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.

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.

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.

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.

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.

Method for laser induced isotope enrichment

DOEpatents

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

2004-09-07

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

Optical spectroscopy of laser-produced plasmas for standoff isotopic analysis

NASA Astrophysics Data System (ADS)

Harilal, S. S.; Brumfield, B. E.; LaHaye, N. L.; Hartig, K. C.; Phillips, M. C.

2018-06-01

Rapid, in-field, and non-contact isotopic analysis of solid materials is extremely important to a large number of applications, such as nuclear nonproliferation monitoring and forensics, geochemistry, archaeology, and biochemistry. Presently, isotopic measurements for these and many other fields are performed in laboratory settings. Rapid, in-field, and non-contact isotopic analysis of solid material is possible with optical spectroscopy tools when combined with laser ablation. Laser ablation generates a transient vapor of any solid material when a powerful laser interacts with a sample of interest. Analysis of atoms, ions, and molecules in a laser-produced plasma using optical spectroscopy tools can provide isotopic information with the advantages of real-time analysis, standoff capability, and no sample preparation requirement. Both emission and absorption spectroscopy methods can be used for isotopic analysis of solid materials. However, applying optical spectroscopy to the measurement of isotope ratios from solid materials presents numerous challenges. Isotope shifts arise primarily due to variation in nuclear charge distribution caused by different numbers of neutrons, but the small proportional nuclear mass differences between nuclei of various isotopes lead to correspondingly small differences in optical transition wavelengths. Along with this, various line broadening mechanisms in laser-produced plasmas and instrumental broadening generated by the detection system are technical challenges frequently encountered with emission-based optical diagnostics. These challenges can be overcome by measuring the isotope shifts associated with the vibronic emission bands from molecules or by using the techniques of laser-based absorption/fluorescence spectroscopy to marginalize the effect of instrumental broadening. Absorption and fluorescence spectroscopy probe the ground state atoms existing in the plasma when it is cooler, which inherently provides narrower

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.

Laser ablation inductively coupled plasma mass spectrometry for direct isotope ratio measurements on solid samples

NASA Astrophysics Data System (ADS)

Pickhardt, Carola; Dietze, Hans-Joachim; Becker, J. Sabine

2005-04-01

Isotope ratio measurements have been increasingly used in quite different application fields, e.g., for the investigation of isotope variation in nature, in geoscience (geochemistry and geochronology), in cosmochemistry and planetary science, in environmental science, e.g., in environmental monitoring, or by the application of the isotope dilution technique for quantification purposes using stable or radioactive high-enriched isotope tracers. Due to its high sensitivity, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is today a challenging mass spectrometric technique for the direct determination of precise and accurate isotope ratios in solid samples. In comparison to laser ablation quadrupole ICP-MS (LA-ICP-QMS), laser ablation coupled to a double-focusing sector field ICP-MS (LA-ICP-SFMS) with single ion detection offers a significant improvement of sensitivity at low mass resolution, whereby isotope ratios can be measured with a precision to 0.1% relative standard deviation (R.S.D.). In LA-ICP-SFMS, many disturbing isobaric interferences of analyte and molecular ions can be separated at the required mass resolution (e.g., 40Ar16O+ and 56Fe+ for iron isotope ratio measurements). The precision on isotope ratio measurements was improved by one order of magnitude via the simultaneous detection of mass-separated ion currents of isotopes using multiple ion collectors in LA-ICP-MS (LA-MC-ICP-MS). The paper discusses the state of the art, the challenges and limits in isotope ratio measurements by LA-ICP-MS using different instrumentations at the trace and ultratrace level in different fields of application as in environmental and biological research, geochemistry and geochronology with respect to their precision and accuracy.

Optical spectroscopy of laser-produced plasmas for standoff isotopic analysis

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

Harilal, Sivanandan S.; Brumfield, Brian E.; LaHaye, Nicole L.

2018-04-20

This review article covers the present status of isotope detection through emission, absorption, and fluorescence spectroscopy of atoms and molecules in a laser-produced plasma formed from a solid sample. A description of the physics behind isotope shifts in atoms and molecules is presented, followed by the physics behind solid sampling of laser ablation plumes, optical methods for isotope measurements, the suitable physical conditions of laser-produced plasma plumes for isotopic analysis, and the current status. Finally, concluding remarks will be made on the existing gaps between previous works in the literature and suggestions for future work.

Optical spectroscopy of laser-produced plasmas for standoff isotopic analysis

DOE PAGES

Harilal, S. S.; Brumfield, B. E.; LaHaye, N. L.; ...

2018-04-20

This review article covers the present status of isotope detection through emission, absorption, and fluorescence spectroscopy of atoms and molecules in a laser-produced plasma formed from a solid sample. A description of the physics behind isotope shifts in atoms and molecules is presented, followed by the physics behind solid sampling of laser ablation plumes, optical methods for isotope measurements, the suitable physical conditions of laser-produced plasma plumes for isotopic analysis, and the current status. Lastly, concluding remarks will be made on the existing gaps between previous works in the literature and suggestions for future work.

Optical spectroscopy of laser-produced plasmas for standoff isotopic analysis

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

Harilal, S. S.; Brumfield, B. E.; LaHaye, N. L.

This review article covers the present status of isotope detection through emission, absorption, and fluorescence spectroscopy of atoms and molecules in a laser-produced plasma formed from a solid sample. A description of the physics behind isotope shifts in atoms and molecules is presented, followed by the physics behind solid sampling of laser ablation plumes, optical methods for isotope measurements, the suitable physical conditions of laser-produced plasma plumes for isotopic analysis, and the current status. Lastly, concluding remarks will be made on the existing gaps between previous works in the literature and suggestions for future work.

Optical spectroscopy of laser-produced plasmas for standoff isotopic analysis

DOE PAGES

Harilal, S. S.; Brumfield, B. E.; LaHaye, N. L.; ...

2018-06-01

This review article covers the present status of isotope detection through emission, absorption, and fluorescence spectroscopy of atoms and molecules in a laser-produced plasma formed from a solid sample. A description of the physics behind isotope shifts in atoms and molecules is presented, followed by the physics behind solid sampling of laser ablation plumes, optical methods for isotope measurements, the suitable physical conditions of laser-produced plasma plumes for isotopic analysis, and the current status. Finally, concluding remarks will be made on the existing gaps between previous works in the literature and suggestions for future work.

Optical spectroscopy of laser-produced plasmas for standoff isotopic analysis

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

Harilal, S. S.; Brumfield, B. E.; LaHaye, N. L.

This review article covers the present status of isotope detection through emission, absorption, and fluorescence spectroscopy of atoms and molecules in a laser-produced plasma formed from a solid sample. A description of the physics behind isotope shifts in atoms and molecules is presented, followed by the physics behind solid sampling of laser ablation plumes, optical methods for isotope measurements, the suitable physical conditions of laser-produced plasma plumes for isotopic analysis, and the current status. Finally, concluding remarks will be made on the existing gaps between previous works in the literature and suggestions for future work.

Laser spectrometer for CO2 clumped isotope analysis

NASA Astrophysics Data System (ADS)

Prokhorov, Ivan; Kluge, Tobias; Janssen, Christof

2017-04-01

Carbon dioxide clumped isotope thermometry has proven to be a reliable method for biogeochemical and atmospheric research. We present a new laser spectroscopic instrument for doubly-substituted isotopologues analysis. In contrast to a conventional isotope ratio mass spectrometry (IRMS), tunable laser direct absorption spectroscopy (TLDAS) has the advantage of isotopologue-specific determination free of isobaric interferences. Tunable infrared laser based spectrometer for clumped isotope analysis is being developed in collaboration between Heidelberg University, Germany, and LERMA-IPSL, CNRS, France. The instrument employs two continuous intraband cascade lasers (ICL) tuned at 4439 and 4329 nm. The spectral windows covered by the lasers contain absorption lines of the six most abundant CO2 isotopologues, including the two doubly substituted species 16O13C18O and 16O13C17O, and all singly substituted isotopologues with 13C, 18O and 17O. A Herriott-type multi-pass cell provides two different absorption pathlengths to compensate the abundance difference between singly- and doubly-substituted isotopologues. We have reached the sub-permill precision required for clumped isotope measurements within the integration time of several seconds. The test version of the instrument demonstrates a performance comparable to state of the art IRMS. We highlight the following features of the instrument that are strong advantages compared to conventional mass spectrometry: measurement cycle in the minute range, simplified sample preparation routine, table-top layout with a potential for in-situ applications.

Characterization of extreme ultraviolet laser ablation mass spectrometry for actinide trace analysis and nanoscale isotopic imaging

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

Green, Tyler; Kuznetsov, Ilya; Willingham, David

The purpose of this research was to characterize Extreme Ultraviolet Time-of-Flight (EUV TOF) Laser Ablation Mass Spectrometry for high spatial resolution elemental and isotopic analysis. We compare EUV TOF results with Secondary Ionization Mass Spectrometry (SIMS) to orient the EUV TOF method within the overall field of analytical mass spectrometry. Using the well-characterized NIST 61x glasses, we show that the EUV ionization approach produces relatively few molecular ion interferences in comparison to TOF SIMS. We demonstrate that the ratio of element ion to element oxide ion is adjustable with EUV laser pulse energy and that the EUV TOF instrument hasmore » a sample utilization efficiency of 0.014%. The EUV TOF system also achieves a lateral resolution of 80 nm and we demonstrate this lateral resolution with isotopic imaging of closely spaced particles or uranium isotopic standard materials.« less

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.

Isotope shifts from collinear laser spectroscopy of doubly charged yttrium isotopes

NASA Astrophysics Data System (ADS)

Vormawah, L. J.; Vilén, M.; Beerwerth, R.; Campbell, P.; Cheal, B.; Dicker, A.; Eronen, T.; Fritzsche, S.; Geldhof, S.; Jokinen, A.; Kelly, S.; Moore, I. D.; Reponen, M.; Rinta-Antila, S.; Stock, S. O.; Voss, A.

2018-04-01

Collinear laser spectroscopy has been performed on doubly charged ions of radioactive yttrium in order to study the isotope shifts of the 294.6-nm 5 s 1/2 2S →5 p 1/2 2P line. The potential of such an alkali-metal-like transition to improve the reliability of atomic-field-shift and mass-shift factor calculations, and hence the extraction of nuclear mean-square radii, is discussed. Production of yttrium ion beams for such studies is available at the IGISOL IV Accelerator Laboratory, Jyväskylä, Finland. This newly recommissioned facility is described here in relation to the on-line study of accelerator-produced short-lived isotopes using collinear laser spectroscopy and application of the technique to doubly charged ions.

Towards absolute laser spectroscopic CO2 isotope ratio measurements

NASA Astrophysics Data System (ADS)

Anyangwe Nwaboh, Javis; Werhahn, Olav; Ebert, Volker

2017-04-01

Knowledge of isotope composition of carbon dioxide (CO2) in the atmosphere is necessary to identify sources and sinks of this key greenhouse gas. In the last years, laser spectroscopic techniques such as cavity ring-down spectroscopy (CRDS) and tunable diode laser absorption spectroscopy (TDLAS) have been shown to perform accurate isotope ratio measurements for CO2 and other gases like water vapour (H2O) [1,2]. Typically, isotope ratios are reported in literature referring to reference materials provided by e.g. the International Atomic Energy Agency (IAEA). However, there could be some benefit if field deployable absolute isotope ratio measurement methods were developed to address issues such as exhausted reference material like the Pee Dee Belemnite (PDB) standard. Absolute isotope ratio measurements would be particularly important for situations where reference materials do not even exist. Here, we present CRDS and TDLAS-based absolute isotope ratios (13C/12C ) in atmospheric CO2. We demonstrate the capabilities of the used methods by measuring CO2 isotope ratios in gas standards. We compare our results to values reported for the isotope certified gas standards. Guide to the expression of uncertainty in measurement (GUM) compliant uncertainty budgets on the CRDS and TDLAS absolute isotope ratio measurements are presented, and traceability is addressed. We outline the current impediments in realizing high accuracy absolute isotope ratio measurements using laser spectroscopic methods, propose solutions and the way forward. Acknowledgement Parts of this work have been carried out within the European Metrology Research Programme (EMRP) ENV52 project-HIGHGAS. The EMRP is jointly funded by the EMRP participating countries within EURAMET and the European Union. References [1] B. Kühnreich, S. Wagner, J. C. Habig,·O. Möhler, H. Saathoff, V. Ebert, Appl. Phys. B 119:177-187 (2015). [2] E. Kerstel, L. Gianfrani, Appl. Phys. B 92, 439-449 (2008).

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.

Stable isotope laser spectrometer for exploration of Mars.

PubMed

Sauke, T B; Becker, J F

1998-01-01

On Earth, measurements of the ratios of stable carbon isotopes have provided much information about geological and biological processes. For example, fractionation of carbon occurs in biotic processes and the retention of a distinctive 2-4% contrast in 13C/12C between organic carbon and carbonates in rocks as old as 3.8 billion years constitutes some of the firmest evidence for the antiquity of life on the Earth. We have developed a prototype tunable diode Laser spectrometer which demonstrates the feasibility of making accurate in situ isotopic ratio measurements on Mars. This miniaturized instrument, with an optical path length of 10 cm, should be capable of making accurate 13C/12C and 15N/14N measurements. Gas samples for measurement are to be produced by pyrolysis using soil samples as small as 50 mg. Measurements of 13C/12C, 18O/16O and 15N/14N have been made to a precision of better than 0.1% and various other isotopes are feasible. This laser technique, which relies on the extremely narrow emission linewidth of tunable diode lasers (<0.001 cm(-1)) has favorable features in comparison to mass spectrometry, the standard method of accurate isotopic ratio measurement. The miniature instrument could be ready to deploy on the 2003 or other Mars lander missions.

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.

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

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

Duffin, Andrew M.; Springer, Kellen WE; Ward, Jesse D.

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 alsomore » allows for spatial analysis and our data indicate that rare uranium concentration inhomogeneities exist in NIST 616 glass.« less

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.

All-diode-laser cooling of Sr+ isotope ions for analytical applications

NASA Astrophysics Data System (ADS)

Jung, Kyunghun; Yamamoto, Kazuhiro; Yamamoto, Yuta; Miyabe, Masabumi; Wakaida, Ikuo; Hasegawa, Shuichi

2017-06-01

Trapping and cooling of Sr+ isotope ions by an all-diode-laser system has been demonstrated in order to develop a novel mass spectrometric technique in combination with ion trap-laser cooling. First, we constructed external cavity diode lasers and associated stabilization apparatus for laser cooling of Sr+ ions. The transition frequencies confirmed by optogalvanic spectroscopy enabled successful cooling of 88Sr+ ions. An image of two trapped ions has been captured by CCD camera. Minor isotopes, 84Sr+ and 86Sr+, were also cooled and trapped. From an analysis of the observed spectra of a string crystal of each isotope, the isotope shifts of the cooling transition (5s 2S1/2 → 5p 2P1/2) of Sr+ ions were determined to be +371(8) MHz for Δν84-88 and +169(8) MHz for Δν86-88. In the case of the repumping transition (4d 2D3/2 → 5p 2P1/2), Δν84-88 and Δν86-88 were measured to be -833(6) and -400(5) MHz, respectively. These values are in good agreement with previously reported values.

Evaluation of uranium transitions for isotopically-selective laser induced fluorescence with diode lasers (technical report for ST064)

NASA Astrophysics Data System (ADS)

Cannon, B. D.

1993-10-01

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

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.

Molecular Isotopic Distribution Analysis (MIDAs) with adjustable mass accuracy.

PubMed

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.

Micro-scale novel stable isotope fractionation during weathering disclosed by femtosecond laser ablation

NASA Astrophysics Data System (ADS)

Schuessler, J. A.; von Blanckenburg, F.

2012-12-01

The stable isotope fractionation of metals and metalloids during chemical weathering and alteration of rocks at low temperature is a topic receiving increasing scientific attention. For these systems, weathering of primary minerals leads to selective partitioning of isotopes between the secondary minerals formed from them, and the dissolved phase of soil or river water. While the isotopic signatures of these processes have been mapped-out at the catchment or the soil scale, the actual isotopic fractionation is occurring at the mineral scale. To identify the processes underlying such micro-scale fractionation, the development of micro-analytical tools allows to investigate mechanisms of isotope fractionation in-situ, in combination with textural information of weathering reactions. We have developed a second-generation UV femtosecond (fs) laser system at GFZ Potsdam. The advantage of UV-fs laser ablation is the reduction of laser-induced isotopic and elemental fractionation by avoiding 'thermal effects' during ablation, such that accurate isotope ratios can be measured by standard-sample-standard bracketing using laser ablation multicollector ICP-MS; where the matrix of the bracketing standard does not need to match that of the sample [1]. Our system consists of the latest generation femtosecond solid-state laser (Newport Spectra Physics Solstice), producing an ultra short pulse width of about 100 femtoseconds at a wavelength of 196 nm. The system is combined with a custom-build computer-controlled sample stage and allows fully automated isotope analyses through synchronised operation of the laser with the Neptune MC-ICP-MS. To assess precision and accuracy of our laser ablation method, we analysed various geological reference materials. We obtained δ30Si values of -0.31 ± 0.23 (2SD, n = 13) for basalt glass BHVO-2G, and -1.25 ± 0.21 (2SD, n = 27) for pure Si IRMM17 when bracketed against NBS-28 quartz. δ56Fe and δ26Mg values obtained from non-matrix matched

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.

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.

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.

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.

Laser cooling of molecular anions.

PubMed

Yzombard, Pauline; Hamamda, Mehdi; Gerber, Sebastian; Doser, Michael; Comparat, Daniel

2015-05-29

We propose a scheme for laser cooling of negatively charged molecules. We briefly summarize the requirements for such laser cooling and we identify a number of potential candidates. A detailed computation study with C_{2}^{-}, the most studied molecular anion, is carried out. Simulations of 3D laser cooling in a gas phase show that this molecule could be cooled down to below 1 mK in only a few tens of milliseconds, using standard lasers. Sisyphus cooling, where no photodetachment process is present, as well as Doppler laser cooling of trapped C_{2}^{-}, are also simulated. This cooling scheme has an impact on the study of cold molecules, molecular anions, charged particle sources, and antimatter physics.

"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.

High-power CO laser with RF discharge for isotope separation employing condensation repression

NASA Astrophysics Data System (ADS)

Baranov, I. Ya.; Koptev, A. V.

2008-10-01

High-power CO laser can be the effective tool in such applications as isotope separation using the free-jet CRISLA method. The way of transfer from CO small-scale experimental installation to industrial high-power CO lasers is proposed through the use of a low-current radio-frequency (RF) electric discharge in a supersonic stream without an electron gun. The calculation model of scaling CO laser with RF discharge in supersonic stream was developed. The developed model allows to calculate parameters of laser installation and optimize them with the purpose of reception of high efficiency and low cost of installation as a whole. The technical decision of industrial CO laser for isotope separation employing condensation repression is considered. The estimated cost of laser is some hundred thousand dollars USA and small sizes of laser head give possibility to install it in any place.

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.

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

Seeking excellence: An evaluation of 235 international laboratories conducting water isotope analyses by isotope-ratio and laser-absorption spectrometry.

PubMed

Wassenaar, L I; Terzer-Wassmuth, S; Douence, C; Araguas-Araguas, L; Aggarwal, P K; Coplen, T B

2018-03-15

Water stable isotope ratios (δ 2 H and δ 18 O values) are widely used tracers in environmental studies; hence, accurate and precise assays are required for providing sound scientific information. We tested the analytical performance of 235 international laboratories conducting water isotope analyses using dual-inlet and continuous-flow isotope ratio mass spectrometers and laser spectrometers through a water isotope inter-comparison test. Eight test water samples were distributed by the IAEA to international stable isotope laboratories. These consisted of a core set of five samples spanning the common δ-range of natural waters, and three optional samples (highly depleted, enriched, and saline). The fifth core sample contained unrevealed trace methanol to assess analyst vigilance to the impact of organic contamination on water isotopic measurements made by all instrument technologies. For the core and optional samples ~73 % of laboratories gave acceptable results within 0.2 ‰ and 1.5 ‰ of the reference values for δ 18 O and δ 2 H, respectively; ~27 % produced unacceptable results. Top performance for δ 18 O values was dominated by dual-inlet IRMS laboratories; top performance for δ 2 H values was led by laser spectrometer laboratories. Continuous-flow instruments yielded comparatively intermediate results. Trace methanol contamination of water resulted in extreme outlier δ-values for laser instruments, but also affected reactor-based continuous-flow IRMS systems; however, dual-inlet IRMS δ-values were unaffected. Analysis of the laboratory results and their metadata suggested inaccurate or imprecise performance stemmed mainly from skill- and knowledge-based errors including: calculation mistakes, inappropriate or compromised laboratory calibration standards, poorly performing instrumentation, lack of vigilance to contamination, or inattention to unreasonable isotopic outcomes. To counteract common errors, we recommend that laboratories include 1-2 'known

Seeking excellence: An evaluation of 235 international laboratories conducting water isotope analyses by isotope-ratio and laser-absorption spectrometry

USGS Publications Warehouse

Wassenaar, L. I.; Terzer-Wassmuth, S.; Douence, C.; Araguas-Araguas, L.; Aggarwal, P. K.; Coplen, Tyler B.

2018-01-01

RationaleWater stable isotope ratios (δ2H and δ18O values) are widely used tracers in environmental studies; hence, accurate and precise assays are required for providing sound scientific information. We tested the analytical performance of 235 international laboratories conducting water isotope analyses using dual-inlet and continuous-flow isotope ratio mass spectrometers and laser spectrometers through a water isotope inter-comparison test.MethodsEight test water samples were distributed by the IAEA to international stable isotope laboratories. These consisted of a core set of five samples spanning the common δ-range of natural waters, and three optional samples (highly depleted, enriched, and saline). The fifth core sample contained unrevealed trace methanol to assess analyst vigilance to the impact of organic contamination on water isotopic measurements made by all instrument technologies.ResultsFor the core and optional samples ~73 % of laboratories gave acceptable results within 0.2 ‰ and 1.5 ‰ of the reference values for δ18O and δ2H, respectively; ~27 % produced unacceptable results. Top performance for δ18O values was dominated by dual-inlet IRMS laboratories; top performance for δ2H values was led by laser spectrometer laboratories. Continuous-flow instruments yielded comparatively intermediate results. Trace methanol contamination of water resulted in extreme outlier δ-values for laser instruments, but also affected reactor-based continuous-flow IRMS systems; however, dual-inlet IRMS δ-values were unaffected.ConclusionsAnalysis of the laboratory results and their metadata suggested inaccurate or imprecise performance stemmed mainly from skill- and knowledge-based errors including: calculation mistakes, inappropriate or compromised laboratory calibration standards, poorly performing instrumentation, lack of vigilance to contamination, or inattention to unreasonable isotopic outcomes. To counteract common errors, we recommend that

The Carbon Isotope Ratio in Local Molecular Clouds

NASA Astrophysics Data System (ADS)

Goto, Miwa; Usuda, Tomonori; Takato, Naruhisa; Masahiko, Hayashi; Sakamoto, Seiichi; Mitchell, George

We report the carbon isotope ratio in nearby molecular clouds LkHα 101, AFGL 490, and Mon R2 IRS 3. The vibrational transition bands of 12CO ν = 2 ← 0 and 13CO ν = 1 ← 0 were observed with high resolution near-infrared spectroscopy (R = 23,000) to measure the relative abundance of 13CO to 12CO. The isotopic ratios are 12CO/13CO = 1379 (LkHα 101), 8649 (AFGL 490), and 158 (Mon R2 IRS 3), which is twice higher than in the solar neighborhood. The molecular clouds are with high visible extinction (AV = 10 70 mag), well shielded from destructive FUV field. It is questionable that the selective photo-destruction of 13CO plays a major role in biasing isotope ratio. Uncertainty in the Doppler parameters of the unresolved absorption lines, and possible emission filling of fundamental transitions are suspected to account for the high 12CO/13CO ratio. Higher resolution spectroscopy (R ~ 100,000) is the key to go for the accurate measurement of isotope ratio.

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.

Ion beam production and study of radioactive isotopes with the laser ion source at ISOLDE

NASA Astrophysics Data System (ADS)

Fedosseev, Valentin; Chrysalidis, Katerina; Day Goodacre, Thomas; Marsh, Bruce; Rothe, Sebastian; Seiffert, Christoph; Wendt, Klaus

2017-08-01

At ISOLDE the majority of radioactive ion beams are produced using the resonance ionization laser ion source (RILIS). This ion source is based on resonant excitation of atomic transitions by wavelength tunable laser radiation. Since its installation at the ISOLDE facility in 1994, the RILIS laser setup has been developed into a versatile remotely operated laser system comprising state-of-the-art solid state and dye lasers capable of generating multiple high quality laser beams at any wavelength in the range of 210-950 nm. A continuous programme of atomic ionization scheme development at CERN and at other laboratories has gradually increased the number of RILIS-ionized elements. At present, isotopes of 40 different elements have been selectively laser-ionized by the ISOLDE RILIS. Studies related to the optimization of the laser-atom interaction environment have yielded new laser ion source types: the laser ion source and trap and the versatile arc discharge and laser ion source. Depending on the specific experimental requirements for beam purity or versatility to switch between different ionization mechanisms, these may offer a favourable alternative to the standard hot metal cavity configuration. In addition to its main purpose of ion beam production, the RILIS is used for laser spectroscopy of radioisotopes. In an ongoing experimental campaign the isotope shifts and hyperfine structure of long isotopic chains have been measured by the extremely sensitive in-source laser spectroscopy method. The studies performed in the lead region were focused on nuclear deformation and shape coexistence effects around the closed proton shell Z = 82. The paper describes the functional principles of the RILIS, the current status of the laser system and demonstrated capabilities for the production of different ion beams including the high-resolution studies of short-lived isotopes and other applications of RILIS lasers for ISOLDE experiments. This article belongs to the Focus on

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

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

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

2016-01-01

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 U-235/U-238 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 U-235/U-238 ratio. Empirical corrections are also included to account for ionization processes that are difficult to calculate from first principles with the available atomic data. Development of this model has highlighted several important considerations for properly interpreting experimental results.« less

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

DOE PAGES

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

2015-12-07

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

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

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

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

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 inmore » 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.« less

Laser separation of lithium isotopes by double resonance enhanced multiphoton ionization of Li/sub 2/

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

Balz, J.G.; Bernheim, R.A.; Gold, L.P.

1987-01-01

Multiphoton ionization spectra of /sup 7/Li/sub 2/, /sup 6/Li/sub 2/, and /sup 7/Li/sup 6/Li vapors have been measured in the 570--650 nm region using a single, low resolution, multimode cw dye laser. A number of wavelengths provide selective multiphoton ionization of one isotopic species demonstrating the possibility of efficient laser-driven isotopic separation in lithium in this wavelength region.

Remote laser evaporative molecular absorption spectroscopy

NASA Astrophysics Data System (ADS)

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

2016-09-01

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

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.

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.

Early diagenesis and organic matter preservation--A molecular stable isotope perspective

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

Macko, S.A.; Engel, M.H.; Qian, Y.

1992-01-01

Through new developments in stable isotope capability, gas chromatography coupled to a stable isotope ratio mass spectrometer (GC/IRMS), the molecular pathways of the diagenetic reactions can be observed on the components themselves. The authors report the results of laboratory-controlled degradation experiments of fresh organic substrates. Isotopically resolvable materials were used. Seagrass showed slight enrichments in [delta]N-15 with little change in [delta]C-13 following four weeks of decomposition. During that period the identifiable amino acid content decreased by approx. 50% for each amino acid. Mixtures of marine sediment with the same seagrass showed enrichments in nitrogen with associated depletions in carbon isotopicmore » compositions over the same time span. Control experiments on the sediments without added fresh seagrass showed no change in isotopic content. These changes are attributed to hydrolysis, deamination and decarboxylation reactions. Isotopic fractionations of similar size and direction have been observed in laboratory studies on peptide hydrolysis and natural samples of particulate organic materials. At the molecular level, using GC/IRMS, certain amino acids are seen to decrease in C-13 content while others become increasingly enriched in C-13. Similar reactions are seen in carbohydrates. The molecular isotope approach indicates that the process of diagenesis and preservation is significantly more complex than simple breakdown and loss. A large portion of the organic matter eventually preserved in organic-rich deposits can be attributed to new production in the deposit.« less

RFQ beam cooler and buncher for collinear laser spectroscopy of rare isotopes

NASA Astrophysics Data System (ADS)

Barquest, B. R.; Bollen, G.; Mantica, P. F.; Minamisono, K.; Ringle, R.; Schwarz, S.; Sumithrarachchi, C. S.

2017-09-01

A radiofrequency quadrupole (RFQ) ion beam cooler and buncher has been developed to deliver bunched beams with low transverse emittance, energy spread, and time spread to the BECOLA collinear laser spectroscopy system at the National Superconducting Cyclotron Laboratory (NSCL) at Michigan State University. The beam cooler and buncher contains new features which enhance performance, especially for high count rate beams, as well as simplifying construction, maintenance, and operation. The transverse emittance, energy spread, and time spread of the bunched beam, as well as buncher efficiency are reported, showcasing the capabilities of the BECOLA facility to perform collinear laser spectroscopy measurements with bunched rare isotope beams at NSCL and at the future Facility for Rare Isotope Beams (FRIB).

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.

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

PubMed

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

2007-12-15

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

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

NASA Astrophysics Data System (ADS)

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

2017-04-01

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

Improved repetition rate mixed isotope CO2 TEA laser

NASA Astrophysics Data System (ADS)

Cohn, D. B.

2014-09-01

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

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

PubMed

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

2005-08-01

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

Shape evolution for neutron-deficient bismuth isotopes studied by resonance laser ionization spectroscopy

NASA Astrophysics Data System (ADS)

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

2017-11-01

In-source laser spectroscopy experiments for bismuth isotopes at the 306.77 nm atomic transition has been carried out at the IRIS (Investigation of Radioactive Isotopes at Synchrocyclotron) facility of Petersburg Nuclear Physics Institute. New data on isotope shifts for 189-198,211Bi isotopes and isomers have been obtained. The changes in the mean-square charge radii were deduced. The large isomer shift has been observed for the intruder isomer states of Bi with spin I = 1/2 ( A = 193, 195, 197). This testifies to the shape coexistence in these nuclei with the intruder isomer states more deformed than the ground states. Marked deviation from the nearly spherical behavior for ground states of the even-neutron Bi isotopes at N < 109 is demonstrated, in contrast to the Pb and Tl isotopic chains.

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.

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

Ab initio design of laser pulses to control molecular motion

NASA Astrophysics Data System (ADS)

Balint-Kurti, Gabriel; Ren, Qinghua; Manby, Frederick; Artamonov, Maxim; Ho, Tak-San; Rabitz, Herschel; Zou, Shiyang; Singh, Harjinder

2007-03-01

Our recent attempts to design laser pulses entirely theoretically, in a quantitative and accurate manner, so as to fully understand the underlying mechanisms active in the control process will be outlined. We have developed a new Born-Oppenheimer like separation called the electric-nuclear Born-Oppenheimer (ENBO) approximation. In this approximation variations of both the nuclear geometry and of the external electric field are assumed to be slow compared with the speed at which the electronic degrees of freedom respond to these changes. This assumption permits the generation of a potential energy surface that depends not only on the relative geometry of the nuclei, but also on the electric field strength and on the orientation of the molecule with respect to the electric field. The range of validity of the ENBO approximation is discussed. Optimal control theory is used along with the ENBO approximation to design laser pulses for exciting vibrational and rotational motion in H2 and CO molecules. Progress on other applications, including controlling photodissociation processes, isotope separation, stabilization of molecular Bose-Einstein condensates as well as applications to biological molecules also be presented. *Support acknowledged from EPSRC.

Isotopic determination of uranium in soil by laser induced breakdown spectroscopy

DOE PAGES

Chan, George C. -Y.; Choi, Inhee; Mao, Xianglei; ...

2016-03-26

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 spectralmore » 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

Brome isotope selective control of CF3Br molecule clustering by IR laser radiation in gas-dynamic expansion of CF3Br - Ar mixture

NASA Astrophysics Data System (ADS)

Apatin, V. M.; Lokhman, V. N.; Makarov, G. N.; Ogurok, N.-D. D.; Ryabov, E. A.

2018-02-01

We report the results of research on the experimental control of CF3Br molecule clustering under gas-dynamic expansion of the CF3Br - Ar mixture at a nozzle exit by using IR laser radiation. A cw CO2 laser is used for exciting molecules and clusters in the beam and a time-of-flight mass-spectrometer with laser UV ionisation of particles for their detection. The parameters of the gas above the nozzle are determined (compositions and pressure) at which intensive molecule clustering occurs. It is found that in the case of the CF3Br gas without carrier when the pressure P0 above the nozzle does not exceed 4 atm, molecular clusters actually are not generated in the beam. If the gas mixture of CF3Br with argon is used at a pressure ratio 1 : N, where N >= 3, and the total pressure above the nozzle is P0 >= 2 atm, then there occurs molecule clustering. We study the dependences of the efficiency of suppressing the molecule clustering on parameters of the exciting pulse, gas parameters above the nozzle, and on a distance of the molecule irradiation zone from the nozzle exit section. It is shown that in the case of resonant vibrational excitation of gas-dynamically cooled CF3Br molecules at the nozzle exit one can realise isotope-selective suppression of molecule clustering with respect to bromine isotopes. With the CF3Br - Ar mixtures having the pressure ratio 1 : 3 and 1 : 15, the enrichment factors obtained with respect to bromine isotopes are kenr ≈ 1.05 ± 0.005 and kenr ≈ 1.06 ± 0.007, respectively, under jet irradiation by laser emission in the 9R(30) line (1084.635 cm-1). The results obtained let us assume that this method can be used to control clustering of molecules comprising heavy element isotopes, which have a small isotopic shift in IR absorption spectra.

Oxygen isotopic fractionation of O₂ during adsorption and desorption processes using molecular sieve at low temperatures.

PubMed

Ahn, Insu; Kusakabe, Minoru; Lee, Jong Ik

2014-06-15

Cryogenic trapping using molecular sieves is commonly used to collect O2 extracted from silicates for (17)O/(16)O and (18)O/(16)O analyses. However, gases which interfere with (17)O/(16)O analysis, notably NF3, are also trapped and their removal is essential for accurate direct measurement of the (17)O/(16)O ratio. It is also necessary to identify and quantify any isotopic fractionation associated with the use of cryogenic trapping using molecular sieves. The oxygen isotopic compositions of O2 before and after desorption from, and adsorption onto, 13X and 5A molecular sieves (MS13X and MS5A) at 0°C, -78°C, -114°C, and -130°C were measured in order to determine the oxygen isotopic fractionation at these temperatures. We also investigated whether isotopic fractionation occurred when O2 gas was transferred sequentially into a second cold finger, also containing molecular sieve. It was confirmed that significant oxygen isotopic fractionation occurs between the gaseous O2 and that adsorbed onto molecular sieve, if desorption and adsorption are incomplete. As the fraction of released or untrapped O2 becomes smaller with decreasing trapping temperature (from 0 to -130°C), the isotopic fractionation becomes larger. Approximately half of the total adsorbed O2 is released from the molecular sieve during desorption at -114°C, which is the temperature recommended for separation from NF3 (retained on the molecular sieve), and this will interfere with (17)O/(16)O measurements. The use of a single cold finger should be avoided, because partial desorption is accompanied by oxygen isotopic fractionation, thereby resulting in inaccurate isotopic data. The use of a dual cold finger arrangement is recommended because, as we have confirmed, the transfer of O2 from the first trap to the second is almost 100%. However, even under these conditions, a small isotopic fractionation (0.18 ± 0.05‰ in δ(17)O values and 0.26 ± 0.06‰ in δ(18)O values) occurred, with O2 in

Measurement of the Carbon Isotopic Composition of Methane Using Helicoidal Laser Eigenstates

NASA Astrophysics Data System (ADS)

Jacob, D.; Le Floch, A.; Bretenaker, F.; Guenot, P.

1996-06-01

The spatially generalized Jones matrix formalism is used to design a laser cavity to make intracavity measurements of the carbon isotopic composition of methane. the method is based on a double optical lever effect for helicoidally polarized eigenstates, permitting to measure successively the ^{12}CH_4 and ^{13}CH_4 concentrations. To choose the probed isotope, one simply tunes the frequency of the laser by Zeeman effect. The experiment exhibits a good agreement with the predictions and permits to measure the ^{13}CH4/^{12}CH_4 composition ratio of methane with an uncertainty of the order of ± 0.07% for a sample containing only 6× 10^{-9} mole of methane. On utilise le formalisme des matrices de Jones généralisées spatialement pour concevoir une cavité laser permettant la mesure intra-cavité de la composition isotopique du carbone présent dans le méthane. La méthode est fondée sur une double application de l'effet de levier optique pour les états propres hélicoïdaux, permettant de mesurer successivement les concentrations de ^{12}CH_4 et de ^{13}CH_4. Pour passer d'un isotope à l'autre, on ajuste simplement la fréquence du laser par effet Zeeman. L'expérience est en bon accord avec les prédictions et permet d'effectuer la mesure du rapport isotopique ^{13}CH4/^{12}CH_4 avec une fourchette d'incertitude de ± 0,07% pour des échantillons de gaz ne contenant que 6× 10^{-9} mole de méthane.

Negligible fractionation of Kr and Xe isotopes by molecular diffusion in water

NASA Astrophysics Data System (ADS)

Tyroller, Lina; Brennwald, Matthias S.; Busemann, Henner; Maden, Colin; Baur, Heinrich; Kipfer, Rolf

2018-06-01

Molecular diffusion is a key transport process for noble gases in water. Such diffusive transport is often thought to cause a mass-dependent fractionation of noble gas isotopes that is inversely proportional to the square root of the ratio of their atomic mass, referred to as the square root relation. Previous studies, challenged the commonly held assumption that the square root relation adequately describes the behaviour of noble gas isotopes diffusing through water. However, the effect of diffusion on noble gas isotopes has only been determined experimentally for He, Ne and Ar to date, whereas the extent of fractionation of Kr and Xe has not been measured. In the present study the fractionation of Kr and Xe isotopes diffusing through water immobilised by adding agar was quantified through measuring the respective isotope ratio after diffusing through the immobilised water. No fractionation of Kr and Xe isotopes was observed, even using high-precision noble gas analytics. These results complement our current understanding on isotopic fractionation of noble gases diffusing through water. Therefore this complete data set builds a robust basis to describe molecular diffusion of noble gases in water in a physical sound manner which is fundamental to assess the physical aspects of gas dynamics in aquatic systems.

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.

Preferential flow pathways revealed by field based stable isotope analysis of CO2 by mid-infrared laser spectroscopy

NASA Astrophysics Data System (ADS)

van Geldern, Robert; Nowak, Martin; Zimmer, Martin; Szizybalski, Alexandra; Myrttinen, Anssi; Barth, Johannes A. C.; Jost, Hj

2016-04-01

A newly developed and commercially available isotope ratio laser spectrometer for CO2 analyses has been tested during a 10-day field monitoring campaign at the Ketzin pilot site for CO2 storage in northern Germany. 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 minutes 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 2σ analytical precision (<0.3 ‰). This proves the capability of the new mid-infrared direct absorption technique to measure high precision and accurate real-time table isotope data directly in the field. The injected CO2 tracer had a distinct δ13C value that was largely different from the reservoir background value. The laser spectroscopy data revealed a prior to this study unknown, intensive dynamic with fast changing δ13C 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 new technique might contribute to a better tracing of the migration of the underground CO2 plume and help to ensure the long-term integrity of the reservoir.

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

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

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

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

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.more » 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.« less

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.

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.

Analysis of the differentially expressed low molecular weight peptides in human serum via an N-terminal isotope labeling technique combining nano-liquid chromatography/matrix-assisted laser desorption/ionization mass spectrometry.

PubMed

Leng, Jiapeng; Zhu, Dong; Wu, Duojiao; Zhu, Tongyu; Zhao, Ningwei; Guo, Yinlong

2012-11-15

Peptidomics analysis of human serum is challenging due to the low abundance of serum peptides and interference from the complex matrix. This study analyzed the differentially expressed (DE) low molecular weight peptides in human serum integrating a DMPITC-based N-terminal isotope labeling technique with nano-liquid chromatography and matrix-assisted laser desorption/ionization mass spectrometry (nano-LC/MALDI-MS). The workflow introduced a [d(6)]-4,6-dimethoxypyrimidine-2-isothiocyanate (DMPITC)-labeled mixture of aliquots from test samples as the internal standard. The spiked [d(0)]-DMPITC-labeled samples were separated by nano-LC then spotted on the MALDI target. Both quantitative and qualitative studies for serum peptides were achieved based on the isotope-labeled peaks. The DMPITC labeling technique combined with nano-LC/MALDI-MS not only minimized the errors in peptide quantitation, but also allowed convenient recognition of the labeled peptides due to the 6 Da mass difference. The data showed that the entire research procedure as well as the subsequent data analysis method were effective, reproducible, and sensitive for the analysis of DE serum peptides. This study successfully established a research model for DE serum peptides using DMPITC-based N-terminal isotope labeling and nano-LC/MALDI-MS. Application of the DMPITC-based N-terminal labeling technique is expected to provide a promising tool for the investigation of peptides in vivo, especially for the analysis of DE peptides under different biological conditions. Copyright © 2012 John Wiley & Sons, Ltd.

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

Electron Impact Cross Sections for Molecular Lasers

DTIC Science & Technology

1984-04-27

range coumunication and surveillance, isotope separation, and controlled thermonuclear fussion . Among all kinds of lasers, the gaseous discharge...shape resonance of n symmetry (reviewed by Schulz, 1976). Like vibrational excitation from the ground state, such process from nuclear -excited states as...energy range specifically in the 1-4 eV resonant region. 4 - A. Vibrational Excitation of Nuclear -Excited N2 For vibrational excitation by

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

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

Cohn, D. B., E-mail: dbctechnology@earthlink.net

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. Relatedmore » work shows capability for long term sealed operation with a catalyst and an agile tuner at a wavelength shift rate of 200 Hz.« less

Two-dimensional fluorescence spectroscopy of uranium isotopes in femtosecond laser ablation plumes

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

Phillips, Mark C.; Brumfield, Brian E.; LaHaye, Nicole

Here, we demonstrate measurement of uranium isotopes in femtosecond laser ablation plumes using two-dimensional fluorescence spectroscopy (2DFS). The high-resolution, tunable CW-laser spectroscopy technique clearly distinguishes atomic absorption from 235U and 238U in natural and highly enriched uranium metal samples. We present analysis of spectral resolution and analytical performance of 2DFS as a function of ambient pressure. Simultaneous measurement using time-resolved absorption spectroscopy provides information on temporal dynamics of the laser ablation plume and saturation behavior of fluorescence signals. The rapid, non-contact measurement is promising for in-field, standoff measurements of uranium enrichment for nuclear safety and security.

Two-dimensional fluorescence spectroscopy of uranium isotopes in femtosecond laser ablation plumes

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

Phillips, Mark C.; Brumfield, Brian E.; LaHaye, Nicole L.

We demonstrate measurement of uranium isotopes in femtosecond laser ablation plumes using two-dimensional fluorescence spectroscopy (2DFS). The high-resolution, tunable CW-laser spectroscopy technique clearly distinguishes atomic absorption from 235U and 238U in natural and highly enriched uranium metal samples. We present analysis of spectral resolution and analytical performance of 2DFS as a function of ambient pressure. Simultaneous measurement using time-resolved absorption spectroscopy provides information on temporal dynamics of the laser ablation plume and saturation behavior of fluorescence signals. The rapid, non-contact measurement is promising for in-field, standoff measurements of uranium enrichment for nuclear safety and security applications.

Two-dimensional fluorescence spectroscopy of uranium isotopes in femtosecond laser ablation plumes

DOE PAGES

Phillips, Mark C.; Brumfield, Brian E.; LaHaye, Nicole; ...

2017-06-19

Here, we demonstrate measurement of uranium isotopes in femtosecond laser ablation plumes using two-dimensional fluorescence spectroscopy (2DFS). The high-resolution, tunable CW-laser spectroscopy technique clearly distinguishes atomic absorption from 235U and 238U in natural and highly enriched uranium metal samples. We present analysis of spectral resolution and analytical performance of 2DFS as a function of ambient pressure. Simultaneous measurement using time-resolved absorption spectroscopy provides information on temporal dynamics of the laser ablation plume and saturation behavior of fluorescence signals. The rapid, non-contact measurement is promising for in-field, standoff measurements of uranium enrichment for nuclear safety and security.

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

Probing Molecular Ions With Laser-Cooled Atomic Ions

DTIC Science & Technology

2017-10-11

Sept. 23, 2015 Precision Chemical Dynamics and Quantum Control of Ultracold Molecular Ion Reactions , Cold Molecular Ions at the Quantum limit (COMIQ...ken.brown@chemistry.gatech.edu This work solved an old mystery about the lifetime of Ca+ due to reactions with background gases in laser-cooling experiments...Relative to other alkaline earths, Ca+ had a much slower reaction rate. We discovered the reason is that the Doppler cooling laser is near

Development of a laser system of the laboratory AVLIS complex for producing isotopes and radionuclides

NASA Astrophysics Data System (ADS)

D'yachkov, A. B.; Gorkunov, A. A.; Labozin, A. V.; Mironov, S. M.; Panchenko, V. Ya.; Firsov, V. A.; Tsvetkov, G. O.

2018-01-01

The use of atomic vapour laser isotope separation (AVLIS) for solving a number of urgent problems (formation of 177Lu radionuclides for medical applications, 63Ni radionuclides for betavoltaic power supplies and 150Nd isotope for searching for neutrinoless double β decay and neutrino mass) is considered. An efficient three-step scheme of photoionisation of neodymium atoms through the 50474-cm-1 autoionising state with radiation wavelengths of the corresponding stages of λ1 = 6289.7 Å, λ2 = 5609.4 Å and λ3 = 5972.1 Å is developed. The average saturation intensity of the autoionising transition is ˜6 W cm-2, a value consistent with the characteristics of the previously developed photoionisation schemes for lutetium and nickel. A compact laser system for the technological AVLIS complex, designed to produce radionuclides and isotopes under laboratory conditions, is developed based on the experimental results.

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

On the potential of laser driven isotope generation at ELI-NP for positron emission tomography

NASA Astrophysics Data System (ADS)

Cucoanes, A. S.; Balabanski, D. L.; Canova, F.; Cuong, P.; Negoita, F.; Puicea, F.; Tanaka, K. A.

2017-05-01

The huge progress made in the laser driven ion acceleration had open the possibility of using ions generated in high power laser interactions with solid targets for the production of medical isotopes. Indeed, lasers could provide several key features with respect to the traditional method where the target activation is produced by particle beams delivered by cyclotrons. The price and the dimensions of high power lasers are on a descendant slope and the quality of the produced ion beams is continuously increasing. However, in order to compete with cyclotrons, the average proton current intensity has to be increased for example by increasing the frequency of the laser pulses. In our contribution, we review the general ideas of the laser-based radioisotope production and we present our analysis on the potential of the medical isotope generation at ELI-NP with a focus on 18F. We use estimations of the proton beam parameters and a code implemented in Geant4 for computing the yield of the main production channel taking into account the experimental conditions available soon at ELI-NP. The obtained results are compatible with previous studies and will be verified by experiments foreseen at the future ELI-NP facility, under construction now in Magurele, Romania.

Thermal and molecular investigation of laser tissue welding

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

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 themore » 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.« less

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.

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

Rapid and high-resolution stable isotopic measurement of biogenic accretionary carbonate using an online CO2 laser ablation system: Standardization of the analytical protocol.

PubMed

Sreemany, Arpita; Bera, Melinda Kumar; Sarkar, Anindya

2017-12-30

The elaborate sampling and analytical protocol associated with conventional dual-inlet isotope ratio mass spectrometry has long hindered high-resolution climate studies from biogenic accretionary carbonates. Laser-based on-line systems, in comparison, produce rapid data, but suffer from unresolvable matrix effects. It is, therefore, necessary to resolve these matrix effects to take advantage of the automated laser-based method. Two marine bivalve shells (one aragonite and one calcite) and one fish otolith (aragonite) were first analysed using a CO 2 laser ablation system attached to a continuous flow isotope ratio mass spectrometer under different experimental conditions (different laser power, sample untreated vs vacuum roasted). The shells and the otolith were then micro-drilled and the isotopic compositions of the powders were measured in a dual-inlet isotope ratio mass spectrometer following the conventional acid digestion method. The vacuum-roasted samples (both aragonite and calcite) produced mean isotopic ratios (with a reproducibility of ±0.2 ‰ for both δ 18 O and δ 13 C values) almost identical to the values obtained using the conventional acid digestion method. As the isotopic ratio of the acid digested samples fall within the analytical precision (±0.2 ‰) of the laser ablation system, this suggests the usefulness of the method for studying the biogenic accretionary carbonate matrix. When using laser-based continuous flow isotope ratio mass spectrometry for the high-resolution isotopic measurements of biogenic carbonates, the employment of a vacuum-roasting step will reduce the matrix effect. This method will be of immense help to geologists and sclerochronologists in exploring short-term changes in climatic parameters (e.g. seasonality) in geological times. Copyright © 2017 John Wiley & Sons, Ltd.

Thermal and molecular investigation of laser tissue welding

NASA Astrophysics Data System (ADS)

Small, Ward, IV

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 on 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 the probability of long-term success. Molecular effects induced in the tissue by laser irradiation were investigated by measuring the concentrations of specific collagen covalent crosslinks and measuring the infrared absorption spectra before and after the laser exposure. This investigation yielded results pertaining to both the methods and mechanisms of laser tissue welding. The combination of two-color infrared thermometry to obtain accurate surface temperatures free from emissivity bias and computer modeling illustrated the importance of including evaporation in the simulations, which effectively serves as an inherent cooling mechanism during laser irradiation. Moreover, the hydration state predicted by the model was useful in assessing the role of electrostatic versus covalent bonding in the fusion. These tools also helped elicit differences between dye- enhanced liquid solders and solid-matrix patches in laser-assisted tissue welding, demonstrating the significance of repeatable energy delivery. Surprisingly, covalent bonds

Dynamics of photoionization from molecular electronic wavepacket states in intense pulse laser fields: A nonadiabatic electron wavepacket study.

PubMed

Matsuoka, Takahide; Takatsuka, Kazuo

2017-04-07

A theory for dynamics of molecular photoionization from nonadiabatic electron wavepackets driven by intense pulse lasers is proposed. Time evolution of photoelectron distribution is evaluated in terms of out-going electron flux (current of the probability density of electrons) that has kinetic energy high enough to recede from the molecular system. The relevant electron flux is in turn evaluated with the complex-valued electronic wavefunctions that are time evolved in nonadiabatic electron wavepacket dynamics in laser fields. To uniquely rebuild such wavefunctions with its electronic population being lost by ionization, we adopt the complex-valued natural orbitals emerging from the electron density as building blocks of the total wavefunction. The method has been implemented into a quantum chemistry code, which is based on configuration state mixing for polyatomic molecules. Some of the practical aspects needed for its application will be presented. As a first illustrative example, we show the results of hydrogen molecule and its isotope substitutes (HD and DD), which are photoionized by a two-cycle pulse laser. Photon emission spectrum associated with above threshold ionization is also shown. Another example is taken from photoionization dynamics from an excited state of a water molecule. Qualitatively significant effects of nonadiabatic interaction on the photoelectron spectrum are demonstrated.

Generation of Raman lasers from nitrogen molecular ions driven by ultraintense laser fields

NASA Astrophysics Data System (ADS)

Yao, Jinping; Chu, Wei; Liu, Zhaoxiang; Xu, Bo; Chen, Jinming; Cheng, Ya

2018-03-01

Atmospheric lasing has aroused much interest in the past few years. The ‘air–laser’ opens promising potential for remote chemical sensing of trace gases with high sensitivity and specificity. At present, several approaches have been successfully implemented for generating highly coherent laser beams in atmospheric condition, including both amplified-spontaneous emission, and narrow-bandwidth stimulated emission in the forward direction in the presence of self-generated or externally injected seed pulses. Here, we report on generation of multiple-wavelength Raman lasers from nitrogen molecular ions ({{{N}}}2+), driven by intense mid-infrared laser fields. Intuitively, the approach appears problematic for the small nonlinear susceptibility of {{{N}}}2+ ions, whereas the efficiency of Raman laser can be significantly promoted in near-resonant condition. More surprisingly, a Raman laser consisting of a supercontinuum spanning from ∼310 to ∼392 nm has been observed resulting from a series near-resonant nonlinear processes including four-wave mixing, stimulated Raman scattering and cross phase modulation. To date, extreme nonlinear optics in molecular ions remains largely unexplored, which provides an alternative means for air–laser-based remote sensing applications.

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.

Studies on the optogalvanic effect and isotope-selective excitation of ytterbium in a hollow cathode discharge lamp using a pulsed dye laser.

PubMed

Kumar, Pankaj; Kumar, Jitendra; Prakash, Om; Saini, Vinod K; Dixit, Sudhir K; Nakhe, Shankar V

2013-09-01

This paper presents studies on the pulsed optogalvanic effect and isotope-selective excitation of Yb 555.648 nm (0 cm(-1) → 17 992.007 cm(-1)) and 581.067 nm (17 992.007 cm(-1) → 35 196.98 cm(-1)) transitions, in a Yb/Ne hollow cathode lamp. The Yb atoms were excited by narrow linewidth (500-1000 MHz) Rh110 and Rh6G dye based pulsed lasers. Optogalvanic signal inversion for ground state transition at 555.648 nm was observed beyond a hollow cathode discharge current of 8.5 mA, in contrast to normal optogalvanic signal at 581.067 nm up to maximum current of 14 mA. The isotope-selective excitation studies of Yb were carried out by recording Doppler limited optogalvanic signals as a function of dye laser wavelength. For the 581.067 nm transition, three even isotopes, (172)Yb, (174)Yb, and (176)Yb, and one odd isotope, (171)Yb, were clearly resolved. These data were compared with selective isotope excitation by 10 MHz linewidth continuous-wave dye laser. For 555.648 nm transition, isotopes were not clearly resolved, although isotope peaks of low modulation were observed.

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.

Molecular and isotopic analyses of Tagish Lake alkyl dicarboxylic acids

NASA Astrophysics Data System (ADS)

Pizzarello, Sandra; Huang, Yongsong

2002-05-01

The Tagish Lake meteorite soluble organic suite has a general composition that differs from those of both CI- and CM chondrites. These differences suggest that distinct processes may have been involved in the formation of different groups of organics in meteorites. Tagish Lake alkyl dicarboxylic acids have a varied, abundant distribution and are, with carboxylated pyridines, the only compounds to have an occurrence comparable to that of the Murchison meteorite. This study has undertaken their molecular and isotopic characterization, with the aim to understand their origin and to gain insights into the evolutionary history of the meteorite parent body. Tagish Lake alkyl dicarboxylic acids are present as a homologous series of saturated and unsaturated species with three through ten-carbon atom chain length. Linear saturated acids are predominant and show decreasing amounts with increasing chain length. A total of forty-four of these compounds were detected with the most abundant, succinic acid, present at ~40 nmoles/g. met. Overall the molecular distribution of Tagish Lake dicarboxylic acids shows a remarkable compound to compound correspondence with those observed in the Murchison and Murray meteorites. In both Tagish Lake and Murchison, the imides of the more abundant dicarboxylic acids were also observed. The hydrogen and carbon isotopic compositions of individual Tagish Lake dicarboxylic acids were determined and compared to those of the corresponding acids in the Murchison meteorite. All delta D and delta 13C values for Tagish Lake acids are positive and show a substantial isotopic enrichment. Delta D values vary from, approximately, + 1120 deg for succinic acid to + 1530 deg for methyl glutaric acid. Delta 13C values ranged from + 12.6 deg for methyl glutaric acid to + 22.9 deg for glutaric acid, with adipic acid having a significantly lower value (+ 5.5 deg). Murchison dicarboxylic acid showed similar isotopic values: their delta 13C values were generally

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

PubMed

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

2017-03-22

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

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.

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

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.

Quantum control of molecular fragmentation in strong laser fields

NASA Astrophysics Data System (ADS)

Zohrabi, Mohammad

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

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

NASA Astrophysics Data System (ADS)

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

2017-04-01

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

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

In Situ Carbon Isotope Analysis by Laser Ablation MC-ICP-MS.

PubMed

Chen, Wei; Lu, Jue; Jiang, Shao-Yong; Zhao, Kui-Dong; Duan, Deng-Fei

2017-12-19

Carbon isotopes have been widely used in tracing a wide variety of geological and environmental processes. The carbon isotope composition of bulk rocks and minerals was conventionally analyzed by isotope ratio mass spectrometry (IRMS), and, more recently, secondary ionization mass spectrometry (SIMS) has been widely used to determine carbon isotope composition of carbon-bearing solid materials with good spatial resolution. Here, we present a new method that couples a RESOlution S155 193 nm laser ablation system with a Nu Plasma II MC-ICP-MS, with the aim of measuring carbon isotopes in situ in carbonate minerals (i.e., calcite and aragonite). Under routine operating conditions for δ 13 C analysis, instrumental bias generally drifts by 0.8‰-2.0‰ in a typical analytical session of 2-3 h. Using a magmatic calcite as the standard, the carbon isotopic composition was determined for a suite of calcite samples with δ 13 C values in the range of -6.94‰ to 1.48‰. The obtained δ 13 C data are comparable to IRMS values. The combined standard uncertainty for magmatic calcite is <0.3‰ (1s). No significant matrix effects have been identified in calcite with the amplitude of chemical composition variation (i.e., MnO, SrO, MgO, or FeO) up to 2.5 wt %. Two modern corals were investigated using magmatic calcite as the calibration standard, and the average δ 13 C values for both corals are similar to the bulk IRMS values. Moreover, coral exhibits significant heterogeneity in carbon isotope compositions, with differences up to 4.85‰ within an individual coral. This study indicates that LA-MC-ICP-MS can serve as an appropriate method to analyze carbon isotopes of carbonate minerals in situ.

Linear and Nonlinear Molecular Spectroscopy with Laser Frequency Combs

NASA Astrophysics Data System (ADS)

Picque, Nathalie

2013-06-01

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

Molecular carbon isotopic evidence for the origin of geothermal hydrocarbons

NASA Technical Reports Server (NTRS)

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

1981-01-01

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

Cryogenic separation of an oxygen-argon mixture in natural air samples for the determination of isotope and molecular ratios.

PubMed

Keedakkadan, Habeeb Rahman; Abe, Osamu

2015-04-30

The separation and purification of oxygen-argon mixtures are critical in the high-precision analysis of Δ(17) O and δ(O2 /Ar) for geochemical applications. At present, chromatographic methods are used for the separation and purification of oxygen-argon mixtures or pure oxygen, but these methods require the use of high-purity helium as a carrier gas. Considerable interest has been expressed in the development of a helium-free cryogenic separation of oxygen-argon mixtures in natural air samples. The precise and simplified cryogenic separation of oxygen-argon mixtures from natural air samples presented here was made possible using a single 5A (30/60 mesh) molecular sieve column. The method involves the trapping of eluted gases using molecular sieves at liquid nitrogen temperature, which is associated with isotopic fractionation. We tested the proposed method for the determination of isotopic fractionations during the gas exchange between water and atmospheric air at equilibrium. The dependency of fractionation was studied at different water temperatures and for different methods of equilibration (bubbling and stirring). Isotopic and molecular fractionations during gas desorption from molecular sieves were studied for different amounts and types of molecular sieves. Repeated measurements of atmospheric air yielded a reproducibility (±SD) of 0.021 ‰, 0.044 ‰, 15 per meg and 1.9 ‰ for δ(17) O, δ(18) O, Δ(17) O and δ(O2 /Ar) values, respectively. We applied the method to determine equilibrium isotope fractionation during gas exchange between air and water. Consistent δ(18) O and Δ(17) O results were obtained with the latest two studies, whereas there was a significant difference in δ(18) O values between seawater and deionized water. We have revised a helium-free, cryogenic separation of oxygen-argon mixtures in natural air samples for isotopic and molecular ratio analysis. The use of a single 13X (1/8" pellet) molecular sieve yielded the smallest isotopic

Molecular dynamics study of lubricant depletion by pulsed laser heating

NASA Astrophysics Data System (ADS)

Seo, Young Woo; Rosenkranz, Andreas; Talke, Frank E.

2018-05-01

In this study, molecular dynamics simulations were performed to numerically investigate the effect of pulsed laser heating on lubricant depletion. The maximum temperature, the lubricant depletion width, the number of evaporated lubricant beads and the number of fragmented lubricant chains were studied as a function of laser peak power, pulse duration and repetition rate. A continuous-wave laser and a square pulse laser were simulated and compared to a Gaussian pulse laser. With increasing repetition rate, pulsed laser heating was found to approach continuous-wave laser heating.

Quantitative measurement of carbon isotopic composition in CO2 gas reservoir by Micro-Laser Raman spectroscopy

NASA Astrophysics Data System (ADS)

Li, Jiajia; Li, Rongxi; Zhao, Bangsheng; Guo, Hui; Zhang, Shuan; Cheng, Jinghua; Wu, Xiaoli

2018-04-01

The use of Micro-Laser Raman spectroscopy technology for quantitatively determining gas carbon isotope composition is presented. In this study, 12CO2 and 13CO2 were mixed with N2 at various molar fraction ratios to obtain Raman quantification factors (F12CO2 and F13CO2), which provide a theoretical basis for calculating the δ13C value. And the corresponding values were 0.523 (0 < C12CO2/CN2 < 2) and 1.11998 (0 < C13CO2/CN2 < 1.5) respectively. It has shown that the representative Raman peak area can be used for the determination of δ13C values within the relative errors range of 0.076% to 1.154% in 13CO2/12CO2 binary mixtures when F12CO2/F13CO2 is 0.466972625. In addition, measurement of δ13C values by Micro-Laser Raman analysis were carried out on natural CO2 gas from Shengli Oil-field at room temperature under different pressures. The δ13C values obtained by Micro-Laser Raman spectroscopy technology and Isotope Ratio Mass Spectrometry (IRMS) technology are in good agreement with each other, and the relative errors range of δ13C values is 1.232%-6.964%. This research provides a fundamental analysis tool for determining gas carbon isotope composition (δ13C values) quantitatively by using Micro-Laser Raman spectroscopy. Experiment of results demonstrates that this method has the potential for obtaining δ13C values in natural CO2 gas reservoirs.

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

NASA Technical Reports Server (NTRS)

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

1977-01-01

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

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)

Characterization of nanoparticle mediated laser transfection by femtosecond laser pulses for applications in molecular medicine.

PubMed

Schomaker, Markus; Heinemann, Dag; Kalies, Stefan; Willenbrock, Saskia; Wagner, Siegfried; Nolte, Ingo; Ripken, Tammo; Murua Escobar, Hugo; Meyer, Heiko; Heisterkamp, Alexander

2015-02-03

In molecular medicine, the manipulation of cells is prerequisite to evaluate genes as therapeutic targets or to transfect cells to develop cell therapeutic strategies. To achieve these purposes it is essential that given transfection techniques are capable of handling high cell numbers in reasonable time spans. To fulfill this demand, an alternative nanoparticle mediated laser transfection method is presented herein. The fs-laser excitation of cell-adhered gold nanoparticles evokes localized membrane permeabilization and enables an inflow of extracellular molecules into cells. The parameters for an efficient and gentle cell manipulation are evaluated in detail. Efficiencies of 90% with a cell viability of 93% were achieved for siRNA transfection. The proof for a molecular medical approach is demonstrated by highly efficient knock down of the oncogene HMGA2 in a rapidly proliferating prostate carcinoma in vitro model using siRNA. Additionally, investigations concerning the initial perforation mechanism are conducted. Next to theoretical simulations, the laser induced effects are experimentally investigated by spectrometric and microscopic analysis. The results indicate that near field effects are the initial mechanism of membrane permeabilization. This methodical approach combined with an automated setup, allows a high throughput targeting of several 100,000 cells within seconds, providing an excellent tool for in vitro applications in molecular medicine. NIR fs lasers are characterized by specific advantages when compared to lasers employing longer (ps/ns) pulses in the visible regime. The NIR fs pulses generate low thermal impact while allowing high penetration depths into tissue. Therefore fs lasers could be used for prospective in vivo applications.

Optimizing isotope substitution in graphene for thermal conductivity minimization by genetic algorithm driven molecular simulations

NASA Astrophysics Data System (ADS)

Davies, Michael; Ganapathysubramanian, Baskar; Balasubramanian, Ganesh

2017-03-01

We present results from a computational framework integrating genetic algorithm and molecular dynamics simulations to systematically design isotope engineered graphene structures for reduced thermal conductivity. In addition to the effect of mass disorder, our results reveal the importance of atomic distribution on thermal conductivity for the same isotopic concentration. Distinct groups of isotope-substituted graphene sheets are identified based on the atomic composition and distribution. Our results show that in structures with equiatomic compositions, the enhanced scattering by lattice vibrations results in lower thermal conductivities due to the absence of isotopic clusters.

Molecular laser stabilization for LISA

NASA Astrophysics Data System (ADS)

Halloin, Hubert; Acef, Ouali; Argence, Berengere; Jeannin, Olivier; Prat, Pierre; de Vismes, Eden; Plagnol, Eric; Brillet, Alain; Mondin, Linda; Berthon, Jacques; Turazza, Oscar

2017-11-01

The expected performance of LISA relies on two main technical challenges: the ability for the spacecrafts to precisely follow the free-flying masses and the outstanding precision of the phase shift measurement. This latter constraint requires frequency stabilized lasers and efficient numerical algorithms to account for the redundant, delayed noise propagation, thus cancelling laser phase noise by many orders of magnitude (TDI methods). Recently involved in the technical developments for LISA, the goal of our team at APC (France) is to contribute on these two subjects: frequency reference for laser stabilization and benchtop simulation of the interferometer. In the present design of LISA, two stages of laser stabilization are used (not accounting for the "post-processed" TDI algorithm): laser pre-stabilization on a frequency reference and lock on the ultra stable distance between spacecrafts (arm-locking). While the foreseen (and deeply studied) laser reference consists of a Fabry-Perot cavity, other techniques may be suitable for LISA or future metrology missions. In particular, locking to a molecular reference (namely iodine in the case of the LISA Nd:YAG laser) is an interesting alternative. It offers the required performance with very good long-term stability (absolute frequency reference) though the reference can be slightly tuned to account for arm-locking. This technique is currently being investigated by our team and optimized for LISA (compactness, vacuum compatibility, ease of use and initialization, etc.). A collaboration with a French laboratory (the SYRTE) had been started aiming to study a second improved technique consisting in inserting the iodine cell in a Fabry-Perot cavity. Ongoing results and prospects to increase the performance of the system are presented in the present article.

Frequency stabilization of quantum cascade laser for spectroscopic CO2 isotope analysis

NASA Astrophysics Data System (ADS)

Han, Luo; Xia, Hua; Pang, Tao; Zhang, Zhirong; Wu, Bian; Liu, Shuo; Sun, Pengshuai; Cui, Xiaojuan; Wang, Yu; Sigrist, Markus W.; Dong, Fengzhong

2018-06-01

Using off-axis integrated cavity output spectroscopy, named OA-ICOS, the absorption spectrum of CO2 at 4.32 μm is recorded by using a quantum cascade laser (QCL). The concentration of the three isotopologues 16O12C16O, 16O13C16O and 16O12C18O is detected simultaneously. The isotope abundance ratio of 13C and 18O in CO2 gas can be obtained, which is most useful for ecological research. Since the ambient temperature has a serious influence on the output wavelength of the laser, even small temperature variations seriously affect the stability and sensitivity of the system. In this paper, a wavelength locking technique for QCL is proposed. The output of a digital potentiometer integrated in the laser current driver control is modified by software, resulting in a correction of the driving current of the laser and thus of its wavelength. This method strongly reduces the influence of external factors on the wavelength drift of lasers and thus substantially improves the stability and performance of OA-ICOS as is demonstrated with long-time measurements on CO2 in laboratory air.

Quantitative measurement of carbon isotopic composition in CO2 gas reservoir by Micro-Laser Raman spectroscopy.

PubMed

Li, Jiajia; Li, Rongxi; Zhao, Bangsheng; Guo, Hui; Zhang, Shuan; Cheng, Jinghua; Wu, Xiaoli

2018-04-15

The use of Micro-Laser Raman spectroscopy technology for quantitatively determining gas carbon isotope composition is presented. In this study, 12 CO 2 and 13 CO 2 were mixed with N 2 at various molar fraction ratios to obtain Raman quantification factors (F 12CO2 and F 13CO2 ), which provide a theoretical basis for calculating the δ 13 C value. And the corresponding values were 0.523 (0Laser Raman analysis were carried out on natural CO 2 gas from Shengli Oil-field at room temperature under different pressures. The δ 13 C values obtained by Micro-Laser Raman spectroscopy technology and Isotope Ratio Mass Spectrometry (IRMS) technology are in good agreement with each other, and the relative errors range of δ 13 C values is 1.232%-6.964%. This research provides a fundamental analysis tool for determining gas carbon isotope composition (δ 13 C values) quantitatively by using Micro-Laser Raman spectroscopy. Experiment of results demonstrates that this method has the potential for obtaining δ 13 C values in natural CO 2 gas reservoirs. Copyright © 2018. Published by Elsevier B.V.

Molecular carbon isotopic evidence for the origin of geothermal hydrocarbons

USGS Publications Warehouse

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

1981-01-01

Previous interest in light hydrocarbons from geothermal systems has focused principally on the origin of the methane1 and the estimation of subsurface temperatures from the carbon isotopic content of coexisting methane and carbon dioxide1-3. Higher molecular weight hydrocarbons were first reported in gases from Yellowstone National Park4, and have since been found to occur commonly in geothermal emanations in the western United States5. Isotopic measurements of individual geothermal hydrocarbons are now reported which help to explain the origin of these hydrocarbons. The thermal decomposition of sedimentary or groundwater organic matter is a principal source of hydrocarbons in four geothermal areas in western North America. ?? 1981 Nature Publishing Group.

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.

Spatially resolved δ13C analysis using laser ablation isotope ratio mass spectrometry

NASA Astrophysics Data System (ADS)

Moran, J.; Riha, K. M.; Nims, M. K.; Linley, T. J.; Hess, N. J.; Nico, P. S.

2014-12-01

Inherent geochemical, organic matter, and microbial heterogeneity over small spatial scales can complicate studies of carbon dynamics through soils. Stable isotope analysis has a strong history of helping track substrate turnover, delineate rhizosphere activity zones, and identifying transitions in vegetation cover, but most traditional isotope approaches are limited in spatial resolution by a combination of physical separation techniques (manual dissection) and IRMS instrument sensitivity. We coupled laser ablation sampling with isotope measurement via IRMS to enable spatially resolved analysis over solid surfaces. Once a targeted sample region is ablated the resulting particulates are entrained in a helium carrier gas and passed through a combustion reactor where carbon is converted to CO2. Cyrotrapping of the resulting CO2 enables a reduction in carrier gas flow which improves overall measurement sensitivity versus traditional, high flow sample introduction. Currently we are performing sample analysis at 50 μm resolution, require 65 ng C per analysis, and achieve measurement precision consistent with other continuous flow techniques. We will discuss applications of the laser ablation IRMS (LA-IRMS) system to microbial communities and fish ecology studies to demonstrate the merits of this technique and how similar analytical approaches can be transitioned to soil systems. Preliminary efforts at analyzing soil samples will be used to highlight strengths and limitations of the LA-IRMS approach, paying particular attention to sample preparation requirements, spatial resolution, sample analysis time, and the types of questions most conducive to analysis via LA-IRMS.

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

Molecular long-wavelength lasers and their future prospects (review)

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

Molevich, N.E.; Oraevskii, A.N.

A review is given of the main types of molecular lasers emitting at wavelengths lambda> or =15 ..mu.. as a result of electric-discharge, optical, or chemical excitation. Attention is drawn to new developments in long-wavelength lasers based on the VRT relaxation mechanism of a series of diatomic molecules containing hydrogen.

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

DOE PAGES

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

2016-06-17

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

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

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

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

2016-08-01

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, formore » 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 Fe-58 and Ni-58 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, similar to 10 nm lateral resolution and 30-40% useful yield.« less

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.

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

NASA Technical Reports Server (NTRS)

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

1986-01-01

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

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. Copyright © 2011 John Wiley & Sons, Ltd.

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…

Advancing an In situ Laser Spectrometer for Carbon Isotope Analyses in the Deep Ocean

NASA Astrophysics Data System (ADS)

Michel, A.; Wankel, S. D.; Kapit, J.; Girguis, P. R.

2016-02-01

Development of in situ chemical sensors is critical for improving our understanding of deep-ocean biogeochemistry and recent advances in chemical sensors are already expanding the breadth and depth of deep sea/seafloor exploration and research. Although initially developed for high sensitivity measurements of atmospheric gases, laser-based spectroscopic sensors are now being developed for research in the deep sea by incorporating the use of semi-permeable membranes. Here we present on recent deep-sea deployments of an in situ laser-based analyzer of carbon isotopes of methane (δ13CH4), highlighting several advances including a new capability for also measuring δ13C of DIC or CO2 by incorporating a second laser and an in line acidification module. A bubble trapping approach was designed and implemented for the collection and analysis of both CH4 and CO2 from deep-sea bubbles. The newly advanced laser spectrometer was deployed at both Kick `Em Jenny volcano off of the island of Grenada and in a brine pool in the western Gulf of Mexico ("The Jacuzzi of Despair") using the E/V Nautilus and the ROV Hercules. At Kick `Em Jenny, seafloor measurements were made of both emanating fluids and bubbles from within and around the crater - revealing high levels of magmatic CO2 with minor amounts of CH4 and hydrogen sulfide. At the brine pool, spot measurements and depth profile measurements into the brine pool were made for chemical mapping, revealing fluids that were saturated with respect to methane. New technologies such as the laser spectrometer will enable us to obtain high resolution and near real-time, in situ chemical and isotopic data and to make geochemical maps over a range of spatial and temporal scales.

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.

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.

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

PubMed Central

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

2016-01-01

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

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

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

Harilal, Sivanandan S.; Yeak, J.; Brumfield, Brian E.

2016-06-15

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

First field determination of the 13C/12C isotope ratio in volcanic CO2 by diode-laser.

PubMed

Castrillo, A; Casa, G; van Burgel, M; Tedesco, D; Gianfrani, L

2004-12-27

Carbon isotope ratio analysis using a laser-based technique has been performed in the field, on the gaseous emissions from an active volcano. We here describe that 13CO2/12CO2 determinations can be carried out in a quasi-continuous regime using a compact, selective and sensitive diode laser spectrometer at a wavelength of 2 mum. Within the Solfatara crater (near Naples, Italy), in a very harsh environment, we were able to determine relative 13CO2/12CO2 values, on the highest flux fumarole, with an accuracy of 0.5 per thousand. Regular and frequent observations of the carbon isotopes in volcanic gases, which become possible with our methodology, are of the utmost importance for geochemical surveillance of volcanoes.

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.

Diffusion coefficients of Mg isotopes in enstatite and forsterite melts calculated by first-principles molecular dynamic simulations

NASA Astrophysics Data System (ADS)

Huang, F.; Qi, Y.; Liu, X.; He, L.

2016-12-01

Stable isotopes can be fractionated by kinetic chemical diffusion because diffusion coefficients (D) of isotopes are mass-dependent. Diffusive isotopic fractionation recorded in rocks and minerals provide unique temporal constrains on geological processes. The mass dependence of D can be described in the form of Di/Dj= (mj/mi)β, where m denotes masses of isotope i and j, and β is an emperical parameter used to quantify the diffusive transport of isotopes [1]. β values can be estimated by experimental calibration and observation of natural samples, which are still rarely reported because it is challenging to precisely quantify the boundary conditions of diffusion processes [2,3,4]. Recent advances in computation technique provide a new way to theoretically calculate β values. For instance, classical molecular dynamics with empirical potential have been used to simulate interactions between atoms and estimate β of Mg isotopes in MgSiO3 melt [3]. Here, to further consider the effect of bonding and electron properties on β values, we apply first-principles Born-Oppenheimer Molecular Dynamics and pseudo-isotope methods (assuming mj/mi = 1/24, 1/4, 2, and 5) to estimate β for MgSiO3 and Mg2SiO4 melts. Our calculation shows that β of Mg isotopes with pseudo-mass ratios are consistent, indicating the reliability of the pseudo-isotope method. For MgSiO3 melt, β is 0.18 at 4000K and 0 GPa, higher than the value calculatedusing molecular dynamics simulations (0.135) [3]. For Mg2SiO4 melt at 0 GPa, β values are: 0.23 ± 0.04 at 2300K, 0.24 ± 0.07 at 3000K, and 0.24 ± 0.01 at 4000K. Notably, β of MgSiO3 and Mg2SiO4 melts are significantly higher than the value determined by diffusion experiments (0.05) [2]. These results indicate that β values are not sensitive to temperature, but dependent on melt composition.

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

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

NASA Astrophysics Data System (ADS)

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=1016-1019W 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 τ=25 fs), elucidating outer ionization dynamics, nanoplasma screening effects (being significant for I⩽1017 W cm-2), and the attainment of cluster vertical ionization (CVI) (at I=1017 W cm-2 for cluster radius R0⩽31 Å). Nuclear kinematic effects on heterocluster Coulomb explosion are governed by the kinematic parameter η=qCmA/qAmC for (CA4)n clusters (A=H,D), where qj and mj (j=A,C) are the ionic charges and masses. Nonuniform heterocluster Coulomb explosion (η>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 (C4+ for I=1017-1018W cm-2 and C6+ for I=1019 W cm-2), as well as for kinematic effects. Based on the CVI assumption, scaling laws for the cluster size (radius R0) dependence of the energetics of uniform Coulomb explosion of heteroclusters (η=1) were derived, with the size dependence of the average (Ej,av) and maximal (Ej,M) ion energies being Ej,av=aR02 and Ej,M=(5a/3)R02, as well as for the ion energy distributions P(Ej)∝Ej1/2; Ej⩽Ej,M. These results for uniform Coulomb explosion serve as benchmark reference data for the assessment of

Isoscalar giant monopole resonance in Sn isotopes using a quantum molecular dynamics model

NASA Astrophysics Data System (ADS)

Tao, C.; Ma, Y. G.; Zhang, G. Q.; Cao, X. G.; Fang, D. Q.; Wang, H. W.; Xu, J.

2013-12-01

The isoscalar giant monopole resonance (GMR) in Sn isotopes and other nuclei is investigated in the framework of the isospin-dependent quantum molecular dynamics (IQMD) model. The spectrum of GMR is calculated by taking the rms radius of a nucleus as its monopole moment. The peak energy, the FWHM, and the strength of the GMR extracted by a Gaussian fit to the spectrum have been studied. The GMR peak energies for Sn isotopes from the calculations using a mass-number-dependent Gaussian wave-packet width σr for nucleons are found to be overestimated and show a weak dependence on the mass number compared with the experimental data. However, it is found that experimental data of the GMR peak energies for 56Ni, 90Zr, and 208Pb as well as Sn isotopes can be nicely reproduced after taking into account the isospin dependence in isotope chains in addition to the mass-number dependence of σr for nucleons in the IQMD model calculation.

Direct and comprehensive analysis of dyes based on integrated molecular and structural information via laser desorption laser postionization mass spectrometry.

PubMed

Liu, Rong; Yin, Zhibin; Leng, Yixin; Hang, Wei; Huang, Benli

2018-01-01

Laser desorption laser postionization time-of-flight mass spectrometry (LDPI-TOFMS) was employed for direct analysis and determination of typical basic dyes. It was also used for the analysis and comprehensive understanding of complex materials such as blue ballpoint pen inks. Simultaneous emergences of fragmental and molecular information largely simplify and facilitate unambiguous identification of dyes via variable energy of 266nm postionization laser. More specifically, by optimizing postionization laser energy with the same energy of desorption laser, the structurally significant results show definite differences in the fragmentation patterns, which offer opportunities for discrimination of isomeric species with identical molecular weight. Moreover, relatively high spectra resolution can be acquired without the expense of sensitivity. In contrast to laser desorption/ionization mass spectrometry (LDI-MS), LDPI-MS simultaneously offers valuable molecular information about dyes in traces, solvents and additives about inks, thereby offering direct determination and comprehensive understanding of blue ballpoint inks and giving a high level of confidence to discriminate the complicated evidentiary samples. In addition, direct analysis of the inks not only allows the avoidance of the tedious sample preparation processes, significantly shortening the overall analysis time and improving throughput, but allows minimized sample consumption which is important for rare and precious samples. Copyright © 2017 Elsevier B.V. All rights reserved.

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.

Control of electron excitation and localization in the dissociation of H2(+) and its isotopes using two sequential ultrashort laser pulses.

PubMed

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 Schrödinger equation. While the first ultraviolet pulse is used to excite the electron wave packet on the dissociative 2psigma{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.

Making molecular balloons in laser-induced explosive boiling of polymer solutions.

PubMed

Leveugle, Elodie; Sellinger, Aaron; Fitz-Gerald, James M; Zhigilei, Leonid V

2007-05-25

The effect of the dynamic molecular rearrangements leading to compositional segregation is revealed in coarse-grained molecular dynamics simulations of short pulse laser interaction with a polymer solution in a volatile matrix. An internal release of matrix vapor at the onset of the explosive boiling of the overheated liquid is capable of pushing polymer molecules to the outskirts of a transient bubble, forming a polymer-rich surface layer enclosing the volatile matrix material. The results explain unexpected "deflated balloon" structures observed in films deposited by the matrix-assisted pulsed laser evaporation technique.

[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.

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

Optofluidic lasers with a single molecular layer of gain

PubMed Central

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

2014-01-01

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 respectively 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 1012/cm2, 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. PMID:25312306

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

NASA Astrophysics Data System (ADS)

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

2000-06-01

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

A field-deployable compound-specific isotope analyzer based on quantum cascade laser and hollow waveguide

NASA Astrophysics Data System (ADS)

Wu, Sheng; Deev, Andrei

2013-01-01

A field deployable Compound Specific Isotope Analyzer (CSIA) coupled with capillary chromatogrpahy based on Quantum Cascade (QC) lasers and Hollow Waveguide (HWG) with precision and chemical resolution matching mature Mass Spectroscopy has been achieved in our laboratory. The system could realize 0.3 per mil accuracy for 12C/13C for a Gas Chromatography (GC) peak lasting as short as 5 seconds with carbon molar concentration in the GC peak less than 0.5%. Spectroscopic advantages of HWG when working with QC lasers, i.e. single mode transmission, noiseless measurement and small sample volume, are compared with traditional free space and multipass spectroscopy methods.

Elemental, isotopic and molecular abundances in comets

NASA Technical Reports Server (NTRS)

Delsemme, A. H.

1986-01-01

The chemical composition of comet nuclei and the factors affecting it are discussed, summarizing the results of recent theoretical, experimental, and observational investigations. Consideration is given to the evidence supporting the view that the nucleus is radially differentiation (except for a thin outer layer), surface differentiation by heat processing and outgassing, and mantle buildup on an undifferentiated core. The nature of the refractory and volatile components is examined, and the elemental and isotopic compositions are given in tables and characterized. The uncertain (except for H2O) molecular composition of the volatile fraction is considered, and it is suggested that some oxides or aldehydes (such as CO, CO2, and H2CO), but no large amounts of fully hydrogenated compounds (such as CH4 and NH3) are included.

Laser desorption mass spectrometry for molecular diagnosis

NASA Astrophysics Data System (ADS)

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

1996-04-01

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

Hydrogen isotope separation using molecular sieve of synthetic zeolite 3A

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

Kotoh, K.; Kimura, K.; Nakamura, Y.

2008-07-15

It is known that hydrogen isotope molecules can be adsorbed easily onto synthetic zeolite 4A, 5A, and 13X at the liquid-nitrogen temperature of 77.4 K. We show here that hydrogen and deuterium are not adsorptive onto zeolite 3A at the same temperature. This phenomenon is explained by assuming the molecular sieve function in zeolite-3A-crystalline lattice structure. From a series of pseudo-isobaric experiments, it is also shown that the sieving phenomenon appears in a range above 77.4 K. This behavior is interpreted as resulting on the dependence of sieve's mesh size on temperature, where the sieving effect is considered to appearmore » at a certain temperature. In this interpretation, an isotopic difference between hydrogen and deuterium is suggested to exist in the sieving effect appearance temperatures. This is endorsed in the result of pseudo-isobaric experiments. This temperature deference is very significant because that indicates the possibility of an effective method of hydrogen isotope separation. This possibility is verified through an experimental series of adsorption-desorption with a mixture of H{sub 2} and D{sub 2}, where the gas samples adsorbed through the sieve operated at intentionally selected temperatures are isolated and then analyzed. The result demonstrates remarkable values of isotope separation factor. (authors)« less

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

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

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

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

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 selectivemore » 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.« less

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.

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

Molecular formation in the stagnation region of colliding laser-produced plasmas

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

Al-Shboul, K. F.; Hassan, S. M.; Harilal, S. S.

2016-10-27

The laser-produced colliding plasmas have numerous attractive applications and stagnation layer formed during collisions between plasmas is a useful system for understanding particle collisions and molecular formation in a controlled way. In this article, we explore carbon dimer formation and its evolutionary paths in a stagnation layer formed during the interaction of two laser-produced plasmas. Colliding laser produced plasmas are generated by splitting a laser beam into two sub-beams and then focus them into either a single flat (laterally colliding plasmas) or a V-shaped graphite targets (orthogonally colliding plasmas). The C2 formation in the stagnation region of both colliding plasmamore » schemes is investigated using optical spectroscopic means and compared with emission features from single seed plasma. Our results show that the collisions among the plasmas followed by the stagnation layer formation lead to rapid cooling causing enhanced carbon dimer formation. In addition, plasma electron temperature, density and C2 molecular temperature were measured for the stagnation zone and compared with seed plasma.« less

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.

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

Stable oxygen and hydrogen isotopes of brines - comparing isotope ratio mass spectrometry and isotope ratio infrared spectroscopy

NASA Astrophysics Data System (ADS)

Ahrens, Christian; Koeniger, Paul; van Geldern, Robert; Stadler, Susanne

2013-04-01

Today's standard analytical methods for high precision stable isotope analysis of fluids are gas-water equilibration and high temperature pyrolysis coupled to isotope ratio mass spectrometers (IRMS). In recent years, relatively new laser-based analytical instruments entered the market that are said to allow high isotope precision data on nearly every media. This optical technique is referred to as isotope ratio infrared spectroscopy (IRIS). The objective of this study is to evaluate the capability of this new instrument type for highly saline solutions and a comparison of the analytical results with traditional IRMS analysis. It has been shown for the equilibration method that the presence of salts influences the measured isotope values depending on the salt concentration (see Lécuyer et al, 2009; Martineau, 2012). This so-called 'isotope salt effect' depends on the salt type and salt concentration. These factors change the activity in the fluid and therefore shift the isotope ratios measured by the equilibration method. Consequently, correction factors have to be applied to these analytical data. Direct conversion techniques like pyrolysis or the new laser instruments allow the measurement of the water molecule from the sample directly and should therefore not suffer from the salt effect, i.e. no corrections of raw values are necessary. However, due to high salt concentrations this might cause technical problems with the analytical hardware and may require labor-intensive sample preparation (e.g. vacuum distillation). This study evaluates the salt isotope effect for the IRMS equilibration technique (Thermo Gasbench II coupled to Delta Plus XP) and the laser-based IRIS instruments with liquid injection (Picarro L2120-i). Synthetic salt solutions (NaCl, KCl, CaCl2, MgCl2, MgSO4, CaSO4) and natural brines collected from the Stassfurt Salt Anticline (Germany; Stadler et al., 2012) were analysed with both techniques. Salt concentrations ranged from seawater salinity

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.

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

PubMed

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

2006-01-01

The isotope ratio of atmospheric water vapour is determined by wide-ranging feedback effects from the isotope ratio of water in biological water pools, soil surface horizons, open water bodies and precipitation. Accurate determination of atmospheric water vapour isotope ratios is important for a broad range of research areas from leaf-scale to global-scale isotope studies. In spite of the importance of stable isotopic measurements of atmospheric water vapour, there is a paucity of published data available, largely because of the requirement for liquid nitrogen or dry ice for quantitative trapping of water vapour. We report results from a non-cryogenic method for quantitatively trapping atmospheric water vapour using 3A molecular sieve, although water is removed from the column using standard cryogenic methods. The molecular sieve column was conditioned with water of a known isotope ratio to 'set' the background signature of the molecular sieve. Two separate prototypes were developed, one for large collection volumes (3 mL) and one for small collection volumes (90 microL). Atmospheric water vapour was adsorbed to the column by pulling air through the column for several days to reach the desired final volume. Water was recovered from the column by baking at 250 degrees C in a dry helium or nitrogen air stream and cryogenically trapped. For the large-volume apparatus, the recovered water differed from water that was simultaneously trapped by liquid nitrogen (the experimental control) by 2.6 per thousand with a standard deviation (SD) of 1.5 per thousand for delta(2)H and by 0.3 per thousand with a SD of 0.2 per thousand for delta(18)O. Water-vapour recovery was not satisfactory for the small volume apparatus. Copyright (c) 2006 John Wiley & Sons, Ltd.

On-line Differential Thermal Isotope Analysis: A New Method for Measuring Oxygen and Hydrogen Isotopes of Hydration Water in Minerals

NASA Astrophysics Data System (ADS)

Bauska, T.; Hodell, D. A.; Walters, G.

2016-12-01

Oxygen (16O,17O,18O) and hydrogen (H,D) isotopes of hydration water in minerals provide a rich source of information about the conditions under which hydrated minerals form on Earth and other planetary bodies (e.g. Mars). We have developed a new method for measuring different types of bonded water (e.g., molecular, hydroxyl) contained in hydrated minerals by coupling a thermal gravimeter (TG) and a cavity ringdown laser spectrometer (CRDS). The method involves step heating a mineral sample, precisely measuring the weight loss and enthalpy as the sample undergoes dehydration and dehydroxylation, whilst simultaneously determining the oxygen and hydrogen isotopes of the water vapor evolved from the mineral sample by cavity ring-down laser spectroscopy (CRDS). Nitrogen carrier gas is used to transfer the sample from the TG to the CRDS via a heated line and interface box. The interface includes the capability of (i) cryogenic trapping discrete types of water for samples containing small amounts of water; (ii) injecting small quantities of water of known isotopic value for calibration; and (iii) converting volatile organic compounds to nascent amounts of water using a catalyst. The CRDS continually measures water vapor concentration in the optical cavity and hydrogen and oxygen isotope ratios. Isotopic values are calculated by integrating the product of the water amount and its isotopic value for the separated peaks after correcting for background. Precision of the method was estimated by comparing isotope results of total water for gypsum measured by DTIA with our conventional method of extraction and analysis (Gázquez et al., 2015. Rapid Communications in Mass Spectrometry, 29, 1997-2006). Errors for the isotopic values of total hydration water vary between ±0.08 and ±0.34 ‰ for δ18O and between ±0.16 and ±0.86 ‰ for δD. We demonstrate the application of the DTIA method to a variety of hydrous minerals and mineraloids including gypsum, clays, and amorphous

Composition analysis by scanning femtosecond laser ultraprobing (CASFLU).

DOEpatents

Ishikawa, Muriel Y.; Wood, Lowell L.; Campbell, E. Michael; Stuart, Brent C.; Perry, Michael D.

2002-01-01

The composition analysis by scanning femtosecond ultraprobing (CASFLU) technology scans a focused train of extremely short-duration, very intense laser pulses across a sample. The partially-ionized plasma ablated by each pulse is spectrometrically analyzed in real time, determining the ablated material's composition. The steering of the scanned beam thus is computer directed to either continue ablative material-removal at the same site or to successively remove nearby material for the same type of composition analysis. This invention has utility in high-speed chemical-elemental, molecular-fragment and isotopic analyses of the microstructure composition of complex objects, e.g., the oxygen isotopic compositions of large populations of single osteons in bone.

CW molecular iodine laser pumped with a low power DPSSL

NASA Astrophysics Data System (ADS)

Luhs, W.; Wellegehausen, B.; Goyal, M.

2017-04-01

Cw oscillation of molecular iodine on many lines in the range of 557-802 nm pumped with a low power common diode pumped and frequency doubled solid state laser DPSSL is reported. The DPSSL is temperature stabilized, operates in single frequency and can be tuned by about 2 nm at 532 nm. Operation conditions of this simple and low cost iodine ring laser will be described and possible applications will be discussed.

Atomic and Molecular Systems in Intense Ultrashort Laser Pulses

NASA Astrophysics Data System (ADS)

Saenz, A.

2008-07-01

The full quantum mechanical treatment of atomic and molecular systems exposed to intense laser pulses is a so far unsolved challenge, even for systems as small as molecular hydrogen. Therefore, a number of simplified qualitative and quantitative models have been introduced in order to provide at least some interpretational tools for experimental data. The assessment of these models describing the molecular response is complicated, since a comparison to experiment requires often a number of averages to be performed. This includes in many cases averaging of different orientations of the molecule with respect to the laser field, focal volume effects, etc. Furthermore, the pulse shape and even the peak intensity is experimentally not known with very high precision; considering, e.g., the exponential intensity dependence of the ionization signal. Finally, experiments usually provide only relative yields. As a consequence of all these averagings and uncertainties, it is possible that different models may successfully explain some experimental results or features, although these models disagree substantially, if their predictions are compared before averaging. Therefore, fully quantum-mechanical approaches at least for small atomic and molecular systems are highly desirable and have been developed in our group. This includes efficient codes for solving the time-dependent Schrodinger equation of atomic hydrogen, helium or other effective one- or two-electron atoms as well as for the electronic motion in linear (effective) one-and two-electron diatomic molecules like H_2.Very recently, a code for larger molecular systems that adopts the so-called single-active electron approximation was also successfully implemented and applied. In the first part of this talk popular models describing intense laser-field ionization of atoms and their extensions to molecules are described. Then their validity is discussed on the basis of quantum-mechanical calculations. Finally, some

Laser-based methods for the analysis of low molecular weight compounds in biological matrices.

PubMed

Kiss, András; Hopfgartner, Gérard

2016-07-15

Laser-based desorption and/or ionization methods play an important role in the field of the analysis of low molecular-weight compounds (LMWCs) because they allow direct analysis with high-throughput capabilities. In the recent years there were several new improvements in ionization methods with the emergence of novel atmospheric ion sources such as laser ablation electrospray ionization or laser diode thermal desorption and atmospheric pressure chemical ionization and in sample preparation methods with the development of new matrix compounds for matrix-assisted laser desorption/ionization (MALDI). Also, the combination of ion mobility separation with laser-based ionization methods starts to gain popularity with access to commercial systems. These developments have been driven mainly by the emergence of new application fields such as MS imaging and non-chromatographic analytical approaches for quantification. This review aims to present these new developments in laser-based methods for the analysis of low-molecular weight compounds by MS and several potential applications. Copyright © 2016 Elsevier Inc. All rights reserved.

Dynamic molecular structure retrieval from low-energy laser-induced electron diffraction spectra

NASA Astrophysics Data System (ADS)

Vu, Dinh-Duy T.; Phan, Ngoc-Loan T.; Hoang, Van-Hung; Le, Van-Hoang

2017-12-01

A recently developed quantitative rescattering theory showed that a laser-free elastic cross section can be separated from laser-induced electron diffraction (LIED) spectra. Based upon this idea, Blaga et al investigated the possibility of reconstructing molecular structure from LIED spectra (2012 Nature 483 7388). In the above study, an independent atoms model (IAM) was used to interpret high-energy electron-molecule collisions induced by a mid-infrared laser. Our research aims to extend the application range of this structural retrieval method to low-energy spectra induced by more common near-infrared laser sources. The IAM is insufficient in this case, so we switch to a more comprehensive model—the multiple scattering (MS) theory. From the original version concerning only neutral targets, we upgrade the model so that it is compatible with electron-ion collisions at low energy. With available LIED experiment data of CO2 and O2, the upgraded MS is shown to be greatly effective as a tool for molecular imaging from spectra induced by a near-infrared laser. The captured image is at about 2 fs after the ionization, shorter than the period 4-6 fs by using the mid-infrared laser in Blaga’s experiment.

Late-Quaternary Molecular Isotopic Paleohydrology of Lake Junin, Peru

NASA Astrophysics Data System (ADS)

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

2013-12-01

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

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.

Laser ablation-miniature mass spectrometer for elemental and isotopic analysis of rocks.

PubMed

Sinha, M P; Neidholdt, E L; Hurowitz, J; Sturhahn, W; Beard, B; Hecht, M H

2011-09-01

A laser ablation-miniature mass spectrometer (LA-MMS) for the chemical and isotopic measurement of rocks and minerals is described. In the LA-MMS method, neutral atoms ablated by a pulsed laser are led into an electron impact ionization source, where they are ionized by a 70 eV electron beam. This results in a secondary ion pulse typically 10-100 μs wide, compared to the original 5-10 ns laser pulse duration. Ions of different masses are then spatially dispersed along the focal plane of the magnetic sector of the miniature mass spectrometer (MMS) and measured in parallel by a modified CCD array detector capable of detecting ions directly. Compared to conventional scanning techniques, simultaneous measurement of the ion pulse along the focal plane effectively offers a 100% duty cycle over a wide mass range. LA-MMS offers a more quantitative assessment of elemental composition than techniques that detect ions directly generated by the ablation process because the latter can be strongly influenced by matrix effects that vary with the structure and geometry of the surface, the wavelength of the laser beam, and the not well characterized ionization efficiencies of the elements in the process. The above problems attendant to the direct ion analysis has been minimized in the LA-MMS by analyzing the ablated neutral species after their post-ionization by electron impaction. These neutral species are much more abundant than the directly ablated ions in the ablated vapor plume and are, therefore, expected to be characteristic of the chemical composition of the solid. Also, the electron impact ionization of elements is well studied and their ionization cross sections are known and easy to find in databases. Currently, the LA-MMS limit of detection is 0.4 wt.%. Here we describe LA-MMS elemental composition measurements of various minerals including microcline, lepidolite, anorthoclase, and USGS BCR-2G samples. The measurements of high precision isotopic ratios including (41)K

Transforming Benzophenoxazine Laser Dyes into Chromophores for Dye-Sensitized Solar Cells: A Molecular Engineering Approach

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

Schröder, Florian A. Y. N.; Cole, Jacqueline M.; Waddell, Paul G.

2015-02-03

The re-functionalization of a series of four well-known industrial laser dyes, based on benzophenoxazine, is explored with the prospect of molecularly engineering new chromophores for dye-sensitized solar cell (DSC) applications. Such engineering is important since a lack of suitable dyes is stifling the progress of DSC technology. The conceptual idea involves making laser dyes DSC-active by chemical modification, while maintaining their key property attributes that are attractive to DSC applications. This molecular engineering follows a step-wise approach. Firstly, molecular structures and optical absorption properties are determined for the parent laser dyes: Cresyl Violet (1); Oxazine 170 (2); Nile Blue Amore » (3), Oxazine 750 (4). These reveal structure-property relationships which define the prerequisites for computational molecular design of DSC dyes; the nature of their molecular architecture (D-π-A) and intramolecular charge transfer. Secondly, new DSC dyes are computationally designed by the in silico addition of a carboxylic acid anchor at various chemical substitution points in the parent laser dyes. A comparison of the resulting frontier molecular orbital energy levels with the conduction band edge of a TiO2 DSC photoanode and the redox potential of two electrolyte options I-/I3- and Co(II/III)tris(bipyridyl) suggests promise for these computationally designed dyes as co-sensitizers for DSC applications.« less

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.

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.

Laser-driven clockwise molecular rotation for a transient spinning waveplate.

PubMed

York, Andrew G

2009-08-03

Our simulations show a copropagating pair of laser pulses polarized in two different directions can selectively excite clockwise or counterclockwise molecular rotation in a gas of linear molecules. The resulting birefringence of the gas rotates on a femtosecond timescale and shows a periodic revival structure. The total duration of the pulse pair can be subpicosecond, allowing molecular alignment at the high densities and temperatures necessary to create a transient spinning waveplate.

Method of separating boron isotopes

DOEpatents

Jensen, R.J.; Thorne, J.M.; Cluff, C.L.

1981-01-23

A method of boron isotope enrichment involving the isotope preferential photolysis of (2-chloroethenyl)-dichloroborane as the feed material. The photolysis can readily by achieved with CO/sub 2/ laser radiation and using fluences significantly below those required to dissociate BCl/sub 3/.

Method of separating boron isotopes

DOEpatents

Jensen, Reed J.; Thorne, James M.; Cluff, Coran L.; Hayes, John K.

1984-01-01

A method of boron isotope enrichment involving the isotope preferential photolysis of (2-chloroethenyl)dichloroborane as the feed material. The photolysis can readily be achieved with CO.sub.2 laser radiation and using fluences significantly below those required to dissociate BCl.sub.3.

CO2 laser oscillators for laser radar applications

NASA Technical Reports Server (NTRS)

Freed, C.

1990-01-01

This paper reviews the spectral purity, frequency stability, and long-term stabilization of newly developed CO2 isotope lasers. Extremely high spectral purity, and short-term stability of less than 1.5 x 10 to the -13th have been achieved. A brief description on using CO2 isotope lasers as secondary frequency standards and in optical radar is given. The design and output characteristics of a single frequency, TEM00q mode, variable pulse width, hybrid TE CO2 laser system is also described. The frequency chirp in the output has been measured and almost completely eliminated by means of a novel technique.

Study on molecular sieve absorption of ground state HF molecules in a non-chain pulsed HF Laser

NASA Astrophysics Data System (ADS)

Ma, Lianying; Zhou, Songqing; Chao, Huang; Huang, Ke; Zhu, Feng; Luan, Kunpeng; Chen, Hongwei

2017-05-01

This paper describes the principle of non-chain pulsed HF laser, and analyzes the reason why the laser energy dropped severely with the accumulation of shots when the HF laser was in repetitive operation. In order to solve this problem, a molecular sieve absorption device was designed and mounted in the recirculation loop of the HF laser. Measurements of flow velocity indicated that the absorption device would just introduce a small decrease of flow velocity which would not influence the laser operation. Several types of molecular sieve (3A,4A,5A,13X) were used in absorbing experiments and the experiment results inferred that 3A molecular sieve was the most effective sorbent. All the experiments showed that the average drop of the output energy was not more than 5% after 1000 shots at 50Hz/20s. Compared to the energy drop of about 40% without the device, the absorption device could significantly improve the stability of the HF laser output energy and prolong the lifespan of laser medium gases.

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.

Coherent control of molecular alignment of homonuclear diatomic molecules by analytically designed laser pulses.

PubMed

Zou, Shiyang; Sanz, Cristina; Balint-Kurti, Gabriel G

2008-09-28

We present an analytic scheme for designing laser pulses to manipulate the field-free molecular alignment of a homonuclear diatomic molecule. The scheme is based on the use of a generalized pulse-area theorem and makes use of pulses constructed around two-photon resonant frequencies. In the proposed scheme, the populations and relative phases of the rovibrational states of the molecule are independently controlled utilizing changes in the laser intensity and in the carrier-envelope phase difference, respectively. This allows us to create the correct coherent superposition of rovibrational states needed to achieve optimal molecular alignment. The validity and efficiency of the scheme are demonstrated by explicit application to the H(2) molecule. The analytically designed laser pulses are tested by exact numerical solutions of the time-dependent Schrodinger equation including laser-molecule interactions to all orders of the field strength. The design of a sequence of pulses to further enhance molecular alignment is also discussed and tested. It is found that the rotating wave approximation used in the analytic design of the laser pulses leads to small errors in the prediction of the relative phase of the rotational states. It is further shown how these errors may be easily corrected.

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

DOEpatents

Barty, Christopher P. J. [Hayward, CA; Hartemann, Frederic V [San Ramon, CA; McNabb, Dennis P [Alameda, CA; Pruet, Jason A [Brentwood, CA

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.

Sulfate and sulfide sulfur isotopes (δ34S and δ33S) measured by solution and laser ablation MC-ICP-MS: An enhanced approach using external correction

USGS Publications Warehouse

Pribil, Michael; Ridley, William I.; Emsbo, Poul

2015-01-01

Isotope ratio measurements using a multi-collector inductively coupled plasma mass spectrometer (MC-ICP-MS) commonly use standard-sample bracketing with a single isotope standard for mass bias correction for elements with narrow-range isotope systems measured by MC-ICP-MS, e.g. Cu, Fe, Zn, and Hg. However, sulfur (S) isotopic composition (δ34S) in nature can range from at least − 40 to + 40‰, potentially exceeding the ability of standard-sample bracketing using a single sulfur isotope standard to accurately correct for mass bias. Isotopic fractionation via solution and laser ablation introduction was determined during sulfate sulfur (Ssulfate) isotope measurements. An external isotope calibration curve was constructed using in-house and National Institute of Standards and Technology (NIST) Ssulfate isotope reference materials (RM) in an attempt to correct for the difference. The ability of external isotope correction for Ssulfate isotope measurements was evaluated by analyzing NIST and United States Geological Survey (USGS) Ssulfate isotope reference materials as unknowns. Differences in δ34Ssulfate between standard-sample bracketing and standard-sample bracketing with external isotope correction for sulfate samples ranged from 0.72‰ to 2.35‰ over a δ34S range of 1.40‰ to 21.17‰. No isotopic differences were observed when analyzing Ssulfide reference materials over a δ34Ssulfide range of − 32.1‰ to 17.3‰ and a δ33S range of − 16.5‰ to 8.9‰ via laser ablation (LA)-MC-ICP-MS. Here, we identify a possible plasma induced fractionation for Ssulfate and describe a new method using external isotope calibration corrections using solution and LA-MC-ICP-MS.

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.

A new isotopic reference material for stable hydrogen and oxygen isotope-ratio measurements of water—USGS50 Lake Kyoga Water

USGS Publications Warehouse

Coplen, Tyler B.; Wassenaar, Leonard I; Mukwaya, Christine; Qi, Haiping; Lorenz, Jennifer M.

2015-01-01

This isotopic reference material, designated as USGS50, is intended as one of two reference waters for daily normalization of stable hydrogen and oxygen isotopic analysis of water with an isotope-ratio mass spectrometer or a laser absorption spectrometer, of use especially for isotope-hydrology laboratories analyzing freshwater samples from equatorial and tropical regions.

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

NASA Astrophysics Data System (ADS)

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

2013-12-01

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

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

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

NASA Astrophysics Data System (ADS)

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

2012-04-01

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

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.

Fundamental studies in the molecular basis of laser-induced retinal damage. Annual report, September 1981-August 1982

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

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 Dropletmore » 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.« less

Laser pattern generator challenges in airborne molecular contamination protection

NASA Astrophysics Data System (ADS)

Ekberg, Mats; Skotte, Per-Uno; Utterback, Tomas; Paul, Swaraj; Kishkovich, Oleg P.; Hudzik, James S.

2003-08-01

The introduction of photomask laser pattern generators presents new challenges to system designers and manufacturers. One of the laser pattern generator's environmental operating challenges is Airborne Molecular Contamination (AMC), which affects both chemically amplified resists (CAResist) and laser optics. Similar challenges in CAResist protection have already been addressed in semiconductor wafer lithography with reasonable solutions and experience gained by all those involved. However, photomask and photomask equipment manufacturers have not previously had a comparable experience, and some photomask AMC issues differ from those seen in semiconductor wafer lithography. Culminating years of AMC experience, the authors discuss specific requirements of Photomask AMC. Air sampling and material of construction analysis were performed to understand these particular AMC challenges and used to develop an appropriate filtration specification for different classes of contaminates. The authors portray the importance of cooperation between tool designers and AMC experts early in the design stage to assure goal attainment to maximize both process stability and machine productivity in advanced mask making. In conclusion, the authors provide valuable recommendations to both laser tool users and other equipment manufacturers.

Dual-comb spectroscopy of laser-induced plasmas

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

Bergevin, Jenna; Wu, Tsung-Han; Yeak, Jeremy

Dual-comb spectroscopy has become a powerful spectroscopic technique in applications that rely on its broad spectral coverage combined with high frequency resolution capabilities. Experiments to date have primarily focused on detection and analysis of multiple gas species under semi-static conditions, with applications ranging from environmental monitoring of greenhouse gases to high resolution molecular spectroscopy. Here, we utilize dual-comb spectroscopy to demonstrate broadband, high-resolution, and time-resolved measurements in a laser induced plasma for the first time. As a first demonstration, we simultaneously detect trace amounts of Rb and K in solid samples with a single laser ablation shot, with transitions separatedmore » by over 6 THz (13 nm) and spectral resolution sufficient to resolve isotopic and ground state hyperfine splittings of the Rb D2 line. This new spectroscopic approach offers the broad spectral coverage found in the powerful techniques of laser-induced breakdown spectroscopy (LIBS) while providing the high-resolution and accuracy of cw laser-based spectroscopies.« less

Constructing oxide interfaces and heterostructures by atomic layer-by-layer laser molecular beam epitaxy

NASA Astrophysics Data System (ADS)

Lei, Qingyu; Golalikhani, Maryam; Davidson, Bruce A.; Liu, Guozhen; Schlom, Darrell G.; Qiao, Qiao; Zhu, Yimei; Chandrasena, Ravini U.; Yang, Weibing; Gray, Alexander X.; Arenholz, Elke; Farrar, Andrew K.; Tenne, Dmitri A.; Hu, Minhui; Guo, Jiandong; Singh, Rakesh K.; Xi, Xiaoxing

2017-12-01

Advancements in nanoscale engineering of oxide interfaces and heterostructures have led to discoveries of emergent phenomena and new artificial materials. Combining the strengths of reactive molecular-beam epitaxy and pulsed-laser deposition, we show here, with examples of Sr1+xTi1-xO3+δ, Ruddlesden-Popper phase Lan+1NinO3n+1 (n = 4), and LaAl1+yO3(1+0.5y)/SrTiO3 interfaces, that atomic layer-by-layer laser molecular-beam epitaxy significantly advances the state of the art in constructing oxide materials with atomic layer precision and control over stoichiometry. With atomic layer-by-layer laser molecular-beam epitaxy we have produced conducting LaAlO3/SrTiO3 interfaces at high oxygen pressures that show no evidence of oxygen vacancies, a capability not accessible by existing techniques. The carrier density of the interfacial two-dimensional electron gas thus obtained agrees quantitatively with the electronic reconstruction mechanism.

Hydrodynamic Determinants of Cell Necrosis and Molecular Delivery Produced by Pulsed Laser Microbeam Irradiation of Adherent Cells

PubMed Central

Compton, Jonathan L.; Hellman, Amy N.; Venugopalan, Vasan

2013-01-01

Time-resolved imaging, fluorescence microscopy, and hydrodynamic modeling were used to examine cell lysis and molecular delivery produced by picosecond and nanosecond pulsed laser microbeam irradiation in adherent cell cultures. Pulsed laser microbeam radiation at λ = 532 nm was delivered to confluent monolayers of PtK2 cells via a 40×, 0.8 NA microscope objective. Using laser microbeam pulse durations of 180–1100 ps and pulse energies of 0.5–10.5 μJ, we examined the resulting plasma formation and cavitation bubble dynamics that lead to laser-induced cell lysis, necrosis, and molecular delivery. The cavitation bubble dynamics are imaged at times of 0.5 ns to 50 μs after the pulsed laser microbeam irradiation, and fluorescence assays assess the resulting cell viability and molecular delivery of 3 kDa dextran molecules. Reductions in both the threshold laser microbeam pulse energy for plasma formation and the cavitation bubble energy are observed with decreasing pulse duration. These energy reductions provide for increased precision of laser-based cellular manipulation including cell lysis, cell necrosis, and molecular delivery. Hydrodynamic analysis reveals critical values for the shear-stress impulse generated by the cavitation bubble dynamics governs the location and spatial extent of cell necrosis and molecular delivery independent of pulse duration and pulse energy. Specifically, cellular exposure to a shear-stress impulse J≳0.1 Pa s ensures cell lysis or necrosis, whereas exposures in the range of 0.035≲J≲0.1 Pa s preserve cell viability while also enabling molecular delivery of 3 kDa dextran. Exposure to shear-stress impulses of J≲0.035 Pa s leaves the cells unaffected. Hydrodynamic analysis of these data, combined with data from studies of 6 ns microbeam irradiation, demonstrates the primacy of shear-stress impulse in determining cellular outcome resulting from pulsed laser microbeam irradiation spanning a nearly two

Laser-based measurements of δ13 C and δ2 H methane isotope signatures: precisions competitive with mass spectrometry methods

NASA Astrophysics Data System (ADS)

Yacovitch, Tara; Shorter, Joanne; Nelson, David; Herndon, Scott; Agnese, Mike; McManus, Barry; Zahniser, Mark

2017-04-01

In order to understand how and why methane (CH4 ) concentrations change over time, it is necessary to understand their sources and sinks. Stable isotope measurements of 13 CH4 :12 CH4 and CH3 D:12 CH4 ratios constrain the inventory of these sinks and sources. Current measurements often depend on Isotope Ratio Mass Spectrometry (IRMS), which requires extensive sample preparation including cryogenic separation of methane from air and subsequent conversion to either CO2 or H2 . Here, we detail improvements to a direct-absorption laser spectrometer that enable fast and precise measurements of methane isotope ratios (δ13 C and δ2 H ) of ambient air samples, without such sample preparation. The measurement system consists of a laser-based direct absorption spectrometer configured with a sample manifold for measurement of discrete samples (as opposed to flow-through measurements). Samples are trapped in the instrument using a rapid sample switching technique that compares each flask sample against a monitor tank sample. This approach reduces instrument drift and results in excellent precision. Precisions of 0.054 o/oo for δ13 C and 1.4 o/oo for δ2 H have been achieved (Allan-Werle deviations). These results are obtained in 20 minutes using 4 replicate comparisons to a monitor tank.

Precise and accurate isotope ratio measurements by ICP-MS.

PubMed

Becker, J S; Dietze, H J

2000-09-01

The precise and accurate determination of isotope ratios by inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation ICP-MS (LA-ICP-MS) is important for quite different application fields (e.g. for isotope ratio measurements of stable isotopes in nature, especially for the investigation of isotope variation in nature or age dating, for determining isotope ratios of radiogenic elements in the nuclear industry, quality assurance of fuel material, for reprocessing plants, nuclear material accounting and radioactive waste control, for tracer experiments using stable isotopes or long-lived radionuclides in biological or medical studies). Thermal ionization mass spectrometry (TIMS), which used to be the dominant analytical technique for precise isotope ratio measurements, is being increasingly replaced for isotope ratio measurements by ICP-MS due to its excellent sensitivity, precision and good accuracy. Instrumental progress in ICP-MS was achieved by the introduction of the collision cell interface in order to dissociate many disturbing argon-based molecular ions, thermalize the ions and neutralize the disturbing argon ions of plasma gas (Ar+). The application of the collision cell in ICP-QMS results in a higher ion transmission, improved sensitivity and better precision of isotope ratio measurements compared to quadrupole ICP-MS without the collision cell [e.g., for 235U/238U approximately 1 (10 microg x L(-1) uranium) 0.07% relative standard deviation (RSD) vs. 0.2% RSD in short-term measurements (n = 5)]. A significant instrumental improvement for ICP-MS is the multicollector device (MC-ICP-MS) in order to obtain a better precision of isotope ratio measurements (with a precision of up to 0.002%, RSD). CE- and HPLC-ICP-MS are used for the separation of isobaric interferences of long-lived radionuclides and stable isotopes by determination of spallation nuclide abundances in an irradiated tantalum target.

Barium Isotopes in Single Presolar Grains

NASA Technical Reports Server (NTRS)

Pellin, M. J.; Davis, A. M.; Savina, M. R.; Kashiv, Y.; Clayton, R. N.; Lewis, R. S.; Amari, S.

2001-01-01

Barium isotopic compositions of single presolar grains were measured by laser ablation laser resonant ionization mass spectrometry and the implications of the data for stellar processes are discussed. Additional information is contained in the original extended abstract.

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)

A Pulsed Laser and Molecular Beam Apparatus for Surface Studies

DTIC Science & Technology

1985-03-01

will be carried out are in part described in the proposal A Pulsed Laser and Molecular Beam Apparatus for Surface Studies submitted by Howard ... University in November 1982 for review by AFOSR, under the DOD University Instrumentation Program. This report describes the progress made during the

Manipulation of Molecular Quantum Wavepackets with Ultrashort Laser Pulses for Non-destructive Detection of Volatile Explosives

DTIC Science & Technology

2013-02-01

DTRA-TR-12-65 Manipulation of Molecular Quantum Wavepackets with Ultrashort Laser Pulses for Non-destructive Detection of Volatile Explosives ...Manipulation of Molecular Quantum Wavepackets with Ultrashort Laser Pulses for Non-destructive Detection of Volatile Explosives HDTRA1-09-1-0021 Valery...destructive detection of volatile explosives . Moshe Shapiro1, Valery Milner1 and Jun Ye2 1University of British Columbia, Vancouver, Canada 2JILA

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

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

Moran, James J.; Doll, Charles G.; Bernstein, Hans C.

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.

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

Volume Measurements of Laser-generated Pits for in Situ Geochronology Using KArLE (Potassium-Argon Laser Experiment)

NASA Technical Reports Server (NTRS)

French, R. A.; Cohen, B. A.; Miller, J. S.

2014-01-01

KArLE (Potassium-­-Argon Laser Experiment) has been developed for in situ planetary geochronology using the K - Ar (potassium-­-argon) isotope system, where material ablated by LIBS (Laser-­-Induced Breakdown Spectroscopy) is used to calculate isotope abundances. We are determining the accuracy and precision of volume measurements of these pits using stereo and laser microscope data to better understand the ablation process for isotope abundance calculations. If a characteristic volume can be determined with sufficient accuracy and precision for specific rock types, KArLE will prove to be a useful instrument for future planetary rover missions.

Zinc isotope ratio imaging of rat brain thin sections from stable isotope tracer studies by LA-MC-ICP-MS.

PubMed

Urgast, Dagmar S; Hill, Sarah; Kwun, In-Sook; Beattie, John H; Goenaga-Infante, Heidi; Feldmann, Jörg

2012-10-01

Zinc stable isotope tracers (⁶⁷Zn and ⁷⁰Zn) were injected into rats at two different time points to investigate the feasibility of using tracers to study zinc kinetics at the microscale within distinct tissue features. Laser ablation coupled to multi-collector ICP-MS was used to analyse average isotope ratios in liver thin sections and to generate bio-images showing zinc isotope ratio distribution in brain thin sections. Average isotope ratios of all samples from treated animals were found to be statistically different (P < 0.05) from samples from untreated control animals. Furthermore, differing isotope ratios in physiological features of the brain, namely hippocampus, amygdala, cortex and hypothalamus, were identified. This indicates that these regions differ in their zinc metabolism kinetics. While cortex and hypothalamus contain more tracer two days after injection than 14 days after injection, the opposite is true for hippocampus and amygdala. This study showed that stable isotope tracer experiments can be combined with laser ablation MC-ICP-MS to measure trace element kinetics in tissues at a microscale level.

QCL- and CO_2 Laser-Based Mid-Ir Spectrometers for High Accuracy Molecular Spectroscopy

NASA Astrophysics Data System (ADS)

Sow, P. L. T.; Chanteau, B.; Auguste, F.; Mejri, S.; Tokunaga, S. K.; Argence, B.; Lopez, O.; Chardonnet, C.; Amy-Klein, A.; Daussy, C.; Darquie, B.; Nicolodi, D.; Abgrall, M.; Le Coq, Y.; Santarelli, G.

2013-06-01

With their rich internal structure, molecules can play a decisive role in precision tests of fundamental physics. They are now being used, for example in our group, to test fundamental symmetries such as parity and time reversal, and to measure either absolute values of fundamental constants or their temporal variation. Most of those experiments can be cast as the measurement of molecular frequencies. Ultra-stable and accurate sources in the mid-IR spectral region, the so-called molecular fingerprint region that hosts many intense rovibrational signatures, are thus highly desirable. We report on the development of a widely tunable quantum cascade laser (QCL) based spectrometer. Our first characterization of a free-running cw near-room-temperature DFB 10.3 μm QCL led to a ˜200 kHz linewidth beat-note with our frequency-stabilized CO_2 laser. Narrowing of the QCL linewidth was achieved by straightforwardly phase-locking the QCL to the CO_2 laser. The great stability of the CO_2 laser was transferred to the QCL resulting in a record linewidth of a few tens of hertz. The use of QCLs will allow the study of any species showing absorption between 3 and 25 μm which will broaden the scope of our experimental setups dedicated to molecular spectroscopy-based precision measurements. Eventually we want to lock the QCL to a frequency comb itself stabilized to an ultra-stable near-IR reference provided via a 43-km long fibre by the French metrological institute and monitored against atomic fountain clocks. We report on the demonstration of this locking-scheme with a ˜10 μm CO_2 laser resulting in record 10^{-14}-10^{-15} fractional accuracy and stability. Stabilizing a QCL this way will free us from having to lock it to a molecular transition or a CO_2 laser. It will make it possible for any laboratory to have a stabilized QCL at any desired wavelength with spectral performances currently only achievable in the visible and near-IR, in metrological institutes.

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

PubMed

Wysocki, Gerard; Weidmann, Damien

2010-12-06

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.

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.

Symmetry in circularly polarized molecular high-order harmonic generation with intense bicircular laser pulses

NASA Astrophysics Data System (ADS)

Yuan, Kai-Jun; Bandrauk, André D.

2018-02-01

We present symmetry effects of laser fields and molecular geometries in circularly polarized high-order harmonic generation by bichromatic counter-rotating circularly polarized laser pulses. Simulations are performed on oriented molecules by numerically solving time-dependent Schrödinger equations. We discuss how electron recollision trajectories by the orthogonal laser field polarizations influence the harmonic polarization by using a time-frequency analysis of harmonics. It is found that orientation-dependent asymmetric ionization in linear molecules due to Coulomb potentials gives rise to a dependence of the polarization on the harmonic frequency. Effects of Coriolis forces are also presented on harmonic generation. Electron recollision trajectories illustrate the effects of the relative symmetry of the field and the molecule, thus paving a method for circularly polarized attosecond pulse generation and molecular orbital imaging in more complex systems.

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.

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.

Simultaneous measurement of sulfur and lead isotopes in sulfides using nanosecond laser ablation coupled with two multi-collector inductively coupled plasma mass spectrometers

NASA Astrophysics Data System (ADS)

Yuan, Honglin; Liu, Xu; Chen, Lu; Bao, Zhian; Chen, Kaiyun; Zong, Chunlei; Li, Xiao-Chun; Qiu, Johnson Wenhong

2018-04-01

We herein report the coupling of a nanosecond laser ablation system with a large-scale multi-collector inductively coupled plasma mass spectrometer (Nu1700 MC-ICPMS, NP-1700) and a conventional Nu Plasma II MC-ICPMS (NP-II) for the simultaneous laser ablation and determination of in situ S and Pb isotopic compositions of sulfide minerals. We found that the required aerosol distribution between the two spectrometers depended on the Pb content of the sample. For example, for a sulfide containing 100-3000 ppm Pb, the aerosol was distributed between the NP-1700 and the NP-II spectrometers in a 1:1 ratio, while for lead contents >3000 and <100 ppm, these ratios were 5:1 and 1:3, respectively. In addition, S isotopic analysis showed a pronounced matrix effect, so a matrix-matched external standard was used for standard-sample bracketing correction. The NIST NBS 977 (NBS, National Bureau of Standards; NIST, National Institute of Standards & Technology) Tl (thallium) dry aerosol internal standard and the NIST SRM 610 (SRM, standard reference material) external standard were employed to obtain accurate results for the analysis of Pb isotopes. In tandem experiments where airflow conditions were similar to those employed during stand-alone analyses, small changes in the aerosol carrier gas flow did not significantly influence the accurate determination of S and Pb isotope ratios. In addition, careful optimization of the flow ratio of the aerosol carrier (He) and makeup (Ar) gases to match stand-alone analytical conditions allowed comparable S and Pb isotope ratios to be obtained within an error of 2 s analytical uncertainties. Furthermore, the results of tandem analyses obtained using our method were consistent with those of previously reported stand-alone techniques for the S and Pb isotopes of chalcopyrite, pyrite, galena, and sphalerite, thus indicating that this method is suitable for the simultaneous analysis of S and Pb isotopes of natural sulfide minerals, and provides

Probing Sizes and Shapes of Nobelium Isotopes by Laser Spectroscopy

NASA Astrophysics Data System (ADS)

Raeder, S.; Ackermann, D.; Backe, H.; Beerwerth, R.; Berengut, J. C.; Block, M.; Borschevsky, A.; Cheal, B.; Chhetri, P.; Düllmann, Ch. E.; Dzuba, V. A.; Eliav, E.; Even, J.; Ferrer, R.; Flambaum, V. V.; Fritzsche, S.; Giacoppo, F.; Götz, S.; Heßberger, F. P.; Huyse, M.; Kaldor, U.; Kaleja, O.; Khuyagbaatar, J.; Kunz, P.; Laatiaoui, M.; Lautenschläger, F.; Lauth, W.; Mistry, A. K.; Minaya Ramirez, E.; Nazarewicz, W.; Porsev, S. G.; Safronova, M. S.; Safronova, U. I.; Schuetrumpf, B.; Van Duppen, P.; Walther, T.; Wraith, C.; Yakushev, A.

2018-06-01

Until recently, ground-state nuclear moments of the heaviest nuclei could only be inferred from nuclear spectroscopy, where model assumptions are required. Laser spectroscopy in combination with modern atomic structure calculations is now able to probe these moments directly, in a comprehensive and nuclear-model-independent way. Here we report on unique access to the differential mean-square charge radii of No 252 ,253 ,254 , and therefore to changes in nuclear size and shape. State-of-the-art nuclear density functional calculations describe well the changes in nuclear charge radii in the region of the heavy actinides, indicating an appreciable central depression in the deformed proton density distribution in No,254252 isotopes. Finally, the hyperfine splitting of No 253 was evaluated, enabling a complementary measure of its (quadrupole) deformation, as well as an insight into the neutron single-particle wave function via the nuclear spin and magnetic moment.

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.

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

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

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

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

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

NASA Technical Reports Server (NTRS)

Wannier, P. G.; Sahai, R.

1987-01-01

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

Direct quantitative comparison of molecular responses in photodamaged human skin to fractionated and fully ablative carbon dioxide laser resurfacing.

PubMed

Orringer, Jeffrey S; Sachs, Dana L; Shao, Yuan; Hammerberg, Craig; Cui, Yilei; Voorhees, John J; Fisher, Gary J

2012-10-01

Fractionated ablative laser resurfacing has become a widely used treatment modality. Its clinical results are often found to approach those of traditional fully ablative laser resurfacing. To directly compare the molecular changes that result from fractionated and fully ablative carbon dioxide (CO(2)) laser resurfacing in photodamaged human skin. Photodamaged skin of 34 adult volunteers was focally treated at distinct sites with a fully ablative CO(2) laser and a fractionated CO(2) laser. Serial skin samples were obtained at baseline and several time points after treatment. Real-time reverse transcriptase polymerase chain reaction technology and immunohistochemistry were used to quantify molecular responses to each type of laser treatment. Fully ablative and fractionated CO(2) laser resurfacing induced significant dermal remodeling and collagen induction. After a single treatment, fractionated ablative laser resurfacing resulted in collagen induction that was approximately 40% to 50% as pronounced as that induced by fully ablative laser resurfacing. The fundamental cutaneous responses that result from fully ablative and fractionated carbon dioxide laser resurfacing are similar but differ in magnitude and duration, with the fully ablative procedure inducing relatively greater changes including more pronounced collagen induction. However, the molecular data reported here provide substantial support for fractionated ablative resurfacing as an effective treatment modality for improving skin texture. © 2012 by the American Society for Dermatologic Surgery, Inc. Published by Wiley Periodicals, Inc.

Measurement of longitudinal sulfur isotopic variations by laser ablation MC-ICP-MS in single human hair strands.

PubMed

Santamaria-Fernandez, Rebeca; Giner Martínez-Sierra, Justo; Marchante-Gayón, J M; García-Alonso, J Ignacio; Hearn, Ruth

2009-05-01

A new method for the measurement of longitudinal variations of sulfur isotope amount ratios in single hair strands using a laser ablation system coupled to a multicollector inductively coupled plasma mass spectrometer (LA-MC-ICP-MS) is reported here for the first time. Ablation parameters have been optimized for the measurement of sulfur isotope ratios in scalp human hair strands of 80-120-microm thickness and different washing procedures have been evaluated. The repeatability of the method has been tested and the ability to measure sulfur isotopic variations in 1,000-microm-long hair segments has been evaluated. A horse hair sample previously characterized for carbon and nitrogen isotope ratios in an interlaboratory study has been characterized by LA-MC-ICP-MS to be used as an in-house standard for the bracketing of human hair strands. (34)S/(32)S isotope amount ratios have been measured and corrected for instrumental mass bias adopting the external standardization approach using National Institute of Standards and Technology (NIST) RM8553 and full uncertainty budgets have been calculated using the Kragten approach. Results are reported as both (34)S/(32)S isotope amount ratios and deltaS(V-CDT) values (sulfur isotopic differences relative to a reference sample expressed in the Vienna Canyon Diablo Troilite (V-CDT) scale) calculated using NIST RM8553, NIST RM8554, and NIST RM8556 to anchor results to the V-CDT scale. The main advantage of the new method versus conventional gas source isotope ratio mass spectrometry measurements is that longitudinal variations in sulfur isotope amount ratios can be resolved. Proof of concept is shown with human scalp hair strands from three individuals, two UK residents and one traveler (long periods of time abroad). The method enables monitoring of longitudinal isotope ratio variations in single hair strands. Absolute ratios are reported and delta(34)S(V-CDT) values are plotted for comparison. Slight variations of <1.2 per

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.

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

PubMed Central

Khan, Imran; Tang, Elieza; Arany, Praveen

2015-01-01

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

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

PubMed

Khan, Imran; Tang, Elieza; Arany, Praveen

2015-06-01

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

Ionization cross section, pressure shift and isotope shift measurements of osmium

NASA Astrophysics Data System (ADS)

Hirayama, Yoshikazu; Mukai, Momo; Watanabe, Yutaka; Oyaizu, Michihiro; Ahmed, Murad; Kakiguchi, Yutaka; Kimura, Sota; Miyatake, Hiroari; Schury, Peter; Wada, Michiharu; Jeong, Sun-Chan

2017-11-01

In-gas-cell laser resonance ionization spectroscopy of neutral osmium atoms was performed with the use of a two-color two-step laser resonance ionization technique. Saturation curves for the ionization scheme were measured, and the ionization cross section was experimentally determined by solving the rate equations for the ground, intermediate and ionization continuum populations. The pressure shift and pressure broadening in the resonance spectra of the excitation transition were measured. The electronic factor {F}247 for the transition {λ }1=247.7583 nm to the intermediate state was deduced from the measured isotope shifts of stable {}{188,189,{190,192}}Os isotopes. The efficient ionization scheme, pressure shift, nuclear isotope shift and {F}247 are expected to be useful for applications of laser ion sources to unstable nuclei and for nuclear spectroscopy based on laser ionization techniques.

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.

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.

Emission ratio and isotopic signatures of molecular hydrogen emissions from tropical biomass burning

NASA Astrophysics Data System (ADS)

Haumann, F. A.; Batenburg, A. M.; Pieterse, G.; Gerbig, C.; Krol, M. C.; Röckmann, T.

2013-09-01

In this study, we identify a biomass-burning signal in molecular hydrogen (H2) over the Amazonian tropical rainforest. To quantify this signal, we measure the mixing ratios of H2 and several other species as well as the H2 isotopic composition in air samples that were collected in the BARCA (Balanço Atmosférico Regional de Carbono na Amazônia) aircraft campaign during the dry season. We derive a relative H2 emission ratio with respect to carbon monoxide (CO) of 0.31 ± 0.04 ppb ppb-1 and an isotopic source signature of -280 ± 41‰ in the air masses influenced by tropical biomass burning. In order to retrieve a clear source signal that is not influenced by the soil uptake of H2, we exclude samples from the atmospheric boundary layer. This procedure is supported by data from a global chemistry transport model. The ΔH2 / ΔCO emission ratio is significantly lower than some earlier estimates for the tropical rainforest. In addition, our results confirm the lower values of the previously conflicting estimates of the H2 isotopic source signature from biomass burning. These values for the emission ratio and isotopic source signatures of H2 from tropical biomass burning can be used in future bottom-up and top-down approaches aiming to constrain the strength of the biomass-burning source for H2. Hitherto, these two quantities relied only on combustion experiments or on statistical relations, since no direct signal had been obtained from in-situ observations.

Emission ratio and isotopic signatures of molecular hydrogen emissions from tropical biomass burning

NASA Astrophysics Data System (ADS)

Haumann, F. A.; Batenburg, A. M.; Pieterse, G.; Gerbig, C.; Krol, M. C.; Röckmann, T.

2013-04-01

In this study, we identify a biomass-burning signal in molecular hydrogen (H2) over the Amazonian tropical rainforest. To quantify this signal, we measure the mixing ratios of H2 and several other species as well as the H2 isotopic composition in air samples that were collected in the BARCA (Balanço Atmosférico Regional de Carbono na Amazônia) aircraft campaign during the dry season. We derive a relative H2 emission ratio with respect to carbon monoxide (CO) of 0.31 ± 0.04 ppb/ppb and an isotopic source signature of -280 ± 41‰ in the air masses influenced by tropical biomass burning. In order to retrieve a clear source signal that is not influenced by the soil uptake of H2, we exclude samples from the atmospheric boundary layer. This procedure is supported by data from a global chemistry transport model. The ΔH2/ΔCO emission ratio is significantly lower than some earlier estimates for the tropical rainforest. In addition, our results confirm the lower values of the previously conflicting estimates of the H2 isotopic source signature from biomass burning. These values for the emission ratio and isotopic source signatures of H2 from tropical biomass burning can be used in future bottom-up and top-down approaches aiming to constrain the strength of the biomass-burning source for H2. Hitherto, these two quantities relied only on combustion experiments or on statistical relations, since no direct signal had been obtained from in-situ observations.

Note: Micro-channel array crucible for isotope-resolved laser spectroscopy of high-temperature atomic beams

DOE PAGES

Lebedev, Vyacheslav; Bartlett, Joshua H.; Malyzhenkov, Alexander; ...

2017-12-06

Here, we present a novel compact design for a multichannel atomic oven which generates collimated beams of refractory atoms for fieldable laser spectroscopy. Using this resistively heated crucible, we demonstrate spectroscopy of an erbium sample at 1300 °C with improved isotopic resolution with respect to a single-channel design. In addition, our oven has a high thermal efficiency. By minimizing the surface area of the crucible, we achieve 2000 °C at 140 W of applied electrical power. As a result, the design does not require any active cooling and is compact enough to allow for its incorporation into fieldable instruments.

Note: Micro-channel array crucible for isotope-resolved laser spectroscopy of high-temperature atomic beams

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

Lebedev, Vyacheslav; Bartlett, Joshua H.; Malyzhenkov, Alexander

Here, we present a novel compact design for a multichannel atomic oven which generates collimated beams of refractory atoms for fieldable laser spectroscopy. Using this resistively heated crucible, we demonstrate spectroscopy of an erbium sample at 1300 °C with improved isotopic resolution with respect to a single-channel design. In addition, our oven has a high thermal efficiency. By minimizing the surface area of the crucible, we achieve 2000 °C at 140 W of applied electrical power. As a result, the design does not require any active cooling and is compact enough to allow for its incorporation into fieldable instruments.

N and O isotope (δ15 Nα , δ15 Nβ , δ18 O, δ17 O) analyses of dissolved NO3- and NO2- by the Cd-azide reduction method and N2 O laser spectrometry.

PubMed

Wassenaar, Leonard I; Douence, Cedric; Altabet, Mark A; Aggarwal, Pradeep K

2018-02-15

The nitrogen and oxygen (δ 15 N, δ 18 O, δ 17 O) isotopic compositions of NO 3 - and NO 2 - are important tracers of nutrient dynamics in soil, rain, groundwater and oceans. The Cd-azide method was used to convert NO 3 - or NO 2 - to N 2 O for N and triple-O isotopic analyses by N 2 O laser spectrometry. A protocol for laser-based headspace isotope analyses was compared with isotope ratio mass spectrometry. Lasers provide the ability to directly measure 17 O anomalies which can help discern atmospheric N sources. δ 15 N, δ 18 O and δ 17 O values were measured on N/O stable isotopic reference materials (IAEA, USGS) by conversion to N 2 O using the Cd-azide method and headspace N 2 O laser spectrometry. A 15 N tracer test assessed the position-specific routing of N to the α or β positions in the N 2 O molecule. A data processing algorithm was used to correct for isotopic dependencies on N 2 O concentration, cavity pressure and water content. NO 3 - /NO 2 - nitrogen is routed to the 15 N α position of N 2 O in the azide reaction; hence the δ 15 N α value should be used for N 2 O laser spectrometry results. With corrections for cavity pressure, N 2 O concentration and water content, the δ 15 N α AIR , δ 18 O VSMOW and δ 17 O VSMOW values (‰) of international reference materials were +4.8 ± 0.1, +25.9 ± 0.3, +12.7 ± 0.2 (IAEA NO 3 ), -1.7 ± 0.1, -26.8 ± 0.8, -14.4 ± 1.1 (USGS34) and +2.6 ± 0.1, +57.6 ± 1.2, +51.2 ± 2.0 (USGS35), in agreement with their values and with the isotope ratio mass spectrometry results. The 17 O excess for USGS35 was +21.2 ± 9‰, in good agreement with previous results. The Cd-azide method yielded excellent results for routine determination of δ 15 N, δ 18 O and δ 17 O values (and the 17 O excess) of nitrate or nitrite by laser spectrometry. Disadvantages are the toxicity of Cd-azide chemicals and the lack of automated sampling devices for N 2 O laser spectrometers. The 15 N-enriched tracer test revealed potential

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.

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

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.

Theoretical calculation of polarizability isotope effects.

PubMed

Moncada, Félix; Flores-Moreno, Roberto; Reyes, Andrés

2017-03-01

We propose a scheme to estimate hydrogen isotope effects on molecular polarizabilities. This approach combines the any-particle molecular orbital method, in which both electrons and H/D nuclei are described as quantum waves, with the auxiliary density perturbation theory, to calculate analytically the polarizability tensor. We assess the performance of method by calculating the polarizability isotope effect for 20 molecules. A good correlation between theoretical and experimental data is found. Further analysis of the results reveals that the change in the polarizability of a X-H bond upon deuteration decreases as the electronegativity of X increases. Our investigation also reveals that the molecular polarizability isotope effect presents an additive character. Therefore, it can be computed by counting the number of deuterated bonds in the molecule.

Status of the TRIGA-LASER experiment

NASA Astrophysics Data System (ADS)

Gorges, C.; Kaufmann, S.; Geppert, Ch.; Krämer, J.; Sánchez, R.; Nörtershäuser, W.

2017-11-01

We report on the newly developed control system called TRITON and the new data acquisition called TILDA as well as on improved isotope shift measurements of the isotopes 40,42,44,48Ca in the 4 s 2S1/2 → 4 p 2P3/2 (D2) transition at the TRIGA-LASER experiment in Mainz using collinear laser spectroscopy. Well known isotope shift measurements in the 4 s 2S1/2 → 4 p 2P1/2 (D1) transition act as calibration points to reduce the uncertainties in the D2-line to provide reference values for the determination of nuclear charge radii and quadrupole moments of neutron rich calcium isotopes at COLLAPS.

Current developments with TRIUMF's titanium-sapphire laser based resonance ionization laser ion source. An overview

NASA Astrophysics Data System (ADS)

Lassen, J.; Li, R.; Raeder, S.; Zhao, X.; Dekker, T.; Heggen, H.; Kunz, P.; P. Levy, C. D.; Mostanmand, M.; Teigelhöfer, A.; Ames, F.

2017-11-01

Developments at TRIUMF's isotope separator and accelerator (ISAC) resonance ionization laser ion source (RILIS) in the past years have concentrated on increased reliability for on-line beam delivery of radioactive isotopes to experiments, as well as increasing the number of elements available through resonance ionization and searching for ionization schemes with improved efficiency. The current status of these developments is given with a list of two step laser ionization schemes implemented recently.

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.

Hydrogen and oxygen stable isotope signatures of goethite hydration waters by thermogravimetry-enabled laser spectroscopy

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

Oerter, Erik; Singleton, Michael; Davisson, Lee

The hydrogen and oxygen stable isotope composition (δ 2H and δ 18O values) of mineral hydration waters can give information on the environment of mineral formation. Here we present and validate an approach for the stable isotope analysis of mineral hydration waters based on coupling a thermogravimetric analyzer with a laser-based isotope ratio infrared spectroscopy instrument (Picarro L-2130i), which we abbreviate as TGA-IRIS. TGA-IRIS generates δ 2H and δ 18O values of liquid water samples with precision for δ 2H of ± 1.2‰, and for δ 18O of ± 0.17‰. For hydration waters in goethite, precision for δ 2H rangesmore » from ± 0.3‰ to 1.6‰, and for δ 18O ranges from ± 0.17‰ to 0.27‰. The ability of TGA-IRIS to generate detailed water yield data and δ 2H and δ 18O values of water at varying temperatures allows for the differentiation of water in varying states of binding on mineral surfaces and within the mineral matrix. TGA-IRIS analyses of hydrogen isotopes in goethite yields δ 2H values that reflect the hydrogen of the OH – phase in the mineral and are comparable to that made by IRMS and found in the literature. In contrast, δ 18O values on goethite reflect the oxygen in OH – groups bound to Fe (Fe-OH group), and not the oxygen bound only to Fe (Fe-O group) in the mineral crystal lattice, and may not be comparable to literature δ 18O values made by IRMS that reflect the total O in the mineral. TGA-IRIS presents the possibility to isotopically differentiate the various oxygen reservoirs in goethite, which may allow the mineral to be used as a single mineral geothermometer. As a result, TGA-IRIS measurements of hydration waters are likely to open new avenues and possibilities for research on hydrated minerals.« less

Hydrogen and oxygen stable isotope signatures of goethite hydration waters by thermogravimetry-enabled laser spectroscopy

DOE PAGES

Oerter, Erik; Singleton, Michael; Davisson, Lee

2017-10-22

The hydrogen and oxygen stable isotope composition (δ 2H and δ 18O values) of mineral hydration waters can give information on the environment of mineral formation. Here we present and validate an approach for the stable isotope analysis of mineral hydration waters based on coupling a thermogravimetric analyzer with a laser-based isotope ratio infrared spectroscopy instrument (Picarro L-2130i), which we abbreviate as TGA-IRIS. TGA-IRIS generates δ 2H and δ 18O values of liquid water samples with precision for δ 2H of ± 1.2‰, and for δ 18O of ± 0.17‰. For hydration waters in goethite, precision for δ 2H rangesmore » from ± 0.3‰ to 1.6‰, and for δ 18O ranges from ± 0.17‰ to 0.27‰. The ability of TGA-IRIS to generate detailed water yield data and δ 2H and δ 18O values of water at varying temperatures allows for the differentiation of water in varying states of binding on mineral surfaces and within the mineral matrix. TGA-IRIS analyses of hydrogen isotopes in goethite yields δ 2H values that reflect the hydrogen of the OH – phase in the mineral and are comparable to that made by IRMS and found in the literature. In contrast, δ 18O values on goethite reflect the oxygen in OH – groups bound to Fe (Fe-OH group), and not the oxygen bound only to Fe (Fe-O group) in the mineral crystal lattice, and may not be comparable to literature δ 18O values made by IRMS that reflect the total O in the mineral. TGA-IRIS presents the possibility to isotopically differentiate the various oxygen reservoirs in goethite, which may allow the mineral to be used as a single mineral geothermometer. As a result, TGA-IRIS measurements of hydration waters are likely to open new avenues and possibilities for research on hydrated minerals.« less

Monitoring of catalyst performance in CO2 lasers using frequency modulation spectroscopy with diode lasers

NASA Technical Reports Server (NTRS)

Wang, Liang-Guo; Sachse, Glen

1990-01-01

Closed-cycle CO2 laser operation with removal of O2 and regeneration of CO2 can be achieved by catalytic CO-O2 recombination. Both parametric studies of the optimum catalyst formulation and long-term performance tests require on line monitoring of CO, O2 and CO2 concentrations. There are several existing methods for molecular oxygen detection. These methods are either intrusive (such as electrochemical method or mass spectrometry) or very expensive (such as CARS, UV laser absorption). Researchers demonstrated a high-sensitivity spectroscopic measurement of O2 using the two-tone frequency modulation spectroscopy (FMS) technique with a near infrared GaAlAs diode laser. Besides its inexpensive cost, fast response time, nonintrusive measurements and high sensitivity, this technique may also be used to differentiate between isotopes due to its high spectroscopic resolution. This frequency modulation spectroscopy technique could also be applied for the on-line monitoring of CO and CO2 using InGaAsP diode lasers operation in the 1.55 microns region and H2O in the 1.3 microns region. The existence of single mode optical fibers at the near infrared region makes it possible to combine FMS with optical fiber technology. Optical fiber FMS is particularly suitable for making point-measurements at one or more locations in the CO2 laser/catalyst system.

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.

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

NASA Technical Reports Server (NTRS)

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

1991-01-01

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

Development of laser ablation multi-collector inductively coupled plasma mass spectrometry for boron isotopic measurement in marine biocarbonates: new improvements and application to a modern Porites coral.

PubMed

Thil, François; Blamart, Dominique; Assailly, Caroline; Lazareth, Claire E; Leblanc, Thierry; Butsher, John; Douville, Eric

2016-02-15

Laser Ablation coupled to Multi-Collector Inductively Coupled Plasma Mass Spectrometry (LA-MC-ICPMS) is a powerful tool for the high-precision measurement of the isotopic ratios of many elements in geological samples, with the isotope ratio ((11) B/(10) B) of boron being used as an indicator of the pH of oceanic waters. Most geological samples or standards are polished and ablation occurs on flat surfaces. However, the shape and the irregularities of marine biocarbonates (e.g., corals, foraminifera) can make precise isotopic measurements of boron difficult. Even after polishing, the porosity properties and the presence of holes or micro-fractures affect the signal and the isotopic ratio when ablating the material, especially in raster mode. The effect of porosity and of the crater itself on the (11) B signal and the isotopic ratio acquired by LA-MC-ICPMS in both raster and spot mode was studied. Characterization of the craters was then performed with an optical profilometer to determine their shapes and depths. Surface state effects were examined by analyzing the isotopic fractionation of boron in silicate (NIST-SRM 612 and 610 standards) and in carbonate (corals). Surface irregularities led to a considerable loss of signal when the crater depth exceeded 20 µm. The stability and precision were degraded when ablation occurred in a deep cavity. The effect of laser focusing and of blank correction was also highlighted and our observations indicate that the accuracy of the boron isotopic ratio does not depend on the shape of the surface. After validation of the analytical protocol for boron isotopes, a raster application on a Porites coral, which grew for 18 months in an aquarium after field sampling, was carried out. This original LA-MC-ICPMS study revealed a well-marked boron isotope ratio temporal variability, probably related to growth rate and density changes, irrespective of the pH of the surrounding seawater. Copyright © 2015 John Wiley & Sons, Ltd. Copyright

Application of Laser Induced Breakdown Spectroscopy under Polar Conditions

NASA Astrophysics Data System (ADS)

Clausen, J. L.; Hark, R.; Bol'shakov, A.; Plumer, J.

2015-12-01

Over the past decade our research team has evaluated the use of commercial-off-the-shelf laser-induced breakdown spectroscopy (LIBS) for chemical analysis of snow and ice samples under polar conditions. One avenue of research explored LIBS suitability as a detector of paleo-climate proxy indicators (Ca, K, Mg, and Na) in ice as it relates to atmospheric circulation. LIBS results revealed detection of peaks for C and N, consistent with the presence of organic material, as well as major ions (Ca, K, Mg, and Na) and trace metals (Al, Cu, Fe, Mn, Ti). The detection of Ca, K, Mg, and Na confirmed that LIBS has sufficient sensitivity to be used as a tool for characterization of paleo-climate proxy indicators in ice-core samples. Techniques were developed for direct analysis of ice as well as indirect measurements of ice via melting and filtering. Pitfalls and issues of direct ice analysis using several cooling techniques to maintain ice integrity will be discussed. In addition, a new technique, laser ablation molecular isotopic spectroscopy (LAMIS) was applied to detection of hydrogen and oxygen isotopes in ice as isotopic analysis of ice is the main tool in paleoclimatology and glaciology studies. Our results demonstrated that spectra of hydroxyl isotopologues 16OH, 18OH, and 16OD can be recorded with a compact spectrograph to determine hydrogen and oxygen isotopes simultaneously. Quantitative isotopic calibration for ice analysis can be accomplished using multivariate chemometric regression as previously realized for water vapor. Analysis with LIBS and LAMIS required no special sample preparation and was about ten times faster than analysis using ICP-MS. Combination of the two techniques in one portable instrument for in-field analysis appears possible and would eliminate the logistical and cost issues associated with ice core management.

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.

Strontium isotope measurement of basaltic glasses by laser ablation multiple collector inductively coupled plasma mass spectrometry based on a linear relationship between analytical bias and Rb/Sr ratios.

PubMed

Zhang, Le; Ren, Zhong-Yuan; Wu, Ya-Dong; Li, Nan

2018-01-30

In situ strontium (Sr) isotope analysis of geological samples by laser ablation multiple collector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) provides useful information about magma mixing, crustal contamination and crystal residence time. Without chemical separation, during Sr isotope analysis with laser ablation, many kinds of interference ions (such as Rb + and Kr + ) are on the Sr isotope spectrum. Most previous in situ Sr isotope studies only focused on Sr-enriched minerals (e.g. plagioclase, calcite). Here we established a simple method for in situ Sr isotope analysis of basaltic glass with Rb/Sr ratio less than 0.14 by LA-MC-ICP-MS. Seven Faraday cups, on a Neptune Plus MC-ICP-MS instrument, were used to receive the signals on m/z 82, 83, 84, 85, 86, 87 and 88 simultaneously for the Sr isotope analysis of basaltic glass. The isobaric interference of 87 Rb was corrected by the peak stripping method. The instrumental mass fractionation of 87 Sr/ 86 Sr was corrected to 86 Sr/ 88 Sr = 0.1194 with an exponential law. Finally, the residual analytical biases of 87 Sr/ 86 Sr were corrected with a relationship between the deviation of 87 Sr/ 86 Sr from the reference values and the measured 87 Rb/ 86 Sr. The validity of the protocol present here was demonstrated by measuring the Sr isotopes of four basaltic glasses, a plagioclase crystal and a piece of modern coral. The measured 87 Sr/ 86 Sr ratios of all these samples agree within 100 ppm with the reference values. In addition, the Sr isotopes of olivine-hosted melt inclusions from the Emeishan large igneous province (LIP) were measured to show the application of our method to real geological samples. A simple but accurate approach for in situ Sr isotope measurement by LA-MC-ICP-MS has been established, which should greatly facilitate the wider application of in situ Sr isotope geochemistry, especially to volcanic rock studies. Copyright © 2017 John Wiley & Sons, Ltd.

Effect of diatomic molecular properties on binary laser pulse optimizations of quantum gate operations.

PubMed

Zaari, Ryan R; Brown, Alex

2011-07-28

The importance of the ro-vibrational state energies on the ability to produce high fidelity binary shaped laser pulses for quantum logic gates is investigated. The single frequency 2-qubit ACNOT(1) and double frequency 2-qubit NOT(2) quantum gates are used as test cases to examine this behaviour. A range of diatomics is sampled. The laser pulses are optimized using a genetic algorithm for binary (two amplitude and two phase parameter) variation on a discretized frequency spectrum. The resulting trends in the fidelities were attributed to the intrinsic molecular properties and not the choice of method: a discretized frequency spectrum with genetic algorithm optimization. This is verified by using other common laser pulse optimization methods (including iterative optimal control theory), which result in the same qualitative trends in fidelity. The results differ from other studies that used vibrational state energies only. Moreover, appropriate choice of diatomic (relative ro-vibrational state arrangement) is critical for producing high fidelity optimized quantum logic gates. It is also suggested that global phase alignment imposes a significant restriction on obtaining high fidelity regions within the parameter search space. Overall, this indicates a complexity in the ability to provide appropriate binary laser pulse control of diatomics for molecular quantum computing. © 2011 American Institute of Physics

Isotope shifts in francium isotopes Fr 206 - 213 and Fr 221

DOE PAGES

Collister, R.; Gwinner, G.; Tandecki, M.; ...

2014-11-07

We present the isotope shifts of the 7s 1/2 to 7p 1/2 transition for francium isotopes ²⁰⁶⁻²¹³Fr with reference to ²²¹Fr collected from two experimental periods. The shifts are measured on a sample of atoms prepared within a magneto-optical trap by a fast sweep of radio-frequency sidebands applied to a carrier laser. King plot analysis, which includes literature values for 7s 1/2 to 7p 3/2 isotope shifts, provides a field shift constant ratio of 1.0520(10) and a difference between the specific mass shift constants of 170(100) GHz amu between the D₁ and D₂ transitions, of sufficient precision to differentiate betweenmore » ab initio calculations.« less

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

Biomedical applications of laser photoionization

NASA Astrophysics Data System (ADS)

Xiong, Xiaoxiong; Moore, Larry J.; Fassett, John R.; O'Haver, Thomas C.

1991-07-01

Trace elements are important for many essential metabolic functions. Zinc is a structural/functional component in more than 200 enzymes active in the biochemistry of cell division and tissue growth, neurology and endocrine control. Calcium is involved in intracellular control mechanisms and in skeletal bone building and resorption processes related to osteoporosis. Sensitive and selective laser photoionization is being developed to understand mechanisms in smaller samples and biological units approaching the cellular domain. Zinc has an ionization potential of 9.4 eV, or 75766.8 cm-1. Several processes are being explored, including two-photon resonant, three- photon ionization utilizing sequential UV transitions, e.g., 4s2 1S0 yields 4s4p 3P1 and 4s4p 3P1 yields 4s5d 3D1. Preliminary zinc stable isotope ratio data obtained by thermal atomization and laser photoionization agree with accepted values within 2 to 5%, except for anomalous 67Zn. Photoionization of calcium is being studied for isotope enrichment and ratio measurement using narrow and medium bandwidth lasers. Several ionization pathways, e.g., 4s2 1S0 - 2hv1 yields 4s10s - hv2 yields Ca+ (4s2S), are being investigated for isotopically selective ionization. Auto-ionization pathways are explored for greater efficiency in isotopic analysis. All studies have utilized a Nd:YAG- pumped laser system with one or two frequency-doubled tunable dye lasers coupled either to a magnetic sector or time-of-flight mass spectrometer.

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.;

Novel hybrid isotope separation scheme and apparatus

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 the specific isotope is to be isolated, radiating the gas with frequencies characteristic of the absorption of a particular isotope of the atomic or molecular gas, thereby inducing a photoionization reaction of the desired isotope, and collecting the specific isotope ion by suitable ion collection means.

Detection of boron nitride radicals by emission spectroscopy in a laser-induced plasma

NASA Astrophysics Data System (ADS)

Dutouquet, C.; Acquaviva, S.; Hermann, J.

2001-06-01

Several vibrational bands of boron nitride radicals have been observed in a plasma produced by pulsed-laser ablation of a boron nitride target in low-pressure nitrogen or argon atmospheres. Using time- and space-resolved emission spectroscopic measurements with a high dynamic range, the most abundant isotopic species B 11N have been detected. The emission bands in the spectral range from 340 to 380 nm belong to the Δυ =-1, 0, +1 sequences of the triplet system (transition A 3Π-X 3Π). For positive identification, the molecular emission bands have been compared with synthetic spectra obtained by computer simulations. Furthermore, B 10N emission bands have been reproduced by computer simulation using molecular constants which have been deduced from the B 11N constants. Nevertheless, the presence of the lower abundant isotopic radical B 10N was not proved due the noise level which masked the low emission intensity of the B 10N band heads.

Deproteinization assessment using isotopically enriched compounds to trace the coprecipitation of low-molecular-weight selenium species with proteins.

PubMed

Godin, Simon; Bouzas-Ramos, Diego; Fontagné-Dicharry, Stéphanie; Bouyssière, Brice; Bueno, Maïté

2017-08-01

Studies have shown that information related to the presence of low-molecular-weight metabolites is frequently lost after deproteinization of complex matrices, such as blood and plasma, during sample preparation. Therefore, the effect of several deproteinization reagents on low-molecular-weight selenium species has been compared by species-specific isotope labeling. Two isotopically enriched selenium tracers were used to mimic models of small inorganic anionic ( 77 Se-selenite) and organic zwitterionic ( 76 Se-selenomethionine) species. The results presented here show that the use of a methanol-acetonitrile-acetone (1:1:1 v/v/v) mixture provided approximately two times less tracer loss from plasma samples in comparison with the classic procedure using acetonitrile, which may not be optimal as it leads to important losses of low-molecular-weight selenium species. In addition, the possible interactions between selenium tracers and proteins were investigated, revealing that both coprecipitation phenomena and association with proteins were potentially responsible for selenite tracer losses during protein precipitation in blood samples. However, coprecipitation phenomena were found to be fully responsible for losses of both tracers observed in plasma samples and of the selenomethionine tracer in blood samples. This successfully applied strategy is anticipated to be useful for more extensive future studies in selenometabolomics. Copyright © 2017 Elsevier Inc. All rights reserved.

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

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

Havrilla, George Joseph; McIntosh, Kathryn Gallagher; Judge, Elizabeth

2016-10-20

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

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

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

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 elementalmore » 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.« less

Evaluation of UV-fs-LA-MC-ICP-MS for precise in situ copper isotopic microanalysis of cubanite.

PubMed

Ikehata, Kei; Hirata, Takafumi

2013-01-01

We evaluated the capabilities of an in situ method for measuring copper isotopes of cubanite using UV-fs-LA-MC-ICP-MS. A comparison of the UV-fs laser results with those obtained from the NIR-fs laser system shows that there is obviously an improvement in the precision (<0.10‰, 2SE) when using the UV-fs laser. In both wavelength modes, matrix-matched standards are required for reliable in situ copper isotope analysis of cubanite. This method was applied to determinations for copper isotopes of minute cubanite grains in a skarn ore. Copper isotopic ratios of cubanite grains near a weathered surface of the sample are lower than those of intact cubanite grains within the sample, suggesting that selective leaching of heavier copper isotope in primary minerals occurred during weathering.

Novel hybrid isotope separation scheme and apparatus

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 the specific isotope is to be isolated, radiating the gas with frequencies characteristic of the absorption of a particular isotope of the atomic or molecular gas, thereby inducing a photoionization reaction of the desired isotope, and collecting the specific isotope ion by suitable ion collection means. 3 figures.

In-situ Pb isotope analysis of Fe-Ni-Cu sulphides by laser ablation multi-collector ICPMS: New insights into ore formation in the Sudbury impact melt sheet

NASA Astrophysics Data System (ADS)

Darling, J. R.; Storey, C. D.; Hawkesworth, C. J.; Lightfoot, P. C.

2012-12-01

Laser-ablation (LA) multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS) is ideally suited to in situ determination of isotope ratios in sulphide minerals. Using samples of magmatic sulphide ore from the Sudbury impact structure, we test LA-MC-ICPMS analytical protocols that aim to meet a range of analytical challenges in the analysis of Pb isotopes. These include: potential matrix sensitive isotopic fractionation; interferences on Pb isotopes; low melting points of many sulphide minerals; the availability of standards. Magmatic sulphides of wide ranging mineralogy (pyrrhotite, pentlandite, chalcopyrite, pyrite and sphalerite) were analysed for Pb isotopic composition, using the silicate glass NIST SRM 610 as an external standard to correct for instrumental mass-fractionation. Despite matrix sensitive melting and re-deposition around ablation pits, several lines of evidence indicate that all analyses are accurate, within typical analytical uncertainties of 0.003-2% (2σ), and that the defined approach is insensitive to compositional diversity in sample matrix: (a) laser ablation and dissolution based measurements of sulphide powders are in agreement; (b) analyses from each sample define isochron ages within uncertainty of the known crystallization age (1850 Ma); (c) the results of sulphide measurements by laser ablation are consistent with age-corrected feldspar analyses from the same samples. The results have important implications for ore formation in Sudbury. The Pb isotope data regressions are consistent with age corrected feldspar analyses from each respective sample, which together with time integrated Th/U ratios that match whole rock values (3.1, 4.0 and 6.1 for the Worthington, Copper Cliff and Parkin Offset Dykes, respectively) indicate chemical equilibrium between the silicate and sulphide systems during ore formation. The sulphides within each respective sample have indistinguishable model initial Pb isotope ratios (207Pb/204Pbm

Laser-induced optical breakdown spectroscopy of polymer materials based on evaluation of molecular emission bands

NASA Astrophysics Data System (ADS)

Trautner, Stefan; Jasik, Juraj; Parigger, Christian G.; Pedarnig, Johannes D.; Spendelhofer, Wolfgang; Lackner, Johannes; Veis, Pavel; Heitz, Johannes

2017-03-01

Laser-induced breakdown spectroscopy (LIBS) for composition analysis of polymer materials results in optical spectra containing atomic and ionic emission lines as well as molecular emission bands. In the present work, the molecular bands are analyzed to obtain spectroscopic information about the plasma state in an effort to quantify the content of different elements in the polymers. Polyethylene (PE) and a rubber material from tire production are investigated employing 157 nm F2 laser and 532 nm Nd:YAG laser ablation in nitrogen and argon gas background or in air. The optical detection reaches from ultraviolet (UV) over the visible (VIS) to the near infrared (NIR) spectral range. In the UV/VIS range, intense molecular emissions, C2 Swan and CN violet bands, are measured with an Echelle spectrometer equipped with an intensified CCD camera. The measured molecular emission spectra can be fitted by vibrational-rotational transitions by open access programs and data sets with good agreement between measured and fitted spectra. The fits allow determining vibrational-rotational temperatures. A comparison to electronic temperatures Te derived earlier from atomic carbon vacuum-UV (VUV) emission lines show differences, which can be related to different locations of the atomic and molecular species in the expanding plasma plume. In the NIR spectral region, we also observe the CN red bands with a conventional CDD Czerny Turner spectrometer. The emission of the three strong atomic sulfur lines between 920 and 925 nm is overlapped by these bands. Fitting of the CN red bands allows a separation of both spectral contributions. This makes a quantitative evaluation of sulfur contents in the start material in the order of 1 wt% feasible.

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

2014-12-03

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. Copyright © 2014 Elsevier B.V. All rights reserved.

TDLAS a laser diode sensor for the in situ monitoring of H2O, CO2 and their isotopes in the Martian atmosphere

NASA Astrophysics Data System (ADS)

Le Barbu, T.; Vinogradov, I.; Durry, G.; Korablev, O.; Chassefière, E.; Bertaux, J.-L.

2006-01-01

Within the framework of Pasteur-Exomars, we have proposed to measure in situ water vapor (H2O, HDO, H218O, H217O) and carbon dioxide (CO2, 13C16O2, 16O12C18O, 16O12C17O) isotopes and also CO, CH4 and N2O by absorption spectroscopy using near infrared laser diodes. The Service d’Aéronomie has a relevant experience in trace-gas detection with laser diodes. We have developed, with the support of the CNES and the CNRS, the SDLA diode laser spectrometer to measure in situ H2O (at 1.39 μm), CH4 (1.65 μm) and CO2 (at 1.60 μm) in the middle atmosphere from stratospheric balloons. The concentrations are obtained with a precision error of a few percent and with a high temporal resolution that ranges from 10 ms to 1 s. The developed laser probing technique should be also highly efficient to study the Martian atmosphere as there are much higher amounts of water vapor and carbon dioxide in the Martian atmosphere than in the lower stratosphere (H2O: 200 ppmv at 6 hPa on Mars, 5 ppmv at 10 hPa in the low stratosphere (LS); CO2 95% on Mars, 360 ppmv in the LS). Hence, we propose to adapt the laser probing technique to the Martian atmosphere. The main objectives are to determine water vapor and carbon dioxide fluxes and to study boundary layer properties. The sensor will provide in situ daily, diurnally resolved measurements of near-surface H2O and CO2 concentrations over seasonal time scales. The additional isotopic measurements will provide quantitative constraints on the evolution of atmospheric composition and on the history of water on Mars.

Molecular Dynamics Simulation of the Three-Dimensional Ordered State in Laser-Cooled Heavy-Ion Beams

NASA Astrophysics Data System (ADS)

Yuri, Yosuke

A molecular dynamics simulation is performed to study the formation of three-dimensional ordered beams by laser cooling in a cooler storage ring. Ultralow-temperature heavy-ion beams are generated by transverse cooling with displaced Gaussian lasers and resonant coupling. A three-dimensional ordered state of the ion beam is attained at a high line density. The ordered beam exhibits several unique characteristics different from those of an ideal crystalline beam.

Generation of nanoclusters by ultrafast laser ablation of Al: Molecular dynamics study

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

Miloshevsky, Alexander; Phillips, Mark C.; Harilal, Sivanandan S.

The laser ablation of materials induced by an ultrashort femtosecond pulse is a complex phenomenon, which depends on both the material properties and the properties of the laser pulse. The unique capability of a combination of molecular dynamics (MD) and Momentum Scaling Model (MSM) methods is developed and applied to a large atomic system for studying the process of ultrafast laser-material interactions, behavior of matter in a highly non-equilibrium state, material disintegration, and formation of nanoparticles (NPs). Laser pulses with several fluences in the range from 500 J/m2 to 5000 J/m2 interacting with a large system of aluminum atoms aremore » simulated. The response of Al material to the laser energy deposition is investigated within the finite-size laser spot. It is found that the shape of the plasma plume is dynamically changing during an expansion process. At several tens of picoseconds it can be characterized as a long hollow ellipsoid surrounded by atomized and nano-clustered particles. The time evolution of NP clusters in the plume is investigated. The collisions between the single Al atoms and generated NPs and fragmentation of large NPs determine the fractions of different-size NP clusters in the plume. The MD-MSM simulations show that laser fluence greatly affects the size distribution of NPs, their polar angles, magnitude and direction vectors of NP velocities. These results and predictions are supported by the experimental data and previous MD simulations.« less

Isotope separation by photodissociation of Van der Waal's molecules

DOEpatents

Lee, Yuan T.

1977-01-01

A method of separating isotopes based on the dissociation of a Van der Waal's complex. A beam of molecules of a Van der Waal's complex containing, as one partner of the complex, a molecular species in which an element is present in a plurality of isotopes is subjected to radiation from a source tuned to a frequency which will selectively excite vibrational motion by a vibrational transition or through electronic transition of those complexed molecules of the molecular species which contain a desired isotope. Since the Van der Waal's binding energy is much smaller than the excitational energy of vibrational motion, the thus excited Van der Waal's complex dissociate into molecular components enriched in the desired isotope. The recoil velocity associated with vibrational to translational and rotational relaxation will send the separated molecules away from the beam whereupon the product enriched in the desired isotope can be separated from the constituents of the beam.

Laser-stimulated electric quadrupole transitions in the molecular hydrogen ion H2+

NASA Astrophysics Data System (ADS)

Korobov, V. I.; Danev, P.; Bakalov, D.; Schiller, S.

2018-03-01

Molecular hydrogen ions are of metrological relevance due to the possibility of precise theoretical evaluation of their spectrum and of external-field-induced shifts. We report the results of the calculations of the rate of laser-induced electric quadrupole transitions between a large set of ro-vibrational states of H2+. The hyperfine and Zeeman structure of the E 2 transition spectrum and the effects of the laser polarization are treated in detail. The treatment is generally applicable to molecules in 2Σ states. We also present the nuclear spin-electron spin-coupling constants, computed with a precision ten times higher than previously obtained.

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.

Isotopic Discrimination During Leaf Litter Decomposition

NASA Astrophysics Data System (ADS)

Ngao, J.; Rubino, M.

2006-12-01

implement an advanced laser spectrometry technology to measure the isotopic composition in respired CO2. The laser spectrometer will be used to investigate the isotopic discrimination during soil respiration, in laboratory and field studies.

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

NASA Astrophysics Data System (ADS)

Rothfuss, Youri; Vereecken, Harry; Brüggemann, Nicolas

2013-06-01

In soils, the isotopic composition of water (δ2H and δ18O) provides qualitative (e.g., location of the evaporation front) and quantitative (e.g., evaporation flux and root water uptake depths) information. However, the main disadvantage of the isotope methodology is that contrary to other soil state variables that can be monitored over long time periods, δ2H and δ18O are typically analyzed following destructive sampling. Here we present a nondestructive method for monitoring soil liquid water δ2H and δ18O over a wide range of water availability conditions and temperatures by sampling water vapor equilibrated with soil water using gas-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°C and 24°C, we demonstrate that our new method is capable of monitoring δ2H and δ18O in soils online with high precision and after calibration, also with high accuracy. Our sampling protocol enabled detecting changes of δ2H and δ18O following nonfractionating addition and removal of liquid water and water vapor of different isotopic compositions. Finally, 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.

Following Carbon Isotopes from Methane to Molecules

NASA Astrophysics Data System (ADS)

Freeman, K. H.

2017-12-01

Continuous-flow methods introduced by Hayes (Matthews and Hayes, 1978; Freeman et al., 1990; Hayes et al., 1990) for compound-specific isotope analyses (CSIA) transformed how we study the origins and fates of organic compounds. This analytical revolution launched several decades of research in which researchers connect individual molecular structures to diverse environmental and climate processes affecting their isotopic profiles. Among the first applications, and one of the more dramatic isotopically, was tracing the flow of natural methane into cellular carbon and cellular biochemical constituents. Microbial oxidation of methane can be tracked by strongly 13C-depleted organic carbon in early Earth sedimentary environments, in marine and lake-derived biomarkers in oils, and in modern organisms and their environments. These signatures constrain microbial carbon cycling and inform our understanding of ocean redox. The measurement of molecular isotopes has jumped forward once again, and it is now possible to determine isotope abundances at specific positions within increasingly complex organic structures. In addition, recent analytical developments have lowered sample sensitivity limits of CSIA to picomole levels. These new tools have opened new ways to measure methane carbon in the natural environment and within biochemical pathways. This talk will highlight how molecular isotope methods enable us to follow the fate of methane carbon in complex environments and along diverse metabolic pathways, from trace fluids to specific carbon positions within microbial biomarkers.

Robust generation of Fourier-synthesized laser fields and their estimation of the optical phase by using quantum control of molecular tunneling ionization

NASA Astrophysics Data System (ADS)

Yoshida, Tsuyoshi; Saito, Naoaki; Ohmura, Hideki

2018-03-01

Intense (5.0 × 1012 W cm-2) nanosecond Fourier-synthesized laser fields consisting of fundamental, second-, third-, and fourth-harmonic light generated by an interferometer-free Fourier-synthesized laser field generator induce orientation-selective ionization based on directionally asymmetric molecular tunneling ionization (TI). The laser field generator ensures adjustment-free operation, high stability, and high reproducibility. Phase-sensitive, orientation-selective molecular TI provides a simple way to estimate the relative phase differences between the fundamental light and each harmonic by data-fitting analysis. This application of Fourier-synthesized laser fields will facilitate not only lightwave engineering but also the control of matter.

Influences of kerogen-rich bedrock on the molecular and isotopic composition of modern soils; implications for global C cycling

NASA Astrophysics Data System (ADS)

Longbottom, T. L.; Hockaday, W. C.

2016-12-01

Kerogen represents the largest terrestrial organic carbon (OC) reservoir on earth and is vulnerable to remineralization upon exposure to earth's atmosphere. Oxidative weathering of ancient sedimentary organic matter is an immensely transformative process with poorly-constrained mechanisms and flux values in contemporary carbon cycle models. The weathered residuum of organic-rich mudrocks serves as parent material for many modern soils, and it is likely that the structure and dynamics of the resulting soil organic matter pool is inherited directly from kerogen-rich bedrock. We used a combination of solid-state 13-C nuclear magnetic resonance (NMR) spectroscopy, and carbon isotope techniques to describe molecular and isotopic changes that occur throughout oxidative weathering of marine kerogens, and the subsequent formation of modern soils, in two outcropping Cretaceous mudstones of the Eagle Ford and Pepper Formations in central, TX. Gradational production of O-containing functionalities was observed, coupled with reductions in characteristically abundant polymethylenic components of type II kerogens. Organic matter structural parameters, derived from C-H dephasing NMR experiments, also provide the basis for a novel weathering index that accounts for the degree of post-sedimentary diagenetic alteration of samples along the kerogen-soil continuum. Molecular and isotopic mixing models were employed in estimating the proportions of modern and ancient C in soils, as increased incorporation and vulnerability of ancient OC under climatic shifts in temperature and/or precipitation is likely.

IV INTERNATIONAL CONFERENCE ON ATOM AND MOLECULAR PULSED LASERS (AMPL'99): Efficiency of an H2—SF6 laser with electron-beam initiation of chemical reactions

NASA Astrophysics Data System (ADS)

Erofeev, M. V.; Orlovskii, Viktor M.; Skakun, V. S.; Sosnin, E. A.; Tarasenko, Viktor F.

2000-06-01

The spectral and amplitude—time characteristics of HF lasers pumped by a nonchain chemical reaction and initiated by radially convergent and planar electron beams were investigated. The principal channels leading to the formation of vibrationally excited HF molecules were analysed. It was confirmed that high efficiencies (~10%) of a nonchain HF laser may be attained only as a result of the simultaneous formation of atomic and molecular fluorine when the active mixture is acted upon by an electron beam and of the participation of molecular fluorine in population inversion. It was shown that a laser pulse has a complex spectral—temporal profile caused by the successive generation of P-lines and the overlap during the radiation pulse of both the rotational lines of the same vibrational band and of individual vibrational bands.

Deposition of Cubic AlN Films on MgO (100) Substrates by Laser Molecular Beam Epitaxy

NASA Astrophysics Data System (ADS)

Mo, Z. K.; Yang, W. J.; Weng, Y.; Fu, Y. C.; He, H.; Shen, X. M.

2017-12-01

Cubic AlN (c-AlN) films were deposited on MgO (100) substrates by laser molecular beam epitaxy (LMBE) technique. The crystal structure and surface morphology of deposited films with various laser pulse energy and substrate temperature were investigated. The results indicate that c-AlN films exhibit the (200) preferred orientation, showing a good epitaxial relationship with the substrate. The surface roughness of c-AlN films increases when the laser pulse energy and substrate temperature increase. The film grown at laser pulse energy of 150 mJ and substrate temperature of 700 °C shows the best crystalline quality and relatively smooth surface.

Laser ionization time of flight mass spectrometer for isotope mass detection and elemental analysis of materials

NASA Astrophysics Data System (ADS)

Ahmed, Nasar; Ahmed, Rizwan; Umar, Z. A.; Aslam Baig, M.

2017-08-01

In this paper we present the construction and modification of a linear time-of-flight mass spectrometer to improve its mass resolution. This system consists of a laser ablation/ionization section based on a Q-switched Nd:YAG laser (532 nm, 500 mJ, 5 ns pulse duration) integrated with a one meter linear time-of-flight mass spectrometer coupled with an electric sector and a magnetic lens and outfitted with a channeltron electron multiplier for ion detection. The resolution of the system has been improved by optimizing the accelerating potential and inserting a magnetic lens after the extraction region. The isotopes of lithium, lead and cadmium samples have been resolved and detected in accordance with their natural abundance. The capability of the system has been further exploited to determine the elemental composition of a brass alloy, having a certified composition of zinc and copper. Our results are in excellent agreement with its certified composition. This setup is found to be extremely efficient and convenient for fast analyses of any solid sample.

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.

Water isotope ratio (δ2H and δ18O) measurements in atmospheric moisture using an optical feedback cavity enhanced absorption laser spectrometer

NASA Astrophysics Data System (ADS)

Iannone, Rosario Q.; Romanini, Daniele; Cattani, Olivier; Meijer, Harro A. J.; Kerstel, Erik R. Th.

2010-05-01

Water vapor isotopes represent an innovative and excellent tool for understanding complex mechanisms in the atmospheric water cycle over different time scales, and they can be used for a variety of applications in the fields of paleoclimatology, hydrology, oceanography, and ecology. We use an ultrasensitive near-infrared spectrometer, originally designed for use on airborne platforms in the upper troposphere and lower stratosphere, to measure the water deuterium and oxygen-18 isotope ratios in situ, in ground-level tropospheric moisture, with a high temporal resolution (from 300 s down to less than 1 s). We present some examples of continuous monitoring of near-surface atmospheric moisture, demonstrating that our infrared laser spectrometer could be used successfully to record high-concentration atmospheric water vapor mixing ratios in continuous time series, with a data coverage of ˜90%, interrupted only for daily calibration to two isotope ratio mass spectrometry-calibrated local water standards. The atmospheric data show that the water vapor isotopic composition exhibits a high variability that can be related to weather conditions, especially to changes in relative humidity. Besides, the results suggest that observed spatial and temporal variations of the stable isotope content of atmospheric water vapor are strongly related to water vapor transport in the atmosphere.

Diode-laser-based RIMS measurements of strontium-90

NASA Astrophysics Data System (ADS)

Bushaw, B. A.; Cannon, B. D.

1998-12-01

Double- and triple-resonance excitation schemes for the ionization of strontium are presented. Use of single-mode diode lasers for the resonance excitations provides a high degree of optical isotopic selectivity: with double-resonance, selectivity of >104 for 90Sr against the stable Sr isotopes has been demonstrated. Measurement of lineshapes and stable isotope shifts in the triple-resonance process indicate that optical selectivity should increase to ˜109. When combined with mass spectrometer selectivity this is sufficient for measurement of 90Sr at background environmental levels. Additionally, autoionizing resonances have been investigated for improving ionization efficiency with lower power lasers.

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

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.

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

Do birds of like feather flock together? The use of a novel 13C+D combustion isotope analyzer to track bird migration

NASA Astrophysics Data System (ADS)

Saad, N.

2011-12-01

Information on spring migration routes, geographic linkages among winter, spring, and breeding locations, and potential geographic effects on arrival body condition of a variety of avian species is so far little known. Stable isotope ratios are exquisitely sensitive to the biochemistry of living organisms and the nutrients available to them. Isotope ratios provide detailed knowledge useful in a variety of fields, including birds migration, through a combination of stable-isotope measurements of carbon (13C/12C) and hydrogen (D/H) isotopes of flight feathers and breast feathers of tissues representing different periods of dietary integration and body composition analyses. Associations among specific geographic areas, habitat use, and arrival condition can be elucidated through the measurement of these dual isotopes. We report here on the development of a novel laser spectroscopy based system for the simultaneous analysis of the stable isotope ratios of carbon (13C/12C) and hydrogen (D/H) that is robust, easy-to-use, and is the first stable isotope ratio analysis system to combine the measurement of 13C/12C and D/H in one simple analysis from a bulk organic sample with an application to bird migration. The system comprises a combustion module to convert the organic sample into CO2 and H2O and a Cavity Ring-Down Spectrometer (CRDS) that analyzes the combustion species inside an optical cavity based on the molecular absorption of individual isotopomers. This CRDS uses dual lasers to target the four isotpomers of interest: 12CO2, 13CO2, H2O and HDO. The system delivers a typical precision of 0.1 permil for δ13C and 1.5 permil for δD that parallels that achieved by IRMS, but with an unprecedented simplicity that allows ecologists to leverage the science and elucidate the avian migration patterns.

Nanostructured solid substrates for efficient laser desorption/ionization mass spectrometry (LDI-MS) of low molecular weight compounds.

PubMed

Silina, Yuliya E; Volmer, Dietrich A

2013-12-07

Analytical applications often require rapid measurement of compounds from complex sample mixtures. High-speed mass spectrometry approaches frequently utilize techniques based on direct ionization of the sample by laser irradiation, mostly by means of matrix-assisted laser desorption/ionization (MALDI). Compounds of low molecular weight are difficult to analyze by MALDI, however, because of severe interferences in the low m/z range from the organic matrix used for desorption/ionization. In recent years, surface-assisted laser desorption/ionization (SALDI) techniques have shown promise for small molecule analysis, due to the unique properties of nanostructured surfaces, in particular, the lack of a chemical background in the low m/z range and enhanced production of analyte ions by SALDI. This short review article presents a summary of the most promising recent developments in SALDI materials for MS analysis of low molecular weight analytes, with emphasis on nanostructured materials based on metals and semiconductors.

Colloquium: Laser probing of neutron-rich nuclei in light atoms

NASA Astrophysics Data System (ADS)

Lu, Z.-T.; Mueller, P.; Drake, G. W. F.; Nörtershäuser, W.; Pieper, Steven C.; Yan, Z.-C.

2013-10-01

The neutron-rich He6 and He8 isotopes exhibit an exotic nuclear structure that consists of a tightly bound He4-like core with additional neutrons orbiting at a relatively large distance, forming a halo. Recent experimental efforts have succeeded in laser trapping and cooling these short-lived, rare helium atoms and have measured the atomic isotope shifts along the He4-He6-He8 chain by performing laser spectroscopy on individual trapped atoms. Meanwhile, the few-electron atomic structure theory, including relativistic and QED corrections, has reached a comparable degree of accuracy in the calculation of the isotope shifts. In parallel efforts, also by measuring atomic isotope shifts, the nuclear charge radii of lithium and beryllium isotopes have been studied. The techniques employed were resonance ionization spectroscopy on neutral, thermal lithium atoms and collinear laser spectroscopy on beryllium ions. Combining advances in both atomic theory and laser spectroscopy, the charge radii of these light halo nuclei have now been determined for the first time independent of nuclear structure models. The results are compared with the values predicted by a number of nuclear structure calculations and are used to guide our understanding of the nuclear forces in the extremely neutron-rich environment.

Development of a Field-Deployable Methane Carbon Isotope Analyzer

NASA Astrophysics Data System (ADS)

Dong, Feng; Baer, Douglas

2010-05-01

Methane is a potent greenhouse gas, whose atmospheric surface mixing ratio has almost doubled compared with preindustrial values. Methane can be produced by biogenic processes, thermogenic processes or biomass, with different isotopic signatures. As a key molecule involved in the radiative forcing in the atmosphere, methane is thus one of the most important molecules linking the biosphere and atmosphere. Therefore precise measurements of mixing ratios and isotopic compositions will help scientists to better understand methane sources and sinks. To date, high precision isotope measurements have been exclusively performed with conventional isotope ratio mass spectrometry, which involves intensive labor and is not readily field deployable. Optical studies using infrared laser spectroscopy have also been reported to measure the isotopic ratios. However, the precision of optical-based analyses, to date, is typically unsatisfactory without pre-concentration procedures. We present characterization of the performance of a portable Methane Carbon Isotope Analyzer (MCIA), based on cavity enhanced laser absorption spectroscopy technique, that provides in-situ measurements of the carbon isotope ratio (13C/12C or del_13C) and methane mixing ratio (CH4). The sample is introduced to the analyzer directly without any requirement for pretreatment or preconcentration. A typical precision of less than 1 per mill (< 0.1%) with a 10-ppm methane sample can be achieved in a measurement time of less than 100 seconds. The MCIA can report carbon isotope ratio and concentration measurements over a very wide range of methane concentrations. Results of laboratory tests and field measurements will be presented.

A Study of the Microbial Spatial Heterogeneity of Bahamian Thrombolites Using Molecular, Biochemical, and Stable Isotope Analyses

NASA Astrophysics Data System (ADS)

Louyakis, Artemis S.; Mobberley, Jennifer M.; Vitek, Brooke E.; Visscher, Pieter T.; Hagan, Paul D.; Reid, R. Pamela; Kozdon, Reinhard; Orland, Ian J.; Valley, John W.; Planavsky, Noah J.; Casaburi, Giorgio; Foster, Jamie S.

2017-05-01

Thrombolites are buildups of carbonate that exhibit a clotted internal structure formed through the interactions of microbial mats and their environment. Despite recent advances, we are only beginning to understand the microbial and molecular processes associated with their formation. In this study, a spatial profile of the microbial and metabolic diversity of thrombolite-forming mats of Highborne Cay, The Bahamas, was generated by using 16S rRNA gene sequencing and predictive metagenomic analyses. These molecular-based approaches were complemented with microelectrode profiling and in situ stable isotope analysis to examine the dominant taxa and metabolic activities within the thrombolite-forming communities. Analyses revealed three distinctive zones within the thrombolite-forming mats that exhibited stratified populations of bacteria and archaea. Predictive metagenomics also revealed vertical profiles of metabolic capabilities, such as photosynthesis and carboxylic and fatty acid synthesis within the mats that had not been previously observed. The carbonate precipitates within the thrombolite-forming mats exhibited isotopic geochemical signatures suggesting that the precipitation within the Bahamian thrombolites is photosynthetically induced. Together, this study provides the first look at the spatial organization of the microbial populations within Bahamian thrombolites and enables the distribution of microbes to be correlated with their activities within modern thrombolite systems.

Multiple core-hole formation by free-electron laser radiation in molecular nitrogen

NASA Astrophysics Data System (ADS)

Banks, H. I. B.; Little, D. A.; Emmanouilidou, A.

2018-05-01

We investigate the formation of multiple-core-hole states of molecular nitrogen interacting with a free-electron laser pulse. In previous work, we obtained bound and continuum molecular orbitals in the single-center expansion scheme and used these orbitals to calculate photo-ionization and auger decay rates. We extend our formulation to track the proportion of the population that accesses single-site versus two-site double-core-hole (TSDCH) states, before the formation of the final atomic ions. We investigate the pulse parameters that favor the formation of the single-site and TSDCH as well as triple-core-hole states for 525 and 1100 eV photons.

Interstellar Isotopes: Prospects with ALMA

NASA Technical Reports Server (NTRS)

Charnley Steven B.

2010-01-01

Cold molecular clouds are natural environments for the enrichment of interstellar molecules in the heavy isotopes of H, C, N and O. Anomalously fractionated isotopic material is found in many primitive Solar System objects, such as meteorites and comets, that may trace interstellar matter that was incorporated into the Solar Nebula without undergoing significant processing. Models of the fractionation chemistry of H, C, N and O in dense molecular clouds, particularly in cores where substantial freeze-out of molecules on to dust has occurred, make several predictions that can be tested in the near future by molecular line observations. The range of fractionation ratios expected in different interstellar molecules will be discussed and the capabilities of ALMA for testing these models (e.g. in observing doubly-substituted isotopologues) will be outlined.

Experimental Investigation of Molecular Species Formation in Metal Plasmas During Laser Ablation

NASA Astrophysics Data System (ADS)

Radousky, H.; Crowhurst, J.; Rose, T.; Armstrong, M.; Stavrou, E.; Zaug, J.; Weisz, D.; Azer, M.; Finko, M.; Curreli, D.

2016-10-01

Atomic and molecular spectra on metal plasmas generated by laser ablation have been measured using single, nominally 6-7 ns pulses at 1064 nm, and with energies less than 50 mJ. The primary goal for these studies is to constrain the physical and chemical mechanisms that control the distribution of radionuclides in fallout after a nuclear detonation. In this work, laser emission spectroscopy was used to obtain in situdata for vapor phase molecular species as they form in a controlled oxygen atmosphere for a variety of metals such as Fe, Al, as well as preliminary results for U. In particular, the ablation plumes created from these metals have been imaged with a resolution of 10 ns, and it is possible to observe the expansion of the plume out to 0.5 us. These data serve as one set of inputs for a semi-empirical model to describe the chemical fractionation of uranium during fallout formation. Prepared by LLNL under Contract DE-AC52-07NA27344. This project was sponsored by the Department of the Defense, Defense Threat Reduction Agency, under Grant Number HDTRA1-16-1-0020.

Measurement of isotope ratio of Ca{sup +} ions in a linear Paul Trap

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

Hashimoto, Y.; Minamino, K.; Nagamoto, D.

2009-03-17

Measurement of isotope ratios of Calcium is very useful in many fields. So we demonstrated the measurement of isotope ratios of {sup 40}Ca{sup +}(abundance 96.4%) to {sup 44}Ca{sup +}(2.09%) ions in a linear Paul trap with several laser lights tuning to the isotope shifts. And we found that the experimental parameters had large influences on the measurement of the isotope ratios.

Cr-doped scandium borate laser

DOEpatents

Chai, Bruce H.; Lai, Shui T.; Long, Margaret N.

1989-01-01

A broadly wavelength-tunable laser is provided which comprises as the laser medium a single crystal of MBO.sub.3 :Cr.sup.3+, where M is selected from the group of Sc, In and Lu. The laser may be operated over a broad temperature range from cryogenic temperatures to elevated temperatures. Emission is in a spectral range from red to infrared, and the laser is useful in the fields of defense, communications, isotope separation, photochemistry, etc.

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

Influence of Molecular Structure on the Laser-Induced Plasma Emission of the Explosive RDX and Organic Polymers

NASA Astrophysics Data System (ADS)

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.

System and method for high precision isotope ratio destructive analysis

DOEpatents

Bushaw, Bruce A; Anheier, Norman C; Phillips, Jon R

2013-07-02

A system and process are disclosed that provide high accuracy and high precision destructive analysis measurements for isotope ratio determination of relative isotope abundance distributions in liquids, solids, and particulate samples. The invention utilizes a collinear probe beam to interrogate a laser ablated plume. This invention provides enhanced single-shot detection sensitivity approaching the femtogram range, and isotope ratios that can be determined at approximately 1% or better precision and accuracy (relative standard deviation).

Molecular-beam epitaxy of 7-8 μm range quantum-cascade laser heterostructures

NASA Astrophysics Data System (ADS)

Babichev, A. V.; Denisov, D. V.; Filimonov, A. V.; Nevedomsky, V. N.; Kurochkin, A. S.; Gladyshev, A. G.; Karachinsky, L. Ya; Sokolovskii, G. S.; Novikov, I. I.; Bousseksou, A.; Egorov, A. Yu

2017-11-01

The method of molecular beam epitaxy demonstrates the possibility to create high quality heterostructures of quantum cascade lasers in a spectral range of 7-8 μm containing 50 quantum cascades in an active region. Design based on the principle of two-phonon resonant scattering is used. X-ray diffraction and transmission electron microscopy experiments confirm high structural properties of the created heterostructures, e.g. the identity of the composition and thickness of epitaxial layers in all 50 cascades. Edge-emitting lasers based on the grown heterostructure demonstrate lasing with threshold current density of 2.8 kA/cm2 at a temperature of 78 K.

Isotope specific arbitrary material flow meter

DOEpatents

Barty, Christopher P. J.; Post, John C.; Jones, Edwin

2016-10-25

A laser-based mono-energetic gamma-ray source is used to provide non-destructive and non-intrusive, quantitative determination of the absolute amount of a specific isotope contained within pipe as part of a moving fluid or quasi-fluid material stream.

High-order-harmonic generation from H2+ molecular ions near plasmon-enhanced laser fields

NASA Astrophysics Data System (ADS)

Yavuz, I.; Tikman, Y.; Altun, Z.

2015-08-01

Simulations of plasmon-enhanced high-order-harmonic generation are performed for a H2+ molecular cation near the metallic nanostructures. We employ the numerical solution of the time-dependent Schrödinger equation in reduced coordinates. We assume that the main axis of H2+ is aligned perfectly with the polarization direction of the plasmon-enhanced field. We perform systematic calculations on plasmon-enhanced harmonic generation based on an infinite-mass approximation, i.e., pausing nuclear vibrations. Our simulations show that molecular high-order-harmonic generation from plasmon-enhanced laser fields is possible. We observe the dispersion of a plateau of harmonics when the laser field is plasmon enhanced. We find that the maximum kinetic energy of the returning electron follows 4 Up . We also find that when nuclear vibrations are enabled, the efficiency of the harmonics is greatly enhanced relative to that of static nuclei. However, the maximum kinetic energy 4 Up is largely maintained.

Laser cooling and imaging of individual radioactive +90Sr ions

NASA Astrophysics Data System (ADS)

Jung, Kyunghun; Iwata, Yoshihiro; Miyabe, Masabumi; Yamamoto, Kazuhiro; Yonezu, Tomohisa; Wakaida, Ikuo; Hasegawa, Shuichi

2017-10-01

We have developed an apparatus integrating resonance-ionization, ion-trap, and laser-cooling techniques for an ultratrace radioactive isotope 90Sr analysis. Trapped +90Sr isotope ions were laser cooled, and their 4 d 3/2 2D →5 p 1/2 2P transition isotope shift was experimentally measured to be -281 (17 ) MHz by comparing individual spectra of +88Sr and +90Sr ions. Crystallization of +90Sr was carried out using the resonance frequency value confirmed in our experiment, and then +90Sr individual ions were successfully observed.

"Wave" signal-smoothing and mercury-removing device for laser ablation quadrupole and multiple collector ICPMS analysis: application to lead isotope analysis.

PubMed

Hu, Zhaochu; Zhang, Wen; Liu, Yongsheng; Gao, Shan; Li, Ming; Zong, Keqing; Chen, Haihong; Hu, Shenghong

2015-01-20

A novel "wave" signal-smoothing and mercury-removing device has been developed for laser ablation quadrupole and multiple collector ICPMS analysis. With the wave stabilizer that has been developed, the signal stability was improved by a factor of 6.6-10 and no oscillation of the signal intensity was observed at a repetition rate of 1 Hz. Another advantage of the wave stabilizer is that the signal decay time is similar to that without the signal-smoothing device (increased by only 1-2 s for a signal decay of approximately 4 orders of magnitude). Most of the normalized elemental signals (relative to those without the stabilizer) lie within the range of 0.95-1.0 with the wave stabilizer. Thus, the wave stabilizer device does not significantly affect the aerosol transport efficiency. These findings indicate that this device is well-suited for routine optimization of ICPMS, as well as low repetition rate laser ablation analysis, which provides smaller elemental fractionation and better spatial resolution. With the wave signal-smoothing and mercury-removing device, the mercury gas background is reduced by 1 order of magnitude. More importantly, the (202)Hg signal intensity produced in the sulfide standard MASS-1 by laser ablation is reduced from 256 to 0.7 mV by the use of the wave signal-smoothing and mercury-removing device. This result suggests that the mercury is almost completely removed from the sample aerosol particles produced by laser ablation with the operation of the wave mercury-removing device. The wave mercury-removing device that we have designed is very important for Pb isotope ratio and accessory mineral U-Pb dating analysis, where removal of the mercury from the background gas and sample aerosol particles is highly desired. The wave signal-smoothing and mercury-removing device was applied successfully to the determination of the (206)Pb/(204)Pb isotope ratio in samples with low Pb content and/or high Hg content.

Molecular effects of fractional carbon dioxide laser resurfacing on photodamaged human skin.

PubMed

Reilly, Michael J; Cohen, Marc; Hokugo, Akishige; Keller, Gregory S

2010-01-01

Objective To elucidate the sequential changes in protein expression that play a role in the clinically beneficial results seen with fractional carbon dioxide (CO(2)) laser resurfacing of the face and neck. Methods Nine healthy volunteers were recruited for participation from the senior author's facial plastic surgery practice. After informed consent was obtained, each volunteer underwent a 2-mm punch biopsy from a discrete area of infra-auricular neck skin prior to laser treatment. Patients then immediately underwent laser resurfacing of photodamaged face and neck skin at a minimal dose (30 W for 0.1 second) with the Pixel Perfect fractional CO(2) laser. On completion of the treatment, another biopsy specimen was taken adjacent to the first site. Additional biopsy specimens were subsequently taken from adjacent skin at 2 of 3 time points (day 7, day 14, or day 21). RNA was extracted from the specimens, and reverse transcriptase-polymerase chain reaction and protein microarray analysis were performed. Comparisons were then made between time points using pairwise comparison testing. Results We found statistically significant changes in the gene expression of several matrix metalloproteinases (MMPs). The data demonstrate a consistent up-regulation of MMPs 1, 3, 9, and 13, all of which have been previously reported for fully ablative CO(2) laser resurfacing. There was also a statistically significant increase in MMP-10 and MMP-11 levels in this data set. Conclusion This study suggests that the molecular mechanisms of action are similar for both fractional and fully ablative CO(2) laser resurfacing.

Characterization of cocoa butter and cocoa butter equivalents by bulk and molecular carbon isotope analyses: implications for vegetable fat quantification in chocolate.

PubMed

Spangenberg, J E; Dionisi, F

2001-09-01

The fatty acids from cocoa butters of different origins, varieties, and suppliers and a number of cocoa butter equivalents (Illexao 30-61, Illexao 30-71, Illexao 30-96, Choclin, Coberine, Chocosine-Illipé, Chocosine-Shea, Shokao, Akomax, Akonord, and Ertina) were investigated by bulk stable carbon isotope analysis and compound specific isotope analysis. The interpretation is based on principal component analysis combining the fatty acid concentrations and the bulk and molecular isotopic data. The scatterplot of the two first principal components allowed detection of the addition of vegetable fats to cocoa butters. Enrichment in heavy carbon isotope ((13)C) of the bulk cocoa butter and of the individual fatty acids is related to mixing with other vegetable fats and possibly to thermally or oxidatively induced degradation during processing (e.g., drying and roasting of the cocoa beans or deodorization of the pressed fat) or storage. The feasibility of the analytical approach for authenticity assessment is discussed.

Method for enriching a gaseous isotopic mixture with at least one isotope

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

de Mevergnies, M.N.; Fettweis, P.

1982-02-02

There is described a method for enriching a gas-like isotopic mixture with at least one isotope, in which a mixture of Cf2Cl2 and O2 is irradiated by means of a pulsed and focalized laser beam having an optical frequency corresponding to a wave number lying in the band from 920 to 945 cm-1 to enrich the residual Cf2Cl2 with 37Cl, in the band from 1050 to 1075 cm-1 to produce CoF2 enriched with 13C and/or in the band from 1080 to 1095 cm-1 to enrich the residual Cf2Cl2 with 35Cl and 13C.

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.

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

Research on Molecular Lasers

DTIC Science & Technology

1974-11-01

double resonance experiments to study vibration to rotation energy transfer; chemical laser initiation and pumping by electrical discharges in...8217) + HF(v=0,J2’). (7) Ihe experiment consists of the use of one HF laser to pump the IIFfv^jp molecules in less than 500 nanoseconds and the...each stage of diöüUaUcm, Ihc mid- dle 90’c of the .-.ample was rolained." The distilled sam- ple was condensed and pumped on at TV K in r

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

NASA Astrophysics Data System (ADS)

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

2011-06-01

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

Method for isotope enrichment by photoinduced chemiionization

DOEpatents

Dubrin, James W.

1985-01-01

Isotope enrichment, particularly .sup.235 U enrichment, is achieved by irradiating an isotopically mixed vapor feed with radiant energy at a wavelength or wavelengths chosen to selectively excite the species containing a desired isotope to a predetermined energy level. The vapor feed if simultaneously reacted with an atomic or molecular reactant species capable of preferentially transforming the excited species into an ionic product by a chemiionization reaction. The ionic product, enriched in the desired isotope, is electrostatically or electromagnetically extracted from the reaction system.

Isotope-selective high-order interferometry with large organic molecules in free fall

NASA Astrophysics Data System (ADS)

Rodewald, Jonas; Dörre, Nadine; Grimaldi, Andrea; Geyer, Philipp; Felix, Lukas; Mayor, Marcel; Shayeghi, Armin; Arndt, Markus

2018-03-01

Interferometry in the time domain has proven valuable for matter-wave based measurements. This concept has recently been generalized to cold molecular clusters using short-pulse standing light waves which realized photo-depletion gratings, arranged in a time-domain Talbot–Lau interferometer (OTIMA). Here we extend this idea further to large organic molecules and demonstrate a new scheme to scan the emerging molecular interferogram in position space. The capability of analyzing different isotopes of the same monomer under identical conditions opens perspectives for studying the interference fringe shift as a function of time in gravitational free fall. The universality of OTIMA interferometry allows one to handle a large variety of particles. In our present work, quasi-continuous laser evaporation allows transferring fragile organic molecules into the gas phase, covering more than an order of magnitude in mass between 614 amu and 6509 amu, i.e. 300% more massive than in previous OTIMA experiments. For all masses, we find about 30% fringe visibility.

The Determination of Molecular Structure from Rotational Spectra

DOE R&D Accomplishments Database

Laurie, V. W.; Herschbach, D. R.

1962-07-01

An analysis is presented concerning the average molecular configuration variations and their effects on molecular structure determinations. It is noted that the isotopic dependence of the zero-point is often primarily governed by the isotopic variation of the average molecular configuration. (J.R.D.)

Safety approaches for high power modular laser operation

NASA Astrophysics Data System (ADS)

Handren, R. T.

1993-03-01

Approximately 20 years ago, a program was initiated at the Lawrence Livermore National Laboratory (LLNL) to study the feasibility of using lasers to separate isotopes of uranium and other materials. Of particular interest was the development of a uranium enrichment method for the production of commercial nuclear power reactor fuel to replace current more expensive methods. The Uranium Atomic Vapor Laser Isotope Separation (U-AVLIS) Program progressed to the point where a plant-scale facility to demonstrate commercial feasibility was built and is being tested. The U-AVLIS Program uses copper vapor lasers which pump frequency selective dye lasers to photoionize uranium vapor produced by an electron beam. The selectively ionized isotopes are electrostatically collected. The copper lasers are arranged in oscillator/amplifier chains. The current configuration consists of 12 chains, each with a nominal output of 800 W for a system output in excess of 9 kW. The system requirements are for continuous operation (24 h a day, 7 days a week) and high availability. To meet these requirements, the lasers are designed in a modular form allowing for rapid change-out of the lasers requiring maintenance. Since beginning operation in early 1985, the copper lasers have accumulated over 2 million unit hours at a greater than 90% availability. The dye laser system provides approximately 2.5 kW average power in the visible wavelength range. This large-scale laser system has many safety considerations, including high-power laser beams, high voltage, and large quantities (approximately 3000 gal) of ethanol dye solutions. The Laboratory's safety policy requires that safety controls be designed into any process, equipment, or apparatus in the form of engineering controls. Administrative controls further reduce the risk to an acceptable level. Selected examples of engineering and administrative controls currently being used in the U-AVLIS Program are described.

Measurements of Forest-Atmosphere Isotopic CO2 Exchange by Eddy Covariance

NASA Astrophysics Data System (ADS)

Wehr, R. A.; Munger, J. W.; Nelson, D. D.; McManus, J. B.; Zahniser, M. S.; Saleska, S. R.

2010-12-01

Isotopic CO2 flux measurements are a promising means for partitioning the net ecosystem exchange of CO2 into photosynthetic and respiratory components. This approach to partitioning is possible in principle because of the distinct isotopic signatures of respired and photosynthesized CO2, but has been infeasible in practice—especially in forests—because of the difficulty of measuring isotopic ratios with sufficient precision and time response for use in eddy covariance (EC) flux calculations. Recent advances in laser spectroscopic instrumentation have changed that. We report measurements of isotopic (13C and 18O) CO2 exchange made by eddy covariance at Harvard Forest between April and December, 2010. The measurements were made using a continuous-wave quantum cascade laser spectrometer (Aerodyne Research Inc.) sampling at 4 Hz and are, to our knowledge, the first EC isotopic flux measurements at a forest site. The spectrometer can measure δ13C and δ18O with internal precisions (standard deviation of 1-minute averages) of 0.03 ‰, and [CO2] with an internal precision of 15 ppb; the instrumental accuracy, calibration, and long-term stability are discussed in detail. The isotopic data are considered in relation to environmental variables (PAR, temperature, humidity, soil temperature and moisture), and a first attempt at flux partitioning using the isotopic fluxes is presented.

Unraveling the Environmental Record of the Early Solar System: High Precision Laser Ablation Al-Mg Isotopes of Igneous CAIs

NASA Astrophysics Data System (ADS)

Young, E. D.; Simon, J. I.; Russell, S. S.; Tonui, E.; Krot, A.

2004-12-01

Variations in intrinsic Mg isotope compositions provide a potentially rich record of the physiochemical evolution of CAIs. Moreover, Mg excesses from the short-lived 26Al chronometer can be used to constrain when these processes occurred; e.g., during the nebular phase and/or during the development of planetisimals (< 4 Myr). We obtained in situ UV (213 nm) laser ablation MC-ICPMS measurements of Al and Mg isotope ratios within core-to-rim traverses of igneous CAIs to place temporal constraints on when features of CAIs formed. Results provide tests of models for the chemical and isotopic evolution of CAIs involving volatilization and recondensation of elements in the solar nebula. We studied five CV3 CAIs, including Allende 3576-1 "b", Allende M5, Leoville 144A, Leoville MRS3, and Efremovka E44. Our sample-standard comparison approach affords a precision <0.2 \\permil per amu (2s) for intrinsic Mg isotope measurements and <0.3 \\permil (2s) for measured 26Mg excesses. Intra-object variation in \\delta25Mg exists with values ranging from as low as -2 \\permil and as high as +8 \\permil (compared to DSM3). The distinct Mg isotope patterns in the CAIs are difficult to explain by a single process or within a single nebular environment and likely require changing conditions or transfer of CAIs from one nebular environment to another. The ˜pristine Mg isotope profile of Leoville 144A is compared to results produced by implicit finite difference modeling. Model curves reflect isotopic fractionation at the moving surface of a shrinking molten sphere coupled with diffusion-limited transport within the sphere. We find that using mass-dependant diffusivities increases \\delta25Mg with evaporation, but does not produce the tight curvature in the edgeward increases in \\delta25Mg characteristic of Leoville 144A. Three CAIs that exhibit edgeward \\delta25Mg decreases are well described by diffusion in a Mg-rich chondritic environment suggestive of nebular temperatures and

Short wavelength (visible) GaAs quantum well lasers grown by molecular beam epitaxy

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

Woodbridge, K.; Blood, P.; Fletcher, E.D.

1984-07-01

GaAs-AlGaAs multiple quantum well (MQW) injection lasers with well widths from 55 to 13 A have been grown by molecular beam epitaxy and operated at room temperature, showing emission at wavelengths down to 704 nm, the shortest reported for a MQW injection laser with GaAs wells. In a device with 25-A wells some evidence of coupling was apparent when barrier widths were reduced to 40 A. For devices with 80-A barriers there is a difference of about 20 nm between the calculated n = 1 (e--hh) transition wavelength and the lasing wavelength, whereas the calculation agrees with photovoltage absorption measurementsmore » on the same structures.« less

Standoff analysis of laser-produced plasmas using laser-induced fluorescence

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

Harilal, S. S.; Brumfield, B. E.; Phillips, M. C.

We report the use of laser-induced fluorescence (LIF) of laser ablation plumes for standoff applications. The standoff analysis of Al species, as major and minor species in samples, is performed in a nanosecond laser-produced plasma created at a distance ~10 m. The LIF analysis is performed by resonantly exciting an Al transition at 394.4 nm using a continuous wave (cw) tunable laser and by collecting the direct-line fluorescence signal at 396.15 nm. The spectral resolution of LIF is obtained by scanning the cw tunable LIF laser across the selected Al transition. Our results highlight that LIF provides enhanced signal intensity,more » emission persistence, and spectral resolution when compared to thermally-excited emission, and these are crucial considerations for using laser-produced plasma for standoff isotopic analysis.« less

Evaluation of laser ablation double-focusing SC-ICPMS for “common” lead isotopic measurements in silicate glasses and mineral

USGS Publications Warehouse

Pietruszka, Aaron J.; Neymark, Leonid

2017-01-01

An analytical method for the in situ measurement of “common” Pb isotope ratios in silicate glasses and minerals using a 193-nm excimer laser ablation (LA) system with a double-focusing single-collector (SC)-ICPMS is presented and evaluated as a possible alternative to multiple-collector (MC)-ICPMS. This LA-SC-ICPMS technique employs fast-scanning ion deflectors to sequentially place a series of flat-topped isotope peaks into a single ion-counting detector at a fixed accelerating voltage and magnetic field strength. Reference materials (including NIST, MPI-DING, and USGS glasses) are used to identify two analytical artifacts on the Pb isotope ratios (expressed here as heavier/lighter isotopes) when corrected for mass bias relative to NIST SRM610. The first artifact is characterized by anomalously low Pb isotope ratios (~0.1%/AMU) when SRM610 is analyzed in raster mode as an unknown at small spot sizes (<25 µm), which may indicate that (1) SRM610 is isotopically heterogeneous on a small length scale and/or (2) there is a non-spectral matrix effect on the Pb isotope ratios related to differences in spot size. The second artifact is characterized by anomalously high Pb isotope ratios (<0.1%/AMU) for NIST SRM612 (in raster mode) and some Fe-rich glass reference materials (BCR-2G, GOR132-G, and T1-G). These offsets are thought to be caused by one or more non-spectral matrix effects related to differences in the ablation behavior, composition, or physical properties of these reference materials compared to the bracketing SRM610 standard. The precision (±2SD) of our LA-SC-ICPMS Pb isotopic measurements is similar to (207Pb/206Pb and 208Pb/206Pb, or 20XPb/206Pb) or better than (206Pb/204Pb,207Pb/204Pb, and 208Pb/204Pb, or 20XPb/204Pb) a series of published studies that used a different type of SC-ICPMS and obtained a factor of ~3-4 higher sensitivity for Pb. An increase in the sensitivity of our LA-SC-ICPMS would likely improve the precision of the 20XPb/206Pb and 20

Method of isotope separation by chemi-ionization

DOEpatents

Wexler, Sol; Young, Charles E.

1977-05-17

A method for separating specific isotopes present in an isotopic mixture by aerodynamically accelerating a gaseous compound to form a jet of molecules, and passing the jet through a stream of electron donor atoms whereby an electron transfer takes place, thus forming negative ions of the molecules. The molecular ions are then passed through a radiofrequency quadrupole mass filter to separate the specific isotopes. This method may be used for any compounds having a sufficiently high electron affinity to permit negative ion formation, and is especially useful for the separation of plutonium and uranium isotopes.

Determination of the absolute molecular weight averages and molecular weight distributions of alginates used as ice cream stabilizers by using multiangle laser light scattering measurements.

PubMed

Turquois, T; Gloria, H

2000-11-01

High-performance size exclusion chromatography with multiangle laser light scattering detection (HPSEC-MALLS) was used for characterizing complete molecular weight distributions for a range of commercial alginates used as ice cream stabilizers. For the samples investigated, molecular weight averages were found to vary between 115 000 and 321 700 g/mol and polydispersity indexes varied from 1. 53 to 3.25. These samples displayed a high content of low molecular weights. Thus, the weight percentage of material below 100 000 g/mol ranged between 6.9 and 54.4%.

Preliminary results of an aircraft system based on near-IR diode lasers for continuous measurements of the concentration of methane, carbon dioxide, water and its isotopes

NASA Astrophysics Data System (ADS)

Nadezhdinsky, A. I.; Ponurovsky, Ya. Ya.; Shapovalov, Y. P.; Popov, I. P.; Stavrovsky, D. B.; Khattatov, V. U.; Galaktionov, V. V.; Kuzmichev, A. S.

2012-11-01

The Federal Agency for Hydrometeorology of the Russian Federation created the flying laboratory on board the passenger airplane Yak-42D for geophysical monitoring of the environment, including aircraft measurements of vertical concentrations of greenhouse gases in the troposphere. Within the limits of this project, General Physics Institute of the Russian Academy of Science developed airborne tunable diode laser spectrometer (TDLS) on the basis of diode lasers of a near-IR range for measurement of the altitude profiles of CO2, CH4, H2O and its isotopes. TDLS complex was integrated aboard in standard 19-in. rack. Air samples, taken over an aircraft on the pipeline, were injected into the optical cell. Using the system of inflow and heating, the air was set laminar with a flowrate of 0.2 l/s at a reduced pressure of 100 mbar for detecting narrow absorption lines of water vapor isotopes. For registration of the absorption spectra and for the measurement of greenhouse gas concentrations in online mode, modulation-correlation technique was used. Diode laser spectrometer output data were transferred to the airborne central computer. Sensitivity of TDLS measurements was 20-30 ppm for water, 3-4 ppm for CO2 and 20-25 ppb for CH4. Time of one-unit measurement is about 30 ms.

Atomic and Molecular Beam Scattering: Characterizing Structure and Dynamics of Hybrid Organic-Semiconductor Interfaces and Introducing Novel Isotope Separation Techniques

NASA Astrophysics Data System (ADS)

Nihill, Kevin John

This thesis details a range of experiments and techniques that use the scattering of atomic beams from surfaces to both characterize a variety of interfaces and harness mass-specific scattering conditions to separate and enrich isotopic components in a mixture of gases. Helium atom scattering has been used to characterize the surface structure and vibrational dynamics of methyl-terminated Ge(111), thereby elucidating the effects of organic termination on a rigid semiconductor interface. Helium atom scattering was employed as a surface-sensitive, non-destructive probe of the surface. By means of elastic gas-surface diffraction, this technique is capable of providing measurements of atomic spacing, step height, average atomic displacement as a function of surface temperature, gas-surface potential well depth, and surface Debye temperature. Inelastic time-of-flight studies provide highly resolved energy exchange measurements between helium atoms and collective lattice vibrations, or phonons; a collection of these measurements across a range of incident kinematic parameters allowed for a thorough mapping of low-energy phonons (e.g., the Rayleigh wave) across the surface Brillouin zone and subsequent comparison with complementary theoretical calculations. The scattering of molecular beams - here, hydrogen and deuterium from methyl-terminated Si(111) - enables the measurement of the anisotropy of the gas-surface interaction potential through rotationally inelastic diffraction (RID), whereby incident atoms can exchange internal energy between translational and rotational modes and diffract into unique angular channels as a result. The probability of rotational excitations as a function of incident energy and angle were measured and compared with electronic structure and scattering calculations to provide insight into the gas-surface interaction potential and hence the surface charge density distribution, revealing important details regarding the interaction of H2 with an

ToF diagnostic of Tin resonant laser photoionization in SPES laser offline laboratory

NASA Astrophysics Data System (ADS)

Scarpa, D.; Fedorov, D.; Andrighetto, A.; Mariotti, E.; Nicolosi, P.; Sottili, L.; Tomaselli, A.; Cecchi, R.; Stiaccini, L.

2016-09-01

Tin is the principal element of interest in the SPES ISOL facility, which is under construction at Legnaro INFN Laboratories. Atomic nuclei have a shell structure in which nuclei with \\textquoteleft magic numbers\\textquoteright of protons and neutrons are analogous to the noble gasses in atomic physics. In particular, recent theoretical studies, reveal double-magic nature of radioactive 132Sn. For this reason the nuclear physics community demonstrated, in the last years, a huge interest to produce and study this radioactive neutron rich isotope. Experiments on Tin laser resonant ionization have been performed in the offline SPES laser laboratory to investigate the capability of the new home-made Time of Flight (ToF) mass spectrometer. Several three-step, two color ionization schemes have been tested by comparing fast and slow optogalvanic signals from a Tin Hollow Cathode Lamp (HCL) and Time of Flight signals from the spectrometer. By scanning the wavelength of one of the two dye lasers across the specific resonance, comparisons of ionization signals from both the ToF and the HCL have been made, finding perfect agreement. Furthermore, with the mass spectrometer, resolved peaks of all the natural Tin isotopes have been detected. The natural abundances extracted from these measurements are in agreement with the table values for Tin isotopes. This work, with comparison of OGE and ToF signals, confirm the fully functional SPES offline laser laboratory capability in order to develop scheme studies also for the other possible Radioactive Ion Beam (RIB) elements.

Isotopic Analysis and Evolved Gases

NASA Technical Reports Server (NTRS)

Swindle, Timothy D.; Boynton, William V.; Chutjian, Ara; Hoffman, John H.; Jordan, Jim L.; Kargel, Jeffrey S.; McEntire, Richard W.; Nyquist, Larry

1996-01-01

Precise measurements of the chemical, elemental, and isotopic composition of planetary surface material and gases, and observed variations in these compositions, can contribute significantly to our knowledge of the source(s), ages, and evolution of solar system materials. The analyses discussed in this paper are mostly made by mass spectrometers or some other type of mass analyzer, and address three broad areas of interest: (1) atmospheric composition - isotopic, elemental, and molecular, (2) gases evolved from solids, and (3) solids. Current isotopic data on nine elements, mostly from in situ analysis, but also from meteorites and telescopic observations are summarized. Potential instruments for isotopic analysis of lunar, Martian, Venusian, Mercury, and Pluto surfaces, along with asteroid, cometary and icy satellites, surfaces are discussed.

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. Copyright 2010 John Wiley & Sons, Ltd.

Charge radii of neutron-deficient Ca isotopes

NASA Astrophysics Data System (ADS)

Miller, A. J.; Minamisono, K.; Klose, A.; Everett, N.; Kalman, C.; Powel, R. C.; Watkins, J.; Garand, D.; Sumithrarachchi, C.; Krämer, J.; Maa, B.; Nörtershäuser, W.; Rossi, D. M.; Kujawa, C.; Pineda, S.; Lantis, J.; Liu, Y.; Mantica, P. F.; Pearson, M. R.

2017-09-01

Nucleon shell closures are generally associated with a local minimum in mean-square charge radii, 〈r2 〉 , along an isotopic chain. The 〈r2 〉 of 18Ar and 19K isotopes, however, do not show this signature at the N = 20 neutron shell closure. To gain a microscopic understanding of this abnormal behavior, measurements of 〈r2 〉 of neutron-deficient Ca isotopes below N = 20 have been proposed at the BEam COoling and LAser spectroscopy (BECOLA) facility at NSCL/MSU. Preliminary results will be presented and the deduced charge radii will be compared to theoretical calculations and the trends in the nearby isotopic chains. Work supported in part by NSF Grant PHY-15-65546, U.S. DOE Grant DE-NA0002924 and by the Deutsche Forschungsgemeinschaft through Grant SFB 1245.

Isotopic abundance in atom trap trace analysis

DOEpatents

Lu, Zheng-Tian; Hu, Shiu-Ming; Jiang, Wei; Mueller, Peter

2014-03-18

A method and system for detecting ratios and amounts of isotopes of noble gases. The method and system is constructed to be able to measure noble gas isotopes in water and ice, which helps reveal the geological age of the samples and understand their movements. The method and system uses a combination of a cooled discharge source, a beam collimator, a beam slower and magneto-optic trap with a laser to apply resonance frequency energy to the noble gas to be quenched and detected.

A new instrument of VUV laser desorption/ionization mass spectrometry imaging with micrometer spatial resolution and low level of molecular fragmentation.

PubMed

Wang, Jia; Liu, Feng; Mo, Yuxiang; Wang, Zhaoying; Zhang, Sichun; Zhang, Xinrong

2017-11-01

Mass spectrometry imaging (MSI) has important applications in material research, biology, and medicine. The MSI method based on UV laser desorption/ionization (UVLDI) can obtain images of intact samples, but has a high level of molecular fragmentation. In this work, we report a new MSI instrument that uses a VUV laser (125.3 nm) as a desorption/ionization source to exploit its advantages of high single photon energy and small focus size. The new instrument was tested by the mass spectra of Nile red and FGB (Fibrinogen beta chain) samples and mass spectrometric images of a fly brain section. For the tested samples, the VUVDI method offers lower levels of molecular fragmentations and higher sensitivities than those of the UVLDI method and second ion mass spectrometry imaging method using a Bi 3 + beam. The ablation crater produced by the focused VUV laser on a quartz plate has an area of 10 μm 2 . The VUV laser is prepared based on the four-wave mixing method using three collimated laser beams and a heated Hg cell.

A new instrument of VUV laser desorption/ionization mass spectrometry imaging with micrometer spatial resolution and low level of molecular fragmentation

NASA Astrophysics Data System (ADS)

Wang, Jia; Liu, Feng; Mo, Yuxiang; Wang, Zhaoying; Zhang, Sichun; Zhang, Xinrong

2017-11-01

Mass spectrometry imaging (MSI) has important applications in material research, biology, and medicine. The MSI method based on UV laser desorption/ionization (UVLDI) can obtain images of intact samples, but has a high level of molecular fragmentation. In this work, we report a new MSI instrument that uses a VUV laser (125.3 nm) as a desorption/ionization source to exploit its advantages of high single photon energy and small focus size. The new instrument was tested by the mass spectra of Nile red and FGB (Fibrinogen beta chain) samples and mass spectrometric images of a fly brain section. For the tested samples, the VUVDI method offers lower levels of molecular fragmentations and higher sensitivities than those of the UVLDI method and second ion mass spectrometry imaging method using a Bi3+ beam. The ablation crater produced by the focused VUV laser on a quartz plate has an area of 10 μm2. The VUV laser is prepared based on the four-wave mixing method using three collimated laser beams and a heated Hg cell.

Isotopically selective two-photon ionization of aniline in supersonic beams

NASA Astrophysics Data System (ADS)

Leutwyler, S.; Even, U.

1981-08-01

Tunable laser two-photon ionization of aniline cooled in supersonic expansions combined with TOF mass spectrometry reveal an isotopic shift of the vibronic origin at 2938 Å (ππ ∗; 1B 2← 1A 1 transition). The shift (+4.6 cm -1) is smaller than the rotational bandwidth and would be unobservable by laser-induced fluorescence.

Ionization and dissociation of molecular ion beams by intense ultrafast laser pulses

NASA Astrophysics Data System (ADS)

Ben-Itzhak, Itzik

2007-06-01

Laser-induced dissociation and ionization of a diatomic molecular-ion beam were simultaneously measured using coincidence 3D momentum imaging, with direct separation of the two processes even where the fragment kinetic energy is the same for both processes. We mainly focus on the fundamental H2^+ molecule in 7-135 fs laser pulses having 10^13-10^15 W/cm^2 peak intensity. At high intensities the kinetic energy release (KER) distribution following ionization of H2^+ was measured to be broad and structureless. Its centroid shifts toward higher energies as the laser intensity is increased indicating that ionization shifts to smaller internuclear distances. In contrast, a surprising structure is observed near the ionization threshold, which we call above threshold Coulomb explosion (ATCE) [1]. The angular distributions of the two H^+ fragments are strongly peaked along the laser polarization, and the angular distribution is described well by [cos^2θ]^n, where n is the number of photons predicted by our ATCE model [1]. Our data indicates that n varies with the laser wavelength as predicted by the model. The KER and angular distributions of H2^+ dissociation change dramatically with decreasing pulse width over the 7-135 fs range in contrast to the reported trend for longer pulses. Others contributing to this work: A.M. Sayler, P.Q. Wang, J. McKenna, B. Gaire, Nora G. Johnson, E. Parke, K.D. Carnes, and B.D. Esry. Thank are due to Professor Zenghu Chang for providing the intense laser beams and Dr. Charles Fehrenbach for his help with the ion beams. [1] B.D. Esry, A.M. Sayler, P.Q. Wang, K.D. Carnes, and I. Ben-Itzhak, Phys. Rev. Lett. 97, 013003 (2006).

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

Molecular Switch for Sub-Diffraction Laser Lithography by Photoenol Intermediate-State Cis-Trans Isomerization.

PubMed

Mueller, Patrick; Zieger, Markus M; Richter, Benjamin; Quick, Alexander S; Fischer, Joachim; Mueller, Jonathan B; Zhou, Lu; Nienhaus, Gerd Ulrich; Bastmeyer, Martin; Barner-Kowollik, Christopher; Wegener, Martin

2017-06-27

Recent developments in stimulated-emission depletion (STED) microscopy have led to a step change in the achievable resolution and allowed breaking the diffraction limit by large factors. The core principle is based on a reversible molecular switch, allowing for light-triggered activation and deactivation in combination with a laser focus that incorporates a point or line of zero intensity. In the past years, the concept has been transferred from microscopy to maskless laser lithography, namely direct laser writing (DLW), in order to overcome the diffraction limit for optical lithography. Herein, we propose and experimentally introduce a system that realizes such a molecular switch for lithography. Specifically, the population of intermediate-state photoenol isomers of α-methyl benzaldehydes generated by two-photon absorption at 700 nm fundamental wavelength can be reversibly depleted by simultaneous irradiation at 440 nm, suppressing the subsequent Diels-Alder cycloaddition reaction which constitutes the chemical core of the writing process. We demonstrate the potential of the proposed mechanism for STED-inspired DLW by covalently functionalizing the surface of glass substrates via the photoenol-driven STED-inspired process exploiting reversible photoenol activation with a polymerization initiator. Subsequently, macromolecules are grown from the functionalized areas and the spatially coded glass slides are characterized by atomic-force microscopy. Our approach allows lines with a full-width-at-half-maximum of down to 60 nm and line gratings with a lateral resolution of 100 nm to be written, both surpassing the diffraction limit.

Applications of Ultra-Intense, Short Laser Pulses

NASA Astrophysics Data System (ADS)

Ledingham, Ken W. D.

The high intensity laser production of electron, proton, ion and photon beams is reviewed particularly with respect to the laser-plasma interaction which drives the acceleration process. A number of applications for these intense short pulse beams is discussed e.g. ion therapy, PET isotope production and laser driven transmutation studies. The future for laser driven nuclear physics at the huge new, multi-petawatt proposed laser installation ELI in Bucharest is described. Many people believe this will take European nuclear research to the next level.

Lake Louise Water (USGS47): A new isotopic reference water for stable hydrogen and oxygen isotope measurements

USGS Publications Warehouse

Qi, Haiping; Lorenz, Jennifer M.; Coplen, Tyler B.; Tarbox, Lauren V.; Mayer, Bernhard; Taylor, Steve

2014-01-01

RESULTS: The δ2H and δ18O values of this reference water are –150.2 ± 0.5 ‰ and –19.80 ± 0.02 ‰, respectively, relative to VSMOW on scales normalized such that the δ2H and δ18O values of SLAP reference water are, respectively, –428 and –55.5 ‰. Each uncertainty is an estimated expanded uncertainty (U = 2uc) about the reference value that provides an interval that has about a 95-percent probability of encompassing the true value. CONCLUSION: This isotopic reference material, designated as USGS47, is intended as one of two isotopic reference waters for daily normalization of stable hydrogen and stable oxygen isotopic analysis of water with a mass spectrometer or a laser absorption spectrometer. "

Mid-infrared, long wave infrared (4-12 μm) molecular emission signatures from pharmaceuticals using laser-induced breakdown spectroscopy (LIBS).

PubMed

Yang, Clayton S-C; Brown, Ei E; Kumi-Barimah, Eric; Hommerich, Uwe H; Jin, Feng; Trivedi, Sudhir B; Samuels, Alan C; Snyder, A Peter

2014-01-01

In an effort to augment the atomic emission spectra of conventional laser-induced breakdown spectroscopy (LIBS) and to provide an increase in selectivity, mid-wave to long-wave infrared (IR), LIBS studies were performed on several organic pharmaceuticals. Laser-induced breakdown spectroscopy signature molecular emissions of target organic compounds are observed for the first time in the IR fingerprint spectral region between 4-12 μm. The IR emission spectra of select organic pharmaceuticals closely correlate with their respective standard Fourier transform infrared spectra. Intact and/or fragment sample molecular species evidently survive the LIBS event. The combination of atomic emission signatures derived from conventional ultraviolet-visible-near-infrared LIBS with fingerprints of intact molecular entities determined from IR LIBS promises to be a powerful tool for chemical detection.

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.

Utilizing Stable Isotopes and Isotopic Anomalies to Study Early Solar System Formation Processes

NASA Technical Reports Server (NTRS)

Simon, Justin

2017-01-01

Chondritic meteorites contain a diversity of particle components, i.e., chondrules and calcium-, aluminum-rich refractory inclusions (CAIs), that have survived since the formation of the Solar System. The chemical and isotopic compositions of these materials provide a record of the conditions present in the protoplanetary disk where they formed and can aid our understanding of the processes and reservoirs in which solids formed in the solar nebula, an important step leading to the accretion of planetesimals. Isotopic anomalies associated with nucleosynthetic processes are observed in these discrete materials, and can be compared to astronomical observations and astrophysical formation models of stars and more recently proplyds. The existence and size of these isotopic anomalies are typically thought to reflect a significant state of isotopic heterogeneity in the earliest Solar System, likely left over from molecular cloud heterogeneities on the grain scale, but some could also be due to late stellar injection. The homogenization of these isotopic anomalies towards planetary values can be used to track the efficiency and timescales of disk wide mixing,

Laser photodetachment of radioactive 128 I -

DOE PAGES

Rothe, Sebastian; Sundberg, Julia; Welander, Jakob; ...

2017-08-31

The first experimental investigation of the electron affinity (EA) of a radioactive isotope has been conducted at the CERN-ISOLDE radioactive ion beam facility. The EA of the radioactive iodine isotope 128I ($t$ 1/2 = 25 min) was determined to be 3.059 052(38) eV. The experiment was conducted using the newly developed Gothenburg ANion Detector for Affinity measurements by Laser PHotodetachment (GANDALPH) apparatus, connected to a CERN-ISOLDE experimental beamline. 128I was produced in fission induced by 1.4 GeV protons striking a thorium/tantalum foil target and then extracted as singly charged negative ions at a beam energy of 20 keV. Laser photodetachmentmore » of the fast ion beam was performed in a collinear geometry inside the GANDALPH chamber. Neutral atoms produced in the photodetachment process were detected by allowing them to impinge on a glass surface, creating secondary electrons which were then detected using a channel electron multiplier. The photon energy of the laser was tuned across the threshold of the photodetachment process and the detachment threshold data were fitted to a Wigner law function in order to extract the EA. In conclusion, this first successful demonstration of photodetachment at an isotope separator on line facility opens up the opportunity for future studies of the fundamental properties of negatively charged radioactive isotopes such as the EA of astatine and polonium.« less

Isotopic constraints on the origin of meteoritic organic matter

NASA Technical Reports Server (NTRS)

Kerridge, J. F.

1991-01-01

Salient features of the isotopic distribution of H, C and N in the organic material found in carbonaceous meteorites are noted. Most organic fractions are strongly enriched in D with respect to the D/H ratio characteristic of H2 in the protosolar system; substantial variations in C-13/C-12 ratio are found among different molecular species, with oxidised species tending to be C-13 enriched relative to reduced species; some homologous series reveal systematic decrease in C-13/C-12 with increasing C number; considerable variation in N-15/N-14 ratio is observed within organic matter, though no systematic pattern to its distribution has yet emerged; no interelement correlations have been observed between isotope enrichments for the different biogenic elements. The isotopic complexity echoes the molecular diversity observed in meteoritic organic matter and suggests that the organic matter was formed by multiple processes and/or from multiple sources. However, existence of a few systematic patterns points towards survival of isotopic signatures characteristic of one or more specific processes. The widespread D enrichment implies either survival of many species of interstellar molecule or synthesis from a reservoir containing a significant interstellar component. Several of the questions raised above can be addressed by more detailed determination of the distribution of the H, C and N isotopes among different well-characterized molecular fractions. Thus, the present study is aimed at discovering whether the different amino acids have comparable D enrichments, which would imply local synthesis from a D-enriched reservoir, or very viable D enrichments, which would imply survival of some interstellar amino acids. The same approach is also being applied to polycyclic aromatic hydrocarbons. Because the analytical technique employed (secondary ion mass spectrometry) can acquire data for all three isotopic systems from each molecular fraction, any presently obscured interelement

Molecular diffusion of stable water isotopes in polar firn as a proxy for past temperatures

NASA Astrophysics Data System (ADS)

Holme, Christian; Gkinis, Vasileios; Vinther, Bo M.

2018-03-01

Polar precipitation archived in ice caps contains information on past temperature conditions. Such information can be retrieved by measuring the water isotopic signals of δ18O and δD in ice cores. These signals have been attenuated during densification due to molecular diffusion in the firn column, where the magnitude of the diffusion is isotopologue specific and temperature dependent. By utilizing the differential diffusion signal, dual isotope measurements of δ18O and δD enable multiple temperature reconstruction techniques. This study assesses how well six different methods can be used to reconstruct past surface temperatures from the diffusion-based temperature proxies. Two of the methods are based on the single diffusion lengths of δ18O and δD , three of the methods employ the differential diffusion signal, while the last uses the ratio between the single diffusion lengths. All techniques are tested on synthetic data in order to evaluate their accuracy and precision. We perform a benchmark test to thirteen high resolution Holocene data sets from Greenland and Antarctica, which represent a broad range of mean annual surface temperatures and accumulation rates. Based on the benchmark test, we comment on the accuracy and precision of the methods. Both the benchmark test and the synthetic data test demonstrate that the most precise reconstructions are obtained when using the single isotope diffusion lengths, with precisions of approximately 1.0 °C . In the benchmark test, the single isotope diffusion lengths are also found to reconstruct consistent temperatures with a root-mean-square-deviation of 0.7 °C . The techniques employing the differential diffusion signals are more uncertain, where the most precise method has a precision of 1.9 °C . The diffusion length ratio method is the least precise with a precision of 13.7 °C . The absolute temperature estimates from this method are also shown to be highly sensitive to the choice of fractionation factor

First on-line isotopic characterization of N2O emitted from intensively managed grassland

NASA Astrophysics Data System (ADS)

Wolf, B.; Merbold, L.; Decock, C.; Tuzson, B.; Harris, E.; Six, J.; Emmenegger, L.; Mohn, J.

2015-01-01

The analysis of the four main isotopic N2O species (14N14N16O, 14N15N16O, 15N14N16O, 14N14N18O) and especially the intramolecular distribution of 15N (site preference, SP) has been suggested as a tool to distinguish source processes and to help constrain the global N2O budget. However, current studies suffer from limited spatial and temporal resolution capabilities due to the combination of discrete flask sampling with subsequent laboratory-based mass spectrometric analysis. Quantum cascade laser absorption spectroscopy (QCLAS) allows selective high-precision analysis of N2O isotopic species at trace levels and is suitable for in situ measurements. Here, we present results from the first field campaign, conducted on an intensively managed grassland in central Switzerland. N2O mole fractions and isotopic composition were determined in the atmospheric surface layer (2 m height) at high temporal resolution with a modified state-of-the-art laser spectrometer connected to an automated N2O preconcentration unit. The analytical performance was determined from repeated measurements of a compressed air tank and resulted in measurement repeatability of 0.20, 0.12 and 0.11‰ for δ15Nα, δ15Nβ and δ18O, respectively. Simultaneous eddy-covariance N2O flux measurements were used to determine the flux-averaged isotopic signature of soil-emitted N2O. Our measurements indicate that in general, nitrifier-denitrification and denitrification were the prevalent sources of N2O during the campaign, and that variations in isotopic composition were rather due to alterations in the extent to which N2O was reduced to N2, than other pathways such as hydroxylamine oxidation. Management and rewetting events were characterized by low values of the intra-molecular 15N site preference (SP), δ15Nbulk and δ18O, suggesting nitrifier denitrification and incomplete heterotrophic bacterial denitrification responded most strongly to the induced disturbances. Flux-averaged isotopic composition of N

A model of early formation of uranium molecular oxides in laser-ablated plasmas

NASA Astrophysics Data System (ADS)

Finko, Mikhail; Curreli, Davide; Azer, Magdi; Weisz, David; Crowhurst, Jonathan; Rose, Timothy; Koroglu, Batikan; Radousky, Harry; Zaug, Joseph; Armstrong, Mike

2017-10-01

An important problem within the field of nuclear forensics is fractionation: the formation of post-detonation nuclear debris whose composition does not reflect that of the source weapon. We are investigating uranium fractionation in rapidly cooling plasma using a combined experimental and modeling approach. In particular, we use laser ablation of uranium metal samples to produce a low-temperature plasma with physical conditions similar to a condensing nuclear fireball. Here we present a first plasma-chemistry model of uranium molecular species formation during the early stage of laser ablated plasma evolution in atmospheric oxygen. The system is simulated using a global kinetic model with rate coefficients calculated according to literature data and the application of reaction rate theory. The model allows for a detailed analysis of the evolution of key uranium molecular species and represents the first step in producing a uranium fireball model that is kinetically validated against spatially and temporally resolved spectroscopy measurements. This project was sponsored by the DoD, Defense Threat Reduction Agency, Grant HDTRA1-16- 1-0020. This work was performed in part under the auspices of the U.S. DoE by Lawrence Livermore National Laboratory under Contract DE-AC52- 07NA27344.

Lasers '81

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

Collins, C.B.

1982-01-01

Progress in lasers is discussed. The subjects addressed include: excimer lasers, surface spectroscopy, modern laser spectroscopy, free electron lasers, cavities and propagation, lasers in medicine, X-ray and gamma ray lasers, laser spectroscopy of small molecules and clusters, optical bistability, excitons, nonlinear optics in the X-ray and gamma ray regions, collective atomic phenomena, tunable IR lasers, far IR/submillimeter lasers, and laser-assisted collisions. Also treated are: special applications, multiphoton processes in atoms and small molecules, nuclear pumped lasers, material processing and applications, polarization, high energy lasers, laser chemistry, IR molecular lasers, laser applications of collision and dissociation phenomena, solid state laser materials,more » phase conjugation, advances in laser technology for fusion, metal vapor lasers, picosecond phenomena, laser ranging and geodesy, and laser photochemistry of complex molecules.« less

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

Differentiation of molecular chain entanglement structure through laser Raman spectrum measurement of High strength PET fibers under stress

NASA Astrophysics Data System (ADS)

Go, D.; Takarada, W.; Kikutani, T.

2017-10-01

The aim of this study was to investigate the mechanism for the improvement of mechanical properties of poly(ethylene terephthalate) (PET) fibers based on the concept of controlling the state of molecular entanglement. For this purpose, five different PET fibers were prepared through either the conventional melt spinning and drawing/annealing process or the high-speed melt spinning process. In both cases, the melt spinning process was designed so as to realize different Deborah number conditions. The prepared fibers were subjected to the laser Raman spectroscopy measurement and the characteristics of the scattering peak at around 1616 cm-1, which corresponds to the C-C/C=C stretching mode of the aromatic ring in the main chain, were investigated in detail. It was revealed that the fibers drawn and annealed after the melt spinning process of lower Deborah number showed higher tensile strength as well as lower value of full width at half maximum (FWHM) in the laser Raman spectrum. Narrow FWHM was considered to represent the homogeneous state of entanglement structure, which may lead to the higher strength and toughness of fibers because individual molecular chains tend to bare similar level of tensile stress when the fiber is stretched. In case of high-speed spun fibers prepared with a high Deborah number condition, the FWHM was narrow presumably because much lower tensile stress in comparison with the drawing/annealing process was applied when the fiber structure was developed, however the value increased significantly upon applying tensile load to the fibers during the laser Raman spectrum measurement. From these results, it was concluded that the Laser Raman spectroscopy could differentiate molecular chain entanglement structure of various fiber samples, in that low FWHM, which corresponds to either homogeneous state of molecular entanglement or lower level of mean residual stress, and small increase of FWTH upon applying tensile stress are considered to be the key

Cavity-enhanced Raman spectroscopy with optical feedback cw diode lasers for gas phase analysis and spectroscopy.

PubMed

Salter, Robert; Chu, Johnny; Hippler, Michael

2012-10-21

A variant of cavity-enhanced Raman spectroscopy (CERS) is introduced, in which diode laser radiation at 635 nm is coupled into an external linear optical cavity composed of two highly reflective mirrors. Using optical feedback stabilisation, build-up of circulating laser power by 3 orders of magnitude occurs. Strong Raman signals are collected in forward scattering geometry. Gas phase CERS spectra of H(2), air, CH(4) and benzene are recorded to demonstrate the potential for analytical applications and fundamental molecular studies. Noise equivalent limits of detection in the ppm by volume range (1 bar sample) can be achieved with excellent linearity with a 10 mW excitation laser, with sensitivity increasing with laser power and integration time. The apparatus can be operated with battery powered components and can thus be very compact and portable. Possible applications include safety monitoring of hydrogen gas levels, isotope tracer studies (e.g., (14)N/(15)N ratios), observing isotopomers of hydrogen (e.g., radioactive tritium), and simultaneous multi-component gas analysis. CERS has the potential to become a standard method for sensitive gas phase Raman spectroscopy.

Excimer lasers

NASA Technical Reports Server (NTRS)

Palmer, A. J.; Hess, L. D.; Stephens, R. R.; Pepper, D. M.

1977-01-01

The results of a two-year investigation into the possibility of developing continuous wave excimer lasers are reported. The program included the evaluation and selection of candidate molecular systems and discharge pumping techniques. The K Ar/K2 excimer dimer molecules and the xenon fluoride excimer molecule were selected for study; each used a transverse and capillary discharges pumping technique. Experimental and theoretical studies of each of the two discharge techniques applied to each of the two molecular systems are reported. Discharge stability and fluorine consumption were found to be the principle impediments to extending the XeF excimer laser into the continuous wave regime. Potassium vapor handling problems were the principal difficulty in achieving laser action on the K Ar/K2 system. Of the four molecular systems and pumping techniques explored, the capillary discharge pumped K Ar/K2 system appears to be the most likely candidate for demonstrating continuous wave excimer laser action primarily because of its predicted lower pumping threshold and a demonstrated discharge stability advantage.

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

2013-10-03

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.

Partial Least Squares Calibration Modeling Towards the Multivariate Limit of Detection for Enriched Isotopic Mixtures via Laser Ablation Molecular Isotopic Spectroscopy

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

Harris, Candace; Profeta, Luisa; Akpovo, Codjo

The psuedo univariate limit of detection was calculated to compare to the multivariate interval. ompared with results from the psuedounivariate LOD, the multivariate LOD includes other factors (i.e. signal uncertainties) and the reveals the significance in creating models that not only use the analyte’s emission line but also its entire molecular spectra.

A model of early formation of uranium molecular oxides in laser-ablated plasmas

NASA Astrophysics Data System (ADS)

Finko, Mikhail S.; Curreli, Davide; Weisz, David G.; Crowhurst, Jonathan C.; Rose, Timothy P.; Koroglu, Batikan; Radousky, Harry B.; Armstrong, Michael R.

2017-12-01

In this work, we present a newly constructed U x O y reaction mechanism that consists of 30 reaction channels (21 of which are reversible channels) for 11 uranium molecular species (including ions). Both the selection of reaction channels and calculation of corresponding rate coefficients is accomplished via a comprehensive literature review and application of basic reaction rate theory. The reaction mechanism is supplemented by a detailed description of oxygen plasma chemistry (19 species and 142 reaction channels) and is used to model an atmospheric laser ablated uranium plume via a 0D (global) model. The global model is used to analyze the evolution of key uranium molecular species predicted by the reaction mechanism, and the initial stage of formation of uranium oxide species.

The shift of harmonics with different initial vibrational states in the H{}_{2}^{+} molecular ion

NASA Astrophysics Data System (ADS)

Zhang, Jun; Pan, Xue-Fei; Xu, Tong-Tong; Liu, Xue-Shen

2017-05-01

Molecular high-order harmonic generation of H{}2+ and its isotopes is investigated by numerical simulations of the non-Born-Oppenheimer time-dependent Schrödinger equations. The general characteristic of the typical high-order harmonic generation (HHG) spectra for the H{}2+ molecule indicates that only the odd harmonics can be generated. Here we show that how the initial vibrational states and nuclear dynamics break down this standard characteristic, i.e. a redshift or blueshift of the harmonics appears. We investigate the effect of the initial vibrational states on the redshift or blueshift of the HHG spectrum under trapezoidal laser pulses. The ionization probability and time-frequency analysis are used to illustrate the physical mechanism of the shift of the harmonics. We also show the HHG spectra from the different isotopes of H2+ molecule with different initial vibrational states.

Continuous-wave, single-frequency 229  nm laser source for laser cooling of cadmium atoms.

PubMed

Kaneda, Yushi; Yarborough, J M; Merzlyak, Yevgeny; Yamaguchi, Atsushi; Hayashida, Keitaro; Ohmae, Noriaki; Katori, Hidetoshi

2016-02-15

Continuous-wave output at 229 nm for the application of laser cooling of Cd atoms was generated by the fourth harmonic using two successive second-harmonic generation stages. Employing a single-frequency optically pumped semiconductor laser as a fundamental source, 0.56 W of output at 229 nm was observed with a 10-mm long, Brewster-cut BBO crystal in an external cavity with 1.62 W of 458 nm input. Conversion efficiency from 458 nm to 229 nm was more than 34%. By applying a tapered amplifier (TA) as a fundamental source, we demonstrated magneto-optical trapping of all stable Cd isotopes including isotopes Cd111 and Cd113, which are applicable to optical lattice clocks.

Carbon Isotope Measurements of Experimentally-Derived Hydrothermal Mineral-Catalyzed Organic Products by Pyrolysis-Isotope Ratio Mass Spectrometry

NASA Technical Reports Server (NTRS)

Socki, Richard A.; Fu, Qi; Niles, Paul B.

2011-01-01

We report results of experiments to measure the C isotope composition of mineral catalyzed organic compounds derived from high temperature and high pressure synthesis. These experiments make use of an innovative pyrolysis technique designed to extract and measure C isotopes. To date, our experiments have focused on the pyrolysis and C isotope ratio measurements of low-molecular weight intermediary hydrocarbons (organic acids and alcohols) and serve as a proof of concept for making C and H isotope measurements on more complicated mixtures of solid-phase hydrocarbons and intermediary products produced during high temperature and high pressure synthesis on mineral-catalyzed surfaces. The impetus for this work stems from recently reported observations of methane detected within the Martian atmosphere [1-4], coupled with evidence showing extensive water-rock interaction during Martian history [5-7]. Methane production on Mars could be the result of synthesis by mineral surface-catalyzed reduction of CO2 and/or CO by Fischer-Tropsch Type (FTT) reactions during serpentization reactions [8,9]. Others have conducted experimental studies to show that FTT reactions are plausible mechanisms for low-molecular weight hydrocarbon formation in hydrothermal systems at mid-ocean ridges [10-12]. Further, recent experiments by Fu et al. [13] focus on examining detailed C isotope measurements of hydrocarbons produced by surface-catalyzed mineral reactions. Work described in this paper details the experimental techniques used to measure intermediary organic reaction products (alcohols and organic acids).

An All-Solid-State High Repetiton Rate Titanium:Sapphire Laser System For Resonance Ionization Laser Ion Sources

NASA Astrophysics Data System (ADS)

Mattolat, C.; Rothe, S.; Schwellnus, F.; Gottwald, T.; Raeder, S.; Wendt, K.

2009-03-01

On-line production facilities for radioactive isotopes nowadays heavily rely on resonance ionization laser ion sources due to their demonstrated unsurpassed efficiency and elemental selectivity. Powerful high repetition rate tunable pulsed dye or Ti:sapphire lasers can be used for this purpose. To counteract limitations of short pulse pump lasers, as needed for dye laser pumping, i.e. copper vapor lasers, which include high maintenance and nevertheless often only imperfect reliability, an all-solid-state Nd:YAG pumped Ti:sapphire laser system has been constructed. This could complement or even replace dye laser systems, eliminating their disadvantages but on the other hand introduce shortcomings on the side of the available wavelength range. Pros and cons of these developments will be discussed.

Research on catalysts for long-life closed-cycle CO2 laser oaperation

NASA Technical Reports Server (NTRS)

Sidney, Barry D.; Schryer, David R.; Upchurch, Billy T.; Hess, Robert V.; Wood, George M.

1987-01-01

Long-life, closed-cycle operation of pulsed CO2 lasers requires catalytic CO-O2 recombination both to remove O2, which is formed by discharge-induced CO2 decomposition, and to regenerate CO2. Platinum metal on a tin-oxide substrate (Pt/SnO2) has been found to be an effective catalyst for such recombination in the desired temperature range of 25 to 100 C. This paper presents a description of ongoing research at NASA-Langley on Pt/SnO2 catalyzed CO-O2 recombination. Included are studies with rare-isotope gases since rare-isotope CO2 is desirable as a laser gas for enhanced atmospheric transmission. Results presented include: (1) the effects of various catalyst pretreatment techniques on catalyst efficiency; (2) development of a technique, verified in a 30-hour test, to prevent isotopic scrambling when C(O-18) and (O-18)2 are reacted in the presence of a common-isotope Pt/Sn(O-16)2 catalyst; and (3) development of a mathematical model of a laser discharge prior to catalyst introduction.

Isotopic Changes During Digestion: Protein

NASA Astrophysics Data System (ADS)

Tuross, N.

2013-12-01

Nutrient and hydrological inputs traverse a complicated route of pH, enzymatic and cellular processes in digestion in higher animals. The end products of digestion are the starting products for biosynthesis that are often used to interpret past life-ways. Using an artificial gut system, the isotopic changes (dD, d18O, d13C and d15N) of protein are documented. Three separate protein sources are subjected to the conditions, chemical and enzymatic, found in the stomach and upper small intestine with only a small shift in the oxygen isotopic composition of the proteins observed. Middle to lower small intestine parameters produced both greater isotopic effects and significantly lower molecular weight products. The role of the gastric enterocyte and the likely involvement of the internal milieu of this cell in the isotopic composition of amino acids that are transported to the liver are reported.

Laser technologies for ultrasensitive groundwater dating using long-lived isotopes

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

Backus, Sterling

In this phase I work, we propose to construct and demonstrate a 103 nm laser based on resonantly enhanced and phase matched fifth harmonic generation in hollow waveguides driven by a high power, low cost and compact ultrafast fiber laser. (Figure 4) This VUV laser source can potentially produce >100 milliwatts of VUV light at 103 nm with pulse repetition-rates of 100 kHz to 100 MHz, ideal for the above-mentioned applications. This technology is state-of-the-art and potentially compact, fieldable, low-cost, and of broad interest for a variety of science and technology applications. Laser-based VUV sources in the past have exhibitedmore » low repetition rate, low efficiency, low beam quality, and are based on expensive laser sources. Our approch is to combine ultrafast fiber laser drive technology, ultrafast pulses, and our proven waveguide technology, to create a high repetition rate, high average power VUV source for producing high yield metastable Krypton. At KMLabs we have been offering EUV light sources employing the high harmonic generation (HHG) process driven by high-power femtosecond lasers for >5 years now. Recently, we have developed much smaller scale (briefcase size), but still high average power femtosecond fiber laser sources to supply other markets, and create new ones. By combining these new laser sources with our patented waveguide frequency upconversion technology, we expect to be able to obtain >20mW average power initially, with potentially much higher powers depending on wavelength, in an affordable VUV product. For comparison, our current EUV light sources based on ti:sapphire generate an average power of ~5 µW (albeit at shorter 29 nm wavelength), and we are aware of one other supplier that has developed a VUV (112 nm) light source with ~10-20 µW power.« less

Two-dimensional imaging of molecular hydrogen in H2-air diffusion flames using two-photon laser-induced fluorescence

NASA Technical Reports Server (NTRS)

Lempert, W.; Kumar, V.; Glesk, I.; Miles, R.; Diskin, G.

1991-01-01

The use of a tunable ArF laser at 193.26 nm to record simultaneous single-laser-shot, planar images of molecular hydrogen and hot oxygen in a turbulent H2-air diffusion flame. Excitation spectra of fuel and oxidant-rich flame zones confirm a partial overlap of the two-photon H2 and single-photon O2 Schumann-Runge absorption bands. UV Rayleigh scattering images of flame structure and estimated detection limits for the H2 two-photon imaging are also presented.

Using Carbon-14 Isotope Tracing to Investigate Molecular Structure Effects of the Oxygenate Dibutyl Maleate on Soot Emissions from a DI Diesel Engine

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

Buchholz, B A; Mueller, C J; Upatnieks, A

2004-01-07

The effect of oxygenate molecular structure on soot emissions from a DI diesel engine was examined using carbon-14 ({sup 14}C) isotope tracing. Carbon atoms in three distinct chemical structures within the diesel oxygenate dibutyl maleate (DBM) were labeled with {sup 14}C. The {sup 14}C from the labeled DBM was then detected in engine-out particulate matter (PM), in-cylinder deposits, and CO{sub 2} emissions using accelerator mass spectrometry (AMS). The results indicate that molecular structure plays an important role in determining whether a specific carbon atom either does or does not form soot. Chemical-kinetic modeling results indicate that structures that produce CO{submore » 2} directly from the fuel are less effective at reducing soot than structures that produce CO before producing CO{sub 2}. Because they can follow individual carbon atoms through a real combustion process, {sup 14}C isotope tracing studies help strengthen the connection between actual engine emissions and chemical-kinetic models of combustion and soot formation/oxidation processes.« less

Monolithic integration of multiple wavelength vertical-cavity surface-emitting lasers by mask molecular beam epitaxy

NASA Astrophysics Data System (ADS)

Saito, Hideaki; Ogura, Ichiro; Sugimoto, Yoshimasa; Kasahara, Kenichi

1995-05-01

The monolithic incorporation and performance of vertical-cavity surface-emitting lasers (VCSELs) emitting at two distinct wavelengths, which were suited for application to wavelength division multiplexing (WDM) systems were reported. The monolithic integration of two-wavelength VCSEL arrays was achieved by using mask molecular beam epitaxy. This method can generate arrays that have the desired integration area size and wavelength separation.

Anharmonic resonance absorption of short laser pulses in clusters: A molecular dynamics simulation study

NASA Astrophysics Data System (ADS)

Mahalik, S. S.; Kundu, M.

2016-12-01

Linear resonance (LR) absorption of an intense 800 nm laser light in a nano-cluster requires a long laser pulse >100 fs when Mie-plasma frequency ( ω M ) of electrons in the expanding cluster matches the laser frequency (ω). For a short duration of the pulse, the condition for LR is not satisfied. In this case, it was shown by a model and particle-in-cell (PIC) simulations [Phys. Rev. Lett. 96, 123401 (2006)] that electrons absorb laser energy by anharmonic resonance (AHR) when the position-dependent frequency Ω [ r ( t ) ] of an electron in the self-consistent anharmonic potential of the cluster satisfies Ω [ r ( t ) ] = ω . However, AHR remains to be a debate and still obscure in multi-particle plasma simulations. Here, we identify AHR mechanism in a laser driven cluster using molecular dynamics (MD) simulations. By analyzing the trajectory of each MD electron and extracting its Ω [ r ( t ) ] in the self-generated anharmonic plasma potential, it is found that electron is outer ionized only when AHR is met. An anharmonic oscillator model, introduced here, brings out most of the features of MD electrons while passing the AHR. Thus, we not only bridge the gap between PIC simulations, analytical models, and MD calculations for the first time but also unequivocally prove that AHR process is a universal dominant collisionless mechanism of absorption in the short pulse regime or in the early time of longer pulses in clusters.

A model of early formation of uranium molecular oxides in laser-ablated plasmas

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

Finko, Mikhail S.; Curreli, Davide; Weisz, David G.

Here, in this work, we present a newly constructed U xO y reaction mechanism that consists of 30 reaction channels (21 of which are reversible channels) for 11 uranium molecular species (including ions). Both the selection of reaction channels and calculation of corresponding rate coefficients is accomplished via a comprehensive literature review and application of basic reaction rate theory. The reaction mechanism is supplemented by a detailed description of oxygen plasma chemistry (19 species and 142 reaction channels) and is used to model an atmospheric laser ablated uranium plume via a 0D (global) model. Finally, the global model is usedmore » to analyze the evolution of key uranium molecular species predicted by the reaction mechanism, and the initial stage of formation of uranium oxide species.« less

A model of early formation of uranium molecular oxides in laser-ablated plasmas

DOE PAGES

Finko, Mikhail S.; Curreli, Davide; Weisz, David G.; ...

2017-10-12

Here, in this work, we present a newly constructed U xO y reaction mechanism that consists of 30 reaction channels (21 of which are reversible channels) for 11 uranium molecular species (including ions). Both the selection of reaction channels and calculation of corresponding rate coefficients is accomplished via a comprehensive literature review and application of basic reaction rate theory. The reaction mechanism is supplemented by a detailed description of oxygen plasma chemistry (19 species and 142 reaction channels) and is used to model an atmospheric laser ablated uranium plume via a 0D (global) model. Finally, the global model is usedmore » to analyze the evolution of key uranium molecular species predicted by the reaction mechanism, and the initial stage of formation of uranium oxide species.« less

Time-resolved molecular imaging

NASA Astrophysics Data System (ADS)

Xu, Junliang; Blaga, Cosmin I.; Agostini, Pierre; DiMauro, Louis F.

2016-06-01

Time-resolved molecular imaging is a frontier of ultrafast optical science and physical chemistry. In this article, we review present and future key spectroscopic and microscopic techniques for ultrafast imaging of molecular dynamics and show their differences and connections. The advent of femtosecond lasers and free electron x-ray lasers bring us closer to this goal, which eventually will extend our knowledge about molecular dynamics to the attosecond time domain.

Semiconductor Laser Joint Study Program with Rome Laboratory

DTIC Science & Technology

1994-09-01

VCSELs 3.3 Laser Wafer Growth by Molecular Beam Epitaxy 8 The VCSEL structures were grown by molecular beam ...cavity surface emittimg lasers ( VCSEL ), Optical 40 interconnects, Moelcular beam epitaxy It CECOOE 17. SECURfTY CLASWICATION SECURFlY CLASSIFICATION 1 Q...7 3.3 Laser Wafer Growth by Molecular Beam Epitax. ............ 8 3.4 VCSEL Fabrication Process ................................................

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

High power gas laser - Applications and future developments

NASA Technical Reports Server (NTRS)

Hertzberg, A.

1977-01-01

Fast flow can be used to create the population inversion required for lasing action, or can be used to improve laser operation, for example by the removal of waste heat. It is pointed out that at the present time all lasers which are capable of continuous high-average power employ flow as an indispensable aspect of operation. High power laser systems are discussed, taking into account the gasdynamic laser, the HF supersonic diffusion laser, and electric discharge lasers. Aerodynamics and high power lasers are considered, giving attention to flow effects in high-power gas lasers, aerodynamic windows and beam manipulation, and the Venus machine. Applications of high-power laser technology reported are related to laser material working, the employment of the laser in controlled fusion machines, laser isotope separation and photochemistry, and laser power transmission.

Laser-induced desorption of atomic and molecular fragments from a tin dioxide surface modified by a thin organic covering of copper phthalocyanine

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

Komolov, A. S., E-mail: akomolov07@ya.ru; Komolov, S. A.; Lazneva, E. F.

2012-01-15

The systematic features of laser-induced desorption from an SnO{sub 2} surface exposed to 10-ns pulsed neodymium laser radiation are studied at the photon energy 2.34 eV, in the range of pulse energy densities 1 to 50 mJ/cm{sup 2}. As the threshold pulse energy 28 mJ/cm{sup 2} is achieved, molecular oxygen O{sub 2} is detected in the desorption mass spectra from the SnO{sub 2} surface; as the threshold pulse energy 42 mJ/cm{sup 2} is reached, tin Sn, and SnO and (SnO){sub 2} particle desorption is observed. The laser desorption mass spectra from the SnO{sub 2} surface coated with an organic coppermore » phthalocyanine (CuPc) film 50 nm thick are measured. It is shown that laser irradiation causes the fragmentation of CuPc molecules and the desorption of molecular fragments in the laser pulse energy density range 6 to 10 mJ/cm{sup 2}. Along with the desorption of molecular fragments, a weak desorption signal of the substrate components O{sub 2}, Sn, SnO, and (SnO){sub 2} is observed in the same energy range. Desorption energy thresholds of substrate atomic components from the organic film surface are approximately five times lower than thresholds of their desorption from the atomically clean SnO{sub 2} surface, which indicates the diffusion of atomic components of the SnO{sub 2} substrate to the bulk of the deposited organic film.« less

Dehydrogenation involved Coulomb explosion of molecular C2H4FBr in an intense laser field

NASA Astrophysics Data System (ADS)

Pei, Minjie; Yang, Yan; Zhang, Jian; Sun, Zhenrong

2018-04-01

The dissociative double ionization (DDI) of molecular 1-fluo-2-bromoethane (FBE) in an intense laser field has been investigated by dc-slice imaging technology. The DDI channels involved with dehydrogenation are revealed and it's believed both the charge distribution and the bound character of real potential energy surfaces of parent ions play important roles in the dissociation process. The relationship between the potential energy surfaces of the precursor species and the photofragment ejection angles are also discussed and analyzed. Furthermore, the competition between the DDI channels has been studied and the Csbnd C bond cleavages dominate the DDI process at relative higher laser intensity.

An Assessment of Molecular Dynamic Force Fields for Silica for Use in Simulating Laser Damage Mitigation

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

Soules, T F; Gilmer, G H; Matthews, M J

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 tomore » laser mitigation experiments.« less

Laser ion source for isobaric heavy ion collider experiment.

PubMed

Kanesue, T; Kumaki, M; Ikeda, S; Okamura, M

2016-02-01

Heavy-ion collider experiment in isobaric system is under investigation at Relativistic Heavy Ion Collider. For this experiment, ion source is required to maximize the abundance of the intended isotope. The candidate of the experiment is (96)Ru + (96)Zr. Since the natural abundance of particular isotope is low and composition of isotope from ion source depends on the composites of the target, an isotope enriched material may be needed as a target. We studied the performance of the laser ion source required for the experiment for Zr ions.

Cyan laser diode grown by plasma-assisted molecular beam epitaxy

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

Turski, H., E-mail: henryk@unipress.waw.pl; Muziol, G.; Wolny, P.

We demonstrate AlGaN-cladding-free laser diodes (LDs), operating in continuous wave (CW) mode at 482 nm grown by plasma-assisted molecular beam epitaxy (PAMBE). The maximum CW output power was 230 mW. LDs were grown on c-plane GaN substrates obtained by hydride vapor phase epitaxy. The PAMBE process was carried out in metal-rich conditions, supplying high nitrogen flux (Φ{sub N}) during quantum wells (QWs) growth. We found that high Φ{sub N} improves quality of high In content InGaN QWs. The role of nitrogen in the growth of InGaN on (0001) GaN surface as well as the influence of LDs design on threshold currentmore » density are discussed.« less

Diode Lasers and Practical Trace Analysis.

ERIC Educational Resources Information Center

Imasaka, Totaro; Nobuhiko, Ishibashi

1990-01-01

Applications of lasers to molecular absorption spectrometry, molecular fluorescence spectrometry, visible semiconductor fluorometry, atomic absorption spectrometry, and atomic fluorescence spectrometry are discussed. Details of the use of the frequency-doubled diode laser are provided. (CW)

Isotope separation by photoselective dissociative electron capture

DOEpatents

Stevens, Charles G. [Pleasanton, CA

1978-08-29

A method of separating isotopes based on photoselective electron capture dissociation of molecules having an electron capture cross section dependence on the vibrational state of the molecule. A molecular isotope source material is irradiated to selectively excite those molecules containing a desired isotope to a predetermined vibrational state having associated therewith an electron capture energy region substantially non-overlapping with the electron capture energy ranges associated with the lowest vibration states of the molecules. The isotope source is also subjected to electrons having an energy corresponding to the non-overlapping electron capture region whereby the selectively excited molecules preferentially capture electrons and dissociate into negative ions and neutrals. The desired isotope may be in the negative ion product or in the neutral product depending upon the mechanism of dissociation of the particular isotope source used. The dissociation product enriched in the desired isotope is then separated from the reaction system by conventional means. Specifically, .sup.235 UF.sub.6 is separated from a UF.sub.6 mixture by selective excitation followed by dissociative electron capture into .sup.235 UF.sub.5 - and F.

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.

Process for producing enriched uranium having a .sup.235 U content of at least 4 wt. % via combination of a gaseous diffusion process and an atomic vapor laser isotope separation process to eliminate uranium hexafluoride tails storage

DOEpatents

Horton, James A.; Hayden, Jr., Howard W.

1995-01-01

An uranium enrichment process capable of producing an enriched uranium, having a .sup.235 U content greater than about 4 wt. %, is disclosed which will consume less energy and produce metallic uranium tails having a lower .sup.235 U content than the tails normally produced in a gaseous diffusion separation process and, therefore, eliminate UF.sub.6 tails storage and sharply reduce fluorine use. The uranium enrichment process comprises feeding metallic uranium into an atomic vapor laser isotope separation process to produce an enriched metallic uranium isotopic mixture having a .sup.235 U content of at least about 2 wt. % and a metallic uranium residue containing from about 0.1 wt. % to about 0.2 wt. % .sup.235 U; fluorinating this enriched metallic uranium isotopic mixture to form UF.sub.6 ; processing the resultant isotopic mixture of UF.sub.6 in a gaseous diffusion process to produce a final enriched uranium product having a .sup.235 U content of at least 4 wt. %, and up to 93.5 wt. % or higher, of the total uranium content of the product, and a low .sup.235 U content UF.sub.6 having a .sup.235 U content of about 0.71 wt. % of the total uranium content of the low .sup.235 U content UF.sub.6 ; and converting this low .sup.235 U content UF.sub.6 to metallic uranium for recycle to the atomic vapor laser isotope separation process.

Process for producing enriched uranium having a {sup 235}U content of at least 4 wt. % via combination of a gaseous diffusion process and an atomic vapor laser isotope separation process to eliminate uranium hexafluoride tails storage

DOEpatents

Horton, J.A.; Hayden, H.W. Jr.

1995-05-30

An uranium enrichment process capable of producing an enriched uranium, having a {sup 235}U content greater than about 4 wt. %, is disclosed which will consume less energy and produce metallic uranium tails having a lower {sup 235}U content than the tails normally produced in a gaseous diffusion separation process and, therefore, eliminate UF{sub 6} tails storage and sharply reduce fluorine use. The uranium enrichment process comprises feeding metallic uranium into an atomic vapor laser isotope separation process to produce an enriched metallic uranium isotopic mixture having a {sup 235} U content of at least about 2 wt. % and a metallic uranium residue containing from about 0.1 wt. % to about 0.2 wt. % {sup 235} U; fluorinating this enriched metallic uranium isotopic mixture to form UF{sub 6}; processing the resultant isotopic mixture of UF{sub 6} in a gaseous diffusion process to produce a final enriched uranium product having a {sup 235}U content of at least 4 wt. %, and up to 93.5 wt. % or higher, of the total uranium content of the product, and a low {sup 235}U content UF{sub 6} having a {sup 235}U content of about 0.71 wt. % of the total uranium content of the low {sup 235}U content UF{sub 6}; and converting this low {sup 235}U content UF{sub 6} to metallic uranium for recycle to the atomic vapor laser isotope separation process. 4 figs.

Cross Sections for Ionization of Rare Gas Excimers by Electron Impact and Atomic and Molecular Processes in Excimer Lasers.

DTIC Science & Technology

1980-03-01

6.1 Excimers and Exciplexes : Background 55 6.2 Rare Gas-Halide Lasers 58 6.3 Formation, Quenching and Absorption Processes for Rare Gas-Halides 60... exciplex such as KrF* and XeF* laser systems as well as in various types of gas discharges. They are also of fundamental significance in their own...collision processes contributing to the formation and quenching of the excited molecular states in exciplex (such as KrF ) and excimer (such as Xe2

[Laser microdissection for biology and medicine].

PubMed

Podgornyĭ, O V; Lazarev, V N; Govorun, V M

2012-01-01

For routine extraction of DNA, RNA, proteins and metabolites, small tissue pieces are placed into lysing solution. These tissue pieces in general contain different cell types. For this reason, lysate contains components of different cell types, which complicates the interpretation of molecular analysis results. The laser microdissection allows overcoming this trouble. The laser microdissection is a method to procure tissue samples contained defined cell subpopulations, individual cells and even subsellular components under direct microscopic visualization. Collected samples can be undergone to different downstream molecular assays: DNA analysis, RNA transcript profiling, cDNA library generation and gene expression analysis, proteomic analysis and metabolite profiling. The laser microdissection has wide applications in oncology (research and routine), cellular and molecular biology, biochemistry and forensics. This paper reviews the principles of different laser microdissection instruments, examples of laser microdissection application and problems of sample preparation for laser microdissection.

Theoretical studies of solar-pumped lasers

NASA Technical Reports Server (NTRS)

Harries, W. L.

1983-01-01

Possible types of lasers were surveyed for solar power conversion. The types considered were (1) liquid dye lasers, (2) vapor dye lasers, and (3) nondissociative molecular lasers. These are discussed.

High energy chemical laser system

DOEpatents

Gregg, D.W.; Pearson, R.K.

1975-12-23

A high energy chemical laser system is described wherein explosive gaseous mixtures of a reducing agent providing hydrogen isotopes and interhalogen compounds are uniformly ignited by means of an electrical discharge, flash- photolysis or an electron beam. The resulting chemical explosion pumps a lasing chemical species, hydrogen fluoride or deuterium fluoride which is formed in the chemical reaction. The generated lasing pulse has light frequencies in the 3- micron range. Suitable interhalogen compounds include bromine trifluoride (BrF$sub 3$), bromine pentafluoride (BrF$sub 5$), chlorine monofluoride (ClF), chlorine trifluoride (ClF$sub 3$), chlorine pentafluoride (ClF$sub 5$), iodine pentafluoride (IF$sub 5$), and iodine heptafluoride (IF$sub 7$); and suitable reducing agents include hydrogen (H$sub 2$), hydrocarbons such as methane (CH$sub 4$), deuterium (D$sub 2$), and diborane (B$sub 2$H$sub 6$), as well as combinations of the gaseous compound and/or molecular mixtures of the reducing agent.

PALOMA : An instrument to measure the molecular, elemental and isotopic composition of Mars atmosphere from a landed platform (MSL 09, EXOMARS)

NASA Astrophysics Data System (ADS)

Chassefière, E.; Paloma Team

2003-04-01

An instrument to analyze the molecular, elemental and isotopic composition of Mars atmosphere from a landed platform is being developed under CNES funding. This instrument, called PALOMA (PAyload for Local Observation of Mars Atmosphere), will be proposed in response to the AO for the instrumentation of the NASA Mars Smart Lander mission, planned to be launched in 2009. It might be part as well of the EXOMARS mission presently studied at ESA in the frame of the Aurora program. Noble gases (He, Ne, Ar, Xr, Xe) and stable isotopes (C, H, O, N) will be analyzed by using a system of gas purification and separation, coupled with a mass spectrometer. The heaviest, radioactive, noble gas (Rn) and its short-lived daughters will be measured using a small additional device (alpha particle detector). Detailed search for trace constituents of astrobiological interest, like CH_4, H_2CO, N_2O, H_2S (abundances, isotopic ratios, time variability) will be done on a regular temporal basis during one Martian year. Isotopic ratios will be measured with an accuracy of about 1 ppm, or better, in order to provide a clear diagnosis of possible life signatures, to allow a detailed comparison of Earth and Mars atmospheric fractionation patterns and, finally, to accurately disentangle escape, climatic, geochemical and hypothesized biological effects. High sensitivity is required for elemental and isotopic compositions of trace gases of interest (a small fraction of ppbv). Such an accurate monitoring of Mars atmosphere volatile composition is expected to provide the necessary reference for future composition studies of minerals, soils, bio-markers, polar cap material, either by in-situ measurement, or from laboratory analyses of returned samples. The PALOMA instrument consists of : a gas purification and separation line, using techniques of chemical and cryogenic trapping, and possibly membrane permeation, a mass spectrometer working in static mode, a turbo-molecular pump that provides the

Investigation of laser-tissue interaction in medicine by means of laser spectroscopic measurements

NASA Astrophysics Data System (ADS)

Lademann, Juergen; Weigmann, Hans-Juergen

1995-01-01

Toxic and carcinogenic substances were produced during laser application in medicine for the cutting and evaporation of tissue. The laser smoke presents a danger potential for the medical staff and the patients. The laser tissue interaction process was investigated by means of laser spectroscopic measurements which give the possibility of measuring metastable molecular states directly as a prerequisite to understand and to influence fundamental laser tissue interaction processes in order to reduce the amount of harmful chemicals. Highly excited atomic and molecular states and free radicals (CN, OH, C2, CH, CH2) have been detected applying spontaneous and laser induced fluorescence methods. It was found that the formation of harmful substances in the laser plumes can be reduced significantly by optimization of the surrounding gas atmosphere. A high content of oxygen or water in the interaction zone has been found, in agreement with the results of classical and analytical methods, as a suitable way to decrease pollutant emission. The experimental methods and the principal results are applicable not only in laser medicine but in laser material treatment generally.

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.

Direct uranium isotope ratio analysis of single micrometer-sized glass particles

PubMed Central

Kappel, Stefanie; Boulyga, Sergei F.; Prohaska, Thomas

2012-01-01

We present the application of nanosecond laser ablation (LA) coupled to a ‘Nu Plasma HR’ multi collector inductively coupled plasma mass spectrometer (MC-ICP-MS) for the direct analysis of U isotope ratios in single, 10–20 μm-sized, U-doped glass particles. Method development included studies with respect to (1) external correction of the measured U isotope ratios in glass particles, (2) the applied laser ablation carrier gas (i.e. Ar versus He) and (3) the accurate determination of lower abundant 236U/238U isotope ratios (i.e. 10−5). In addition, a data processing procedure was developed for evaluation of transient signals, which is of potential use for routine application of the developed method. We demonstrate that the developed method is reliable and well suited for determining U isotope ratios of individual particles. Analyses of twenty-eight S1 glass particles, measured under optimized conditions, yielded average biases of less than 0.6% from the certified values for 234U/238U and 235U/238U ratios. Experimental results obtained for 236U/238U isotope ratios deviated by less than −2.5% from the certified values. Expanded relative total combined standard uncertainties Uc (k = 2) of 2.6%, 1.4% and 5.8% were calculated for 234U/238U, 235U/238U and 236U/238U, respectively. PMID:22595724

Direct uranium isotope ratio analysis of single micrometer-sized glass particles.

PubMed

Kappel, Stefanie; Boulyga, Sergei F; Prohaska, Thomas

2012-11-01

We present the application of nanosecond laser ablation (LA) coupled to a 'Nu Plasma HR' multi collector inductively coupled plasma mass spectrometer (MC-ICP-MS) for the direct analysis of U isotope ratios in single, 10-20 μm-sized, U-doped glass particles. Method development included studies with respect to (1) external correction of the measured U isotope ratios in glass particles, (2) the applied laser ablation carrier gas (i.e. Ar versus He) and (3) the accurate determination of lower abundant (236)U/(238)U isotope ratios (i.e. 10(-5)). In addition, a data processing procedure was developed for evaluation of transient signals, which is of potential use for routine application of the developed method. We demonstrate that the developed method is reliable and well suited for determining U isotope ratios of individual particles. Analyses of twenty-eight S1 glass particles, measured under optimized conditions, yielded average biases of less than 0.6% from the certified values for (234)U/(238)U and (235)U/(238)U ratios. Experimental results obtained for (236)U/(238)U isotope ratios deviated by less than -2.5% from the certified values. Expanded relative total combined standard uncertainties U(c) (k = 2) of 2.6%, 1.4% and 5.8% were calculated for (234)U/(238)U, (235)U/(238)U and (236)U/(238)U, respectively. Copyright © 2012 Elsevier Ltd. All rights reserved.

A vastly improved method for in situ stable isotope analysis of very small water samples.

NASA Astrophysics Data System (ADS)

Coleman, M. L.; Christensen, L. E.; Kriesel, J.; Kelly, J.; Moran, J.; Vance, S.

2016-12-01

The stable isotope compositions of hydrogen and oxygen in water, ice and hydrated minerals are key characteristics to determine the origin and history of the material. Originally, analyses were performed by separating hydrogen and preparing CO2 from the oxygen in water for stable isotope ratio mass spectrometry. Subsequently, infrared absorption spectrometry in either a Herriot cell or by cavity ring down allowed direct analysis of water vapor. We are developing an instrument, intended for spaceflight and in situ deployment, which will exploit Capillary Absorption Spectrometry (CAS) for the H and O isotope analysis and a laser to sample planetary ices and hydrated minerals. The Tunable Laser Spectrometer (TLS) instrument (part of SAM on the MSL rover Curiosity) works by infrared absorption and we use its performance as a benchmark for comparison. TLS has a relatively large sample chamber to contain mirrors which give a long absorption pathlength. CAS works on the same principle but utilizes a hollow optic fiber, greatly reducing the sample volume. The fiber is a waveguide, enhancing the laser - water-vapor interaction and giving more than four orders of magnitude increase in sensitivity, despite a shorter optical path length. We have calculated that a fiber only 2 m long will be able to analyze 5 nanomoles of water with a precision of less than 1 per mil for D?H. The fiber is coiled to minimize instrument volume. Our instrument will couple this analytical capability with laser sampling to free water from hydrated minerals and ice and ideally we would use the same laser via a beam-splitter both for sampling and analysis. The ability to analyze very small samples is of benefit in two ways. In this concept it will allow much faster analysis of small sub-samples, while the high spatial sampling resolution offered by the laser will allow analysis of the heterogeneity of isotopic composition within grains or crystals, revealing the history of their growth.

Oxygen isotopes and the moon-forming giant impact.

PubMed

Wiechert, U; Halliday, A N; Lee, D C; Snyder, G A; Taylor, L A; Rumble, D

2001-10-12

We have determined the abundances of 16O, 17O, and 18O in 31 lunar samples from Apollo missions 11, 12, 15, 16, and 17 using a high-precision laser fluorination technique. All oxygen isotope compositions plot within +/-0.016 per mil (2 standard deviations) on a single mass-dependent fractionation line that is identical to the terrestrial fractionation line within uncertainties. This observation is consistent with the Giant Impact model, provided that the proto-Earth and the smaller impactor planet (named Theia) formed from an identical mix of components. The similarity between the proto-Earth and Theia is consistent with formation at about the same heliocentric distance. The three oxygen isotopes (delta17O) provide no evidence that isotopic heterogeneity on the Moon was created by lunar impacts.

Oxygen isotope geochemistry of the amphiboles: isotope effects of cation substitutions in minerals

NASA Astrophysics Data System (ADS)

Kohn, Matthew J.; Valley, John W.

1998-06-01

The occurrence of coexisting amphiboles in rocks and the likelihood of concurrent isotope closure allows equilibrium oxygen isotope fractionations among the amphiboles to be recovered from natural samples. Oxygen isotope analyses of mineral separates using laser fluorination show that coexisting amphiboles increasingly partition 18O in the order: hornblende ≪ gedrite < cummingtonite ≤ anthophyllite. The observed fractionations at ˜575°C are: Δ(Ged-Hbl) = 0.8‰, Δ(Cum-Hbl) = 0.9, Δ(Cum-Ged) = 0.2, Δ(Ath-Ged) = 0.3, and Δ(Ath-Hbl) > 0.9. Previously published data for hornblende, actinolite, glaucophane, and garnet show that Δ(Act-Hbl) ˜ 0.2, Δ(Gln-Grt) ≫ 1, and Δ(Hbl-Grt) ˜ 0. Thus, glaucophane strongly partitions 18O relative to the calcic amphiboles. The fractionation between two amphiboles of arbitrary composition can be predicted from the known fractionations for mica endmembers, pyroxene endmembers, and exchange components such as CaAl(NaSi) -1, NaAl(CaMg) -1, CaMg -1, MgFe -1, FeMn -1, KNa -1, KAl( Si) -1, and Fe 3+Al -1. Applications of the exchange component method reproduce measured amphibole fractionations to within ±0.1 to ±0.2‰, whereas other predictive methods cause misfit for typical metamorphic hornblende of ≥0.5‰ at 575°C. Although the isotope effects of cation exchanges may be small at high-T, they magnify dramatically for minerals formed in surficial, diagenetic, and low-T metamorphic environments. Different composition clays are predicted to have equilibrium δ 18O differences of 2-9‰. If the isotope fractionation can be determined for one mineral endmember, then calibrated exchanges allow accurate prediction of the isotope fractionations for intermediate compositions of most ortho-, ring-, chain-, and sheet-silicates.

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. © 2012 Society for

Frequency modulation spectroscopy with a THz quantum-cascade laser.

PubMed

Eichholz, R; Richter, H; Wienold, M; Schrottke, L; Hey, R; Grahn, H T; Hübers, H-W

2013-12-30

We report on a terahertz spectrometer for high-resolution molecular spectroscopy based on a quantum-cascade laser. High-frequency modulation (up to 50 MHz) of the laser driving current produces a simultaneous modulation of the frequency and amplitude of the laser output. The modulation generates sidebands, which are symmetrically positioned with respect to the laser carrier frequency. The molecular transition is probed by scanning the sidebands across it. In this way, the absorption and the dispersion caused by the molecular transition are measured. The signals are modeled by taking into account the simultaneous modulation of the frequency and amplitude of the laser emission. This allows for the determination of the strength of the frequency as well as amplitude modulation of the laser and of molecular parameters such as pressure broadening.