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Sample records for molecular laser isotope

  1. Laser Ablation Molecular Isotopic Spectrometry

    NASA Astrophysics Data System (ADS)

    Russo, Richard E.; Bol'shakov, Alexander A.; Mao, Xianglei; McKay, Christopher P.; Perry, Dale L.; Sorkhabi, Osman

    2011-02-01

    A new method of performing optical isotopic analysis of condensed samples in ambient air and at ambient pressure has been developed: Laser Ablation Molecular Isotopic Spectrometry (LAMIS). The technique uses radiative transitions from molecular species either directly vaporized from a sample or formed by associative mechanisms of atoms or ions in a laser ablation plume. This method is an advanced modification of a known atomic emission technique called laser-induced breakdown spectroscopy (LIBS). The new method — LAMIS — can determine not only chemical composition but also isotopic ratios of elements in the sample. Isotopic measurements are enabled by significantly larger isotopic shifts found in molecular spectra relative to atomic spectra. Analysis can be performed from a distance and in real time. No sample preparation or pre-treatment is required. Detection of the isotopes of hydrogen, boron, carbon, and oxygen are discussed to illustrate the technique.

  2. Laser Ablation Molecular Isotopic Spectrometry: Strontium and its isotopes

    NASA Astrophysics Data System (ADS)

    Mao, Xianglei; Bol'shakov, Alexander A.; Choi, Inhee; McKay, Christopher P.; Perry, Dale L.; Sorkhabi, Osman; Russo, Richard E.

    2011-11-01

    The experimental details are reported of Laser Ablation Molecular Isotopic Spectrometry (LAMIS) and its application for performing optical isotopic analysis of solid strontium-containing samples in ambient atmospheric air at normal pressure. The LAMIS detection method is described for strontium isotopes from samples of various chemical and isotopic compositions. The results demonstrate spectrally resolved measurements of the three individual 86Sr, 87Sr, and 88Sr isotopes that are quantified using multivariate calibration of spectra. The observed isotopic shifts are consistent with those calculated theoretically. The measured spectra of diatomic oxide and halides of strontium generated in laser ablation plasmas demonstrate the isotopic resolution and capability of LAMIS. In particular, emission spectra of SrO and SrF molecular radicals provided clean and well resolved spectral signatures for the naturally occurring strontium isotopes. A possibility is discussed of using LAMIS of strontium isotopes for radiogenic age determination.

  3. Laser ablation molecular isotopic spectrometry of carbon isotopes

    NASA Astrophysics Data System (ADS)

    Bol‧shakov, Alexander A.; Mao, Xianglei; Jain, Jinesh; McIntyre, Dustin L.; Russo, Richard E.

    2015-11-01

    Quantitative determination of carbon isotopes using Laser Ablation Molecular Isotopic Spectrometry (LAMIS) is described. Optical emission of diatomic molecules CN and C2 is used in these measurements. Two quantification approaches are presented: empirical calibration of spectra using a set of reference standards and numerical fitting of a simulated spectrum to the experimental one. Formation mechanisms of C2 and CN in laser ablation plasma are briefly reviewed to provide insights for implementation of LAMIS measurements. A simulated spectrum of the 12C2 Swan system was synthesized using four constituents within 473.5-476.5 nm. Simulation included three branches of 12C2 (1-0), branches R(0-0) and R(1-1), and branch P(9-8) of 12C2. Spectral positions of the tail lines in R(0-0) and R(1-1) were experimentally measured, since they were not accurately known before. The Swan band (1-0) of the isotopologue 13C12C was also simulated. Fitting to the experimental spectrum yielded the ratio 13C/12C = 1.08% in a good agreement with measurements by isotope ratio mass spectrometry. LAMIS promises to be useful in coal, oil and shale exploration, carbon sequestration monitoring, and agronomy studies.

  4. Carbon isotope separation and molecular formation in laser-induced plasmas by laser ablation molecular isotopic spectrometry.

    PubMed

    Dong, Meirong; Mao, Xianglei; Gonzalez, Jhanis J; Lu, Jidong; Russo, Richard E

    2013-03-05

    Laser ablation molecular isotopic spectrometry (LAMIS) recently was reported for rapid isotopic analysis by measuring molecular emission from laser-induced plasmas at atmospheric pressure. This research utilized the LAMIS approach to study C2 molecular formation from laser ablation of carbon isotopic samples in a neon gas environment at 0.1 MPa. The isotopic shift for the Swan system of the C2 Δν = 1 band was chosen for carbon isotope analysis. Temporal and spatial resolved measurements of (12)C2, (12)C(13)C, and (13)C2 show that C2 forms from recombination reactions in the plasma. A theoretical simulation was used to determine the temperature from the molecular bands and to extract the isotopic ratio of (12)C/(13)C derived from (12)C2, (12)C(13)C, and (13)C2. Our data show that the ratio of (12)C/(13)C varies with time after the laser pulse and with distance above the sample. (12)C/(13)C deviates from the nominal ratio (2:1) at early times and closest to the sample surface. These measurements provide understanding of the chemical processes in the laser plasma and analytical improvement using LAMIS.

  5. Mid-IR enhanced laser ablation molecular isotopic spectrometry

    NASA Astrophysics Data System (ADS)

    Brown, Staci; Ford, Alan; Akpovo, Codjo A.; Johnson, Lewis

    2016-08-01

    A double-pulsed laser-induced breakdown spectroscopy (DP-LIBS) technique utilizing wavelengths in the mid-infrared (MIR) for the second pulse, referred to as double-pulse LAMIS (DP-LAMIS), was examined for its effect on detection limits compared to single-pulse laser ablation molecular isotopic spectrometry (LAMIS). A MIR carbon dioxide (CO2) laser pulse at 10.6 μm was employed to enhance spectral emissions from nanosecond-laser-induced plasma via mid-IR reheating and in turn, improve the determination of the relative abundance of isotopes in a sample. This technique was demonstrated on a collection of 10BO and 11BO molecular spectra created from enriched boric acid (H3BO3) isotopologues in varying concentrations. Effects on the overall ability of both LAMIS and DP-LAMIS to detect the relative abundance of boron isotopes in a starting sample were considered. Least-squares fitting to theoretical models was used to deduce plasma parameters and understand reproducibility of results. Furthermore, some optimization for conditions of the enhanced emission was achieved, along with a comparison of the overall emission intensity, plasma density, and plasma temperature generated by the two techniques.

  6. CO2 TEA Laser-Enhanced Laser Ablation Molecular Isotopic Spectrometry (TELLAMIS)

    NASA Astrophysics Data System (ADS)

    Brown, Staci R.; Akpovo, Charlemagne A.; Ford, Alan; Herbert, Kenley; Johnson, Lewis

    2014-03-01

    Recently, it has been shown that the relative abundance of isotopes in enriched materials can be determined via laser-induced breakdown spectroscopy (LIBS) in a technique known as laser-ablation molecular isotopic spectroscopy (LAMIS). The original LAMIS work has focused on single-pulse (SP) LIBS for the excitation. However, dual-pulse (DP) LIBS reduces shot-to-shot variation and can lower detection limits of an element by about an order of magnitude or more. It also has the potential to improve the accuracy of the determination of the relative abundances of isotopes in LAMIS by minimizing the signal-to-noise ratio. In this work, a DP-LIBS technique for improving LAMIS relative-abundance information from a sample is presented. The new technique, called (TEA) Transverse-Excited breakdown in Atmosphere Laser-Enhanced Laser Ablation Molecular Isotopic Spectrometry (TELLAMIS), uses a carbon dioxide (CO2) laser to increase the breakdown emission from LIBS in the LAMIS method. This technique is demonstrated on a collection of relative abundance isotopes of boron- 10 and boron-11 in varying concentrations in boric acid. Least-squares fitting to theoretical models are used to deduce plasma parameters and understand reproducibility of results. DTRA.

  7. Standoff Detection of Uranium and its Isotopes by Femtosecond Filament Laser Ablation Molecular Isotopic Spectrometry

    PubMed Central

    Hartig, Kyle C.; Ghebregziabher, Isaac; Jovanovic, Igor

    2017-01-01

    The ability to perform not only elementally but also isotopically sensitive detection and analysis at standoff distances is impor-tant for remote sensing applications in diverse ares, such as nuclear nonproliferation, environmental monitoring, geophysics, and planetary science. We demonstrate isotopically sensitive real-time standoff detection of uranium by the use of femtosecond filament-induced laser ablation molecular isotopic spectrometry. A uranium oxide molecular emission isotope shift of 0.05 ± 0.007 nm is reported at 593.6 nm. We implement both spectroscopic and acoustic diagnostics to characterize the properties of uranium plasma generated at different filament-uranium interaction points. The resulting uranium oxide emis-sion exhibits a nearly constant signal-to-background ratio over the length of the filament, unlike the uranium atomic and ionic emission, for which the signal-to-background ratio varies significantly along the filament propagation. This is explained by the different rates of increase of plasma density and uranium oxide density along the filament length resulting from spectral and temporal evolution of the filament along its propagation. The results provide a basis for the optimal use of filaments for standoff detection and analysis of uranium isotopes and indicate the potential of the technique for a wider range of remote sensing applications that require isotopic sensitivity. PMID:28272450

  8. Standoff Detection of Uranium and its Isotopes by Femtosecond Filament Laser Ablation Molecular Isotopic Spectrometry

    NASA Astrophysics Data System (ADS)

    Hartig, Kyle C.; Ghebregziabher, Isaac; Jovanovic, Igor

    2017-03-01

    The ability to perform not only elementally but also isotopically sensitive detection and analysis at standoff distances is impor-tant for remote sensing applications in diverse ares, such as nuclear nonproliferation, environmental monitoring, geophysics, and planetary science. We demonstrate isotopically sensitive real-time standoff detection of uranium by the use of femtosecond filament-induced laser ablation molecular isotopic spectrometry. A uranium oxide molecular emission isotope shift of 0.05 ± 0.007 nm is reported at 593.6 nm. We implement both spectroscopic and acoustic diagnostics to characterize the properties of uranium plasma generated at different filament-uranium interaction points. The resulting uranium oxide emis-sion exhibits a nearly constant signal-to-background ratio over the length of the filament, unlike the uranium atomic and ionic emission, for which the signal-to-background ratio varies significantly along the filament propagation. This is explained by the different rates of increase of plasma density and uranium oxide density along the filament length resulting from spectral and temporal evolution of the filament along its propagation. The results provide a basis for the optimal use of filaments for standoff detection and analysis of uranium isotopes and indicate the potential of the technique for a wider range of remote sensing applications that require isotopic sensitivity.

  9. Standoff Detection of Uranium and its Isotopes by Femtosecond Filament Laser Ablation Molecular Isotopic Spectrometry.

    PubMed

    Hartig, Kyle C; Ghebregziabher, Isaac; Jovanovic, Igor

    2017-03-08

    The ability to perform not only elementally but also isotopically sensitive detection and analysis at standoff distances is impor-tant for remote sensing applications in diverse ares, such as nuclear nonproliferation, environmental monitoring, geophysics, and planetary science. We demonstrate isotopically sensitive real-time standoff detection of uranium by the use of femtosecond filament-induced laser ablation molecular isotopic spectrometry. A uranium oxide molecular emission isotope shift of 0.05 ± 0.007 nm is reported at 593.6 nm. We implement both spectroscopic and acoustic diagnostics to characterize the properties of uranium plasma generated at different filament-uranium interaction points. The resulting uranium oxide emis-sion exhibits a nearly constant signal-to-background ratio over the length of the filament, unlike the uranium atomic and ionic emission, for which the signal-to-background ratio varies significantly along the filament propagation. This is explained by the different rates of increase of plasma density and uranium oxide density along the filament length resulting from spectral and temporal evolution of the filament along its propagation. The results provide a basis for the optimal use of filaments for standoff detection and analysis of uranium isotopes and indicate the potential of the technique for a wider range of remote sensing applications that require isotopic sensitivity.

  10. Matrix Effects on Boron Containing Materials due to Laser Ablation Molecular Isotopic Spectrometry (LAMIS)

    NASA Astrophysics Data System (ADS)

    Brown, Staci R.; Akpovo, Charlemagne A.; Martinez, Jorge; Ford, Alan; Herbert, Kenley; Johnson, Lewis

    2014-03-01

    Laser Induced Breakdown Spectroscopy (LIBS) is a spectroscopic technique that is used for the qualitative and quantitative analysis of materials in the liquid, solid, or gas phase. LIBS can also be used for the detection of isotopic shifts in atomic and diatomic species via Laser-Ablation Molecular Isotopic Spectroscopy (LAMIS). However, any additional elements that are entrained into the plasma other than the element of interest, can affect the extent of ablation and quality of spectra and hence, potentially obscure or aid in the relative abundance assessment for a given element. To address the importance of matrix effects, the isotopic analysis of boron obtained from boron oxide (BO) emission originating from different boron-containing compounds, such as boron nitride (BN), boric acid (H3BO3) , and borax (Na2B4O710H2O), via LIBS has been performed here. Each of these materials has different physical properties and elemental composition in order to illustrate possible challenges for the LAMIS method. A calibration-free model similar to that for the original LAMIS work is used to determine properties of the plasma as the matrix is changed. DTRA

  11. Laser isotope separation

    DOEpatents

    Robinson, C.P.; Reed, J.J.; Cotter, T.P.; Boyer, K.; Greiner, N.R.

    1975-11-26

    A process and apparatus for separating isotopes by selective excitation of isotopic species of a volatile compound by tuned laser light is described. A highly cooled gas of the volatile compound is produced in which the isotopic shift is sharpened and defined. Before substantial condensation occurs, the cooled gas is irradiated with laser light precisely tuned to a desired wavelength to selectively excite a particular isotopic species in the cooled gas. The laser light may impart sufficient energy to the excited species to cause it to undergo photolysis, photochemical reaction or even to photoionize. Alternatively, a two-photon irradiation may be applied to the cooled gas to induce photolysis, photochemical reaction or photoionization. The process is particularly applicable to the separation of isotopes of uranium.

  12. Laser isotope separation

    DOEpatents

    Robinson, C. Paul; Jensen, Reed J.; Cotter, Theodore P.; Boyer, Keith; Greiner, Norman R.

    1988-01-01

    A process and apparatus for separating isotopes by selective excitation of isotopic species of a volatile compound by tuned laser light. A highly cooled gas of the volatile compound is produced in which the isotopic shift is sharpened and defined. Before substantial condensation occurs, the cooled gas is irradiated with laser light precisely tuned to a desired wavelength to selectively excite a particular isotopic species in the cooled gas. The laser light may impart sufficient energy to the excited species to cause it to undergo photolysis, photochemical reaction or even to photoionize. Alternatively, a two-photon irradiation may be applied to the cooled gas to induce photolysis, photochemical reaction or photoionization. The process is particularly applicable to the separation of isotopes of uranium.

  13. Stable isotope analysis of molecular oxygen from silicates and oxides using CO2 laser extraction

    NASA Technical Reports Server (NTRS)

    Perry, Eugene

    1996-01-01

    A laser-excited system for determination of the oxygen isotope composition of small quantities of silicate and oxide minerals was constructed and tested at JSC. This device is the first reported to use a commercially available helium cryostat to transfer and purify oxygen gas quantitatively within the system. The system uses oxygen gas instead of the conventional CO2 for mass spectrometer analyses. This modification of technique permits determination of all three stable oxygen isotopes, an essential requirement for oxygen isotope analysis of meteoritic material. Tests of the system included analysis of standard silicate materials NBS 28 and UWMG2 garnet, six SNC meteorites, and inclusions and chondrules from the Allende meteorite. Calibration with terrestrial standards was excellent. Meteorite values are close to published values and show no evidence of terrestrial oxygen contamination. The one limitation observed is that, in some runs on fine-grained SNC matrix material, sample results were affected by other samples in the sample holder within the reaction chamber. This reemphasizes the need for special precautions in dealing with fine-grained, reactive samples. Performance of the JSC instrument compares favorably with that of any other instrument currently producing published oxygen isotope data.

  14. Selective IR multiphoton dissociation of molecules in a pulsed gas-dynamically cooled molecular flow interacting with a solid surface as an alternative to low-energy methods of molecular laser isotope separation

    NASA Astrophysics Data System (ADS)

    Makarov, G. N.; Petin, A. N.

    2016-03-01

    We report the results of studies on the isotope-selective infrared multiphoton dissociation (IR MFD) of SF6 and CF3I molecules in a pulsed, gas-dynamically cooled molecular flow interacting with a solid surface. The productivity of this method in the conditions of a specific experiment (by the example of SF6 molecules) is evaluated. A number of low-energy methods of molecular laser isotope separation based on the use of infrared lasers for selective excitation of molecules are analysed and their productivity is estimated. The methods are compared with those of selective dissociation of molecules in the flow interacting with a surface. The advantages of this method compared to the low-energy methods of molecular laser isotope separation and the IR MPD method in the unperturbed jets and flows are shown. It is concluded that this method could be a promising alternative to the low-energy methods of molecular laser isotope separation.

  15. Laser isotope separation by multiple photon absorption

    DOEpatents

    Robinson, C.P.; Rockwood, S.D.; Jensen, R.J.; Lyman, J.L.; Aldridge, J.P. III.

    1987-04-07

    Multiple photon absorption from an intense beam of infrared laser light may be used to induce selective chemical reactions in molecular species which result in isotope separation or enrichment. The molecular species must have a sufficient density of vibrational states in its vibrational manifold that, is the presence of sufficiently intense infrared laser light tuned to selectively excite only those molecules containing a particular isotope, multiple photon absorption can occur. By this technique, for example, intense CO[sub 2] laser light may be used to highly enrich [sup 34]S in natural SF[sub 6] and [sup 11]B in natural BCl[sub 3]. 8 figs.

  16. Laser isotope separation by multiple photon absorption

    DOEpatents

    Robinson, C. Paul; Rockwood, Stephen D.; Jensen, Reed J.; Lyman, John L.; Aldridge, III, Jack P.

    1987-01-01

    Multiple photon absorption from an intense beam of infrared laser light may be used to induce selective chemical reactions in molecular species which result in isotope separation or enrichment. The molecular species must have a sufficient density of vibrational states in its vibrational manifold that, is the presence of sufficiently intense infrared laser light tuned to selectively excite only those molecules containing a particular isotope, multiple photon absorption can occur. By this technique, for example, intense CO.sub.2 laser light may be used to highly enrich .sup.34 S in natural SF.sub.6 and .sup.11 B in natural BCl.sub.3.

  17. Laser isotope separation by multiple photon absorption

    DOEpatents

    Robinson, C. Paul; Rockwood, Stephen D.; Jensen, Reed J.; Lyman, John L.; Aldridge, III, Jack P.

    1977-01-01

    Multiple photon absorption from an intense beam of infrared laser light may be used to induce selective chemical reactions in molecular species which result in isotope separation or enrichment. The molecular species must have a sufficient density of vibrational states in its vibrational manifold that, in the presence of sufficiently intense infrared laser light tuned to selectively excite only those molecules containing a particular isotope, multiple photon absorption can occur. By this technique, for example, intense CO.sub.2 laser light may be used to highly enrich .sup.34 S in natural SF.sub.6 and .sup.11 B in natural BCl.sub.3.

  18. Selective IR multiphoton dissociation of molecules in a pulsed gas-dynamically cooled molecular flow interacting with a solid surface as an alternative to low-energy methods of molecular laser isotope separation

    SciTech Connect

    Makarov, G N; Petin, A N

    2016-03-31

    We report the results of studies on the isotope-selective infrared multiphoton dissociation (IR MFD) of SF{sub 6} and CF{sub 3}I molecules in a pulsed, gas-dynamically cooled molecular flow interacting with a solid surface. The productivity of this method in the conditions of a specific experiment (by the example of SF{sub 6} molecules) is evaluated. A number of low-energy methods of molecular laser isotope separation based on the use of infrared lasers for selective excitation of molecules are analysed and their productivity is estimated. The methods are compared with those of selective dissociation of molecules in the flow interacting with a surface. The advantages of this method compared to the low-energy methods of molecular laser isotope separation and the IR MPD method in the unperturbed jets and flows are shown. It is concluded that this method could be a promising alternative to the low-energy methods of molecular laser isotope separation. (laser separation of isotopes)

  19. Isotope separation by laser means

    DOEpatents

    Robinson, C. Paul; Jensen, Reed J.; Cotter, Theodore P.; Greiner, Norman R.; Boyer, Keith

    1982-06-15

    A process for separating isotopes by selective excitation of isotopic species of a volatile compound by tuned laser light. A highly cooled gas of the volatile compound is produced in which the isotopic shift is sharpened and defined. Before substantial condensation occurs, the cooled gas is irradiated with laser light precisely tuned to a desired wavelength to selectively excite a particular isotopic species in the cooled gas. The laser light may impart sufficient energy to the excited species to cause it to undergo photochemical reaction or even to photoionize. Alternatively, a two-photon irradiation may be applied to the cooled gas to induce photochemical reaction or photoionization. The process is particularly applicable to the separation of isotopes of uranium and plutonium.

  20. Laser Isotope Separation Employing Condensation Repression

    SciTech Connect

    Eerkens, Jeff W.; Miller, William H.

    2004-09-15

    Molecular laser isotope separation (MLIS) techniques using condensation repression (CR) harvesting are reviewed and compared with atomic vapor laser isotope separation (AVLIS), gaseous diffusion (DIF), ultracentrifuges (UCF), and electromagnetic separations (EMS). Two different CR-MLIS or CRISLA (Condensation Repression Isotope Separation by Laser Activation) approaches have been under investigation at the University of Missouri (MU), one involving supersonic super-cooled free jets and dimer formation, and the other subsonic cold-wall condensation. Both employ mixtures of an isotopomer (e.g. {sup i}QF{sub 6}) and a carrier gas, operated at low temperatures and pressures. Present theories of VT relaxation, dimerization, and condensation are found to be unsatisfactory to explain/predict experimental CRISLA results. They were replaced by fundamentally new models that allow ab-initio calculation of isotope enrichments and predictions of condensation parameters for laser-excited and non-excited vapors which are in good agreement with experiment. Because of supersonic speeds, throughputs for free-jet CRISLA are a thousand times higher than cold-wall CRISLA schemes, and thus preferred for large-quantity Uranium enrichments. For small-quantity separations of (radioactive) medical isotopes, the simpler coldwall CRISLA method may be adequate.

  1. Laser system for isotope separation

    NASA Astrophysics Data System (ADS)

    Shirayama, Shimpey; Mikatsura, Takefumi; Ueda, Hiroaki; Konagai, Chikara

    1990-06-01

    Atomic vapor laser isotope separation (AVLIS) is regarded as the most promising method to obtain srightly enriched economical nuclear fuel for a nuclear power plant. However, achieving a high power laser seems to be the bottle neck in its industrialization. In 1985, after successful development of high power lasers, the U.S. announced that AVLIS would be used for future methods of uranium enrichment. In Japan , Laser Atomic Separation Enrichment Research Associates of Japan (LASER-J), a joint Japanese utility companies research organization, was founded in April, 1987, to push a development program for laser uranium enrichment. Based on research results obtained from Japanese National Labs, and Universities , Laser-J is now constructing an AVLIS experimental facility at Tokai-mura. It is planned to have a 1-ton swu capacity per year in 1991. Previous to the experimental facility construction , Toshiba proceeded with the preliminary testing of an isotope separation system, under contract with Laser-J. Since the copper vapor laser (CVL) and the dye laser (DL) form a good combination , which can obtain high power tunable visible lights ,it is suitable to resonate uranium atoms. The laser system was built and was successfully operated in Toshiba for two years. The system consist of three copper vapor lasers , three dye lasers and appropriate o Atomic vapor laser isotope separation (AVLIS) is regarded as the most promising method to obtain srightly enriched economical nuclear fuel for a nuclear power plant. However, achieving a high power laser seems to be the bottle neck in its industrialization. In 1985, after successful development of high power lasers, the U.S. announced that AVLIS would be used for future methods of uranium enrichment. In Japan , Laser Atomic Separation Enrichment Research Associates of Japan (LASER-J) , a joint Japanese utility companies research organization , was founded in April, 1987, to push a development program for laser uranium enrichment

  2. Lasers utilizing CO2 isotopes

    NASA Astrophysics Data System (ADS)

    Pechenin, Yu V.; Domanov, M. S.

    1980-08-01

    The lasing spectra and energy characteristics were investigated for lasers operating with the isotopes 12C16O2, 13C16O2, 12C18O2, and 12C16O18O. It was found that the output power of a laser utilizing the CO2 isotopes was determined by the content of a particular isotope in the carbon dioxide gas. For equal enrichments, all the isotopes investigated, with the exception of 12C16O18O, gave comparable output powers. The unsaturated gains were identical for the most intense transitions of the symmetric molecules; the gain was a factor of two less for the asymmetric molecule. The gain rose linearly with increasing enrichment. The ultimate specific power output, given by the product of the saturation power density and the gain, was practically independent of the enrichment.

  3. Reduction of spectral interferences and noise effects in laser ablation molecular isotopic spectrometry with partial least square regression - a computer simulation study

    NASA Astrophysics Data System (ADS)

    Mao, Xianglei; Chan, George C.-Y.; Zorba, Vassilia; Russo, Richard E.

    2016-08-01

    The fundamental analytical accuracies and precisions attainable by laser ablation molecular isotopic spectrometry (LAMIS), with emphasis on the impacts from spectral interferences and measurement noise, were investigated by means of computer simulation. The study focused on the analysis of a minor isotope at sub- to single-percentage abundance level. With a natural abundance about 1.1% for 13C, the C2 Swan band (d3Πg-a3Πu) with Δν = + 1 was selected as a representative system. The characteristics (e.g., noise amplitude and distribution, signal strength, and signal-to-background ratio) of the simulated spectra were experimentally characterized. Partial least square (PLS) regression was used to extract isotopic information from the simulated molecular spectra. In the absence of any spectral interference and with the use of a calibration set consisting of eleven isotopic standards, the theoretical accuracies and precisions with signal accumulation from 100 laser shots are about 0.002% and 0.001%, respectively, in absolute percentage abundance of 13C. The theoretical analytical accuracies slightly degrade, but are adequate for many applications, to 0.004% and 0.008% respectively, for calibrations involving only three and two isotopic standards. It was found that PLS regression is not only immune to both source-flicker and photon-shot noise, but is also effective in differentiating the spectral patterns from the analyte against those from spectral interferences. The influences of spectral interference from single or multiple atomic emission lines were simulated, and new ways to minimize their impacts were formulated and demonstrated. It was found that the wavelength range selected for the computation of the normalization factor should not contain any spectral-interfering peak, and a properly chosen wavelength range increases the tolerance of spectral interference by at least one order of magnitude. With matrix-matched calibration standards, the precisions (expressed

  4. Atomic vapor laser isotope separation process

    DOEpatents

    Wyeth, R.W.; Paisner, J.A.; Story, T.

    1990-08-21

    A laser spectroscopy system is utilized in an atomic vapor laser isotope separation process. The system determines spectral components of an atomic vapor utilizing a laser heterodyne technique. 23 figs.

  5. Lasers utilizing CO2 isotopes

    NASA Astrophysics Data System (ADS)

    Pechenin, Iu. V.; Domanov, M. S.

    1980-08-01

    The emission spectra and power characteristics of CW (C-12)(O-16)2, (C-13)(O-16)2, (C-12)(O-16)(O-18)2 and (C-12)(O-18) lasers are investigated. Laser output power is found to depend equally on the proportion of carbon and oxygen isotopes in the active medium for all isotopes except the asymmetrical (C-12)(O-16)(O-18), in which maximum output power is four to five times less due to the doubling of emission lines and limited enrichment caused by recombination into (C-12)(O-16)2 and (C-12)(O-18)2 molecules during discharge. The unsaturated gain is observed to increase linearly with enrichment, with that of nonsymmetrical molecules half that of the symmetrical molecules, while the maximum power output is independent of enrichment.

  6. Method for laser induced isotope enrichment

    DOEpatents

    Pronko, Peter P.; Vanrompay, Paul A.; Zhang, Zhiyu

    2004-09-07

    Methods for separating isotopes or chemical species of an element and causing enrichment of a desired isotope or chemical species of an element utilizing laser ablation plasmas to modify or fabricate a material containing such isotopes or chemical species are provided. This invention may be used for a wide variety of materials which contain elements having different isotopes or chemical species.

  7. Handbook of molecular lasers

    NASA Astrophysics Data System (ADS)

    Cheo, Peter K.

    The technology and applications of molecular lasers (MLs) are examined in chapters contributed by leading experts. Topics addressed include ML emission spectra, CO2 TEA lasers, RF-discharge-excited CO2 lasers, high-energy short-pulse CO2 lasers, high-power electron-beam-controlled CO2 lasers, HF/DF chemical lasers, optically pumped FIR MLs, and transients and instabilities in FIR MLs. Extensive diagrams, drawings, graphs, photographs, and tables of numerical data are provided.

  8. Atomic vapor laser isotope separation

    SciTech Connect

    Stern, R.C.; Paisner, J.A.

    1985-11-08

    Atomic vapor laser isotope separation (AVLIS) is a general and powerful technique. A major present application to the enrichment of uranium for light-water power reactor fuel has been under development for over 10 years. In June 1985 the Department of Energy announced the selection of AVLIS as the technology to meet the nation's future need for the internationally competitive production of uranium separative work. The economic basis for this decision is considered, with an indicated of the constraints placed on the process figures of merit and the process laser system. We then trace an atom through a generic AVLIS separator and give examples of the physical steps encountered, the models used to describe the process physics, the fundamental parameters involved, and the role of diagnostic laser measurements.

  9. Laser isotope separation of erbium and other isotopes

    DOEpatents

    Haynam, Christopher A.; Worden, Earl F.

    1995-01-01

    Laser isotope separation is accomplished using at least two photoionization pathways of an isotope simultaneously, where each pathway comprises two or more transition steps. This separation method has been applied to the selective photoionization of erbium isotopes, particularly for the enrichment of .sup.167 Er. The hyperfine structure of .sup.167 Er was used to find two three-step photoionization pathways having a common upper energy level.

  10. Laser isotope separation of erbium and other isotopes

    DOEpatents

    Haynam, C.A.; Worden, E.F.

    1995-08-22

    Laser isotope separation is accomplished using at least two photoionization pathways of an isotope simultaneously, where each pathway comprises two or more transition steps. This separation method has been applied to the selective photoionization of erbium isotopes, particularly for the enrichment of {sup 167}Er. The hyperfine structure of {sup 167}Er was used to find two three-step photoionization pathways having a common upper energy level. 3 figs.

  11. Possible application of laser isotope separation

    NASA Technical Reports Server (NTRS)

    Delionback, L. M.

    1975-01-01

    The laser isotope separation process is described and its special economic features discussed. These features are its low cost electric power operation, capital investment costs, and the costs of process materials.

  12. Carbon isotope controlled molecular switches

    NASA Astrophysics Data System (ADS)

    Foster, Brian K.

    Single molecules represent one fundamental limit to the downscaling of electronics. As a prototype element for carbon-based nanoscale science and technology, the detailed behavior of carbon monoxide (CO) on the copper surface Cu(111) has been investigated. These investigations span from individual carbon isotope resolution, to single molecules, to compact clusters assembled by molecular manipulation via a homemade scanning tunneling microscope (STM). Sub-nanoscale devices, composed of only a few molecules, which exploit both lone CO properties and molecule-molecule interaction, have been designed and assembled. The devices function as bi-stable switches and can serve as classical bits with densities > 50 Tbits/cm2. Operated in the nuclear mass sensitive regime, each switch can also function as a molecular "centrifuge" capable of identifying the isotope of a single carbon atom in real-time. A model, based on electron-vibron couping and inelastic tunneling, has been developed and explains the dynamic behavior of the switch. The interaction between pairs of switches was also explored and it was found that their behavior ranges from completely independent to strongly coupled. Larger nanostructures, which were composed of many sub-switches organized to leverage the fully coupled interaction, link two spatially separated "bits" on the surface. Such a linked system can set or read a state non-locally, which is equivalent to bidirectional information transfer. The linked system has also exhibited logic functionality. These experiments demonstrate scalable molecular cells for information storage, and for information processing through cellular automata logic schemes.

  13. Ion laser isotope enrichment by photo-predissociation of formaldehyde

    DOEpatents

    Marling, John B.

    1977-06-17

    Enrichment of carbon, hydrogen and/or oxygen isotopes by means of isotopically selective photo-predissociation of formaldehyde is achieved by irradiation with a fixed frequency ion laser, specifically, a neon, cadmium, or xenon ion laser.

  14. Atomic vapor laser isotope separation of lead-210 isotope

    DOEpatents

    Scheibner, Karl F.; Haynam, Christopher A.; Johnson, Michael A.; Worden, Earl F.

    1999-01-01

    An isotopically selective laser process and apparatus for removal of Pb-210 from natural lead that involves a one-photon near-resonant, two-photon resonant excitation of one or more Rydberg levels, followed by field ionization and then electrostatic extraction. The wavelength to the near-resonant intermediate state is counter propagated with respect to the second wavelength required to populate the final Rydberg state. This scheme takes advantage of the large first excited state cross section, and only modest laser fluences are required. The non-resonant process helps to avoid two problems: first, stimulated Raman Gain due to the nearby F=3/2 hyperfine component of Pb-207 and, second, direct absorption of the first transition process light by Pb-207.

  15. Atomic vapor laser isotope separation of lead-210 isotope

    SciTech Connect

    Scheibner, K.F.; Haynam, C.A.; Johnson, M.A.; Worden, E.F.

    1999-08-31

    An isotopically selective laser process and apparatus for removal of Pb-210 from natural lead that involves a one-photon near-resonant, two-photon resonant excitation of one or more Rydberg levels, followed by field ionization and then electrostatic extraction. The wavelength to the near-resonant intermediate state is counter propagated with respect to the second wavelength required to populate the final Rydberg state. This scheme takes advantage of the large first excited state cross section, and only modest laser fluences are required. The non-resonant process helps to avoid two problems: first, stimulated Raman Gain due to the nearby F=3/2 hyperfine component of Pb-207 and, second, direct absorption of the first transition process light by Pb-207. 5 figs.

  16. Optically pumped isotopic ammonia laser system

    DOEpatents

    Buchwald, Melvin I.; Jones, Claude R.; Nelson, Leonard Y.

    1982-01-01

    An optically pumped isotopic ammonia laser system which is capable of producing a plurality of frequencies in the middle infrared spectral region. Two optical pumping mechanisms are disclosed, i.e., pumping on R(J) and lasing on P(J) in response to enhancement of rotational cascade lasing including stimulated Raman effects, and, pumping on R(J) and lasing on P(J+2). The disclosed apparatus for optical pumping include a hole coupled cavity and a grating coupled cavity.

  17. Laser-assisted isotope separation of tritium

    DOEpatents

    Herman, Irving P.; Marling, Jack B.

    1983-01-01

    Methods for laser-assisted isotope separation of tritium, using infrared multiple photon dissociation of tritium-bearing products in the gas phase. One such process involves the steps of (1) catalytic exchange of a deuterium-bearing molecule XYD with tritiated water DTO from sources such as a heavy water fission reactor, to produce the tritium-bearing working molecules XYT and (2) photoselective dissociation of XYT to form a tritium-rich product. By an analogous procedure, tritium is separated from tritium-bearing materials that contain predominately hydrogen such as a light water coolant from fission or fusion reactors.

  18. Laser spectroscopic measurement of helium isotope ratios.

    SciTech Connect

    Wang, L.-B.; Mueller, P.; Holt, R. J.; Lu, Z.-T.; O'Connor, T. P.; Sano, Y.; Sturchio, N.; Univ. of Illinois; Univ. of Tokyo; Univ. of Illinois at Chicago

    2003-06-13

    A sensitive laser spectroscopic method has been applied to the quantitative determination of the isotope ratio of helium at the level of {sup 3}He/{sup 4}He = 10{sup -7}--10{sup -5}. The resonant absorption of 1083 nm laser light by the metastable {sup 3}He atoms in a discharge cell was measured with the frequency modulation saturation spectroscopy technique while the abundance of {sup 4}He was measured by a direct absorption technique. The results on three different samples extracted from the atmosphere and commercial helium gas were in good agreement with values obtained with mass spectrometry. The achieved 3{sigma} detection limit of {sup 3}He in helium is 4 x 10{sup -9}. This demonstration required a 200 {mu}L STP sample of He. The sensitivity can be further improved, and the required sample size reduced, by several orders of magnitude with the addition of cavity enhanced spectroscopy.

  19. Carbon Isotope Chemistry in Molecular Clouds

    NASA Technical Reports Server (NTRS)

    Robertson, Amy N.; Willacy, Karen

    2012-01-01

    Few details of carbon isotope chemistry are known, especially the chemical processes that occur in astronomical environments like molecular clouds. Observational evidence shows that the C-12/C-13 abundance ratios vary due to the location of the C-13 atom within the molecular structure. The different abundances are a result of the diverse formation pathways that can occur. Modeling can be used to explore the production pathways of carbon molecules in an effort to understand and explain the chemical evolution of molecular clouds.

  20. Isotope shifts in spectra of molecular liquids

    NASA Astrophysics Data System (ADS)

    Dubrovskaya, E. V.; Kolomiitsova, T. D.; Shurukhina, A. V.; Shchepkin, D. N.

    2016-02-01

    In the IR absorption spectra of low-temperature molecular liquids, we have observed anomalously large isotope shifts of frequencies of vibrational bands that are strong in the dipole absorption. The same effect has also been observed in their Raman spectra. At the same time, in the spectra of cryosolutions, the isotope shifts of the same bands coincide with a high accuracy (±(0.1-0.5) cm-1) with the shifts that are observed in the spectra of the gas phase. The difference between the spectra of examined low-temperature systems is caused by the occurrence of resonant dipole-dipole interactions between spectrally active identical molecules. The calculation of the band contour in the spectrum of liquid freon that we have performed in this work taking into account the resonant interaction between states of simultaneous transitions in isotopically substituted molecules can explain this effect.

  1. Laser Isotope Enrichment for Medical and Industrial Applications

    SciTech Connect

    Leonard Bond

    2006-07-01

    Laser Isotope Enrichment for Medical and Industrial Applications by Jeff Eerkens (University of Missouri), Jay Kunze (Idaho State University), and Leonard Bond (Idaho National Laboratory) The principal isotope enrichment business in the world is the enrichment of uranium for commercial power reactor fuels. However, there are a number of other needs for separated isotopes. Some examples are: 1) Pure isotopic targets for irradiation to produce medical radioisotopes. 2) Pure isotopes for semiconductors. 3) Low neutron capture isotopes for various uses in nuclear reactors. 4) Isotopes for industrial tracer/identification applications. Examples of interest to medicine are targets to produce radio-isotopes such as S-33, Mo-98, Mo-100, W-186, Sn-112; while for MRI diagnostics, the non-radioactive Xe-129 isotope is wanted. For super-semiconductor applications some desired industrial isotopes are Si-28, Ga-69, Ge-74, Se-80, Te-128, etc. An example of a low cross section isotope for use in reactors is Zn-68 as a corrosion inhibitor material in nuclear reactor primary systems. Neutron activation of Ar isotopes is of interest in industrial tracer and diagnostic applications (e.g. oil-logging). . In the past few years there has been a sufficient supply of isotopes in common demand, because of huge Russian stockpiles produced with old electromagnetic and centrifuge separators previously used for uranium enrichment. Production of specialized isotopes in the USA has been largely accomplished using old ”calutrons” (electromagnetic separators) at Oak Ridge National Laboratory. These methods of separating isotopes are rather energy inefficient. Use of lasers for isotope separation has been considered for many decades. None of the proposed methods have attained sufficient proof of principal status to be economically attractive to pursue commercially. Some of the authors have succeeded in separating sulfur isotopes using a rather new and different method, known as condensation

  2. Atomic Beam Laser Spectrometer for In-field Isotopic Analysis

    SciTech Connect

    Castro, Alonso

    2016-06-22

    This is a powerpoint presentation for the DTRA quarterly program review that goes into detail about the atomic beam laser spectrometer for in-field isotopic analysis. The project goals are the following: analysis of post-detonation debris, determination of U and Pu isotopic composition, and fieldable prototype: < 2ft3, < 1000W.

  3. Advances in laser-based isotope ratio measurements: selected applications

    NASA Astrophysics Data System (ADS)

    Kerstel, E.; Gianfrani, L.

    2008-09-01

    Small molecules exhibit characteristic ro-vibrational transitions in the near- and mid-infrared spectral regions, which are strongly influenced by isotopic substitution. This gift of nature has made it possible to use laser spectroscopy for the accurate analysis of the isotopic composition of gaseous samples. Nowadays, laser spectroscopy is clearly recognized as a valid alternative to isotope ratio mass spectrometry. Laser-based instruments are leaving the research laboratory stage and are being used by a growing number of isotope researchers for significant advances in their own field of research. In this review article, we discuss the current status and new frontiers of research on high-sensitivity and high-precision laser spectroscopy for isotope ratio analyses. Although many of our comments will be generally applicable to laser isotope ratio analyses in molecules of environmental importance, this paper concerns itself primarily with water and carbon dioxide, two molecules that were studied extensively in our respective laboratories. A complete coverage of the field is practically not feasible in the space constraints of this issue, and in any case doomed to fail, considering the large body of work that has appeared ever since the review by Kerstel in 2004 ( Handbook of Stable Isotope Analytical Techniques, Chapt. 34, pp. 759-787).

  4. Ultratrace Uranium Fingerprinting with Isotope Selective Laser Ionization Spectrometry

    SciTech Connect

    Ziegler, Summer L.; Bushaw, Bruce A.

    2008-08-01

    Uranium isotope ratios can provide source information for tracking uranium contamination in a variety of fields, ranging from occupational bioassay to monitoring aftereffects of nuclear accidents. We describe the development of Isotope Selective Laser Ionization Spectrometry (ISLIS) for ultratrace measurement of the minor isotopes 234U, 235U, and 236U with respect to 238U. Optical isotopic selectivity in three-step excitation with single-mode continuous wave lasers is capable of measuring the minor isotopes at relative abundances below 1 ppm, and is not limited by isobaric interferences such as 235UH+ during measurement of 236U. This relative abundance limit approaches the threshold for measurement of uranium minor isotopes with conventional mass spectrometry, typically 10-7, but without mass spectrometric analysis of the laser-created ions. Uranyl nitrate standards from an international blind comparison were used to test analytical performance for different isotopic compositions and with quantities ranging from 11 ng to 10 µg total uranium. Isotopic ratio determination was demonstrated over a linear dynamic range of 7 orders of magnitude with a few percent relative precision and detection limits below 500 fg for the minor isotopes.

  5. Tunable Molecular Lasers.

    DTIC Science & Technology

    1986-09-01

    Lett. 2, 64-66 (1978). 13. R. Burnham, "Discharge pumped mercuric halide dissociation lasers," Appl. Phys. Lett. 33, 156-159 (1978). 14. W. L. Nighan...University of Illinois. The goal of this research program was two-fold: 1) to develop new sources of tunable coherent radiation in the visible and...efficiency for converting XeF radiation (X - 351 nm) into blue-green output is 23% which corresponds to a photon conversion efficiency of approximately 1/3

  6. Isotope shifts and hyperfine structure in polonium isotopes by atomic-beam laser spectroscopy

    NASA Astrophysics Data System (ADS)

    Kowalewska, D.; Bekk, K.; Göring, S.; Hanser, A.; Kälber, W.; Meisel, G.; Rebel, H.

    1991-08-01

    Laser-induced fluorescence spectroscopy in a collimated atomic beam has been applied to determine isotope shifts and the hyperfine structure of an isotopic chain of the radioactive element polonium (200Po, 202Po, 204-210Po). The relative isotope shifts show a striking similarity with results for other elements in the vicinity of Pb, even reproducing details of the odd-even staggering.

  7. Isotope separation using tuned laser and electron beam

    NASA Technical Reports Server (NTRS)

    Trajmar, Sandor (Inventor)

    1987-01-01

    The apparatus comprises means for producing an atomic beam containing the isotope of interest and other isotopes. Means are provided for producing a magnetic field traversing the path of the atomic beam of an intensity sufficient to broaden the energy domain of the various individual magnetic sublevels of the isotope of interest and having the atomic beam passing therethrough. A laser beam is produced of a frequency and polarization selected to maximize the activation of only individual magnetic sublevels of the isotope of interest with the portion of its broadened energy domain most removed from other isotopes with the stream. The laser beam is directed so as to strike the atomic beam within the magnetic field and traverse the path of the atomic beam whereby only the isotope of interest is activated by the laser beam. The apparatus further includes means for producing a collimated and high intensity beam of electrons of narrow energy distribution within the magnetic field which is aimed so as to strike the atomic beam while the atomic beam is simultaneously struck by the laser beam and at an energy level selected to ionize the activated isotope of interest but not ground state species included therewith. Deflection means are disposed in the usual manner to collect the ions.

  8. Pulsed CO laser for isotope separation of uranium

    SciTech Connect

    Baranov, Igor Y.; Koptev, Andrey V.

    2012-07-30

    This article proposes a technical solution for using a CO laser facility for the industrial separation of uranium used in the production of fuel for nuclear power plants, employing a method of laser isotope separation of uranium with condensation repression in a free jet. The laser operation with nanosecond pulse irradiation can provide an acceptable efficiency in the separating unit and a high efficiency of the laser with the wavelength of 5.3 {mu}m. In the present work we also introduce a calculation model and define the parameters of a mode-locked CO laser with a RF discharge in the supersonic stream. The average pulsed CO laser power of 3 kW is sufficient for efficient industrial isotope separation of uranium in one stage.

  9. Cost Estimate for Laser Isotope Separation for RIA

    SciTech Connect

    Scheibner, K

    2004-11-01

    Isotope enrichment of some elements is required in support of the Rare Isotope Accelerator (RIA) in order to obtain the beam intensities, source efficiencies and/or source lifetime required by RIA. The economics of using Atomic Vapor Laser Isotope Separation (AVLIS) technology as well as ElectroMagnetic (EM) separation technology has been evaluated. It is concluded that such an AVLIS would be about 10 times less expensive than a facility based on electromagnetic separation - $17 M versus $170 M. In addition, the AVLIS facility footprint would be about 10 times smaller, and operations would require about 4 years (including 2 years of startup) versus about 11 years for an EM facility.

  10. Observations of Molecular Isotope Fractionation in Prestellar Cores

    NASA Technical Reports Server (NTRS)

    Milam, Stefanie N.

    2010-01-01

    Anomalously fractionated isotopic material is found in many primitive Solar System objects, such as meteorites and comets. It has been suggested that these extreme isotope ratios, are tracers of interstellar chemistry. We will present observations of the nitrogen and carbon fractionation chemistry in dense molecular clouds, particularly in cores where sUbstantial freeze-out of molecules, namely CO, onto dust has occurred. Recent models have suggested that non-depleted species, carbon and nitrogen-rich, may undergo isotopic enhancements in these conditions. The fractionation ratios measured in different interstellar molecules will be discussed and compared to the ratios determined in molecular clouds, comets, and meteoritic material.

  11. Large Deformation Change in Iridium Isotopes from Laser Spectroscopy

    SciTech Connect

    D. Verney; L. Cabaret; J. Crawford; H.T. Duong; J. Genevey; G. Hubert; F. Ibrahim; M. Krieg; F. Le Blanc; J.K.P. Lee; G. Le Scornet; D. Lunney; J. Obert; J. Oms; J. Pinard; J.C. Putaux; B. Roussiere; J. Sauvage; V. Sebastian

    1999-12-31

    Laser spectroscopy measurements have been performed on neutron-deficient iridium isotopes. The hyperfine structure and isotope shift of the optical Ir I transition 5d{sup 7}6s{sup 2} {sup 4}F{sub 9/2} {yields}5d{sup 7}6s6p {sup 6}F{sub 11/2} have been studied for the {sup 182-189}Ir, {sup 186}Ir{sup m} and {sup 191,193}Ir isotopes. The nuclear magnetic and quadrupole moments were obtained from the hyperfine splitting measurements and the changes of the mean square charge radii from the isotope shift measurements. A large deformation change between {sup 187}Ir and {sup 186}Ir and between {sup 186}Ir{sup m} and {sup 186}Ir{sup g} has been observed.

  12. A Mass Spectrometry Study of Isotope Separation in the Laser Plume

    NASA Astrophysics Data System (ADS)

    Suen, Timothy Wu

    Accurate quantification of isotope ratios is critical for both preventing the development of illicit weapons programs in nuclear safeguards and identifying the source of smuggled material in nuclear forensics. While isotope analysis has traditionally been performed by mass spectrometry, the need for in situ measurements has prompted the development of optical techniques, such as laser-induced breakdown spectroscopy (LIBS) and laser ablation molecular isotopic spectrometry (LAMIS). These optical measurements rely on laser ablation for direct solid sampling, but several past studies have suggested that the distribution of isotopes in the ablation plume is not uniform. This study seeks to characterize isotope separation in the laser plume through the use of orthogonal-acceleration time-of-flight mass spectrometry. A silver foil was ablated with a Nd:YAG at 355 nm at an energy of 50 muJ with a spot size of 71 mum, for a fluence of 1.3 J/cm2 and an irradiance of 250 MW/cm2. Flat-plate repellers were used to sample the plume, and a temporal profile of the ions was obtained by varying the time delay on the high-voltage pulse. A spatial profile along the axis of the plume was generated by changing the position of the sample, which yielded snapshots of the isotopic composition with time. In addition, the reflectron time-of-flight system was used as an energy filter in conjunction with the repellers to sample slices of the laser plasma orthogonal to the plume axis. Mass spectrometry of the plume revealed a fast ion distribution and a slow ion distribution. Measurements taken across the entire plume showed the fast 109Ag ions slightly ahead in both space and time, causing the 107Ag fraction to drop to 0.34 at 3 mus, 4 mm from the sample surface. Although measurements centered on the near side of the plume did not show isotope separation, the slow ions on the far side of the plume included much more 109Ag than 107Ag. In addition to examining the isotope content of the ablation

  13. LLNL medical and industrial laser isotope separation: large volume, low cost production through advanced laser technologies

    SciTech Connect

    Comaskey, B.; Scheibner, K. F.; Shaw, M.; Wilder, J.

    1998-09-02

    The goal of this LDRD project was to demonstrate the technical and economical feasibility of applying laser isotope separation technology to the commercial enrichment (>lkg/y) of stable isotopes. A successful demonstration would well position the laboratory to make a credible case for the creation of an ongoing medical and industrial isotope production and development program at LLNL. Such a program would establish LLNL as a center for advanced medical isotope production, successfully leveraging previous LLNL Research and Development hardware, facilities, and knowledge.

  14. Stable Isotope Laser Spectrometer for Exploration of Mars

    NASA Technical Reports Server (NTRS)

    Sauke, Todd B.; Becker, Joseph F.

    1998-01-01

    On Earth, measurements of the ratios of stable carbon isotopes have providet much information about geological and biological processes. For example, fractionation of carbon occur in biotic processes and the retention of a distinctive 2-4% contrast in C-13/C-12 between organic carbon and carbonates in rocks as old as 3.8 billion years constitutes some of the firmest evidence for the antiquity of life on the Earth. We have developed a prototype tunable diode laser spectrometer which demonstrates the feasibility of making accurate in situ isotopic ratio measurements on Mars. This miniaturized instrument, with an optical path length of 10 cm should be capable of making accurate C-13/C-12 and N-15/N-14 measurements. Gas samples for measurement are to be produced by pyrolysis using soil samples as small as 50 mg. Measurements of C-13/C-12, O-18/O-16 and N-15/N-14 have been made to a precision of better than 0.1%, and various other isotopes are feasible. This laser technique, which relies on the extremely narrow emission linewidth of tunable diode lasers (less than 0.001/ cm),has favorable features in comparison to mass spectrometry, the standard method of accurate isotopic ratio measurement. The miniature instrument could be ready to deploy c 2003 or other Mars lander missions.

  15. Molecular Isotopic Distribution Analysis (MIDAs) with Adjustable Mass Accuracy

    NASA Astrophysics Data System (ADS)

    Alves, Gelio; Ogurtsov, Aleksey Y.; Yu, Yi-Kuo

    2014-01-01

    In this paper, we present Molecular Isotopic Distribution Analysis (MIDAs), a new software tool designed to compute molecular isotopic distributions with adjustable accuracies. MIDAs offers two algorithms, one polynomial-based and one Fourier-transform-based, both of which compute molecular isotopic distributions accurately and efficiently. The polynomial-based algorithm contains few novel aspects, whereas the Fourier-transform-based algorithm consists mainly of improvements to other existing Fourier-transform-based algorithms. We have benchmarked the performance of the two algorithms implemented in MIDAs with that of eight software packages (BRAIN, Emass, Mercury, Mercury5, NeutronCluster, Qmass, JFC, IC) using a consensus set of benchmark molecules. Under the proposed evaluation criteria, MIDAs's algorithms, JFC, and Emass compute with comparable accuracy the coarse-grained (low-resolution) isotopic distributions and are more accurate than the other software packages. For fine-grained isotopic distributions, we compared IC, MIDAs's polynomial algorithm, and MIDAs's Fourier transform algorithm. Among the three, IC and MIDAs's polynomial algorithm compute isotopic distributions that better resemble their corresponding exact fine-grained (high-resolution) isotopic distributions. MIDAs can be accessed freely through a user-friendly web-interface at http://www.ncbi.nlm.nih.gov/CBBresearch/Yu/midas/index.html.

  16. Atomic vapor laser isotope separation using resonance ionization

    SciTech Connect

    Comaskey, B.; Crane, J.; Erbert, G.; Haynam, C.; Johnson, M.; Morris, J.; Paisner, J.; Solarz, R.; Worden, E.

    1986-09-01

    Atomic vapor laser isotope separation (AVLIS) is a general and powerful technique. A major present application to the enrichment of uranium for light-water power-reactor fuel has been under development for over 10 years. In June 1985, the Department of Energy announced the selection of AVLIS as the technology to meet the nation's future need for enriched uranium. Resonance photoionization is the heart of the AVLIS process. We discuss those fundamental atomic parameters that are necessary for describing isotope-selective resonant multistep photoionization along with the measurement techniques that we use. We illustrate the methodology adopted with examples of other elements that are under study in our program.

  17. Nanoparticle Enhanced Laser Induced Breakdown Spectroscopy for Improving the Detection of Molecular Bands

    NASA Astrophysics Data System (ADS)

    Koral, Can; De Giacomo, Alessandro; Mao, Xianglei; Zorba, Vassilia; Russo, Richard E.

    2016-11-01

    Enhancement of molecular band emission in laser-induced plasmas is important for improving sensitivity and limits of detection in molecular sensing and molecular isotope analysis. In this work we introduce the use of Nanoparticle Enhanced Laser Induced Breakdown (NELIBS) for the enhancement of molecular band emission in laser-induced plasmas, and study the underlying mechanisms responsible for the observed enhancement. The use of Ag nanoparticles leads to an order of magnitude enhancement for AlO (B2Σ+ → Χ+ Σ+) system emission from an Al-based alloy. We demonstrate that the mechanism responsible for the enhancement of molecular bands differs from that of atomic emission, and can be traced down to the increased number of atomic species in NELIBS which lead to AlO molecular formation. These findings showcase the potential of NELIBS as a simple and viable technology for enhancing molecular band emission in laser-induced plasmas.

  18. Improved repetition rate mixed isotope CO2 TEA laser

    NASA Astrophysics Data System (ADS)

    Cohn, D. B.

    2014-09-01

    A compact CO2 TEA laser has been developed for remote chemical detection that operates at a repetition rate of 250 Hz. It emits 700 mJ/pulse at 10.6 μm in a multimode beam with the 12C16O2 isotope. With mixed 12C16O2 plus 13C16O2 isotopes it emits multiple lines in both isotope manifolds to improve detection of a broad range of chemicals. In particular, output pulse energies are 110 mJ/pulse at 9.77 μm, 250 mJ/pulse at 10 μm, and 550 mJ/pulse at 11.15 μm, useful for detection of the chemical agents Sarin, Tabun, and VX. Related work shows capability for long term sealed operation with a catalyst and an agile tuner at a wavelength shift rate of 200 Hz.

  19. Improved repetition rate mixed isotope CO₂ TEA laser.

    PubMed

    Cohn, D B

    2014-09-01

    A compact CO2 TEA laser has been developed for remote chemical detection that operates at a repetition rate of 250 Hz. It emits 700 mJ/pulse at 10.6 μm in a multimode beam with the (12)C(16)O2 isotope. With mixed (12)C(16)O2 plus (13)C(16)O2 isotopes it emits multiple lines in both isotope manifolds to improve detection of a broad range of chemicals. In particular, output pulse energies are 110 mJ/pulse at 9.77 μm, 250 mJ/pulse at 10 μm, and 550 mJ/pulse at 11.15 μm, useful for detection of the chemical agents Sarin, Tabun, and VX. Related work shows capability for long term sealed operation with a catalyst and an agile tuner at a wavelength shift rate of 200 Hz.

  20. Multiple Isotope Magneto Optical Trap from a single diode laser

    NASA Astrophysics Data System (ADS)

    Gomez, Eduardo; Valenzuela, Victor; Hamzeloui, Saeed; Gutierrez, Monica

    2013-05-01

    We present a simple design for a Dual Isotope Magneto Optical Trap. The system requires a single diode laser, a fiber modulator and a tapered amplifier to trap and completely control both 85Rb and 87Rb. We generate all the frequencies needed for trapping both species using the fiber intensity modulator. All the frequencies are amplified simultaneously with the tapered amplifier. The position and power of each frequency is now controlled independently on the RF rather than on the optical side. This introduces an enormous simplification for laser cooling that often requires an acousto-optic modulator for each frequency. The range of frequency changes is much bigger than what is available with acousto-optic modulators since in our case is determined by the modulator bandwidth (10 GHz). Additional isotopes can be simply added by including additional RF frequencies to the modulator and extra beams for other uses can be produced the same way. Support from CONACYT, PROMEP and UASLP.

  1. Isotope enrichment by frequency-tripled temperature tuned neodymium laser photolysis of formaldehyde

    DOEpatents

    Marling, John B.

    1977-01-01

    Enrichment of carbon, hydrogen and/or oxygen isotopes by means of isotopically selective photo-predissociation of formaldehyde is achieved by irradiation provided by a frequency-tripled, temperature tuned neodymium laser.

  2. Development of a Laser Probe for Argon Isotope Studies.

    NASA Astrophysics Data System (ADS)

    McConville, Paul

    Available from UMI in association with The British Library. The first objective of this study was to develop a laser outgassing facility for argon isotope studies. Apart from the laser and construction of the laser sample port, existing vacuum and mass spectrometer systems were used. Laser performance and optimum operating conditions were investigated. The second objective was test and evaluate the laser extraction technique by studies of simple geological samples. Previous laser ^{40} Ar-^{39}Ar dating studies by other workers had not systematically established the basis or characteristics of the method. Results from laser and complementary stepped heating studies of the ^{40}Ar-^ {39}Ar dating standard hornblende, hb3gr; a phlogopite sample from the Palabora (Phalaborwa) Complex; and biotites in a thin section of the Hamlet Bjerg granite from East Greenland, verified that: (1) Laser extraction reproduced within experimental error the stepped heating ^{40}Ar-^ {39}Ar and K-Ar ages of simple samples. (2) The precision of the technique i.e. the amount of sample required to give reliable ages, was limited in the present experiments largely by the level of the blanks and backgrounds to 10-100 ug samples. (3) Sample outgassing appeared to be limited to the order of 10 um outside the physical size of the laser pit, consistent with other estimates of the spatial definition in the literature. This could be understood by thermal diffusion and the length of the laser pulse. (4) The efficiency of the laser pulse in melting and outgassing mineral samples was shown to be dependent on silicate latent heats and mineral absorption at the laser wavelength. In addition, the ^{40} Ar-^{39}Ar age of the geologically significant Palabora Complex was determined as (2053 +/- 5) Ma. Excess argon led to a discrepancy between the laser and stepped heating ages of biotite and muscovite, (405 +/- 5) Ma, and laser ages of feldspars (510 +/- 20) Ma in the Hamlet Bjerg granite. This illustrated

  3. Elemental, Isotopic, and Organic Analysis on Mars with Laser TOF-MS

    NASA Technical Reports Server (NTRS)

    Brinckerhoff, W. B.; Cornish, T. J.

    2000-01-01

    The in-depth landed exploration of Mars will require increasingly sophisticated robotic analytical tools for both in situ composition science [1] and reconnaissance for sample return [2]. Beyond dust, rock surfaces, and topsoil, samples must be accessed within rocks and ice, well below surface soil, and possibly in elevated deposit layers. A range of spatial scales will be studied, and for the most information-rich microscopic analyses, samples must be acquired, prepared, and positioned with high precision. In some cases samples must also be brought into a vacuum chamber. After expending such resources, it will be important to apply techniques that provide a wide range of information about the samples. Microscopy, mineralogy, and molecular/organic, elemental, and isotopic analyses are all needed, at a minimum, to begin to address the in situ goals at Mars. These techniques must work as an efficient suite to provide layers of data, each layer helping to determine if further analysis on a given sample is desired. In the spirit of broad-band and efficient data collection, we are developing miniature laser time-of-flight mass spectrometers (TOF-MS) for elemental, isotopic, and molecular/organic microanalysis of unprepared solid samples. Laser TOF-MS uses a pulsed laser to volatilize and ionize material from a small region on the sample. The laser energy and focus can be adjusted for atomic and molecular content, sampling area, and depth. Ions travel through the instrument and are detected at a sequence of times proportional to the square root of their mass-to- charge ratios. Thus, each laser pulse produces a complete mass spectrum (in less than 50 microseconds). These instruments can now be significantly miniaturized (potentially to the size of a soda can) without a loss in performance. This effort is reviewed here with an emphasis on applications to Mars exploration.

  4. Elemental, Isotopic, and Organic Analysis on Mars with Laser TOF-MS

    NASA Astrophysics Data System (ADS)

    Brinckerhoff, W. B.; Cornish, T. J.

    2000-07-01

    The in-depth landed exploration of Mars will require increasingly sophisticated robotic analytical tools for both in situ composition science [1] and reconnaissance for sample return [2]. Beyond dust, rock surfaces, and topsoil, samples must be accessed within rocks and ice, well below surface soil, and possibly in elevated deposit layers. A range of spatial scales will be studied, and for the most information-rich microscopic analyses, samples must be acquired, prepared, and positioned with high precision. In some cases samples must also be brought into a vacuum chamber. After expending such resources, it will be important to apply techniques that provide a wide range of information about the samples. Microscopy, mineralogy, and molecular/organic, elemental, and isotopic analyses are all needed, at a minimum, to begin to address the in situ goals at Mars. These techniques must work as an efficient suite to provide layers of data, each layer helping to determine if further analysis on a given sample is desired. In the spirit of broad-band and efficient data collection, we are developing miniature laser time-of-flight mass spectrometers (TOF-MS) for elemental, isotopic, and molecular/organic microanalysis of unprepared solid samples. Laser TOF-MS uses a pulsed laser to volatilize and ionize material from a small region on the sample. The laser energy and focus can be adjusted for atomic and molecular content, sampling area, and depth. Ions travel through the instrument and are detected at a sequence of times proportional to the square root of their mass-to- charge ratios. Thus, each laser pulse produces a complete mass spectrum (in less than 50 microseconds). These instruments can now be significantly miniaturized (potentially to the size of a soda can) without a loss in performance. This effort is reviewed here with an emphasis on applications to Mars exploration.

  5. Optically pumped molecular bromine laser. Master's thesis

    SciTech Connect

    Morrison, J.W.

    1990-12-01

    An optically pumped molecular bromine laser was studied to investigate the quenching kinetics state of Br2. This included characterization of the pressure dependence of the laser output power. The approach was to excite molecular bromine in a sealed cell with a Nd:YAG pumped dye laser. Unresolved side fluorescence and amplified stimulated emission (ASE) spectra were recorded. ASE offered the advantage of a simpler optical system with no externally induced wavelength dependencies. Stimulated emission as a signal monitor offered greater resolution than side fluorescence spectra and facilitated spectroscopic assignment. (JS)

  6. Molecular carbon isotopic evidence for the origin of geothermal hydrocarbons

    NASA Technical Reports Server (NTRS)

    Des Marais, D. J.; Donchin, J. H.; Nehring, N. L.; Truesdell, A. H.

    1981-01-01

    Isotopic measurements of individual geothermal hydrocarbons that are, as a group, of higher molecular weight than methane are reported. It is believed in light of this data that the principal source of hydrocarbons in four geothermal areas in western North America is the thermal decomposition of sedimentary or groundwater organic matter.

  7. New laser setup for the selective isotope production and investigation in a laser ion source at the IRIS (Investigation of Radioactive Isotopes on Synchrocyclotron) facility

    SciTech Connect

    Barzakh, A. E.; Fedorov, D. V.; Ivanov, V. S.; Molkanov, P. L.; Panteleev, V. N.; Volkov, Yu. M.

    2012-02-15

    New laser installation for the resonance ionization spectroscopy in a laser ion source and for rare isotope production has been recently put into operation at the IRIS (Investigation of Radioactive Isotopes on Synchrocyclotron) facility (Petersburg Nuclear Physics Institute, Gatchina). This is a significant improvement of a previous target-laser ion source device of the IRIS mass-separator, working on-line with 1 GeV proton beam of PNPI (Petersburg Nuclear Physics Institute) synchrocyclotron. It makes possible for us to get the isobarically clean radioactive isotope beams of a great number of chemical elements. New laser setup provides the two- or three-resonance step ionization in the range of wavelength of 265-850 nm. The first results obtained at the laser setup for Tl isotopes are presented.

  8. Frontiers of QC Laser spectroscopy for high precision isotope ratio analysis of greenhouse gases

    NASA Astrophysics Data System (ADS)

    Emmenegger, Lukas; Mohn, Joachim; Harris, Eliza; Eyer, Simon; Ibraim, Erkan; Tuzson, Béla

    2016-04-01

    An important milestone for laser spectroscopy was achieved when isotope ratios of greenhouse gases were reported at precision levels that allow addressing research questions in environmental sciences. Real-time data with high temporal resolution at moderate cost and instrument size make the optical approach highly attractive, complementary to the well-established isotope-ratio mass-spectrometry (IRMS) method. Especially appealing, in comparison to IRMS, is the inherent specificity to structural isomers having the same molecular mass. Direct absorption in the MIR in single or dual QCL configuration has proven highly reliable for the sta-ble isotopes of CO2, N2O and CH4. The longest time series of real-time measurements is currently available for δ13C and δ18O in CO2 at the high-alpine station Jung-fraujoch. At this well-equipped site, QCL based direct absorption spectroscopy (QCLAS) measurements are ongoing since 2008 1,2. Applications of QCLAS for N2O and CH4 stable isotopes are considerably more challenging because of the lower atmospheric mixing ratios, especially for the less abundant species, such as N218O and CH3D. For high precision (< 0.1 ‰) measurements in ambient air, QCLAS may be combined with a fully automated preconcentration unit yielding an up to 500 times concentration increase and the capability to separate the target gas from spectral interferants by se-quential desorption 3. Here, we review our recent developments on high precision isotope ratio analysis of greenhouse gases, with special focus on the isotopic species of N2O and CH4. Furthermore, we show environ-mental applications illustrating the highly valuable information that isotope ratios of atmospheric trace gases can carry. For example, the intramolecular distribution of 15N in N2O gives important information on the geochemical cycle of N2O4-6, while the analysis of δ13C and δ D in CH4 may be applied to disentangle microbial, fossil and landfill sources 7. 1 Sturm, P., Tuzson, B

  9. Isotope selective excitation of 155Gd and 157Gd isotopes from 9D° 2-6 states using broadband lasers

    NASA Astrophysics Data System (ADS)

    Sankari, M.; Suryanarayana, M. V.; Gangadharan, S.

    1999-01-01

    The feasibility of isotope enrichment of 155Gd and 157Gd isotopes using relatively broadband lasers within the tuning range of rhodamine-6G dye has been studied. A new set of photoionization schemes have been proposed for using in the industrial scale enrichment of these isotopes. These photoionization schemes result in better photon economy compared to the photoionization schemes reported earlier. The enriched isotopic mixture results in a 50% increase in the neutron absorption cross-section and a 70% reduction in the residual neutron absorption. The degree of enrichment of the odd isotopes is adequate for using the enriched mixture as an efficient burnable poison. The effect of linewidth of the excitation laser and Doppler width of the atom source on the degree of enrichment have been theoretically evaluated and experimentally verified. The computed selectivities were in good agreement with the experimental results.

  10. Mars Molecular and Isotopic Analysis Research Study

    NASA Technical Reports Server (NTRS)

    Manning, Heidi L. K.

    1998-01-01

    Recently, the Martian atmosphere and surface constituents have become of great interest. The Viking in situ gas chromatograph mass spectrometer experiment contributed greatly to our knowledge of the composition of the Martian atmosphere. However, important questions remain such as the abundance of water on Mars. The Viking experiment employed solid reagents to enhance their carbon measurements. Techniques of chemical conversion using simple solid reagents have advanced considerably in the past 20 years. In this investigation we researched the advancements in techniques to reversibly adsorb and desorb water and focused on the techniques potentially useful for the temperatures and pressures on the Martian surface. During the granting period from June 15, 1998 to August 14, 1998, a literature study of the material appropriate for use in a chemical conversion device and the availability of these materials were undertaken. The focus of this investigation was searching for methods and materials potentially useful in enhancing the measurements of water. Three different methods were considered for the means to extract water from a given gas sample. These methods included adsorption in a desiccant, adsorption on a clean metal surface, and adsorption in a carbon molecular sieve or zeolite. Each method was evaluated with feasibility and reversibility in mind. By far the simplest and perhaps cheapest way to remove water from a gaseous sample is by means of a bulk desiccant. Desiccants are commercially available from many companies including those that supply chemicals. The main feature of a desiccant is its ability to rapidly bind or absorb water from the atmosphere. Calcium chloride, for example, is frequently incorporated into drying tubes by organic chemists when reactions require the absence of water. Other desiccants include sodium hydroxide, calcium hydride, and commercial products such as Drierite, available from Aldrich Chemical. The disadvantage to most desiccants is

  11. Laser desorption mass spectrometry for molecular diagnosis

    NASA Astrophysics Data System (ADS)

    Chen, C. H. Winston; Taranenko, N. I.; Zhu, Y. F.; Allman, S. L.; Tang, K.; Matteson, K. J.; Chang, L. Y.; Chung, C. N.; Martin, Steve; Haff, Lawrence

    1996-04-01

    Laser desorption mass spectrometry has been used for molecular diagnosis of cystic fibrosis. Both 3-base deletion and single-base point mutation have been successfully detected by clinical samples. This new detection method can possibly speed up the diagnosis by one order of magnitude in the future. It may become a new biotechnology technique for population screening of genetic disease.

  12. Remote laser evaporative molecular absorption spectroscopy

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

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

  13. Laser manipulation of atomic and molecular flows

    NASA Astrophysics Data System (ADS)

    Lilly, Taylor C.

    The continuing advance of laser technology enables a range of broadly applicable, laser-based flow manipulation techniques. The characteristics of these laser-based flow manipulations suggest that they may augment, or be superior to, such traditional electro-mechanical methods as ionic flow control, shock tubes, and small scale wind tunnels. In this study, methodology was developed for investigating laser flow manipulation techniques, and testing their feasibility for a number of aerospace, basic physics, and micro technology applications. Theories for laser-atom and laser-molecule interactions have been under development since the advent of laser technology. The theories have yet to be adequately integrated into kinetic flow solvers. Realizing this integration would greatly enhance the scaling of laser-species interactions beyond the realm of ultra-cold atomic physics. This goal was realized in the present study. A representative numerical investigation, of laser-based neutral atomic and molecular flow manipulations, was conducted using near-resonant and non-resonant laser fields. To simulate the laser interactions over a range of laser and flow conditions, the following tools were employed: a custom collisionless gas particle trajectory code and a specifically modified version of the Direct Simulation Monte Carlo statistical kinetic solver known as SMILE. In addition to the numerical investigations, a validating experiment was conducted. The experimental results showed good agreement with the numerical simulations when experimental parameters, such as finite laser line width, were taken into account. Several areas of interest were addressed: laser induced neutral flow steering, collimation, direct flow acceleration, and neutral gas heating. Near-resonant continuous wave laser, and non-resonant pulsed laser, interactions with cesium and nitrogen were simulated. These simulations showed trends and some limitations associated with these interactions, used for flow

  14. Bioinspired laser-operated molecular locomotive.

    PubMed

    Wang, Zhisong

    2004-09-01

    Biomotors kinesin and dynein show us that robust track-walking is possible down to molecular scale. Here I design a laser-powered molecular locomotive that is able to do that on an easily constructed track. The core of the machine is its work cycle that periodically converts optical energy into mechanical work, which is further rectified into processive, directional motion. Thus the molecular locomotive is essentially beyond the famous design of molecular shuttles. Under automated laser operation, the locomotive can move a few mum per second comparable to its biological counterparts. However, this artificial motor is capable of conveniently switchable, dual directional motion in contrast to common unidirectionality of biomotors. The locomotive is also different from the big category of Brownian motors in the sense that move of the locomotive is not a result of biasing pre-existing fluctuations, rather it is directly and decisively driven by optomechanical strokes of the work cycle, generating a pulling force ten times greater than those of biomotors. Being a novel type of molecular motor as well as a powerful molecular engine, this machine will potentially enable automatic, forceful delivery of molecular building blocks with nanometer accuracy. Well within reach of established techniques, its implementation will be a significant advance in nanoscience and nanotechnology.

  15. Temperature method for measuring the concentration of {sup 127}I and {sup 129}I isotopes based on laser-induced fluorescence

    SciTech Connect

    Kireev, S.V.; Shnyrev, S.L.

    1995-05-01

    A method for measuring the concentration of {sup 129}I and {sup 127}I isotopes are based on differences in the temperature behavior of the fluorescence intensity of molecular iodine isotopes is proposed. The {sup 129}I: {sup 127}I ratio, obtained with a He{sup 3}-Ne{sup 22} (633 nm) laser, was found to be not worse than 10{sup -2}. 10 refs., 2 figs.

  16. Least destructive sampling of human remains using laser drilling for Sr isotope analysis by TIMS

    NASA Astrophysics Data System (ADS)

    Willmes, Malte; Moffat, Ian; Grün, Rainer; Armstrong, Richard; Kinsley, Les; McMorrow, Linda

    2013-04-01

    Strontium isotope ratios (87Sr/86Sr) measured in ancient human remains can be used to reconstruct migration patterns of ancient human populations. This application is based on the fact that different geologic regions have distinct Sr isotope signatures that are cycled through the soils, plants and rivers, and eventually enter the food cycle. Sr isotope ratios measured in skeletal remains (bones and teeth) reflect the average of dietary Sr that was consumed when the tissue was formed, allowing the investigation of human migration between geologically distinct terrains. The analysis of human remains is always a sensitive topic requiring minimal damage to the sample, while at the same time providing highly precise and accurate results. Samples can be analysed either by solution methods like thermal ionisation mass spectrometry (TIMS), or by in-situ laser ablation MC-ICP-MS. For TIMS a drill is used to extract a small amount of sample, which is then digested in acid and Sr is separated out using ion exchange chromatography. This technique provides highly precise and accurate results, because any isobaric interferences are removed during chemical separation. The drawback is that drilling may cause visible damage to the sample, restricting access to precious human remains. LA-MC-ICP-MS analysis is very fast and nearly destruction free. However, the accuracy and precision of LA-MC-ICP-MS is limited by a number of factors including large instrumental mass discrimination, laser-induced isotopic and elemental fractionations and molecular interferences on 87Sr. Its application thus requires rigorous data reduction, which can introduce significant uncertainties into the analysis. This is especially true for samples with relatively low Sr concentrations such as human teeth (e.g., Woodhead et al., 2005; Horstwood et al., 2008; Vroon et al., 2008). In addition, LA-MC-ICP-MS has traditionally required a flat sample surface, thus an unbroken tooth needs to be cut, which is rather

  17. Laser induced fluorescence of trapped molecular ions

    SciTech Connect

    Winn, J.S.

    1980-10-01

    Laser induced fluoresence (LIF) spectra (laser excitation spectra) are conceptually among the most simple spectra to obtain. One need only confine a gaseous sample in a suitable container, direct a laser along one axis of the container, and monitor the sample's fluorescence at a right angle to the laser beam. As the laser wavelength is changed, the changes in fluorescence intensity map the absorption spectrum of the sample. (More precisely, only absorption to states which have a significant radiative decay component are monitored.) For ion spectroscopy, one could benefit in many ways by such an experiment. Most optical ion spectra have been observed by emission techniques, and, aside from the problems of spectral analysis, discharge emission methods often produce the spectra of many species, some of which may be unknown or uncertain. Implicit in the description of LIF given above is certainty as to the chemical identity of the carrier of the spectrum. This article describes a method by which the simplifying aspects of LIF can be extended to molecular ions (albeit with a considerable increase in experimental complexity over that necessary for stable neutral molecules).

  18. A non-mass-dependent oxygen isotope effect in the production of ozone from molecular oxygen - The role of molecular symmetry in isotope chemistry

    NASA Technical Reports Server (NTRS)

    Heidenreich, J. E., III; Thiemens, M. H.

    1986-01-01

    It was previously reported that the reaction products from the synthesis of ozone in an electric discharge through molecular oxygen display a nonmass-dependent (NoMaDic) oxygen isotope effect. In this paper, a detailed characterization of the isotope effect, including the effect of molecular oxygen pressure, and the presence of a chemically inert third body (helium), is reported. The NoMaDic effect is due to an isotopically selective stabilization of the O3 formation reaction intermediate, possibly resulting from the ability of the different isotopomers to exhibit different molecular symmetries.

  19. Method for separating different isotopes in compounds by means of laser radiation

    SciTech Connect

    Meyer-Kretschmer, G.; Jetter, H.; Toennies, P.

    1984-05-29

    A method is claimed for separating isotopes of a compound having molecules in the gaseous state which comprises exciting the gas with laser radiation having a frequency capable of exciting a selected isotope thereof, interacting the excited gas with electrons having an energy sufficient to form position ions therein and separating the ionized molecules from the other molecules in the gas.

  20. Infrared laser system

    DOEpatents

    Cantrell, Cyrus D.; Carbone, Robert J.; Cooper, Ralph

    1982-01-01

    An infrared laser system and method for isotope separation may comprise a molecular gas laser oscillator to produce a laser beam at a first wavelength, Raman spin flip means for shifting the laser to a second wavelength, a molecular gas laser amplifier to amplify said second wavelength laser beam to high power, and optical means for directing the second wavelength, high power laser beam against a desired isotope for selective excitation thereof in a mixture with other isotopes. The optical means may include a medium which shifts the second wavelength high power laser beam to a third wavelength, high power laser beam at a wavelength coincidental with a corresponding vibrational state of said isotope and which is different from vibrational states of other isotopes in the gas mixture.

  1. Infrared laser system

    DOEpatents

    Cantrell, Cyrus D.; Carbone, Robert J.; Cooper, Ralph S.

    1977-01-01

    An infrared laser system and method for isotope separation may comprise a molecular gas laser oscillator to produce a laser beam at a first wavelength, Raman spin flip means for shifting the laser to a second wavelength, a molecular gas laser amplifier to amplify said second wavelength laser beam to high power, and optical means for directing the second wavelength, high power laser beam against a desired isotope for selective excitation thereof in a mixture with other isotopes. The optical means may include a medium which shifts the second wavelength high power laser beam to a third wavelength, high power laser beam at a wavelength coincidental with a corresponding vibrational state of said isotope and which is different from vibrational states of other isotopes in the gas mixture.

  2. Late-Quaternary Molecular Isotopic Paleohydrology of Lake Junin, Peru

    NASA Astrophysics Data System (ADS)

    Polissar, P. J.; Liu, C.; Rodbell, D. T.; Abbott, M. B.

    2013-12-01

    fluctuations, at least during the Holocene. Changing proportions of aquatic plant-wax sources may have had some influence as shorter-chain acids from aquatic macrophytes are more abundant in the early Holocene. However, aridity likely had a major role through greater evaporative isotopic enrichment of leaf and/or soil water. Early Holocene lake waters were significantly more highly evaporated indicating overall more arid conditions when leaf-wax δD values are most positive. Comparison of Lake Junin plant-wax and water δD values over the past 20,000 years indicate that although δDwax reflects trends in water δD, there are potentially large influences from evapotranspiration and shifting proportions of aquatic sources. While these factors have been previously identified in spatial calibration studies, our temporal calibration results emphasize the need to critically evaluate these influences on molecular δD at a single location through time.

  3. tritium isotope separation by CO 2 laser-induced multiphoton dissociation of CTF 3

    NASA Astrophysics Data System (ADS)

    Makide, Yoshihiro; Hagiwara, Satoru; Tominaga, Takeshi; Takeuchi, Kazuo; Nakane, Ryohei

    1981-08-01

    Isotope separation of tritium at ppm concentration level was achieved by CO 2 laser-induced multiphoton dissociation of CTF 3 in CHF 3 with single-step separation factors exceeding 500. The effects of laser frequency, pulse energy, pulse duration, irradiation geometry, tritium concentration, sample pressure, and buffer gas were investigated.

  4. Femtosecond Laser Ablation Multicollector ICPMS Analysis of Uranium Isotopes in NIST Glass

    SciTech Connect

    Duffin, Andrew M.; Springer, Kellen WE; Ward, Jesse D.; Jarman, Kenneth D.; Robinson, John W.; Endres, Mackenzie C.; Hart, Garret L.; Gonzalez, Jhanis J.; Oropeza, Dayana; Russo, Richard; Willingham, David G.; Naes, Benjamin E.; Fahey, Albert J.; Eiden, Gregory C.

    2015-02-06

    We have utilized femtosecond laser ablation coupled to multi-collector inductively couple plasma mass spectrometry to measure the uranium isotopic content of NIST 61x (x=0,2,4,6) glasses. The uranium content of these glasses is a linear two-component mixing between isotopically natural uranium and the isotopically depleted spike used in preparing the glasses. Laser ablation results match extremely well, generally within a few ppm, with solution analysis following sample dissolution and chemical separation. In addition to isotopic data, sample utilization efficiency measurements indicate that over 1% of ablated uranium atoms reach a mass spectrometer detector, making this technique extremely efficient. Laser sampling also allows for spatial analysis and our data indicate that rare uranium concentration inhomogeneities exist in NIST 616 glass.

  5. A status of progress for the Laser Isotope Separation (LIS) process

    NASA Technical Reports Server (NTRS)

    Delionback, L. M.

    1976-01-01

    An overview of the Laser Isotope Separation (LIS) methodology is given together with illustrations showing a simplified version of the LIS technique, an example of the two-photon photoionization category, and a diagram depicting how the energy levels of various isotope influence the LIS process. Applications were proposed for the LIS system which, in addition to enriching uranium, could in themselves develop into programs of tremendous scope and breadth. These include the treatment of radioactive wastes from light-water nuclear reactors, enriching the deuterium isotope to make heavy-water, and enriching the light isotopes of such elements as titanium for aerospace weight-reducing programs. Economic comparisons of the LIS methodology with the current method of gaseous diffusion indicate an overwhelming advantage; the laser process promises to be 1000 times more efficient. The technique could also be utilized in chemical reactions with the tuned laser serving as a universal catalyst to determine the speed and direction of a chemical reaction.

  6. Isotope Effects in Collisional VT Relaxation of Molecular Hydrogen

    NASA Technical Reports Server (NTRS)

    Bieniek, R. J.

    2006-01-01

    A simple exponential-potential model of molecular collisions leads to a two-parameter analytic expression for rates of collisionally induced vibrational-translation (VT) energy exchange that has been shown to be accurate over variations of orders of magnitude as a function of temperature in a variety of systems. This includes excellent agreement with reported experimental and theoretical results for the fundamental self-relaxation rate of molecular hydrogen H2(v = 1) + H2 yields H2(v = 0) + H2. The analytic rate successfully follows the five-orders-of-magnitude change in experimental values for the temperature range 50-2000 K. This approach is now applied to isotope effects in the vibrational relaxation rates of excited HD and D2 in collision with H2: HD(v = 1)+H2 yields HD(v = 0)+H2 and D2(v = 1)+H2 yields D2(v = 0)+H2. The simplicity of the analytic expression for the thermal rate lends itself to convenient application in modeling the evolving vibrational populations of molecular hydrogen in shocked astrophysical environments.

  7. The laser microprobe: A technique for extracting carbon, nitrogen, and oxygen from solid samples for isotopic measurements

    NASA Astrophysics Data System (ADS)

    Franchi, I. A.; Wright, I. P.; Gibson, E. K.; Pillinger, C. T.

    1986-09-01

    The laser microprobe extraction technique has been adapted for the determination of concentrations and stable isotopic compositions of carbon, nitrogen, and oxygen. The power from a focused laser beam is used to selectively pyrolyse, or combust, specific areas of a solid sample of interest, which is located within a vacuum extraction line. Gases released from the sample are collected, purified, and then admitted to an appropriate mass spectrometer as either molecular nitrogen (for δ15N measurements) or carbon dioxide (for δ13C and δ18O measurements). The minimum amounts of gas that can be measured isotopically are less than a nanomole. A number of samples have been analysed in order to evaluate the efficacy of the laser microprobe including two carbonate minerals (calcite and siderite), graphite, and titanium nitride. Initial studies on the distribution of nitrogen in an iron meteorite (Uwet) and a carbonaceous chondrite (Murchison) have been undertaken. Nitrogen in Uwet was found to be concentrated in the phosphide mineral schreibersite rather than in the kamacite. Laser extractions of the dark matrix of Murchison reveal 620 to 790 ppm of nitrogen with a δ15N=+38.5 to +44.7% (in agreement with stepped heating extractions of bulk Murchison) while much lower concentrations, down to 80 ppm (and δ15N=+12 to +60%), were found in the light-coloured high-temperature inclusions. For carbon-containing phases, there appears to be an isotope fractionation associated with the formation of CO2 and CO. However, preliminary results suggest that the extent of isotope fractionation may be reproducible, allowing suitable corrections to be applied to the raw data.

  8. Accurate Hf isotope determinations of complex zircons using the "laser ablation split stream" method

    NASA Astrophysics Data System (ADS)

    Fisher, Christopher M.; Vervoort, Jeffery D.; DuFrane, S. Andrew

    2014-01-01

    The "laser ablation split stream" (LASS) technique is a powerful tool for mineral-scale isotope analyses and in particular, for concurrent determination of age and Hf isotope composition of zircon. Because LASS utilizes two independent mass spectrometers, a large range of masses can be measured during a single ablation, and thus, the same sample volume can be analyzed for multiple geochemical systems. This paper describes a simple analytical setup using a laser ablation system coupled to a single-collector (for U-Pb age determination) and a multicollector (for Hf isotope analyses) inductively coupled plasma mass spectrometer (MC-ICPMS). The ability of the LASS for concurrent Hf + age technique to extract meaningful Hf isotope compositions in isotopically zoned zircon is demonstrated using zircons from two Proterozoic gneisses from northern Idaho, USA. These samples illustrate the potential problems associated with inadvertently sampling multiple age and Hf components in zircons, as well as the potential of LASS to recover meaningful Hf isotope compositions. We suggest that such inadvertent sampling of differing age and Hf components can be a significant cause of excess scatter in Hf isotope analyses and demonstrate that the LASS approach offers a robust solution to these issues. The veracity of the approach is demonstrated by accurate analyses of 10 reference zircons with well-characterized age and Hf isotopic composition, using laser spot diameters of 30 and 40 µm. In order to expand the database of high-precision Lu-Hf isotope analyses of reference zircons, we present 27 new isotope dilution-MC-ICPMS Lu-Hf isotope measurements of five U-Pb zircon standards: FC1, Temora, R33, QGNG, and 91500.

  9. A computer modeling study of isotopically selective, laser photodissociation of OCS in cryogenic solutions

    SciTech Connect

    Zittel, P.F.

    1991-12-23

    Computer model calculations are presented for enrichments of carbon, oxygen, and sulfur isotopes by two-step, IR/UV, laser photodissociation of OCS in rare gas liquid solutions. The model calculations are based on previously measured fundamental physical properties, including spectroscopic parameters of the IR absorption bands of OCS in cryogenic solution, UV photodissociation cross sections for specific vibrational levels of OCS, and rates for vibrational relaxation of OCS by cryogenic solvents. Results are presented for both pulsed and continuous wave laser sources. Photodissociation through both the 2{nu}{sub 2} and {nu}{sub 1} intermediate vibrational levels of OCS is investigated. The laser characteristics required to obtain optimum enrichments are determined by modeling the dependence of enrichment on laser wavelength and intensity, as well as pulse width and timing for pulsed sources. Optimum carbon and oxygen isotope enrichment factors of 9--14 are found for two-step photodissociation through the OCS(2{nu}{sub 2}) vibrational level, using pulsed CO{sub 2} and KrF excimer laser sources. Optimum sulfur isotope enrichment factors of 5--6 are found for photodissociation through the OCS({nu}{sub 1}) level, using a pulsed 12 {mu}m laser and a KrF excimer laser. The enrichments found for continuous wave laser sources are smaller than those for pulsed sources. 19 figs., 4 tabs.

  10. Biomarker and molecular isotope approaches to deconvolve the terrestrial carbon isotope record: modern and Eocene calibrations

    NASA Astrophysics Data System (ADS)

    Diefendorf, A. F.; Freeman, K. H.; Wing, S.; Currano, E. D.

    2010-12-01

    generally 2-3‰ enriched relative to angiosperm leaves, we project that the far more abundant angiosperm lipids will be about 4-6 ‰ depleted relative to small amounts of conifer n-alkanes in natural samples. In addition, we report carbon isotope values of the terpenoids from the MVA (triterpenoids) and MEP (diterpenoids) synthesis pathways for our plant sample set. Bulk leaf tissue-to-lipid fractionation factors for terpenoids are similar and generally small, -0.4 and -0.6‰, for MVA and MEP products, respectively. Estimates of precipitation from fossil leaves at the Fifteenmile site allow us to predict leaf fractionation values for different plant types (bulk) and for triterpenoid and diterpenoid compound classes. Our fractionation factors, when applied to an estimate for the δ13C value of late Eocene CO2, agree well with bulk and molecular data. An understanding of molecular production biases greatly improves our ability to reconstruct both paleovegetation and δ13C of atmospheric CO2.

  11. Evaluation of uranium transitions for isotopically-selective laser induced fluorescence with diode lasers (Technical Report for ST064)

    SciTech Connect

    Cannon, B.D.

    1993-10-01

    Isotopically-selective excitation of uranium atoms by diode lasers can be the basis for a portable instrument to perform uranium isotopic assays in the field. Such an instrument would improve the ability of on-site inspections to detect and deter nuclear proliferation. Published and unpublished spectroscopic data on atomic uranium were examined to identify candidate transitions for isotopically-selective laser excitation with diode lasers. Eleven candidate transitions were identified and evaluated for their potential usefulness for a portable uranium assay instrument. Eight of these transitions are suitable for laser induced fluorescence using different excitation and detection wavelengths, which will improve sensitivity and elemental selectivity. Data sheets on the 25 uranium transitions in the wavelength range 629 nm to 1,000 nm that originate in the ground or first excited states of neutral atomic uranium are included. Each data sheet provides the wavelength, upper and lower energy levels, angular momentum quantum numbers, {sup 235}U isotope shift (relative to {sup 238}U), and high-resolution spectra of weapons-grade uranium (93% {sup 235}U and 7% {sup 238}U).

  12. LASER BIOLOGY AND MEDICINE: Laser analysis of the 13C/12C isotope ratio in CO2 in exhaled air

    NASA Astrophysics Data System (ADS)

    Stepanov, E. V.

    2002-11-01

    Tunable diode lasers (TDLs) are applied to the diagnostics of gastroenterological diseases using respiratory tests and preparations enriched with the stable 13C isotope. This method of the analysis of the 13C/12C isotope ratio in CO2 in exhaled air is based on the selective measurement of the resonance absorption at the vibrational — rotational structure of 12CO2 and 13CO2. The CO2 transmission spectra in the region of 4.35 μm were measured with a PbEuSe double-heterostructure TDL. The accuracy of carbon isotope ratio measurements in CO2 of exhaled air performed with the TDL was ~0.5%. The data of clinical tests of the developed laser-based analyser are presented.

  13. CO2-laser isotope separation of tritium with pentafluoroethane-T (C2TF5)

    NASA Astrophysics Data System (ADS)

    Makide, Y.; Kato, S.; Tominaga, T.; Takeuchi, K.

    1982-08-01

    Isotope separation of tritium by CO2 laser-induced multiphoton dissociation (MPD) of C2TF5 is reported for the first time. The MPD spectrum obtained for C2TF5 comprised a broad peak at about 940 cm-1 where C2HF5 was nearly transparent. The unimolecular dissociation of C2TF5 was induced with much lower laser fluence than that for CTF3, another working molecule we proposed for laser isotope separation of tritium. The mechanisms and kinetics of the dissociation of C2TF5 and C2HF5 were investigated under various experimental conditions: laser frequency, pulse energy, pulse duration, tritium concentration, sample pressure, buffer gas pressure and irradiation geometry. Single-step separation factors exceeding 500 were achieved with the most efficient P(20) line in 00o 10o0 transition at 944.2 cm-1.

  14. Collisionless dissociation and isotopic enrichment of SF6 using high-powered CO2 laser radiation

    NASA Technical Reports Server (NTRS)

    Gower, M. C.; Billman, K. W.

    1977-01-01

    Dissociation of S-32F6 and the resultant isotopic enrichment of S-34F6 using high-powered CO2 laser radiation has been studied with higher experimental sensitivity than previously reported. Enrichment factors have been measured as a function of laser pulse number, wavelength, energy and time duration. A geometry independent dissociation cross section is introduced and measured values are presented. Threshold energy densities, below which no dissociation was observed, were also determined.

  15. Laser enhanced microwave plasma isotope separation. Final report, September 30, 1992--September 29, 1995

    SciTech Connect

    Brake, M.L.; Gilgenbach, R.M.

    1996-06-01

    The experimental research was to focus on laser excitation of a low abundance isotope and then ionize and separate the isotope of low abundance using a microwave/ECR discharge at 2.45 GHz. A small compact electron cyclotron resonance ion source, which uses permanent magnets, was constructed during this project. The dye laser was purchased and later an excimer laser had to also be purchased because it turned out that the dye laser could not be pumped by our copper laser. It was intended that the dye laser be tuned to a wavelength of 670.8 nm, which would excite {sup 6}Li which would then be preferentially ionized by the ECR source and collected with a charged grid. The degree of enrichment was to be determined using thermal ionization mass spectrometry. The final objective of this project was to assess the feasibility of this system to large-scale production of stable isotopes. However the funding of this project was interrupted and we were not able to achieve all of our goals.

  16. Ultrafast molecular imaging by laser-induced electron diffraction

    SciTech Connect

    Peters, M.; Nguyen-Dang, T. T.; Cornaggia, C.; Saugout, S.; Charron, E.; Keller, A.; Atabek, O.

    2011-05-15

    We address the feasibility of imaging geometric and orbital structures of a polyatomic molecule on an attosecond time scale using the laser-induced electron diffraction (LIED) technique. We present numerical results for the highest molecular orbitals of the CO{sub 2} molecule excited by a near-infrared few-cycle laser pulse. The molecular geometry (bond lengths) is determined within 3% of accuracy from a diffraction pattern which also reflects the nodal properties of the initial molecular orbital. Robustness of the structure determination is discussed with respect to vibrational and rotational motions with a complete interpretation of the laser-induced mechanisms.

  17. An ion guide laser ion source for isobar-suppressed rare isotope beams

    SciTech Connect

    Raeder, Sebastian Ames, Friedhelm; Bishop, Daryl; Bricault, Pierre; Kunz, Peter; Mjøs, Anders; Heggen, Henning; Lassen, Jens Teigelhöfer, Andrea

    2014-03-15

    Modern experiments at isotope separator on-line (ISOL) facilities like ISAC at TRIUMF often depend critically on the purity of the delivered rare isotope beams. Therefore, highly selective ion sources are essential. This article presents the development and successful on-line operation of an ion guide laser ion source (IG-LIS) for the production of ion beams free of isobaric contamination. Thermionic ions from the hot ISOL target are suppressed by an electrostatic potential barrier, while neutral radio nuclides effusing out are resonantly ionized by laser radiation within a quadrupole ion guide behind this barrier. The IG-LIS was developed through detailed thermal and ion optics simulation studies and off-line tests with stable isotopes. In a first on-line run with a SiC target a suppression of surface-ionized Na contaminants in the ion beam of up to six orders of magnitude was demonstrated.

  18. The molecular mechanism of Mo isotope fractionation during adsorption to birnessite

    USGS Publications Warehouse

    Wasylenki, L.E.; Weeks, C.L.; Bargar, J.R.; Spiro, T.G.; Hein, J.R.; Anbar, A.D.

    2011-01-01

    Fractionation of Mo isotopes during adsorption to manganese oxides is a primary control on the global ocean Mo isotope budget. Previous attempts to explain what drives the surprisingly large isotope effect ??97/95Modissolved-??97/95Moadsorbed=1.8??? have not successfully resolved the fractionation mechanism. New evidence from extended X-ray absorption fine structure analysis and density functional theory suggests that Mo forms a polymolybdate complex on the surfaces of experimental and natural samples. Mo in this polynuclear structure is in distorted octahedral coordination, while Mo remaining in solution is predominantly in tetrahedral coordination as MoO42- Our results indicate that the difference in coordination environment between dissolved Mo and adsorbed Mo is the cause of isotope fractionation. The molecular mechanism of metal isotope fractionation in this system should enable us to explain and possibly predict metal isotope effects in other systems where transition metals adsorb to mineral surfaces. ?? 2011 Elsevier Ltd.

  19. Laser fluorescence on radio-active isotopes produced in very low yield

    NASA Astrophysics Data System (ADS)

    Dancy, M. P.; Billowes, J.; Grant, I. S.; Evans, D. E.; Griffith, J. A. R.; Wells, S. A.; Eastham, D. A.; Groves, J.; Smith, J. R. H.; Tolfree, D. W. L.; Walker, P. M.

    1990-08-01

    East particle-photon coincidence techniques, developed at Daresbury with strontium isotopes, allow ultrasensitive laser fluorescence spectroscopy of beams of radio-active isotopes which can only be produced in very low yields. The technique has now been applied to neutron-deficient barium isotopes down to120Ba. From measured hyperfine splittings and isotope shifts, nuclear moments and changes in mean square radii have been determined. The work has revealed an abrupt increase in the mean square radius for121Ba large enough to disrupt the systematic staggering of nuclear size seen for the series. In a recent experiment an isomeric state of127Ba with a half-life of about 2 seconds has been produced in a very low yield; nevertheless we have succeeded in obtaining a fluorescence spectrum.

  20. Developments towards in-gas-jet laser spectroscopy studies of actinium isotopes at LISOL

    NASA Astrophysics Data System (ADS)

    Raeder, S.; Bastin, B.; Block, M.; Creemers, P.; Delahaye, P.; Ferrer, R.; Fléchard, X.; Franchoo, S.; Ghys, L.; Gaffney, L. P.; Granados, C.; Heinke, R.; Hijazi, L.; Huyse, M.; Kron, T.; Kudryavtsev, Yu.; Laatiaoui, M.; Lecesne, N.; Luton, F.; Moore, I. D.; Martinez, Y.; Mogilevskiy, E.; Naubereit, P.; Piot, J.; Rothe, S.; Savajols, H.; Sels, S.; Sonnenschein, V.; Traykov, E.; Van Beveren, C.; Van den Bergh, P.; Van Duppen, P.; Wendt, K.; Zadvornaya, A.

    2016-06-01

    To study exotic nuclides at the borders of stability with laser ionization and spectroscopy techniques, highest efficiencies in combination with a high spectral resolution are required. These usually opposing requirements are reconciled by applying the in-gas-laser ionization and spectroscopy (IGLIS) technique in the supersonic gas jet produced by a de Laval nozzle installed at the exit of the stopping gas cell. Carrying out laser ionization in the low-temperature and low density supersonic gas jet eliminates pressure broadening, which will significantly improve the spectral resolution. This article presents the required modifications at the Leuven Isotope Separator On-Line (LISOL) facility that are needed for the first on-line studies of in-gas-jet laser spectroscopy. Different geometries for the gas outlet and extraction ion guides have been tested for their performance regarding the acceptance of laser ionized species as well as for their differential pumping capacities. The specifications and performance of the temporarily installed high repetition rate laser system, including a narrow bandwidth injection-locked Ti:sapphire laser, are discussed and first preliminary results on neutron-deficient actinium isotopes are presented indicating the high capability of this novel technique.

  1. Measurement of sulfur isotope compositions by tunable laser spectroscopy of SO2.

    PubMed

    Christensen, Lance E; Brunner, Benjamin; Truong, Kasey N; Mielke, Randall E; Webster, Christopher R; Coleman, Max

    2007-12-15

    Sulfur isotope measurements offer comprehensive information on the origin and history of natural materials. Tunable laser spectroscopy is a powerful analytical technique for isotope analysis that has proven itself readily adaptable for in situ terrestrial and planetary measurements. Measurements of delta(34)S in SO2 were made using tunable laser spectroscopy of combusted gas samples from six sulfur-bearing solids with delta(34)S ranging from -34 to +22 per thousand (also measured with mass spectrometry). Standard deviation between laser and mass spectrometer measurements was 3.7 per thousand for sample sizes of 200 +/- 75 nmol SO(2). Although SO(2)(g) decreased 9% over 15 min upon entrainment in the analysis cell from wall uptake, observed fractionation was insignificant (+0.2 +/- 0.6 per thousand). We also describe a strong, distinct (33)SO(2) rovibrational transition in the same spectral region, which may enable simultaneous delta(34)S and Delta(33)S measurements.

  2. "Application of Tunable Diode Laser Spectrometry to Isotopic Studies for Exobiology"

    NASA Technical Reports Server (NTRS)

    Sauke, Todd B.

    1999-01-01

    Computer-controlled electrically-activated valves for rapid gas-handling have been incorporated into the Stable Isotope Laser Spectrometer (SILS) which now permits rapid filling and evacuating of the sample and reference gas cells, Experimental protocols have been developed to take advantage of the fast gas handling capabilities of the instrument and to achieve increased accuracy which results from reduced instrumental drift during rapid isotopic ratio measurements. Using these protocols' accuracies of 0.5 del (0.05%) have been achieved in measurements of 13C/12C in carbon dioxide. Using the small stable isotope laser spectrometer developed in a related PIDDP project of the Co-I, protocols for acquisition of rapid sequential calibration spectra were developed which resulted in 0.5 del accuracy also being achieved in this less complex instrument. An initial version of software for automatic characterization of tunable diode lasers has been developed and diodes have been characterized in order to establish their spectral output properties. A new state-of-the-art high operating temperature (200 K) mid infrared diode laser was purchased (through NASA procurement) and characterized. A thermo-electrically cooled mid infrared tunable diode laser system for use with high temperature operation lasers was developed. In addition to isotopic ratio measurements of carbon and oxygen, measurements of a third biologically important element (15N/14N in N2O gas) have been achieved to a preliminary accuracy of about 0.2%. Transfer of the basic SILS technology to the commercial sector is proceeding under an unfunded Space Act Agreement between NASA and SpiraMed, a medical diagnostic instrument company. Two patents have been issued. Foreign patents based on these two US patents have been applied for and are expected to be issued. A preliminary design was developed for a thermo-electrically cooled SILS instruments for application to planetary space flight exploration missions.

  3. Microscopic observation of kinetic molecular sieving of hydrogen isotopes in a nanoporous material.

    PubMed

    Nguyen, T X; Jobic, H; Bhatia, S K

    2010-08-20

    We report quasielastic neutron scattering studies of H2-D2 diffusion in a carbon molecular sieve, demonstrating remarkable quantum effects, with the heavier isotope diffusing faster below 100 K, confirming our recent predictions. Our transition state theory and molecular dynamics calculations show that while it is critical for this effect to have narrow windows of size comparable to the de Broglie wavelength, high flux requires that the energy barrier be reduced through small cages. Such materials will enable novel processes for kinetic molecular sieving of hydrogen isotopes.

  4. Microscopic Observation of Kinetic Molecular Sieving of Hydrogen Isotopes in a Nanoporous Material

    NASA Astrophysics Data System (ADS)

    Nguyen, T. X.; Jobic, H.; Bhatia, S. K.

    2010-08-01

    We report quasielastic neutron scattering studies of H2-D2 diffusion in a carbon molecular sieve, demonstrating remarkable quantum effects, with the heavier isotope diffusing faster below 100 K, confirming our recent predictions. Our transition state theory and molecular dynamics calculations show that while it is critical for this effect to have narrow windows of size comparable to the de Broglie wavelength, high flux requires that the energy barrier be reduced through small cages. Such materials will enable novel processes for kinetic molecular sieving of hydrogen isotopes.

  5. Isotope shifts of natural Sr+ measured by laser fluorescence in a sympathetically cooled Coulomb crystal

    NASA Astrophysics Data System (ADS)

    Dubost, B.; Dubessy, R.; Szymanski, B.; Guibal, S.; Likforman, J.-P.; Guidoni, L.

    2014-03-01

    We measured by laser spectroscopy the isotope shifts between naturally occurring even isotopes of strontium ions for both the 5s2S1/2→5p2P1/2 (violet) and the 4d2D3/2→5p2P1/2 (infrared) dipole-allowed optical transitions. Fluorescence spectra were taken by simultaneous measurements on a two-component Coulomb crystal in a linear Paul trap containing 103-104 laser-cooled Sr+ ions. The isotope shifts are extracted from the experimental spectra by fitting the data with the analytical solution of the optical Bloch equations describing a three-level atom interacting with two laser beams. This technique allowed us to increase the precision with respect to previously reported data obtained by optogalvanic spectroscopy or fast atomic-beam techniques. The results for the 5s2S1/2→5p2P1/2 transition are ν88-ν84=+378(4) MHz and ν88-ν86=+170(3) MHz, in agreement with previously reported measurements. In the case of the previously unexplored 4d2D3/2→5p2P1/2 transition we find ν88-ν84=-828(4) MHz and ν88-ν86=-402(2) MHz. These results provide more data for stringent tests of theoretical calculations of the isotope shifts of alkali-metal-like atoms. Moreover, they simplify the identification and the addressing of Sr+ isotopes for ion frequency standards or quantum-information-processing applications in the case of multi-isotope ion strings.

  6. Molecular Dynamics Simulations of Laser Powered Carbon Nanotube Gears

    NASA Technical Reports Server (NTRS)

    Srivastava, Deepak; Globus, Al; Han, Jie; Chancellor, Marisa K. (Technical Monitor)

    1997-01-01

    Dynamics of laser powered carbon nanotube gears is investigated by molecular dynamics simulations with Brenner's hydrocarbon potential. We find that when the frequency of the laser electric field is much less than the intrinsic frequency of the carbon nanotube, the tube exhibits an oscillatory pendulam behavior. However, a unidirectional rotation of the gear with oscillating frequency is observed under conditions of resonance between the laser field and intrinsic gear frequencies. The operating conditions for stable rotations of the nanotube gears, powered by laser electric fields are explored, in these simulations.

  7. Upgrade of the resonance ionization laser ion source at ISOLDE on-line isotope separation facility: New lasers and new ion beamsa)

    NASA Astrophysics Data System (ADS)

    Fedosseev, V. N.; Berg, L.-E.; Fedorov, D. V.; Fink, D.; Launila, O. J.; Losito, R.; Marsh, B. A.; Rossel, R. E.; Rothe, S.; Seliverstov, M. D.; Sjödin, A. M.; Wendt, K. D. A.

    2012-02-01

    The resonance ionization laser ion source (RILIS) produces beams for the majority of experiments at the ISOLDE on-line isotope separator. A substantial improvement in RILIS performance has been achieved through a series of upgrade steps: replacement of the copper vapor lasers by a Nd:YAG laser; replacement of the old homemade dye lasers by new commercial dye lasers; installation of a complementary Ti:Sapphire laser system. The combined dye and Ti:Sapphire laser system with harmonics is capable of generating beams at any wavelength in the range of 210-950 nm. In total, isotopes of 31 different elements have been selectively laser-ionized and separated at ISOLDE, including recently developed beams of samarium, praseodymium, polonium, and astatine.

  8. Application of diode lasers to the isotopically selective determination of uranium in oxides by optogalvanic spectroscopy

    SciTech Connect

    Young, J.P.; Barshick, C.M.; Shaw, R.W.; Ramsey, J.M.

    1994-09-01

    We have observed isotopically selective diode laser-excited optogalvanic effects in uranium at 778.42 and 776.19 nm. The samples were natural abundance uranium oxide, as well as depleted (0.3% {sup 235}U), natural (0.7% {sup 235}U) and enriched (9.75% {sup 235}U) uranium metal or powders. The measurements were carried out in a demountable-cathode glow discharge cell. Preliminary evaluations of precision for uranium isotopic ratios measured using this technique suggest that it should have broad analytical applications for uranium and other amenable actinides or lanthanides.

  9. Molecular Iodine Fluorescence Using a Green Helium-Neon Laser

    ERIC Educational Resources Information Center

    Williamson, J. Charles

    2011-01-01

    Excitation of molecular iodine vapor with a green (543.4 nm) helium-neon laser produces a fluorescence spectrum that is well suited for the upper-level undergraduate physical chemistry laboratory. Application of standard evaluation techniques to the spectrum yields ground electronic-state molecular parameters in good agreement with literature…

  10. Advances in the measurement of sulfur isotopes using laser ablation MC-ICP- MS

    NASA Astrophysics Data System (ADS)

    Ridley, W. I.; Pribil, M. J.; Koenig, A. E.; Fayek, M.; Slack, J. F.

    2008-05-01

    Although sulfur is poorly ionized in an argon plasma, there are many applications for sulfur isotope analysis using an ICP source. Studies using a desolvation system (DSN) and an aqueous source of sulfur, where the sulfur is complexed with a cation to form a sulfur salt, e.g., calcium or sodium to provide a stable delivery of sulfur through the sample introduction system indicate that precision (~ 0.3 per mil) and accuracy are maintained at sulfur concentrations as low as 1 mg/L. Based on this data, solid sampling of sulfides and sulfates can provide an adequate amount supply of sulfur to an ICP source, even allowing for the relatively poor transport efficiency of laser ablation systems. The main limitations on accuracy and precision are the initial sampling volume, principally a function of spot size and laser fluence and the decreased instrument sensitivity resulting from the pseudo- medium or high resolution mode of analysis required to eliminate polyatomic isobaric interferences. These factors, in turn, determine the minimal grain size necessary for analysis. There are also fit-for-purpose considerations. For instance, many base metal sulfide systems have large variations in sulfur isotope composition, so that precision as poor as one per mil can still provide useful information. Here, we describe the methodology used at the USGS for laser ablation analysis of sulfides and sulfates using a second generation MC-ICP-MS and demonstrate the accuracy of the method based upon a grain-by-grain comparison of laser ablation and ion microprobe sulfur isotope data. A laser ablation MC-ICP-MS study of base metal mineralization at Dry Creek deposit, east-central Alaska demonstrates that the range in sulfur isotope composition of pyrite, sphalerite and galena, based on analysis of individual grains, is almost twice that reported for any other individual VMS deposit. Analysis on the microscopic scale thus provides additional insights into the potential sources of sulfur for

  11. Diode laser operating on an atomic transition limited by an isotope ⁸⁷Rb Faraday filter at 780 nm.

    PubMed

    Tao, Zhiming; Hong, Yelong; Luo, Bin; Chen, Jingbiao; Guo, Hong

    2015-09-15

    We demonstrate an extended cavity Faraday laser system using an antireflection-coated laser diode as the gain medium and the isotope (87)Rb Faraday anomalous dispersion optical filter (FADOF) as the frequency selective device. Using this method, the laser wavelength works stably at the highest transmission peak of the isotope (87)Rb FADOF over the laser diode current from 55 to 140 mA and the temperature from 15°C to 35°C. Neither the current nor the temperature of the laser diode has significant influence on the output frequency. Compared with previous extended cavity laser systems operating at frequencies irrelevant to spectacular atomic transition lines, the laser system realized here provides a stable laser source with the frequency operating on atomic transitions for many practical applications.

  12. Isotopic Analysis of Uranium in NIST SRM Glass by Femtosecond Laser Ablation

    SciTech Connect

    Duffin, Andrew M.; Hart, Garret L.; Hanlen, Richard C.; Eiden, Gregory C.

    2013-05-19

    We employed femtosecond Laser Ablation Multicollector Inductively Coupled Mass Spectrometry for the 11 determination of uranium isotope ratios in a series of standard reference material glasses (NIST 610, 612, 614, and 12 616). This uranium concentration in this series of SRM glasses is a combination of isotopically natural uranium in 13 the materials used to make the glass matrix and isotopically depleted uranium added to increase the uranium 14 elemental concentration across the series. Results for NIST 610 are in excellent agreement with literature values. 15 However, other than atom percent 235U, little information is available for the remaining glasses. We present atom 16 percent and isotope ratios for 234U, 235U, 236U, and 238U for all four glasses. Our results show deviations from the 17 certificate values for the atom percent 235U, indicating the need for further examination of the uranium isotopes in 18 NIST 610-616. Our results are fully consistent with a two isotopic component mixing between the depleted 19 uranium spike and natural uranium in the bulk glass.

  13. A laser GC-IRMS technique for in situ stable isotope analyses of carbonates and phosphates

    NASA Astrophysics Data System (ADS)

    Sharp, Z. D.; Cerling, T. E.

    1996-08-01

    A technique is described whereby in situ carbon and oxygen isotope analyses of carbonates and organic phosphates can be made with the use of a CO 2 laser. The CO 2 gas generated by thermal decarbonation from the laser is entrained in a helium carrier gas, passes through a chromatographic column (GC), and is admitted directly into the isotope ratio mass spectrometer (IRMS). No vacuum systems, pumps, or cryogenic traps are used. All carbonates and biogenic phosphates can be analyzed, no special sample preparation is required and analyses can be made every 3 minutes. The use of a helium carrier gas allows for extremely small samples to be analyzed and the GC column effectively separates CO 2 from any other potential contaminating gases (e.g., SO 2 which is a particular problem in organic apatite). The average reproducibility of calcite, dolomite, magnesite, rhodochrosite, siderite, and smithsonite (ZnCO 3) is 0.29‰ for oxygen and 0.1‰ for carbon (1σ); the most "homogeneous" samples are reproducible to better than 0.1‰ for carbon and 0.2‰ for oxygen. The difference between the laser and conventional values for carbon isotope ratios [Δ 13C (laser-conv)] is 0.05 ± 0.30‰ for all carbonates (excluding siderite). The Δ 18O(laser-conv) value varies from carbonate to carbonate and may be related to the electronegativities of the cations, grain size (or crystallinity), formation of CO and O 2, and reaction with included organic matter. For calcite and rhodochrosite, the Δ 18O(laser-conv) value is 0.3 ± 0.4‰; for siderite, magnesite, and dolomite, the Δ 18O(laser-conv) value is 1.7 ± 0.3‰. The δ 13C values of tooth enamel are the same as those obtained by conventional acid digestion. The laser δ 18O values are equal to the δ 18O values of the phosphate, and approx. 7‰ lighter than the "carbonate" oxygen. The carbonate group in the apatite (equiv. 7.6% oxygen) exchanges with the (PO 4=)-bound oxygen to produce CO 2 with a δ 18O equal to the phosphate

  14. Isotopic determination of uranium in soil by laser induced breakdown spectroscopy

    NASA Astrophysics Data System (ADS)

    Chan, George C.-Y.; Choi, Inhee; Mao, Xianglei; Zorba, Vassilia; Lam, Oanh P.; Shuh, David K.; Russo, Richard E.

    2016-08-01

    Laser-induced breakdown spectroscopy (LIBS) operated under ambient pressure has been evaluated for isotopic analysis of uranium in real-world samples such as soil, with U concentrations in the single digit percentage levels. The study addresses the requirements for spectral decomposition of 235U and 238U atomic emission peaks that are only partially resolved. Although non-linear least-square fitting algorithms are typically able to locate the optimal combination of fitting parameters that best describes the experimental spectrum even when all fitting parameters are treated as free independent variables, the analytical results of such an unconstrained free-parameter approach are ambiguous. In this work, five spectral decomposition algorithms were examined, with different known physical properties (e.g., isotopic splitting, hyperfine structure) of the spectral lines sequentially incorporated into the candidate algorithms as constraints. It was found that incorporation of such spectral-line constraints into the decomposition algorithm is essential for the best isotopic analysis. The isotopic abundance of 235U was determined from a simple two-component Lorentzian fit on the U II 424.437 nm spectral profile. For six replicate measurements, each with only fifteen laser shots, on a soil sample with U concentration at 1.1% w/w, the determined 235U isotopic abundance was (64.6 ± 4.8)%, and agreed well with the certified value of 64.4%. Another studied U line - U I 682.691 nm possesses hyperfine structure that is comparatively broad and at a significant fraction as the isotopic shift. Thus, 235U isotopic analysis with this U I line was performed with spectral decomposition involving individual hyperfine components. For the soil sample with 1.1% w/w U, the determined 235U isotopic abundance was (60.9 ± 2.0)%, which exhibited a relative bias about 6% from the certified value. The bias was attributed to the spectral resolution of our measurement system - the measured line

  15. Laser photochemical lead isotopes separation for harmless nuclear power engineering

    NASA Astrophysics Data System (ADS)

    Bokhan, P. A.; Fateev, N. V.; Kim, V. A.; Zakrevsky, D. E.

    2016-09-01

    The collisional quenching of the metastable 3 P 1,2 and 1 D 2 lead atoms is studied experimentally in the gas flow of the lead atoms, reagent-molecules and a carrier gas Ar. The experimental parameters were similar to the conditions that are required in the operation of the experimental setup for photochemical isotope separation. Excited atoms are generated under electron impact conditions created by a gas glow discharge through the mixture of gases and monitored photoelectrically by attenuation of atomic resonance radiation from hollow cathode 208Pb lamp. The decay of the excited atoms has been studied in the presence various molecules and total cross section data are reported. The flow tube measurements has allowed to separate the physical and chemical quenching channels and measure the rates of the chemical reaction excited lead with N2O, CH2Cl2, SF6 and CuBr molecules. These results are discussed in the prospects of the obtaining isotopically modified lead as a promising coolant in the reactors on the fast-neutron.

  16. Optically Pumped Far Infrared Molecular Lasers.

    DTIC Science & Technology

    1980-04-01

    third and fifth order nonlinear processes can exceed first order laser processes. An experimental study of the generation of a 22.653 GHz signal (the...prime, practical sources. There are no counterparts in the far infrared of devices like IMPATTs, magnetrons, laser diodes, gyrotrons , etc. While in...1,000 GHz , the only proven, high spectral quality, modest technology, coherent source available to all researchers in the area, is the opti- cally

  17. Laser ablation inductively coupled plasma mass spectrometry measurement of isotope ratios in depleted uranium contaminated soils.

    PubMed

    Seltzer, Michael D

    2003-09-01

    Laser ablation of pressed soil pellets was examined as a means of direct sample introduction to enable inductively coupled plasma mass spectrometry (ICP-MS) screening of soils for residual depleted uranium (DU) contamination. Differentiation between depleted uranium, an anthropogenic contaminant, and naturally occurring uranium was accomplished on the basis of measured 235U/238U isotope ratios. The amount of sample preparation required for laser ablation is considerably less than that typically required for aqueous sample introduction. The amount of hazardous laboratory waste generated is diminished accordingly. During the present investigation, 235U/238U isotope ratios measured for field samples were in good agreement with those derived from gamma spectrometry measurements. However, substantial compensation was required to mitigate the effects of impaired pulse counting attributed to sample inhomogeneity and sporadic introduction of uranium analyte into the plasma.

  18. Understanding N2O sources and sinks with laser based isotopic analysis

    NASA Astrophysics Data System (ADS)

    Mohn, J.

    2015-12-01

    Nitrous oxide (N2O) is a potent greenhouse gas and the strongest stratospheric ozone-destroying substance released in the 21st century. Main N2O emissions are linked to different microbial pathways, therefore sources are disperse and highly variable, complicating their interpretation. Isotopic measurements have great potential to distinguish between individual source and sink processes. Developments in laser spectroscopy allow both the intramolecular distribution of 15N substitutions (15N14N16O versus 14N15N16O) and the oxygen isotopic composition of N2O to be measured in real-time, at high precision and in excellent compatibility to IRMS [1]. In a number of laboratory and pilot plant studies we investigated the isotopic signature of distinct microbial and abiotic N2O production and consumption pathways in soil and aqueous solution [e.g. 2-4]. Specific pathways were favoured by selection of the nitrogen substrates and process conditions and their isotopic signatures identified by real-time laser spectroscopic analysis. Results from our laboratory studies are in accordance with pure culture experiments and can therefore be applied to other ecosystems. High precision isotopic analysis at ambient N2O concentration is feasible by combining laser spectroscopy with automated preconcentration. Field deployment was demonstrated by real-time monitoring of the isotopic composition of N2O emissions above an intensively managed grassland in central Switzerland. The responses of the N2O isotopic signatures were analysed with respect to management events and climatic conditions [5]. In a follow-up project we combine real-time N2O isotopic analysis at a tall tower in central Switzerland with atmospheric transport simulations and a biogeochemical model of surface fluxes of N2O isotopomers. The working hypothesis is that this approach will allow us to quantify regional N2O sources, identify emission hot spots, and constrain source processes, which will significantly advance our

  19. Laser Development in Support of the JUMPer Program for Laser Isotope Separation.

    DTIC Science & Technology

    Contents: Growth and characterization of infrared nonlinear crystals; Application of infrared nonlinear crystals; Optically pumped lasers; CO2 laser development and evaluation; Related work not supported by LASL/ERDA.

  20. Isotope separation apparatus and method

    DOEpatents

    Feldman, Barry J.

    1985-01-01

    The invention relates to an improved method and apparatus for laser isotope separation by photodeflection. A molecular beam comprising at least two isotopes to be separated intersects, preferably substantially perpendicular to one broad side of the molecular beam, with a laser beam traveling in a first direction. The laser beam is reflected back through the molecular beam, preferably in a second direction essentially opposite to the first direction. Because the molecules in the beam occupy various degenerate energy levels, if the laser beam comprises chirped pulses comprising selected wavelengths, the laser beam will very efficiently excite substantially all unexcited molecules and will cause stimulated emission of substantially all excited molecules of a selected one of the isotopes in the beam which such pulses encounter. Excitation caused by first direction chirped pulses moves molecules of the isotope excited thereby in the first direction. Stimulated emission of excited molecules of the isotope is brought about by returning chirped pulses traveling in the second direction. Stimulated emission moves emitting molecules in a direction opposite to the photon emitted. Because emitted photons travel in the second direction, emitting molecules move in the first direction. Substantial molecular movement of essentially all the molecules containing the one isotope is accomplished by a large number of chirped pulse-molecule interactions. A beam corer collects the molecules in the resulting enriched divergent portions of the beam.

  1. Molecular dispersion spectroscopy – new capabilities in laser chemical sensing

    PubMed Central

    Nikodem, Michal; Wysocki, Gerard

    2012-01-01

    Laser spectroscopic techniques suitable for molecular dispersion sensing enable new applications and strategies in chemical detection. This paper discusses the current state-of-the art and provides an overview of recently developed chirped laser dispersion spectroscopy (CLaDS) based techniques. CLaDS and its derivatives allow for quantitative spectroscopy of trace-gases and enable new capabilities such as extended dynamic range of concentration measurements, high immunity to photodetected intensity fluctuations, or capability of direct processing of spectroscopic signals in optical domain. Several experimental configurations based on quantum cascade lasers and examples of molecular spectroscopic data are presented to demonstrate capabilities of molecular dispersion spectroscopy in the mid-infrared spectral region. PMID:22809459

  2. Development of a sensitive setup for laser spectroscopy studies of very exotic calcium isotopes

    NASA Astrophysics Data System (ADS)

    Garcia Ruiz, R. F.; Gorges, C.; Bissell, M.; Blaum, K.; Gins, W.; Heylen, H.; Koenig, K.; Kaufmann, S.; Kowalska, M.; Krämer, J.; Lievens, P.; Malbrunot-Ettenauer, S.; Neugart, R.; Neyens, G.; Nörtershäuser, W.; Yordanov, D. T.; Yang, X. F.

    2017-04-01

    An experimental setup for sensitive high-resolution measurements of hyperfine structure spectra of exotic calcium isotopes has been developed and commissioned at the COLLAPS beam line at ISOLDE, CERN. The technique is based on the radioactive detection of decaying isotopes after optical pumping and state selective neutralization (ROC) (Vermeeren et al 1992 Phys. Rev. Lett. 68 1679). The improvements and developments necessary to extend the applicability of the experimental technique to calcium isotopes produced at rates as low as few ions s–1 are discussed. Numerical calculations of laser-ion interaction and ion-beam simulations were explored to obtain the optimum performance of the experimental setup. Among the implemented features are a multi-step optical pumping region for sensitive measurements of isotopes with hyperfine splitting, a high-voltage platform for adequate control of low-energy ion beams and simultaneous β-detection of neutralized and remaining ions. The commissioning of the experimental setup, and the first online results on neutron-rich calcium isotopes are presented.

  3. High-Frequency Isotope Measurements in Nitrous Oxide by Using Mid-Ir Laser Absorption Spectroscopy

    NASA Astrophysics Data System (ADS)

    Dong, F.; Baer, D. S.

    2010-12-01

    The stable isotope composition of atmosphere trace gases provides information of their origin and fate that cannot be determined from their concentration measurements alone. Biological source and loss processes, like bacterial production of N2O, are typically accompanied by isotopic selectivity associated with the kinetics of bond formation and destruction. Of the three important biologically mediated greenhouse gases (CO2, CH4 and N2O), the understanding of N2O isotopic budget in air lags far behind the other two gases. One of the reasons of this is due to the low concentration of N2O in ambient air (~320 ppbv), which leads to inherent difficulties in collection, extraction and analysis. We report on the development of novel instrumentation for real-time measurements of nitrogen-isotope ratio (δ15N) and mixing ratio [N2O] of nitrous oxide over a very wide range of mixing ratios. This novel technology, which employs cavity enhanced absorption and a mid-infrared laser and does not require any cryogenic components, has been developed for in situ simultaneous measurements of the mixing ratios of three main isotopomers - 14N14N16O, 15N14N16O and 14N15N16O, which leads to the nitrogen-isotope ratio (δ15N) and the 15N position-dependent enrichment. A precision of better than 1 per mil may be achieved in ambient air (300 ppbv N2O) in less than 300 seconds measurement time.

  4. Space interferometry application of laser frequency stabilization with molecular iodine.

    PubMed

    Leonhardt, Volker; Camp, Jordan B

    2006-06-10

    A number of planned space interferometry missions, including the Laser Interferometer Space Antenna (LISA) gravitational wave detector, require a laser system with high-frequency stability over long time scales. A 1064 nm wavelength nonplanar ring oscillator (NPRO) laser stabilized to a resonant transition in molecular iodine is suitable for these missions, providing high-frequency stability at an absolute reference frequency. The iodine stabilized laser also offers low sensitivity to temperature and alignment fluctuations and allows frequency tuning. We have evaluated the noise performance of a NPRO laser stabilized to iodine using frequency modulation spectroscopy and have found an Allan standard deviation of 10(-14) over 100 s. Simplified optical configurations and the radiation hardness of the frequency-doubling crystals have also been investigated.

  5. Molecular dynamics investigation of mechanisms of femtosecond laser ablation

    NASA Astrophysics Data System (ADS)

    Cheng, Changrui

    Laser micro-machining has been widely applied for material processing in many industries. A phenomenon called "laser ablation" is usually involved in the laser micro-machining process. Laser ablation is the process of material removal after the irradiation of a laser beam onto the material. It is commonly characterized by small temporal and spatial scales, extremely high material temperature and pressure, and strong non-equilibrium thermodynamic state. In this work, molecular dynamics (MD) simulation is conducted to study the femtosecond laser ablation of metals (nickel and copper) and dielectrics (fused silica, or glass). The laser heating and the ablation processes are numerically modeled, and the computation is accelerated by parallel processing technique. Both the pair-wise Morse potential and the many-body EAM (Embedded-Atom Method) potential are employed for metals. In the simulation of fused silica, the BKS (van Beest, Kramer and van Santen) potential is used, and the generation of free electrons, the energy transport from laser beam to free electrons and energy coupling between electrons and the lattice are considered. The main goal of this work is to illustrate the detailed processes of femtosecond laser ablation and to study its mechanisms. From the MD results, it is found that the mechanism of femtosecond laser ablation is strongly dependent on the laser fluences. For metals, low fluence laser ablation is mainly through phase explosion (homogeneous gas bubble nucleation), while spinodal decomposition is responsible for high fluence ablation. Ablation mechanism is determined by whether or not the material (liquid) temperature exceeds the critical temperature. For fused silica, the generation and existence of free electrons are found to affect ablation significantly, especially at low fluence, where Coulomb explosion is found to play an important role in material separation.

  6. The molecular physics of photolytic fractionation of sulfur and oxygen isotopes in planetary atmospheres (Invited)

    NASA Astrophysics Data System (ADS)

    Johnson, M. S.; Schmidt, J. A.; Hattori, S.; Danielache, S.; Meusinger, C.; Schinke, R.; Ueno, Y.; Nanbu, S.; Kjaergaard, H. G.; Yoshida, N.

    2013-12-01

    Atmospheric photochemistry is able to produce large mass independent anomalies in atmospheric trace gases that can be found in geological and cryospheric records. This talk will present theoretical and experimental investigations of the molecular mechanisms producing photolytic fractionation of isotopes with special attention to sulfur and oxygen. The zero point vibrational energy (ZPE) shift and reflection principle theories are starting points for estimating isotopic fractionation, but these models ignore effects arising from isotope-dependent changes in couplings between surfaces, excited state dynamics, line densities and hot band populations. The isotope-dependent absorption spectra of the isotopologues of HCl, N2O, OCS, CO2 and SO2 have been examined in a series of papers and these results are compared with experiment and ZPE/reflection principle models. Isotopic fractionation in planetary atmospheres has many interesting applications. The UV absorption of CO2 is the basis of photochemistry in the CO2-rich atmospheres of the ancient Earth, and of Mars and Venus. For the first time we present accurate temperature and isotope dependent CO2 absorption cross sections with important implications for photolysis rates of SO2 and H2O, and the production of a mass independent anomaly in the Ox reservoir. Experimental and theoretical results for OCS have implications for the modern stratospheric sulfur budget. The absorption bands of SO2 are complex with rich structure producing isotopic fractionation in photolysis and photoexcitation.

  7. Lasers '83. Proceedings of the international conference

    SciTech Connect

    Powell, R.C.

    1985-01-01

    Among the topics discussed are the development history of the semiconductor diode laser, laser material processing, nonlinear spectroscopy, recent advancements in diode lasers, laser-driven particle accelerators, laser applications in the atmospheric sciences, laser-assisted collisions, novel (garnet and alexandrite) solid state laser materials, IR molecular lasers, devices and components for fiber-optic communications, free-electron lasers and masers, and picosecond optical phenomena. Also covered are laser-stimulated materials surface processes, color center laser developments, blue-green and metal vapor lasers, laser chemistry, nonlinear effects, high energy lasers, excimer lasers, laser trapping of ions, optical cavities and propagation, laser isotope separation, laser trapping of atoms, laser applications in biochemistry, tunable coherent short wavelength radiation, laser spectroscopy, picosecond studies of condensed phase molecular systems, and combustion and plasma diagnostics.

  8. Highly isotopically depleted isoprenoids: Molecular markers for ancient methane venting

    SciTech Connect

    Thiel, V.; Peckmann, J.; Seifert, R.; Wehrung, P.; Reitner, J.; Michaelis, W.

    1999-12-01

    The authors propose that organic compounds found in a Miocene limestone from Marmorito (Northern Italy) are source markers for organic matter present in ancient methane vent systems (cold seeps). The limestone contains high concentrations of the tail-to-tail linked, acyclic C{sub 20} isoprenoid 2,6,11,15-tetramethylhexadecane (crocetane), a C{sub 25} homolog 2,6,10,15,19-pentamethylicosane (PME), and a distinctive glycerol ether lipid containing 3,7,11,15-tetramethylhexadecyl (phytanyl-) moieties. The chemical structures of these biomarkers indicate a common origin from archaea. Their extremely {sup 13}C-depleted isotope compositions ({delta}{sup 13}C {approximately} {minus}108 to {minus}115.6% PDB) suggest that the respective archaea have directly or indirectly introduced isotopically depleted, methane-derived carbon into their biomass. The authors postulate that a second major cluster of biomarkers showing heavier isotope values ({delta}{sup 13}C {approximately} {minus}88%) is derived from sulfate-reducing bacteria (SRB). The observed biomarkers sustain the idea that methanogenic bacteria, in a syntrophic community with SRB, are responsible for the anaerobic oxidation of methane in marine sediments. Marmorito may thus represent a conceivable ancient scenario for methane consumption performed by a defined, two-membered bacterial consortium: (1) archaea that perform reversed methanogenesis by oxidizing methane and producing CO{sub 2} and H{sub 2}; and (2) SRB that consume the resulting H{sub 2}. Furthermore, the respective organic molecules are, unlike other compounds, tightly bound to the crystalline carbonate phase. The Marmorito carbonates can thus be regarded as cold seep microbialites rather than mere antigenic carbonates.

  9. Quantifying Uranium Isotope Ratios Using Resonance Ionization Mass Spectrometry: The Influence of Laser Parameters on Relative Ionization Probability

    SciTech Connect

    Isselhardt, Brett H.

    2011-09-01

    Resonance Ionization Mass Spectrometry (RIMS) has been developed as a method to measure relative uranium isotope abundances. In this approach, RIMS is used as an element-selective ionization process to provide a distinction between uranium atoms and potential isobars without the aid of chemical purification and separation. We explore the laser parameters critical to the ionization process and their effects on the measured isotope ratio. Specifically, the use of broad bandwidth lasers with automated feedback control of wavelength was applied to the measurement of 235U/238U ratios to decrease laser-induced isotopic fractionation. By broadening the bandwidth of the first laser in a 3-color, 3-photon ionization process from a bandwidth of 1.8 GHz to about 10 GHz, the variation in sequential relative isotope abundance measurements decreased from >10% to less than 0.5%. This procedure was demonstrated for the direct interrogation of uranium oxide targets with essentially no sample preparation. A rate equation model for predicting the relative ionization probability has been developed to study the effect of variation in laser parameters on the measured isotope ratio. This work demonstrates that RIMS can be used for the robust measurement of uranium isotope ratios.

  10. Utility of 5A molecular sieves to measure carbon isotope ratios in lipid biomarkers.

    PubMed

    Tolosa, Imma; Ogrinc, Nives

    2007-09-21

    A procedure using 5A zeolite sorption to separate cyclic/branched organic compounds from the linear ones was developed and carbon isotopic fractionation effects were investigated in different families of compounds, e.g. within the hydrocarbon and alcohol compounds. The 5A sieve has a pore size such that only linear components can be incorporated into the pores whereas the cyclic/branched compounds are remaining free in the organic solution. The sorbed compounds were released from the molecular sieve with HF and solvent extracted with hexane. The method enables the isolation of linear saturated classes, such as n-alkanes and n-fatty alcohols from branched/cyclic compounds without isotopic fractionation for compound-specific isotope analysis (CSIA) of delta(13)C. However, alkene hydrocarbons, sterols and some aromatics were completely or partly degraded with the molecular sieve.

  11. Linear and Nonlinear Molecular Spectroscopy with Laser Frequency Combs

    NASA Astrophysics Data System (ADS)

    Picque, Nathalie

    2013-06-01

    The regular pulse train of a mode-locked femtosecond laser can give rise to a comb spectrum of millions of laser modes with a spacing precisely equal to the pulse repetition frequency. Laser frequency combs were conceived a decade ago as tools for the precision spectroscopy of atomic hydrogen. They are now becoming enabling tools for an increasing number of applications, including molecular spectroscopy. Recent experiments of multi-heterodyne frequency comb Fourier transform spectroscopy (also called dual-comb spectroscopy) have demonstrated that the precisely spaced spectral lines of a laser frequency comb can be harnessed for new techniques of linear absorption spectroscopy. The first proof-of-principle experiments have demonstrated a very exciting potential of dual-comb spectroscopy without moving parts for ultra-rapid and ultra-sensitive recording of complex broad spectral bandwidth molecular spectra. Compared to conventional Michelson-based Fourier transform spectroscopy, recording times could be shortened from seconds to microseconds, with intriguing prospects for spectroscopy of short lived transient species. The resolution improves proportionally to the measurement time. Therefore longer recordings allow high resolution spectroscopy of molecules with extreme precision, since the absolute frequency of each laser comb line can be known with the accuracy of an atomic clock. Moreover, since laser frequency combs involve intense ultrashort laser pulses, nonlinear interactions can be harnessed. Broad spectral bandwidth ultra-rapid nonlinear molecular spectroscopy and imaging with two laser frequency combs is demonstrated with coherent Raman effects and two-photon excitation. Real-time multiplex accessing of hyperspectral images may dramatically expand the range of applications of nonlinear microscopy. B. Bernhardt et al., Nature Photonics 4, 55-57 (2010); A. Schliesser et al. Nature Photonics 6, 440-449 (2012); T. Ideguchi et al. arXiv:1201.4177 (2012) T

  12. Molecular and isotopic insights into methane oxidation in Lake Kivu

    NASA Astrophysics Data System (ADS)

    Zigah, P. K.; Wehrli, B.; Schubert, C. J.

    2013-12-01

    Lake Kivu is a meromictic lake in the East African Rift Valley, located between the Republic of Rwanda and the Democratic Republic of Congo. The hypolimnion is permanently stratified and contain an unusually high amount of dissolved methane (CH4; ~ 60 km3) and carbon dioxide (CO2; ~300 km3) at standard temperature and pressure. While microbial-mediated methane oxidation is an important sink of methane in the lake, little is known about the distribution of microbes involved in the methane oxidation. To provide insights into methanotrophy in the lake, we analyzed depth profile of CH4, δ13C-CH4 and δ13C-DIC, δ13C-POC and the biomarkers of methanotrophic archaea and bacteria and their stable carbon isotopic composition from suspended particulate matter isolated from the lake water column. Our preliminary data show enhanced methane oxidation in oxic-anoxic transition zone in the water column. Depth distribution of diagnostic methanotrophic archaeal biomarkers such as archaeol and hydroxyarchaeol suggest archaea might be involved in anaerobic methane oxidation. Phospholipid fatty acids and diplopterol distribution and carbon isotopic signatures indicate bacteria-mediated anaerobic (and aerobic) methane oxidation in the lake.

  13. Rate equation model of laser induced bias in uranium isotope ratios measured by resonance ionization mass spectrometry

    DOE PAGES

    Isselhardt, B. H.; Prussin, S. G.; Savina, M. R.; ...

    2015-12-07

    Resonance Ionization Mass Spectrometry (RIMS) has been developed as a method to measure uranium isotope abundances. In this approach, RIMS is used as an element-selective ionization process between uranium atoms and potential isobars without the aid of chemical purification and separation. The use of broad bandwidth lasers with automated feedback control of wavelength was applied to the measurement of the 235U/238U ratio to decrease laser-induced isotopic fractionation. In application, isotope standards are used to identify and correct bias in measured isotope ratios, but understanding laser-induced bias from first-principles can improve the precision and accuracy of experimental measurements. A rate equationmore » model for predicting the relative ionization probability has been developed to study the effect of variations in laser parameters on the measured isotope ratio. The model uses atomic data and empirical descriptions of laser performance to estimate the laser-induced bias expected in experimental measurements of the 235U/238U ratio. Empirical corrections are also included to account for ionization processes that are difficult to calculate from first principles with the available atomic data. As a result, development of this model has highlighted several important considerations for properly interpreting experimental results.« less

  14. Rate equation model of laser induced bias in uranium isotope ratios measured by resonance ionization mass spectrometry

    SciTech Connect

    Isselhardt, B. H.; Prussin, S. G.; Savina, M. R.; Willingham, D. G.; Knight, K. B.; Hutcheon, I. D.

    2015-12-07

    Resonance Ionization Mass Spectrometry (RIMS) has been developed as a method to measure uranium isotope abundances. In this approach, RIMS is used as an element-selective ionization process between uranium atoms and potential isobars without the aid of chemical purification and separation. The use of broad bandwidth lasers with automated feedback control of wavelength was applied to the measurement of the 235U/238U ratio to decrease laser-induced isotopic fractionation. In application, isotope standards are used to identify and correct bias in measured isotope ratios, but understanding laser-induced bias from first-principles can improve the precision and accuracy of experimental measurements. A rate equation model for predicting the relative ionization probability has been developed to study the effect of variations in laser parameters on the measured isotope ratio. The model uses atomic data and empirical descriptions of laser performance to estimate the laser-induced bias expected in experimental measurements of the 235U/238U ratio. Empirical corrections are also included to account for ionization processes that are difficult to calculate from first principles with the available atomic data. As a result, development of this model has highlighted several important considerations for properly interpreting experimental results.

  15. Acousto-optically tuned isotopic CO{sub 2} lasers for long-range differential absorption LIDAR

    SciTech Connect

    Thompson, D.C.; Busch, G.E.; Hewitt, C.J.; Remelius, D.K.; Shimada, Tsutomu; Strauss, C.E.M.; Wilson, C.W.

    1998-12-01

    The authors are developing 2--100 kHz repetition rate CO{sub 2} lasers with milliJoule pulse energies, rapid acousto-optic tuning and isotopic gas mixes, for Differential Absorption LIDAR (DIAL) applications. The authors explain the tuning method, which uses a pair of acousto-optic modulators and is capable of random access to CO{sub 2} laser lines at rates of 100 kHz or more. The laser system is also described, and they report on performance with both normal and isotopic gas mixes.

  16. Determination of tin isotope ratios in cassiterite by femtosecond laser ablation multicollector inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Schulze, Marie; Ziegerick, Marco; Horn, Ingo; Weyer, Stefan; Vogt, Carla

    2017-04-01

    In comparison to isotope analysis of dissolved samples femtosecond laser ablation multicollector inductively coupled plasma mass spectrometry (fs-LA-MC-ICP-MS) enables precise isotope ratio analyses consuming much less sample material and with a minimum effort in sample preparation. This is especially important for the investigation of valuable historical objects for which visual traces of sampling are unwanted. The present study provides a basis for tin isotope ratio measurements using LA-MC-ICP-MS technique. For this, in house isotope standards had to be defined. Investigations on interferences and matrix effects illustrate that beside Sb only high Te contents (with values above those to be expected in cassiterite) result in a significant shift of the measured tin isotope ratios. This effect can partly be corrected for using natural isotope abundances. However, a natural isotope fractionation of Te cannot be excluded. Tin beads reduced from cassiterite were analysed by laser ablation and after dissolution. It was shown that tin isotope ratios can be determined accurately by using fs-LA-MC-ICP-MS. Furthermore the homogeneity of tin isotope ratios in cassiterite was proven.

  17. Matrix and energy effects during in-situ determination of Cu isotope ratios by ultraviolet-femtosecond laser ablation multicollector inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Lazarov, Marina; Horn, Ingo

    2015-09-01

    Copper isotope compositions in Cu-bearing metals and minerals have been measured by deep (194 nm) ultraviolet femtosecond laser ablation multi-collector inductively coupled plasma mass spectrometry (UV-fsLA-MC-ICP-MS). Pure Cu-metal, brass, and several Cu-rich minerals (chalcopyrite, enargite, covellite, malachite and cuprite) have been investigated. A long-term reproducibility of better than 0.08‰ at the 95% confidence limit on the NIST SRM 976 (National Institute of Standards and Technology) Cu-metal standard has been achieved with this technique. The δ65Cu values for all samples have been calculated by standard-sample-standard bracketing with NIST SRM 976. All analyses have been carried out using Ni as a mass discrimination monitor added by nebulization prior to entering the plasma torch. For further verification samples have been analysed by conventional solution nebulization MC-ICP-MS and the results obtained have been compared with those from UV-fsLA-MC-ICP-MS. Several potential matrix-induced molecular interferences on the mineral copper isotope ratio, such as (32S33S)+ and (32S-16O17O)+ do not affect the Cu isotope measurements on sulfides, while hydrides, such as Zn-H or doubly-charged Sn2 + that interfere Ni isotopes can be either neglected or stripped by calculation. Matrix independent Cu-isotope measurements are sensitive to the energy density (fluence) applied onto the sample and can produce artificial shifts in the obtained δ65Cu values which are on the order of 3‰ for Cu-metal, 0.5‰ for brass and 0.3‰ for malachite when using energy density of up to 2 J/cm2 for ablation. A positive correlation between applied energy density and the magnitude of the isotope ratio shift has been found in the energy density range from 0.2 to 1.3 J/cm2 which is below the ablation threshold for ns-laser ablation. The results demonstrate that by using appropriate low fluence it is possible to measure Cu isotopic ratios in native copper and Cu-bearing sulfides

  18. Thermal and molecular investigation of laser tissue welding

    SciTech Connect

    Small, W., IV

    1998-06-01

    Despite the growing number of successful animal and human trials, the exact mechanisms of laser tissue welding remain unknown. Furthermore, the effects of laser heating on tissue on the molecular scale are not fully understood. To address these issues, a multi-front attack oil both extrinsic (solder/patch mediated) and intrinsic (laser only) tissue welding was launched using two-color infrared thermometry, computer modeling, weld strength assessment, biochemical assays, and vibrational spectroscopy. The coupling of experimentally measured surface temperatures with the predictive numerical simulations provided insight into the sub-surface dynamics of the laser tissue welding process. Quantification of the acute strength of the welds following the welding procedure enabled comparison among trials during an experiment, with previous experiments, and with other studies in the literature. The acute weld integrity also provided an indication of tile probability of long-term success. Molecular effects induced In the tissue by laser irradiation were investigated by measuring tile concentrations of specific collagen covalent crosslinks and characterizing the Fourier-Transform infrared (FTIR) spectra before and after the laser exposure.

  19. Understanding N2O sources and sinks with laser based isotopic analysis

    NASA Astrophysics Data System (ADS)

    Mohn, Joachim; Harris, Eliza; Tuzson, Béla; Emmenegger, Lukas

    2015-04-01

    Nitrous oxide (N2O) is a potent greenhouse gas and the strongest ozone-destroying substance. The main emissions of N2O are linked to different microbial processes, therefore the sources are disperse and highly variable, complicating the development of effective mitigation strategies. Isotopic measurements have great potential to unravel spatial and temporal variations in sources, sinks and chemistry of N2O. Recent developments in quantum cascade laser spectroscopy (QCLAS) [1] allow both the intermolecular distribution of 15N substitutions ('site preference'; 15N14N16O versus 14N15N16O) and the oxygen isotopic composition (d18O) of N2O to be measured in real-time and at high precision of <0.2 ‰ [2]. Additionally, N2O isotopic analysis by QCLAS has demonstrated excellent compatibility to the standard technique isotope-ratio mass-spectrometry [3]. In a number of laboratory and pilot plant studies we investigated the isotopic signature of distinct microbial and abiotic N2O production and consumption pathways in soil and aqueous solution [e.g. 4]. Specific pathways were favoured by selection of the nitrogen substrates and process conditions and their isotopic signatures identified by real-time laser spectroscopic analysis. Results from our laboratory studies are in accordance with pure culture experiments and can therefore be applied to other ecosystems. Recently, high precision isotopic analysis at ambient N2O is also feasible by combining laser spectroscopy with automated preconcentration [5]. The field deployment was demonstrated by real-time monitoring isotopic composition of N2O emissions from an intensively managed grassland in central Switzerland for three months. The responses of the N2O isotopic signatures were analysed with respect to management events and weather influences [2]. In a follow-up project we intend to combine real-time N2O isotopic analysis at a tall tower in central Switzerland with atmospheric transport simulations and a biogeochemical model

  20. Direct Imaging of Laser-driven Ultrafast Molecular Rotation.

    PubMed

    Mizuse, Kenta; Fujimoto, Romu; Mizutani, Nobuo; Ohshima, Yasuhiro

    2017-02-04

    We present a method for visualizing laser-induced, ultrafast molecular rotational wave packet dynamics. We have developed a new 2-dimensional Coulomb explosion imaging setup in which a hitherto-impractical camera angle is realized. In our imaging technique, diatomic molecules are irradiated with a circularly polarized strong laser pulse. The ejected atomic ions are accelerated perpendicularly to the laser propagation. The ions lying in the laser polarization plane are selected through the use of a mechanical slit and imaged with a high-throughput, 2-dimensional detector installed parallel to the polarization plane. Because a circularly polarized (isotropic) Coulomb exploding pulse is used, the observed angular distribution of the ejected ions directly corresponds to the squared rotational wave function at the time of the pulse irradiation. To create a real-time movie of molecular rotation, the present imaging technique is combined with a femtosecond pump-probe optical setup in which the pump pulses create unidirectionally rotating molecular ensembles. Due to the high image throughput of our detection system, the pump-probe experimental condition can be easily optimized by monitoring a real-time snapshot. As a result, the quality of the observed movie is sufficiently high for visualizing the detailed wave nature of motion. We also note that the present technique can be implemented in existing standard ion imaging setups, offering a new camera angle or viewpoint for the molecular systems without the need for extensive modification.

  1. Molecular controls on Cu and Zn isotopic fractionation in Fe-Mn crusts

    NASA Astrophysics Data System (ADS)

    Little, S. H.; Sherman, D. M.; Vance, D.; Hein, J. R.

    2014-06-01

    The isotopic systems of the transition metals are increasingly being developed as oceanic tracers, due to their tendency to be fractionated by biological and/or redox-related processes. However, for many of these promising isotope systems the molecular level controls on their isotopic fractionations are only just beginning to be explored. Here we investigate the relative roles of abiotic and biotic fractionation processes in controlling modern seawater Cu and Zn isotopic compositions. Scavenging to Fe-Mn oxides represents the principal output for Cu and Zn to sediments deposited under normal marine (oxic) conditions. Using Fe-Mn crusts as an analogue for these dispersed phases, we investigate the phase association and crystal chemistry of Cu and Zn in such sediments. We present the results of an EXAFS study that demonstrate unequivocally that Cu and Zn are predominantly associated with the birnessite (δ-MnO2) phase in Fe-Mn crusts, as previously predicted from sequential leaching experiments (e.g., Koschinsky and Hein, 2003). The crystal chemistry of Cu and Zn in the crusts implies a reduction in coordination number in the sorbed phase relative to the free metal ion in seawater. Thus, theory would predict equilibrium fractionations that enrich the heavy isotope in the sorbed phase (e.g., Schauble, 2004). In natural samples, Fe-Mn crusts and nodules are indeed isotopically heavy in Zn isotopes (at ∼1‰) compared to deep seawater (at ∼0.5‰), consistent with the predicted direction of equilibrium isotopic fractionation based on our observations of the coordination environment of sorbed Zn. Further, ∼50% of inorganic Zn‧ is chloro-complexed (the other ∼50% is present as the free Zn2+ ion), and complexation by Cl- is also predicted to favour equilibrium partitioning of light Zn isotopes into the dissolved phase. The heavy Zn isotopic composition of Fe-Mn crusts and nodules relative to seawater can therefore be explained by an inorganic fractionation during

  2. Isotope fractionation of mercury during its photochemical reduction by low-molecular-weight organic compounds.

    PubMed

    Zheng, Wang; Hintelmann, Holger

    2010-04-01

    Photochemical reduction of Hg(II) by various low-molecular-weight organic compounds (LMWOC) was investigated to evaluate the effect of specific functional groups that are typically encountered in natural dissolved organic matters (DOM) on the photoreactivity and isotope fractionation of Hg. LMWOC with reduced sulfur functional groups (e.g., cysteine, glutathione) resulted in slower photochemical reduction of Hg(II) than those without reduced sulfur groups (e.g., serine, oxalic acid). Reduction rate constants were specifically determined for two contrasting LMWOC: dl-serine (0.640 h(-1)) and l-cysteine (0.047 h(-1)). Different mass independent isotope effects of Hg were induced by the two types of LMWOC. S-containing ligands specifically enriched magnetic isotopes ((199)Hg and (201)Hg) in the product (Hg(0)) while sulfurless ligands enriched (199)Hg and (201)Hg in the reactant (Hg(II)), suggesting that opposite magnetic isotope effects were produced by different types of ligands. The nuclear field shift effect was also observed in the photochemical reduction by serine. These isotope effects are related to specific functional groups and reduction mechanisms, and may be used to distinguish between primary and secondary photochemical reduction mechanisms of Hg(II) and to explain isotope fractionation during the photochemical reduction of Hg(II) by natural DOM, which provides mixed bonding conditions.

  3. Laser Excited Molecular Fluorescence of Solutions.

    ERIC Educational Resources Information Center

    Lytle, F. E.

    1982-01-01

    Major instrumental concerns in molecular solution fluorimetry have recently turned away from sensitivity enhancement to an orientation more directed toward selectivity. This trend simply recognizes that such methodology has historically been blank limited. Thus, the described uses of liquid chromatography, line narrowing, and time resolution…

  4. Molecular photoelectron holography with circularly polarized laser pulses.

    PubMed

    Yang, Weifeng; Sheng, Zhihao; Feng, Xingpan; Wu, Miaoli; Chen, Zhangjin; Song, Xiaohong

    2014-02-10

    We investigate the photoelectron momentum distribution of molecular-ion H2+driven by ultrashort intense circularly polarized laser pulses. Both numerical solutions of the time-dependent Schrödinger equation (TDSE) and a quasiclassical model indicate that the photoelectron holography (PH) with circularly polarized pulses can occur in molecule. It is demonstrated that the interference between the direct electron wave and rescattered electron wave from one core to its neighboring core induces the PH. Moreover, the results of the TDSE predict that there is a tilt angle between the interference pattern of the PH and the direction perpendicular to the molecular axis. Furthermore, the tilt angle is sensitively dependent on the wavelength of the driven circularly polarized pulse, which is confirmed by the quasiclassical calculations. The PH induced by circularly polarized laser pulses provides a tool to resolve the electron dynamics and explore the spatial information of molecular structures.

  5. Molecular and stable carbon isotopic characterization of PAH contaminants at McMurdo Station, Antarctica.

    PubMed

    Kim, Moonkoo; Kennicutt, Mahlon C; Qian, Yaorong

    2006-12-01

    The molecular and stable carbon isotopic compositions of contaminant polycyclic aromatic hydrocarbons (PAHs) at McMurdo Station, Antarctica were analyzed in samples collected from land and sub-tidal area. PAHs in the study areas were characterized by high amounts of naphthalene and alkylated naphthalenes from petroleum products introduced by human activities in the area. Principal component analysis (PCA) of PAH composition data identified multiple sources of PAH contamination in the study area. Compositional assignments of origins were confirmed using compound specific stable carbon isotopic analysis.

  6. In-gas-cell laser ionization studies of plutonium isotopes at IGISOL

    NASA Astrophysics Data System (ADS)

    Pohjalainen, I.; Moore, I. D.; Kron, T.; Raeder, S.; Sonnenschein, V.; Tomita, H.; Trautmann, N.; Voss, A.; Wendt, K.

    2016-06-01

    In-gas-cell resonance laser ionization has been performed on long-lived isotopes of Pu at the IGISOL facility, Jyväskylä. This initiates a new programme of research towards high-resolution optical spectroscopy of heavy actinide elements which can be produced in sufficient quantities at research reactors and transported to facilities elsewhere. In this work a new gas cell has been constructed for fast extraction of laser-ionized elements. Samples of 238-240,242Pu and 244Pu have been evaporated from Ta filaments, laser ionized, mass separated and delivered to the collinear laser spectroscopy station. Here we report on the performance of the gas cell through studies of the mass spectra obtained in helium and argon, before and after the radiofrequency quadrupole cooler-buncher. This provides valuable insight into the gas phase chemistry exhibited by Pu, which has been additionally supported by measurements of ion time profiles. The resulting monoatomic yields are sufficient for collinear laser spectroscopy. A gamma-ray spectroscopic analysis of the Pu samples shows a good agreement with the assay provided by the Mainz Nuclear Chemistry department.

  7. Optimization of post-run corrections for water stable isotope measurements by laser spectroscopy

    NASA Astrophysics Data System (ADS)

    van Geldern, Robert; Barth, Johannes A. C.

    2013-04-01

    Light stable isotope analyses of hydrogen and oxygen of water are used in numerous aquatic studies from various scientific fields. The advantage of using stable isotope ratios is that water molecules serve as ubiquitous and already present natural tracers. Traditionally, the samples were analyzed in the laboratory by isotope ratio mass spectrometry (IRMS). Within recent years these analyses have been revolutionized by the development of new isotope ratio laser spectroscopy (IRIS) systems that are said to be cheaper, more robust and mobile compared to IRMS. Although easier to operate, laser systems also need thorough calibration with international reference materials and raw data need correction for analytical effects. A major issue in systems that use liquid injection via a vaporizer module is the memory effect, i.e. the carry-over from the previous analyzed sample in a sequence. This study presents an optimized and simple post-run correction procedure for liquid water injection developed for a Picarro water analyzer. The Excel(TM) template will rely exclusively on standard features implemented in MS Office without the need to run macros, additional code written in Visual Basic for Applications (VBA) or to use a database-related software such as MS Access or SQL Server. These protocols will maximize precision, accuracy and sample throughput via an efficient memory correction. The number of injections per unknown sample can be reduced to 4 or less. This procedure meets the demands of faster throughput with reduced costs per analysis. Procedures were verified by an international proficiency test and traditional IRMS techniques. The template is available free for scientific use from the corresponding author or the journals web site (van Geldern and Barth, 2012). References van Geldern, R. and Barth, J.A.C. (2012) Limnol. Oceanogr. Methods 10:1024-1036 [doi: 10.4319/lom.2012.10.1024

  8. A molecular organic carbon isotope record of miocene climate changes

    SciTech Connect

    Schoell, M. ); Schouten, S.; Sinninghe Damste', J.S.; Leeuw, J.W. de ); Summons, R.E. )

    1994-02-25

    The difference in carbon-13 ([sup 13]C) contents of hopane and sterane biomarkers in the Monterey formation (Naples Beach, California) parallels the Miocene inorganic record of the change in [sup 18]O ([delta][sup 18]O), reflecting the Miocene evolution from a well-mixed to a highly stratified photic zone (upper 100 meters) in the Pacific. Steranes ([delta][sup 13]C = 25.4 [+-] 0.7 per mil versus the Pee Dee belemnite standard) from shallow photic-zone organisms do not change isotopically throughout the Miocene. In contrast, sulfur-bound C[sub 35] hopanes (likely derived from bacterial plankton living at the base of the photic zone) have systematically decreasing [sup 13]C concentrations in Middle and Late Miocene samples ([delta][sup 13]C = 29.5 to [minus]31.5 per mil), consistent with the Middle Miocene formation of a carbon dioxide-rich cold water mass at the base of the photic zone.

  9. Krypton and argon isotope analysis by collinear fast beam diode laser spectroscopy

    SciTech Connect

    Lehmann, Bernhard; Ludin, Andrea; Tschannen, Thomas

    1995-04-01

    Argon and Krypton ions are accelerated and focused through a Cs-vapour charge exchange cell. Neutral atoms in the emerging beam are optically excited from the metastable 1s5 state to the 2pg state by tunable cw diode lasers at 811.5nm. At 10keV beam energy the spectra of Ar and Kr are separated by {approx}0.5nm with counterpropagating beams and by less than 0.1 nm with copropagating beams. The absorption lines of the individual isotopes cover a spectral range of {approx}10GHz for each element. Linewidths of less than 100 MHz were observed.

  10. Anomalous gain in an isotopically mixed CO2 laser and application to absolute wavelength calibration

    NASA Technical Reports Server (NTRS)

    Hewagama, Tilak; Oppenheim, Uri P.; Mumma, Michael J.

    1991-01-01

    Measurements are reported on a grating-tuned CO2 laser, containing an isotropic mixture of O-16C-12O-16, O-16C-12O-18, and O-18C-12O-18. The P6 and R14 lines of O-16C-12O-16 were found to have anomalously high intensities. These anomalies are produced by the near coincidence of the transition frequencies in two distinct isotopes, permitting them to act as a single indistinguishable population. These two lines can be used to identify the rotational quantum numbers in the P and R branch spectra, thereby permitting absolute wavelength calibration to be achieved.

  11. Isotope effects in the harmonic response from hydrogenlike muonic atoms in strong laser fields

    SciTech Connect

    Shahbaz, Atif; Mueller, Carsten; Buervenich, Thomas J.

    2010-07-15

    High-order harmonic generation from hydrogenlike muonic atoms exposed to ultraintense high-frequency laser fields is studied. Systems of low nuclear-charge number Z are considered where a nonrelativistic description applies. By comparing the radiative response for different isotopes, we demonstrate characteristic signatures of the finite nuclear mass and size in the harmonic spectra. In particular, for Z>1, an effective muon charge appears in the Schroedinger equation for the relative particle motion, which influences the position of the harmonic cutoff. Cutoff energies in the million-electron-volt domain can be achieved, offering prospects for the generation of ultrashort coherent {gamma}-ray pulses.

  12. Atmospheric odd oxygen production due to the photodissociation of ordinary and isotopic molecular oxygen

    NASA Technical Reports Server (NTRS)

    Omidvar, K.; Frederick, J. E.

    1987-01-01

    Line-by-line calculations are performed to determine the contributions of the Schumann-Runge bands of ordinary and isotopic oxygen to the photodissociation of these molecules at different altitudes. The contributions to the dissociation rates of the satellite lines and of the first and higher vibrational states of the initial molecular states are found to be insignificant. At 70 km, (O-16)(O-18) is found to produce 10 times as much odd oxygen as would be produced if the isotope did not have selective absorption, and 6 percent of the odd oxygen produced is due to this isotope. It is noted that the excess odd oxygen produced is not enough to explain the excess quantity of ozone observed in the atmosphere, which cannot be accounted for in photochemical models. Comparison with previous results is made.

  13. Performance Of A Laser Based CO2 Isotope Ratio Infrared Spectrometer To Study Biosphere-Atmosphere Exchange

    NASA Astrophysics Data System (ADS)

    Jost, Hans-Juerg; Wapelhorst, Eric; Schlueter, Hans-Juergen; Kracht, Oliver; Radke, Jens; Hilkert, Andreas; Gangi, Laura; Bol, Roland; Brueggemann, Nicolas; Van Leeuwen, Charlotte; Meijer, Harro

    2014-05-01

    We are presenting results from a mid-infrared laser-based Isotope Ratio Infrared Spectrometers (IRIS) that is capable of simultaneously determining both δ18O and δ13C isotope ratios of carbon dioxide utilizing a simple, direct absorption approach with a robust multi pass cell and a cryogen free setup. A simulation of ambient measurement conditions with a 75 ppm per hour change in CO2 concentration from 350-650 ppm showed a precision of

  14. Isotopic ratios at z = 0.68 from molecular absorption lines toward B 0218+357

    NASA Astrophysics Data System (ADS)

    Wallström, S. H. J.; Muller, S.; Guélin, M.

    2016-11-01

    Isotopic ratios of heavy elements are a key signature of the nucleosynthesis processes in stellar interiors. The contribution of successive generations of stars to the metal enrichment of the Universe is imprinted on the evolution of isotopic ratios over time. We investigate the isotopic ratios of carbon, nitrogen, oxygen, and sulfur through millimeter molecular absorption lines arising in the z = 0.68 absorber toward the blazar B 0218+357. We find that these ratios differ from those observed in the Galactic interstellar medium, but are remarkably close to those in the only other source at intermediate redshift for which isotopic ratios have been measured to date, the z = 0.89 absorber in front of PKS 1830-211. The isotopic ratios in these two absorbers should reflect enrichment mostly from massive stars, and they are indeed close to the values observed toward local starburst galaxies. Our measurements set constraints on nucleosynthesis and chemical evolution models. The reduced spectra are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/595/A96

  15. Isotope effects in water as investigated by neutron diffraction and path integral molecular dynamics

    NASA Astrophysics Data System (ADS)

    Zeidler, Anita; Salmon, Philip S.; Fischer, Henry E.; Neuefeind, Jörg C.; Simonson, J. Mike; Markland, Thomas E.

    2012-07-01

    The structures of heavy and light water at 300 K were investigated by using a joint approach in which the method of neutron diffraction with oxygen isotope substitution was complemented by path integral molecular dynamics simulations. The diffraction results, which give intra-molecular O-D and O-H bond distances of 0.985(5) and 0.990(5) Å, were found to be in best agreement with those obtained by using the flexible anharmonic TTM3-F water model. Both techniques show a difference of ≃ 0.5% between the O-D and O-H intra-molecular bond lengths, and the results support a competing quantum effects model for water in which its structural and dynamical properties are governed by an offset between intra-molecular and inter-molecular quantum contributions. Further consideration of the O-O correlations is needed in order to improve agreement with experiment.

  16. Laser-induced stress transients: applications for molecular delivery

    NASA Astrophysics Data System (ADS)

    Flotte, Thomas J.; Lee, Shun; Zhang, Hong; McAuliffe, Daniel J.; Douki, Tina; Doukas, Apostolos G.

    1995-05-01

    Lasers can be used to enhance the delivery of a number of molecules. Other investigators have demonstrated local release of molecules from liposomes following laser irradiation, microbeam disruption of the cell membrane to increase cell transport, microbeam ablation of the zona pellucida surrounding the ovum to increase the chances of fertilization, and increased transcutaneous transport following ablation of the stratum corneum. Our experiments have shown that laser-induced stress transients can be utilized as a vector for intracellular delivery of molecules that may or may not normally cross the cell membrane. These two conditions have been tested with Photofrin and DNA. This technology may have applications in cell and molecular biology, cancer therapy, gene therapy, and others.

  17. Quantum control of molecular fragmentation in strong laser fields

    NASA Astrophysics Data System (ADS)

    Zohrabi, Mohammad

    Present advances in laser technology allow the production of ultrashort (<˜5 fs, approaching single cycle at 800 nm), intense tabletop laser pulses. At these high intensities laser-matter interactions cannot be described with perturbation theory since multiphoton processes are involved. This is in contrast to photodissociation by the absorption of a single photon, which is well described by perturbation theory. For example, at high intensities (<˜5x1013 W/cm2) the fragmentation of molecular hydrogen ions has been observed via the absorption of three or more photons. In another example, an intriguing dissociation mechanism has been observed where molecular hydrogen ions seem to fragment by apparently absorbing no photons. This is actually a two photon process, photoabsorption followed by stimulated emission, resulting in low energy fragments. We are interested in exploring these kinds of multiphoton processes. Our research group has studied the dynamics and control of fragmentation induced by strong laser fields in a variety of molecular targets. The main goal is to provide a basic understanding of fragmentation mechanisms and possible control schemes of benchmark systems such as H2+. This knowledge is further extended to more complex systems like the benchmark H3+ polyatomic and other molecules. In this dissertation, we report research based on two types of experiments. In the first part, we describe laser-induced fragmentation of molecular ion-beam targets. In the latter part, we discuss the formation of highly-excited neutral fragments from hydrogen molecules using ultrashort laser pulses. In carrying out these experiments, we have also extended experimental techniques beyond their previous capabilities. We have performed a few experiments to advance our understanding of laser-induced fragmentation of molecular-ion beams. For instance, we explored vibrationally resolved spectra of O2+ dissociation using various wavelengths. We observed a vibrational suppression

  18. Improved repetition rate mixed isotope CO{sub 2} TEA laser

    SciTech Connect

    Cohn, D. B.

    2014-09-15

    A compact CO{sub 2} TEA laser has been developed for remote chemical detection that operates at a repetition rate of 250 Hz. It emits 700 mJ/pulse at 10.6 μm in a multimode beam with the {sup 12}C{sup 16}O{sub 2} isotope. With mixed {sup 12}C{sup 16}O{sub 2} plus {sup 13}C{sup 16}O{sub 2} isotopes it emits multiple lines in both isotope manifolds to improve detection of a broad range of chemicals. In particular, output pulse energies are 110 mJ/pulse at 9.77 μm, 250 mJ/pulse at 10 μm, and 550 mJ/pulse at 11.15 μm, useful for detection of the chemical agents Sarin, Tabun, and VX. Related work shows capability for long term sealed operation with a catalyst and an agile tuner at a wavelength shift rate of 200 Hz.

  19. High-resolution laser spectroscopy of long-lived plutonium isotopes

    NASA Astrophysics Data System (ADS)

    Voss, A.; Sonnenschein, V.; Campbell, P.; Cheal, B.; Kron, T.; Moore, I. D.; Pohjalainen, I.; Raeder, S.; Trautmann, N.; Wendt, K.

    2017-03-01

    Long-lived isotopes of plutonium were studied using two complementary techniques, high-resolution resonance ionization spectroscopy (HR-RIS) and collinear laser spectroscopy (CLS). Isotope shifts have been measured on the 5 f67 s27F0→5 f56 d27 s (J =1 ) and 5 f67 s27F1→5 f67 s 7 p (J =2 ) atomic transitions using the HR-RIS method and the hyperfine factors have been extracted for the odd mass nuclei Pu,241239. CLS was performed on the 5 f67 s 8F1 /2→J =1 /2 (27 523.61 cm-1) ionic transition with the hyperfine A factors measured for 239Pu. Changes in mean-squared charge radii have been extracted and show a good agreement with previous nonoptical methods, with an uncertainty improvement by approximately one order of magnitude. Plutonium represents the heaviest element studied to date using collinear laser spectroscopy.

  20. A quantum cascade laser-based water vapor isotope analyzer for environmental monitoring

    SciTech Connect

    Wang, W. E.; Tsai, T.; Wysocki, G.; Michel, A. P. M.; Wang, L.; Baeck, M. L.; Smith, J. A.

    2014-09-15

    A field-deployable mid-infrared quantum cascade laser-based spectrometer was designed and developed for measurements of H{sub 2}{sup 16}O and H{sub 2}{sup 18}O at 7.12 μm. H{sub 2}{sup 16}O and H{sub 2}{sup 18}O absorption features at 1390.52 cm{sup −1} and 1389.91 cm{sup −1}, respectively, accessible within current tuning range of the laser, were targeted. The target lines were carefully selected to assure similar absorption levels and similar temperature sensitivities of the line strength due to comparable lower state energies. A real-time spectral fitting algorithm was implemented for isotopic concentration retrieval. Detection limits for H{sub 2}{sup 16}O and H{sub 2}{sup 18}O of 2.2 ppm and 7.0 ppb, respectively, were achieved at a dew point of 14 °C (volume mixing ratio of 15 766 ppm) in 1 s integration time, which resulted in a δ{sup 18}O isotopic ratio measurement precision of 0.25‰. The ultimate minimum detection limits obtained after 160 s integration time for H{sub 2}{sup 16}O and H{sub 2}{sup 18}O, and δ{sup 18}O measurements were 0.6 ppm, 1.7 ppb, and 0.05‰, respectively.

  1. Optofluidic lasers with a single molecular layer of gain.

    PubMed

    Chen, Qiushu; Ritt, Michael; Sivaramakrishnan, Sivaraj; Sun, Yuze; Fan, Xudong

    2014-12-21

    We achieve optofluidic lasers with a single molecular layer of gain, in which green fluorescent protein, dye-labeled bovine serum albumin, and dye-labeled DNA, are used as the gain medium and attached to the surface of a ring resonator via surface immobilization biochemical methods. It is estimated that the surface density of the gain molecules is on the order of 10(12) cm(-2), sufficient for lasing under pulsed optical excitation. It is further shown that the optofluidic laser can be tuned by energy transfer mechanisms through biomolecular interactions. This work not only opens a door to novel photonic devices that can be controlled at the level of a single molecular layer but also provides a promising sensing platform to analyze biochemical processes at the solid-liquid interface.

  2. Interstellar dust laser explorer: a new instrument for elemental and isotopic analysis and imaging of interstellar and interplanetary dust.

    PubMed

    Henkel, Torsten; Tizard, Julia; Blagburn, David J; Lyon, Ian C

    2007-05-01

    We present the performance characteristics of a time-of-flight secondary ion mass spectrometer designed for 157 nm laser postionization of sputtered neutrals for high sensitivity elemental and isotopic analyses. The instrument was built with the aim of analyzing rare element abundances in micron to submicron samples such as interstellar grains and cometary dust. Relative sensitivity factors have been determined for secondary ion mass spectrometry which show an exponential dependency against the first ionization potential. This allows elemental abundances to be measured with errors below 25% for most major elements. The accuracy for isotope ratios, where isotopes can be resolved from isobaric interferences, is usually limited only by counting statistics. In laser secondary neutral mass spectrometry, the spatial and temporal overlaps between the laser and sputtered neutral atoms are modeled and predictions of total detection efficiency and isotopic and elemental fractionation are compared with experimental data. Relative sensitivity factors for laser-ionized secondary neutrals from a stainless steel standard are found to vary less than 3% above saturation laser pulse energy enabling more accurate quantification.

  3. A molecular and isotopic study of the organic matter from the Paris Basin, France

    NASA Technical Reports Server (NTRS)

    Lichtfouse, E.; Albrecht, P.; Behar, F.; Hayes, J. M.

    1994-01-01

    Thirteen Liassic sedimentary rocks of increasing depth and three petroleums from the Paris Basin were studied for 13C/12C isotopic compositions and biological markers, including steranes, sterenes, methylphenanthrenes, methylanthracenes, and triaromatic steroids. The isotopic compositions of n-alkanes from mature sedimentary rocks and petroleums fall in a narrow range (2%), except for the deepest Hettangian rock and the Trias petroleum, for which the short-chain n-alkanes are enriched and depleted in 13C, respectively. Most of the molecular parameters increase over the 2000-2500 m depth range, reflecting the transformation of the organic matter at the onset of petroleum generation. In this zone, carbonate content and carbon isotopic composition of carbonates, as well as molecular parameters, are distinct for the Toarcian and Hettangian source rocks and suggest a migration of organic matter from these two formations. Two novel molecular parameters were defined for this task: one using methyltriaromatic steroids from organic extracts; the other using 1-methylphenanthrene and 2-methylanthracene from kerogen pyrolysates. The anomalous high maturity of the Dogger petroleum relative to the maturity-depth trend of the source rocks is used to estimate the minimal vertical distance of migration of the organic matter from the source rock to the reservoir.

  4. Molecular and mass spectroscopic analysis of isotopically labeled organic residues

    NASA Technical Reports Server (NTRS)

    Mendoza-Gomez, Celia X.; Greenberg, J. Mayo; Mccain, P.; Ferris, J. P.; Briggs, R.; Degroot, M. S.; Schutte, Willem A.

    1989-01-01

    Experimental studies aimed at understanding the evolution of complex organic molecules on interstellar grains were performed. The photolysis of frozen gas mixtures of various compositions containing H2O, CO, NH3, and CH4 was studied. These species were chosen because of their astrophysical importance as deducted from observational as well as theoretical studies of ice mantles on interstellar grains. These ultraviolet photolyzed ices were warmed up in order to produce refractory organic molecules like the ones formed in molecular clouds when the icy mantles are being irradiated and warmed up either by a nearby stellar source or impulsive heating. The laboratory studies give estimates of the efficiency of production of such organic material under interstellar conditions. It is shown that the gradual carbonization of organic mantles in the diffuse cloud phase leads to higher and higher visual absorptivity - yellow residues become brown in the laboratory. The obtained results can be applied to explaining the organic components of comets and their relevance to the origin of life.

  5. Airborne molecular contamination: quality criterion for laser and optical components

    NASA Astrophysics Data System (ADS)

    Otto, Michael

    2015-02-01

    Airborne molecular contaminations (AMCs) have been recognized as a major problem in semiconductor fabrication. Enormous technical and financial efforts are made to remove or at least reduce these contaminations in production environments to increase yield and process stability. It can be shown that AMCs from various sources in laser devices have a negative impact on quality and lifetime of lasers and optical systems. Outgassing of organic compounds, especially condensable compounds were identified as the main source for deterioration of optics. These compounds can lead to hazing on surfaces of optics, degradation of coating, reducing the signal transmission or the laser signal itself and can enhance the probability of laser failure and damage. Sources of organic outgassing can be molding materials, resins, seals, circuit boards, cable insulation, coatings, paints and others. Critical compounds are siloxanes, aromatic amines and high boiling aromatic hydrocarbons like phthalates which are used as softeners in plastic materials. Nowadays all sensitive assembly steps are performed in controlled cleanroom environments to reduce risks of contamination. We will demonstrate a high efficient air filter concept to remove AMCs for production environments with special AMC filters and methods for the qualification and monitoring of these environments. Additionally, we show modern techniques and examples for the pre-qualification of materials. For assembled components, we provide sampling concepts for a routine measurement for process, component and product qualification. A careful selection of previously tested and certified materials and components is essential to guarantee the quality of lasers and optical devices.

  6. Isotope separation apparatus and method

    DOEpatents

    Cotter, Theodore P.

    1982-12-28

    The invention relates to a method and apparatus for laser isotope separation by photodeflection. A molecular beam comprising at least two isotopes to be separated intersects, preferable substantially perpendicular to one broad side of the molecular beam, with a laser beam traveling in a first direction. The laser beam is reflected back through the molecular beam, preferably in a second direction essentially opposite to the first direction. The laser beam comprises .pi.-pulses of a selected wavelength which excite unexcited molecules, or cause stimulated emission of excited molecules of one of the isotopes. Excitation caused by first direction .pi.-pulses moves molecules of the isotope excited thereby in the first direction. Stimulated emission of excited molecules of the isotope is brought about by returning .pi.-pulses traveling in the second direction. Stimulated emission moves emitting molecules in a direction opposite to the photon emitted. Because emitted photons travel in the second direction, emitting molecules move in the first direction. Substantial molecular movement is accomplished by a large number of .pi.-pulse-molecule interactions. A beam corer collects the molecules in the resulting enriched divergent portions of the beam.

  7. Isotope dilution ICP-MS with laser-assisted sample introduction for direct determination of sulfur in petroleum products.

    PubMed

    Boulyga, Sergei F; Heilmann, Jens; Heumann, Klaus G

    2005-08-01

    Inductively coupled plasma isotope dilution mass spectrometry (ICP-IDMS) with direct laser-assisted introduction of isotope-diluted samples into the plasma, using a laser ablation system with high ablation rates, was developed for accurate sulfur determinations in different petroleum products such as 'sulfur-free' premium gasoline, diesel fuel, and heating oil. Two certified gas oil reference materials were analyzed for method validation. Two different 34S-enriched spike compounds, namely, elementary sulfur dissolved in xylene and dibenzothiophene in hexane, were synthesized and tested for their usefulness in this isotope dilution technique. The isotope-diluted sample was adsorbed on a filter-paper-like material, which was fixed in a special holder for irradiation by the laser beam. Under these conditions no time-dependent spike/analyte fractionation was only observed for the dibenzothiophene spike during the laser ablation process, which means that the measured 34S/32S isotope ratio of the isotope-diluted sample remained constant-a necessary precondition for accurate results with the isotope dilution technique. A comparison of LA-ICP-IDMS results with the certified values of the gas oil reference materials and with results obtained from ICP-IDMS analyses with wet sample digestion demonstrated the accuracy of the new LA-ICP-IDMS method in the concentration range of 9.2 microg g(-1) ('sulfur-free' premium gasoline) to 10.4 mg g(-1) (gas oil reference material BCR 107). The detection limit for sulfur by LA-ICP-IDMS is 0.04 microg g(-1) and the analysis time is only about 10 min, which therefore also qualifies this method for accurate determinations of low sulfur contents in petroleum products on a routine level.

  8. Isotopic evidence for biogenic molecular hydrogen production in the Atlantic Ocean

    NASA Astrophysics Data System (ADS)

    Walter, S.; Kock, A.; Steinhoff, T.; Fiedler, B.; Fietzek, P.; Kaiser, J.; Krol, M. C.; Popa, M. E.; Chen, Q.; Tanhua, T.; Röckmann, T.

    2015-10-01

    Oceans are a net source of molecular hydrogen (H2) to the atmosphere. The production of marine H2 is assumed to be mainly biological by N2 fixation, but photochemical pathways are also discussed. We present measurements of mole fraction and isotopic composition of dissolved and atmospheric H2 from the southern and northern Atlantic between 2008 and 2010. In total almost 400 samples were taken during five cruises along a transect between Punta Arenas (Chile) and Bremerhaven (Germany), as well as at the coast of Mauretania. The isotopic source signatures of dissolved H2 extracted from surface water are highly deuterium-depleted and correlate negatively with temperature, showing δD values of (-629 ± 54) ‰ for water temperatures at (27 ± 3) °C and (-249 ± 88) ‰ below (19 ± 1) °C. The results for warmer water masses are consistent with biological production of H2. This is the first time that marine H2 excess has been directly attributed to biological production by isotope measurements. However, the isotope values obtained in the colder water masses indicate that beside possible biological production a significant different source should be considered. The atmospheric measurements show distinct differences between both hemispheres as well as between seasons. Results from the global chemistry transport model TM5 reproduce the measured H2 mole fractions and isotopic composition well. The climatological global oceanic emissions from the GEMS database are in line with our data and previously published flux calculations. The good agreement between measurements and model results demonstrates that both the magnitude and the isotopic signature of the main components of the marine H2 cycle are in general adequately represented in current atmospheric models despite a proposed source different from biological production or a substantial underestimation of nitrogen fixation by several authors.

  9. Isotopic evidence for biogenic molecular hydrogen production in the Atlantic Ocean

    NASA Astrophysics Data System (ADS)

    Walter, S.; Kock, A.; Steinhoff, T.; Fiedler, B.; Fietzek, P.; Kaiser, J.; Krol, M.; Popa, M. E.; Chen, Q.; Tanhua, T.; Röckmann, T.

    2016-01-01

    Oceans are a net source of molecular hydrogen (H2) to the atmosphere. The production of marine H2 is assumed to be mainly biological by N2 fixation, but photochemical pathways are also discussed. We present measurements of mole fraction and isotopic composition of dissolved and atmospheric H2 from the southern and northern Atlantic between 2008 and 2010. In total almost 400 samples were taken during 5 cruises along a transect between Punta Arenas (Chile) and Bremerhaven (Germany), as well as at the coast of Mauritania.

    The isotopic source signatures of dissolved H2 extracted from surface water are highly deuterium-depleted and correlate negatively with temperature, showing δD values of (-629 ± 54) ‰ for water temperatures at (27 ± 3) °C and (-249 ± 88) ‰ below (19 ± 1) °C. The results for warmer water masses are consistent with the biological production of H2. This is the first time that marine H2 excess has been directly attributed to biological production by isotope measurements. However, the isotope values obtained in the colder water masses indicate that beside possible biological production, a significant different source should be considered.

    The atmospheric measurements show distinct differences between both hemispheres as well as between seasons. Results from the global chemistry transport model TM5 reproduce the measured H2 mole fractions and isotopic composition well. The climatological global oceanic emissions from the GEMS database are in line with our data and previously published flux calculations. The good agreement between measurements and model results demonstrates that both the magnitude and the isotopic signature of the main components of the marine H2 cycle are in general adequately represented in current atmospheric models despite a proposed source different from biological production or a substantial underestimation of nitrogen fixation by several authors.

  10. In situ analysis of silicon isotopes using UV-femtosecond laser ablation MC-ICP- MS

    NASA Astrophysics Data System (ADS)

    Chmeleff, J.; Horn, I.; Steinhoefel, G.; von Blanckenburg, F.

    2006-12-01

    Here we present results from the development of a novel in situ approach to measure accurate and precise ^{30}Si/^{28}Si and ^{29}Si/^{28}Si ratios in minerals and glasses. Silicon is the most abundant non- volatile element in the solar system and after oxygen, the second most abundant in upper crust. It is the dominant solute in rivers that drain our continents, supplying 80% of the dissolved Si entering the oceans. Weathering of continents is thus providing material for the formation of clays and soils, and nutrients for the aquatic biosphere. The ratios of stable silicon isotopes fingerprint many of these processes, and them ^{30}Si/^{28}Si ratios in terrestrial reservoirs (represented as δ ^{30}Si) range from -4 to +3 per mil. To date, most silicon isotope studies have been measured by gas source MS or, more recently, MC- ICPMS after sample decomposition and Si purification. While SIMS studies have presented the first in situ- measurements, laser ablation stable isotope ratio analysis is an obvious alternative. However, principle limitations of the ablation physics introduced by the nanosecond lasers traditionally employed have prevented the measurement of accurate isotope ratios. Our in-house built 196nm UV-femtosecond laser ablation system coupled to high-resolution MC-ICPMS avoids these difficulties (Horn et al. 2006, GCA 70). We have developed an in situ-method for precise and rapid measurements of ^{29}Si/^{28}Si and ^{30}Si/^{28}Si ratios in silicates at a spatial resolution of 50 micrometers. Sample-standard bracketing is used to correct for the mass discrimination and the possible drift occurring between two measurements. δ^{30}Si is calculated with NIST NBS28 (synthetic quartz sand) as bracketing standard. Two international standards were measured and compared: IRMM017 (pure metal) gives a δ^{29}Si of -0.680±0.030 (2 sigma n=25) per mil and δ^{30}Si of -1.32±0.040 (2 sigma n=25) per mil against NBS28, which is in accordance with previous

  11. Molecular isotopic engineering (MIE): industrial manufacture of naproxen of predetermined stable carbon-isotopic compositions for authenticity and security protection and intellectual property considerations

    NASA Astrophysics Data System (ADS)

    Jasper, J. P.; Farina, P.; Pearson, A.; Mezes, P. S.; Sabatelli, A. D.

    2016-05-01

    Molecular Isotopic Engineering (MIE) is the directed stable-isotopic synthesis of chemical products for reasons of product identification and of product security, and also for intellectual property considerations. We report here a generally excellent correspondence between the observed and predicted stable carbon-isotopic (δ13C) results for a successful directed synthesis of racemic mixture from its immediate precursors. The observed results are readily explained by the laws of mass balance and isotope mass balance. Oxygen- and hydrogen isotopic results which require an additional assessment of the effects of O and H exchange, presumably due to interaction with water in the reaction solution, are addressed elsewhere. A previous, cooperative study with the US FDA-DPA showed that individual manufacturers of naproxen could readily be differentiated by their stable-isotopic provenance (δ13C, δ18O, and δD ref. 1). We suggest that MIE can be readily employed in the bio/pharmaceutical industry without alteration of present manufacturing processes other than isotopically selecting and/or monitoring reactants and products.

  12. Calculations on Isotope Separation by Laser Induced Photodissociation of Polyatomic Molecules. Final Report

    DOE R&D Accomplishments Database

    Lamb, W. E. Jr.

    1978-11-01

    This report describes research on the theory of isotope separation produced by the illumination of polyatomic molecules by intense infrared laser radiation. Newton`s equations of motion were integrated for the atoms of the SF{sub 6} molecule including the laser field interaction. The first year`s work has been largely dedicated to obtaining a suitable interatomic potential valid for arbitrary configurations of the seven particles. This potential gives the correct symmetry of the molecule, the equilibrium configuration, the frequencies of the six distinct normal modes of oscillation and the correct (or assumed) value of the total potential energy of the molecule. Other conditions can easily be imposed in order to obtain a more refined potential energy function, for example, by making allowance for anharmonicity data. A suitable expression was also obtained for the interaction energy between a laser field and the polyatomic molecule. The electromagnetic field is treated classically, and it would be easily possible to treat the cases of time dependent pulses, frequency modulation and noise.

  13. The laser microprobe: a technique for extracting carbon, nitrogen, and oxygen from solid samples for isotopic measurements.

    NASA Astrophysics Data System (ADS)

    Franchi, I. A.; Wright, I. P.; Gibson, E. K., Jr.; Pillinger, C. T.

    1986-03-01

    The laser microprobe extraction technique has been adapted for the determination of concentrations and stable isotopic compositions of carbon, nitrogen, and oxygen. Initial studies on the distribution of nitrogen in an iron meteorite (Uwet) and a carbonaceous chondrite (Murchison) have been undertaken.

  14. Spatially tracking 13C labeled substrate (bicarbonate) accumulation in microbial communities using laser ablation isotope ratio mass spectrometry

    SciTech Connect

    Moran, James J.; Doll, Charles G.; Bernstein, Hans C.; Renslow, Ryan S.; Cory, Alexandra B.; Hutchison, Janine R.; Lindemann, Stephen R.; Fredrickson, Jim K.

    2014-08-25

    This is a manuscript we would like to submit for publication in Environmental Microbiology Reports. This manuscript contains a description of a laser ablation isotope ratio mass spectrometry methodology developed at PNNL and applied to a microbial system at a PNNL project location – Hot Lake, Washington. I will submit a word document containing the entire manuscript with this Erica input request form.

  15. Nd Isotope and U-Th-Pb Age Mapping of Single Monazite Grains by Laser Ablation Split Stream Analysis

    NASA Astrophysics Data System (ADS)

    Fisher, C. M.; Hanchar, J. M.; Miller, C. F.; Phillips, S.; Vervoort, J. D.; Martin, W.

    2015-12-01

    Monazite is a common accessory mineral that occurs in medium to high grade metamorphic and Ca-poor felsic igneous rocks, and often controls the LREE budget (including Sm and Nd) of the host rock in which it crystallizes. Moreover, it contains appreciable U and Th, making it an ideal mineral for determining U-Th-Pb ages and Sm-Nd isotopic compositions, both of which are readily determined using in situ techniques with very high spatial resolution like LA-MC-ICPMS. Here, we present the results of laser ablation split stream analyses (LASS), which allows for simultaneous determination of the age and initial Nd isotopic composition in a single analysis. Analyses were done using a 20mm laser spot that allowed for detailed Nd isotope mapping of monazite grains (~30 analyses per ~250mm sized grain). Combined with LREE ratios (e.g., Sm/Nd, Ce/Gd, and Eu anomalies) these results yield important petrogenetic constraints on the evolution of peraluminous granites from the Old Woman-Piute batholith in southeastern California. Our findings also allow an improved understanding of the causes of isotope heterogeneity in granitic rocks. U-Th-Pb age mapping across the crystals reveals a single Cretaceous age for all grains with precision and accuracy typical of laser ablation analyses (~2%). In contrast, the concurrent Nd isotope mapping yields homogeneous initial Nd isotope compositions for some grains and large initial intra-grain variations of up to 8 epsilon units in others. The grains that yield homogeneous Nd isotope compositions have REE ratios suggesting that they crystallized in a fractionally crystallizing magma. Conversely, other grains, which also record fractional crystallization of both feldspar and LREE rich minerals, demonstrate a change in the Nd isotope composition of the magma during crystallization of monazite. Comparison of inter- and intra-grain Nd isotope compositions reveals further details on the potential mechanisms responsible for isotope heterogeneity

  16. 87Sr/86Sr isotope ratio measurements by laser ablation multicollector inductively coupled plasma mass spectrometry: Reconsidering matrix interferences in bioapatites and biogenic carbonates

    NASA Astrophysics Data System (ADS)

    Irrgeher, Johanna; Galler, Patrick; Prohaska, Thomas

    2016-11-01

    This study is dedicated to the systematic investigation of the effect of interferences on Sr isotopic analyses in biological apatite and carbonate matrices using laser ablation multicollector inductively coupled plasma mass spectrometry (LA-MC ICP-MS). Trends towards higher 87Sr/86Sr ratios for LA-MC ICP-MS compared to solution-nebulization based MC ICP-MS when analysing bioapatite matrices (e.g. human teeth) and lower ratios in case of calcium carbonates (e.g. fish ear stones) were observed. This effect can be related to the presence of significant matrix-related interferences such as molecular ions (e.g. (40Ca-31P-16O)+, (40Ar-31P-16O)+, (42Ca-44Ca)+, (46Ca40Ar)+) as well as in many cases concomitant atomic ions (e.g. 87Rb+, 174Hf2 +). Direct 87Sr/86Sr ratio measurements in Ca-rich samples are conducted without the possibility of prior sample separation, which can be accomplished routinely for solution-based analysis. The presence of Ca-Ar and Ca-Ca molecular ion interferences in the mass range of Sr isotopes is shown using the mass resolving capabilities of a single collector inductively coupled plasma sector field mass spectrometer operated in medium mass resolution when analysing bioapatites and calcium carbonate samples. The major focus was set on analysing human tooth samples, fish hard parts and geological carbonates. Potential sources of interferences were identified and corrected for. The combined corrections of interferences and adequate instrumental isotopic fractionation correction procedures lead to accurate data even though increased uncertainties have to be taken into account. The results are discussed along with approaches presented in literature for data correction in laser ablation analysis.

  17. Laser-induced fluorescence detection of hot molecular oxygen in flames using an alexandrite laser.

    PubMed

    Kiefer, Johannes; Zhou, Bo; Zetterberg, Johan; Li, Zhongshan; Alden, Marcus

    2014-01-01

    The use of an alexandrite laser for laser-induced fluorescence (LIF) spectroscopy and imaging of molecular oxygen in thermally excited vibrational states is demonstrated. The laser radiation after the third harmonic generation was used to excite the B-X (0-7) band at 257 nm in the Schumann-Runge system of oxygen. LIF emission was detected between 270 and 380 nm, revealing distinct bands of the transitions from B(0) to highly excited vibrational states in the electronic ground state, X (v > 7). At higher spectral resolution, these bands reveal the common P- and R-branch line splitting. Eventually, the proposed LIF approach was used for single-shot imaging of the two-dimensional distribution of hot oxygen molecules in flames.

  18. Abundances in red giant stars - Carbon and oxygen isotopes in carbon-rich molecular envelopes

    NASA Technical Reports Server (NTRS)

    Wannier, P. G.; Sahai, R.

    1987-01-01

    Millimeter-wave observations have been made of isotopically substituted CO toward the envelopes of 11 carbon-rich stars. In every case, C-13O was detected and model calculations were used to estimate the C-12/C-13 abundance ratio. C-17O was detected toward three, and possibly four, envelopes, with sensitive upper limits for two others. The CO-18 variant was detected in two envelopes. New results include determinations of oxygen isotopic ratios in the two carbon-rich protoplanetary nebulae CRL 26688 and CRL 618. As with other classes of red giant stars, the carbon-rich giants seem to be significantly, though variably, enriched in O-17. These results, in combination with observations in interstellar molecular clouds, indicate that current knowledge of stellar production of the CNO nuclides is far from satisfactory.

  19. Numerical optimization of laser fields to control molecular orientation

    SciTech Connect

    Ben Haj-Yedder, A.; Auger, A.; Dion, C.M.; Cances, E.; Le Bris, C.; Keller, A.; Atabek, O.

    2002-12-01

    A thorough numerical illustration of an optimal control scenario dealing with the laser-induced orientation of a diatomic molecule (LiF) is presented. Special emphasis is laid on the definition of the various targets dealing with different orientation characteristics, identified in terms of maximum efficiency (i.e., molecular axis direction closest to the direction of the laser polarization vector), maximum duration (i.e., the time interval during which this orientation is maintained), or of a compromise between efficiency and duration. Excellent postpulse orientation is achieved by sudden, intense pulses. Thermal effects are also studied with an extension of the control scenarios to Boltzmann averaged orientation dynamics at T=5 K.

  20. Detection of radioactive isotopes by using laser Compton scattered γ-ray beams

    NASA Astrophysics Data System (ADS)

    Hajima, R.; Kikuzawa, N.; Nishimori, N.; Hayakawa, T.; Shizuma, T.; Kawase, K.; Kando, M.; Minehara, E.; Toyokawa, H.; Ohgaki, H.

    2009-09-01

    Non-destructive detection and assay of nuclear materials is one of the most critical issues for both the management of nuclear waste and the non-proliferation of nuclear materials. We use laser Compton scattered (LCS) γ-ray beams and the nuclear resonance fluorescence (NRF) for the non-destructive detection of radioactive materials. Quasi-monochromatic and energy-tunable LCS γ-ray beams help improve the signal-to-noise ratio during NRF measurements. We developed the conceptual design of a high-flux γ-ray source with an energy-recovery linac, which produces a γ-ray beam at the flux of 1013 photons/s. In this paper, we discuss the execution of simulation studies using a Monte Carlo code, results of a proof-of-principle experiment for isotope detection, and the status of the development of LCS X-ray and γ-ray facilities.

  1. Equilibrium fractionation of H and O isotopes in water from path integral molecular dynamics

    NASA Astrophysics Data System (ADS)

    Pinilla, Carlos; Blanchard, Marc; Balan, Etienne; Ferlat, Guillaume; Vuilleumier, Rodolphe; Mauri, Francesco

    2014-06-01

    The equilibrium fractionation factor between two phases is of importance for the understanding of many planetary and environmental processes. Although thermodynamic equilibrium can be achieved between minerals at high temperature, many natural processes involve reactions between liquids or aqueous solutions and solids. For crystals, the fractionation factor α can be theoretically determined using a statistical thermodynamic approach based on the vibrational properties of the phases. These calculations are mostly performed in the harmonic approximation, using empirical or ab-initio force fields. In the case of aperiodic and dynamic systems such as liquids or solutions, similar calculations can be done using finite-size molecular clusters or snapshots obtained from molecular dynamics (MD) runs. It is however difficult to assess the effect of these approximate models on the isotopic fractionation properties. In this work we present a systematic study of the calculation of the D/H and 18O/16O equilibrium fractionation factors in water for the liquid/vapour and ice/vapour phases using several levels of theory within the simulations. Namely, we use a thermodynamic integration approach based on Path Integral MD calculations (PIMD) and an empirical potential model of water. Compared with standard MD, PIMD takes into account quantum effects in the thermodynamic modeling of systems and the exact fractionation factor for a given potential can be obtained. We compare these exact results with those of modeling strategies usually used, which involve the mapping of the quantum system on its harmonic counterpart. The results show the importance of including configurational disorder for the estimation of isotope fractionation in liquid phases. In addition, the convergence of the fractionation factor as a function of parameters such as the size of the simulated system and multiple isotope substitution is analyzed, showing that isotope fractionation is essentially a local effect in

  2. Hydrogen isotope correction for laser instrument measurement bias at low water vapor concentration using conventional isotope analyses: application to measurements from Mauna Loa Observatory, Hawaii.

    PubMed

    Johnson, L R; Sharp, Z D; Galewsky, J; Strong, M; Van Pelt, A D; Dong, F; Noone, D

    2011-03-15

    The hydrogen and oxygen isotope ratios of water vapor can be measured with commercially available laser spectroscopy analyzers in real time. Operation of the laser systems in relatively dry air is difficult because measurements are non-linear as a function of humidity at low water concentrations. Here we use field-based sampling coupled with traditional mass spectrometry techniques for assessing linearity and calibrating laser spectroscopy systems at low water vapor concentrations. Air samples are collected in an evacuated 2 L glass flask and the water is separated from the non-condensable gases cryogenically. Approximately 2 µL of water are reduced to H(2) gas and measured on an isotope ratio mass spectrometer. In a field experiment at the Mauna Loa Observatory (MLO), we ran Picarro and Los Gatos Research (LGR) laser analyzers for a period of 25 days in addition to periodic sample collection in evacuated flasks. When the two laser systems are corrected to the flask data, they are strongly coincident over the entire 25 days. The δ(2)H values were found to change by over 200‰ over 2.5 min as the boundary layer elevation changed relative to MLO. The δ(2)H values ranged from -106 to -332‰, and the δ(18)O values (uncorrected) ranged from -12 to -50‰. Raw data from laser analyzers in environments with low water vapor concentrations can be normalized to the international V-SMOW scale by calibration to the flask data measured conventionally. Bias correction is especially critical for the accurate determination of deuterium excess in dry air.

  3. EFFECT OF LASER LIGHT ON MATTER. LASER PLASMAS: Films containing heavy hydrogen isotopes in laser thermonuclear fusion targets

    NASA Astrophysics Data System (ADS)

    Abramov, Yu A.; Bessarab, A. V.; Veselov, A. V.; Gavrilov, P. I.; Druzhinin, A. A.; Izgorodin, V. M.; Karel'skaya, T. V.; Kirillov, G. A.; Komleva, G. V.; Lyamin, G. A.; Nikolaev, G. P.; Pinegin, A. V.; Punin, V. T.; Rabinovich, K. G.; Romaev, V. N.; Rogachev, V. G.; Solomatina, E. Yu; Tarasova, N. N.; Tachaev, G. V.; Andryushin, V. V.; Emel'yanov, S. A.; Kryuchenkov, V. B.; Markelov, N. N.; Markushkin, Yu E.; Chirin, N. A.

    1994-02-01

    An investigation was made of fuel films in targets used in experiments on laser thermonuclear fusion in Iskra-4 and Iskra-5 systems. These films were formed from condensed deuterium and a deuterium—tritium mixture, and also from metal hydrides and polyethylene containing deuterium and tritium.

  4. Comparison of femtosecond and nanosecond laser ablation inductively coupled plasma mass spectrometry for uranium isotopic measurements

    SciTech Connect

    Havrilla, George Joseph; McIntosh, Kathryn Gallagher; Judge, Elizabeth; Dirmyer, Matthew R.; Campbell, Keri; Gonzalez, Jhanis J.

    2016-10-20

    Feasibility tests were conducted using femtosecond and nanosecond laser ablation inductively coupled plasma mass spectrometry for rapid uranium isotopic measurements. The samples used in this study consisted of a range of pg quantities of known 235/238 U solutions as dried spot residues of 300 pL drops on silicon substrates. The samples spanned the following enrichments of 235U: 0.5, 1.5, 2, 3, and 15.1%. In this direct comparison using these particular samples both pulse durations demonstrated near equivalent data can be produced on either system with respect to accuracy and precision. There is no question that either LA-ICP-MS method offers the potential for rapid, accurate and precise isotopic measurements of U10Mo materials whether DU, LEU or HEU. The LA-ICP-MS equipment used for this work is commercially available. The program is in the process of validating this work for large samples using center samples strips from Y-12 MP-1 LEU-Mo Casting #1.

  5. In situ iron isotope ratio determination using UV-femtosecond laser ablation with application to hydrothermal ore formation processes

    NASA Astrophysics Data System (ADS)

    Horn, Ingo; von Blanckenburg, Friedhelm; Schoenberg, Ronny; Steinhoefel, Grit; Markl, Gregor

    2006-07-01

    The feasibility of in situ stable Fe isotope ratio measurements using UV-femtosecond laser ablation connected to a multiple-collector inductively coupled plasma mass spectrometer (MC-ICP-MS) has been investigated. Different types of matrices, independently determined by solution MC-ICP-MS after chromatographic separation of Fe, have been analysed by laser ablation using the isotopically certified iron reference material IRMM-014 as the bracketing standard. The samples have been pure iron metal (JM Puratronic), Fe-meteorites (North Chile, Glenormiston and Toluca), the meteorite phases kamacite and taenite in Toluca and Fe-sulphides. Furthermore, Fe isotope ratios from hydrothermal hematite, siderite and goethite from an old mining area in the Schwarzwald, Germany, and of magnetite from the metamorphic Biwabik iron formation have been determined. The results show that a precision of better than 0.1‰ (2 sigma) can be achieved with laser ablation and that all the results obtained agree with those determined by solution ICP to better than 0.1‰. This precision and accuracy is achievable in both raster and spot ablation mode. A matrix-matched bracketing standard is not required , and all these materials can be measured accurately against a metal standard. The hydrothermal minerals show significant Fe isotope zonations. In some samples the range of δ56Fe in a single aggregate encompasses the entire spectrum of ratios found by bulk solution analyses in multiple samples distributed over the whole mining district. For example, isotopic zonations found in secondary fibrous hematites show a continuous change in the δ56Fe values from -0.5‰ in the core to -1.8‰ in the rim. Primary hydrothermal siderite shows the reverse pattern with lighter values in the core than in the rim. While the siderite is thought to record primary fluid histories, the hematite pattern is interpreted as a reworked isotopic signature generated by oxic dissolution of primary zoned siderite and

  6. Control of multiphoton molecular excitation with shaped femtosecond laser pulses

    NASA Astrophysics Data System (ADS)

    Xu, Bingwei

    The work presented in this dissertation describes the use of shaped femtosecond laser pulses to control the outcome of nonlinear optical process and thus to achieve the selectivity for multiphoton molecular transitions. This research could lead to applications in various fields including nonlinear optical spectroscopy, chemical identification, biological imaging, communications, photodynamic therapy, etc. In order to realize accurate pulse shaping of the femtosecond laser pulses, it is essential to measure and correct the spectral phase distortion of such pulses. A method called multiphoton intrapulse interference phase scan is used to do so throughout this dissertation. This method is highly accurate and reproducible, and has been proved in this work to be compatible with any femtosecond pulses regardless of bandwidth, intensity and repetition rate of the laser. The phase control of several quasi-octave laser sources is demonstrated in this dissertation, with the generation of 4.3 fs and 5.9 fs pulses that reach the theoretically predicted transform-limited pulse duration. The excellent phase control achieved also guarantees the reproducibility for selective multiphoton excitations by accurate phase and/or amplitude shaping. Selective two-photon excitation, stimulated Raman scattering and coherent anti-Stokes Raman scattering with a single broadband laser source are demonstrated in this dissertation. Pulse shaping is used to achieve a fast and robust approach to measure the two-photon excitation spectrum from fluorescent molecules, which provide important information for two-photon biological imaging. The selective excitation concept is also applied in the field of remote chemical identification. Detection of characteristic Raman lines for several chemicals using a single beam coherent anti-Stokes Raman scattering spectroscopy from a 12 meter standoff distance is shown, providing a promising approach to standoff detection of chemicals, hazardous contaminations

  7. Molecular dynamics simulations studies of laser ablation in metals

    SciTech Connect

    Roth, Johannes; Sonntag, Steffen; Karlin, Johannes; Paredes, Carolina Trichet; Sartison, Marc; Krauss, Armin; Trebin, Hans-Rainer

    2012-07-30

    An overview of several aspects of our recent molecular dynamics simulations of femtosecond laser ablation is presented. This includes the study of phase diagrams for suitable interactions, analysis of ablated material and bubble formation below threshold, study of two-pulse ablation and the classification of materials with respect to electron properties and electron-phonon coupling in the two-temperature model. A treatment of boundary conditions and of an extended twotemperature model is also included. Most of the results apply to aluminum, others also to copper and iron, and to metals in general.

  8. Dynamics of Molecular Emission Features from Nanosecond, Femtosecond Laser and Filament Ablation Plasmas

    SciTech Connect

    Harilal, Sivanandan S.; Yeak, J.; Brumfield, Brian E.; Suter, Jonathan D.; Phillips, Mark C.

    2016-06-15

    The evolutionary paths of molecular species and nanoparticles in laser ablation plumes are not well understood due to the complexity of numerous physical processes that occur simultaneously in a transient laser-plasma system. It is well known that the emission features of ions, atoms, molecules and nanoparticles in a laser ablation plume strongly depend on the laser irradiation conditions. In this letter we report the temporal emission features of AlO molecules in plasmas generated using a nanosecond laser, a femtosecond laser and filaments generated from a femtosecond laser. Our results show that, at a fixed laser energy, the persistence of AlO is found to be highest and lowest in ns and filament laser plasmas respectively while molecular species are formed at early times for both ultrashort pulse (fs and filament) generated plasmas. Analysis of the AlO emission band features show that the vibrational temperature of AlO decays rapidly in filament assisted laser ablation plumes.

  9. Laser Spectroscopic Study on Oxygen Isotope Effects in Ozone Surface Decomposition

    NASA Astrophysics Data System (ADS)

    Minissale, Marco; Boursier, Corinne; Elandaloussi, Hadj; Te, Yao; Jeseck, Pascal; Rouille, Christian; Zanon-Willette, Thomas; Janssen, Christof

    2016-04-01

    The isotope kinetics of ozone formation in the Chapman reaction [1] O + O2 + M → O3 + M (1) provides the primary example for a chemically induced oxygen isotope anomaly and is associated with large [2] and mass independent [3] oxygen isotope enrichments in the product molecule, linked to a symmetry selection in the ozone formation kinetics [4-5]. The isotopic composition of ozone and its transfer to other molecules is a powerful tracer in the atmospheric and biogeochemical sciences [6] and serves as a primary model for a possible explanation of the oxygen isotopic heterogeneity in the Solar system [7-8]. Recently, the isotope fractionation in the photolytic decomposition process O3 + hν → O2 + O (2) using visible light has been studied in detail [9-10]. Much less is currently known about the isotope fractionation in the dry deposition or in the gas phase thermal decomposition of ozone O3 + M → O2 + O +M. (3) Here we report on first spectroscopic studies of non-photolytic ozone decomposition using a cw-quantum cascade laser at 9.5 μm. The concentration of individual ozone isotopomers (16O3,16O16O17O, and 16O17O16O) in a teflon coated reaction cell is followed in real time at temperatures between 25 and 150 °C. Observed ozone decay rates depend on homogeneous (reaction (3)) processes in the gas phase and on heterogeneous reactions on the wall. A preliminary analysis reveals agreement with currently recommended ozone decay rates in the gas phase and the absence of a large symmetry selection in the surface decomposition process, indicating the absence of a mass independent fractionation effect. This result is in agreement with previous mass spectrometer (MS) studies on heterogeneous ozone formation on pyrex [11], but contradicts an earlier MS study [12] on ozone surface decomposition on pyrex and quartz. Implications for atmospheric chemistry will be discussed. [1] Morton, J., Barnes, J., Schueler, B. and Mauersberger, K. J. Geophys. Res. 95, 901 - 907 (1990

  10. Compact laser molecular beam epitaxy system using laser heating of substrate for oxide film growth

    NASA Astrophysics Data System (ADS)

    Ohashi, S.; Lippmaa, M.; Nakagawa, N.; Nagasawa, H.; Koinuma, H.; Kawasaki, M.

    1999-01-01

    A high-temperature, oxygen compatible, and compact laser molecular beam epitaxy (laser MBE) system has been developed. The 1.06 μm infrared light from a continuous wave neodymium-doped yttrium aluminum garnet (Nd:YAG) laser was used to achieve a wide range and rapid control of substrate temperature in ultrahigh vacuum and at up to 1 atm oxygen pressure. The maximum usable temperature was limited to 1453 °C by the melting point of the nickel sample holder. To our knowledge, this is the highest temperature reported for pulsed laser deposition of oxide films. The efficient laser heating combined with temperature monitoring by a pyrometer and feedback control of the Nd:YAG laser power by a personal computer made it possible to regulate the substrate temperature accurately and to achieve high sample heating and cooling rates. The oxygen pressure and ablation laser triggering were also controlled by the computer. The accurate growth parameter control was combined with real-time in situ surface structure monitoring by reflection high energy electron diffraction to investigate oxide thin film growth in detail over a wide range of temperatures, oxygen partial pressures, and deposition rates. We have demonstrated the performance of this system by the fabrication of homoepitaxial SrTiO3 films as well as heteroepitaxial Sr2RuO4, and SrRuO3 films on SrTiO3 substrates at temperatures of up to 1300 °C. This temperature was high enough to change the film growth mode from layer by layer to step flow.

  11. Device and method for separating oxygen isotopes

    DOEpatents

    Rockwood, Stephen D.; Sander, Robert K.

    1984-01-01

    A device and method for separating oxygen isotopes with an ArF laser which produces coherent radiation at approximately 193 nm. The output of the ArF laser is filtered in natural air and applied to an irradiation cell where it preferentially photodissociates molecules of oxygen gas containing .sup.17 O or .sup.18 O oxygen nuclides. A scavenger such as O.sub.2, CO or ethylene is used to collect the preferentially dissociated oxygen atoms and recycled to produce isotopically enriched molecular oxygen gas. Other embodiments utilize an ArF laser which is narrowly tuned with a prism or diffraction grating to preferentially photodissociate desired isotopes. Similarly, desired mixtures of isotopic gas can be used as a filter to photodissociate enriched preselected isotopes of oxygen.

  12. Isotopic imaging via nuclear resonance fluorescence with laser-based Thomson radiation

    DOEpatents

    Barty, Christopher P. J.; Hartemann, Frederic V.; McNabb, Dennis P.; Pruet, Jason A.

    2009-07-21

    The present invention utilizes novel laser-based, high-brightness, high-spatial-resolution, pencil-beam sources of spectrally pure hard x-ray and gamma-ray radiation to induce resonant scattering in specific nuclei, i.e., nuclear resonance fluorescence. By monitoring such fluorescence as a function of beam position, it is possible to image in either two dimensions or three dimensions, the position and concentration of individual isotopes in a specific material configuration. Such methods of the present invention material identification, spatial resolution of material location and ability to locate and identify materials shielded by other materials, such as, for example, behind a lead wall. The foundation of the present invention is the generation of quasimonochromatic high-energy x-ray (100's of keV) and gamma-ray (greater than about 1 MeV) radiation via the collision of intense laser pulses from relativistic electrons. Such a process as utilized herein, i.e., Thomson scattering or inverse-Compton scattering, produces beams having diameters from about 1 micron to about 100 microns of high-energy photons with a bandwidth of .DELTA.E/E of approximately 10E.sup.-3.

  13. Metrology for laser spectroscopic concentration and isotope ratio measurements of atmospheric greenhouse gases

    NASA Astrophysics Data System (ADS)

    Nwaboh, Javis; Manninen, Albert; Mohn, Joachim; Petersen, Jan C.; Werhahn, Olav; Ebert, Volker

    2015-04-01

    Continuous, accurate and precise measurements of greenhouse gases (GHG) and their isotopic composition are required to understand the global cycle as well as source and sink processes of these environmentally harmful substances. Part of the EMRP project HIGHGAS (Metrology for high-impact greenhouse gases) [1] focuses on spectroscopic methods for GHG isotopic composition measurements and optical transfer standards. Harmonization of terminologies and concepts used in the GHG measurement communities and the metrology community are in focus, especially for isotope ratio measurements by laser spectroscopy, where gas metrology is still at an early stage. The focus of the HIGHGAS project here is on 13C/12C and 18O/16O ratios in CO2, 15N/14N ratios in N2O and 13C/12C and 2H/1H ratios in CH4. As an alternative and complement of gas mixture standards, optical spectroscopic transfer standards for CO2 and CO shall be developed providing concentration results that are directly traceable to the international system of units (SI). Optical transfer standards offer an alternative in situ calibration route for other GHG measurement devices operating in the field. An optical transfer standard becomes particularly interesting when measuring sticky or reactive gases where cylinder-based reference gas mixtures may not be feasible. We present an approach to perform IR-spectrometry on gases with results directly traceable to the SI. This is crucial for the development of optical spectroscopic transfer standards providing SI-traceability to field measurements. Ideas for spectroscopic isotope ratio measurements aiming at SI-traceability will be discussed. Finally, we demonstrate the current performance and limitations of our measurement approaches and project possible solutions. Acknowledgement Parts of this work have been carried out within the European Metrology Research Programme (EMRP) ENV52 project-HIGHGAS (Metrology for high-impact greenhouse gases). The EMRP is jointly funded by the

  14. Highly accurate isotope composition measurements by a miniature laser ablation mass spectrometer designed for in situ investigations on planetary surfaces

    NASA Astrophysics Data System (ADS)

    Riedo, A.; Meyer, S.; Heredia, B.; Neuland, M. B.; Bieler, A.; Tulej, M.; Leya, I.; Iakovleva, M.; Mezger, K.; Wurz, P.

    2013-10-01

    An experimental procedure for precise and accurate measurements of isotope abundances by a miniature laser ablation mass spectrometer for space research is described. The measurements were conducted on different untreated NIST standards and galena samples by applying pulsed UV laser radiation (266 nm, 3 ns and 20 Hz) for ablation, atomisation, and ionisation of the sample material. Mass spectra of released ions are measured by a reflectron-type time-of-flight mass analyser. A computer controlled performance optimiser was used to operate the system at maximum ion transmission and mass resolution. At optimal experimental conditions, the best relative accuracy and precision achieved for Pb isotope compositions are at the per mill level and were obtained in a range of applied laser irradiances and a defined number of accumulated spectra. A similar relative accuracy and precision was achieved in the study of Pb isotope compositions in terrestrial galena samples. The results for the galena samples are similar to those obtained with a thermal ionisation mass spectrometer (TIMS). The studies of the isotope composition of other elements yielded relative accuracy and precision at the per mill level too, with characteristic instrument parameters for each element. The relative accuracy and precision of the measurements is degrading with lower element/isotope concentration in a sample. For the elements with abundances below 100 ppm these values drop to the percent level. Depending on the isotopic abundances of Pb in minerals, 207Pb/206Pb ages with accuracy in the range of tens of millions of years can be achieved.

  15. Role of molecular photodissociation in ultrafast laser surgery

    NASA Astrophysics Data System (ADS)

    Wang, Jenny; Schuele, Georg; Huie, Phil; Palanker, Daniel V.

    2015-03-01

    Transparent ocular tissues such as cornea and crystalline lens can be precisely ablated or dissected using ultrafast ultraviolet, visible, and infrared lasers. In refractive or cataract surgery, cutting of the cornea, lens, and lens capsule is typically produced by dielectric breakdown in the focus of a short-pulse laser which results in explosive vaporization of the interstitial water and mechanically ruptures the surrounding tissue. Here, we report that tissue can also be disrupted below the threshold of bubble appearance using 400 nm femtosecond pulses with minimal mechanical damage. Using gel electrophoresis and liquid chromatography/mass spectrometry, we assessed photodissociation of proteins and polypeptides by 400 nm femtosecond pulses both below and above the cavitation bubble threshold. Negligible protein dissociation was observed with 800 nm femtosecond lasers even above the threshold of dielectric breakdown. Scanning electron microscopy of the cut edges in porcine lens capsule demonstrated that plasma-mediated cutting results in the formation of grooves. Below the cavitation bubble threshold, precise cutting could still be produced with 400 nm femtosecond pulses, possibly due to molecular photodissociation of the tissue structural proteins.

  16. Molecular Isotopic Characterization of the ALH 85013.50 Meteorite: Defining the Extraterrestrial Organic Compounds

    NASA Technical Reports Server (NTRS)

    Fuller, M.; Huang, Y.

    2003-01-01

    The Antarctic Meteorite Program has returned over 16,000 meteorites from the ice sheets of the Antarctic. This more than doubles the number of preexisting meteorite collection and adds important and rare specimens to the assemblage. The CM carbonaceous chondrites are of particular interest because of their high organic component. The Antarctic carbonaceous chondrites provide a large, previously uninvestigated suite of meteorites. Of the 161 CM chondrites listed in the Catalogue of Meteorites 138 of them have been recovered from the Antarctic ice sheets,. However, these meteorites have typically been exposed to Earth s conditions for long periods of time. The extent of terrestrial organic contamination and weathering that has taken place on these carbonaceous chondrites is unknown. In the past, stable isotope analysis was used to identify bulk organics that were extraterrestrial in origin. Although useful, this method could not exclude the possibility of terrestrial contamination contributing to the isotopic measurement. Compound specific isotope analysis of organic meteorite material has provided the opportunity to discern the terrestrial contamination from extraterrestrial organic compounds on the molecular level.

  17. On-line experimental results of an argon gas cell-based laser ion source (KEK Isotope Separation System)

    NASA Astrophysics Data System (ADS)

    Hirayama, Y.; Watanabe, Y. X.; Imai, N.; Ishiyama, H.; Jeong, S. C.; Jung, H. S.; Miyatake, H.; Oyaizu, M.; Kimura, S.; Mukai, M.; Kim, Y. H.; Sonoda, T.; Wada, M.; Huyse, M.; Kudryavtsev, Yu.; Van Duppen, P.

    2016-06-01

    KEK Isotope Separation System (KISS) has been developed at RIKEN to produce neutron rich isotopes with N = 126 to study the β -decay properties for application to astrophysics. The KISS is an element-selective mass-separation system which consists of an argon gas cell-based on laser ion source for atomic number selection and an ISOL mass-separation system. The argon gas cell of KISS is a key component to stop and collect the unstable nuclei produced in a multi-nucleon transfer reaction, where the isotopes of interest will be selectively ionized using laser resonance ionization. We have performed off- and on-line experiments to study the basic properties of the gas cell as well as of the KISS. We successfully extracted the laser-ionized stable 56Fe (direct implantation of a 56Fe beam into the gas cell) atoms and 198Pt (emitted from the 198Pt target by elastic scattering with a 136Xe beam) atoms from the KISS during the commissioning on-line experiments. We furthermore extracted laser-ionized unstable 199Pt atoms and confirmed that the measured half-life was in good agreement with the reported value.

  18. Stable carbon isotope analyses of nanogram quantities of particulate organic carbon (pollen) with laser ablation nano combustion gas chromatography/isotope ratio mass spectrometry

    PubMed Central

    Sluijs, Appy; Laks, Jelmer J.; Reichart, Gert‐Jan

    2016-01-01

    Rationale Analyses of stable carbon isotope ratios (δ 13C values) of organic and inorganic matter remains have been instrumental for much of our understanding of present and past environmental and biological processes. Until recently, the analytical window of such analyses has been limited to samples containing at least several μg of carbon. Methods Here we present a setup combining laser ablation, nano combustion gas chromatography and isotope ratio mass spectrometry (LA/nC/GC/IRMS). A deep UV (193 nm) laser is used for optimal fragmentation of organic matter with minimum fractionation effects and an exceptionally small ablation chamber and combustion oven are used to reduce the minimum sample mass requirement compared with previous studies. Results Analyses of the international IAEA CH‐7 polyethylene standard show optimal accuracy, and precision better than 0.5‰, when measuring at least 42 ng C. Application to untreated modern Eucalyptus globulus (C3 plant) and Zea mays (C4 plant) pollen grains shows a ~ 16‰ offset between these species. Within each single Z. mays pollen grain, replicate analyses show almost identical δ 13C values. Conclusions Isotopic offsets between individual pollen grains exceed analytical uncertainties, therefore probably reflecting interspecimen variability of ~0.5–0.9‰. These promising results set the stage for investigating both δ 13C values and natural carbon isotopic variability between single specimens of a single population of all kinds of organic particles yielding tens of nanograms of carbon. © 2016 The Authors. Rapid Communications in Mass Spectrometry Published by John Wiley & Sons Ltd. PMID:27766694

  19. Stable hydrogen isotopic analysis of nanomolar molecular hydrogen by automatic multi-step gas chromatographic separation.

    PubMed

    Komatsu, Daisuke D; Tsunogai, Urumu; Kamimura, Kanae; Konno, Uta; Ishimura, Toyoho; Nakagawa, Fumiko

    2011-11-15

    We have developed a new automated analytical system that employs a continuous flow isotope ratio mass spectrometer to determine the stable hydrogen isotopic composition (δD) of nanomolar quantities of molecular hydrogen (H(2)) in an air sample. This method improves previous methods to attain simpler and lower-cost analyses, especially by avoiding the use of expensive or special devices, such as a Toepler pump, a cryogenic refrigerator, and a special evacuation system to keep the temperature of a coolant under reduced pressure. Instead, the system allows H(2) purification from the air matrix via automatic multi-step gas chromatographic separation using the coolants of both liquid nitrogen (77 K) and liquid nitrogen + ethanol (158 K) under 1 atm pressure. The analytical precision of the δD determination using the developed method was better than 4‰ for >5 nmol injections (250 mL STP for 500 ppbv air sample) and better than 15‰ for 1 nmol injections, regardless of the δD value, within 1 h for one sample analysis. Using the developed system, the δD values of H(2) can be quantified for atmospheric samples as well as samples of representative sources and sinks including those containing small quantities of H(2) , such as H(2) in soil pores or aqueous environments, for which there is currently little δD data available. As an example of such trace H(2) analyses, we report here the isotope fractionations during H(2) uptake by soils in a static chamber. The δD values of H(2) in these H(2)-depleted environments can be useful in constraining the budgets of atmospheric H(2) by applying an isotope mass balance model.

  20. Using a laser-based CO2 carbon isotope analyser to investigate gas transfer in geological media

    NASA Astrophysics Data System (ADS)

    Guillon, S.; Pili, E.; Agrinier, P.

    2012-05-01

    CO2 stable carbon isotopes are very attractive in environmental research to investigate both natural and anthropogenic carbon sources. Laser-based CO2 carbon isotope analysis provides continuous measurement at high temporal resolution and is a promising alternative to isotope ratio mass spectrometry (IRMS). We performed a thorough assessment of a commercially available CO2 Carbon Isotope Analyser (CCIA DLT-100, Los Gatos Research) that allows in situ measurement of δ 13C in CO2. Using a set of reference gases of known CO2 concentration and carbon isotopic composition, we evaluated the precision, long-term stability, temperature sensitivity and concentration dependence of the analyser. Despite good precision calculated from Allan variance (5.0 ppm for CO2 concentration, and 0.05 ‰ for δ 13C at 60 s averaging), real performances are altered by two main sources of error: temperature sensitivity and dependence of δ 13C on CO2 concentration. Data processing is required to correct for these errors. Following application of these corrections, we achieve an accuracy of 8.7 ppm for CO2 concentration and 1.3 ‰ for δ 13C, which is worse compared to mass spectrometry performance, but still allowing field applications. With this portable analyser we measured CO2 flux degassed from rock in an underground tunnel. The obtained carbon isotopic composition agrees with IRMS measurement, and can be used to identify the carbon source.

  1. Improvement on Fermionic properties and new isotope production in molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    Wang, Ning; Wu, Tong; Zeng, Jie; Yang, Yongxu; Ou, Li

    2016-06-01

    By considering momentum transfer in the Fermi constraint procedure, the stability of the initial nuclei and fragments produced in heavy-ion collisions can be further improved in quantum molecular dynamics simulations. The case of a phase-space occupation probability larger than one is effectively reduced with the proposed procedure. Simultaneously, the energy conservation can be better described for both individual nuclei and heavy-ion reactions. With the revised version of the improved quantum molecular dynamics model, the fusion excitation functions of 16O+186W and the central collisions of Au+Au at 35 AMeV are re-examined. The fusion cross sections at sub-barrier energies and the charge distribution of fragments are relatively better reproduced due to the reduction of spurious nucleon emission. The charge and isotope distribution of fragments in Xe+Sn, U+U and Zr+Sn at intermediate energies are also predicted. More unmeasured extremely neutron-rich fragments with Z = 16-28 are observed in the central collisions of 238U+238U than that of 96Zr+124Sn, which indicates that multi-fragmentation of U+U may offer a fruitful pathway to new neutron-rich isotopes.

  2. Predicting molecular formulas of fragment ions with isotope patterns in tandem mass spectra.

    PubMed

    Zhang, Jingfen; Gao, Wen; Cai, Jinjin; He, Simin; Zeng, Rong; Chen, Runsheng

    2005-01-01

    A number of different approaches have been proposed to predict elemental component formulas (or molecular formulas) of molecular ions in low and medium resolution mass spectra. Most of them rely on isotope patterns, enumerate all possible formulas for an ion, and exclude certain formulas violating chemical constraints. However, these methods cannot be well generalized to the component prediction of fragment ions in tandem mass spectra. In this paper, a new method, FFP (Fragment ion Formula Prediction), is presented to predict elemental component formulas of fragment ions. In the FFP method, the prediction of the best formulas is converted into the minimization of the distance between theoretical and observed isotope patterns. And, then, a novel local search model is proposed to generate a set of candidate formulas efficiently. After the search, FFP applies a new multiconstraint filtering to exclude as many invalid and improbable formulas as possible. FFP is experimentally compared with the previous enumeration methods, and shown to outperform them significantly. The results of this paper can help to improve the reliability of de novo in the identification of peptide sequences.

  3. Organic Geochemistry of the Hamersley Province: Relationships Among Organic Carbon Isotopes, Molecular Fossils, and Lithology

    NASA Technical Reports Server (NTRS)

    Eigenbrode, Jennifer L.

    2012-01-01

    Molecular fossils are particularly valuable ancient biosignatures that can provide key insight about microbial sources and ecology in early Earth studies. In particular, hopanes carrying 2-methyl or 3-methyl substituents are proposed to be derived from cyanobacteria and oxygen-respiring methanotrophs, respectively, based on both their modem occurrences and their Proterozoic and Phanerozoic sedimentary distributions. Steranes are likely from ancestral eukaryotes. The distribution of methylhopanes, steranes, and other biomarkers in 2.72-2.56 billion-year-old rocks from the Hamersley Province, Western Australia show relationships to lithology, facies, and isotopes of macromolecular carbon, and other biomarkers. These observations support biomarker syngenicity and thermal maturity. Moreover, ecological signatures are revealed, including a surprising relationship between isotopic values for bulk macromolecular carbon and the biomarker for methanotrophs. The record suggests that cyanobacteria were likely key organisms of shallow-water microbial ecosystems providing molecular oxygen, fixed carbon, and possibly fixed nitrogen, and methanotrophs were not alone in recycling methane and other C-13-depleted substrates.

  4. IV INTERNATIONAL CONFERENCE ON ATOM AND MOLECULAR PULSED LASERS (AMPL'99): IV International Conference on Atomic and Molecular Pulsed Gas Lasers (AMPL'99)

    NASA Astrophysics Data System (ADS)

    Evtushenko, Gennadii S.; Kopylova, T. N.; Soldatov, A. N.; Tarasenko, Viktor F.; Yakovlenko, Sergei I.; Yancharina, A. M.

    2000-06-01

    A brief review of the most interesting papers presented at the IV International Conference on Atomic and Molecular Pulsed Gas Lasers (AMPL'99), which was held in Tomsk, September 13-17, 1999, is provided.

  5. Isotopic evidence for primordial molecular cloud material in metal-rich carbonaceous chondrites

    PubMed Central

    Van Kooten, Elishevah M. M. E.; Wielandt, Daniel; Schiller, Martin; Nagashima, Kazuhide; Thomen, Aurélien; Olsen, Mia B.; Nordlund, Åke; Krot, Alexander N.; Bizzarro, Martin

    2016-01-01

    The short-lived 26Al radionuclide is thought to have been admixed into the initially 26Al-poor protosolar molecular cloud before or contemporaneously with its collapse. Bulk inner Solar System reservoirs record positively correlated variability in mass-independent 54Cr and 26Mg*, the decay product of 26Al. This correlation is interpreted as reflecting progressive thermal processing of in-falling 26Al-rich molecular cloud material in the inner Solar System. The thermally unprocessed molecular cloud matter reflecting the nucleosynthetic makeup of the molecular cloud before the last addition of stellar-derived 26Al has not been identified yet but may be preserved in planetesimals that accreted in the outer Solar System. We show that metal-rich carbonaceous chondrites and their components have a unique isotopic signature extending from an inner Solar System composition toward a 26Mg*-depleted and 54Cr-enriched component. This composition is consistent with that expected for thermally unprocessed primordial molecular cloud material before its pollution by stellar-derived 26Al. The 26Mg* and 54Cr compositions of bulk metal-rich chondrites require significant amounts (25–50%) of primordial molecular cloud matter in their precursor material. Given that such high fractions of primordial molecular cloud material are expected to survive only in the outer Solar System, we infer that, similarly to cometary bodies, metal-rich carbonaceous chondrites are samples of planetesimals that accreted beyond the orbits of the gas giants. The lack of evidence for this material in other chondrite groups requires isolation from the outer Solar System, possibly by the opening of disk gaps from the early formation of gas giants. PMID:26858438

  6. Isotopic evidence for primordial molecular cloud material in metal-rich carbonaceous chondrites.

    PubMed

    Van Kooten, Elishevah M M E; Wielandt, Daniel; Schiller, Martin; Nagashima, Kazuhide; Thomen, Aurélien; Larsen, Kirsten K; Olsen, Mia B; Nordlund, Åke; Krot, Alexander N; Bizzarro, Martin

    2016-02-23

    The short-lived (26)Al radionuclide is thought to have been admixed into the initially (26)Al-poor protosolar molecular cloud before or contemporaneously with its collapse. Bulk inner Solar System reservoirs record positively correlated variability in mass-independent (54)Cr and (26)Mg*, the decay product of (26)Al. This correlation is interpreted as reflecting progressive thermal processing of in-falling (26)Al-rich molecular cloud material in the inner Solar System. The thermally unprocessed molecular cloud matter reflecting the nucleosynthetic makeup of the molecular cloud before the last addition of stellar-derived (26)Al has not been identified yet but may be preserved in planetesimals that accreted in the outer Solar System. We show that metal-rich carbonaceous chondrites and their components have a unique isotopic signature extending from an inner Solar System composition toward a (26)Mg*-depleted and (54)Cr-enriched component. This composition is consistent with that expected for thermally unprocessed primordial molecular cloud material before its pollution by stellar-derived (26)Al. The (26)Mg* and (54)Cr compositions of bulk metal-rich chondrites require significant amounts (25-50%) of primordial molecular cloud matter in their precursor material. Given that such high fractions of primordial molecular cloud material are expected to survive only in the outer Solar System, we infer that, similarly to cometary bodies, metal-rich carbonaceous chondrites are samples of planetesimals that accreted beyond the orbits of the gas giants. The lack of evidence for this material in other chondrite groups requires isolation from the outer Solar System, possibly by the opening of disk gaps from the early formation of gas giants.

  7. Online induction heating for determination of isotope composition of woody stem water with laser spectrometry: A methods assessment

    USGS Publications Warehouse

    Lazarus, Brynne E.; Germino, Matthew; Vander Veen, Jessica L.

    2016-01-01

    Application of stable isotopes of water to studies of plant–soil interactions often requires a substantial preparatory step of extracting water from samples without fractionating isotopes. Online heating is an emerging approach for this need, but is relatively untested and major questions of how to best deliver standards and assess interference by organics have not been evaluated. We examined these issues in our application of measuring woody stem xylem of sagebrush using a Picarro laser spectrometer with online induction heating. We determined (1) effects of cryogenic compared to induction-heating extraction, (2) effects of delivery of standards on filter media compared to on woody stem sections, and (3) spectral interference from organic compounds for these approaches (and developed a technique to do so). Our results suggest that matching sample and standard media improves accuracy, but that isotopic values differ with the extraction method in ways that are not due to spectral interference from organics.

  8. Online induction heating for determination of isotope composition of woody stem water with laser spectrometry: a methods assessment.

    PubMed

    Lazarus, Brynne E; Germino, Matthew J; Vander Veen, Jessica L

    2016-06-01

    Application of stable isotopes of water to studies of plant-soil interactions often requires a substantial preparatory step of extracting water from samples without fractionating isotopes. Online heating is an emerging approach for this need, but is relatively untested and major questions of how to best deliver standards and assess interference by organics have not been evaluated. We examined these issues in our application of measuring woody stem xylem of sagebrush using a Picarro laser spectrometer with online induction heating. We determined (1) effects of cryogenic compared to induction-heating extraction, (2) effects of delivery of standards on filter media compared to on woody stem sections, and (3) spectral interference from organic compounds for these approaches (and developed a technique to do so). Our results suggest that matching sample and standard media improves accuracy, but that isotopic values differ with the extraction method in ways that are not due to spectral interference from organics.

  9. Nuclear Charge Radii of Neutron-Deficient Lead Isotopes Beyond N=104 Midshell Investigated by In-Source Laser Spectroscopy

    SciTech Connect

    Witte, H. de; Cocolios, T. E.; Dean, S.; Huyse, M.; Lesher, S. R.; Mukha, I.; Stefanescu, I.; Vel, K. van de; Walle, J. van de; Duppen, P. van; Andreyev, A. N.; Barre, N.; Roussiere, B.; Sauvage, J.; Bender, M.; Fedoseyev, V. N.; Fraile, L. M.; Jeppessen, H.

    2007-03-16

    The shape of exotic even-mass {sup 182-190}Pb isotopes was probed by measurement of optical isotope shifts providing mean square charge radii ({delta}). The experiment was carried out at the isolde (cern) on-line mass separator, using in-source laser spectroscopy. Small deviations from the spherical droplet model are observed, but when compared to model calculations, those are explained by high sensitivity of {delta} to beyond mean-field correlations and small admixtures of intruder configurations in the ground state. The data support the predominantly spherical shape of the ground state of the proton-magic Z=82 lead isotopes near neutron midshell (N=104)

  10. Tracking isotopic signatures of CO2 at Jungfraujoch with laser spectroscopy: analytical improvements and exemplary results

    NASA Astrophysics Data System (ADS)

    Sturm, P.; Tuzson, B.; Henne, S.; Emmenegger, L.

    2013-01-01

    We present the continuous data record of atmospheric CO2 isotopes measured by laser absorption spectroscopy for an almost four year period at the High Altitude Research Station Jungfraujoch (3580 m a.s.l.), Switzerland. The mean annual cycles derived from data of December 2008 to September 2012 exhibit peak-to-peak amplitudes of 11.0 μmol mol-1 for CO2, 0.60‰ for δ13C and 0.81‰ for δ18O. The high temporal resolution of the measurements also allow to capture variations on hourly and diurnal time scales. For CO2 the mean diurnal peak-to-peak amplitude is about 1 μmol mol-1 in spring, autumn and winter and about 2 μmol mol-1 in summer. The mean diurnal variability in the isotope ratios is largest during the summer months too, with an amplitude of about 0.1‰ both in the δ13C and δ18O, and a smaller or no discernible diurnal cycle during the other seasons. The day-to-day variability, however, is much larger and depends on the origin of the air masses arriving at Jungfraujoch. Backward Lagrangian particle dispersion model simulations revealed a close link between air composition and prevailing transport regimes and could be used to explain part of the observed variability in terms of transport history and influence region. A footprint clustering showed significantly different wintertime CO2, δ13C and δ18O values depending on the origin and surface residence times of the air masses. Based on the experiences gained from our measurements, several major updates on the instrument and the calibration procedures were performed in order to further improve the data quality. We describe the new measurement and calibration setup in detail and demonstrate the enhanced performance of the analyser. A precision of about 0.02‰ for both isotope ratios has been obtained for an averaging time of 10 min.

  11. Theoretical Studies of Laser-Induced Molecular Rate Processes: Topics in Line Broadening and Spectroscopy.

    DTIC Science & Technology

    1985-10-01

    GROUP SU. GRF. MOLECULAR RATE PROCESSES MOLECULAR DYNAMICS LASER-INDUCED LINE BROADENING THEORETICAL STUDIES SPECTROSCOPY 19. ABSI*ACT (Continue On...approaches half the band-gap energy. -q 14 This idea of using a laser to "charge" the surface region has fomed the basis of a semiclassical theory of charge

  12. CHILI – the Chicago Instrument for Laser Ionization – a new tool for isotope measurements in cosmochemistry

    SciTech Connect

    Stephan, Thomas; Trappitsch, Reto; Davis, Andrew M.; Pellin, Michael J.; Rost, Detlef; Savina, Michael R.; Yokochi, Reika; Liu, Nan

    2016-06-17

    Here, we describe CHILI, the Chicago Instrument for Laser Ionization, a new resonance ionization mass spectrometer developed for isotopic analysis at high spatial resolution and high sensitivity of small samples like contemporary interstellar dust grains returned by the Stardust spacecraft. We explain how CHILI addresses the technical challenges associated with such analyses by pushing most technical specifications towards their physical limits. As an initial demonstration, after many years of designing and developing CHILI, we have analyzed presolar silicon carbide grains for their isotopic compositions of strontium, zirconium, and barium. Subsequently, after further technical improvements, we have used CHILI to analyze, for the first time without interference, all stable isotopes of iron and nickel simultaneously in presolar silicon carbide grains. With a special timing scheme for the ionization lasers, we separated iron and nickel isotopes in the time-of-flight spectrum such that the isobaric interference between 58Fe and 58Ni was resolved. In-depth discussion of the astrophysical implications of the presolar grain results is deferred to dedicated later publications. Here we focus on the technical aspects of CHILI, its status quo, and further developments necessary to achieve CHILI’s ultimate goals, 10 nm lateral resolution and 30–40% useful yield.

  13. CHILI – the Chicago Instrument for Laser Ionization – a new tool for isotope measurements in cosmochemistry

    DOE PAGES

    Stephan, Thomas; Trappitsch, Reto; Davis, Andrew M.; ...

    2016-06-17

    Here, we describe CHILI, the Chicago Instrument for Laser Ionization, a new resonance ionization mass spectrometer developed for isotopic analysis at high spatial resolution and high sensitivity of small samples like contemporary interstellar dust grains returned by the Stardust spacecraft. We explain how CHILI addresses the technical challenges associated with such analyses by pushing most technical specifications towards their physical limits. As an initial demonstration, after many years of designing and developing CHILI, we have analyzed presolar silicon carbide grains for their isotopic compositions of strontium, zirconium, and barium. Subsequently, after further technical improvements, we have used CHILI to analyze,more » for the first time without interference, all stable isotopes of iron and nickel simultaneously in presolar silicon carbide grains. With a special timing scheme for the ionization lasers, we separated iron and nickel isotopes in the time-of-flight spectrum such that the isobaric interference between 58Fe and 58Ni was resolved. In-depth discussion of the astrophysical implications of the presolar grain results is deferred to dedicated later publications. Here we focus on the technical aspects of CHILI, its status quo, and further developments necessary to achieve CHILI’s ultimate goals, 10 nm lateral resolution and 30–40% useful yield.« less

  14. Standardless determination of Nd and Sr isotope ratios in geological samples using LA-MC-ICP-MS with a low-oxide molecular yield interface setup

    NASA Astrophysics Data System (ADS)

    Kimura, J.; Chang, Q.; Takahashi, T.; Kawabata, H.

    2013-12-01

    We investigated an appropriate instrumental setup for a laser-ablation multiple-collector inductively coupled plasma mass spectrometer (LA-MC-ICP-MS) and found that a reduced oxide setting allowed accurate and precise analyses of Sr and Nd isotope ratios in geological samples with concomitant interfering elements (Kr and Rb on Sr and Sm on Nd). We used an Aridus II solution-excimer laser dual-intake system. The ICP interface used normal sample and skimmer cones with torch shield switched-OFF and an additional large interface rotary pump. The setting accomplished reduced oxide levels NdO+/Nd+ <0.01%, without significant sacrifice of the instrumental sensitivity (c.a. 70%). Oxide molecular ions for the lighter elements were negligible and accurate internal mass bias corrections were achieved for Sr, Sm, and Nd using isotopic ratios derived from thermal ionization mass spectrometry measurements. However, elemental fractionation between Rb and Sr and Nd and Sm still exists due perhaps to elemental fractionation in the ICP preventing standardless determination of parent-daughter ratios. For Sr isotope measurement, a new analytical protocol was developed for correcting Kr baseline-induced biases. Residual analytical biases of 84Sr/86Sr and 87Sr/86Sr were observed after applying on-peak background subtractions and mass-fractionation corrections using internal normalization. The residual biases occurred only for samples analysed with LA and not for solution analyses using Aridus II with the same instrumental setup. We concluded that this was due to suppression and enhancement of the Kr baseline by loading of the LA sample aerosols and by the introduction of Kr from the samples, respectively. We found that both the 84Sr/86Sr and 87Sr/86Sr isotope ratios were affected proportionally by the baseline biases of the LA analyses of an isotopically homogeneous anorthite plagioclase, and similar result were seen in theoretical calculations. A theoretical bias correction for the 87

  15. 238U, 232Th profiling and U-series isotope analysis of fossil teeth by laser ablation-ICPMS

    NASA Astrophysics Data System (ADS)

    Eggins, Stephen; Grün, Rainer; Pike, Alistair W. G.; Shelley, Michael; Taylor, Lois

    2003-05-01

    U and Th concentration profiles in fossil hominid and faunal teeth have been measured by laser ablation ICPMS. These profiles record diverse modes of U and Th uptake, particularly within enamel, that can be broadly related to the state of sample preservation. Observed U profiles are in general inconsistent with existing diffusion-adsorption models developed for U-uptake in bone and teeth. Where the models appear applicable, calculated diffusion rates are several orders of magnitude smaller than previous estimates. Laser ablation ICPMS offers a means of rapidly characterizing U and Th distributions in the enamel and dentine components of teeth as a precursor to ESR and U-series dating. In particular, it should allow the identification of teeth (and also bone) samples that have simple U-uptake histories and are amenable to precise dating by time-consuming and expensive Th-U and Pa-U TIMS techniques. We also demonstrated the use of laser ablation ICPMS to measure U-series isotopes in dentine and enamel samples with relatively high U concentrations (>20 ppm). These results, obtained using a quadrupole ICPMS, illustrate significant promise for in situ U-series isotope analysis, particularly when combined with the greater sensitivity and multi-collection capabilities of new sector ICPMS instrumentation. The latter may permit precise isotope ratio measurements on samples containing only a few ppm of U.

  16. Determination of iodine in oyster tissue by isotope dilution laser resonance ionization mass spectrometry

    SciTech Connect

    Fassett, J.D.; Murphy, T.J. )

    1990-02-15

    The technique of laser resonance ionization mass spectrometry has been combined with isotope dilution analysis to determine iodine in oyster tissue. The long-lived radioisotope, 129I, was used to spike the samples. Samples were equilibrated with the 129I, wet ashed under controlled conditions, and iodine separated by coprecipitation with silver chloride. The analyte was dried as silver ammonium iodide upon a tantalum filament from which iodine was thermally desorbed in the resonance ionization mass spectrometry instrument. A single-color, two-photon resonant plus one-photon ionization scheme was used to form positive iodine ions. Long-lived iodine signals were achieved from 100 ng of iodine. The precision of 127I/129I measurement has been evaluated by replicate determinations of the spike, the spike calibration samples, and the oyster tissue samples and was 1.0%. Measurement precision among samples was 1.9% for the spike calibration and 1.4% for the oyster tissue. The concentration of iodine determined in SRM 1566a, Oyster Tissue, was 4.44 micrograms/g with an estimate of the overall uncertainty for the analysis of +/- 0.12 microgram/g.

  17. Determination of iodine in oyster tissue by isotope dilution laser resonance ionization mass spectrometry.

    PubMed

    Fassett, J D; Murphy, T J

    1990-02-15

    The technique of laser resonance ionization mass spectrometry has been combined with isotope dilution analysis to determine iodine in oyster tissue. The long-lived radioisotope, 129I, was used to spike the samples. Samples were equilibrated with the 129I, wet ashed under controlled conditions, and iodine separated by coprecipitation with silver chloride. The analyte was dried as silver ammonium iodide upon a tantalum filament from which iodine was thermally desorbed in the resonance ionization mass spectrometry instrument. A single-color, two-photon resonant plus one-photon ionization scheme was used to form positive iodine ions. Long-lived iodine signals were achieved from 100 ng of iodine. The precision of 127I/129I measurement has been evaluated by replicate determinations of the spike, the spike calibration samples, and the oyster tissue samples and was 1.0%. Measurement precision among samples was 1.9% for the spike calibration and 1.4% for the oyster tissue. The concentration of iodine determined in SRM 1566a, Oyster Tissue, was 4.44 micrograms/g with an estimate of the overall uncertainty for the analysis of +/- 0.12 microgram/g.

  18. Assessment of chloroethene biodegradation in the subsurface by microbiological, molecular and isotopic tools

    NASA Astrophysics Data System (ADS)

    Schmidt, K. R.; Kranzioch, I.; Heidinger, M.; Ertl, S.; Tiehm, A.

    2012-04-01

    A multiple lines of evidence approach to assess the biodegradation potential of contaminated sites includes - site investigation analysing pollutant distribution (compounds, concentrations, isotopic composition) and hydrochemical conditions (redox conditions) - determination of the presence of pollutant degrading bacteria in the field by microbiological (most probable number, MPN) and molecular (polymerase chain reaction, PCR) methods - analysis of degradation processes in the laboratory by microcosms with determination of site specific isotopic enrichment factors enabling the quantification of biodegradation processes in the field. Results will be shown of the application of such a multiple lines of evidence approach at a chloroethene-contaminated site in Frankenthal, Germany. In anaerobic groundwater microcosms, reductive transformation of perchloroethene (PCE) and trichloroethene (TCE) was observed to mainly proceed to cis-1,2-dichloroethene (cDCE). 16S-PCR analysis showed a wide distribution of halorespiring bacteria capable of PCE degradation to cDCE, whereas Dehalococcoides - the only organisms described so far being able of complete reductive dechlorination down to ethene - was only found in one groundwater sample. Aerobic microcosms showed metabolic degradation of the lower chlorinated compounds cDCE and vinyl chloride (VC). Co-metabolic degradation of cDCE with VC as auxiliary substrate occurred, too. Significant stable carbon isotope fractionation was observed during anaerobic degradation of PCE and TCE as well as during aerobic degradation of cDCE and VC. Compiling the results of the different assessment methods, sequential dechlorination - PCE/TCE to cDCE anaerobically and cDCE to CO2 aerobically - was demonstrated to occur at the Frankenthal site. The extent of biodegradation in the field was calculated based on the enrichment factors determined in microcosms and the 13C-isotopic composition of the contaminants on site. The application of molecular

  19. Boron Isotopes Analyses of Carbonates, Phosphates and Silicates by Laser Ablation MC-ICP-MS: the Influence of Sample Matrix

    NASA Astrophysics Data System (ADS)

    Gerdes, A.

    2013-12-01

    Methods for in-situ analyses of boron isotopes by laser ablation MC-ICP-MS, although presented by 3 labs over the last years, are still not routinely applied despite of the growing interest in B isotopes, e.g. in palaeoclimate research. This study evaluates the ability to analyse boron isotopes by laser ablation at levels down to 0.2 ppm in biogenic carbonates as well as in various minerals (e.g., calcit, garnet, cpx, apatite, hematite, quartz, diamond ...) and natural and synthetic glass (NIST, USGS, and MPI-DING). Mounted and polished samples were ablated in a two-volume Helix cell using a RESOlution 193nm Excimer laser coupled to a Thermo-Finnigan Neptune (No. 1, build in 2000). Due to high sensitivity isotope signals were detected using Faraday collectors (1011 Ohm resistors). Analyses were performed as static spots over 25s with diameters of 235 to 7 μm depending on boron concentration, which yield typical 11B signals of about 0.04 (≤ 1ppm; e.g., cherts) to >0.6 V (3wt.%; tourmaline). Therefore, sample amount consumed during analyses range from 1 nanogram to 10 microgram with total analysed B content in the range of 5 to 1000 picogram. For correction of drift and mass fractionation soda-lime glass NIST-612 or NIST-610 were analysed every 30min. The applied method yields for various materials a typical analytical precision and reproducibility (1σ) of the 11B/10B of about 0.5‰ or better at boron concentration of more than 2 ppm. The effect of various parameters such as gas background, surface contamination, cross contamination, spot size, laser energy, and depth drilling will be discussed briefly. However, crucial for in-situ analyse is the evaluation of the accuracy and the influence of the sample matrix on it. Approaches to test this are still hampered by the lack of well-characterized low-B (e.g. <20ppm) reference materiel of different sample matrix. Nevertheless, in contrast to previous studies an effect of sample matrix on the boron isotope ratio was

  20. Molecular and isotopic characteristics of gas hydrate-bound hydrocarbons in southern and central Lake Baikal

    NASA Astrophysics Data System (ADS)

    Hachikubo, Akihiro; Khlystov, Oleg; Krylov, Alexey; Sakagami, Hirotoshi; Minami, Hirotsugu; Nunokawa, Yutaka; Yamashita, Satoshi; Takahashi, Nobuo; Shoji, Hitoshi; Nishio, Shin'ya; Kida, Masato; Ebinuma, Takao; Kalmychkov, Gennadiy; Poort, Jeffrey

    2010-06-01

    We investigated the molecular composition (methane, ethane, and propane) and stable isotope composition (methane and ethane) of hydrate-bound gas in sediments of Lake Baikal. Hydrate-bearing sediment cores were retrieved from eight gas seep sites, located in the southern and central Baikal basins. Empirical classification of the methane stable isotopes (δ13C and δD) for all the seep sites indicated the dominant microbial origin of methane via methyl-type fermentation; however, a mixture of thermogenic and microbial gases resulted in relatively high methane δ13C signatures at two sites where ethane δ13C indicated a typical thermogenic origin. At one of the sites in the southern Baikal basin, we found gas hydrates of enclathrated microbial ethane in which 13C and deuterium were both highly depleted (mean δ13C and δD of -61.6‰ V-PDB and -285.4‰ V-SMOW, respectively). To the best of our knowledge, this is the first report of C2 δ13C-δD classification for hydrate-bound gas in either freshwater or marine environments.

  1. Tracking down sulphate-reducing microorganisms by molecular and isotope-labelling techniques

    NASA Astrophysics Data System (ADS)

    Loy, Alexander

    2010-05-01

    Sulphate-reducing microorganisms (SRM) are of great ecological importance for carbon compound degradation and sulphur cycling in many anoxic ecosystems, including marine sediments, peatlands, and oil reservoirs. However, the activity of SRM can result in oil souring and pipeline corrosion and thus is also an economic burden for the oil industry. Molecular diversity surveys based on rRNA genes and dsrAB, genes that encode major subunits of the dissimilatory sulfite reductase, indicate that our view of the natural diversity of SRM (as we know it from cultivation) is far from being complete. This enormous phylogenetic diversity complicates unbiased identification and quantification of SRM by molecular methods such as fluorescence in situ hybridization, real-time PCR or DNA microarrays. Combining these 16S rRNA and dsrAB-based molecular methods with substrate-mediated isotope labelling techniques is a potential solution for identification and functional characterization of yet uncultivated SRM. Using SRM in peatlands as an example, the problems and opportunities of these techniques for diagnosing and monitoring SRM in the environment will be discussed in this talk.

  2. Performance Evaluation of a New, Tunable-Diode Laser Trace-Gas Analyzer for Isotope Ratios of Carbon Dioxide

    NASA Astrophysics Data System (ADS)

    Sargent, S.

    2015-12-01

    Newly available interband cascade lasers (ICLs) have enabled the development of a family of tunable-diode laser trace-gas analyzers that do not require liquid nitrogen to cool the laser. The lasers are available in the 3000 to 6000 nm range, providing access to the strong mid-infrared absorption lines for important gases such as methane, nitrous oxide, and carbon dioxide. These ICLs are fabricated with distributed feedback to improve their stability and spectroscopic quality. A recently released trace-gas analyzer for carbon dioxide isotopes (TGA200A, Campbell Scientific, Inc.) was evaluated for short- and long-term precision using Allan variance. Accuracy and linearity of CO2 mole fraction was assessed with a set of seven NOAA standard reference gases ranging from 298.35 to 971.48 ppm. Dilution of high-concentration CO2 with CO2-free air demonstrated the linearity of isotope ratio measurements beyond 1000 ppm CO2. Two analyzer variants were tested: one for CO2, δ13C and δ18O; and the other for CO2 and δ13C at enhanced precision.

  3. Spatially resolved analysis of plutonium isotopic signatures in environmental particle samples by laser ablation-MC-ICP-MS.

    PubMed

    Konegger-Kappel, Stefanie; Prohaska, Thomas

    2016-01-01

    Laser ablation-multi-collector-inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) was optimized and investigated with respect to its performance for determining spatially resolved Pu isotopic signatures within radioactive fuel particle clusters. Fuel particles had been emitted from the Chernobyl nuclear power plant (ChNPP) where the 1986 accident occurred and were deposited in the surrounding soil, where weathering processes caused their transformation into radioactive clusters, so-called micro-samples. The size of the investigated micro-samples, which showed surface alpha activities below 40 mBq, ranged from about 200 to 1000 μm. Direct single static point ablations allowed to identify variations of Pu isotopic signatures not only between distinct fuel particle clusters but also within individual clusters. The resolution was limited to 100 to 120 μm as a result of the applied laser ablation spot sizes and the resolving power of the nuclear track radiography methodology that was applied for particle pre-selection. The determined (242)Pu/(239)Pu and (240)Pu/(239)Pu isotope ratios showed a variation from low to high Pu isotope ratios, ranging from 0.007(2) to 0.047(8) for (242)Pu/(239)Pu and from 0.183(13) to 0.577(40) for (240)Pu/(239)Pu. In contrast to other studies, the applied methodology allowed for the first time to display the Pu isotopic distribution in the Chernobyl fallout, which reflects the differences in the spent fuel composition over the reactor core. The measured Pu isotopic signatures are in good agreement with the expected Pu isotopic composition distribution that is typical for a RBMK-1000 reactor, indicating that the analyzed samples are originating from the ill-fated Chernobyl reactor. The average Pu isotope ratios [(240)Pu/(239)Pu = 0.388(86), (242)Pu/(239)Pu = 0.028(11)] that were calculated from all investigated samples (n = 48) correspond well to previously published results of Pu analyses in contaminated samples from

  4. Clumped Isotope Thermometry of Geologic Methane (13CH3D) using Tunable Laser Mid-Infrared Spectroscopy

    NASA Astrophysics Data System (ADS)

    Ono, S.; Zahniser, M. S.; McManus, J. B.; Nelson, D. D.

    2013-12-01

    Methane is both an alternative energy source as well as a significant greenhouse gas, and holds the potential for rapid release to the atmosphere, possibly triggering abrupt climate change in the past and in the future. The majority of methane on the Earth is biogenic, originating from microbial methanogenesis, or thermogenic sourced from previously formed biogenic organic materials. Methane can be also produced abiogenically during serpentinization and even mantle-sourced methane has been implicated. Carbon (13C/12C) and hydrogen (D/H) isotope ratios of methane and associated short chain hydrocarbons provide critical information about the abiogenic/biogenic origin of methane but data can be inconclusive. We have developed and tested a Tunable Infrared Laser Direct Absorption Spectroscopy (TILDAS) Instrument to be used for precise measurements of the abundance of doubly isotope-substituted methane (13CH3D). The TILDAS instrument measures direct absorption in the mid-infrared (~ 8 μm) region using continuous wave quantum cascade laser combined with a 76 m pathlength astigmatic absorption cell. Initial test result indicates the precision for 13CH4, 12CH3D and 13CH3D for 0.2 ‰ or better for comparison between two reference gases. Accuracy of the methods for δ13C and δD is evaluated by comparing measurements by conventional isotope ratio mass spectrometry. Calibration of clumped isotope scale (δ13CH3D) is underway using methane produced at various temperatures. Following an isotope exchange reaction (13CH4 + 12CH3D ↔ 13CH3D + 12CH4), precise measurements of 13CH3D abundance is expected to provide new and critical information about the temperature at which methane was formed (or thermally equilibrated). Biogenic origin becomes highly unlikely, for example, if the estimated temperature is higher than 120°C, i.e., current high-temperature limit of microbial methanogenesis. Although significant questions remain regarding isotope exchange kinetics, and clumped

  5. Dynamic dual-isotope molecular imaging elucidates principles for optimizing intrathecal drug delivery

    PubMed Central

    Wolf, Daniel A.; Hesterman, Jacob Y.; Sullivan, Jenna M.; Orcutt, Kelly D.; Silva, Matthew D.; Lobo, Merryl; Wellman, Tyler; Hoppin, Jack

    2016-01-01

    The intrathecal (IT) dosing route offers a seemingly obvious solution for delivering drugs directly to the central nervous system. However, gaps in understanding drug molecule behavior within the anatomically and kinetically unique environment of the mammalian IT space have impeded the establishment of pharmacokinetic principles for optimizing regional drug exposure along the neuraxis. Here, we have utilized high-resolution single-photon emission tomography with X-ray computed tomography to study the behavior of multiple molecular imaging tracers following an IT bolus injection, with supporting histology, autoradiography, block-face tomography, and MRI. Using simultaneous dual-isotope imaging, we demonstrate that the regional CNS tissue exposure of molecules with varying chemical properties is affected by IT space anatomy, cerebrospinal fluid (CSF) dynamics, CSF clearance routes, and the location and volume of the injected bolus. These imaging approaches can be used across species to optimize the safety and efficacy of IT drug therapy for neurological disorders. PMID:27699254

  6. Isotopic Soret effect in ternary mixtures: Theoretical predictions and molecular simulations

    SciTech Connect

    Artola, Pierre-Arnaud; Rousseau, Bernard

    2015-11-07

    In this paper, we study the Soret effect in ternary fluid mixtures of isotopic argon like atoms. Soret coefficients have been computed using non-equilibrium molecular dynamics and a theoretical approach based on our extended Prigogine model (with mass effect) and generalized to mixtures with any number of components. As is well known for binary mixture studies, the heaviest component always accumulates on the cold side whereas the lightest species accumulate on the hot side. An interesting behavior is observed for the species with the intermediate mass: it can accumulate on both sides, depending on composition and mass ratios. A simple picture can be given to understand this change of sign: the intermediate mass species can be seen as evolving in an equivalent fluid whose species mass varies with composition. An excellent prediction of all simulated data has been obtained using our model including the change of sign of the Soret coefficient for species with intermediate mass.

  7. Geometric isotope effects on small chloride ion water clusters with path integral molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    Wang, Qi; Suzuki, Kimichi; Nagashima, Umpei; Tachikawa, Masanori; Yan, Shiwei

    2013-11-01

    The geometric isotope effects on the structures of hydrated chloride ionic hydrogen bonded clusters are explored by carrying out path integral molecular dynamics simulations. First, an outer shell coordinate is selected to display the rearrangement of single and multi hydration shell cluster structures. Next, to show the competition of intramolecular and intermolecular nuclear quantum effects, the intramolecular OH∗ stretching and intermolecular ion-water wagging motions are studied for single and multi shell structures, respectively. The results indicate that the intermolecular nuclear quantum effects stabilize the ionic hydrogen bonds in single shell structures, while they are destabilized through the competition with intramolecular nuclear quantum effects in multi shell structures. In addition, the correlations between ion-water stretching motion and other cluster vibrational coordinates are discussed. The results indicate that the intermolecular nuclear quantum effects on the cluster structures are strongly related to the cooperation of the water-water hydrogen bond interactions.

  8. Laser-induced separation of hydrogen isotopes in the liquid phase

    DOEpatents

    Freund, Samuel M.; Maier, II, William B.; Beattie, Willard H.; Holland, Redus F.

    1980-01-01

    Hydrogen isotope separation is achieved by either (a) dissolving a hydrogen-bearing feedstock compound in a liquid solvent, or (b) liquefying a hydrogen-bearing feedstock compound, the liquid phase thus resulting being kept at a temperature at which spectral features of the feedstock relating to a particular hydrogen isotope are resolved, i.e., a clear-cut isotope shift is delineated, irradiating the liquid phase with monochromatic radiation of a wavelength which at least preferentially excites those molecules of the feedstock containing a first hydrogen isotope, inducing photochemical reaction in the excited molecules, and separating the reaction product containing the first isotope from the liquid phase.

  9. Enhancing molecular orientation by combining electrostatic and four-color laser fields

    NASA Astrophysics Data System (ADS)

    Xu, Shuwu; Yao, Yunhua; Lu, Chenhui; Jia, Tianqing; Ding, Jingxin; Zhang, Shian; Sun, Zhenrong

    2014-09-01

    We propose a scheme to enhance molecular orientation by combing an intense electrostatic field and a four-color laser field. We show that molecular orientation by the combined field can be obtained under a laser-field-free condition, and the maximal orientation degree can be enhanced by comparing with the sum of that individually created by the electrostatic field and the four-color laser field. Our results show that the orientation enhancement results from the larger asymmetry of the four-color laser field because of the existence of the electrostatic field. Furthermore, we also discuss the dependence of the orientation enhancement on the carrier-envelope phase, laser intensity, and pulse duration of the four-color laser field and the molecular rotational temperature.

  10. Emissions of molecular hydrogen (H2) and its isotopic signature from residential heaters and waste incinerators

    NASA Astrophysics Data System (ADS)

    Vollmer, M. K.; Walter, S.; Mohn, J.; Steinbacher, M.; Bond, S. W.; Roeckmann, T.; Reimann, S.

    2011-12-01

    Atmospheric molecular hydrogen (H2) has recently received increased interest in the scientific community because of a potential shift to a global hydrogen energy economy which could potentially alter the atmospheric budget of H2 due to substantial leakage. This calls for an improved understanding of the present day's atmospheric H2 budget. One of the major sources of H2 are emissions from incomplete combustion of fossil fuel. While emissions of H2 from car exhaust have been studied extensively, those from fossil fuel based heating systems have remained a matter of speculation. Here we present results from measurements of a variety of residential heating systems covering oil, gas, and wood heating with various burner capacities. For oil and gas heating systems we surprisingly find no net H2 emissions, i.e. the exhaust air contains H2 at or below the mole fractions of the intake air (approx. 0.5 ppm). While H2 emissions are virtually absent, those of carbon monoxide (CO) are not. As a consequence, caution has to be exercised when modeling H2 emissions based on assumed H2/CO ratios and using CO emission inventories. We also find that the molecular hydrogen in the approx. 0.5 ppm exhaust air is isotopically strongly depleted (-20 permil to -200 permil) compared to the ambient air (+130 permil). This suggests that H2 is involved in the combustion processes, and therefore the H2 of the intake air is not the same H2 in the exhaust air. Exhausts from waste incinerator plants are generally also depleted in H2 mole fractions and in their H/D isotopic composition.

  11. Molecular carbon isotope variations in core samples taken at the Permian-Triassic boundary layers in southern China

    NASA Astrophysics Data System (ADS)

    Wang, Ruiliang; Zhang, Shuichang; Brassell, Simon; Wang, Jiaxue; Lu, Zhengyuan; Ming, Qingzhong; Wang, Xiaomei; Bian, Lizeng

    2012-07-01

    Stable carbon isotope composition (δ13C) of carbonate sediments and the molecular (biomarker) characteristics of a continuous Permian-Triassic (PT) layer in southern China were studied to obtain geochemical signals of global change at the Permian-Triassic boundary (PTB). Carbonate carbon isotope values shifted toward positive before the end of the Permian period and then shifted negative above the PTB into the Triassic period. Molecular carbon isotope values of biomarkers followed the same trend at and below the PTB and remained negative in the Triassic layer. These biomarkers were acyclic isoprenoids, ranging from C15 to C40, steranes (C27 dominates) and terpenoids that were all significantly more abundant in samples from the Permian layer than those from the Triassic layer. The Triassic layer was distinguished by the dominance of higher molecular weight (waxy) n-alkanes. Stable carbon isotope values of individual components, including n-alkanes and acyclic isoprenoids such as phytane, isop-C25, and squalane, are depleted in δ13C by up to 8-10‰ in the Triassic samples as compared to the Permian. Measured molecular and isotopic variations of organic matter in the PT layers support the generally accepted view of Permian oceanic stagnation followed by a massive upwelling of toxic deep waters at the PTB. A series of large-scale (global) outgassing events may be associated with the carbon isotope shift we measured. This is also consistent with the lithological evidence we observed of white thin-clay layers in this region. Our findings, in context with a generally accepted stagnant Permian ocean, followed by massive upwelling of toxic deep waters might be the major causes of the largest global mass extinction event that occurred at the Permian-Triassic boundary.

  12. Catalytic recombination of dissociation products with Pt/SnO2 for rare and common isotope long-life, closed-cycle CO2 lasers

    NASA Technical Reports Server (NTRS)

    Brown, Kenneth G.; Sidney, B. D.; Schryer, D. R.; Upchurch, B. T.; Miller, I. M.

    1986-01-01

    This paper reports results on recombination of pulsed CO2 laser dissociation products with Pt/SnO2 catalysts, and supporting studies in a surrogate laboratory catalyst reactor. The closed-cycle, pulsed CO2 laser has been continuously operated for one million pulses with an overall power degradation of less than 5 percent by flowing the laser gas mixture through a 2-percent Pt/SnO2 catalyst bed. In the surrogate laboratory reactor, experiments have been conducted to determine isotopic exchange with the catalyst when using rare-isotope gases. The effects of catalyst pretreatment, sample weight, composition, and temperature on catalyst efficiency have also been determined.

  13. [High-precision in situ analysis of the lead isotopic composition in copper using femtosecond laser ablation MC-ICP-MS and the application in ancient coins].

    PubMed

    Chen, Kai-Yun; Fan, Chao; Yuan, Hong-Lin; Bao, Zhi-An; Zong, Chun-Lei; Dai, Meng-Ning; Ling, Xue; Yang, Ying

    2013-05-01

    In the present study we set up a femtosecond laser ablation MC-ICP-MS method for lead isotopic analysis. Pb isotopic composition of fifteen copper (brass, bronze) standard samples from the National Institute of Standards Material were analyzed using the solution method (MC-ICP-MS) and laser method (fLA-MC-ICPMS) respectively, the results showed that the Pb isotopic composition in CuPb12 (GBW02137) is very homogeneous, and can be used as external reference material for Pb isotopic in situ analysis. On CuPb12 112 fLA-MC-ICPMS Pb isotope analysis, the weighted average values of the Pb isotopic ratio are in good agreement with the results analyzed by bulk solution method within 2sigma error, the internal precision RSEs of the 208 Pb/204 Pb ratio and 207 Pb/206 Pb ratio are less than 90 and 40 ppm respectively, and the external precision RSDs of them are less than 60 and 30 ppm respectively. Pb isotope of thirteen ancient bronze coins was analyzed via fLA-MC-ICPMS, the results showed that the Pb isotopic composition of ancient coins of different dynasties is significantly different, and not all the Pb isotopic compositions in the coins even from the same dynasty are in agreement with each other.

  14. Short path thermal desorption GC/MS for screening of molecular contamination in laser systems

    NASA Astrophysics Data System (ADS)

    Canham, John S.

    2005-02-01

    In high intensity laser systems, molecular contamination represents a risk to the optics. In most situations, molecular contamination is somewhat of a wild card. It is known that it is not required that the contaminant be condensible to initiate damage within a laser system. It is also known that in many cases materials that pass ASTM E-595, are known to precipitate laser optic damage. What has not been known is why. Methods have been developed for the identification, and potential quantitation of trace material emissions that initiate laser optic damage.

  15. Diverging effects of isotopic fractionation upon molecular diffusion of noble gases in water: mechanistic insights through ab initio molecular dynamics simulations.

    PubMed

    Pinto de Magalhães, Halua; Brennwald, Matthias S; Kipfer, Rolf

    2017-02-10

    Atmospheric noble gases are routinely used as natural tracers to analyze gas transfer processes in aquatic systems. Their isotopic ratios can be employed to discriminate between different physical transport mechanisms by comparison to the unfractionated atmospheric isotope composition. In many applications of aquatic systems molecular diffusion was thought to cause a mass dependent fractionation of noble gases and their isotopes according to the square root ratio of their masses. However, recent experiments focusing on isotopic fractionation within a single element challenged this broadly accepted assumption. The determined fractionation factors of Ne, Ar, Kr and Xe isotopes revealed that only Ar follows the prediction of the so-called square root relation, whereas within the Ne, Kr and Xe elements no mass-dependence was found. The reason for this unexpected divergence of Ar is not yet understood. The aim of our computational exercise is to establish the molecular-resolved mechanisms behind molecular diffusion of noble gases in water. We make the hypothesis that weak intermolecular interactions are relevant for the dynamical properties of noble gases dissolved in water. Therefore, we used ab initio molecular dynamics to explicitly account for the electronic degrees of freedom. Depending on the size and polarizability of the hydrophobic particles such as noble gases, their motion in dense and polar liquids like water is subject to different diffusive regimes: the inter-cavity hopping mechanism of small particles (He, Ne) breaks down if a critical particle size achieved. For the case of large particles (Kr, Xe), the motion through the water solvent is governed by mass-independent viscous friction leading to hydrodynamical diffusion. Finally, Ar falls in between the two diffusive regimes, where particle dispersion is propagated at the molecular collision time scale of the surrounding water molecules.

  16. Laser microprobe analyses of noble gas isotopes and halogens in fluid inclusions: Analyses of microstandards and synthetic inclusions in quartz

    USGS Publications Warehouse

    Böhlke, J.K.; Irwin, J.J.

    1992-01-01

    Ar, Kr, Xe, Cl, Br, I, and K abundances and isotopic compositions have been measured in microscopic fluid inclusions in minerals by noble gas mass spectrometry following neutron irradiation and laser extraction. The laser microprobe noble gas mass spectrometric (LMNGMS) technique was quantified by use of microstandards, including air-filled capillary tubes, synthetic basalt glass grains, standard hornblende grains, and synthetic fluid inclusions in quartz. Common natural concentrations of halogens (Cl, Br, and I) and noble gases (Ar and Kr) in trapped groundwaters and hydrothermal fluids can be analyzed simultaneously by LMNGMS in as little as 10-11 L of inclusion fluid, with accuracy and precision to within 5-10% for element and isotope ratios. Multicomponent element and isotope correlations indicate contaminants or persistent reservoirs of excess Xe and/or unfractionated air in some synthetic and natural fluid inclusion samples. LMNGMS analyses of natural fluid inclusions using the methods and calibrations reported here may be used to obtain unique information on sources of fluids, sources of fluid salinity, mixing, boiling (or unmixing), and water-rock interactions in ancient fluid flow systems. ?? 1992.

  17. Hydrogen isotope detection in metal matrix using double-pulse laser-induced breakdown-spectroscopy

    NASA Astrophysics Data System (ADS)

    Fantoni, Roberta; Almaviva, Salvatore; Caneve, Luisa; Colao, Francesco; Maddaluno, Giorgio; Gasior, Pawel; Kubkowska, Monika

    2017-03-01

    The amount of hydrogen isotopes retained in plasma facing components (PFCs) and the determination of their surface layer composition are among the most critical issues for the next generation fusion device, ITER, under construction in Cadarache (France). Laser Induced Breakdown Spectroscopy (LIBS) is currently under evaluation as a technique suitable for quantitative, in situ, non-invasive measurements of these quantities. In order to detect traces of contaminant in metallic samples and improve its limit of detection (LOD), the Double Pulse LIBS (DP-LIBS) variant can be used instead of the standard Single Pulse LIBS (SP-LIBS), as it has been proven by several authors that DP-LIBS can considerably raise the analytical performances of the technique. In this work Mo samples coated with a 1.5-1.8 μm thick W-Al mixed layer, contaminated with co-deposited deuterium (D) were measured by SP- and DP-LIBS under vacuum (p 5 × 10- 5 mbar), with an experimental set-up simulating conditions that can be found in a real fusion device between plasma discharges. A partial Calibration Free procedure (pCF) was applied to the LIBS data in order to retrieve the relative concentration of W and Al in the mixed layer. The amount of deuterium was then inferred by using tungsten as internal standard, accounting for the intensity ratio between the Dα line and nearby W I lines. The results are in satisfactory agreement with those obtained from preliminary Ion Beam Analysis measurements performed immediately after the specimen's realization.

  18. Sulphur stable isotope systematics in diagenetic pyrite from the North Sea hydrocarbon reservoirs revealed by laser combustion analysis.

    PubMed

    Fallick, Anthony E; Boyce, Adrian J; McConville, Paul

    2012-01-01

    Our study focuses on pyrite nodules developed in the Brent Group sandstones, which host the Brent Oilfield, one of the North Sea's greatest oil and gas producers. Timing of nodule formation is equivocal, but due to the forceful, penetrative textures that abound, it is considered late. This pyrite offers a research opportunity because it records the development of the supply of H(2)S in a hydrocarbon reservoir and its sulphur isotopic composition. Laser-based analysis of δ(34)S reveals an extraordinary diversity in values and patterns. The values range from-27 to+72‰, covering half the terrestrial range, with large variations at the submillimetre scale. Isotopically heavy (δ(34)S ∼+30‰ or higher) sulphide is endemic, but low δ(34)S pyrite is also present and appears to represent a temporally though not spatially (on the ∼cm scale) distinct pyritisation event. The distribution of δ(34)S values within individual concretions can be normal (Gaussian), but in some cases may reflect progressive isotope fractionation process(es), conceivably of Rayleigh type. The source of the sulphur and the identity of the isotope fractionation process(es) remain enigmatic.

  19. Reliable determination of oxygen and hydrogen isotope ratios in atmospheric water vapour adsorbed on 3A molecular sieve.

    PubMed

    Han, Liang-Feng; Gröning, Manfred; Aggarwal, Pradeep; Helliker, Brent R

    2006-01-01

    The isotope ratio of atmospheric water vapour is determined by wide-ranging feedback effects from the isotope ratio of water in biological water pools, soil surface horizons, open water bodies and precipitation. Accurate determination of atmospheric water vapour isotope ratios is important for a broad range of research areas from leaf-scale to global-scale isotope studies. In spite of the importance of stable isotopic measurements of atmospheric water vapour, there is a paucity of published data available, largely because of the requirement for liquid nitrogen or dry ice for quantitative trapping of water vapour. We report results from a non-cryogenic method for quantitatively trapping atmospheric water vapour using 3A molecular sieve, although water is removed from the column using standard cryogenic methods. The molecular sieve column was conditioned with water of a known isotope ratio to 'set' the background signature of the molecular sieve. Two separate prototypes were developed, one for large collection volumes (3 mL) and one for small collection volumes (90 microL). Atmospheric water vapour was adsorbed to the column by pulling air through the column for several days to reach the desired final volume. Water was recovered from the column by baking at 250 degrees C in a dry helium or nitrogen air stream and cryogenically trapped. For the large-volume apparatus, the recovered water differed from water that was simultaneously trapped by liquid nitrogen (the experimental control) by 2.6 per thousand with a standard deviation (SD) of 1.5 per thousand for delta(2)H and by 0.3 per thousand with a SD of 0.2 per thousand for delta(18)O. Water-vapour recovery was not satisfactory for the small volume apparatus.

  20. Apparatus for extraction and separation of a preferentially photo-dissociated molecular isotope into positive and negative ions by means of an electric field

    NASA Technical Reports Server (NTRS)

    Wilhelm, H. E. (Inventor)

    1978-01-01

    Molecules of one and the same isotope were preferentially photodissociated by a laser and an ultraviolet source, or by multiphoton absorption of laser radiation. The resultant ions were confined with a magnetic field, moved in opposite directions by an electric field, extracted from the photodissociation region by means of screening and accelerating grids, and collected in ducts.

  1. Upper limit on the rate constant for isotope exchange between molecular oxygen and ozone at 298 K

    NASA Technical Reports Server (NTRS)

    Anderson, S. M.; Morton, J.; Mauersberger, K.

    1987-01-01

    The gas phase bimolecular isotope exchange reaction between molecular oxygen and ozone has been investigated directly for the first time. Its rate coefficient is found to be less than 2 x 10 to the -25th cu cm/sec at 298 K, over six orders of magnitude below recent estimates. Much faster exchange was observed over condensed ozone at 77 K, suggesting isotopic scrambling is catalyzed under these conditions. The low rate coefficient implies that homogeneous exchange between ground state oxygen and ozone molecules cannot play a significant role in heavy ozone chemistry.

  2. Multichannel optoacoustic spectroscopy of molecular gases with pulsed lasers

    NASA Astrophysics Data System (ADS)

    Ponomarev, Iu. N.

    1989-05-01

    The linear and nonlinear absorption of laser radiation by H20 and CO2 is studied using dual-channel optoacoustic spectroscopy (OAS) with pulsed ruby and CO2 lasers. The possibility of VT-relaxation time determination is studied with allowance made for its dependence on laser radiation intensity. The advantages of the OAS method are outlined.

  3. Trace isotope analysis of Ricinus communis seed core for provenance determination by laser ablation-ICP-MS.

    PubMed

    Bagas, Christina K; Scadding, Rachel L; Scadding, Cameron J; Watling, R John; Roberts, Warren; Ovenden, Simon P B

    2017-01-01

    The castor bean plant, Ricinus communis, grows wild throughout many regions of Australia. The seeds of the plant contain the schedule 1 chemical agent ricin, a type II ribosomal inhibiting protein. Currently there are limited analytical techniques that can be applied in analysis of the seeds to establish attribution. In this study, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used for the analysis of seeds collected from 68 plants across 38 locations around Australia. Of the 92 elemental isotopes measured, fifteen ((24)Mg, (27)Al, (44)Ca, (53)Cr, (55)Mn, (57)Fe, (60)Ni, (65)Cu, (66)Zn, (75)As, (85)Rb, (88)Sr, (98)Mo, (138)Ba and (202)Hg) yielded data that were relevant to all collection sites. Data were further analysed using multivariate statistical analysis which facilitated the potential for the identification of unique provenance isotopes. Furthermore, this analysis indicated that (59)Co was present at significant levels in Victorian and Sydney specimens only.

  4. A miniaturized laser-ablation mass spectrometer for in-situ measurements of isotope composition on solar body surfaces

    NASA Astrophysics Data System (ADS)

    Riedo, A.; Meyer, S.; Tulej, M.; Neuland, M.; Bieler, A.; Iakovleva, M.; Wurz, P.

    2012-04-01

    The in-situ analysis of extraterrestrial material onboard planetary rovers and landers is of considerable interest for future planetary space missions. Due to the low detection sensitivity of spectroscopic instruments, e.g. α-particle X-ray, γ-ray or neutron spectrometers, it is frequently possible to measure only major/minor elements in extraterrestrial materials. Nevertheless, the knowledge of minor/trace elements is of considerable interest to cosmochemistry. Chemistry puts constraints on the origin of solar system and its evolution enabling also a deeper inside to planetary transformation processes (e.g. volcanic surface alteration, space weathering). The isotopes play special role in analysis of the origin and transformation of planetary matter. They are robust tracers of the early events because their abundances are less disturbed as the elemental once. Nevertheless, if the isotope abundance ratios are fractionated, the underlying chemical and physical processes can be then encoded from the variations of abundance ratios. A detailed analysis of isotopic patterns of radiogenic elements can allow age dating of minerals and temporal evolution of planetary matter. High accuracy and sensitive measurements of isotopic pattern of bio-relevant elements, i.e., sulfur, found on planetary surfaces can be helpful for the identification of possible past and present extraterrestrial life in terms of biomarker identification. Our group has designed a self-optimizing miniaturized laser ablation time-of-flight mass spectrometer (LMS) for in situ planetary measurements (Wurz et al., 2012; Rohner et al., 2003). Initial studies utilizing IR laser radiation for ablation, atomization and ionization of solid materials indicated a high instrumental performance in terms of sensitivity and mass resolution (Tulej et al., 2011). Current studies are conducted with a UV radiation and a high spatial resolution is achieved by focussing the laser beam to 20µm spots onto the sample. The

  5. The stable isotopic composition of molecular hydrogen in the tropopause region probed by the CARIBIC aircraft

    NASA Astrophysics Data System (ADS)

    Batenburg, A. M.; Schuck, T. J.; Baker, A. K.; Zahn, A.; Brenninkmeijer, C. A. M.; Röckmann, T.

    2012-01-01

    More than 450 air samples that were collected in the upper troposphere - lower stratosphere (UTLS) region around the tropopause (TP) by the CARIBIC aircraft (Civil Aircraft for the Regular Investigation of the Atmosphere Based on an Instrument Container) have been analyzed for molecular hydrogen (H2) mixing ratios (m(H2)) and H2 isotopic composition (deuterium content, δD). More than 120 of the analysed samples consisted of air from the lowermost stratosphere (LMS). These show that m(H2) does not vary appreciably with O3-derived height above the thermal TP, whereas δD does increase with height. The isotope enrichment is caused by competing H2 production and destruction processes that enrich the stratospheric H2 reservoir in deuterium (D); the exact shapes of the profiles are mainly determined by mixing of stratospheric with tropospheric air. Tight negative correlations are found between δD and the mixing ratios of methane (CH4) and nitrous oxide (N2O), as a result of the relatively long lifetimes of these three species. The correlations are described by δ D [‰]=-0.35 · m(CH4)[ppb]+768 and δD [‰]=-1.90 · m(N2O)[ppb]+745. These correlations are similar to previously published results and likely hold globally. Samples that were collected from the Indian subcontinent up to 40° N before, during and after the summer monsoon season show no significant seasonal change in m(H2), but δD is up to 15‰ lower in the July, August and September monsoon samples. This δD lowering is correlated with m(CH4) increase. The significant correlation with m(CH4) and the absence of a perceptible m(H2) increase that accompanies the δD lowering indicates that microbial production of very D-depleted H2 in the wet season may contribute to this phenomenon. Some of the samples have very high m(H2) and very low δD values, which indicates a pollution effect. Aircraft engine exhaust plumes are a suspected cause, since the effect mostly occurs in samples collected close to airports

  6. The stable isotopic composition of molecular hydrogen in the tropopause region probed by the CARIBIC aircraft

    NASA Astrophysics Data System (ADS)

    Batenburg, A. M.; Schuck, T. J.; Baker, A. K.; Zahn, A.; Brenninkmeijer, C. A. M.; Röckmann, T.

    2012-05-01

    More than 450 air samples that were collected in the upper troposphere - lower stratosphere (UTLS) region by the CARIBIC aircraft (Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container) have been analyzed for molecular hydrogen (H2) mixing ratios (χ(H2)) and H2 isotopic composition (deuterium content, δD). More than 120 of the analyzed samples contained air from the lowermost stratosphere (LMS). These show that χ(H2) does not vary appreciably with O3-derived height above the thermal tropopause (TP), whereas δD does increase with height. The isotope enrichment is caused by H2 production and destruction processes that enrich the stratospheric H2 reservoir in deuterium (D); the exact shapes of the profiles are mainly determined by mixing of stratospheric with tropospheric air. Tight negative correlations are found between δD and the mixing ratios of methane (χ(CH4)) and nitrous oxide (χ(N2O)), as a result of the relatively long lifetimes of these three species. The correlations are described by δD[‰]=-0.35 · χ(CH4)[ppb]+768 and δD[‰]=-1.90· χ(N2O)[ppb]+745. These correlations are similar to previously published results and likely hold globally for the LMS. Samples that were collected from the Indian subcontinent up to 40° N before, during and after the summer monsoon season show no significant seasonal change in χ(H2), but δD is up to 12.3‰ lower in the July, August and September monsoon samples. This δD decrease is correlated with the χ(CH4) increase in these samples. The significant correlation with χ(CH4) and the absence of a perceptible χ(H2) increase that accompanies the δD decrease indicates that microbial production of very D-depleted H2 in the wet season may contribute to this phenomenon. Some of the samples have very high χ(H2) and very low δD values, which indicates a pollution effect. Aircraft engine exhaust plumes are a suspected cause, since the effect mostly occurs in samples

  7. Reconstruction of two-dimensional molecular structure with laser-induced electron diffraction from laser-aligned polyatomic molecules

    DOE PAGES

    Yu, Chao; Wei, Hui; Wang, Xu; ...

    2015-10-27

    Imaging the transient process of molecules has been a basic way to investigate photochemical reactions and dynamics. Based on laser-induced electron diffraction and partial one-dimensional molecular alignment, here we provide two effective methods for reconstructing two-dimensional structure of polyatomic molecules. We demonstrate that electron diffraction images in both scattering angles and broadband energy can be utilized to retrieve complementary structure information, including positions of light atoms. Lastly, with picometre spatial resolution and the inherent femtosecond temporal resolution of lasers, laser-induced electron diffraction method offers significant opportunities for probing atomic motion in a large molecule in a typical pump-probe measurement.

  8. Electron and nuclear dynamics of molecular clusters in ultraintense laser fields. IV. Coulomb explosion of molecular heteroclusters.

    PubMed

    Last, Isidore; Jortner, Joshua

    2004-11-01

    In this paper we present a theoretical and computational study of the temporal dynamics and energetics of Coulomb explosion of (CD4)(n) and (CH4)(n) (n=55-4213) molecular heteroclusters in ultraintense (I=10(16)-10(19) W cm(-2)) laser fields, addressing the manifestation of electron dynamics, together with nuclear energetic and kinematic effects on the heterocluster Coulomb instability. The manifestations of the coupling between electron and nuclear dynamics were explored by molecular dynamics simulations for these heteroclusters coupled to Gaussian laser fields (pulse width tau=25 fs), elucidating outer ionization dynamics, nanoplasma screening effects (being significant for I< or =10(17) W cm(-2)), and the attainment of cluster vertical ionization (CVI) (at I=10(17) W cm(-2) for cluster radius R(0)< or =31 A). Nuclear kinematic effects on heterocluster Coulomb explosion are governed by the kinematic parameter eta=q(C)m(A)/q(A)m(C) for (CA(4))(n) clusters (A=H,D), where q(j) and m(j) (j=A,C) are the ionic charges and masses. Nonuniform heterocluster Coulomb explosion (eta >1) manifests an overrun effect of the light ions relative to the heavy ions, exhibiting the expansion of two spatially separated subclusters, with the light ions forming the outer subcluster at the outer edge of the spatial distribution. Important features of the energetics of heterocluster Coulomb explosion originate from energetic triggering effects of the driving of the light ions by the heavy ions (C(4+) for I=10(17)-10(18) W cm(-2) and C(6+) for I=10(19) W cm(-2)), as well as for kinematic effects. Based on the CVI assumption, scaling laws for the cluster size (radius R(0)) dependence of the energetics of uniform Coulomb explosion of heteroclusters (eta=1) were derived, with the size dependence of the average (E(j,av)) and maximal (E(j,M)) ion energies being E(j,av)=aR(0) (2) and E(j,M)=(5a/3)R(0) (2), as well as for the ion energy distributions P(E(j)) proportional to E(j) (1/2); E(j)< or

  9. Recent Progress in Development of a Laser Based, Ultra-High Precision Isotope Monitor for Carbon Dioxide

    NASA Astrophysics Data System (ADS)

    Nelson, D. D.; McManus, J. B.; Herndon, S. C.; Zahniser, M. S.

    2015-12-01

    Greenhouse gas (GHG) emissions are the primary drivers of global climate change and hence there is a crucial need to quantify their sources and sinks. A general technique to help constrain source and sink strengths in GHG exchange processes is the analysis of the relative proportions of isotopic variants of GHG's. Very high precision measurements of isotopologue ratios are necessary in order to identify sources and sinks because the characteristic changes are small. The standard method of isotopologue measurement has been mass spectrometry, but this technique typically requires significant sample preparation and relatively high instrument maintenance. Laser spectroscopy has the potential to ease these burdens and also to allow easy separation and analysis of interfering isobars such as 13C-CO2 and 17O-CO2. We present recent results demonstrating ultra-high precision measurements of carbon dioxide isotope ratios which rival the accuracy of mass spectrometric measurements. These measurements were performed using Tunable Infrared Laser Direct Absorption Spectroscopy (TILDAS). We have developed a method for analyzing air samples from canisters by alternately and rapidly trapping sample gas and working reference gas in the optical cell. Using this technique, we have obtained isotopic measurement precisions of ~7 per meg for both 13C-CO2 and 18O-CO2 while measuring trapped ambient air samples with volumes as small as 200 ml with a 16 minute measurement duration. The figure shows a histogram of 2 minute measurements. Our current measurement precision for 17O-CO2 is 30 per meg, but we expect to reduce this to 10 per meg by working in a better spectral region. Our ultimate goal is to create an automated, ultra-high accuracy carbon dioxide isotope monitor able to quantify 13C-, 18O-, and 17O-CO2at the 10 per meg level using small (~100 standard ml), discreet air samples. We will also discuss recent progress in the measurement of the clumped isotopes of carbon dioxide in

  10. Measurement of in situ sulfur isotopes by laser ablation multi-collector ICPMS: opening Pandora’s Box

    USGS Publications Warehouse

    Ridley, William I.; Pribil, Michael; Koenig, Alan E.; Slack, John F.

    2015-01-01

    Laser ablation multi-collector ICPMS is a modern tool for in situ measurement of S isotopes. Advantages of the technique are speed of analysis and relatively minor matrix effects combined with spatial resolution sufficient for many applications. The main disadvantage is a more destructive sampling mechanism relative to the ion microprobe technique. Recent advances in instrumentation allow precise measurement with spatial resolutions down to 25 microns. We describe specific examples from economic geology where increased spatial resolution has greatly expanded insights into the sources and evolution of fluids that cause mineralization and illuminated genetic relations between individual deposits in single mineral districts.

  11. Practical-scale tests of cryogenic molecular sieve for separating low-concentration hydrogen isotopes from helium

    NASA Astrophysics Data System (ADS)

    Willms, R. S.; Taylor, D. J.; Enoeda, Mikio; Okuno, Kenji

    1994-04-01

    Earlier bench-scale work at the Tritium Systems Test Assembly (TSTA) at Los Alamos National Laboratory examined a number of adsorbents for their suitability for separating low-concentration hydrogen (no tritium) from helium. One of the effective adsorbents was Linde 5A molecular sieve. Recently, experiments including tritium were conducted using practical-scale adsorbers. These tests used existing cryogenic molecular sieve beds (CMSB's) which each contain about 1.6 kg of Linde 5A molecular sieve. They are part of the TSTA integrated tritium processing system. Gas was fed to each CMSB at about 13 SLPM with a nominal composition of 99% He, 0.98% H2, and 0.02% HT. In all cases, for an extended period of time, the beds allowed no detectable (via Raman spectroscopy) hydrogen isotopes to escape in the bed effluent. Thereafter, the hydrogen isotopes appeared in the bed exit with a relatively sharp breakthrough curve. This work concludes that cryogenic molecular sieve adsorption is a practical and effective means of separating low-concentration hydrogen isotopes from a helium carrier.

  12. Spatial subsidies in spider diets vary with shoreline structure: Complementary evidence from molecular diet analysis and stable isotopes.

    PubMed

    Hambäck, Peter A; Weingartner, Elisabeth; Dalén, Love; Wirta, Helena; Roslin, Tomas

    2016-12-01

    Inflow of matter and organisms may strongly affect the local density and diversity of organisms. This effect is particularly evident on shores where organisms with aquatic larval stages enter the terrestrial food web. The identities of such trophic links are not easily estimated as spiders, a dominant group of shoreline predator, have external digestion. We compared trophic links and the prey diversity of spiders on different shore types along the Baltic Sea: on open shores and on shores with a reed belt bordering the water. A priori, we hypothesized that the physical structure of the shoreline reduces the flow between ecosystem and the subsidies across the sea-land interface. To circumvent the lack of morphologically detectable remains of spider prey, we used a combination of stable isotope and molecular gut content analyses. The two tools used for diet analysis revealed complementary information on spider diets. The stable isotope analysis indicated that spiders on open shores had a marine signal of carbon isotopes, while spiders on reedy shores had a terrestrial signal. The molecular analysis revealed a diverse array of dipteran and lepidopteran prey, where spiders on open and reedy shores shared a similar diet with a comparable proportion of chironomids, the larvae of which live in the marine system. Comparing the methods suggests that differences in isotope composition of the two spider groups occurred because of differences in the chironomid diets: as larvae, chironomids of reedy shores likely fed on terrestrial detritus and acquired a terrestrial isotope signature, while chironomids of open shores utilized an algal diet and acquired a marine isotope signature. Our results illustrate how different methods of diet reconstruction may shed light on complementary aspects of nutrient transfer. Overall, they reveal that reed belts can reduce connectivity between habitats, but also function as a source of food for predators.

  13. Field-based stable isotope analysis of carbon dioxide by mid-infrared laser spectroscopy for carbon capture and storage monitoring.

    PubMed

    van Geldern, Robert; Nowak, Martin E; Zimmer, Martin; Szizybalski, Alexandra; Myrttinen, Anssi; Barth, Johannes A C; Jost, Hans-Jürg

    2014-12-16

    A newly developed isotope ratio laser spectrometer for CO2 analyses has been tested during a tracer experiment at the Ketzin pilot site (northern Germany) for CO2 storage. For the experiment, 500 tons of CO2 from a natural CO2 reservoir was injected in supercritical state into the reservoir. The carbon stable isotope value (δ(13)C) of injected CO2 was significantly different from background values. In order to observe the breakthrough of the isotope tracer continuously, the new instruments were connected to a stainless steel riser tube that was installed in an observation well. The laser instrument is based on tunable laser direct absorption in the mid-infrared. The instrument recorded a continuous 10 day carbon stable isotope data set with 30 min resolution directly on-site in a field-based laboratory container during a tracer experiment. To test the instruments performance and accuracy the monitoring campaign was accompanied by daily CO2 sampling for laboratory analyses with isotope ratio mass spectrometry (IRMS). The carbon stable isotope ratios measured by conventional IRMS technique and by the new mid-infrared laser spectrometer agree remarkably well within analytical precision. This proves the capability of the new mid-infrared direct absorption technique to measure high precision and accurate real-time stable isotope data directly in the field. The laser spectroscopy data revealed for the first time a prior to this experiment unknown, intensive dynamic with fast changing δ(13)C values. The arrival pattern of the tracer suggest that the observed fluctuations were probably caused by migration along separate and distinct preferential flow paths between injection well and observation well. The short-term variances as observed in this study might have been missed during previous works that applied laboratory-based IRMS analysis. The new technique could contribute to a better tracing of the migration of the underground CO2 plume and help to ensure the long

  14. Stark effect in optically pumped molecular submillimeter lasers

    NASA Astrophysics Data System (ADS)

    Rak, V. G.; Dyubko, S. F.

    1980-06-01

    A theoretical analysis is made of the effects which take place in optically pumped lasers whose active medium is subjected to a dc electric Geld. The possibilities are discussed of tuning the frequency and modulating the intensity of the radiation emitted by a laser. The gain characteristics of an active medium in an electric field are calculated for a CH3F laser operating on a wavelength of 496 μ. It is shown that the frequency tuning limits of the output radiation of such a laser can reach 3 GHz, if the active medium allows electric fields of up to 30 kV/cm to be applied.

  15. Molecular modeling and assignment of IR spectra of the hydrated excess proton in isotopically dilute water

    NASA Astrophysics Data System (ADS)

    Biswas, Rajib; Carpenter, William; Voth, Gregory A.; Tokmakoff, Andrei

    2016-10-01

    Infrared (IR) spectroscopy of the water O-H stretch has been widely used to probe both the local hydrogen-bonding structure and dynamics of aqueous systems. Although of significant interest, the IR spectroscopy of excess protons in water remains difficult to assign as a result of extensive and strong intermolecular interactions in hydrated proton complexes. As an alternate approach, we develop a mixed quantum-classical model for the vibrational spectroscopy of the excess proton in isotopically dilute water that draws on frozen proton-water clusters taken from reactive molecular dynamics trajectories of the latest generation multi-state empirical valence bond proton model (MS-EVB 3.2). A semi-empirical single oscillator spectroscopic map for the instantaneous transition frequency and transition dipole moment is constructed using potential energy surfaces for the O-H stretch coordinate of the excess proton using electronic structure calculations. Calculated spectra are compared with experimental spectra of dilute H+ in D2O obtained from double-difference FTIR to demonstrate the validity of the map. The model is also used to decompose IR spectra into contributions from different aqueous proton configurations. We find that the O-H transition frequency continuously decreases as the oxygen-oxygen length for a special pair proton decreases, shifting from Eigen- to Zundel-like configurations. The same shift is accompanied by a shift of the flanking water stretches of the Zundel complex to higher frequency than the hydronium O-H vibrations.

  16. Laser scattered images observed from carbon plasma stagnation and following molecular formation

    SciTech Connect

    Nishimura, K.; Shibata, R.; Yabuuchi, T.; Tanaka, K. A.; Sunahara, A.

    2014-06-16

    Two carbon targets were irradiated to create plasma plumes to collide at right angle with two UV laser pulses each other at 10 J/cm{sup 2}/pulse. The collision results in carbon plasma stagnation. Laser scattered imaging indicates that the carbon large molecular formation takes place much later in time after the laser irradiation and stagnation. Compared with the temporal history of electron density (n{sub e}), ion density (n{sub i}), and plasma self-emission dominated by carbon Swan band, it is estimated that the carbon large molecular formation has been initiated with the ion collision followed by the C{sub 2} formation.

  17. Accurate measurements of transition frequencies and isotope shifts of laser-trapped francium.

    PubMed

    Sanguinetti, S; Calabrese, R; Corradi, L; Dainelli, A; Khanbekyan, A; Mariotti, E; de Mauro, C; Minguzzi, P; Moi, L; Stancari, G; Tomassetti, L; Veronesi, S

    2009-04-01

    An interferometric method is used to improve the accuracy of the 7S-7P transition frequencies of three francium isotopes by 1 order of magnitude. The deduced isotope shifts for 209-211Fr confirm the ISOLDE data. The frequency of the D2 transition of 212Fr--the accepted reference for all Fr isotope shifts--is revised, and a significant difference with the ISOLDE value is found. Our results will be a benchmark for the accuracy of the theory of Fr energy levels, a necessary step to investigate fundamental symmetries.

  18. Computer programs for the interpretation of low resolution mass spectra: Program for calculation of molecular isotopic distribution and program for assignment of molecular formulas

    NASA Technical Reports Server (NTRS)

    Miller, R. A.; Kohl, F. J.

    1977-01-01

    Two FORTRAN computer programs for the interpretation of low resolution mass spectra were prepared and tested. One is for the calculation of the molecular isotopic distribution of any species from stored elemental distributions. The program requires only the input of the molecular formula and was designed for compatability with any computer system. The other program is for the determination of all possible combinations of atoms (and radicals) which may form an ion having a particular integer mass. It also uses a simplified input scheme and was designed for compatability with any system.

  19. Laser-induced perturbation into molecular dynamics localized in neuronal cell

    NASA Astrophysics Data System (ADS)

    Hosokawa, Chie; Takeda, Naoko; Kudoh, Suguru N.; Taguchi, Takahisa

    2015-03-01

    Molecular dynamics at synaptic terminals in neuronal cells is essential for synaptic plasticity and subsequent modulation of cellular functions in a neuronal network. For realizing artificial control of living neuronal network, we demonstrate laser-induced perturbation into molecular dynamics in the neuronal cells. The optical trapping of cellular molecules such as synaptic vesicles or neural cell adhesion molecules labeled with quantum dots was evaluated by fluorescence imaging and fluorescence correlation spectroscopy. The trapping and assembling dynamics was revealed that the molecular motion was constrained at the focal spot of a focused laser beam due to optical trapping force. Our method has a potential to manipulate synaptic transmission at single synapse level.

  20. Analysis of hydrogen isotope mixtures

    DOEpatents

    Villa-Aleman, Eliel

    1994-01-01

    An apparatus and method for determining the concentrations of hydrogen isotopes in a sample. Hydrogen in the sample is separated from other elements using a filter selectively permeable to hydrogen. Then the hydrogen is condensed onto a cold finger or cryopump. The cold finger is rotated as pulsed laser energy vaporizes a portion of the condensed hydrogen, forming a packet of molecular hydrogen. The desorbed hydrogen is ionized and admitted into a mass spectrometer for analysis.

  1. Optimal buffer gas pressure for laser-induced fluorescence detection of the iodine-129 isotope in the atmosphere

    SciTech Connect

    Kireev, S.V.; Pit`ko, A.V.; Shnyrev, S.L.

    1995-06-01

    The effect of atmospheric air pressure on the intensity of iodine-129 vapor fluorescence excited by a He-Ne (633 nm) laser is studied. It is shown that to achieve the maximum intensity of fluorescence of molecular iodine-129, it is advantageous, first, to use a {sup 3}He-{sup 20}Ne laser for excitation, and second, to detect atmospheric iodine impurities in the gas mixture under analysis evacuated to 2 x 10{sup 18} - 4 x 10{sup 18} mol/cm{sup 3}. In this case, the sensitivity increases about twofold. 7 refs., 4 figs.

  2. CO/sub 2/ laser absorption and saturation studies of molecular impurities in alkali halide crystals

    SciTech Connect

    Sievers, A.J.

    1980-12-01

    The objective of this research program has been to explore the equilibrium and non-equilibrium dynamical properties of ReO/sub 4//sup -/ molecules embedded in alkali halide lattices using electromagnetic radiation. Both incoherent sources and CO/sub 2/ laser radiation have been used to explore the full dynamic range of the molecular vibrational modes. To achieve this objective stable molecular dopant - alkali halide combinations have been fabricated which have vibrational modes near the CO/sub 2/ laser frequencies. In order to uncouple the molecular modes from the lattice modes, to simplify the analysis as much as possible, low temperature spectroscopic measurements were required. In general, it was found that the molecular vibrational modes in the low temperature quiescent lattice had extremely narrow linewidths (less than 0.1 cm/sup -1/) so that most of the coincidences with the CO/sub 2/ laser lines were eliminated.

  3. Interaction of UV-Laser Radiation with Molecular Surface Films.

    DTIC Science & Technology

    2014-09-26

    reverse if nee~tary an~d Identify by biock number) FIEL GROP SU GR- Laser, Microelectronics , Surface Chemistry 19 ABSTRACT i CoiEIDue on reverset of...direct writing are also being pursued at the Microelectronics Sciences Laboratories at Columbia under separate funding. In addition, extensive interchange...R.M. Osgood and T.F. Deutsch, "Laser-Induced Chemistry for Microelectronics ," Science, Vol.277, pp. 709-714, 1985. R.M. Osgood and H.H. Gilgen, "Laser

  4. Application of copper vapour lasers for controlling activity of uranium isotopes

    SciTech Connect

    Barmina, E V; Sukhov, I A; Lepekhin, N M; Priseko, Yu S; Filippov, V G; Simakin, Aleksandr V; Shafeev, Georgii A

    2013-06-30

    Beryllium nanoparticles are generated upon ablation of a beryllium target in water by a copper vapour laser. The average size of single crystalline nanoparticles is 12 nm. Ablation of a beryllium target in aqueous solutions of uranyl chloride leads to a significant (up to 50 %) decrease in the gamma activity of radionuclides of the uranium-238 and uranium-235 series. Data on the recovery of the gamma activity of these nuclides to new steady-state values after laser irradiation are obtained. The possibility of application of copper vapour lasers for radioactive waste deactivation is discussed. (laser applications and other topics in quantum electronics)

  5. Equilibrium magnesium isotope fractionation between aqueous Mg2+ and carbonate minerals: Insights from path integral molecular dynamics

    NASA Astrophysics Data System (ADS)

    Pinilla, Carlos; Blanchard, Marc; Balan, Etienne; Natarajan, Suresh K.; Vuilleumier, Rodolphe; Mauri, Francesco

    2015-08-01

    The theoretical determination of the isotopic fractionation between an aqueous solution and a mineral is of utmost importance in Earth sciences. While for crystals, it is well established that equilibrium isotopic fractionation factors can be calculated using a statistical thermodynamic approach based on the vibrational properties, several theoretical methods are currently used to model ions in aqueous solution. In this work, we present a systematic study to determine the reduced partition function ratio (β-factor) of aqueous Mg2+ using several levels of theory within the simulations. In particular, using an empirical force field, we compare and discuss the performance of the exact results obtained from path integral molecular dynamics (PIMD) simulations, with respect to the more traditional methods based on vibrational properties and the cluster approximation. The results show the importance of including configurational disorder for the estimation of the equilibrium isotope fractionation factor. We also show that using the vibrational frequencies computed from snapshots taken from equilibrated classical molecular dynamics represents a good approximation for the study of aqueous ions. Based on these conclusions, the β-factor of aqueous Mg2+ have been estimated from a Car-Parrinello molecular dynamics (CPMD) simulation with an ab initio force field, and combined with the β-factors of carbonate minerals (magnesite, dolomite, calcite and aragonite). Mg β-factor of Mg-bearing aragonite, calculated here for the first time, displays a lower value than the three other carbonate minerals. This is explained by a strong distortion of the cationic site leading to a decrease of the coordination number during Ca-Mg substitution. Overall, the equilibrium magnesium isotope fractionation factors between aqueous Mg2+ and carbonate minerals that derive from this methodological study support the previous theoretical results obtained from embedded cluster models.

  6. Study of Molecular Collision Dynamics for Chemical Laser Systems.

    DTIC Science & Technology

    1982-03-01

    have concentrated our studies on photosensitive oxidizers such as chlorine dioxide (ClO 2) and hydrazoic acid (HN3) combined with carbon -containing fuel...resulting in intense emission throughout the visible spectrum. The emission was observed well downstream from the UV laser ignition region in an observation...sustaining by branched chain kinetics and no significant excitation by the initial UV laser pulse occurred. -- - - I a*- - - - . -a | .. nNI.. 6 As one

  7. Laser-Assisted Field Evaporation and Three-Dimensional Atom-by-Atom Mapping of Diamond Isotopic Homojunctions.

    PubMed

    Mukherjee, Samik; Watanabe, Hideyuki; Isheim, Dieter; Seidman, David N; Moutanabbir, Oussama

    2016-02-10

    It addition to its high evaporation field, diamond is also known for its limited photoabsorption, strong covalent bonding, and wide bandgap. These characteristics have been thought for long to also complicate the field evaporation of diamond and make its control hardly achievable on the atomistic-level. Herein, we demonstrate that the unique behavior of nanoscale diamond and its interaction with pulsed laser lead to a controlled field evaporation thus enabling three-dimensional atom-by-atom mapping of diamond (12)C/(13)C homojunctions. We also show that one key element in this process is to operate the pulsed laser at high energy without letting the dc bias increase out of bounds for diamond nanotip to withstand. Herein, the role of the dc bias in evaporation of diamond is essentially to generate free charge carriers within the nanotip via impact ionization. The mobile free charges screen the internal electric field, eventually creating a hole rich surface where the pulsed laser is effectively absorbed leading to an increase in the nanotip surface temperature. The effect of this temperature on the uncertainty in the time-of-flight of an ion, the diffusion of atoms on the surface of the nanotip, is also discussed. In addition to paving the way toward a precise manipulation of isotopes in diamond-based nanoscale and quantum structures, this result also elucidates some of the basic properties of dielectric nanostructures under high electric field.

  8. Three-dimensional nanoscale molecular imaging by extreme ultraviolet laser ablation mass spectrometry

    PubMed Central

    Kuznetsov, Ilya; Filevich, Jorge; Dong, Feng; Woolston, Mark; Chao, Weilun; Anderson, Erik H.; Bernstein, Elliot R.; Crick, Dean C.; Rocca, Jorge J.; Menoni, Carmen S.

    2015-01-01

    Analytical probes capable of mapping molecular composition at the nanoscale are of critical importance to materials research, biology and medicine. Mass spectral imaging makes it possible to visualize the spatial organization of multiple molecular components at a sample's surface. However, it is challenging for mass spectral imaging to map molecular composition in three dimensions (3D) with submicron resolution. Here we describe a mass spectral imaging method that exploits the high 3D localization of absorbed extreme ultraviolet laser light and its fundamentally distinct interaction with matter to determine molecular composition from a volume as small as 50 zl in a single laser shot. Molecular imaging with a lateral resolution of 75 nm and a depth resolution of 20 nm is demonstrated. These results open opportunities to visualize chemical composition and chemical changes in 3D at the nanoscale. PMID:25903827

  9. Heterodyne laser spectroscopy system

    DOEpatents

    Wyeth, Richard W.; Paisner, Jeffrey A.; Story, Thomas

    1989-01-01

    A heterodyne laser spectroscopy system utilizes laser heterodyne techniques for purposes of laser isotope separation spectroscopy, vapor diagnostics, processing of precise laser frequency offsets from a reference frequency and the like, and provides spectral analysis of a laser beam.

  10. Heterodyne laser spectroscopy system

    DOEpatents

    Wyeth, Richard W.; Paisner, Jeffrey A.; Story, Thomas

    1990-01-01

    A heterodyne laser spectroscopy system utilizes laser heterodyne techniques for purposes of laser isotope separation spectroscopy, vapor diagnostics, processing of precise laser frequency offsets from a reference frequency, and provides spectral analysis of a laser beam.

  11. Hybrid organic semiconductor lasers for bio-molecular sensing.

    PubMed

    Haughey, Anne-Marie; Foucher, Caroline; Guilhabert, Benoit; Kanibolotsky, Alexander L; Skabara, Peter J; Burley, Glenn; Dawson, Martin D; Laurand, Nicolas

    2014-01-01

    Bio-functionalised luminescent organic semiconductors are attractive for biophotonics because they can act as efficient laser materials while simultaneously interacting with molecules. In this paper, we present and discuss a laser biosensor platform that utilises a gain layer made of such an organic semiconductor material. The simple structure of the sensor and its operation principle are described. Nanolayer detection is shown experimentally and analysed theoretically in order to assess the potential and the limits of the biosensor. The advantage conferred by the organic semiconductor is explained, and comparisons to laser sensors using alternative dye-doped materials are made. Specific biomolecular sensing is demonstrated, and routes to functionalisation with nucleic acid probes, and future developments opened up by this achievement, are highlighted. Finally, attractive formats for sensing applications are mentioned, as well as colloidal quantum dots, which in the future could be used in conjunction with organic semiconductors.

  12. BaH molecular spectroscopy with relevance to laser cooling

    NASA Astrophysics Data System (ADS)

    Tarallo, M. G.; Iwata, G. Z.; Zelevinsky, T.

    2016-03-01

    We describe a simple experimental apparatus for laser ablation of barium monohydride (BaH) molecules and the study of their rovibrational spectra relevant to direct laser cooling. BaH is a promising candidate for laser cooling and ultracold fragmentation, both of which are precursors to novel experiments in many-body physics and precision measurement. We present a detailed analysis of the properties of ablation plumes that can improve the understanding of surface ablation and deposition technologies. A range of absorption spectroscopy and collisional thermalization regimes has been studied. We directly measured the Franck-Condon factor of the B 2Σ+(v'=0 ) ←X 2Σ+(v''=1 ) cycling transition. Prospects for production of a high luminosity cryogenic BaH beam are outlined.

  13. Molecular ionization of cyclohexanone in femtosecond laser fields: An application of ADK theory

    NASA Astrophysics Data System (ADS)

    Wang, Q. Q.; Mineo, H.; Wu, D.; Jin, M. X.; Chin, C. H.; Teranishi, Y.; Chao, S. D.; Ding, D.; Lin, S. H.

    2009-08-01

    The mechanisms of ionization and dissociation of cyclohexanone (C6H10O) in a 90 fs, 788 nm linearly polarized laser field ranging from 1013 to 1014 W/cm2 by a time-of-flight mass spectrometer (TOF-MS) have been investigated. The ion yields as a function of laser intensity have been measured experimentally. By comparison with the Ammosov-Delone-Krainov (ADK) theory based on a hydrogen-like model, the ionization mechanism of cyclohexanone in this intense femtosecond laser field has been understood. Considering the importance of molecular nuclear motions, we propose that the Franck-Condon (F-C) factor can provide the excess vibrational energy in the molecular ion. This energy is required for the decomposition of the molecular ion which finally results in the observed mass spectrum.

  14. Kinetic model of atomic and molecular emissions in laser-induced breakdown spectroscopy of organic compounds.

    PubMed

    Ma, Qianli; Dagdigian, Paul J

    2011-07-01

    A kinetic model previously developed to predict the relative intensities of atomic emission lines in laser-induced breakdown spectroscopy has been extended to include processes related to CN and C(2) molecular emissions. Simulations with this model were performed to predict the relative excited-state populations. The results from the simulations are compared with experimentally determined excited-state populations from 1,064 nm laser irradiation of organic residues on aluminum foil. The model reasonably predicts the relative intensity of the molecular emissions. Significantly, the model reproduces the vastly different temporal profiles of the atomic and molecular emissions. The latter are found to extend to much longer times after the laser pulse, and this appears to be due to the increasing concentration of the molecules versus time. From the simulations, the important processes affecting the CN and C(2) concentrations are identified.

  15. Mars Atmospheric Escape Recorded by H, C and O Isotope Ratios in Carbon Dioxide and Water Measured by the Sam Tunable Laser Spectrometer on the Curiosity Rover

    NASA Technical Reports Server (NTRS)

    Webster, C. R.; Mahaffy, P. R.; Leshin, L. A.; Atreya, S. K.; Flesch, G. J.; Stern, J.; Christensen, L. E.; Vasavada, A. R.; Owen, T.; Niles, P. B.; Jones, J. H.; Franz, H.

    2013-01-01

    Stable isotope ratios in C, H, N, O and S are powerful indicators of a wide variety of planetary geophysical processes that can identify origin, transport, temperature history, radiation exposure, atmospheric escape, environmental habitability and biological activity [2]. For Mars, measurements to date have indicated enrichment in all the heavier isotopes consistent with atmospheric escape processes, but with uncertainty too high to tie the results with the more precise isotopic ratios achieved from SNC meteoritic analyses. We will present results to date of H, C and O isotope ratios in CO2 and H2O made to high precision (few per mil) using the Tunable Laser Spectrometer (TLS) that is part of the Sample Analysis at Mars (SAM) instrument suite on MSL s Curiosity Rover.

  16. Tunable Solid State Lasers Based on Molecular Ions

    DTIC Science & Technology

    1992-01-01

    Pensylvania University Press, University Park and London, 1980) [2] W. Krupke and M.J. Weber, Prospects for New Dielectric Solid State Lasers , at...Research Office under the Grant DAAL03-88-0103. -13- References [1] W. Krupke and M.J. Weber, Prospects for New Dielectric Solid State Lasers , at Topical...including the time for reviewing instructions. searching existing data sources.AD At9 23 ;ng and retwn h ole~lon of 0n/ormlon. Send commetnts regarding

  17. Plasmon Lasers: Coherent Light Source at Molecular Scales

    DTIC Science & Technology

    2012-01-01

    rates due to cavity damping. From [20]. where, pnth γ1β γgβΓ, with solutions of the form, γs 1 2 p pnth 1 2 p pnth 1 4p ...ers, Company Profiles, Industry Trends, Market study by http://www.freedoniagroup.com (2011), date of last visit: 18 February 2012. www.lpr...Photonics Rev., 1–21 (2012) /DOI 10.1002/lpor.201100040 LASER&PHOTONICS REVIEWS Abstract Plasmon lasers are a new class of coherent optical frequency

  18. Biophysical response to pulsed laser microbeam-induced cell lysis and molecular delivery.

    PubMed

    Hellman, Amy N; Rau, Kaustubh R; Yoon, Helen H; Venugopalan, Vasan

    2008-03-01

    Cell lysis and molecular delivery in confluent monolayers of PtK(2) cells are achieved by the delivery of 6 ns, lambda = 532 nm laser pulses via a 40x, 0.8 NA microscope objective. With increasing distance from the point of laser focus we find regions of (a) immediate cell lysis; (b) necrotic cells that detach during the fluorescence assays; (c) permeabilized cells sufficient to facilitate the uptake of small (3 kDa) FITC-conjugated Dextran molecules in viable cells; and (d) unaffected, viable cells. The spatial extent of cell lysis, cell detachment, and molecular delivery increased with laser pulse energy. Hydrodynamic analysis from time-resolved imaging studies reveal that the maximum wall shear stress associated with the pulsed laser microbeam-induced cavitation bubble expansion governs the location and spatial extent of each of these regions independent of laser pulse energy. Specifically, cells exposed to maximum wall shear stresses tau(w, max) > 190 +/- 20 kPa are immediately lysed while cells exposed to tau(w, max) > 18 +/- 2 kPa are necrotic and subsequently detach. Cells exposed to tau(w, max) in the range 8-18 kPa are viable and successfully optoporated with 3 kDa Dextran molecules. Cells exposed to tau(w, max) < 8 +/- 1 kPa remain viable without molecular delivery. These findings provide the first direct correlation between pulsed laser microbeam-induced shear stresses and subsequent cellular outcome.

  19. A novel method of carbon dioxide clumped isotope analysis with tunable infra-red laser direct absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Prokhorov, Ivan; Kluge, Tobias; Janssen, Christof

    2016-04-01

    Precise clumped isotopes analysis of carbon dioxide opens up new horizons of atmospheric and biogeochemical research. Recent advances in laser and spectroscopic techniques provides us necessary instrumentation to access extremely low sub-permill variations of multiply-substituted isotopologues. We present an advanced analysis method of carbon dioxide clumped isotopes using direct absorption spectroscopy. Our assessments predict the ultimate precision of the new method on the sub-permill level comparable to state of the art mass spectrometry. Among the most auspicious intrinsic properties of this method we highlight genuine Δ16O13C18O and Δ16O13C18O measurements without isobaric interference, measurement cycle duration of several minutes versus hours for mass spectrometric analysis, reduced sample size of ˜ 10 μmol and high flexibility, allowing us to perform in-situ measurements. The pilot version of the instrument is being developed in an international collaboration framework between Heidelberg University, Germany and Pierre and Marie Curie University, Paris, France. It employs two continuous interband quantum cascade lasers tuned at 4.439 μm and 4.329 μm to measure doubly ( 16O13C18O, 16O13C17O) and singly ( 16O12C16O, 16O13C16O, 16O12C17O, 16O12C18O) substituted isotopologues, respectively. Two identical Herriot cells are filled with dry pure CO2 sample and reference gas at working pressure of 1 - 10 mbar. Cells provide optical path lengths of ˜ 17 m for the laser tuned at doubly substituted isotopologues lines and use a single pass for the laser tuned at the stronger lines of singly substituted isotopologues. Light outside of the gas cells is coupled into optical fiber to avoid absorption by ambient air CO2. Simulations predict sub-permill precision at working pressure of 1 mbar and room temperature stabilised at the ±10 mK level. Our prime target is to apply the proposed method for continuous in-situ analysis of CO2. We are foreseeing potential

  20. Comparison of 265 nm Femtosecond and 213 nm Nanosecond Laser Ablation Inductively Coupled Plasma Mass Spectrometry for Pb Isotope Ratio Measurements.

    PubMed

    Ohata, Masaki; Nonose, Naoko; Dorta, Ladina; Günther, Detlef

    2015-01-01

    The analytical performance of 265 nm femtosecond laser ablation (fs-LA) and 213 nm nanosecond laser ablation (ns-LA) systems coupled with multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS) for Pb isotope ratio measurements of solder were compared. Although the time-resolved signals of Pb measured by fs-LA-MC-ICPMS showed smoother signals compared to those obtained by ns-LA-MC-ICPMS, similar precisions on Pb isotope ratio measurements were obtained between them, even though their operating conditions were slightly different. The mass bias correction of the Pb isotope ratio measurement was carried out by a comparison method using a Pb standard solution prepared from NIST SRM 981 Pb metal isotopic standard, which was introduced into the ICP by a desolvation nebulizer (DSN) via a dual-sample introduction system, and it was successfully demonstrated for Pb isotope ratio measurements for either NIST 981 metal isotopic standard or solder by fs-LA-MC-ICPMS since the analytical results agreed well with the certified value as well as the determined value within their standard deviations obtained and the expanded uncertainty of the certified or determined value. The Pb isotope ratios of solder obtained by ns-LA-MC-ICPMS also showed agreement with respect to the determined value within their standard deviations and expanded uncertainty. From these results, it was evaluated that the mass bias correction applied in the present study was useful and both LA-MC-ICPMS could show similar analytical performance for the Pb isotope ratio microanalysis of metallic samples such as solder.

  1. Laser spectroscopies for elemental and molecular analysis in art and archaeology

    NASA Astrophysics Data System (ADS)

    Nevin, Austin; Spoto, Giuseppe; Anglos, Demetrios

    2012-02-01

    Spectroscopic methods using laser sources have significantly improved our capacity to unravel the chemical composition of works of art and archaeological remains. Lasers enhance the performance of spectroscopic techniques which require intense light sources and specific analytical protocols assuring a microanalytical approach for analysis has been established. This review focuses on laser spectroscopic methods used in the field of cultural heritage diagnostics. Emphasis in this work is given to the analytical capabilities of laser-based techniques for elemental and/or molecular analysis and in-situ use, spatial resolution and microanalysis. Analytical methods are classified according to the elemental (LIBS, LA-ICP-MS) and molecular (LIF/LIDAR, time-resolved absorption spectroscopy, laser desorption ionization mass spectrometry) information they yield. For non-destructive laser-induced fluorescence (LIF/LIDAR) and time-resolved fluorescence spectroscopy, imaging applications are described. The advantages provided by combined complementary techniques including but not limited to LIBS-LIF-Raman and LIBS-XRF are presented, as are recent improvements in terms of chemical imaging. Advances and applications of THz spectroscopy, non-linear spectroscopy and imaging are outlined. Finally, laser spectroscopies are described for investigations of different materials and works of art which include Bronze Age ceramics, Minoan archaeological remains, Ancient Roman buildings, Renaissance wall paintings and sculptures, and manuscripts containing iron gall inks and colorants.

  2. Control of laser induced molecular fragmentation of n-propyl benzene using chirped femtosecond laser pulses

    NASA Astrophysics Data System (ADS)

    Goswami, Tapas; Karthick Kumar, S. K.; Dutta, Aveek; Goswami, Debabrata

    2009-06-01

    We present the effect of chirping a femtosecond laser pulse on the fragmentation of n-propyl benzene. An enhancement of an order of magnitude for the relative yields of C3H 3 + and C5H 5 + in the case of negatively chirped pulses and C6H 5 + in the case of positively chirped pulses with respect to the transform-limited pulse indicates that in some fragmentation channel, coherence of the laser field plays an important role. For the relative yield of all other heavier fragment ions, resulting from the interaction of the intense laser field with the molecule, there is no such enhancement effect with the sign of chirp, within experimental errors. The importance of the laser phase is further reinforced through a direct comparison of the fragmentation results with the second harmonic of the chirped laser pulse with identical bandwidth.

  3. Control of laser induced molecular fragmentation of n-propyl benzene using chirped femtosecond laser pulses.

    PubMed

    Goswami, Tapas; Karthick Kumar, S K; Dutta, Aveek; Goswami, Debabrata

    2009-06-12

    We present the effect of chirping a femtosecond laser pulse on the fragmentation of n-propyl benzene. An enhancement of an order of magnitude for the relative yields of C3H3+ and C5H5+ in the case of negatively chirped pulses and C6H5+ in the case of positively chirped pulses with respect to the transform-limited pulse indicates that in some fragmentation channel, coherence of the laser field plays an important role. For the relative yield of all other heavier fragment ions, resulting from the interaction of the intense laser field with the molecule, there is no such enhancement effect with the sign of chirp, within experimental errors. The importance of the laser phase is further reinforced through a direct comparison of the fragmentation results with the second harmonic of the chirped laser pulse with identical bandwidth.

  4. A novel paleo-bleaching proxy using boron isotopes and high-resolution laser ablation to reconstruct coral bleaching events

    NASA Astrophysics Data System (ADS)

    Dishon, G.; Fisch, J.; Horn, I.; Kaczmarek, K.; Bijma, J.; Gruber, D. F.; Nir, O.; Popovich, Y.; Tchernov, D.

    2015-06-01

    Coral reefs occupy only ~0.1% of the oceans habitat, but are the most biologically diverse marine ecosystem. In recent decades, coral reefs have experienced significant global declines due to a variety of causes, one of the major being widespread coral bleaching events. During bleaching the coral expels its symbiotic algae losing its main source of nutrition generally obtained through photosynthesis. While recent coral bleaching events have been extensively investigated, there is no scientific data on historical coral bleaching prior to 1979. In this study, we employ high-resolution femtosecond Laser Ablation Multiple Collector Inductively Coupled Plasma Mass Spectrometry (LA-MC-ICP-MS) to demonstrate a distinct biologically-induced decline of boron (B) isotopic composition (δ11B) as a result of coral bleaching. These findings and methodology offer a new use for a previously developed isotopic proxy to reconstruct paleo-coral bleaching events. Based on a literature review of published δ11B data and our recorded "vital effect" of coral bleaching on the δ11B signal, we also describe at least two possible coral bleaching events since the Last Glacial Maximum. The implementation of this bleaching proxy holds the potential of identifying occurrences of coral bleaching throughout the geological record. A deeper temporal view of coral bleaching will enable scientists to determine if it occurred in the past during times of environmental change and what outcome it may have had on coral population structure.

  5. Laser-Induced Molecular Fluorescence: A Physical Chemistry Experiment.

    ERIC Educational Resources Information Center

    Tellinghuisen, Joel

    1981-01-01

    Describes a companion experiment to the experimental study of the di-iodide visible absorption spectrum. Experimental details, interpretation, and data analysis are provided for an analysis of the di-iodide fluorescence excited by a visible laser, using a Raman instrument. (CS)

  6. Photoelectron momentum distributions of the hydrogen molecular ion driven by multicycle near-infrared laser pulses

    NASA Astrophysics Data System (ADS)

    Murakami, Mitsuko; Chu, Shih-I.

    2016-10-01

    The photoelectron momentum distributions (PMDs) of the hydrogen molecular ion H2+ driven by strong near-infrared laser pulses are studied based on the ab initio numerical solution of the time-dependent Schrödinger equation and the Volkov wave propagation. Both linear and circular polarization are considered, in accordance with the recent experiment by M. Odenweller et al. [Phys. Rev. A 89, 013424 (2014), 10.1103/PhysRevA.89.013424]. We will discuss the difference between the molecular (diatomic) and the atomic PMDs and the effect of molecular potential to the photoelectron energy. In particular, we demonstrate that the above-threshold ionization spectra of H2+ could upshift their energy when driven by a linearly polarized laser field parallel to the molecular axis.

  7. On molecular origin of mass-independent fractionation of oxygen isotopes in the ozone forming recombination reaction

    PubMed Central

    Ivanov, Mikhail V.; Babikov, Dmitri

    2013-01-01

    Theoretical treatment of ozone forming reaction is developed within the framework of mixed quantum/classical dynamics. Formation and stabilization steps of the energy transfer mechanism are both studied, which allows simultaneous capture of the delta zero-point energy effect and η-effect and identification of the molecular level origin of mass-independent isotope fractionation. The central role belongs to scattering resonances; dependence of their lifetimes on rotational excitation, asymmetry; and connection of their vibrational wave functions to two different reaction channels. Calculations, performed within the dimensionally reduced model of ozone, are in semiquantitative agreement with experiment. PMID:23431175

  8. Laser spectroscopy of francium isotopes at the borders of the region of reflection asymmetry

    NASA Astrophysics Data System (ADS)

    Budinčević, I.; Billowes, J.; Bissell, M. L.; Cocolios, T. E.; de Groote, R. P.; De Schepper, S.; Fedosseev, V. N.; Flanagan, K. T.; Franchoo, S.; Garcia Ruiz, R. F.; Heylen, H.; Lynch, K. M.; Marsh, B. A.; Neyens, G.; Procter, T. J.; Rossel, R. E.; Rothe, S.; Strashnov, I.; Stroke, H. H.; Wendt, K. D. A.

    2014-07-01

    The magnetic dipole moments and changes in mean-square charge radii of the neutron-rich 218m,219,229,231Fr isotopes were measured with the newly installed Collinear Resonance Ionization Spectroscopy (CRIS) beam line at the On-Line Isotope Mass Separator (ISOLDE), CERN, probing the 7s2S1/2 to 8p2P3/2 atomic transition. The δA,221 values for 218m,219Fr and 229,231Fr follow the observed increasing slope of the charge radii beyond N =126. The charge radii odd-even staggering in this neutron-rich region is discussed, showing that 220Fr has a weakly inverted odd-even staggering while 228Fr has normal staggering. This suggests that both isotopes reside at the borders of a region of inverted staggering, which has been associated with reflection-asymmetric shapes. The g(219Fr )=+0.69(1) value supports a π1h9/2 shell-model configuration for the ground state. The g(229,231Fr ) values support the tentative Iπ(229,231Fr)=(1/2+) spin and point to a πs1/2-1 intruder ground-state configuration.

  9. Toward an In Situ Organic and Atomic Microprobe with Laser TOF-MS

    NASA Technical Reports Server (NTRS)

    Brinckerhoff, W. B.; Cornish, T. J.; McEntire, R. W.; Cheng, A. F.; Benson, R. C.

    2000-01-01

    We present details of a new miniature laser time-of-flight mass spectrometer (TOF-MS) with improved resolution and sensitivity, for in situ analysis of elemental, isotopic, and organic/molecular composition.

  10. Submillimeter D2O-18 molecular laser with optical pumping

    NASA Astrophysics Data System (ADS)

    Svich, V. A.; Pokormiakho, N. G.; Topkov, A. N.

    1980-11-01

    In the considered investigation, nine new emission lines of the D2O-18 molecule were observed over the wavelength range from 96 to 140 micrometers. In the experiments, a CO2 TEA laser was used for optical pumping. The TEA laser was operated at atmospheric pressure with an output energy up to 2 J and a pulse length of 100 ns. A gaseous mixture with a composition of CO2:N2:He = 1:1:4 was excited by means of a pulsed transverse discharge. A resonator with a length of 1 m was formed by a spherical mirror with a radius of curvature of 10 m, and a gold-plated echelette grating with 100 lines/mm. The submillimeter cell consisted of a glass tube with an inside diameter of 80 mm and a length of 1270 mm, and the spherical mirrors of the submillimeter resonator.

  11. Carbon isotope composition of low molecular weight hydrocarbons and monocarboxylic acids from Murchison meteorite

    NASA Technical Reports Server (NTRS)

    Yuen, G.; Blair, N.; Des Marais, D. J.; Chang, S.

    1984-01-01

    Carbon isotopic compositions have been measured for individual hydrocarbons and monocarboxylic acids from the Murchison meteorite, a C2 carbonaceous chondrite which fell in Australia in 1969. With few exceptions, notably benzene, the volatile products are substantially isotopically heavier than their terrestrial counterparts, signifying their extraterrestrial origin. For both classes of compounds, the ratio of C-13 to C-12 decreases with increasing carbon number in a roughly parallel manner, and each carboxylic acid exhibits a higher isotopic ratio than the hydrocarbon containing the same number of carbon atoms. These trends are consistent with the kinetically controlled synthesis of higher homologues from lower ones. The results suggest the possibility that the production mechanisms for hydrocarbons and carboxylic acids may be similar, and impose constraints on the identity of the reactant species.

  12. Comparison of short-lived medical isotopes activation by laser thin target induced protons and conventional cyclotron proton beams

    NASA Astrophysics Data System (ADS)

    Murray, Joseph; Dudnikova, Galina; Liu, Tung-Chang; Papadopoulos, Dennis; Sagdeev, Roald; Su, J. J.; UMD MicroPET Team

    2014-10-01

    Production diagnostic or therapeutic nuclear medicines are either by nuclear reactors or by ion accelerators. In general, diagnostic nuclear radioisotopes have a very short half-life varying from tens of minutes for PET tracers and few hours for SPECT tracers. Thus supplies of PET and SPECT radiotracers are limited by regional production facilities. For example 18F-fluorodeoxyglucose (FDG) is the most desired tracer for positron emission tomography because its 110 minutes half-life is sufficient long for transport from production facilities to nearby users. From nuclear activation to completing image taking must be done within 4 hours. Decentralized production of diagnostic radioisotopes will be idea to make high specific activity radiotracers available to researches and clinicians. 11 C, 13 N, 15 O and 18 F can be produced in the energy range from 10-20 MeV by protons. Protons of energies up to tens of MeV generated by intense laser interacting with hydrogen containing targets have been demonstrated by many groups in the past decade. We use 2D PIC code for proton acceleration, Geant4 Monte Carlo code for nuclei activation to compare the yields and specific activities of short-lived isotopes produced by cyclotron proton beams and laser driven protons.

  13. Detecting Molecular Properties by Various Laser-Based Techniques

    SciTech Connect

    Hsin, Tse-Ming

    2007-01-01

    Four different laser-based techniques were applied to study physical and chemical characteristics of biomolecules and dye molecules. These techniques are liole burning spectroscopy, single molecule spectroscopy, time-resolved coherent anti-Stokes Raman spectroscopy and laser-induced fluorescence microscopy. Results from hole burning and single molecule spectroscopy suggested that two antenna states (C708 & C714) of photosystem I from cyanobacterium Synechocystis PCC 6803 are connected by effective energy transfer and the corresponding energy transfer time is ~6 ps. In addition, results from hole burning spectroscopy indicated that the chlorophyll dimer of the C714 state has a large distribution of the dimer geometry. Direct observation of vibrational peaks and evolution of coumarin 153 in the electronic excited state was demonstrated by using the fs/ps CARS, a variation of time-resolved coherent anti-Stokes Raman spectroscopy. In three different solvents, methanol, acetonitrile, and butanol, a vibration peak related to the stretch of the carbonyl group exhibits different relaxation dynamics. Laser-induced fluorescence microscopy, along with the biomimetic containers-liposomes, allows the measurement of the enzymatic activity of individual alkaline phosphatase from bovine intestinal mucosa without potential interferences from glass surfaces. The result showed a wide distribution of the enzyme reactivity. Protein structural variation is one of the major reasons that are responsible for this highly heterogeneous behavior.

  14. High-resolution continuous flow analysis setup for water isotopic measurement from ice cores using laser spectroscopy

    NASA Astrophysics Data System (ADS)

    Emanuelsson, B. D.; Baisden, W. T.; Bertler, N. A. N.; Keller, E. D.; Gkinis, V.

    2014-12-01

    Here we present an experimental setup for water stable isotopes (δ18O and δD) continuous flow measurements. It is the first continuous flow laser spectroscopy system that is using Off-Axis Integrated Cavity Output Spectroscopy (OA-ICOS; analyzer manufactured by Los Gatos Research - LGR) in combination with an evaporation unit to continuously analyze sample from an ice core. A Water Vapor Isotopic Standard Source (WVISS) calibration unit, manufactured by LGR, was modified to: (1) increase the temporal resolution by reducing the response time (2) enable measurements on several water standards, and (3) to reduce the influence from memory effects. While this setup was designed for the Continuous Flow Analysis (CFA) of ice cores, it can also continuously analyze other liquid or vapor sources. The modified setup provides a shorter response time (~54 and 18 s for 2013 and 2014 setup, respectively) compared to the original WVISS unit (~62 s), which is an improvement in measurement resolution. Another improvement compared to the original WVISS is that the modified setup has a reduced memory effect. Stability tests comparing the modified WVISS and WVISS setups were performed and Allan deviations (σAllan) were calculated to determine precision at different averaging times. For the 2013 modified setup the precision after integration times of 103 s are 0.060 and 0.070‰ for δ18O and δD, respectively. For the WVISS setup the corresponding σAllan values are 0.030, 0.060 and 0.043‰ for δ18O, δD and δ17O, respectively. For the WVISS setup the precision is 0.035, 0.070 and 0.042‰ after 103 s for δ18O, δD and δ17O, respectively. Both the modified setups and WVISS setup are influenced by instrumental drift with δ18O being more drift sensitive than δD. The σAllan values for δ18O of 0.30 and 0.18‰ for the modified (2013) and WVISS setup, respectively after averaging times of 104 s (2.78 h). The Isotopic Water Analyzer (IWA)-modified WVISS setup used during the

  15. Tracing the oxygen triple isotopic composition of tropospheric molecular oxygen in biogenic apatite - a new tool for palaeoclimatology

    NASA Astrophysics Data System (ADS)

    Pack, A.; Süssenberger, A.; Gehler, A.; Wotzlaw, J.

    2009-04-01

    It has been demonstrated that tropospheric molecular oxygen posses a significant isotope anomaly [1, 2 and refs. therein]. Relative to the rocks- and minerals-defined terrestrial fractionation line (TFL), tropospheric O2 has an anomaly of -0.35‰ [2]. Because almost all oxygen on Earth is contained in rocks, we suggest that the rocks- and minerals-defined TFL [3] should be used as reference when reporting isotope anomalies with ∆17O = δ'17OSMOW - βTFL δ'18OSMOW. We have developed a new technique for the determination of δ17O and δ18O of silicates by means of laser fluorination GC-CF-irmMS. We have determined βTFL to 0.5247 (N > 100), which is identical to the value reported by other laboratories and techniques [2, 3]. The uncertainty in ∆17O is ±0.03 (1σ) for a single analysis. It was suggested that ∆17O of tropospheric O2 can be used as proxy for the global bioactivity rate [GBR, 1] as well as for past atmospheric CO2 concentrations [4]. Past ∆17O of tropospheric O2 can be determined by analyzing O2 trapped in ice [1, 5] or by analyzing sulfates from terrestrial sulphide oxidation [4]. Disadvantage of ice core data is the limitation in time back <1 Myrs. The sulfate approach is used to trace ∆17O of air O2 back to Proterozoic times. Disadvantage of this technique is the uncertainty in the proportion of oxygen from O2 and oxygen from ambient water during oxidation of the sulphides. We suggest that oxygen from tooth and bone phosphate can be used as proxy for the ∆17O of air O2. Mass balance calculations [e.g. 6] suggest that a considerable portion of oxygen in biogenic apatite sources from respired air O2. We have analyzed tooth (enamel, dentine) and bone material by means of direct fluorination for their δ17O and δ18O. We have chosen material of mammals of different body mass (Mb) from Northern Germany (except Indian Elephant). The ∆17O of apatite varies between -0.16‰ for a wood mouse (Apodemus sylvaticus) and +0.04‰ for a wild boar

  16. UV-laser microdissection system - A novel approach for the preparation of high-resolution stable isotope records (δ13C/δ18O) from tree rings

    NASA Astrophysics Data System (ADS)

    Schollaen, Karina; Helle, Gerhard

    2013-04-01

    Intra-annual stable isotope (δ13C and δ18O) studies of tree rings at various incremental resolutions have been attempting to extract valuable seasonal climatic and environmental information or assessing plant ecophysiological processes. For preparing high-resolution isotope samples normally wood segments or cores are mechanically divided in radial direction or cut in tangential direction. After mechanical dissection, wood samples are ground to a fine powder and either cellulose is extracted or bulk wood samples are analyzed. Here, we present a novel approach for the preparation of high-resolution stable isotope records from tree rings using an UV-laser microdissection system. Firstly, tree-ring cellulose is directly extracted from wholewood cross-sections largely leaving the wood anatomical structure intact and saving time as compared to the classical procedure. Secondly, micro-samples from cellulose cross-sections are dissected with an UV-Laser dissection microscope. Tissues of interest from cellulose cross-sections are identified and marked precisely with a screen-pen and dissected via an UV-laser beam. Dissected cellulose segments were automatically collected in capsules and are prepared for stable isotope (δ13C and δ18O) analysis. The new techniques facilitate inter- and intra-annual isotope analysis on tree-ring and open various possibilities for comparisons with wood anatomy in plant eco-physiological studies. We describe the design and the handling of this novel methodology and discuss advantages and constraints given by the example of intra-annual oxygen isotope analysis on tropical trees.

  17. Cavity Ringdown Laser Asorption Spectroscopy(crlas) of Isotopically Labeled Acetylene Between 12,500 - 13,600 wn

    NASA Astrophysics Data System (ADS)

    Lue, Christopher J.; Sullivan, Michael N.; Draganjac, Mark E.; Reeve, Scott W.

    2011-06-01

    About five years ago, Arkansas State University created the Arkansas Center for Laser Applications and Science (ArCLAS) with the intention of making it a state-of-the-art facility for laser-based research and optical spectroscopy in the midSouth. Since that time, University and DoD support has lead to the acquisition of numerous laser based spectrometers including a novel three color picosecond system utilized primarily for STIRAP measurements of bulk gas samples. Over the past few months, we have begun collecting near infrared overtone and combination band spectra for the acetylene molecule with a pulsed cavity ringdown laser absorption spectrometer (CRDLAS) as part of the STIRAP support effort. Certainly acetylene has been extensively studied by a number of different spectroscopic methods. During these CRDLAS investigations a 13C_2H_2 band was discovered which we believe has not been previously reported. Here a complete rovibrational analysis of this band will be presented. See for example, Michel Herman, Jacques lievin, Jean Vander Auwera, and Alain Campargue, in Global and Accurate Vibration Hamiltonians from High Resolution Molecular Spectroscopy, Advances in Chemical Physics Volume 108, John Wiley and Sons, NY, NY (1999) and references therein.

  18. Methane concentration and isotopic composition measurements with a mid-infrared quantum-cascade laser

    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.

    1999-01-01

    A quantum-cascade laser operating at a wavelength of 8.1 micrometers was used for high-sensitivity absorption spectroscopy of methane (CH4). The laser frequency was continuously scanned with current over more than 3 cm-1, and absorption spectra of the CH4 nu 4 P branch were recorded. The measured laser linewidth was 50 MHz. A CH4 concentration of 15.6 parts in 10(6) ( ppm) in 50 Torr of air was measured in a 43-cm path length with +/- 0.5-ppm accuracy when the signal was averaged over 400 scans. The minimum detectable absorption in such direct absorption measurements is estimated to be 1.1 x 10(-4). The content of 13CH4 and CH3D species in a CH4 sample was determined.

  19. Apportioning sources of organic matter in streambed sediments: an integrated molecular and compound-specific stable isotope approach.

    PubMed

    Cooper, Richard J; Pedentchouk, Nikolai; Hiscock, Kevin M; Disdle, Paul; Krueger, Tobias; Rawlins, Barry G

    2015-07-01

    We present a novel application for quantitatively apportioning sources of organic matter in streambed sediments via a coupled molecular and compound-specific isotope analysis (CSIA) of long-chain leaf wax n-alkane biomarkers using a Bayesian mixing model. Leaf wax extracts of 13 plant species were collected from across two environments (aquatic and terrestrial) and four plant functional types (trees, herbaceous perennials, and C3 and C4 graminoids) from the agricultural River Wensum catchment, UK. Seven isotopic (δ13C27, δ13C29, δ13C31, δ13C27-31, δ2H27, δ2H29, and δ2H27-29) and two n-alkane ratio (average chain length (ACL), carbon preference index (CPI)) fingerprints were derived, which successfully differentiated 93% of individual plant specimens by plant functional type. The δ2H values were the strongest discriminators of plants originating from different functional groups, with trees (δ2H27-29=-208‰ to -164‰) and C3 graminoids (δ2H27-29=-259‰ to -221‰) providing the largest contrasts. The δ13C values provided strong discrimination between C3 (δ13C27-31=-37.5‰ to -33.8‰) and C4 (δ13C27-31=-23.5‰ to -23.1‰) plants, but neither δ13C nor δ2H values could uniquely differentiate aquatic and terrestrial species, emphasizing a stronger plant physiological/biochemical rather than environmental control over isotopic differences. ACL and CPI complemented isotopic discrimination, with significantly longer chain lengths recorded for trees and terrestrial plants compared with herbaceous perennials and aquatic species, respectively. Application of a comprehensive Bayesian mixing model for 18 streambed sediments collected between September 2013 and March 2014 revealed considerable temporal variability in the apportionment of organic matter sources. Median organic matter contributions ranged from 22% to 52% for trees, 29% to 50% for herbaceous perennials, 17% to 34% for C3 graminoids and 3% to 7% for C4 graminoids. The results presented here

  20. Quantum control of a molecular ionization process by using Fourier-synthesized laser fields

    NASA Astrophysics Data System (ADS)

    Ohmura, Hideki; Saito, Naoaki

    2015-11-01

    In photoexcitation processes, if the motion of excited electrons can be precisely steered by the instantaneous electric field of an arbitrary waveform of a Fourier-synthesized laser field, the resultant matter response can be achieved within one optical cycle, usually within the attosecond (1 as =10-18s) regime. Fourier synthesis of laser fields has been achieved in various ways. However, the general use of Fourier-synthesized laser fields for the control of matter is extremely limited. Here, we report the quantum control of a nonlinear response of a molecular ionization process by using Fourier-synthesized laser fields. The directionally asymmetric molecular tunneling ionization induced by intense (5.0 ×1012W /c m2) Fourier-synthesized laser fields consisting of fundamental, second-, third-, and fourth-harmonic light achieves the orientation-selective ionization; we utilized the orientation-selective ionization for measurement of the relative phase differences between the fundamental and each harmonic light. Our findings impact not only light-wave engineering but also the control of matter, possibly triggering the creation and establishment of a new methodology that uses Fourier-synthesized laser fields.

  1. Simultaneous in situ determination of U-Pb and Sm-Nd isotopes in monazite by laser ablation ICP-MS

    NASA Astrophysics Data System (ADS)

    Goudie, Dylan J.; Fisher, Christopher M.; Hanchar, John M.; Crowley, James L.; Ayers, John C.

    2014-06-01

    are presented for in situ simultaneous determination of U-Pb and Sm-Nd isotopes in monazite using the Laser Ablation Split-Stream (LASS) method. This method uses a laser ablation system coupled to a magnetic-sector inductively coupled plasma mass spectrometer (HR) (ICP-MS) for measuring U-Pb isotopes and a multicollector (MC) ICP-MS for measuring Sm-Nd isotopes. Ablated material is split using a Y-connector and transported simultaneously to both mass spectrometers. In addition to Sm and Nd isotopes, the MC-ICP-MS is configured to also acquire Ce, Nd, Sm, Eu, and Gd elemental abundances. This approach provides age, tracer isotope, and trace element data in the same ablation volume, reducing sampling problems associated with fine-scale zoning in accessory minerals and minimizing the material needed for ablation. Precision and accuracy of the U-Pb method (and the precision of the Sm-Nd method) is demonstrated with results from well-characterized monazite reference materials. The LASS results agree within uncertainty with the isotope dilution thermal ionization mass spectrometry (ID-TIMS) U-Pb dates. The accuracy of the Sm-Nd method is assessed by comparing the LA-MC-ICP-MS results with ID-TIMS determinations on a well-characterized, in-house monazite reference material. The LASS method is then applied to monazite from the Birch Creek Pluton in the White Mountains of California as a case study to illustrate the utility of this method for solving geologic problems. The U-Pb ages and Sm-Nd isotopic data from the LASS method support the conclusions drawn from previous results that monazite can record timing and information about the source region(s) of hydrothermal fluids.

  2. Molecular microanalysis of pathological specimens in situ with a laser-Raman microprobe.

    PubMed

    Abraham, J L; Etz, E S

    1979-11-09

    A laser-Raman microprobe has been used to identify microscopic inclusions of silicone polymer in standard paraffin sections of lymph node. This example of organic chemical microanalysis in situ in pathological tissue represents an extension of microanalytical capabilities from elemental analysis, performed with electron and ion microprobes, to compound-specific molecular microanalysis.

  3. Molecular above-threshold-ionization angular distributions with attosecond bichromatic intense XUV laser pulses

    NASA Astrophysics Data System (ADS)

    Yuan, Kai-Jun; Bandrauk, André D.

    2012-01-01

    Angular distributions of molecular above-threshold ionization (MATI) in bichromatic attosecond extreme ultraviolet (XUV) linear polarization laser pulses have been theoretically investigated. Multiphoton ionization in a prealigned molecular ion H2+ produces clear MATI spectra which show a forward-backward asymmetry in angular and momentum distributions which is critically sensitive to the carrier envelope phase (CEP) φ, the time delay Δτ between the two laser pulses, and the photoelectron kinetic energies Ee. The features of the asymmetry in MATI angular distributions are described well by multiphoton perturbative ionization models. Phase differences of continuum electron wave functions can be extracted from the CEP φ and time delay Δτ dependent ionization asymmetry ratio created by interfering multiphoton ionization pathways. At large internuclear distances MATI angular distributions exhibit more complex features due to laser-induced electron diffraction where continuum electron wavelengths are less than the internuclear distance.

  4. Method of molecular specie alteration by nonresonant laser induced dielectric breakdown

    DOEpatents

    Ronn, Avigdor M.

    1980-01-01

    Irradiation of a molecular specie by itself or in the presence of a secondary material at a pressure above a threshold value for the particular system by a laser of predetermined minimum power and having a frequency displaced from an absorption line of the specie causes severance of the weakest bond and a yield of products containing at least one dissociative fragment from said specie. A Rogowski type TEA CO.sub.2 --N.sub.2 --He laser has been used successfully on a wide variety of molecular species. Solid, liquid and gaseous end products have been obtained depending upon the starting materials. When solids have been produced they are in the form of microfine particles or microfine aggregates. A neodymium glass laser has also been used successfully.

  5. Molecular Paleohydrology: Interpreting the Hydrogen-Isotopic Composition of Lipid Biomarkers from Photosynthesizing Organisms

    NASA Astrophysics Data System (ADS)

    Sachse, Dirk; Billault, Isabelle; Bowen, Gabriel J.; Chikaraishi, Yoshito; Dawson, Todd E.; Feakins, Sarah J.; Freeman, Katherine H.; Magill, Clayton R.; McInerney, Francesca A.; van der Meer, Marcel T. J.; Polissar, Pratigya; Robins, Richard J.; Sachs, Julian P.; Schmidt, Hanns-Ludwig; Sessions, Alex L.; White, James W. C.; West, Jason B.; Kahmen, Ansgar

    2012-05-01

    Hydrogen-isotopic abundances of lipid biomarkers are emerging as important proxies in the study of ancient environments and ecosystems. A decade ago, pioneering studies made use of new analytical methods and demonstrated that the hydrogen-isotopic composition of individual lipids from aquatic and terrestrial organisms can be related to the composition of their growth (i.e., environmental) water. Subsequently, compound-specific deuterium/hydrogen (D/H) ratios of sedimentary biomarkers have been increasingly used as paleohydrological proxies over a range of geological timescales. Isotopic fractionation observed between hydrogen in environmental water and hydrogen in lipids, however, is sensitive to biochemical, physiological, and environmental influences on the composition of hydrogen available for biosynthesis in cells. Here we review the factors and processes that are known to influence the hydrogen-isotopic compositions of lipids—especially n-alkanes—from photosynthesizing organisms, and we provide a framework for interpreting their D/H ratios from ancient sediments and identify future research opportunities.

  6. Molecular iodine fluorescence spectra generated with helium-neon lasers for spectrometer calibration.

    PubMed

    Williamson, J Charles

    2010-12-01

    Gas-phase molecular iodine laser-induced fluorescence (LIF) spectra were recorded out to 815 nm at 1 cm(-1) resolution using green, yellow, and red helium-neon (HeNe) lasers as excitation sources. Nine previously unreported I(2) B←X absorption transitions accessed by these lasers were identified, and specific rovibronic transition assignments were made for two hundred LIF peaks--more than sixty per laser. These I(2) LIF peaks can be used to calibrate the vacuum wavenumber coordinate of spectrometers to better than 0.1 cm(-1) accuracy. In particular, green HeNe excitation of the I(2) R(106) 28-0 transition leads to strong fluorescence well suited for calibration, with a rotational doublet spacing of 15 cm(-1) and a doublet-to-doublet spacing of 190 cm(-1). Calibration by HeNe I(2) LIF may be an especially valuable technique for Raman spectroscopy applications.

  7. Multielectron effects in molecular dynamics driven by intense laser pulses

    NASA Astrophysics Data System (ADS)

    Xia, Yuqing; Cajiao-Velez, Felipe; Jaron-Becker, Agnieszka

    2014-05-01

    Using time-dependent density functional theory, we study multi-electron effects on high harmonic generation (HHG) and strong field ionization (SFI) from molecules. Both HHG and SFI although related to extreme distortion of an electron wave function in a system in the presence of a strong laser field, were so far successfully studied with theories based on `single active electron' (SAE) approximation such as `Strong Field Approximation'. We show several examples of novel resonant coupling, when the SAE description is not sufficient and analyze situations when it can be observed in experiment. Supported by the NSF (grant number PHY-1068706).

  8. Vibrational Energy Transfer and Kinetics of High Energy Molecular Lasers.

    DTIC Science & Technology

    1979-08-17

    babi1ities were measured for the—MCi, HP—HCN, DF—HCN, and 1~ ‘-HcN systems from 220—450°K. Two—p~otonp~otodissociation of HgC1, Hg~r, and HgI was observed to...HgBr , and MgI are of considerable current interest.(19 24) Laser output has been recently observed from HgBr(B21) and HgI (B2E) molecules produced by

  9. Exploring the Potential of Laser Ablation Carbon Isotope Analysis for Examining Ecology during the Ontogeny of Middle Pleistocene Hominins from Sima de los Huesos (Northern Spain)

    PubMed Central

    Garcia, Nuria; Feranec, Robert S.; Passey, Benjamin H.; Cerling, Thure E.; Arsuaga, Juan Luis

    2015-01-01

    Laser ablation of tooth enamel was used to analyze stable carbon isotope compositions of teeth of hominins, red deer, and bears from middle Pleistocene sites in the Sierra de Atapuerca in northern Spain, to investigate the possibility that this technique could be used as an additional tool to identify periods of physiological change that are not detectable as changes in tooth morphology. Most of the specimens were found to have minimal intra-tooth variation in carbon isotopes (< 2.3‰), suggesting isotopically uniform diets through time and revealing no obvious periods of physiological change. However, one of the two sampled hominin teeth displayed a temporal carbon isotope shift (3.2‰) that was significantly greater than observed for co-occurring specimens. The δ13C value of this individual averaged about -16‰ early in life, and -13‰ later in life. This isotopic change occurred on the canine crown about 4.2 mm from the root, which corresponds to an approximate age of two to four years old in modern humans. Our dataset is perforce small owing to the precious nature of hominid teeth, but it demonstrates the potential utility of the intra-tooth isotope profile method for extracting ontogenetic histories of human ancestors. PMID:26673156

  10. Exploring the Potential of Laser Ablation Carbon Isotope Analysis for Examining Ecology during the Ontogeny of Middle Pleistocene Hominins from Sima de los Huesos (Northern Spain).

    PubMed

    Garcia, Nuria; Feranec, Robert S; Passey, Benjamin H; Cerling, Thure E; Arsuaga, Juan Luis

    2015-01-01

    Laser ablation of tooth enamel was used to analyze stable carbon isotope compositions of teeth of hominins, red deer, and bears from middle Pleistocene sites in the Sierra de Atapuerca in northern Spain, to investigate the possibility that this technique could be used as an additional tool to identify periods of physiological change that are not detectable as changes in tooth morphology. Most of the specimens were found to have minimal intra-tooth variation in carbon isotopes (< 2.3‰), suggesting isotopically uniform diets through time and revealing no obvious periods of physiological change. However, one of the two sampled hominin teeth displayed a temporal carbon isotope shift (3.2‰) that was significantly greater than observed for co-occurring specimens. The δ13C value of this individual averaged about -16‰ early in life, and -13‰ later in life. This isotopic change occurred on the canine crown about 4.2 mm from the root, which corresponds to an approximate age of two to four years old in modern humans. Our dataset is perforce small owing to the precious nature of hominid teeth, but it demonstrates the potential utility of the intra-tooth isotope profile method for extracting ontogenetic histories of human ancestors.

  11. Lasers.

    ERIC Educational Resources Information Center

    Schewe, Phillip F.

    1981-01-01

    Examines the nature of laser light. Topics include: (1) production and characteristics of laser light; (2) nine types of lasers; (3) five laser techniques including holography; (4) laser spectroscopy; and (5) laser fusion and other applications. (SK)

  12. Isotopic and molecular distributions of biochemicals from fresh and buried Rhizophora mangle leaves†

    PubMed Central

    Smallwood, Barbara J; Wooller, Matthew J; Jacobson, Myrna E; Fogel, Marilyn L

    2003-01-01

    Rhizophora mangle L. (red mangrove) is the dominant species of mangrove in the Americas. At Twin Cays, Belize (BZ) red mangroves are present in a variety of stand structures (tall >5 m in height, transition ~2–4 m and dwarf ~1–1.5 m). These height differences are coupled with very different stable carbon and nitrogen isotopic values[1] (mean tall δ13C = -28.3‰, δ15N = 0‰; mean tall δ13C = -25.3‰, δ15N = -10‰). To determine the utility of using these distinct isotopic compositions as 'biomarkers' for paleoenvironmental reconstruction of mangrove ecosystems and nutrient availability, we investigated the distribution and isotopic (δ13C and δ15N) composition of different biochemical fractions (water soluble compounds, free lipids, acid hydrolysable compounds, individual amino acids, and the residual un-extractable compounds) in fresh and preserved red mangrove leaves from dwarf and tall trees. The distribution of biochemicals are similar in dwarf and tall red mangrove leaves, suggesting that, regardless of stand structure, red mangroves use nutrients for biosynthesis and metabolism in a similar manner. However, the δ13C and δ15N of the bulk leaf, the biochemical fractions, and seven amino acids can be used to distinguish dwarf and tall trees at Twin Cays, BZ. The data support the theory that the fractionation of carbon and nitrogen occurs prior to or during uptake in dwarf and tall red mangrove trees. Stable carbon and nitrogen isotopes could, therefore, be powerful tools for predicting levels of nutrient limitation at Twin Cays. The δ13C and δ15N of biochemical fractions within preserved leaves, reflect sedimentary cycling and nitrogen immobilization. The δ15N of the immobilized fraction reveals the overlying stand structure at the time of leaf deposition. The isotopic composition of preserved mangrove leaves could yield significant information about changes in ecosystem dynamics, nutrient limitation and past stand structure in mangrove

  13. Isotope separation by photochromatography

    DOEpatents

    Suslick, K.S.

    1975-10-03

    A photochromatographic method for isotope separation is described. An isotopically mixed molecular species is adsorbed on an adsorptive surface, and the adsorbed molecules are irradiated with radiation of a predetermined wavelength which will selectively excite desired isotopic species. Sufficient energy is transferred to the excited molecules to desorb them from the surface and thus separate them from the undesired isotopic species. The method is particularly applicable to the separation of hydrogen isotopes. (BLM)

  14. Isotope separation by photochromatography

    DOEpatents

    Suslick, Kenneth S.

    1977-01-01

    An isotope separation method which comprises physically adsorbing an isotopically mixed molecular species on an adsorptive surface and irradiating the adsorbed molecules with radiation of a predetermined wavelength which will selectively excite a desired isotopic species. Sufficient energy is transferred to the excited molecules to desorb them from the surface and thereby separate them from the unexcited undesired isotopic species. The method is particularly applicable to the separation of hydrogen isotopes.

  15. Molecular pathway of near-infrared laser phototoxicity involves ATF-4 orchestrated ER stress

    PubMed Central

    Khan, Imran; Tang, Elieza; Arany, Praveen

    2015-01-01

    High power lasers are used extensively in medicine while lower power applications are popular for optical imaging, optogenetics, skin rejuvenation and a therapeutic modality termed photobiomodulation (PBM). This study addresses the therapeutic dose limits, biological safety and molecular pathway of near-infrared (NIR) laser phototoxicity. Increased erythema and tissue damage were noted in mice skin and cytotoxicity in cell cultures at phototoxic laser doses involving generation of reactive oxygen species (ROS) coupled with a rise in surface temperature (>45 °C). NIR laser phototoxicity results from Activating Transcription Factor-4 (ATF-4) mediated endoplasmic reticulum stress and autophagy. Neutralizations of heat or ROS and overexpressing ATF-4 were noted to rescue NIR laser phototoxicity. Further, NIR laser mediated phototoxicity was noted to be non-genotoxic and non-mutagenic. This study outlines the mechanism of NIR laser phototoxicity and the utility of monitoring surface temperature and ATF4 expression as potential biomarkers to develop safe and effective clinical applications. PMID:26030745

  16. In-vivo optical molecular imaging for laser hyperthermia

    NASA Astrophysics Data System (ADS)

    Zeng, Shaoqun; Zhang, Zhihong; Zhou, Wei; Luo, Qingming

    2002-04-01

    Green fluorescent protein (GFP) transfected Hela cell was planted in naked mice, to construct an in vivo model for monitoring the therapeutic effect of laser hyperthermia in real time. A cooled CCD fluorescence imaging system was used to record the tumor fluorescence image during the hyperthermia process. Primary experimental results were presented in this paper. To make sure the fluorescent probe GFP does not have strong effect on the biologic function of the host tumor cell (Hela cell), several conventional biological processes were observed in real time. First, neurons, which are much more tender than tumor cells, were transfected with GFP (cameleons). No morphological inhomogenities were observed, and normal functional responses of the neurons were observed when stimulated with histamine. In the second step, the mitosis process of cultured Hela cell was monitored. The features observed during mitosis confirmed that the transfection does not ruin the mitosis process of the tumor cell. At last, naked mice with tumor cell was constructed, which emit fluorescence in the tumor region when excited with faint laser. This presentation provides an in vivo biological model for quick monitoring of the therapeutic results of tumor hyperthermia.

  17. Development of Laser Desorption Imaging Mass Spectrometry Methods to Investigate the Molecular Composition of Latent Fingermarks

    NASA Astrophysics Data System (ADS)

    Lauzon, Nidia; Dufresne, Martin; Chauhan, Vinita; Chaurand, Pierre

    2015-06-01

    For a century, fingermark analysis has been one of the most important and common methods in forensic investigations. Modern chemical analysis technologies have added the potential to determine the molecular composition of fingermarks and possibly identify chemicals a suspect may have come into contact with. Improvements in analytical detection of the molecular composition of fingermarks is therefore of great importance. In this regard, matrix-assisted laser desorption ionization (MALDI) and laser desorption ionization (LDI) imaging mass spectrometry (IMS) have proven to be useful technologies for fingermark analysis. In these analyses, the choice of ionizing agent and its mode of deposition are critical steps for the identification of molecular markers. Here we propose two novel and complementary IMS approaches for endogenous and exogenous substance detection in fingermarks: sublimation of 2-mercaptobenzothiazol (2-MBT) matrix and silver sputtering.

  18. Study of Laser Produced Plasma of Limiter of the Aditya Tokomak for Detection of Molecular Bands

    NASA Astrophysics Data System (ADS)

    Rai, Awadhesh Kumar

    2016-06-01

    The tokamak wall protection is one of the prime concerns, and for this purpose, limiters are used. Graphite is commonly used as a limiter material and first wall material for complete coverage of the internal vacuum vessel surfaces of the tokamak. From the past few years, we are working to identify and quantify the impurities deposited on the different part of Aditya Tokamak in collaboration with the Scientists at Institute of Plasma Research, Ahmedabad, India using Laser Induced Breakdown Spectroscopy (LIBS) [1-3]. Laser induced breakdown spectroscopy (LIBS) spectra of limiter of Aditya Tokamak have been recorded in the spectral range of 200-900 nm in open atmosphere. Along with atomic and ionic spectral lines of the constituent elements of the limiter (1-3), LIBS spectra also give the molecular bands. When a high power laser beam is focused on the sample, laser induced plasma is produced on its surface. In early stage of the plasma Back ground continuum is dominated due to free-free or free-bound emission. Just after few nanoseconds the light from the plasma is dominated by ionic emission. Atomic emission spectra is dominated from the laser induced plasma during the first few microsecond after an ablation pulse where as molecular spectra is generated later when the plasma further cools down. For this purpose the LIBS spectra has been recorded with varying gate delay and gate width. The spectra of the limiter show the presence of molecular bands of CN and C2. To get better signal to background ratios of the molecular bands, different experimental parameters like gate delay, gate width, collection angle and collection point (spatial analysis off the plasama) of the plasma have been optimized. Thus the present paper deals with the variation of spectral intensity of the molecular bands with different experimental parameters. Keywords: Limiter, Molecular bands, C2, CN. References: 1. Proof-of-concept experiment for On-line LIBS Analysis of Impurity Layer Deposited on

  19. A novel paleo-bleaching proxy using boron isotopes and high-resolution laser ablation to reconstruct coral bleaching events

    NASA Astrophysics Data System (ADS)

    Dishon, G.; Fisch, J.; Horn, I.; Kaczmarek, K.; Bijma, J.; Gruber, D. F.; Nir, O.; Popovich, Y.; Tchernov, D.

    2015-10-01

    Coral reefs occupy only ~ 0.1 percent of the ocean's habitat, but are the most biologically diverse marine ecosystem. In recent decades, coral reefs have experienced a significant global decline due to a variety of causes, one of the major causes being widespread coral bleaching events. During bleaching, the coral expels its symbiotic algae, thereby losing its main source of nutrition generally obtained through photosynthesis. While recent coral bleaching events have been extensively investigated, there is no scientific data on historical coral bleaching prior to 1979. In this study, we employ high-resolution femtosecond Laser Ablation Multiple Collector Inductively Coupled Plasma Mass Spectrometry (LA-MC-ICP-MS) to demonstrate a distinct biologically induced decline of boron (B) isotopic composition (δ11B) as a result of coral bleaching. These findings and methodology offer a new use for a previously developed isotopic proxy to reconstruct paleo-coral bleaching events. Based on a literature review of published δ11B data and our recorded vital effect of coral bleaching on the δ11B signal, we also describe at least two possible coral bleaching events since the Last Glacial Maximum. The implementation of this bleaching proxy holds the potential of identifying occurrences of coral bleaching throughout the geological record. A deeper temporal view of coral bleaching will enable scientists to determine if it occurred in the past during times of environmental change and what outcome it may have had on coral population structure. Understanding the frequency of bleaching events is also critical for determining the relationship between natural and anthropogenic causes of these events.

  20. Pulsed diode laser-based monitor for singlet molecular oxygen

    PubMed Central

    Lee, Seonkyung; Zhu, Leyun; Minhaj, Ahmed M.; Hinds, Michael F.; Vu, Danthu H.; Rosen, David I.; Davis, Steven J.; Hasan, Tayyaba

    2010-01-01

    Photodynamic therapy (PDT) is a promising cancer treatment. PDT uses the affinity of photosensitizers to be selectively retained in malignant tumors. When tumors, pretreated with the photosensitizer, are irradiated with visible light, a photochemical reaction occurs and tumor cells are destroyed. Oxygen molecules in the metastable singlet delta state O2(1Δ) are believed to be the species that destroys cancerous cells during PDT. Monitoring singlet oxygen produced by PDT may lead to more precise and effective PDT treatments. Our approach uses a pulsed diode laser-based monitor with optical fibers and a fast data acquisition system to monitor singlet oxygen during PDT. We present results of in vitro singlet oxygen detection in solutions and in a rat prostate cancer cell line as well as PDT mechanism modeling. PMID:18601555

  1. Laser control of molecular excitations in stochastic dissipative media.

    PubMed

    Tremblay, Jean Christophe

    2011-05-07

    In the present work, ideas for controlling photochemical reactions in dissipative environments using shaped laser pulses are presented. New time-local control algorithms for the stochastic Schrödinger equation are introduced and compared to their reduced density matrix analog. The numerical schemes rely on time-dependent targets for guiding the reaction along a preferred path. The methods are tested on the vibrational control of adsorbates at metallic surfaces and on the ultrafast electron dynamics in a strong dissipative medium. The selective excitation of the specific states is achieved with improved yield when using the new algorithms. Both methods exhibit similar convergence behavior and results compare well with those obtained using local optimal control for the reduced density matrix. The favorable scaling of the methods allows to tackle larger systems and to control photochemical reactions in dissipative media of molecules with many more degrees of freedom.

  2. Demonstration of femtosecond laser ablation inductively coupled plasma mass spectrometry for uranium isotopic measurements in U-10Mo nuclear fuel foils

    SciTech Connect

    Havrilla, George Joseph; Gonzalez, Jhanis

    2015-06-10

    The use of femtosecond laser ablation inductively coupled plasma mass spectrometry was used to demonstrate the feasibility of measuring the isotopic ratio of uranium directly in U-10Mo fuel foils. The measurements were done on both the flat surface and cross sections of bare and Zr clad U-10Mo fuel foil samples. The results for the depleted uranium content measurements were less than 10% of the accepted U235/238 ratio of 0.0020. Sampling was demonstrated for line scans and elemental mapping over large areas. In addition to the U isotopic ratio measurement, the Zr thickness could be measured as well as trace elemental composition if required. A number of interesting features were observed during the feasibility measurements which could provide the basis for further investigation using this methodology. The results demonstrate the feasibility of using fs-LA-ICP-MS for measuring the U isotopic ratio in U-10Mo fuel foils.

  3. Magnesium Isotopes in the Earth, Moon, Mars, and Pallasite Parent Body: High-Precision Analysis of Olivine by Laser-Ablation Multi-Collector ICPMS

    NASA Technical Reports Server (NTRS)

    Norman, M.; McCulloch, M.; ONeill, H.; Brandon, A.

    2004-01-01

    Magnesium isotopes potentially offer new insights into a diverse range of processes including evaporation and condensation in the solar nebula, melting and metasomatism in planetary interiors, and hydrothermal alteration [1,2,3,4]. Volatility-related Mg isotopic variations of up to 10 per mil/amu relative to a terrestrial standard have been found in early nebular phases interpreted as evaporation residues [1], and relatively large variations (up to 3 per mil/amu) in the terrestrial mantle have been reported recently [4]. In order to investigate possible differences in the nebular history of material contributing to the terrestrial planets, and to search for evidence of a high-temperature origin of the Moon, we have measured the magnesium isotopic composition of primitive olivines from the Earth, Moon, Mars, and pallasite parent body using laser-ablation multicollector ICPMS.

  4. The effect of warming on grassland evapotranspiration partitioning using laser-based isotope monitoring techniques

    NASA Astrophysics Data System (ADS)

    Wang, Lixin; Niu, Shuli; Good, Stephen P.; Soderberg, Keir; McCabe, Matthew F.; Sherry, Rebecca A.; Luo, Yiqi; Zhou, Xuhui; Xia, Jianyang; Caylor, Kelly K.

    2013-06-01

    The proportion of transpiration (T) in total evapotranspiration (ET) is an important parameter that provides insight into the degree of biological influence on the hydrological cycles. Studies addressing the effects of climatic warming on the ecosystem total water balance are scarce, and measured warming effects on the T/ET ratio in field experiments have not been seen in the literature. In this study, we quantified T/ET ratios under ambient and warming treatments in a grassland ecosystem using a stable isotope approach. The measurements were made at a long-term grassland warming site in Oklahoma during the May-June peak growing season of 2011. Chamber-based methods were used to estimate the δ2H isotopic composition of evaporation (δE), transpiration (δT) and the aggregated evapotranspiration (δET). A modified commercial conifer leaf chamber was used for δT, a modified commercial soil chamber was used for δE and a custom built chamber was used for δET. The δE, δET and δT were quantified using both the Keeling plot approach and a mass balance method, with the Craig-Gordon model approach also used to calculate δE. Multiple methods demonstrated no significant difference between control and warming plots for both δET and δT. Though the chamber-based estimates and the Craig-Gordon results diverged by about 12‰, all methods showed that δE was more depleted in the warming plots. This decrease in δE indicates that the evaporation flux as a percentage of total water flux necessarily decreased for δET to remain constant, which was confirmed by field observations. The T/ET ratio in the control treatment was 0.65 or 0.77 and the ratio found in the warming treatment was 0.83 or 0.86, based on the chamber method and the Craig-Gordon approach. Sensitivity analysis of the Craig-Gordon model demonstrates that the warming-induced decrease in soil liquid water isotopic composition is the major factor responsible for the observed δE depletion and the temperature

  5. Molecular dynamics simulation of heat-affected zone of copper metal ablated with femtosecond laser

    NASA Astrophysics Data System (ADS)

    Hirayama, Yoichi; Obara, Minoru

    2005-03-01

    Femtosecond laser ablation of materials with high thermal conductivity is of paramount importance, because the chemical composition and properties of the area ablated with femtosecond laser are kept unchanged. The material processing by femtosecond laser can well control the heat-affected zone, compared to nanosecond laser ablation. We report on the heat-affected zone of crystalline copper (Cu) by use of femtosecond laser experimentally and theoretically. Laser ablation of Cu is investigated theoretically by two temperature model and molecular dynamics (MD) simulation. The MD simulation takes into account of electron temperature and thermal diffusion length calculated by two temperature model. The dependence of lattice temperature on time and depth is calculated by the MD simulation and two temperature model. The heat-affected zone estimated from the temperature is mainly studied and calculated to be 3 nm at 0.02 J/cm2 which is below the threshold fluence of 0.137 J/cm2. In addition, the thickness of heat-affected zone of copper crystal ablated with femtosecond Ti:sapphire laser is experimentally studied. As a result of X-ray diffraction (XRD) of the ablated surface, the surface crystallinity is partially changed into disordered structure from crystal form. The residual energy left in the metal, which is not used for ablation, will induce liquid phase, leading to the amorphous phase of the metal during resolidification. The thickness of heat-affected zone depends on laser fluence and is experimentally measured to be less than 1 μm at higher laser fluences than the ablation threshold.

  6. High-resolution continuous-flow analysis setup for water isotopic measurement from ice cores using laser spectroscopy

    NASA Astrophysics Data System (ADS)

    Emanuelsson, B. D.; Baisden, W. T.; Bertler, N. A. N.; Keller, E. D.; Gkinis, V.

    2015-07-01

    Here we present an experimental setup for water stable isotope (δ18O and δD) continuous-flow measurements and provide metrics defining the performance of the setup during a major ice core measurement campaign (Roosevelt Island Climate Evolution; RICE). We also use the metrics to compare alternate systems. Our setup is the first continuous-flow laser spectroscopy system that is using off-axis integrated cavity output spectroscopy (OA-ICOS; analyzer manufactured by Los Gatos Research, LGR) in combination with an evaporation unit to continuously analyze water samples from an ice core. A Water Vapor Isotope Standard Source (WVISS) calibration unit, manufactured by LGR, was modified to (1) enable measurements on several water standards, (2) increase the temporal resolution by reducing the response time and (3) reduce the influence from memory effects. While this setup was designed for the continuous-flow analysis (CFA) of ice cores, it can also continuously analyze other liquid or vapor sources. The custom setups provide a shorter response time (~ 54 and 18 s for 2013 and 2014 setup, respectively) compared to the original WVISS unit (~ 62 s), which is an improvement in measurement resolution. Another improvement compared to the original WVISS is that the custom setups have a reduced memory effect. Stability tests comparing the custom and WVISS setups were performed and Allan deviations (σAllan) were calculated to determine precision at different averaging times. For the custom 2013 setup the precision after integration times of 103 s is 0.060 and 0.070 ‰ for δ18O and δD, respectively. The corresponding σAllan values for the custom 2014 setup are 0.030, 0.060 and 0.043 ‰ for δ18O, δD and δ17O, respectively. For the WVISS setup the precision is 0.035, 0.070 and 0.042 ‰ after 103 s for δ18O, δD and δ17O, respectively. Both the custom setups and WVISS setup are influenced by instrumental drift with δ18O being more drift sensitive than δD. The

  7. Tracking isotopic signatures of CO2 at the high altitude site Jungfraujoch with laser spectroscopy: analytical improvements and representative results

    NASA Astrophysics Data System (ADS)

    Sturm, P.; Tuzson, B.; Henne, S.; Emmenegger, L.

    2013-07-01

    We present the continuous data record of atmospheric CO2 isotopes measured by laser absorption spectroscopy for an almost four year period at the High Altitude Research Station Jungfraujoch (3580 m a.s.l.), Switzerland. The mean annual cycles derived from data of December 2008 to September 2012 exhibit peak-to-peak amplitudes of 11.0 μmol mol-1 for CO2, 0.60‰ for δ13C and 0.81‰ for δ18O. The high temporal resolution of the measurements also allow us to capture variations on hourly and diurnal timescales. For CO2 the mean diurnal peak-to-peak amplitude is about 1 μmol mol-1 in spring, autumn and winter and about 2 μmol mol-1 in summer. The mean diurnal variability in the isotope ratios is largest during the summer months too, with an amplitude of about 0.1‰ both in the δ13C and δ18O, and a smaller or no discernible diurnal cycle during the other seasons. The day-to-day variability, however, is much larger and depends on the origin of the air masses arriving at Jungfraujoch. Backward Lagrangian particle dispersion model simulations revealed a close link between air composition and prevailing transport regimes and could be used to explain part of the observed variability in terms of transport history and influence region. A footprint clustering showed significantly different wintertime CO2, δ13C and δ18O values depending on the origin and surface residence times of the air masses. Several major updates on the instrument and the calibration procedures were performed in order to further improve the data quality. We describe the new measurement and calibration setup in detail and demonstrate the enhanced performance of the analyzer. A measurement precision of about 0.02‰ for both isotope ratios has been obtained for an averaging time of 10 min, while the accuracy was estimated to be 0.1‰, including the uncertainty of the calibration gases.

  8. Tunable Diode Laser Measurements of Leaf-scale Carbon Isotope Discrimination and Ecosystem Respired Carbon and Oxygen Isotope Ratios in a Semi-arid Woodland

    NASA Astrophysics Data System (ADS)

    McDowell, N.; Chris, B.; Hanson, D.; Kern, S.; Meyer, C.; Pockman, W.; Powers, H.

    2005-12-01

    We present results and speculative interpretation of leaf-level carbon isotope discrimination and ecosystem respired carbon and oxygen isotope ratios from a semi-arid, C3/C4 woodland located in northern New Mexico, USA. Overstory leaf area index (LAI) is dominated by live juniper (Juniperus monosperma) trees with an LAI value of approximately 1.0 m2 per m2 ground area, and has a seasonally dynamic understory of mixed C3 forbs and C4 grasses and cacti, with a maximum LAI of 0.30 m2 per m2 ground area. Ecosystem respired carbon isotope ratios showed values characteristic of C3 dominated photosynthesis (Keeling plot intercepts of -35 to -22 per mil). Seasonal variation was typical of that found in wetter, C3 dominated forests, as was the dependence on climate (e.g. relationships with vapor pressure deficit, soil water content, and canopy conductance). Leaf-level carbon isotope discrimination of the junipers, measured by coupling a Li-Cor 6400 photosynthesis system to the TDL, provided discrimination-Ci and discrimination-vpd relationships consistent with measured ecosystem respired carbon isotope ratios. The oxygen isotope ratio of ecosystem respiration was dependent on rain water isotope composition, but was correlated with soil water content during rain-free periods. The cumulative effect of vapor pressure deficit after a rain event was tightly correlated with the oxygen isotope ratio of ecosystem respiration, suggesting the primary drivers are evaporative enrichment of soil water and perhaps nocturnal leaf enrichment. Instrument precision for carbon and oxygen isotope ratios of carbon dioxide is 0.06 to 0.18 per mil; however, overall precision is somewhat lower due to pressure and sampling effects.

  9. A rapid isotope ratio analysis protocol for nuclear solid materials using nano-second laser-ablation time-of-flight ICP-MS.

    PubMed

    Bürger, S; Riciputi, L R

    2009-11-01

    The analysis of the isotopic composition of nuclear or non-nuclear solid materials is performed in a variety of fields, e.g., for quality assurance in the production of nuclear fuels, as signatures in forensics, nuclear safeguards, and non-proliferation control, in material characterization, geology, and archeology. We have investigated the capability of laser ablation (New Wave Research, 213 nm) coupled to time-of-flight (TOF) ICP-MS (GBC OptiMass 8000) as a rapid analytical protocol for multi-isotope screening of nuclear and non-nuclear solid samples. This includes natural and non-natural isotopic compositions for elements including Cu, Zr, Mo, Cd, In, Ba, Ta, W, Re, Pt, Pb, and U, in pure metals, alloys, and glasses. Without correcting for mass bias (mass fractionation), an overall precision and accuracy of about 4% (1 sigma) can be achieved by minimizing the deposited laser power and thus fractionation (mass removal based on thermal properties). The precision and accuracy in combination with literally no or minimized sample preparation enables a rapid isotope screening of solid samples that is of particular interest to support nuclear forensic and safeguard analysis.

  10. An Assessment of Molecular Dynamic Force Fields for Silica for Use in Simulating Laser Damage Mitigation

    SciTech Connect

    Soules, T F; Gilmer, G H; Matthews, M J; Stolken, J S; Feit, M D

    2010-10-21

    We compare force fields (FF's) that have been used in molecular dynamic (MD) simulations of silica in order to assess their applicability for use in simulating IR-laser damage mitigation. Although pairwise FF?s obtained by fitting quantum mechanical calculations such as the BKS and CHIK potentials have been shown to reproduce many of the properties of silica including the stability of silica polymorphs and the densification of the liquid, we show that melting temperatures and fictive temperatures are much too high. Softer empirical force fields give liquid and glass properties at experimental temperatures but may not predict all properties important to laser mitigation experiments.

  11. Parallel implementation of three-dimensional molecular dynamic simulation for laser-cluster interaction

    SciTech Connect

    Holkundkar, Amol R.

    2013-11-15

    The objective of this article is to report the parallel implementation of the 3D molecular dynamic simulation code for laser-cluster interactions. The benchmarking of the code has been done by comparing the simulation results with some of the experiments reported in the literature. Scaling laws for the computational time is established by varying the number of processor cores and number of macroparticles used. The capabilities of the code are highlighted by implementing various diagnostic tools. To study the dynamics of the laser-cluster interactions, the executable version of the code is available from the author.

  12. Molecular collision processes in the presence of picosecond laser pulses

    NASA Technical Reports Server (NTRS)

    Lee, H. W.; George, T. F.

    1979-01-01

    Radiative transitions in molecular collision processes taking place in the presence of picosecond pulses are studied within a semiclassical formalism. An expression for adiabatic potential surfaces in the electronic-field representation is obtained, which directly leads to the evaluation of transition probabilities. Calculations with a Landau-Zener-type model indicate that picosecond pulses can be much more effective in inducing transitions than a single long pulse of the same intensity and the same total energy, if the intensity is sufficiently high that the perturbation treatment is not valid.

  13. Formation and fragmentation of quadruply charged molecular ions by intense femtosecond laser pulses.

    PubMed

    Yatsuhashi, Tomoyuki; Nakashima, Nobuaki

    2010-07-22

    We investigated the formation and fragmentation of multiply charged molecular ions of several aromatic molecules by intense nonresonant femtosecond laser pulses of 1.4 mum with a 130 fs pulse duration (up to 2 x 10(14) W cm(-2)). Quadruply charged states were produced for 2,3-benzofluorene and triphenylene molecular ion in large abundance, whereas naphthalene and 1,1'-binaphthyl resulted only in up to triply charged molecular ions. The laser wavelength was nonresonant with regard to the electronic transitions of the neutral molecules, and the degree of fragmentation was strongly correlated with the absorption of the singly charged cation radical. Little fragmentation was observed for naphthalene (off-resonant with cation), whereas heavy fragmentation was observed in the case of 1,1'-binaphthyl (resonant with cation). The degree of H(2) (2H) and 2H(2) (4H) elimination from molecular ions increased as the charge states increased in all the molecules examined. A striking difference was found between triply and quadruply charged 2,3-benzofluorene: significant suppression of molecular ions with loss of odd number of hydrogen was observed in the quadruply charged ions. The Coulomb explosion of protons in the quadruply charged state and succeeding fragmentation resulted in the formation of triply charged molecular ions with an odd number of hydrogens. The hydrogen elimination mechanism in the highly charged state is discussed.

  14. Mechanistic investigations and molecular medicine applications of gold nanoparticle mediated (GNOME) laser transfection

    NASA Astrophysics Data System (ADS)

    Schomaker, M.; Heinemann, D.; Kalies, S.; Willenbrock, S.; Murua Escobar, H.; Buch, A.; Sodeik, B.; Ripken, T.; Meyer, H.

    2014-03-01

    Alternative high throughput transfection methods are required to understand the molecular network of the cell, which is linked to the evaluation of target genes as therapeutic agents. Besides diagnostic purposes, the transfection of primary- and stem cells is of high interest for therapeutic use. Here, the cell release of trans- or exogene proteins is used to develop immune cancer therapies. The basic requirement to accomplish manipulation of cells is an efficient and gentle transfection method. Therefore, we developed an automatized cell manipulation platform providing high throughput by using GNOME laser transfection. Herein, the interaction of moderately focused laser pulses with gold nanoparticles in close vicinity to the cell membrane mediate transient membrane permeabilization. The exact nature of the involved permeabilization effects depends on the applied particles and laser parameters. Hereinafter, we describe investigations considering the parameter regime, the permeabilization mechanism and the safety profile of GNOME laser transfection. The experimental and calculated results imply a combined permeabilization mechanism consisting of both photochemical and photothermal effects. Furthermore, paramount spatial control achieved either by laser illumination with micrometer precision or targeted gold nanoparticle binding to the cells was demonstrated, allowing selective cell manipulation and destruction. Additionally, the possibility to manipulate difficult to transfect primary cells (neurons) is shown. These results give insights in the basic mechanisms involved in GNOME laser transfection and serve as a strong basis to deliver different molecules for therapeutic (e.g. proteins) and diagnostic (siRNA) use.

  15. An Investigation Into the Molecular and Isotopic Composition of Diatom Frustule-Bound Organic Matter: Method Development for New Proxies

    NASA Astrophysics Data System (ADS)

    Bridoux, M. C.; Ingalls, A. E.

    2009-12-01

    Diatoms are single cell phytoplankton that are ubiquitous in marine ecosystems and are responsible for up to 40% of the carbon fixed annually in the ocean. Their intricately nanopatterned siliceous frustules are formed under the control of template organic molecules, some of which are incorporated into the frustule during growth. Several diatom frustule-based paleoproxies have been developed to exploit these microfossils because they are from a known phytoplankton source that is relatively unaltered from diagenesis. Among these proxies, diatom frustule-bound organic matter (OM) is recognized as a potentially important material for use in paleoreconstructions of past productivity (13C/12C), nutrient utilization (15N/14N) as well as to determine the radiocarbon age of sedimentary frustules (Δ14C). Despite numerous advances, diatom frustule-bound OM remains poorly characterized. Here we focus on the chemical characterization of diatom frustule-bound OM with the goal of developing molecular and compound-specific isotope methods to better reconstruct the past environments of diatom rich regions such as the Southern Ocean and the North Pacific. To do this, we 1) chemically cleaned diatom frustules, 2) dissolve them in HF to release organic compounds embedded in the frustules and 3) unambiguously characterized this organic matter by ion pairing reversed phase liquid chromatography coupled to diode array, electrospray ionization - ion trap mass spectrometry (ESI/IT-MSn) and accurate mass quadrupole time of flight mass spectrometry (Q-TOF). These analyses reveal the presence of low molecular weight, UV light absorbing compounds called mycosporine-like amino acids (MAAs) and a series of long chain polyamines (LCPAs) consisting of N-methylated derivatives of polypropyleneimine units attached to putrescine. LCPAs are known to direct silicification, while MAAs are thought to provide sunscreen to many marine organisms. The presence of these specific biomarkers in sediment

  16. Spectral condensation near molecular transitions in intracavity laser spectroscopy with vertical external cavity surface emitting lasers

    NASA Astrophysics Data System (ADS)

    Bertseva, Elena; Campargue, Alain

    2004-03-01

    Vertical external cavity surface emitting lasers (VeCSELs) are ideal amplification media for intracavity laser absorption spectroscopy (ICLAS) around 1 μm. However, we noted that, in some spectra recorded by ICLAS-VeCSEL, the observed line profiles of very weak overtone transitions were clearly asymmetric, this distortion being more pronounced for the strongest lines. More spectacular effects were observed when we investigated the acetylene spectrum: while the weakest absorption lines appeared as dips superimposed on the baseline as usual in ICLAS, the strongest lines mostly disappeared and were replaced by emission lines slightly blue shifted from the absorption line center. This effect, called "spectral condensation", was, in fact, discovered near atomic transitions, more than 30 years ago, using pulsed lasers. Using acetylene and water as absorbers, we have systematically studied the different factors of importance for spectral condensation and showed that it increases with the pumping rate, the generation time and the line intensity. Spectral condensation was also found to increase with the pressure of the intracavity gas sample up to a value of a few Torrs, and to decrease afterwards. The appearance of spectral condensation has been shown to be highly correlated to time oscillations of the total laser power. Of importance for intensity measurements, this systematic study has showed that condensation effects may appear for long generation times even at low pumping rate and even with extremely weak absorption lines. A discussion of the results in relation with different interpretations available in the literature is presented with a particular emphasis on the theory based on the coherent interaction of electro-magnetic field with optically dense resonant extended medium leading to a parametrical amplification without population inversion.

  17. Molecularly imprinted polymers for the pre-concentration of polar organic micropollutants for compound-specific isotope analysis

    NASA Astrophysics Data System (ADS)

    Bakkour, Rani; Hofstetter, Thomas B.

    2014-05-01

    Compound-specific isotope analysis (CSIA) is a promising tool for assessing transformations of polar organic micropollutants such as pesticides, pharmaceuticals and consumer chemicals in aquatic systems. There are, however, two major challenges: (1) Polar organic micropollutants occur at very low levels and, as a consequence, large amounts of water are required to achieve analyte enrichment with factors of 50'000 and more, inevitably leading to large interferences from the aqueous matrix. (2) The polarity of these micropollutants impedes the use of typical non-polar sorbates for solid-phase enrichment. In view of these challenges, the use of molecularly imprinted polymers (MIP) is a promising approach to produce tailor-made materials for highly selective enrichment of polar organic micropollutants with reduced matrix interferences. In this work, we explore the use of MIP to selectively enrich benzotriazoles, an important class of polar aquatic micropollutants. Polymers were synthesized in the presence of 5,6-dimethyl-1H-benzotriazole as a template, which leaves cavities in the polymer matrix with a very high affinity to the template and closely related structures including our main target analyte, 1H-benzotrizole. After extraction of the template, specific recognition of substituted benzotriazoles is expected by the synthesized MIPs. As the MIP has no specific affinity to the matrix, there is also expected to be negligible enrichment of the matrix. Retention factors of the MIP are compared for different synthetic procedures and to non-imprinted polymers where no specific intermolecular interactions with benzotriazoles are expected. Optimum performance of the MIP is demonstrated in this study in terms of the selectivity of enrichment, recoveries of analytes and the goodness of carbon and nitrogen isotope ratios measured by gas chromatography isotopic ratio mass spectrometry (GC/IRMS). This approach will enable us to enrich large amounts of aqueous samples while

  18. Trace Isotope Detection Enhanced by Coherent Elimination of Power Broadening

    SciTech Connect

    Conde, Alvaro Peralta; Brandt, Lukas; Halfmann, Thomas

    2006-12-15

    The selectivity and spectral resolution of traditional laser-based trace isotope analysis, i.e., resonance ionization mass spectrometry (RIMS), is limited by power broadening of the radiative transition. We use the fact that power broadening does not occur in coherently driven quantum systems when the probing and excitation processes are temporally separated to demonstrate significant improvement of trace element detection, even under conditions of strong signals. Specifically, we apply a coherent variant of RIMS to the detection of traces of molecular nitric oxide (NO) isobars. For large laser intensities, the detected isotope signal can be increased by almost 1 order of magnitude without any loss in spectral resolution.

  19. Trace isotope detection enhanced by coherent elimination of power broadening.

    PubMed

    Conde, Alvaro Peralta; Brandt, Lukas; Halfmann, Thomas

    2006-12-15

    The selectivity and spectral resolution of traditional laser-based trace isotope analysis, i.e., resonance ionization mass spectrometry (RIMS), is limited by power broadening of the radiative transition. We use the fact that power broadening does not occur in coherently driven quantum systems when the probing and excitation processes are temporally separated to demonstrate significant improvement of trace element detection, even under conditions of strong signals. Specifically, we apply a coherent variant of RIMS to the detection of traces of molecular nitric oxide (NO) isobars. For large laser intensities, the detected isotope signal can be increased by almost 1 order of magnitude without any loss in spectral resolution.

  20. Characterization of cocoa butter and cocoa butter equivalents by bulk and molecular carbon isotope analyses: implications for vegetable fat quantification in chocolate.

    PubMed

    Spangenberg, J E; Dionisi, F

    2001-09-01

    The fatty acids from cocoa butters of different origins, varieties, and suppliers and a number of cocoa butter equivalents (Illexao 30-61, Illexao 30-71, Illexao 30-96, Choclin, Coberine, Chocosine-Illipé, Chocosine-Shea, Shokao, Akomax, Akonord, and Ertina) were investigated by bulk stable carbon isotope analysis and compound specific isotope analysis. The interpretation is based on principal component analysis combining the fatty acid concentrations and the bulk and molecular isotopic data. The scatterplot of the two first principal components allowed detection of the addition of vegetable fats to cocoa butters. Enrichment in heavy carbon isotope ((13)C) of the bulk cocoa butter and of the individual fatty acids is related to mixing with other vegetable fats and possibly to thermally or oxidatively induced degradation during processing (e.g., drying and roasting of the cocoa beans or deodorization of the pressed fat) or storage. The feasibility of the analytical approach for authenticity assessment is discussed.

  1. Water isotope ratio (δ2H and δ18O) measurements in atmospheric moisture using an optical feedback cavity enhanced absorption laser spectrometer

    NASA Astrophysics Data System (ADS)

    Iannone, Rosario Q.; Romanini, Daniele; Cattani, Olivier; Meijer, Harro A. J.; Kerstel, Erik R. Th.

    2010-05-01

    Water vapor isotopes represent an innovative and excellent tool for understanding complex mechanisms in the atmospheric water cycle over different time scales, and they can be used for a variety of applications in the fields of paleoclimatology, hydrology, oceanography, and ecology. We use an ultrasensitive near-infrared spectrometer, originally designed for use on airborne platforms in the upper troposphere and lower stratosphere, to measure the water deuterium and oxygen-18 isotope ratios in situ, in ground-level tropospheric moisture, with a high temporal resolution (from 300 s down to less than 1 s). We present some examples of continuous monitoring of near-surface atmospheric moisture, demonstrating that our infrared laser spectrometer could be used successfully to record high-concentration atmospheric water vapor mixing ratios in continuous time series, with a data coverage of ˜90%, interrupted only for daily calibration to two isotope ratio mass spectrometry-calibrated local water standards. The atmospheric data show that the water vapor isotopic composition exhibits a high variability that can be related to weather conditions, especially to changes in relative humidity. Besides, the results suggest that observed spatial and temporal variations of the stable isotope content of atmospheric water vapor are strongly related to water vapor transport in the atmosphere.

  2. Time-Resolved Studies of Molecular Dynamics Using - and Femto-Second Laser Pulses

    NASA Astrophysics Data System (ADS)

    Deliwala, Shrenik Mahendra

    1995-01-01

    This thesis presents the results of two experiments that measure the evolution of laser excited molecules. The experiment performed with 0.1-ps laser pulses elucidates the dynamics of desorption of O_2 and formation of CO_2 on a platinum surface. The experiment performed with nanosecond time resolution reveals the inter- and intra-molecular vibrational dynamics of infrared laser pumped molecules. Desorption of O_2 and formation of CO_2 were induced with subpicosecond laser pulses on a Pt(111) surface dosed with coadsorbed O_2 and CO. Fluence dependent yields obtained over a range of laser wavelengths from 267 to 800 nm, and pulse durations from 80 fs to 3.6 ps are presented. We observe a dependence of the nonlinear desorption yield on wavelength. Two-pulse correlation measurements show two different time-scales relevant to the desorption. The results show that nonthermal electrons play a role in the surface chemistry, and that an equilibrated pre-heating of the surface modes leads to enhanced desorption. In the second set of experiments reported in this thesis, time-resolved coherent anti-Stokes Raman spectroscopy was used to obtain the rovibrational energy distributions in polyatomic molecules following infrared multiphoton excitation. In addition to presenting new results on SF _6, we review previously obtained data on SO_2 and OCS. The data yield new details about infrared multiphoton excitation and intramolecular vibrational energy relaxation. In particular they show the significance of collisions in redistributing vibrational energy following excitation. The results also clearly show stronger inter-mode coupling and higher excitation in systems with increasing numbers of atoms per molecule. In addition, a detailed description is provided of the Ti:Sapphire based ultrashort pulsed amplified laser system. Both, the principles and the design of the laser system are discussed to serve as a manual for the femtosecond laser system constructed for the study of

  3. Rapid and sensitive quantification of isotopic mixtures using a rapidly-swept external cavity quantum cascade laser

    DOE PAGES

    Brumfield, Brian E.; Taubman, Matthew S.; Phillips, Mark C.

    2016-05-23

    A rapidly-swept external-cavity quantum cascade laser with an open-path Herriott cell is used to quantify gas-phase chemical mixtures of D2O and HDO at a rate of 40 Hz (25-ms measurement time). The chemical mixtures were generated by evaporating D2O liquid near the open-path Herriott cell, allowing the H/D exchange reaction with ambient H2O to produce HDO. Fluctuations in the ratio of D2O and HDO on timescales of <1 s due to the combined effects of plume transport and the H/D exchange chemical reaction are observed. Noise-equivalent concentrations (1σ) (NEC) of 147.0 ppbv and 151.6 ppbv in a 25-ms measurement timemore » are determined for D2O and HDO, respectively, with a 127-m optical path. These NECs are improved to 23.0 and 24.0 ppbv with a 1-s averaging time for D2O and HDO, respectively. NECs <200 ppbv are also estimated for N2O, 1,1,1,2–tetrafluoroethane (F134A), CH4, acetone and SO2 for a 25-ms measurement time. Finally, the isotopic precision for measurement of the [D2O]/[HDO] concentration ratio of 33‰ and 5‰ is calculated for the current experimental conditions for measurement times of 25 ms and 1 s, respectively.« less

  4. Origins of natural gases from marine strata in Northeastern Sichuan Basin (China) from carbon molecular moieties and isotopic data

    NASA Astrophysics Data System (ADS)

    Wang, Yunpeng; Zhao, Changyi; Wang, Hongjun; Wang, Zhaoyun; Wang, Zecheng

    2013-03-01

    To determine the origin, maturity, formation mechanism and secondary process of marine natural gases in Northeastern Sichuan area, molecular moieties and carbon isotopic data of the Carboniferous and Triassic gases have been analyzed. Typical samples of marine gas precursors including low-maturity kerogen, dispersed liquid hydrocarbons (DLHs) in source rocks, residual kerogen and oil have been examined in a closed system, and several published geochemical diagrams of gas origins have been calibrated by using laboratory data. Results show that both Carboniferous and Triassic gases in the study area have a thermogenic origin. Migration leads to stronger compositional and weak isotopic fractionation, and is path dependent. Carboniferous gases and low-H2S gases are mainly formed by secondary cracking of oil, whereas high-H2S gases are clearly related to the TSR (Thermal Sulfate Reduction) process. Gases in NE Sichuan show a mixture of heavy (13C-enriched) methane in comparison to the lower maturated ethane of Triassic gas samples, suggesting a similar source and maturity for ethane and propane of Carboniferous gases, and a mixture of heavy ethane to the propane for Triassic gases. Based on the data plotted in the diagram of Chung et al. (1988), the residual kerogen from Silurian marine shale and palaeo oil reservoirs are the main source for Carboniferous gases, and that the residual kerogen from Silurian and Permian marine rocks and Permian paleao oil reservoirs constitute the principal source of Triassic gases.

  5. Deciphering formation processes of banded iron formations from the Transvaal and the Hamersley successions by combined Si and Fe isotope analysis using UV femtosecond laser ablation

    NASA Astrophysics Data System (ADS)

    Steinhoefel, Grit; von Blanckenburg, Friedhelm; Horn, Ingo; Konhauser, Kurt O.; Beukes, Nicolas J.; Gutzmer, Jens

    2010-05-01

    To investigate the genesis of BIFs, we have determined the Fe and Si isotope composition of coexisting mineral phases in samples from the ˜2.5 billion year old Kuruman Iron Formation (Transvaal Supergroup, South Africa) and Dales Gorges Member of the Brockman Iron Formation (Hamersley Group, Australia) by UV femtosecond laser ablation coupled to a MC-ICP-MS. Chert yields a total range of δ 30Si between -1.3‰ and -0.8‰, but the Si isotope compositions are uniform in each core section examined. This uniformity suggests that Si precipitated from well-mixed seawater far removed from its sources such as hydrothermal vents or continental drainage. The Fe isotope composition of Fe-bearing mineral phases is much more heterogeneous compared to Si with δ 56Fe values of -2.2‰ to 0‰. This heterogeneity is likely due to variable degrees of partial Fe(II) oxidation in surface waters, precipitation of different mineral phases and post-depositional Fe redistribution. Magnetite exhibits negative δ 56Fe values, which can be attributed to a variety of diagenetic pathways: the light Fe isotope composition was inherited from the Fe(III) precursor, heavy Fe(II) was lost by abiotic reduction of the Fe(III) precursor or light Fe(II) was gained from external fluids. Micrometer-scale heterogeneities of δ 56Fe in Fe oxides are attributed to variable degrees of Fe(II) oxidation or to isotope exchange upon Fe(II) adsorption within the water column and to Fe redistribution during diagenesis. Diagenetic Fe(III) reduction caused by oxidation of organic matter and Fe redistribution is supported by the C isotope composition of a carbonate-rich sample containing primary siderite. These carbonates yield δ 13C values of ˜-10‰, which hints at a mixed carbon source in the seawater of both organic and inorganic carbon. The ancient seawater composition is estimated to have a minimum range in δ 56Fe of -0.8‰ to 0‰, assuming that hematite and siderite have preserved their primary Fe

  6. Infrared Lasers in Chemistry.

    ERIC Educational Resources Information Center

    John, Phillip

    1982-01-01

    Selected infrared laser chemistry topics are discussed including carbon dioxide lasers, infrared quanta and molecules, laser-induced chemistry, structural isomerization (laser purification, sensitized reactions, and dielectric breakdown), and fundamental principles of laser isotope separation, focusing on uranium isotope separation. (JN)

  7. Kinetic isotope effect for H2 and D2 quantum molecular sieving in adsorption/desorption on porous carbon materials.

    PubMed

    Zhao, Xuebo; Villar-Rodil, Silvia; Fletcher, Ashleigh J; Thomas, K Mark

    2006-05-25

    Adsorption and desorption of H(2) and D(2) from porous carbon materials, such as activated carbon at 77 K, are usually fully reversible with very rapid adsorption/desorption kinetics. The adsorption and desorption of H(2) and D(2) at 77 K on a carbon molecular sieve (Takeda 3A), where the kinetic selectivity was incorporated by carbon deposition, and a carbon, where the pore structure was modified by thermal annealing to give similar pore structure characteristics to the carbon molecular sieve substrate, were studied. The D(2) adsorption and desorption kinetics were significantly faster (up to x1.9) than the corresponding H(2) kinetics for specific pressure increments/decrements. This represents the first experimental observation of kinetic isotope quantum molecular sieving in porous materials due to the larger zero-point energy for the lighter H(2), resulting in slower adsorption/desorption kinetics compared with the heavier D(2). The results are discussed in terms of the adsorption mechanism.

  8. Activation of molecular oxygen by infrared laser radiation in pigment-free aerobic systems.

    PubMed

    Krasnovsky, A A; Drozdova, N N; Ivanov, A V; Ambartsumian, R V

    2003-09-01

    With the goal of mimicking the mechanisms of the biological effects of low energy laser irradiation, we have shown that infrared low intensity laser radiation causes oxygenation of the chemical traps of singlet oxygen dissolved in organic media and water saturated by air at normal atmospheric pressure. The photooxygenation rate was directly proportional to the oxygen concentration and strongly inhibited by the singlet oxygen quenchers. The maximum of the photooxygenation action spectrum coincided with the maximum of the oxygen absorption band at 1270 nm. The data provide unambiguous evidence that photooxygenation is determined by the reactive singlet (1)Delta(g )state formed as a result of direct laser excitation of molecular oxygen. Hence, activation of oxygen caused by its direct photoexcitation may occur in natural systems.

  9. Shock wave mediated plume chemistry for molecular formation in laser ablation plasmas

    SciTech Connect

    Harilal, Sivanandan S.; Brumfield, Brian E.; Cannon, Bret D.; Phillips, Mark C.

    2016-02-16

    Laser ablation is used in a variety of applications albeit formation mechanisms of molecules and nanoclusters are not well understood. We investigated the formation mechanisms of AlO molecules during complex interactions between an Al laser plume expanding into ambient air at atmospheric pressure levels. To produce the plasma a high-purity Al target was ablated using 1064 nm, 6 ns laser pulses. Our results show that the plasma chemistry leading to the formation of AlO is mediated by shock waves. During the early times of plasma expansion, the generated shock waves at the plume edges act as a barrier for the combustion process and the molecular formation is prevalent after the shockwave collapse. The temporally and spatially resolved contour mapping of Al and AlO highlight the formation routes and persistence of species in the plasma and its relation to plume hydrodynamics.

  10. Temperature and isotope effects on water cluster ions with path integral molecular dynamics based on the fourth order Trotter expansion

    NASA Astrophysics Data System (ADS)

    Suzuki, Kimichi; Shiga, Motoyuki; Tachikawa, Masanori

    2008-10-01

    Path integral molecular dynamics simulation based on the fourth order Trotter expansion has been performed to elucidate the geometrical isotope effect of water dimer anions, H3O2-, D3O2-, and T3O2-, at different temperatures from 50 to 600 K. At low temperatures below 200 K the hydrogen-bonded hydrogen nucleus is near the center of two oxygen atoms with mostly O⋯X⋯O geometry (where X =H, D, or T), while at high temperatures above 400 K, hydrogen becomes more delocalized, showing the coexistence between O⋯X-O and O-X⋯O. The OO distance tends to be shorter as the isotopomer is heavier at low temperatures, while this ordering becomes opposite at high temperatures. It is concluded that the coupling between the OO stretching mode and proton transfer modes is a key to understand such a temperature dependence of a hydrogen-bonded structure.

  11. Mechanisms of two-color laser-induced field-free molecular orientation.

    PubMed

    Spanner, Michael; Patchkovskii, Serguei; Frumker, Eugene; Corkum, Paul

    2012-09-14

    Two mechanisms of two-color (ω+2ω) laser-induced field-free molecular orientation, based on the hyperpolarizability and ionization depletion, are explored and compared. The CO molecule is used as a computational example. While the hyperpolarizability mechanism generates small amounts of orientation at intensities below the ionization threshold, ionization depletion quickly becomes the dominant mechanism as soon as ionizing intensities are reached. Only the ionization mechanism leads to substantial orientation (e.g., on the order of ≳0.1). For intensities typical of laser-induced molecular alignment and orientation experiments, the two mechanisms lead to robust, characteristic timings of the field-free orientation wave-packet revivals relative to the alignment revivals and the revival time. The revival timings can be used to detect the active orientation mechanism experimentally.

  12. Generation of circularly polarized attosecond pulses by intense ultrashort laser pulses from extended asymmetric molecular ions

    SciTech Connect

    Yuan, Kai-Jun; Bandrauk, Andre D.

    2011-08-15

    We present a method for generation of single circularly polarized attosecond pulses in extended asymmetric HHe{sup 2+} molecular ions. By employing an intense ultrashort circularly polarized laser pulse with intensity 4.0x10{sup 14} W/cm{sup 2}, wavelength 400 nm, and duration 10 optical cycles, molecular high-order-harmonic generation (MHOHG) spectra with multiple plateaus exhibit characters of circular polarization. Using a classical laser-induced collision model, double collisions of continuum electrons first with neighboring ions and then second with parent ions are presented at a particular internuclear distance and confirmed from numerical solutions of a time-dependent Schroedinger equation. We analyze the MHOHG spectra with a Gabor time window and find that, due to the asymmetry of HHe{sup 2+}, a single collision trajectory of continuum electrons with ions can produce circularly polarized harmonics, leading to single circularly polarized attosecond pulses for specific internuclear distances.

  13. Understanding molecular harmonic emission at relatively long intense laser pulses: Beyond the Born-Oppenheimer approximation

    NASA Astrophysics Data System (ADS)

    Ahmadi, H.; Vafaee, M.; Maghari, A.

    2016-09-01

    The underlying physics behind the molecular harmonic emission in relatively long sin 2-like laser pulses is investigated. We numerically solved the full-dimensional electronic time-dependent Schrödinger equation beyond the Born-Oppenheimer approximation for simple molecular ion H2+ . The occurrence and the effect of electron localization, nonadiabatic redshift, and spatially asymmetric emission are evaluated to understand better complex patterns appearing in the high-order harmonic generation (HHG) spectrum. Results show that the complex patterns in the HHG spectrum originate mainly from a nonadiabatic response of the molecule to the rapidly changing laser field and also from a spatially asymmetric emission along the polarization direction. The effect of electron localization on the HHG spectrum was not observed as opposed to what is reported in the literature.

  14. High degree of molecular orientation by a combination of THz and femtosecond laser pulses

    SciTech Connect

    Kitano, Kenta; Ishii, Nobuhisa; Itatani, Jiro

    2011-11-15

    We propose a method for achieving molecular orientation by two-step excitation with intense femtosecond laser and terahertz (THz) pulses. First, the femtosecond laser pulse induces off-resonant impulsive Raman excitation to create rotational wave packets. Next, a delayed intense THz pulse effectively induces resonant dipole transition between neighboring rotational states. By controlling the intensities of both the pulses and the time delay, we can create rotational wave packets consisting of states with different parities in order to achieve a high degree of molecular orientation under a field-free condition. We numerically demonstrate that the highest degree of orientation of >0.8 in HBr molecules is feasible under experimentally available conditions.

  15. Temporal molecular and isotopic analysis of active bacterial communities in two New Zealand sponges.

    PubMed

    Simister, Rachel; Taylor, Michael W; Rogers, Karyne M; Schupp, Peter J; Deines, Peter

    2013-07-01

    The characterization of changes in microbial communities is an essential step towards a better understanding of host-microbe associations. It is well established that sponges (phylum Porifera) harbour a diverse and abundant microbial community, but it is not known whether these microbial communities change over time. Here, we followed two sponge species (Ancorina alata and Tethya stolonifera) over a 2-year sampling period using RNA (16S rRNA)-based amplicon pyrosequencing and bulk stable isotope analysis (δ(13) C and δ(15)N). A total of 4468 unique operational taxonomic units (OTUs) was identified, which were affiliated with 26 bacterial phyla. Bacterial communities of both sponge species were remarkably stable throughout the monitoring period, driven by a small number of OTUs that dominated their respective communities. Variability of sponge-associated bacterial communities was driven by OTUs that were low in abundance or transient over time. Stable isotope analysis provided evidence of both bacteria- and host-derived nutrients and their variability throughout the season. While δ(15) N values were similar, significant differences were found in δ(13) C of sponge tissue, indicative of a varying reliance on particulate organic matter as a carbon source. Further temporal studies, such as those undertaken here, will be highly valuable to identify which members of a sponge bacterial community are truly symbiotic in nature.

  16. Molecular Spectroscopy of TiO in Laser-Induced Plasma

    NASA Astrophysics Data System (ADS)

    Woods, Alexander C.; Parigger, Christian G.

    2014-03-01

    Potential energy curves can be calculated for many diatomic molecules due to the symmetries and availability of experimental data for the spectral transitions of diatomic molecules. With accurate potential energy curves for diatomic molecules, line strengths can be determined for allowed spectral transitions. Combined with parameters such as temperature and resolution, line strengths allow us to create the molecular spectra. This investigation explores the fitting of computed spectra for selected titanium monoxide (TiO) molecular transitions to measured spectra collected at various times following the generation of laser-induced plasma. Using gated detection, spectral data is gathered during laser ablation of a titanium sample at rest in laboratory air. A Nelder-Mead fitting routine is applied to infer the temperature of the spectral transitions in the plasma. The result is a temperature versus time profile of the transitions of the TiO molecule along the plume. The error associated with each inference is determined by randomly adjusting the spectral baseline, as the measured spectrum is repeatedly fit. Atomic lines, which dominate the early spectra of laser-induced plasma, are also addressed. Center for Laser Applications

  17. Molecular formation in the stagnation region of colliding laser-produced plasmas

    SciTech Connect

    Al-Shboul, K. F.; Hassan, S. M.; Harilal, S. S.

    2016-10-27

    The laser-produced colliding plasmas have numerous attractive applications and stagnation layer formed during collisions between plasmas is a useful system for understanding particle collisions and molecular formation in a controlled way. In this article, we explore carbon dimer formation and its evolutionary paths in a stagnation layer formed during the interaction of two laser-produced plasmas. Colliding laser produced plasmas are generated by splitting a laser beam into two sub-beams and then focus them into either a single flat (laterally colliding plasmas) or a V-shaped graphite targets (orthogonally colliding plasmas). The C2 formation in the stagnation region of both colliding plasma schemes is investigated using optical spectroscopic means and compared with emission features from single seed plasma. Our results show that the collisions among the plasmas followed by the stagnation layer formation lead to rapid cooling causing enhanced carbon dimer formation. In addition, plasma electron temperature, density and C2 molecular temperature were measured for the stagnation zone and compared with seed plasma.

  18. Fundamental Studies in the Molecular Basis of Laser Induced Retinal Damage.

    DTIC Science & Technology

    1986-12-31

    N-retinylidene Schiff bases (NRB) and N-retinylidene protonated Schiff bases (NRBH). The direct method was unable to detect any differences in the...RESOLUTIOM TESI CHAWI NATIONAL BUR[A4 OF STANOARDS 1%,3-A AD__ _ _ _ _ FUNDAMENTAL STUDIES IN THE MOLECULAR BASIS OF LASER INDUCED RETINAL DAMAGE ANNUAL... based on this guiding framework ....................... 8 III. Superresolution Near-field Scanning Optical Microscopy ............. 12 REFERENCES

  19. Measurement of the D/H, 18O/16O, and 17O/16O Isotope Ratios in Water by Laser Absorption Spectroscopy at 2.73 μm

    PubMed Central

    Wu, Tao; Chen, Weidong; Fertein, Eric; Masselin, Pascal; Gao, Xiaoming; Zhang, Weijun; Wang, Yingjian; Koeth, Johannes; Brückner, Daniela; He, Xingdao

    2014-01-01

    A compact isotope ratio laser spectrometry (IRLS) instrument was developed for simultaneous measurements of the D/H, 18O/16O and 17O/16O isotope ratios in water by laser absorption spectroscopy at 2.73 μm. Special attention is paid to the spectral data processing and implementation of a Kalman adaptive filtering to improve the measurement precision. Reduction of up to 3-fold in standard deviation in isotope ratio determination was obtained by the use of a Fourier filtering to remove undulation structure from spectrum baseline. Application of Kalman filtering enables isotope ratio measurement at 1 s time intervals with a precision (<1‰) better than that obtained by conventional 30 s averaging, while maintaining a fast system response. The implementation of the filter is described in detail and its effects on the accuracy and the precision of the isotope ratio measurements are investigated. PMID:24854363

  20. Measurement of the D/H, ¹⁸O/¹⁶O, and ¹⁷O/¹⁶O isotope ratios in water by laser absorption spectroscopy at 2.73 μm.

    PubMed

    Wu, Tao; Chen, Weidong; Fertein, Eric; Masselin, Pascal; Gao, Xiaoming; Zhang, Weijun; Wang, Yingjian; Koeth, Johannes; Brückner, Daniela; He, Xingdao

    2014-05-21

    A compact isotope ratio laser spectrometry (IRLS) instrument was developed for simultaneous measurements of the D/H, 18O/16O and 17O/16O isotope ratios in water by laser absorption spectroscopy at 2.73 μm. Special attention is paid to the spectral data processing and implementation of a Kalman adaptive filtering to improve the measurement precision. Reduction of up to 3-fold in standard deviation in isotope ratio determination was obtained by the use of a Fourier filtering to remove undulation structure from spectrum baseline. Application of Kalman filtering enables isotope ratio measurement at 1 s time intervals with a precision (<1‰) better than that obtained by conventional 30 s averaging, while maintaining a fast system response. The implementation of the filter is described in detail and its effects on the accuracy and the precision of the isotope ratio measurements are investigated.

  1. Realizing A Mid-Infrared Optically Pumped Molecular Gas Laser Inside Hollow-Core Photonic Crystal Fiber

    DTIC Science & Technology

    2012-01-01

    REALIZING A MID-INFRARED OPTICALLY PUMPED MOLECULAR GAS LASER INSIDE HOLLOW-CORE PHOTONIC CRYSTAL FIBER by ANDREW MICHAEL JONES... Laser Inside Hollow-Core Photonic Crystal Fiber 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) 5d. PROJECT NUMBER 5e...optical fibers . These novel lasers are appealing for a variety of applications including frequency metrology in the midinfrared,free-space

  2. Anharmonic resonance absorption of short laser pulses in clusters: A molecular dynamics simulation study

    NASA Astrophysics Data System (ADS)

    Mahalik, S. S.; Kundu, M.

    2016-12-01

    Linear resonance (LR) absorption of an intense 800 nm laser light in a nano-cluster requires a long laser pulse >100 fs when Mie-plasma frequency ( ω M ) of electrons in the expanding cluster matches the laser frequency (ω). For a short duration of the pulse, the condition for LR is not satisfied. In this case, it was shown by a model and particle-in-cell (PIC) simulations [Phys. Rev. Lett. 96, 123401 (2006)] that electrons absorb laser energy by anharmonic resonance (AHR) when the position-dependent frequency Ω [ r ( t ) ] of an electron in the self-consistent anharmonic potential of the cluster satisfies Ω [ r ( t ) ] = ω . However, AHR remains to be a debate and still obscure in multi-particle plasma simulations. Here, we identify AHR mechanism in a laser driven cluster using molecular dynamics (MD) simulations. By analyzing the trajectory of each MD electron and extracting its Ω [ r ( t ) ] in the self-generated anharmonic plasma potential, it is found that electron is outer ionized only when AHR is met. An anharmonic oscillator model, introduced here, brings out most of the features of MD electrons while passing the AHR. Thus, we not only bridge the gap between PIC simulations, analytical models, and MD calculations for the first time but also unequivocally prove that AHR process is a universal dominant collisionless mechanism of absorption in the short pulse regime or in the early time of longer pulses in clusters.

  3. Molecular and Isotopic Signs of Life and Climate in the Hyperarid Atacama Desert

    NASA Astrophysics Data System (ADS)

    Finstad, K. M.; Tuite, M. L., Jr.; Williford, K. H.; Amundson, R.

    2015-12-01

    The hyperarid region of the Atacama Desert is considered one of the driest places on earth. Geomorphological studies suggest that this area has maintained a near-continuous hyperarid climate for at least the past 2 million years. Water-limited biological and geochemical processes have created a unique landscape with many similarities to Mars. While precipitation is rare in the Atacama Desert, coastal fog occurs regularly and microbial communities capable of utilizing fog and dew water are able to persist. Within this region, we found soils with lichen-dominated biological soil crusts living in association with physical sulfate crusts on the soil surface. Due to their high tolerance of desiccation and ability to utilize fog water, biologic soil crusts are able to exist in this hyperarid environment. We chose two sites ~30 km apart along a fog frequency transect which showed visible differences in the degree of biological coverage to study how shifts in fog water availability affect the biogeochemical processes occurring. Our previous radiocarbon dating and δ13C analysis of soil carbonates here indicates that soil in both locations has been accreting for over 15,000 years and confirmed that biological activity and rates of C cycling are greater at the higher fog frequency site. This study expands on that work to characterize the isotopic imprint of extreme aridity and evaporative processes in this environment, examining both organic and inorganic materials. A standard fatty acid extraction method was used and we were able to detect fatty acids in all soils analyzed, even those over 15,000 years old. Compound specific isotope analysis of these fatty acids clearly showed an enrichment of 2H at the drier site, with ~ 25 per mil difference between the surface samples. Similarly, analysis of δ18O of soil carbonates show ~10 per mil enrichment of 18O at the drier site. We attribute these differences to a prolonged and consistently greater evaporative stress at the

  4. A Plio-Pleistocene molecular isotopic record of Turkana Basin vegetation

    NASA Astrophysics Data System (ADS)

    Uno, K. T.; Polissar, P. J.; Bonnefille, R.; Lepre, C. J.; deMenocal, P. B.

    2014-12-01

    Paleovegetation and paleontological data from East Africa suggest that over the last five million years, the evolution of mammals has been significantly influenced by the emergence and expansion of C4 grasslands. Isotopic data from soil carbonate and marine core biomarkers indicate increased C4 grasses on the landscape beginning in the late Miocene. However, most Plio-Pleistocene sediments at vertebrate fossil localities lack sufficient soil carbonates that could allow us to directly link organisms to the particular environment where they lived. Here we take advantage of the organic biomarker record of vegetation in East Africa to understand landscape variability, its long-term evolution, and the relationship to the fossil record. Biomarker isotope records from Omo Group sediments, a fluvial-lacustrine sequence in the Turkana Basin, differ from their marine core counterparts in that they provide a local vegetation signal that can be directly linked to fossil material from the same sediments; they differ from soil carbonate records in that they are not limited to the specific environmental conditions necessary for carbonate precipitation. We present carbon isotope data from n-alkane and n-alkanoic acids from Omo Group sediments that span 3.6 to 1.1 Ma. The δ13C values from nC31 alkanes and nC30 alkanoic acids indicate high landscape variability ranging from C3-dominated to pure C4 environments. In both the Shungura and Nachukui Formations, biomarker data record significantly more C4 vegetation on the landscape than existing soil carbonate data. Biomarker data from the Shungura Formation indicate a more dynamic landscape than what is shown in the soil carbonate record. Biomarker samples come from sediments initially collected for pollen or paleomagnetic analyses that generally do not contain soil carbonates. They represent a wide variety of sediment types and therefore capture a broad range of depositional environments and environmental variability. Combined δ13C

  5. Laser-induced optical breakdown spectroscopy of polymer materials based on evaluation of molecular emission bands

    NASA Astrophysics Data System (ADS)

    Trautner, Stefan; Jasik, Juraj; Parigger, Christian G.; Pedarnig, Johannes D.; Spendelhofer, Wolfgang; Lackner, Johannes; Veis, Pavel; Heitz, Johannes

    2017-03-01

    Laser-induced breakdown spectroscopy (LIBS) for composition analysis of polymer materials results in optical spectra containing atomic and ionic emission lines as well as molecular emission bands. In the present work, the molecular bands are analyzed to obtain spectroscopic information about the plasma state in an effort to quantify the content of different elements in the polymers. Polyethylene (PE) and a rubber material from tire production are investigated employing 157 nm F2 laser and 532 nm Nd:YAG laser ablation in nitrogen and argon gas background or in air. The optical detection reaches from ultraviolet (UV) over the visible (VIS) to the near infrared (NIR) spectral range. In the UV/VIS range, intense molecular emissions, C2 Swan and CN violet bands, are measured with an Echelle spectrometer equipped with an intensified CCD camera. The measured molecular emission spectra can be fitted by vibrational-rotational transitions by open access programs and data sets with good agreement between measured and fitted spectra. The fits allow determining vibrational-rotational temperatures. A comparison to electronic temperatures Te derived earlier from atomic carbon vacuum-UV (VUV) emission lines show differences, which can be related to different locations of the atomic and molecular species in the expanding plasma plume. In the NIR spectral region, we also observe the CN red bands with a conventional CDD Czerny Turner spectrometer. The emission of the three strong atomic sulfur lines between 920 and 925 nm is overlapped by these bands. Fitting of the CN red bands allows a separation of both spectral contributions. This makes a quantitative evaluation of sulfur contents in the start material in the order of 1 wt% feasible.

  6. Laser-induced optical breakdown spectroscopy of polymer materials based on evaluation of molecular emission bands.

    PubMed

    Trautner, Stefan; Jasik, Juraj; Parigger, Christian G; Pedarnig, Johannes D; Spendelhofer, Wolfgang; Lackner, Johannes; Veis, Pavel; Heitz, Johannes

    2017-03-05

    Laser-induced breakdown spectroscopy (LIBS) for composition analysis of polymer materials results in optical spectra containing atomic and ionic emission lines as well as molecular emission bands. In the present work, the molecular bands are analyzed to obtain spectroscopic information about the plasma state in an effort to quantify the content of different elements in the polymers. Polyethylene (PE) and a rubber material from tire production are investigated employing 157nmF2 laser and 532nm Nd:YAG laser ablation in nitrogen and argon gas background or in air. The optical detection reaches from ultraviolet (UV) over the visible (VIS) to the near infrared (NIR) spectral range. In the UV/VIS range, intense molecular emissions, C2 Swan and CN violet bands, are measured with an Echelle spectrometer equipped with an intensified CCD camera. The measured molecular emission spectra can be fitted by vibrational-rotational transitions by open access programs and data sets with good agreement between measured and fitted spectra. The fits allow determining vibrational-rotational temperatures. A comparison to electronic temperatures Te derived earlier from atomic carbon vacuum-UV (VUV) emission lines show differences, which can be related to different locations of the atomic and molecular species in the expanding plasma plume. In the NIR spectral region, we also observe the CN red bands with a conventional CDD Czerny Turner spectrometer. The emission of the three strong atomic sulfur lines between 920 and 925nm is overlapped by these bands. Fitting of the CN red bands allows a separation of both spectral contributions. This makes a quantitative evaluation of sulfur contents in the start material in the order of 1wt% feasible.

  7. QCL- and CO_2 Laser-Based Mid-Ir Spectrometers for High Accuracy Molecular Spectroscopy

    NASA Astrophysics Data System (ADS)

    Sow, P. L. T.; Chanteau, B.; Auguste, F.; Mejri, S.; Tokunaga, S. K.; Argence, B.; Lopez, O.; Chardonnet, C.; Amy-Klein, A.; Daussy, C.; Darquie, B.; Nicolodi, D.; Abgrall, M.; Le Coq, Y.; Santarelli, G.

    2013-06-01

    With their rich internal structure, molecules can play a decisive role in precision tests of fundamental physics. They are now being used, for example in our group, to test fundamental symmetries such as parity and time reversal, and to measure either absolute values of fundamental constants or their temporal variation. Most of those experiments can be cast as the measurement of molecular frequencies. Ultra-stable and accurate sources in the mid-IR spectral region, the so-called molecular fingerprint region that hosts many intense rovibrational signatures, are thus highly desirable. We report on the development of a widely tunable quantum cascade laser (QCL) based spectrometer. Our first characterization of a free-running cw near-room-temperature DFB 10.3 μm QCL led to a ˜200 kHz linewidth beat-note with our frequency-stabilized CO_2 laser. Narrowing of the QCL linewidth was achieved by straightforwardly phase-locking the QCL to the CO_2 laser. The great stability of the CO_2 laser was transferred to the QCL resulting in a record linewidth of a few tens of hertz. The use of QCLs will allow the study of any species showing absorption between 3 and 25 μm which will broaden the scope of our experimental setups dedicated to molecular spectroscopy-based precision measurements. Eventually we want to lock the QCL to a frequency comb itself stabilized to an ultra-stable near-IR reference provided via a 43-km long fibre by the French metrological institute and monitored against atomic fountain clocks. We report on the demonstration of this locking-scheme with a ˜10 μm CO_2 laser resulting in record 10^{-14}-10^{-15} fractional accuracy and stability. Stabilizing a QCL this way will free us from having to lock it to a molecular transition or a CO_2 laser. It will make it possible for any laboratory to have a stabilized QCL at any desired wavelength with spectral performances currently only achievable in the visible and near-IR, in metrological institutes.

  8. Molecular and isotopic composition of lipids in modern and fossil bivalve shells: Records of paleoenvironmental change?

    SciTech Connect

    CoBabe, E.A.

    1995-12-31

    Suites of lipids residing in situ in modern and fossil bivalve shells offer new possibilities for the study of paleoecology and paleoclimatology. Distributions of carbon isotopic compositions of modem shell lipids suggests that many of these compounds, including alkanes, sterols, fatty acids, ketones and phytadienes, are derived from the bivalves and not directly from the surrounding environment. The occurrence of fatty acids in modem and fossil shell material opens up the possibility that saturation levels of these compounds may be used as paleothermometers. To date, the utility of fatty acids in paleoclimate studies has been limited because of the swift breakdown of these compounds in sediment. However, initial results indicate that fatty acids in bivalve shells retain their original structure for at least several million years. Comparison of modem bivalve shell fatty acids from tropical, temperate and polar nearshore marine systems will be presented, along with analogous fossil data.

  9. Isotope labelling to study molecular fragmentation during the dielectric barrier discharge wet reforming of methane

    NASA Astrophysics Data System (ADS)

    Montoro-Damas, Antonio M.; Gómez-Ramírez, Ana; Gonzalez-Elipe, Agustín R.; Cotrino, José

    2016-09-01

    Isotope labelling is used to study the wet plasma reforming of methane in a dielectric barrier discharge reactor using D2O and CH4 as reactants. Besides the formation of CO and hydrogen as main products, different partitions of H and D atoms are found in the hydrogen (i.e., H2, HD, D2), methane (i.e., CH4, CH3D and CH2D2) and water (D2O, DHO) molecules detected by mass spectrometry as outlet gases of the plasma process. The effect of operating parameters such as applied current, residence time and the addition of oxygen to the reaction mixture is correlated with the H/D distribution in these molecules, the overall reaction yield and the energetic efficiency of the process. The results prove the plasma formation of intermediate excited species that rendering water and methane instead of CO and hydrogen greatly contribute to decrease the overall energy efficiency of the reforming process.

  10. Abundances in red giant stars - Nitrogen isotopes in carbon-rich molecular envelopes

    NASA Technical Reports Server (NTRS)

    Wannier, P. G.; Andersson, B.-G.; Olofsson, H.; Ukita, N.; Young, K.

    1991-01-01

    Results are presented of millimeter- and submillimeter-wave observations of HCN and HCCCN that were made of the circmustellar envelopes of eight carbon stars, including the two protoplanetary nebulae CRL 618 and CRL 2688. The observations yield a measure of the double ratio (N-14)(C-13)/(N-15)(C-12). Measured C-12/C-13 ratios are used to estimate the N-14/N-15 abundance ratio, with the resulting lower limits in all eight envelopes and possible direct determinations in two envelopes. The two determinations and four of the remaining six lower limits are found to be in excess of the terrestrial value of N-14/N-15 = 272, indicating an evolution of the nitrogen isotope ratio, which is consistent with stellar CNO processing. Observations of thermal SiO (v = 0, J = 2-1) emission show that the Si-29/Si-28 ratio can be determined in carbon stars, and further observations are indicated.

  11. Measuring carbon and oxygen isotope signals of photosynthesis and respiration: first field results from a chamber system coupled to tunable diode laser spectrometers

    NASA Astrophysics Data System (ADS)

    Wingate, L.; Burlett, R.; Bosc, A.; Cross, A.; Devaux, M.; Grace, J.; Loustau, D.; Seibt, U.; Ogée, J.

    2007-12-01

    Studying the carbon and oxygen stable isotope signals from plants and soils can help us gain insight to mechanistic processes responsible for the net exchange of CO2 and water cycled between terrestrial ecosystems and the atmosphere. Chamber field measurements of component fluxes and their isotopic composition have been reported for a few ecosystems. These observations have revealed that isotopic signals for carbon and oxygen are dynamic over relatively short time scales (hrs and days) for both branches and soils (Seibt et al., 2006a; 2006b; Wingate et al., 2007), and not fully explained by currently available models (Seibt et al., 2006b; Wingate et al., 2007). Ecosystem isotope studies have been limited by flask sampling requirements in the past. To evaluate and refine our models of isotopic fractionation by plants and soil, we need high resolution continuous isotopic measurements over the growing season for different ecosystems. In this study, we coupled chambers with tunable diode laser spectroscopy techniques in the field to continuously capture the isotopic signals from the most important component fluxes contributing to the net ecosystem exchange of CO2 in a Pinus pinaster forest in south-west France. We obtained profiles of the carbon and oxygen isotope content of CO2 within and above the forest canopy. In addition, we measured branch photosynthetic 13C and 18O discrimination alongside the 13C and 18O isotopic composition of the branch, stem and soil respiration during a 6-month period in 2007. In this talk, we will present the first results from this field campaign. References Seibt, U., Wingate, L., Berry, J.A. and Lloyd, J. (2006a) Non steady state effects in diurnal 18O discrimination by Picea sitchensis branches in the field. Plant, Cell and Environment Vol 29, 928-939. Seibt, U., Wingate, L., Lloyd, J. and Berry, J.A. (2006b) Diurnally variable δ18O signatures of soil CO2 fluxes indicate carbonic anhydrase activity in a forest soil. JGR

  12. Inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation ICP-MS for isotope analysis of long-lived radionuclides

    NASA Astrophysics Data System (ADS)

    Becker, J. Sabine

    2005-04-01

    For a few years now inductively coupled plasma mass spectrometry has been increasingly used for precise and accurate determination of isotope ratios of long-lived radionuclides at the trace and ultratrace level due to its excellent sensitivity, good precision and accuracy. At present, ICP-MS and also laser ablation ICP-MS are applied as powerful analytical techniques in different fields such as the characterization of nuclear materials, recycled and by-products (e.g., spent nuclear fuel or depleted uranium ammunitions), radioactive waste control, in environmental monitoring and in bioassay measurements, in health control, in geochemistry and geochronology. Especially double-focusing sector field ICP mass spectrometers with single ion detector or with multiple ion collector device have been used for the precise determination of long-lived radionuclides isotope ratios at very low concentration levels. Progress has been achieved by the combination of ultrasensitive mass spectrometric techniques with effective separation and enrichment procedures in order to improve detection limits or by the introduction of the collision cell in ICP-MS for reducing disturbing interfering ions (e.g., of 129Xe+ for the determination of 129I). This review describes the state of the art and the progress of ICP-MS and laser ablation ICP-MS for isotope ratio measurements of long-lived radionuclides in different sample types, especially in the main application fields of characterization of nuclear and radioactive waste material, environmental research and health controls.

  13. Laser-induced rotational dynamics as a route to molecular frame measurements

    NASA Astrophysics Data System (ADS)

    Makhija, Varun

    In general, molecules in the gas phase are free to rotate, and measurements made on such samples are averaged over a randomly oriented distribution of molecules. Any orientation dependent information is lost in such measurements. The goal of the work presented here is to a) mitigate or completely do away with orientational averaging, and b) make fully resolved orientation dependent measurements. In pursuance of similar goals, over the past 50 years chemists and physicists have developed techniques to align molecules, or to measure their orientation and tag other quantities of interest with the orientation. We focus on laser induced alignment of asymmetric top molecules. The first major contribution of our work is the development of an effective method to align all molecular axes under field-free conditions. The method employs a sequence of nonresonant, impulsive laser pulses with varied ellipticities. The efficacy of the method is first demonstrated by solution of the time dependent Schrodinger equation for iodobenzene, and then experimentally implemented to three dimensionally align 3,5 difluoroiodobenzene. Measurement from molecules aligned in this manner greatly reduces orientational averaging. The technique was developed via a thorough understanding and extensive computations of the dynamics of rotationally excited asymmetric top molecules. The second, and perhaps more important, contribution of our work is the development of a new measurement technique to extract the complete orientation dependence of a variety of molecular processes initiated by ultrashort laser pulses. The technique involves pump-probe measurements of the process of interest from a rotational wavepacket generated by impulsive excitation of asymmetric top molecules. We apply it to make the first measurement of the single ionization probability of an asymmetric top molecule in a strong field as a function of all relevant alignment angles. The measurement and associated calculations help

  14. Molecular distributions and compound-specific stable carbon isotopic compositions of lipids in wintertime aerosols from Beijing.

    PubMed

    Ren, Lujie; Fu, Pingqing; He, Yue; Hou, Juzhi; Chen, Jing; Pavuluri, Chandra Mouli; Sun, Yele; Wang, Zifa

    2016-06-08

    Molecular distributions and stable carbon isotopic compositions (δ(13)C) of n-alkanes, fatty acids and n-alcohols were investigated in urban aerosols from Beijing, northern China to better understand the sources and long-range atmospheric transport of terrestrial organic matter during polluted and clear days in winter. n-Alkanes (C19-C36), fatty acids (C8-C32) and n-alcohols (C16-C32) detected in Beijing aerosols are characterized by the predominance of C23, C16 and C28, respectively. Carbon preference index (CPI) values of n-alkanes, the ratios of the sum of odd-numbered n-alkanes to the sum of even-numbered n-alkanes, are close to 1, indicating a heavy influence of fossil fuel combustion. Relatively higher ratios of C(18:0+16:0)/C(18:n+16:1) (fatty acids) on clear days than polluted days indicate that long-distance transport and/or photochemical aging are more significant during clear days. δ(13)C values of n-alkanes and low molecular weight fatty acids (C16:0, C18:0) ranged from -34.1 to -24.7% and -26.9 to -24.6%, respectively, which are generally heavier on polluted days than those on clear days. Such a wide range suggests that atmospheric lipids in Beijing aerosols originate from multiple sources and encounter complicated atmospheric processes during long-range transport in North China.

  15. Rapid and sensitive quantification of isotopic mixtures using a rapidly-swept external cavity quantum cascade laser

    SciTech Connect

    Brumfield, Brian E.; Taubman, Matthew S.; Phillips, Mark C.

    2016-05-23

    A rapidly-swept external-cavity quantum cascade laser with an open-path Herriott cell is used to quantify gas-phase chemical mixtures of D2O and HDO at a rate of 40 Hz (25-ms measurement time). The chemical mixtures were generated by evaporating D2O liquid near the open-path Herriott cell, allowing the H/D exchange reaction with ambient H2O to produce HDO. Fluctuations in the ratio of D2O and HDO on timescales of <1 s due to the combined effects of plume transport and the H/D exchange chemical reaction are observed. Noise-equivalent concentrations (1σ) (NEC) of 147.0 ppbv and 151.6 ppbv in a 25-ms measurement time are determined for D2O and HDO, respectively, with a 127-m optical path. These NECs are improved to 23.0 and 24.0 ppbv with a 1-s averaging time for D2O and HDO, respectively. NECs <200 ppbv are also estimated for N2O, 1,1,1,2–tetrafluoroethane (F134A), CH4, acetone and SO2 for a 25-ms measurement time. Finally, the isotopic precision for measurement of the [D2O]/[HDO] concentration ratio of 33‰ and 5‰ is calculated for the current experimental conditions for measurement times of 25 ms and 1 s, respectively.

  16. Photochemical isotope separation

    DOEpatents

    Robinson, C. Paul; Jensen, Reed J.; Cotter, Theodore P.; Greiner, Norman R.; Boyer, Keith

    1987-01-01

    A process for separating isotopes by selective excitation of isotopic species of a volatile compound by tuned laser light. A highly cooled gas of the volatile compound is produced in which the isotopic shift is sharpened and defined. Before substantial condensation occurs, the cooled gas is irradiated with laser light precisely tuned to a desired wavelength to selectively excite a particular isotopic species in the cooled gas. The laser light may impart sufficient energy to the excited species to cause it to undergo photochemical reaction or even to photoionize. Alternatively, a two-photon irradiation may be applied to the cooled gas to induce photochemical reaction or photoionization. The process is particularly applicable to the separation of isotopes of uranium and plutonium.

  17. Experimental observation of Anderson localization in laser-kicked molecular rotors

    NASA Astrophysics Data System (ADS)

    Bitter, Martin; Milner, Valery

    2016-05-01

    For the first time, the phenomenon of Anderson localization is observed and studied in a system of true quantum kicked rotors. Nitrogen molecules in a supersonic molecular jet are cooled down to 27 K and are rotationally excited by a periodic train of 24 high-intensity femtosecond pulses. Exponential distribution of the molecular angular momentum - the most unambiguous signature of Anderson localization - is measured directly by means of coherent Raman scattering. We demonstrate the suppressed growth of the molecular rotational energy with the number of laser kicks and study the dependence of the localization length on the kick strength. Both timing and amplitude noise in the pulse train is shown to destroy the localization and revive the diffusive growth of angular momentum.

  18. Lewis Acid-Base, Molecular Modeling, and Isotopic Labeling in a Sophomore Inorganic Chemistry Laboratory

    ERIC Educational Resources Information Center

    Nataro, Chip; Ferguson, Michelle A.; Bocage, Katherine M.; Hess, Brian J.; Ross, Vincent J.; Swarr, Daniel T.

    2004-01-01

    An experiment to prepare a deuterium labeled adduct of a Lewis acid and Lewis base, to use computational methods allowing students to visualize the LUMO of Lewis acids, the HOMO of Lewis bases and the molecular orbitals of the adduct that is formed is developed. This allows students to see the interplay between calculated and experimental results.

  19. Geologic aspects of reservoir souring - Brent Group sandstones, North Sea: The use of conventional and laser extraction techniques in sulfur isotope studies of authigenic pyrite

    SciTech Connect

    Brint, J.F. ); Fallick, A.E. )

    1991-03-01

    The Middle Jurassic Brent Group sandstones are prolific oil reservoirs in the North Sea. Recently, a number of Brent wells have experienced increased levels of hydrogen sulfide contamination during production. A study involving the characterization of all iron-bearing minerals to understand the controls of mineralogy on the nature and timing of souring has been undertaken. The potential of iron minerals to scavenge hydrogen sulfide and hence delay/inhibit souring by precipitation of pyrite has been investigated by determining its distribution, quantity, and origin. Authigenic pyrite occurs as disseminated (framboidal, cubic, and octahedral) crystals and as a pore-filling cement. The pyrite has formed throughout the diagenetic history of the sandstones. however, most of the pyrite is considered to be a late cement formed during burial diagenesis. Conventional separation and sulfur isotope analysis of the authigenic pyrite was conducted on samples from oil- and water-bearing sequences to give a bulk signature for all pyrite present. Subsequently, laser sulfur isotope analysis was used to characterize the signature and origin of the different pyrite morphologies present. The enhanced level of sulfur isotope signature characterization can be used to improve the knowledge of the origin and timing of the different pyrite morphologies. This allows closer reconciliation of the isotopic data to the diagenetic history of the Brent sandstones. Calculations have been made using the known quantities of iron in these minerals and the hydrogen sulfide concentrations present. This indicates the effect of sulfide precipitation on the hydrogen sulfide levels remaining in the reservoir.

  20. Molecular effects of fractional carbon dioxide laser resurfacing on photodamaged human skin.

    PubMed

    Reilly, Michael J; Cohen, Marc; Hokugo, Akishige; Keller, Gregory S

    2010-01-01

    Objective To elucidate the sequential changes in protein expression that play a role in the clinically beneficial results seen with fractional carbon dioxide (CO(2)) laser resurfacing of the face and neck. Methods Nine healthy volunteers were recruited for participation from the senior author's facial plastic surgery practice. After informed consent was obtained, each volunteer underwent a 2-mm punch biopsy from a discrete area of infra-auricular neck skin prior to laser treatment. Patients then immediately underwent laser resurfacing of photodamaged face and neck skin at a minimal dose (30 W for 0.1 second) with the Pixel Perfect fractional CO(2) laser. On completion of the treatment, another biopsy specimen was taken adjacent to the first site. Additional biopsy specimens were subsequently taken from adjacent skin at 2 of 3 time points (day 7, day 14, or day 21). RNA was extracted from the specimens, and reverse transcriptase-polymerase chain reaction and protein microarray analysis were performed. Comparisons were then made between time points using pairwise comparison testing. Results We found statistically significant changes in the gene expression of several matrix metalloproteinases (MMPs). The data demonstrate a consistent up-regulation of MMPs 1, 3, 9, and 13, all of which have been previously reported for fully ablative CO(2) laser resurfacing. There was also a statistically significant increase in MMP-10 and MMP-11 levels in this data set. Conclusion This study suggests that the molecular mechanisms of action are similar for both fractional and fully ablative CO(2) laser resurfacing.

  1. Analytical application of 2f-wavelength modulation for isotope selective diode laser graphite furnace atomic absorption spectroscopy.

    PubMed

    Wizemann, H D

    2000-01-01

    Experiences in the analytical application of the 2f-wavelength modulation technique for isotope selective atomic absorption spectroscopy in a graphite furnace are reported. Experimental as well as calculated results are presented, mainly for the natural lithium isotopes. Sensitivity, linearity, and (isotope) selectivity are studied by intensity modulation and wavelength modulation. High selectivities can be attained, however, on the cost of detection power. It is shown that the method enables the measurement of lithium isotope ratios larger than 2000 by absorption in a low-pressure graphite tube atomizer.

  2. First molecular and isotopic evidence of millet processing in prehistoric pottery vessels

    PubMed Central

    Heron, Carl; Shoda, Shinya; Breu Barcons, Adrià; Czebreszuk, Janusz; Eley, Yvette; Gorton, Marise; Kirleis, Wiebke; Kneisel, Jutta; Lucquin, Alexandre; Müller, Johannes; Nishida, Yastami; Son, Joon-ho; Craig, Oliver E.

    2016-01-01

    Analysis of organic residues in pottery vessels has been successful in detecting a range of animal and plant products as indicators of food preparation and consumption in the past. However, the identification of plant remains, especially grain crops in pottery, has proved elusive. Extending the spectrum is highly desirable, not only to strengthen our understanding of the dispersal of crops from centres of domestication but also to determine modes of food processing, artefact function and the culinary significance of the crop. Here, we propose a new approach to identify millet in pottery vessels, a crop that spread throughout much of Eurasia during prehistory following its domestication, most likely in northern China. We report the successful identification of miliacin (olean-18-en-3β-ol methyl ether), a pentacyclic triterpene methyl ether that is enriched in grains of common/broomcorn millet (Panicum miliaceum), in Bronze Age pottery vessels from the Korean Peninsula and northern Europe. The presence of millet is supported by enriched carbon stable isotope values of bulk charred organic matter sampled from pottery vessel surfaces and extracted n-alkanoic acids, consistent with a C4 plant origin. These data represent the first identification of millet in archaeological ceramic vessels, providing a means to track the introduction, spread and consumption of this important crop. PMID:28004742

  3. First molecular and isotopic evidence of millet processing in prehistoric pottery vessels

    NASA Astrophysics Data System (ADS)

    Heron, Carl; Shoda, Shinya; Breu Barcons, Adrià; Czebreszuk, Janusz; Eley, Yvette; Gorton, Marise; Kirleis, Wiebke; Kneisel, Jutta; Lucquin, Alexandre; Müller, Johannes; Nishida, Yastami; Son, Joon-Ho; Craig, Oliver E.

    2016-12-01

    Analysis of organic residues in pottery vessels has been successful in detecting a range of animal and plant products as indicators of food preparation and consumption in the past. However, the identification of plant remains, especially grain crops in pottery, has proved elusive. Extending the spectrum is highly desirable, not only to strengthen our understanding of the dispersal of crops from centres of domestication but also to determine modes of food processing, artefact function and the culinary significance of the crop. Here, we propose a new approach to identify millet in pottery vessels, a crop that spread throughout much of Eurasia during prehistory following its domestication, most likely in northern China. We report the successful identification of miliacin (olean-18-en-3β-ol methyl ether), a pentacyclic triterpene methyl ether that is enriched in grains of common/broomcorn millet (Panicum miliaceum), in Bronze Age pottery vessels from the Korean Peninsula and northern Europe. The presence of millet is supported by enriched carbon stable isotope values of bulk charred organic matter sampled from pottery vessel surfaces and extracted n-alkanoic acids, consistent with a C4 plant origin. These data represent the first identification of millet in archaeological ceramic vessels, providing a means to track the introduction, spread and consumption of this important crop.

  4. First molecular and isotopic evidence of millet processing in prehistoric pottery vessels.

    PubMed

    Heron, Carl; Shoda, Shinya; Breu Barcons, Adrià; Czebreszuk, Janusz; Eley, Yvette; Gorton, Marise; Kirleis, Wiebke; Kneisel, Jutta; Lucquin, Alexandre; Müller, Johannes; Nishida, Yastami; Son, Joon-Ho; Craig, Oliver E

    2016-12-22

    Analysis of organic residues in pottery vessels has been successful in detecting a range of animal and plant products as indicators of food preparation and consumption in the past. However, the identification of plant remains, especially grain crops in pottery, has proved elusive. Extending the spectrum is highly desirable, not only to strengthen our understanding of the dispersal of crops from centres of domestication but also to determine modes of food processing, artefact function and the culinary significance of the crop. Here, we propose a new approach to identify millet in pottery vessels, a crop that spread throughout much of Eurasia during prehistory following its domestication, most likely in northern China. We report the successful identification of miliacin (olean-18-en-3β-ol methyl ether), a pentacyclic triterpene methyl ether that is enriched in grains of common/broomcorn millet (Panicum miliaceum), in Bronze Age pottery vessels from the Korean Peninsula and northern Europe. The presence of millet is supported by enriched carbon stable isotope values of bulk charred organic matter sampled from pottery vessel surfaces and extracted n-alkanoic acids, consistent with a C4 plant origin. These data represent the first identification of millet in archaeological ceramic vessels, providing a means to track the introduction, spread and consumption of this important crop.

  5. Spin dynamics in HeH(2+) molecular ion in intense laser fields.

    PubMed

    Korani, Youssef; Sabzyan, Hassan

    2016-11-23

    A theoretical study is carried out on the effect of non-dipole interactions on the electron spin dynamics in the asymmetric diatomic HeH(2+) in its first excited state in intense linearly polarized laser fields. The Foldy-Wouthuysen transformation is used to solve the Dirac equation numerically without BOA. Effects of the phase of the laser pulse and alignment of the molecule on the relativistic characteristics, such as the pure spin and the pure spin-orbit current densities, spin-orbit force and spin torque, are investigated. The results of this study demonstrate that population oscillates between the two spin states during the course of interaction and its configuration depends on the molecular axis orientation and initial phase of the laser pulse. Also, a small polarization takes place in the spin states, even in the absence of the spin-orbit coupling. Furthermore, spin and spin-orbit current densities are phase-dependent and affected differently by the phase of the laser pulse.

  6. In Situ Sr Isotope Analysis of Minerals and Groundmass Using Laser Ablation Multi-collector ICPMS: Potentials for Determining Magma Chamber Processes and Residence Times of Phenocrysts

    NASA Astrophysics Data System (ADS)

    Ramos, F. C.; Wolff, J. A.; Tollstrup, D. L.

    2004-05-01

    In situ analyses of Sr isotope ratios using LA-MC-ICPMS hold great promise for identifying the processes and timescales involved in magmagenesis. The rapid analysis time and spatial control of laser ablation analyses offer significant advantages as compared to modern microdrilling techniques, including substantial time-savings. Laser ablation analyses can constrain the effects of contamination on individual mineral crystals and determine individual crystal residence histories. Integrating these analyses with additional isotopic, major and trace element, and mineralogic data allow us an opportunity to build an integrated magmatic history of the processes affecting magmas. The limited applicability of such LA-MC-ICPMS analyses was typically due to its inability to attain similar measurement precision and accuracy as analyses associated with thermal ionization mass spectrometry (TIMS). We introduce a Sr isotope measurement technique that uses LA-MC-ICPMS to obtain Sr isotope ratios that approach the accuracy and precision offered by TIMS. For marine carbonate, LA-MC-ICPMS results are statistically identical to purified samples analyzed by MC-ICPMS. In addition, we have analyzed common, non-abnormally Sr-enriched minerals from alkalic and tholeiitic basalts such as plagioclase, clinopyroxene, and fine-grained groundmass. Results for basaltic minerals and groundmass are generally within 2 sigma accuracy of microdrilled TIMS results on the same minerals. Results can be combined with simple diffusion models to constrain residence ages of individual minerals in magma chambers or identify the effects of processes such as crustal contamination. In addition, differences in signatures between mineral phases can aid in determining the environments in which different minerals crystallize and may offer the best means by which to constrain magma chamber dynamics.

  7. Microanalytical isotope ratio measurements and elemental mapping using laser ablation ICP-MS for tissue thin sections: zinc tracer studies in rats.

    PubMed

    Urgast, Dagmar S; Ou, Ou; Gordon, Margaret-Jane; Raab, Andrea; Nixon, Graeme F; Kwun, In-Sook; Beattie, John H; Feldmann, Jörg

    2012-01-01

    The kinetics of zinc absorption, metabolism and excretion is extensively studied by nutritionists. Stable isotopes of zinc can be used to identify body zinc compartments that have different turnover kinetics. Since the compartments might belong to physiological subsections of different organs, there is a need for microsampling analysis to determine isotope ratios of the trace element zinc in tissue samples. Here, we study the feasibility to use laser ablation coupled to quadrupole ICP-MS for the determination of zinc tracers given to rats at different time points with the aim to generate isotope ratio bioimages of heart tissue. A double tracer ((70)Zn and (67)Zn) experiment with rats was designed to label the exchangeable zinc pool as well as the stable zinc pool. The isotope ratios determined by laser ablation ICP-MS were evaluated by additional measurements of tissue digests. Accumulated tracers which made up more than 0.1% of total zinc could be identified in the tissues of the treated rats. It was established that at least 50 measurements from the microsampling were necessary to distinguish between controls and a tracer treated rat resulting in reduced resolution of the bioimage. With the parameters used, features in the tissue thin sections of at least 250 μm(2) in size are necessary to detect the incorporation of a tracer. When different time points have to be measured, higher precisions are required and therefore a larger area needs to be ablated (1 mm(2)). Using the bioimages and pool measurements from one physiological feature, it was possible to show that the aorta cell walls incorporate the zinc tracer at the different time points.

  8. Molecular marker and stable carbon isotope analyses of carbonaceous Ambassador uranium ores of Mulga Rock in Western Australia

    NASA Astrophysics Data System (ADS)

    Jaraula, C.; Schwark, L.; Moreau, X.; Grice, K.; Bagas, L.

    2013-12-01

    Mulga Rock is a multi-element deposit containing uranium hosted by Eocene peats and lignites deposited in inset valleys incised into Permian rocks of the Gunbarrel Basin and Precambrian rocks of the Yilgarn Craton and Albany-Fraser Orogen. Uranium readily adsorbs onto minerals or phytoclasts to form organo-uranyl complexes. This is important in pre-concentrating uranium in this relatively young ore deposit with rare uraninite [UO2] and coffinite [U(SiO4)1-x(OH)4x], more commonly amorphous and sub-micron uranium-bearing particulates. Organic geochemical and compound-specific stable carbon isotope analyses were conducted to identify possible associations of molecular markers with uranium accumulation and to recognize effect(s) of ionizing radiation on molecular markers. Samples were collected from the Ambassador deposit containing low (<200 ppm) to high (>2000 ppm) uranium concentrations. The bulk rock C/N ratios of 82 to 153, Rock-Eval pyrolysis yields of 316 to 577 mg hydrocarbon/g TOC (Hydrogen Index, HI) and 70 to 102 mg CO2/g TOC (Oxygen Index, OI) are consistent with a terrigenous and predominantly vascular plant OM source deposited in a complex shallow water system, ranging from lacustrine to deltaic, swampy wetland and even shallow lake settings as proposed by previous workers. Organic solvent extracts were separated into saturated hydrocarbon, aromatic hydrocarbon, ketone, and a combined free fatty acid and alcohol fraction. The molecular profiles appear to vary with uranium concentration. In samples with relatively low uranium concentrations, long-chain n-alkanes, alcohols and fatty acids derived from epicuticular plant waxes dominate. The n-alkane distributions (C27 to C31) reveal an odd/even preference (Carbon Preference Index, CPI=1.5) indicative of extant lipids. Average δ13C of -27 to -29 ‰ for long-chain n-alkanes is consistent with a predominant C3 plant source. Samples with relatively higher uranium concentrations contain mostly intermediate

  9. Matrix-Assisted Laser Desorption Ionization Imaging Mass Spectrometry: In Situ Molecular Mapping

    PubMed Central

    Angel, Peggi M.; Caprioli, Richard M.

    2013-01-01

    Matrix-assisted laser desorption ionization imaging mass spectrometry (IMS) is a relatively new imaging modality that allows mapping of a wide range of biomolecules within a thin tissue section. The technology uses a laser beam to directly desorb and ionize molecules from discrete locations on the tissue that are subsequently recorded in a mass spectrometer. IMS is distinguished by the ability to directly measure molecules in situ ranging from small metabolites to proteins, reporting hundreds to thousands of expression patterns from a single imaging experiment. This article reviews recent advances in IMS technology, applications, and experimental strategies that allow it to significantly aid in the discovery and understanding of molecular processes in biological and clinical samples. PMID:23259809

  10. Late Oligocene to Late Miocene Antarctic Climate Reconstructions Using Molecular and Isotopic Biomarker Proxies

    NASA Astrophysics Data System (ADS)

    Duncan, B.; Mckay, R. M.; Bendle, J. A.; Naish, T.; Levy, R. H.; Ventura, G. T.; Moossen, H. M.; Krishnan, S.; Pagani, M.

    2015-12-01

    Major climate and environmental changes occurred during late Oligocene to the late Miocene when atmospheric CO2 ranged between 500 and 300ppm, indicating threshold response of Antarctic ice sheets and climate to relatively modest CO2 variations. This implies that the southern high latitudes are highly sensitive to feedbacks associated with changes in global ice sheet and sea-ice extent, as well as terrestrial and marine ecosystems. This study focuses on two key intervals during the evolution of the Antarctic Ice Sheet: (1) The Late Oligocene and the Oligocene/Miocene boundary, when the East Antarctic Ice Sheet expanded close to present day volume following an extended period of inferred warmth. (2) The Mid-Miocene Climate Optimum (MMCO ~17-15 Ma), a period of global warmth and moderately elevated CO2 (350->500 ppm) which was subsequently followed by rapid cooling at 14-13.5 Ma. Reconstructions of climate and ice sheet variability, and thus an understanding of the various feedbacks that occurred during these intervals, are hampered by a lack of temperature and hydroclimate proxy data from the southern high latitudes. We present proxy climate reconstructions using terrestrial and marine organic biomarkers that provide new insights into Antarctica's climate evolution, using Antarctic drill cores and outcrop samples from a range of depositional settings. Bacterial ether-lipids have been analysed to determine terrestrial mean annual temperatures and soil pH (via the methylation and cyclisation indexes of branched tetraethers - MBT and CBT, respectively). Tetraether-lipids of crenarchaeota found in marine sediments sampled from continental shelves around Antarctica have been used to derive sea surface temperatures using the TEX86 index. Compound specific stable isotopes on n-alkanes sourced from terrestrial plants have been analysed to investigate changes in the hydrological and carbon cycles.

  11. InGaN/GaN self-organized quantum dot lasers grown by molecular beam epitaxy

    NASA Astrophysics Data System (ADS)

    Banerjee, Animesh; Frost, Thomas; Jahangir, Shafat; Stark, Ethan; Bhattacharya, Pallab

    2013-09-01

    Blue-and green-emitting quantum dots have been characterized and ridge waveguide lasers incorporating such quantum dots into the active region have been realized. The laser heteroscturctures were grown by plasma assisted molecular beam epitaxy. Injected carrier lifetimes in the quantum dots have also been measured by temperature dependent and time resolved photoluminescence. A threshold current density of 930 A/cm2 in the blue-emitting lasers was measured under pulsed bias. A tunnel injection scheme to inject holes has been incorporated in the design of the green quantum dot lasers, and a threshold current density of 945 A/cm2 in the green-emitting lasers has been measured under pulsed bias. Slope efficiencies of 0.41 W/A and 0.25 W/A have been measured, corresponding to differential quantum efficiencies of 13.9% and 11.3%, in the blue and green lasers, respectively.

  12. Effects of Low-Molecular-Weight Organic Acids on the Dissolution of Hydroxyapatite Nanoparticles in Batch and Column Experiments: A Perspective from Phosphate Oxygen Isotope Fractionation

    NASA Astrophysics Data System (ADS)

    Wang, D.; Jaisi, D. P.; Jin, Y.

    2015-12-01

    Hydroxyapatite nanoparticles (HANPs) are increasingly being advocated as an efficient and environment-friendly "green" phosphorus nanofertilizer attributed to their nanoscale dimension, large reactive surface area, and low leaching potential. However, knowledge of how naturally occurring low-molecular-weight organic acids (LMWOAs) that are secreted by plant roots mediate the dissolution of HANPs (releasing PO43- ion for plant growth) is nonexistent. Here three most commonly encountered LMWOAs (acetic acid, oxalic acid, and citric acid) at environmentally relevant concentration (1 mM) were evaluated for their effects on HANPs' dissolution in static batch and dynamic column systems. Particularly, phosphate oxygen isotope fractionation of HANPs during dissolution was examined to disentangle mechanisms controlling the evolution of O-isotopic composition of dissolved PO43- ion. Our results reveal that in batch experiments the dissolution of HANPs was fast but the overall dissolution efficiency of HANPs was limited (≤30%). In contrast, ~100% HANPs were dissolved in columns where LMWOAs were continuously injected. The limited dissolution of HANPs in static batch systems was due primarily to pH buffer effect (pH increased sharply when LMWOA was added in HANPs suspension), whereas in dynamic column systems the HANPs were continuously dissolved by low pH LMWOAs and leached away. Regardless of LMWOA type and experimental system, the isotopically light phosphate (P16O4) was preferentially released during dissolution and the O-isotopic composition of dissolved PO43- ion increased gradually with increasing dissolution due to equilibrium isotope effect between dissolved PO43- ion and HANPs. However, the overall magnitude of O-isotopic fractionation of dissolved PO43- ion was less in batch than in column systems, due to less mass transfer between dissolved PO43- ions and HANPs in batch relative to column experiments. Our findings provide new insights into bioavailability

  13. 124 Iodine: a longer-life positron emitter isotope-new opportunities in molecular imaging.

    PubMed

    Cascini, Giuseppe Lucio; Niccoli Asabella, Artor; Notaristefano, Antonio; Restuccia, Antonino; Ferrari, Cristina; Rubini, Domenico; Altini, Corinna; Rubini, Giuseppe

    2014-01-01

    (124)Iodine ((124)I) with its 4.2 d half-life is particularly attractive for in vivo detection and quantification of longer-term biological and physiological processes; the long half-life of (124)I is especially suited for prolonged time in vivo studies of high molecular weight compounds uptake. Numerous small molecules and larger compounds like proteins and antibodies have been successfully labeled with (124)I. Advances in radionuclide production allow the effective availability of sufficient quantities of (124)I on small biomedical cyclotrons for molecular imaging purposes. Radioiodination chemistry with (124)I relies on well-established radioiodine labeling methods, which consists mainly in nucleophilic and electrophilic substitution reactions. The physical characteristics of (124)I permit taking advantages of the higher PET image quality. The availability of new molecules that may be targeted with (124)I represents one of the more interesting reasons for the attention in nuclear medicine. We aim to discuss all iodine radioisotopes application focusing on (124)I, which seems to be the most promising for its half-life, radiation emissions, and stability, allowing several applications in oncological and nononcological fields.

  14. Method for separating boron isotopes

    DOEpatents

    Rockwood, Stephen D.

    1978-01-01

    A method of separating boron isotopes .sup.10 B and .sup.11 B by laser-induced selective excitation and photodissociation of BCl.sub.3 molecules containing a particular boron isotope. The photodissociation products react with an appropriate chemical scavenger and the reaction products may readily be separated from undissociated BCl.sub.3, thus effecting the desired separation of the boron isotopes.

  15. Molecular Ecological and Stable Isotopic Studies of Nitrogen Fixation in Modern Microbial Mats

    NASA Technical Reports Server (NTRS)

    Bebout, B. M.; Crumbliss, L. L.; DesMarais, D. J.; Hogan, M. E.; Omoregie, E.; Turk, K. A.; Zehr, J. P.

    2003-01-01

    Nitrogen is usually the element limiting biological productivity in the marine environment. Microbial mats, laminated microbial communities analogous to some of the oldest forms of life on Earth, are often the sites of high rates of N fixation (the energetically expensive conversion of atmospheric dinitrogen into a biologically useful form). The N fixing enzyme nitrogenase is generally considered to be of ancient origin, and is widely distributed throughout the Bacterial and Archaeal domains of life, indicating an important role for this process over evolutionary time. The stable isotopic signature of N fixation is purportedly recognizable in organic matter (ancient kerogens as well as present-day microbial mats) as a delta (15)N(sub organic) near zero. We studied two microbial mats exhibiting different rates of N fixation in order to better understand the impact of N fixation on the delta (15)N (sub organic) of the mats, as well as what organisms are important in this process. Mats dominated by the cyanobacterium Microcoleus chthonoplastes grow in permanently submerged hypersaline salterns, and exhibit low rates of N fixation, whereas mats dominated by the cyanobacterium Lyngbya spp grow in an intertidal area, and exhibit rates of N fixation an order of magnitude higher. To examine successional stages in mat growth, both developing and established mats at each location were sampled. PCR and RT-PCR based approaches were used to identify, respectively, the organisms containing nifH (one of the genes that encode nitrogenase) as well as those expressing nifH in these mats. Both mats exhibited a distinct diel cycle of N fixation, with highest rates occurring at night. The delta (15)N(sub organic) of the subtidal Microcoleus mats is near zero whereas the delta (15)N(sub organic) is slightly more positive (+ 2-3%), in the intertidal Lyngbya mats, an interesting difference in view of the fact that overall rates of activity in the intertidal mats are much higher that those

  16. Reconstruction of three-dimensional molecular structure from diffraction of laser-aligned molecules

    PubMed Central

    Yang, Jie; Makhija, Varun; Kumarappan, Vinod; Centurion, Martin

    2014-01-01

    Diffraction from laser-aligned molecules has been proposed as a method for determining 3-D molecular structures in the gas phase. However, existing structural retrieval algorithms are limited by the imperfect alignment in experiments and the rotational averaging in 1-D alignment. Here, we demonstrate a two-step reconstruction comprising a genetic algorithm that corrects for the imperfect alignment followed by an iterative phase retrieval method in cylindrical coordinates. The algorithm was tested with simulated diffraction patterns. We show that the full 3-D structure of trifluorotoluene, an asymmetric-top molecule, can be reconstructed with atomic resolution. PMID:26798781

  17. [Evaluation of molecular weights of hyaluronate preparations by multi-angle laser light scattering].

    PubMed

    Yomota, Chikako

    2003-01-01

    Hyaluronate (HA), a glycosaminoglycan polysaccharide, has been used for osteoarthritis, periartritis of the shoulder and rheumatoid arthritis by intraarticular administration, and in ophthalmic surgery such as anterior segment surgery, and eye lotion. In this study, the molecular weight (Mw) of HA preparations were estimated by size-exclusion chromatography (SEC) system consisted of a refractometer (RI) and a multi-angle laser light scattering (MALS). From the results, it has been clarified that a successful characterization of HA samples with Mw up to 2 - 3 x 10(6) g/mol was possible by multidetector system.

  18. Phase locked periodic solutions and synchronous chaos in a model of two coupled molecular lasers

    NASA Astrophysics Data System (ADS)

    Doedel, Eusebius J.; Lambruschini, Carlos L. Pando

    2016-11-01

    We study a rate-equation model for two coupled molecular lasers with a saturable absorber. A numerical bifurcation study shows the existence of isolas for in-phase periodic solutions as physical parameters change. In addition there are other non-isola families of in-phase, anti-phase and intermediate-phase periodic oscillations. In this model the unstable periodic orbits belonging to the in-phase isolas constitute a skeleton of the attractor, when chaotic synchronization sets in for a set of physically relevant control parameters.

  19. Molecular-level mechanisms of nanoparticle detachment in laser-induced plasma shock waves

    SciTech Connect

    Zhou Dong; Cetinkaya, Cetin

    2006-04-24

    Detachment and detachment mechanisms of nanoparticles from flat surfaces subjected to shock waves are investigated by employing molecular gas dynamic simulations using the direct simulation Monte Carlo method and experimental transient pressure data. Two mechanisms for nanoparticle detachment based on rolling moment resistance of the adhesion bond and the elastic restitution effect are introduced. As a result of present simulations, it is computationally demonstrated that the pulsed laser-induced shock waves can generate sufficient rolling moments to detach sub-100-nm particles and initiate removal. The transient moment exerted on a 60 nm polystyrene latex particle on a silicon substrate is presented and discussed.

  20. A laser and molecular beam mass spectrometer study of low-pressure dimethyl ether flames

    SciTech Connect

    Andrew McIlroy; Toby D. Hain; Hope A. Michelsen; Terrill A. Cool

    2000-12-15

    The oxidation of dimethyl ether (DME) is studied in low-pressure flames using new molecular beam mass spectrometer and laser diagnostics. Two 30.0-Torr, premixed DME/oxygen/argon flames are investigated with stoichiometries of 0.98 and 1.20. The height above burner profiles of nine stable species and two radicals are measured. These results are compared to the detailed chemical reaction mechanism of Curran and coworkers. Generally good agreement is found between the model and data. The largest discrepancies are found for the methyl radical profiles where the model predicts qualitatively different trends in the methyl concentration with stoichiometry than observed in the experiment.

  1. Molecular scale shock response: electronic absorption spectroscopy of laser shocked explosives

    NASA Astrophysics Data System (ADS)

    McGrane, Shawn; Whitley, Von; Moore, David; Bolme, Cindy; Eakins, Daniel

    2009-06-01

    Single shot spectroscopies are being employed to answer questions fundamental to shock initiation of explosives. The goals are to: 1) determine the extent to which electronic excitations are, or are not, involved in shock induced reactions, 2) test the multiphonon up-pumping hypothesis in explosives, and 3) provide data on the initial evolution of temperature and chemistry following the shock loading of explosives on scales amenable to comparison to molecular dynamics simulations. The data presented in this talk are focused on answering the first question. Recent experimental results measuring the time history of ultraviolet/visible absorption spectroscopy of laser shocked explosive thin films and single crystals will be discussed.

  2. Theory of molecular rate processes in the presence of intense laser radiation

    NASA Technical Reports Server (NTRS)

    George, T. F.; Zimmerman, I. H.; Devries, P. L.; Yuan, J.-M.; Lam, K.-S.; Bellum, J. C.; Lee, H.-W.; Slutsky, M. S.; Lin, J.-T.

    1979-01-01

    The present paper deals with the influence of intense laser radiation on gas-phase molecular rate processes. Representations of the radiation field, the particle system, and the interaction involving these two entities are discussed from a general rather than abstract point of view. The theoretical methods applied are outlined, and the formalism employed is illustrated by application to a variety of specific processes. Quantum mechanical and semiclassical treatments of representative atom-atom and atom-diatom collision processes in the presence of a field are examined, and examples of bound-continuum processes and heterogeneous catalysis are discussed within the framework of both quantum-mechanical and semiclassical theories.

  3. Molecular distributions and compound-specific stable carbon isotopic compositions of lipids in wintertime aerosols from Beijing

    PubMed Central

    Ren, Lujie; Fu, Pingqing; He, Yue; Hou, Juzhi; Chen, Jing; Pavuluri, Chandra Mouli; Sun, Yele; Wang, Zifa

    2016-01-01

    Molecular distributions and stable carbon isotopic compositions (δ13C) of n-alkanes, fatty acids and n-alcohols were investigated in urban aerosols from Beijing, northern China to better understand the sources and long-range atmospheric transport of terrestrial organic matter during polluted and clear days in winter. n-Alkanes (C19–C36), fatty acids (C8–C32) and n-alcohols (C16–C32) detected in Beijing aerosols are characterized by the predominance of C23, C16 and C28, respectively. Carbon preference index (CPI) values of n-alkanes, the ratios of the sum of odd-numbered n-alkanes to the sum of even-numbered n-alkanes, are close to 1, indicating a heavy influence of fossil fuel combustion. Relatively higher ratios of C(18:0+16:0)/C(18:n+16:1) (fatty acids) on clear days than polluted days indicate that long-distance transport and/or photochemical aging are more significant during clear days. δ13C values of n-alkanes and low molecular weight fatty acids (C16:0, C18:0) ranged from –34.1 to −24.7% and −26.9 to −24.6%, respectively, which are generally heavier on polluted days than those on clear days. Such a wide range suggests that atmospheric lipids in Beijing aerosols originate from multiple sources and encounter complicated atmospheric processes during long-range transport in North China. PMID:27270951

  4. An exceptional kinetic quantum sieving separation effect of hydrogen isotopes on commercially available carbon molecular sieves.

    PubMed

    Xing, Yanlong; Cai, Jinjun; Li, Liangjun; Yang, Menglong; Zhao, Xuebo

    2014-08-14

    The quantum sieving effect of H2/D2 at 77 K on commercially available carbon molecular sieves (1.5GN-H and 3KT-172) was studied. An exceptional reverse kinetic quantum effect is observed on 1.5GN-H where D2 diffuses much faster than H2 with a ratio of up to 5.83 at low pressure, and the difference is still very evident even as the pressure increases up to 1 bar. D2 also diffuses faster than H2 on 3KT-172 with a ratio of up to 1.86. However, the reverse kinetic sieving disappears in a polymer-based carbon (PC). The present kinetic quantum sieving effect of H2 and D2 at 77 K on 1.5GN-H is the highest to date.

  5. Molecular and isotopic evidence for fossil fuel aromatic hydrocarbons in soils

    SciTech Connect

    Lichtfouse, E.; Budzinski, F.H.; Garrigues, P.

    1996-10-01

    The origin of organic molecules occurring in complex media such as soils and sediments is still an enigma. In soils, for example, the occurrence of polycyclic aromatic hydrocarbons (PAH) is a major concern because these potentially toxic compounds may ultimately be transferred into food and drinking water. At present, two main hypotheses can be made for the origin of PAH in soils. PAH, or their precursors, can be synthesized by modem plants, within soil biomass and humic substance degradation. Alternatively, PAH may derive from fossil fuels and associated combustion products. In the present study, soils have been cultivated for 23 years with maize in order to label the organic matter with naturally {sup 13}C-enriched maize-derived carbon. {sup 13}C, {sup 14}C and molecular analysis of aromatic fractions from those soils show that the main part of PAH are ancient, most probably derived from fossil fuel and their combustion products.

  6. Isotopic evidence for the contemporary origin of high-molecular weight organic matter in oceanic environments

    NASA Astrophysics Data System (ADS)

    Santschi, Peter H.; Guo, Laodong; Baskaran, M.; Trumbore, Susan; Southon, John; Bianchi, Thomas S.; Honeyman, Bruce; Cifuentes, Luis

    1995-02-01

    Previous work has suggested that apparent old 14C ages for oceanic DOC are the result of mixing of different organic carbon fractions. This report provides direct evidence for a contemporary 14C age of a high-molecular-weight (HMW) fraction of colloidal organic carbon (≥10 kD). Colloidal organic matter, COM 10 (from 10 kDaltons (kD) to 0.2 μm), isolated from the upper water column of the Gulf of Mexico and the Middle Atlantic Bight (MAB) region, generally has a contemporary age (i.e., younger than a few decades), while COM 1 (from 1 kD to 0.2 μm), is apparently old: 380-4500 y BP. Thus, BMW COM 10 (3-5% of DOC) from the upper water column is derived from living particulate organic matter (POM) and cycles rapidly, while a significant fraction of low-molecular-weight (≤1 kD) DOM is likely more refractory, and cycles on much longer time scales. The presence of pigment biomarker compounds in COM 1 from the upper water column points to selected phytoplankton species as one of the sources of COM. Terrestrial carbon as another source of COM is suggested from the inverse correlation between Δ 14C and δ 13C values, as well as the increasing δ 13C values with increasing salinity. 234Th-derived turnover times of COM 10 and COM 1 from both the Gulf of Mexico and MAB are consistently short, 1-20 and 3-30 days, respectively. These short residence times support the hypothesis that 14C ages of colloidal fractions of DOC are the result of COM fractions being a mixture of several endmembers with fast and slow turnover rates.

  7. Molecular characterization of multivalent bioconjugates by size-exclusion chromatography with multiangle laser light scattering.

    PubMed

    Pollock, Jacob F; Ashton, Randolph S; Rode, Nikhil A; Schaffer, David V; Healy, Kevin E

    2012-09-19

    The degree of substitution and valency of bioconjugate reaction products are often poorly judged or require multiple time- and product-consuming chemical characterization methods. These aspects become critical when analyzing and optimizing the potency of costly polyvalent bioactive conjugates. In this study, size-exclusion chromatography with multiangle laser light scattering was paired with refractive index detection and ultraviolet spectroscopy (SEC-MALS-RI-UV) to characterize the reaction efficiency, degree of substitution, and valency of the products of conjugation of either peptides or proteins to a biopolymer scaffold, i.e., hyaluronic acid (HyA). Molecular characterization was more complete compared to estimates from a protein quantification assay, and exploitation of this method led to more accurate deduction of the molecular structures of polymer bioconjugates. Information obtained using this technique can improve macromolecular engineering design principles and help to better understand multivalent macromolecular interactions in biological systems.

  8. Laser-cooled RaF as a promising candidate to measure molecular parity violation

    SciTech Connect

    Isaev, T. A.; Berger, R.; Hoekstra, S.

    2010-11-15

    The parameter W{sub a}, which characterizes nuclear-spin-dependent parity violation (PV) in the molecular spin-rotational Hamiltonian, was computed with a quasirelativistic Hartree-Fock approach for radium fluoride (RaF) and found to be one of the largest absolute values predicted so far. The peculiar electronic structure of RaF leads to highly diagonal Franck-Condon matrices between the energetically lowest two electronic states, which qualifies RaF for direct laser cooling. A subset of diatomic molecules with a wide range of internal structures suitable for this cooling technique is also indicated. As trapped cold molecules offer superior coherence times, RaF can be considered promising for high-precision experiments aimed at molecular PV.

  9. Lateral band-gap control of InGaAsP multiple quantum wells by laser-assisted metalorganic molecular beam epitaxy for a multiwavelength laser array

    NASA Astrophysics Data System (ADS)

    Iga, Ryuzo; Yamada, Takeshi; Sugiura, Hideo

    1994-02-01

    Multiple asymmetric quantum wells made up of InGaAsP and InAsP layers were fabricated using laser irradiation. They were formed in different irradiated areas during InGaAsP quantum well growth by Ar-ion laser assisted metalorganic molecular beam epitaxy (MOMBE). It was observed that during MOMBE the band gap of InGaAsP MQW was modified. Photoluminescence wavelengths of the MAQWs were studied to observe the variations in the bandgap with a delay in the starting time of laser irradiation. The photoluminescence of the MAQWs ranged from 1.3 to 1.5 micrometer and the PL intensity of the MAQWs in four different areas were all similar. This phenomena enabled the fabrication of multiwavelength laser array on a substrate in a single step growth.

  10. Isotopic and molecular analyses of hydrocarbons and monocarboxylic acids of the Murchison meteorite

    NASA Technical Reports Server (NTRS)

    Krishnamurthy, R. V.; Epstein, S.; Cronin, John R.; Pizzarello, Sandra; Yuen, George U.

    1992-01-01

    The monocarboxylic acids and hydrocarbons of the Murchison meteorite (CM2) were isolated for isotropic analysis. The nonvolatile hydrocarbons were analyzed as crude methanol and benzene-methanol extracts and also after separation by silica gel chromatography into predominantly aliphatic, aromatic, and polar hydrocarbon fractions. The volatile hydrocarbons were obtained after progressive decomposition of the meteorite matrix by freeze-thaw, hot water, and acid treatment. Molecular analyses of the aromatic hydrocarbons showed them to comprise a complex suite of compounds in which pyrene, fluoranthene, phenanthrene, and acenaphthene were the most abundant components, a result similar to earlier analyses. The polar hydrocarbons also comprise a very complex mixture in which aromatic ketones, nitrogen, and sulfur heterocycles were identified. The monocarboxylic acids, aliphatic, aromatic, and polar hydrocarbons, and the indigenous volatile hydrocarbons were found to be D-rich. The deuterium enrichment observed in these compounds is suggestive. In two separate analyses, the delta-D values of the nonvolatile hydrocarbons were observed to increase in the following order: aliphatic-aromatic-polar. This finding is consistent with an early solar system or parent body conversion of aromatic to aliphatic compounds as well as the suggestion of pyrolytic formation of aromatic from aliphatic compounds.

  11. Spectral statistics of molecular resonances in erbium isotopes: How chaotic are they?

    NASA Astrophysics Data System (ADS)

    Mur-Petit, Jordi; Molina, Rafael A.

    2015-10-01

    We perform a comprehensive analysis of the spectral statistics of the molecular resonances in 166Er and 168Er observed in recent ultracold collision experiments [Frisch et al., Nature (London) 507, 475 (2014), 10.1038/nature13137] with the aim of determining the chaoticity of this system. We calculate different independent statistical properties to check their degree of agreement with random matrix theory (RMT), and analyze if they are consistent with the possibility of having missing resonances. The analysis of the short-range fluctuations as a function of the magnetic field points to a steady increase of chaoticity until B ˜30 G. The repulsion parameter decreases for higher magnetic fields, an effect that can be interpreted as due to missing resonances. The analysis of long-range fluctuations allows us to be more quantitative and estimate a 20 %-25 % fraction of missing levels. Finally, a study of the distribution of resonance widths provides additional evidence supporting missing resonances of small width compared with the experimental magnetic field resolution. We conclude that further measurements with increased resolution will be necessary to give a final answer to the problem of missing resonances and the agreement with RMT.

  12. Combining Capillary Electrophoresis Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry and Stable Isotopic Labeling Techniques for Comparative Crustacean Peptidomics

    PubMed Central

    Wang, Junhua; Zhang, Yuzhuo; Xiang, Feng; Zhang, Zichuan; Li, Lingjun

    2010-01-01

    Herein we describe a sensitive and straightforward off-line capillary electrophoresis (CE) matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) interface in conjunction with stable isotopic labeling (SIL) technique for comparative neuropeptidomic analysis in crustacean model organisms. Two SIL schemes, including a binary H/D formaldehyde labeling technique and novel, laboratory-developed multiplexed dimethylated leucine-based isobaric tagging reagents, have been evaluated in these proof-of-concept experiments. We employ these isotopic labeling techniques in conjunction with CE-MALDI MS for quantitative peptidomic analyses of the pericardial organs isolated from two crustacean species, the European green crab Carcinus maenas and the blue crab Callinectes sapidus. Isotopically labeled peptide pairs are found to co-migrate in CE fractions and quantitative changes in relative abundances of peptide pairs are obtained by comparing peak intensities of respective peptide pairs. Several neuropeptide families exhibit changes in response to salinity stress, suggesting potential physiological functions of these signaling peptides. PMID:20334868

  13. Observations of molecular hydrogen mixing ratio and stable isotopic composition at the Cabauw tall tower in the Netherlands

    NASA Astrophysics Data System (ADS)

    Batenburg, A. M.; Popa, M. E.; Vermeulen, A. T.; van den Bulk, W. C. M.; Jongejan, P. A. C.; Fisher, R. E.; Lowry, D.; Nisbet, E. G.; Röckmann, T.

    2016-12-01

    Measurements of the stable isotopic composition (δD(H2) or δD) of atmospheric molecular hydrogen (H2) are a useful addition to mixing ratio (χ(H2)) measurements for understanding the atmospheric H2 cycle. δD datasets published so far consist mostly of observations at background locations. We complement these with observations from the Cabauw tall tower at the CESAR site, situated in a densely populated region of the Netherlands. Our measurements show a large anthropogenic influence on the local H2 cycle, with frequently occurring pollution events that are characterized by χ(H2) values that reach up to ≈1 ppm and low δD values. An isotopic source signature analysis yields an apparent source signature below -400‰, which is much more D-depleted than the fossil fuel combustion source signature commonly used in H2 budget studies. Two diurnal cycles that were sampled at a suburban site near London also show a more D-depleted source signature (≈-340‰), though not as extremely depleted as at Cabauw. The source signature of the Northwest European vehicle fleet may have shifted to somewhat lower values due to changes in vehicle technology and driving conditions. Even so, the surprisingly depleted apparent source signature at Cabauw requires additional explanation; microbial H2 production seems the most likely cause. The Cabauw tower site also allowed us to sample vertical profiles. We found no decrease in χ(H2) at lower sampling levels (20 and 60 m) with respect to higher sampling levels (120 and 200 m). There was a significant shift to lower median δD values at the lower levels. This confirms the limited role of soil uptake around Cabauw, and again points to microbial H2 production during an extended growing season, as well as to possible differences in average fossil fuel combustion source signature between the different footprint areas of the sampling levels. So, although knowledge of the background cycle of H2 has improved over the last decade, surprising

  14. 13CO2/12CO2 isotope ratio analysis in human breath using a 2 μm diode laser

    NASA Astrophysics Data System (ADS)

    Sun, Mingguo; Cao, Zhensong; Liu, Kun; Wang, Guishi; Tan, Tu; Gao, Xiaoming; Chen, Weidong; Yinbo, Huang; Ruizhong, Rao

    2015-04-01

    The bacterium H. pylori is believed to cause peptic ulcer. H. pylori infection in the human stomach can be diagnosed through a CO2 isotope ratio measure in exhaled breath. A laser spectrometer based on a distributed-feedback semiconductor diode laser at 2 μm is developed to measure the changes of 13CO2/12CO2 isotope ratio in exhaled breath sample with the CO2 concentration of ~4%. It is characterized by a simplified optical layout, in which a single detector and associated electronics are used to probe CO2 spectrum. A new type multi-passes cell with 12 cm long base length , 29 m optical path length in total and 280 cm3 volume is used in this work. The temperature and pressure are well controlled at 301.15 K and 6.66 kPa with fluctuation amplitude of 25 mK and 6.7 Pa, respectively. The best 13δ precision of 0.06o was achieved by using wavelet denoising and Kalman filter. The application of denoising and Kalman filter not only improved the signal to noise ratio, but also shorten the system response time.

  15. Molecular-weight distributions of coal and petroleum asphaltenes from laser desorption/ionization experiments

    SciTech Connect

    Ana R. Hortal; Paola Hurtado; Bruno Martinez-Haya; Oliver C. Mullins

    2007-09-15

    Molecular-weight distributions (MWDs) of asphaltenes extracted from coal and petroleum have been measured in laser desorption/ionization (LDI) mass spectrometric experiments. The dried-droplet and solvent-free sample preparation methods are compared. The coal asphaltenes have a relatively narrow MWD (full width 150 amu) with an average molecular weight of 340 amu. The petroleum asphaltenes display a broader MWD (full width 300 amu) and are heavier on average (680 amu). The LDI spectra also provide evidence for the formation of noncovalent clusters of the two types of asphaltenes during the desorption process. Petroleum and coal asphaltenes exhibit aggregation as do large model polycyclic aromatic hydrocarbons (PAHs) with five or more fused rings also included in the study. Smaller PAHs (pyrene) exhibit less aggregation, especially when alkane-chain substituents are incorporated to the molecular structure. This indicates that asphaltenes possess large PAHs and, according to the relatively small molecular weights observed, that there is a preponderance of asphaltene molecules with only a single fused ring system. The coal asphaltenes present a significantly smaller propensity toward aggregation than their crude oil counterparts. This finding, coupled with the fact that (1) alkanes inhibit aggregation in LDI and (2) petroleum asphaltenes possess much more alkane carbon, indicates that coal asphaltenes have smaller PAHs on average than petroleum asphaltenes. This is further corroborated by the stronger ultraviolet absorbance of the coal asphaltenes at wavelengths shorter than 400 nm. 32 refs., 8 figs.

  16. Experimental Investigation of Molecular Species Formation in Metal Plasmas During Laser Ablation

    NASA Astrophysics Data System (ADS)

    Radousky, H.; Crowhurst, J.; Rose, T.; Armstrong, M.; Stavrou, E.; Zaug, J.; Weisz, D.; Azer, M.; Finko, M.; Curreli, D.

    2016-10-01

    Atomic and molecular spectra on metal plasmas generated by laser ablation have been measured using single, nominally 6-7 ns pulses at 1064 nm, and with energies less than 50 mJ. The primary goal for these studies is to constrain the physical and chemical mechanisms that control the distribution of radionuclides in fallout after a nuclear detonation. In this work, laser emission spectroscopy was used to obtain in situdata for vapor phase molecular species as they form in a controlled oxygen atmosphere for a variety of metals such as Fe, Al, as well as preliminary results for U. In particular, the ablation plumes created from these metals have been imaged with a resolution of 10 ns, and it is possible to observe the expansion of the plume out to 0.5 us. These data serve as one set of inputs for a semi-empirical model to describe the chemical fractionation of uranium during fallout formation. Prepared by LLNL under Contract DE-AC52-07NA27344. This project was sponsored by the Department of the Defense, Defense Threat Reduction Agency, under Grant Number HDTRA1-16-1-0020.

  17. Fundamental studies in the molecular basis of laser-induced retinal damage. Annual report, February-September 1981

    SciTech Connect

    Lewis

    1981-09-01

    Laser-spectroscopy experiments have focused on cones in the red-eared swamp turtle, Pseudemys scripta elegans. Choice of this system was based on the desire to correlate molecular data with the extensive data being collected on this system by Dr. Zwick in his studies on laser hazards at LAIR. Thus, a detailed collaborative effort was initiated on this system during the past year. The experiments resulted in important information that opens new avenues to explore fundamental molecular mechanisms of retinal damage with laser irradiation. Results of these experiments are summarized in the following sections: I. Elucidation of the role of oil droplets in the absorption of light by the turtle retina; II. A Selective Probe of Membrane Potentials in Turtle Cone Cells; III. Angstrom Resolution Light Microscopy of Photoreceptor Cells; IV. Identification and Selective Staining of Other Important Molecular Components of Photoreceptor Cells.

  18. Fundamental studies in the molecular basis of laser-induced retinal damage. Annual report, September 1981-August 1982

    SciTech Connect

    Lewis

    1982-09-01

    This research led to new insights in the fundamental mechanisms involved in laser induced retinal damage and some of the fundamental work on these mechanisms lead to new and exciting avenues in the development of rapidly adjustable molecular light filters with important new possibilities for pulsed-laser eye protection. This report summarizes the significant progress of the past year: (1) Development and Fundamental Mechanism of a Rapidly Adjustable Molecular Filter for Pulsed Laser Eye Protection - this research direction resulted from our investigations on cones of the red-eared swamp turtle, Pseudemys scripta elegans. (2) The Optical Density of Turtle Oil Droplet Solutions - it is important both from a practical and fundamental point of view to determine the optical density of turtle oil-droplet suspensions. In view of the high optical densities in this system, tunable-laser resonance Raman spectroscopy, which is the only technique that has been able to provide high-resolution data, is the only technique that is potentially able to obtain the information. (3) Laser-Induced Molecular Alterations in Turtle Retina. (4) Light Driven Enzymatic Reactions in Photoreceptors. (5) Molecular Cytology of Rod Outer Segments.

  19. Precise measurements of the total concentration of atmospheric CO2 and 13CO2/12CO2 isotopic ratio using a lead-salt laser diode spectrometer.

    PubMed

    Croizé, Laurence; Mondelain, Didier; Camy-Peyret, Claude; Delmotte, Marc; Schmidt, Martina

    2008-04-01

    We have developed a tunable diode laser spectrometer, called SIMCO (spectrometer for isotopic measurements of CO(2)), for determining the concentrations of (12)CO(2) and (13)CO(2) in atmospheric air, from which the total concentration of CO(2) and the isotopic composition (expressed in delta units) delta(13)CO(2) are calculated. The two concentrations are measured using a pair of lines around 2290.1 cm(-1), by fitting a line profile model, taking into account the confinement narrowing effect to achieve a better accuracy. Using the Allan variance, we have demonstrated (for an integration time of 25 s) a precision of 0.1 ppmv for the total CO(2) concentration and of 0.3[per thousand] for delta(13)CO(2). The performances on atmospheric air have been tested during a 3 days campaign by comparing the SIMCO instrument with a gas chromatograph (GC) for the measurement of the total CO(2) concentration and with an isotopic ratio mass spectrometer (MS) for the isotopic composition. The CO(2) concentration measurements of SIMCO are in very good agreement with the GC data with a mean difference of Delta(CO(2))=0.16+/-1.20 ppmv for a comparison period of 45 h and the linearity of the concentration between the two instruments is also very good (slope of correlation: 0.9996+/-0.0003) over the range between 380 and 415 ppmv. For delta(13)CO(2), the comparison with the MS data shows a larger mean difference of Delta(delta(13)CO(2))=(-1.9+/-1.2)[per thousand], which could be partly related to small residual fluctuations of the overall SIMCO instrument response.

  20. Self-structured surface patterns on molecular azo glass films induced by laser light irradiation.

    PubMed

    Yin, Jianjun; Ye, Gang; Wang, Xiaogong

    2010-05-04

    In this work, formation of photoinduced self-structured surface pattern and its correlation with chromophoric structures were studied by using a series of star-shaped azo compounds, which exist as stable molecular glass at room temperature. For the synthesis, a star-shaped precursor (Tr-AN) was prepared by a ring-open reaction between 1, 3, 5-triglycidyl isocyanurate and N-methylaniline. The star-shaped azo compounds were then synthesized through azo-coupling reactions between the precursor and diazonium salts of 4-nitroaniline, 2-methyl-4-nitroaniline, and 4-aminobenzonitrile, respectively. Through these steps, three azo compounds were obtained to bear different donor-acceptor type azo chromophores at the peripheral positions. The formation of the photoinduced self-structured patterns was investigated by irradiating solid thin films of the molecular azo glass with a uniform laser beam (532 nm, 200 mW/cm(2)) at normal incidence. For comparison, formation of surface-relief-gratings (SRGs) was also investigated by exposing the thin films to an interference pattern of the laser beams (532 nm, 80 mW/cm(2)). The results show that SRGs can be inscribed on the films of all three star-shaped azo compounds, but self-structured surface patterns is only observed on film of the azo compound containing 4-cyanoazobenzene moieties (Tr-AZ-CN) under the same irradiation condition. The electron-withdrawing groups, which control the absorption band position, show a significant influence on both the self-structured pattern formation and SRG inscription rate. Under proper experimental conditions, both self-structured surface pattern and SRG can simultaneously be observed on the Tr-AZ-CN films. The observations can lead to a deeper understanding of the photoinduced effects, especially their correlation with molecular structures.

  1. Silver nanoparticles on zeolite surface for laser desorption/ionization mass spectrometry of low molecular weight compounds

    NASA Astrophysics Data System (ADS)

    Yang, Mengrui; Fujino, Tatsuya

    2013-06-01

    Silver nanoparticles loaded on NH4+-type zeolite, AgNPs-NH4ZSM5, was developed as an inorganic matrix for laser desorption/ionization mass spectrometry of low molecular weight compounds. It was found that AgNPs-NH4ZSM5 could work as an efficient Ag+ donor to ionize analytes and that zeolite worked as a heat bath to prevent the destruction of AgNPs after the photoexcitation. The AgNPs-NH4ZSM5 was applied to laser desorption/ionization mass spectrometry of biologically active substances with low molecular weights including acetylsalicylic acid, L-histidine, glucose, urea, cholesterol, and those in human serum.

  2. Stable Isotope Composition of Molecular Oxygen in Soil Gas and Groundwater: A Potentially Robust Tracer for Diffusion and Oxygen Consumption Processes

    NASA Astrophysics Data System (ADS)

    Aggarwal, Pradeep K.; Dillon, M. A.

    1998-02-01

    We have measured the concentration and isotopic composition of molecular oxygen in soil gas and groundwater. At a site near Lincoln, Nebraska, USA, soil gas oxygen concentrations ranged from 13.8 to 17.6% at depths of 3-4 m and the δ 18O values ranged mostly from 24.0 to 27.2‰ (SMOW). The concentration of dissolved oxygen in a perched aquifer in the Texas Panhandle (depth to water ˜76 m) was about 5 mg/L and the δ 18O values were 21.2-22.9‰. The δ 18O of soil gas oxygen in our study are higher and those of dissolved oxygen are lower than the δ 18O of atmospheric oxygen (23.5‰). A model for the oxygen concentration and isotopic composition in soil gas was developed using the molecular diffusion theory. The higher δ 18O values in soil gas at the Nebraska site can be explained by the effects of diffusion and soil respiration (plant root and bacterial) on the isotopic composition of molecular oxygen. The lower δ 18O of dissolved oxygen at the Texas site indicates that oxygen consumption below the root zone in the relatively thick unsaturated zone here may have occurred with a different fractionation factor (either due to inorganic consumption or due to low respiration rates) than that observed for the dominant pathways of plant root and bacterial respiration. It is concluded that the use of the concentration and isotopic composition of soil gas and dissolved oxygen should provide a robust tool for studying the subsurface gaseous diffusion and oxygen consumption processes.

  3. Influence of relative abundance of isotopes on depth resolution for depth profiling of metal coatings by laser ablation inductively coupled plasma mass spectrometry.

    PubMed

    Fariñas, Juan C; Coedo, Aurora G; Dorado, Teresa

    2010-04-15

    A systematic study on the influence of relative abundance of isotopes of elements in the coating (A(c)) and in the substrate (A(s)) on both shape of time-resolved signals and depth resolution (Delta z) was performed for depth profile analysis of metal coatings on metal substrates by ultraviolet (266 nm) nanosecond laser ablation inductively coupled plasma quadrupole mass spectrometry. Five coated samples with coating thicknesses of the same order of magnitude (20-30 microm) were tested: nickel coating on aluminium, chromium and copper, and steel coated with copper and zinc. A laser repetition rate of 1 Hz and a laser fluence of 21 J cm(-2) were used. Five different depth profile types were established, which showed a clear dependence on A(c)/A(s) ratio. In general, depth profiles obtained for ratios above 1-10 could not be used to determine Delta z. We found that Delta z increased non-linearly with A(c)/A(s) ratio. The best depth profile types, leading to highest depth resolution and reproducibility, were attained in all cases by using the isotopes with low/medium A(c) values and with the highest A(s) values. In these conditions, an improvement of up to 4 times in Delta z values was achieved. The average ablation rates were in the range from 0.55 microm pulse(-1) for copper coating on steel to 0.83 microm pulse(-1) for zinc coating on steel, and the Delta z values were between 2.74 microm for nickel coating on chromium and 5.91 microm for nickel coating on copper, with RSD values about 5-8%.

  4. Molecular isotopic evidence for anaerobic oxidation of methane in deep-sea hydrothermal vent environment in Okinawa Trough

    NASA Astrophysics Data System (ADS)

    Uchida, M.; Takai, K.; Inagaki, F.

    2003-04-01

    Large amount of methane in anoxic marine sediments as well as cold seeps and hydrothermal vents is recycled through for an anoxic oxidation of methane processes. Now that combined results of field and laboratory studies revealed that microbiological activity associated with syntrophic consortium of archaea performing reversed methanogenesis and sulfate-reducing bacteria is significant roles in methane recycling, anaerobic oxidation of methane (AOM). In this study, we examined the diversity of archaeal and bacterial assemblages of AOM using compound-specific stable carbon isotopic and phylogenetic analyses. "Iheya North" in Okinawa Trough is sediment-rich, back arc type hydrothermal system (27^o47'N, 126^o53'E). Sediment samples were collected from three sites where are "bubbling sites", yellow-colored microbial mats are formed with continuous bubbling from the seafloor bottom, vent mussel's colonies site together with slowly venting and simmering, and control site off 100 m distance from thermal vent. This subsea floor structure has important effect in the microbial ecosystem and interaction between their activity and geochemical processes in the subseafloor habitats. Culture-independent, molecular biological analysis clearly indicated the presence of thermophilic methanogens in deeper area having higher temperatures and potential activity of AMOs consortium in the shallower area. AMO is composed with sulfate-reducing bacterial components (Desulfosarcina spp.) and anoxic methane oxidizing archaea (ANME-2). These results were consistent with the results of compound-specific carbon analysis of archaeal biomarkers. They showed extremely depleted 13C contents (-80 ppm ˜ -100 ppm), which also appeared to be capable of directly oxidizing methane.

  5. Are molecular and isotopic patterns in modern plants representative of ancient floras? Examples from Paleocene and Eocene floras and sediments in the Bighorn Basin (WY, USA)

    NASA Astrophysics Data System (ADS)

    Diefendorf, A. F.; Freeman, K. H.; Wing, S. L.; Currano, E. D.

    2011-12-01

    In modern ecosystems, climate, biome and plant community are important predictors of carbon isotope patterns recorded in leaves, leaf waxes, and leaf terpenoids. However, it is unclear if modern carbon isotope patterns are useful analogs in the past when climate and atmospheric CO2 conditions were drastically different than today. It is also uncertain if molecular carbon isotope approaches are more robust with respect to reconstructing patterns of atmospheric δ13C compared to bulk isotope approaches. To evaluate these questions, we present a study of carbon isotope values of bulk organic matter and biomarkers for terrestrial plants (di- and triterpenoids and n-alkanes) from the late Paleocene (62 MA) to the Early Eocene Climatic Optimum (EECO; 52.6 MA) in the Bighorn Basin (WY, USA). We sampled along eight laterally extensive outcrops from the Fort Union and Willwood Formations. Each unit varies in exposure from tens of meters to eighteen kilometers. Sediment lithology includes carbonaceous mudstones, shales, and lignites with total organic carbon ranging from 0.2% to 55%. Climate during this interval, as determined from fossil leaf metrics, warmed from the cooler Paleocene (~10.5°C) to the hot Eocene (~22.2°C) with mean annual precipitation varying from 110 to 170 cm. We collected multiple samples across a laterally extensive outcrop to capture previously reported spatial variability in flora and depositional environment. Carbon isotopes of bulk organic matter, n-alkanes, and di- and triterpenoids (specific for conifers and angiosperms, respectively) were characterized. To determine if plant biomarker relationships from modern plants are applicable to ancient plants, we reconstructed carbon isotope fractionation during photosynthesis (Δleaf) from biomarker carbon isotope values (n-alkanes and terpenoids) and from δ13C values of atmospheric CO2 estimated from planktonic foraminifera. Reconstructed Δleaf values are consistent with predicted Δleaf values when

  6. Hydrodynamic Determinants of Cell Necrosis and Molecular Delivery Produced by Pulsed Laser Microbeam Irradiation of Adherent Cells

    PubMed Central

    Compton, Jonathan L.; Hellman, Amy N.; Venugopalan, Vasan

    2013-01-01

    Time-resolved imaging, fluorescence microscopy, and hydrodynamic modeling were used to examine cell lysis and molecular delivery produced by picosecond and nanosecond pulsed laser microbeam irradiation in adherent cell cultures. Pulsed laser microbeam radiation at λ = 532 nm was delivered to confluent monolayers of PtK2 cells via a 40×, 0.8 NA microscope objective. Using laser microbeam pulse durations of 180–1100 ps and pulse energies of 0.5–10.5 μJ, we examined the resulting plasma formation and cavitation bubble dynamics that lead to laser-induced cell lysis, necrosis, and molecular delivery. The cavitation bubble dynamics are imaged at times of 0.5 ns to 50 μs after the pulsed laser microbeam irradiation, and fluorescence assays assess the resulting cell viability and molecular delivery of 3 kDa dextran molecules. Reductions in both the threshold laser microbeam pulse energy for plasma formation and the cavitation bubble energy are observed with decreasing pulse duration. These energy reductions provide for increased precision of laser-based cellular manipulation including cell lysis, cell necrosis, and molecular delivery. Hydrodynamic analysis reveals critical values for the shear-stress impulse generated by the cavitation bubble dynamics governs the location and spatial extent of cell necrosis and molecular delivery independent of pulse duration and pulse energy. Specifically, cellular exposure to a shear-stress impulse J≳0.1 Pa s ensures cell lysis or necrosis, whereas exposures in the range of 0.035≲J≲0.1 Pa s preserve cell viability while also enabling molecular delivery of 3 kDa dextran. Exposure to shear-stress impulses of J≲0.035 Pa s leaves the cells unaffected. Hydrodynamic analysis of these data, combined with data from studies of 6 ns microbeam irradiation, demonstrates the primacy of shear-stress impulse in determining cellular outcome resulting from pulsed laser microbeam irradiation spanning a nearly two

  7. Angular correlations of photons from solution diffraction at a free-electron laser encode molecular structure

    PubMed Central

    Mendez, Derek; Watkins, Herschel; Qiao, Shenglan; Raines, Kevin S.; Lane, Thomas J.; Schenk, Gundolf; Nelson, Garrett; Subramanian, Ganesh; Tono, Kensuke; Joti, Yasumasa; Yabashi, Makina; Ratner, Daniel; Doniach, Sebastian

    2016-01-01

    During X-ray exposure of a molecular solution, photons scattered from the same molecule are correlated. If molecular motion is insignificant during exposure, then differences in momentum transfer between correlated photons are direct measurements of the molecular structure. In conventional small- and wide-angle solution scattering, photon correlations are ignored. This report presents advances in a new biomolecular structural analysis technique, correlated X-ray scattering (CXS), which uses angular intensity correlations to recover hidden structural details from molecules in solution. Due to its intense rapid pulses, an X-ray free electron laser (XFEL) is an excellent tool for CXS experiments. A protocol is outlined for analysis of a CXS data set comprising a total of half a million X-ray exposures of solutions of small gold nanoparticles recorded at the Spring-8 Ångström Compact XFEL facility (SACLA). From the scattered intensities and their correlations, two populations of nanoparticle domains within the solution are distinguished: small twinned, and large probably non-twinned domains. It is shown analytically how, in a solution measurement, twinning information is only accessible via intensity correlations, demonstrating how CXS reveals atomic-level information from a disordered solution of like molecules. PMID:27840681

  8. Angular correlations of photons from solution diffraction at a free-electron laser encode molecular structure

    DOE PAGES

    Mendez, Derek; Watkins, Herschel; Qiao, Shenglan; ...

    2016-09-26

    During X-ray exposure of a molecular solution, photons scattered from the same molecule are correlated. If molecular motion is insignificant during exposure, then differences in momentum transfer between correlated photons are direct measurements of the molecular structure. In conventional small- and wide-angle solution scattering, photon correlations are ignored. This report presents advances in a new biomolecular structural analysis technique, correlated X-ray scattering (CXS), which uses angular intensity correlations to recover hidden structural details from molecules in solution. Due to its intense rapid pulses, an X-ray free electron laser (XFEL) is an excellent tool for CXS experiments. A protocol is outlinedmore » for analysis of a CXS data set comprising a total of half a million X-ray exposures of solutions of small gold nanoparticles recorded at the Spring-8 Ångström Compact XFEL facility (SACLA). From the scattered intensities and their correlations, two populations of nanoparticle domains within the solution are distinguished: small twinned, and large probably non-twinned domains. Finally, it is shown analytically how, in a solution measurement, twinning information is only accessible via intensity correlations, demonstrating how CXS reveals atomic-level information from a disordered solution of like molecules.« less

  9. Angular correlations of photons from solution diffraction at a free-electron laser encode molecular structure

    SciTech Connect

    Mendez, Derek; Watkins, Herschel; Qiao, Shenglan; Raines, Kevin S.; Lane, Thomas J.; Schenk, Gundolf; Nelson, Garrett; Subramanian, Ganesh; Tono, Kensuke; Joti, Yasumasa; Yabashi, Makina; Ratner, Daniel; Doniach, Sebastian

    2016-09-26

    During X-ray exposure of a molecular solution, photons scattered from the same molecule are correlated. If molecular motion is insignificant during exposure, then differences in momentum transfer between correlated photons are direct measurements of the molecular structure. In conventional small- and wide-angle solution scattering, photon correlations are ignored. This report presents advances in a new biomolecular structural analysis technique, correlated X-ray scattering (CXS), which uses angular intensity correlations to recover hidden structural details from molecules in solution. Due to its intense rapid pulses, an X-ray free electron laser (XFEL) is an excellent tool for CXS experiments. A protocol is outlined for analysis of a CXS data set comprising a total of half a million X-ray exposures of solutions of small gold nanoparticles recorded at the Spring-8 Ångström Compact XFEL facility (SACLA). From the scattered intensities and their correlations, two populations of nanoparticle domains within the solution are distinguished: small twinned, and large probably non-twinned domains. Finally, it is shown analytically how, in a solution measurement, twinning information is only accessible via intensity correlations, demonstrating how CXS reveals atomic-level information from a disordered solution of like molecules.

  10. Laser cooling of vibrational degrees of freedom of a molecular system.

    PubMed

    Banerjee, Sumana; Gangopadhyay, Gautam

    2005-09-15

    We consider the cooling of vibrational degrees of freedom in a photoinduced excited electronic state of a model molecular system. For the various parameters of the potential surfaces of the ground and excited electronic states and depending on the excitation frequency of a single-mode laser light, the average energy or average vibrational temperature of the excited state passes through a minimum. The amount of cooling is quantified in terms of the overlap integral between the ground and excited electronic states of the molecule. We have given an approach to calculate the Franck-Condon factor for a multimode displaced-distorted-rotated oscillator surface of the molecular system. This is subsequently used to study the effect of displacement, distortion, and Duschinsky rotation on the vibrational cooling in the excited state. The absorption spectra and also the average energy or the effective temperature of the excited electronic state are studied for the above model molecular system. Considering the non-Condon effect for the symmetry-forbidden transitions, we have discussed the absorption spectra and average temperature in the excited-state vibrational manifold.

  11. Hybrid isotope separation scheme

    DOEpatents

    Maya, J.

    1991-06-18

    A method is described for yielding selectively a desired enrichment in a specific isotope including the steps of inputting into a spinning chamber a gas from which a scavenger, radiating the gas with a wave length or frequency characteristic of the absorption of a particular isotope of the atomic or molecular gas, thereby inducing a photochemical reaction between the scavenger, and collecting the specific isotope-containing chemical by using a recombination surface or by a scooping apparatus. 2 figures.

  12. Hybrid isotope separation scheme

    DOEpatents

    Maya, Jakob

    1991-01-01

    A method of yielding selectively a desired enrichment in a specific isotope including the steps of inputting into a spinning chamber a gas from which a scavenger, radiating the gas with a wave length or frequency characteristic of the absorption of a particular isotope of the atomic or molecular gas, thereby inducing a photochemical reaction between the scavenger, and collecting the specific isotope-containing chemical by using a recombination surface or by a scooping apparatus.

  13. Differentiation of Natural and Anthropogenic Organic Compounds on Atmospheric Particles by Molecular and Stable Isotope Composition - Pacific 2001, Lower Fraser Valley Air Shed Study

    NASA Astrophysics Data System (ADS)

    Whiticar, M. J.; Press, R.; Gray, S. L.

    2002-12-01

    This component of the CFCAS Pacific 2001 study examined the character of specific non-volatile organic compounds (nVOCs) extracted from filtered total suspended particulates at the Pacific 2001 sites in the Lower Fraser Valley (LFV), Vancouver, BC region. The objective is to identify or fingerprint spatial and temporal variations in both molecular and stable isotope composition of these organic compounds with the goal of understanding their sources or to provide insights into transport and/or atmospheric chemistry processes. This will provide critical information to help assess the potential type and magnitude of exposure that humans receive from nVOCs in such urban settings, and the associated health risks. Aerosol samples were collected over 24hr to 7-day period on HiVol filters in the LFV at Slocan Park, Golden Ears Park, Langley HS, Sumas Mt., and Cassiar Tunnel (2hr). nVOCs s were solvent-extracted from filters, then separated into different compound classes by silica-gel chromatography. Selected fractions are analysed for their individual compound molecular compositions by Gas Chromatography-Mass Spectrometry (GC/MS) and by Continuous Flow-Isotope Ratio Mass Spectrometry (CF-IRMS) for their stable carbon ratio. Significant variations in nVOC composition are observed for the 5 LFV sites. These are related to a combination of natural and anthropogenic urban activities. The most striking discovery is the strong odd-even carbon number predominance (OEP) observed for BOTH molecular and carbon isotope data. Recent natural release of hydrocarbons from plants have a clear predominance for the odd-carbon numbered n-alkanes. These C23 - C31 compounds are also systematically depleted in 13-C. The carbon isotope range between the odd and even compounds is up to 10 permil for the plant signatures. Anthropogenic and "aged" hydrocarbons have substantially lower molecular and isotope OEPs. This novel biogeochemical approach has good potential for estimating broad source

  14. Measurement of the {}^{{20,22}}Ne {}^{3}{{\\rm{P}}}_{2}{{\\rm{{--}}}}^{3}{{\\rm{D}}}_{3} transition isotope shift using a single, phase-modulated laser beam

    NASA Astrophysics Data System (ADS)

    Ohayon, B.; Gumpel, G.; Ron, G.

    2017-03-01

    We develop a simple technique to accurately measure frequency differences between far-lying resonances in a spectroscopy signal using a single, unlocked laser. This technique was used to measure the isotope shift (IS) of the cooling transition of metastable neon. Our result of 1626.287(53) MHz is the most accurate determination of this value to date.

  15. Methods Development for In Situ Laser-Ablation Pb and Sr Isotopic Analyses Using a Double-Focusing Single-Collector ICPMS

    NASA Astrophysics Data System (ADS)

    Pietruszka, A. J.; Neymark, L. A.

    2014-12-01

    Laser-ablation (LA) ICPMS isotopic analyses of Pb and Sr in geological materials have mostly used multi-collector instruments equipped with Faraday-type detectors (e.g., [1-3]). The main limitation of this approach is that samples with relatively high concentrations of Pb and Sr are typically required. Here we present the development of analytical methods for the accurate and precise in situ measurement of Pb and Sr isotope ratios in relatively low-concentration samples using a laser ablation system (193-nm excimer laser) with a double-focusing single-collector (SC) ICPMS (Nu AttoMTM). Our methods build on published techniques [4-6] that used different LA-SC-ICPMS instrumentation to demonstrate the benefits of fast-scanning ion-counting measurements combined with flat-top peaks. We have paid special attention to the characterization and correction of instrumental artifacts using solutions of the NIST SRM981 Pb and SRM987 Sr standards in "wet plasma" mode. For Pb, this includes correcting for the interference of 204Hg on 204Pb, characterizing the effects of tails from thallium (at masses 203 and 205) on the Pb peaks, evaluating the stability of the instrumental mass bias, and maintaining linearity of the detector response over the full dynamic range. For Sr, this includes correcting for the interference of 86Kr on 86Sr and 87Rb on 87Sr, verifying the accuracy of an internal correction for instrumental mass bias, and calibrating the ion optics scanning parameters. LA-SC-ICPMS results for Pb and Sr isotopic measurements of international glass standards and newly developed in-house mineral and glass reference materials will be presented. [1] Davidson et al. (2001) EPSL 184, 427-442. [2] Ramos et al. (2004) Chem. Geol. 211, 135-158. [3] Simon et al. (2007) GCA 71, 2014-2035. [4] Jochum et al. (2005) IJMS 242, 281-289. [5] Jochum et al. (2006) JAAS 21, 666-675. [6] Jochum et al. (2009) JAAS 24, 1237-1243.

  16. The /A 1 Sigma +/ - /X 1 Sigma +/ system of the isotopic lithium hydrides - The molecular constants, potential energy curves, and their adiabatic corrections

    NASA Technical Reports Server (NTRS)

    Vidal, C. R.; Stwalley, W. C.

    1982-01-01

    The molecular constants and their adiabatic corrections have been determined for the (A 1 Sigma +) - (X 1 Sigma +) system of the isotopic lithium hydrides: (Li-6)H, (Li-7)H, (Li-6)D, and (Li-7)D. Using a fully quantum mechanical variational method, the potential energy curves (IPA potentials) are determined. Extending the variational method, we have obtained for the first time adiabatic corrections of potential energy curves from isotopic spectroscopic data. A significant difference between the potential energy curves of the lithium hydrides and the lithium deuterides has been observed. When Li-6 was replaced by Li-7, a significant difference was only observed for the (A 1 Sigma +) state, but not for the (X 1 Sigma +) state.

  17. H /D isotope effect on the dihydrogen bond of NH4+⋯BeH2 by ab initio path integral molecular dynamics simulation

    NASA Astrophysics Data System (ADS)

    Hayashi, Aiko; Shiga, Motoyuki; Tachikawa, Masanori

    2006-11-01

    In order to investigate the H /D isotope effect on a dihydrogen bonded cation system, we have studied NH4+⋯BeH2 and its isotopomers by ab initio path integral molecular dynamics. It is found that the dihydrogen bond can be exchanged by NH4+ rotation. The deuterated isotopomer (ND4+⋯BeD2; DD) can exchange the dihydrogen bond more easily than other isotopomers such as (NH4+⋯BeH2; HH). This unusual isotope effect is ascribed to the "quantum localization" which occurs when the effective energy barrier for the rotational mode becomes higher by the zero point energy of other modes. We also found that the binding energy of dihydrogen bonds for DD species is the smallest among the isotopomers.

  18. Damage in materials following ablation by ultrashort laser pulses: A molecular-dynamics study

    SciTech Connect

    Bouilly, Delphine; Perez, Danny; Lewis, Laurent J.

    2007-11-01

    The formation of craters following femtosecond- and picosecond-pulse laser ablation in the thermal regime is studied using a generic two-dimensional numerical model based on molecular-dynamics simulations and the Lennard-Jones potential. Femtosecond pulses are found to produce very clean craters through a combination of etching of the walls and the formation of a very thin heat affected zone. Our simulations also indicate that dislocations are emitted continuously during all of the ablation process (i.e., for hundreds of ps). For picosecond pulses, we observe much thicker heat affected zones which result from melting and recrystallization following the absorption of the light. In this case also, continuous emission of dislocations--though fewer in number--takes place throughout the ablation process.

  19. Cyan laser diode grown by plasma-assisted molecular beam epitaxy

    SciTech Connect

    Turski, H. Muziol, G.; Wolny, P.; Cywiński, G.

    2014-01-13

    We demonstrate AlGaN-cladding-free laser diodes (LDs), operating in continuous wave (CW) mode at 482 nm grown by plasma-assisted molecular beam epitaxy (PAMBE). The maximum CW output power was 230 mW. LDs were grown on c-plane GaN substrates obtained by hydride vapor phase epitaxy. The PAMBE process was carried out in metal-rich conditions, supplying high nitrogen flux (Φ{sub N}) during quantum wells (QWs) growth. We found that high Φ{sub N} improves quality of high In content InGaN QWs. The role of nitrogen in the growth of InGaN on (0001) GaN surface as well as the influence of LDs design on threshold current density are discussed.

  20. An intense, cold, velocity-controlled molecular beam by frequency-chirped laser slowing

    NASA Astrophysics Data System (ADS)

    Truppe, S.; Williams, H. J.; Fitch, N. J.; Hambach, M.; Wall, T. E.; Hinds, E. A.; Sauer, B. E.; Tarbutt, M. R.

    2017-02-01

    Using frequency-chirped radiation pressure slowing, we precisely control the velocity of a pulsed CaF molecular beam down to a few m s–1, compressing its velocity spread by a factor of 10 while retaining high intensity: at a velocity of 15 m s–1 the flux, measured 1.3 m from the source, is 7 × 105 molecules per cm2 per shot in a single rovibrational state. The beam is suitable for loading a magneto-optical trap or, when combined with transverse laser cooling, improving the precision of spectroscopic measurements that test fundamental physics. We compare the frequency-chirped slowing method with the more commonly used frequency-broadened slowing method.

  1. Identification and properties of molecular systems of potential use in solar-pumped lasers

    NASA Technical Reports Server (NTRS)

    Micha, D. A.; Oehrn, N. Y.

    1985-01-01

    The concepts and computational tools of theortical chemistry are used to investigate molecular properties needed in direct solar-pumped lasers. Compounds of the type RR'CXY, with R and R' organic groups, and X and Y halide atoms were identified as likely candidates because of their highly enhanced absorption coefficients over compounds with a single halide atom. The use of a combination of vibrational excitation followed by electronic excitation to enhance quantum yields at certain wavelengths is indicated. A self-consistent eikonal approximation to state-to-state transitions was tested for CH3I and is useful for other problems involving electronic energy and charge transfer. An approach to calculate potential energy surfaces and transition dipoles was developed which is based on the generation of eigenstates of the nonrelativisitc Hamiltonian followed by incorporation of the spin-orbit coupling by configuration interaction.

  2. Copper-coated laser-fusion targets using molecular-beam levitation

    SciTech Connect

    Rocke, M.J.

    1981-09-08

    A series of diagnostic experiments at the Shiva laser fusion facility required targets of glass microspheres coated with 1.5 to 3.0 ..mu..m of copper. Previous batch coating efforts using vibration techniques gave poor results due to microsphere sticking and vacuum welding. Molecular Beam Levitation (MBL) represented a noncontact method to produce a sputtered copper coating on a single glassmicrosphere. The coating specifications that were achieved resulted in a copper layer up to 3 ..mu..m thick with the allowance of a maximum variation of 10 nm in surface finish and thickness. These techniques developed with the MBL may be applied to sputter coat many soft metals for fusion target applications.

  3. Experimental Observation of Dynamical Localization in Laser-Kicked Molecular Rotors

    NASA Astrophysics Data System (ADS)

    Bitter, M.; Milner, V.

    2016-09-01

    The periodically kicked rotor is a paradigm system for studying quantum effects on classically chaotic dynamics. The wave function of the quantum rotor localizes in angular momentum space, similarly to Anderson localization of the electronic wave function in disordered solids. Here, we observe dynamical localization in a system of true quantum rotors by subjecting nitrogen molecules to periodic sequences of femtosecond pulses. Exponential distribution of the molecular angular momentum—the hallmark of dynamical localization—is measured directly by means of coherent Raman scattering. We demonstrate the suppressed rotational energy growth with the number of laser kicks and study the dependence of the localization length on the kick strength. Because of its quantum coherent nature, both timing and amplitude noise are shown to destroy the localization and revive the diffusive growth of energy.

  4. Molecular dynamics simulations of laser induced surface melting in orthorhombic Al13Co4

    NASA Astrophysics Data System (ADS)

    Sonntag, S.; Roth, J.; Trebin, H.-R.

    2010-10-01

    Laser induced surface melting of the aluminum-cobalt alloy Al13Co4 is investigated. For the simulations of the lattice ions we use molecular dynamics, while for the time evolution of the electron temperature a generalized heat-conduction equation is solved. Energy transfer between the sub-systems is allowed by an electron-phonon coupling term. This combined treatment of the electronic and atomic systems is an extension of the well-known two-temperature model [Anisimov et al. in JETP Lett. 39(2), 1974]. The alloy shows large structural affinity to decagonal quasicrystals, which have an in-plane five-fold symmetry,while in perpendicular direction the planes are stacked periodically. As a consequence we observe slight anisotropic melting behavior.

  5. Laser-induced breathing modes in metallic nanoparticles: A symmetric molecular dynamics study

    SciTech Connect

    Ng, Ming-Yaw; Chang, Yia-Chung

    2011-03-07

    A highly efficient simulation method based on molecular dynamics and group theory is adopted to investigate the laser-induced breathing oscillation of gold and silver nanospheres. Nanoparticles with size ranging from 5.8 to 46.2 nm are discussed. The effect due to laser-induced heating is modeled by a symmetric sudden expansion of the nanospheres by increasing the interatomic distances. A long-range empirical potential model which is capable of describing the phonon dispersion curves of noble metals in the full frequency range is established. Group theory is fully exploited to increase the computation efficiency, and the oscillation behavior of nanospheres of over 3 x 10{sup 6} atoms can be simulated efficiently. Oscillation frequencies of nanospheres are obtained by calculating the Fourier transform of the velocity autocorrelation function. The breathing modes of nanospheres are identified as the excitation of A{sub 1g} modes with in-phase radial displacement of atoms in the nanospheres. The resulting oscillation spectra are in very good agreement with experimental data.

  6. Molecular fingerprinting with the resolved modes of a femtosecond laser frequency comb.

    PubMed

    Diddams, Scott A; Hollberg, Leo; Mbele, Vela

    2007-02-08

    The control of the broadband frequency comb emitted from a mode-locked femtosecond laser has permitted a wide range of scientific and technological advances--ranging from the counting of optical cycles for next-generation atomic clocks to measurements of phase-sensitive high-field processes. A unique advantage of the stabilized frequency comb is that it provides, in a single laser beam, about a million optical modes with very narrow linewidths and absolute frequency positions known to better than one part in 10(15) (ref. 5). One important application of this vast array of highly coherent optical fields is precision spectroscopy, in which a large number of modes can be used to map internal atomic energy structure and dynamics. However, an efficient means of simultaneously identifying, addressing and measuring the amplitude or relative phase of individual modes has not existed. Here we use a high-resolution disperser to separate the individual modes of a stabilized frequency comb into a two-dimensional array in the image plane of the spectrometer. We illustrate the power of this technique for high-resolution spectral fingerprinting of molecular iodine vapour, acquiring in a few milliseconds absorption images covering over 6 THz of bandwidth with high frequency resolution. Our technique for direct and parallel accessing of stabilized frequency comb modes could find application in high-bandwidth spread-spectrum communications with increased security, high-resolution coherent quantum control, and arbitrary optical waveform synthesis with control at the optical radian level.

  7. Comparative study on atomic and molecular Rydberg-state excitation in strong infrared laser fields

    NASA Astrophysics Data System (ADS)

    Lv, Hang; Zuo, Wanlong; Zhao, Lei; Xu, Haifeng; Jin, Mingxing; Ding, Dajun; Hu, Shilin; Chen, Jing

    2016-03-01

    Rydberg-state excitation of atoms in strong infrared laser fields provides a new complementary aspect of the perspective of atom-strong field interactions. In this article, we perform an experimental and theoretical study on the corresponding process of diatomic molecules, N2 and O2. We show that neutral molecules can also survive strong 800-nm laser fields in high Rydberg states, while their behavior is remarkably different in comparison with their companion atoms, Ar and Xe. The Rydberg excitation of N2 generally behaves similarly to Ar, while that of O2 is more significantly suppressed than the ionization compared to Xe in a high intensity region, which can be understood in the frame of a semiclassical picture, together with their different structures of molecular orbitals. However, distinct quantum features in the Rydberg excitation processes that are apparently beyond the semiclassical picture have been identified, i.e., the less suppressed probability of O2 at low intensity and the oscillation behavior of the ratio between N2 and Ar, indicating that our understanding of the relevant physics is still far from complete.

  8. Subwavenumber charge-coupled device spectrometer calibration using molecular iodine laser-induced fluorescence

    SciTech Connect

    Lambert, Joseph G.; Hernandez-Diaz, Carlos; Williamson, J. Charles

    2010-01-15

    Spectrometers configured with charge-coupled devices (CCD) or other array-based detectors require calibration to convert from the pixel coordinate to a spectral coordinate. A CCD calibration method well suited for Raman spectroscopy has been developed based on the 514.5 nm Ar{sup +} laser-induced fluorescence (LIF) spectrum of room-temperature molecular iodine vapor. Over 360 primary and secondary I{sub 2} LIF calibration lines spanning 510-645 nm were identified as calibrant peaks using an instrumental resolution of 1 cm{sup -1}. Two instrument calibration functions were evaluated with these peaks: a second-order polynomial and a function derived from simple optomechanical considerations. The latter function provided better fitting characteristics. Calibration using I{sub 2} LIF was tested with measurements of both laser light scattering and Raman spectra. The I{sub 2} LIF reference spectra and the signal spectra were recorded simultaneously, with no cross talk, by separating the two signals spatially along the vertical axis of the CCD imager. In this way, every CCD image could be independently calibrated. An accuracy and a precision of {+-}0.05 cm{sup -1} were achieved with this calibration technique.

  9. Laser surface modification of ultra-high-molecular-weight polyethylene (UHMWPE) for biomedical applications

    NASA Astrophysics Data System (ADS)

    Riveiro, A.; Soto, R.; del Val, J.; Comesaña, R.; Boutinguiza, M.; Quintero, F.; Lusquiños, F.; Pou, J.

    2014-05-01

    Ultra-high-molecular-weight polyethylene (UHMWPE) is a synthetic polymer used for biomedical applications because of its high impact resistance, ductility and stability in contact with physiological fluids. Therefore, this material is being used in human orthopedic implants such as total hip or knee replacements. Surface modification of this material relates to changes on its chemistry, microstructure, roughness, and topography, all influencing its biological response. Surface treatment of UHMWPE is very difficult due to its high melt viscosity. This work presents a systematic approach to discern the role of different laser wavelengths (λ = 1064, 532, and 355 nm) on the surface modification of carbon coated UHMWPE samples. Influence of laser processing conditions (irradiance, pulse frequency, scanning speed, and spot overlapping) on the surface properties of this material was determined using an advanced statistical planning of experiments. A full factorial design of experiments was used to find the main effects of the processing parameters. The obtained results indicate the way to maximize surface properties which largely influence cell-material interaction.

  10. Observation of Femtosecond, Sub-Angstrom Molecular Bond Relaxation Using Laser-Induced Electron Diffraction

    NASA Astrophysics Data System (ADS)

    Blaga, Cosmin I.; Dichiara, Anthony D.; Zhang, Kaikai; Sistrunk, Emily; Agostini, Pierre; Dimauro, Louis F.; Xu, Junliang; Lin, Chii-Dong; Miller, Terry A.

    2011-06-01

    Imaging, or the determination of the atomic positions in molecules, has always occupied an essential role in physical, chemical and biological sciences. For structural determination, the well established methods of X-ray and electron diffraction easily achieve sub-Angstrom spatial resolution. However, these conventional approaches are not suitable for investigating structural transformations, such as the reaction of molecules or the function of biological systems that occur on the timescales faster than a picosecond. Over the past decade, major efforts directed at developing femtosecond pulsed sources, e.g. X-ray free-electron lasers and electron beams, have resulted in pioneering investigations on imaging large biological molecules and condensed phase dynamics. We report on a different approach, laser-induced electron diffraction (LIED), for achieving sub-femtosecond, sub-Angstrom spatio-temporal resolution for investigating gas-phase molecular dynamics. In contrast to the above mentioned techniques, the LIED method generates bursts of coherent electron wave packets directly from the molecule under interrogation. The study is performed by measuring the diffracted photoelectron momentum distribution produced by strong-field ionization of oxygen and nitrogen molecules at several mid-infrared wavelengths (1.7-2.3 μm). The bond lengths retrieved from the LIED analysis show sensitivity to a change of 0.05 Å in 1 fs. This initial report provides the first direct evidence of bond relaxation following an electronic excitation and establishes the foundation of the LIED method as a general approach for ultrafast imaging of molecular dynamics.

  11. Determining the stable isotope composition of pore water from saturated and unsaturated zone core: improvements to the direct vapor equilibration laser spectroscopy method

    NASA Astrophysics Data System (ADS)

    Hendry, M. J.; Schmeling, E.; Wassenaar, L. I.; Barbour, S. L.; Pratt, D.

    2015-06-01

    A method to measure the δ2H and δ18O composition of pore waters in saturated and unsaturated geologic core samples using direct vapor equilibration and laser spectroscopy (DVE-LS) was first described in 2008, and has since been widely adopted by others. Here, we describe a number of important methodological improvements and limitations encountered in routine application of DVE-LS over several years. Generally, good comparative agreement and accuracy is obtained between core pore water isotopic data obtained using DVE-LS and that measured on water squeezed from the same core. In complex hydrogeologic settings, high-resolution DVE-LS depth profiles provide greater spatial resolution of isotopic profiles compared to long-screened or nested piezometers. When fluid is used during drilling and coring (e.g., water rotary or wet sonic drill methods), spiking the drill fluid with 2H can be conducted to identify core contamination. DVE-LS analyses yield accurate formational isotopic data for fine-textured core (e.g., clay, shale) samples, but are less effective for cores obtained from saturated permeable (e.g., sand, gravels) geologic media or on chip samples that are easily contaminated by wet rotary drilling fluid. Data obtained from DVE-LS analyses of core samples collected using wet (contamination by drill water) and dry sonic (water loss by heating) methods were also problematic. Accurate DVE-LS results can be obtained on core samples with gravimetric water contents < 5 % by increasing the sample size tested. Inexpensive Ziploc™ gas sampling bags were determined to be as good as, if not better, than other, more expensive bags. Sample storage in gas tight sample bags provides acceptable results for up to 10 days of storage; however, measureable water loss and evaporitic isotopic enrichment occurs for samples stored for up to 6 months. With appropriate care taken during sample collection and storage, the DVE-LS approach for obtaining high resolution pore water

  12. Determining the stable isotope composition of pore water from saturated and unsaturated zone core: improvements to the direct vapour equilibration laser spectrometry method

    NASA Astrophysics Data System (ADS)

    Hendry, M. J.; Schmeling, E.; Wassenaar, L. I.; Barbour, S. L.; Pratt, D.

    2015-11-01

    A method to measure the δ2H and δ18O composition of pore waters in saturated and unsaturated geologic core samples using direct vapour equilibration and laser spectrometry (DVE-LS) was first described in 2008, and has since been rapidly adopted. Here, we describe a number of important methodological improvements and limitations encountered in routine application of DVE-LS over several years. Generally, good comparative agreement, as well as accuracy, is obtained between core pore water isotopic data obtained using DVE-LS and that measured on water squeezed from the same core. In complex hydrogeologic settings, high-resolution DVE-LS depth profiles provide greater spatial resolution of isotopic profiles compared to long-screened or nested piezometers. When fluid is used during drilling and coring (e.g. water rotary or wet sonic drill methods), spiking the drill fluid with 2H can be conducted to identify core contamination. DVE-LS analyses yield accurate formational isotopic data for fine-textured core (e.g. clay, shale) samples, but are less effective for cores obtained from saturated permeable (e.g. sand, gravels) geologic media or on chip samples that are easily contaminated by wet rotary drilling fluid. Data obtained from DVE-LS analyses of core samples collected using wet (contamination by drill water) and dry sonic (water loss by heating) methods were also problematic. Accurate DVE-LS results can be obtained on core samples with gravimetric water contents > 5 % by increasing the sample size tested. Inexpensive Ziploc™ gas-sampling bags were determined to be as good as, if not better than, other, more expensive specialty bags. Sample storage in sample bags provides acceptable results for up to 10 days of storage; however, measurable water loss, as well as evaporitic isotopic enrichment, occurs for samples stored for up to 6 months. With appropriate care taken during sample collection and storage, the DVE-LS approach for obtaining high-resolution pore water

  13. Novel stable isotope laser spectrometry elucidates changing mechanisms of CH4 production and consumption across a climate change sequence in an arctic wetland

    NASA Astrophysics Data System (ADS)

    McCalley, C. K.; Wehr, R.; Crill, P. M.; Chanton, J.; Hodgkins, S. B.; Nelson, D. D.; McManus, J. B.; Zahniser, M. S.; Rich, V.; Tyson, G.; Mondav, R.; Frolking, S.; Li, C.; Saleska, S. R.

    2011-12-01

    Methane flux from high latitude wetlands is both a critical component of the global CH4 budget, and highly sensitive to global climate change, with expected increases in emissions as permafrost thaws. Gaps in our understanding of the mechanisms driving changing CH4 production and consumption dynamics under permafrost thaw, however, limit our ability to predict the magnitude of this response under future climate conditions. To address these gaps, we quantified the isotopic composition of carbon gas fluxes (δ13C of CH4 and CO2) from a high latitude (68° N) wetland in Sweden (Stordalen Mire) to partition net CH4 emissions into its component parts, methanogenesis (including both acetoclastic, and CO2-reductive pathways) and methanotrophy (which consumes CH4 primarily via aerobic metabolism). We used newly developed quantum cascade laser technology, linked to automated chambers, to quantify isotopes at high frequency. Our measurements across a permafrost thaw gradient, going from permafrost-dominated, well-drained palsas to intermediate permafrost sites dominated by Sphagnum spp. to wet sites with no underlying permafrost, dominated by Eriophorum angustifolium, show both large increases in productivity and CH4 emissions as well as shifts in the CH4 production pathway. Across this permafrost thaw gradient the isotopic composition of CH4 becomes 13C enriched, due to increased acetoclastic CH4 production. While the palsa sites have no detectable CH4 emissions, fluxes in the Sphagnum site have an average isotopic composition of -79%, a value indicative of CH4 production dominated by CO2 reduction, in contrast the isotopic composition of CH4 produced in the Eriophorum sites ranged from -71 to -57%, showing increased CH4 production via the acetate pathway. We also observed an increase in acetoclastic methanogenesis as the growing season progressed. Together, these initial results suggest that thaw induced changes in hydrology and plant community composition increase peat

  14. In situ sulfur isotopes (δ(34)S and δ(33)S) analyses in sulfides and elemental sulfur using high sensitivity cones combined with the addition of nitrogen by laser ablation MC-ICP-MS.

    PubMed

    Fu, Jiali; Hu, Zhaochu; Zhang, Wen; Yang, Lu; Liu, Yongsheng; Li, Ming; Zong, Keqing; Gao, Shan; Hu, Shenghong

    2016-03-10

    The sulfur isotope is an important geochemical tracer in diverse fields of geosciences. In this study, the effects of three different cone combinations with the addition of N2 on the performance of in situ S isotope analyses were investigated in detail. The signal intensities of S isotopes were improved by a factor of 2.3 and 3.6 using the X skimmer cone combined with the standard sample cone or the Jet sample cone, respectively, compared with the standard arrangement (H skimmer cone combined with the standard sample cone). This signal enhancement is important for the improvement of the precision and accuracy of in situ S isotope analysis at high spatial resolution. Different cone combinations have a significant effect on the mass bias and mass bias stability for S isotopes. Poor precisions of S isotope ratios were obtained using the Jet and X cones combination at their corresponding optimum makeup gas flow when using Ar plasma only. The addition of 4-8 ml min(-1) nitrogen to the central gas flow in laser ablation MC-ICP-MS was found to significantly enlarge the mass bias stability zone at their corresponding optimum makeup gas flow in these three different cone combinations. The polyatomic interferences of OO, SH, OOH were also significantly reduced, and the interference free plateaus of sulfur isotopes became broader and flatter in the nitrogen mode (N2 = 4 ml min(-1)). However, the signal intensity of S was not increased by the addition of nitrogen in this study. The laser fluence and ablation mode had significant effects on sulfur isotope fractionation during the analysis of sulfides and elemental sulfur by laser ablation MC-ICP-MS. The matrix effect among different sulfides and elemental sulfur was observed, but could be significantly reduced by line scan ablation in preference to single spot ablation under the optimized fluence. It is recommended that the d90 values of the particles in pressed powder pellets for accurate and precise S isotope analysis

  15. Nanostructured solid substrates for efficient laser desorption/ionization mass spectrometry (LDI-MS) of low molecular weight compounds.

    PubMed

    Silina, Yuliya E; Volmer, Dietrich A

    2013-12-07

    Analytical applications often require rapid measurement of compounds from complex sample mixtures. High-speed mass spectrometry approaches frequently utilize techniques based on direct ionization of the sample by laser irradiation, mostly by means of matrix-assisted laser desorption/ionization (MALDI). Compounds of low molecular weight are difficult to analyze by MALDI, however, because of severe interferences in the low m/z range from the organic matrix used for desorption/ionization. In recent years, surface-assisted laser desorption/ionization (SALDI) techniques have shown promise for small molecule analysis, due to the unique properties of nanostructured surfaces, in particular, the lack of a chemical background in the low m/z range and enhanced production of analyte ions by SALDI. This short review article presents a summary of the most promising recent developments in SALDI materials for MS analysis of low molecular weight analytes, with emphasis on nanostructured materials based on metals and semiconductors.

  16. New online method for water isotope analysis of speleothem fluid inclusions using laser absorption spectroscopy (WS-CRDS)

    NASA Astrophysics Data System (ADS)

    Affolter, S.; Fleitmann, D.; Leuenberger, M.

    2014-07-01

    A new online method to analyse water isotopes of speleothem fluid inclusions using a wavelength scanned cavity ring down spectroscopy (WS-CRDS) instrument is presented. This novel technique allows us simultaneously to measure hydrogen and oxygen isotopes for a released aliquot of water. To do so, we designed a new simple line that allows the online water extraction and isotope analysis of speleothem samples. The specificity of the method lies in the fact that fluid inclusions release is made on a standard water background, which mainly improves the δ D robustness. To saturate the line, a peristaltic pump continuously injects standard water into the line that is permanently heated to 140 °C and flushed with dry nitrogen gas. This permits instantaneous and complete vaporisation of the standard water, resulting in an artificial water background with well-known δ D and δ18O values. The speleothem sample is placed in a copper tube, attached to the line, and after system stabilisation it is crushed using a simple hydraulic device to liberate speleothem fluid inclusions water. The released water is carried by the nitrogen/standard water gas stream directly to a Picarro L1102-i for isotope determination. To test the accuracy and reproducibility of the line and to measure standard water during speleothem measurements, a syringe injection unit was added to the line. Peak evaluation is done similarly as in gas chromatography to obtain &delta D; and δ18O isotopic compositions of measured water aliquots. Precision is better than 1.5 ‰ for δ D and 0.4 ‰ for δ18O for water measurements for an extended range (-210 to 0 ‰ for δ D and -27 to 0 ‰ for δ18O) primarily dependent on the amount of water released from speleothem fluid inclusions and secondarily on the isotopic composition of the sample. The results show that WS-CRDS technology is suitable for speleothem fluid inclusion measurements and gives results that are comparable to the isotope ratio mass

  17. New on-line method for water isotope analysis of speleothem fluid inclusions using laser absorption spectroscopy (WS-CRDS)

    NASA Astrophysics Data System (ADS)

    Affolter, S.; Fleitmann, D.; Leuenberger, M.

    2014-01-01

    A new online method to analyse water isotopes of speleothem fluid inclusions using a wavelength scanned cavity ring down spectroscopy (WS-CRDS) instrument is presented. This novel technique allows us to simultaneously measure hydrogen and oxygen isotopes for a released aliquot of water. To do so, we designed a new simple line that allows the on-line water extraction and isotope analysis of speleothem samples. The specificity of the method lies in the fact that fluid inclusions release is made on a standard water background, which mainly improves the δD reliability. To saturate the line, a peristaltic pump continuously injects standard water into the line that is permanently heated to 140 °C and flushed with dry nitrogen gas. This permits instantaneous and complete vaporisation of the standard water resulting in an artificial water background with well-known δD and δ18O values. The speleothem sample is placed into a copper tube, attached to the line and after system stabilisation is crushed using a simple hydraulic device to liberate speleothem fluid inclusions water. The released water is carried by the nitrogen/standard water gas stream directly to a Picarro L1102-i for isotope determination. To test the accuracy and reproducibility of the line and to measure standard water during speleothem measurements a syringe injection unit was added to the line. Peak evaluation is done similarly as in gas chromatography to obtain δD and δ18O isotopic composition of measured water aliquots. Precision is better than 1.5‰ for δD and 0.4‰ for δ18O for water measurement for an extended range (-210 to 0‰ for δD and -27 to 0‰ for δ18O) primarily dependent on the amount of water released from speleothem fluid inclusions and secondarily on the isotopic composition of the sample. The results show that WS-CRDS technology is suitable for speleothem fluid inclusion measurements and gives results that are comparable to Isotope Ratio Mass Spectrometry (IRMS) technique.

  18. Black phosphorus-assisted laser desorption ionization mass spectrometry for the determination of low-molecular-weight compounds in biofluids.

    PubMed

    He, Xiao-Mei; Ding, Jun; Yu, Lei; Hussain, Dilshad; Feng, Yu-Qi

    2016-09-01

    Quantitative analysis of small molecules by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) has been a challenging task due to matrix-derived interferences in low m/z region and poor reproducibility of MS signal response. In this study, we developed an approach by applying black phosphorus (BP) as a matrix-assisted laser desorption ionization (MALDI) matrix for the quantitative analysis of small molecules for the first time. Black phosphorus-assisted laser desorption/ionization mass spectrometry (BP/ALDI-MS) showed clear background and exhibited superior detection sensitivity toward quaternary ammonium compounds compared to carbon-based materials. By combining stable isotope labeling (SIL) strategy with BP/ALDI-MS (SIL-BP/ALDI-MS), a variety of analytes labeled with quaternary ammonium group were sensitively detected. Moreover, the isotope-labeled forms of analytes also served as internal standards, which broadened the analyte coverage of BP/ALDI-MS and improved the reproducibility of MS signals. Based on these advantages, a reliable method for quantitative analysis of aldehydes from complex biological samples (saliva, urine, and serum) was successfully established. Good linearities were obtained for five aldehydes in the range of 0.1-20.0 μM with correlation coefficients (R (2)) larger than 0.9928. The LODs were found to be 20 to 100 nM. Reproducibility of the method was obtained with intra-day and inter-day relative standard deviations (RSDs) less than 10.4 %, and the recoveries in saliva samples ranged from 91.4 to 117.1 %. Taken together, the proposed SIL-BP/ALDI-MS strategy has proved to be a reliable tool for quantitative analysis of aldehydes from complex samples. Graphical Abstract An approach for the determination of small molecules was developed by using black phosphorus (BP) as a matrix-assisted laser desorption ionization (MALDI) matrix.

  19. A miniaturised laser ablation/ionisation analyser for investigation of elemental/isotopic composition with the sub-ppm detection sensitivity

    NASA Astrophysics Data System (ADS)

    Tulej, M.; Riedo, A.; Meyer, S.; Iakovleva, M.; Neuland, M.; Wurz, P.

    2012-04-01

    Detailed knowledge of the elemental and isotopic composition of solar system objects imposes critical constraints on models describing the origin of our solar system and can provide insight to chemical and physical processes taking place during the planetary evolution. So far, the investigation of chemical composition of planetary surfaces could be conducted almost exclusively by remotely controlled spectroscopic instruments from orbiting spacecraft, landers or rovers. With some exceptions, the sensitivity of these techniques is, however, limited and often only abundant elements can be investigated. Nevertheless, the spectroscopic techniques proved to be successful for global chemical mapping of entire planetary objects such as the Moon, Mars and asteroids. A combined afford of the measurements from orbit, landers and rovers can also yield the determination of local mineralogy. New instruments including Laser Induced Breakdown Spectroscopy (LIBS) and Laser Ablation/Ionisation Mass Spectrometer (LIMS), have been recently included for several landed missions. LIBS is thought to improve flexibility of the investigations and offers a well localised chemical probing from distances up to 10-13 m. Since LIMS is a mass spectrometric technique it allows for very sensitive measurements of elements and isotopes. We will demonstrate the results of the current performance tests obtained by application of a miniaturised laser ablation/ionisation mass spectrometer, a LIMS instrument, developed in Bern for the chemical analysis of solids. So far, the only LIMS instrument on a spacecraft is the LAZMA instrument. This spectrometer was a part of the payload for PHOBOS-GRUNT mission and is also currently selected for LUNA-RESURCE and LUNA-GLOB missions to the lunar south poles (Managadze et al., 2011). Our LIMS instrument has the dimensions of 120 x Ø60 mm and with a weight of about 1.5 kg (all electronics included), it is the lightest mass analyser designed for in situ chemical

  20. Long-Term Continuous Isotopic Ratio Measurements of Atmospheric CO2 Using a 4.3 Micron Pulsed Quantum Cascade Laser

    NASA Astrophysics Data System (ADS)

    Nelson, D. D.; McManus, J. B.; Herndon, S. C.; Zahniser, M. S.

    2007-12-01

    Real time methods to monitor the stable isotopic ratios of carbon dioxide are needed to quantify the sources and sinks of this centrally important greenhouse gas. This is an extreme instrumental challenge since the ratios need to be measured with an accuracy of at least one part in ten thousand or 0.1 ". We use tunable infrared laser differential absorption spectroscopy with pulsed QC lasers (QC-TILDAS) to address this challenge. QC lasers are attractive optical sources due to: 1) absence of cryogenic fluids, 2) stable single mode spectral output, 3) optical simplicity. Our optical system employs a dual-cell arrangement with ambient air flowing through the sample cell and a reference gas flowing through the reference cell. Both 13C/12C and 18O/16O ratios can be obtained in a single spectral window near 2310 cm-1. Spectral analysis is applied to the ratio of the sample and reference spectra, canceling correlated noise components. Because the absorption lines of the isotopic species have different temperature dependences, temperature stability is critical. The optical system is temperature controlled and the two multipass cells are thermally coupled and individually monitored with a precision of 1 mK. The ratio technique compensates for temperature sensitivity, as well as for drifts in laser line width, frequency, tuning rate and power variation. The long term stability of the thermally stabilized dual-cell QCL system has been evaluated using the Allan variance technique. The Allan plot shows a 1-sec RMS noise of 0.2 per mil, and a minimum RMS noise of 0.03 per mil after 300 sec integration using a liquid nitrogen cooled detector. We have used this instrument to perform long term (more than 6 months) monitoring of ambient air from the roof top of our laboratory. The data show variations in R13 and R18 that follow diurnal cycles. Winter data show clear correlations with morning and evening signatures of local automobile traffic. Data collected during spring are

  1. Laser Ablation Split Stream (LASS) U-Pb & Lu-Hf Isotope Analysis of Detrital Zircons from the Old Red Sandstone, NW Svalbard: Implications for Northern Caledonian Paleogeography

    NASA Astrophysics Data System (ADS)

    Beranek, L. P.; Gee, D. G.; Fisher, C. M.

    2015-12-01

    The Svalbard archipelago consists of three Caledonian provinces that were assembled by thrusting and transcurrent faulting during the Silurian and Devonian in a location directly northeast of the Greenland Caledonides. Syn- to post-orogenic alluvial strata, referred to as the Old Red Sandstones, filled pull-apart basins adjacent to the transcurrent faults and comprise cover assemblages that help constrain the timing of the Caledonian orogeny. To further investigate the tectonic history and paleogeography of the Raudfjorden-Liefdefjorden-Woodfjorden area of Spitsbergen, NW Svalbard, we analyzed rock samples of the Old Red Sandstones and underlying Precambrian basement complexes for detrital zircon analysis. Laboratory studies of the Old Red Sandstones include the novel Laser Ablation Split Stream (LASS) technique, which allows for simultaneous U-Pb & Lu-Hf isotope analysis of zircon crystals. Lower Devonian Red Bay Group strata contain a range of early Neoproterozoic to Neoarchean detrital zircons with prominent age peaks c. 960, 1050, 1370, 1450, 1650, and 2700 Ma; subordinate Ordovician (c. 460-490 Ma) and Cryogenian (c. 650 Ma) detrital zircons occur in a subset of the samples. Underlying Precambrian metasedimentary rocks are composed of similar earliest Neoproterozoic to Neoarchean age populations, which argues for much of the Red Bay Group to be derived from local basement rocks during thrusting and other faulting. The U-Pb ages and Hf isotope compositions of Paleozoic to Neoarchean detrital zircons are consistent with Arctic crustal evolution, and support the hypothesis that northwestern and northeastern provinces of the Svalbard Caledonides are extruded fragments of the northeast Greenland allochthons. The new Hf isotope results further allow paleogeographic and stratigraphic comparisons with rock assemblages proximal to the North Atlantic Caledonides during the Silurian-Devonian, including the Pearya terrane of Ellesmere Island, Alexander terrane of NW

  2. Validation and application of cavity-enhanced, near-infrared tunable diode laser absorption spectrometry for measurements of methane carbon isotopes at ambient concentrations.

    PubMed

    Mortazavi, Behzad; Wilson, Benjamin J; Dong, Feng; Gupta, Manish; Baer, Doug

    2013-10-15

    Methane is an effective greenhouse gas but has a short residence time in the atmosphere, and therefore, reductions in emissions can alleviate its greenhouse gas warming effect within a decadal time frame. Continuous and high temporal resolution measurements of methane concentrations and carbon isotopic ratios (δ(13)CH4) can inform on mechanisms of formation, provide constraints on emissions sources, and guide future mitigation efforts. We describe the development, validation, and deployment of a cavity-enhanced, near-infrared tunable diode laser absorption spectrometry system capable of quantifying δ(13)CH4 at ambient methane concentrations. Laboratory validation and testing show that the instrument is capable of operating over a wide dynamic range of methane concentration and provides a measurement precision for δ(13)CH4 of better than ± 0.5 ‰ (1σ) over 1000 s of data averaging at ambient methane concentrations. The analyzer is accurate to better than ± 0.5 ‰, as demonstrated by measurements of characterized methane/air samples with minimal dependence (<1 ‰) of measured carbon isotope ratio on methane concentration. Deployment of the instrument at a marsh over multiple days demonstrated how methane fluxes varied by an order of magnitude over 2 day deployment periods, and showed a 17 ‰ variability in δ(13)CH4 of the emitted methane during the growing season.

  3. Environmental site description for a Uranium Atomic Vapor Laser Isotope Separation (U-AVLIS) production plant at the Paducah Gaseous Diffusion Plant site

    SciTech Connect

    Marmer, G.J.; Dunn, C.P.; Moeller, K.L.; Pfingston, J.M.; Policastro, A.J.; Yuen, C.R.; Cleland, J.H.

    1991-09-01

    Uranium enrichment in the United States has utilized a diffusion process to preferentially enrich the U-235 isotope in the uranium product. The U-AVLIS process is based on electrostatic extraction of photoionized U-235 atoms from an atomic vapor stream created by electron-beam vaporization of uranium metal alloy. The U-235 atoms are ionized when precisely tuned laser light -- of appropriate power, spectral, and temporal characteristics -- illuminates the uranium vapor and selectively photoionizes the U-235 isotope. A programmatic document for use in screening DOE site to locate a U-AVLIS production plant was developed and implemented in two parts. The first part consisted of a series of screening analyses, based on exclusionary and other criteria, that identified a reasonable number of candidate sites. These sites were subjected to a more rigorous and detailed comparative analysis for the purpose of developing a short list of reasonable alternative sites for later environmental examination. This environmental site description (ESD) provides a detailed description of the PGDP site and vicinity suitable for use in an environmental impact statement (EIS). The report is based on existing literature, data collected at the site, and information collected by Argonne National Laboratory (ANL) staff during a site visit. 65 refs., 15 tabs.

  4. Bilirubin calculi crushing by laser irradiation at a molecular oscillating region wavelength based on infrared absorption spectrum analysis using a free-electron laser: an experimental study.

    PubMed

    Watanabe, M; Kajiwara, H; Awazu, K; Aizawa, K

    2001-01-01

    We investigated a new laser technique of crushing bilirubin calculi, our aim being to crush calculi in isolation using a minimally invasive procedure. Infrared absorption spectrum analysis of the bilirubin calculi was conducted, revealing maximum absorption spectrum at a wavelength of the C=O stretching vibration of ester binding that exists within the molecular structure of bilirubin calcium. As an experiment to crush calculi using the free-electron laser, we set the laser at the effective irradiation wavelength of ester binding, and conducted noncontact irradiation of the bilirubin calculi. The calculi began to slowly ablate until the irradiated site had been completely obliterated after 20s of irradiation. Moreover, absorption spectrum analysis of the irradiated site, from a comparison of absorption peak ratios, revealed that absorption peak intensities decreased over time at the absorption wavelength of ester binding. These findings suggest that irradiation of molecular oscillating region wavelengths peculiar to calculi based on infrared absorption spectrum analysis results in the gradual crushing of calculi in isolation by breaking down their molecular structure.

  5. Laser capture microdissection enables cellular and molecular studies of tooth root development

    PubMed Central

    Sun, Jian-Xun; Horst, Orapin V; Bumgarner, Roger; Lakely, Bryce; Somerman, Martha J; Zhang, Hai

    2012-01-01

    Epithelial–mesenchymal interactions (EMIs) are critical for tooth development. Molecular mechanisms mediating these interactions in root formation is not well understood. Laser capture microdissection (LCM) and subsequent microarray analyses enable large scale in situ molecular and cellular studies of root formation but to date have been hindered by technical challenges of gaining intact histological sections of non-decalcified mineralized teeth or jaws with well-preserved RNA. Here,we describe a new method to overcome this obstacle that permits LCM of dental epithelia,adjacent mesenchyme,odontoblasts and cementoblasts from mouse incisors and molars during root development. Using this method,we obtained RNA samples of high quality and successfully performed microarray analyses. Robust differences in gene expression,as well as genes not previously associated with root formation,were identified. Comparison of gene expression data from microarray with real-time reverse transcriptase polymerase chain reaction (RT-PCR) supported our findings. These genes include known markers of dental epithelia,mesenchyme,cementoblasts and odontoblasts,as well as novel genes such as those in the fibulin family. In conclusion,our new approach in tissue preparation enables LCM collection of intact cells with well-preserved RNA allowing subsequent gene expression analyses using microarray and RT-PCR to define key regulators of tooth root development. PMID:22422086

  6. Combined molecular ecological and confocal laser scanning microscopic analysis of peat bog methanogen populations.

    PubMed

    Upton, M; Hill, B; Edwards, C; Saunders, J R; Ritchie, D A; Lloyd, D

    2000-12-15

    Confocal laser scanning microscopy, using fluorescently labelled oligonucleotide probes targeting the 16S rRNA of different physiological groups of methanogens, was used to identify which methanogenic genera were present and to describe their in situ spatial locations in samples taken at different depths from blanket peat bog cores. Total bacterial DNA was also extracted and purified from the samples and used as template for amplification of 16S rRNA and regions of methyl CoM reductase-encoding genes using the polymerase chain reaction, as well as for oligonucleotide hybridisation experiments. These techniques, used in concert, demonstrated that methanogens of several physiological groups were present in highest numbers in the mid regions of 25 cm deep peat cores. Some discrepancies were apparent in the findings of the microscopic and molecular methods, though these may be partially accounted for by the different sensitivities of the techniques employed. The combined approaches used in this study gave an insight into the diversity and distribution of methanogens in peat environments not possible using molecular ecological methods alone.

  7. A Combined Molecular and Isotopic Study of Anoxygenic Photosynthesis in Meromictic Lakes of the Northwestern United States

    NASA Astrophysics Data System (ADS)

    Harris, J. H., IV; Gilhooly, W., III; Crane, E. J., III; Steinman, B.; Shelton, M. R.

    2014-12-01

    Sulfur isotope fractionations within the chemocline can be an indication of green and purple sulfur photosynthetic activity. This isotopic signal is, however, small and variable, on the order of +2-6‰ (Zerkle et al. 2009). It is therefore advantageous to investigate the environmental and ecological effects on this signal so that these influences can be taken into account when estimating the contribution of anoxygenic phototrophs to the sulfur cycle in aquatic environments. This project aims to investigate the ways in which anoxygenic phototroph community structure and lake water geochemistry impact the sulfur isotope fractionation expressed during anoxygenic photosynthesis in meromictic lakes. During the summer of 2013, water column profile analysis of six lakes in the Pacific Northwest (located in eastern Washington and western Montana) were conducted to assess photosynthetically available radiation, salinity, pH, temperature, dissolved solids, and specific conductivity. Water column samples were obtained to determine the sulfur isotopic composition of dissolved sulfate and sulfide, major ion and sulfide concentrations. Microbial samples were also collected for genetic sequencing. Initial results found green (e.g., Chlorobiaceae sp.) and purple (e.g., Lamprocystis purpurea) bacteria at the same depth in one of the study lakes. These data, in addition to the same suite of samples collected in the summer of 2014, provide insight into relationships between the isotopic composition of sulfur (in H2S, S0, and SO4), lake water chemistry, and the presence or absence of green and purple sulfur bacteria.

  8. Molecular and isotopic compositions and origin of natural gases from Cambrian and Carboniferous-Lower Permian reservoirs of the onshore Polish Baltic region

    NASA Astrophysics Data System (ADS)

    Kotarba, Maciej J.; Nagao, Keisuke

    2015-01-01

    Natural gases from Middle Cambrian and Carboniferous-Lower Permian reservoirs of the onshore Polish Baltic region were studied for their molecular and stable isotope compositions. The following gas species were analysed: 12,13C in CH4, C2H6, C3H8, n-C4H10, i-C4H10 and CO2, 1,2H in CH4, 14,15N in N2, and stable isotopes of all noble gases. Due to significantly different geological settings and genetic types of source rocks of Eastern and Western Pomerania, the molecular and isotopic compositions of natural gases of these two regions exhibit distinct differences. Hydrocarbon gases associated with oil accumulated in the Middle Cambrian reservoir of Eastern Pomerania were generated during low-temperature thermogenic processes from a single source rock containing Type-II kerogen at one phase of petroleum generation. Non-associated hydrocarbon gases accumulated in the Carboniferous (Mississippian and Pennsylvanian)-Lower Permian (Rotliegend) reservoirs of Western Pomerania originated during at least two phases of gas generation by thermogenic processes from mainly Type-III kerogen and a small component of mixed Type-III/II kerogen. Noble gases are in general heavily enriched in radiogenic and nucleogenic isotopes such as 4He, 40Ar and 21Ne accumulated in the reservoirs. Weak contributions of mantle-derived He and Ne are observed. Radiogenic 4He/40Ar ratios are higher than the average production rate ratio of about 5 for radiogenic 4He/40Ar in crustal materials, which might have been caused by a selective supply of 4He that is lighter than 40Ar from crustal rocks, or (U + Th)/K ratio might be higher than the average in crustal block. Carbon dioxide from gases of both the Western and Eastern Pomerania were mainly generated during thermogenic processes of transformation of organic matter, although gases of Western Pomerania can contain an endogenic component. Molecular nitrogen from the Eastern Pomeranian natural gases was mainly generated during low-temperature thermal

  9. Excitation of rotons in parahydrogen crystals: The laser-induced-molecular-alignment mechanism

    NASA Astrophysics Data System (ADS)

    Lindgren, Johan; Kiljunen, Toni

    2013-10-01

    Solid parahydrogen (p-H2) is known to support long-lived coherences, of the order of 100 ps, which enables high-resolution spectroscopy in the time domain. Rotational Raman-type excitations to sublevels of J=2 are delocalized due to electric-quadrupole-quadrupole coupling in p-H2 crystals, and the resulting states can be characterized as rotons. Wave packets of rotons exhibit molecular alignment with respect to laboratory coordinates. Here the concept of field-free molecular alignment, induced by strong ultrashort laser pulses, is extended into a molecular solid case. We derive a solid-state analog for the gas-phase alignment measure and illustrate the time-dependent alignment degree in p-H2 crystals by numerical simulations. To underscore the Raman gain effect of the solid, general properties of the field-free alignment are revisited by comparing gaseous p-H2 with N2. The interplay between the polarization direction of the excitation pulses and the axis directionality of the crystal is shown to affect the alignment dynamics via the spatial (M=0,±1,±2) composition of the roton wave packets. We simulate experimental traces by incorporating the induced alignment degree in the calculation of heterodyne-detected realization of femtosecond pump-probe optical Kerr effect spectroscopy. With the help of dispersed, two-dimensional resolved images of the calculated signal we reproduce the experiment as a whole. To that end, the effects of probe chirp, shape, and power must be explored in detail. We find good agreement with previous experiments and unravel the ambiguity of tracing back the wave-packet composition from the signal; in particular, we find that the effect of quantum phase factors of all the components should be taken into account when explaining the signal properties.

  10. Application of computational fluid dynamics for the simulation of cryogenic molecular sieve bed absorber of hydrogen isotopes recovery system for Indian LLCB-TBM

    SciTech Connect

    Gayathri Devi, V.; Sircar, A.; Sarkar, B.

    2015-03-15

    One of the most challenging tasks in the design of the fuel cycle system lies in the effective design of Tritium Extraction System (TES) which involves proper extraction and purification of tritium in the fuel cycle of the fusion reactor. Indian Lead Lithium cooled Ceramic Breeder Test Blanket Module (LLCB-TBM) would extract hydrogen isotopes through Cryogenic Molecular Sieve Bed (CMSB) adsorber system. A prototype Hydrogen Isotopes Recovery System (HIRS) is being developed to validate the concepts for tritium extraction by adsorption mass transfer mechanism. In this study, a design model has been developed and analyzed to simulate the adsorption mass transfer kinetics in a fixed bed adsorption column. The simulation leads primarily to effective design of HIRS, which is a state-of-the-art technology. The paper describes the process simulation approach and the results of Computational Fluid Dynamics (CFD) analysis. The effects of different operating conditions are studied to investigate their influence on the hydrogen isotopes adsorption capacity. The results of the present simulation study would be used to understand the best optimized transport phenomenon before realizing the TES as a system for LLCB-TBM. (authors)

  11. Molecular and Stable Carbon Isotope Composition of Organic Compounds from Particles Sampled from the Lower Fraser Valley, BC Urban and Regional Air Shed

    NASA Astrophysics Data System (ADS)

    Whiticar, M. J.; Gray, S. L.

    2001-12-01

    This study examines the character of specific non-volatile organic compounds (N-VOCs) extracted from total suspended particulates. Aerosols are collected on filters by HiVol samplers on monthly intervals, at well-characterized meteorological sites throughout the Lower Fraser Valley. Filters are solvent-extracted , then separated into different compound classes by Silica-gel Chromatography. Selected fractions are analysed for their individual compound molecular compositions by Gas Chromatography-Mass Spectrometry (GC/MS) and by Continuous Flow-Isotope Ratio Mass Spectrometry (CF-IRMS) for their stable carbon isotope ratio. The purpose is to identify spatial and temporal variations in N-VOCs, with the long-term goal of understanding their sources, transport processes and atmospheric chemistry. This Health Canada, Toxic Substance Research Initiative offers insights into the levels and signatures of N-VOCs exposed to humans in congested urban settings. The program is also part of the Pacific 2001 field study. This paper presents the initial year's results on our N-VOCs, including alkanes, organic acids, in comparison with bulk isotope analyses.

  12. Design and performance of a 250 Hz alexandrite laser

    SciTech Connect

    Sam, R.C.; Yeh, J.J.; Leslie, K.R.; Rapoport, W.R.

    1988-06-01

    The design, analysis, and performance of a 250 Hz alexandrite laser are described. Built as the wavelength selective laser for a molecular laser isotope separation program, the laser has to satisfy specifications on its tuning band, linewidth, output energy, temporal behavior, and repetition rate required by the process. The key design feature is the use of a tandem rod oscillator with concave curvature on rod ends for thermal lensing compensation. A model was developed to project the stability range and beam quality relative to repetition rate. The performance results of a delivered system are presented and future developments are discussed.

  13. Barium Isotopes in Single Presolar Grains

    NASA Technical Reports Server (NTRS)

    Pellin, M. J.; Davis, A. M.; Savina, M. R.; Kashiv, Y.; Clayton, R. N.; Lewis, R. S.; Amari, S.

    2001-01-01

    Barium isotopic compositions of single presolar grains were measured by laser ablation laser resonant ionization mass spectrometry and the implications of the data for stellar processes are discussed. Additional information is contained in the original extended abstract.

  14. CONTROL OF LASER RADIATION PARAMETERS: Effect of the 129I impurity on the radiation frequency of a stabilised He — Ne/127I2 laser

    NASA Astrophysics Data System (ADS)

    Negriyko, Anatolii M.; Boyko, Oleksei V.; Kachalova, Nataliya M.; Khodakovskii, Vladimir M.

    2004-05-01

    The radiation frequency of a He — Ne/127I2 laser stabilised to the hyperfine structure component of molecular iodine exhibits shifts caused by the presence of impurities in the iodine cell. The specific effect of the 129I impurity on the radiation frequency of a stabilised laser is considered. It is shown that even for a 0.25 % concentration of 129I, the frequency shift in a He — Ne/127I2 laser caused by this isotope plays a decisive role. To exclude the possible effect of other iodine isotopes on the accuracy of reproducibility of the frequency of metrological lasers, it is expedient to carry out the laser fluorescence test of the cells to check for the presence of heteroisotopic molecular iodine impurity.

  15. The effect of laser energy on V2O5 thin film growth prepared by laser assisted molecular beam deposition

    NASA Astrophysics Data System (ADS)

    Abdel Samad, B.; Ashrit, P. V.

    2014-09-01

    Vanadium pentoxide V2O5 thin films were grown on glass substrates by the LAMBD deposition system with different laser energies. The structure, composition and optical properties of the films have been investigated with atomic force microscopy, x-ray photoemission spectroscopy, ellipsometry and the transmittance analysis. Upon the increase of laser energy, the results showed that the changes in the optical constants are consistent with the thickness changes of the film. The refractive index increases and the absorption coefficient increases when the laser energy increases. The AFM analysis showed a change of the roughness and structure of the deposited films at different laser energies. The prepared films deposited by LAMBD showed interesting properties with correct V2O5 phase without need of annealing after deposition.

  16. Process for producing enriched uranium having a {sup 235}U content of at least 4 wt. % via combination of a gaseous diffusion process and an atomic vapor laser isotope separation process to eliminate uranium hexafluoride tails storage

    DOEpatents

    Horton, J.A.; Hayden, H.W. Jr.

    1995-05-30

    An uranium enrichment process capable of producing an enriched uranium, having a {sup 235}U content greater than about 4 wt. %, is disclosed which will consume less energy and produce metallic uranium tails having a lower {sup 235}U content than the tails normally produced in a gaseous diffusion separation process and, therefore, eliminate UF{sub 6} tails storage and sharply reduce fluorine use. The uranium enrichment process comprises feeding metallic uranium into an atomic vapor laser isotope separation process to produce an enriched metallic uranium isotopic mixture having a {sup 235} U content of at least about 2 wt. % and a metallic uranium residue containing from about 0.1 wt. % to about 0.2 wt. % {sup 235} U; fluorinating this enriched metallic uranium isotopic mixture to form UF{sub 6}; processing the resultant isotopic mixture of UF{sub 6} in a gaseous diffusion process to produce a final enriched uranium product having a {sup 235}U content of at least 4 wt. %, and up to 93.5 wt. % or higher, of the total uranium content of the product, and a low {sup 235}U content UF{sub 6} having a {sup 235}U content of about 0.71 wt. % of the total uranium content of the low {sup 235}U content UF{sub 6}; and converting this low {sup 235}U content UF{sub 6} to metallic uranium for recycle to the atomic vapor laser isotope separation process. 4 figs.

  17. Process for producing enriched uranium having a .sup.235 U content of at least 4 wt. % via combination of a gaseous diffusion process and an atomic vapor laser isotope separation process to eliminate uranium hexafluoride tails storage

    DOEpatents

    Horton, James A.; Hayden, Jr., Howard W.

    1995-01-01

    An uranium enrichment process capable of producing an enriched uranium, having a .sup.235 U content greater than about 4 wt. %, is disclosed which will consume less energy and produce metallic uranium tails having a lower .sup.235 U content than the tails normally produced in a gaseous diffusion separation process and, therefore, eliminate UF.sub.6 tails storage and sharply reduce fluorine use. The uranium enrichment process comprises feeding metallic uranium into an atomic vapor laser isotope separation process to produce an enriched metallic uranium isotopic mixture having a .sup.235 U content of at least about 2 wt. % and a metallic uranium residue containing from about 0.1 wt. % to about 0.2 wt. % .sup.235 U; fluorinating this enriched metallic uranium isotopic mixture to form UF.sub.6 ; processing the resultant isotopic mixture of UF.sub.6 in a gaseous diffusion process to produce a final enriched uranium product having a .sup.235 U content of at least 4 wt. %, and up to 93.5 wt. % or higher, of the total uranium content of the product, and a low .sup.235 U content UF.sub.6 having a .sup.235 U content of about 0.71 wt. % of the total uranium content of the low .sup.235 U content UF.sub.6 ; and converting this low .sup.235 U content UF.sub.6 to metallic uranium for recycle to the atomic vapor laser isotope separation process.

  18. Laser Polarization Effect on Molecular Harmonic and Elliptically Polarized Attosecond Pulse Generation

    NASA Astrophysics Data System (ADS)

    Feng, Li-Qiang; Li, Wen-Liang; Liu, Hang

    2017-01-01

    Molecular harmonic spectra of {{{H}}}2+ driven by the linearly polarized laser pulses with different polarized angles have been theoretically investigated through solving the two-dimensional time-dependent Schrödinger equation. (i) Below-threshold harmonic spectra show a visible enhanced peak around the 7th harmonic (H7), which produces a red-shift phenomenon as the internuclear distance increased. Theoretical analyses show the red-shift enhanced peak is caused by the laser-induced electron transfer between the ground state and the 1st excited state of {{{H}}}2+. (ii) Due to the two-centre interference phenomenon, the above-threshold harmonic spectra exhibit many maxima and minima. (iii) With the introduction of the polarized angle, the anomalous elliptically polarized harmonics can be found. But, with the introduction of the spatial inhomogeneous effect, not only the ellipticities of the harmonics are equal to a stable value of \\varepsilon ∼ 0.1–0.3, but also the harmonic cutoffs are extended. As a result, four super-bandwidths of 407 eV, 310 eV, 389 eV, and 581 eV can be obtained. Time profiles of the harmonic generations have been shown to explain the harmonic characteristics. Finally, a series of elliptically polarized (\\varepsilon ∼ 0.1–0.3) attosecond X-ray pulses with durations from 18as to 25as can be directly produced through Fourier transformation of the spectral continuum. Supported by National Natural Science Foundation of China under Grant No. 11504151, Doctoral Scientific Research Foundation of Liaoning Province under Grant No. 201501123 and Scientific Research Fund of Liaoning Provincial Education Department under Grant No. L2014242

  19. Picosecond infrared laser-induced all-atom nonequilibrium molecular dynamics simulation of dissociation of viruses.

    PubMed

    Hoang Man, Viet; Van-Oanh, Nguyen-Thi; Derreumaux, Philippe; Li, Mai Suan; Roland, Christopher; Sagui, Celeste; Nguyen, Phuong H

    2016-04-28

    Since the discovery of the plant pathogen tobacco mosaic virus as the first viral entity in the late 1800s, viruses traditionally have been mainly thought of as pathogens for disease-resistances. However, viruses have recently been exploited as nanoplatforms with applications in biomedicine and materials science. To this aim, a large majority of current methods and tools have been developed to improve the physical stability of viral particles, which may be critical to the extreme physical or chemical conditions that viruses may encounter during purification, fabrication processes, storage and use. However, considerably fewer studies are devoted to developing efficient methods to degrade or recycle such enhanced stability biomaterials. With this in mind, we carry out all-atom nonequilibrium molecular dynamics simulation, inspired by the recently developed mid-infrared free-electron laser pulse technology, to dissociate viruses. Adopting the poliovirus as a representative example, we find that the primary step in the dissociation process is due to the strong resonance between the amide I vibrational modes of the virus and the tuned laser frequencies. This process is determined by a balance between the formation and dissociation of the protein shell, reflecting the highly plasticity of the virus. Furthermore, our method should provide a feasible approach to simulate viruses, which is otherwise too expensive for conventional equilibrium all-atom simulations of such very large systems. Our work shows a proof of concept which may open a new, efficient way to cleave or to recycle virus-based materials, provide an extremely valuable tool for elucidating mechanical aspects of viruses, and may well play an important role in future fighting against virus-related diseases.

  20. Molecular distributions and isotopic compositions of marine aerosols over the western North Atlantic: Dicarboxylic acids, ketoacids, α-dicarbonyls (glyoxal and methylglyoxal), fatty acids, sugars, and SOA tracers

    NASA Astrophysics Data System (ADS)

    Kawamura, K.; Ono, K.; Tachibana, E.; Quinn, P.; Bates, T. S.

    2013-12-01

    Marine aerosols were collected over the western North Atlantic from off the coast of Boston to Bermuda during the WACS (Western Atlantic Climate Study) cruise of R/V Ronald H. Brown in August 2012 using a high volume air sampler and pre-combusted quartz fiber filters. Aerosol filter samples (n=5) were analyzed for OC/EC, major inorganic ions, low molecular weight dicarboxylic acids and various secondary organic aerosol (SOA) tracers using carbon analyzer, ion chromatograph, GC/FID and GC/MS, respectively. Homologous series (C2-C12) of dicarboxylic acids (31-335 ng m-3) were detected with a predominance of oxalic acid. Total carbon and nitrogen and their stable isotope ratios were determined as well as stable carbon isotopic compositions of individual diacids using IRMS. Diacids were found to be the most abundant compound class followed by monoterpene-SOA tracers > isoprene-SOA tracers > sugar compounds > ketoacids > fatty alcohols > fatty acids > α-dicarbonyls > aromatic acids > n-alkanes. The concentrations of these compounds were higher in the coastal site and decreased in the open ocean. However, diacids stayed relatively high even in the remote ocean. Interestingly, contributions of oxalic acid to total aerosol carbon increased from the coast (2.3%) to the remote ocean (5.6%) during long-range atmospheric transport. Stable carbon isotopic composition of oxalic acid increased from the coast (-17.5‰) to open ocean (-12.4‰), suggesting that photochemical aging of organic aerosols occurred during the atmospheric transport over the ocean. Stable carbon isotope ratios of bulk aerosol carbon also increased from the coast near Boston to the open ocean near Bermuda.

  1. The Structure of Human Apolipoprotein A-IV as Revealed by Stable Isotope-assisted Cross-linking, Molecular Dynamics, and Small Angle X-ray Scattering*

    PubMed Central

    Walker, Ryan G.; Deng, Xiaodi; Melchior, John T.; Morris, Jamie; Tso, Patrick; Jones, Martin K.; Segrest, Jere P.; Thompson, Thomas B.; Davidson, W. Sean

    2014-01-01

    Apolipoprotein (apo)A-IV plays important roles in dietary lipid and glucose metabolism, and knowledge of its structure is required to fully understand the molecular basis of these functions. However, typical of the entire class of exchangeable apolipoproteins, its dynamic nature and affinity for lipid has posed challenges to traditional high resolution structural approaches. We previously reported an x-ray crystal structure of a dimeric truncation mutant of apoA-IV, which showed a unique helix-swapping molecular interface. Unfortunately, the structures of the N and C termini that are important for lipid binding were not visualized. To build a more complete model, we used chemical cross-linking to derive distance constraints across the full-length protein. The approach was enhanced with stable isotope labeling to overcome ambiguities in determining molecular span of the cross-links given the remarkable similarities in the monomeric and dimeric apoA-IV structures. Using 51 distance constraints, we created a starting model for full-length monomeric apoA-IV and then subjected it to two modeling approaches: (i) molecular dynamics simulations and (ii) fitting to small angle x-ray scattering data. This resulted in the most detailed models yet for lipid-free monomeric or dimeric apoA-IV. Importantly, these models were of sufficient detail to direct the experimental identification of new functional residues that participate in a “clasp” mechanism to modulate apoA-IV lipid affinity. The isotope-assisted cross-linking approach should prove useful for further study of this family of apolipoproteins in both the lipid-free and -bound states. PMID:24425874

  2. Using Carbon-14 Isotope Tracing to Investigate Molecular Structure Effects of the Oxygenate Dibutyl Maleate on Soot Emissions from a DI Diesel Engine

    SciTech Connect

    Buchholz, B A; Mueller, C J; Upatnieks, A; Martin, G C; Pitz, W J; Westbrook, C K

    2004-01-07

    The effect of oxygenate molecular structure on soot emissions from a DI diesel engine was examined using carbon-14 ({sup 14}C) isotope tracing. Carbon atoms in three distinct chemical structures within the diesel oxygenate dibutyl maleate (DBM) were labeled with {sup 14}C. The {sup 14}C from the labeled DBM was then detected in engine-out particulate matter (PM), in-cylinder deposits, and CO{sub 2} emissions using accelerator mass spectrometry (AMS). The results indicate that molecular structure plays an important role in determining whether a specific carbon atom either does or does not form soot. Chemical-kinetic modeling results indicate that structures that produce CO{sub 2} directly from the fuel are less effective at reducing soot than structures that produce CO before producing CO{sub 2}. Because they can follow individual carbon atoms through a real combustion process, {sup 14}C isotope tracing studies help strengthen the connection between actual engine emissions and chemical-kinetic models of combustion and soot formation/oxidation processes.

  3. The Molecular Mechanisms of the Antibacterial Effect of Picosecond Laser Generated Silver Nanoparticles and Their Toxicity to Human Cells.

    PubMed

    Korshed, Peri; Li, Lin; Liu, Zhu; Wang, Tao

    2016-01-01

    Silver nanoparticles (Ag NPs) are known to have antibacterial properties. They are commonly produced by chemical synthesis which involves the use of harmful reducing agents. Contras, the laser technique is able to generate high-purity Ag NPs in water with specified surface charge characteristics. In the past, the molecular mechanisms contributing to the bactericidal effects of Ag NPs have been investigated extensively, but little is known of the antibacterial and toxic effects and mechanisms involved in laser-generated Ag NPs. In the current study Ag NPs were generated by picosecond laser ablation. Their antibacterial activity was determined on the gram-negative bacteria E. coli and Pseudomonas aeruginosa, and the gram positive bacteria Staphylococcus aureus including the methicillin resistant strain MRSA. Results showed that the laser generated Ag NPs exhibited strong dose-dependent antibacterial activity against all the three bacterial strains tested. Using E.coli as a model system, the laser Ag NPs treatment induced significantly high levels of reactive oxygen species (ROS). These ROS did not include detectable hydroxyl radicals, suggesting for the first time the selective ROS induction in bacterial cells by laser generated Ag NPs. The increased ROS was accompanied by significantly reduced cellular glutathione, and increased lipid peroxidation and permeability, suggesting ROS related bacterial cell damage. The laser generated Ag NPs exhibited low toxicity (within 72 hours) to five types of human cells although a weak significant decrease in cell survival was observed for endothelial cells and the lung cells. We conclude that picosecond laser generated Ag NPs have a broad spectrum of antibacterial effects against microbes including MRSA with minimal human cell toxicity. The oxidative stress is likely the key mechanism underlying the bactericidal effect, which leads to lipid peroxidation, depletion of glutathione, DNA damages and eventual disintegration of the

  4. The Molecular Mechanisms of the Antibacterial Effect of Picosecond Laser Generated Silver Nanoparticles and Their Toxicity to Human Cells

    PubMed Central

    Korshed, Peri; Li, Lin; Liu, Zhu; Wang, Tao

    2016-01-01

    Silver nanoparticles (Ag NPs) are known to have antibacterial properties. They are commonly produced by chemical synthesis which involves the use of harmful reducing agents. Contras, the laser technique is able to generate high-purity Ag NPs in water with specified surface charge characteristics. In the past, the molecular mechanisms contributing to the bactericidal effects of Ag NPs have been investigated extensively, but little is known of the antibacterial and toxic effects and mechanisms involved in laser-generated Ag NPs. In the current study Ag NPs were generated by picosecond laser ablation. Their antibacterial activity was determined on the gram-negative bacteria E. coli and Pseudomonas aeruginosa, and the gram positive bacteria Staphylococcus aureus including the methicillin resistant strain MRSA. Results showed that the laser generated Ag NPs exhibited strong dose-dependent antibacterial activity against all the three bacterial strains tested. Using E.coli as a model system, the laser Ag NPs treatment induced significantly high levels of reactive oxygen species (ROS). These ROS did not include detectable hydroxyl radicals, suggesting for the first time the selective ROS induction in bacterial cells by laser generated Ag NPs. The increased ROS was accompanied by significantly reduced cellular glutathione, and increased lipid peroxidation and permeability, suggesting ROS related bacterial cell damage. The laser generated Ag NPs exhibited low toxicity (within 72 hours) to five types of human cells although a weak significant decrease in cell survival was observed for endothelial cells and the lung cells. We conclude that picosecond laser generated Ag NPs have a broad spectrum of antibacterial effects against microbes including MRSA with minimal human cell toxicity. The oxidative stress is likely the key mechanism underlying the bactericidal effect, which leads to lipid peroxidation, depletion of glutathione, DNA damages and eventual disintegration of the

  5. Chemical and Isotopic Analysis of Trace Organic Matter on Meteorites and Interstellar Dust Using a Laser Microprobe Instrument

    NASA Technical Reports Server (NTRS)

    Zare, Richard N.; Boyce, Joseph M. (Technical Monitor)

    2001-01-01

    Polycyclic Aromatic Hydrocarbons (PAHs) are of considerable interest today because they are ubiquitous on Earth and in the interstellar medium (ISM). In fact, about 20% of cosmic carbon in the galaxy is estimated to be in the form of PAHs. Investigation of these species has obvious uses for determining the cosmochemistry of the solar system. Work in this laboratory has focused on four main areas: 1) Mapping the spatial distribution of PAHs in a variety of meteoritic samples and comparing this distribution with mineralogical features of the meteorite to determine whether a correlation exists between the two. 2) Developing a method for detection of fullerenes in extraterrestrial samples using microprobe Laser Desorption Ionization Mass Spectroscopy and utilizing this technique to investigate fullerene presence, while exploring the possibility of spatially mapping the fullerene distribution in these samples through in situ detection. 3) Investigating a possible formation pathway for meteoritic and ancient terrestrial kerogen involving the photochemical reactions of PAHs with alkanes under prebiotic and astrophysically relevant conditions. 4) Studying reaction pathways and identifying the photoproducts generated during the photochemical evolution of PAH-containing interstellar ice analogs as part of an ongoing collaboration with researchers at the Astrochemistry Lab at NASA Ames. All areas involve elucidation of the solar system formation and chemistry using microprobe Laser Desorption Laser Ionization Mass Spectrometry. A brief description of microprobe Laser Desorption Ionization Mass Spectroscopy, which allows selective investigation of subattomole levels of organic species on the surface of a sample at 10-40 micrometer spatial resolution, is given.

  6. Molecular modeling of the effects of 40Ar recoil in illite particles on their K-Ar isotope dating

    NASA Astrophysics Data System (ADS)

    Szczerba, Marek; Derkowski, Arkadiusz; Kalinichev, Andrey G.; Środoń, Jan

    2015-06-01

    The radioactive decay of 40K to 40Ar is the basis of isotope age determination of micaceous clay minerals formed during diagenesis. The difference in K-Ar ages between fine and coarse grained illite particles has been interpreted using detrital-authigenic components system, its crystallization history or post-crystallization diffusion. Yet another mechanism should also be considered: natural 40Ar recoil. Whether this recoil mechanism can result in a significant enough loss of 40Ar to provide observable decrease of K-Ar age of the finest illite crystallites at diagenetic temperatures - is the primary objective of this study which is based on molecular dynamics (MD) computer simulations. All the simulations were performed for the same kinetic energy (initial velocity) of the 40Ar atom, but for varying recoil angles that cover the entire range of their possible values. The results show that 40Ar recoil can lead to various deformations of the illite structure, often accompanied by the displacement of OH groups or breaking of the Si-O bonds. Depending on the recoil angle, there are four possible final positions of the 40Ar atom with respect to the 2:1 layer at the end of the simulation: it can remain in the interlayer space or end up in the closest tetrahedral, octahedral or the opposite tetrahedral sheet. No simulation angles were found for which the 40Ar atom after recoil passes completely through the 2:1 layer. The energy barrier for 40Ar passing through the hexagonal cavity from the tetrahedral sheet into the interlayer was calculated to be 17 kcal/mol. This reaction is strongly exothermic, therefore there is almost no possibility for 40Ar to remain in the tetrahedral sheet of the 2:1 layer over geological time periods. It will either leave the crystal, if close enough to the edge, or return to the interlayer space. On the other hand, if 40Ar ends up in the octahedral sheet after recoil, a substantially higher energy barrier of 55 kcal/mol prevents it from leaving

  7. Molecular Gas-Filled Hollow Optical Fiber Lasers in the Near Infrared

    DTIC Science & Technology

    2012-01-12

    HOLLOW OPTICAL FIBER LASERS IN THE NEAR F A9550-08-l-0344 INFRARED Sb. GRANT NUMBER Sc. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) Sd. PROJECT NUMBER...SUPPLEMENTARY NOTES 14. ABSTRACT We have demonstrated of a new class of optically pumped gas lasers inside a hollow-core photonic crystal fibers . Here, a...crystal fiber . These lasers are the first in a new class of infrared lasers based on the combination of hollow- fiber and optically pumped-gas

  8. Chirped Grating Tunable Lasers for the Infrared Molecular Fingerprint Spectral Region

    DTIC Science & Technology

    2013-09-01

    then to the cold finger of liquid nitrogen Dewar. In characterization, a thulium fiber laser at 1.908 nm wavelength is chosen to be the pump laser...Temperature r----..t....---, Controller 1908-nm Thulium Fiber Laser Beam• 0 Cube Dump a - olarizer EJ...l.908~Lm Pump Stripe -----------------------------~ .......... Temperature r----..t....---, Controller 1908-nm Thulium Fiber Laser Beam• 0 Cube

  9. Method of separating boron isotopes

    SciTech Connect

    Jensen, R.J.; Cluff, C.L.; Hayes, J.K.; Thorne, J.M.

    1984-05-08

    A method of boron isotope enrichment involving the isotope preferential photolysis of (2-chloroethenyl)dichloroborane as the feed material. The photolysis can readily be achieved with CO/sub 2/ laser radiation and using fluences significantly below those required to dissociate BCl/sub 3/.

  10. Method of separating boron isotopes

    DOEpatents

    Jensen, R.J.; Thorne, J.M.; Cluff, C.L.

    1981-01-23

    A method of boron isotope enrichment involving the isotope preferential photolysis of (2-chloroethenyl)-dichloroborane as the feed material. The photolysis can readily by achieved with CO/sub 2/ laser radiation and using fluences significantly below those required to dissociate BCl/sub 3/.

  11. Method of separating boron isotopes

    DOEpatents

    Jensen, Reed J.; Thorne, James M.; Cluff, Coran L.; Hayes, John K.

    1984-01-01

    A method of boron isotope enrichment involving the isotope preferential photolysis of (2-chloroethenyl)dichloroborane as the feed material. The photolysis can readily be achieved with CO.sub.2 laser radiation and using fluences significantly below those required to dissociate BCl.sub.3.

  12. Femtosecond laser ablation of CuxZr1-x bulk metallic glasses: A molecular dynamics study

    NASA Astrophysics Data System (ADS)

    Marinier, Sébastien; Lewis, Laurent J.

    2015-11-01

    Molecular-dynamics simulations combined with a two-temperature model are used to study laser ablation in CuxZr1-x (x =0.33 ,0.50 ,0.67 ) metallic glasses as well as crystalline CuZr2 in the C11b (MoSi2) structure. Ablation thresholds are found to be 430 ±10 ,450 ±10 ,510 ±10 , and 470 ±10 J/m 2 for a-Cu2Zr , a-CuZr, a-CuZr2, and c-CuZr2, respectively. The larger threshold in amorphous CuZr2 results from a weaker electron-phonon coupling and thus longer electron-ion equilibration time. We observe that the velocity of the pressure waves in the amorphous samples is not affected by the fluence, in contrast to the crystal; this is due to differences in the behavior of the shear modulus with increasing pressure. The heat-affected zone in the different systems is characterized in terms of the melting depth as well as inelastic deformations. The melting depth is found to be smaller in the crystal than in the amorphous targets because of its higher melting temperature. The inelastic deformations are investigated in terms of the von Mises shear strain invariant ηMises; the homogeneous nucleation of shear transformation zones is observed in the glass as reported in previous theoretical and experimental studies. The coalescence of the shear transformation zones is also found at higher fluence.

  13. Three-body fragmentation of triatomic molecular ions in a strong laser field

    NASA Astrophysics Data System (ADS)

    Ablikim, U.; Zohrabi, M.; Jochim, Bethany; Berry, Ben; Carnes, K. D.; Ben-Itzhak, I.

    2014-05-01

    Coincidence three-dimensional momentum imaging measurements of three-body fragmentation of transient triply-charged CO2 molecules reveal competing fragmentation paths involving bending, symmetric and asymmetric stretching, as well as the more complex sequential breakup (i.e. one bond at a time). We have extended these studies using a CO2+molecular-ion-beam target, providing similar results for the breakup of the transient CO23+ --> O+ + C+ + O+. The detection of neutral fragments also enables kinematically complete measurements of the three-body breakup of the transient CO22+ . Our results, for CO2+in ultrashort (~26 fs) intense (1015 to 1016 W/cm2) laser pulses at 790 nm, suggest significant bending in the C+ + O+ + O+ channel as well as sequential breakup. In contrast, sequential breakup is suppressed in the O+ + C+ + O and O+ + C +O+ channels. Supported by the Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Office of Science, U.S.

  14. Molecular uranates - laser synthesis of uranium oxide anions in the gas phase

    SciTech Connect

    Marcalo, Joaquim; Santos, Marta; Pires de Matos, Antonio; Gibson, John K

    2009-12-14

    Laser ablation of solid UO{sub 3} or (NH{sub 4}){sub 2}U{sub 2}O{sub 7} yielded in the gas phase molecular uranium oxide anions with compositions ranging from [UO{sub n}]{sup -} (n = 2-4) to [U{sub 14}O{sub n}]{sup -} (n = 32-35), as detected by Fourier transform ion cyclotron resonance mass spectrometry. The cluster series [U{sub x}O{sub 3x}]{sup -} for x {le} 6 and various [U{sub x}O{sub 3x-y}]{sup -}, in which y increased with increasing x, could be identified. A few anions with H atoms were also present, and their abundance increased when hydrated UO{sub 3} was used in place of anhydrous UO{sub 3}. Collision-induced dissociation experiments with some of the lower m/z cluster anions supported extended structures in which neutral UO{sub 3} constitutes the building block. Cationic uranium oxide clusters [U{sub x}O{sub n}]{sup +} (x = 2-9; n = 3-24) could also be produced and are briefly discussed. Common trends in the O/U ratios for both negative and positive clusters could be unveiled.

  15. Tracking nuclear wave-packet dynamics in molecular oxygen ions with few-cycle infrared laser pulses

    SciTech Connect

    De, S.; Bocharova, I. A.; Magrakvelidze, M.; Ray, D.; Cao, W.; Thumm, U.; Cocke, C. L.; Bergues, B.; Kling, M. F.; Litvinyuk, I. V.

    2010-07-15

    We have tracked nuclear wave-packet dynamics in doubly charged states of molecular oxygen using few-cycle infrared laser pulses. Bound and dissociating wave packets were launched and subsequently probed via a pair of 8-fs pulses of 790 nm radiation. Ionic fragments from the dissociating molecules were monitored by velocity-map imaging. Pronounced oscillations in the delay-dependent kinetic energy release spectra were observed. The occurrence of vibrational revivals permits us to identify the potential curves of the O{sub 2} dication which are most relevant to the molecular dynamics. These studies show the accessibility to the dynamics of such higher-charged molecules.

  16. Photoelectron angular distributions in molecular above threshold ionization by two colour circularly polarized ultrashort UV laser pulses

    NASA Astrophysics Data System (ADS)

    Yuan, Kai-Jun; Bandrauk, André D.

    2013-10-01

    Photoionization of an aligned molecular ion H? has been investigated with two colour circularly polarized ultrashort UV laser pulses by numerically solving the corresponding time dependent Schrödinger equation. Photoelectron angular distributions (PADs) in molecular above threshold ionization (MATI) exhibit: (i) asymmetry resulting from interference of coherent electron wave packets from multiple pathway ionization, which depends critically on the relative carrier envelope phase (CEP) ? between the two colour laser pulses and photoelectron kinetic energies; (ii) rotation with respect to the molecular symmetry axes due to effects of the nonspheri