, tyrosine, and phenylalanine residues result in changes of their absorption spectra. In most cases the changes are small and can be measured only in a differential mode.

  4. 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.

  5. 3D local structure around copper site of rabbit prion-related protein: Quantitative determination by XANES spectroscopy combined with multiple-scattering calculations

    NASA Astrophysics Data System (ADS)

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

    2014-02-01

    Prion-related protein (PrP), a cell-surface copper-binding glycoprotein, is considered to be responsible for a number of transmissible spongiform encephalopathies (TSEs). The structural conversion of PrP from the normal cellular isoform (PrPC) to the post-translationally modified form (PrPSc) is thought to be relevant to Cu2+ binding to histidine residues. Rabbits are one of the few mammalian species that appear to be resistant to TSEs, because of the structural characteristics of the rabbit prion protein (RaPrPC) itself. Here we determined the three-dimensional local structure around the C-terminal high-affinity copper-binding sites using X-ray absorption near-edge structure combined with ab initio calculations in the framework of the multiple-scattering (MS) theory. Result shows that two amino acid resides, Gln97 and Met108, and two histidine residues, His95 and His110, are involved in binding this copper(II) ion. It might help us understand the roles of copper in prion conformation conversions, and the molecular mechanisms of prion-involved diseases.

  6. 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.

  7. Biomimetic mono- and dinuclear Ni(I) and Ni(II) complexes studied by X-ray absorption and emission spectroscopy and quantum chemical calculations

    NASA Astrophysics Data System (ADS)

    Schuth, N.; Gehring, H.; Horn, B.; Holze, P.; Kositzki, R.; Schrapers, P.; Limberg, C.; Haumann, M.

    2016-05-01

    Five biomimetic mono- or dinuclear nickel complexes featuring Ni(I) or Ni(II) sites were studied by X-ray absorption and emission spectroscopy and DFT calculations. Ni K-edge XANES spectra and Kβ main and satellite emission lines were collected on powder samples. The pre-edge absorption transitions (core-to-valence excitation) and Kβ2,5 emission transitions (valence-to-core decay) were calculated using DFT (TPSSh/TZVP) on crystal structures. This yielded theoretical ctv and vtc spectra in near-quantitative agreement with the experiment, showing the adequacy of the DFT approach for electronic structure description, emphasizing the sensitivity of the XAS/XES spectra for ligation/redox changes at nickel, and revealing the configuration of unoccupied and occupied valence levels, as well as the spin-coupling modes in the dinuclear complexes. XAS/XES-DFT is valuable for molecular and electronic structure analysis of synthetic complexes and of nickel centers in H2 or COx converting metalloenzymes.

  8. 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.

  9. 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.

  10. 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.

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

    SciTech Connect

    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.

  12. Speciation and characterization of arsenic in gold ores and cyanidation tailings using X-ray absorption spectroscopy

    USGS Publications Warehouse

    Paktunc, D.; Foster, A.; Heald, S.; Laflamme, G.

    2004-01-01

    The knowledge of mineralogy and molecular structure of As is needed to better understand the stability of As in wastes resulting from processing of gold ores. In this study, optical microscopy, scanning electron microscopy, electron microprobe, X-ray diffraction and X-ray absorption fine structure (XAFS) spectroscopy (including both XANES and EXAFS regimes) were employed to determine the mineralogical composition and local coordination environment of As in gold ores and process tailings from bench-scale tests designed to mimic a common plant practice. Arsenic-bearing minerals identified in the ores and tailings include iron (III) oxyhydroxides, scorodite (FeAsO4??2H2O), ferric arsenates, arseniosiderite (Ca2Fe3 (AsO4)3O2??3H2O), Ca-Fe arsenates, pharmacosiderite (KFe4 (AsO4)3(OH)4??6-7H2O), jarosite (K2Fe6(SO4)4 (OH)12) and arsenopyrite (FeAsS). Iron (III) oxyhydroxides contain variable levels of As from trace to about 22 wt% and Ca up to approximately 9 wt%. Finely ground ore and tailings samples were examined by bulk XAFS and selected mineral grains were analyzed by microfocused XAFS (micro-EXAFS) spectroscopy to reconcile the ambiguities of multiple As sources in the complex bulk EXAFS spectra. XANES spectra indicated that As occurs as As5+in all the samples. Micro-EXAFS spectra of individual iron (III) oxyhydroxide grains with varying As concentrations point to inner-sphere bidentate-binuclear arsenate complexes as the predominant form of As. There are indications for the presence of a second Fe shell corresponding to bidentate-mononuclear arrangement. Iron (III) oxyhydroxides with high As concentrations corresponding to maximum adsorption densities probably occur as nanoparticles. The discovery of Ca atoms around As in iron (III) oxyhydroxides at interatomic distances of 4.14-4.17 A?? and the coordination numbers suggest the formation of arseniosiderite-like nanoclusters by coprecipitation rather than simple adsorption of Ca onto iron (III) oxyhydroxides

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

    NASA Astrophysics Data System (ADS)

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

    2010-05-01

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

  14. Investigation of damaged interior walls using synchrotron-based XPS and XANES.

    PubMed

    Poo-arporn, Yingyot; Thachepan, Surachai; Palangsuntikul, Rungtiva

    2015-01-01

    Evidence of internal sulfate attack in field exposure was demonstrated by the damaged interior wall of a three-year-old house situated in Nakhon Ratchasima Province, Thailand. Partial distension of the mortar was clearly observed together with an expansion of a black substance. Removal of the black substance revealed a dense black layer. This layer was only found in the vicinity of the damaged area, suggesting that this black material is possibly involved in the wall cracking. By employing synchrotron-based X-ray photoelectron spectroscopy (XPS) and X-ray absorption near-edge structure (XANES) techniques, the unknown sample was chemically identified. The S 2p and O 1s XPS results mutually indicated the existence of sulfate species in the materials collected from the damaged area. The XANES results indicated the presence of ferrous (II) sulfate, confirming sulfate-induced expansion and cracking. The sulfate attack in the present case appeared to physically affect the structure whereas the chemical integrity at the molecular level of the calcium silicate hydrate phase was retained since there was a lack of spectroscopic evidence for calcium sulfate. It was speculated that internal sulfate probably originated from the contaminated aggregates used during the construction. The current findings would be beneficial for understanding the sulfate-attack mechanism as well as for future prevention against sulfate attack during construction.

  15. Time-resolved diffuse optical spectroscopy: a differential absorption approach

    NASA Astrophysics Data System (ADS)

    Taroni, Paola; Bassi, Andrea; Spinelli, Lorenzo; Cubeddu, Rinaldo; Pifferi, Antonio

    2009-07-01

    A method was developed to estimate spectral changes of the absorption properties of turbid media from time-resolved reflectance/transmittance measurements. It was derived directly from the microscopic Beer-Lambert law, and tested against simulations and phantom measurements.

  16. [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

  17. Element distribution and iron speciation in mature wheat grains (Triticum aestivum L.) using synchrotron X-ray fluorescence microscopy mapping and X-ray absorption near-edge structure (XANES) imaging.

    PubMed

    De Brier, Niels; Gomand, Sara V; Donner, Erica; Paterson, David; Smolders, Erik; Delcour, Jan A; Lombi, Enzo

    2016-08-01

    Several studies have suggested that the majority of iron (Fe) and zinc (Zn) in wheat grains are associated with phytate, but a nuanced approach to unravel important tissue-level variation in element speciation within the grain is lacking. Here, we present spatially resolved Fe-speciation data obtained directly from different grain tissues using the newly developed synchrotron-based technique of X-ray absorption near-edge spectroscopy imaging, coupling this with high-definition μ-X-ray fluorescence microscopy to map the co-localization of essential elements. In the aleurone, phosphorus (P) is co-localized with Fe and Zn, and X-ray absorption near-edge structure imaging confirmed that Fe is chelated by phytate in this tissue layer. In the crease tissues, Zn is also positively related to P distribution, albeit less so than in the aleurone. Speciation analysis suggests that Fe is bound to nicotianamine rather than phytate in the nucellar projection, and that more complex Fe structures may also be present. In the embryo, high Zn concentrations are present in the root and shoot primordium, co-occurring with sulfur and presumably bound to thiol groups. Overall, Fe is mainly concentrated in the scutellum and co-localized with P. This high resolution imaging and speciation analysis reveals the complexity of the physiological processes responsible for element accumulation and bioaccessibility. PMID:27038325

  18. Element distribution and iron speciation in mature wheat grains (Triticum aestivum L.) using synchrotron X-ray fluorescence microscopy mapping and X-ray absorption near-edge structure (XANES) imaging.

    PubMed

    De Brier, Niels; Gomand, Sara V; Donner, Erica; Paterson, David; Smolders, Erik; Delcour, Jan A; Lombi, Enzo

    2016-08-01

    Several studies have suggested that the majority of iron (Fe) and zinc (Zn) in wheat grains are associated with phytate, but a nuanced approach to unravel important tissue-level variation in element speciation within the grain is lacking. Here, we present spatially resolved Fe-speciation data obtained directly from different grain tissues using the newly developed synchrotron-based technique of X-ray absorption near-edge spectroscopy imaging, coupling this with high-definition μ-X-ray fluorescence microscopy to map the co-localization of essential elements. In the aleurone, phosphorus (P) is co-localized with Fe and Zn, and X-ray absorption near-edge structure imaging confirmed that Fe is chelated by phytate in this tissue layer. In the crease tissues, Zn is also positively related to P distribution, albeit less so than in the aleurone. Speciation analysis suggests that Fe is bound to nicotianamine rather than phytate in the nucellar projection, and that more complex Fe structures may also be present. In the embryo, high Zn concentrations are present in the root and shoot primordium, co-occurring with sulfur and presumably bound to thiol groups. Overall, Fe is mainly concentrated in the scutellum and co-localized with P. This high resolution imaging and speciation analysis reveals the complexity of the physiological processes responsible for element accumulation and bioaccessibility.

  19. X-ray absorption spectroscopy of chicken sulfite oxidase crystals

    SciTech Connect

    George, G.N.; Pickering, I.J.; Kisker, C.

    1999-05-17

    Sulfite oxidase catalyzes the physiologically vital oxidation of sulfite to sulfate. Recently, the crystal structure of chicken sulfite oxidase has been reported at 1.9 {angstrom} resolution. In contrast to the information available from previous X-ray absorption spectroscopic studies, the active site indicated by crystallography was a mono-oxo species. Because of this the possibility that the crystals did in fact contain a reduced molybdenum species was considered in the crystallographic work. The authors report herein an X-ray absorption spectroscopic study of polycrystalline sulfite oxidase prepared in the same manner as the previous single-crystal samples, and compare this with data for frozen solutions of oxidized and reduced enzyme.

  20. Differential optical spectroscopy for absorption characterization of scattering media.

    PubMed

    Billet, Cyril; Sablong, Raphaël

    2007-11-15

    Reflectance techniques are commonly used to characterize the optical properties of tissues. However, the precise determination of local chromophore concentrations in turbid media is usually difficult because of the nonlinear dependence of light intensity as a function of scattering and absorption coefficients. A technique is presented to easily determine absorbent compound concentration ratios in a turbid media from three optical reflectance spectra, in the visible range, measured for source-detector distances less than 1cm. The validity of the method is experimentally established, in cases of sets of diluted milk containing absorbent inks, over a relatively wide range of absorption (0.05-0.5 cm(-1)) and reduced scattering (10-20 cm(-1)) coefficients.

  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. Two-photon absorption spectroscopy of rubrene single crystals

    NASA Astrophysics Data System (ADS)

    Irkhin, Pavel; Biaggio, Ivan

    2014-05-01

    We determine the wavelength dependence of the two-photon absorption cross section in rubrene single crystals both by direct measurement of nonlinear transmission and from the two-photon excitation spectrum of the photoluminescence. The peak two-photon absorption coefficient for b-polarized light was found to be (4.6±1)×10-11 m/W at a wavelength of 850±10 nm. It is 2.3 times larger for c-polarized light. The lowest energy two-photon excitation peak corresponds to an excited state energy of 2.92±0.04 eV and it is followed by a vibronic progression of higher energy peaks separated by ˜0.14 eV.

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

    NASA Technical Reports Server (NTRS)

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

    2014-01-01

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

  4. 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.

  5. A heated chamber burner for atomic absorption spectroscopy.

    PubMed

    Venghiattis, A A

    1968-07-01

    A new heated chamber burner is described. The burner is of the premixed type, and burner heads of the types conventionally used in atomic absorption may be readily adapted to it. This new sampling system has been tested for Ag, Al, Ca, Cu, Fe, Mg, Mn, Ni, Pb, Si, Ti, and Zn in aqueous solutions. An improvement of the order of ten times has been obtained in sensitivity, and in detection limits as well, for the elements determined. Interferences controllable are somewhat more severe than in conventional burners but are controllable.

  6. 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

  7. 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.

  8. [Retrieval of tropospheric NO2 by multi axis differential optical absorption spectroscopy].

    PubMed

    Xu, Jin; Xie, Pin-hua; Si, Fu-qi; Dou, Ke; Li, Ang; Liu, Yu; Liu, Wen-qing

    2010-09-01

    A method of retrieving NO2 in troposphere based on multi axis differential optical absorption spectroscopy (MAX-DOAS) was introduced. The differential slant column density (dSCD) of NO2 was evaluated by differential optical absorption spectroscopy (DOAS), removing the Fraunhofer structure and Ring effect. Combining the results of different observing directions, the tropospheric NO2 differential slant column density (deltaSCD) was evaluated, and the air mass factor (AMF) was calculated with the radiative transfer model SCIATRAN and the tropospheric NO2 vertical column density (VCD) was retrieved. To ensure the accuracy of the results, it was compared with the results of long path differential optical absorption spectroscopy (LP-DOAS), a good accordance was shown with the correlation coefficients of 0.94027 and 0.96924. PMID:21105419

  9. Simulation-based comparison of noise effects in wavelength modulation spectroscopy and direct absorption TDLAS

    NASA Astrophysics Data System (ADS)

    Lins, B.; Zinn, P.; Engelbrecht, R.; Schmauss, B.

    2010-08-01

    A simulative investigation of noise effects in wavelength modulation spectroscopy (WMS) and direct absorption diode laser absorption spectroscopy is presented. Special attention is paid to the impact of quantization noise of the analog-to-digital conversion (ADC) of the photodetector signal in the two detection schemes with the goal of estimating the necessary ADC resolution for each technique. With laser relative intensity noise (RIN), photodetector shot noise and thermal amplifier noise included, the strategies used for noise reduction in direct and wavelength modulation spectroscopy are compared by simulating two respective systems. Results show that because of the combined effects of dithering by RIN and signal averaging, the resolutions required for the direct absorption setup are only slightly higher than for the WMS setup. Only for small contributions of RIN an increase in resolution will significantly improve signal quality in the direct scheme.

  10. Pristine and reacted surfaces of pyrrhotite and arsenopyrite as studied by X-ray absorption near-edge structure spectroscopy

    NASA Astrophysics Data System (ADS)

    Mikhlin, Yu.; Tomashevich, Ye.

    2005-05-01

    Fe L-, S L-, and O K-edge X-ray absorption spectra of natural monoclinic and hexagonal pyrrhotites, Fe1-xS, and arsenopyrite, FeAsS, have been measured and compared with the spectra of minerals oxidized in air and treated in aqueous acidic solutions, as well as with the previous XPS studies. The Fe L-edge X-ray absorption near-edge structure (XANES) of vacuum-cleaved pyrrhotites showed the presence of, aside from high-spin Fe2+, small quantity of Fe3+, which was higher for a monoclinic mineral. The spectra of the essentially metal-depleted surfaces produced by the non-oxidative and oxidative acidic leaching of pyrrhotites exhibit substantially enhanced contributions of Fe3+ and a form of high-spin Fe2+ with the energy of the 3d orbitals increased by 0.3 0.8 eV; low-spin Fe2+ was not confidently distinguished, owing probably to its rapid oxidation. The changes in the S L-edge spectra reflect the emergence of Fe3+ and reduced density of S s Fe 4s antibonding states. The Fe L-edge XANES of arsenopyrite shows almost unsplit eg band of singlet Fe2+ along with minor contributions attributable to high-spin Fe2+ and Fe3+. Iron retains the low-spin state in the sulphur-excessive layer formed by the oxidative leaching in 0.4 M ferric chloride and ferric sulphate acidic solutions. The S L-edge XANES of arsenopyrite leached in the ferric chloride, but not ferric sulphate, solution has considerably decreased pre-edge maxima, indicating the lesser admixture of S s states to Fe 3d orbitals in the reacted surface layer. The ferric nitrate treatment produces Fe3+ species and sulphur in oxidation state between +2 and +4.

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  12. Properties of Liquid Silicon Observed by Time-Resolved X-Ray Absorption Spectroscopy

    NASA Astrophysics Data System (ADS)

    Johnson, S. L.; Heimann, P. A.; Lindenberg, A. M.; Jeschke, H. O.; Garcia, M. E.; Chang, Z.; Lee, R. W.; Rehr, J. J.; Falcone, R. W.

    2003-10-01

    Time-resolved x-ray spectroscopy at the Si L edges is used to probe the electronic structure of an amorphous Si foil as it melts following absorption of an ultrafast laser pulse. Picosecond temporal resolution allows observation of the transient liquid phase before vaporization and before the liquid breaks up into droplets. The melting causes changes in the spectrum that match predictions of molecular dynamics and ab initio x-ray absorption codes.

  13. Three Dimensional Mapping of Nicle Oxidation States Using Full Field Xray Absorption Near Edge Structure Nanotomography

    SciTech Connect

    Nelson, G.J.; Chu, Y.; Harris, W.M.; Izzo, J.R.; Grew, K.N., Chiu, W.K.S.; Yi, J.; Andrews, J.C.; Liu, Y., Pierro, P.

    2011-04-28

    The reduction-oxidation cycling of the nickel-based oxides in composite solid oxide fuel cells and battery electrodes is directly related to cell performance. A greater understanding of nickel redox mechanisms at the microstructural level can be achieved in part using transmission x-ray microscopy (TXM) to explore material oxidation states. X-ray nanotomography combined with x-ray absorption near edge structure (XANES) spectroscopy has been applied to study samples containing distinct regions of nickel and nickel oxide (NiO) compositions. Digitally processed images obtained using TXM demonstrate the three-dimensional chemical mapping and microstructural distribution capabilities of full-field XANES nanotomography.

  14. 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

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

    PubMed

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

    2015-01-01

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

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

    PubMed

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

    2015-01-01

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

  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. Electronic Structure of Manganites Determined by Spin-Polarized X-Ray Absorption Spectroscopy

    NASA Astrophysics Data System (ADS)

    Qian, Qing; Tyson, Trevor; Savrassov, S.; Kao, C.-C.; Croft, M.

    2003-03-01

    A systematic study of spin dependent Mn K-edge x-ray absorption spectra was performed on La_1-xCa_xMnO3 and other Mn oxide systems. A model was developed to predict the temperature dependent changes in the local magnetic ordering based on changes in spin-polarized Mn K-Edge measurements. With this model, one can ascertain the change of local ordering that occurs on transiting the magnetic ordering temperature. Parallel LDA and LDA+U computations are used to label the symmetries of the unoccupied bands, determine the degree of electron correlation and to provide a direct comparison with the band ordering predicted by the temperature dependent spin-polarized measurements. The spin magnetic moment and ordering of the t_2g and eg states are also determined. We find that the occupied t_2g orbitals are always ordered with lobes near 45° to the local Mn-O directions. The Mn K-Edge main line splitting is discussed in terms of the effective spin-polarized charge density. Comparison with bandstructure computations are made. The oxygen hole contribution to the net magnetic moment is seen to be important. We survey the spin-polarized XANES spectra of a large group of manganese oxides showing the general trends in the main line spin splitting as a function of valence. This work is supported by NSF Career Grant DMR-9733862 and DMR-0216858.

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

    PubMed

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

    2014-10-22

    Synchrotron-based in situ X-ray near-edge absorption spectroscopy (XANES) has been used to study the valence state evolution of the vanadium ion for both the catholyte and anolyte in all-vanadium redox flow batteries (VRB) under realistic cycling conditions. The results indicate that, when using the widely used charge-discharge profile during the first charge process (charging the VRB cell to 1.65 V under a constant current mode), the vanadium ion valence did not reach V(V) in the catholyte and did not reach V(II) in the anolyte. Consequently, the state of charge (SOC) for the VRB cell was only 82%, far below the desired 100% SOC. Thus, such incompletely charged mix electrolytes results in not only wasting the electrolytes but also decreasing the cell performance in the following cycles. On the basis of our study, we proposed a new charge-discharge profile (first charged at a constant current mode up to 1.65 V and then continuously charged at a constant voltage mode until the capacity was close to the theoretical value) for the first charge process that achieved 100% SOC after the initial charge process. Utilizing this new charge-discharge profile, the theoretical charge capacity and the full utilization of electrolytes has been achieved, thus having a significant impact on the cost reduction of the electrolytes in VRB. PMID:25191695

  1. Investigation of a porous NiSi2/Si composite anode material used for lithium-ion batteries by X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Zhou, Dong; Jia, Haiping; Rana, Jatinkumar; Placke, Tobias; Klöpsch, Richard; Schumacher, Gerhard; Winter, Martin; Banhart, John

    2016-08-01

    Local structural changes in a porous NiSi2/Si composite anode material are investigated by X-ray absorption spectroscopy. It is observed that the NiSi2 phase shows a strong metal-metal bond character and no clear changes can be observed in XANES during lithiation and de-lithiation. The variation of the number of nearest neighbors of the Ni atom for the 1st coordinate Ni-Si shell and σ2 in the 1st cycle, both determined by refinement, demonstrates that NiSi2 can partially react with lithium during discharge and charge. A partially reversible non-stoichiometric compound NiSi2-y is formed during cell operation, the crystal structure of which is the same as that of the NiSi2 phase. It can be concluded that NiSi2 in the composite not only accommodates the pronounced volume changes caused by the lithium uptake into silicon, but also contributes to the reversible capacity of the cell.

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

    PubMed

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

    2014-10-22

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

  3. Mechanisms of mercury removal by biochars produced from different feedstocks determined using X-ray absorption spectroscopy.

    PubMed

    Liu, Peng; Ptacek, Carol J; Blowes, David W; Landis, Richard C

    2016-05-01

    Thirty-six biochars produced from distinct feedstocks at different temperatures were evaluated for their potential to remove mercury (Hg) from aqueous solution at environmentally relevant concentrations. Concentrations of total Hg (THg) decreased by >90% in batch systems containing biochars produced at 600 and 700 °C and by 40-90% for biochars produced at 300 °C. Elevated concentrations of SO4(2-) (up to 1000 mg L(-1)) were observed in solutions mixed with manure-based biochars. Sulfur X-ray absorption near edge structure (XANES) analyses indicate the presence of both reduced and oxidized S species in both unwashed and washed biochars. Sulfur XANES spectra obtained from biochars with adsorbed Hg were similar to those of washed biochars. Micro-X-ray fluorescence mapping results indicate that Hg was heterogeneously distributed across biochar particles. Extended X-ray absorption fine structure modeling indicates Hg was bound to S in biochars with high S content and to O and Cl in biochars with low S content. The predominant mechanisms of Hg removal are likely the formation of chemical bonds between Hg and various functional groups on the biochar. This investigation provides information on the effectiveness and mechanisms of Hg removal that is critical for evaluating biochar applications for stabilization of Hg in surface water, groundwater, soils, and sediments. PMID:26844404

  4. Examination of the local structure in composite and lowdimensional semiconductor by X-ray Absorption Spectroscopy

    SciTech Connect

    Lawniczak-Jablonska, K.; Demchenko, I.N.; Piskorska, E.; Wolska,A.; Talik, E.; Zakharov, D.N.; Liliental-Weber, Z.

    2006-09-25

    X-ray absorption methods have been successfully used to obtain quantitative information about local atomic composition of two different materials. X-ray Absorption Near Edge Structure analysis and X-Ray Photoelectron Spectroscopy allowed us to determine seven chemical compounds and their concentrations in c-BN composite. Use of Extended X-ray Absorption Fine Structure in combination with Transmission Electron Microscopy enabled us to determine the composition and size of buried Ge quantum dots. It was found that the quantum dots consisted out of pure Ge core covered by 1-2 monolayers of a layer rich in Si.

  5. Chemical imaging of single catalyst particles with scanning μ-XANES-CT and μ-XRF-CT.

    PubMed

    Price, S W T; Ignatyev, K; Geraki, K; Basham, M; Filik, J; Vo, N T; Witte, P T; Beale, A M; Mosselmans, J F W

    2015-01-01

    The physicochemical state of a catalyst is a key factor in determining both activity and selectivity; however these materials are often not structurally or compositionally homogeneous. Here we report on the 3-dimensional imaging of an industrial catalyst, Mo-promoted colloidal Pt supported on carbon. The distribution of both the active Pt species and Mo promoter have been mapped over a single particle of catalyst using microfocus X-ray fluorescence computed tomography. X-ray absorption near edge spectroscopy (XANES) and extended X-ray absorption fine structure revealed a mixed local coordination environment, including the presence of both metallic Pt clusters and Pt chloride species, but also no direct interaction between the catalyst and Mo promoter. We also report on the benefits of scanning μ-XANES computed tomography for chemical imaging, allowing for 2- and 3-dimensional mapping of the local electronic and geometric environment, in this instance for both the Pt catalyst and Mo promoter throughout the catalyst particle.

  6. Temperature and density dependence of XANES spectra in warm dense aluminum plasmas

    NASA Astrophysics Data System (ADS)

    Recoules, V.; Mazevet, S.

    2009-08-01

    Using ab initio molecular-dynamics simulations combined with linear-response theory, we calculate the density and temperature dependence of the x-ray absorption near-edge structure (XANES) of a dense aluminum plasma. At solid density and for temperatures increasing up to 6 eV, we see that the XANES spectrum loses its well-known room-temperature structure, first due to melting and second due to loss of correlation in the liquid. Similarly, as the density decreases and the system evolves from a liquid to a plasma, the XANES spectrum becomes less structured. As the density is further lowered and the system turns into an atomic fluid, a pre-edge forms as the 3p state becomes bound. We suggest that direct measurements of the XANES spectra in this density region is a unique opportunity to validate pressure ionization models routinely used in plasma physics modeling.

  7. [Novel analysis algorithms for differential optical absorption spectroscopy for pollution monitoring].

    PubMed

    Zhang, Xue-Dian; Huang, Xian; Xu, Ke-Xin

    2007-11-01

    Differential optical absorption spectroscopy, or DOAS, is a widely used method to determine concentrations of atmospheric species. The principle of DOAS for measuring the concentration of air pollutants is presented in briefly. Using the linear relationship between the area of the measured differential absorbance curve and that of the differential absorption cross-section curve as taken from the literature, an alternative method for calculating the gas concentration on the basis of the proportionality between differential absorbance and differential absorption cross section of the gas under study was developed. The method can be used on its own for single-component analysis or as a complement to the standard technique in multi-component cases. The procedure can be used with differential absorption cross sections measured in the laboratory or taken from the literature. In addition, the method provides a criterion to discriminate between different species having absorption features in the same wavelength range.

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

    SciTech Connect

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

    2006-08-15

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

  9. 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.

  10. Application of x-ray absorption spectroscopy to the study of corrosion and inhibition

    SciTech Connect

    Davenport, A.J.; Isaacs, H.S.

    1991-01-01

    X-ray absorption spectroscopy is a powerful technique for determination of valency and coordination. Measurements can be made in air or in situ under electrochemical control. The technique will be described and its application to the analysis of passive oxide films, corrosion products, and inhibitors will be reviewed.

  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. Gas concentration measurement by optical similitude absorption spectroscopy: methodology and experimental demonstration.

    PubMed

    Anselmo, Christophe; Welschinger, Jean-Yves; Cariou, Jean-Pierre; Miffre, Alain; Rairoux, Patrick

    2016-06-13

    We propose a new methodology to measure gas concentration by light-absorption spectroscopy when the light source spectrum is larger than the spectral width of one or several molecular gas absorption lines. We named it optical similitude absorption spectroscopy (OSAS), as the gas concentration is derived from a similitude between the light source and the target gas spectra. The main OSAS-novelty lies in the development of a robust inversion methodology, based on the Newton-Raphson algorithm, which allows retrieving the target gas concentration from spectrally-integrated differential light-absorption measurements. As a proof, OSAS is applied in laboratory to the 2ν3 methane absorption band at 1.66 µm with uncertainties revealed by the Allan variance. OSAS has also been applied to non-dispersive infra-red and the optical correlation spectroscopy arrangements. This all-optics gas concentration retrieval does not require the use of a gas calibration cell and opens new tracks to atmospheric gas pollution and greenhouse gases sources monitoring.

  14. Gas concentration measurement by optical similitude absorption spectroscopy: methodology and experimental demonstration.

    PubMed

    Anselmo, Christophe; Welschinger, Jean-Yves; Cariou, Jean-Pierre; Miffre, Alain; Rairoux, Patrick

    2016-06-13

    We propose a new methodology to measure gas concentration by light-absorption spectroscopy when the light source spectrum is larger than the spectral width of one or several molecular gas absorption lines. We named it optical similitude absorption spectroscopy (OSAS), as the gas concentration is derived from a similitude between the light source and the target gas spectra. The main OSAS-novelty lies in the development of a robust inversion methodology, based on the Newton-Raphson algorithm, which allows retrieving the target gas concentration from spectrally-integrated differential light-absorption measurements. As a proof, OSAS is applied in laboratory to the 2ν3 methane absorption band at 1.66 µm with uncertainties revealed by the Allan variance. OSAS has also been applied to non-dispersive infra-red and the optical correlation spectroscopy arrangements. This all-optics gas concentration retrieval does not require the use of a gas calibration cell and opens new tracks to atmospheric gas pollution and greenhouse gases sources monitoring. PMID:27410280

  15. 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.

  16. 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.

  17. 3D Imaging of Nickel Oxidation States using Full Field X-ray Absorption Near Edge Structure Nanotomography

    SciTech Connect

    Nelson, George; Harris, William; Izzo, John; Grew, Kyle N.

    2012-01-20

    Reduction-oxidation (redox) cycling of the nickel electrocatalyst phase in the solid oxide fuel cell (SOFC) anode can lead to performance degradation and cell failure. A greater understanding of nickel redox mechanisms at the microstructural level is vital to future SOFC development. Transmission x-ray microscopy (TXM) provides several key techniques for exploring oxidation states within SOFC electrode microstructure. Specifically, x-ray nanotomography and x-ray absorption near edge structure (XANES) spectroscopy have been applied to study samples of varying nickel (Ni) and nickel oxide (NiO) compositions. The imaged samples are treated as mock SOFC anodes containing distinct regions of the materials in question. XANES spectra presented for the individual materials provide a basis for the further processing and analysis of mixed samples. Images of composite samples obtained are segmented, and the distinct nickel and nickel oxide phases are uniquely identified using full field XANES spectroscopy. Applications to SOFC analysis are discussed.

  18. Surface relaxation in liquid water and methanol studied by x-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Wilson, Kevin R.; Schaller, R. D.; Co, D. T.; Saykally, R. J.; Rude, Bruce S.; Catalano, T.; Bozek, J. D.

    2002-10-01

    X-ray absorption spectroscopy is a powerful probe of local electronic structure in disordered media. By employing extended x-ray absorption fine structure spectroscopy of liquid microjets, the intermolecular O-O distance has been observed to undergo a 5.9% expansion at the liquid water interface, in contrast to liquid methanol for which there is a 4.6% surface contraction. Despite the similar properties of liquid water and methanol (e.g., abnormal heats of vaporization, boiling points, dipole moments, etc.), this result implies dramatic differences in the surface hydrogen bond structure, which is evidenced by the difference in surface tension of these liquids. This result is consistent with surface vibrational spectroscopy, which indicates both stronger hydrogen bonding and polar ordering at the methanol surface as a consequence of "hydrophobic packing" of the methyl group.

  19. Ultra-soft x-ray absorption spectroscopy: A bulk and surface probe of materials

    SciTech Connect

    Fischer, D.A. ); Mitchell, G.E.; Dekoven, B.M. ); Yeh, A.T.; Gland, J.L. ); Moodenbaugh, A.R. )

    1993-01-01

    Direct comparisons between surface and bulk of diverse materials can be made by simultaneous electron yield (5 nm depth sensitivity) and fluorescence yield (200 nm) ultra soft x-ray absorption spectroscopy measurements utilizing a rapid sample interchange apparatus. For example the orientations of functional groups have been characterized at and near the surface of a series of model polymeric materials highlighting the chemical and molecular sensitivity of ultra soft x-ray absorption spectroscopy. In addition we discuss a bulk sensitive use of fluorescence yield to non destructively study a buried metal polymer interface. A second bulk sensitive example is the use of fluorescence yield oxygen K near edge x-ray spectroscopy as a method to determine the hole state density of high Tc materials.

  20. Ultra-soft x-ray absorption spectroscopy: A bulk and surface probe of materials

    SciTech Connect

    Fischer, D.A.; Mitchell, G.E.; Dekoven, B.M.; Yeh, A.T.; Gland, J.L.; Moodenbaugh, A.R.

    1993-06-01

    Direct comparisons between surface and bulk of diverse materials can be made by simultaneous electron yield (5 nm depth sensitivity) and fluorescence yield (200 nm) ultra soft x-ray absorption spectroscopy measurements utilizing a rapid sample interchange apparatus. For example the orientations of functional groups have been characterized at and near the surface of a series of model polymeric materials highlighting the chemical and molecular sensitivity of ultra soft x-ray absorption spectroscopy. In addition we discuss a bulk sensitive use of fluorescence yield to non destructively study a buried metal polymer interface. A second bulk sensitive example is the use of fluorescence yield oxygen K near edge x-ray spectroscopy as a method to determine the hole state density of high Tc materials.

  1. [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

  2. [The Diagnostics of Detonation Flow External Field Based on Multispectral Absorption Spectroscopy Technology].

    PubMed

    Lü, Xiao-jing; Li, Ning; Weng, Chun-sheng

    2016-03-01

    Compared with traditional sampling-based sensing method, absorption spectroscopy technology is well suitable for detonation flow diagnostics, since it can provide with us fast response, nonintrusive, sensitive solution for situ measurements of multiple flow-field parameters. The temperature and concentration test results are the average values along the laser path with traditional absorption spectroscopy technology, while the boundary of detonation flow external field is unknown and it changes all the time during the detonation engine works, traditional absorption spectroscopy technology is no longer suitable for detonation diagnostics. The trend of line strength with temperature varies with different absorption lines. By increasing the number of absorption lines in the test path, more information of the non-uniform flow field can be obtained. In this paper, based on multispectral absorption technology, the reconstructed model of detonation flow external field distribution was established according to the simulation results of space-time conservation element and solution element method, and a diagnostic method of detonation flow external field was given. The model deviation and calculation error of the least squares method adopted were studied by simulation, and the maximum concentration and temperature calculation error was 20.1% and 3.2%, respectively. Four absorption lines of H2O were chosen and detonation flow was scanned at the same time. The detonation external flow testing system was set up for the valveless gas-liquid continuous pulse detonation engine with the diameter of 80 mm. Through scanning H2O absorption lines with a high frequency of 10 kHz, the on-line detection of detonation external flow was realized by direct absorption method combined with time-division multiplexing technology, and the reconstruction of dynamic temperature distribution was realized as well for the first time, both verifying the feasibility of the test method. The test results

  3. [The Diagnostics of Detonation Flow External Field Based on Multispectral Absorption Spectroscopy Technology].

    PubMed

    Lü, Xiao-jing; Li, Ning; Weng, Chun-sheng

    2016-03-01

    Compared with traditional sampling-based sensing method, absorption spectroscopy technology is well suitable for detonation flow diagnostics, since it can provide with us fast response, nonintrusive, sensitive solution for situ measurements of multiple flow-field parameters. The temperature and concentration test results are the average values along the laser path with traditional absorption spectroscopy technology, while the boundary of detonation flow external field is unknown and it changes all the time during the detonation engine works, traditional absorption spectroscopy technology is no longer suitable for detonation diagnostics. The trend of line strength with temperature varies with different absorption lines. By increasing the number of absorption lines in the test path, more information of the non-uniform flow field can be obtained. In this paper, based on multispectral absorption technology, the reconstructed model of detonation flow external field distribution was established according to the simulation results of space-time conservation element and solution element method, and a diagnostic method of detonation flow external field was given. The model deviation and calculation error of the least squares method adopted were studied by simulation, and the maximum concentration and temperature calculation error was 20.1% and 3.2%, respectively. Four absorption lines of H2O were chosen and detonation flow was scanned at the same time. The detonation external flow testing system was set up for the valveless gas-liquid continuous pulse detonation engine with the diameter of 80 mm. Through scanning H2O absorption lines with a high frequency of 10 kHz, the on-line detection of detonation external flow was realized by direct absorption method combined with time-division multiplexing technology, and the reconstruction of dynamic temperature distribution was realized as well for the first time, both verifying the feasibility of the test method. The test results

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

    NASA Astrophysics Data System (ADS)

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

    2001-09-01

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

  5. Measurements of the mass absorption cross section of atmospheric soot particles using Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Nordmann, S.; Birmili, W.; Weinhold, K.; Müller, K.; Spindler, G.; Wiedensohler, A.

    2013-11-01

    Soot particles are a major absorber of shortwave radiation in the atmosphere. The mass absorption cross section is an essential quantity to describe this light absorption process. This work presents new experimental data on the mass absorption cross section of soot particles in the troposphere over Central Europe. Mass absorption cross sections were derived as the ratio between the light absorption coefficient determined by multiangle absorption photometry (MAAP) and the soot mass concentration determined by Raman spectroscopy. The Raman method is sensitive to graphitic structures present in the particle samples and was calibrated in the laboratory using Printex®90 model particles. Mass absorption cross sections were determined for a number of seven observation sites, ranging between 3.9 and 7.4 m2 g-1depending on measurement site and observational period. The highest values were found in a continentally aged air mass in winter, where soot particles were assumed to be mainly internally mixed. Our values are in the lower range of previously reported values, possibly due to instrumental differences to the former photometer and mass measurements. Overall, a value of 5.3m2 g-1from orthogonal regression over all samples is considered to be representative for the soot mass absorption cross section in the troposphere over Central Europe.

  6. 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…

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

    PubMed

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

    2016-02-15

    The charge distributions in α-Na2UO4, Na3NpO4, α-Na2NpO4, Na4NpO5, Na5NpO6, Na2PuO3, Na4PuO5, and Na5PuO6 are investigated in this work using X-ray absorption near-edge structure (XANES) spectroscopy at the U-L3, Np-L3, and Pu-L3 edges. In addition, a Rietveld refinement of monoclinic Na2PuO3, in space group C2/c, is reported for the first time, and the existence of the isostructural Na2NpO3 phase is revealed. In contrast to measurements in solution, the number of published XANES data for neptunium and plutonium solid phases with a valence state higher than IV is very limited. The present results cover a wide range of oxidation states, namely, IV to VII, and can serve as reference for future investigations. The sodium actinide series show a variety of local coordination geometries, and correlations between the shape of the XANES spectra and the local structural environments are discussed herein. PMID:26835549

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

    PubMed

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

    2016-02-15

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

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

    NASA Astrophysics Data System (ADS)

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

    2008-05-01

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

  10. 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

  11. 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.

  12. 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.

  13. Secondary Structure and Pd(II) Coordination in S-Layer Proteins from Bacillus sphaericus Studied by Infrared and X-Ray Absorption Spectroscopy

    PubMed Central

    Fahmy, Karim; Merroun, Mohamed; Pollmann, Katrin; Raff, Johannes; Savchuk, Olesya; Hennig, Christoph; Selenska-Pobell, Sonja

    2006-01-01

    The S-layer of Bacillus sphaericus strain JG-A12, isolated from a uranium-mining site, exhibits a high metal-binding capacity, indicating that it may provide a protective function by preventing the cellular uptake of heavy metals and radionuclides. This property has allowed the use of this and other S-layers as self-assembling organic templates for the synthesis of nanosized heavy metal cluster arrays. However, little is known about the molecular basis of the metal-protein interactions and their impact on secondary structure. We have studied the secondary structure, protein stability, and Pd(II) coordination in S-layers from the B. sphaericus strains JG-A12 and NCTC 9602 to elucidate the molecular basis of their biological function and of the metal nanocluster growth. Fourier transform infrared spectroscopy reveals similar secondary structures, containing ∼35% β-sheets and little helical structure. pH-induced infrared absorption changes of the side-chain carboxylates evidence a remarkably low pK < 3 in both strains and a structural stabilization when Pd(II) is bound. The COO−-stretching absorptions reveal a predominant Pd(II) coordination by chelation/bridging by Asp and Glu residues. This agrees with XANES and EXAFS data revealing oxygens as coordinating atoms to Pd(II). The additional participation of nitrogen is assigned to side chains rather than to the peptide backbone. The topology of nitrogen- and carboxyl-bearing side chains appears to mediate heavy metal binding to the large number of Asp and Glu in both S-layers at particularly low pH as an adaptation to the environment from which the strain JG-A12 has been isolated. These side chains are thus prime targets for the design of engineered S-layer-based nanoclusters. PMID:16698775

  14. 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

  15. The oxidation state of sulfur in synthetic and natural glasses determined by X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Métrich, Nicole; Berry, Andrew J.; O'Neill, Hugh St. C.; Susini, Jean

    2009-04-01

    Sulfur K-edge X-ray absorption near edge structure (XANES) spectra were recorded for experimental glasses of various compositions prepared at different oxygen fugacities ( fO 2) in one-atmosphere gas-mixing experiments at 1400 °C. This sample preparation method only results in measurable S concentrations under either relatively reduced (log fO 2 < -9) or oxidised (log fO 2 > -2) conditions. The XANES spectra of the reduced samples are characterised by an absorption edge crest at 2476.4 eV, typical of S 2-. In addition, spectra of Fe-bearing compositions exhibit a pronounced absorption edge shoulder. Spectra for all the Fe-free samples are essentially identical, as are the spectra for the Fe-bearing compositions, despite significant compositional variability within each group. The presence of a sulfide phase, such as might exsolve on cooling, can be inferred from a pre-edge feature at 2470.5 eV. The XANES spectra of the oxidised samples are characterised by an intense transition at 2482.1 eV, typical of the sulfate anion SO 42-. Sulfite (SO 32-) has negligible solubility in silicate melts at low pressures. The previous identification of sulfite species in natural glass samples is attributed to an artefact of the analysis (photoreduction of S 6+). S 4+ does, however, occur unambiguously with S 6+ in Fe-free and Fe-poor compositions prepared in equilibrium with CaSO 4 at 4-16 kbar, and when buffered with Re/ReO 2 at 10 kbar. Solubility of S 4+ thus requires partial pressures of SO 2 considerably in excess of 1 bar. A number of experiments were undertaken in an attempt to access intermediate fO 2s more applicable to terrestrial volcanism. Although these were largely unsuccessful, S 2- and S 6+ were found to coexist in some samples that were not in equilibrium with the imposed fO 2. The XANES spectra of natural olivine-hosted melt inclusions and submarine glasses representative of basalts at, or close to, sulfide saturation show mainly dissolved S 2-, but with minor

  16. 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. PMID:27091905

  17. [The principle and technical analysis of methane detection using infrared absorption spectroscopy].

    PubMed

    Zhang, Yu; Wang, Yi-Ding; Li, Li; Zheng, Chuan-Tao; An, Yu-Peng; Song, Zhen-Yu

    2008-11-01

    There has been considerable interest recently in methane sensor based on infrared absorption spectroscopy for industrial detection and environment monitoring. The present paper presents the intensites of methane mid-infrared fundamental absorption bands, near-infrared combination band of v2 + 2v3 and overtone band of 2v3, and it was found that the absorption strengths of fundamental bands are two orders of magnitude higher than those of overtone bands and three orders of magnitude higher than those of the combinations. Theoretically, mid-infrared detection system is much better. However, because the near-infrared source and detector are more maturely developed and cheaper, near-infrared technology is widely used. Furthermore, the near-infrared radiation can be transmitted through ordinary low-loss silica fiber, suitable for long-distance methane sensing system, meeting the needs of industrial mining and other aspects. But with the development of mid-infrared detector and high-power high-sensitivity devices, low priced micro sensor modules will be more and more developed. The development of optical methane sensors is reported in this paper. Several detection technologies were investigated such as differential absorption, harmonic detection, cavity spectroscopy enhancement and photoacoustic spectroscopy. The theoretical formula, sensitivity and system structure of these technologies are presented. PMID:19271479

  18. 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

  19. 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.

  20. Three-dimensional mapping of nickel oxidation states using full field x-ray absorption near edge structure nanotomography

    SciTech Connect

    Nelson, George J.; Harris, William M.; Izzo, John R. Jr.; Grew, Kyle N.; Chiu, Wilson K. S.; Chu, Yong S.; Yi, Jaemock; Andrews, Joy C.; Liu Yijin; Pianetta, Piero

    2011-04-25

    The reduction-oxidation cycling of the nickel-based oxides in composite solid oxide fuel cells and battery electrodes is directly related to cell performance. A greater understanding of nickel redox mechanisms at the microstructural level can be achieved in part using transmission x-ray microscopy (TXM) to explore material oxidation states. X-ray nanotomography combined with x-ray absorption near edge structure (XANES) spectroscopy has been applied to study samples containing distinct regions of nickel and nickel oxide (NiO) compositions. Digitally processed images obtained using TXM demonstrate the three-dimensional chemical mapping and microstructural distribution capabilities of full-field XANES nanotomography.

  1. Three-dimensional mapping of nickel oxidation states using full field x-ray absorption near edge structure nanotomography

    NASA Astrophysics Data System (ADS)

    Nelson, George J.; Harris, William M.; Izzo, John R.; Grew, Kyle N.; Chiu, Wilson K. S.; Chu, Yong S.; Yi, Jaemock; Andrews, Joy C.; Liu, Yijin; Pianetta, Piero

    2011-04-01

    The reduction-oxidation cycling of the nickel-based oxides in composite solid oxide fuel cells and battery electrodes is directly related to cell performance. A greater understanding of nickel redox mechanisms at the microstructural level can be achieved in part using transmission x-ray microscopy (TXM) to explore material oxidation states. X-ray nanotomography combined with x-ray absorption near edge structure (XANES) spectroscopy has been applied to study samples containing distinct regions of nickel and nickel oxide (NiO) compositions. Digitally processed images obtained using TXM demonstrate the three-dimensional chemical mapping and microstructural distribution capabilities of full-field XANES nanotomography.

  2. 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.

  3. Photodissociation of thioglycolic acid studied by femtosecond time-resolved transient absorption spectroscopy

    SciTech Connect

    Attar, Andrew R.; Blumling, Daniel E.; Knappenberger, Kenneth L. Jr.

    2011-01-14

    Steady-state and time-resolved spectroscopies were employed to study the photodissociation of both the neutral (HS-CH{sub 2}-COOH) and doubly deprotonated ({sup -}S-CH{sub 2}-COO{sup -}) forms of thioglycolic acid (TGA), a common surface-passivating ligand used in the aqueous synthesis and organization of semiconducting nanostructures. Room temperature UV-Vis absorption spectroscopy indicated strong absorption by the S{sub 1} and S{sub 2} excited states at 250 nm and 185 nm, respectively. The spectrum also contained a weaker absorption band that extended to approximately 550 nm, which was assigned to the {pi}{sub CO}{sup *}(leftarrow)n{sub O} transition. Femtosecond time-resolved transient absorption spectroscopy was performed on TGA using 400 nm excitation and a white-light continuum probe to provide the temporally and spectrally resolved data. Both forms of TGA underwent a photoinduced dissociation from the excited state to form an {alpha}-thiol-substituted acyl radical ({alpha}-TAR, S-CH{sub 2}-CO). For the acidic form of TGA, radical formation occurred with an apparent time constant of 60 {+-} 5 fs; subsequent unimolecular decay took 400 {+-} 60 fs. Similar kinetics were observed for the deprotonated form of TGA (70 {+-} 10 fs radical formation; 420 {+-} 40 fs decay). The production of the {alpha}-TAR was corroborated by the observation of its characteristic optical absorption. Time-resolved data indicated that the photoinduced dissociation of TGA via cleavage of the C-OH bond occurred rapidly ({<=}100 fs). The prevalence of TGA in aqueous semiconducting nanoparticles makes its absorption in the visible spectral region and subsequent dissociation key to understanding the behavior of nanoscale systems.

  4. Infrared-laser spectroscopy using a long-pathlength absorption cell

    SciTech Connect

    Kim, K.C.; Briesmeister, R.A.

    1983-01-01

    The absorption measurements in an ordinary cell may require typically a few torr pressure of sample gas. At these pressures the absorption lines are usually pressure-broadened and, therefore, closely spaced transitions are poorly resolved even at diode-laser resolution. This situation is greatly improved in Doppler-limited spectroscopy at extremely low sample pressures. Two very long-pathlength absorption cells were developed to be used in conjunction with diode lasers. They were designed to operate at controlled temperatures with the optical pathlength variable up to approx. 1.5 km. Not only very low sample pressures are used for studies with such cells but also the spectroscopic sensitivity is enhanced over conventional methods by a factor of 10/sup 3/ to 10/sup 4/, improving the analytical capability of measuring particle densities to the order of 1 x 10'' molecules/cm/sup 3/. This paper presents some analytical aspects of the diode laser spectroscopy using the long-pathlength absorption cells in the areas of absorption line widths, pressure broadening coefficients, isotope composition measurements and trace impurity analysis.

  5. Hard X-ray photoelectron and X-ray absorption spectroscopy characterization of oxidized surfaces of iron sulfides

    NASA Astrophysics Data System (ADS)

    Mikhlin, Yuri; Tomashevich, Yevgeny; Vorobyev, Sergey; Saikova, Svetlana; Romanchenko, Alexander; Félix, Roberto

    2016-11-01

    Hard X-ray photoelectron spectroscopy (HAXPES) using an excitation energy range of 2 keV to 6 keV in combination with Fe K- and S K-edge XANES, measured simultaneously in total electron (TEY) and partial fluorescence yield (PFY) modes, have been applied to study near-surface regions of natural polycrystalline pyrite FeS2 and pyrrhotite Fe1-xS before and after etching treatments in an acidic ferric chloride solution. It was found that the following near-surface regions are formed owing to the preferential release of iron from oxidized metal sulfide lattices: (i) a thin, no more than 1-4 nm in depth, outer layer containing polysulfide species, (ii) a layer exhibiting less pronounced stoichiometry deviations and low, if any, concentrations of polysulfide, the composition and dimensions of which vary for pyrite and pyrrhotite and depend on the chemical treatment, and (iii) an extended almost stoichiometric underlayer yielding modified TEY XANES spectra, probably, due to a higher content of defects. We suggest that the extended layered structure should heavily affect the near-surface electronic properties, and processes involving the surface and interfacial charge transfer.

  6. Diamond solid state ionization chambers for x-ray absorption spectroscopy applications

    SciTech Connect

    De Sio, A.; Bocci, A.; Pace, E.; Castellano, C.; Cinque, G.; Tartoni, N.; D'Acapito, F.

    2008-08-25

    The photoresponse of a diamond detector has been compared with a standard ionization chamber in x-ray absorption spectroscopy applications. A photoconductive device based on a nitrogen-doped single crystal diamond has been tested by synchrotron radiation. Time stability and linearity have been studied by x rays at 10 keV to assess its performances. Finally, extended x-ray absorption fine structure at the Fe K-edge was carried on a standard iron target using both the diamond device and the IC. Spectroscopical results have been compared including references to literature.

  7. 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.

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

    SciTech Connect

    Kim, Do Heui; Szanyi, Janos; Kwak, Ja Hun; Wang, Xianqin; Hanson, Jonathan C.; Engelhard, Mark H.; Peden, Charles HF

    2009-04-03

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

  9. Three-dimensional local structure refinement using a full-potential XANES analysis

    SciTech Connect

    Smolentsev, G.; Soldatov, A. V.; Feiters, M. C.

    2007-04-01

    A technique of three-dimensional (3D) local structure refinement is proposed and demonstrated by applying it to the metal complex Ni(acacR){sub 2}. The method is based on the fitting of experimental x-ray absorption near-edge structure (XANES) using a multidimensional interpolation of spectra and full potential calculations of XANES. The low number of calculations required is the main advantage of the method, which allows a computationally time-expensive method using a non-muffin-tin potential to be applied. The possibility to determine bond angles in addition to bond lengths accessible to extended x-ray-absorption fine structure opens new perspectives of XANES as a 3D structure probe.

  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. Extraction of local coordination structure in a low-concentration uranyl system by XANES.

    PubMed

    Zhang, Linjuan; Zhou, Jing; Zhang, Jianyong; Su, Jing; Zhang, Shuo; Chen, Ning; Jia, Yunpeng; Li, Jiong; Wang, Yu; Wang, Jian Qiang

    2016-05-01

    Obtaining structural information of uranyl species at an atomic/molecular scale is a critical step to control and predict their physical and chemical properties. To obtain such information, experimental and theoretical L3-edge X-ray absorption near-edge structure (XANES) spectra of uranium were studied systematically for uranyl complexes. It was demonstrated that the bond lengths (R) in the uranyl species and relative energy positions (ΔE) of the XANES were determined as follows: ΔE1 = 168.3/R(U-Oax)(2) - 38.5 (for the axial plane) and ΔE2 = 428.4/R(U-Oeq)(2) - 37.1 (for the equatorial plane). These formulae could be used to directly extract the distances between the uranium absorber and oxygen ligand atoms in the axial and equatorial planes of uranyl ions based on the U L3-edge XANES experimental data. In addition, the relative weights were estimated for each configuration derived from the water molecule and nitrate ligand based on the obtained average equatorial coordination bond lengths in a series of uranyl nitrate complexes with progressively varied nitrate concentrations. Results obtained from XANES analysis were identical to that from extended X-ray absorption fine-structure (EXAFS) analysis. XANES analysis is applicable to ubiquitous uranyl-ligand complexes, such as the uranyl-carbonate complex. Most importantly, the XANES research method could be extended to low-concentration uranyl systems, as indicated by the results of the uranyl-amidoximate complex (∼40 p.p.m. uranium). Quantitative XANES analysis, a reliable and straightforward method, provides a simplified approach applied to the structural chemistry of actinides. PMID:27140156

  12. 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.

  13. 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.

  14. 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.

  15. Narrow-band, tunable, semiconductor-laser-based source for deep-UV absorption spectroscopy.

    PubMed

    Kliner, D A; Koplow, J P; Goldberg, L

    1997-09-15

    Tunable, narrow-bandwidth (<200-MHz), ~215-nm radiation was produced by frequency quadrupling the ~860-nm output of a high-power, pulsed GaAlAs tapered amplifier seeded by an external-cavity diode laser. Pulsing the amplifier increased the 860 nm?215 nm conversion efficiency by 2 orders of magnitude with respect to cw operation. Detection of nitric oxide and sulfur dioxide by high-resolution absorption spectroscopy was demonstrated. PMID:18188256

  16. Nile blue shows its true colors in gas-phase absorption and luminescence ion spectroscopy.

    PubMed

    Stockett, M H; Houmøller, J; Brøndsted Nielsen, S

    2016-09-14

    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. PMID:27634256

  17. Nile blue shows its true colors in gas-phase absorption and luminescence ion spectroscopy.

    PubMed

    Stockett, M H; Houmøller, J; Brøndsted Nielsen, S

    2016-09-14

    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.

  18. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2008-07-01

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

  20. X-ray microprobe for micro x-ray fluorescence and absorption spectroscopies at GSECARS

    NASA Astrophysics Data System (ADS)

    Newville, M.; Sutton, S.; Rivers, M.

    2002-12-01

    The hard x-ray microprobe for x-ray fluorescence and absorption spectroscopy at GeoSoilEnviroCARS is presented. Using focused synchrotron radiation from an undulator beamline at the Advanced Photon Source at Argonne National Lab, the x-ray microprobe provides bright, monochromatic x-rays with typical spot sizes down to 1x1 μm for x-ray fluorescence and absorption spectroscopies. Quantitative x-ray fluorescence (XRF) analysis gives precise elemental composition and correlations, while x-ray absorption spectroscopy (XAS) gives the chemical state and local atomic coordination for a selected atomic species. These two techniques can be used in conjunction with one another on a wide range of samples, including minerals, glasses, fluid inclusions, soils, sediments, and plant tissue. This x-ray microprobe is part of the GeoSoilEnviroCARS user facility, available for use in all areas geological, soil, and environmental sciences, and selected examples from these fields will be given.

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

    PubMed

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

    2014-12-12

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

  2. 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.

  3. 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.

  4. The potential of UV-VIS-NIR absorption spectroscopy in glass studies

    NASA Astrophysics Data System (ADS)

    Meulebroeck, Wendy; Baert, Kitty; Ceglia, Andrea; Cosyns, Peter; Wouters, Hilde; Nys, Karin; Terryn, Herman; Thienpont, Hugo

    Absorption spectroscopy is the technique that measures the absorption of radiation as a function of wavelength, due to its interaction with the material. During a research project funded by our home university, we were able to investigate the possibilities of this technique to study ancient glasses. One of our main conclusions is that UV-VIS-NIR absorption spectroscopy is especially suited to characterize colored artifacts in terms of composition and furnace conditions. Moreover, for naturally colored window glasses, we have shown that this technique allows us to classify fragments based on differences in iron impurity levels. It is a semi-quantitative analysis tool that can be applied for a first-line analysis of (large) glass collections. Thanks to the commercial available portable instruments, these measurements can be performed at relative high speed and this in-situ if necessary. To illustrate the possibilities of this technique, we describe in this paper two case-studies. In a first test-case we analyze 63 naturally colored window glasses and demonstrate how groups with different iron concentrations can be identified by calculating the absorption edge position from the measured optical spectrum. In a second case-study 8 modern naturally colored and 31 intentionally colored Roman glass fragments are the point of focus. For these samples we first estimate which samples are potentially fabricated under the same furnace conditions. This is done based on the calculated color values. Finally we identify the type of applied colorants.

  5. Biogeochemical reductive release of soil embedded arsenate around a crater area (Guandu) in northern Taiwan using X-ray absorption near-edge spectroscopy.

    PubMed

    Chiang, Kai-Ying; Chen, Tsan-Yao; Lee, Chih-Hao; Lin, Tsang-Lang; Wang, Ming-Kuang; Jang, Ling-Yun; Lee, Jyh-Fu

    2013-03-01

    This study investigates biogeochemical reductive release of arsenate from beudantite into solution in a crater area in northern Taiwan, using a combination of X-ray absorption near-edge structure (XANES) and atomic absorption spectrometry. Total arsenic (As) concentrations in the soil were more than 200 mg/kg. Over four months of laboratory experiments, less than 0.8% As was released into solution after reduction experiments. The 71% to 83% As was chemically reduced into arsenite (As(III)) and partially weathering into the soluble phase. The kinetic dissolution and re-precipitation of As, Fe, Pb and sulfate in this area of paddy soils merits further study.

  6. Biogeochemical reductive release of soil embedded arsenate around a crater area (Guandu) in northern Taiwan using X-ray absorption near-edge spectroscopy.

    PubMed

    Chiang, Kai-Ying; Chen, Tsan-Yao; Lee, Chih-Hao; Lin, Tsang-Lang; Wang, Ming-Kuang; Jang, Ling-Yun; Lee, Jyh-Fu

    2013-03-01

    This study investigates biogeochemical reductive release of arsenate from beudantite into solution in a crater area in northern Taiwan, using a combination of X-ray absorption near-edge structure (XANES) and atomic absorption spectrometry. Total arsenic (As) concentrations in the soil were more than 200 mg/kg. Over four months of laboratory experiments, less than 0.8% As was released into solution after reduction experiments. The 71% to 83% As was chemically reduced into arsenite (As(III)) and partially weathering into the soluble phase. The kinetic dissolution and re-precipitation of As, Fe, Pb and sulfate in this area of paddy soils merits further study. PMID:23923437

  7. 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

  8. Theory of dynamic absorption spectroscopy of nonstationary states. 4. Application to 12-fs resonant impulsive Raman spectroscopy of bacteriorhodopsin

    SciTech Connect

    Pollard, W.T.; Peteanu, L.A.; Mathies, R.A.

    1992-07-23

    A time-dependent theory for femtosecond dynamic absorption spectroscopy is used to describe the creation and observation of molecular ground-state vibrational coherence through the resonance impulsive stimulated Raman mechanism. Model calculations show that the oscillatory absorption signal that arises from this ground-state coherence is maximized for a limited range of pulse lengths and that there is a complex relationship between the probe wavelength and the strength of the spectral oscillations. The generalized time-dependent linear susceptibility of the nonstationary system created by the impulsive pump pulse is defined and used to discuss the strong dependence of the measured signals on the properties of the probe pulse. Finally, calculations are presented to analyze the high-frequency oscillations ({approximately}20-fs period) recently observed in the transient absorption spectra of light-adapted bacteriorhodopsin (BR{sub 568}) following excitation with a 12-fs optical pulse. At the probe wavelengths used in this experiment, the contribution of stimulated emission is negligible at long times because of the extremely rapid excited-state isomerization; as a result, the spectral oscillations observed after this time are due to the impulsive excitation of coherent vibrations in the ground state. The transient response observed for BR{sub 568} is calculated using a 29-mode harmonic potential surface derived from a prior resonance Raman intensity analysis. Both the oscillatory signals and their dependence on the probe wavelength are satisfactorily reproduced. 68 refs., 11 figs.

  9. K-edge shift and XANES investigation of laser driven reshock-compressed Aluminum

    NASA Astrophysics Data System (ADS)

    Benuzzi-Mounaix, Alessandra; Ravasio, Alessandra; Koenig, Michel; Festa, Floriane; Amadou, Nourou; Levy, Anna; Brambrink, Erik; Dorchies, Fabien; Peyrusse, Olivier; Mazevet, Stéphane; Recoules, Vanina; Hall, Tom

    2010-11-01

    The physical properties of warm dense matter, specially their structural properties, are still poorly known. In this work, K-edge shift and X-ray Absorption Near Edge Spectroscopy (XANES) of reshocked Aluminum have been investigated with the aim of bringing information on the evolution of its electronic structure. The experiment was performed at LULI where we used one long pulse (500 ps, IL 8 10^13 W/cm^2) to create the shock and a second picosecond beam (IL 10^17 W/cm^2) to generate an ultra-short broadband X-ray source near the Al K-edge. The spectra were registered by using two conical KAP Bragg crystals. By changing the delay between the two beams, we have been able to observe the modification of absorption spectra for different and extreme Al conditions, up to now unexplored (ρ <= 3 ρ0 and T <= 8 eV). The hydrodynamical Al conditions were measured by using VISARs interferometers and self-emission diagnostic. Experimental data are compared to various calculations.

  10. X-ray absorption spectroscopy study of parent misfit-layered cobalt oxide [Sr₂O₂]q}CoO₂

    SciTech Connect

    Chou, Ta-Lei; Chan, Ting-Shan; Chen, Jin-Ming; Yamauchi, Hisao; Karppinen, Maarit

    2013-06-01

    Here we present a comprehensive X-ray absorption spectroscopy study carried out at Co-L₂,₃, Co-K, O-K and Sr-K edges for the parent misfit-layered cobalt oxide phase [Sr₂O₂]₀.₅₂CoO₂; comparison is made to another misfit-layered oxide [CoCa₂O₃]₀.₆₂CoO₂ and the perovskite oxide LaCoO₃. A high-quality sample of [Sr₂O₂]₀.₅₂CoO₂ was obtained through ultra-high-pressure synthesis using Sr₃Co₂O₆ and Sr(OH)₂∙8H₂O as starting materials. Different dosages of KClO₃ were mixed with the raw materials as an oxygen source and tested, but it was found that the window for the redox control of [Sr₂O₂]₀.₅₂CoO₂ is rather narrow. From Co-K and Co-L₂,₃ spectra a mixed III/IV valence state is revealed for cobalt in [Sr₂O₂]₀.₅₂}CoO₂, but the average valence value is a little lower than in [CoCa₂O₃]₀.₆₂CoO₂. Then, Sr-K spectrum indicates that the [Sr₂O₂] double-layer block in [Sr₂O₂]₀.₅₂CoO₂ clearly deviates from the cubic SrO rock-salt structure, suggesting a more complicated coordination environment for strontium. This together with a somewhat low Co-valence value and the fact that the phase formation of [Sr₂O₂]₀.₅₂CoO₂ required the presence of Sr(OH)₂∙8H₂O in the high-pressure synthesis suggest that the [Sr₂O₂] block contains ---OH groups, i.e. [Sr₂(O,OH)₂]₀.₅₂CoO₂. - Graphical abstract: [Sr₂O₂]₀.₅₂CoO₂ obtained through high-pressure synthesis is a parent of misfit-layered cobalt oxides, such as [CoCa₂O₃]₀.₆₂CoO₂ or [MmA₂O2+m]qCoO₂ in general. Our comprehensive X-ray absorption spectroscopy study shows that both [Sr₂O₂]₀.₅₂CoO₂ and [CoCa₂O₃]₀.₆₂CoO₂ possess mixed III/IV valence cobalt, but the average Co-valence is a little lower in the former. This is tentatively believed to be due to OH--- groups replacing part of O²⁻ ions in the [Sr

  11. A split imaging spectrometer for temporally and spatially resolved titanium absorption spectroscopy.

    PubMed

    Hager, J D; Lanier, N E; Kline, J L; Flippo, K A; Bruns, H C; Schneider, M; Saculla, M; McCarville, T

    2014-11-01

    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 SiO2 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. PMID:25430177

  12. 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.

  13. [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. PMID:21284148

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

    PubMed

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

    2016-06-22

    Copper ferrite, CuFe2O4, is a promising candidate for application as a high energy electrode material in lithium based batteries. Mechanistic insight on the electrochemical reduction and oxidation processes was gained through the first X-ray absorption spectroscopic study of lithiation and delithiation of CuFe2O4. A phase pure tetragonal CuFe2O4 material was prepared and characterized using laboratory and synchrotron X-ray diffraction, Raman spectroscopy, and transmission electron microscopy. Ex situ X-ray absorption spectroscopy (XAS) measurements were used to study the battery redox processes at the Fe and Cu K-edges, using X-ray absorption near-edge structure (XANES), extended X-ray absorption fine structure (EXAFS), and transmission X-ray microscopy (TXM) spectroscopies. EXAFS analysis showed upon discharge, an initial conversion of 50% of the copper(ii) to copper metal positioned outside of the spinel structure, followed by a migration of tetrahedral iron(iii) cations to octahedral positions previously occupied by copper(ii). Upon charging to 3.5 V, the copper metal remained in the metallic state, while iron metal oxidation to iron(iii) was achieved. The results provide new mechanistic insight regarding the evolution of the local coordination environments at the iron and copper centers upon discharging and charging. PMID:27292604

  15. Infrared Cavity Ringdown Laser Absorption Spectroscopy of jet-cooled clusters

    NASA Astrophysics Data System (ADS)

    Provencal, Robert Allen

    Infrared Cavity Ringdown Laser Absorption Spectroscopy (IR-CRLAS) employing stimulated Raman scattering (SRS) of pulsed dye lasers as the tunable IR source has been developed. This technique allows highly sensitive (ca. 1 ppm fractional absorption) direct absorption measurements to be performed in the 2-8 μm spectral range with complete wavelength coverage. Basic CR-LAS principles and essential SRS theory are reviewed. IR- CRLAS spectrometers based on both a Raman shifted dye laser and a pulsed Alexandrite ring laser are described. The IR-CRLAS spectrometer has been used in a comparative study of the O-H-stretching vibrations of small alcohol clusters. Results indicate an increase in the hydrogen bond strength as the alcohol chain length increases. An IR-CRLAS investigation of the aromatic C-H stretches of benzene and berizene/methane mixtures, performed in an effort to provide experimental support for a theoretically proposed ``antihydrogen bond'', produced negative results. Similarly, negative results from a visible CRLAS search for water cluster absorptions in connection with the anomalous atmospheric absorption of solar radiation are presented. Infrared laser spectroscopic studies of the structures and bonding in jet-cooled carbon clusters are discussed. The measurement and analysis of a rovibrational band at 2074 cm-1, tentatively assigned to linear C10 is presented. The astrophysical significance of carbon clusters is also discussed in conjunction with the first detection of a non polar molecule (C3) in a cold interstellar dust forming region, performed using far-infrared heterodyne spectroscopy aboard the Kuiper Airborne Observatory.

  16. Synchrotron-based X-ray absorption near-edge spectroscopy imaging for laterally resolved speciation of selenium in fresh roots and leaves of wheat and rice

    PubMed Central

    Wang, Peng; Menzies, Neal W.; Lombi, Enzo; McKenna, Brigid A.; James, Simon; Tang, Caixian; Kopittke, Peter M.

    2015-01-01

    Knowledge of the distribution of selenium (Se) species within plant tissues will assist in understanding the mechanisms of Se uptake and translocation, but in situ analysis of fresh and highly hydrated plant tissues is challenging. Using synchrotron-based fluorescence X-ray absorption near-edge spectroscopy (XANES) imaging to provide laterally resolved data, the speciation of Se in fresh roots and leaves of wheat (Triticum aestivum L.) and rice (Oryza sativa L.) supplied with 1 μM of either selenate or selenite was investigated. For plant roots exposed to selenate, the majority of the Se was efficiently converted to C-Se-C compounds (i.e. methylselenocysteine or selenomethionine) as selenate was transported radially through the root cylinder. Indeed, even in the rhizodermis which is exposed directly to the bulk solution, only 12–31% of the Se was present as uncomplexed selenate. The C-Se-C compounds were probably sequestered within the roots, whilst much of the remaining uncomplexed Se was translocated to the leaves—selenate accounting for 52–56% of the total Se in the leaves. In a similar manner, for plants exposed to selenite, the Se was efficiently converted to C-Se-C compounds within the roots, with only a small proportion of uncomplexed selenite observed within the outer root tissues. This resulted in a substantial decrease in translocation of Se from the roots to leaves of selenite-exposed plants. This study provides important information for understanding the mechanisms responsible for the uptake and subsequent transformation of Se in plants. PMID:26019258

  17. Synchrotron-based X-ray absorption near-edge spectroscopy imaging for laterally resolved speciation of selenium in fresh roots and leaves of wheat and rice.

    PubMed

    Wang, Peng; Menzies, Neal W; Lombi, Enzo; McKenna, Brigid A; James, Simon; Tang, Caixian; Kopittke, Peter M

    2015-08-01

    Knowledge of the distribution of selenium (Se) species within plant tissues will assist in understanding the mechanisms of Se uptake and translocation, but in situ analysis of fresh and highly hydrated plant tissues is challenging. Using synchrotron-based fluorescence X-ray absorption near-edge spectroscopy (XANES) imaging to provide laterally resolved data, the speciation of Se in fresh roots and leaves of wheat (Triticum aestivum L.) and rice (Oryza sativa L.) supplied with 1 μM of either selenate or selenite was investigated. For plant roots exposed to selenate, the majority of the Se was efficiently converted to C-Se-C compounds (i.e. methylselenocysteine or selenomethionine) as selenate was transported radially through the root cylinder. Indeed, even in the rhizodermis which is exposed directly to the bulk solution, only 12-31% of the Se was present as uncomplexed selenate. The C-Se-C compounds were probably sequestered within the roots, whilst much of the remaining uncomplexed Se was translocated to the leaves-selenate accounting for 52-56% of the total Se in the leaves. In a similar manner, for plants exposed to selenite, the Se was efficiently converted to C-Se-C compounds within the roots, with only a small proportion of uncomplexed selenite observed within the outer root tissues. This resulted in a substantial decrease in translocation of Se from the roots to leaves of selenite-exposed plants. This study provides important information for understanding the mechanisms responsible for the uptake and subsequent transformation of Se in plants.

  18. Ab initio calculation of x-ray absorption of iron up to 3 Mbar and 8000 K

    NASA Astrophysics Data System (ADS)

    Mazevet, S.; Recoules, V.; Bouchet, J.; Guyot, F.; Harmand, M.; Ravasio, A.; Benuzzi-Mounaix, A.

    2014-03-01

    Using ab initio simulations within the generalized gradient approximation, we calculate x-ray absorption near edge spectra (XANES) at the iron K edge throughout the high-pressure phase diagram and up to extreme density and temperature conditions that are representative of the Earth's inner core (up to 3 Mbar and 8000 K). We show that XANES spectra near the Fe K edge exhibit clear signatures for the different high-temperature, high-pressure phases of iron. This suggests that XANES spectroscopy might be used to resolve ongoing controversies regarding both the high-pressure melting curve of iron and the nature of the solid phases undergoing melting up to several Mbar. In contrast to diffraction measurements, it also offers a severe constraint for density functional theory predictions of the transport properties of iron by providing direct information on the electronic structure of iron at these extreme conditions.

  19. Study on the d state of platinum in Pt/SiO sub 2 and Na/Pt/SiO sub 2 catalysts under C double bond C hydrogenation conditions by X-ray absorption near-edge structure spectroscopy

    SciTech Connect

    Yoshitake, Hideaki; Iwasawa, Yasuhiro )

    1991-09-19

    The change in the d-electron density of platinum during D{sub 2} + CH{sub 2}{double bond}CHX reactions on Pt/SiO{sub 2} and Na/Pt/SiO{sub 2} catalysts and its influence on the catalysis were studied by X-ray absorption near-edge structure (XANES) spectroscopy, kinetics and FT-IR. It was demonstrated from the change of the white lines in XANES spectra at Pt L{sub 2} and L{sub 3} edges that CH{sub 2}{double bond}CHX (X = H, CH{sub 3}, COCH{sub 3}, CF{sub 3}, and CN) is adsorbed on the Pt surface and extracts the electrons of the d state. Hence, the deuterogenation rate is reduced as the value of Hammett's {sigma}{sub P} increases. The linear free energy relationship between the reaction rate and {sigma}{sub P} was observed for the deuterogenation of CH{sub 2}{double bond}CHX. The rate of ethene deuterogenation was promoted by Na{sub 2}O addition. The electron density of unoccupied d states of pt under vacuum decreased by Na{sub 2}O addition, indicating the electron donation from Na{sub 2}O addition. The electron density of unoccupied d states of Pt under vacuum decreased by Na{sub 2}O addition, indicating the electron donation from Na{sub 2}O addition. However, most of these additional electrons were observed to move to ethene under reaction conditions. The acceptor of the electrons was suggested by di-{sigma}-ethene by the shift of {upsilon}(C-H). The kinetic parameters are discussed in relation to the change in the d state of Pt as a function of {sigma}{sub P} and Na quantity.

  20. 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. PMID:26385430

  1. High Speed H2O Concentration Measurements Using Absorption Spectroscopy to Monitor Exhaust Gas

    SciTech Connect

    Kranendonk, Laura; Parks, II, James E; Prikhodko, Vitaly Y; Partridge Jr, William P

    2008-01-01

    This paper demonstrates the potential for fast absorption spectroscopy measurements in diesel-engine exhaust to track H2O concentration transients. Wavelength-agile absorption spectroscopy is an optical technique that measures broadband absorption spectra between 10kHz and 100 MHz. From these measured spectra, gas temperature and absorber concentration can be determined. The Fourier-domain mode-locking (FDML) laser is becoming recognized as one of the most robust and reliable wavelength-agile sources available. H2O concentration measurements during combustion events at crank angle resolved speeds are beneficial for a wide variety of applications, such as product improvements for industry, control and reliability checks for experimental researchers, and measures of fit for numerical simulations. The difficulties associated with measuring diesel exhaust compared to in-cylinder measurements are discussed. A full description of the experimental configuration and data processing is explained. Measurements of engine exhaust H2O transients with 10- s temporal resolution are presented for a range of engine conditions.

  2. [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.

  3. 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.

  4. 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.

  5. Femtosecond x-ray absorption spectroscopy with hard x-ray free electron laser

    SciTech Connect

    Katayama, Tetsuo; Togashi, Tadashi; Tono, Kensuke; Kameshima, Takashi; Inubushi, Yuichi; Sato, Takahiro; Hatsui, Takaki; Yabashi, Makina; Obara, Yuki; Misawa, Kazuhiko; Bhattacharya, Atanu; Kurahashi, Naoya; Ogi, Yoshihiro; Suzuki, Toshinori

    2013-09-23

    We have developed a method of dispersive x-ray absorption spectroscopy with a hard x-ray free electron laser (XFEL), generated by a self-amplified spontaneous emission (SASE) mechanism. A transmission grating was utilized for splitting SASE-XFEL light, which has a relatively large bandwidth (ΔE/E ∼ 5 × 10{sup −3}), into several branches. Two primary split beams were introduced into a dispersive spectrometer for measuring signal and reference spectra simultaneously. After normalization, we obtained a Zn K-edge absorption spectrum with a photon-energy range of 210 eV, which is in excellent agreement with that measured by a conventional wavelength-scanning method. From the analysis of the difference spectra, the noise ratio was evaluated to be ∼3 × 10{sup −3}, which is sufficiently small to trace minute changes in transient spectra induced by an ultrafast optical laser. This scheme enables us to perform single-shot, high-accuracy x-ray absorption spectroscopy with femtosecond time resolution.

  6. Infrared reflection-absorption spectroscopy of hyperfine layers on surfaces of semiconductors and dielectrics

    NASA Astrophysics Data System (ADS)

    Gruzinov, S. N.; Tolstoy, V. P.

    1988-02-01

    Infrared reflection-absorption spectroscopy of film son surfaces of transparent or weakly absorbing semiconductor and dielectric substrates is analyzed theoretically, the purpose being to establish the conditions for maximum sensitivity of this method. The absorption factor, namely the relative change of the reflection coefficient upon formation of a film on the substrate surface, is selected as the sensitivity criterion. The analysis is based on exact relations, one for a homogeneous isotopic absorbing film between substrate and ambient medium with plane-parallel boundaries and one for a reflecting layer with the possibility of multiple reflections taken into account. Calculations have been programmed on a computer for up to 60 nm thick SiO2 films on various substrates and infrared radiation within the 8 to 11 gmm waveband. The results indicate that the dependence of the absorption factor on the radiation wavelength and on the film thickness is different with the radiation s-polarized than with the radiation p-polarized. Calculations have also yielded the dispersion of optical constants characterizing a SiO2 film. According to these results, infrared spectroscopy is most sensitive to films on substrates with a small refractive index and when done with p-polarized radiation incident at exactly or approximately the Brewster angle for a determination of their presence and their composition respectively, also when no multiple reflections occur.

  7. 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.

  8. Core and valence excitations in resonant X-ray spectroscopy using restricted excitation window time-dependent density functional theory

    PubMed Central

    Zhang, Yu; Biggs, Jason D.; Healion, Daniel; Govind, Niranjan; Mukamel, Shaul

    2012-01-01

    We report simulations of X-ray absorption near edge structure (XANES), resonant inelastic X-ray scattering (RIXS) and 1D stimulated X-ray Raman spectroscopy (SXRS) signals of cysteine at the oxygen, nitrogen, and sulfur K and \\documentclass[12pt]{minimal}\\begin{document}$\\textrm {L}_{2,3}$\\end{document}L2,3 edges. Comparison of the simulated XANES signals with experiment shows that the restricted window time-dependent density functional theory is more accurate and computationally less expensive than the static exchange method. Simulated RIXS and 1D SXRS signals give some insights into the correlation of different excitations in the molecule. PMID:23181305

  9. Core and Valence Excitations in Resonant X-ray Spectroscopy using Restricted Excitation Window Time-dependent Density Functional Theory

    SciTech Connect

    Zhang, Yu; Biggs, Jason D.; Healion, Daniel; Govind, Niranjan; Mukamel, Shaul

    2012-11-21

    We report simulations of X-ray absorption near edge structure (XANES), resonant inelastic X-ray scattering (RIXS) and 1D stimulated X-ray Raman spectroscopy (SXRS) signals of cysteine at the oxygen, nitrogen and sulfur K and L2,3 edges. The simulated XANES signals from the restricted window time-dependent density functional theory (REW-TDDFT) and the static exchange (STEX) method are compared with experiments, showing that REW-TDDFT is more accurate and computationally less expensive than STEX. Simulated RIXS and 1D SXRS signals from REW-TDDFT give some insights on the correlation of different excitations in the molecule.

  10. Evaluating the Oxidation State of Fe in Oxide Minerals using Fe K-edge XANES

    NASA Astrophysics Data System (ADS)

    Marcus, M. A.

    2006-12-01

    Synchrotron based X-ray absorption spectroscopy has proven to be a useful tool for examining the chemical state of various elements in earth and space materials, ranging from soils to ferromanganese ocean nodules to meteorites. Iron is the most common redox-active element in the Earth's crust, and determining its oxidation state in-situ is vital in many applications. XANES (X-ray absorption near-edge spectroscopy) promises to provide the sought-for information, but it is surprisingly difficult to inspect a spectrum and read off the average oxidation state. In general, even for oxide minerals, the energy or shape of a single feature isn't enough to yield a reliable figure. Methods have been proposed in the past for the interpretation of Fe XANES spectra (1-3), but they tend to rely either on a detailed analysis of the weak pre-edge features, or on very accurate measurements of the energies of features. These requirements often make it impossible to use data of ordinary quality to determine the oxidation state of an unknown. Therefore, a new method is proposed which is usable with only ordinary levels of energy resolution, signal/noise, and energy calibration accuracy. The inflection point of the pre-edge feature is taken as the energy zero, thus rendering the method self-calibrating. Then, the energy positions of the "white-line" maximum and the halfway-up points are plotted. When this procedure is done with a variety of Fe2+, Fe3+ and mixed-valent standards, it becomes clear that contours of constant valence can be drawn. A polynomial fit of valence to these energy coordinates is done, which can then be applied to any unknown. This method is accurate to about 0.25 valence units for all available divalent, trivalent and mixed- valent oxide standards. We found that the Fe sulfides such as pyrite occupy a different area on the graph than do the oxides. Examples of the use of this method with unknowns will be presented. 1) M. Wilke, F. Farges, P.-E. Petit, G. E. Brown

  11. Broadband spectroscopy with external cavity quantum cascade lasers beyond conventional absorption measurements.

    PubMed

    Lambrecht, Armin; Pfeifer, Marcel; Konz, Werner; Herbst, Johannes; Axtmann, Felix

    2014-05-01

    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.

  12. XRD micro-XANES EMPA and SIMS investigation on phlogopite single crystals from Mt. Vulture (Italy)

    SciTech Connect

    F Scordari; M Dyar; E Schingaro; M Lacalamita; L Ottolini

    2011-12-31

    Selected phlogopite flakes from Mt. Vulture in southern Italy were studied using a combination of single-crystal techniques: electron microprobe analysis (EMPA), secondary ion mass spectrometry (SIMS), single-crystal X-ray diffraction (SCXRD), and micro-X-ray absorption near-edge spectroscopy (XANES). The latter technique was employed to analyze the structure of the Fe-K absorption edge over the region from 7080-8100 eV and to determine Fe{sup 3+}/{Sigma}Fe at a micrometer scale, albeit with large error bars due to known effects of orientation on pre-edge energy. The annite component, Fe/(Mg+Fe), of the samples studied ranged from 0.16 to 0.31, the Ti content from 0.11 to 0.27 atoms per formula unit (apfu) and the Ba content from 0.03 to 0.09 apfu. SIMS analysis showed H{sub 2}O (wt%) = 1.81-3.30, F (wt%) = 0.44-1.29, and Li{sub 2}O (wt%) = 0.001-0.027. The intra single-crystal chemical variability for major/minor elements (Mg, Fe, Al, Ba, Ti, and K) was found particularly significant for samples VUT191{_}11 and PG5{_}1, less significant for the other samples of the set. SIMS data relative to crystals VUT187{_}24, VUT191{_}10, VUT191{_}11, and VUT187{_}28 showed a noteworthy variation in the concentrations of some light elements (H, Li, and F) with coefficient of variation CV (as 1{sigma}%) up to {approx}18% for H{sub 2}O. The analyzed micas belong to the 1M polytype. Structure refinements using anisotropic displacement parameters were performed in space group C2/m and converged at 3.08 {<=} R {<=} 3.63, 3.32 {<=} R{sub w} {<=} 3.98%. Micro-XANES results yielded Fe{sup 3+}/{Sigma}Fe from 51-93%. Previous Moessbauer data from powdered samples suggested Fe{sup 3+}/{Sigma}Fe values ranging from 49-87%. However, the Fe{sup 3+} content determined by both techniques is sometimes remarkably different, in part because of the large errors ({+-}10-15%) presently associated with the micro-XANES technique and in part because the Fe{sup 3+} content of a single crystal may

  13. Cavity Enhanced absorption spectroscopy with an Optical Comb: Detection of atmospheric radicals in the near UV.

    NASA Astrophysics Data System (ADS)

    Méjean, G.; Kassi, S.; Romanini, D.

    2009-04-01

    The atmospheric chemistry community suffers a lack of fast, reliable and space resolved measurement for a wide set of very reactive molecules (e.g. radicals such as OH, NO3, BrO, IO, etc.). Due to their high reactivity, these molecules largely control the lifetime and concentration of numerous key atmospheric species. The concentrations of radicals are extremely low (ppbv or less) and highly variable in time and space. Measuring their concentration is often extremely laborious, expensive and requires heavy equipment (chemical sampling and treatment followed by mass spectrometry and/or chromatography). We recently introduced an optical spectroscopy technique based on a femtosecond laser oscillator, "Mode-Locked Cavity-Enhanced Absorption Spectroscopy", that we propose to develop into an instrument for in situ measurement of local concentration of traces of reactive molecules [1-3]. We have already demonstrated the possibility of measuring part in 1E12 by volume concentrations of radicals of high atmospheric interest, such as IO or BrO [4], as needed for monitoring these species in the environment. We apply cavity-enhanced absorption spectroscopy in the near UV range using a frequency-doubled Ti:Sa modelocked femtosecond laser. Efficient broadband injection of a high finesse cavity is obtained by matching this optical frequency-comb source to the comb of cavity transmission resonances. A grating spectrograph and a detector array disperse and detect the spectrum transmitted by the cavity carrying the absorption features of intracavity molecules. IO traces were obtained by mixing together controlled flows of gaseous iodine and ozone inside a high finesse cavity (F~6000). A Chameleon Ultra II ML-Laser (gracefully lent during 1 month by Coherent Inc.) was frequency doubled to address an absorption band of IO at 436 nm. A locking scheme allowed the cavity transmission to be smooth and stable. The transmitted light was dispersed using a high resolution (0.07nm) grating

  14. 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.

  15. 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

    2013-06-01

    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. PMID:23736618

  16. Simple Monte Carlo methods to estimate the spectra evaluation error in differential-optical-absorption spectroscopy.

    PubMed

    Hausmann, M; Brandenburger, U; Brauers, T; Dorn, H P

    1999-01-20

    Differential-optical-absorption spectroscopy (DOAS) permits the sensitive measurement of concentrations of trace gases in the atmosphere. DOAS is a technique of well-defined accuracy; however, the calculation of a statistically sound measurement precision is still an unsolved problem. Usually one evaluates DOAS spectra by performing least-squares fits of reference absorption spectra to the measured atmospheric absorption spectra. Inasmuch as the absorbance from atmospheric trace gases is usually very weak, with optical densities in the range from 10(-5) to 10(-3), interference caused by the occurrence of nonreproducible spectral artifacts often determines the detection limit and the measurement precision. These spectral artifacts bias the least-squares fitting result in two respects. First, spectral artifacts to some extent are falsely interpreted as real absorption, and second, spectral artifacts add nonstatistical noise to spectral residuals, which results in a significant misestimation of the least-squares fitting error. We introduce two new approaches to investigate the evaluation errors of DOAS spectra accurately. The first method, residual inspection by cyclic displacement, estimates the effect of false interpretation of the artifact structures. The second method applies a statistical bootstrap algorithm to estimate properly the error of fitting, even in cases when the condition of random and independent scatter of the residual signal is not fulfilled. Evaluation of simulated atmospheric measurement spectra shows that a combination of the results of both methods yields a good estimate of the spectra evaluation error to within an uncertainty of ~10%.

  17. Stability of widely tuneable, continuous wave external-cavity quantum cascade laser for absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Kasyutich, Vasili L.; Raja Ibrahim, R. K.; Martin, Philip A.

    2010-09-01

    The performance of widely tuneable, continuous wave (cw) external-cavity quantum cascade laser (EC-QCL) has been evaluated for direct absorption spectroscopy measurements of nitric oxide (NO) in the wavenumber range 1872-1958 cm -1 and with a 13.5 cm long optical cell. In order to reduce the absorption measurement errors due to the large variations of laser intensity, normalisation with a reference channel was used. Wavelength stability within the scans was analysed using the Allan plot technique for the reduced wavenumber range of 1892.4-1914.5 cm -1. The Allan variances of the NO absorption peak centres and areas were observed to increase with successive scan averaging for all absorption peaks across the wavelength scan, thus revealing short- and long-term drifts of the cw EC-QCL wavelength between successive scans. As an example application, the cw EC-QCL was used for NO measurements in the exhaust of an atmospheric pressure packed-bed plasma reactor applied to the decomposition of dichloromethane in waste gas streams. Etalon noise was reduced by subtracting a reference spectrum recorded when the plasma was off. The NO limit of detection (SNR = 1) was estimated to be ˜2 ppm at atmospheric pressure in a 20.5 cm long optical cell with a double pass and a single 7 s scan over 1892.4-1914.5 cm -1.

  18. Multiwavelength diode-laser absorption spectroscopy using external intensity modulation by semiconductor optical amplifiers.

    PubMed

    Karagiannopoulos, Solon; Cheadle, Edward; Wright, Paul; Tsekenis, Stylianos; McCann, Hugh

    2012-12-01

    A novel opto-electronic scheme for line-of-sight Near-IR gas absorption measurement based on direct absorption spectroscopy (DAS) is reported. A diode-laser-based, multiwavelength system is designed for future application in nonintrusive, high temporal resolution tomographic imaging of H2O in internal combustion engines. DAS is implemented with semiconductor optical amplifiers (SOAs) to enable wavelength multiplexing and to induce external intensity modulation for phase-sensitive detection. Two overtone water transitions in the Near-IR have been selected for ratiometric temperature compensation to enable concentration measurements, and an additional wavelength is used to account for nonabsorbing attenuation. A wavelength scanning approach was used to evaluate the new modulation technique, and showed excellent absorption line recovery. Fixed-wavelength, time-division-multiplexing operation with SOAs has also been demonstrated. To the best of our knowledge this is the first time SOAs have been used for modulation and switching in a spectroscopic application. With appropriate diode laser selection this scheme can be also used for other chemical species absorption measurements. PMID:23207374

  19. 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

    2013-06-01

    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.

  20. Multiwavelength diode-laser absorption spectroscopy using external intensity modulation by semiconductor optical amplifiers.

    PubMed

    Karagiannopoulos, Solon; Cheadle, Edward; Wright, Paul; Tsekenis, Stylianos; McCann, Hugh

    2012-12-01

    A novel opto-electronic scheme for line-of-sight Near-IR gas absorption measurement based on direct absorption spectroscopy (DAS) is reported. A diode-laser-based, multiwavelength system is designed for future application in nonintrusive, high temporal resolution tomographic imaging of H2O in internal combustion engines. DAS is implemented with semiconductor optical amplifiers (SOAs) to enable wavelength multiplexing and to induce external intensity modulation for phase-sensitive detection. Two overtone water transitions in the Near-IR have been selected for ratiometric temperature compensation to enable concentration measurements, and an additional wavelength is used to account for nonabsorbing attenuation. A wavelength scanning approach was used to evaluate the new modulation technique, and showed excellent absorption line recovery. Fixed-wavelength, time-division-multiplexing operation with SOAs has also been demonstrated. To the best of our knowledge this is the first time SOAs have been used for modulation and switching in a spectroscopic application. With appropriate diode laser selection this scheme can be also used for other chemical species absorption measurements.

  1. [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. PMID:21428087

  2. 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.

  3. 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.

  4. 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

  5. Melting of iron determined by X-ray absorption spectroscopy to 100 GPa.

    PubMed

    Aquilanti, Giuliana; Trapananti, Angela; Karandikar, Amol; Kantor, Innokenty; Marini, Carlo; Mathon, Olivier; Pascarelli, Sakura; Boehler, Reinhard

    2015-09-29

    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.

  6. 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.

  7. Note: cavity enhanced self-absorption spectroscopy: a new diagnostic tool for light emitting matter.

    PubMed

    Walsh, Anton J; Zhao, Dongfeng; Linnartz, Harold

    2013-02-01

    We introduce the concept of Cavity Enhanced Self-Absorption Spectroscopy (CESAS), a new sensitive diagnostic tool for analyzing light-emitting samples. The technique works without an additional light source and its implementation is straight forward. In CESAS, a sample (plasma, flame, or combustion source) is located in an optically stable cavity consisting of two high reflectivity mirrors, and here it acts both as light source and absorbing medium. A modest portion of the emitted light is trapped inside the cavity, making 10(4)-10(5) cavity round trips while crossing the sample and an artificial augmentation of the path length of the absorbing medium occurs as the light transverses the cavity. Light leaking out of the cavity simultaneously provides emission and absorption features. The performance is illustrated by CESAS results on supersonically expanding pulsed hydrocarbon plasma. We expect CESAS to become a generally applicable analytical tool for real time and in situ diagnostics.

  8. 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.

  9. Measurement of exhaled nitric oxide in beef cattle using tunable diode laser absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Roller, C. B.; Holland, B. P.; McMillen, G.; Step, D. L.; Krehbiel, C. R.; Namjou, K.; McCann, P. J.

    2007-03-01

    Measurement of nitric oxide (NO) in the expired breath of crossbred calves received at a research facility was performed using tunable diode laser absorption spectroscopy. Exhaled NO (eNO) concentrations were measured using NO absorption lines at 1912.07 cm-1 and employing background subtraction. The lower detection limit and measurement precision were determined to be ˜330 parts in 1012 per unit volume. A custom breath collection system was designed to collect lower airway breath of spontaneously breathing calves while in a restraint chute. Breath was collected and analyzed from calves upon arrival and periodically during a 42 day receiving period. There was a statistically significant relationship between eNO, severity of bovine respiratory disease (BRD) in terms of number of times treated, and average daily weight gain over the first 15 days postarrival. In addition, breathing patterns and exhaled CO2 showed a statistically significant relationship with BRD morbidity.

  10. Intra-cavity absorption spectroscopy with narrow-ridge microfluidic quantum cascade lasers.

    PubMed

    Belkin, Mikhail A; Loncar, Marko; Lee, Benjamon G; Pflugl, Christian; Audet, Ross; Diehl, Laurent; Capasso, Federico; Bour, David; Corzine, Scott; Hofler, Gloria

    2007-09-01

    We demonstrate microfluidic laser intra-cavity absorption spectroscopy with mid-infrared lambda approximately 9mum quantum cascade lasers. A deepetched narrow ridge waveguide laser is placed in a microfluidic chamber. The evanescent tails of the laser mode penetrate into a liquid on both sides of the ridge. The absorption lines of the liquid modify the laser waveguide loss, resulting in significant changes in the laser emission spectrum and the threshold current. A volume of liquid as small as ~10pL may, in principle, be sufficient for sensing using the proposed technique. This method, similar to the related gas-phase technique, shows promise as a sensitive means of detecting chemicals in small volumes of solutions.

  11. 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.

  12. Tunable erbium-doped fiber ring laser for applications of infrared absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Ryu, Han Young; Lee, Won-Kyu; Moon, Han Seb; Suh, Ho Suhng

    2007-07-01

    We fabricate a low noise erbium-doped fiber ring laser that can be continuously tuned over 102 nm by insertion of the fiber Fabry-Perot tunable filter (FFP-TF) in the ring cavity with a novel cavity structure and the optimal gain medium length. As an application of this fiber ring laser, we performed the absorption spectroscopy of acetylene (13C2H2) and hydrogen cyanide (H13C14N) and measure the absorption spectra of more than 50 transition lines of these gases with an excellent signal to noise ratio (SNR). The pressure broadening coefficients of four acetylene transition lines are obtained using this fiber ring laser and an external cavity laser diode.

  13. Picosecond time-resolved X-ray absorption spectroscopy of ultrafast aluminum plasmas.

    PubMed

    Audebert, P; Renaudin, P; Bastiani-Ceccotti, S; Geindre, J-P; Chenais-Popovics, C; Tzortzakis, S; Nagels-Silvert, V; Shepherd, R; Matsushima, I; Gary, S; Girard, F; Peyrusse, O; Gauthier, J-C

    2005-01-21

    We have used point-projection K-shell absorption spectroscopy to infer the ionization and recombination dynamics of transient aluminum plasmas. Two femtosecond beams of the 100 TW laser at the LULI facility were used to produce an aluminum plasma on a thin aluminum foil (83 or 50 nm), and a picosecond x-ray backlighter source. The short-pulse backlighter probed the aluminum plasma at different times by adjusting the delay between the two femtosecond driving beams. Absorption x-ray spectra at early times are characteristic of a dense and rather homogeneous plasma. Collisional-radiative atomic physics coupled with hydrodynamic simulations reproduce fairly well the measured average ionization as a function of time. PMID:15698184

  14. Electronic structure investigation of highly compressed aluminum with K edge absorption spectroscopy.

    PubMed

    Benuzzi-Mounaix, A; Dorchies, F; Recoules, V; Festa, F; Peyrusse, O; Levy, A; Ravasio, A; Hall, T; Koenig, M; Amadou, N; Brambrink, E; Mazevet, S

    2011-10-14

    The electronic structure evolution of highly compressed aluminum has been investigated using time resolved K edge x-ray absorption spectroscopy. A long laser pulse (500 ps, I(L)≈8×10(13) W/cm(2)) was used to create a uniform shock. A second ps pulse (I(L)≈10(17)  W/cm(2)) generated an ultrashort broadband x-ray source near the Al K edge. The main target was designed to probe aluminum at reshocked conditions up to now unexplored (3 times the solid density and temperatures around 8 eV). The hydrodynamical conditions were obtained using rear side visible diagnostics. Data were compared to ab initio and dense plasma calculations, indicating potential improvements in either description. This comparison shows that x-ray-absorption near-edge structure measurements provide a unique capability to probe matter at these extreme conditions and severally constrains theoretical approaches currently used. PMID:22107398

  15. 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.

  16. Space Launch System Base Heating Test: Tunable Diode Laser Absorption Spectroscopy

    NASA Technical Reports Server (NTRS)

    Parker, Ron; Carr, Zak; MacLean, Matthew; 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.

  17. Application of terahertz absorption spectroscopy to evaluation of aging variation of medicine.

    PubMed

    Kawase, Masaya; Saito, Tadashi; Ogawa, Masafumi; Uejima, Hideki; Hatsuda, Yasutoshi; Kawanishi, Sonoyo; Hirotani, Yoshihiko; Myotoku, Michiaki; Ikeda, Kenji; Konishi, Hiroki; Iga, Ikumi; Yamakawa, Junji; Nishizawa, Seizi; Yamamoto, Kohji; Tani, Masahiko

    2011-01-01

    The absorption spectra of three kinds of medicines both before and after the expiration date: Amlodin OD(®) (5 mg), Basen OD(®) (0.2 mg) and Gaster D(®) (10 mg) have been measured by terahertz time domain spectroscopy (THz-TDS). All the medicines show some differences in the THz absorption spectra between medicines before and after the expiration dates. X-Ray powder diffraction (XRD) studies of all medicines suggest that the polymorph of the main effective compound is not changed before and after the expiration date. Therefore, the differences in the THz spectra between medicines before and after the expiration dates arise from aging variation of diluting agents and/or from modifications of intermolecular interaction between the effective compounds and diluting agents. PMID:21321447

  18. Ground-based imaging differential optical absorption spectroscopy of atmospheric gases.

    PubMed

    Lohberger, Falko; Hönninger, Gerd; Platt, Ulrich

    2004-08-20

    We describe a compact remote-sensing instrument that permits spatially resolved mapping of atmospheric trace gases by passive differential optical absorption spectroscopy (DOAS) and present our first applications of imaging of the nitrogen dioxide contents of the exhaust plumes of two industrial emitters. DOAS permits the identification and quantification of various gases, e.g., NO2, SO2, and CH2O, from their specific narrowband (differential) absorption structures with high selectivity and sensitivity. With scattered sunlight as the light source, DOAS is used with an imaging spectrometer that is simultaneously acquiring spectral information on the incident light in one spatial dimension (column). The second spatial dimension is scanned by a moving mirror. PMID:15352396

  19. [Measurement of OH radicals in flame with high resolution differential optical absorption spectroscopy].

    PubMed

    Liu, Yu; Liu, Wen-Qing; Kan, Rui-Feng; Si, Fu-Qi; Xu, Zhen-Yu; Hu, Ren-Zhi; Xie, Pin-Hua

    2011-10-01

    The present paper describes a new developed high resolution differential optical absorption spectroscopy instrument used for the measurement of OH radicals in flame. The instrument consists of a Xenon lamp for light source; a double pass high resolution echelle spectrometer with a resolution of 3.3 pm; a multiple-reflection cell of 20 meter base length, in which the light reflects in the cell for 176 times, so the whole path length of light can achieve 3 520 meters. The OH radicals'6 absorption lines around 308 nm were simultaneously observed in the experiment. By using high resolution DOAS technology, the OH radicals in candles, kerosene lamp, and alcohol burner flames were monitored, and their concentrations were also inverted. PMID:22250529

  20. Real Time Observation of X-ray-Induced Surface Modification Using Simultaneous XANES and XEOL-XANES

    PubMed Central

    2013-01-01

    In experiments preliminary to the design of an X-ray-excited optical luminescence (XEOL)-based chemical mapping tool we have used X-ray micro (4.5 × 5.2 μm) and macro (1 × 6 mm) beams with similar total fluxes to assess the effects of a high flux density beam of X-rays at energies close to an absorption edge on inorganic surfaces in air. The near surface composition of corroded cupreous alloys was analyzed using parallel X-ray and optical photoemission channels to collect X-ray absorption near-edge structure (XANES) data at the Cu K edge. The X-ray fluorescence channel is characteristic of the composition averages over several micrometers into the surface, whereas the optical channel is surface specific to about 200 nm. While the X-ray fluorescence data were mostly insensitive to the X-ray dose, the XEOL-XANES data from the microbeam showed significant dose-dependent changes to the superficial region, including surface cleaning, changes in the oxidation state of the copper, and destruction of surface compounds responsible for pre-edge fluorescence or phosphorescence in the visible. In one case, there was evidence that the lead phase in a bronze had melted. Conversely, data from the macrobeam were stable over several hours. Apart from localized heating effects, the microbeam damage is probably associated with the O3 loading of the surface and increased reaction rate with atmospheric water vapor. PMID:24044633

  1. Real time observation of X-ray-induced surface modification using simultaneous XANES and XEOL-XANES.

    PubMed

    Adriaens, Annemie; Quinn, Paul; Nikitenko, Sergey; Dowsett, Mark G

    2013-10-15

    In experiments preliminary to the design of an X-ray-excited optical luminescence (XEOL)-based chemical mapping tool we have used X-ray micro (4.5 × 5.2 μm) and macro (1 × 6 mm) beams with similar total fluxes to assess the effects of a high flux density beam of X-rays at energies close to an absorption edge on inorganic surfaces in air. The near surface composition of corroded cupreous alloys was analyzed using parallel X-ray and optical photoemission channels to collect X-ray absorption near-edge structure (XANES) data at the Cu K edge. The X-ray fluorescence channel is characteristic of the composition averages over several micrometers into the surface, whereas the optical channel is surface specific to about 200 nm. While the X-ray fluorescence data were mostly insensitive to the X-ray dose, the XEOL-XANES data from the microbeam showed significant dose-dependent changes to the superficial region, including surface cleaning, changes in the oxidation state of the copper, and destruction of surface compounds responsible for pre-edge fluorescence or phosphorescence in the visible. In one case, there was evidence that the lead phase in a bronze had melted. Conversely, data from the macrobeam were stable over several hours. Apart from localized heating effects, the microbeam damage is probably associated with the O3 loading of the surface and increased reaction rate with atmospheric water vapor.

  2. Fluorescence and UV/VIS absorption spectroscopy studies on polymer blend films for photovoltaics

    NASA Astrophysics Data System (ADS)

    van Stam, Jan; Lindqvist, Camilla; Hansson, Rickard; Ericsson, Leif; Moons, Ellen

    2015-08-01

    The quinoxaline-based polymer TQ1 (poly[2,3-bis-(3-octyloxyphenyl)quinoxaline-5,8-diyl-alt-thiophene-2,5- diyl]) is a promising candidate as electron donor in organic solar cells. In combination with the electron acceptor [6,6]- phenyl-C71- butyric acid methyl ester (PC70BM), TQ1 has resulted in solar cells with power conversion efficiencies of 7 %. We have studied TQ1 films, with and without PC70BM, spin-casted from different solvents, by fluorescence spectroscopy and UV/VIS absorption spectroscopy. We used chloroform (CF), chlorobenzene (CB), and odichlorobenzene (o-DCB) as solvents for the coating solutions and 1-chloronaphthalene (CN) as solvent additive. CN addition has been shown to enhance photo-conversion efficiency of these solar cells. Phase-separation causes lateral domain formation in the films and the domain size depends on the solvent . These morphological differences coincide with changes in the spectroscopic patterns of the films. From a spectroscopic point of view, TQ1 acts as fluorescent probe and PC70BM as quencher. The degree of fluorescence quenching is coupled to the morphology through the distance between TQ1 and PC70BM. Furthermore, if using a bad solvent for PC70BM, morphological regions rich in the fullerene yield emission characteristic for aggregated PC70BM. Clear differences were found, comparing the TQ1:PC70BM blend films casted from different solvents and at different ratios between the donor and acceptor. The morphology also influences the UV/VIS absorption spectra, yielding further information on the composition. The results show that fluorescence and UV/VIS absorption spectroscopy can be used to detect aggregation in blended films and that these methods extend the morphological information beyond the scale accessible with microscopy.

  3. 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. PMID:26798792

  4. Laser plasma x-ray source for ultrafast time-resolved x-ray absorption spectroscopy

    DOE PAGES

    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 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

  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. 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.

  7. 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

  8. 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.

  9. 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.

  10. 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.

  11. Determining beryllium in drinking water by graphite furnace atomic absorption spectroscopy

    SciTech Connect

    Lytle, D.A.; Schock, M.R.; Dues, N.R.; Doerger, J.U.

    1993-01-01

    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 successfully eliminated common chemical interferences in drinking water samples analyzed for beryllium content, as well as interferences encountered during jar testing of beryllium removal by alum coagulation. The method proved to be a simple, accurate, and precise alternative to the method of standard additions. Method detection limit was 0.09 microgram/l, with a linear calibration range of 0 to 6 microgram/l.

  12. X-Ray Absorption Spectroscopy Study of Copper Doped ZnO Thin Films

    SciTech Connect

    Ma Qing

    2007-02-02

    X-ray absorption spectroscopy technique is used to study copper-doped ZnO thin films, prepared by pulsed-laser deposition. The samples with various doping levels are examined. It is found that the samples contain metallic clusters with the sizes {<=} 2 nm as well as Cu1+ and Cu2+ states. The Cu1+ states exist as stable oxide clusters, while the Cu2+ ones participate in the ZnO lattice some of which may be pertaining to the surfaces of the Cu clusters as well. The copper clusters of {approx}1 nm are unstable and fragment under monochromatic x-ray beam illumination.

  13. 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

    2015-09-01

    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. PMID:26382674

  14. Iron location in O-carboxymethyl chitosans determined by X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Klepka, Marcin T.; Lawniczak-Jablonska, Krystyna; Wolska, Anna; Slawska-Waniewska, Anna; Rodrigues, Clóvis A.; Lorini, Josiane; Cruz, Karianne Araujo da

    2011-01-01

    Chitosans represent a class of functional natural polymers. Their unique attribute is the capability to bind metal ions into their structure. This property can be exploited in many biomedical applications, but before that, some questions about metal binding mechanism must be answered. O-carboxymethyl chitosans with accumulated Fe atoms were studied by X-ray absorption spectroscopy. It was shown that iron bonding depends on the technological processes used in chitosan production. The applied technology allows for the selective introduction of either oxygen alone or of nitrogen and oxygen into the nearest neighbourhood of Fe. Therefore, it is possible to control the surroundings of a metal atom depending on requirements.

  15. [Real-time forecasting model for monitoring pollutant with differential optical absorption spectroscopy].

    PubMed

    Li, Su-Wen; Liu, Wen-Qing; Xie, Pin-Hua; Wang, Feng-Sui; Yang, Yi-Jun

    2009-11-01

    For real-time and on-line monitoring DOAS (differential optical absorption spectroscopy) system, a model based on an improved Elman network for monitoring pollutant concentrations was proposed. In order to reduce the systematical complexity, the forecasting factors have been obtained based on the step-wise regression method. The forecasting factors were current concentrations, temperature and relative humidity, and wind speed and wind direction. The dynamic back propagation (BP) algorithm was used for creating training set. The experiment results show that the predicted value follows the real well. So the modified Elman network can meet the demand of DOAS system's real time forecasting.

  16. Quantum cascade laser absorption spectroscopy as a plasma diagnostic tool: an overview.

    PubMed

    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.

  17. 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.

  18. Thermal Expansion Behaviour of Silver Examined by Extended X-Ray Absorption Fine Structure Spectroscopy

    SciTech Connect

    Dubiel, M.; Chasse, A.; Haug, J.; Schneider, R.; Kruth, H.

    2007-02-02

    EXAFS (extended X-ray absorption fine structure) investigations are reported concerning the thermal expansion behaviour of silver in an extended range of temperature from 10 K to about 950 K measured in transmission mode. Both the ratio method and an EXAFS fitting procedure were applied to reveal the temperature dependence of EXAFS parameters. Models based on quantum and classical thermodynamic perturbation theory have been used to interpret experimental data and compared to XRD (X-ray diffraction) results of bulk silver material. The description of thermodynamic data of thermal expansion of silver in the complete range of temperature by EXAFS Spectroscopy was successful by first calculations using third order quantum perturbation theory.

  19. Direct MD Simulations of Terahertz Absorption and 2D Spectroscopy Applied to Explosive Crystals.

    PubMed

    Katz, G; Zybin, S; Goddard, W A; Zeiri, Y; Kosloff, R

    2014-03-01

    A direct molecular dynamics simulation of the THz spectrum of a molecular crystal is presented. A time-dependent electric field is added to a molecular dynamics simulation of a crystal slab. The absorption spectrum is composed from the energy dissipated calculated from a series of applied pulses characterized by a carrier frequency. The spectrum of crystalline cyclotrimethylenetrinitramine (RDX) and triacetone triperoxide (TATP) were simulated with the ReaxFF force field. The proposed direct method avoids the linear response and harmonic approximations. A multidimensional extension of the spectroscopy is suggested and simulated based on the nonlinear response to a single polarized pulse of radiation in the perpendicular polarization direction. PMID:26274066

  20. Total Absorption Spectroscopy Study of 92Rb Decay: A Major Contributor to Reactor Antineutrino Spectrum Shape

    NASA Astrophysics Data System (ADS)

    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.; ńystö, 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.

    2015-09-01

    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. 92Rb 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 92Rb 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.

  1. 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

  2. Logarithmic conversion of absorption detection in wavelength modulation spectroscopy with a current-modulated diode laser.

    PubMed

    Wang, Yuntao; Cai, Haiwen; Geng, Jianxin; Fang, Zujie

    2009-07-20

    Logarithmic-conversion data processing used in wavelength modulation spectroscopy (WMS) with a current-modulated diode laser as its source is analyzed and compared with second-to-first ratio detection. Analytic Fourier coefficients of logarithmic-converted residual amplitude modulation (RAM) of a light source are given. An experimental setup for methane absorption detection at 1650 nm is described. It is shown theoretically and experimentally that logarithmic-converted WMS cannot only eliminate the fluctuation of received light power, but also improve the signal-to-noise ratio significantly. PMID:19623220

  3. Infrared laser absorption spectroscopy of the ν7 band of jet-cooled iron pentacarbonyl

    NASA Astrophysics Data System (ADS)

    Loroño, M.; Cruse, H. A.; Davies, P. B.

    2000-02-01

    The ν7 parallel band of Fe(CO) 5 has been measured in the 620 cm -1 region using high-resolution diode laser absorption spectroscopy in a free jet expansion. A comparison with simulated band profiles indicated a rotational temperature of between 2 and 3 K in the jet. At these temperatures the K-structure of the Q-branch is partly resolved. The following molecular parameters were obtained: ν0=619.95747(12) cm -1, B7=0.026743(2) cm -1, A7=0.030721(1) cm -1. Approximate values of the quartic centrifugal distortion constants were also obtained from fitting the spectra.

  4. 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}.

  5. 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.

  6. Two attosecond pulse transient absorption spectroscopy and extraction of the instantaneous AC Stark shift in helium

    NASA Astrophysics Data System (ADS)

    Bækhøj, Jens E.; Bojer Madsen, Lars

    2016-07-01

    In two attosecond pulse absorption spectroscopy (TAPAS) the use of two attosecond XUV pulses allows the extraction of atomic and molecular quantum mechanical dipole phases from spectroscopic measurements. TAPAS relies on interference between processes that individually only include a single XUV photon, and therefore does not rely on high intensity attosecond pulses. To show the usefulness and limitations of the TAPAS method we investigate its capability of capturing the instantaneous AC Stark shift induced by a midinfrared 3200 nm pulse in the | 1{{s}}2{{p}}> state of helium.

  7. [Real-time forecasting model for monitoring pollutant with differential optical absorption spectroscopy].

    PubMed

    Li, Su-Wen; Liu, Wen-Qing; Xie, Pin-Hua; Wang, Feng-Sui; Yang, Yi-Jun

    2009-11-01

    For real-time and on-line monitoring DOAS (differential optical absorption spectroscopy) system, a model based on an improved Elman network for monitoring pollutant concentrations was proposed. In order to reduce the systematical complexity, the forecasting factors have been obtained based on the step-wise regression method. The forecasting factors were current concentrations, temperature and relative humidity, and wind speed and wind direction. The dynamic back propagation (BP) algorithm was used for creating training set. The experiment results show that the predicted value follows the real well. So the modified Elman network can meet the demand of DOAS system's real time forecasting. PMID:20101985

  8. Transient absorption spectroscopy detection of sensitized delayed fluorescence in chiral benzophenone/naphthalene systems

    NASA Astrophysics Data System (ADS)

    Bonancía, Paula; Jiménez, M. Consuelo; Miranda, Miguel A.

    2011-10-01

    Transient absorption spectroscopy has proven to be a powerful tool to investigate the formation and decay of excited singlet states upon triplet-triplet annihilation, following T-T energy transfer from a selectively excited sensitizer. Thus, upon selective excitation of benzophenone (BZP) by laser flash photolysis (LFP) at λ = 355 nm in the presence of naphthalene (NPT), a negative band centered at 340 nm has been detected, with growth and decay in the microsecond timescale. It has been assigned to the P-type NPT delayed-fluorescence. In the case of chiral BZP/NPT systems, stereodifferentiation has been observed in the kinetics of the involved photophysical processes.

  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. Automated system for x-ray absorption spectroscopy of nanoparticle nucleation and growth

    SciTech Connect

    Calvin, S.; Carpenter, E.E.; Cestone, V.; Kurihara, L.K.; Harris, V.G.; Brown, E.C.

    2005-01-01

    X-ray absorption spectroscopy (XAS) is a useful tool for studying nanoparticle synthesis and growth. Described here is a system for automating synthesis and data collection, allowing time-resolved XAS measurements at a synchrotron to be accurately combined with measurements made under identical conditions elsewhere, and promising the ability to use XAS with experiments in combinatorial chemistry. The primary components of this system are a commercial parallel processor and a custom flow cell. The system has been used to collect data on the synthesis of iron oxides from iron(II) acetylacetonate.

  11. Sensing atmospheric reactive species using light emitting diode by incoherent broadband cavity enhanced absorption spectroscopy.

    PubMed

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

    2016-05-16

    We overview our recent progress in the developments and applications of light emitting diode-based incoherent broadband cavity enhanced absorption spectroscopy (LED-IBBCEAS) techniques for real-time optical sensing chemically reactive atmospheric species (HONO, NO3, NO2) in intensive campaigns and in atmospheric simulation chamber. New application of optical monitoring of NO3 concentration-time profile for study of the NO3-initiated oxidation process of isoprene in a smog chamber is reported. PMID:27409951

  12. Combination of optical emission and broadband absorption spectroscopy for diagnostics of HID lamps

    NASA Astrophysics Data System (ADS)

    Ruhrmann, Cornelia; Bergner, Andre; Hoebing, Thomas; Mentel, Juergen; Awakowicz, Peter

    2011-11-01

    HID lamps are used in several fields of application e.g. in street or automotive lighting as well as in video projection systems. Most of these lamps contain mercury to generate a high pressure buffer gas filling and thereby an appropriate power input into the arc. Due to its toxicity, the replacement of mercury is of particular interest in recent research of HID lamps. Currently, the emission coefficient of a mercury double line is used to determine the plasma temperature and thereby particle densities inside an HID lamp. A combination of optical emission and broadband absorption spectroscopy allows evaluating the plasma temperature without the need of mercury emission lines. It offers in combination with emission spectroscopy the possibility to calculate the total density of atoms and ions of elements also inside a mercury-free HID lamp. In this paper the measuring method is applied to a mercury-containing special research HID lamp (YAG lamp), seeded with rare earth iodines.

  13. In situ characterization of few-cycle laser pulses in transient absorption spectroscopy.

    PubMed

    Blättermann, Alexander; Ott, Christian; Kaldun, Andreas; Ding, Thomas; Stooß, Veit; Laux, Martin; Rebholz, Marc; Pfeifer, Thomas

    2015-08-01

    Attosecond transient absorption spectroscopy has thus far been lacking the capability to simultaneously characterize the intense laser pulses at work within a time-resolved quantum-dynamics experiment. However, precise knowledge of these pulses is key to extracting quantitative information in strong-field highly nonlinear light-matter interactions. Here, we introduce and experimentally demonstrate an ultrafast metrology tool based on the time-delay-dependent phase shift imprinted on a strong-field-driven resonance. Since we analyze the signature of the laser pulse interacting with the absorbing spectroscopy target, the laser pulse duration and intensity are determined in situ. As we also show, this approach allows for the quantification of time-dependent bound-state dynamics in one and the same experiment. In the future, such experimental data will facilitate more precise tests of strong-field dynamics theories.

  14. Wavelet transform based on the optimal wavelet pairs for tunable diode laser absorption spectroscopy signal processing.

    PubMed

    Li, Jingsong; Yu, Benli; Fischer, Horst

    2015-04-01

    This paper presents a novel methodology-based discrete wavelet transform (DWT) and the choice of the optimal wavelet pairs to adaptively process tunable diode laser absorption spectroscopy (TDLAS) spectra for quantitative analysis, such as molecular spectroscopy and trace gas detection. The proposed methodology aims to construct an optimal calibration model for a TDLAS spectrum, regardless of its background structural characteristics, thus facilitating the application of TDLAS as a powerful tool for analytical chemistry. The performance of the proposed method is verified using analysis of both synthetic and observed signals, characterized with different noise levels and baseline drift. In terms of fitting precision and signal-to-noise ratio, both have been improved significantly using the proposed method.

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

    PubMed Central

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

    2013-01-01

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

  16. 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. PMID:26899024

  17. 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.

  18. In situ XANES Spectroscopic Investigation of the Pre-Reduction of Iron-Based Catalysts for Non-Oxidative Alkane Dehydrogenation

    SciTech Connect

    Huggins, F.; Shen, W; Cprek, N; Shah, N; Marinkovic, N; Huffman, G

    2008-01-01

    The reduction in a methane atmosphere of two as-prepared ferric oxide catalysts for the non-oxidative dehydrogenation of alkanes has been investigated by in situ X-ray absorption near-edge structure (XANES) spectroscopy using a novel X-ray transmission reaction cell. The two catalysts were prepared by different synthesis methods (incipient wetness and nanoparticle impregnation) and were supported on Al-substituted magnesium oxide obtained by decomposition of a synthetic hydrotalcite. The reduction of the ferric oxides by methane was followed by iron XANES spectroscopy at temperatures up to 650 C complemented by a residual gas analyzer (RGA) used to track changes in the product gas. Results showed that the ferric oxides in the two catalysts underwent a stepwise reduction to first ferrous oxide, releasing mainly H{sub 2}O in the case of the nanoparticle catalyst but H{sub 2} and CO in the case of the incipient wetness formulation at temperatures between 200 and 550 C, and then more slowly to metallic iron at higher temperatures. Reaction of the ferrous oxide with the support to form magnesiowstite also occurred in conjunction with the reduction. This in situ investigation confirms that metallic iron is the active catalytic phase for alkane dehydrogenation and that observations of ferric iron in samples investigated at room temperature after reduction and reaction are most likely due to re-oxidation of the iron in the catalyst upon exposure to air rather than incomplete reduction of the original ferric iron in the catalyst.

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

    NASA Astrophysics Data System (ADS)

    Tanaka, Isao; Mizoguchi, Teruyasu; Yamamoto, Tomoyuki

    2009-03-01

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

  20. X-ray absorption spectroscopy on magnetic nanoscale systems for modern applications

    NASA Astrophysics Data System (ADS)

    Schmitz-Antoniak, Carolin

    2015-06-01

    X-ray absorption spectroscopy facilitated by state-of-the-art synchrotron radiation technology is presented as a powerful tool to study nanoscale systems, in particular revealing their static element-specific magnetic and electronic properties on a microscopic level. A survey is given on the properties of nanoparticles, nanocomposites and thin films covering a broad range of possible applications. It ranges from the ageing effects of iron oxide nanoparticles in dispersion for biomedical applications to the characterisation on a microscopic level of nanoscale systems for data storage devices. In this respect, new concepts for electrically addressable magnetic data storage devices are highlighted by characterising the coupling in a BaTiO3/CoFe2O4 nanocomposite as prototypical model system. But classical magnetically addressable devices are also discussed on the basis of tailoring the magnetic properties of self-assembled ensembles of FePt nanoparticles for data storage and the high-moment material Fe/Cr/Gd for write heads. For the latter cases, the importance is emphasised of combining experimental approaches in x-ray absorption spectroscopy with density functional theory to gain a more fundamental understanding.

  1. Glucose sensing by waveguide-based absorption spectroscopy on a silicon chip

    PubMed Central

    Ryckeboer, E.; Bockstaele, R.; Vanslembrouck, M.; Baets, R.

    2014-01-01

    In this work, we demonstrate in vitro detection of glucose by means of a lab-on-chip absorption spectroscopy approach. This optical method allows label-free and specific detection of glucose. We show glucose detection in aqueous glucose solutions in the clinically relevant concentration range with a silicon-based optofluidic chip. The sample interface is a spiral-shaped rib waveguide integrated on a silicon-on-insulator (SOI) photonic chip. This SOI chip is combined with micro-fluidics in poly(dimethylsiloxane) (PDMS). We apply aqueous glucose solutions with different concentrations and monitor continuously how the transmission spectrum changes due to glucose. Based on these measurements, we derived a linear regression model, to relate the measured glucose spectra with concentration with an error-of-fitting of only 1.14 mM. This paper explains the challenges involved and discusses the optimal configuration for on-chip evanescent absorption spectroscopy. In addition, the prospects for using this sensor for glucose detection in complex physiological media (e.g. serum) is briefly discussed. PMID:24877021

  2. Novel focal point multipass cell for absorption spectroscopy on small sized atmospheric pressure plasmas

    NASA Astrophysics Data System (ADS)

    Winter, Jörn; Hänel, Mattis; Reuter, Stephan

    2016-04-01

    A novel focal point multipass cell (FPMPC) was developed, in which all laser beams propagate through a common focal point. It is exclusively constructed from standard optical elements. Main functional elements are two 90∘ off-axis parabolic mirrors and two retroreflectors. Up to 17 laser passes are demonstrated with a near-infrared laser beam. The number of laser passes is precisely adjustable by changing the retroreflector distance. At the focal point beams are constricted to fit through an aperture of 0.8 mm. This is shown for 11 beam passes. Moreover, the fast temporal response of the cell permits investigation of transient processes with frequencies up to 10 MHz. In order to demonstrate the applicability of the FPMPC for atmospheric pressure plasma jets, laser absorption spectroscopy on the lowest excited argon state (1s5) was performed on a 1 MHz argon atmospheric pressure plasma jet. From the obtained optical depth profiles, the signal-to-noise ratio was deduced. It is shown that an elevation of the laser pass number results in an proportional increase of the signal-to-noise ratio making the FPMPC an appropriate tool for absorption spectroscopy on plasmas of small dimensions.

  3. 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.

  4. 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

  5. Interpretation of X-ray absorption spectra of As(III) in solution using Monte Carlo simulations.

    PubMed

    Canche-Tello, Jesus; Vargas, M Cristina; Hérnandez-Cobos, Jorge; Ortega-Blake, Iván; Leclercq, Amelie; Solari, Pierre Lorenzo; Den Auwer, Christophe; Mustre de Leon, José

    2014-11-20

    We performed X-ray absorption spectroscopy measurements on the arsenic K-edge of As(III) in solution under acidic conditions. Extended X-ray absorption fine structure (EXAFS) and X-ray near edge structure (XANES) spectra were compared with theoretical calculations which use local atomic structure configurations, either derived from density functional theory (DFT) energy minimization (EM) calculations or based on classical Monte Carlo (MC) simulations, for a As(OH)3 cluster surrounded by water molecules. The nearest arsenic-oxygen distances obtained from the fit of the XAFS spectra are consistent with the distances present in configurations derived from Monte Carlo simulations but not with those obtained from DFT-EM calculations. Calculations of XANES using either DFT-EM or the average configuration obtained from MC simulations do not reproduce the XANES spectra in the vicinity of the absorption edge. However, specific local atomic structural configurations of the As(OH)3 and water molecules, obtained from MC simulations, which show some ordering of water molecules up to 5 Å from the arsenic, reproduce qualitatively the experimental spectra. These results highlight the capability of XANES to yield information about hydration of ions in solution.

  6. Sulphur speciation in bitumens and asphaltenes by X-ray absorption fine structure spectroscopy

    NASA Astrophysics Data System (ADS)

    Kasrai, Masoud; Bancroft, G. Michael; Brunner, Roger W.; Jonasson, Ralph G.; Brown, James R.; Tan, Kim H.; Feng, Xinghong

    1994-07-01

    The S L-edge and K-edge XANES spectra were collected on bitumen and asphaltene samples as well as model compounds in order to determine the feasibility of monitoring transformations of organic sulphur in bitumen during genesis, processing, and upgrading. Using the spectra of model compounds as fingerprints, it was possible to speciate the sulphur forms in bitumen and asphaltene. The reduced form of sulphur such as thiophenes are the predominant form of sulphur in the bitumen and asphaltene samples analyzed. No significant amounts of oxidized sulphur forms could be detected. Spectra collected using total electron yield and fluorescence yield were identical, confirming that there is no preferential partitioning at the bitumen/air interface, or oxidation during sample handling. Also important was the finding that bitumen could be analyzed at moderately high vacuum (10 -8 torr). Thus XANES represents a rapid, nondestructive mean of characterizing specific classes of compounds in complex matrices, such as bitumen.

  7. 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.

  8. Exhaust gas monitoring based on absorption spectroscopy in the process industry

    NASA Astrophysics Data System (ADS)

    Zhang, Shuai; Liu, Wen-qing; Zhang, Yu-jun; Shu, Xiao-wen; Kan, Rui-feng; Cui, Yi-ben; He, Ying; Xu, Zhen-yu; Geng, Hui; Liu, Jian-guo

    2009-07-01

    This non-invasive gas monitor for exhaust gas monitoring must has high reliability and requires little maintenance. Monitor for in-situ measurements using tunable diode laser absorption spectroscopy (TDLAS) in the near infrared, can meet these requirements. TDLAS has evolved over the past decade from a laboratory especially to an accepted, robust and reliable technology for trace gas sensing. With the features of tunability and narrow linewidth of the distributed feedback (DFB) diode laser and by precisely tuning the laser output wavelength to a single isolated absorption line of the gas, TDLAS technique can be utilized to measure gas concentration with high sensitivity. Typical applications for monitoring of H2S, NH3, HC1 and HF are described here together by wavelength modulation spectroscopy with second-harmonic(WMS-2F) detection. This paper will illustrate the problems related to on-line applications, in particular, the overfall effects, automatic light intensity correction, temperature correction, which impacted on absorption coefficient and give details of how effect of automatic correction is necessary. The system mainly includes optics and electronics, optical system mainly composed of fiber, fiber coupler and beam expander, the electron part has been placed in safe analysis room not together with the optical part. Laser merely passes through one-meter-long pipes by the fiber coupling technology, so the system itself has anti-explosion. The results of the system are also presented in the end, the system's response time is only 0.5s, and can be achieved below 1×10-5 the detection limit at the volume fraction, it can entirely replace the traditional methods of detection exhaust gas in the process industry.

  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. Saturation dynamics and working limits of saturated absorption cavity ringdown spectroscopy.

    PubMed

    Sadiek, Ibrahim; Friedrichs, Gernot

    2016-08-17

    Cavity ringdown spectroscopy (CRDS) in the linear absorption regime is a well-established method for sensitive trace gas detection, but only a few studies have addressed quantitative measurements in the presence of a saturated sample. In fact, saturation is usually avoided in order to escape from the required complex modeling of the saturation process that depends on the characteristics of the absorbing species, its interaction with the surrounding gas as well as on the temporal and spectral characteristics of the cavity excitation. Conversely, the novel saturated-absorption cavity ringdown spectroscopy approach (SCAR/Sat-CRDS) takes advantage of sample saturation in order to allow one to extract both the gas absorption and the empty cavity loss rates from a single ringdown event. Using a new continuous-wave infrared CRD spectrometer equipped with a tunable narrow-bandwidth high-power OPO laser system and a 18 bit digitizer, the transient dynamics of absorption saturation and the working limits of the Sat-CRDS approach in terms of its ability to extract reliable trace gas concentrations have been experimentally studied in this work. Using a strong methane transition as a test case, the excitation power P0 and saturation power PS have been systematically varied to explore a wide range of saturation regimes. At pressures 5 μbar < p < 2 mbar, the saturation intensity revealed a nearly linear pressure dependence showing that non-collisional processes contribute to the overall relaxation. A ratio of P0/PS ≈ 15 turned out to be optimal with working limits of 5 < P0/PS < 300. Moreover, the ratio of the absorption and empty cavity loss rates, γg/γc, has been varied to test the dynamic range of the method. At γg > γc, a pronounced coupling between the two parameters has been observed. Finally, a standard error analysis was performed revealing that the Sat-CRDS approach holds its advantages over conventional CRDS implementations in particular when the attainable

  11. Soft X-Ray Absorption Spectroscopy at an X-ray Free Electron Laser

    NASA Astrophysics Data System (ADS)

    Higley, Daniel; Schlotter, William; Turner, Joshua; Moeller, Stefan; Mitra, Ankush; Tsukamoto, Arata; Marvel, Robert; Haglund, Richard; Durr, Hermann; Stohr, Joachim; Dakovski, Georgi

    2015-03-01

    X-ray free electron lasers, providing coherent, ultrafast, high intensity x-ray pulses, have enabled groundbreaking scattering experiments to probe the atomic structure of materials on femtosecond timescales. Nonetheless, x-ray absorption spectroscopy (XAS), one of the most fundamental and common x-ray techniques practiced at synchrotron light sources, has proven challenging to conduct with satisfactory signal-to-noise levels at soft x-ray energies using free electron laser sources. The ability to routinely collect high quality XAS spectra, especially in a time-resolved manner, will open many new scientific possibilities in the areas of ultrafast demagnetization, phase transitions and chemical dynamics to highlight a few. Here, we report how XAS using total fluorescence yield detection yields high signal-to-noise x-ray absorption spectra at an x-ray free electron laser source. Data were collected over multiple absorption edges on technologically relevant materials. These measurements were recorded on the Soft X-Ray Materials Science instrument at the Linac Coherent Light Source. The results are easily extendable to time-resolved measurements.

  12. Vacuum-UV absorption spectroscopy of interstellar ice analogues. III. Isotopic effects

    NASA Astrophysics Data System (ADS)

    Cruz-Diaz, G. A.; Caro, G. M. Muñoz; Chen, Y.-J.

    2014-04-01

    This paper reports the first measurements of solid-phase vacuum-ultraviolet (VUV) absorption cross-sections of heavy isotopologues present in icy dust grain mantles of dense interstellar clouds and cold circumstellar environments. Pure ices composed of D2O, CD3OD, 13CO2, and 15N15N were deposited at 8 K, a value similar to the coldest dust temperatures in space. The column density of the ice samples was measured in situ by infrared spectroscopy in transmittance. VUV spectra of the ice samples were collected in the 120-160 nm (10.33-7.74 eV) range using a commercial microwave discharged hydrogen flow lamp as the VUV source. Prior to this work, we have recently submitted a similar study of the light isotopologues (Cruz-Diaz, Muñoz Caro & Chen). The VUV spectra are compared to those of the light isotopologues in the solid phase, and to the gas phase spectra of the same molecules. Our study is expected to improve very significantly the models that estimate the VUV absorption of ice mantles in space, which have often used the available gas phase data as an approximation of the absorption cross sections of the molecular ice components. We will show that this work has also important implications for the estimation of the photodesorption rates per absorbed photon in the ice.

  13. 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. PMID:27176993

  14. Probing the Inner Regions of Protoplanetary Disks with CO Absorption Line Spectroscopy

    NASA Astrophysics Data System (ADS)

    McJunkin, Matthew; France, Kevin; Burgh, Eric B.; Herczeg, Gregory J.; Schindhelm, Eric; Brown, Joanna M.; Brown, Alexander

    2013-03-01

    Carbon monoxide (CO) is the most commonly used tracer of molecular gas in the inner regions of protoplanetary disks. CO can be used to constrain the excitation and structure of the circumstellar environment. Absorption line spectroscopy provides an accurate assessment of a single line of sight through the protoplanetary disk system, giving more straightforward estimates of column densities and temperatures than CO and molecular hydrogen (H2) emission line studies. We analyze new observations of ultraviolet CO absorption from the Hubble Space Telescope along the sightlines to six classical T Tauri stars. Gas velocities consistent with the stellar velocities, combined with the moderate-to-high disk inclinations, argue against the absorbing CO gas originating in a fast-moving disk wind. We conclude that the far-ultraviolet observations provide a direct measure of the disk atmosphere or possibly a slow disk wind. The CO absorption lines are reproduced by model spectra with column densities in the range N(12CO) ~ 1016-1018 cm-2 and N(13CO) ~ 1015-1017 cm-2, rotational temperatures T rot(CO) ~ 300-700 K, and Doppler b-values, b ~ 0.5-1.5 km s-1. We use these results to constrain the line-of-sight density of the warm molecular gas (n CO ~ 70-4000 cm-3) and put these observations in context with protoplanetary disk models.

  15. Direct single-mode fibre-coupled miniature White cell for laser absorption spectroscopy.

    PubMed

    Kühnreich, Benjamin; Höh, Matthias; Wagner, Steven; Ebert, Volker

    2016-02-01

    We present the design, setup, and characterization of a new lens-free fibre-coupled miniature White cell for extractive gas analysis using direct tunable diode laser absorption spectroscopy (dTDLAS). The construction of this cell is based on a modified White cell design and allows for an easy variation of the absorption length in the range from 29 cm to 146 cm. The design avoids parasitic absorption paths outside the cell by using direct, lensless fibre coupling and allows small physical cell dimensions and cell volumes. To characterize the cell performance, different H2O and CH4 concentration levels were measured using dTDLAS. Detection limits of 2.5 ppm ⋅ m for CH4 (at 1.65 μm) and 1.3 ppm ⋅ m for H2O (at 1.37 μm) were achieved. In addition, the gas exchange time and its flow-rate dependence were determined for both species and found to be less than 15 s for CH4 and up to a factor of thirteen longer for H2O. PMID:26931838

  16. Direct single-mode fibre-coupled miniature White cell for laser absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Kühnreich, Benjamin; Höh, Matthias; Wagner, Steven; Ebert, Volker

    2016-02-01

    We present the design, setup, and characterization of a new lens-free fibre-coupled miniature White cell for extractive gas analysis using direct tunable diode laser absorption spectroscopy (dTDLAS). The construction of this cell is based on a modified White cell design and allows for an easy variation of the absorption length in the range from 29 cm to 146 cm. The design avoids parasitic absorption paths outside the cell by using direct, lensless fibre coupling and allows small physical cell dimensions and cell volumes. To characterize the cell performance, different H2O and CH4 concentration levels were measured using dTDLAS. Detection limits of 2.5 ppm ṡ m for CH4 (at 1.65 μm) and 1.3 ppm ṡ m for H2O (at 1.37 μm) were achieved. In addition, the gas exchange time and its flow-rate dependence were determined for both species and found to be less than 15 s for CH4 and up to a factor of thirteen longer for H2O.

  17. 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.

  18. Microplasmas as vacuum ultraviolet source for Cl-atom density measurements by resonance absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Martin, Virginie; Bauville, Gérard; Sadeghi, Nader; Puech, Vincent

    2011-11-01

    A micro-hollow cathode discharge was used to generate radiation on the chlorine atom resonance lines. Such radiation could be used to measure, by resonance absorption spectroscopy, the density of chlorine atoms in either ground state (3p5 2P3/2) or in the fine structure metastable state (3p5 2P1/2), which is located at 882.35 cm-1. Among the nine analysed lines in the 132-142 nm spectral region, only those at 137.953 and 139.653 nm, which are strong enough and are not affected by the self-absorption, can be used for the resonance absorption diagnostic of the ground state and the metastable state, respectively. The best operating conditions of the lamp source are 0.5% of Cl2 in argon at 150 mbar and 4 mA discharge current. The measured 800 ± 30 K gas temperature of the microplasma, indicates that under these specific conditions, these two lines are dominantly Doppler broadened. So their profile is Gaussian shaped with full widths at half maximum of (4.7 ± 0.1) × 10-4 nm.

  19. Diagnostics of O Atoms in Inductively Coupled O2 Plasma Employing Vacuum Ultraviolet Absorption Spectroscopy

    NASA Astrophysics Data System (ADS)

    Nagai, Hisao; Hori, Masaru; Goto, Toshio; Hiramatsu, Mineo; Takashima, Seigou

    2002-10-01

    The compact measurement system for absolute densities of oxygen (O) atom has been developed employing a vacuum ultraviolet absorption spectroscopy (VUVAS) technique with a high-pressure micro-discharge hollow cathode lamp (MHCL) as a light source. The influences of self-absorption, emission line profiles of the MHCL, and the background absorption on determination of absolute O atom density were investigated. This system has been applied for measuring of absolute O atom densities in an inductively coupled O2 plasma. O atom densities were estimated to be on the order of 4 x 10^11 -4 x 10^12 cm-3, at an O2 pressure ranging from 1.3 to 26.7 Pa. The behavior of O atom density measured using VUVAS technique was consistent with that obtained by actinometry technique using 844.6 nm and 777.2 nm. Moreover, the lifetime of O atom in the afterglow plasma has been investigated. The decay curves of the O atom density were fitted with exponential functions. The extinction process of O atom in the inductively coupled O2 plasma is discussed.

  20. 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.

  1. Laser-induced micro-plasmas in air for incoherent broadband cavity-enhanced absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Ruth, Albert; Dixneuf, Sophie; Orphal, Johannes

    2016-04-01

    Incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS) is an experimentally straightforward absorption method where the intensity of light transmitted by an optically stable (high finesse) cavity is measured. The technique is realized using broadband incoherent sources of radiation and therefore the amount of light transmitted by a cavity consisting of high reflectance mirrors (typically R > 99.9%) can be low. In order to find an alternative to having an incoherent light source outside the cavity, an experiment was devised, where a laser-induced plasma in ambient air was generated inside a quasi-confocal cavity by a high-power femtosecond laser. The emission from the laser-induced plasma was utilized as pulsed broadband light source. The time-dependent spectra of the light leaking from the cavity were compared with those of the laser-induced plasma emission without the cavity. It was found that the light emission was sustained by the cavity despite the initially large optical losses caused by the laser-induced plasma in the cavity. The light sustained by the cavity was used to measure part of the S1 ← S0 absorption spectrum of gaseous azulene at its vapour pressure at room temperature in ambient air, as well as the strongly forbidden γ-band in molecular oxygen (b1Σ(2,0) ← X3Σ(0,0)).

  2. 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.

  3. Improvement of differential optical absorption spectroscopy with a multichannel scanning technique.

    PubMed

    Brauers, T; Hausmann, M; Brandenburger, U; Dorn, H P

    1995-07-20

    Differential optical absorption spectroscopy (DOAS) of atmospheric trace gases requires the detection of optical densities below 0.1%. Photodiode arrays are used more and more as detectors for DOAS because they allow one to record larger spectral intervals simultaneously. This type of optical multichannel analyzer (OMA), however, shows sensitivity differences among the individual photodiodes (pixels), which are of the order of 1%. To correct for this a sensitivity reference spectrum is usually recorded separately from the trace-gas measurements. Because of atmospheric turbulence the illumination of the detector while an atmospheric absorption spectrum is being recorded is different from the conditions during the reference measurement. As a result the sensitivity patterns do not exactly match, and the corrected spectra still show a residual structure that is due to the sensitivity difference. This effect usually limits the detection of optical densities to approximately 3 × 10(-4). A new method for the removal of the sensitivity pattern is presented in this paper: Scanning the spectrometer by small wavelength increments after each readout of the OMA allows one to separate the OMA-fixed pattern and the wavelength-fixed structures (absorption lines). The properties of the new method and its applicability are demonstrated with simulated spectra. Finally, first atmospheric measurements with a laser long-path instrument demonstrate a detection limit of 3 × 10(-5) of a DOAS experiment. PMID:21052280

  4. A preliminary investigation of chlorine XANES in silicate glasses

    NASA Astrophysics Data System (ADS)

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

    2008-10-01

    Chlorine speciation in silicate melts affects volatile exsolution, rheology, and thermodynamic properties of the melt but is poorly known. X-Ray Absorption Near Edge Structure (XANES) spectra have been used to investigate Cl speciation in 26 silicate glasses and to test the hypothesis that Cl in silicate melts is hosted by species that combine Cl and network-modifying cations such as Ca and Mg. Results indicate that Cl in CMAS (CaO-MgO-Al2O3-SiO2) plus Na2O, K2O, or MnO silicate glasses exists as a combination of Ca-Clx and Mg-Clx species or, possibly, as mixed Ca-Mgy-Clx species. The geometry and stoichiometry of the proposed species is unknown, but there are similarities between spectra from Ca-bearing melts and the spectra of hydrated CaCl2.2H2O, suggesting that the Ca-Clx species could have a salt-like atomic arrangement and ionic bonding. Further investigations using XANES, alternative spectroscopic techniques, and forward modeling approaches are required to distinguish between these possibilities.

  5. Local structure of Ge quantum dots determined by combined numerical analysis of EXAFS and XANES data.

    PubMed

    Zhang, Yuanpeng; Ersoy, Osman; Karatutlu, Ali; Little, William; Sapelkin, Andrei

    2016-01-01

    The sensitivity of X-ray absorption near-edge structure (XANES) to the local symmetry has been investigated in small (∼4 nm) matrix-free Ge quantum dots. The FDMNES package was used to calculate the theoretical XANES spectra that were compared with the experimental data of as-prepared and annealed nanoparticles. It was found that XANES data for an as-prepared sample can only be adequately described if the second coordination shell of the diamond-type structural model is included in the FDMNES calculations. This is in contrast to the extended X-ray absorption fine-structure data that show only the first-shell signal. These results suggest that, despite the high degree of disorder and a large surface-to-volume ratio, as-prepared small Ge quantum dots retain the diamond-type symmetry beyond the first shell. Furthermore, we utilized this sensitivity of XANES to the local symmetry to study annealed Ge quantum dots and found evidence for significant structural distortion which we attribute to the existence of surface disorder in the annealed oxygen-free Ge quantum dots. PMID:26698071

  6. Scanning transmission X-ray microscopy and X-ray absorption near-edge structure studies of N-doped carbon nanotubes sealed with N2 gas

    NASA Astrophysics Data System (ADS)

    Xie, Tian; Zhao, Yu; Zhong, Jun; Hu, Zheng; Sun, Xuhui

    2012-06-01

    N-doped carbon nanotubes (NCNTs) were synthesized and their electronic structures have been explored by X-ray absorption near-edge structure (XANES) spectroscopy. With a surface sensitive mode, XANES confirms the N-doping in NCNTs. However, with a more bulk sensitive detection mode of XANES, large amount of gaseous N2 have been found to be sealed in NCNTs, even in a high vacuum environment. The encapsulation of the ferrocene residues in carbon nanotubes had been revealed by scanning transmission X-ray microscopy (STXM), which may help for the N2 sealing. The results suggest that the easily sealed gas should be taken into consideration for CNT-based applications.

  7. RE L(3) x-ray absorption study of REO(1-x)F(x)FeAs (RE = La, Pr, Nd, Sm) oxypnictides.

    PubMed

    Joseph, B; Iadecola, A; Fratini, M; Bianconi, A; Marcelli, A; Saini, N L

    2009-10-28

    Rare earth L(3)-edge x-ray absorption near-edge structure (XANES) spectroscopy has been used to study REOFeAs (RE = La, Pr, Nd, Sm) oxypnictides. The Nd L(3) XANES due to the [Formula: see text] transition shows a substantial change in both white line (WL) spectral weight and the higher energy multiple scattering resonances with the partial substitution of O by F. A systematic change in the XANES features is seen due to varying lattice parameters with ionic radius of the rare earth. On the other hand, we hardly see any change across the structural phase transition. The results provide timely information on the local atomic correlations showing the importance of the local structural chemistry of the REO spacer layer and interlayer coupling in the competing superconductivity and itinerant striped magnetic phase of the oxypnictides.

  8. 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).

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

    NASA Astrophysics Data System (ADS)

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

    2009-04-01

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

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

    PubMed

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

    2007-01-31

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

  11. XANES Demonstrates the Release of Calcium Phosphates from Alkaline Vertisols to Moderately Acidified Solution.

    PubMed

    Andersson, Karl O; Tighe, Matthew K; Guppy, Christopher N; Milham, Paul J; McLaren, Timothy I; Schefe, Cassandra R; Lombi, Enzo

    2016-04-19

    Calcium phosphate (CaP) minerals may comprise the main phosphorus (P) reserve in alkaline soils, with solubility dependent on pH and the concentration of Ca and/or P in solution. Combining several techniques in a novel way, we studied these phenomena by progressively depleting P from suspensions of two soils (low P) using an anion-exchange membrane (AEM) and from a third soil (high P) with AEM together with a cation-exchange membrane. Depletions commenced on untreated soil, then continued as pH was manipulated and maintained at three constant pH levels: the initial pH (pHi) and pH 6.5 and 5.5. Bulk P K-edge X-ray absorption near-edge structure (XANES) spectroscopy revealed that the main forms of inorganic P in each soil were apatite, a second more soluble CaP mineral, and smectite-sorbed P. With moderate depletion of P at pHi or pH 6.5, CaP minerals became more prominent in the spectra compared to sorbed species. The more soluble CaP minerals were depleted at pH 6.5, and all CaP minerals were exhausted at pH 5.5, showing that the CaP species present in these alkaline soils are soluble with decreases of pH in the range achievable by rhizosphere acidification. PMID:26974327

  12. 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.

  13. Quantitative treatment of coarsely binned low-resolution recordings in molecular absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Spietz, Peter; Martín, Juan Carlos Gómez; Burrows, John P.

    2006-06-01

    Optical multichannel detectors like photodiode arrays or CCD cameras combined with grating spectrometers are commonly used as detection systems in quantitative absorption spectroscopy. As a trade-off to broad spectral coverage, banded spectral features are sometimes recorded with insufficient spectral resolution and/or insufficiently fine detector binning. This renders the true physical spectrum of recorded intensities changed by instrumental and spectrum specific artefacts thus impeding comparability between results from different set-ups. In this work, it is demonstrated that in the case of a "well-behaved" - i.e. free of ro-vibronic structure - absorption band like the iodine monoxide IO(4 ← 0) transition, these effects can easily change the apparent peak absorption by up to 50%. Also deviations from the strict linearity (Beer-Lambert's law) between absorber concentration and apparent, i.e. pixelwise optical density occur. This can be critical in studies of chemical kinetics. It is shown that the observed non-linearity can cause errors of up to 50% in the determination of a second order rate coefficient for the IO self reaction. To overcome the problem, a consistent and rigorous integral approach for the treatment of intensity recordings is developed. Linearity between optical density and absorber concentration thereby is re-established. The method is validated using artificial test data as well as experimental data of the IO(4 ← 0) absorption transition, obtained in the context of I 2/O 3 photochemistry studies. The agreement is accurate to within ±2% (test data) and ±3% (experimental data) supporting the validity of the approach. Possible consequences for other spectroscopic work are indicated.

  14. 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.

  15. A X-Ray Absorption Spectroscopy Study of Manganese Containing Compounds and Photosynthetic Spinach Chloroplasts.

    NASA Astrophysics Data System (ADS)

    Kirby, Jon Allan

    The manganese sites in chloroplasts, long thought to be involved in photosynthetic oxygen evolution have been examined and partially characterized by X-ray Absorption Spectroscopy (XAS) using synchrotron radiation. The local environment about the manganese atoms is estimated from an analysis of the extended X-ray Absorption Fine Structure (EXAFS). Comparisons with and simulations of the manganese EXAFS for several reference compounds leads to a model in which the chloroplast manganese atoms are contained in a binuclear complex similar to di-u-oxo -tetrakis-(2,2'-bipyridine) dimanganese. It is suggested that the partner metal is another manganese. The bridging ligands are most probably oxygen. The remaining manganese ligands are carbon, oxygen, or nitrogen. A roughly linear correlation between the X-ray K edge onset energy and the "coordination charge" of a large number of manganese coordination complexes and compounds has been developed. Entry of the chloroplast manganese edge energy onto this correlation diagram establishes that the active pool of manganese is in an oxidation state greater than +2. If the manganese is in a dimeric form the oxidation states are most probably (II,III). Underlying these results is an extensive data analysis methodology. The method developed involves the use of many different background removal techniques, Fourier transforms and ultimately curve fitting to the modulations in the x-ray absorption cross sections. A large number of model compounds were used to evaluate the analysis method. These analyses are used to show that the two major curve fitting models available are essentially equivalent. Due to its greater versatility, the theoretical model of Teo and Lee is preferred (J. Am. Chem. Soc. (1979), 101, 2815). The results are also used to determine the informational limitations of XAS within the limits of the present understanding of X-ray absorption phenomena by inner shell electrons for atoms with atomic number greater than that

  16. 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

  17. Understanding the sensitivity of cavity-enhanced absorption spectroscopy: pathlength enhancement versus noise suppression

    NASA Astrophysics Data System (ADS)

    Ouyang, B.; Jones, R. L.

    2012-12-01

    Cavity-enhanced absorption spectroscopy is now widely used as an ultrasensitive technique in observing weak spectroscopic absorptions. Photons inside the cavity are reflected back and forth between the mirrors with reflectivities R close to one and thus (on average) exploit an absorption pathlength L that is 1/(1 - R) longer than a single pass measurement. As suggested by the Beer-Lambert law, this increase in L results in enhanced absorbance A (given by αL with α being the absorption coefficient) which in turn favours the detection of weak absorptions. At the same time, however, only (1 - R) of the incident light can enter the cavity [assuming that mirror transmission T is equal to (1 - R)], so that the reduction in transmitted light intensity Δ I caused by molecular absorption equates to that would be obtained if in fact no cavity were present. The enhancement in A = Δ I/ I, where I is the total transmitted light intensity, achievable from CEAS therefore comes not from an increase in Δ I, but a sharp decrease in I. In this paper, we calculate the magnitudes of these two terms before and after a cavity is introduced, and aim at interpreting the sensitivity improvement offered by cavity-enhanced absorption spectroscopy from this observable-oriented (i.e. Δ I and I) perspective. It is first shown that photon energy stored in the cavity is at best as intense as the input light source, implying that any absorbing sample within the cavity is exposed to the same or even lower light intensity after the cavity is formed. As a consequence, the intensity of the light absorbed or scattered by the sample, which corresponds to the Δ I term aforementioned, is never greater than would be the case in a single pass measurement. It is then shown that while this "numerator" term is not improved, the "denominator" term, I, is reduced considerably; therefore, the increase in contrast ratio Δ I/ I is solely contributed by the attenuation of transmitted background light I and is

  18. 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

  19. Total fluxes of sulfur dioxide from the Italian volcanoes Etna, Stromboli, and Vulcano measured by differential absorption lidar and passive differential optical absorption spectroscopy

    SciTech Connect

    Edner, H.; Ragnarson, P.; Svanberg, S.; Wallinder, E.; Ferrara, R.; Cioni, R.; Raco, B.; Taddeucci, G.

    1994-09-20

    The authors present measurements of the total flux of sulfur dioxide from three Italian volcanoes Etna, Stromboli, and Vulcano, measured in a three day period in Sept, 1992. The fluxes were measured from shipboard by means of an active differential absorption lidar technique, and a passive differential optical absorption spectroscopy technique. Corrections had to be applied to the passive optical technique because the light source paths were not well defined. The total fluxes were found to be roughly 25, 180, and 1300 tons/day for Vulcano, Stromboli, and Etna, respectively. 43 refs., 10 figs., 6 tabs.

  20. Inside and Outside: X-ray Absorption Spectroscopy Mapping of Chemical Domains in Graphene Oxide.

    PubMed

    De Jesus, Luis R; Dennis, Robert V; Depner, Sean W; Jaye, Cherno; Fischer, Daniel A; Banerjee, Sarbajit

    2013-09-19

    The oxidative chemistry of graphite has been investigated for over 150 years and has attracted renewed interest given the importance of exfoliated graphene oxide as a precursor to chemically derived graphene. However, the bond connectivities, steric orientations, and spatial distribution of functional groups remain to be unequivocally determined for this highly inhomogeneous nonstoichiometric material. Here, we demonstrate the application of principal component analysis to scanning transmission X-ray microscopy data for the construction of detailed real space chemical maps of graphene oxide. These chemical maps indicate very distinct functionalization motifs at the edges and interiors and, in conjunction with angle-resolved near-edge X-ray absorption fine structure spectroscopy, enable determination of the spatial location and orientations of functional groups. Chemical imaging of graphene oxide provides experimental validation of the modified Lerf-Klinowski structural model. Specifically, we note increased contributions from carboxylic acid moieties at edge sites with epoxide and hydroxyl species dominant within the interior domains.

  1. 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

  2. X-ray absorption spectroscopy study in the BaFe2As2 family

    NASA Astrophysics Data System (ADS)

    Koh, Yoonyoung; Kim, Yeongkwan; Yang, Wanli; Kim, Changyoung

    2012-02-01

    One of the representative Fe-based superconductor families, BaFe2As2 (Tc =38K) is a semimetal with the same number of hole and electron carriers, and is in a spin density wave state below 139K. It has been reported that various types of ``doped'' BaFe2As2 systems can obtained by substitution of Ba, Fe, and As atoms. However, an important issue has been recently raised regarding whether each type of substitution indeed induces effective charge doping or not. It is essential to clarify whether each type of substitution indeed induce an effective doping in BaFe2As2 system. To clarify the carrier doping issue, we performed high resolution X-ray absorption spectroscopy experiment on Ba(Fe,Co)2As2, Ba(Fe,Ru)2As2, BaFe2(As,P)2 which are representative ``doped'' BaFe2As2 systems.

  3. Electronic topological transition in zinc under pressure: An x-ray absorption spectroscopy study

    NASA Astrophysics Data System (ADS)

    Aquilanti, G.; Trapananti, A.; Minicucci, M.; Liscio, F.; Twaróg, A.; Principi, E.; Pascarelli, S.

    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.

  4. X-ray absorption spectroscopy to probe interfacial issues in photolithography.

    SciTech Connect

    Angelopoulos, Marie (IBM, T.J. Watson Research Center, Yorktown Heights, NY); Lenhart, Joseph Ludlow; Wu, Wen-li (National Institute of Standards and Technology, Gaithersburg, MD); Sambasivan, Sharadha (National Institute of Standards and Technology, Gaithersburg, MD); Fischer, Daniel A. (National Institute of Standards and Technology, Gaithersburg, MD); Jones, Ronald L. (National Institute of Standards and Technology, Gaithersburg, MD); Soles, Christopher L. (National Institute of Standards and Technology, Gaithersburg, MD); Lin, Eric K. (National Institute of Standards and Technology, Gaithersburg, MD); Goldfarb, Dario L. (IBM, T.J. Watson Research Center, Yorktown Heights, NY)

    2003-03-01

    We utilize near edge X-ray absorption fine structure spectroscopy (NEXASFS) to provide detailed chemical insight into two interfacial problems facing sub-100 nm patterning. First, chemically amplified photo-resists are sensitive to surface phenomenon, which causes deviations in the pattern profile near the interface. Striking examples include T-topping, closure, footing, and undercutting. NEXAFS was used to examine surface segregation of a photo-acid generator at the resist/air interface and to illustrate that the surface extent of deprotection in a model resist film can be different than the bulk extent of deprotection. Second, line edge roughness becomes increasingly critical with shrinking patterns, and may be intimately related to the line edge deprotection profile. A NEXAFS technique to surface depth profile for compositional gradients is described with the potential to provide chemical information about the resist line edge.

  5. 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.

  6. 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.

  7. 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.

  8. 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

  9. Infrared Absorption Spectroscopy and Chemical Kinetics of Free Radicals, Final Technical Report

    DOE R&D Accomplishments Database

    Curl, Robert F.; Glass, Graham P.

    2004-11-01

    This research was directed at the detection, monitoring, and study of the chemical kinetic behavior by infrared absorption spectroscopy of small free radical species thought to be important intermediates in combustion. Work on the reaction of OH with acetaldehyde has been completed and published and work on the reaction of O({sup 1}D) with CH{sub 4} has been completed and submitted for publication. In the course of our investigation of branching ratios of the reactions of O({sup 1}D) with acetaldehyde and methane, we discovered that hot atom chemistry effects are not negligible at the gas pressures (13 Torr) initially used. Branching ratios of the reaction of O({sup 1}D) with CH{sub 4} have been measured at a tenfold higher He flow and fivefold higher pressure.

  10. High resolution electron energy loss spectroscopy: A new probe of subgap absorption in amorphous solids

    SciTech Connect

    Lopinski, G.P.; Lannin, J.S.

    1996-10-01

    The use of high resolution electron energy spectroscopy (HREELS) as a new method for studies of subgap absorption in thin films of amorphous semiconductors is demonstrated. For a-Si films, the {alpha}({omega}) values extracted from the measured loss spectra are in quantitative agreement with previous optical measurements. The method is also applied to both threefold and diamond-like amorphous carbon films, yielding {alpha}({omega}) down to considerably lower energies ({approximately}50 meV) than previously reported. The HREELS method is shown to be complementary to existing techniques in that it can access the regime of low energies and ultrathin films which is difficult to investigate with the conventional methods. {copyright} {ital 1996 American Institute of Physics.}

  11. Studies of fluorine in catalysts with ultrasoft X-ray absorption spectroscopy

    SciTech Connect

    Davis, S.M. ); Meitzner, G.D. ); Fischer, D.A. ); Gland, J. )

    1993-08-01

    The structures of fluorine-doped alumina catalyst powders have been studied by fluorescence yield ultrasoft X-ray absorption spectroscopy. The results presented here demonstrate that important local structural information can be obtained by the technique. It is established that fluoride ions are substituted for oxygen in alumina at low concentration of adsorbed fluorine. For doping levels larger than those required for saturation of the monolayer, the authors observed AlF[sub 3]-like features in the radial structure function. These results are in agreement with previous observations of bulk AlF[sub 3] in aluminas with high levels of fluorine doping. The fluorescence yield method is well suited for determining structures of a wide range of ceramic materials. 22 refs., 4 figs.

  12. Infrared reflection-absorption spectroscopy: principles and applications to lipid-protein interaction in Langmuir films.

    PubMed

    Mendelsohn, Richard; Mao, Guangru; Flach, Carol R

    2010-04-01

    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

  13. Axial segregation in high intensity discharge lamps measured by laser absorption spectroscopy

    SciTech Connect

    Flikweert, A.J.; Nimalasuriya, T.; Groothuis, C.H.J.M.; Kroesen, G.M.W.; Stoffels, W.W.

    2005-10-01

    High intensity discharge lamps have a high efficiency. These lamps contain rare-earth additives (in our case dysprosium iodide) which radiate very efficiently. A problem is color separation in the lamp because of axial segregation of the rare-earth additives, caused by diffusion and convection. Here two-dimensional atomic dysprosium density profiles are measured by means of laser absorption spectroscopy; the order of magnitude of the density is 10{sup 22} m{sup -3}. The radially resolved atomic density measurements show a hollow density profile. In the outer parts of the lamp molecules dominate, while the center is depleted of dysprosium atoms due to ionization. From the axial profiles the segregation parameter is determined. It is shown that the lamp operates on the right-hand side of the Fischer curve [J. Appl. Phys. 47, 2954 (1976)], i.e., a larger convection leads to less segregation.

  14. 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.

  15. 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.

  16. Xe nanocrystals in Si studied by x-ray absorption fine structure spectroscopy

    SciTech Connect

    Faraci, Giuseppe; Pennisi, Agata R.; Zontone, Federico

    2007-07-15

    The structural configuration of Xe clusters, obtained by ion implantation in a Si matrix, has been investigated as a function of the temperature by x-ray absorption fine structure spectroscopy. In contrast with previous results, we demonstrate that an accurate analysis of the data, using high order cumulants, gives evidence of Xe fcc nanocrystals at low temperature, even in the as-implanted Si; expansion of the Xe lattice is always found as a function of the temperature, with no appreciable overpressure. We point out that a dramatic modification of these conclusions can be induced by an incorrect analysis using standard symmetrical pair distribution function G(r); for this reason, all the results were checked by x-ray diffraction measurements.

  17. [Air pollutants study by differential optical absorption spectroscopy with transmit-receive fibers].

    PubMed

    Wei, Yong-Jie; Geng, Xiao-Juan; Chen, Bo; Liu, Cui-Cui; Chen, Wen-Liang

    2013-10-01

    The differential optical absorption spectroscopy system is presented to monitor air pollutants, such as SO2, NO2, etc. The system employs a reflective telescope to collimate light source and focus absorbed light. A combined transmitting and receiving fiber bundle is set to the focus of a concave mirror. A Xenon lamp works as the light source. The light is coupled into the transmitting fiber, and then collimated by the reflective telescope system. After absorbed by the pollutants, the light is reflected by a pyramid mirror far away the telescope. Then the absorbed light is incident on the concave mirror the second time, and focused on the focal plane again. The receiving fiber induces the light which carries the information of the measured gas into a spectrometer. We can get the concentration of the pollutants by DOAS algorithm. Experimental results show that the proposed method can be adopted to measure some pollutants in air quality monitoring.

  18. Laser absorption spectroscopy diagnostics of helium metastable atoms generated in dielectric barrier discharge cryoplasmas

    NASA Astrophysics Data System (ADS)

    Urabe, Keiichiro; Muneoka, Hitoshi; Stauss, Sven; Sakai, Osamu; Terashima, Kazuo

    2015-10-01

    Cryoplasmas, which are plasmas whose gas temperatures are below room temperature (RT), have shown dynamic changes in their physical and chemical characteristics when the gas temperature in the plasmas (Tgp) was decreased from RT. In this study, we measured the temporal behavior of helium metastable (Hem) atoms generated in a parallel-plate dielectric barrier discharge at ambient gas temperatures (Tga) of 300, 100, and 14 K and with a gas density similar to atmospheric conditions by laser absorption spectroscopy. The increments of Tgp to Tga were less than 20 K. We found from the results that the Hem lifetime and maximum density become longer and larger over one order of magnitude for lower Tga. The reasons for the long Hem lifetime at low Tga are decreases in the rate coefficients of three-body Hem quenching reactions and in the amounts of molecular impurities with boiling points higher than that of He.

  19. High resolution absorption coefficients for Freon-12. [by using tunable diode laser spectroscopy

    NASA Technical Reports Server (NTRS)

    Hoell, J. M.; Bair, C. H.; Williams, B.; Harward, C.

    1979-01-01

    The ultra high resolution absorption coefficients of the Q-branch of Freon-12 obtained with tunable diode laser spectroscopy are presented. Continuous spectra are presented from 1155/cm to 1163/cm, and absolute wavelength calibration was obtained using SO2 spectra as a standard and a 5 cm Ge etalon for relative calibration between SO2 lines. The Freon-12 data obtained at a pressure of 0.05 torr showed a rich and highly structured spectra, but with the exception of three isolated features, collisional broadening reduces the spectra to a structureless continuum for nitrogen pressures greater than 20 torr. The spectra at 1161/cm continue to exhibit structure at atmospheric pressure.

  20. 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.