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Sample records for molecular laser isotope

  1. 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.

  2. 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.

  3. 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.

  4. Multikilowatt TEA-CO2 laser system for molecular laser isotope separation

    NASA Astrophysics Data System (ADS)

    Ronander, Einar; Rohwer, Erich G.

    1993-05-01

    Laser-induced chemistry has received much attention in the past few years. The economics of such applications are dominated by the costs of photons and the quantum yield of the specific reaction. For a typical multiple-IR-photon process the quantum yield can be as low as 10-4 which emphasizes the importance of reducing the cost of laser photons. Based on 1982 technology, CO2 TEA laser operating costs were approximately $100/watt per year for a laser with an electrical efficiency of 6% and an average power of more than 100 kW. Capital costs dominated the energy cost as well as the maintenance and labor costs. At the South African Atomic Energy Corp. we have been involved in the development of high pulse frequency, high average power TEA-CO2 lasers for the application in the field of laser-induced chemistry. Much of the attention, however, has been focused on the application to separate the isotopes of uranium via a multiwavelength infrared irradiation scheme. The progress that has been made towards the establishment of CO2-lasers and laser chains for industrial use has been quite outstanding.

  5. 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

  6. 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.

  7. 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.

  8. 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.

  9. Isotopic effects on the control of molecular handedness of H 2 POSH by ultrashort laser pulses

    NASA Astrophysics Data System (ADS)

    Leal, A. S.; Kröner, D.; González, L.

    2001-05-01

    The selective preparation of an enantiomer starting from a pure state of H2POSH representing a 50%:50% mixture of two enantiomers with opposite chiralities is extended to its deuterated counterpart, H2POSD. A one-dimensional model involving the torsional angle of S-H/D around a pre-oriented P-S axis is used. The design of an appropriate sequence of ultrashort infrared laser pulses to achieve molecular handedness for H2POSH/D is based on the characteristic level splitting and tunneling times of both molecules. A simple scheme of two linearly polarized laser pulses involving a three level system serves to convert the different isotopomers to opposite enantiomers, for any given mixture of H2POSH and H2POSD molecules.

  10. 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.

  11. 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.

  12. 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.

  13. Dye laser chain for laser isotope separation

    NASA Astrophysics Data System (ADS)

    Doizi, Denis; Jaraudias, Jean; Pochon, E.; Salvetat, G.

    1993-05-01

    Uranium enrichment by laser isotope separation uses a three step operation which requires four visible wavelengths to boost an individual U235 isotope from a low lying atomic energy level to an autoionizing state. The visible wavelengths are delivered by dye lasers pumped by copper vapor lasers (CVL). In this particular talk, a single dye chain consisting of a master oscillator and amplifier stages will be described and some of its performance given.

  14. 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.

  15. 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.

  16. 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

  17. 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

  18. Improvement of multi jet low pressure impactor for high collection efficiency of UF5 in the molecular laser isotope separation of uranium

    NASA Astrophysics Data System (ADS)

    Kuga, Yoshikazu; Jurcik, Benjamin; Satooka, Sakae; Takeuchi, Kazuo

    1995-07-01

    A numerical and experimental study for the collection of photo-produced UF 5 particles was performed for the low pressure impactors which have different design factors at typical flow conditions (upstream pressure of the impactor = 10-15 Torr, pressure ratio of downstream to upstream of the impactor, {P down}/{P up} = 0.2-0.5 ) in the molecular laser isotope separation of uranium at RIKEN (RIMLIS). Smaller {H}/{W} ratios (the distance between the impactor orifice exit and the impaction plate, H, divided by the orifice diameter of the impactor, W) and the smaller {P down}/{P up} were found to be preferable to obtain a higher collection efficiency from both numerical and experimental investigations. In addition it was experimentally demonstrated that the use of a 16 μm laser system for the selective reaction of 235UF 6 to form 235UF 5 was not relevant for the study of the collection of UF 5 particles. So, we used an ultraviolet laser system (fourth harmonic YAG laser (266 nm) and an excimer laser (KrF, 248 nm)) which was more convenient to cope with various operating conditions. The collection efficiency was found to increase with the initial concentration of UF 5 molecules produced. Applying the improved impactor stage, we obtained a collection efficiency which was approximately 10 times higher than that of our previous work. Higher collection efficiencies of photo-produced UF 5 particles enriched in 235U reduce the enrichment cost.

  19. 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.

  20. Separating Isotopes With Laser And Electron Beams

    NASA Technical Reports Server (NTRS)

    Trajmar, Sandor

    1989-01-01

    Need for second laser eliminated. In scheme for separation of isotopes, electrons of suitable kinetic energy ionize specific isotope excited by laser beam in magnetic field. Ionization by electron beams cheap and efficient in comparison to ionization by laser beams, and requires no special technical developments. Feasibility of new scheme demonstrated in selective ionization of Ba138, making possible separation of isotope from Ba isotopes of atomic weight 130, 132, 134, 135, 136, and 137.

  1. Isotope separation using metallic vapor lasers

    NASA Technical Reports Server (NTRS)

    Russell, G. R.; Chen, C. J.; Harstad, K. G. (Inventor)

    1977-01-01

    The isotope U235 is separated from a gasified isotope mixture of U235 and U238 by selectively exciting the former from the ground state utilizing resonant absorption of radiation from precisely tuned lasers. The excited isotope is then selectively ionized by electron bombardment. It then is separated from the remaining isotope mixture by electromagnetic separation.

  2. Method for laser induced isotope enrichment

    SciTech Connect

    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.

  3. 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.

  4. Atomic vapor laser isotope separation

    NASA Astrophysics Data System (ADS)

    Paisner, J. A.

    1988-07-01

    Atomic Vapor Laser Isotope Separation (AVLIS) is a general and powerful technique applicable to many elements. A major present application to the enrichement of uranium for lightwater power reactor fuel has been under development at the Lawrence Livermore National Laboratory since 1973. In June 1985, the Department of Energy announced the selection of AVLIS as the technology to meet future U.S. needs for the internationally competitive production of uranium separative work. Major features of the AVLIS process will be discussed with consideration of the process figures of merit.

  5. 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.

  6. 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.

  7. 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.

  8. Atomic-vapor-laser isotope separation

    SciTech Connect

    Davis, J.I.

    1982-10-01

    This paper gives a brief history of the scientific considerations leading to the development of laser isotope separation (LIS) processes. The close relationship of LIS to the broader field of laser-induced chemical processes is evaluated in terms of physical criteria to achieve an efficient production process. Atomic-vapor LIS processes under development at Livermore are reviwed. 8 figures.

  9. Miniature Laser Spectrometer for Stable Isotope Measurements

    NASA Technical Reports Server (NTRS)

    Becker, J. F.; Kojiro, D. R.

    1999-01-01

    As a first step in successfully measuring carbon isotopes optically we have previously demonstrated the measurement of C-13/C-12 to a precision of 0.1% using a tunable diode laser and CO2 spectral lines in the 2300/cm spectral region. This precision of 0.1% (1 per mil) for carbon isotopes is a value sufficiently precise to provide important isotopic data of interest to astrobiologists. The precision presently attainable in gases is sufficient to permit our instrument to be used in the measurement of isotopic ratios of interest to astrobiologists as well as geologists and planetary scientists.

  10. 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.

  11. [Laser-induced isotopic discrimination effect in laser resonance ionization process of lead atom].

    PubMed

    Wang, Xin-Shun; Li, Ying; Dai, Lin; Zheng, Rong-Er

    2008-07-01

    Isotope ratio measurements have been increasingly used in geochemistry, geochronology, cosmos chemistry and environmental science. Precise and accurate isotope ratio measurements are an important task in many applications such as the determination of isotope variations in geological and cosmic samples. Due to its high sensitivity, high ionization efficiency and high element selectivity, laser resonance ionization spectroscopy has nowadays become one of the key techniques, including isotope ratio measurements and trace amount analyses. Because of the isotope shifts and hyperfine structure, there is laser-induced isotopic discrimination effect in the process of laser resonance ionization. The different isotope ionization efficiency can affect precise and accurate measurement of isotope ratios. In the present paper, the dependences of the laser-induced isotopic discrimination effect on some of the laser parameters were studied by theoretical methods. Based on the numerical simulation of the population rate equations, laser-induced isotopic discrimination effect of lead isotopes was studied, by calculating laser resonance ionization transition "6s2 6p23 P0-6s2 6p7 s3 P1(0) --> ionization". The population rate equations was approximated considering some factors which affect the probability of laser resonance transition such as spectral lines width of laser and atom, isotope shifts and hyperfine structure. According to the approximated population rate equations, "1+1" laser resonant ionization process was employed to calculate the ionization probability of lead isotopes by means of computer simulation. The dependences of laser-induced isotopic discrimination effect on the laser parameters, such as laser central wavelength, bandwidth and intensity were investigated. The calculated results show that the laser-induced isotopic discrimination effect of lead isotopes could be almost eliminated by operating at optimized wavelength and could be lessened by using wide band laser

  12. High-power laser chains used for laser isotope separation

    NASA Astrophysics Data System (ADS)

    Lompre, Louis A.

    2000-01-01

    Since 1985, France has chosen to focus on the selective photo-ionization process called SILVA for uranium enrichment. The general SILVA schedule has led to the construction of a pilot facility called ASTER, aimed to a general assessment of SILVA. It utilizes a mid power dye laser chain pumped by copper vapor laser chains. An alternative solution to pump dye laser is under development. It is based on high-power diode-pumped frequency doubled Nd:YAG modules. Performances as high as 150 Watts, at 532 nm, 10 kHz and pulse duration shorter than 75 ns have been obtained. The electrical efficiency overpasses 5 percent. The paper will give a description of the high power laser chains used or proposed for laser isotope separation.

  13. 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.

  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

    DOEpatents

    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. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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

  1. Diode laser absorption spectroscopy of lithium isotopes

    NASA Astrophysics Data System (ADS)

    Olivares, Ignacio E.; González, Iván A.

    2016-10-01

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

  2. Isotope Enrichment Detection by Laser Ablation - Laser Absorption Spectrometry: Automated Environmental Sampling and Laser-Based Analysis for HEU Detection

    SciTech Connect

    Anheier, Norman C.; Bushaw, Bruce A.

    2010-01-01

    The global expansion of nuclear power, and consequently the uranium enrichment industry, requires the development of new safeguards technology to mitigate proliferation risks. Current enrichment monitoring instruments exist that provide only yes/no detection of highly enriched uranium (HEU) production. More accurate accountancy measurements are typically restricted to gamma-ray and weight measurements taken in cylinder storage yards. Analysis of environmental and cylinder content samples have much higher effectiveness, but this approach requires onsite sampling, shipping, and time-consuming laboratory analysis and reporting. Given that large modern gaseous centrifuge enrichment plants (GCEPs) can quickly produce a significant quantity (SQ ) of HEU, these limitations in verification suggest the need for more timely detection of potential facility misuse. The Pacific Northwest National Laboratory (PNNL) is developing an unattended safeguards instrument concept, combining continuous aerosol particulate collection with uranium isotope assay, to provide timely analysis of enrichment levels within low enriched uranium facilities. This approach is based on laser vaporization of aerosol particulate samples, followed by wavelength tuned laser diode spectroscopy to characterize the uranium isotopic ratio through subtle differences in atomic absorption wavelengths. Environmental sampling (ES) media from an integrated aerosol collector is introduced into a small, reduced pressure chamber, where a focused pulsed laser vaporizes material from a 10 to 20-µm diameter spot of the surface of the sampling media. The plume of ejected material begins as high-temperature plasma that yields ions and atoms, as well as molecules and molecular ions. We concentrate on the plume of atomic vapor that remains after the plasma has expanded and then cooled by the surrounding cover gas. Tunable diode lasers are directed through this plume and each isotope is detected by monitoring absorbance

  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. 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.

  5. 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.

  6. Pulsed CO laser for isotope separation of uranium

    NASA Astrophysics Data System (ADS)

    Baranov, Igor Y.; Koptev, Andrey V.

    2012-07-01

    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 μm. 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.

  7. Laser-cooled atomic ions as probes of molecular ions

    SciTech Connect

    Brown, Kenneth R.; Viteri, C. Ricardo; Clark, Craig R.; Goeders, James E.; Khanyile, Ncamiso B.; Vittorini, Grahame D.

    2015-01-22

    Trapped laser-cooled atomic ions are a new tool for understanding cold molecular ions. The atomic ions not only sympathetically cool the molecular ions to millikelvin temperatures, but the bright atomic ion fluorescence can also serve as a detector of both molecular reactions and molecular spectra. We are working towards the detection of single molecular ion spectra by sympathetic heating spectroscopy. Sympathetic heating spectroscopy uses the coupled motion of two trapped ions to measure the spectra of one ion by observing changes in the fluorescence of the other ion. Sympathetic heating spectroscopy is a generalization of quantum logic spectroscopy, but does not require ions in the motional ground state or coherent control of the ion internal states. We have recently demonstrated this technique using two isotopes of Ca{sup +} [Phys. Rev. A, 81, 043428 (2010)]. Limits of the method and potential applications for molecular spectroscopy are discussed.

  8. Ultraviolet laser spectroscopy of the neutron-deficient bismuth isotopes

    NASA Astrophysics Data System (ADS)

    Xu, Fei

    1997-12-01

    The isotope shifts and nuclear moments of the neutron deficient bismuth isotopes 201-204Bi have been measured at Stony Brook with a highly sensitive gas cell technique. The isotopes were populated with the nuclear reactions 197Au(10B,6n)201Po and 197Au(11B,xn)208-xPo, with boron beams from the SUNY Stony Brook tandem-linac accelerator. The bismuth samples that accumulated from the Po decay were evaporated from the target material and illuminated with 1-2mW of 306.7nm radiation from an intra-cavity frequency doubled ring dye laser. By measuring and analyzing the fluorescence spectra of the bismuth isotopes, the isotope shifts and hyperfine constants were obtained and the nuclear moments were extracted. The systematic behaviour of isotope shifts of the neutron-deficient bismuth isotopes is discussed and compared with the Po, Pb, Tl and Fr isotope shifts. It was found that the isotonic and isotopic trends, around the doubly magic core of 208Pb, are nearly identical. This implies that the h9/2 valence proton in the bismuth isotopes does not have a strong effect on the deformation of the core.

  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. Separation of Copper Isotopes in the Laser Plume

    SciTech Connect

    Suen, Timothy Wu; Mao Xianglei; Russo, Richard E.

    2010-10-08

    Isotopic separation was observed during ablation of standard copper samples by a nanosecond Nd-YAG laser and a femtosecond Ti:sapphire laser at 266 nm. A time-of-flight mass spectrometer, orthogonal to the direction of the laser plume, was used to measure the isotopic composition of the plasma. A voltage was applied to the pulser at different delay times after the laser was ired in order to obtain a temporal profile as the plume expanded. The fraction of {sup 63}Cu in the plasma detected by the mass spectrometer reaches a maximum of 0.83 at 6 US and 3 {mu}s after the laser is fired for the nanosecond and femtosecond lasers respectively, before falling back to the natural abundance ratio of 0.69. As reported in the literature, the ion peaks are centered at two different delay times, representing fast and slow ion energy distributions. A mechanism based on the electric ield interactions between the electrons and ions is proposed to explain the separation of isotopes in the plume.

  12. 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.

  13. 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.

  14. 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

  15. 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.

  16. Innovative lasers for uranium isotope separation. [Progress report

    SciTech Connect

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

    1991-06-01

    Copper vapor lasers have important applications to uranium atomic vapor laser isotope separation (AVLIS). The authors have spent the first two years of their project investigating two innovative methods of exciting/pumping copper vapor lasers which have the potential to improve the efficiency and scaling of large laser systems used in uranium isotope separation. Experimental research has focused on the laser discharge kinetics of (1) microwave, and (2) electron beam excitation/pumping of large-volume copper vapor lasers. During the first year, the experiments have been designed and constructed and initial data has been taken. During the second year these experiments have been diagnosed. Highlights of some of the second year results as well as plans for the future include the following: Microwave resonant cavity produced copper vapor plasmas at 2.45 GHz, have been investigated. A CW (0--500 W) signal heats and vaporizes the copper chloride to provide the atomic copper vapor. A pulsed (5 kW, 0.5--5kHz) signal is added to the incoming CW signal via a hybrid mixer to excite the copper states to the laser levels. An enhancement of the visible radiation has been observed during the pulsed pardon of the signal. Electrical probe measurements have been implemented on the system to verify the results of the electromagnetic model formulated last year. Laser gain measurements have been initiated with the use of a commercial copper vapor laser. Measurements of the spatial profile of the emission are also currently being made. The authors plan to increase the amount of pulsed microwave power to the system by implementing a high power magnetron. A laser cavity will be designed and added to this system.

  17. Two-step laser ionization schemes for in-gas laser ionization and spectroscopy of radioactive isotopes

    SciTech Connect

    Kudryavtsev, Yu. Ferrer, R.; Huyse, M.; Van den Bergh, P.; Van Duppen, P.; Vermeeren, L.

    2014-02-15

    The in-gas laser ionization and spectroscopy technique has been developed at the Leuven isotope separator on-line facility for the production and in-source laser spectroscopy studies of short-lived radioactive isotopes. In this article, results from a study to identify efficient optical schemes for the two-step resonance laser ionization of 18 elements are presented.

  18. Isotopically Enriched Films and Nanostructures by Ultrafast Pulsed Laser Deposition

    SciTech Connect

    Peter Pronko

    2004-12-13

    This project involved a systematic study to apply newly discovered isotopic enrichment effects in laser ablation plumes to the fabrication of isotopically engineered thin films, superlattices, and nanostructures. The approach to this program involved using ultrafast lasers as a method for generating ablated plasmas that have preferentially structured isotopic content in the body of the ablation plasma plumes. In examining these results we have attempted to interpret the observations in terms of a plasma centrifuge process that is driven by the internal electro-magnetic fields of the plasma itself. The research plan involved studying the following phenomena in regard to the ablation plume and the isotopic mass distribution within it: (1) Test basic equations of steady state centrifugal motion in the ablation plasma. (2) Investigate angular distribution of ions in the ablation plasmas. (3) Examine interactions of plasma ions with self-generated magnetic fields. (3) Investigate ion to neutral ratios in the ablation plasmas. (5) Test concepts of plasma pumping. (6) Fabricate isotopically enriched nanostructures.

  19. 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.

  20. Laser annealing of neutron irradiated boron-10 isotope doped diamond

    SciTech Connect

    Jagannadham, K.; Butler, J. E.

    2011-01-01

    10B isotope doped p-type diamond epilayer grown by chemical vapor deposition on (110) oriented type IIa diamond single crystal substrate was subjected to neutron transmutation at a fluence of 2.4 9 1020 thermal and 2.4 9 1020 fast neutrons. After neutron irradiation, the epilayer and the diamond substrate were laser annealed using Nd YAG laser irradiation with wave length, 266 nm and energy, 150 mJ per pulse. The neutron irradiated diamond epilayer and the substrate were characterized before and after laser annealing using different techniques. The characterization techniques include optical microscopy, secondary ion mass spectrometry, X-ray diffraction, Raman, photoluminescence and Fourier Transform Infrared spectroscopy, and electrical sheet conductance measurement. The results indicate that the structure of the irradiation induced amorphous epilayer changes to disordered graphite upon laser annealing. The irradiated substrate retains the (110) crystalline structure with neutron irradiation induced defects.

  1. Experimental and computer modeling studies of isotopically selective two-step laser photodissociation of small molecules

    SciTech Connect

    Zittel, P.F.

    1992-03-25

    The approach to laser isotope separation taken in this study is based on isotopically selective, two-step, laser photodissociation of small molecules. A primary goal of this study is the measurement of fundamental molecular processes which control the two-step, photodissociative isotope enrichment process. This objective has led to experimental measurements of uv photodissociation cross sections for vibrationally excited states of several small molecules, including the first cross section reported for any neutral molecule in a specific, excited vibrational state. A second goal of this study has been the laboratory demonstration of isotope enrichment for isotopes of practical interest and for processes with a potential for larger scale production. Where possible, efforts have focussed on the separation of middle isotopes, such as {sup 17}O and {sup 33}S, which are expensive and difficult to separate using other techniques. Considerable success has been achieved in demonstrating the enrichment of isotopes of bromine, carbon, oxygen and a third goal of this study has been the application of computer modeling to the two-step enrichment process. Experimental measurements define as many as possible of the critical photophysical and chemical parameters required by an ab initio computer model of the enrichment process. Progress toward these goals has been documented in detail in a variety of journal articles and technical reports. It is not the objective of this final report to discuss each aspect of the work done under this contract/grant in detail. A general overview of the program, touches briefly on each of the problems addressed by the study and provides references to more detailed discussions. 19 refs.

  2. 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.

  3. Quantitative estimates of precision for molecular isotopic measurements.

    PubMed

    Jasper, J P

    2001-01-01

    At least three methods of calculating the random errors or variance of molecular isotopic data are presently in use. The major components of variance are differentiated and quantified here into least three to four individual components. The measurement of error of the analyte relative to a working (whether an internal or an external) standard is quantified via the statistical pooled estimate of error. A statistical method for calculating the total variance associated with the difference of two individual isotopic compositions from two isotope laboratories is given, including the variances of the laboratory (secondary) and working standards, as well as those of the analytes. An abbreviated method for estimation of of error typical for chromatographic/isotope mass spectrometric methods is also presented.

  4. Exciton polariton dispersion for molecular crystal with isotopic replacement defects.

    NASA Astrophysics Data System (ADS)

    Rumyantsev, Vladimir; Fedorov, Stanislav; Shtaerman, Esfir

    2001-03-01

    This summary presents peculiarities of exciton polariton spectrum conditional by availability of isotopic replacement defects in molecular crystal. In the examined case of binary crystal configuration dependence of molecular currents, energies and intermolecular resonance interaction matrix W is weak as well as W-components are small. It enabled to describe main exciton spectrum peculiarities in approach similar to orientated gas model and to obtain polariton dispersion low in analytical form. The specific of dispersion curves is that the pair of curves reflecting isotopic replacement effect is added to the typical polariton curves for perfect crystal. The value of "the bottle throat" of added curves has been evaluated. Non-collinearity of the molecule dipole moments in crystalline matrix and the moments of isotopic replacement admixture determines it.

  5. 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

  6. 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.

  7. 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.

  8. 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

  9. 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.

  10. Generation of tunable far-infrared radiation by optical pumping molecular gas lasers

    NASA Astrophysics Data System (ADS)

    Schatz, W.

    1995-01-01

    This paper summarizes the results obtained by optical pumping molecular gas lasers by use of a 20 atm high-pressure CO 2-laser. The far-infrared laser gases investigated were several isotopes of the methylhalides (CH 3X; X  F, Cl, Br, I), heavy water (D 2O) and ammonia (NH 3), that delivered around 1000 laser lines with wavelengths ranging from the millimeter region down to 40 μm. By exploiting the continuous tunability of the CO 2-laser to pump either a waveguide laser or a multipass Raman-cell broadly tunable FIR emission can be generated via stimulated Raman scattering. Moreover the observed far-infrared laser pulses were found to have pulse durations of less than 100 ps.

  11. 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

  12. 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

  13. Solar Wind Neon Isotopic Analyses by UV Laser Ablation on the Genesis Concentrator Gold Cross for Calibration of Oxygen Isotope Data

    NASA Astrophysics Data System (ADS)

    Heber, V. S.; Wiens, R. C.; Burnett, D. S.; Baur, H.; Wiechert, U. H.; Wieler, R.

    2005-12-01

    To determine the oxygen isotopic composition of the present day solar wind, a proxy for the solar nebula, is one of the key goals of the Genesis solar wind (SW) collection mission. In order to increase analytical precision on measured O isotopes, ions of incoming SW in the mass range to 28 amu were accelerated and focussed onto the target by an electrostatic mirror. The concentration factor is about 20. However, these processes are expected to fractionate the isotopic composition of SW ions, with fractionation varying as a function of target radius. We will directly measure the instrumental fractionation factors by analysing Ne isotopes with high precision and spatial resolution along the radius on the electroplated Au cross that framed the concentrator targets. Ne isotopes are most suitable to investigate fractionation because of i) it is an abundant element in the Sun, ii) its isotopic composition in SW is well understood, and iii) Ne is hardly influenced by terrestrial contamination. We will analyse Ne isotopes by UV laser ablation (248 nm) of small areas (0.1 x 0.1 mm) using a very sensitive noble gas mass spectrometer equipped with a molecular drag pump conveying the gas almost quantitatively into the ion source. The target precision of O isotopic composition is about 0.1% (2-sigma). Therefore, the most important issue for us is to achieve a similar high precision of the Ne isotope data allowing to determine the trend of instrumental fractionation along the target radius, which is computed to be in total about 2%. Currently, we obtain a reproducibility of <0.2% using standard calibration gas containing similar Ne amounts as expected. Blank analyses of the ultra-clean electroplated Au target result in absolutely negligible amounts of Ne. At the meeting we will present first Ne results of the first arm analysed of the Au cross.

  14. 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

  15. 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.

  16. Experimental and computer modeling studies of isotopically selective two-step laser photodissociation of small molecules. Final report

    SciTech Connect

    Zittel, P.F.

    1992-03-25

    The approach to laser isotope separation taken in this study is based on isotopically selective, two-step, laser photodissociation of small molecules. A primary goal of this study is the measurement of fundamental molecular processes which control the two-step, photodissociative isotope enrichment process. This objective has led to experimental measurements of uv photodissociation cross sections for vibrationally excited states of several small molecules, including the first cross section reported for any neutral molecule in a specific, excited vibrational state. A second goal of this study has been the laboratory demonstration of isotope enrichment for isotopes of practical interest and for processes with a potential for larger scale production. Where possible, efforts have focussed on the separation of middle isotopes, such as {sup 17}O and {sup 33}S, which are expensive and difficult to separate using other techniques. Considerable success has been achieved in demonstrating the enrichment of isotopes of bromine, carbon, oxygen and a third goal of this study has been the application of computer modeling to the two-step enrichment process. Experimental measurements define as many as possible of the critical photophysical and chemical parameters required by an ab initio computer model of the enrichment process. Progress toward these goals has been documented in detail in a variety of journal articles and technical reports. It is not the objective of this final report to discuss each aspect of the work done under this contract/grant in detail. A general overview of the program, touches briefly on each of the problems addressed by the study and provides references to more detailed discussions. 19 refs.

  17. 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.

  18. 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.

  19. Nuclear Proliferation Using Laser Isotope Separation -- Verification Options

    SciTech Connect

    Erickson, S A

    2001-10-15

    -related procedures will need to be adapted to keep up with them. In order to make 93+2 inspections more useful, a systematic way of finding clues to nuclear proliferation would be useful. Also, to cope with the possible use of newer technology for proliferation, the list of clues might need to be expanded. This paper discusses the development and recognition of such clues. It concentrates on laser isotope separation (LIS) as a new proliferation technology, and uses Uranium Atomic Vapor Laser Isotope Separation (U-AVLIS) as an example of LIS that is well known.

  20. Neutron-rich B isotopes studied with antisymmetrized molecular dynamics

    SciTech Connect

    Kanada-En`yo, Y.; Horiuchi, H.

    1995-08-01

    Structure of odd-even B isotopes up to the neutron dripline is studied systematically with the antisymmetrized molecular dynamics (AMD). The AMD method has already proved to be a powerful theoretical approach for the systematic study of nuclear structure in extensive region including exotic neutron-rich nuclei as well as ordinary nuclei. It is owing to its flexible nature free from any model assumptions such as the existence of clusters. The energies and other observed data of B isotopes are reproduced well. Especially very good reproduction of electromagnetic properties is obtained. The systematic behavior of the electromagnetic properties is explained in relation to the drastic change between clustering structure and shell-model-like structure. This explanation gives us an important indication that clustering structure in neutron-rich B nuclei is strongly suggested by the experimental data. It is shown that the structure change with increase of the neutron number is largely governed by the shell effect of neutron orbits. Exotic structure with new type of clustering is suggested to evolve in neutron-rich nuclei near the dripline.

  1. Isotopic and molecular fractionation in combustion; three routes to molecular marker validation, including direct molecular 'dating' (GC/AMS)

    NASA Astrophysics Data System (ADS)

    Currie, L. A.; Klouda, G. A.; Benner, B. A.; Garrity, K.; Eglinton, T. I.

    The identification of unique isotopic, elemental, and molecular markers for sources of combustion aerosol has growing practical importance because of the potential effects of fine particle aerosol on health, visibility and global climate. It is urgent, therefore, that substantial efforts be directed toward the validation of assumptions involving the use of such tracers for source apportionment. We describe here three independent routes toward carbonaceous aerosol molecular marker identification and validation: (1) tracer regression and multivariate statistical techniques applied to field measurements of mixed source, carbonaceous aerosols; (2) a new development in aerosol 14C metrology: direct, pure compound accelerator mass spectrometry (AMS) by off-line GC/AMS ('molecular dating'); and (3) direct observation of isotopic and molecular source emissions during controlled laboratory combustion of specific fuels. Findings from the combined studies include: independent support for benzo( ghi)perylene as a motor vehicle tracer from the first (statistical) and second (direct 'dating') studies; a new indication, from the third (controlled combustion) study, of a relation between 13C isotopic fractionation and PAH molecular fractionation, also linked with fuel and stage of combustion; and quantitative data showing the influence of both fuel type and combustion conditions on the yields of such species as elemental carbon and PAH, reinforcing the importance of exercising caution when applying presumed conservative elemental or organic tracers to fossil or biomass burning field data as in the first study.

  2. 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.

  3. 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.

  4. Molecular dynamic simulation of non-melt laser annealing process

    NASA Astrophysics Data System (ADS)

    Liren, Yan; Dai, Li; Wei, Zhang; Zhihong, Liu; Wei, Zhou; Quan, Wang

    2016-03-01

    Molecular dynamic simulation is performed to study the process of material annealing caused by a 266 nm pulsed laser. A micro-mechanism describing behaviors of silicon and impurity atoms during the laser annealing at a non-melt regime is proposed. After ion implantation, the surface of the Si wafer is acted by a high energy laser pulse, which loosens the material and partially frees both Si and impurity atoms. While the residual laser energy is absorbed by valence electrons, these atoms are recoiled and relocated to finally form a crystal. Energy-related movement behavior is observed by using the molecular dynamic method. The non-melt laser anneal appears to be quite sensitive to the energy density of the laser, as a small excess energy may causes a significant impurity diffusion. Such a result is also supported by our laser anneal experiment.

  5. Improving precision in resonance ionization mass spectrometry : influence of laser bandwidth in uranium isotope ratio measurements.

    SciTech Connect

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

    2011-03-01

    The use of broad bandwidth lasers with automated feedback control of wavelength was applied to the measurement of {sup 235}U/{sup 238}U ratios by resonance ionization mass spectrometry (RIMS) to decrease laser-induced isotopic fractionation. By broadening the bandwidth of the first laser in a three-color, three-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.

  6. Molecular dispersion spectroscopy--new capabilities in laser chemical sensing.

    PubMed

    Nikodem, Michal; Wysocki, Gerard

    2012-07-01

    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.

  7. Laser-microprobe studies of rare gas isotopes in meteorites

    SciTech Connect

    Kirschbaum, C.L.

    1986-01-01

    A new rare gas mass spectrometer of high sensitivity coupled to a laser microprobe extraction system (constructed by the author) is described. The laser microprobe is applied to a long standing problem in cosmochemistry - determining the minerals which carry /sup 129/Xe from the decay of the extinct radioactive isotope /sup 129/I (this /sup 129/Xe is referred to as /sup 129/Xe/sub r/). The /sup 129/Xe/sub r//sup 127/I ratios and the inferred relative formation times of these minerals are also determined. In the Allende meteorite, sodalite (Na/sub 8/(Al/sub 6/Si/sub 6/O/sub 24/)Cl/sub 2/) has been verified to be the major carrier for /sup 129/Xe/sub r/ in fine-grained inclusions. Although the exact mineral phase responsible has not been identified a carrier other than sodalite is also present in matrix from Allende. The /sup 129/Xe/sub r/ of this carrier is physically correlated with trapped xenon in the matrix and has a chlorine/iodine ratio which is lower than the ratio in the fine-grained inclusions. The /sup 129/Xe/sub r///sup 127/I ratios for sodalite from the fine-grained inclusions, and matrix are similar - between 1.25 and 1.35 x 10/sup -4/. This implies an age for these samples within 2 million years of the Bjurbole meteorite (Bjurbole is commonly used as a standard for meteorite formation intervals). The /sup 129/Xe/sub r///sup 127/I ratio of the sample of the fine-grained inclusion in which sodalite was thermally decomposed by laboratory preheating, is 2.4 x 10/sup -4/ or 16 million years before Bjurbole. The alteration-product-free coarse-grained inclusion on the other hand showed a ratio of 3.15 x 10/sup -5/ or 35 million years after Bjurbole. These relative formation intervals are much longer than expected for nebular processes and hence are either due to parent body processes or heterogeneity of the /sup 129/I//sup 127/I ratio in the early solar system.

  8. 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.

  9. Resonance ionization laser ion sources for on-line isotope separators (invited).

    PubMed

    Marsh, B A

    2014-02-01

    A Resonance Ionization Laser Ion Source (RILIS) is today considered an essential component of the majority of Isotope Separator On Line (ISOL) facilities; there are seven laser ion sources currently operational at ISOL facilities worldwide and several more are under development. The ionization mechanism is a highly element selective multi-step resonance photo-absorption process that requires a specifically tailored laser configuration for each chemical element. For some isotopes, isomer selective ionization may even be achieved by exploiting the differences in hyperfine structures of an atomic transition for different nuclear spin states. For many radioactive ion beam experiments, laser resonance ionization is the only means of achieving an acceptable level of beam purity without compromising isotope yield. Furthermore, by performing element selection at the location of the ion source, the propagation of unwanted radioactivity downstream of the target assembly is reduced. Whilst advances in laser technology have improved the performance and reliability of laser ion sources and broadened the range of suitable commercially available laser systems, many recent developments have focused rather on the laser/atom interaction region in the quest for increased selectivity and/or improved spectral resolution. Much of the progress in this area has been achieved by decoupling the laser ionization from competing ionization processes through the use of a laser/atom interaction region that is physically separated from the target chamber. A new application of gas catcher laser ion source technology promises to expand the capabilities of projectile fragmentation facilities through the conversion of otherwise discarded reaction fragments into high-purity low-energy ion beams. A summary of recent RILIS developments and the current status of laser ion sources worldwide is presented. PMID:24593628

  10. Resonance ionization laser ion sources for on-line isotope separators (invited)

    SciTech Connect

    Marsh, B. A.

    2014-02-15

    A Resonance Ionization Laser Ion Source (RILIS) is today considered an essential component of the majority of Isotope Separator On Line (ISOL) facilities; there are seven laser ion sources currently operational at ISOL facilities worldwide and several more are under development. The ionization mechanism is a highly element selective multi-step resonance photo-absorption process that requires a specifically tailored laser configuration for each chemical element. For some isotopes, isomer selective ionization may even be achieved by exploiting the differences in hyperfine structures of an atomic transition for different nuclear spin states. For many radioactive ion beam experiments, laser resonance ionization is the only means of achieving an acceptable level of beam purity without compromising isotope yield. Furthermore, by performing element selection at the location of the ion source, the propagation of unwanted radioactivity downstream of the target assembly is reduced. Whilst advances in laser technology have improved the performance and reliability of laser ion sources and broadened the range of suitable commercially available laser systems, many recent developments have focused rather on the laser/atom interaction region in the quest for increased selectivity and/or improved spectral resolution. Much of the progress in this area has been achieved by decoupling the laser ionization from competing ionization processes through the use of a laser/atom interaction region that is physically separated from the target chamber. A new application of gas catcher laser ion source technology promises to expand the capabilities of projectile fragmentation facilities through the conversion of otherwise discarded reaction fragments into high-purity low-energy ion beams. A summary of recent RILIS developments and the current status of laser ion sources worldwide is presented.

  11. Resonance ionization laser ion sources for on-line isotope separators (invited).

    PubMed

    Marsh, B A

    2014-02-01

    A Resonance Ionization Laser Ion Source (RILIS) is today considered an essential component of the majority of Isotope Separator On Line (ISOL) facilities; there are seven laser ion sources currently operational at ISOL facilities worldwide and several more are under development. The ionization mechanism is a highly element selective multi-step resonance photo-absorption process that requires a specifically tailored laser configuration for each chemical element. For some isotopes, isomer selective ionization may even be achieved by exploiting the differences in hyperfine structures of an atomic transition for different nuclear spin states. For many radioactive ion beam experiments, laser resonance ionization is the only means of achieving an acceptable level of beam purity without compromising isotope yield. Furthermore, by performing element selection at the location of the ion source, the propagation of unwanted radioactivity downstream of the target assembly is reduced. Whilst advances in laser technology have improved the performance and reliability of laser ion sources and broadened the range of suitable commercially available laser systems, many recent developments have focused rather on the laser/atom interaction region in the quest for increased selectivity and/or improved spectral resolution. Much of the progress in this area has been achieved by decoupling the laser ionization from competing ionization processes through the use of a laser/atom interaction region that is physically separated from the target chamber. A new application of gas catcher laser ion source technology promises to expand the capabilities of projectile fragmentation facilities through the conversion of otherwise discarded reaction fragments into high-purity low-energy ion beams. A summary of recent RILIS developments and the current status of laser ion sources worldwide is presented.

  12. Radioactive Carbon Isotope Monitoring System Based on Cavity Ring-down Laser Spectroscopy for Decommissioning Process of Nuclear Facilities

    NASA Astrophysics Data System (ADS)

    Tomita, Hideki; Watanabe, Kenichi; Takiguchi, Yu; Kawarabayashi, Jun; Iguchi, Tetsuo

    In decommissioning process of nuclear facilities, large amount of radioactive isotopes are discharged as waste. Radioactive carbon isotope (14C) is one of the key nuclides to determine the upper limit of concentration in the waste disposal. In particular, 14C on the graphite reactor decommissioning should be separated from stable carbon isotopes (12C and 13C) and monitored for the public health and safety. We propose an isotope analysis system based on cavity ring-down laser spectroscopy (CRDS) to monitor the carbon isotopes (12C, 13C and 14C) in the isotope separation process for the graphite reactor decommissioning. This system is compact and suitable for a continuous monitoring, because the concentration of molecules including the carbon isotope is derived from its photo absorbance with ultra high sensitive laser absorption spectroscopy. Here are presented the necessary conditions of CRDS system for 14C isotope analysis through the preliminary experimental results of 13C isotope analysis with a prototype system.

  13. 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.

  14. Laser isotope separation in nuclear-waste by-product utilization

    NASA Astrophysics Data System (ADS)

    Dubrin, J. W.

    1983-02-01

    Various by-products in spent nuclear fuels including strategic metals are uniquely useful and of high intrinsic value. Isotope separation is necessary to achieve the full benefits of fission product partitioning, increasing the specific activity of radioactive modifications or reducing the intrinsic radiation associated with various elements. The atomic vapor laser isotope separation process, under large scale development of uranium enrichment, applies to most of the spent fuel nuclides and offers attractive benefit to costs.

  15. Laser Ablation Analyses of Pb Isotopes in Ancient Feldspars: Application to a Polymetamorphic Terrane, West Greenland

    NASA Astrophysics Data System (ADS)

    Krogstad, E. J.; Baker, J. A.; Waight, T. E.

    2001-12-01

    Laser ablation was used to sample the Pb isotopic compositions of various feldspars, as well as isotopic standards. The ablated material was analyzed by MC-ICP-MS. The resulting accuracy and external precision are comparable to conventional (i.e., not double or triple-spiked) feldspar Pb isotope analyses done by TIMS. However, the data can be acquired with no chemical separation and require only a few minutes per sample. A pilot study was made of the feldspars from a polymetamorphic terrane in West Greenland, in which Late Archean gneisses were deformed and metamorphosed during the Early Proterozoic. In this terrane, isotopic contrasts have long been sought to delineate any suture between discrete Archean continental blocks that might mark the site of ocean closure. Previous whole rock Nd and Pb isotopic studies had yielded equivocal results on the presence of such an isotopic discontinuity. The laser ablation feldspar data presented here, combined with existing whole rock Pb data, point to real differences in the sources of gneisses from various parts of the orogen. This indicates that the laser ablation method of sampling feldspar Pb holds real potential for future reconnaissance studies of old continental crust in a manner similar to that of zircon U-Pb geochronology studies.

  16. Multiple Ionization Bursts in Laser-Driven Hydrogen Molecular Ion

    SciTech Connect

    Takemoto, Norio; Becker, Andreas

    2010-11-12

    Theoretical study on H{sub 2}{sup +} in an intense infrared laser field on the attosecond time scale reveals that the molecular ion shows multiple bursts of ionization within a half-cycle of the laser field oscillation, in contrast to the widely accepted tunnel ionization picture for an atom. These bursts are found to be induced by transient localization of the electron at one of the nuclei, and a relation between the time instants of the localization and the vector potential of the laser light is derived. A scheme is proposed to probe the localization dynamics by an extreme ultraviolet laser pulse.

  17. 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.

  18. 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…

  19. Laser spectroscopic investigation of isotope shifts in Nd II lines

    NASA Astrophysics Data System (ADS)

    Koczorowski, W.; Stachowska, E.; Furmann, B.; Stefańska, D.; Jarosz, A.; Krzykowski, A.; Walaszyk, A.; Szawioła, G.; Buczek, A.

    2005-04-01

    The isotope shift of 11 optical transitions in Nd II in the spectral range 420-450 nm have been recorded (in all cases but one for all pairs of even Nd isotopes). For all observed transitions the values of the field shifts, the specific mass shifts and Δ∣ ψ(0)∣ 2 have been evaluated. Using our new data, combined with data reported in earlier papers, term isotope shifts for all pairs of even Nd isotopes have been determined for 27 energy levels and for the configurations: 4 f46 s, 4 f45 d, 4 f35 d6 s and 4 f46 p as well. It is shown that configuration assignment of a level on the basis of term shift values only is in some cases not satisfactory (as e.g. of the level at 22,696 cm -1) and obviously additional information is required.

  20. 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.

  1. 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.

  2. Chemical consequences of laser-induced breakdown in molecular gases

    NASA Astrophysics Data System (ADS)

    Babánková, Dagmar; Civiš, Svatopluk; Juha, Libor

    This article gives an account of chemical reactions initiated by laser-induced dielectric breakdown (LIDB) in homogeneous molecular gases. The systematic part of the article describes the laser-plasma-chemical behavior of simple inorganic gases and their mixtures, metal carbonyls and organometallics, and organic molecular gases. Research on LIDB-initiated chemical reactions producing well-defined fine solid particles has been triggered again recently by the advent of nanotechnologies. Laser ignition of fuel mixtures is also a well researched branch of laser-plasma chemistry because of strong commercial and military interests. However, the strongest current impulses for studying laser-spark chemistry come from planetary sciences, where laser sparks have been used as a laboratory model of high-energy-density phenomena (e.g., impact of extraterrestrial bodies, lightning) in planetary atmospheres. A single pulse from a high-power laser system was used to develop an improved method for investigating this phenomenon. The particular processes responsible for the chemical action of a laser spark are identified and described in detail by the end of the article.

  3. Interchange for Joint Research Entitled: Miniature Laser Spectrometer for Stable Isotope Measurements

    NASA Technical Reports Server (NTRS)

    Becker, J. F.; Kojiro, D. R.

    1999-01-01

    As a first step in successfully measuring carbon isotopes optically we have previously demonstrated the measurement of C-13/C-12 to a precision of 0.1% using a tunable diode laser and CO2 spectral lines in the 2300/cm spectral region. This precision of 0.1% (1 per mil) for carbon isotopes is a value sufficiently precise to provide important isotopic data of interest to astrobiologists. The precision presently attainable in gases is sufficient to permit our instrument to be used in the measurement of isotopic ratios of interest to astrobiologists as well as geologists and planetary scientists. A small stable isotope laser spectrometer with a 10 cm path gas cell was designed and constructed. The cell was integrated with a liquid nitrogen cooled tunable diode laser and indium antimonide detector for evaluation. Using the small gas cell, preliminary measurements of 13C/12C in CO2 were made employing single-beam sequential acquisitions of the required spectral data. The results indicate an accuracy of 0.1% which is sufficiently high to make meaningful measurements of martian samples. In addition, improvements in the spectrometer gas handling system have been made to markedly reduce C-13/C-12 isotopic fractionation during sample gas cell loading which we expect will lead to further improvements in precision and accuracy. An important part of making isotopic ratio measurements in solid samples using diode lasers is the conversion of the elements of interest to molecules that have absorption spectra in the mid-ir spectral range accessible by tunable diode lasers. In this project we have investigated the necessary sample preparation procedures to extract carbon, an element of astrobiological importance, from model soil compounds and to convert it to CO2, a molecule with appropriate optical absorption characteristics for reliable laser spectrometer isotopic ratio measurements of 13C/12C. We have considered calcium carbonate as a model for a component of the martian regolith

  4. 41Ca ultratrace determination with isotopic selectivity > 10(12) by diode-laser-based RIMS.

    PubMed

    Müller, P; Bushaw, B A; Blaum, K; Diel, S; Geppert, C; Nähler, A; Trautmann, N; Nörtershäuser, W; Wendt, K

    2001-07-01

    41Ca ultratrace determination by diode-laser-based resonance ionization mass spectrometry with extremely high isotopic selectivity is presented. Application to environmental dosimetry of nuclear reactor components, to cosmochemical investigations of production cross sections, and biomedical isotope-tracer studies of human calcium kinetics are discussed. Future investigations are possible use in 41Ca-radiodating. Depending on the application, 41Ca isotopic abundances in the range of 10(-9) to 10(-15) relative to the dominant stable isotope 40Ca must be determined. Either double- or triple-resonance optical excitation with narrow-band extended cavity diode lasers and subsequent non-resonant photoionization of calcium in a collimated atomic beam were used. The resulting photoions are detected with a quadrupole mass spectrometer optimized for background reduction and neighboring mass suppression. Applying the full triple-resonance scheme provides a selectivity of approximately 5 x 10(12) in the suppression of neighboring isotopes and > 10(8) for isobars, together with an overall detection efficiency of approximately 5 x 10(-5). Measurements on a variety of sample types are discussed; the accuracy and reproducibility of the resulting 41Ca/40Ca isotope ratios was better than 5%.

  5. Correcting Laser-Based Water Stable Isotope Readings Biased by Carrier Gas Changes.

    PubMed

    Gralher, Benjamin; Herbstritt, Barbara; Weiler, Markus; Wassenaar, Leonard I; Stumpp, Christine

    2016-07-01

    Recently, laser-based water stable isotope spectrometers have become popular as they enable previously impossible approaches of environmental observations. Consequently, they have been subjected to increasingly heterogeneous atmospheric conditions. However, there is still a severe lack of data on the impact of nonstandardized gas matrices on analyzer performances. Against this background, we investigated the influence of changing proportions of N2, O2, and CO2 in the carrier gas on the isotope measurements of a typical laser-based water stable isotope analyzer (Picarro L2120-i). We combined environmentally relevant mixtures of N2, O2, and CO2 with referenced, flash-evaporated water and found that isotope readings of the same water were altered by up to +14.57‰ for δ(18)O and -35.9‰ for δ(2)H. All tested relationships between carrier gas changes and respective isotope readings were strongly linearly correlated (R(2) > 0.99). Furthermore, an analyzer-measured variable allowed for reliable postcorrection of the biased isotope readings, which we additionally tested on field data. Our findings are of importance for environmental data obtained by analyzers based on the same technology. They are relevant for assays where inconsistent gas matrices or a mismatch in this regard between unknown and reference analyses cannot be excluded, which is in particular common when investigating the soil-vegetation-atmosphere continuum. PMID:27291718

  6. 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.

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

    SciTech Connect

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

    2010-08-20

    We report quasielastic neutron scattering studies of H{sub 2}-D{sub 2} 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.

  8. Molecular design concept for x-ray laser research

    SciTech Connect

    Rhodes, C.K.; Luk, Ting Shan; McPherson, A.; Boyer, K.

    1991-09-17

    The goal of this program is the construction of an x-ray laser in the kilovolt regime. Recent experimental results indicate that a new technique for the generation of strong amplification of x-ray wavelengths is feasible. It involves the combination of (1) a new ultrahigh brightness subpicosecond laser technology and (2) a recently discovered unique mode of strong-field interaction, particularly applicable to molecules. A concept of molecular x-ray laser design emerges from these considerations which matches the mode of excitation to the structure of the molecular system. The molecular approach enables the combination of very highly electronically excited conditions with an environment characteristic of dense cold matter, a general situation exceptionally conducive to x-ray amplification. Both high efficiency and wavelength tunability are intrinsic features of this method. 19 refs., 4 figs.

  9. 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

  10. Molecular dispersion spectroscopy--new capabilities in laser chemical sensing.

    PubMed

    Nikodem, Michal; Wysocki, Gerard

    2012-07-01

    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

  11. Highly efficient and isotope selective photo-ionization of barium atoms using diode laser and LED light

    NASA Astrophysics Data System (ADS)

    Wang, B.; Zhang, J. W.; Gao, C.; Wang, L. J.

    2011-08-01

    We demonstrated a simple method to photo-ionize barium atoms using 791 nm diode laser together with 310 nm UV LED. It solved the bottle-neck problem of previous method using 791 nm diode laser and 337 nm N2 laser, whose ionization rate was limited by the repetition rate of N2 laser. Compared with previous method, it has advantages of high efficiency together with simple and cheap setups. By tuning the frequency of 791 nm laser to be resonant with the desired isotope, isotope selective photo-ionization has been realized.

  12. Highly efficient and isotope selective photo-ionization of barium atoms using diode laser and LED light.

    PubMed

    Wang, B; Zhang, J W; Gao, C; Wang, L J

    2011-08-15

    We demonstrated a simple method to photo-ionize barium atoms using 791 nm diode laser together with 310 nm UV LED. It solved the bottle-neck problem of previous method using 791 nm diode laser and 337 nm N(2) laser, whose ionization rate was limited by the repetition rate of N(2) laser. Compared with previous method, it has advantages of high efficiency together with simple and cheap setups. By tuning the frequency of 791 nm laser to be resonant with the desired isotope, isotope selective photo-ionization has been realized. PMID:21935008

  13. 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.

  14. Laser enhanced microwave plasma isotope separation. Progress report, September 30, 1992--April 15, 1993

    SciTech Connect

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

    1993-04-01

    We are developing an innovative method of isotope enrichment using laser enhanced microwave/electron cyclotron resonance (ECR) discharges. Experimental research is focusing on laser excitation of a low abundance isotope and then ionization and separation using a microwave/ECR discharge at 2.45 GHz. The first six months of the grant period have focused on modifying the plans for the ion source to include accessibility for laser excitation. Construction of the ion source has begun and is close to completion. During the next six months we plan to test the performance of the ion source. During the next fiscal year we plan to purchase a dye amplifier which will be pumped by our copper vapor laser. The dye laser, tuned to a wavelength of 670.8 mn, will excite {sup 6}Li which win then be preferentially ionized by the ECR source and collected with a charged grid. The degree of enrichment will be determined using thermal ionization mass spectrometry. The Dept. of Geology is currently calibrating their mass spectrometry system for {sup 6}Li/{sup 7}Li ratios. The final objective of this project will be to assess the feasibility of this system to large-scale prod?action of stable isotopes.

  15. Isotope shift in erbium I by laser-atomic-beam spectroscopy

    NASA Astrophysics Data System (ADS)

    Okamura, H.; Matsuki, S.

    1987-04-01

    High-resolution laser spectroscopy has been performed on an atomic beam of natural erbium isotopes. The isotope shift in the 582.7 nm transitions [4f126s2( 3H6)-->4f12( 3H6)66( 3P01)J=7] for the pairs of 162,164,166,167,168,170Er I was obtained with an accuracy of about 4 MHz. Relative changes of mean-square nuclear charge radii δ for these isotopes were thus deduced. The isotope shift in 167Er, obtained from the well-resolved hyperfine components, shows similar even-odd staggering effect in δ found in the nearby elements.

  16. Molecular isotopic effects on coupled electronic and nuclear fluxes

    SciTech Connect

    Kenfack, A.; Paulus, B.; Barth, I.; Marquardt, F.

    2010-12-15

    A full quantum treatment shows that coupled electronic and nuclear fluxes exhibit a strong sensitivity to a small mass change in a vibrating molecule. This has been exemplified with the existing isotopes of H{sub 2}{sup +} as well as few fictitious ones. We find that the fluxes undergo a significant change as one goes from one isotope of reduced mass {mu} to another. Other well-defined observables are likewise affected. It turns out that as a general rule, the heavier the isotope, the larger the flux, the smaller the dispersion, and the longer the revival period. While we were able to confirm analytically that the time at the first turning point scales as {radical}({mu}) and that the revival period changes linearly with {mu}, the mechanism of other observables remains subtle as the result of quantum interference highlighted by the pronounced difference observed on the dispersion pattern.

  17. Molecular collisions in a laser field - Effect of the laser linewidth

    NASA Technical Reports Server (NTRS)

    Lee, H. W.; Devries, P. L.; George, T. F.

    1978-01-01

    The effect of the laser linewidth on molecular collision processes taking place in a laser field is studied, using an approximation scheme that replaces the actual frequency distribution of the field by a finite number of frequencies and weights. The choice of the frequencies and weights is conveniently accomplished by the method of Gaussian quadrature. Close-coupling calculations are performed on model systems, and the results indicate that the neglect of the laser linewidth may be justified in most collision processes in a laser field.

  18. "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.

  19. Isotope effects in lithium hydride and lithium deuteride crystals by molecular dynamics simulations.

    PubMed

    Dammak, Hichem; Antoshchenkova, Ekaterina; Hayoun, Marc; Finocchi, Fabio

    2012-10-31

    Molecular dynamics (MD) simulations have been carried out to study isotope effects in lithium hydride and lithium deuteride crystals. Quantum effects on nuclear motion have been included through a quantum thermal bath (QTB). The interatomic forces were described either within the density functional theory (DFT) in the generalized gradient approximation (GGA) or by the phenomenological approach using the shell model. For both models, the isotopic shift in the lattice parameter can be successfully predicted by QTB-MD simulations. The slope of the experimental isotopic shift in pressure is satisfactorily reproduced by QTB-MD within DFT-GGA, in contrast to both density functional perturbation theory and QTB-MD with the shell model. We have analyzed the reasons for these discrepancies through the vibrational densities of states and the isotopic shifts in bulk modulus. The results illustrate the importance of anharmonic contributions to vibrations and to the isotopic pressure shift between LiH and LiD.

  20. Laser-enhanced dynamics in molecular rate processes

    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.

    1978-01-01

    The present discussion deals with some theoretical aspects associated with the description of molecular rate processes in the presence of intense laser radiation, where the radiation actually interacts with the molecular dynamics. Whereas for weak and even moderately intense radiation, the absorption and stimulated emission of photons by a molecular system can be described by perturbative methods, for intense radiation, perturbation theory is usually not adequate. Limiting the analysis to the gas phase, an attempt is made to describe nonperturbative approaches applicable to the description of such processes (in the presence of intense laser radiation) as electronic energy transfer in molecular (in particular atom-atom) collisions; collision-induced ionization and emission; and unimolecular dissociation.

  1. 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.

  2. Upgrade of the resonance ionization laser ion source at ISOLDE on-line isotope separation facility: new lasers and new ion beams.

    PubMed

    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. PMID:22380244

  3. Advances in laser ablation MC-ICPMS isotopic analysis of rock materials

    NASA Astrophysics Data System (ADS)

    Young, E. D.

    2007-12-01

    Laser ablation multiple-collector inductively coupled plasma-source mass spectrometry (LA-MC-ICPMS) is a rapid method for obtaining high-precision isotope ratio measurements in geological samples. The method has been used with success for measuring isotope ratios of numerous elements, including Pb, Hf, Mg, Si, and Fe in terrestrial and extraterrestrial samples. It fills the gap between the highest precision obtainable with acid digestion together with MC-ICPMS and thermal ionization mass spectrometry (TIMS) and the maximum spatial resolution afforded by secondary ion mass spectrometry (SIMS). Matrix effects have been shown to be negligible for Pb isotopic analysis by LA-MC-ICPMS (Simon et al., 2007). Glass standards NBS 610, 612, and 614 have Pb/matrix ratios spanning two orders of magnitude. Our sample-standard bracketing laser ablation technique gives accurate and precise 208Pb/206Pb and 207Pb/206Pb for these glasses. The accuracy is superior to that obtained when using Tl to correct for mass fractionation. Accuracy and precision (± 0.2 ‰) for Pb in feldspars is comparable to that for double-spike TIMS. Data like these have been used to distinguish distinct sources of magmas in the Long Valley silicic magma system. LA-MC-ICPMS analyses of Mg isotope ratios in calcium-aluminum-rich inclusions (CAIs) from carbonaceous chondrite meteorites have revealed a wealth of new information about the history of these objects. A byproduct of this work has been recognition of the importance of different mass fractionation laws among three isotopes of a given element. Kinetic and equilibrium processes define distinct fractionation laws. Reservoir effects can further modify these laws. The result is that the linear coefficient β that relates the logarithms of the ratios n2/n1 and n3/n1 (ni refers to the number of atoms of isotope i) of isotopes with masses m3 > m2 > m1 is not unique. Rather, it is process dependent. In the case of Mg, this coefficient ranges from 0.521 for

  4. Quantum Localization in Laser-Driven Molecular Rotation

    NASA Astrophysics Data System (ADS)

    Averbukh, Ilya

    2016-05-01

    Recently we predicted that several celebrated solid state quantum localization phenomena - Anderson localization, Bloch oscillations, and Tamm-Shockley surface states - may manifest themselves in the rotational dynamics of laser-kicked molecules. In this talk, I will present these new rotational effects in a gas of linear molecules subject to a moderately long periodic train of femtosecond laser pulses. A small detuning of the train period from the rotational revival time causes Anderson localization in the angular momentum space above some critical value of J - the Anderson wall. This wall marks an impenetrable border stopping any further rotational excitation. Below the Anderson wall, the rotational excitation oscillates with the number of pulses due to a mechanism similar to Bloch oscillations in crystalline solids. I will present the results of the first experimental observation of the laser-induced rotational Bloch oscillations in molecular nitrogen at ambient conditions (Stanford & Weizmann, 2015). We will also discuss the prospects of observing the rotational analogues of the Tamm surface states in a similar experimental setup. Our results offer laser-driven molecular rotation as a new platform for studies on the localization phenomena in quantum transport. These effects are important for many processes involving highly excited rotational states, including coherent optical manipulations in molecular mixtures, and propagation of powerful laser pulses in atmosphere.

  5. A Widely Tunable Infrared Laser Spectrometer for Measurements of Isotopic Ratios of Carbon Cycle Gases

    SciTech Connect

    Joanne H. Shorter; J. Barry McManus; David D. Nelson; Charles E. Kolb; Mark S. Zahniser; Ray Bambha; Uwe Lehmann; Tomas Kulp; Stanley C. Tyler

    2005-01-31

    The atmospheric abundances of carbon dioxide and methane have increased dramatically during the industrial era. Measurements of the isotopic composition of these gases can provide a powerful tool for quantifying their sources and sinks. This report describes the development of a portable instrument for isotopic analysis CO{sub 2} and CH{sub 4} using tunable infrared laser absorption spectroscopy. This instrument combines novel optical design and signal processing methods with a widely tunable mid-infrared laser source based on difference frequency generation (DFG) which will can access spectral regions for all the isotopes of CO{sub 2} and CH{sub 4} with a single instrument. The instrument design compensates for the large difference in concentration between major and minor isotopes by measuring them with path lengths which differ by a factor of 100 within the same multipass cell. During Phase I we demonstrated the basic optical design and signal processing by determining {sup 13}CO{sub 2} isotopic ratios with precisions as small as 0.2{per_thousand} using a conventional lead salt diode laser. During Phase II, the DFG laser source was coupled with the optical instrument and was demonstrated to detect {sup 13}CH{sub 4}/{sup 12}CH{sub 4} ratios with a precision of 0.5{per_thousand} and an averaging time of 20 s using concentrated methane in air with a mixing ratio of 2700 ppm. Methods for concentrating ambient air for isotopic analysis using this technique have been evaluated. Extensions of this instrument to other species such as {sup 13}CO{sub 2}, C{sup 18}OO, and CH{sub 3}D are possible by substituting lasers at other wavelengths in the DFG source module. The immediate commercial application of this instrument will be to compete with existing mass spectrometric isotope instruments which are expensive, large and relatively slow. The novel infrared source developed in this project can be applied to the measurement of many other gas species and will have wide

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

    NASA Astrophysics Data System (ADS)

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

    1995-04-01

    We have observed isotopically selective diode laser-excited optogalvanic effects in uranium at 778.42 and 776.10 nm. The samples were natural abundance uranium oxide, as well as depleted (0.3% 235U), natural (0.7% 235U) and enriched (9.75% 235U) 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.

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

    NASA Astrophysics Data System (ADS)

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

    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% U-235), natural (0.7% U-235) and enriched (9.75% U-235) 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.

  8. 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.

  9. 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.

  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. Control of molecular handedness using pump-dump laser pulses

    NASA Astrophysics Data System (ADS)

    Hoki, Kunihito; González, Leticia; Fujimura, Yuichi

    2002-02-01

    A theoretical method for controlling handedness of preoriented enantiomers starting from an equal mixture of right(R)-handed and left(L)-handed molecules using linearly polarized femtosecond laser pulses is presented. The essence of the method lies in the fact that the molecular handedness of oriented enantiomers is reflected in the direction of the electronic transition moment vector. A pump-dump control scheme via an electronic excited state is considered for controlling molecular handedness in a femtosecond time scale. The direction of the polarization vector of the pump pulse and that of the dump pulse are determined in such a way that there is the largest interaction between the laser and the L-(R-) handed molecules, while the interaction with R-(L-) handed ones vanishes. In the case in which both the pump and dump pulses are independent of each other with no overlap between them, an analytical expression for the yield of molecular handedness is derived by solving the equation of motion of the density matrix. This expression shows that both the pump and dump lasers with π-pulse area produce the maximum transfer yield of molecular handedness. The effectiveness of the laser control method is demonstrated by numerical simulation of dynamic chirality of pre-oriented H2POSH in a racemic mixture via the first electronic singlet excited state.

  12. 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

  13. Scanning Laser Infrared Molecular Spectrometer (SLIMS)

    NASA Technical Reports Server (NTRS)

    Scott, David C.; Rickey, Kelly; Ksendzov, Alexander; George, Warren P.; Aljabri, Abdullah S.; Steinkraus, Joel M.

    2012-01-01

    This prototype innovation is a novel design that achieves very long, effective laser path lengths that are able to yield ppb (parts per billion) and sub-ppb measurements of trace gases. SLIMS can also accommodate multiple laser channels covering a wide range of wavelengths, resulting in detection of more chemicals of interest. The mechanical design of the mirror cell allows for the large effective path length within a small footprint. The same design provides a robust structure that lends itself to being immune to some of the alignment challenges that similar cells face. By taking a hollow cylinder and by cutting an elliptically or spherically curved surface into its inner wall, the basic geometry of a reflecting ring is created. If the curved, inner surface is diamond-turned and highly polished, a surface that is very highly reflective can be formed. The surface finish can be further improved by adding a thin chrome or gold film over the surface. This creates a high-quality, curved, mirrored surface. A laser beam, which can be injected from a small bore hole in the wall of the cylinder, will be able to make many low-loss bounces around the ring, creating a large optical path length. The reflecting ring operates on the same principle as the Herriott cell. The difference exists in the mirror that doesn't have to be optically aligned, and which has a relatively large, internal surface area that lends itself to either open air or evacuated spectroscopic measurements. This solid, spherical ring mirror removes the possibility of mirror misalignment caused by thermal expansion or vibrations, because there is only a single, solid reflecting surface. Benefits of the reflecting ring come into play when size constraints reduce the size of the system, especially for space missions in which mass is at a premium.

  14. 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.

  15. Theoretical and experimental studies of optically pumped molecular gas lasers

    NASA Astrophysics Data System (ADS)

    Ratanavis, Amarin

    Optically pumped molecular gas lasers based on vibrational-rotational transitions in the infrared spectral region were studied experimentally and theoretically. A model was developed to predict the performance of such lasers and explore their potentials for energy and power scaling. This rate equation model was applied to explore the performance of a second-overtone (pulsed) and a first-overtone (CW) pumped HBr laser. Experimental improvements concerning temperature spectral tuning and frequency stabilization of a Nd:YAG laser that pumped HBr were accomplished. Lasing at 4 microns was demonstrated from such a system. We identified acetylene and hydrogen cyanide as potential laser gases that can be pumped with lasers emitting in the attractive telecommunication C band region at about 1.5 microns. Estimations and fluorescence measurements suggest the possibility of lasing in the 3 micron region. Lasing was demonstrated for the first time with a 5 ns pump pulse from an optical parametric oscillator using traditional cavities. The first gas filled hollow fiber laser based on population inversion was demonstrated with C2H2 and emission in the 3 micron region was observed. An analytical model indicates the possibility of CW lasing with small Stokes shift in both C2H 2 and HCN.

  16. 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.

  17. 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

  18. 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.

  19. [Laser microdissection in the molecular oncology of prostate cancer].

    PubMed

    Wernert, N

    2004-06-01

    Nearly all diseases, including prostate cancer (PCA), occur in mixed tissues with different cell types interconnected by multiple interactions. Laser microdissection permits a separate analysis of specific cell types necessary to understand tumorigenesis. Microdissection can be combined with different molecular methods for analyses at the levels of the genome, the transcriptome or the proteome. With respect to the molecular pathogenesis of PCA, normal glands can be compared to preneoplasias, and these in turn to the carcinoma. Different malignancy grades, as well as intra- and extraprostatic tumor parts, can be specifically analysed and molecular markers of aggressiveness can be identified. The molecular signatures obtained provide the basis for functional studies. New prognostic markers and therapeutic targets can be expected from such approaches in the near future. A far reaching goal is the computer representation of multiple molecular components and their interactions, "E-cell in cyberspace", in which prognostic behaviour and therapeutic responsiveness can be approximately predicted. PMID:15098090

  20. Reducing magnetic zero drift by optimizing proportions of neon dual isotopes in laser gyros

    NASA Astrophysics Data System (ADS)

    Di, Nan; Zhao, Jian-lin

    2012-03-01

    The relationships among the proportions of the neon dual isotopes ratio, scale factor corrections (SFCs), light intensities, environmental magnetic field and magnetic zero drift are discussed in detail by numerical simulations. The results show that the unification of the optimal operating point (OP) and the frequency stabilization operating point (FSP) is achievable by adjusting the proportions of neon dual isotopes accurately and tuning the cavity length with frequency stabilization system exactly. In that case, the left-rotation and right-rotation gyros can obtain the same SFC, which can decrease the magnetic sensitivity of the laser gyro efficiently. The Zeeman effect zero drift and the Faraday bias zero drift are both reduced by two orders of magnitude, while the magnetic shielding requirement of laser tube is decreased by 1-2 orders of magnitude.

  1. Application of atomic vapor laser isotope separation to the enrichment of mercury

    SciTech Connect

    Crane, J.K.; Erbert, G.V.; Paisner, J.A.; Chen, H.L.; Chiba, Z.; Beeler, R.G.; Combs, R.; Mostek, S.D.

    1986-09-01

    Workers at GTE/Sylvania have shown that the efficiency of fluorescent lighting may be markedly improved using mercury that has been enriched in the /sup 196/Hg isotope. A 5% improvement in the efficiency of fluorescent lighting in the United States could provide a savings of approx. 1 billion dollars in the corresponding reduction of electrical power consumption. We will discuss the results of recent work done at our laboratory to develop a process for enriching mercury. The discussion will center around the results of spectroscopic measurements of excited state lifetimes, photoionization cross sections and isotope shifts. In addition, we will discuss the mercury separator and supporting laser mesurements of the flow properties of mercury vapor. We will describe the laser system which will provide the photoionization and finally discuss the economic details of producing enriched mercury at a cost that would be attractive to the lighting industry.

  2. Application of an orthogonally polarized laser scheme for selective photoionization of palladium isotopes

    NASA Astrophysics Data System (ADS)

    Locke, Clayton R.; Kobayashi, Tohru; Nakajima, Takashi; Midorikawa, Katsumi

    2016-09-01

    We present a technique using two orthogonal linearly polarized lasers to improve practical implementation of the separation of odd- and even-mass-number palladium isotopes. Dye lasers are used for a three-step photoionization of vaporized palladium, where due to the transition selection rules only odd-mass-number isotopes are ionized and removed from the palladium beam via an electric field. Schemes presented in the literature use two counter-propagating circularly polarized beams, which are in practice difficult to implement perfectly. In contrast, two counter-propagating orthogonally polarized beams are technically less demanding to implement, yet the scheme retains the same high selectivity demonstrated in this work of >1200 (or 99.7 ± 0.3 %).

  3. 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.

  4. 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. PMID:14611049

  5. 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

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

    NASA Astrophysics Data System (ADS)

    Thiel, Volker; Peckmann, Jörn; Seifert, Richard; Wehrung, Patrick; Reitner, Joachim; Michaelis, Walter

    1999-12-01

    We 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 20 isoprenoid 2,6,11,15-tetramethylhexadecane (crocetane), a C 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 13C-depleted isotope compositions (δ 13C ≈ -108 to -115.6‰ PDB) suggest that the respective archaea have directly or indirectly introduced isotopically depleted, methane-derived carbon into their biomass. We postulate that a second major cluster of biomarkers showing heavier isotope values (δ 13C ≈ -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 2 and H 2; and (2) SRB that consume the resulting H 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 "authigenic" carbonates.

  7. Laser-field-free three-dimensional molecular orientation

    NASA Astrophysics Data System (ADS)

    Takei, Daisuke; Mun, Je Hoi; Minemoto, Shinichirou; Sakai, Hirofumi

    2016-07-01

    Laser-field-free three-dimensional orientation, corresponding to the complete control of spatial directions of asymmetric top molecules, is achieved with combined weak electrostatic and elliptically polarized laser fields with an 8-ns turnon and a 150-fs turnoff, which is shaped by a plasma shutter. Rotationally cold 3,4-dibromothiophene molecules are used as a sample, and their lower-lying rotational states are selected by a molecular deflector to increase the degrees of orientation. After the rapid turnoff of the pump pulse, higher degrees of orientation are maintained for 5-10 ps, which is long enough for various applications including electronic stereodynamics in molecules with femtosecond pulses.

  8. 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.

  9. 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.

  10. Innovative lasers for uranium isotope separation. Final report, September 1, 1989--April 1, 1993

    SciTech Connect

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

    1993-07-01

    Copper vapor laser have important applications to uranium atomic vapor laser isotope separation (AVLIS). We have investigated two innovative methods of exciting/pumping copper vapor lasers which have the potential to improve the efficiency and scaling of large laser systems used in uranium isotope separation. Experimental research has focused on the laser discharge kinetics of (1) microwave, and (2) electron beam excitation/pumping of large-volume copper vapor lasers. Microwave resonant cavity produced copper vapor plasmas at 2.45 GHz, have been investigated in three separate experimental configurations. The first examined the application of CW (0-500W) power and was found to be an excellent method for producing an atomic copper vapor from copper chloride. The second used a pulsed (5kW, 0.5--5 kHz) signal superimposed on the CW signal to attempt to produce vaporization, dissociation and excitation to the laser states. Enhanced emission of the optical radiation was observed but power densities were found to be too low to achieve lasing. In a third experiment we attempted to increase the applied power by using a high power magnetron to produce 100 kW of pulsed power. Unfortunately, difficulties with the magnetron power supply were encountered leaving inconclusive results. Detailed modeling of the electromagnetics of the system were found to match the diagnostics results well. An electron beam pumped copper vapor system (350 kV, 1.0 kA, 300 ns) was investigated in three separate copper chloride heating systems, external chamber, externally heated chamber and an internally heated chamber. Since atomic copper spectral lines were not observed, it is assumed that a single pulse accelerator is not capable of both dissociating the copper chloride and exciting atomic copper and a repetitively pulsed electron beam generator is needed.

  11. Laser pulse induced multiple exciton kinetics in molecular ring structures

    NASA Astrophysics Data System (ADS)

    Hou, Xiao; Wang, Luxia

    2016-11-01

    Multiple excitons can be formed upon strong optical excitation of molecular aggregates and complexes. Based on a theoretical approach on exciton-exciton annihilation dynamics in supramolecular systems (May et al., 2014), exciton interaction kinetics in ring aggregates of two-level molecules are investigated. Excited by the sub-picosecond laser pulse, multiple excitons keep stable in the molecular ring shaped as a regular polygon. If the symmetry is destroyed by changing the dipole of a single molecule, the excitation of different molecules becomes not identical, and the changed dipole-dipole interaction initiates subsequent energy redistribution. Depending on the molecular distance and the dipole configuration, the kinetics undergo different types of processes, but all get stable within some hundreds of femtoseconds. The study of exciton kinetics will be helpful for further investigations of the efficiency of optical devices based on molecular aggregates.

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

    PubMed

    Schoell, M; Schouten, S; Damsté, J S; de Leeuw, J W; Summons, R E

    1994-02-25

    The difference in carbon-13 ((13)C) contents of hopane and sterane biomarkers in the Monterey formation (Naples Beach, California) parallels the Miocene inorganic record of the change in (18)O (delta(18)O), reflecting the Miocene evolution from a well-mixed to a highly stratified photic zone (upper 100 meters) in the Pacific. Steranes (delta(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(35) hopanes (likely derived from bacterial plankton living at the base of the photic zone) have systematically decreasing (13)C concentrations in Middle and Late Miocene samples (delta(13)C = -29.5 to -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.

  13. 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.

  14. Femtosecond laser pulse induced desorption: A molecular dynamics simulation

    NASA Astrophysics Data System (ADS)

    Lončarić, Ivor; Alducin, Maite; Saalfrank, Peter; Juaristi, J. Iñaki

    2016-09-01

    In recent simulations of femtosecond laser induced desorption of molecular oxygen from the Ag(110) surface, it has been shown that depending on the properties (depth and electronic environment) of the well in which O2 is adsorbed, the desorption can be either induced dominantly by hot electrons or via excitations of phonons. In this work we explore whether the ratios between the desorption yields from different adsorption wells can be tuned by changing initial surface temperature and laser pulse properties. We show that the initial surface temperature is an important parameter, and that by using low initial surface temperatures the electronically mediated process can be favored. In contrast, laser properties seem to have only a modest influence on the results.

  15. 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.

  16. Low-threshold terahertz molecular laser optically pumped by a quantum cascade laser

    NASA Astrophysics Data System (ADS)

    Pagies, A.; Ducournau, G.; Lampin, J.-F.

    2016-06-01

    We demonstrate a low-threshold, compact, room temperature, and continuous-wave terahertz molecular laser optically pumped by a mid-infrared quantum cascade laser. These characteristics are obtained, thanks to large dipole transitions of the active medium: NH3 (ammonia) in gas state. The low-power (<60 mW) laser pumping excites the molecules, thanks to intense mid-infrared transitions around 10.3 μm. The molecules de-excite by stimulated emission on pure inversion "umbrella-mode" quantum transitions allowed by the tunnel effect. The tunability of the quantum cascade laser gives access to several pure inversion transitions with different rotation states: we demonstrate the continuous-wave generation of ten laser lines around 1 THz. At 1.07 THz, we measure a power of 34 μW with a very low-threshold of 2 mW and a high differential efficiency of 0.82 mW/W. The spectrum was measured showing that the linewidth is lower than 1 MHz. To our knowledge, this is the first THz molecular laser pumped by a solid-state source and this result opens the way for compact, simple, and efficient THz source at room temperature for imaging applications.

  17. 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.

  18. The laser ion source trap for highest isobaric selectivity in online exotic isotope productiona)

    NASA Astrophysics Data System (ADS)

    Schwellnus, F.; Blaum, K.; Catherall, R.; Crepieux, B.; Fedosseev, V.; Gottwald, T.; Kluge, H.-J.; Marsh, B.; Mattolat, C.; Rothe, S.; Stora, T.; Wendt, K.

    2010-02-01

    The improvement in the performance of a conventional laser ion source in the laser ion source and trap (LIST) project is presented, which envisages installation of a repeller electrode and a linear Paul trap/ion guide structure. This approach promises highest isobaric purity and optimum temporal and spatial control of the radioactive ion beam produced at an online isotope separator facility. The functionality of the LIST was explored at the offline test separators of University of Mainz (UMz) and ISOLDE/CERN, using the UMz solid state laser system. Ionization efficiency and selectivity as well as time structure and transversal emittance of the produced ion beam was determined. Next step after complete characterization is the construction and installation of the radiation-hard final trap structure and its first online application.

  19. The laser ion source trap for highest isobaric selectivity in online exotic isotope production.

    PubMed

    Schwellnus, F; Blaum, K; Catherall, R; Crepieux, B; Fedosseev, V; Gottwald, T; Kluge, H-J; Marsh, B; Mattolat, C; Rothe, S; Stora, T; Wendt, K

    2010-02-01

    The improvement in the performance of a conventional laser ion source in the laser ion source and trap (LIST) project is presented, which envisages installation of a repeller electrode and a linear Paul trap/ion guide structure. This approach promises highest isobaric purity and optimum temporal and spatial control of the radioactive ion beam produced at an online isotope separator facility. The functionality of the LIST was explored at the offline test separators of University of Mainz (UMz) and ISOLDE/CERN, using the UMz solid state laser system. Ionization efficiency and selectivity as well as time structure and transversal emittance of the produced ion beam was determined. Next step after complete characterization is the construction and installation of the radiation-hard final trap structure and its first online application. PMID:20192370

  20. Source identification of Malaysian atmospheric polycyclic aromatic hydrocarbons nearby forest fires using molecular and isotopic compositions

    NASA Astrophysics Data System (ADS)

    Okuda, Tomoaki; Kumata, Hidetoshi; Zakaria, Mohamad Pauzi; Naraoka, Hiroshi; Ishiwatari, Ryoshi; Takada, Hideshige

    We report measurements of molecular and carbon isotopic compositions of Malaysian atmospheric polycyclic aromatic hydrocarbons (PAHs) in smoke haze from the 1997 Indonesian forest fire. Comparison of the carbon isotopic compositions ( δ13C) of individual PAHs from the smoke haze, with those from other PAHs sources (soot collected from gasoline and diesel vehicle muffler, woodburning smoke), enables us to discriminate among the diverse sources of atmospheric PAHs. Soot PAHs extracted from gasoline and diesel vehicles show heavy isotopic signatures with a large inter-species δ13C variation from -12.9‰ to -26.6‰, compared to soot PAHs extracted from woodburning smoke which are isotopically light, and have a small inter-species δ13C variation from -26.8‰ to -31.6‰. Values from -17.7‰ to -27.9‰ were obtained for the corresponding PAHs extracted from the smoke haze, indicating that they are derived mainly from automotive exhaust. Molecular and isotopic compositions of PAHs extracted from smoke haze were similar to those extracted from non-haze aerosol. Quantitative estimation shows that woodburning contribution to Malaysian atmospheric PAHs ranges from 25% to 35% with no relation to haze intensity, while automotive contribution ranges from 65% to 75%. These results suggest that the major contributor of PAHs in Malaysian air is automotive exhaust whether smoke haze is observed or not.

  1. The effect of warming on grassland evapotranspiration partition using laser-based isotope monitoring techniques

    NASA Astrophysics Data System (ADS)

    Wang, L.; Niu, S.; Zhou, X.; Xia, J.; Luo, Y.; Good, S. P.; Caylor, K. K.; McCabe, M. F.

    2011-12-01

    The proportion of transpiration (T) in total evapotranspiration (ET) is an important index indicating the degree of biological influence on hydrological cycles. How climatic warming affects the T/ET ratio is not readily seen in the literature. In this study, we aim to quantify and compare T/ET ratios under ambient and warming treatments in grassland ecosystems, and test the applicability of coupled laser-based isotope analyzer and chamber methods for estimation of isotope end members (e.g., δT and δET). The experiment was conducted at a long-term grassland warming site in Oklahoma in May-June 2011. The δT, δET and δE (isotopic composition of evaporation) were quantified using mass balance method coupling laser-based isotope analyzer and various chambers (a modified Licor conifer leaf chamber for δT, a modified Licor soil chamber for δE and a customized chamber for δET). We note that the chamber method may not always be successful for δE estimate, however, due to small quantity of evaporation in many occasions, and the δE was also calculated using the Craig-Gordon model. The preliminary results showed an increase in T/ET ratio for the warming treatments than the control treatments. We found the ratio of T/ET in the control treatment is about 60% and the ratio found in the warming treatment is about 80%. The results indicate that δT and δET can be reliably estimated by the coupled the laser analyzer and appropriate chambers. The implications of the increased T/ET under the warming treatment are discussed.

  2. ARTICLES: Isotope separation by multiphoton dissociation of molecules using high-power CO2 laser radiation. Scaling of the process for carbon isotopes

    NASA Astrophysics Data System (ADS)

    Abdushelishvili, G. I.; Avatkov, O. N.; Bagratashvili, Viktor N.; Baranov, V. Yu; Bakhtadze, A. B.; Velikhov, E. P.; Vetsko, V. M.; Gverdtsiteli, I. G.; Dolzhikov, V. S.; Esadze, G. G.; Kazakov, S. A.; Kolomiĭskiĭ, Yu R.; Letokhov, V. S.; Pigul'skiĭ, S. V.; Pis'mennyĭ, V. D.; Ryabov, Evgenii A.; Tkeshelashvili, G. I.

    1982-04-01

    Data are presented on multiphoton dissociation of halogenated methanes, CF3I and CF3Br, in a pulsed CO2 laser field in the single-pulse irradiation regime. It is shown that the high parameters of an elementary separation event (dissociation yield and selectivity, quantum efficiency) for these molecules can be used to achieve efficient laser separation of the carbon isotopes 12C and 13C. An analysis is made of problems involved in organizing the chemical cycle when the process is scaled up. A description is given of an apparatus for scaled-up laser isotope separation, including a pulse-periodic CO2 laser with a kilowatt average power, and a laser separation cell. Experiments carried out using this apparatus showed that the high parameters obtained in the single-pulse regime can also be achieved using this design and a yield rate comparable with that of traditional separation systems can be achieved for fairly low energy losses. These results make it possible to develop a commercial system for laser isotope separation using multiphoton dissociation of molecules.

  3. 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

  4. 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.

  5. 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.

  6. 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.; 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 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

  7. Iron isotope composition of particles produced by UV-femtosecond laser ablation of natural oxides, sulfides, and carbonates.

    PubMed

    d'Abzac, Francois-Xavier; Beard, Brian L; Czaja, Andrew D; Konishi, Hiromi; Schauer, James J; Johnson, Clark M

    2013-12-17

    The need for femtosecond laser ablation (fs-LA) systems coupled to MC-ICP-MS to accurately perform in situ stable isotope analyses remains an open question, because of the lack of knowledge concerning ablation-related isotopic fractionation in this regime. We report the first iron isotope analysis of size-resolved, laser-induced particles of natural magnetite, siderite, pyrrhotite, and pyrite, collected through cascade impaction, followed by analysis by solution nebulization MC-ICP-MS, as well as imaging using electron microscopy. Iron mass distributions are independent of mineralogy, and particle morphology includes both spheres and agglomerates for all ablated phases. X-ray spectroscopy shows elemental fractionation in siderite (C-rich agglomerates) and pyrrhotite/pyrite (S-rich spheres). We find an increase in (56)Fe/(54)Fe ratios of +2‰, +1.2‰, and +0.8‰ with increasing particle size for magnetite, siderite, and pyrrhotite, respectively. Fe isotope differences in size-sorted aerosols from pyrite ablation are not analytically resolvable. Experimental data are discussed using models of particles generation by Hergenröder and elemental/isotopic fractionation by Richter. We interpret the isotopic fractionation to be related to the iron condensation time scale, dependent on its saturation in the gas phase, as a function of mineral composition. Despite the isotopic variations across aerosol size fractions, total aerosol composition, as calculated from mass balance, confirms that fs-LA produces a stoichiometric sampling in terms of isotopic composition. Specifically, both elemental and isotopic fractionation are produced by particle generation processes and not by femtosecond laser-matter interactions. These results provide critical insights into the analytical requirements for laser-ablation-based stable isotope measurements of high-precision and accuracy in geological samples, including the importance of quantitative aerosol transport to the ICP. PMID

  8. 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.

  9. Molecular cloud origin for the oxygen isotope heterogeneity in the solar system.

    PubMed

    Yurimoto, Hisayoshi; Kuramoto, Kiyoshi

    2004-09-17

    Meteorites and their components have anomalous oxygen isotopic compositions characterized by large variations in 18O/16O and 17O/16O ratios. On the basis of recent observations of star-forming regions and models of accreting protoplanetary disks, we suggest that these variations may originate in a parent molecular cloud by ultraviolet photodissociation processes. Materials with anomalous isotopic compositions were then transported into the solar nebula by icy dust grains during the collapse of the cloud. The icy dust grains drifted toward the Sun in the disk, and their subsequent evaporation resulted in the 17O- and 18O-enrichment of the inner disk gas. PMID:15375265

  10. Imaging of Isotopically Enhanced Molecular Targeting Agents Final Report

    SciTech Connect

    Quong, J N

    2004-02-19

    The goal of this project is to develop experimental and computational protocols to use SIMS to image the chemical composition of biological samples, focusing on optimizing sample preparation protocols and developing multivariate data analysis methods. Our results on sample preparation, molecular imaging, and multivariate analysis have been presented at several meeting abstracts (UCRL151797ABS, UCRL151797ABSREV1, UCRL151426ABS, UCRL201277, UCRL154757). A refereed paper describing our results for sample preparation and molecular imaging of various endogenous biomolecules as well as the mutagen PhIP has been accepted for publication (UCRL-JC-151797). We are also preparing two additional papers describing our multivariate analysis methods to analyze spectral data. As these papers have not been submitted, their content is included in this final report.

  11. 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

  12. 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.

  13. 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

  14. Laser isotope purification of lead for use in semiconductor chip interconnects

    SciTech Connect

    Scheibner, K.; Haynam, C.; Worden, E.; Esser, B.

    1996-03-19

    Lead, used throughout the electronics industries, typically contains small amounts of radioactive {sup 210}Pb (a daughter product of the planets ubiquitous {sup 238}U) whose {sup 210}Po daughter emits an {alpha}-particle that is known to cause soft errors in electronic circuits. The {sup 210}Pb is not separable by chemical means. This paper describes the generic Atomic Vapor Laser Isotope Separation (AVLIS) process developed at the Lawrence Livermore National Laboratory (LLNL) over the last 20 years, with particular emphasis on recent efforts to develop the process physics and component technologies required to remove the offending {sup 210}Pb using lasers. We have constructed a developmental facility that includes a process laser development area and a test bed for the vaporizer and ion and product collectors. We will be testing much of the equipment and demonstrating pilot scale AVLIS on a surrogate material later this year. Detection of the very low alpha emission even from commercially available low-alpha lead is challenging. LLNL`s detection capabilities will be described. The goal of the development of lead purification technology is to demonstrate the capability in FY97, and to deploy a production machine capable of up to several MT/y of isotopically purified material, possible beginning in FY98.

  15. Laser isotope purification of lead for use in semiconductor chip interconnects

    SciTech Connect

    Scheibner, K.; Haynam, C.; Worden, E.; Esser, B.

    1996-02-01

    Lead, used throughout the electronics industries, typically contains small amounts of radioactive {sup 210}Pb (a daughter product of the planet`s ubiquitous {sup 210}U) whose {sup 210}Po daughter emits and {alpha}-particle that is known to cause soft errors in electronic circuits. The {sup 210}Pb is not easily separable by chemical means. This paper describes the generic Atomic Vapor Laser Isotope Separation (AVLIS) process developed at the Lawrence Livermore National Laboratory (LLNL) over the last 20 years, with particular emphasis on recent efforts to develop the process physics and component technologies required to remove the offending {sup 210}Pb using lasers. We have constructed a developmental facility that includes a process laser development area and a test bed for the vaporizer and ion and product collectors. We will be testing much of the equipment and demonstrating pilot-scale AVLIS on a surrogate material later this year. Detection of the very low alpha emission even from commercially available low-alpha lead is challenging. LLNL`s detection capabilities will be described. The goal of the development of lead purification technology is to demonstrate the capability in FY97, and to begin filling orders of up to several MT/y of isotopically purified material in FY98.

  16. 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.

  17. 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

  18. 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.

  19. Tritium isotope separation by CO2-laser irradiation at low temperatures

    NASA Astrophysics Data System (ADS)

    Takeuchi, K.; Satooka, S.; Makide, Y.

    1984-02-01

    Tritium isotope separation by CO2-laser induced multiphoton dissociation of CTF3 is investigated. For the optimization of the performance of this working substance, trifluoromethane, the conditions to yield high-selectivity at high-operating pressure and low-critical fluence for complete dissociation are studied using our deconvolution procedure. The irradiation conditions are varied over the following ranges; wavenumber: 1052 1087 cm-1, gas temperature: 25°C to -78°C, CHF3 pressure: 5 205 Torr. The selectivities exceeding 104 are observed for 85 205 Torr CHF3 at -78°C by the irradiation at 1057 cm-1.

  20. 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.

  1. 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.

  2. 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.

  3. 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. PMID:25279538

  4. Peculiarities of exciton polariton dispersion for ternary molecular crystal with isotopic replacement defects.

    NASA Astrophysics Data System (ADS)

    Rumyantsev, Vladimir V.; Fedorov, Stanislav A.

    2002-03-01

    The peculiarities of exciton polariton spectrum caused of isotopic replacement defects in ternary molecular crystal have been studied. In the examined case configuration dependence of molecular currents, energies and intermolecular resonance interaction matrix W is weak as well as W-components are small. It enabled to describe main exciton spectrum peculiarities in approach similar to orientated gas model [1] and to obtain polariton dispersion low in analytical form. Three specific dispersion curves having two “the bottle throat” and reflecting isotopic replacement effect is added to the pair of typical polariton curves for perfect crystal. The values of “the bottle throats” of that curves has been evaluated. Non-collinearity of the molecule dipole moments in crystalline matrix and the moments of isotopic replacement admixture determine it. 1.Rumyantsev V.V., Fedorov S.A. Polariton propagation in mixed molecular crystals.Fizika i Tekhnika Vysokikh Davlenii. 2001, v.11, N.4 (special issue).-P.112-117.

  5. 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.

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

    PubMed

    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.

  7. Isotope separation of {sup 17}O by photodissociation of ozone with near-infrared laser irradiation

    SciTech Connect

    Hayashida, Shigeru; Kambe, Takashi; Sato, Tetsuya; Igarashi, Takehiro; Kuze, Hiroaki

    2012-04-01

    Oxygen-17 is a stable oxygen isotope useful for various diagnostics in both engineering and medical applications. Enrichment of {sup 17}O, however, has been very costly due to the lack of appropriate methods that enable efficient production of {sup 17}O on an industrial level. In this paper, we report the first {sup 17}O-selective photodissociation of ozone at a relatively high pressure, which has been achieved by irradiating a gas mixture of 10 vol% O{sub 3}-90 vol% CF{sub 4} with narrowband laser. The experiment was conducted on a pilot-plant scale. A total laser power of 1.6 W was generated by external-cavity diode lasers with all the laser wavelengths fixed at the peak of an absorption line of {sup 16}O{sup 16}O{sup 17}O around 1 {mu}m. The beams were introduced into a 25 -m long photoreaction cell under the sealed-off condition with a total pressure of 20 kPa. Lower cell temperature reduced the background decomposition of ozone, and at the temperature of 158 K, an {sup 17}O enrichment factor of 2.2 was attained.

  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. Multiphoton absorption and decomposition of fluoroform-d: Laser isotope separation of deuterium

    SciTech Connect

    Evans, D.K.; McAlpine, R.D.; Adams, H.M.

    1982-10-01

    Multiphoton absorption (MPA) studies of fluoroform-d, a molecule of interest for potential laser based hydrogen isotope separation processes, are reported for CDF/sub 3/ pressures 0.2--1.3 kPa, and for a variety of 10 ..mu..m CO/sub 2/ laser lines with pulse widths of 2 or 6 ns and fluences within the range 10/sup -3/--70 J/cm/sup 2/. Unlike SF/sub 6/, no red shift of the MPA spectrum relative to the small signal spectrum was observed at high fluence. Selective multiphoton decomposition (MPD) experiments using the 10R(26) line, 6 ns pulse to excite the CDF/sub 3/ component in natural-abundance CHF/sub 3/ (approx. 150 ppm D/H) at a pressure of 13.3 kPa resulted in the recovery of water enriched up to 30% in deuterium: a measured isotope enrichment of > or =2000 fold. This demonstrates that a product, highly enriched in deuterium, can be recovered from the selective MPD of fluoroform.

  11. 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.

  12. 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.

  13. The ejection of triatomic molecular hydrogen ions H3+ produced by the interaction of benzene molecules with ultrafast laser pulses

    NASA Astrophysics Data System (ADS)

    Kaziannis, S.; Liontos, I.; Karras, G.; Corsi, C.; Bellini, M.; Kosmidis, C.

    2009-10-01

    The ejection process of triatomic molecular hydrogen ions produced by the interaction of benzene with ultrafast laser pulses of moderate strong intensity (˜1014 W/cm2) is studied by means of TOF mass spectrometry. The H3+ formation can only take place through the rupture of two C-H bonds and the migration of hydrogen atoms within the molecular structure. The H3+ fragments are released with high kinetic energy (typically 2-8 eV) and at laser intensities ≥1014 W/cm2, well above that required for the double ionization of benzene, suggesting that its formation is taking place within multiply charged parent ions. The relative ejection efficiency of H3+ molecular hydrogen ions with respect to the atomic ones is found to be strongly decreasing as a function of the laser intensity and pulse duration (67-25 fs). It is concluded that the H3+ formation is only feasible within parent molecular precursors of relatively low charged states and before significant elongation of their structure takes place, while the higher multiply charged molecular ions preferentially dissociate into H+ ions. The ejection of H2+ ions is also discussed in comparison to the production of H3+ and H+ ions. Finally, by recording the mass spectra of two deuterium label isotopes of benzene (1,2-C6H4D2, 1,4-C6H4D2) it is verified that the ejection efficiency of some molecular fragments, such as D2H+, DH+, is dependent on the specific position of hydrogen atoms in the molecular skeleton prior dissociation.

  14. 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.

  15. Molecular laser stabilization at low frequencies for the LISA mission

    SciTech Connect

    Argence, B.; Halloin, H.; Jeannin, O.; Prat, P.; Turazza, O.; Vismes, E. de; Auger, G.; Plagnol, E.

    2010-04-15

    We have developed a 532 nm iodine stabilized laser system that may be suitable for the LISA mission (Laser Interferometer Space Antenna) or other future spaceborne missions. This system is based on an externally frequency-doubled Nd:YAG laser source and uses the molecular transfer spectroscopy technique for the frequency stabilization. This technique has been optimized for LISA: compactness (less than 1.1x1.1 m{sup 2}), vacuum compatibility, ease of use and initialization, minimization of the number of active components (acousto-optic modulators are both used for frequency shifting and phase modulating the pump beam). By locking on the a{sub 10} hyperfine component of the R(56)32-0 transition, we find an Allan standard deviation ({sigma}) of 3x10{sup -14} at 1 s and {sigma}<2x10{sup -14} for 20 s{<=}{tau}{<=}10{sup 3} s. In terms of linear spectral density, this roughly corresponds to a stability better than 30 Hz/{radical}(Hz) between 10{sup -2} and 1 Hz with a stability decrease close to 1/f below 10 mHz.

  16. 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.

  17. Reply to comment on "Molecular controls on Cu and Zn isotopic fractionation in Fe-Mn crusts"

    NASA Astrophysics Data System (ADS)

    Sherman, David M.; Little, Susan H.; Vance, Derek

    2015-02-01

    In our paper "Molecular controls on Cu and Zn isotopic fractionation in Fe-Mn crusts", we present an explanation for the observed isotopic fractionations of Cu and Zn in seawater. We hypothesise that the isotopic fractionation of Cu and Zn is driven by the scavenging of these metals by particulate Fe-Mn oxides as reflected in the isotopic composition of Zn and Cu in marine ferromanganese crusts. Zn sorbed to ferromanganese crusts is isotopically heavier than dissolved Zn in seawater by 0.5‰. EXAFS spectra show that Zn in ferromanganese crusts is sorbed to birnessite and in tetrahedral coordination. Dissolved inorganic Zn in seawater, however, is primarily octahedrally coordinated as Zn(H2O)+26. The difference in the Zn coordination environment gives a qualitative explanation for the sorption (scavenging) of isotopically heavy Zn by ferromanganese crusts (predominantly birnessite).

  18. 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.

  19. Interpretation of intermolecular geometric isotope effect in hydrogen bonds: nuclear orbital plus molecular orbital study.

    PubMed

    Ikabata, Yasuhiro; Imamura, Yutaka; Nakai, Hiromi

    2011-03-01

    The intermolecular geometric isotope effect (GIE) in hydrogen bond A-X···B (X = H and D) is investigated theoretically using the nuclear orbital plus molecular orbital (NOMO) theory. To interpret the GIE in terms of physically meaningful energy components such as electrostatic and exchange-repulsion interactions, the reduced variational space self-consistent-field method is extended to the NOMO scheme. The intermolecular GIE is analyzed as a two-stage process: the intramolecular bond shrinkage and the intermolecular bond elongation. According to the isotopic shifts of energy components described by the NOMO/MP2 method, the intermolecular GIE is approximately interpreted as a process reducing the exchange-repulsion interaction after the decrease of electrostatic interaction. PMID:21306139

  20. 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.

  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. 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.

  3. 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.

  4. 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

  5. XUV spectroscopy of laser plasma from molecular coated metal targets

    NASA Astrophysics Data System (ADS)

    Papanyan, Valeri O.; Nersisyan, Gagik T.; Tittel, Frank K.

    1999-12-01

    Metal targets covered by micrometer layers of metal- phthalocyanines or fullerenes are studied here. An increase in XUV yield due to the optimized absorption of the laser field is reported. Effects of high-temperature plasma rapid expansion (velocity about 106 cm/s) were observed. Moderate power nanosecond and picosecond neodymium lasers are used to produce an incident intensity of 1011 to 1013 W/cm2 on the targets. The plasma electron density was measured by fitting observed spectral profiles to the theoretical profiles. Collisional, Doppler, and Stark broadening mechanisms were considered in the calculations. Our measurement technique permits us to determine the electron density and temperature dependence on distances from the target surface from 1 mm (where Ne approximately equals 1018 cm-3 and Te approximately equals 14 eV are measured for aluminum plasma) up to approximately 5 mm (where Ne molecular coated targets is greater by a factor of approximately 1.5 than measured from bulk solid metal targets.

  6. XUV spectroscopy of laser plasma from molecular coated metal targets

    NASA Astrophysics Data System (ADS)

    Papanyan, Valeri O.; Nersisyan, Gagik T.; Tittel, Frank K.

    1999-10-01

    Metal targets covered by micrometer layers of metal- phthalocyanines are studied here. An increase in EUV yield due to optimized absorption of the laser field is reported. Effects of high-temperature plasma rapid expansion (velocity about 106 cm/s) were observed. Moderate power nanosecond and picosecond neodymium lasers are used to product an incident intensity of 1011 to 1013 W/cm2 on the targets. The plasma electron density was measured by fitting observed spectral profiles to theoretical profiles. Collisional, Doppler, and Stark broadening mechanisms were considered in the calculations. Our measurement technique makes it possible to determine the electron density and temperature dependence on distances from the target surface from 1 mm (where Ne equals 2.0 (+/- 0.5)1018 cm-3 and Te equals 14 eV are measured for aluminum plasma) up to approximately 5 mm (where Ne molecular coated targets is greater by a factor of approximately 1.5 than measured from bulk solid metal targets.

  7. Laser cooling of {sup 173}Yb for isotope separation and precision hyperfine spectroscopy

    SciTech Connect

    Das, Dipankar; Natarajan, Vasant

    2007-12-15

    The hyperfine transitions in the 399 nm {sup 1}S{sub 0}{r_reversible}{sup 1}P{sub 1} line in {sup 173}Yb overlap with the transition in {sup 172}Yb. We use transverse laser cooling on this line to selectively deflect {sup 173}Yb atoms from a thermal beam containing both isotopes. We then use an acousto-optic modulator to span the frequency difference between the hyperfine transitions, and hence measure hyperfine structure in the {sup 1}P{sub 1} state. Our precise values for the hyperfine constants, A{sub 173}=57.693{+-}0.006 MHz and B{sub 173}=609.028{+-}0.056 MHz, improve previous values significantly.

  8. 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.

  9. Influence of production variables and starting material on charcoal stable isotopic and molecular characteristics

    NASA Astrophysics Data System (ADS)

    Ascough, P. L.; Bird, M. I.; Wormald, P.; Snape, C. E.; Apperley, D.

    2008-12-01

    We present a systematic study on the effect of starting species, gas composition, temperature, particle size and duration of heating upon the molecular and stable isotope composition of high density (mangrove) and low density (pine) wood. In both pine and mangrove, charcoal was depleted in δ 13C relative to the starting wood by up to 1.6‰ and 0.8‰, respectively. This is attributed predominantly to the progressive loss of isotopically heavier polysaccharides, and kinetic effects of aromatization during heating. However, the pattern of δ 13C change was dependant upon both starting species and atmosphere, with different structural changes associated with charcoal production from each wood type elucidated by Solid-State 13C Nuclear Magnetic Resonance Spectroscopy. These are particularly evident at lower temperatures, where variation in the oxygen content of the production atmosphere results in differences in the thermal degradation of cellulose and lignin. It is concluded that production of charcoal from separate species in identical conditions, or from a single sample exposed to different production variables, can result in significantly different δ 13C of the resulting material, relative to the initial wood. These results have implications for the use of charcoal isotope composition to infer past environmental change.

  10. Isotope selective analysis of CO(2) with tunable diode laser (TDL) spectroscopy in the NIR.

    PubMed

    Horner, Gerald; Lau, Steffen; Kantor, Zoltan; Lohmannsroben, Hans-Gerd

    2004-08-01

    The performance of a home-built tunable diode laser (TDL) spectrometer, aimed at multi-line detection of carbon dioxide, has been evaluated and optimized. In the regime of the (30(0)1)(III) <-- (000) band of (12)CO(2) around 1.6 microm, the dominating isotope species (12)CO(2), (13)CO(2), and (12)C(18)O(16)O were detected simultaneously without interference by water vapor. Detection limits in the range of few ppmv were obtained for each species utilizing wavelength modulation (WM) spectroscopy with balanced detection in a long-path absorption cell set-up. High sensitivity in conjunction with high precision -- typically +/-1 (per thousand) and +/-6 (per thousand) for 3% and 0.7% of CO(2), respectively -- renders this experimental approach a promising analytical concept for isotope-ratio determination of carbon dioxide in soil and breath gas. For a moderate (12)CO(2) line, the pressure dependence of the line profile was characterized in detail, to account for pressure effects on sensitive measurements.

  11. 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. PMID:21290447

  12. ATOMIC AND MOLECULAR PHYSICS: Isotopic effect of Cl2+ rovibronic spectra in the A-X system

    NASA Astrophysics Data System (ADS)

    Wu, Ling; Yang, Xiao-Hua; Chen, Yang-Qin

    2009-07-01

    This paper studies the isotopic effect of Cl2+ rovibronic spectra in the A2IIu (Ω = 1/2) - X2IIg (Ω = 1/2) system. Based on the experimental results of the molecular constants of 35Cl2+, it calculates the vibrational isotope shifts of the (2, 7) and (3, 7) band between the isotopic species 35Cl2+, 35Cl37Cl+ and 37Cl2+, and estimates the rotational constants of both A2IIu and X2IIg states for the minor isotopic species 35Cl37Cl+ and 37Cl2+. The experimental results of the spectrum of 35Cl37Cl+ (3, 7) band proves the above mentioned theoretical calculation. The molecular constants and thus resultant rovibronic spectrum for 37Cl2+ were predicted, which will be helpful for further experimental investigation.

  13. Calcium isotope fractionation in groundwater: Molecular scale processes influencing field scale behavior

    NASA Astrophysics Data System (ADS)

    Druhan, Jennifer L.; Steefel, Carl I.; Williams, Kenneth H.; DePaolo, Donald J.

    2013-10-01

    It is the purpose of this study to demonstrate that the molecular scale reaction mechanisms describing calcite precipitation and calcium isotope fractionations under highly controlled laboratory conditions also reproduce field scale measurements of δ44Ca in groundwater systems. We present data collected from an aquifer during active carbonate mineral precipitation and develop a reactive transport model capturing the observed chemical and isotopic variations. Carbonate mineral precipitation and associated fluid δ44Ca data were measured in multiple clogged well bores during organic carbon amended biogenic reduction of a uranium contaminated aquifer in western Colorado, USA. Secondary mineral formation induced by carbonate alkalinity generated during the biostimulation process lead to substantial permeability reduction in multiple electron-donor injection wells at the field site. These conditions resulted in removal of aqueous calcium from a background concentration of 6 mM to <1 mM while δ44Ca enrichment ranged from 1‰ to greater than 2.5‰. The relationship between aqueous calcium removal and isotopic enrichment did not conform to Rayleigh model behavior. Explicit treatment of the individual isotopes of calcium within the CrunchFlow reactive transport code demonstrates that the system did not achieve isotopic reequilibration over the time scale of sample collection. Measured fluid δ44Ca values are accurately reproduced by a linear rate law when the Ca2+:CO32- activity ratio remains substantially greater than unity. Variation in the measured δ44Ca between wells is shown to originate from a difference in carbonate alkalinity generated in each well bore. The influence of fluid Ca2+:CO32- ratio on the precipitation rate and δ44Ca is modeled by coupling the CrunchFlow reactive transport code to an ion by ion growth model. This study presents the first coupled ion-by-ion and reactive transport model for isotopic enrichment and demonstrates that reproducing field

  14. 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

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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

  1. 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.

  2. 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.

  3. 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.

  4. Isotope-specific detection of low-density materials with laser-based monoenergetic gamma-rays.

    PubMed

    Albert, F; Anderson, S G; Anderson, G A; Betts, S M; Gibson, D J; Hagmann, C A; Hall, J; Johnson, M S; Messerly, M J; Semenov, V A; Shverdin, M Y; Tremaine, A M; Hartemann, F V; Siders, C W; McNabb, D P; Barty, C P J

    2010-02-01

    What we believe to be the first demonstration of isotope-specific detection of a low-Z and low density object shielded by a high-Z and high-density material using monoenergetic gamma rays is reported. The isotope-specific detection of LiH shielded by Pb and Al is accomplished using the nuclear resonance fluorescence line of L7i at 478 keV. Resonant photons are produced via laser-based Compton scattering. The detection techniques are general, and the confidence level obtained is shown to be superior to that yielded by conventional x-ray and gamma-ray techniques in these situations.

  5. Isotope-specific detection of low-density materials with laser-based monoenergetic gamma-rays.

    PubMed

    Albert, F; Anderson, S G; Anderson, G A; Betts, S M; Gibson, D J; Hagmann, C A; Hall, J; Johnson, M S; Messerly, M J; Semenov, V A; Shverdin, M Y; Tremaine, A M; Hartemann, F V; Siders, C W; McNabb, D P; Barty, C P J

    2010-02-01

    What we believe to be the first demonstration of isotope-specific detection of a low-Z and low density object shielded by a high-Z and high-density material using monoenergetic gamma rays is reported. The isotope-specific detection of LiH shielded by Pb and Al is accomplished using the nuclear resonance fluorescence line of L7i at 478 keV. Resonant photons are produced via laser-based Compton scattering. The detection techniques are general, and the confidence level obtained is shown to be superior to that yielded by conventional x-ray and gamma-ray techniques in these situations. PMID:20125719

  6. Stable isotope studies

    SciTech Connect

    Ishida, T.

    1992-01-01

    The research has been in four general areas: (1) correlation of isotope effects with molecular forces and molecular structures, (2) correlation of zero-point energy and its isotope effects with molecular structure and molecular forces, (3) vapor pressure isotope effects, and (4) fractionation of stable isotopes. 73 refs, 38 figs, 29 tabs.

  7. Atomic and Molecular Isotope Ratios in Circumstellar Envelopes: Fractionation vs. Nucleosynthesis

    NASA Astrophysics Data System (ADS)

    Milam, Stefanie

    (e.g. oxygen-rich vs. carbon-rich). The isotope ratios of 12C/13C, 14N/15N, 16O/17O, and 16O/18O will be determined and compared to previous studies conducted on species now considered to be affected by chemistry in the circumstellar shell. These observations will provide constraints on the true internal processes that are occurring in evolved stars as well as photo-selective chemistry affecting molecular abundances in the envelopes. The data analysis program proposed here will provide a self-consistent study of the natal isotopic composition of circumstellar envelopes and test recent theories of circumstellar chemistry. This fundamental information on the isotopic composition of material ejected from evolved stars will help improve current models of Galactic chemical evolution and help constrain star formation rates and stellar ages. Isotopically enriched matter found in some primitive materials has been associated with dust derived from these objects, though there is a lack of data currently available to fully constrain the origins. This work will allow a detailed comparison of laboratory analyses of extraterrestrial materials with a comprehensive astronomical dataset, and strongly constrain theoretical models of circumstellar chemistry. Realization of our project goals will greatly enhance the scientific return from the Herschel Space Observatory, and provide powerful context and motivation for astronomical observations to be made by future missions such as JWST and SOFIA as well as future ground-based studies. This work is highly relevant to the Astrophysics Data Analysis Program by focusing on the analysis of archival data from NASA space astrophysics missions and will address questions difficult to answer in the individual observing programs.

  8. The stable isotopic signature of biologically produced molecular hydrogen (H2)

    NASA Astrophysics Data System (ADS)

    Walter, S.; Laukenmann, S.; Stams, A. J. M.; Vollmer, M. K.; Gleixner, G.; Röckmann, T.

    2011-12-01

    Biologically produced molecular hydrogen (H2) is characterized by a very strong depletion in deuterium. Although the biological source to the atmosphere is small compared to photochemical or combustion sources, it makes an important contribution to the global isotope budget of molecular hydrogen (H2). Large uncertainties exist in the quantification of the individual production and degradation processes that contribute to the atmospheric budget, and isotope measurements are a tool to distinguish the contributions from the different sources. Measurements of δD from the various H2 sources are scarce and for biologically produced H2 only very few measurements exist. Here the first systematic study of the isotopic composition of biologically produced H2 is presented. We investigated δD of H2 produced in a biogas plant, covering different treatments of biogas production, and from several H2 producing microorganisms such as bacteria or green algae. A Keeling plot analysis provides a robust overall source signature of δD = -712‰ (±13‰) for the samples from the biogas reactor (at 38 °C, δDH2O = 73.4‰), with a fractionation constant ϵH2-H2O of -689‰ (±20‰). The pure culture samples from different microorganisms give a mean source signature of δD = -728‰ (±39‰), and a fractionation constant ϵH2-H2O of -711‰ (±45‰) between H2 and the water, respectively. The results confirm the massive deuterium depletion of biologically produced H2 as was predicted by calculation of the thermodynamic fractionation factors for hydrogen exchange between H2 and water vapor. As expected for a thermodynamic equilibrium, the fractionation factor is largely independent of the substrates used and the H2 production conditions. The predicted equilibrium fractionation coefficient is positively correlated with temperature and we measured a change of 2.2‰/°C between 45 °C and 60 °C. This is in general agreement with the theoretical predictions. Our

  9. A method for in situ monitoring of the isotope composition of tree xylem water using laser spectroscopy.

    PubMed

    Volkmann, Till H M; Kühnhammer, Kathrin; Herbstritt, Barbara; Gessler, Arthur; Weiler, Markus

    2016-09-01

    Field studies analyzing the stable isotope composition of xylem water are providing important information on ecosystem water relations. However, the capacity of stable isotopes to characterize the functioning of plants in their environment has not been fully explored because of methodological constraints on the extent and resolution at which samples could be collected and analysed. Here, we introduce an in situ method offering the potential to continuously monitor the stable isotope composition of tree xylem water via its vapour phase using a commercial laser-based isotope analyser and compact microporous probes installed into the xylem. Our technique enables efficient high-frequency measurement with intervals of only a few minutes per sample while eliminating the need for costly and cumbersome destructive collection of plant material and laboratory-based processing. We present field observations of xylem water hydrogen and oxygen isotope compositions obtained over several days including a labelled irrigation event and compare them against results from concurrent destructive sampling with cryogenic distillation and mass spectrometric analysis. The data demonstrate that temporal changes as well as spatial patterns of integration in xylem water isotope composition can be resolved through direct measurement. The new technique can therefore present a valuable tool to study the hydraulic architecture and water utilization of trees.

  10. 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.

  11. A method for in situ monitoring of the isotope composition of tree xylem water using laser spectroscopy.

    PubMed

    Volkmann, Till H M; Kühnhammer, Kathrin; Herbstritt, Barbara; Gessler, Arthur; Weiler, Markus

    2016-09-01

    Field studies analyzing the stable isotope composition of xylem water are providing important information on ecosystem water relations. However, the capacity of stable isotopes to characterize the functioning of plants in their environment has not been fully explored because of methodological constraints on the extent and resolution at which samples could be collected and analysed. Here, we introduce an in situ method offering the potential to continuously monitor the stable isotope composition of tree xylem water via its vapour phase using a commercial laser-based isotope analyser and compact microporous probes installed into the xylem. Our technique enables efficient high-frequency measurement with intervals of only a few minutes per sample while eliminating the need for costly and cumbersome destructive collection of plant material and laboratory-based processing. We present field observations of xylem water hydrogen and oxygen isotope compositions obtained over several days including a labelled irrigation event and compare them against results from concurrent destructive sampling with cryogenic distillation and mass spectrometric analysis. The data demonstrate that temporal changes as well as spatial patterns of integration in xylem water isotope composition can be resolved through direct measurement. The new technique can therefore present a valuable tool to study the hydraulic architecture and water utilization of trees. PMID:27260852

  12. Control of Electron Excitation and Localization in the Dissociation of H{sub 2}{sup +} and Its Isotopes Using Two Sequential Ultrashort Laser Pulses

    SciTech Connect

    He Feng; Ruiz, Camilo; Becker, Andreas

    2007-08-24

    We study the control of dissociation of the hydrogen molecular ion and its isotopes exposed to two ultrashort laser pulses by solving the time-dependent Schroedinger equation. While the first ultraviolet pulse is used to excite the electron wave packet on the dissociative 2p{sigma}{sub u} state, a second time-delayed near-infrared pulse steers the electron between the nuclei. Our results show that by adjusting the time delay between the pulses and the carrier-envelope phase of the near-infrared pulse, a high degree of control over the electron localization on one of the dissociating nuclei can be achieved (in about 85% of all fragmentation events). The results demonstrate that current (sub-)femtosecond technology can provide a control over both electron excitation and localization in the fragmentation of molecules.

  13. Isotope ratio determination of uranium by optical emission spectroscopy on a laser-produced plasma - basic investigations and analytical results

    NASA Astrophysics Data System (ADS)

    Pietsch, W.; Petit, A.; Briand, A.

    1998-05-01

    We report in this paper, the first determination of the isotope ratio (238/235) in an uranium sample by optical emission spectroscopy on a laser-produced plasma at reduced pressure (2.67 Pa). Investigations aimed at developing a new application of laser ablation for analytical isotope control of uranium are presented. Optimized experimental conditions allow one to obtain atomic emission spectra characterized by the narrowest possible line widths of the order of 0.01 nm for the investigated transition UII 424.437 nm. We show the possibility to achieve a relative precision in the range of 5% for an enrichment of 3.5% 235U. The influence of different relevant plasma parameters on the measured line width is discussed.

  14. 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.

  15. RECONSTRUCTING LAURENTIDE ICE SHEET MELTWATER GEOCHEMISTRY USING COMBINED STABLE ISOTOPE AND LASER ABLATION TRACE ELEMENT ANALYSES

    NASA Astrophysics Data System (ADS)

    Vetter, L.; Spero, H. J.; Eggins, S. M.; Flower, B. P.; Williams, C. C.

    2009-12-01

    Little is known about the oxygen isotope evolution of Northern hemisphere ice sheets during past glacial cycles, with the exception of results from models and calculations based on whole ocean δ18O change. Reconstructing changes in the δ18Owater of the global ocean assumes a homogeneous δ18O value for contributions from Northern hemisphere ice sheets with a mass balance contribution from the Southern hemisphere. Because oceanic δ18Ow forms a crucial baseline for deconvolving the combined signal of temperature and hydrologic changes recorded in foraminiferal calcite, constraints on the contributions of melting ice sheets form a fundamental component of reconstructions of global ocean δ18Ow changes on glacial timescales. Here we present a novel geochemical technique to compute the oxygen isotopic composition of Laurentide Ice Sheet (LIS) meltwater flowing into the Gulf of Mexico during periods of rapid ice sheet melting. The technique combines data from different types of geochemical analyses on individual shells of the planktonic foraminifera Orbulina universa to compute meltwater geochemistry, using laser ablation ICP-MS to measure Mg/Ca (a temperature proxy) and Ba/Ca (a salinity proxy) and isotope ratio mass spectrometry to measure δ18O (a temperature and δ18Owater proxy) on remaining shell material. O. universa has a very large temperature and salinity tolerance (9-30°C; 23-45 psu) and broad depth habitat (0-80 m), so an assemblage of individual shells from a single core interval records a range of water conditions. We have selected deglacial meltwater intervals from core MD02-2550 (26.95°N, 91.35°W, 2245 m water depth), collected from the anoxic Orca Basin in the Gulf of Mexico, for a proof of concept demonstration. From each interval, we combine measurements of Mg/Ca, Ba/Ca, and δ18O on 30-100 individual O. universa. The δ18O from each shell reflects the combined influence of temperature and δ18Owater, where this latter value is a function of

  16. 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.

  17. Engineering Studies of a Pilot Plant for Laser Isotope Separation of CARBON-13 by Multiphoton Dissociation of Chlorodifluoromethane

    NASA Astrophysics Data System (ADS)

    Mehmetli, Bulent Ahmet

    Recent research in laser isotope separation by multiphoton dissociation (LISMPD) of ^{13 }C suggests that an LISMPD commercial process is more economical than the cryogenic CO distillation technology currently used to meet most of the world's ^ {13}C demand. In this dissertation, experimental studies of an engineering process for LISMPD of polyatomic molecules is examined. The experimental results have been obtained by MPD of chlorodifluoromethane (CF_2 HCl) to yield ^{13}C -enriched tetrafluoroethylene rm(C_2F _4). Emphasis is on research leading to the development of a practical chemical plant for the preparation of stable isotopes by this method. The experimental program has achieved the design, construction, and operation of a laboratory-scale ^{13}C separation apparatus and parametric dependences of enrichment factors and dissociated fractions. In this experiment, the reactant gas, industrial grade CF_2HCl, flows continuously along the axis of a stainless steel reaction cell. The beam of a commercial CO_2 TEA laser, delivering up to 3 J/pulse at a single wavelength, is focused into the cell to induce isotope-selective multiphoton dissociation. The ^{13}C-enriched reaction product, rm C_2F_4, is analyzed by mass spectroscopy for its isotopic content. Typical production rates of the setup are about 10 g/year ^{13}C at an enrichment of 15% or 1 g/year at an enrichment of 65%. The results of a detailed cost analysis, which takes into account different reaction conditions and laser types, showed that at production rates of 7,000 kg per year, the cost of ^{13}C can be as low as 4/g. This figure is about an order of magnitude less than the cost of ^13 C obtained by cryogenic distillation of CO. The design, construction, and operation of a CO _2 MOPA (Master Oscillator/ Power Amplifier) laser is proposed because a MOPA combines the advantages of favorable isotope separation reaction conditions of TEA lasers and the cheaper photons of cw discharges. Analytical

  18. 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.

  19. 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

  20. 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.

  1. Defects in tungsten responsible for molecular hydrogen isotope retention after exposure to low energy plasmas

    NASA Astrophysics Data System (ADS)

    Causey, R. A.; Doerner, R.; Fraser, H.; Kolasinski, R. D.; Smugeresky, J.; Umstadter, K.; Williams, R.

    2009-06-01

    Recent work on hydrogen isotope retention in tungsten has shown a substantial fraction of the retained hydrogen to be in the form of molecules. It can be expected that hydrogen permeating through a material such as tungsten, that has a very low solubility for hydrogen, would come out of solution and combine into molecules at voids located throughout the bulk. The purpose of this report is to determine the type of voids responsible for the molecular retention. High purity tungsten provided by Plansee Aktiengesellschaft was first polished, annealed at 1273 K in vacuum for one hour, and then exposed to high fluxes and high fluences of deuterium in the PISCES facility. High resolution Transmission Electron Microscopy was then used to examine the samples for voids. The results of these experiments were used to interpret the expected behavior of tungsten to be used as the divertor of the ITER fusion device.

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

    DOE PAGES

    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,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

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

    SciTech Connect

    Yu, Chao; Wei, Hui; Wang, Xu; Le, Anh -Thu; Lu, Ruifeng; Lin, C. D.

    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.

  4. 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

  5. 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

  6. Interaction of toluene with two-color asymmetric laser fields: Controlling the directional emission of molecular hydrogen fragments

    SciTech Connect

    Kaziannis, S.; Kotsina, N.; Kosmidis, C.

    2014-09-14

    The interaction of toluene with strong asymmetric two-color laser irradiation of 40 fs duration is studied by means of Time of flight mass spectrometry. Highly energetic H{sub 2}{sup +} and H{sub 3}{sup +} fragment ions are produced through an isomerization process taking place within transient multiply charged parent ions. Comparative study of deuterium labeled toluene isotopes enables the discrimination between molecular hydrogen fragments formed exclusively within the CH{sub 3}- part from those that require hydrogen atom exchange between the former and the phenyl moiety. It is demonstrated that by manipulating the relative phase of the ω/2ω field components the selective ionization of oriented toluene molecules can be used as a tool to control the directional emission of the H{sub 2}{sup +}, H{sub 3}{sup +} species.

  7. Accurate CO{sub 2} laser frequencies and molecular constants of regular and new hot-band lines

    SciTech Connect

    Chou, Che-Chung; Shy, Jow-Tsong; Maki, A.G.

    1994-12-31

    A new, high-resolution, highly efficient, cw, CO{sub 2} laser oscillating on more than 250 lines including over 40 lines in the new 9 {mu}m hot band has been built at NIST, Boulder. The frequencies of the 9 and 10 {mu}m hot band lines and high J (to J=66) regular band lines of {sup 12}C{sup 16}O{sub 2} , which now fill the gap between the 9 and 10 {mu}m regions, have been locked to saturated fluorescence signals in CO{sub 2}, and measured. New molecular constants and more accurate frequencies of the four common isotopes of CO{sub 2} have been obtained.

  8. 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.

  9. Innovative lasers for uranium isotope separation. Progress report for the period September 1, 1989--May 31, 1990

    SciTech Connect

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

    1990-06-01

    Copper vapor lasers have important applications to uranium atomic vapor laser isotope separation (AVLIS). The authors have spent the first year of the project investigating two innovative methods of exciting/pumping copper vapor lasers which have the potential to improve the efficiency and scaling of large laser systems used in uranium isotope separation. Experimental research has focused on the laser discharge kinetics of (1) microwave and (2) electron beam excitation/pumping of large-volume copper vapor lasers. During the first year, the experiments have been designed and constructed and initial data has been taken. Highlights of some of the first year results as well as plans for the future include the following: Microwave resonant cavity produced copper vapor plasmas at 2.45 GHz, both pulsed (5 kW, 5kHz) and CW (0--500 Watts) have been investigated using heated copper chloride as the copper source. The visible emitted light has been observed and intense lines at 510.6 nm and 578.2 nm have been observed. Initial measurements of the electric field strengths have been taken with probes, the plasma volume has been measured with optical techniques, and the power has been measured with power meters. A self-consistent electromagnetic model of the cavity/plasma system which uses the above data as input shows that the copper plasma has skin depths around 100 cm, densities around 10{sup 12} {number_sign}/cc, collisional frequencies around 10{sup 11}/sec., conductivities around 0.15 (Ohm-meter){sup {minus}1}. A simple model of the heat transfer predicts temperatures of {approximately}900 K. All of these parameters indicate that microwave discharges may be well suited as a pump source for copper lasers. These preliminary studies will be continued during the second year with additional diagnostics added to the system to verify the model results. Chemical kinetics of the system will also be added to the model.

  10. 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.

  11. [Atomic Vapor Laser Isotope Separation (AVLIS) program]. Final report, [January--July 1992

    SciTech Connect

    Not Available

    1992-12-04

    This report summarizes work performed for the Atomic Vapor Laser Isotope Separation (AVLIS) program from January through July, 1992. Each of the tasks assigned during this period is described, and results are presented. Section I details work on sensitivity matrices for the UDS relay telescope. These matrices show which combination of mirror motions may be performed in order to effect certain changes in beam parameters. In Section II, an analysis is given of transmission through a clipping aperture on the launch telescope deformable mirror. Observed large transmission losses could not be simulated in the analysis. An EXCEL spreadsheet program designed for in situ analysis of UDS optical systems is described in Section III. This spreadsheet permits analysis of changes in beam first-order characteristics due to changes in any optical system parameter, simple optimization to predict mirror motions needed to effect a combination of changes in beam parameters, and plotting of a variety of first-order data. Optical systems may be assembled directly from OSSD data. A CODE V nonsequential model of the UDS optical system is described in Section IV. This uses OSSD data to build the UDS model; mirror coordinates may thus be verified. Section V summarizes observations of relay telescope performance. Possible procedures which allow more accurate assessment of relay telescope performance are given.

  12. Direct determination of halogens in powdered geological and environmental samples using isotope dilution laser ablation ICP-MS

    NASA Astrophysics Data System (ADS)

    Boulyga, Sergei F.; Heumann, Klaus G.

    2005-04-01

    Laser ablation inductively coupled plasma isotope dilution mass spectrometry (LA-ICP-IDMS) with a special laser ablation system for bulk analyses (LINA-Spark(TM)-Atomiser) was applied for direct determinations of chlorine, bromine, and iodine in rock and sediment samples. Special attention was focused on possible inter-halogen fractionations and analyte/spike isotope fractionations by using LA-ICP-MS and LA-ICP-IDMS, respectively. A variation of Br/Cl and I/Cl element intensity ratios by a factor of 1.3-3 was observed when changing the nebulizer gas flow rate in the range of 0.84-1.0 L min-1 and the laser power density in the range of 2-10 GW cm-2, respectively. When using an internal standard for halogen quantification in LA-ICP-MS, this inter-element fractionation can cause systematic errors, which can be avoided by applying the isotope dilution technique. However, at high laser power densities (>5.7 GW cm-2 for iodine and >4.0 GW cm-2 for bromine and chlorine) the corresponding measured isotope ratio of the isotope-diluted sample deviates significantly from the target value. Under optimised conditions concentrations in the range of 30 [mu]g g-1-16 × 103 [mu]g g-1 for chlorine, <2-140 [mu]g g-1 for bromine, and <0.1-31 [mu]g g-1 for iodine were determined by LA-ICP-IDMS in two sediment reference materials (SRM 1646, SRM 2704) and three rock reference samples (GS-N, Granite; BX-N, Bauxite; DT-N, Disthene), which have not been certified for these halogens. The sediment results agree well within the given uncertainties with indicative values by different methods and the results of the rock samples with those obtained by negative thermal ionisation isotope dilution mass spectrometry. The detection limits of LA-ICP-IDMS are 8 [mu]g g-1 for chlorine, 1.7 [mu]g g-1 for bromine, and 0.1 [mu]g g-1 for iodine.

  13. 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.

  14. 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

  15. 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

  16. 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

  17. Recent progress in development of a laser based, ultra-high precision isotope monitor for carbon dioxide

    NASA Astrophysics Data System (ADS)

    Nelson, David; McManus, Barry; Herndon, Scott; Zahniser, Mark

    2015-04-01

    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 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 have the potential to rival the accuracy of mass spectrometric measurements. These measurements were performed using Tunable Infrared Laser Direct Absorption Spectroscopy (TILDAS). We have obtained isotopic measurement precisions of ~10 per meg for both 13C-CO2 and 18O-CO2 while measuring ambient air samples with continuous flow. We have also developed a method for analyzing air samples from canisters by alternately and rapidly trapping sample gas and reference gas in the optical cell. The ultimate goal is to create an automated, ultra-high accuracy carbon dioxide isotope monitor able to quantify small (~100 standard ml), discreet air samples. We will also discuss current instrument performance results and prospects for the measurement of the clumped isotopes of carbon dioxide in ambient air samples.

  18. 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.

  19. 10 CFR Appendix F to Part 110 - Illustrative List of Laser-Based Enrichment Plant Equipment and Components Under NRC Export...

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... separation (AVLIS or SILVA); second category-molecular laser isotope separation (MLIS or MOLIS) and chemical reaction by isotope selective laser activation (CRISLA). The systems, equipment and components for laser... to feed the vapor of a uranium compound for photo-dissociation or chemical activation; (b) devices...

  20. 10 CFR Appendix F to Part 110 - Illustrative List of Laser-Based Enrichment Plant Equipment and Components Under NRC Export...

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... separation (AVLIS or SILVA); second category-molecular laser isotope separation (MLIS or MOLIS) and chemical reaction by isotope selective laser activation (CRISLA). The systems, equipment and components for laser... to feed the vapor of a uranium compound for photo-dissociation or chemical activation; (b) devices...

  1. 10 CFR Appendix F to Part 110 - Illustrative List of Laser-Based Enrichment Plant Equipment and Components Under NRC Export...

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... separation (AVLIS or SILVA); second category-molecular laser isotope separation (MLIS or MOLIS) and chemical reaction by isotope selective laser activation (CRISLA). The systems, equipment and components for laser... to feed the vapor of a uranium compound for photo-dissociation or chemical activation; (b) devices...

  2. Molecular delivery into live cells using gold nanoparticle coated substrates fabricated by pulsed laser annealing

    NASA Astrophysics Data System (ADS)

    Wu, Ting-Hsiang; Xiao, Fan; Teitell, Michael A.; Chiou, Pei-Yu

    2010-02-01

    A massively-parallel molecular delivery system for mammalian cells is demonstrated by pulsed-laser irradiation of a gold-nanoparticles-coated substrate situated below a cell monolayer. This system is capable of high throughput and spatially-targeted delivery into desired areas of a cell culture by designing the laser irradiation pattern. Large area, rapid fabrication of the gold-nanoparticle-coated substrate is achieved by pulsed laser annealing of a continuous gold thin film. Randomly distributed gold nanoparticles and periodic gold nanoparticle arrays were obtained by pulsed laser flood exposure and by polymer mold guided laser annealing respectively. Optical image patterned molecular delivery into adherent cells were demonstrated in HeLa and HEK 293T cells. Delivery efficiencies of fluorescent dye, calcein, were as high as >90% with high cell viability (>90%) in HEK 293T using this device.

  3. The stable isotopic signature of biologically produced molecular hydrogen (H2)

    NASA Astrophysics Data System (ADS)

    Walter, S.; Laukenmann, S.; Stams, A. J. M.; Vollmer, M. K.; Gleixner, G.; Röckmann, T.

    2012-10-01

    Biologically produced molecular hydrogen (H2) is characterised by a very strong depletion in deuterium. Although the biological source to the atmosphere is small compared to photochemical or combustion sources, it makes an important contribution to the global isotope budget of H2. Large uncertainties exist in the quantification of the individual production and degradation processes that contribute to the atmospheric budget, and isotope measurements are a tool to distinguish the contributions from the different sources. Measurements of δ D from the various H2 sources are scarce and for biologically produced H2 only very few measurements exist. Here the first systematic study of the isotopic composition of biologically produced H2 is presented. In a first set of experiments, we investigated δ D of H2 produced in a biogas plant, covering different treatments of biogas production. In a second set of experiments, we investigated pure cultures of several H2 producing microorganisms such as bacteria or green algae. A Keeling plot analysis provides a robust overall source signature of δ D = -712‰ (±13‰) for the samples from the biogas reactor (at 38 °C, δ DH2O= +73.4‰), with a fractionation constant ϵH2-H2O of -689‰ (±20‰) between H2 and the water. The five experiments using pure culture samples from different microorganisms give a mean source signature of δ D = -728‰ (±28‰), and a fractionation constant ϵH2-H2O of -711‰ (±34‰) between H2 and the water. The results confirm the massive deuterium depletion of biologically produced H2 as was predicted by the calculation of the thermodynamic fractionation factors for hydrogen exchange between H2 and water vapour. Systematic errors in the isotope scale are difficult to assess in the absence of international standards for δ D of H2. As expected for a thermodynamic equilibrium, the fractionation factor is temperature dependent, but largely independent of the substrates used and

  4. Remote monitoring of 129I and 127I isotopes in the atmosphere using the laser-induced fluorescence method

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

    This paper reports the experimental and calculation research of the development of the remote laser-induced fluorescence method for the detection of 129I and 127I molecular iodine isotopologues in atmospheric air in real time. As an excitation source we used a frequency-doubled neodymium laser (~532 nm). We estimated the sensitivity of 127I129I and 129I2 detection in the atmosphere. Detection sensitivity of molecular iodine is 4 · 1013 cm-3 for a sensing distance of 6 km.

  5. Remote monitoring of 129I and 127I isotopes in the atmosphere using the laser-induced fluorescence method

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

    This paper reports the experimental and calculation research of the development of the remote laser-induced fluorescence method for the detection of 129I and 127I molecular iodine isotopologues in atmospheric air in real time. As an excitation source we used a frequency-doubled neodymium laser (~532 nm). We estimated the sensitivity of 127I129I and 129I2 detection in the atmosphere. Detection sensitivity of molecular iodine is 4 · 1013 cm‑3 for a sensing distance of 6 km.

  6. Carbon sources in the Beaufort Sea revealed by molecular lipid biomarkers and compound specific isotope analysis

    NASA Astrophysics Data System (ADS)

    Tolosa, I.; Fiorini, S.; Gasser, B.; Martín, J.; Miquel, J. C.

    2012-10-01

    Molecular lipid biomarkers (hydrocarbons, alcohols, sterols and fatty acids) and compound specific isotope analysis of suspended particulate organic matter (SPM) and surface sediments of the Mackenzie Shelf and slope (Southeast Beaufort Sea, Arctic Ocean), were studied in summer 2009. The concentrations of the molecular lipid markers, characteristic of known organic matter sources, were grouped and used as proxies to evaluate the relative importance of fresh algal, detrital algal, fossil, C3 terrestrial plants, bacterial and zooplankton material in the sedimentary organic matter (OM). Fossil and detrital algal contributions were the major fractions of the freshwater SPM from the Mackenzie River with ~34% each of the total molecular biomarkers. Fresh algal, C3 terrestrial, bacterial and zooplanktonic components represented much lower percentages, 17, 10, 4 and < 1%, respectively. In marine SPM from the Mackenzie slope, the major contributions were fresh and detrital algal components (> 80%) with a minor contribution of fossil and C3 terrestrial biomarkers. Characterization of the sediments revealed a major sink of refractory algal material mixed with some fresh algal material, fossil hydrocarbons and a small input of C3 terrestrial sources. In particular, the sediments from the shelf and at the mouth of the Amundsen Gulf presented the highest contribution of detrital algal material (60-75%) whereas those from the slope contained the highest proportion of fossil (40%) and C3 terrestrial plant material (10%). Overall, considering that the detrital algal material is marine derived, autochthonous sources contributed more than allochthonous sources to the OM lipid pool. Using the ratio of an allochthonous biomarker (normalized to total organic carbon, TOC) found in the sediments to those measured at the river mouth water, we estimated that the fraction of terrestrial material preserved in the sediments accounted for 30-40% of the total carbon in the inner shelf sediments

  7. 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.

  8. [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.

  9. 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.

  10. Contributions to the development of SLM TEA CO2 laser sources for high resolution molecular spectroscopy

    NASA Astrophysics Data System (ADS)

    Rob, Mohammad Abdur

    1989-03-01

    The emission spectrum of the carbon-dioxide (CO2) laser has an excellent overlap with the ro-vibrational absorption spectrum of a large number of polar molecules. Optical pumping of these molecules by CO2 lasers has produced well over 3000 far-infrared (FIR) laser lines. The molecular transitions for a large number of lines pumped by the narrow-band CW CO2 laser were identified. However, very few lines pumped by the pulsed TEA CO2 laser were assigned. This is due, in part, to the large uncertainty in both the pump and the FIR laser frequencies. Moreover, pumping with a given rotational line in the TEA CO2 laser output spectrum usually produces multiple FIR laser lines. This situation could be improved by the development of a narrow-band TEA CO2 laser, comparable in bandwidth to the width of typical absorption lines, in the FIR laser medium. Spectroscopic techniques making use of narrow-linewidth pulsed pump lasers would greatly facilitate the assignment of the infrared absorption transitions and the FIR laser lines. The narrow-linewidth pulsed laser would also be useful in many other applications. In the present series of experiments, three different techniques were investigated that produce high-power, tunable, single-longitudinal-mode (SLM) operation in a TEA CO2 laser. For the first time, the three SLM TEA CO2 laser configurations which were developed, along with another promising technique which is described in the literature, were analyzed on a common basis; so that their respective performance characteristics can be readily compared. This analysis facilitates the choice of the optimum laser system for a given task. Using a wedged etalon and a pyroelectric detector array combination, it was also shown directly that the intermodal tuning curve for the SLM TEA CO2 laser is a simple staircase function, with the laser output moving discontinuously from one mode to the next in a very regular fashion as the wavelength scan proceeds. To investigate the usefulness of

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

    SciTech Connect

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

    1994-06-01

    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% H{sub 2} 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 an practical and effective means of separating low-concentration hydrogen isotopes from a helium carrier.

  12. On-line double isotope dilution laser ablation inductively coupled plasma mass spectrometry for the quantitative analysis of solid materials.

    PubMed

    Fernández, Beatriz; Rodríguez-González, Pablo; García Alonso, J Ignacio; Malherbe, Julien; García-Fonseca, Sergio; Pereiro, Rosario; Sanz-Medel, Alfredo

    2014-12-01

    We report on the determination of trace elements in solid samples by the combination of on-line double isotope dilution and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The proposed method requires the sequential analysis of the sample and a certified natural abundance standard by on-line IDMS using the same isotopically-enriched spike solution. In this way, the mass fraction of the analyte in the sample can be directly referred to the certified standard so the previous characterization of the spike solution is not required. To validate the procedure, Sr, Rb and Pb were determined in certified reference materials with different matrices, including silicate glasses (SRM 610, 612 and 614) and powdered samples (PACS-2, SRM 2710a, SRM 1944, SRM 2702 and SRM 2780). The analysis of powdered samples was carried out both by the preparation of pressed pellets and by lithium borate fusion. Experimental results for the analysis of powdered samples were in agreement with the certified values for all materials. Relative standard deviations in the range of 6-21% for pressed pellets and 3-21% for fused solids were obtained from n=3 independent measurements. Minimal sample preparation, data treatment and consumption of the isotopically-enriched isotopes are the main advantages of the method over previously reported approaches.

  13. 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.

  14. Global scale observations of atmospheric molecular hydrogen and its stable isotopic composition

    NASA Astrophysics Data System (ADS)

    Batenburg, A. M.

    2012-09-01

    With average mixing ratios (χ) around 550 ppb (nmole/mole), molecular hydrogen (H2) is the most abundant reduced gas in our atmosphere after methane (CH4), but considerably less studied. H2 is also a promising energy carrier that might replace fossil fuels in vehicles with great sustainability advantages, but there may be environmental side effects. Large-scale leakage of H2 into the atmosphere might affect the atmosphere’s oxidative capacity and stratospheric ozone chemistry. To assess these risks, a better understanding of the atmospheric H2 cycle is needed. Stable isotopic composition measurements can be used to constrain the source and sink terms in the budgets of atmospheric trace gases, as the different processes affect the stable isotopic composition of the gases in different ways. For H2, the effects are particularly large, due to the large relative mass difference between the isotopes (H and D). The largest source, hydrocarbon oxidation, yields D-enriched H2, whereas the smaller combustion-related sources and the minor microbial sources yield D-depleted and extremely D-depleted H2, respectively. Both sink processes, uptake in soils and reaction with hydroxyl radicals (OH), have a D-enriching effect, but the effect is much stronger for OH. Despite its usefulness, few environmental observations of H2 isotopic composition (δD(H2)) are available. We present three new χ(H2) and δD(H2) datasets to fill this gap. First, we present one- to five-year long time series from six globally distributed, predominantly background stations. As expected, average χ(H2) and δD(H2) values were larger in the southern hemisphere (SH) than in the northern hemisphere (NH). The minimum in δD(H2) was found at the NH midlatitude stations, likely a result of fossil fuel combustion. At the three NH coastal and island stations, seasonal δD(H2)-cycles were observed, which were five to six months out-of-phase with the χ(H2)-cycles. No δD(H2)-cycles were observed at the other

  15. Metastable structures and isotope exchange reactions in polyoxometalate ions provide a molecular view of oxide dissolution.

    PubMed

    Rustad, James R; Casey, William H

    2012-03-01

    Reactions involving minerals and glasses in water are slow and difficult to probe spectroscopically but are fundamental to the performance of oxide materials in green technologies such as automotive thermoelectric power generation, CO2 capture and storage and water-oxidation catalysis; these must be made from geochemically common elements and operate in hydrous environments. Polyoxometalate ions (POMs) have structures similar to condensed oxide phases and can be used as molecular models of the oxide/water interface. Oxygen atoms in POM exchange isotopes at different rates, but, at present, there is no basis for predicting how the coordination environment and metal substitution influences rates and mechanisms. Here we identify low-energy metastable configurations that form from the breaking of weak bonds between metals and underlying highly coordinated oxygen atoms, followed by facile hydroxide, hydronium or water addition. The mediation of oxygen exchange by these stuffed structures suggests a new view of the relationship between structure and reactivity at the oxide/solution interface. PMID:22231599

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

    NASA Astrophysics Data System (ADS)

    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.

    2015-04-01

    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.

  17. 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

  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. Photoelectron momentum distributions of atomic and molecular systems in strong circularly or elliptically polarized laser fields

    NASA Astrophysics Data System (ADS)

    He, Pei-Lun; Takemoto, Norio; He, Feng

    2015-06-01

    Photoelectron momentum distributions of a hydrogen atom in an elliptically polarized laser field and a hydrogen molecular ion in a circularly polarized laser field are studied by simulating the time-dependent Schrödinger equation. We demonstrate that, in both systems, the Coulomb interaction between a liberated electron and its parent ion is essential for the photoelectron momentum angular drift in a laser polarization plane. By decomposing the wave packet into the rescattered and directly ionized components in the case of a hydrogen molecular ion, we reveal that the rescattered component drifts by a larger angle. The drift angle of the photoelectron of the hydrogen atom decreases monotonically with longer wavelength, while a nonmonotonic dependence is shown for H2+. We attribute such nonmonotonicity to the fluctuation of the instant of ionization for H2 + as the laser wavelength is changed.

  20. A miniature laser ablation mass spectrometer for in situ elemental and isotopic composition measurements of planetary rocks and soils

    NASA Astrophysics Data System (ADS)

    Neuland, M. B.; Mezger, K.; Riedo, A.; Tulej, M.; Wurz, P.

    2014-04-01

    A miniature laser ablation mass spectrometer (LMS) is presented. The LMS is designed as a flight instrument for planetary and space research and optimised for in situ measurements of the chemical composition of rocks and soils on a planetary surface. By means of measurements of standard reference materials, minerals and a sample of the Allende meteorite it is demonstrated that LMS is an suitable instrument for in situ measurements of elemental and isotopic composition with high precision and accuracy. Furthermore, it is shown that LMS data allows a derivation of the material mineralogy, petrology with high spatial resolution.

  1. 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.

  2. 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

  3. Laser Induced Molecular Spectroscopy of Zn{sub 2} Molecule

    SciTech Connect

    Singh, Subhash C.; Gopal, Ram

    2008-11-14

    Laser produced spectra of zinc molecule have been recorded in the region of 540-670 nm using second harmonics of Nd: YAG laser, computer--controlled TRIAX 320 M monochromator with a reciprocal linear dispersion 2.64 nm/mm fitted with ICCD detector. The spectrum consists of 35 bands, which are classified into D ({sup 1} product {sub u}){yields}A({sup 3} product {sub g}) and C ({sup 1}{sigma}{sub u}{sup +}){yields}A({sup 3} product {sub g}) systems. We have recorded the florescence spectrum of zinc dimer by pumping and probing with the same laser, which proves that produced molecules are stable for more than 0.1 seconds.

  4. 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.

  5. 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.

  6. 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.

  7. 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

  8. 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

  9. Laser micromanipulation systems as universal tools in cellular and molecular biology and in medicine.

    PubMed

    Schütze, K; Pösl, H; Lahr, G

    1998-07-01

    The UV-laser microbeam has been established as a valuable tool in a wide area of molecular biology as well as in medical research and applications. This system allows to cut or fuse microscopically small specimen. An important application of the cutting laser is laser microbeam microdissection (LMM) combined with laser pressure catapulting (LPC), which allows to procure single cells or small homogeneous cell areas for subsequent molecular analysis in an entirely "non-contact" manner. With LMM minute tissue areas, single cells or chromosomes are microdissected and separated from their surroundings. Subsequently, LPC ejects the dissectates directly into the cap of a sample tube without any mechanical contact. This enables the rapid procurement of homogeneous specimen from less than one up to several hundreds of micrometers in diameter without encroachment of the adjacent region. The mRNA information of the selected specimen as well as of the remaining probe are well preserved, as demonstrated with laser isolated samples from a routinely prepared tissue section of a differentiated colorectal adenocarcinoma. Reverse transcription of specific mRNA coding for cytoplasmic beta-actin and subsequent hemi-nested PCR amplification was not impaired. Any kind of tissue, as well as single cells from different sources and even subcellular structures can be captured using this laser method. Wherever homogeneous samples are required to analyze cell or chromosome-specific genetic alterations such as in cancer research or prenatal diagnosis this unique and rapid laser micropreparation method will become a key technology of great value.

  10. Molecular wave-packet dynamics on laser-controlled transition states

    NASA Astrophysics Data System (ADS)

    Fischer, Andreas; Gärttner, Martin; Cörlin, Philipp; Sperl, Alexander; Schönwald, Michael; Mizuno, Tomoya; Sansone, Giuseppe; Senftleben, Arne; Ullrich, Joachim; Feuerstein, Bernold; Pfeifer, Thomas; Moshammer, Robert

    2016-01-01

    We present a kinematically complete and time-resolved study of the dissociation dynamics of H2+ using ultrashort extreme-ultraviolet and near-infrared laser pulses. The reaction kinematics can be controlled by varying the time delay between the two pulses. We demonstrate that a time-dependent laser-dressed potential-energy curve enables the control of the nuclear motion. The dynamics is well reproduced by intuitive semiclassical trajectories on a time-dependent potential curve. From this most fundamental scenario we gain insight in the underlying mechanisms which may be applied as design principles for molecular quantum control, particularly for ultrafast molecular reactions involving the motion of protons.

  11. Optimization of field-free molecular alignment by phase-shaped laser pulses

    SciTech Connect

    Hertz, E.; Rouzee, A.; Guerin, S.; Lavorel, B.; Faucher, O.

    2007-03-15

    We theoretically demonstrate the optimization of field-free molecular alignment by phase-shaped femtosecond laser pulses. The effect is assessed in O{sub 2} at T=60 K under realistic conditions of intensity and pulse shaping. The spectral laser phase is sampled through 128 control parameters and a self-learning evolutionary algorithm combined with a nonperturbative regime calculation is used in order to design the specific phase that maximizes the degree of alignment. The postpulse molecular alignment appears significantly enhanced compared to a Fourier-transform-limited pulse of same energy. The analysis of the target state reveals that the solution is close to the optimal one.

  12. Triple-isotope analysis of oxygen in water by cavity ring-down laser spectroscopy

    NASA Astrophysics Data System (ADS)

    Steig, E. J.; Gkinis, V.; Schauer, A. J.; Schoenemann, S. W.; Samek, K.; Hoffnagle, J.; Tan, S. M.; Dennis, K. J.

    2013-12-01

    High precision analysis of the 17O/16O isotope ratio in water is an important new tool for many areas of Earth science. Of special interest is '17O-excess': 17O-excess = ln(δ17O+1)-0.528 ln(δ18O +1) (Eq. 1) where 0.528 represents the slope of the Global Meteoric Water Line (GMWL) in a plot of ln(δ17O+1) vs. ln(δ18O+1). 17O-excess is sensitive to kinetic fractionation processes and nearly invariant with temperature (Barkan and Luz, 2005). These attributes make it a useful tool for expanding our understanding of the hydrological cycle. To be useful in most applications, measurements of 17O-excess must be at a precision of better than 10 per meg (0.01 ‰). Conventional high-precision measurements of 17O-excess are time consuming and labor intensive. Small quantities (~2 μL) of H2O are reduced to O2 using reduction on CoF3 at 370°C, followed by dual-inlet mass spectrometry taking 2 to 3 hours per sample. We present a novel method that utilizes cavity ring-down laser spectroscopy (CRDS). CRDS is commonly used for the measurement of δ18O or δD in water (e.g. Crosson, 2008; Iannone et al., 2010; Gkinis et al., 2011), but the use of CRDS for 17O-excess poses unique challenges. While a H217O absorption region is available in instruments designed for δ18O, the absorbance is small and is influenced by the broad tail in the H216O spectrum. The resulting precision is inadequate to distinguish samples from the GMWL (Eq. 1). We describe a new CRDS system that provides high precision 17O-excess measurements. Key innovations include 1) the use of two lasers that measure absorption in two different IR regions; 2) a sample introduction system that permits the continuous introduction of water vapor from liquid water vials at steady concentrations over a long time period; and 3) novel improvements to the spectroscopy. Single samples are analyzed at water vapor concentrations held at 20,000 ppm (+/-100 ppm) over the course of up to several hours. A combination of long

  13. 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. PMID:19340162

  14. 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.

  15. Study of atomic and molecular emission spectra of Sr by laser induced breakdown spectroscopy (LIBS).

    PubMed

    Bhatt, Chet R; Alfarraj, Bader; Ayyalasomayajula, Krishna K; Ghany, Charles; Yueh, Fang Y; Singh, Jagdish P

    2015-12-01

    Laser Induced Breakdown Spectroscopy (LIBS) is an ideal analytical technique for in situ analysis of elemental composition. We have performed a comparative study of the quantitative and qualitative analysis of atomic and molecular emission from LIBS spectra. In our experiments, a mixture of SrCl2 and Al2O3 in powder form was used as a sample. The atomic emission from Sr and molecular emission from SrCl and SrO observed in LIBS spectra were analyzed. The optimum laser energies, gate delays, and gate widths for selected atomic lines and molecular bands were determined from spectra recorded at various experimental parameters. These optimum experimental conditions were used to collect calibration data, and the calibration curves were used to predict the Sr concentration. Limits of detection (LODs) for selected atomic and molecular emission spectra were determined.

  16. Development of a Tunable Laser Spectroscopic Method for Determining Multiple Sulfur Isotope Composition of Nanomoles of SO2

    NASA Astrophysics Data System (ADS)

    Guo, W.; Christensen, L. E.

    2013-12-01

    Multiple sulfur isotope (32S, 33S, 34S, 36S) analyses of geological material provide important constraints on the sulfur cycles on Earth [1] and other planetary bodies, e.g., Mars [2]. However, most current multiple sulfur isotope measurements are performed on magnetic sector isotope ratio mass spectrometers (IRMS) and thus require relatively large sample size (usually about several micromoles of sulfur, except the MC-ICPMS and SIMS methods) and time-consuming sample preparation procedures. More importantly, these IRMS methods demand relatively sophisticated instrumentation, and are not ideal for field measurements or flight missions. In contrast, laser spectroscopic methods provide opportunities for significantly reducing the sample size requirement and enabling real-time monitoring in the field, and have been proven to be of great importance in the isotopic measurements of many molecules in nature, e.g. CO2, H2O, N2O, CH4. Based on a prototype built for measuring δ34S of SO2 [3], we're developing a new tunable laser spectrometer (TLS) for simultaneously determining the δ34S and Δ33S of nanomoles of pure SO2. We have identified a new spectral window (<1 cm-1 wide) suitable for measuring 32SO2, 33SO2, 34SO2 simultaneously. Ongoing work focuses on increasing the optical path length of the analysis cell and determining the optimal analytical conditions, with the goal of achieving ≤0.5‰ precision in both δ34S and Δ33S over 30 seconds of analysis duration of ~20 nmol of pure SO2. Progress of these developments and comparison with conventional IRMS methods will be presented at the meeting. As a case study, we will also present preliminary TLS results from laboratory low pressure SO2 UV photolysis experiments where δ34S and Δ33S of the residual SO2 are expected to decrease as the photolysis proceeds [4]. Future developments of this method will involve the coupling of a sample introduction system to enable multiple sulfur isotope analysis of samples other than

  17. 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.

  18. 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.

  19. 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.

  20. Monitoring water stable isotope composition in soils using gas-permeable tubing and infrared laser absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Rothfuss, Youri; Vereecken, Harry; Brüggemann, Nicolas

    2013-04-01

    -permeable polypropylene tubing and a cavity ring-down laser absorption spectrometer. By analyzing water vapor δ2H and δ18O sampled with the tubing from a fine sand for temperatures ranging between 8-24° C, we demonstrate that (i) our new method is capable of monitoring δ2H and δ18O in soils online with high precision and, after calibration, also with high accuracy, (ii) our sampling protocol enabled detecting changes of δ2H and δ18O following non-fractionating addition and removal of liquid water and water vapor of different isotopic compositions, and (iii) the time needed for the tubing to monitor these changes is compatible with the observed variations of δ2H and δ18O in soils under natural conditions.

  1. 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)

  2. Free-electron laser induced processes in thin molecular ice.

    PubMed

    Siemer, Björn; Roling, Sebastian; Frigge, Robert; Hoger, Tim; Mitzner, Rolf; Zacharias, Helmut

    2014-01-01

    Intermolecular reactions in and on icy films on silicate and carbonaceous grains constitute a major route for the formation of new molecular constituents in interstellar molecular clouds. In more diffuse regions and in protoplanetary discs, energetic radiation can trigger reaction routes far from thermal equilibrium. As an analog of interstellar ice-covered dust grains, highly-oriented pyrolytic graphite (HOPG) covered with D2O, NO, and H atoms is irradiated by ultrashort XUV pulses and the desorbing ionic and neutral products are analysed. The yields of several products show a nonlinear intensity dependence and thus enable the elucidation of reaction dynamics by two-pulse correlated desorption.

  3. Molecular dispersion spectroscopy for chemical sensing using chirped mid-infrared quantum cascade laser.

    PubMed

    Wysocki, Gerard; Weidmann, Damien

    2010-12-01

    A spectroscopic method of molecular detection based on dispersion measurements using a frequency-chirped laser source is presented. An infrared quantum cascade laser emitting around 1912 cm(-1) is used as a tunable spectroscopic source to measure dispersion that occurs in the vicinity of molecular ro-vibrational transitions. The sample under study is a mixture of nitric oxide in dry nitrogen. Two experimental configurations based on a coherent detection scheme are investigated and discussed. The theoretical models, which describe the observed spectral signals, are developed and verified experimentally. The method is particularly relevant to optical sensing based on mid-infrared quantum cascade lasers as the high chirp rates available with those sources can significantly enhance the magnitude of the measured dispersion signals. The method relies on heterodyne beatnote frequency measurements and shows high immunity to variations in the optical power received by the photodetector.

  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. 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.

  6. 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.

  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. Ultrafast electronic motion in hydrogen molecular ions induced by a high power intense laser

    NASA Astrophysics Data System (ADS)

    Mineo, H.; Teranishi, Y.; Chao, S. D.; Lin, S. H.

    2010-10-01

    In this Letter we report a method for controlling electronic localization in a molecular ion, on an attosecond time scale, using a high-intensity laser, based on two different excitation mechanisms. One takes place during ionization, and the other takes place sequentially, following ionization. The electronic excited states of the hydrogen molecular ion are created during ionization by taking the configuration interaction mixing of neutral molecules into account. We detect the ultrafast oscillatory electronic motion between two atoms in a hydrogen molecular ion occurring due to the creation of excited states during the course of ionization.

  9. Imaging Ultra-fast Molecular Dynamics in Free Electron Laser Field

    NASA Astrophysics Data System (ADS)

    Zhang, Y. Z.; Jiang, Y. H.

    The free electron laser (FEL) provides the coherent, brilliant and ultrashort light pulse in short wavelength (extreme ultraviolet and X-ray) regimes, opening up possibilities to study ultra-fast molecular dynamics in photo-induced chemical reactions with new methodologies. In this chapter, we introduce the time-resolved pump-probe experiments on gas-phase targets with FEL facilities to image the nuclear and electronic motions in molecular reactions, which serve as a benchmark for further FEL applications like coherent diffraction imaging and coherent control of functional dynamics in complex molecular reactions.

  10. 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.

  11. 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.

  12. Buried-heterostructure quantum-cascade laser overgrown by gas-source molecular-beam epitaxy

    NASA Astrophysics Data System (ADS)

    Chashnikova, M.; Monastyrskyi, G.; Aleksandrova, A.; Klinkmüller, M.; Semtsiv, M. P.; Masselink, W. T.

    2012-05-01

    We describe the realization of buried-heterostructure quantum-cascade lasers (QCLs) using gas-source molecular beam epitaxy both for the growth of the active region as well as for the regrowth of InP:Fe. The regrowth of the semi-insulating InP:Fe layer was carried out at 470 °C, which is more than 100 °C below the standard growth temperature during metal-organic vapor-phase epitaxy, the standard method for laser overgrowth. The electrical resistivity of the InP:Fe insulation layer, measured in test samples grown on (001) InP, is as large as 2×108Ωcm. High-resistivity InP:Fe is overgrown non-selectively over the etched laser ridge, followed by the top contact alloyed through it to the active region. The processed quantum-cascade lasers show no evidence of parallel leakage current and exhibit lower threshold current density than lasers using SiO2 as an insulator. The ability to fabricate buried heterostructure lasers without exceeding 600 °C is important for strain-compensated AlAs-InGaAs quantum cascade lasers with large internal strain because these devices do not typically withstand temperatures used to grow InP:Fe using vapor-phase epitaxy.

  13. 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.

  14. Molecular and isotopic stratigraphy in an ombrotrophic mire for paleoclimate reconstruction

    NASA Astrophysics Data System (ADS)

    Xie, Shucheng; Nott, Chris J.; Avsejs, Luke A.; Maddy, Darrel; Chambers, Frank M.; Evershed, Richard P.

    2004-07-01

    A 40 cm deep Sphagnum-dominated peat monolith from Bolton Fell Moss in Northern England was systematically investigated by lipid molecular stratigraphy and compound-specific δ 13C and δD analysis using gas chromatography (GC), GC-mass spectrometry (GC-MS), GC-combustion-isotope ratio-MS (GC-C-IRMS) and GC-thermal conversion-IRMS (GC-TC-IRMS) techniques. 210Pb dating showed the monolith accumulated during the last ca. 220 yr, a period encompassing the second part of Little Ice Age. While the distributions of lipids, including n-alkan-1-ols, n-alkan-2-ones, wax esters, sterols, n-alkanoic acids, α,ω-alkandioic acids and ω-hydroxy acids, display relatively minor changes with depth, the cooler climate event was recorded in the concentrations of n-alkanes and organic carbon, CPI values of n-alkanes and n-alkanoic acids, and the ratio of 5- n-alkylresorcinols/sterols. Superimposed on the fossil fuel effect, the relatively cooler climate event was also recorded by δ 13C values of individual hydrocarbons, especially the C 23n-alkane, a major compound in certain Sphagnum spp. The δD values of the C 29 and C 33n-alkanes correlated mainly with plant composition and were relatively insensitive to climatic change. In contrast the C 23n-alkane displayed variation that correlated strongly with recorded temperature for the period represented by the monolith, agreeing with previously reported deuterium records in tree ring cellulose spanning the same period in Scotland, Germany and the USA, with more negative values occurring during the second part of Little Ice Age. These biomarker characteristics, including the compound-specific δ 13C and δD records, provide a new set of proxies of climatic change, potentially independent of preserved macrofossils which will be of value in deeper sections of the bog where the documentary records of climate are unavailable and humification is well advanced.

  15. 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

  16. 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

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

    PubMed

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

    2008-01-01

    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(1Delta) 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.

  18. Molecular imaging using X-ray free-electron lasers.

    PubMed

    Barty, Anton; Küpper, Jochen; Chapman, Henry N

    2013-01-01

    The opening of hard X-ray free-electron laser facilities, such as the Linac Coherent Light Source (LCLS) at SLAC National Accelerator Laboratory in the United States, has ushered in a new era in structural determination. With X-ray pulse durations down to 10 fs or shorter, and up to 10(13) transversely coherent photons per pulse in a narrow spectral bandwidth, focused irradiances of 10(18) to 10(21) W cm(-2) or higher can be produced at X-ray energies ranging from 500 eV to 10 keV. New techniques for determining the structure of systems that cannot be crystallized and for studying the time-resolved behavior of irreversible reactions at femtosecond timescales are now available.

  19. Molecular Imaging Using X-Ray Free-Electron Lasers

    NASA Astrophysics Data System (ADS)

    Barty, Anton; Küpper, Jochen; Chapman, Henry N.

    2013-04-01

    The opening of hard X-ray free-electron laser facilities, such as the Linac Coherent Light Source (LCLS) at SLAC National Accelerator Laboratory in the United States, has ushered in a new era in structural determination. With X-ray pulse durations down to 10 fs or shorter, and up to 1013 transversely coherent photons per pulse in a narrow spectral bandwidth, focused irradiances of 1018 to 1021 W cm-2 or higher can be produced at X-ray energies ranging from 500 eV to 10 keV. New techniques for determining the structure of systems that cannot be crystallized and for studying the time-resolved behavior of irreversible reactions at femtosecond timescales are now available.

  20. Molecular imaging using X-ray free-electron lasers.

    PubMed

    Barty, Anton; Küpper, Jochen; Chapman, Henry N

    2013-01-01

    The opening of hard X-ray free-electron laser facilities, such as the Linac Coherent Light Source (LCLS) at SLAC National Accelerator Laboratory in the United States, has ushered in a new era in structural determination. With X-ray pulse durations down to 10 fs or shorter, and up to 10(13) transversely coherent photons per pulse in a narrow spectral bandwidth, focused irradiances of 10(18) to 10(21) W cm(-2) or higher can be produced at X-ray energies ranging from 500 eV to 10 keV. New techniques for determining the structure of systems that cannot be crystallized and for studying the time-resolved behavior of irreversible reactions at femtosecond timescales are now available. PMID:23331310

  1. Organosulfur Compounds: Molecular and Isotopic Evolution from Biota to Oil and Gas

    NASA Astrophysics Data System (ADS)

    Amrani, Alon

    2014-05-01

    Organosulfur compounds (OSCs) play important roles in the formation, preservation, and thermal degradation of sedimentary organic matter and the associated petroleum generation. Improved analytical techniques for S isotope analysis have recently enhanced our understanding of the mechanisms for OSC formation and maturation and their associated S isotope distributions. The close interaction of OSCs with inorganic S species throughout their formation and maturation affects their 34S/32S isotopic ratio (δ34S), forming specific signatures for distinct sources and processes. Ultimately, thermal maturation homogenizes the δ34S values of different fractions and individual compounds. Reservoir processes such as thermochemical sulfate reduction (TSR) introduce exogenous and isotopically distinct S into hydrocarbons and can significantly change the δ34S of petroleum or kerogen. Specific OSCs react at different rates and thus can be used to evaluate the extent of processes such as TSR. This article reviews factors that affect the 34S/32S isotopic distribution of OSCs along pathways of formation, diagenesis, and thermal alteration.

  2. Probing Molecular Dynamics by Laser-Induced Backscattering Holography.

    PubMed

    Haertelt, Marko; Bian, Xue-Bin; Spanner, Michael; Staudte, André; Corkum, Paul B

    2016-04-01

    We use differential holography to overcome the forward scattering problem in strong-field photoelectron holography. Our differential holograms of H_{2} and D_{2} molecules exhibit a fishbonelike structure, which arises from the backscattered part of the recolliding photoelectron wave packet. We demonstrate that the backscattering hologram can resolve the different nuclear dynamics between H_{2} and D_{2} with subangstrom spatial and subcycle temporal resolution. In addition, we show that attosecond electron dynamics can be resolved. These results open a new avenue for ultrafast studies of molecular dynamics in small molecules. PMID:27081975

  3. Probing Molecular Dynamics by Laser-Induced Backscattering Holography

    NASA Astrophysics Data System (ADS)

    Haertelt, Marko; Bian, Xue-Bin; Spanner, Michael; Staudte, André; Corkum, Paul B.

    2016-04-01

    We use differential holography to overcome the forward scattering problem in strong-field photoelectron holography. Our differential holograms of H2 and D2 molecules exhibit a fishbonelike structure, which arises from the backscattered part of the recolliding photoelectron wave packet. We demonstrate that the backscattering hologram can resolve the different nuclear dynamics between H2 and D2 with subangstrom spatial and subcycle temporal resolution. In addition, we show that attosecond electron dynamics can be resolved. These results open a new avenue for ultrafast studies of molecular dynamics in small molecules.

  4. 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

  5. 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

  6. 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.

  7. 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.

  8. 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.

  9. Theoretical analysis of fluorescence signals in filamentation of femtosecond laser pulses in nitrogen molecular gas

    SciTech Connect

    Arevalo, E.; Becker, A.

    2005-10-15

    We study numerically and analytically the role of the combined effect of self-focusing, geometrical focusing, and the plasma defocusing in the formation of the fluorescence signal during the filamentation of a Ti:sapphire laser pulse in nitrogen molecular gas. Results of numerical simulations are used to estimate the number of excited ions in the focal volume, which is proportional to the fluorescence signal. We find good agreement between the theoretical results and the experimental data, showing that such data can be used to get further insight into the effective focal volume during filamentation of femtosecond laser pulses in transparent media.

  10. 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

  11. 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.

  12. 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. PMID:20578764

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

    NASA Astrophysics Data System (ADS)

    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.

  14. 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)

  15. 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.

  16. 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.

  17. 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. PMID:26656823

  18. 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.

  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. Photochemical processes in laser ablation of organic solids: Molecular dynamics study

    NASA Astrophysics Data System (ADS)

    Yingling, Yaroslava G.

    In this thesis, a comprehensive study of the effect of the photochemical processes on laser ablation mechanisms has been conducted using molecular dynamics simulations. We developed a new concept for modeling photochemical processes in laser ablation of organic films using a mesoscopic coarse-grain breathing sphere model for molecular dynamics simulations. The main advantage of our model is the ability to study the dynamics of the system at the mesoscopic length scale, a regime that is not accessible either with atomistic or continuum computational methods. The photodecomposition of the excited molecules and the chemical reaction patterns in our simulations are based on the photochemistry of chlorobenzene due to ease of its fragmentation and available experimental data. Interpretation of the experimental data is the main objective of our theoretical efforts. Molecular dynamics simulations are used to investigate the effect of photochemical processes on molecular ejection mechanisms in 248-nm laser irradiation of organic solids. Photochemical reactions are found to release additional energy into the irradiated sample and decrease the average cohesive energy, therefore decreasing the value of the ablation threshold. The yield of emitted fragments becomes significant only above the ablation threshold. Below the ablation threshold, only the most volatile photoproduct, HCl, is ejected in very small amounts, whereas the remainder of photoproducts are trapped inside the sample. The presence of photochemical decomposition processes and subsequent chemical reactions changes the temporal and spatial energy deposition profile from pure photothermal ablation. The chemical reactions create an additional local pressure build up and, as a result, generate a strong and broad acoustic pressure wave propagating toward the bottom of the computational cell. The strong pressure wave in conjunction with the temperature increase in the absorbing region causes the ejection of hot massive

  1. Molecular and stable carbon isotopic compositions of hopanoids in seep carbonates from the South China Sea continental slope

    NASA Astrophysics Data System (ADS)

    Guan, Hongxiang; Sun, Yongge; Mao, Shengyi; Zhu, Xiaowei; Wu, Nengyou

    2014-10-01

    The lipid biomarkers of hopanoids in cold seep carbonates from the South China Sea continental slope were investigated by gas chromatography-mass spectrometer (GC-MS) and gas chromatography-isotope ratio-mass spectrometer (GC-ir-MS). The distribution of hopanes/hopenes shows a preference for the ‘biological’ 17β(H), 21β(H)-over the ‘geological’ 17α(H), 21β(H)-configuration. This interpretation is in agreement with the strong odd-even preference of long-chain n-alkanes in those samples, suggesting that the ββ hopanes may be the early diagenetic products of biohopanoids and the αβ, βα configurations of hopanes were mainly derived from allochthonous sources contributing to the organic matter of the carbonates. In terms of hopanoid acids, the C30 to C33 17β(H), 21β(H)-hopanoid acids were detected with C32 17β(H), 21β(H)-hopanoid acid being the most abundant. However, there is a significant difference in stable carbon isotopic compostions of the C32 17β(H), 21β(H)-hopanoic acid among samples (-30.7‰ to -69.8‰). The δ13C values match well with the carbon isotopic compositions of SRB-derived iso-/anteiso-C15:0 fatty acids in the samples, which strongly depend on the carbon utilization types by microbe. The most abundant compound of hopanols detected in the samples, C30-17β(H), 21β(H)-hopanol, may be a good indicator of diagenetic product of type I methanotrophs. The molecular and carbon isotopic compositions of hopanoids demonstrate clearly that there is a combination contribution of both SRB and type I or type X methanotrophs to the source organism in the seep carbonates from the South China Sea continental slope.

  2. 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.

  3. A molecular stable carbon isotope study of organic matter in immature Miocene Monterey sediments, Pismo basin

    NASA Astrophysics Data System (ADS)

    Schouten, Stefan; Schoell, Martin; Rijpstra, W. Irene C.; Sinninghe Damsté, Jaap S.; de Leeuw, Jan W.

    1997-05-01

    The 300 m section of the Miocene Monterey Formation outcropping at Shell Beach (Pismo basin; ca. 15-11 Ma) is composed of calcareous phosphatic (15.1-14.5 Ma) and siliceous facies (14.5-11.0 Ma). An objective of this paper is to document lateral paleoenvironmental changes in the Miocene Moneterey Formation by comparing the Shell Beach (SB) profile with the Naples Beach (NB) section in the Santa Barbara-Ventura basin (Schouten et al., 1997) which is ˜80 km to the south. Eight samples (one sample representing, on average, a time period of ca. 2000 y) from this section were analyzed for variations of extractable biomarkers and their carbon isotopic signatures as indicators for paleoenvironmental change during the Miocene. Saturated hydrocarbons present include 28,30-dinorhopane, phytane, n-alkanes (C 17sbnd C 31), lycopane, and 17β,21β(H)-homohopane. The biomarkers released after desulfurization of the polar fractions predominantly consist of phytane, 2,6,10,14-tetramethyl-7-(3-methylpentyl)pentadecane, C 17sbnd C 31n-alkanes, regular 5α- and 5β-steranes, dinosteranes, and (22R)-17β,21β(H)-pentakishomohopane. Steranes have similar carbon isotopic compositions (-25 to -27‰) throughout the section and are isotopically similar at both sites, indicating laterally similar and vertically stable environmental conditions for algae living in the upper part of the photic zone. Free and S-bound n-alkanes at SB mainly originate from marine organisms and not from terrestrial sources as in the NB section. S-bound pentakishomohopane is ca. 1-4‰ depleted compared to the steranes and is thought to be derived from the deeper water dwelling cyanobacteria. These findings are consistent with stable carbon isotopic data obtained for these compounds from Middle Miocene Monterey sediments at Naples Beach and indicates similar environmental conditions in the depositional environments of the Santa Barbara-Ventura and the Pismo basin. S-bound highly branched isoprenoids have, at both

  4. Evaluation of parameters influencing the molecular delivery by biodegradable microsphere-mediated perforation using femtosecond laser

    NASA Astrophysics Data System (ADS)

    Mitsuhashi, Tatsuki; Terakawa, Mitsuhiro

    2014-01-01

    The parameters critically influencing the delivery rate on the biodegradable microsphere-mediated femtosecond (fs) laser perforation are investigated in detail with the aim of developing efficient molecular delivery. Cell membrane was perforated by the irradiation of weakly focused fs laser pulses to the spherical polylactic acid microspheres conjugated to the cell membrane. The delivery of fluorescein isothiocyanate-dextran and fluorescent silica particles to A431 cells is investigated in detail. The increase in the number of irradiated laser pulses had resulted in the increase of delivery rate. The delivery rate depends on the size and functionalization of fluorescent silica particles in which silica particles of 100 nm in diameter were able to be delivered into 20% of the irradiated cells, suggesting that the pore sizes are large enough for the delivery of therapeutic agents into cells. These findings contribute to the development of an efficient and safe phototherapy and drug delivery.

  5. 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.

  6. 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.

  7. Field-free molecular alignment induced by elliptically polarized laser pulses: Noninvasive three-dimensional characterization

    SciTech Connect

    Hertz, E.; Guerin, S.; Jauslin, H. R.; Lavorel, B.; Faucher, O.; Daems, D.

    2007-10-15

    An investigation of field-free molecular alignment produced by elliptically polarized laser pulses is reported. Experiments are conducted in CO{sub 2} at room temperature. A noninvasive all-optical technique, based on the cross defocusing of a probe pulse, is used to measure the alignment along two orthogonal directions which is sufficient to provide a three-dimensional characterization. The field-free molecular alignment produced by a laser of elliptical polarization is in good agreement in terms of amplitude and shape with theoretical predictions. It turns out to be almost equivalent to the superposition of the effects that one would obtain with two individual cross-polarized pulses. The investigation highlights notably the occurrence of field-free two-direction alignment alternation for a suitably chosen degree of ellipticity. The analogy between this specific ellipticity and the well-known 'magic angle' used in time-resolved spectroscopy to prevent rotational contributions is discussed.

  8. 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.

  9. 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.

  10. 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.

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

    PubMed

    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

    1999-12-01

    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.

  12. 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

  13. 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.

  14. 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

  15. The combination of laser micro-boring and high resolution α-spectroscopy for the analysis of α-emitting isotopes in irradiated high-temperature-reactor fuel

    NASA Astrophysics Data System (ADS)

    Helmbold, M.; Allelein, H. J.; Koch, H. R.

    1980-02-01

    A new method for the determination of α-emitting isotopes in irradiated high-temperature-reactor fuel has been developed. By use of a laser micro-boring system it is possible to prepare extremely thin α-spectroscopy samples out of any part of the fuel with a spatial resolution of about 10 μm. The measurement of the samples with a silicon barrier detector yields α-spectra of high resolution, allowing the determination of the content of most of the heavy metal isotopes. The method can be extended to the analysis of any kind of nuclear fuel.

  16. 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.

  17. Water vapor isotopes measurements at Mauna Loa, Hawaii: Comparison of laser spectroscopy and remote sensing with traditional methods, and the need for ongoing monitoring

    NASA Astrophysics Data System (ADS)

    Galewsky, J.; Noone, D.; Sharp, Z.; Worden, J.

    2009-04-01

    The isotopic composition of water vapor (2H/1H and 18O/16 ratios) provides unique information on the transport pathways that link water sources to regional sinks, and thus proves useful in understanding large scale atmospheric humidity budgets. Recent advances in measurement technology allow the monitoring of water vapor isotope composition in ways which has can revolutionize investigations of atmospheric hydrology. Traditional measurement of isotopic composition requires trapping of samples with either large volume vacuum flasks or by trapping liquid samples with cryogens for later analyses using mass spectrometry, and are laborious and seldom span more than just short dedicated observational periods. On the other hand, laser absorption spectroscopy can provide almost continuous and autonomous in situ measurements of isotope abundances with precision almost that of traditional mass spectrometry, and observations from spacecraft can make almost daily maps of the global isotope distributions. In October of 2008 three laser based spectrometers were deployed at the Mauna Loa Laboratory in Hawaii to make continuous measurement of the 2H and 18O abundance of free tropospheric water vapor. These results are compared with traditional measurements and with measurements from two satellite platforms. While providing field validation of the new methodologies, the data show variability which captures the transport processes in the region. The data are used to characterize the role of large scale mixing of dry air, the influence of the boundary layer and the importance of moist convection in controlling the low humidity of subtropical air near Hawaii. Although the record is short, it demonstrates the usefulness of using robust isotope measurements to understand the budgets of the most important greenhouse gas. This work motivates establishing a continuous record of isotopes measurement at baseline sites, like Mauna Loa, such that the changes in water cycle can be understood and

  18. Water vapor isotopes measurements at Mauna Loa, Hawaii: Comparison of laser spectroscopy and remote sensing with traditional methods, and the need for ongoing monitoring

    NASA Astrophysics Data System (ADS)

    Noone, D.; Galewsky, J.; Sharp, Z.; Worden, J.

    2008-12-01

    The isotopic composition of water vapor (2H/1H and 18O/16 ratios) provides unique information on the transport pathways that link the water sources to regional sinks, and thus proves useful in understanding the large scale humidity budgets. Recent advances in measurement technology allow the monitoring of water vapor isotope composition in ways which has can revolutionize investigations of atmospheric hydrology. Traditional measurement of isotopic composition requires trapping of samples with either large volume vacuum flasks or by trapping liquid samples with cryogens for later analyses using mass spectrometry, and are laborious and seldom span more than just short dedicated observational periods. On the other hand, laser absorption spectroscopy can provide almost continuous and autonomous in situ measurements of isotope abundances with precision almost that of traditional mass spectrometry, and observations from spacecraft can make almost daily maps of the global isotope distributions. In October of 2008 three laser based spectrometers were deployed at the Mauna Loa Laboratory in Hawaii to make continuous measurement of the 2H and 18O abundance of free tropospheric water vapor. These results are compared with traditional measurements and with measurements from two satellite platforms. While providing field validation of the new methodologies, the data show variability which captures the transport processes in the region. The data are used to characterize the role of large scale mixing of dry air, the influence of the boundary layer and the importance of moist convection in controlling the low humidity of subtropical air near Hawaii. Although the record is short, it demonstrates the usefulness of using robust isotope measurements to understand the budgets of the most important greenhouse gas. This work motivates establishing a continuous record of isotopes measurement at baseline sites, like Mauna Loa, such that the changes in water cycle can be understood and

  19. Molecular and Higher Precision Isotopic Measurements of the Mars Atmosphere and Subsurface Volatiles

    NASA Technical Reports Server (NTRS)

    Mahaffy, P. R.; Atreya, S. K.; Owen, T. C.; Niemann, H. B.; Jones, J.; Gorevan, S.

    2000-01-01

    In response to the question 'what to do next' at Mars we explore the value of a high precision in situ measurement of isotopic and trace gas constituents in the atmosphere combined with a similar analysis of gas extracted from near surface rocks and soils. The scientific goals are to advance our understanding of the evolution of the Martian atmosphere and to search for fossils of past geochemical conditions. One element of this program that ties directly to the goals of the Astrobiology Program will be a sensitive search for simple or complex organic molecules contained in the atmosphere and in the solid phase. The broad chemical and isotopic analysis planned insures that a highly successful program will be carried out even if no organics are detected. We will demonstrate that the technology to carry out this Program is presently in hand.

  20. A molecular stable carbon isotope study of organic matter in immature Miocene Monterey sediments, Pismo basin

    SciTech Connect

    Schouten, S.; Rijpstra, I.C.; De Leeuw, J.W.

    1997-05-01

    The 300 m section of the Miocene Monterey Formation outcropping at Shell Beach is composed of calcareous phosphatic (15.1 -14.5 Ma) and siliceous facies (14.5-11.0 Ma). An objective of this paper is to document lateral paleoenvironmental changes in the Miocene Monterey Formation by comparing the Shell Beach (SB) profile with the Naples Beach (NB) section in the Santa Barbara-Ventura basin. Eight samples (one sample representing, on average, a time period of ca. 2000 y) from this section were analyzed for variations of extractable biomarkers and their carbon isotopic signatures as indicators for paleoenvironmental change during the Miocene. Saturated hydrocarbons present include 28,30-dinorhopane, phytane, n-alkanes (C{sub 17}-C{sub 31}), lycopane, and 17{beta}, 21{beta}(H)-homohopane. The biomarkers released after desulfurization of the polar fractions predominantly consist of phytane, 2,6.10,14-tetramethyl-7-(3-methylpentyl)pentadecane, C{sub 17}-C{sub 31} n-alkanes. regular 5{alpha}- and 5{beta}-steranes, dinosteranes, and (22R)-17{beta},21{beta}(H)-pentakishomohopane. Steranes have similar carbon isotopic compositions (-25 to -27{per_thousand}) throughout the section and are isotopically similar at both sites, indicating laterally similar and vertically stable environmental conditions for algae living in the upper part of the photic zone. Free and S-bound n-alkanes at SB mainly originate from marine organisms and not from terrestrial sources as in the NB section. S-bound pentakishomohopane is ca. 1-49{per_thousand} depleted compared to the steranes and is thought to be derived from the deeper water dwelling cyanobacteria. These findings are consistent with stable carbon isotopic data obtained for these compounds from Middle Miocene Monterey sediments at Naples Beach and indicates similar environmental conditions in the depositional environments of the Santa Barbara-Ventura and the Pismo basin. 64 refs., 14 figs., 6 tabs.

  1. 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. PMID:26673156

  2. 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

  3. 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

  4. Determining the isotopic compositions of uranium and fission products in radioactive environmental microsamples using laser ablation ICP-MS with multiple ion counters.

    PubMed

    Boulyga, Sergei F; Prohaska, Thomas

    2008-01-01

    This paper presents the application of a multicollector inductively coupled plasma mass spectrometer (MC-ICP-MS)--a Nu Plasma HR--equipped with three ion-counting multipliers and coupled to a laser ablation system (LA) for the rapid and sensitive determination of the 235U/238U, 236U/238U, 145Nd/143Nd, 146Nd/143Nd, 101Ru/(99Ru+99Tc) and 102Ru/(99Ru+99Tc) isotope ratios in microsamples collected in the vicinity of Chernobyl. Microsamples with dimensions ranging from a hundred mum to about 1 mm and with surface alpha activities of 3-38 mBq were first identified using nuclear track radiography. U, Nd and Ru isotope systems were then measured sequentially for the same microsample by LA-MC-ICP-MS. The application of a zoom ion optic for aligning the ion beams into the ion counters allows fast switching between different isotope systems, which enables all of the abovementioned isotope ratios to be measured for the same microsample within a total analysis time of 15-20 min (excluding MC-ICP-MS optimization and calibration). The 101Ru/(99Ru+99Tc) and 102Ru/(99Ru+99Tc) isotope ratios were measured for four microsamples and were found to be significantly lower than the natural ratios, indicating that the microsamples were contaminated with the corresponding fission products (Ru and Tc). A slight depletion in 146Nd of about 3-5% was observed in the contaminated samples, but the Nd isotopic ratios measured in the contaminated samples coincided with natural isotopic composition within the measurement uncertainty, as most of the Nd in the analyzed samples originates from the natural soil load of this element. The 235U/238U and 236U/238U isotope ratios were the most sensitive indicators of irradiated uranium. The present work yielded a significant variation in uranium isotope ratios in microsamples, in contrast with previously published results from the bulk analysis of contaminated samples originating from the vicinity of Chernobyl. Thus, the 235U/238U ratios measured in ten

  5. Determining the isotopic compositions of uranium and fission products in radioactive environmental microsamples using laser ablation ICP-MS with multiple ion counters.

    PubMed

    Boulyga, Sergei F; Prohaska, Thomas

    2008-01-01

    This paper presents the application of a multicollector inductively coupled plasma mass spectrometer (MC-ICP-MS)--a Nu Plasma HR--equipped with three ion-counting multipliers and coupled to a laser ablation system (LA) for the rapid and sensitive determination of the 235U/238U, 236U/238U, 145Nd/143Nd, 146Nd/143Nd, 101Ru/(99Ru+99Tc) and 102Ru/(99Ru+99Tc) isotope ratios in microsamples collected in the vicinity of Chernobyl. Microsamples with dimensions ranging from a hundred mum to about 1 mm and with surface alpha activities of 3-38 mBq were first identified using nuclear track radiography. U, Nd and Ru isotope systems were then measured sequentially for the same microsample by LA-MC-ICP-MS. The application of a zoom ion optic for aligning the ion beams into the ion counters allows fast switching between different isotope systems, which enables all of the abovementioned isotope ratios to be measured for the same microsample within a total analysis time of 15-20 min (excluding MC-ICP-MS optimization and calibration). The 101Ru/(99Ru+99Tc) and 102Ru/(99Ru+99Tc) isotope ratios were measured for four microsamples and were found to be significantly lower than the natural ratios, indicating that the microsamples were contaminated with the corresponding fission products (Ru and Tc). A slight depletion in 146Nd of about 3-5% was observed in the contaminated samples, but the Nd isotopic ratios measured in the contaminated samples coincided with natural isotopic composition within the measurement uncertainty, as most of the Nd in the analyzed samples originates from the natural soil load of this element. The 235U/238U and 236U/238U isotope ratios were the most sensitive indicators of irradiated uranium. The present work yielded a significant variation in uranium isotope ratios in microsamples, in contrast with previously published results from the bulk analysis of contaminated samples originating from the vicinity of Chernobyl. Thus, the 235U/238U ratios measured in ten

  6. 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

  7. 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.

  8. A novel quantification strategy of transferrin and albumin in human serum by species-unspecific isotope dilution laser ablation inductively coupled plasma mass spectrometry (ICP-MS).

    PubMed

    Feng, Liuxing; Zhang, Dan; Wang, Jun; Shen, Dairui; Li, Hongmei

    2015-07-16

    Species-specific (SS) isotope dilution analysis with gel electrophoresis (GE)-laser ablation (LA)-ICP-MS is a promising technique for the quantification of particular metal-binding proteins in biological samples. However, unavailable isotopically enriched spike and metal losses in GE separation are main limitations for SS-isotope dilution PAGE-LA-ICP-MS. In this study, we report for the first time the absolute quantification of transferrin (Tf) and albumin (Alb) in human serum by non-denaturing (native) GE combined with species-unspecific isotope dilution mass spectrometry (IDMS). In order to achieve a homogeneous distribution of both protein and isotope-enriched spike (simulated isotope equilibration), immersing the protein strips with (34)S spike solution after gel electrophoresis was demonstrated to be an effective way of spike addition. Furthermore, effects of immersion time and (34)S spike concentration were investigated to obtain optimal conditions of the post-electrophoresis isotope dilution method. The relative mass of spike and ablated sample (m(sp)/m(sam)) in IDMS equation was calculated by standard Tf and Alb proteins, which could be applied to the quantification of Tf and Alb in ERM-DA470k/IFCC for method confirmation. The results were in agreement with the certified value with good precision and small uncertainty (1.5-3%). In this method, species-specific spike protein is not necessary and the integrity of the heteroatom-protein could be maintained in sample preparation process. Moreover, the application of species-unspecific isotope dilution GE-LA-ICP-MS has the potential to offer reliable, direct and simultaneous quantification of proteins after conventional 1D and 2D gel electrophoretic separations.

  9. 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)

  10. 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.

  11. 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

  12. 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.

  13. 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.

  14. Influence of longitudinal isotope substitution on the thermal conductivity of carbon nanotubes: Results of nonequilibrium molecular dynamics and local density functional calculations

    SciTech Connect

    Leroy, Frédéric Böhm, Michael C.; Schulte, Joachim; Balasubramanian, Ganesh

    2014-04-14

    We report reverse nonequilibrium molecular dynamics calculations of the thermal conductivity of isotope substituted (10,10) carbon nanotubes (CNTs) at 300 K. {sup 12}C and {sup 14}C isotopes both at 50% content were arranged either randomly, in bands running parallel to the main axis of the CNTs or in bands perpendicular to this axis. It is found that the systems with randomly distributed isotopes yield significantly reduced thermal conductivity. In contrast, the systems where the isotopes are organized in patterns parallel to the CNTs axis feature no reduction in thermal conductivity when compared with the pure {sup 14}C system. Moreover, a reduction of approximately 30% is observed in the system with the bands of isotopes running perpendicular to the CNT axis. The computation of phonon dispersion curves in the local density approximation and classical densities of vibrational states reveal that the phonon structure of carbon nanotubes is conserved in the isotope substituted systems with the ordered patterns, yielding high thermal conductivities in spite of the mass heterogeneity. In order to complement our conclusions on the {sup 12}C-{sup 14}C mixtures, we computed the thermal conductivity of systems where the {sup 14}C isotope was turned into pseudo-atoms of 20 and 40 atomic mass units.

  15. 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.

  16. 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

  17. Structure of molten CaSiO3: neutron diffraction isotope substitution with aerodynamic levitation and molecular dynamics study.

    PubMed

    Skinner, L B; Benmore, C J; Weber, J K R; Tumber, S; Lazareva, L; Neuefeind, J; Santodonato, L; Du, J; Parise, J B

    2012-11-15

    We have performed neutron diffraction isotopic substitution experiments on aerodynamically levitated droplets of CaSiO(3), to directly extract intermediate and local structural information on the Ca environment. The results show a substantial broadening of the first Ca-O peak in the pair distribution function of the melt compared to the glass, which comprises primarily of 6- and 7-fold coordinated Ca-polyhedra. The broadening can be explained by a redistribution of Ca-O bond lengths, especially toward longer distances in the liquid. The first order neutron difference function provides a test of recent molecular dynamics simulations and supports the MD model which contains short chains or channels of edge shared Ca-octahedra in the liquid state. It is suggested that the polymerization of Ca-polyhedra is responsible for the fragile viscosity behavior of the melt and the glass forming ability in CaSiO(3). PMID:23106223

  18. 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)

  19. Elemental analyses of soil and sediment fused with lithium borate using isotope dilution laser ablation-inductively coupled plasma-mass spectrometry.

    PubMed

    Malherbe, Julien; Claverie, Fanny; Alvarez, Aitor; Fernandez, Beatriz; Pereiro, Rosario; Molloy, John L

    2013-09-01

    Quantitative analysis using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) remains challenging primarily due to the lack of appropriate reference materials available for the wide variety of samples of interest and to elemental fractionation effects. Isotopic dilution mass spectrometry (IDMS) is becoming the methodology of choice to address these issues because the different isotopes of an element represent near-perfect internal standards. In this work, we investigated the lithium borate fusion of powdered solid samples, including soils, sediments, rock mine waste and a meteorite, as a strategy to homogenously distribute, i.e. equilibrate the elements and the added isotopically enriched standards. A comparison of this methodology using two pulsed laser ablation systems (ArF* excimer and Nd:YAG) with different wavelengths as well as two ICP-MS instruments (quadrupole and double-focusing sector field) was performed. Emphasis was put on using standard equipment to show the potential of the proposed strategy for its application in routine laboratories. Cr, Zn, Ba, Sr and Pb were successfully determined by LA-ICP-IDMS in six Standard Reference Materials (SRMs) representing different matrices of environmental interest. Experimental results showed the SRM fused glasses exhibited a low level of heterogeneity (intra- and inter-sample) for both natural abundance and isotopically enriched samples (RSD <3%, n=3, 1σ). A good agreement between experimental results and the certified values was also observed.

  20. Elemental analyses of soil and sediment fused with lithium borate using isotope dilution laser ablation-inductively coupled plasma-mass spectrometry.

    PubMed

    Malherbe, Julien; Claverie, Fanny; Alvarez, Aitor; Fernandez, Beatriz; Pereiro, Rosario; Molloy, John L

    2013-09-01

    Quantitative analysis using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) remains challenging primarily due to the lack of appropriate reference materials available for the wide variety of samples of interest and to elemental fractionation effects. Isotopic dilution mass spectrometry (IDMS) is becoming the methodology of choice to address these issues because the different isotopes of an element represent near-perfect internal standards. In this work, we investigated the lithium borate fusion of powdered solid samples, including soils, sediments, rock mine waste and a meteorite, as a strategy to homogenously distribute, i.e. equilibrate the elements and the added isotopically enriched standards. A comparison of this methodology using two pulsed laser ablation systems (ArF* excimer and Nd:YAG) with different wavelengths as well as two ICP-MS instruments (quadrupole and double-focusing sector field) was performed. Emphasis was put on using standard equipment to show the potential of the proposed strategy for its application in routine laboratories. Cr, Zn, Ba, Sr and Pb were successfully determined by LA-ICP-IDMS in six Standard Reference Materials (SRMs) representing different matrices of environmental interest. Experimental results showed the SRM fused glasses exhibited a low level of heterogeneity (intra- and inter-sample) for both natural abundance and isotopically enriched samples (RSD <3%, n=3, 1σ). A good agreement between experimental results and the certified values was also observed. PMID:23953208

  1. Isotopic studies of trans- and cis-HOCO using rotational spectroscopy: Formation, chemical bonding, and molecular structures.

    PubMed

    McCarthy, Michael C; Martinez, Oscar; McGuire, Brett A; Crabtree, Kyle N; Martin-Drumel, Marie-Aline; Stanton, John F

    2016-03-28

    HOCO is an important intermediate in combustion and atmospheric processes because the OH + CO → H + CO2 reaction represents the final step for the production of CO2 in hydrocarbon oxidation, and theoretical studies predict that this reaction proceeds via various intermediates, the most important being this radical. Isotopic investigations of trans- and cis-HOCO have been undertaken using Fourier transform microwave spectroscopy and millimeter-wave double resonance techniques in combination with a supersonic molecular beam discharge source to better understand the formation, chemical bonding, and molecular structures of this radical pair. We find that trans-HOCO can be produced almost equally well from either OH + CO or H + CO2 in our discharge source, but cis-HOCO appears to be roughly two times more abundant when starting from H + CO2. Using isotopically labelled precursors, the OH + C(18)O reaction predominately yields HOC(18)O for both isomers, but H(18)OCO is observed as well, typically at the level of 10%-20% that of HOC(18)O; the opposite propensity is found for the (18)OH + CO reaction. DO + C(18)O yields similar ratios between DOC(18)O and D(18)OCO as those found for OH + C(18)O, suggesting that some fraction of HOCO (or DOCO) may be formed from the back-reaction H + CO2, which, at the high pressure of our gas expansion, can readily occur. The large (13)C Fermi-contact term (aF) for trans- and cis-HO(13)CO implicates significant unpaired electronic density in a σ-type orbital at the carbon atom, in good agreement with theoretical predictions. By correcting the experimental rotational constants for zero-point vibration motion calculated theoretically using second-order vibrational perturbation theory, precise geometrical structures have been derived for both isomers.

  2. Isotopic studies of trans- and cis-HOCO using rotational spectroscopy: Formation, chemical bonding, and molecular structures

    NASA Astrophysics Data System (ADS)

    McCarthy, Michael C.; Martinez, Oscar; McGuire, Brett A.; Crabtree, Kyle N.; Martin-Drumel, Marie-Aline; Stanton, John F.

    2016-03-01

    HOCO is an important intermediate in combustion and atmospheric processes because the OH + CO → H + CO2 reaction represents the final step for the production of CO2 in hydrocarbon oxidation, and theoretical studies predict that this reaction proceeds via various intermediates, the most important being this radical. Isotopic investigations of trans- and cis-HOCO have been undertaken using Fourier transform microwave spectroscopy and millimeter-wave double resonance techniques in combination with a supersonic molecular beam discharge source to better understand the formation, chemical bonding, and molecular structures of this radical pair. We find that trans-HOCO can be produced almost equally well from either OH + CO or H + CO2 in our discharge source, but cis-HOCO appears to be roughly two times more abundant when starting from H + CO2. Using isotopically labelled precursors, the OH + C18O reaction predominately yields HOC18O for both isomers, but H18OCO is observed as well, typically at the level of 10%-20% that of HOC18O; the opposite propensity is found for the 18OH + CO reaction. DO + C18O yields similar ratios between DOC18O and D18OCO as those found for OH + C18O, suggesting that some fraction of HOCO (or DOCO) may be formed from the back-reaction H + CO2, which, at the high pressure of our gas expansion, can readily occur. The large 13C Fermi-contact term (aF) for trans- and cis-HO13CO implicates significant unpaired electronic density in a σ-type orbital at the carbon atom, in good agreement with theoretical predictions. By correcting the experimental rotational constants for zero-point vibration motion calculated theoretically using second-order vibrational perturbation theory, precise geometrical structures have been derived for both isomers.

  3. Lasic -Cavity-enhanced molecular iodine laser frequency stabilization for space projects

    NASA Astrophysics Data System (ADS)

    Turazza, Oscar; Acef, O.; Auger, G.; Halloin, H.; Duburck, F.; Plagnol, E.; Holleville, D.; Dimarcq, N.; Binetruy, P.; Brillet, A.; Lemonde, P.; Devismes, E.; Prat, P.; Lours, M.; Tuckey, P.; Argence, B.

    We present work in progress at SYRTE, APC and ARTEMIS aiming at stabilizing the frequency of a Nd:YAG laser using saturated absorption spectroscopy of molecular iodine 127I2. The novel design of the LASIC project allows for robustness and compacity while achieving high-performance phase noise suppression. The project is a follow-up of the laser stabilization work started at Artemis and continued at APC. The use of a low-finesse bow-tie optical cavity around the iodine absorber, combined with an adapted high-frequency modulation of the laser phase -NICE-OHMS technique-yields shot-noise limited saturated absorption signals with cavity-enhanced signal-to-noise ratios. Residual fractional frequency instability in terms of Allan Std. Deviation is expected below 10-14 @1s integration time and down to 10-15 over several hours. The compact iodine / cavity design, and performance well above LISA requirements make this project an interesting candidate for the space-based Gravitational Waves detector. We discuss the scientific background and outline of this project within the LISA framework, as well as its potential impact on other stringent technical requirements of the LISA project (e.g. U.S.O. clock-stability, arm-length measurements. . . ). We also present other possible applications for space projects involving interferometry, laser ranging or onboard ultrastable oscillators.

  4. Energy transport analysis in ultrashort pulse laser ablation through combined molecular dynamics and Monte Carlo simulation

    SciTech Connect

    Hu Wenqian; Shin, Yung C.; King, Galen

    2010-09-01

    Mechanisms of energy transport during ultrashort laser pulses (USLPs) ablation are investigated in this paper. Nonequilibrium electron-transport, material ionization, as well as density change effects, are studied using atomistic models--the molecular dynamics (MD) and Monte Carlo (MC) methods, in addition to the previously studied laser absorption, heat conduction, and stress wave propagation. The target material is treated as consisting of two subsystems: valence-electron system and lattice system. MD method is applied to analyze the motion of atoms while MC method is applied for simulating electron dynamics and multiscattering events between particles. Early-time laser-energy absorption and redistribution as well as later-time material ablation and expansion processes are analyzed. This model is validated in terms of ablation depth, lattice/electron temperature distribution as well as evolution, and plume front velocity, through comparisons with experimental or theoretical results in literature. It is generally believed that the hydrodynamic motion of the ablated material is negligible for USLP but this study shows it is true only for its effect on laser-energy deposition. This study shows that the consideration of hydrodynamic expansion and fast density change in both electron and lattice systems is important for obtaining a reliable energy transport mechanism in the locally heated zone.

  5. 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.

  6. 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.

  7. Molecular recognition using receptor-free nanomechanical infrared spectroscopy based on a quantum cascade laser

    PubMed Central

    Kim, Seonghwan; Lee, Dongkyu; Liu, Xunchen; Van Neste, Charles; Jeon, Sangmin; Thundat, Thomas

    2013-01-01

    Speciation of complex mixtures of trace explosives presents a formidable challenge for sensors that rely on chemoselective interfaces due to the unspecific nature of weak intermolecular interactions. Nanomechanical infrared (IR) spectroscopy provides higher selectivity in molecular detection without using chemoselective interfaces by measuring the photothermal effect of adsorbed molecules on a thermally sensitive microcantilever. In addition, unlike conventional IR spectroscopy, the detection sensitivity is drastically enhanced by increasing the IR laser power, since the photothermal signal comes from the absorption of IR photons and nonradiative decay processes. By using a broadly tunable quantum cascade laser for the resonant excitation of molecules, we increased the detection sensitivity by one order of magnitude compared to the use of a conventional IR monochromator. Here, we demonstrate the successful speciation and quantification of picogram levels of ternary mixtures of similar explosives (trinitrotoluene (TNT), cyclotrimethylene trinitramine (RDX), and pentaerythritol tetranitrate (PETN)) using nanomechanical IR spectroscopy. PMID:23346368

  8. The laser annealing induced phase transition in silicon: a molecular dynamics study

    NASA Astrophysics Data System (ADS)

    Marqués, Luis A.; Pelaz, Lourdes; Aboy, María.; Barbolla, Juan

    2004-02-01

    Laser thermal annealing of pre-amorphized silicon can be used to achieve sharp junctions with enhanced dopant activation. The changes in the properties of silicon as a consequence of the phase transition form amorphous to liquid caused by the laser annealing could influence the subsequent recrystallization and the activation of the dopants. In this work we have used the molecular dynamics simulation technique to study the physics of the amorphous-to-liquid transition in silicon. The changes in density, internal energy, structure and diffusion behavior are obtained from the simulations and analyzed. We have observed that for temperatures between the amorphous and crystal melting points there exists an intermediate phase which shares some of the properties of the amorphous and liquid silicon.

  9. Control of ultrafast molecular photodissociation by laser-field-induced potentials

    NASA Astrophysics Data System (ADS)

    Corrales, M. E.; González-Vázquez, J.; Balerdi, G.; Solá, I. R.; de Nalda, R.; Bañares, L.

    2014-09-01

    Experiments aimed at understanding ultrafast molecular processes are now routine, and the notion that external laser fields can constitute an additional reagent is also well established. The possibility of externally controlling a reaction with radiation increases immensely when its intensity is sufficiently high to distort the potential energy surfaces at which chemists conceptualize reactions take place. Here we explore the transition from the weak- to the strong-field regimes of laser control for the dissociation of a polyatomic molecule, methyl iodide. The control over the yield of the photodissociation reaction proceeds through the creation of a light-induced conical intersection. The control of the velocity of the product fragments requires external fields with both high intensities and short durations. This is because the mechanism by which control is exerted involves modulating the potentials around the light-induced conical intersection, that is, creating light-induced potentials.

  10. Molecular recognition using receptor-free nanomechanical infrared spectroscopy based on a quantum cascade laser.

    PubMed

    Kim, Seonghwan; Lee, Dongkyu; Liu, Xunchen; Van Neste, Charles; Jeon, Sangmin; Thundat, Thomas

    2013-01-01

    Speciation of complex mixtures of trace explosives presents a formidable challenge for sensors that rely on chemoselective interfaces due to the unspecific nature of weak intermolecular interactions. Nanomechanical infrared (IR) spectroscopy provides higher selectivity in molecular detection without using chemoselective interfaces by measuring the photothermal effect of adsorbed molecules on a thermally sensitive microcantilever. In addition, unlike conventional IR spectroscopy, the detection sensitivity is drastically enhanced by increasing the IR laser power, since the photothermal signal comes from the absorption of IR photons and nonradiative decay processes. By using a broadly tunable quantum cascade laser for the resonant excitation of molecules, we increased the detection sensitivity by one order of magnitude compared to the use of a conventional IR monochromator. Here, we demonstrate the successful speciation and quantification of picogram levels of ternary mixtures of similar explosives (trinitrotoluene (TNT), cyclotrimethylene trinitramine (RDX), and pentaerythritol tetranitrate (PETN)) using nanomechanical IR spectroscopy.

  11. Molecular recognition using receptor-free nanomechanical infrared spectroscopy based on a quantum cascade laser

    NASA Astrophysics Data System (ADS)

    Kim, Seonghwan; Lee, Dongkyu; Liu, Xunchen; van Neste, Charles; Jeon, Sangmin; Thundat, Thomas

    2013-01-01

    Speciation of complex mixtures of trace explosives presents a formidable challenge for sensors that rely on chemoselective interfaces due to the unspecific nature of weak intermolecular interactions. Nanomechanical infrared (IR) spectroscopy provides higher selectivity in molecular detection without using chemoselective interfaces by measuring the photothermal effect of adsorbed molecules on a thermally sensitive microcantilever. In addition, unlike conventional IR spectroscopy, the detection sensitivity is drastically enhanced by increasing the IR laser power, since the photothermal signal comes from the absorption of IR photons and nonradiative decay processes. By using a broadly tunable quantum cascade laser for the resonant excitation of molecules, we increased the detection sensitivity by one order of magnitude compared to the use of a conventional IR monochromator. Here, we demonstrate the successful speciation and quantification of picogram levels of ternary mixtures of similar explosives (trinitrotoluene (TNT), cyclotrimethylene trinitramine (RDX), and pentaerythritol tetranitrate (PETN)) using nanomechanical IR spectroscopy.

  12. 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

  13. 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

  14. 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

  15. Sensing signatures mediated by chemical structure of molecular solids in laser-induced plasmas.

    PubMed

    Serrano, Jorge; Moros, Javier; Laserna, J Javier

    2015-03-01

    Laser ablation of organic compounds has been investigated for almost 30 years now, either in the framework of pulse laser deposition for the assembling of new materials or in the context of chemical sensing. Various monitoring techniques such as atomic and molecular fluorescence, time-of-flight mass spectrometry, and optical emission spectroscopy have been used for plasma diagnostics in an attempt to understand the spectral signature and potential origin of gas-phase ions and fragments from organic plasmas. Photochemical and photophysical processes occurring within these systems are generally much more complex than those suggested by observation of optical emission features. Together with laser ablation parameters, the structural and chemical-physical properties of molecules seem to be closely tied to the observed phenomena. The present manuscript, for the first time, discusses the role of molecular structure in the optical emission of organic plasmas. Factors altering the electronic distribution within the organic molecule have been found to have a direct impact on its ensuing optical emissions. The electron structure of an organic molecule, resulting from the presence, nature, and position of its atoms, governs the breakage of the molecule and, as a result, determines the extent of atomization and fragmentation that has proved to directly impact the emissions of CN radicals and C2 dimers. Particular properties of the molecule respond more positively depending on the laser irradiation wavelength, thereby redirecting the ablation process through photochemical or photothermal decomposition pathways. It is of paramount significance for chemical identification purposes how, despite the large energy stored and dissipated by the plasma and the considerable number of transient species formed, the emissions observed never lose sight of the original molecule. PMID:25668318

  16. Probing ultrafast electronic and molecular dynamics with free-electron lasers

    NASA Astrophysics Data System (ADS)

    Fang, L.; Osipov, T.; Murphy, B. F.; Rudenko, A.; Rolles, D.; Petrovic, V. S.; Bostedt, C.; Bozek, J. D.; Bucksbaum, P. H.; Berrah, N.

    2014-06-01

    Molecular dynamics is an active area of research, focusing on revealing fundamental information on molecular structures and photon-molecule interaction and with broad impacts in chemical and biological sciences. Experimental investigation of molecular dynamics has been advanced by the development of new light sources and techniques, deepening our understanding of natural processes and enabling possible control and modification of chemical and biomolecular processes. Free-electron lasers (FELs) deliver unprecedented intense and short photon pulses in the vacuum ultraviolet and x-ray spectral ranges, opening a new era for the study of electronic and nuclear dynamics in molecules. This review focuses on recent molecular dynamics investigations using FELs. We present recent work concerning dynamics of molecular interaction with FELs using an intrinsic clock within a single x-ray pulse as well as using an external clock in a pump-probe scheme. We review the latest developments on correlated and coincident spectroscopy in FEL-based research and recent results revealing photo-induced interaction dynamics using these techniques. We also describe new instrumentations to conduct x-ray pump-x-ray probe experiments with spectroscopy and imaging detectors.

  17. 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.

  18. 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.

  19. 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.

  20. Efficient Calculation of Free Energy Differences Associated with Isotopic Substitution Using Path-Integral Molecular Dynamics.

    PubMed

    Marsalek, Ondrej; Chen, Pei-Yang; Dupuis, Romain; Benoit, Magali; Méheut, Merlin; Bačić, Zlatko; Tuckerman, Mark E

    2014-04-01

    The problem of computing free energy differences due to isotopic substitution in chemical systems is discussed. The shift in the equilibrium properties of a system upon isotopic substitution is a purely quantum mechanical effect that can be quantified using the Feynman path integral approach. In this paper, we explore two developments that lead to a highly efficient path integral scheme. First, we employ a mass switching function inspired by the work of Ceriotti and Markland [ J. Chem. Phys. 2013, 138, 014112] that is based on the inverse square root of the mass and which leads to a perfectly constant free energy derivative with respect to the switching parameter in the harmonic limit. We show that even for anharmonic systems, this scheme allows a single-point thermodynamic integration approach to be used in the construction of free energy differences. In order to improve the efficiency of the calculations even further, however, we derive a set of free energy derivative estimators based on the fourth-order scheme of Takahashi and Imada [ J. Phys. Soc. Jpn. 1984, 53, 3765]. The Takahashi-Imada procedure generates a primitive fourth-order estimator that allows the number of imaginary time slices in the path-integral approach to be reduced substantially. However, as with all primitive estimators, its convergence is plagued by numerical noise. In order to alleviate this problem, we derive a fourth-order virial estimator based on a transferring of the difference between second- and fourth-order primitive estimators, which remains relatively constant as a function of the number of configuration samples, to the second-order virial estimator. We show that this new estimator converges as smoothly as the second-order virial estimator but requires significantly fewer imaginary time points. PMID:26580362

  1. Development of routines for simultaneous in situ chemical composition and stable Si isotope ratio analysis by femtosecond laser ablation inductively coupled plasma mass spectrometry.

    PubMed

    Frick, Daniel A; Schuessler, Jan A; von Blanckenburg, Friedhelm

    2016-09-28

    Stable metal (e.g. Li, Mg, Ca, Fe, Cu, Zn, and Mo) and metalloid (B, Si, Ge) isotope ratio systems have emerged as geochemical tracers to fingerprint distinct physicochemical reactions. These systems are relevant to many Earth Science questions. The benefit of in situ microscale analysis using laser ablation (LA) over bulk sample analysis is to use the spatial context of different phases in the solid sample to disclose the processes that govern their chemical and isotopic compositions. However, there is a lack of in situ analytical routines to obtain a samples' stable isotope ratio together with its chemical composition. Here, we evaluate two novel analytical routines for the simultaneous determination of the chemical and Si stable isotope composition (δ(30)Si) on the micrometre scale in geological samples. In both routines, multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) is combined with femtosecond-LA, where stable isotope ratios are corrected for mass bias using standard-sample-bracketing with matrix-independent calibration. The first method is based on laser ablation split stream (LASS), where the laser aerosol is split and introduced simultaneously into both the MC-ICP-MS and a quadrupole ICP-MS. The second method is based on optical emission spectroscopy using direct observation of the MC-ICP-MS plasma (LA-MC-ICP-MS|OES). Both methods are evaluated using international geological reference materials. Accurate and precise Si isotope ratios were obtained with an uncertainty typically better than 0.23‰, 2SD, δ(30)Si. With both methods major element concentrations (e.g., Na, Al, Si, Mg, Ca) can be simultaneously determined. However, LASS-ICP-MS is superior over LA-MC-ICP-MS|OES, which is limited by its lower sensitivity. Moreover, LASS-ICP-MS offers trace element analysis down to the μg g(-1)-range for more than 28 elements due to lower limits of detection, and with typical uncertainties better than 15%. For in situ simultaneous

  2. Development of routines for simultaneous in situ chemical composition and stable Si isotope ratio analysis by femtosecond laser ablation inductively coupled plasma mass spectrometry.

    PubMed

    Frick, Daniel A; Schuessler, Jan A; von Blanckenburg, Friedhelm

    2016-09-28

    Stable metal (e.g. Li, Mg, Ca, Fe, Cu, Zn, and Mo) and metalloid (B, Si, Ge) isotope ratio systems have emerged as geochemical tracers to fingerprint distinct physicochemical reactions. These systems are relevant to many Earth Science questions. The benefit of in situ microscale analysis using laser ablation (LA) over bulk sample analysis is to use the spatial context of different phases in the solid sample to disclose the processes that govern their chemical and isotopic compositions. However, there is a lack of in situ analytical routines to obtain a samples' stable isotope ratio together with its chemical composition. Here, we evaluate two novel analytical routines for the simultaneous determination of the chemical and Si stable isotope composition (δ(30)Si) on the micrometre scale in geological samples. In both routines, multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) is combined with femtosecond-LA, where stable isotope ratios are corrected for mass bias using standard-sample-bracketing with matrix-independent calibration. The first method is based on laser ablation split stream (LASS), where the laser aerosol is split and introduced simultaneously into both the MC-ICP-MS and a quadrupole ICP-MS. The second method is based on optical emission spectroscopy using direct observation of the MC-ICP-MS plasma (LA-MC-ICP-MS|OES). Both methods are evaluated using international geological reference materials. Accurate and precise Si isotope ratios were obtained with an uncertainty typically better than 0.23‰, 2SD, δ(30)Si. With both methods major element concentrations (e.g., Na, Al, Si, Mg, Ca) can be simultaneously determined. However, LASS-ICP-MS is superior over LA-MC-ICP-MS|OES, which is limited by its lower sensitivity. Moreover, LASS-ICP-MS offers trace element analysis down to the μg g(-1)-range for more than 28 elements due to lower limits of detection, and with typical uncertainties better than 15%. For in situ simultaneous

  3. Application of laser ablation multicollector inductively coupled plasma mass spectrometry for the measurement of calcium and lead isotope ratios in packaging for discriminatory purposes.

    PubMed

    Santamaria-Fernandez, Rebeca; Wolff, Jean-Claude

    2010-07-30

    The potential of high-precision calcium and lead isotope ratio measurements using laser ablation coupled to multicollector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) to aid distinction between four genuine and five counterfeit pharmaceutical packaging samples and further classification of counterfeit packaging samples has been evaluated. We highlight the lack of reference materials for LA-MC-ICP-MS isotope ratio measurements in solids. In this case the problem is minimised by using National Institute of Standards and Technology Standard Reference Material (NIST SRM) 915a calcium carbonate (as solid pellets) and NIST SRM610 glass disc for sample bracketing external standardisation. In addition, a new reference material, NIST SRM915b calcium carbonate, has been characterised in-house for Ca isotope ratios and is used as a reference sample. Significant differences have been found between genuine and counterfeit samples; the method allows detection of counterfeits and aids further classification of packaging samples. Typical expanded uncertainties for measured-corrected Ca isotope ratio values ((43)Ca/(44)Ca and (42)Ca/(44)Ca) were found to be below 0.06% (k = 2, 95% confidence) and below 0.2% for measured-corrected Pb isotope ratios ((207)Pb/(206)Pb and (208)Pb/(206)Pb). This is the first time that Ca isotope ratios have been measured in packaging materials using LA coupled to a multicollector (MC)-ICP-MS instrument. The use of LA-MC-ICP-MS for direct measurement of Ca and Pb isotopic variations in cardboard/ink in packaging has definitive potential to aid counterfeit detection and classification. PMID:20552700

  4. Application of laser ablation multicollector inductively coupled plasma mass spectrometry for the measurement of calcium and lead isotope ratios in packaging for discriminatory purposes.

    PubMed

    Santamaria-Fernandez, Rebeca; Wolff, Jean-Claude

    2010-07-30

    The potential of high-precision calcium and lead isotope ratio measurements using laser ablation coupled to multicollector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) to aid distinction between four genuine and five counterfeit pharmaceutical packaging samples and further classification of counterfeit packaging samples has been evaluated. We highlight the lack of reference materials for LA-MC-ICP-MS isotope ratio measurements in solids. In this case the problem is minimised by using National Institute of Standards and Technology Standard Reference Material (NIST SRM) 915a calcium carbonate (as solid pellets) and NIST SRM610 glass disc for sample bracketing external standardisation. In addition, a new reference material, NIST SRM915b calcium carbonate, has been characterised in-house for Ca isotope ratios and is used as a reference sample. Significant differences have been found between genuine and counterfeit samples; the method allows detection of counterfeits and aids further classification of packaging samples. Typical expanded uncertainties for measured-corrected Ca isotope ratio values ((43)Ca/(44)Ca and (42)Ca/(44)Ca) were found to be below 0.06% (k = 2, 95% confidence) and below 0.2% for measured-corrected Pb isotope ratios ((207)Pb/(206)Pb and (208)Pb/(206)Pb). This is the first time that Ca isotope ratios have been measured in packaging materials using LA coupled to a multicollector (MC)-ICP-MS instrument. The use of LA-MC-ICP-MS for direct measurement of Ca and Pb isotopic variations in cardboard/ink in packaging has definitive potential to aid counterfeit detection and classification.

  5. [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.

  6. 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.

  7. Synthesis, characterization, and pulsed laser ablation of molecular sieves for thin film applications

    NASA Astrophysics Data System (ADS)

    Munoz, Trinidad, Jr.

    1998-12-01

    Molecular sieves are one class of crystalline low density metal oxides which are made up of one-, two-, and three dimensional pores and/or cages. We have investigated the synthesis and characterization of metal substituted aluminophosphates and all silica molecular sieves for thin film applications. A new copper substituted aluminophosphate, CuAPO-5 has been synthesized and characterized using x-ray powder diffraction, FT-IR spectroscopy and scanning electron microscopy. Electron spin resonance and electron spin echo modulation provided supporting evidence of framework incorporation of Cu(II) ions. Thus, an exciting addition has been added to the family of metal substituted aluminophosphates where substitution of the metal has been demonstrated as framework species. Also presented here is the synthesis and characterization of an iron substituted aluminophosphate, FeAPO-5, and an all silica zeolite, UTD-1 for thin film applications. Pulsed laser ablation has been employed as the technique to generate thin films. Here an excimer laser (KrFsp*, 248 nm) was used to deposit the molecular sieves on a variety of substrates including polished silicon, titanium nitride, and porous stainless steel disks. The crystallinity of the deposited films was enhanced by a post hydrothermal treatment. A vapor phase treatment of the laser deposited FeAPO-5 films has been shown to increase the crystallinity of the film without increasing film thickness. Thin films of the FeAPO-5 molecular sieves were subsequently used as the dielectric phase in capacitive type chemical sensors. The capacitance change of the FeAPO-5 devices to the relative moisture makes them potential humidity sensors. The all silica zeolite UTD-1 thin films were deposited on polished silicon and porous supports. A brief post hydrothermal treatment of the laser deposited films deposited on polished silicon and porous metal supports resulted in oriented film growth lending these films to applications in gas separations

  8. Dynamics of CO(2) laser pulse filamentation in air influenced by spectrally selective molecular absorption.

    PubMed

    Geints, Yuri E; Zemlyanov, Alexander A

    2014-09-01

    The theoretical aspects of self-focusing and filamentation of high-power pulsed CO(2) laser radiation with carrier wavelength 10.6 μm in air are considered. The spectrally selective molecular absorption of realistic atmospheric air is included in the theoretical model. In the conditions of strong pulse self-phase modulation and pulse spectral broadening, the supercontinual radiation spectrum is substantially influenced by the selective atmospheric absorption that destabilizes the filamentation process and results in considerable shortening of the filamentation length. PMID:25321358

  9. 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.

  10. Dominant deuteron acceleration with a high-intensity laser for isotope production and neutron generation

    SciTech Connect

    Maksimchuk, A.; Raymond, A.; Yu, F.; Dollar, F.; Willingale, L.; Zulick, C.; Krushelnick, K.; Petrov, G. M.; Davis, J.

    2013-05-13

    Experiments on the interaction of an ultra-short pulse laser with heavy-water, ice-covered copper targets, at an intensity of 2 Multiplication-Sign 10{sup 19} W/cm{sup 2}, were performed demonstrating the generation of a 'pure' deuteron beam with a divergence of 20 Degree-Sign , maximum energy of 8 MeV, and a total of 3 Multiplication-Sign 10{sup 11} deuterons with energy above 1 MeV-equivalent to a conversion efficiency of 1.5%{+-} 0.2%. Subsequent experiments on irradiation of a {sup 10}B sample with deuterons and neutron generation from d-d reactions in a pitcher-catcher geometry, resulted in the production of {approx}10{sup 6} atoms of the positron emitter {sup 11}C and a neutron flux of (4{+-}1) Multiplication-Sign 10{sup 5} neutrons/sterad, respectively.

  11. 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

    2016-01-01

    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. PMID:27270951

  12. 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.

  13. Laser-cooled RaF as a promising candidate to measure molecular parity violation

    NASA Astrophysics Data System (ADS)

    Isaev, T. A.; Hoekstra, S.; Berger, R.

    2010-11-01

    The parameter Wa, 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.

  14. 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.

  15. Laser spectroscopy and its applications

    SciTech Connect

    Radziemski, L.J.; Solarz, R.W.; Paisner, J.A.

    1987-01-01

    Laser spectroscopy has applications in diverse fields ranging from combustion studies and trace-sample detection to biological research. At the same time, it has also contributed greatly to the discovery of hundreds of new lasers. This symbiotic relationship has promoted an especially rapid expansion of the field. This book provides a review of the subject. It includes, for example, chapters on laser isotope separation techniques, enabling scientists to compare their relative advantages and drawbacks. This volume also gives numerous tables that summarize important features of lasers, experiments, and parameters for quick reference. In addition, it presents diagrams for visualizing rotational molecular energy levels of high J in order to enhance our understanding of molecular motions and their relationship to molecular energy levels. Offering insights into how experts think this technology will improve, it considers research and development in each topic discussed.

  16. 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.

  17. 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

  18. 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.

  19. Organic molecular and carbon isotopic records of the Japan Sea over the past 30 kyr

    NASA Astrophysics Data System (ADS)

    Ishiwatari, R.; Yamada, K.; Matsumoto, K.; Houtatsu, M.; Naraoka, H.

    1999-04-01

    The organic and isotopic geochemical study of two sediment cores (KH-79-3, L-3, and KH-79-3, C-3) from the Oki Ridge in the Japan Sea has revealed that total organic carbon (TOC) mass accumulation rates are extremely high in the 12-11 ka (calendar age) interval and TOC in the sections in the 24-17 ka interval is depleted in 13C by 3.5‰ relative to Holocene sediments. Alkenone sea surface temperature (SST) shows a decrease from 18° to 14°C from 17.5 to 11.6 ka and a sharp increase from 14° to 19°C from 11.6 to 11.1 ka. The SST changes are associated with the inflow of cold seawater with the vertical water mixing and the inflowof warm Tsushima Current into the Japan Sea. The δ13C values for both 24-methylcholesta-5,22-dien-3β-ol (diatom marker) and dinosterol (dinoflagellate marker), are at their minimum from 24 to 17 ka, while those for long-chain alkenones are not. The theoretical considerations on δ13C for biomarkers suggest low photosynthetic carbon demand of diatoms and dinoflagellates from 24 to 17 ka.

  20. Red vertical-cavity surface-emitting lasers grown by solid-source molecular beam epitaxy

    NASA Astrophysics Data System (ADS)

    Saarinen, M.; Xiang, N.; Vilokkinen, V.; Melanen, P.; Orsila, S.; Uusimaa, P.; Savolainen, P.; Toivonen, M.; Pessa, M.

    2001-07-01

    Plastic optical fibres, which have a local attenuation minimum at 650 nm, have attracted much interest for low-cost short-haul communication systems. Red vertical-cavity surface-emitting lasers (VCSELs) provide a potential solution as light sources for these systems. The operation of vertical cavity emitters is based on a Fabry-Perot microcavity, which is formed by placing an optically active region inside of two parallel mirrors. These mirrors are usually formed epitaxially. So far, metal organic chemical vapour deposition (MOCVD) has been the major technology used for growing visible VCSELs. Recently, an alternative growth method—solid-source molecular beam epitaxy (SSMBE)—has been introduced to be a viable solution to the fabrication of these structures. The authors present the first MBE-grown visible AlGaInP vertical-cavity surface-emitting lasers. A laser with a 10 μm emitting window has an external quantum efficiency of 6.65% under continuous wave operation and it is still lasing at 45°C. Furthermore, a threshold current less than 1.0 mA is obtained for a device, which has an 8 μm emitting window.

  1. 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

  2. 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.

  3. 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.

  4. ATOMIC AND MOLECULAR PHYSICS: Simulation of Chromium Atom Deposition Pattern in a Gaussain Laser Standing Wave with Different Laser Power

    NASA Astrophysics Data System (ADS)

    Zhang, Wen-Tao; Zhu, Bao-Hua

    2009-07-01

    One-dimensional deposition of a neutral chromium atomic beam focused by a near-resonant Gaussian standing-laser field is discussed by using a fourth-order Runge-Kutta type algorithm. The deposition pattern of neutral chromium atoms in a laser standing wave with different laser power is discussed and the simulation result shows that the full width at half maximum (FWHM) of a nanometer stripe is 115 nm and the contrast is 2.5:1 with laser power 3.93 mW; the FWHM is 0.8 nm and the contrast is 27:1 with laser power 16 mW, the optimal laser power; but with laser power increasing to 50 mW, the nanometer structure forms multi-crests and the quality worsens quickly with increasing laser power.

  5. 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.

  6. Specific features of propagation of femtosecond laser pulses through a molecular gaseous medium under conditions of efficient alignment of molecules

    SciTech Connect

    Gulyaev, A V; Tikhonova, O V

    2013-07-31

    The propagation of femtosecond laser pulses in a molecular gaseous medium is studied with the rotational dynamics of molecules under the action of these pulses taken into account. Based on the simultaneous numerical solution of the wave equation describing the laser pulse evolution and the Schroedinger equation that determines the quantum state evolution of the medium molecules, the rotational dynamics of molecules in the laser field and the laser pulse evolution are analysed with their mutual influence taken into account. Efficient dynamic alignment of molecules along the direction of laser radiation polarisation is observed, which causes variation in the spatiotemporal pulse profile, as well as significant broadening and deformation of its spectrum in the course of propagation through the medium. The physical mechanisms of the observed phenomena are analysed by using the approximate analytical solution of the problem, derived for the case of preliminary excitation of the medium by a pump pulse (the pump-probe scheme). (nonlinear optical phenomena)

  7. 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.

  8. Improving Precision and Accuracy of Isotope Ratios from Short Transient Laser Ablation-Multicollector-Inductively Coupled Plasma Mass Spectrometry Signals: Application to Micrometer-Size Uranium Particles.

    PubMed

    Claverie, Fanny; Hubert, Amélie; Berail, Sylvain; Donard, Ariane; Pointurier, Fabien; Pécheyran, Christophe

    2016-04-19

    The isotope drift encountered on short transient signals measured by multicollector inductively coupled plasma mass spectrometry (MC-ICPMS) is related to differences in detector time responses. Faraday to Faraday and Faraday to ion counter time lags were determined and corrected using VBA data processing based on the synchronization of the isotope signals. The coefficient of determination of the linear fit between the two isotopes was selected as the best criterion to obtain accurate detector time lag. The procedure was applied to the analysis by laser ablation-MC-ICPMS of micrometer sized uranium particles (1-3.5 μm). Linear regression slope (LRS) (one isotope plotted over the other), point-by-point, and integration methods were tested to calculate the (235)U/(238)U and (234)U/(238)U ratios. Relative internal precisions of 0.86 to 1.7% and 1.2 to 2.4% were obtained for (235)U/(238)U and (234)U/(238)U, respectively, using LRS calculation, time lag, and mass bias corrections. A relative external precision of 2.1% was obtained for (235)U/(238)U ratios with good accuracy (relative difference with respect to the reference value below 1%). PMID:27031645

  9. XAS molecular-level speciation and isotopes to assess the biogeochemistry of trace elements in soils and sediments : Few examples on Zn

    NASA Astrophysics Data System (ADS)

    Juillot, F.; Marechal-Chenevier, C.; Noël, V. S.; Morin, G.; Cacaly, S.; Louvat, P.; Telouk, P.; Hazemann, J.; Proux, O.; gelabert, A.; Jouvin, D.; Voegelin, A.; Mueller, B.; Brown, G. E.

    2011-12-01

    Since the mid of the 90's, multi-Collector Inductively-Coupled-Plasma Mass Spectrometry (MC-ICP-MS) offers the possibility of measuring the relative proportions of isotopes for a broad range of environmentally relevant elements labelled as ''non traditional isotopes'' (Cr, Fe, Ni, Cu, Zn, Se, Hg,...). These recent analytical possibilities have already been used in a large set of studies in Earth and Environmental Sciences to depict the biogeochemical behavior of these elements (Johnson et al., 2004; Weiss et al., 2008). However, establishing the link between the isotopes signature of a given element in a given system at a given time and its biogeochemical history (sources and pathways) is not always straightforward and complementary information on the actual speciation of this element can reveal very useful to address this issue. Since the end of the 80's, synchrotron-based X-Ray Absorption Spectroscopy has revealed as one of the most efficient way to directly assess the molecular-level speciation of an element in a natural system (Brown and Sturchio, 2002). Although this technique has been restricted to heavily polluted systems at the beginning because of its low detection limit, third- and fourth-generation synchrotron facilities now offer the possibility of obtaining this kind of information on very dilute systems, which makes it useful for almost all natural systems. The aim of this presentation will be to show how combining isotopes and molecular-level XAS speciation in natural and laboratory systems can reveal really powerful to help at understanding how isotopes fractionate in nature and, in turn, how these isotopes can be used to improve our understanding of the biogeochemical behavior of trace elements in continental systems (soils and sediments). Examples presented will concern Zn because this trace element is the most frequently encountered in soils and sediments and because it can act as a nutrient or as a poison, depending on its concentration.

  10. 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

  11. The 14C-Cluster and Molecular bands in the Oxygen Isotopes 18,20O

    NASA Astrophysics Data System (ADS)

    von Oertzen, W.; Dorsch, T.; Bohlen, H. G.

    2009-08-01

    We have studied states in 18O and 20O with the (7Li,p) reaction on 12C and 14C targets at Elab(7Li) = 44 MeV, using the high resolution Q3D magnetic spectrometer at the Maier-Leibnitz-Laboratory in Munich. The systematics of the excitation energies and cross sections were used to construct rotational bands with high moments of inertia. The bands observed are discussed in terms of underlying (14C⊗4He)-cluster structure for 18O, and for 20O the cluster structures are (14C⊗6He) and (14C⊗2n⊗α). The intrinsically reflection asymmetric shapes give rise to molecular bands, which appear as parity inversion doublets.

  12. 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.

  13. Molecular distributions and compound-specific stable carbon isotopic compositions of lipids in wintertime aerosols from Beijing

    NASA Astrophysics Data System (ADS)

    Ren, Lujie; Fu, Pingqing; He, Yue; Hou, Juzhi; Chen, Jing; Pavuluri, Chandra Mouli; Sun, Yele; Wang, Zifa

    2016-06-01

    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.

  14. 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

  15. 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

  16. Hydrogen tunneling in adenosylcobalamin-dependent glutamate mutase: evidence from intrinsic kinetic isotope effects measured by intra-molecular competition †

    PubMed Central

    Yoon, Miri; Song, Hangtian; Håkansson, Kristina; Marsh, E. Neil G.

    2010-01-01

    Hydrogen atom transfer reactions between substrate and coenzyme are a key mechanistic feature of all AdoCbl-dependent enzymes. For one of these enzymes, glutamate mutase, we have investigated whether hydrogen tunneling makes a significant contribution to the mechanism by examining the temperature-dependence of the deuterium kinetic isotope effect associated with hydrogen atom transfer from methylaspartate to the coenzyme. To do this we designed a novel intra-molecular competition experiment that allowed us to measure the intrinsic kinetic isotope effect, even though hydrogen transfer may not be rate determining. From the Arrhenius plot of the kinetic isotope effect, the ratio of the pre-exponential factors AH/AD was 0.17 ± 0.04 and the isotope effect on the activation energy, ΔEa(D – H) was 1.94 ± 0.13 kcal/mol. The results imply that significant degree of hydrogen tunneling occurs in glutamate mutase, even though the intrinsic kinetic isotope effects are well within the semi-classical limit and are much smaller than those measured for other AdoCbl enzymes and model reactions for which hydrogen tunneling has been implicated. PMID:20225826

  17. Source characterization of sedimentary organic matter using molecular and stable carbon isotopic composition of n-alkanes and fatty acids in sediment core from Lake Dianchi, China.

    PubMed

    Fang, Jidun; Wu, Fengchang; Xiong, Yongqiang; Li, Fasheng; Du, Xiaoming; An, Da; Wang, Lifang

    2014-03-01

    The distribution and compound-specific carbon isotope ratios of n-alkanes and fatty acids in a sediment core (63 cm) collected from Lake Dianchi were examined to investigate organic matter sources in the eutrophic lake. Fatty acids included free and bound fatty acids. The carbon isotope compositions of individual n-alkanes and fatty acids from Lake Dianchi sediments were determined using gas chromatography/isotope ratio mass spectrometry (GC-IRMS). The δ(13)C values of individual n-alkanes (C16-C31) varied between -24.1‰ and -35.6‰, suggesting a dominance of (13)C-depleted n-alkanes that originated from C3 plants and lacustrine algae. Fatty acids from the sediment extracts were analyzed for their abundances and carbon isotopic compositions. Molecular and isotopic evidence indicates that most of the short-chain fatty acids from Lake Dianchi sediment extracts are sourced from intense microbial recycling and resynthesis of organic matter. Long-chain free fatty acids are mainly derived from terrestrial sources. However, long-chain bound fatty acids are sourced from a combination of terrestrial organic matter, bacteria and algae, with the contribution from algal sources higher in the hypereutrophic stage.

  18. Free-electron lasers: new avenues in molecular physics and photochemistry.

    PubMed

    Ullrich, Joachim; Rudenko, Artem; Moshammer, Robert

    2012-01-01

    Free-electron lasers are fourth-generation light sources that deliver extremely intense (>10(12) photons per pulse), ultrashort (∼10(-14) s = 10 fs) light pulses at up to kilohertz repetition rates with unprecedented coherence properties and span a broad wavelength regime from soft (∼10 eV) to hard X-ray energies (∼15 keV). They thus enable a whole suite of novel experiments in molecular physics and chemistry: Inspecting radiation-induced reactions in cold molecular ions provides unprecedented insight into the photochemistry of interstellar clouds and upper planetary atmospheres; double core-hole photoelectron spectroscopy offers enhanced sensitivity for chemical analysis; the dynamics of highly excited molecular states, pumped by vacuum ultraviolet pulses, can be inspected; and vacuum ultraviolet or X-ray probe pulses generally hold the promise to trace chemical reactions along an entire reaction coordinate with atomic spatial and temporal resolution. This review intends to provide a first overview on upcoming possibilities, emerging technologies, pioneering results, and future perspectives in this exciting field.

  19. 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.

  20. Photochemical isotope separation

    DOEpatents

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

    1987-04-28

    A process is described 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. 8 figs.

  1. Laser-induced fluorescence method for on-line molecular isotopologues of iodine-127, iodine-129, iodine-131 detected in gaseous media using a tunable diode laser

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

    The letter reports on the development of a laser-induced fluorescence method for on-line selective measurement of 127I2, 129I2, 131I2, 129I127I, 127I131I, 129I131I isotopologue concentrations in gaseous media. The method is based on the excitation of molecular iodine isotopologues’ fluorescence by tunable diode laser (632–637 nm) radiation at three or four wavelengths corresponding to the 127I2, 131I2, 129I127I, 129I131I absorption line centers. Boundary relations for concentrations of simultaneously measured iodine isotopologues is about 10‑5–10‑6.

  2. Freezing of molecular hydrogen and its isotopes in porous Vycor glass

    SciTech Connect

    Beaudoin, G.; Haljan, P.; Paetkau, M.; Beamish, J.R.

    1996-10-01

    The authors have made a detailed ultrasonic study of freezing and melting of molecular H{sub 2}, HD and D{sub 2} in the pores of Vycor glass. The behavior was similar to that seen in previous measurements with argon and helium. The hydrogen liquids undercooled about 2.5 K below their bulk triple points before freezing began and there was substantial hysteresis between freezing and melting. The velocity and attenuation began to increase suddenly at the onset of freezing. The velocity continued to increase to the lowest temperatures (2K) and the attenuation had a broad peak at about two thirds of the freezing temperature. The authors attribute these effects to stress relaxation via thermally activated vacancy motion in the solid hydrogen, an interpretation confirmed by looking at the frequency dependence of the velocity and attenuation. The magnitude of the velocity and attenuation changes increased in going from H{sub 2} to HD to D{sub 2}, as expected based on their increasing densities and elastic constants. However, there were no qualitative differences between the boson (H{sub 2} and D{sub 2}) and fermion (HD) cases nor, for that matter, between hydrogen and argon. The authors believe that essentially all the hydrogen was frozen a few tenths of a kelvin below T{sub F}, at the point where the melting;freezing hysteresis began. If even a few per cent of the hydrogen had remained liquid and become superfluid at some lower temperature, it would have been seen as a further increase in the velocity and a critical attenuation peak. The sensitivity of the ultrasonic measurements allowed the authors to make accurate measurements of the freezing and melting temperatures of the different liquids in Vycor. They found that the fractional undercooling, (T{sub B} {minus} T{sub F})/T{sub B}, increased as the molecular mass decreased which may indicate the importance of quantum effects on the liquid-solid interfacial energy {sigma}{sub Is}.

  3. 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.

  4. 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.

  5. 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.

  6. Surface 3D nanostructuring by tightly focused laser pulse: simulations by Lagrangian code and molecular dynamics

    NASA Astrophysics Data System (ADS)

    Inogamov, Nail A.; Zhakhovsky, Vasily V.

    2016-02-01

    There are many important applications in which the ultrashort diffraction-limited and therefore tightly focused laser pulses irradiates metal films mounted on dielectric substrate. Here we present the detailed picture of laser peeling and 3D structure formation of the thin (relative to a depth of a heat affected zone in the bulk targets) gold films on glass substrate. The underlying physics of such diffraction-limited laser peeling was not well understood previously. Our approach is based on a physical model which takes into consideration the new calculations of the two-temperature (2T) equation of state (2T EoS) and the two-temperature transport coefficients together with the coupling parameter between electron and ion subsystems. The usage of the 2T EoS and the kinetic coefficients is required because absorption of an ultrashort pulse with duration of 10-1000 fs excites electron subsystem of metal and transfers substance into the 2T state with hot electrons (typical electron temperatures 1-3 eV) and much colder ions. It is shown that formation of submicrometer-sized 3D structures is a result of the electron-ion energy transfer, melting, and delamination of film from substrate under combined action of electron and ion pressures, capillary deceleration of the delaminated liquid metal or semiconductor, and ultrafast freezing of molten material. We found that the freezing is going in non-equilibrium regime with strongly overcooled liquid phase. In this case the Stefan approximation is non-applicable because the solidification front speed is limited by the diffusion rate of atoms in the molten material. To solve the problem we have developed the 2T Lagrangian code including all this reach physics in. We also used the high-performance combined Monte- Carlo and molecular dynamics code for simulation of surface 3D nanostructuring at later times after completion of electron-ion relaxation.

  7. 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.

  8. 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.

  9. 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.

  10. State selective laser photofragment spectroscopy of OH in the MPD of CH 3OH in a molecular beam

    NASA Astrophysics Data System (ADS)

    Schmiedl, R.; Meier, U.; Welge, K. H.

    1981-06-01

    The internal and recoil energy of OH from the IR MPD ofCH 30H has been investigated under molecular-beam conditions by laser-induced fluorescence. The recoil energy has been obtained by Doppler spectroscopy. A Boltzmann-type distribution is found for rotation in v' = 0 and translation with temperatures Trot = (630 ± 60) and Tkin = (400 ± 20) K.

  11. Nonadiabatic dynamics and multiphoton resonances in strong-field molecular ionization with few-cycle laser pulses

    NASA Astrophysics Data System (ADS)

    Tagliamonti, Vincent; Sándor, Péter; Zhao, Arthur; Rozgonyi, Tamás; Marquetand, Philipp; Weinacht, Thomas

    2016-05-01

    We study strong-field molecular ionization using few- (four to ten) cycle laser pulses. Employing a supercontinuum light source, we are able to tune the optical laser wavelength (photon energy) over a range of ˜200 nm (500 meV). We measure the photoelectron spectrum for a series of different molecules as a function of laser intensity, frequency, and bandwidth and illustrate how the ionization dynamics vary with these parameters. We find that multiphoton resonances and nonadiabatic dynamics (internal conversion) play an important role and result in ionization to different ionic continua. Interestingly, while nuclear dynamics can be "frozen" for sufficiently short laser pulses, we find that resonances strongly influence the photoelectron spectrum and final cationic state of the molecule regardless of pulse duration—even for pulses that are less than four cycles in duration.

  12. Molecular and isotopic investigation of eroding reliefs of the East Siberian Arctic Coastal-Ice complex

    NASA Astrophysics Data System (ADS)

    Sánchez-García, L.; Vonk, J.; Alling, V.; Pugach, S.; van Dongen, B.; Charkin, A.; Kosmach, D.; Dudarev, O.; Semiletov, I.; Gustafsson, Ö.

    2010-05-01

    parameters (salinity, turbidity, aromatic moieties, DOC, humic substances). The ratio of high-molecular weight (HMW) n-alkanoic acids over n-alkanes showed lower values for the older soil samples collected from the lower reliefs of Muostakh. This, together with larger CO2 fluxes and higher abundance of short-chain n-alkanes (C27 ), illustrate the higher extent of degradation at the low part of the island. The higher exposure of the low reliefs to wave impact and coastal erosion facilitates the OC remobilization and makes it potentially available for biodegradation. Once in the water column, larger contents of POC and aromatic moietieswere observed close to land, showing a rapid decrease with distance from the coast. The coupling between both parameters suggesting similar terrestrial sources related with coastal erosion. The higher POC values observed in erosion affected sites, in contrast to higher DOC values derived from river origin, make the POC/DOC ratio a useful tool to distinguish between river (ratios < 0.2) and coastal erosion sources (ratios ≥ 0.2). The highest POC/DOC ratios (up to 0.5) and largest content of aromatic moieties were measured nearby Muostakh, manifesting the intensity of erosion affecting the island. References [1] NOAA (National Oceanic and Atmospheric Administration), 2006. State of the Arctic Report. [2] Guo, L. and MacDonald, R.W., 2006. Global Biogeochem. Cycles 20, GB2011, doi:10.1029/2005GB002593. [3] Stein, R. and MacDonald, R.W., 2004. The organic carbon cycle in the Arctic Ocean 363 pp, Springer, Berlin.

  13. Comment on "Molecular controls on Cu and Zn isotopic fractionation in Fe-Mn crusts" by Little et al.

    NASA Astrophysics Data System (ADS)

    Manceau, Alain; Nagy, Kathryn L.

    2015-02-01

    Isotopic fractionation of metals between seawater and ferromanganese deposits in marine sediments is determined at equilibrium at least in part by the strength of the chemical bonding of the metals in the two environments. A generally accepted rule is that heavy isotopes are concentrated in constituents that form the stiffest bonds with these elements, where greater stiffness empirically corresponds to shorter and stronger bonds, as is the case for lower coordination numbers (Schauble, 2004). Correlatively, light isotopes are depleted. Fe-Mn oxides are enriched in heavy Zn isotope (66Zn) compared to seawater (at ∼ 1.0 ‰ vs. ∼ 0.5 ‰) and also in light Cu isotope (63Cu, at ∼ 0.4 ‰ vs. 0.9‰) (Albarède, 2004; Little et al., 2014a; Maréchal et al., 2000), which suggests that the two elements may be coordinated differently in the Zn- and Cu-bearing oxide phases.

  14. Raman analysis of SF 6 molecular beams excited by a cw CO 2 laser

    NASA Astrophysics Data System (ADS)

    Luijks, G.; Timmerman, J.; Stolte, S.; Reuss, J.

    1983-06-01

    In a molecular beam the effects of vibrational pumping of SF 6 (ν 3 = 948 cm -1) are studied, using a line-tunable cw CO 2 laser. Intracavity spontaneous Raman scattering is used for analysis. For excitation in the collision regime ( xE/ D ≤ 1), a thermal redistribution of the ν 3 excitation over all vibrational modes is found, together with an average absorption up to six photons per molecule. The infrared absorption profile shows a red-shift of 6 cm -1. For excitation in the relatively rare collision regime ( xE/ D ⩾ 4), a structured non-thermal ν 1 Raman spectrum is observed, especially in the case of seeded molecular beams (10% in He). The observed hot-band peaks can be explained in terms of single-photon absorptions and collision-induced near-resonant V-V energy transfer, leading to single, double and triple excitations of the ν 3 mode. The value of Trot in the beam is found to influence sensitively the non-resonant energy-transfer rate [e.g. hν 3(948 cm -1)+Δ Erot → h(ν 4 + ν 6)(962 cm -1) relative to the near-resonant transfer rate ( hν 3 + hν 3 → 2 hν 3 + 3.5 cm -1)].

  15. Quantum control of molecular orientation by two-color laser fields.

    PubMed

    Ohmura, Hideki; Nakanaga, Taisuke

    2004-03-15

    We demonstrate molecular orientation by using phase-controlled two-color omega+2omega laser pulses with an intensity of 1.0x10(12) W/cm(2) and a pulse duration of 130 fs. The orientation of three iodine-containing molecules (IBr, CH(3)I, and C(3)H(5)I) was monitored by the directional asymmetries of the photofragment angular distribution in dissociative ionization. In all three molecules, the directional asymmetry showed an oscillating behavior dependent on the relative phase difference between omega and 2omega pulses. The phase dependence of the directional asymmetry observed in iodine ions and counterpart ions were out of phase with each other. This result shows that a phase-controlled omega+2omega optical field discriminates between parallel and antiparallel configurations of aligned molecules that have a permanent dipole. This method performed well because (1) molecular orientation can be achieved by all-optical fields; (2) the direction of orientation is easily switched by changing the sign of the quantum interference; and (3) this method is free from any resonance constraint and thus can be applied to any molecule.

  16. 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.

  17. Inverse relation between summer and winter monsoon strength during late Holocene: continental molecular isotopic record from the Indian subcontinent

    NASA Astrophysics Data System (ADS)

    Sanyal, P.; Basu, S.; Pillai, A.; Singh, P.; Ratnam, J.; Sankaran, M.; Amibili, A.

    2015-12-01

    The Indian monsoon shapes the livelihood of ca. 40% of world's population. Despite dedicated efforts, comprehensive picture of monsoon variability has proved elusive largely due to the absence of long-term qualitative high-resolution record from key climatic zones and variability of monsoon with respect to various forcing mechanisms (e.g., solar insolation) and teleconnections (e.g., El Niño-Southern Oscillation, Indian Ocean Dipole). In this study, high-resolution molecular (n-alkane) isotopic (δD and δ13C ratios) reconstruction of mid-late Holocene (~5.0 cal ka) climate has been undertaken using lacustrine sediments from two climatically sensitive regions; (i) Arid Banni grasslands, western India with dominant moisture source derived from Indian summer monsoon (June-September) and (ii) Semi-arid Ennamangalam lake, south India with significant fraction of rainfall received during winter period (October to December) from Northeast (NE) monsoon. The climate reconstruction from western India based on δDn-alkane values shows prevalence of intensified monsoon until ca. 3 cal ka followed by gradual decrease in the precipitation. In contrast, climate reconstruction from south India is characterized by more negative δDn-alkane (intensified precipitation) values during late Holocene (~2.5 cal ka). The compilation of paleoclimate records shows that the precipitation pattern in Banni region responded linearly to gradually changing insolation and additionally amplified by climate systems like ENSO. However, intensified monsoon in South India shows strengthened NE monsoonal precipitation during late Holocene. The spatial inhomogeneity in the palaeohydrological record can be attributed to the persistence of inverse relationship between summer and winter monsoon. In addition, strong positive correlation between δDn-alkane and δ13Cn-alkane values from both region shows that the relative abundance of C3-C4 plants in the contemporary ecosystems are governed by rainfall

  18. 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.

  19. Comparison between experiments and molecular dynamic simulations of spallation induced by ultra-short laser shock on micrometric Tantalum targets

    NASA Astrophysics Data System (ADS)

    Cuq-Lelandais, Jean-Paul; Boustie, Michel; Soulard, Laurent; Berthe, Laurent; Sollier, Arnaud; Bontaz-Carion, Joelle; Combis, Patrick; de Resseguier, Thibaut; Lescoute, Emilien

    2009-06-01

    Shock wave propagation and the spallation within materials induced by laser shock have been investigated for roughly two decades. With the latest laser technologies evolution, one can access to shorter regimes in durations, going below the picosecond range. Shots performed with the LULI 100TW facility evidence the possibility to obtain spallation in a few microns thick metallic target. Such conditions provide an experimental data layout directly comparable with molecular dynamic simulations accessible to these scales. Molecular dynamic simulations on a single crystal of Tantalum have been performed with the CEA TERA 10 computer. First, the Hugoniot calculated by the equilibrium molecular dynamics has been compared with experimental data to check the potential (EAM) relevance to reproduce the shock wave propagation. Then, a large scale simulation on a micrometric target has been performed. We have observed the microscopic ductile damage process, the pore apparition and their time and space evolution. The results are compared with experimental results and classical one- dimensional hydrodynamic simulations.

  20. Explosion, ion acceleration, and molecular fragmentation of methane clusters in the pulsed beam of a free-electron laser

    NASA Astrophysics Data System (ADS)

    Iwan, B.; Andreasson, J.; Bergh, M.; Schorb, S.; Thomas, H.; Rupp, D.; Gorkhover, T.; Adolph, M.; Möller, T.; Bostedt, C.; Hajdu, J.; Tîmneanu, N.

    2012-09-01

    X-ray lasers offer new possibilities for creating and probing extreme states of matter. We used intense and short x-ray pulses from the FLASH soft x-ray laser to trigger the explosions of CH4 and CD4 molecules and their clusters. The results show that the explosion dynamics depends on cluster size and indicate a transition from Coulomb explosion to hydrodynamic expansion in larger clusters. The explosion of CH4 and CD4 clusters shows a strong isotope effect: The heavier deuterons acquire higher kinetic energies than the lighter protons. This may be due to an extended inertial confinement of deuterons vs. protons near a rapidly charging cluster core during exposure.

  1. 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.

  2. 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

  3. Charge-radius change and nuclear moments in the heavy tin isotopes from laser spectroscopy: Charge radius of {sup 132}Sn

    SciTech Connect

    Le Blanc, F.; Cottereau, E.; Essabaa, S.; Obert, J.; Oms, J.; Ouchrif, A.; Roussiere, B.; Sauvage, J.; Verney, D.; Cabaret, L.; Pinard, J.; Crawford, J.E.; Lee, J.K.P.; Genevey, J.; Le Scornet, G.; Lettry, J.; Ravn, H.

    2005-09-01

    Laser spectroscopy measurements have been carried out on the neutron-rich tin isotopes with the COMPLIS experimental setup. Using the 5s{sup 2}5p{sup 23}P{sub 0}{yields}5s{sup 2}5p6s {sup 3}P{sub 1} optical transition, hyperfine spectra of {sup 126-132}Sn and {sup 125,127,129-131}Sn{sup m} were recorded for the first time. The nuclear moments and the mean square charge radius variation ({delta}) were extracted. From the quadrupole moment values, these nuclei appear to be spherical. The magnetic moments measured are thus compared with those predicted by spherical basis approaches. From the measured {delta}, the absolute charge radii of these isotopes were deduced in particular that of the doubly magic {sup 132}Sn nucleus. The comparison of the results with several mean-field-type calculations have shown that dynamical effects play an important role in the tin isotopes.

  4. 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. PMID:27382971

  5. 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.

  6. Application of nanosecond-UV laser ablation-inductively coupled plasma mass spectrometry for the isotopic analysis of single submicrometer-size uranium particles.

    PubMed

    Pointurier, Fabien; Pottin, Anne-Claire; Hubert, Amélie

    2011-10-15

    For the first time, laser ablation-inductively coupled plasma mass spectrometry (LA-ICPMS) was used to carry out isotopic measurement on single submicrometer-size uranium particles. The analytical procedure was applied on two particle-containing samples already analyzed in the same laboratory by established techniques for particle analysis: combination of the fission track technique with thermo-ionization mass spectrometry (FT-TIMS) and secondary ion mass spectrometry (SIMS). Particles were extracted from their initial matrix with ethanol and deposited on a polycarbonate disk where they were fixed in a layer of an organic compound (collodion). Prior to the isotopic analysis, particles were precisely located on the disk's surface by scanning electron microscopy (SEM) for one sample and using the fission track technique for the other sample. Most of the particles were smaller than 1 μm, and their (235)U content was in the femtogram range. (235)U/(238)U ratios were successfully analyzed for all located particles using a nanosecond-UV laser (Cetac LSX 213 nm) coupled to a quadrupole-based ICPMS (Thermo "X-Series II"). LA-ICPMS results, although less precise and accurate (typically 10%) than the ones obtained by FT-TIMS and SIMS due to short (20-40 s), transient, and noisy signals, are in good agreement with the certified values or with the results obtained with other techniques. Thanks to good measurement efficiency (~6 × 10(-4)) and high signal/noise ratio during the analysis, LA-ICPMS can be considered a very promising technique for fast particle analysis, provided that uranium-bearing particles are fixed on the sample holder and located prior to isotope measurement. PMID:21875035

  7. Multiple spiking species-specific isotope dilution analysis by molecular mass spectrometry: simultaneous determination of inorganic mercury and methylmercury in fish tissues.

    PubMed

    Castillo, Angel; Rodríguez-González, Pablo; Centineo, Giuseppe; Roig-Navarro, Antoni Francesc; García Alonso, J Ignacio

    2010-04-01

    This work demonstrates, for the first time, the applicability of multiple spiking isotope dilution analysis to molecular mass spectrometry exemplified by the speciation analysis of mercury using GC(EI)MS instrumentation. A double spike isotope dilution approach using isotopically enriched mercury isotopes has been applied for the determination of inorganic mercury Hg(II) and methylmercury (MeHg) in fish reference materials. The method is based on the application of isotope pattern deconvolution for the simultaneous determination of degradation-corrected concentrations of methylmercury and inorganic mercury. Mass isotopomer distributions are employed instead of isotope ratios to calculate the corrected concentrations of the Hg species as well as the extent of species degradation reactions. The isotope pattern deconvolution equations developed here allow the calculation of the different molar fractions directly from the GC(EI)MS mass isotopomer distribution pattern and take into account possible impurities present in the spike solutions employed. The procedure has been successfully validated with the analysis of two different certified reference materials (BCR-464 and DOLT-4) and with the comparison of the results obtained by GC(ICP)MS. For the tuna fish matrix (BCR-464), no interconversion reactions were observed at the optimized conditions of open focused microwave extraction at 70 degrees C during 8 min. However, significant demethylation was found under the same conditions in the case of the certified dogfish liver DOLT-4. Methylation and demethylation factors were confirmed by GC(ICP)MS. Transformation reactions have been found to depend on the sample matrix and on the derivatization reagent employed. Thus, it is not possible to recommend optimum extraction conditions suitable for all types of matrices demonstrating the need to apply multiple spiking methodologies for the determination of MeHg and Hg(II) in biological samples. Double spike isotope dilution

  8. Multiple spiking species-specific isotope dilution analysis by molecular mass spectrometry: simultaneous determination of inorganic mercury and methylmercury in fish tissues.

    PubMed

    Castillo, Angel; Rodríguez-González, Pablo; Centineo, Giuseppe; Roig-Navarro, Antoni Francesc; García Alonso, J Ignacio

    2010-04-01

    This work demonstrates, for the first time, the applicability of multiple spiking isotope dilution analysis to molecular mass spectrometry exemplified by the speciation analysis of mercury using GC(EI)MS instrumentation. A double spike isotope dilution approach using isotopically enriched mercury isotopes has been applied for the determination of inorganic mercury Hg(II) and methylmercury (MeHg) in fish reference materials. The method is based on the application of isotope pattern deconvolution for the simultaneous determination of degradation-corrected concentrations of methylmercury and inorganic mercury. Mass isotopomer distributions are employed instead of isotope ratios to calculate the corrected concentrations of the Hg species as well as the extent of species degradation reactions. The isotope pattern deconvolution equations developed here allow the calculation of the different molar fractions directly from the GC(EI)MS mass isotopomer distribution pattern and take into account possible impurities present in the spike solutions employed. The procedure has been successfully validated with the analysis of two different certified reference materials (BCR-464 and DOLT-4) and with the comparison of the results obtained by GC(ICP)MS. For the tuna fish matrix (BCR-464), no interconversion reactions were observed at the optimized conditions of open focused microwave extraction at 70 degrees C during 8 min. However, significant demethylation was found under the same conditions in the case of the certified dogfish liver DOLT-4. Methylation and demethylation factors were confirmed by GC(ICP)MS. Transformation reactions have been found to depend on the sample matrix and on the derivatization reagent employed. Thus, it is not possible to recommend optimum extraction conditions suitable for all types of matrices demonstrating the need to apply multiple spiking methodologies for the determination of MeHg and Hg(II) in biological samples. Double spike isotope dilution

  9. 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

  10. Molecular and isotopic composition of hydrate-bound and dissolved gases in the southern basin of Lake Baikal, based on an improved headspace gas method

    NASA Astrophysics Data System (ADS)

    Sakagami, Hirotoshi; Takahashi, Nobuo; Hachikubo, Akihiro; Minami, Hirotsugu; Yamashita, Satoshi; Shoji, Hitoshi; Khlystov, Oleg; Kalmychkov, Gennadiy; Grachev, Mikhail; De Batist, Marc

    2012-12-01

    Assessments of the molecular and isotopic composition of hydrate-bound and dissolved gases in pore water were conducted during the multi-phase gas hydrate project (MHP-09) cruise VER09-03 to the southern basin of Lake Baikal in September 2009. To avoid changes in gas composition during core sampling and transport, various headspace methods were investigated aimed at preserving the dissolved gases in pore water. When distilled water was added to the sediment samples, the concentrations of carbon dioxide and oxygen decreased because of dissolution into the water and/or microbial consumption. When the headspace was not flushed with inert gases, trace levels of hydrogen and ethylene were detected. The findings suggest that best preparation is achieved by flushing the headspace with helium, and adding a saturated aqueous solution of sodium chloride. This improved headspace method served to examine the molecular and isotopic compositions of gas samples retrieved at several new sites in the southern basin. Methane was the major component, and the proportion of ethane ranged widely from 0.0009 to 1.67 mol% of the total hydrocarbon gases. The proportions of propane and higher hydrocarbons were small or less than their detection limits. The carbon isotope signatures suggest that microbial-sourced methane and ethane were dominant in the Peschanka study area, whereas ethane was of thermogenic origin at all other study sites in the southern basin of Lake Baikal.

  11. Efficient removal of foxing from a medieval Ptolemaic map using a molecular fluorine laser at 157 nm

    NASA Astrophysics Data System (ADS)

    Cefalas, A. C.; Sarantopoulou, E.; Kollia, Z.

    In this communication, we have used a molecular fluorine laser at 157 nm to remove foxing marks, for the first time, from a medieval Ptolemaic map published in 1580 AD. By applying laser-ablation experimental techniques, the absorption coefficient and the threshold-energy fluence of the paper manuscript were determined . The absorption coefficient at 157 nm was found to be one order of magnitude higher than at 248 nm. There was no evidence of oxidising of the paper substrate following laser treatment of foxing areas at 157 nm (yellowish colour). In order to investigate the basic photo-chemical mechanism of the photo-dissociation dynamics of the paper's cellulose fibres under vacuum ultraviolet irradiation, we applied mass-spectroscopic techniques. Mass spectroscopy reveals that there is breaking of the molecular bonds of the cellulose, even at low laser energy at 157 nm. The cellulose monomer is disintegrated into small photo-fragments, which fly apart with supersonic speed. There were no photo-fragments observed for m/e higher than 32 amu (atomic mass units of m/e). Fragments with two carbon atoms have a relatively higher probability to be dissociated from the parent cellulose molecule than heavier ones. These experimental findings suggest that the bound potential excited electronic states of the parent molecule correlate with dissociative excited electronic states of the molecular photo-fragments at 7.8 eV (λ=157 nm), in agreement with previous results for various organic polymers of similar chemical structure.

  12. Isotope Exchange in Oxide Catalyst

    NASA Technical Reports Server (NTRS)

    Hess, Robert V.; Miller, Irvin M.; Schryer, David R.; Sidney, Barry D.; Wood, George M., Jr.; Hoyt, Ronald F.; Upchurch, Billy T.; Brown, Kenneth G.

    1987-01-01

    Replacement technique maintains level of CO2/18 in closed-cycle CO2 lasers. High-energy, pulsed CO2 lasers using rare chemical isotopes must be operated in closed cycles to conserve gas. Rare isotopes operated in closed cycles to conserve gas. Rare isotopes as CO2/18 used for improved transmission of laser beam in atmosphere. To maintain laser power, CO2 must be regenerated, and O2 concentration kept below few tenths of percent. Conditions achieved by recombining CO and O2.

  13. Monitoring uranium, hydrogen, and lithium and their isotopes using a compact laser-induced breakdown spectroscopy (LIBS) probe and high-resolution spectrometer.

    PubMed

    Cremers, David A; Beddingfield, Alan; Smithwick, Robert; Chinni, Rosemarie C; Jones, C Randy; Beardsley, Burt; Karch, Larry

    2012-03-01

    The development of field-deployable instruments to monitor radiological, nuclear, and explosive (RNE) threats is of current interest for a number of assessment needs such as the on-site screening of suspect facilities and nuclear forensics. The presence of uranium and plutonium and radiological materials can be determined through monitoring the elemental emission spectrum using relatively low-resolution spectrometers. In addition, uranium compounds, explosives, and chemicals used in nuclear fuel processing (e.g., tributyl-phosphate) can be identified by applying chemometric analysis to the laser-induced breakdown (LIBS) spectrum recorded by these spectrometers. For nuclear forensic applications, however, isotopes of U and Pu and other elements (e.g., H and Li) must also be determined, requiring higher resolution spectrometers given the small magnitude of the isotope shifts for some of these elements (e.g., 25 pm for U and 13 pm for Pu). High-resolution spectrometers will be preferred for several reasons but these must fit into realistic field-based analysis scenarios. To address the need for field instrumentation, we evaluated a previously developed field-deployable hand-held LIBS interrogation probe combined with two relatively new high-resolution spectrometers (λ/Δλ ~75,000 and ~44,000) that have the potential to meet field-based analysis needs. These spectrometers are significantly smaller and lighter in weight than those previously used for isotopic analysis and one unit can provide simultaneous wide spectral coverage and high resolution in a relatively small package. The LIBS interrogation probe was developed initially for use with low resolution compact spectrometers in a person-portable backpack LIBS instrument. Here we present the results of an evaluation of the LIBS probe combined with a high-resolution spectrometer and demonstrate rapid detection of isotopes of uranium and hydrogen and highly enriched samples of (6)Li and (7)Li.

  14. Modifying molecule-surface scattering by ultrashort laser pulses

    SciTech Connect

    Khodorkovsky, Yuri; Averbukh, Ilya Sh.; Manson, J. R.

    2011-11-15

    In recent years it has become possible to align molecules in free space using ultrashort laser pulses. Here we explore two schemes for controlling molecule-surface scattering processes and which are based on laser-induced molecular alignment. In the first scheme, a single ultrashort nonresonant laser pulse is applied to a molecular beam hitting the surface. This pulse modifies the angular distribution of the incident molecules and causes the scattered molecules to rotate with a preferred sense of rotation (clockwise or counterclockwise). In the second scheme, two properly delayed laser pulses are applied to a molecular beam composed of two chemically close molecular species (isotopes, or nuclear-spin isomers). As the result of the double-pulse excitation, these species are selectively scattered to different angles after the collision with the surface. These effects may provide new means for the analysis and separation of molecular mixtures.

  15. 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.

  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. Molecular Imaging-Assisted Optimization of Hsp70 Expression during Laser-Induced Thermal Preconditioning for Wound Repair Enhancement

    PubMed Central

    Wilmink, Gerald J.; Opalenik, Susan R.; Beckham, Joshua T.; Abraham, Alexander A.; Nanney, Lillian B.; Mahadevan-Jansen, Anita; Davidson, Jeffrey M.; Jansen, E. Duco

    2013-01-01

    Patients at risk for impaired healing may benefit from prophylactic measures aimed at improving wound repair. Several photonic devices claim to enhance repair by thermal and photochemical mechanisms. We hypothesized that laser-induced thermal preconditioning would enhance surgical wound healing that was correlated with hsp70 expression. Using a pulsed diode laser (λ =1.85 μm, τp=2 ms, 50 Hz, H =7.64 mJcm−2), the skin of transgenic mice that contain an hsp70 promoter-driven luciferase was preconditioned 12 hours before surgical incisions were made. Laser protocols were optimized in vitro and in vivo using temperature, blood flow, and hsp70-mediated bioluminescence measurements as benchmarks. Biomechanical properties and histological parameters of wound healing were evaluated for up to 14 days. Bioluminescent imaging studies indicated that an optimized laser protocol increased hsp70 expression by 10-fold. Under these conditions, laser-preconditioned incisions were two times stronger than control wounds. Our data suggest that this molecular imaging approach provides a quantitative method for optimization of tissue preconditioning and that mild laser-induced heat shock may be a useful therapeutic intervention prior to surgery. PMID:18580963

  18. Anomalous 13C isotope abundances in C3S and C4H observed toward the cold interstellar cloud, Taurus Molecular Cloud-1.

    PubMed

    Sakai, Nami; Takano, Shuro; Sakai, Takeshi; Shiba, Shoichi; Sumiyoshi, Yoshihiro; Endo, Yasuki; Yamamoto, Satoshi

    2013-10-01

    We have studied the abundances of the (13)C isotopic species of C3S and C4H in the cold molecular cloud, Taurus Molecular Cloud-1 (Cyanopolyyne Peak), by radioastronomical observations of their rotational emission lines. The CCCS/(13)CCCS and CCCS/C(13)CCS ratios are determined to be >206 and 48 ± 15, respectively. The CC(13)CS line is identified with the aid of laboratory microwave spectroscopy, and the range of the CCCS/CC(13)CS ratio is found to be from 30 to 206. The abundances of at least two (13)C isotopic species of C3S are thus found to be different. Similarly, it is found that the abundances of the four (13)C isotopic species of C4H are not equivalent. The CCCCH/(13)CCCCH, CCCCH/C(13)CCCH, CCCCH/CC(13)CCH, and CCCCH/CCC(13)CH ratios are evaluated to be 141 ± 44, 97 ± 27, 82 ± 15, and 118 ± 23, respectively. Here the errors denote 3 times the standard deviation. These results will constrain the formation pathways of C3S and C4H, if the nonequivalence is caused during the formation processes of these molecules. The exchange reactions after the formation of these two molecules may also contribute to the nonequivalence. In addition, we have confirmed that the (12)C/(13)C ratio of some species are significantly higher than the interstellar elemental (12)C/(13)C ratio of 60-70. The observations of the (13)C isotopic species provide us with rich information on chemical processes in cold interstellar clouds.

  19. 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

  20. 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

  1. 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.

  2. High-order-harmonic generation in molecular sequential double ionization by intense circularly polarized laser pulses

    NASA Astrophysics Data System (ADS)

    Yuan, Kai-Jun; Lu, Huizhong; Bandrauk, André D.

    2015-08-01

    We present effects of electron energy transfer by electron collisions on high-order-harmonic generation (HHG) in molecular sequential double ionization by intense circularly polarized laser pulses. Results from numerical solutions of time-dependent Schrödinger equations for extended (large internuclear distance) H2 where electrons are entangled and hence delocalized by exchange show that HHG with cutoff energy up to Ip+24 Up can be obtained, where Ip is the molecule ionization potential and Up=I0/4 ω02 (in atomic units) is the ponderomotive energy for pulse intensity I0 and frequency ω0. A time-frequency analysis is employed to identify electron collisions for the generation of harmonics. Extended HHG arises from electron energy exchange, which agrees well with the prediction of a classical two electron collision model. Results for nonsymmetric HHe+ where initially electrons are localized on He are also compared and confirm the role of initial electron delocalization via entanglement for obtaining extended HHG plateaus.

  3. 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.

  4. On multiple component detection in molecular plasmas using cw external-cavity quantum cascade infrared lasers

    NASA Astrophysics Data System (ADS)

    Lopatik, Dmitry; Lang, Norbert; Macherius, Uwe; Zimmermann, Henrik; Roepcke, Juergen

    2012-10-01

    Several cw external cavity quantum cascade lasers (EC-QCLs) have been tested as radiation sources for an absorption spectrometer focused on the analysis of molecular plasmas. Based on the wide spectral tunability of EC-QCLs multiple species detection is demonstrated in low pressure Ar/N2 MW plasmas containing CH4 as hydrocarbon precursor. Using the direct absorption technique the evolution of the concentrations of CH4, C2H2, HCN and H2O has been monitored depending on the discharge conditions (p= 0.5 mbar, f= 2.45 GHz) in a planar MW plasma reactor. The concentrations were found to be in the range of 10 ^11 -- 10 ^14 molecules cm-3. Based on the profiles of absorption lines the gas temperature Tg has been calculated in dependence on the discharge power. Changing the discharge power from 0.2 kW to 1 kW leads to an increase of Tg from 400 to 700 K. The typical spectral line width of the EC-QCLs under the study was about 30 MHz. Varying the power values of an EC-QCL for direct absorption measurements at low pressure conditions no saturation effects in determining the concentrations of CH4 and C2H2 could be found under the used conditions.

  5. 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.

  6. Influence of molecular structure on the laser-induced plasma emission of the explosive RDX and organic polymers.

    PubMed

    De Lucia, Frank C; Gottfried, Jennifer L

    2013-10-01

    A series of organic polymers and the military explosive cyclotrimethylenetrinitramine (RDX) were studied using the light emission from a femtosecond laser-induced plasma under an argon atmosphere. The relationship between the molecular structure and plasma emission was established by using the percentages of the atomic species (C, H, N, O) and bond types (C-C, C═C, C-N, and C≡N) in combination with the atomic/molecular emission intensities and decay rates. In contrast to previous studies of organic explosives in which C2 was primarily formed by recombination, for the organic materials in this study the percentage of C-C (and C═C) bonds was strongly correlated to the molecular C2 emission. Time-resolved emission spectra were collected to determine the lifetimes of the atomic and molecular species in the plasma. Observed differences in decay rates were attributed to the differences in both the molecular structure of the organic polymers or RDX and the chemical reactions that occur within the plasma. These differences could potentially be exploited to improve the discrimination of explosive residues on organic substrates with laser-induced breakdown spectroscopy.

  7. 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

  8. 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.

  9. 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.

  10. Authentication of vegetable oils by bulk and molecular carbon isotope analyses with emphasis on olive oil and pumpkin seed oil.

    PubMed

    Spangenberg, J E; Ogrinc, N

    2001-03-01

    The authenticity of vegetable oils consumed in Slovenia and Croatia was investigated by carbon isotope analysis of the individual fatty acids by the use of gas chromatography-combustion-isotope ratio mass spectrometry (GC/C/IRMS), and through carbon isotope analysis of the bulk oil. The fatty acids from samples of olive, pumpkin, sunflower, maize, rape, soybean, and sesame oils were separated by alkaline hydrolysis and derivatized to methyl esters for chemical characterization by capillary gas chromatography/mass spectrometry (GC/MS) prior to isotopic analysis. Enrichment in heavy carbon isotope ((13)C) of the bulk oil and of the individual fatty acids are related to (1) a thermally induced degradation during processing (deodorization, steam washing, or bleaching), (2) hydrolytic rancidity (lipolysis) and oxidative rancidity of the vegetable oils during storage, and (3) the potential blend with refined oil or other vegetable oils. The impurity or admixture of different oils may be assessed from the delta(13)C(16:0) vs. delta(13)C(18:1) covariations. The fatty acid compositions of Slovenian and Croatian olive oils are compared with those from the most important Mediterranean producer countries (Spain, Italy, Greece, and France).

  11. 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.

  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. 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.

  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. 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

  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. Kinetic-Fluid Coupling in the Field of the Atomic Vapor Laser Isotopic Separation: Numerical Results in the Case of a Monospecies Perfect Gas

    NASA Astrophysics Data System (ADS)

    Dellacherie, Stéphane

    2003-05-01

    To describe the uranium gas expansion in the field of the Atomic Vapor Laser Isotopic Separation (AVLIS; SILVA in french) with a reasonable CPU time, we have to couple the resolution of the Boltzmann equation with the resolution of the Euler system. The resolution of the Euler system uses a kinetic scheme and the boundary condition at the kinetic - fluid interface — which defines the boundary between the Boltzmann area and the Euler area — is defined with the positive and negative half fluxes of the kinetic scheme. Moreover, in order to take into account the effect of the Knudsen layer through the resolution of the Euler system, we propose to use a Marshak condition to asymptoticaly match the Euler area with the uranium source. Numerical results show an excellent agreement between the results obtained with and without kinetic - fluid coupling.

  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. 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)