Review of footnotes and annotations to the 1949–2013 tables of standard atomic weights and tables of isotopic compositions of the elements (IUPAC Technical Report)

USGS Publications Warehouse

Coplen, Tyler B.; Holden, Norman E.

2016-01-01

The Commission on Isotopic Abundances and Atomic Weights uses annotations given in footnotes that are an integral part of the Tables of Standard Atomic Weights to alert users to the possibilities of quite extraordinary occurrences, as well as sources with abnormal atomic-weight values outside an otherwise acceptable range. The basic need for footnotes to the Standard Atomic Weights Table and equivalent annotations to the Table of Isotopic Compositions of the Elements arises from the necessity to provide users with information that is relevant to one or more elements, but that cannot be provided using numerical data in columns. Any desire to increase additional information conveyed by annotations to these Tables is tempered by the need to preserve a compact format and a style that can alert users, who would not be inclined to consult either the last full element-by-element review or the full text of a current Standard Atomic Weights of the Elements report. Since 1989, the footnotes of the Tables of Standard Atomic Weights and the annotations in column 5 of the Table of Isotopic Compositions of the Elements have been harmonized by use of three lowercase footnotes, “g”, “m”, and “r”, that signify geologically exceptionally specimens (“g”), modified isotopic compositions in material subjected to undisclosed or inadvertent isotopic fractionation (“m”), and the range in isotopic composition of normal terrestrial material prevents more precise atomic-weight value being given (“r”). As some elements are assigned intervals for their standard atomic-weight values (applies to 12 elements since 2009), footnotes “g” and “r” are no longer needed for these elements.

Compilation of minimum and maximum isotope ratios of selected elements in naturally occurring terrestrial materials and reagents

USGS Publications Warehouse

Coplen, T.B.; Hopple, J.A.; Böhlke, J.K.; Peiser, H.S.; Rieder, S.E.; Krouse, H.R.; Rosman, K.J.R.; Ding, T.; Vocke, R.D.; Revesz, K.M.; Lamberty, A.; Taylor, P.; De Bievre, P.

2002-01-01

Documented variations in the isotopic compositions of some chemical elements are responsible for expanded uncertainties in the standard atomic weights published by the Commission on Atomic Weights and Isotopic Abundances of the International Union of Pure and Applied Chemistry. This report summarizes reported variations in the isotopic compositions of 20 elements that are due to physical and chemical fractionation processes (not due to radioactive decay) and their effects on the standard atomic weight uncertainties. For 11 of those elements (hydrogen, lithium, boron, carbon, nitrogen, oxygen, silicon, sulfur, chlorine, copper, and selenium), standard atomic weight uncertainties have been assigned values that are substantially larger than analytical uncertainties because of common isotope abundance variations in materials of natural terrestrial origin. For 2 elements (chromium and thallium), recently reported isotope abundance variations potentially are large enough to result in future expansion of their atomic weight uncertainties. For 7 elements (magnesium, calcium, iron, zinc, molybdenum, palladium, and tellurium), documented isotope-abundance variations in materials of natural terrestrial origin are too small to have a significant effect on their standard atomic weight uncertainties. This compilation indicates the extent to which the atomic weight of an element in a given material may differ from the standard atomic weight of the element. For most elements given above, data are graphically illustrated by a diagram in which the materials are specified in the ordinate and the compositional ranges are plotted along the abscissa in scales of (1) atomic weight, (2) mole fraction of a selected isotope, and (3) delta value of a selected isotope ratio. There are no internationally distributed isotopic reference materials for the elements zinc, selenium, molybdenum, palladium, and tellurium. Preparation of such materials will help to make isotope ratio measurements among laboratories comparable. The minimum and maximum concentrations of a selected isotope in naturally occurring terrestrial materials for selected chemical elements reviewed in this report are given below: Isotope Minimum mole fraction Maximum mole fraction -------------------------------------------------------------------------------- 2H 0 .000 0255 0 .000 1838 7Li 0 .9227 0 .9278 11B 0 .7961 0 .8107 13C 0 .009 629 0 .011 466 15N 0 .003 462 0 .004 210 18O 0 .001 875 0 .002 218 26Mg 0 .1099 0 .1103 30Si 0 .030 816 0 .031 023 34S 0 .0398 0 .0473 37Cl 0 .240 77 0 .243 56 44Ca 0 .020 82 0 .020 92 53Cr 0 .095 01 0 .095 53 56Fe 0 .917 42 0 .917 60 65Cu 0 .3066 0 .3102 205Tl 0 .704 72 0 .705 06 The numerical values above have uncertainties that depend upon the uncertainties of the determinations of the absolute isotope-abundance variations of reference materials of the elements. Because reference materials used for absolute isotope-abundance measurements have not been included in relative isotope abundance investigations of zinc, selenium, molybdenum, palladium, and tellurium, ranges in isotopic composition are not listed for these elements, although such ranges may be measurable with state-of-the-art mass spectrometry. This report is available at the url: http://pubs.water.usgs.gov/wri014222.

Sediment Tracking Using Carbon and Nitrogen Stable Isotopes

NASA Astrophysics Data System (ADS)

Fox, J. F.; Papanicolaou, A.

2002-12-01

As landscapes are stripped of valuable, nutrient rich topsoils and streams are clouded with habitat degrading fine sediment, it becomes increasingly important to identify and mitigate erosive surfaces. Particle tracking using vegetative derived carbon (C) and nitrogen (N) isotopic signatures and carbon/nitrogen (C/N) atomic ratios offer a promising technique to identify such problematic sources. Consultants and researchers successfully use C, N, and other stable isotopes of water for hydrologic purposes, such as quantifying groundwater vs. surface water contribution to a hydrograph. Recently, C and N isotopes and C/N atomic ratios of sediment were used to determine sediment mass balance within estuarine environments. The current research investigates C and N isotopes and C/N atomic ratios of source sediment for two primary purposes: (1) to establish a blueprint methodology for estimating sediment source and erosion rates within a watershed using this isotopic technology coupled with mineralogy fingerprinting techniques, radionuclide transport monitoring, and erosion-transport models, and (2) to complete field studies of upland erosion processes, such as, solifluction, mass wasting, creep, fluvial erosion, and vegetative induced erosion. Upland and floodplain sediment profiles and riverine suspended sediment were sampled on two occasions, May 2002 and August 2002, in the upper Palouse River watershed of northern Idaho. Over 300 samples were obtained from deep intermountain valley (i.e. forest) and rolling crop field (i.e. agriculture) locations. Preliminary sample treatment was completed at the Washington State University Water Quality Laboratory where samples were dried, removed of organic constituents, and prepared for isotopic analysis. C and N isotope and C/N atomic ratio analyses was performed at the University of Idaho Natural Resources Stable Isotope Laboratory using a Costech 4010 Elemental Combustion System connected with a continuous flow inlet system to the Finnigan MAT Delta Plus isotope ratio mass spectrometer. Results indicate distinct N isotopic signatures and C/N atomic ratios for forest and agriculture sediment sources. In addition, unique C and N isotopic signatures and C/N atomic ratios exist within floodplain and upland surfaces, and within the 10 centimeter profiles of erosion and deposition locations. Suspended sediment analyses are preliminary at this time. Conclusions indicate that sediment C and N isotopic signature and C/N atomic ratio are dependent upon land use and soil moisture conditions, and will serve as a useful technique in quantifying erosive source rates and understanding upland erosion processes.

On the several molecules and nanostructures of water.

PubMed

Whitney, Cynthia Kolb

2012-01-01

This paper investigates the water molecule from a variety of viewpoints. Water can involve different isotopes of Hydrogen and Oxygen, it can form differently shaped isomer molecules, and, when frozen, it occupies space differently than most other substances do. The tool for conducting the investigation of all this is called 'Algebraic Chemistry'. This tool is a quantitative model for predicting the energy budget for all sorts of changes between different ionization states of atoms that are involved in chemical reactions and in changes of physical state. The model is based on consistent patterns seen in empirical data about ionization potentials, together with rational scaling laws that can interpolate and extrapolate for situations where no data are available. The results of the investigation of the water molecule include comments, both positive and negative, about technologies involving heavy water, poly water, Brown's gas, and cold fusion.

On the Several Molecules and Nanostructures of Water

PubMed Central

Whitney, Cynthia Kolb

2012-01-01

This paper investigates the water molecule from a variety of viewpoints. Water can involve different isotopes of Hydrogen and Oxygen, it can form differently shaped isomer molecules, and, when frozen, it occupies space differently than most other substances do. The tool for conducting the investigation of all this is called ‘Algebraic Chemistry’. This tool is a quantitative model for predicting the energy budget for all sorts of changes between different ionization states of atoms that are involved in chemical reactions and in changes of physical state. The model is based on consistent patterns seen in empirical data about ionization potentials, together with rational scaling laws that can interpolate and extrapolate for situations where no data are available. The results of the investigation of the water molecule include comments, both positive and negative, about technologies involving heavy water, poly water, Brown’s gas, and cold fusion. PMID:22312305

Reporting of nitrogen-isotope abundances (Technical Report)

USGS Publications Warehouse

Coplen, Tyler B.; Krouse, H.R.; Böhlke, John Karl

1992-01-01

To eliminate possible confusion in the reporting of nitrogen-isotope analyses, the Commission on Atomic Weights and Isotopic Abundances recommends that the value 272 be employed for the 14N/15N value of N2 in air for calculating atom percent 15N from measured δ15N values.

Isotope analysis in the transmission electron microscope.

PubMed

Susi, Toma; Hofer, Christoph; Argentero, Giacomo; Leuthner, Gregor T; Pennycook, Timothy J; Mangler, Clemens; Meyer, Jannik C; Kotakoski, Jani

2016-10-10

The Ångström-sized probe of the scanning transmission electron microscope can visualize and collect spectra from single atoms. This can unambiguously resolve the chemical structure of materials, but not their isotopic composition. Here we differentiate between two isotopes of the same element by quantifying how likely the energetic imaging electrons are to eject atoms. First, we measure the displacement probability in graphene grown from either 12 C or 13 C and describe the process using a quantum mechanical model of lattice vibrations coupled with density functional theory simulations. We then test our spatial resolution in a mixed sample by ejecting individual atoms from nanoscale areas spanning an interface region that is far from atomically sharp, mapping the isotope concentration with a precision better than 20%. Although we use a scanning instrument, our method may be applicable to any atomic resolution transmission electron microscope and to other low-dimensional materials.

Ar39 Detection at the 10-16 Isotopic Abundance Level with Atom Trap Trace Analysis

NASA Astrophysics Data System (ADS)

Jiang, W.; Williams, W.; Bailey, K.; Davis, A. M.; Hu, S.-M.; Lu, Z.-T.; O'Connor, T. P.; Purtschert, R.; Sturchio, N. C.; Sun, Y. R.; Mueller, P.

2011-03-01

Atom trap trace analysis, a laser-based atom counting method, has been applied to analyze atmospheric Ar39 (half-life=269yr), a cosmogenic isotope with an isotopic abundance of 8×10-16. In addition to the superior selectivity demonstrated in this work, the counting rate and efficiency of atom trap trace analysis have been improved by 2 orders of magnitude over prior results. The significant applications of this new analytical capability lie in radioisotope dating of ice and water samples and in the development of dark matter detectors.

Atomic weights of the elements--Review 2000 (IUPAC Technical Report)

USGS Publications Warehouse

de Laeter, John R.; Böhlke, John Karl; De Bièvre, P.; Hidaka, H.; Peiser, H.S.; Rosman, K.J.R.; Taylor, P.D.P.

2003-01-01

A consistent set of internationally accepted atomic weights has long been an essential aim of the scientific community because of the relevance of these values to science and technology, as well as to trade and commerce subject to ethical, legal, and international standards. The standard atomic weights of the elements are regularly evaluated, recommended, and published in updated tables by the Commission on Atomic Weights and Isotopic Abundances (CAWIA) of the International Union of Pure and Applied Chemistry (IUPAC). These values are invariably associated with carefully evaluated uncertainties. Atomic weights were originally determined by mass ratio measurements coupled with an understanding of chemical stoichiometry, but are now based almost exclusively on knowledge of the isotopic composition (derived from isotope-abundance ratio measurements) and the atomic masses of the isotopes of the elements. Atomic weights and atomic masses are now scaled to a numerical value of exactly 12 for the mass of the carbon isotope of mass number 12. Technological advances in mass spectrometry and nuclear-reaction energies have enabled atomic masses to be determined with a relative uncertainty of better than 1 ×10−7 . Isotope abundances for an increasing number of elements can be measured to better than 1 ×10−3 . The excellent precision of such measurements led to the discovery that many elements, in different specimens, display significant variations in their isotope-abundance ratios, caused by a variety of natural and industrial physicochemical processes. While such variations increasingly place a constraint on the uncertainties with which some standard atomic weights can be stated, they provide numerous opportunities for investigating a range of important phenomena in physical, chemical, cosmological, biological, and industrial processes. This review reflects the current and increasing interest of science in the measured differences between source-specific and even sample-specific atomic weights. These relative comparisons can often be made with a smaller uncertainty than is achieved in the best calibrated “absolute ” (=SI-traceable) atomic-weight determinations. Accurate determinations of the atomic weights of certain elements also influence the values of fundamental constants such as the Avogadro, Faraday, and universal gas constants. This review is in two parts: the first summarizes the development of the science of atomic-weight determinations during the 20th century; the second summarizes the changes and variations that have been recognized in the values and uncertainties of atomic weights, on an element-by-element basis, in the latter part of the 20th century.

Melting point of high-purity germanium stable isotopes

NASA Astrophysics Data System (ADS)

Gavva, V. A.; Bulanov, A. D.; Kut'in, A. M.; Plekhovich, A. D.; Churbanov, M. F.

2018-05-01

The melting point (Tm) of germanium stable isotopes 72Ge, 73Ge, 74Ge, 76Ge was determined by differential scanning calorimetry. With the increase in atomic mass of isotope the decrease in Tm is observed. The decrease was equal to 0.15 °C per the unit of atomic mass which qualitatively agrees with the value calculated by Lindemann formula accounting for the effect of "isotopic compression" of elementary cell.

Atomic weights of the elements 1999

USGS Publications Warehouse

Coplen, T.B.

2001-01-01

The biennial review of atomic-weight, Ar(E), determinations and other cognate data have resulted in changes for the standard atomic weights of the following elements: Presented are updated tables of the standard atomic weights and their uncertainties estimated by combining experimental uncertainties and terrestrial variabilities. In addition, this report again contains an updated table of relative atomic-mass values and half-lives of selected radioisotopes. Changes in the evaluated isotopic abundance values from those published in 1997 are so minor that an updated list will not be published for the year 1999. Many elements have a different isotopic composition in some nonterrestrial materials. Some recent data on parent nuclides that might affect isotopic abundances or atomic-weight values are included in this report for the information of the interested scientific community.

Combinatorial effects on clumped isotopes and their significance in biogeochemistry

NASA Astrophysics Data System (ADS)

Yeung, Laurence Y.

2016-01-01

The arrangement of isotopes within a collection of molecules records their physical and chemical histories. Clumped-isotope analysis interrogates these arrangements, i.e., how often rare isotopes are bound together, which in many cases can be explained by equilibrium and/or kinetic isotope fractionation. However, purely combinatorial effects, rooted in the statistics of pairing atoms in a closed system, are also relevant, and not well understood. Here, I show that combinatorial isotope effects are most important when two identical atoms are neighbors on the same molecule (e.g., O2, N2, and D-D clumping in CH4). When the two halves of an atom pair are either assembled with different isotopic preferences or drawn from different reservoirs, combinatorial effects cause depletions in clumped-isotope abundance that are most likely between zero and -1‰, although they could potentially be -10‰ or larger for D-D pairs. These depletions are of similar magnitude, but of opposite sign, to low-temperature equilibrium clumped-isotope effects for many small molecules. Enzymatic isotope-pairing reactions, which can have site-specific isotopic fractionation factors and atom reservoirs, should express this class of combinatorial isotope effect, although it is not limited to biological reactions. Chemical-kinetic isotope effects, which are related to a bond-forming transition state, arise independently and express second-order combinatorial effects related to the abundance of the rare isotope. Heteronuclear moeties (e.g., Csbnd O and Csbnd H), are insensitive to direct combinatorial influences, but secondary combinatorial influences are evident. In general, both combinatorial and chemical-kinetic factors are important for calculating and interpreting clumped-isotope signatures of kinetically controlled reactions. I apply this analytical framework to isotope-pairing reactions relevant to geochemical oxygen, carbon, and nitrogen cycling that may be influenced by combinatorial clumped-isotope effects. These isotopic signatures, manifest as either directly bound isotope ;clumps; or as features of a molecule's isotopic anatomy, are linked to molecular mechanisms and may eventually provide additional information about biogeochemical cycling on environmentally relevant spatial scales.

Cellular Metabolic Activity and the Oxygen and Hydrogen Stable Isotope Composition of Intracellular Water and Metabolites

NASA Astrophysics Data System (ADS)

Kreuzer-Martin, H. W.; Hegg, E. L.

2008-12-01

Intracellular water is an important pool of oxygen and hydrogen atoms for biosynthesis. Intracellular water is usually assumed to be isotopically identical to extracellular water, but an unexpected experimental result caused us to question this assumption. Heme O isolated from Escherichia coli cells grown in 95% H218O contained only a fraction of the theoretical value of labeled oxygen at a position where the O atom was known to be derived from water. In fact, fewer than half of the oxygen atoms were labeled. In an effort to explain this surprising result, we developed a method to determine the isotope ratios of intracellular water in cultured cells. The results of our experiments showed that during active growth, up to 70% of the oxygen atoms and 50% of the hydrogen atoms in the intracellular water of E. coli are generated during metabolism and can be isotopically distinct from extracellular water. The fraction of isotopically distinct atoms was substantially less in stationary phase and chilled cells, consistent with our hypothesis that less metabolically-generated water would be present in cells with lower metabolic activity. Our results were consistent with and explained the result of the heme O labeling experiment. Only about 40% of the O atoms on the heme O molecule were labeled because, presumably, only about 40% of the water inside the cells was 18O water that had diffused in from the culture medium. The rest of the intracellular water contained 16O atoms derived from either nutrients or atmospheric oxygen. To test whether we could also detect metabolically-derived hydrogen atoms in cellular constituents, we isolated fatty acids from log-phase and stationary phase E. coli and determined the H isotope ratios of individual fatty acids. The results of these experiments showed that environmental water contributed more H atoms to fatty acids isolated in stationary phase than to the same fatty acids isolated from log-phase cells. Stable isotope analyses of biomass of Bacillus subtilis, a Gram-positive bacterium, showed the same pattern. Rapidly-dividing cells derived fewer of their O and H atoms from environmental water than did more slowly-growing cells and spores. To test whether a eukaryotic cell, surrounded by only a membrane, would also maintain an isotopic gradient and a detectable percentage of metabolic water, we applied our approach to cultured rat fibroblasts. Preliminary results showed that approximately 50% of the O and H atoms in exponentially growing cells were derived from metabolic activity. In quiescent cells, metabolic activity generated approximately 25% of the O and H atoms in intracellular water. Thus far, the data we have obtained is consistent with the following model: (1) Intracellular water is composed of water that diffuses in from the extracellular environment and water that is created as a result of metabolic activity. (2) The relative amounts of environmental and metabolic water inside a cell are a function of the cell's metabolic activity. (3) The oxygen and hydrogen isotope ratios of cellular metabolites are a function of those of intracellular water, and therefore reflect the metabolic activity of the cell at the time of biosynthesis.

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.

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. 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. 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.

Isotopic Compositions of the Elements, 2001

NASA Astrophysics Data System (ADS)

Böhlke, J. K.; de Laeter, J. R.; De Bièvre, P.; Hidaka, H.; Peiser, H. S.; Rosman, K. J. R.; Taylor, P. D. P.

2005-03-01

The Commission on Atomic Weights and Isotopic Abundances of the International Union of Pure and Applied Chemistry completed its last review of the isotopic compositions of the elements as determined by isotope-ratio mass spectrometry in 2001. That review involved a critical evaluation of the published literature, element by element, and forms the basis of the table of the isotopic compositions of the elements (TICE) presented here. For each element, TICE includes evaluated data from the "best measurement" of the isotope abundances in a single sample, along with a set of representative isotope abundances and uncertainties that accommodate known variations in normal terrestrial materials. The representative isotope abundances and uncertainties generally are consistent with the standard atomic weight of the element Ar(E) and its uncertainty U[Ar(E)] recommended by CAWIA in 2001.

Isotopic Clues to Mars Crust-Atmosphere Interactions

NASA Image and Video Library

2016-09-29

Chemistry that takes place in the surface material on Mars can explain why particular xenon (Xe) and krypton (Kr) isotopes are more abundant in the Martian atmosphere than expected. The isotopes -- variants that have different numbers of neutrons -- are formed in the loose rocks and material that make up the regolith -- the surface layer down to solid rock. The chemistry begins when cosmic rays penetrate into the surface material. If the cosmic rays strike an atom of barium (Ba), the barium can lose one or more of its neutrons (n0). Atoms of xenon can pick up some of those neutrons – a process called neutron capture – to form the isotopes xenon-124 and xenon-126. In the same way, atoms of bromine (Br) can lose some of their neutrons to krypton, leading to the formation of krypton-80 and krypton-82 isotopes. These isotopes can enter the atmosphere when the regolith is disturbed by impacts and abrasion, allowing gas to escape. http://photojournal.jpl.nasa.gov/catalog/PIA20847

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

Detection of Metabolic Fluxes of O and H Atoms into Intracellular Water in Mammalian Cells

PubMed Central

Kreuzer, Helen W.; Quaroni, Luca; Podlesak, David W.; Zlateva, Theodora; Bollinger, Nikki; McAllister, Aaron; Lott, Michael J.; Hegg, Eric L.

2012-01-01

Metabolic processes result in the release and exchange of H and O atoms from organic material as well as some inorganic salts and gases. These fluxes of H and O atoms into intracellular water result in an isotopic gradient that can be measured experimentally. Using isotope ratio mass spectroscopy, we revealed that slightly over 50% of the H and O atoms in the intracellular water of exponentially-growing cultured Rat-1 fibroblasts were isotopically distinct from growth medium water. We then employed infrared spectromicroscopy to detect in real time the flux of H atoms in these same cells. Importantly, both of these techniques indicate that the H and O fluxes are dependent on metabolic processes; cells that are in lag phase or are quiescent exhibit a much smaller flux. In addition, water extracted from the muscle tissue of rats contained a population of H and O atoms that were isotopically distinct from body water, consistent with the results obtained using the cultured Rat-1 fibroblasts. Together these data demonstrate that metabolic processes produce fluxes of H and O atoms into intracellular water, and that these fluxes can be detected and measured in both cultured mammalian cells and in mammalian tissue. PMID:22848359

Fast, low-level detection of strontium-90 and strontium-89 in environmental samples by collinear resonance ionization spectroscopy

NASA Astrophysics Data System (ADS)

Monz, L.; Hohmann, R.; Kluge, H.-J.; Kunze, S.; Lantzsch, J.; Otten, E. W.; Passler, G.; Senne, P.; Stenner, J.; Stratmann, K.; Swendt, K.; Zimmer, K.; Herrmann, G.; Trautmann, N.; Walter, K.

1993-12-01

Environmental assessment in the wake of a nuclear accident requires the rapid determination of the radiotoxic isotopes 89Sr and 90Sr. Useful measurements must be able to detect 10 8 atoms in the presence of about 10 18 atoms of the stable, naturally occurring isotopes. This paper describes a new approach to this problem using resonance ionization spectroscopy in collinear geometry, combined with classical mass separation. After collection and chemical separation, the strontium from a sample is surface-ionized and the ions are accelerated to an energy of about 30 keV. Initially, a magnetic mass separator provides an isotopic selectivity of about 10 6. The ions are then neutralized by charge exchange and the resulting fast strontium atoms are selectively excited into high-lying atomic Rydberg states by narrow-band cw laser light in collinear geometry. The Rydberg atoms are then field-ionized and detected. Thus far, a total isotopic selectivity of S > 10 10 and an overall efficiency of ξ = 5 × 10 -6 have been achieved. The desired detection limit of 10 8 atoms 90Sr has been demonstrated with synthetic samples.

Equilibrium stable-isotope fractionation of thallium and mercury

NASA Astrophysics Data System (ADS)

Schauble, E. A.

2005-12-01

In this study first-principles quantum mechanical and empirical force-field models are used to estimate equilibrium mass-dependent isotopic fractionations among a variety of thallium and mercury compounds. High-precision MC-ICP-MS measurements have recently uncovered evidence of stable isotope fractionation for many elements, including 2-4‰ variability in the isotopic compositions of thallium[1] (atomic no. 81) and mercury[2] (atomic no. 80). The observed thallium- and mercury-isotope fractionations are remarkable, given that the magnitude of isotopic fractionation typically decreases as atomic number increases[3]. Stable isotope measurements could improve our understanding of geochemical and biogeochemical cycling of both elements, but little is known about the mechanisms driving these fractionations. A better understanding of the chemical processes controlling stable isotope compositions could help maximize the utility of these new geochemical tracers. Standard equilibrium stable isotope fractionation theory holds that the energy driving fractionation comes from isotopic effects on vibrational frequencies, which have generally not been measured. In the present study both quantum-mechanical and empirical force fields are used to estimate unknown frequencies. Results suggest that thallium and mercury fractionations of ≥ 0.5‰ are likely during the relevant redox reactions Tl+ ↔ Tl3+ and HgO ↔ Hg2+. Methyl-mercury and mercury-halide compounds like CH3HgCl will have ~ 1‰ higher 202Hg/198Hg than atomic vapor at room temperature. Fractionations between coexisting Hg2+ species appear to be much smaller, however. 205Tl/203Tl in Tl(H2O)_63+ is predicted to be ~0.5‰ higher than in coexisting Tl+-bearing substances. This result is in qualitative agreement with data from ferromanganese crusts [1], suggesting that Tl3+ in manganese-oxides will have higher 205Tl/203Tl than aqueous Tl+. Equilibrium fractionations for both elements are much smaller than the observed range of isotopic fractionations, however, which could point to a major role for kinetic-fractionation or Rayleigh-like distillation processes. Refs.: [1] Rehämper et al. (2002) EPSL 197:65. [2] Xie et al. (2005) J. Anal. Atomic Spectrom. 20:515. [3] Bigeleisen and Mayer (1947) J. Chem. Phys. 15:261.

Hg-201 (+) CO-Magnetometer for HG-199(+) Trapped Ion Space Atomic Clocks

NASA Technical Reports Server (NTRS)

Burt, Eric A. (Inventor); Taghavi, Shervin (Inventor); Tjoelker, Robert L. (Inventor)

2011-01-01

Local magnetic field strength in a trapped ion atomic clock is measured in real time, with high accuracy and without degrading clock performance, and the measurement is used to compensate for ambient magnetic field perturbations. First and second isotopes of an element are co-located within the linear ion trap. The first isotope has a resonant microwave transition between two hyperfine energy states, and the second isotope has a resonant Zeeman transition. Optical sources emit ultraviolet light that optically pump both isotopes. A microwave radiation source simultaneously emits microwave fields resonant with the first isotope's clock transition and the second isotope's Zeeman transition, and an optical detector measures the fluorescence from optically pumping both isotopes. The second isotope's Zeeman transition provides the measure of magnetic field strength, and the measurement is used to compensate the first isotope's clock transition or to adjust the applied C-field to reduce the effects of ambient magnetic field perturbations.

Isotopic compositions of the elements, 2001

USGS Publications Warehouse

Böhlke, J.K.; De Laeter, J. R.; De Bievre, P.; Hidaka, H.; Peiser, H.S.; Rosman, K.J.R.; Taylor, P.D.P.

2005-01-01

The Commission on Atomic Weights and Isotopic Abundances of the International Union of Pure and Applied Chemistry completed its last review of the isotopic compositions of the elements as determined by isotope-ratio mass spectrometry in 2001. That review involved a critical evaluation of the published literature, element by element, and forms the basis of the table of the isotopic compositions of the elements (TICE) presented here. For each element, TICE includes evaluated data from the “best measurement” of the isotope abundances in a single sample, along with a set of representative isotope abundances and uncertainties that accommodate known variations in normal terrestrial materials. The representative isotope abundances and uncertainties generally are consistent with the standard atomic weight of the element Ar(E)">Ar(E)Ar(E) and its uncertainty U[Ar(E)]">U[Ar(E)]U[Ar(E)] recommended by CAWIA in 2001.

Isotope effects on desorption kinetics of hydrogen isotopes implanted into stainless steel by glow discharge

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

Matsuyama, M.; Kondo, M.; Noda, N.

2015-03-15

In a fusion device the control of fuel particles implies to know the desorption rate of hydrogen isotopes by the plasma-facing materials. In this paper desorption kinetics of hydrogen isotopes implanted into type 316L stainless steel by glow discharge have been studied by experiment and numerical calculation. The temperature of a maximum desorption rate depends on glow discharge time and heating rate. Desorption spectra observed under various experimental conditions have been successfully reproduced by numerical simulations that are based on a diffusion-limited process. It is suggested, therefore, that desorption rate of a hydrogen isotope implanted into the stainless steel ismore » limited by a diffusion process of hydrogen isotope atoms in bulk. Furthermore, small isotope effects were observed for the diffusion process of hydrogen isotope atoms. (authors)« less

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 organic-functionalized semiconductor interface. Aside from their use as probes for surface structure and dynamics, atomic beam sources are also demonstrated to enable the efficient separation of gaseous mixtures of isotopes by means of diffraction and differential condensation. In the former method, the kinematic conditions for elastic diffraction result in an incident beam of natural abundance neon diffracting into isotopically distinct angles, resulting in the enrichment of a desired isotope; this purification can be improved by exploiting the difference in arrival times of the two isotopes at a given final angle. In the latter method, the identical incident velocities of coexpanded isotopes lead to minor but important differences in their incident kinetic energies, and thus their probability of adsorbing on a sufficiently cold surface, resulting in preferential condensation of a given isotope that depends on the energy of the incident beam. Both of these isotope separation techniques are made possible by the narrow velocity distribution and velocity seeding effect offered only by high-Mach number supersonic beam sources. These experiments underscore the utility of supersonically expanded atomic and molecular beam sources as both extraordinarily precise probes of surface structure and dynamics and as a means for high-throughput, non-dissociative isotopic enrichment methods.

Isotope exchange in oxide-containing catalyst

NASA Technical Reports Server (NTRS)

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

1989-01-01

A method of exchanging rare-isotope oxygen for common-isotope oxygen in the top several layers of an oxide-containing catalyst is disclosed. A sample of an oxide-containing catalyst is exposed to a flowing stream of reducing gas in an inert carrier gas at a temperature suitable for the removal of the reactive common-isotope oxygen atoms from the surface layer or layers of the catalyst without damaging the catalyst structure. The reduction temperature must be higher than any at which the catalyst will subsequently operate. Sufficient reducing gas is used to allow removal of all the reactive common-isotope oxygen atoms in the top several layers of the catalyst. The catalyst is then reoxidized with the desired rare-isotope oxygen in sufficient quantity to replace all of the common-isotope oxygen that was removed.

Method and apparatus for noble gas atom detection with isotopic selectivity

DOEpatents

Hurst, G. Samuel; Payne, Marvin G.; Chen, Chung-Hsuan; Parks, James E.

1984-01-01

Apparatus and methods of operation are described for determining, with isotopic selectivity, the number of noble gas atoms in a sample. The analysis is conducted within an evacuated chamber which can be isolated by a valve from a vacuum pumping system capable of producing a pressure of 10.sup.-8 Torr. Provision is made to pass pulses of laser beams through the chamber, these pulses having wavelengths appropriate for the resonance ionization of atoms of the noble gas under analysis. A mass filter within the chamber selects ions of a specific isotope of the noble gas, and means are provided to accelerate these selected ions sufficiently for implantation into a target. Specific types of targets are discussed. An electron measuring device produces a signal relatable to the number of ions implanted into the target and thus to the number of atoms of the selected isotope of the noble gas removed from the gas sample. The measurement can be continued until a substantial fraction, or all, of the atoms in the sample have been counted. Furthermore, additional embodiments of the apparatus are described for bunching the atoms of a noble gas for more rapid analysis, and for changing the target for repetitive cycling of the gas in the chamber. The number of repetitions of the cyclic steps depend upon the concentration of the isotope of interest, the separative efficiency of the mass filter, etc. The cycles are continued until a desired selectivity is achieved. Also described are components and a method of operation for a pre-enrichment operation for use when an introduction of a total sample would elevate the pressure within the chamber to levels in excess of those for operation of the mass filter, specifically a quadrupole mass filter. Specific examples of three noble gas isotope analyses are described.

Measurement of the oxygen isotopic composition of nitrate in seawater and freshwater using the denitrifier method

USGS Publications Warehouse

Casciotti, K.L.; Sigman, D.M.; Hastings, M. Galanter; Böhlke, J.K.; Hilkert, A.

2002-01-01

We report a novel method for measurement of the oxygen isotopic composition (18O/16O) of nitrate (NO3-) from both seawater and freshwater. The denitrifier method, based on the isotope ratio analysis of nitrous oxide generated from sample nitrate by cultured denitrifying bacteria, has been described elsewhere for its use in nitrogen isotope ratio (15N/14N) analysis of nitrate.1Here, we address the additional issues associated with 18O/16O analysis of nitrate by this approach, which include (1) the oxygen isotopic difference between the nitrate sample and the N2O analyte due to isotopic fractionation associated with the loss of oxygen atoms from nitrate and (2) the exchange of oxygen atoms with water during the conversion of nitrate to N2O. Experiments with 18O-labeled water indicate that water exchange contributes less than 10%, and frequently less than 3%, of the oxygen atoms in the N2O product for Pseudomonas aureofaciens. In addition, both oxygen isotope fractionation and oxygen atom exchange are consistent within a given batch of analyses. The analysis of appropriate isotopic reference materials can thus be used to correct the measured 18O/16O ratios of samples for both effects. This is the first method tested for 18O/16O analysis of nitrate in seawater. Benefits of this method, relative to published freshwater methods, include higher sensitivity (tested down to 10 nmol and 1 μM NO3-), lack of interference by other solutes, and ease of sample preparation.

ATTA - A New Method of Ultrasensitive Trace-Isotope Analysis

NASA Astrophysics Data System (ADS)

Lu, Z.-T.; Bailey, K.; Chen, C. Y.; Du, X.; Li, Y. M.; O'Connor, T. P.; Young, L.; Winkler, G.

2000-10-01

We have developed a new method of ultrasensitive trace-isotope analysis based upon the technique of laser manipulation of neutral atoms [1]. This new method allows us to count individual 85Kr and 81Kr atoms present in a natural krypton sample with isotopic abundances in the range of 10-11 and 10-13, respectively. Isotope analysis of 81Kr can be used to date polar ice, and 85Kr is a tracer used in monitoring nuclear wastes. In this experiment metastable Kr atoms were produced in a discharge, decelerated via the Zeeman slowing technique, and captured by a Magneto-Optical Trap where the atoms were counted by measuring their fluorescence. At present our system is capable of counting, in average, one 81Kr atom for about 12 minutes with a total efficiency of 2x10-7. We are currently working to improve our system efficiency by applying cryogenic cooling to the Kr atoms in the discharge region and by recirculating the gas in the vacuum system. This method can be used to analyze many other isotope tracers for a wide range of applications including measuring solar neutrino flux, searching for exotic particles, tracing atmospheric and oceanic currents, archeological and geological dating, medical diagnostics, monitoring fission products in the environment for nuclear waste management, etc. This work is supported by the U.S. Department of Energy, Nuclear Physics Division; L.Young is supported by the Office of Basic Energy Sciences, Division of Chemical Sciences (Contract W-31-109-ENG-38). [1] C.Y. Chen et. al., Science 286, 1139 (1999).

The Pressure Dependence of Oxygen Isotope Exchange Rates Between Solution and Apical Oxygen Atoms on the [UO2(OH)4]2- Ion

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

Harley, Steven J.; Ohlin, C. André; Johnson, Rene L.

2011-04-06

Under pressure: The pressure dependence of isotope exchange rate was determined for apical oxygen atoms in the [UO2(OH)4]2-(aq) ion (see picture). The results can be interpreted to indicate an associative character of the reaction.

Search for variation of fundamental constants and violations of fundamental symmetries using isotope comparisons

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

Berengut, J. C.; Flambaum, V. V.; Kava, E. M.

2011-10-15

Atomic microwave clocks based on hyperfine transitions, such as the caesium standard, tick with a frequency that is proportional to the magnetic moment of the nucleus. This magnetic moment varies strongly between isotopes of the same atom, while all atomic electron parameters remain the same. Therefore the comparison of two microwave clocks based on different isotopes of the same atom can be used to constrain variation of fundamental constants. In this paper, we calculate the neutron and proton contributions to the nuclear magnetic moments, as well as their sensitivity to any potential quark-mass variation, in a number of isotopes ofmore » experimental interest including {sup 201,199}Hg and {sup 87,85}Rb, where experiments are underway. We also include a brief treatment of the dependence of the hyperfine transitions to variation in nuclear radius, which in turn is proportional to any change in quark mass. Our calculations of expectation values of proton and neutron spin in nuclei are also needed to interpret measurements of violations of fundamental symmetries.« less

Laser photochemical lead isotopes separation for harmless nuclear power engineering

NASA Astrophysics Data System (ADS)

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

2016-09-01

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

Isotope reference materials

USGS Publications Warehouse

Coplen, Tyler B.

2010-01-01

Measurement of the same isotopically homogeneous sample by any laboratory worldwide should yield the same isotopic composition within analytical uncertainty. International distribution of light element isotopic reference materials by the International Atomic Energy Agency and the U.S. National Institute of Standards and Technology enable laboratories to achieve this goal.

Heavy atom labeled nucleotides for measurement of kinetic isotope effects.

PubMed

Weissman, Benjamin P; Li, Nan-Sheng; York, Darrin; Harris, Michael; Piccirilli, Joseph A

2015-11-01

Experimental analysis of kinetic isotope effects represents an extremely powerful approach for gaining information about the transition state structure of complex reactions not available through other methodologies. The implementation of this approach to the study of nucleic acid chemistry requires the synthesis of nucleobases and nucleotides enriched for heavy isotopes at specific positions. In this review, we highlight current approaches to the synthesis of nucleic acids enriched site specifically for heavy oxygen and nitrogen and their application in heavy atom isotope effect studies. This article is part of a special issue titled: Enzyme Transition States from Theory and Experiment. Copyright © 2015 Elsevier B.V. All rights reserved.

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).

Impact of isotopic disorders on thermal transport properties of nanotubes and nanowires

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

Sun, Tao; Kang, Wei; Wang, Jianxiang, E-mail: jxwang@pku.edu.cn

2015-01-21

We present a one-dimensional lattice model to describe thermal transport in isotopically doped nanotubes and nanowires. The thermal conductivities thus predicted, as a function of isotopic concentration, agree well with recent experiments and other simulations. Our results display that for any given concentration of isotopic atoms in a lattice without sharp atomic interfaces, the maximum thermal conductivity is attained when isotopic atoms are placed regularly with an equal space, whereas the minimum is achieved when they are randomly inserted with a uniform distribution. Non-uniformity of disorder can further tune the thermal conductivity between the two values. Moreover, the dependence ofmore » the thermal conductivity on the nanoscale feature size becomes weak at low temperature when disorder exists. In addition, when self-consistent thermal reservoirs are included to describe diffusive nanomaterials, the thermal conductivities predicted by our model are in line with the results of macroscopic theories with an interfacial effect. Our results suggest that the disorder provides an additional freedom to tune the thermal properties of nanomaterials in many technological applications including nanoelectronics, solid-state lighting, energy conservation, and conversion.« less

Ion current as a precise measure of the loading rate of a magneto-optical trap

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

Jiang, W.; Bailey, K.; Lu, Z. -T.

2014-01-01

We have demonstrated that the ion current resulting from collisions between metastable krypton atoms in a magneto-optical trap can be used to precisely measure the trap loading rate. We measured both the ion current of the abundant isotope Kr-83 (isotopic abundance = 11%) and the single-atom counting rate of the rare isotope Kr-85 (isotopic abundance similar to 1 x 10(-11)), and found the two quantities to be proportional at a precision level of 0.9%. This work results in a significant improvement in using the magneto-optical trap as an analytical tool for noble-gas isotope ratio measurements, and will benefit both atomicmore » physics studies and applications in the earth sciences. (C) 2014 Optical Society of America« less

Continental sedimentary processes decouple Nd and Hf isotopes

NASA Astrophysics Data System (ADS)

Garçon, Marion; Chauvel, Catherine; France-Lanord, Christian; Huyghe, Pascale; Lavé, Jérôme

2013-11-01

The neodymium and hafnium isotopic compositions of most crustal and mantle rocks correlate to form the "Terrestrial Array". However, it is now well established that whereas coarse detrital sediments follow this trend, fine-grained oceanic sediments have high Hf ratios relative to their Nd isotopic ratios. It remains uncertain whether this "decoupling" of the two isotopic systems only occurs in the oceanic environment or if it is induced by sedimentary processes in continental settings. In this study, the hafnium and neodymium isotopic compositions of sediments in large rivers is expressly used to constrain the behavior of the two isotopic systems during erosion and sediment transport from continent to ocean. We report major and trace element concentrations together with Nd and Hf isotopic compositions of bedloads, suspended loads and river banks from the Ganges River and its tributaries draining the Himalayan Range i.e. the Karnali, the Narayani, the Kosi and the Marsyandi Rivers. The sample set includes sediments sampled within the Himalayan Range in Nepal, at the Himalayan mountain front, and also downstream on the floodplain and at the outflow of the Ganges in Bangladesh. Results show that hydrodynamic sorting of minerals explains the entire Hf isotopic range, i.e. more than 10 εHf units, observed in the river sediments but does not affect the Nd isotopic composition. Bedloads and bank sediments have systematically lower εHf values than suspended loads sampled at the same location. Coarse-grained sediments lie below or on the Terrestrial Array in an εHf vs. εNd diagram. In contrast, fine-grained sediments, including most of the suspended loads, deviate from the Terrestrial Array toward higher εHf relative to their εNd, as is the case for oceanic terrigenous clays. The observed Nd-Hf decoupling is explained by mineralogical sorting processes that enrich bottom sediments in coarse and dense minerals, including unradiogenic zircons, while surface sediments are enriched in fine material with radiogenic Hf signatures. The data also show that Nd-Hf isotopic decoupling increases with sediment transport in the floodplain to reach its maximum at the river mouth. This implies that the Nd-Hf isotopic decoupling observed in worldwide oceanic clays and river sediments is likely to have the same origin. Finally, we estimated the Nd-Hf isotopic composition of the present-day mantle if oceanic sediments had never been subducted and conclude that the addition of oceanic sediments with their anomalous Nd-Hf isotopic compositions has slowly shifted the composition of the Earth's mantle towards more radiogenic Hf values through time.

Nuclear Data on the WWW

NASA Astrophysics Data System (ADS)

Firestone, Richard B.; Chu, S. Y. Frank; Ekstrom, L. Peter; Wu, Shiu-Chin; Singh, Balraj

1997-10-01

The Isotopes Project is developing Internet home pages to provide data for radioactive decay, nuclear structure, nuclear astrophysics, spontaneous fission, thermal neutron capture, and atomic masses. These home pages can be accessed from the Table of Isotopes home page at http://isotopes.lbl.gov/isotopes/toi.html. Data from the Evaluated Nuclear Structure Data File (ENSDF) is now available on the WWW in Nuclear Data Sheet style tables, complete with comments and hypertext linked footnotes. Bibliographic information from the Nuclear Science Reference (NSR) file can be searched on the WWW by combinations of author, A, Z, reaction, and various keywords. Decay gamma-ray data from several databases can be searched by energy. The Table of Superdeformed Nuclear Bands and Fission Isomers is continously updated. Reaction rates from Hoffman and Woosley and from Thielemann, fission yields from England and Rider, thermal neutron cross-sections from BNL-325, atomic masses from Audi, and skeleton scheme drawings and nuclear charts from the Table of Isotopes are among the information available through these websites. The nuclear data home pages are accessed by over 3500 different users each month.

Isolating and moving single atoms using silicon nanocrystals

DOEpatents

Carroll, Malcolm S.

2010-09-07

A method is disclosed for isolating single atoms of an atomic species of interest by locating the atoms within silicon nanocrystals. This can be done by implanting, on the average, a single atom of the atomic species of interest into each nanocrystal, and then measuring an electrical charge distribution on the nanocrystals with scanning capacitance microscopy (SCM) or electrostatic force microscopy (EFM) to identify and select those nanocrystals having exactly one atom of the atomic species of interest therein. The nanocrystals with the single atom of the atomic species of interest therein can be sorted and moved using an atomic force microscope (AFM) tip. The method is useful for forming nanoscale electronic and optical devices including quantum computers and single-photon light sources.

Using stable isotopes to monitor forms of sulfur during desulfurization processes: A quick screening method

USGS Publications Warehouse

Liu, Chao-Li; Hackley, Keith C.; Coleman, D.D.; Kruse, C.W.

1987-01-01

A method using stable isotope ratio analysis to monitor the reactivity of sulfur forms in coal during thermal and chemical desulfurization processes has been developed at the Illinois State Geological Survey. The method is based upon the fact that a significant difference exists in some coals between the 34S/32S ratios of the pyritic and organic sulfur. A screening method for determining the suitability of coal samples for use in isotope ratio analysis is described. Making these special coals available from coal sample programs would assist research groups in sorting out the complex sulfur chemistry which accompanies thermal and chemical processing of high sulfur coals. ?? 1987.

Nuclear energy in the service of biomedicine: the U.S. Atomic Energy Commission's radioisotope program, 1946-1950.

PubMed

Creager, Angela N H

2006-01-01

The widespread adoption of radioisotopes as tools in biomedical research and therapy became one of the major consequences of the "physicists' war" for postwar life science. Scientists in the Manhattan Project, as part of their efforts to advocate for civilian uses of atomic energy after the war, proposed using infrastructure from the wartime bomb project to develop a government-run radioisotope distribution program. After the Atomic Energy Bill was passed and before the Atomic Energy Commission (AEC) was formally established, the Manhattan Project began shipping isotopes from Oak Ridge. Scientists and physicians put these reactor-produced isotopes to many of the same uses that had been pioneered with cyclotron-generated radioisotopes in the 1930s and early 1940s. The majority of early AEC shipments were radioiodine and radiophosphorus, employed to evaluate thyroid function, diagnose medical disorders, and irradiate tumors. Both researchers and politicians lauded radioisotopes publicly for their potential in curing diseases, particularly cancer. However, isotopes proved less successful than anticipated in treating cancer and more successful in medical diagnostics. On the research side, reactor-generated radioisotopes equipped biologists with new tools to trace molecular transformations from metabolic pathways to ecosystems. The U.S. government's production and promotion of isotopes stimulated their consumption by scientists and physicians (both domestic and abroad), such that in the postwar period isotopes became routine elements of laboratory and clinical use. In the early postwar years, radioisotopes signified the government's commitment to harness the atom for peace, particularly through contributions to biology, medicine, and agriculture.

Large disparity between gallium and antimony self-diffusion in gallium antimonide.

PubMed

Bracht, H; Nicols, S P; Walukiewicz, W; Silveira, J P; Briones, F; Haller, E E

2000-11-02

The most fundamental mass transport process in solids is self-diffusion. The motion of host-lattice ('self-') atoms in solids is mediated by point defects such as vacancies or interstitial atoms, whose formation and migration enthalpies determine the kinetics of this thermally activated process. Self-diffusion studies also contribute to the understanding of the diffusion of impurities, and a quantitative understanding of self- and foreign-atom diffusion in semiconductors is central to the development of advanced electronic devices. In the past few years, self-diffusion studies have been performed successfully with isotopically controlled semiconductor heterostructures of germanium, silicon, gallium arsenide and gallium phosphide. Self-diffusion studies with isotopically controlled GaAs and GaP have been restricted to Ga self-diffusion, as only Ga has two stable isotopes, 69Ga and 71Ga. Here we report self-diffusion studies with an isotopically controlled multilayer structure of crystalline GaSb. Two stable isotopes exist for both Ga and Sb, allowing the simultaneous study of diffusion on both sublattices. Our experiments show that near the melting temperature, Ga diffuses more rapidly than Sb by over three orders of magnitude. This surprisingly large difference in atomic mobility requires a physical explanation going beyond standard diffusion models. Combining our data for Ga and Sb diffusion with related results for foreign-atom diffusion in GaSb (refs 8, 9), we conclude that the unusually slow Sb diffusion in GaSb is a consequence of reactions between defects on the Ga and Sb sublattices, which suppress the defects that are required for Sb diffusion.

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.

Atomic weights of the elements 1999

USGS Publications Warehouse

Coplen, T.B.

2001-01-01

The biennial review of atomic-weight, Ar(E), determinations and other cognate data have resulted in changes for the standard atomic weights of the following elements: from to nitrogen 14.006 74??0.000 07 14.0067??0.0002 sulfur 32.066??0.006 32.065??0.005 chlorine 35.4527??0.0009 35.453??0.002 germanium 72.61??0.02 72.64??0.01 xenon 131.29??0.02 131.293??0.006 erbium 167.26??0.03 167.259??0.003 uranium 238.0289??0.0001 238.028 91??0.000 03 Presented are updated tables of the standard atomic weights and their uncertainties estimated by combining experimental uncertainties and terrestrial variabilities. In addition, this report again contains an updated table of relative atomic mass values and half-lives of selected radioisotopes. Changes in the evaluated isotopic abundance values from those published in 1997 are so minor that an updated list will not be published for the year 1999. Many elements have a different isotopic composition in some nonterrestrial materials. Some recent data on parent nuclides that might affect isotopic abundances or atomic-weight values are included in this report for the information of the interested scientific community. ?? 2001 American Institute of Physics.

RADIOACTIVE ELEMENTS IN THE STANDARD ATOMIC WEIGHTS TABLE

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

Holden, N.E.; Holden, N.; Holden,N.E.

2011-07-27

In the 1949 Report of the Atomic Weights Commission, a series of new elements were added to the Atomic Weights Table. Since these elements had been produced in the laboratory and were not discovered in nature, the atomic weight value of these artificial products would depend upon the production method. Since atomic weight is a property of an element as it occurs in nature, it would be incorrect to assign an atomic weight value to that element. As a result of that discussion, the Commission decided to provide only the mass number of the most stable (or longest-lived) known isotopemore » as the number to be associated with these entries in the Atomic Weights Table. As a function of time, the mass number associated with various elements has changed as longer-lived isotopes of a particular element has been found in nature, or as improved half-life values of an element's isotopes might cause a shift in the longest-lived isotope from one mass to another. In the 1957 Report of the Atomic Weights Commission, it was decided to discontinue the listing of the mass number in the Atomic Weights Table on the grounds that the kind of information supplied by the mass number is inconsistent with the primary purpose of the Table, i.e., to provide accurate values of 'these constants' for use in various chemical calculations. In addition to the Table of Atomic Weights, the Commission included an auxiliary Table of Radioactive Elements for the first time, where the entry would be the isotope of that element which was the most stable, i.e., the one with the longest known half-life. In their 1973 Report, the Commission noted that the users of the main Table of Atomic Weights were dissatisfied with the omission of values for some elements in that Table and it was decided to reintroduce the mass number for the radioactive elements into the main Table. In their 1983 Report, the Commission decided that radioactive elements were considered to lack a characteristic terrestrial isotopic composition, from which an atomic weight value could be calculated to five or more figure accuracy, without prior knowledge of the sample involved. These elements were again listed in the Atomic Weights Table with no further information, i.e., with no mass number or atomic weight value. For the elements, which have no stable characteristic terrestrial isotopic composition, the data on the half-lives and the relative atomic masses for the nuclides of interest for those elements have been evaluated. The values of the half-lives with their uncertainties are listed in the table. The uncertainties are given for the last digit quoted of the half-life and are given in parentheses. A half-life entry for the Table having a value and an uncertainty of 7 {+-} 3 is listed in the half-life column as 7 (3). The criteria to include data in this Table, is to be the same as it has been for over sixty years. It is the same criteria, which are used for all data that are evaluated for inclusion in the Standard Table of Atomic Weights. If a report of data is published in a peer-reviewed journal, that data is evaluated and considered for inclusion in the appropriate table of the biennial report of the Atomic Weights Commission. As better data becomes available in the future, the information that is contained in either of the Tables of Standard Atomic Weights or in the Table of Radioactive Elements may be modified. It should be noted that the appearance of any datum in the Table of the Radioactive Elements is merely for the purposes of calculating an atomic mass value for any sample of a radioactive material, which might have a variety of isotopic compositions and it has no implication as to the priority for claiming discovery of a given element and is not intended to. The atomic mass values have been taken primarily from the 2003 Atomic Mass Table. Mass values for those radioisotopes that do not appear in the 2003 Atomic mass Table have been taken from preliminary data of the Atomic Mass Data Center. Most of the quoted half-lives.« less

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

Evaluation of on-line pyrolysis coupled to isotope ratio mass spectrometry for the determination of position-specific (13)C isotope composition of short chain n-alkanes (C6-C12).

PubMed

Gilbert, Alexis; Yamada, Keita; Yoshida, Naohiro

2016-06-01

We measured (13)C intramolecular isotopic composition of commercially available short-chain hydrocarbons (n-C6-n-C12) using (13)C-NMR. Results show that the main variation is between the terminal and the sub-terminal C-atom positions. Site-preference (difference in δ(13)C values between terminal and sub-terminal C-atom positions) among all the samples varies between -12.2‰ and +8.4‰. Comparison of these results with those obtained using on-line pyrolysis coupled with GC-C-IRMS show that the thermal cracking of hydrocarbons occurs with a good isotopic fidelity between terminal and sub-terminal C-atom positions of the starting material and the related pyrolysis products (methane and ethylene). On-line pyrolysis coupled with GC-C-IRMS can thus be used for tracing hydrocarbons biogeochemical processes. Copyright © 2016 Elsevier B.V. All rights reserved.

Equation-of-State Scaling Factors

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

Scannapieco, Anthony J.

2016-06-28

Equation-of-State scaling factors are needed when using a tabular EOS in which the user de ned material isotopic fractions di er from the actual isotopic fractions used by the table. Additionally, if a material is dynamically changing its isotopic structure, then an EOS scaling will again be needed, and will vary in time and location. The procedure that allows use of a table to obtain information about a similar material with average atomic mass Ms and average atomic number Zs is described below. The procedure is exact for a fully ionized ideal gas. However, if the atomic number is replacemore » by the e ective ionization state the procedure can be applied to partially ionized material as well, which extends the applicability of the scaling approximation continuously from low to high temperatures.« less

The Inglorious Death of Jumbo

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

Meade, Roger Allen

In the summer of 1944, J. Robert Oppenheimer and Los Alamos faced a crisis. An isotopic impurity in Plutonium rendered the metal unusable in a gun-assembled atomic bomb (i.e., Little Boy). Making this situation worse was a shortage of Uranium. The combination of these two problems threatened the entire wartime project. The answer to this dilemma, in part, was to develop a novel assembly method for Plutonium using the supersonic shock waves created by several tons of high explosives to compress a ball of Plutonium into a supercritical state. Since this method, implosion, was not much more than a theoreticalmore » construct, the Trinity test was devised to proof test the process. Given the speculative nature of implosion, Trinity was a gamble of sorts. If the test failed (i.e., little or no nuclear yield), the blast of the high explosives would scatter the scarce and expensive Plutonium over the surrounding desert. Since the probability of failure remained high into the early summer of 1945, some method of containing a failed nuclear explosion was needed. Jumbo was the answer.« less

A (201)Hg+ Comagnetometer for (199)Hg+ Trapped Ion Space Atomic Clocks

NASA Technical Reports Server (NTRS)

Burt, Eric A.; Taghavi, Shervin; Tjoelker, Robert L.

2011-01-01

A method has been developed for unambiguously measuring the exact magnetic field experienced by trapped mercury ions contained within an atomic clock intended for space applications. In general, atomic clocks are insensitive to external perturbations that would change the frequency at which the clocks operate. On a space platform, these perturbative effects can be much larger than they would be on the ground, especially in dealing with the magnetic field environment. The solution is to use a different isotope of mercury held within the same trap as the clock isotope. The magnetic field can be very accurately measured with a magnetic-field-sensitive atomic transition in the added isotope. Further, this measurement can be made simultaneously with normal clock operation, thereby not degrading clock performance. Instead of using a conventional magnetometer to measure ambient fields, which would necessarily be placed some distance away from the clock atoms, first order field-sensitive atomic transition frequency changes in the atoms themselves determine the variations in the magnetic field. As a result, all ambiguity over the exact field value experienced by the atoms is removed. Atoms used in atomic clocks always have an atomic transition (often referred to as the clock transition) that is sensitive to magnetic fields only in second order, and usually have one or more transitions that are first-order field sensitive. For operating parameters used in the (199)Hg(+) clock, the latter can be five orders of magnitude or more sensitive to field fluctuations than the clock transition, thereby providing an unambiguous probe of the magnetic field strength.

Handbook explaining the fundamentals of nuclear and atomic physics

NASA Technical Reports Server (NTRS)

Hanlen, D. F.; Morse, W. J.

1969-01-01

Indoctrination document presents nuclear, reactor, and atomic physics in an easy, straightforward manner. The entire subject of nuclear physics including atomic structure ionization, isotopes, radioactivity, and reactor dynamics is discussed.

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.

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 lineshapes, as opposed to emission spectroscopy which requires higher plasma temperatures to be able to detect thermally excited emission. Improvements in laser and detection systems and spectroscopic techniques have allowed for isotopic measurements to be carried out at standoff distances under ambient atmospheric conditions, which have expanded the applicability of optical spectroscopy-based isotopic measurements to a variety of scientific fields. These technological advances offer an in-situ measurement capability that was previously not available. This review will focus on 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 knowledge/technological gaps identified from the current literature and suggestions for the future work.

Isotope scattering and phonon thermal conductivity in light atom compounds: LiH and LiF

DOE PAGES

Lindsay, Lucas R.

2016-11-08

Engineered isotope variation is a pathway toward modulating lattice thermal conductivity (κ) of a material through changes in phonon-isotope scattering. The effects of isotope variation on intrinsic thermal resistance is little explored, as varying isotopes have relatively small differences in mass and thus do not affect bulk phonon dispersions. However, for light elements isotope mass variation can be relatively large (e.g., hydrogen and deuterium). Using a first principles Peierls-Boltzmann transport equation approach the effects of isotope variance on lattice thermal transport in ultra-low-mass compound materials LiH and LiF are characterized. The isotope mass variance modifies the intrinsic thermal resistance viamore » modulation of acoustic and optic phonon frequencies, while phonon-isotope scattering from mass disorder plays only a minor role. This leads to some unusual cases where values of isotopically pure systems ( 6LiH, 7Li 2H and 6LiF) are lower than the values from their counterparts with naturally occurring isotopes and phonon-isotope scattering. However, these differences are relatively small. The effects of temperature-driven lattice expansion on phonon dispersions and calculated κ are also discussed. This work provides insight into lattice thermal conductivity modulation with mass variation and the interplay of intrinsic phonon-phonon and phonon-isotope scattering in interesting light atom systems.« less

Pre-Service Physics Teachers' Ideas on Size, Visibility and Structure of the Atom

ERIC Educational Resources Information Center

Unlu, Pervin

2010-01-01

Understanding the atom gives the opportunity to both understand and conceptually unify the various domains of science, such as physics, chemistry, biology, astronomy and geology. Among these disciplines, physics teachers are expected to be particularly well educated in this topic. It is important that pre-service physics teachers know what sort of…

Uranium Isotopic Ratio Measurements of U3O8 Reference Materials by Atom Probe Tomography

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

Fahey, Albert J.; Perea, Daniel E.; Bartrand, Jonah AG

2016-01-01

We report results of measurements of isotopic ratios obtained with atom probe tomography on U3O8 reference materials certified for their isotopic abundances of uranium. The results show good agreement with the certified values. High backgrounds due to tails from adjacent peaks complicate the measurement of the integrated peak areas as well as the fact that only oxides of uranium appear in the spectrum, the most intense of which is doubly charged. In addition, lack of knowledge of other instrumental parameters, such as the dead time, may bias the results. Isotopic ratio measurements can be performed at the nanometer-scale with themore » expectation of sensible results. The abundance sensitivity and mass resolving power of the mass spectrometer are not sufficient to compete with magnetic-sector instruments but are not far from measurements made by ToF-SIMS of other isotopic systems. The agreement of the major isotope ratios is more than sufficient to distinguish most anthropogenic compositions from natural.« less

Impact of nuclear transmutations on the primary damage production: The example of Ni based steels

NASA Astrophysics Data System (ADS)

Luneville, Laurence; Sublet, Jean Christphe; Simeone, David

2018-07-01

The recent nuclear evaluations describe more accurately the elastic and inelastic neutron-atoms interactions and allow calculating more realistically primary damage induced by nuclear reactions. Even if these calculations do not take into account relaxation processes occurring at the end of the displacement cascade (calculations are performed within the Binary Collision Approximation), they can accurately describe primary and recoil spectra in different reactors opening the door for simulating aging of nuclear materials with Ion Beam facilities. Since neutrons are only sensitive to isotopes, these spectra must be calculated weighting isotope spectra by the isotopic composition of materials under investigation. To highlight such a point, primary damage are calculated in pure Ni exhibiting a meta-stable isotope produced under neutron flux by inelastic neutron-isotope processes. These calculations clearly point out that the instantaneous primary damage production, the displacement per atom rate (dpa/s), responsible for the micro-structure evolution, strongly depends on the 59N i isotopic fractions closely related to the inelastic neutron isotope processes. Since the isotopic composition of the meta-stable isotope vanishes for large fluences, the long term impact of this isotope does not largely modify drastically the total dpa number in Ni based steels materials irradiate in nuclear plants.

Early Onset of Ground State Deformation in Neutron Deficient Polonium Isotopes

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

Cocolios, T. E.; Van de Walle, J.; ISOLDE, CERN, CH-1211 Geneva 23

2011-02-04

In-source resonant ionization laser spectroscopy of the even-A polonium isotopes {sup 192-210,216,218}Po has been performed using the 6p{sup 3}7s {sup 5}S{sub 2} to 6p{sup 3}7p {sup 5}P{sub 2} ({lambda}=843.38 nm) transition in the polonium atom (Po-I) at the CERN ISOLDE facility. The comparison of the measured isotope shifts in {sup 200-210}Po with a previous data set allows us to test for the first time recent large-scale atomic calculations that are essential to extract the changes in the mean-square charge radius of the atomic nucleus. When going to lighter masses, a surprisingly large and early departure from sphericity is observed, whichmore » is only partly reproduced by beyond mean field calculations.« less

Optical magnetic resonances induced by the interference of reactive components in the near radiation-field zone of atoms in a glow discharge of a mixture of even neon isotopes

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

Saprykin, E. G., E-mail: Saprykin@gorodok.net

2016-02-15

Four types of anomalous optical magnetic resonances shifted with respect to the zero magnetic field and with different shapes are found in radiation of a glow discharge in a mixture of even neon isotopes placed in a swept longitudinal magnetic field. This testifies to the manifestation of collective processes of synchronous light emission by oscillators belonging to isotopically different spatially separated atoms in discharge plasma. The origin of resonances is associated with nonstationary interference of reactive fields in the near radiation-field zones of emission of atoms, averaged over the lifetime of the fields (interference), while different types of resonances aremore » associated with different methods of synchronization of the phases of the fields.« less

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.

Atomic Weights of the Elements 1999

NASA Astrophysics Data System (ADS)

Coplen, T. B.

2001-05-01

The biennial review of atomic-weight, Ar(E), determinations and other cognate data have resulted in changes for the standard atomic weights of the following elements: from to nitrogen 14.006 74±0.000 07¯r 14.0067±0.0002¯ sulfur 32.066±0.006 32.065±0.005 chlorine 35.4527±0.0009 35.453±0.002 germanium 72.61±0.02 72.64±0.01 xenon 131.29±0.02 131.293±0.006 erbium 167.26±0.03 167.259±0.003 uranium 238.0289±0.0001 238.028 91±0.000 03 Presented are updated tables of the standard atomic weights and their uncertainties estimated by combining experimental uncertainties and terrestrial variabilities. In addition, this report again contains an updated table of relative atomic mass values and half-lives of selected radioisotopes. Changes in the evaluated isotopic abundance values from those published in 1997 are so minor that an updated list will not be published for the year 1999. Many elements have a different isotopic composition in some nonterrestrial materials. Some recent data on parent nuclides that might affect isotopic abundances or atomic-weight values are included in this report for the information of the interested scientific community.

SIMSISH Technique Does Not Alter the Apparent Isotopic Composition of Bacterial Cells

PubMed Central

Chapleur, Olivier; Wu, Ting-Di; Guerquin-Kern, Jean-Luc; Mazéas, Laurent; Bouchez, Théodore

2013-01-01

In order to identify the function of uncultured microorganisms in their environment, the SIMSISH method, combining in situ hybridization (ISH) and nanoscale secondary ion mass spectrometry (nanoSIMS) imaging, has been proposed to determine the quantitative uptake of specific labelled substrates by uncultured microbes at the single cell level. This technique requires the hybridization of rRNA targeted halogenated DNA probes on fixed and permeabilized microorganisms. Exogenous atoms are introduced into cells and endogenous atoms removed during the experimental procedures. Consequently differences between the original and the apparent isotopic composition of cells may occur. In the present study, the influence of the experimental procedures of SIMSISH on the isotopic composition of carbon in E. coli cells was evaluated with nanoSIMS and compared to elemental analyser-isotopic ratio mass spectrometer (EA-IRMS) measurements. Our results show that fixation and hybridization have a very limited, reproducible and homogeneous influence on the isotopic composition of cells. Thereby, the SIMSISH procedure minimizes the contamination of the sample by exogenous atoms, thus providing a means to detect the phylogenetic identity and to measure precisely the carbon isotopic composition at the single cell level. This technique was successfully applied to a complex sample with double bromine – iodine labelling targeting a large group of bacteria and a specific archaea to evaluate their specific 13C uptake during labelled methanol anaerobic degradation. PMID:24204855

Dietary change and stable isotopes: a model of growth and dormancy in cave bears.

PubMed Central

Lidén, K; Angerbjörn, A

1999-01-01

In order to discuss dietary change over time by the use of stable isotopes, it is necessary to sort out the underlying processes in isotopic variation. Together with the dietary signal other processes have been investigated, namely metabolic processes, collagen turnover and physical growth. However, growth and collagen turnover time have so far been neglected in dietary reconstruction based on stable isotopes. An earlier study suggested that cave bears (Ursus spelaeus) probably gave birth to cubs during dormancy. We provide an estimate of the effect on stable isotopes of growth and metabolism and discuss collagen turnover in a population of cave bears. Based on a quantitative model, we hypothesized that bear cubs lactated their mothers during their first and second winters, but were fed solid food together with lactation during their first summer. This demonstrates the need to include physical growth, metabolism and collagen turnover in dietary reconstruction. Whereas the effects of diet and metabolism are due to fractionation, growth and collagen turnover are dilution processes. PMID:10518325

Stable Isotopes in Evaluation of Greenhouse Gas Emissions

USDA-ARS?s Scientific Manuscript database

Isotopes offer a unique way to have natural tracers present in the ecosystem to track produced greenhouse gases (GHG) through multiple scales. Isotopes are simply atoms of the same element (same number of protons) with differing number of neutrons. This differing number of neutrons leads to differen...

Characterization of Minerals of Geochronological Interest by EPMA and Atom Probe Tomography

NASA Astrophysics Data System (ADS)

Snoeyenbos, D.; Jercinovic, M. J.; Reinhard, D. A.; Hombourger, C.

2012-12-01

Isotopic and chemical dating techniques for zircon and monazite rely on several assumptions: that initial common Pb is low to nonexistent, that the analyzed domain is chronologically homogeneous, and that any relative migration of radiogenic Pb and its parent isotopes has not exceeded the analyzed domain. Yet, both zircon and monazite commonly contain significant submicron heterogeneities that may challenge these assumptions and can complicate the interpretation of chemical and isotopic data. Compositional mapping and submicron quantitative analysis by EPMA and FE-EPMA have been found to be useful techniques both for the characterization of these heterogeneities, and for quantitative geochronological determinations within the analytical limits of these techniques and the statistics of submicron sampling. Complementary to high-resolution EPMA techniques is Atom Probe Tomography (APT), wherein a specimen with dimensions of a few hundreds of nanometers is field evaporated atom by atom. The original position of each atom is identified, along with its atomic species and isotope. The result is a reconstruction allowing quantitative three-dimensional study of the specimen at the atomic scale, with low detection limits and high mass resolution. With the introduction of laser-induced thermal pulsing to achieve field evaporation, the technique is no longer limited to conductive specimens. There exists the capability to explore the compositional and isotopic structure of insulating materials at sub-nanometer resolution. Minerals of geochronological interest have been studied by an analytical method involving first compositional mapping and submicron quantitative analysis by EPMA and FE-EPMA, and subsequent use of these data to select specific sites for APT specimen extraction by FIB. Examples presented include 1) zircon from the Taconian of New England, USA, containing a fossil resorption front included between an unmodified igneous core, and a subsequent metamorphic overgrowth, with significant redistribution of U, Th, P and Y along microfracture arrays extending into the overgrowth, and 2) Paleoproterozoic monazite in thin bands <1μm wide along cleavage planes within much older (Neoarchean) monazite from the Boothia mainland of the Western Churchill Province, Canada.

The first investigation of Wilms' tumour atomic structure-nitrogen and carbon isotopic composition as a novel biomarker for the most individual approach in cancer disease

PubMed Central

Taran, Katarzyna; Frączek, Tomasz; Sikora-Szubert, Anita; Sitkiewicz, Anna; Młynarski, Wojciech; Kobos, Józef; Paneth, Piotr

2016-01-01

The paper describes a novel approach to investigating Wilms' tumour (nephroblastoma) biology at the atomic level. Isotope Ratio Mass Spectrometry (IRMS) was used to directly assess the isotope ratios of nitrogen and carbon in 84 Wilms' tumour tissue samples from 28 cases representing the histological spectrum of nephroblastoma. Marked differences in nitrogen and carbon isotope ratios were found between nephroblastoma histological types and along the course of cancer disease, with a breakout in isotope ratio of the examined elements in tumour tissue found between stages 2 and 3. Different isotopic compositions with regard to nitrogen and carbon content were observed in blastemal Wilms' tumour, with and without focal anaplasia, and in poorly- and well-differentiated epithelial nephroblastoma. This first assessment of nitrogen and carbon isotope ratio reveals the previously unknown part of Wilms' tumour biology and represents a potential novel biomarker, allowing for a highly individual approach to treating cancer. Furthermore, this method of estimating isotopic composition appears to be the most sensitive tool yet for cancer tissue evaluation, and a valuable complement to established cancer study methods with prospective clinical impact. PMID:27732932

Deciphering the "chemical" nature of the exotic isotopes of hydrogen by the MC-QTAIM analysis: the positively charged muon and the muonic helium as new members of the periodic table.

PubMed

Goli, Mohammad; Shahbazian, Shant

2014-04-14

This report is a primarily survey on the chemical nature of some exotic species containing the positively charged muon and the muonic helium, i.e., the negatively charged muon plus helium nucleus, as exotic isotopes of hydrogen, using the newly developed multi-component quantum theory of atoms in molecules (MC-QTAIM) analysis, employing ab initio non-Born-Oppenhiemer wavefunctions. Accordingly, the "atoms in molecules" analysis performed on various asymmetric exotic isotopomers of the hydrogen molecule, recently detected experimentally [Science, 2011, 331, 448], demonstrates that both the exotic isotopes are capable of forming atoms in molecules and retaining the identity of hydrogen atoms. Various derived properties of atomic basins containing the muonic helium cast no doubt that apart from its short life time, it is a heavier isotope of hydrogen while the properties of basins containing the positively charged muon are more remote from those of the orthodox hydrogen basins, capable of appreciable donation of electrons as well as large charge polarization. However, with some tolerance, they may also be categorized as hydrogen basins though with a smaller electronegativity. All in all, the present study also clearly demonstrates that the MC-QTAIM analysis is an efficient approach to decipher the chemical nature of species containing exotic constituents, which are difficult to elucidate by experimental and/or alternative theoretical schemes.

An experimental investigation of fractionation by sputter deposition. [application to solar wind irradiation of lunar soil

NASA Technical Reports Server (NTRS)

Paruso, D. M.; Cassidy, W. A.; Hapke, B. W.

1978-01-01

Artificial glass targets composed of elements varying widely in atomic weight were irradiated at an angle of incidence of 45 deg by 2-keV hydrogen ions at a current density of .33 mA/sq cm, and sputtered atoms were caught on a molybdenum film. Analyses of the sputter-deposited films and unsputtered target glasses were carried out by electron microprobe. The backward-sputtered component was found to be enriched in elements of low atomic weight, while the forward-sputtered component was enriched in heavy atoms. These results indicate that at the lunar surface lighter elements and isotopes would tend to be ejected in backward directions, escaping directly through the openings which admit bombarding ions without first striking an adjacent grain surface; heavy elements and isotopes would be forward-sputtered deeper into the soil and be preferentially retained, contributing to the reported enrichments of heavy elements and isotopes. Additional results show that the binding energy of an element in its oxide form influences the sticking coefficient of a sputtered atom; elements of low binding energy are likely to desorb, while elements of high binding energy tend to stick to the first bounce surface.

Development of a collinear laser spectrometer facility at VECC: First test result

NASA Astrophysics Data System (ADS)

Ali, Md Sabir; Ray, Ayan; Raja, Waseem; Bandyopadhyay, Arup; Naik, Vaishali; Polley, Asish; Chakrabarti, Alok

2018-04-01

We report here the development of collinear laser spectroscopy (CLS) system at VECC for the study of hyperfine spectrum and isotopic shift of stable and unstable isotopes. The facility is first of its kind in the country allowing measurement of hyperfine splitting of atomic levels using atomic beams. The CLS system is installed downstream of the focal plane of the existing isotope separator online (ISOL) facility at VECC and is recently commissioned by successfully resolving the fluorescence spectrum of the hyperfine levels in ^{85,87}Rb. The atomic beams of Rb were produced by charge exchange of 8 keV Rb ion beam which were produced, extracted and transported to the charge exchange cell using the ion sources, extractor and the beam-line magnets of the ISOL facility. The laser propagating opposite to the ion / atom beam direction was allowed to interact with the atom beam and fluorescence spectrum was recorded. The experimental set-up and the experiment conducted are reported in detail. The measures needed to be carried out for improving the sensitivity to a level necessary for studying short-lived exotic nuclei have also been discussed.

Clarifying Atomic Weights: A 2016 Four-Figure Table of Standard and Conventional Atomic Weights

ERIC Educational Resources Information Center

Coplen, Tyler B.; Meyers, Fabienne; Holden, Norman E.

2017-01-01

To indicate that atomic weights of many elements are not constants of nature, in 2009 and 2011 the Commission on Isotopic Abundances and Atomic Weights (CIAAW) of the International Union of Pure and Applied Chemistry (IUPAC) replaced single-value standard atomic weight values with atomic weight intervals for 12 elements (hydrogen, lithium, boron,…

Calculation of individual isotope equilibrium constants for implementation in geochemical models

USGS Publications Warehouse

Thorstenson, Donald C.; Parkhurst, David L.

2002-01-01

Theory is derived from the work of Urey to calculate equilibrium constants commonly used in geochemical equilibrium and reaction-transport models for reactions of individual isotopic species. Urey showed that equilibrium constants of isotope exchange reactions for molecules that contain two or more atoms of the same element in equivalent positions are related to isotope fractionation factors by , where is n the number of atoms exchanged. This relation is extended to include species containing multiple isotopes, for example and , and to include the effects of nonideality. The equilibrium constants of the isotope exchange reactions provide a basis for calculating the individual isotope equilibrium constants for the geochemical modeling reactions. The temperature dependence of the individual isotope equilibrium constants can be calculated from the temperature dependence of the fractionation factors. Equilibrium constants are calculated for all species that can be formed from and selected species containing , in the molecules and the ion pairs with where the subscripts g, aq, l, and s refer to gas, aqueous, liquid, and solid, respectively. These equilibrium constants are used in the geochemical model PHREEQC to produce an equilibrium and reaction-transport model that includes these isotopic species. Methods are presented for calculation of the individual isotope equilibrium constants for the asymmetric bicarbonate ion. An example calculates the equilibrium of multiple isotopes among multiple species and phases.

Size dependence of chondrule textural types

NASA Technical Reports Server (NTRS)

Goswami, J. N.

1984-01-01

Chrondrule textural types were studied for size sorted chondrules from the ordinary chondrites Dhajala, Eston and Chainpur and the CM chondrite Murchison. Aliquot samples from size sorted Dhajala chondrules were studied for their oxygen isotopic composition and chondrules from Weston were studied for their precompaction irradiation records by nuclear track technique. Correlations between chondrule textural types and oxygen isotope or track data were identified. A distinct dependence of chondrule textural type on chondrule size was evident in the data for both Dhajala and Weston chondrules. No significant deviation was noticed in the abundance pattern of nonporphyritic chondrules within individual size fractions in the 200 to 800 micron size interval. Overabundance is found of nonporphyritic chondrules in the 100 to 200 micron size fraction of Murchison chondrules, the trend is not as distinct for Chainpur chondrules. Two hundred microns is suggested as the cutoff size below which radiative cooling is extremely efficient during the chondrule forming process. It is suggested that this offers a possibility for use of physical and chemical characteristics of small chondrules to constrain the temperature history during the chondrule formation process.

How Good Are the Standard Atomic Weights?

ERIC Educational Resources Information Center

Peiser, H. Steffen

1985-01-01

This review of standard atomic weights is written chiefly for chemical analysts who may place too much confidence in the accuracy of these values. Topics considered include Frank Clarke's atomic weights, effects of radioactivity and other anomalies in isotopic abundance, atomic weight limitations from experimental uncertainties, and others. (JN)

Precision atomic mass spectrometry with applications to fundamental constants, neutrino physics, and physical chemistry

NASA Astrophysics Data System (ADS)

Mount, Brianna J.; Redshaw, Matthew; Myers, Edmund G.

2011-07-01

We present a summary of precision atomic mass measurements of stable isotopes carried out at Florida State University. These include the alkalis 6Li, 23Na, 39,41K, 85,87Rb, 133Cs; the rare gas isotopes 84,86Kr and 129,130,132,136Xe; 17,18O, 19F, 28Si, 31P, 32S; and various isotope pairs of importance to neutrino physics, namely 74,76Se/74,76Ge, 130Xe/130Te, and 115In/115Sn. We also summarize our Penning trap measurements of the dipole moments of PH + and HCO + .

Synthetic use of the primary kinetic isotope effect in hydrogen atom transfer 2: generation of captodatively stabilised radicals.

PubMed

Wood, Mark E; Bissiriou, Sabine; Lowe, Christopher; Windeatt, Kim M

2013-04-28

Using C-3 di-deuterated morpholin-2-ones bearing N-2-iodobenzyl and N-3-bromobut-3-enyl radical generating groups, only products derived from the more stabilised C-3, rather than the less stabilised C-5 translocated radicals, were formed after intramolecular 1,5-hydrogen atom transfer, suggesting that any kinetic isotope effect present was not sufficient to offset captodative stabilisation.

Rapid processing of 85Kr/Kr ratios using Atom Trap Trace Analysis

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

Zappala, J. C.; Bailey, K.; Mueller, P.

In this paper, we report a methodology for measuring 85Kr/Kr isotopic abundances using Atom Trap Trace Analysis (ATTA) that increases sample measurement throughput by over an order of magnitude to six samples per 24 h. The noble gas isotope 85Kr (half-life = 10.7 years) is a useful tracer for young groundwater in the age range of 5–50 years. ATTA, an efficient and selective laser-based atom counting method, has recently been applied to 85Kr/Kr isotopic abundance measurements, requiring 5–10 μL of krypton gas at STP extracted from 50 to 100 L of water. Previously, a single such measurement required 48 h.more » In conclusion, our new method demonstrates that we can measure 85Kr/Kr ratios with 3–5% relative uncertainty every 4 h, on average, with the same sample requirements.« less

Rapid processing of 85Kr/Kr ratios using Atom Trap Trace Analysis

DOE PAGES

Zappala, J. C.; Bailey, K.; Mueller, P.; ...

2017-03-11

In this paper, we report a methodology for measuring 85Kr/Kr isotopic abundances using Atom Trap Trace Analysis (ATTA) that increases sample measurement throughput by over an order of magnitude to six samples per 24 h. The noble gas isotope 85Kr (half-life = 10.7 years) is a useful tracer for young groundwater in the age range of 5–50 years. ATTA, an efficient and selective laser-based atom counting method, has recently been applied to 85Kr/Kr isotopic abundance measurements, requiring 5–10 μL of krypton gas at STP extracted from 50 to 100 L of water. Previously, a single such measurement required 48 h.more » In conclusion, our new method demonstrates that we can measure 85Kr/Kr ratios with 3–5% relative uncertainty every 4 h, on average, with the same sample requirements.« less

Stable Isotopes, Quantum Computing and Consciousness

NASA Astrophysics Data System (ADS)

Berezin, Alexander A.

2000-10-01

Recent proposals of quantum computing/computers (QC) based on nuclear spins suggest that consciousness (CON) activity may be related (assisted) to subset of C13 atoms incorporated randomly, or quasirandomly, in neural structures. Consider two DNA chains. Even if they are completely identical chemically (same sequence of codons), patterns of 12C and 13C isotopes in them are different (possible origin of personal individuality). Perhaps it is subsystem of nuclear spins of 13C "sublattice" which forms dynamical system capable of QC and on which CON is "spanned". Some issues related to this hypothesis are: (1) existence of CON-driven positional correlations among C13 atoms, (2) motion (hopping) of C13 via enhanced neutron tunneling, cf. quantum "anti Zeno-effect", (3) possible optimization of concentration of QC-active C13 atoms above their standard isotopic abundance, (4) characteristic time-scales for operation of C13-based QC (perrhaps, broad range of scales), (5) reflection of QC dynamics of C13 on CON, (6) possibility that C13-based QC operates "above" level of "regular" CON (perhaps, Jungian sub/super-CON), (7) isotopicity as connector to universal Library of Patterns ("Platonic World"), (8) self-stabilization of coherence in C13 (sub)system. Some of this questions are, in principle, experimentally addressable through shifting of isotopic abundances.

Fabrication of Carbon Nanotube Networks on Three-Dimensional Building Blocks and Their Applications

DTIC Science & Technology

2012-10-27

increases the detection efficiency via sorting of analyte. There are some reports for sorting or separating blood cell, colloidal and bacteria by...the substrates for cyclic voltammetry (CV), pulsed bias of ECD was applied at -1.2 V during 90, 120 and 150 sec for 1, 3 and 5 μm pillar substrates...Deposition with Al2O3: The atomic layer deposition (ALD, Cyclic 4000, Genitech) was introduced to deposit the Al2O3 on the surfaces of network

Quantum noise limits to matter-wave interferometry

NASA Technical Reports Server (NTRS)

Scully, Marlan O.; Dowling, Jonathan P.

1994-01-01

We derive the quantum limits for an atomic interferometer in which the atoms obey either Bose-Einstein or Fermi-Dirac statistics. It is found that the limiting quantum noise is due to the uncertainty associated with the particle sorting between the two branches of the interferometer. As an example, the quantum-limited sensitivity of a matter-wave gyroscope is calculated and compared with that of laser gyroscopes.

"Anticlumping" and Other Combinatorial Effects on Clumped Isotopes: Implications for Tracing Biogeochemical Cycling

NASA Astrophysics Data System (ADS)

Yeung, L.

2015-12-01

I present a mode of isotopic ordering that has purely combinatorial origins. It can be important when identical rare isotopes are paired by coincidence (e.g., they are neighbors on the same molecule), or when extrinsic factors govern the isotopic composition of the two atoms that share a chemical bond. By itself, combinatorial isotope pairing yields products with isotopes either randomly distributed or with a deficit relative to a random distribution of isotopes. These systematics arise because of an unconventional coupling between the formation of singly- and multiply-substituted isotopic moieties. In a random distribution, rare isotopes are symmetrically distributed: Single isotopic substitutions (e.g., H‒D and D‒H in H2) occur with equal probability, and double isotopic substitutions (e.g., D2) occur according to random chance. The absence of symmetry in a bond-making complex can yield unequal numbers of singly-substituted molecules (e.g., more H‒D than D‒H in H2), which is recorded in the product molecule as a deficit in doubly-substituted moieties and an "anticlumped" isotope distribution (i.e., Δn < 0). Enzymatic isotope pairing reactions, which can have site-specific isotopic fractionation factors and atom reservoirs, should express this class of combinatorial isotope effect. Chemical-kinetic isotope effects, which are related to the bond-forming transition state, arise independently and express second-order combinatorial effects. In general, both combinatorial and chemical factors are important for calculating and interpreting clumped-isotope signatures of individual reactions. In many reactions relevant to geochemical oxygen, carbon, and nitrogen cycling, combinatorial isotope pairing likely plays a strong role in the clumped isotope distribution of the products. These isotopic signatures, manifest as either directly bound isotope clumps or as features of a molecule's isotopic anatomy, could be exploited as tracers of biogeochemistry that can relate molecular mechanisms to signals observable at environmentally relevant spatial scales.

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.

Practical experience using speleothem data in multi-proxy climate reconstructions

NASA Astrophysics Data System (ADS)

Graham, N.

2009-04-01

Speleothem records have clear potential to extend and sharpen our understanding of past climate change. Many speleothem records feature both high sample resolution and precision age models, characteristics generally available only in tree-ring records, among terrestrial climate proxies. Speleothem records also avoid some processes that add uncertainty to the interpretation of biological proxy records. At the same time, model results suggest that even if speleothems did provide long and perfect records of meteoric water isotope concentrations, it would not be always be obvious how to interpret the isotopic fluctuations unambiguously in terms of precipitation or temperature variability. Other uncertainties can arise from local hydrologic and speleothem growth processes, as well as sampling and calibration uncertainties. Similar comments apply to other sorts of speleothem-derived records, e.g., verve thickness. These issues of interpretation are especially important in cases where data availability makes calibration to local climate data problematic and when past climate conditions limit the relevance of such calibrations. The presentation will focus broadly on the use of speleothem records together with other sorts of proxy records either to get a general idea of climatic change during some period, or for more formal climate field reconstruction. Examples from few such efforts will be given. Results from simulations with models incorporating stable water isotopes will be discussed, with consideration of what the results imply about the climatic interpretation of speleothem isotope records. The views will be those a climate scientist trying to make better use of speleothem data, a perspective which will highlight 1) where climate researchers would benefit from better understanding of isotope and speleothem processes, and 2) what steps that speleothem researchers could take to tighten the physical interpretation of their records. Convergence on these points will allow us to take better take advantage of the precision and spatial distribution of speleothem records offer for the understanding of past climate.

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.

Guidelines and recommended terms for expression of stable-isotope-ratio and gas-ratio measurement results

USGS Publications Warehouse

Coplen, Tyler B.

2011-01-01

To minimize confusion in the expression of measurement results of stable isotope and gas-ratio measurements, recommendations based on publications of the Commission on Isotopic Abundances and Atomic Weights of the International Union of Pure and Applied Chemistry (IUPAC) are presented. Whenever feasible, entries are consistent with the Système International d'Unités, the SI (known in English as the International System of Units), and the third edition of the International Vocabulary of Basic and General Terms in Metrology (VIM, 3rd edition). The recommendations presented herein are approved by the Commission on Isotopic Abundances and Atomic Weights and are designed to clarify expression of quantities related to measurement of isotope and gas ratios to ensure that quantity equations instead of numerical value equations are used for quantity definitions. Examples of column headings consistent with quantity calculus (also called the algebra of quantities) and examples of various deprecated usages connected with the terms recommended are presented.

Atom Trap Trace Analysis for radiokrypton and radioargon dating

NASA Astrophysics Data System (ADS)

Williams, William; Jiang, Wei; Sun, Yun; Bailey, Kevin; Davis, Andrew; Hu, Shuiming; Lu, Zheng-Tian; Mueller, Peter; O'Connor, Thomas; Purtschert, Roland; Sturchio, Neil

2011-05-01

Atom Trap Trace Analysis (ATTA), a MOT-based atom counting method, is used to analyze three noble gas radioisotopes (81Kr, 85Kr, 39Ar) covering a wide range of geological ages and applications in the earth sciences. Their isotopic abundances are extremely low, in the range of 10-16 - 10-11. Yet, ATTA can trap and unmistakably detect these rare isotopes one atom at a time. The system is currently limited by the excitation efficiency of the RF discharge that produces the metastable atoms (Kr* & Ar*) needed for laser trapping. To further improve the MOT loading rate, we plan to replace the RF discharge with a photon excitation scheme that employs a VUV light source at 124 nm. The VUV source can be a lamp or a free electron laser. This work is supported by DOE, Office of Nuclear Physics and by NSF, Division of Earth Sciences.

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.

Isotopic compositions of the elements 2013 (IUPAC Technical Report)

USGS Publications Warehouse

Meija, Juris; Coplen, Tyler B.; Berglund, Michael; Brand, Willi A.; De Bièvre, Paul; Gröning, Manfred; Holden, Norman E.; Irrgeher, Johanna; Loss, Robert D.; Walczyk, Thomas; Prohaska, Thomas

2016-01-01

The Commission on Isotopic Abundances and Atomic Weights (ciaaw.org) of the International Union of Pure and Applied Chemistry (iupac.org) has revised the Table of Isotopic Compositions of the Elements (TICE). The update involved a critical evaluation of the recent published literature. The new TICE 2013 includes evaluated data from the “best measurement” of the isotopic abundances in a single sample, along with a set of representative isotopic abundances and uncertainties that accommodate known variations in normal terrestrial materials.

Signal or noise? Separating grain size-dependent Nd isotope variability from provenance shifts in Indus delta sediments, Pakistan

NASA Astrophysics Data System (ADS)

Jonell, T. N.; Li, Y.; Blusztajn, J.; Giosan, L.; Clift, P. D.

2017-12-01

Rare earth element (REE) radioisotope systems, such as neodymium (Nd), have been traditionally used as powerful tracers of source provenance, chemical weathering intensity, and sedimentary processes over geologic timescales. More recently, the effects of physical fractionation (hydraulic sorting) of sediments during transport have called into question the utility of Nd isotopes as a provenance tool. Is source terrane Nd provenance resolvable if sediment transport strongly induces noise? Can grain-size sorting effects be quantified? This study works to address such questions by utilizing grain size analysis, trace element geochemistry, and Nd isotope geochemistry of bulk and grain-size fractions (<63μm, 63-125 μm, 125-250 μm) from the Indus delta of Pakistan. Here we evaluate how grain size effects drive Nd isotope variability and further resolve the total uncertainties associated with Nd isotope compositions of bulk sediments. Results from the Indus delta indicate bulk sediment ɛNd compositions are most similar to the <63 µm fraction as a result of strong mineralogical control on bulk compositions by silt- to clay-sized monazite and/or allanite. Replicate analyses determine that the best reproducibility (± 0.15 ɛNd points) is observed in the 125-250 µm fraction. The bulk and finest fractions display the worst reproducibility (±0.3 ɛNd points). Standard deviations (2σ) indicate that bulk sediment uncertainties are no more than ±1.0 ɛNd points. This argues that excursions of ≥1.0 ɛNd points in any bulk Indus delta sediments must in part reflect an external shift in provenance irrespective of sample composition, grain size, and grain size distribution. Sample standard deviations (2s) estimate that any terrigenous bulk sediment composition should vary no greater than ±1.1 ɛNd points if provenance remains constant. Findings from this study indicate that although there are grain-size dependent Nd isotope effects, they are minimal in the Indus delta such that resolvable provenance-driven trends can be identified in bulk sediment ɛNd compositions over the last 20 k.y., and that overall provenance trends remain consistent with previous findings.

Probing atomic Higgs-like forces at the precision frontier

NASA Astrophysics Data System (ADS)

Delaunay, Cédric; Ozeri, Roee; Perez, Gilad; Soreq, Yotam

2017-11-01

We propose a novel approach to probe new fundamental interactions using isotope shift spectroscopy in atomic clock transitions. As a concrete toy example we focus on the Higgs boson couplings to the building blocks of matter: the electron and the up and down quarks. We show that the attractive Higgs force between nuclei and their bound electrons, which is poorly constrained, might induce effects that are larger than the current experimental sensitivities. More generically, we discuss how new interactions between the electron and the neutrons, mediated via light new degrees of freedom, may lead to measurable nonlinearities in a King plot comparison between isotope shifts of two different transitions. Given state-of-the-art accuracy in frequency comparison, isotope shifts have the potential to be measured with sub-Hz accuracy, thus potentially enabling the improvement of current limits on new fundamental interactions. A candidate atomic system for this measurement requires two different clock transitions and four zero nuclear spin isotopes. We identify several systems that satisfy this requirement and also briefly discuss existing measurements. We consider the size of the effect related to the Higgs force and the requirements for it to produce an observable signal.

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.

Atomic line emission analyzer for hydrogen isotopes

DOEpatents

Kronberg, J.W.

1993-03-30

Apparatus for isotopic analysis of hydrogen comprises a low pressure chamber into which a sample of hydrogen is introduced and then exposed to an electrical discharge to excite the electrons of the hydrogen atoms to higher energy states and thereby cause the emission of light on the return to lower energy states, a Fresnel prism made at least in part of a material anomalously dispersive to the wavelengths of interest for dispersing the emitted light, and a photodiode array for receiving the dispersed light. The light emitted by the sample is filtered to pass only the desired wavelengths, such as one of the lines of the Balmer series for hydrogen, the wavelengths of which differ slightly from one isotope to another. The output of the photodiode array is processed to determine the relative amounts of each isotope present in the sample. Additionally, the sample itself may be recovered using a metal hydride.

Atomic line emission analyzer for hydrogen isotopes

DOEpatents

Kronberg, J.W.

1991-05-08

Apparatus for isotopic analysis of hydrogen comprises a low pressure chamber into which a sample of hydrogen is introduced and then exposed to an electrical discharge to excite the electrons of the hydrogen atoms to higher energy states and thereby cause the emission of light on the return to lower energy states, a Fresnel prism made at least in part of a material anomalously dispersive to the wavelengths of interest for dispersing the emitted light, and a photodiode array for receiving the dispersed light. The light emitted by the sample is filtered to pass only the desired wavelengths, such as one of the lines of the Balmer series for hydrogen, the wavelengths of which differ slightly from one isotope to another. The output of the photodiode array is processed to determine the relative amounts of each isotope present in the sample. Additionally, the sample itself may be recovered using, a metal hydride.

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.

Atomic line emission analyzer for hydrogen isotopes

DOEpatents

Kronberg, James W.

1993-01-01

Apparatus for isotopic analysis of hydrogen comprises a low pressure chamber into which a sample of hydrogen is introduced and then exposed to an electrical discharge to excite the electrons of the hydrogen atoms to higher energy states and thereby cause the emission of light on the return to lower energy states, a Fresnel prism made at least in part of a material anomalously dispersive to the wavelengths of interest for dispersing the emitted light, and a photodiode array for receiving the dispersed light. The light emitted by the sample is filtered to pass only the desired wavelengths, such as one of the lines of the Balmer series for hydrogen, the wavelengths of which differ slightly from one isotope to another. The output of the photodiode array is processed to determine the relative amounts of each isotope present in the sample. Additionally, the sample itself may be recovered using a metal hydride.

Electric Dipole Moment Measurements with Rare Isotopes

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

Chupp, Timothy

The origin of matter is one of the deepest questions addressed by science and remains a mystery because our understanding of the Big Bang suggests that equal amounts of matter as antimatter would be created and annihilate leaving nothing from which stars, galaxies, planets and ultimately life as we know it was created. We know this is not the case in the universe, and so the explanation that the laws of physics can distinguish the difference of moving forward and backward in time and provide mechanisms that produce more matter that antimatter so that a little bit was left over.more » These same laws of physics affect our world today and would very slightly change the shape of an atom, stretching is along the direction of the spin of its nucleus. This subtle shape change has been searched in many systems - the neutron, atoms and molecules, but has not yet been detected, even as the motivation is strengthened by our understanding of their structure. We therefore look to new systems that have special features that make these effects stand out. Rare isotopes provide one possibility and specific radon atoms are our choice. We have developed techniques to make these measurements with short-lived radioactive atoms, studied the nuclei to provide deeper understanding of how these affect arise in such atoms (including radium) and developed new laser-based techniques to measure and control the magnetic fields necessary to perform these exquisitely sensitive measurements. In this work we have shown that radioactive radon atoms can be produced and transported to an apparatus that lines up the spins of the atoms. We have also shown that the nuclei of nearby radium are pear shaped and that the radon nuclei likely oscillate from one pear shape to its mirror reflection. We have also used the techniques which control nuclear spin to study the magnetic environment in a magnetically shielded room, which has the smallest magnetic field in a large volume in the universe. Measuring magnetic fields and detecting noble atoms' shapes using lasers will provide new techniques for these measurements and impact a broad range of applications including measurements of the neutron EDM. Harvesting rare isotopes at the future FRIB facility at Michigan State University will provide much stronger sources of the isotopes of radon and radium for future-generation experiments and also provide new isotopes for applications including medicine.« less

ISO/GUM UNCERTAINTIES AND CIAAW (UNCERTAINTY TREATMENT FOR RECOMMENDED ATOMIC WEIGHTS AND ISOTOPIC ABUNDANCES)

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

HOLDEN,N.E.

2007-07-23

The International Organization for Standardization (ISO) has published a Guide to the expression of Uncertainty in Measurement (GUM). The IUPAC Commission on Isotopic Abundance and Atomic Weight (CIAAW) began attaching uncertainty limits to their recommended values about forty years ago. CIAAW's method for determining and assigning uncertainties has evolved over time. We trace this evolution to their present method and their effort to incorporate the basic ISO/GUM procedures into evaluations of these uncertainties. We discuss some dilemma the CIAAW faces in their present method and whether it is consistent with the application of the ISO/GUM rules. We discuss the attemptmore » to incorporate variations in measured isotope ratios, due to natural fractionation, into the ISO/GUM system. We make some observations about the inconsistent treatment in the incorporation of natural variations into recommended data and uncertainties. A recommendation for expressing atomic weight values using a tabulated range of values for various chemical elements is discussed.« less

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.

Oxygen isotope exchange with quartz during pyrolysis of silver sulfate and silver nitrate.

PubMed

Schauer, Andrew J; Kunasek, Shelley A; Sofen, Eric D; Erbland, Joseph; Savarino, Joel; Johnson, Ben W; Amos, Helen M; Shaheen, Robina; Abaunza, Mariana; Jackson, Terri L; Thiemens, Mark H; Alexander, Becky

2012-09-30

Triple oxygen isotopes of sulfate and nitrate are useful metrics for the chemistry of their formation. Existing measurement methods, however, do not account for oxygen atom exchange with quartz during the thermal decomposition of sulfate. We present evidence for oxygen atom exchange, a simple modification to prevent exchange, and a correction for previous measurements. Silver sulfates and silver nitrates with excess (17)O were thermally decomposed in quartz and gold (for sulfate) and quartz and silver (for nitrate) sample containers to O(2) and byproducts in a modified Temperature Conversion/Elemental Analyzer (TC/EA). Helium carries O(2) through purification for isotope-ratio analysis of the three isotopes of oxygen in a Finnigan MAT253 isotope ratio mass spectrometer. The Δ(17)O results show clear oxygen atom exchange from non-zero (17)O-excess reference materials to zero (17)O-excess quartz cup sample containers. Quartz sample containers lower the Δ(17)O values of designer sulfate reference materials and USGS35 nitrate by 15% relative to gold or silver sample containers for quantities of 2-10 µmol O(2). Previous Δ(17)O measurements of sulfate that rely on pyrolysis in a quartz cup have been affected by oxygen exchange. These previous results can be corrected using a simple linear equation (Δ(17)O(gold) = Δ(17)O(quartz) * 1.14 + 0.06). Future pyrolysis of silver sulfate should be conducted in gold capsules or corrected to data obtained from gold capsules to avoid obtaining oxygen isotope exchange-affected data. Copyright © 2012 John Wiley & Sons, Ltd.

pH-dependent equilibrium isotope fractionation associated with the compound specific nitrogen and carbon isotope analysis of substituted anilines by SPME-GC/IRMS.

PubMed

Skarpeli-Liati, Marita; Turgeon, Aurora; Garr, Ashley N; Arnold, William A; Cramer, Christopher J; Hofstetter, Thomas B

2011-03-01

Solid-phase microextraction (SPME) coupled to gas chromatography/isotope ratio mass spectrometry (GC/IRMS) was used to elucidate the effects of N-atom protonation on the analysis of N and C isotope signatures of selected aromatic amines. Precise and accurate isotope ratios were measured using polydimethylsiloxane/divinylbenzene (PDMS/DVB) as the SPME fiber material at solution pH-values that exceeded the pK(a) of the substituted aniline's conjugate acid by two pH-units. Deviations of δ(15)N and δ(13)C-values from reference measurements by elemental analyzer IRMS were small (<0.9‰) and within the typical uncertainties of isotope ratio measurements by SPME-GC/IRMS. Under these conditions, the detection limits for accurate isotope ratio measurements were between 0.64 and 2.1 mg L(-1) for δ(15)N and between 0.13 and 0.54 mg L(-1) for δ(13)C, respectively. Substantial inverse N isotope fractionation was observed by SPME-GC/IRMS as the fraction of protonated species increased with decreasing pH leading to deviations of -20‰ while the corresponding δ(13)C-values were largely invariant. From isotope ratio analysis at different solution pHs and theoretical calculations by density functional theory, we derived equilibrium isotope effects, EIEs, pertinent to aromatic amine protonation of 0.980 and 1.001 for N and C, respectively, which were very similar for all compounds investigated. Our work shows that N-atom protonation can compromise accurate compound-specific N isotope analysis of aromatic amines.

Atomic transport during solid-phase epitaxial recrystallization of amorphous germanium

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

Radek, M.; Bracht, H., E-mail: bracht@uni-muenster.de; Johnson, B. C.

2015-08-24

The atomic mixing of matrix atoms during solid-phase epitaxy (SPE) is studied by means of isotopically enriched germanium (Ge) multilayer structures that were amorphized by Ge ion implantation up to a depth of 1.5 μm. Recrystallization of the amorphous structure is performed at temperatures between 350 °C and 450 °C. Secondary-ion-mass-spectrometry is used to determine the concentration-depth profiles of the Ge isotope before and after SPE. An upper limit of 0.5 nm is deduced for the displacement length of the Ge matrix atoms by the SPE process. This small displacement length is consistent with theoretical models and atomistic simulations of SPE, indicating that themore » SPE mechanism consists of bond-switching with nearest-neighbours across the amorphous-crystalline (a/c) interface.« less

Get Your Atoms in Order--An Open-Source Implementation of a Novel and Robust Molecular Canonicalization Algorithm.

PubMed

Schneider, Nadine; Sayle, Roger A; Landrum, Gregory A

2015-10-26

Finding a canonical ordering of the atoms in a molecule is a prerequisite for generating a unique representation of the molecule. The canonicalization of a molecule is usually accomplished by applying some sort of graph relaxation algorithm, the most common of which is the Morgan algorithm. There are known issues with that algorithm that lead to noncanonical atom orderings as well as problems when it is applied to large molecules like proteins. Furthermore, each cheminformatics toolkit or software provides its own version of a canonical ordering, most based on unpublished algorithms, which also complicates the generation of a universal unique identifier for molecules. We present an alternative canonicalization approach that uses a standard stable-sorting algorithm instead of a Morgan-like index. Two new invariants that allow canonical ordering of molecules with dependent chirality as well as those with highly symmetrical cyclic graphs have been developed. The new approach proved to be robust and fast when tested on the 1.45 million compounds of the ChEMBL 20 data set in different scenarios like random renumbering of input atoms or SMILES round tripping. Our new algorithm is able to generate a canonical order of the atoms of protein molecules within a few milliseconds. The novel algorithm is implemented in the open-source cheminformatics toolkit RDKit. With this paper, we provide a reference Python implementation of the algorithm that could easily be integrated in any cheminformatics toolkit. This provides a first step toward a common standard for canonical atom ordering to generate a universal unique identifier for molecules other than InChI.

Progress in the Use of Isotopes: The Atomic Triad - Reactors, Radioisotopes and Radiation

DOE R&D Accomplishments Database

Libby, W. F.

1958-08-04

Recent years have seen a substantial growth in the use of isotopes in medicine, agriculture, and industry: up to the minute information on the production and use of isotopes in the U.S. is presented. The application of radioisotopes to industrial processes and manufacturing operations has expanded more rapidly than any one except its most ardent advocates expected. New uses and new users are numerous. The adoption by industry of low level counting techniques which make possible the use of carbon-14 and tritium in the control of industrial processes and in certain exploratory and research problems is perhaps most promising of current developments. The latest information on savings to industry will be presented. The medical application of isotopes has continued to develop at a rapid pace. The current trend appears to be in the direction of improvements in technique and the substitution of more effective isotopes for those presently in use. Potential and actual benefits accruing from the use of isotopes in agriculture are reviewed. The various methods of production of radioisotopes are discussed. Not only the present methods but also interesting new possibilities are covered. Although isotopes are but one of the many peaceful uses of the atom, it is the first to pay its way. (auth)

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.

Using Beads and Divided Containers to Study Kinetic and Equilibrium Isotope Effects in the Laboratory and in the Classroom

ERIC Educational Resources Information Center

Campbell, Dean J.; Brewer, Emily R.; Martinez, Keri A.; Fitzjarrald, Tamara J.

2017-01-01

The purpose of this laboratory experiment is to study fundamental concepts of kinetics and equilibria and the isotope effects associated with both of these concepts. The concepts of isotopes in introductory and general chemistry courses are typically used within the contexts of atomic weights and radioactivity. Kinetic and equilibrium isotope…

Atomic Mass and Nuclear Binding Energy for I-131 (Iodine)

NASA Astrophysics Data System (ADS)

Sukhoruchkin, S. I.; Soroko, Z. N.

This document is part of the Supplement containing the complete sets of data of Subvolume A `Nuclei with Z = 1 - 54' of Volume 22 `Nuclear Binding Energies and Atomic Masses' of Landolt-Börnstein - Group I `Elementary Particles, Nuclei and Atoms'. It provides atomic mass, mass excess, nuclear binding energy, nucleon separation energies, Q-values, and nucleon residual interaction parameters for atomic nuclei of the isotope I-131 (Iodine, atomic number Z = 53, mass number A = 131).

Atomic Mass and Nuclear Binding Energy for F-22 (Fluorine)

NASA Astrophysics Data System (ADS)

Sukhoruchkin, S. I.; Soroko, Z. N.

This document is part of the Supplement containing the complete sets of data of Subvolume A `Nuclei with Z = 1 - 54' of Volume 22 `Nuclear Binding Energies and Atomic Masses' of Landolt-Börnstein - Group I `Elementary Particles, Nuclei and Atoms'. It provides atomic mass, mass excess, nuclear binding energy, nucleon separation energies, Q-values, and nucleon residual interaction parameters for atomic nuclei of the isotope F-22 (Fluorine, atomic number Z = 9, mass number A = 22).

Mass-independent isotope fractionation of Mo, Ru, Cd, and Te

NASA Astrophysics Data System (ADS)

Fujii, T.; Moynier, F.; Albarède, F.

2006-12-01

The variation of the mean charge distribution in the nucleus with the neutron number of different isotopes induces a tenuous shift of the nuclear field. The mass fractionation induced during phase changes is irregular, notably with 'staggering' between odd and even masses, and becomes increasingly non-linear for neutron-rich isotopes. A strong correlation is observed between the deviation of the isotopic effects from the linear dependence with mass and the corresponding nuclear charge radii. We first demonstrated on a number of elements the existence of such mass-independent isotope fractionation in laboratory experiments of solvent extraction with a macrocyclic compound. The isotope ratios were analyzed by multiple-collector inductively coupled plasma mass spectrometry with a typical precision of <100 ppm. The isotopes of odd and even atomic masses are enriched in the solvent to an extent that closely follows the variation of their nuclear charge radii. The present results fit Bigeleisen's (1996) model, which is the standard mass-dependent theory modified to include a correction term named the nuclear field shift effect. For heavy elements like uranium, the mass-independent effect is important enough to dominate the mass-dependent effect. We subsequently set out to compare the predictions of Bigeleisen's theory with the isotopic anomalies found in meteorites. Some of these anomalies are clearly inconsistent with nucleosynthetic effects (either s- or r-processes). Isotopic variations of Mo and Ru in meteorites, especially in Allende (CV3), show a clear indication of nucleosynthetic components. However, the mass-independent anomaly of Ru observed in Murchison (CM2) is a remarkable exception which cannot be explained by the nucleosynthetic model, but fits the nuclear field shift theory extremely well. The abundances of the even atomic mass Te isotopes in the leachates of carbonaceous chondrites, Allende, Murchison, and Orgueil, fit a mass-dependent law well, but the odd atomic mass isotope ^{125}Te clearly deviates from this correlation. The nuclear field shift theory shows that there is no effect on ^{130}Te but that the ^{125}Te anomaly is real. Carbonaceous chondrites do not reveal significant isotope fractionation of Cd isotopes, but a nuclear field shift effect is clearly present in type-3 (unequilibrated) ordinary chondrites. The nuclear field shift effect is temperature dependent and is probably more frequent in nature than commonly thought. It remains, together with nucleosynthetric anomalies, perfectly visible through the normalization of isotopic ratios to a reference value. In meteorites, this effect may originate both during condensation/evaporation processes in the nebular gas and during the metamorphism of the meteorite parent bodies.

Motion of W and He atoms during formation of W fuzz

NASA Astrophysics Data System (ADS)

Doerner, R. P.; Nishijima, D.; Krasheninnikov, S. I.; Schwarz-Selinger, T.; Zach, M.

2018-06-01

Measurements are conducted to identify the motion of tungsten and helium atoms during the formation of tungsten fuzz. In a first series of experiments the mobility of helium within the growing fuzz was measured by adding 3He to the different stages of plasma exposure under conditions that promoted tungsten fuzz growth. Ion beam analysis was used to quantify the amount of 3He remaining in the samples following the plasma exposure. The results indicate that the retention of helium in bubbles within tungsten is a dynamic process with direct implantation rather than diffusion into the bubbles, best describing the motion of the helium atoms. In the second experiment, an isotopically enriched layer of tungsten (~92.99% 182W) is deposited on the surface of a bulk tungsten sample with the natural abundance of the isotopes. This sample is then exposed to helium plasma at the conditions necessary to support the formation of tungsten ‘fuzz’. Depth profiles of the concentration of each of the tungsten isotopes are obtained using secondary ion mass spectrometry (SIMS) before and after the plasma exposure. The depth profiles clearly show mixing of tungsten atoms from the bulk sample toward the surface of the fuzz. This supports a physical picture of the dynamic behavior of helium bubbles which, also, causes an enhanced mixing of tungsten atoms.

Motion of W and He atoms during formation of W fuzz

DOE PAGES

Doerner, R. P.; Nishijima, D.; Krasheninnikov, S. I.; ...

2018-04-11

Measurements are conducted to identify the motion of tungsten and helium atoms during the formation of tungsten fuzz. In a first series of experiments the mobility of helium within the growing fuzz was measured by adding 3He to the different stages of plasma exposure under conditions that promoted tungsten fuzz growth. Ion beam analysis was used to quantify the amount of 3He remaining in the samples following the plasma exposure. The results indicate that the retention of helium in bubbles within tungsten is a dynamic process with direct implantation rather than diffusion into the bubbles, best describing the motion ofmore » the helium atoms. In the second experiment, an isotopically enriched layer of tungsten (~92.99% 182W) is deposited on the surface of a bulk tungsten sample with the natural abundance of the isotopes. This sample is then exposed to helium plasma at the conditions necessary to support the formation of tungsten 'fuzz'. Depth profiles of the concentration of each of the tungsten isotopes are obtained using secondary ion mass spectrometry (SIMS) before and after the plasma exposure. The depth profiles clearly show mixing of tungsten atoms from the bulk sample toward the surface of the fuzz. Lastly, this supports a physical picture of the dynamic behavior of helium bubbles which, also, causes an enhanced mixing of tungsten atoms.« less

Spectroscopic investigation of H atom transfer in a gas-phase dissociation reaction: McLafferty rearrangement of model gas-phase peptide ions.

PubMed

Van Stipdonk, Michael J; Kerstetter, Dale R; Leavitt, Christopher M; Groenewold, Gary S; Steill, Jeffrey; Oomens, Jos

2008-06-14

Wavelength-selective infrared multiple-photon photodissociation (WS-IRMPD) was used to study isotopically-labeled ions generated by McLafferty rearrangement of nicotinyl-glycine-tert-butyl ester and betaine-glycine-tert-butyl ester. The tert-butyl esters were incubated in a mixture of D(2)O and CH(3)OD to induce solution-phase hydrogen-deuterium exchange and then converted to gas-phase ions using electrospray ionization. McLafferty rearrangement was used to generate the free-acid forms of the respective model peptides through transfer of an H atom and elimination of butene. The specific aim was to use vibrational spectra generated by WS-IRMPD to determine whether the H atom remains at the acid group, or migrates to one or more of the other exchangeable sites. Comparison of the IRMPD results in the region from 1200-1900 cm(-1) to theoretical spectra for different isotopically-labeled isomers clearly shows that the H atom is situated at the C-terminal acid group and migration to amide positions is negligible on the time scale of the experiment. The results of this study suggest that use of the McLafferty rearrangement for peptide esters could be an effective approach for generation of H-atom isotope tracers, in situ, for subsequent investigation of intramolecular proton migration during peptide fragmentation studies.

Isotopic effects in the muon transfer from pmu and dmu to heavier atoms.

PubMed

Dupays, Arnaud

2004-07-23

The results of accurate hyperspherical calculations of the muon-transfer rates from muonic protium and deuterium atoms to nitrogen, oxygen, and neon are reported. Very good agreement with measured rates is obtained and, for the three systems, the isotopic effect is perfectly reproduced. The transfer rate is higher for deuterium in the cases of nitrogen and neon due to constructive interferences between two transfer paths. The lower transfer rate for deuterium in the case of oxygen results from a large resonant contribution. Copyright 2004 The American Physical Society

On the atomic structure of liquid Ni-Si alloys: a neutron diffraction study

NASA Astrophysics Data System (ADS)

Gruner, S.; Marczinke, J.; Hennet, L.; Hoyer, W.; Cuello, G. J.

2009-09-01

The atomic structure of the liquid NiSi and NiSi2 alloys is investigated by means of neutron diffraction experiments with isotopic substitution. From experimental data-sets obtained using four Ni isotopes, partial structure factors and pair correlation functions are obtained by applying a reverse Monte Carlo modelling approach. Both alloys were found to exhibit a strong tendency to hetero-coordination within the first coordination shell. In particular, covalent Si-Si bonds with somewhat greater distances seem to influence the structure of the liquid NiSi alloy.

On the atomic structure of liquid Ni-Si alloys: a neutron diffraction study.

PubMed

Gruner, S; Marczinke, J; Hennet, L; Hoyer, W; Cuello, G J

2009-09-23

The atomic structure of the liquid NiSi and NiSi(2) alloys is investigated by means of neutron diffraction experiments with isotopic substitution. From experimental data-sets obtained using four Ni isotopes, partial structure factors and pair correlation functions are obtained by applying a reverse Monte Carlo modelling approach. Both alloys were found to exhibit a strong tendency to hetero-coordination within the first coordination shell. In particular, covalent Si-Si bonds with somewhat greater distances seem to influence the structure of the liquid NiSi alloy.

ATOMIC PHYSICS, AN AUTOINSTRUCTIONAL PROGRAM, VOLUME 2, SUPPLEMENT.

ERIC Educational Resources Information Center

DETERLINE, WILLIAM A.; KLAUS, DAVID J.

THE AUTOINSTRUCTIONAL MATERIALS IN THIS TEXT WERE PREPARED FOR USE IN AN EXPERIMENTAL STUDY, OFFERING SELF-TUTORING MATERIAL FOR LEARNING ATOMIC PHYSICS. THE TOPICS COVERED ARE (1) ISOTOPES AND MASS NUMBERS, (2) MEASURING ATOMIC MASS, (3) DISCOVERY OF THE NUCLEUS, (4) STRUCTURE OF THE NUCLEUS, (5) DISCOVERY OF THE NEUTRON, (6) NUCLEAR REACTIONS,…

Determination of lithium isotopes at natural abundance levels by atomic absorption spectrometry

USGS Publications Warehouse

Meier, A.L.

1982-01-01

The relationships of the absorption of 6Li and 7Li hollow cathode lamp emissions are used to determine lithium isotopic composition in the natural abundance range of geologic materials. Absorption was found to have a nonlinear dependence upon total lithium concentration and isotopic composition. A method using nonlinear equations to describe the relationship of the absorption of 6Li and 7Li lamp radiation is proposed as a means of calculating isotopic composition that is independent of total lithium concentration.

Further analysis of the IRIS iron isotope experiment

NASA Technical Reports Server (NTRS)

Tarle, G.; Ahlen, S. P.; Cartwright, B. G.; Solarz, M.

1980-01-01

The IRIS Fe isotope experiment was extended to atomic charges of Z = 19, with isotopic distributions for 500 events ranging from 18 to 28. Normalization of the detector response functions at Fe-56 produced a single well resolved peak at Sc-45, establishing the resolution and mass scale of the device over the entire charge region. The abundance distributions for the predominantly primary isotopes Ca-40, Fe-54, Fe-56, Ni-58, and Ni-60 do not indicate a large admixture of material with distinctly nonsolar abundances.

IUPAC Periodic Table of the Isotopes

USGS Publications Warehouse

Holden, N.E.; Coplen, T.B.; Böhlke, J.K.; Wieser, M.E.; Singleton, G.; Walczyk, T.; Yoneda, S.; Mahaffy, P.G.; Tarbox, L.V.

2011-01-01

For almost 150 years, the Periodic Table of the Elements has served as a guide to the world of elements by highlighting similarities and differences in atomic structure and chemical properties. To introduce students, teachers, and society to the existence and importance of isotopes of the chemical elements, an IUPAC Periodic Table of the Isotopes (IPTI) has been prepared and can be found as a supplement to this issue.

Nuclear Explosion Monitoring Research and Development Roadmaps

DTIC Science & Technology

2010-09-01

environment, a radionuclide event is the release of radioactive atoms. Radionuclide sources include nuclear explosions, normal or anomalous reactor ...isotopes (e.g., potassium, uranium, and thorium and their decay products) and isotopes produced from the interactions of cosmic rays with the...and reactor emissions. For example, the IMS detected a pair of xenon isotopes at a Japanese station shortly after the 2009 DPRK event. The ratio of

Atomic weights of the elements 2013 (IUPAC Technical Report)

USGS Publications Warehouse

Meija, Juris; Coplen, Tyler B.; Berglund, Michael; Brand, Willi A.; De Bièvre, Paul; Gröning, Manfred; Holden, Norman E.; Irrgeher, Johanna; Loss, Robert D.; Walczyk, Thomas; Prohaska, Thomas

2016-01-01

The biennial review of atomic-weight determinations and other cognate data has resulted in changes for the standard atomic weights of 19 elements. The standard atomic weights of four elements have been revised based on recent determinations of isotopic abundances in natural terrestrial materials:cadmium to 112.414(4) from 112.411(8),molybdenum to 95.95(1) from 95.96(2),selenium to 78.971(8) from 78.96(3), andthorium to 232.0377(4) from 232.038 06(2). The Commission on Isotopic Abundances and Atomic Weights (ciaaw.org) also revised the standard atomic weights of fifteen elements based on the 2012 Atomic Mass Evaluation:aluminium (aluminum) to 26.981 5385(7) from 26.981 5386(8),arsenic to 74.921 595(6) from 74.921 60(2),beryllium to 9.012 1831(5) from 9.012 182(3),caesium (cesium) to 132.905 451 96(6) from 132.905 4519(2),cobalt to 58.933 194(4) from 58.933 195(5),fluorine to 18.998 403 163(6) from 18.998 4032(5),gold to 196.966 569(5) from 196.966 569(4),holmium to 164.930 33(2) from 164.930 32(2),manganese to 54.938 044(3) from 54.938 045(5),niobium to 92.906 37(2) from 92.906 38(2),phosphorus to 30.973 761 998(5) from 30.973 762(2),praseodymium to 140.907 66(2) from 140.907 65(2),scandium to 44.955 908(5) from 44.955 912(6),thulium to 168.934 22(2) from 168.934 21(2), andyttrium to 88.905 84(2) from 88.905 85(2). The Commission also recommends the standard value for the natural terrestrial uranium isotope ratio, N(238U)/N(235U)=137.8(1).

Sensitive sub-Doppler nonlinear spectroscopy for hyperfine-structure analysis using simple atomizers

NASA Astrophysics Data System (ADS)

Mickadeit, Fritz K.; Kemp, Helen; Schafer, Julia; Tong, William M.

1998-05-01

Laser wave-mixing spectroscopy is presented as a sub-Doppler method that offers not only high spectral resolution, but also excellent detection sensitivity. It offers spectral resolution suitable for hyperfine structure analysis and isotope ratio measurements. In a non-planar backward- scattering four-wave mixing optical configuration, two of the three input beams counter propagate and the Doppler broadening is minimized, and hence, spectral resolution is enhanced. Since the signal is a coherent beam, optical collection is efficient and signal detection is convenient. This simple multi-photon nonlinear laser method offers un usually sensitive detection limits that are suitable for trace-concentration isotope analysis using a few different types of simple analytical atomizers. Reliable measurement of hyperfine structures allows effective determination of isotope ratios for chemical analysis.

Lead isotope data bank; 2,624 samples and analyses cited

USGS Publications Warehouse

Doe, Bruce R.

1976-01-01

The Lead Isotope Data Bank (LIDB) was initiated to facilitate plotting data. Therefore, the Bank reflects data most often used in plotting rather than comprises a comprehensive tabulation of lead isotope data. Up until now, plotting was done using card decks processed by computer with tapes plotted by a Gerber plotter and more recently a CRT using a batch mode. Lack of a uniform format for sample identification was not a great impediment. With increase in the size of the bank, hand sorting is becoming prohibitive and ·plans are underway to put the bank into a uniform format on DISK with a card backup so that it may be accessed by use of IRIS on the DECK 10 computer at the U.S.G.S. facility in Denver. Plots will be constructed on a CRT. Entry of the bank into the IRIS accessing program is scheduled for completion in FY 1976

Multiconfiguration calculations of electronic isotope shift factors in Al i

NASA Astrophysics Data System (ADS)

Filippin, Livio; Beerwerth, Randolf; Ekman, Jörgen; Fritzsche, Stephan; Godefroid, Michel; Jönsson, Per

2016-12-01

The present work reports results from systematic multiconfiguration Dirac-Hartree-Fock calculations of electronic isotope shift factors for a set of transitions between low-lying levels of neutral aluminium. These electronic quantities together with observed isotope shifts between different pairs of isotopes provide the changes in mean-square charge radii of the atomic nuclei. Two computational approaches are adopted for the estimation of the mass- and field-shift factors. Within these approaches, different models for electron correlation are explored in a systematic way to determine a reliable computational strategy and to estimate theoretical error bars of the isotope shift factors.

Carbon dioxide in the atmosphere: isotopic exchange with ozone and its use as a tracer in the middle atmosphere

NASA Technical Reports Server (NTRS)

Yung, Y. L.; Lee, A. Y.; Irion, F. W.; DeMore, W. B.; Wen, J.

1997-01-01

Atmospheric heavy ozone is enriched in the isotopes 18O and 17O. The magnitude of this enhancement, of the order of 100%, is very large compared with that commonly known in atmospheric chemistry and geochemistry. The heavy oxygen atom in heavy ozone is therefore useful as a tracer of chemical species and pathways that involve ozone or its derived products. As a test of the isotopic exchange reactions, we successfully carry out a series of numerical experiments to simulate the results of the laboratory experiments performed by Wen and Thiemens [1993] on ozone and CO2. A small discrepancy between the experimental and the model values for 17O exchange is also revealed. The results are used to compute the magnitude of isotopic exchange between ozone and carbon dioxide via the excited atom O(1D) in the middle atmosphere. The model for 18O is in good agreement with the observed values.

Isotope labeling for studying RNA by solid-state NMR spectroscopy.

PubMed

Marchanka, Alexander; Kreutz, Christoph; Carlomagno, Teresa

2018-04-12

Nucleic acids play key roles in most biological processes, either in isolation or in complex with proteins. Often they are difficult targets for structural studies, due to their dynamic behavior and high molecular weight. Solid-state nuclear magnetic resonance spectroscopy (ssNMR) provides a unique opportunity to study large biomolecules in a non-crystalline state at atomic resolution. Application of ssNMR to RNA, however, is still at an early stage of development and presents considerable challenges due to broad resonances and poor dispersion. Isotope labeling, either as nucleotide-specific, atom-specific or segmental labeling, can resolve resonance overlaps and reduce the line width, thus allowing ssNMR studies of RNA domains as part of large biomolecules or complexes. In this review we discuss the methods for RNA production and purification as well as numerous approaches for isotope labeling of RNA. Furthermore, we give a few examples that emphasize the instrumental role of isotope labeling and ssNMR for studying RNA as part of large ribonucleoprotein complexes.

Unexpectedly large charge radii of neutron-rich calcium isotopes

DOE PAGES

Garcia Ruiz, R. F.; Bissell, M. L.; Blaum, K.; ...

2016-02-08

Here, despite being a complex many-body system, the atomic nucleus exhibits simple structures for certain ‘magic’ numbers of protons and neutrons. The calcium chain in particular is both unique and puzzling: evidence of doubly magic features are known in 40,48Ca, and recently suggested in two radioactive isotopes, 52,54Ca. Although many properties of experimentally known calcium isotopes have been successfully described by nuclear theory, it is still a challenge to predict the evolution of their charge radii. Here we present the first measurements of the charge radii of 49,51,52Ca, obtained from laser spectroscopy experiments at ISOLDE, CERN. The experimental results aremore » complemented by state-of-the-art theoretical calculations. The large and unexpected increase of the size of the neutron-rich calcium isotopes beyond N = 28 challenges the doubly magic nature of 52Ca and opens new intriguing questions on the evolution of nuclear sizes away from stability, which are of importance for our understanding of neutron-rich atomic nuclei.« less

Isotopic analysis of individual refractory metal nuggets using atom probe tomography

NASA Astrophysics Data System (ADS)

Daly, L.; Bland, P.; Schaefer, B. F.; Saxey, D. W.; Reddy, S.; Fougerouse, D.; William, R. D. A.; Forman, L. V.; Trimby, P.; La Fontaine, A.; Yang, L.; Cairney, J.; Ringer, S.

2016-12-01

Sub-micrometre metallic alloys of the highly siderophile elements, known as refractory metal nuggets (RMNs), can be found in primitive carbonaceous chondrites. There has been some suggestion that these grains may have a pre-solar origin, however their <1 µm size has meant that isotopic analysis of individual grains has not previously been possible. Atom probe microscopy has sufficient spatial resolution to quantify the isotopic compositions, across the entire mass range, of small sample volumes (<0.02 µm3) with high sensitivity and precision. We present analyses of four individual RMNs from the same refractory inclusion within the ALH 77307 meteorite. The results indicate that these RMNs have significant isotopic deviations from solar relative isotope abundances and therefore preserve a pre-solar isotopic signature. All RMNs exhibit large p-process enrichments in 98Ru and depletions in s-process 186Os. Two RMNs have a similar isotopic signature, suggesting formation in the same stellar environment. This similarity between two RMNs indicates that there may be a significant contribution of material to our solar system from a single source. The other two RMNs are isotopically dissimilar. Finally, three of the RMNs plot on a 187Re -187Os isochron from which we can derive a galactic age of 12.5 Ga ±1.8. To the best of our knowledge this is the first direct determination of the age of the Milky Way through physical analysis of non-solar material.

Clarifying atomic weights: A 2016 four-figure table of standard and conventional atomic weights

USGS Publications Warehouse

Coplen, Tyler B.; Meyers, Fabienne; Holden, Norman E.

2017-01-01

To indicate that atomic weights of many elements are not constants of nature, in 2009 and 2011 the Commission on Isotopic Abundances and Atomic Weights (CIAAW) of the International Union of Pure and Applied Chemistry (IUPAC) replaced single-value standard atomic weight values with atomic weight intervals for 12 elements (hydrogen, lithium, boron, carbon, nitrogen, oxygen, magnesium, silicon, sulfur, chlorine, bromine, and thallium); for example, the standard atomic weight of nitrogen became the interval [14.00643, 14.00728]. CIAAW recognized that some users of atomic weight data only need representative values for these 12 elements, such as for trade and commerce. For this purpose, CIAAW provided conventional atomic weight values, such as 14.007 for nitrogen, and these values can serve in education when a single representative value is needed, such as for molecular weight calculations. Because atomic weight values abridged to four figures are preferred by many educational users and are no longer provided by CIAAW as of 2015, we provide a table containing both standard atomic weight values and conventional atomic weight values abridged to four figures for the chemical elements. A retrospective review of changes in four-digit atomic weights since 1961 indicates that changes in these values are due to more accurate measurements over time or to the recognition of the impact of natural isotopic fractionation in normal terrestrial materials upon atomic weight values of many elements. Use of the unit “u” (unified atomic mass unit on the carbon mass scale) with atomic weight is incorrect because the quantity atomic weight is dimensionless, and the unit “amu” (atomic mass unit on the oxygen scale) is an obsolete term: Both should be avoided.

Energy levels for Ac-212 (Actinium-212)

NASA Astrophysics Data System (ADS)

Sukhoruchkin, S. I.; Soroko, Z. N.

This document is part of Subvolume C `Tables of Excitations of Proton- and Neutron-rich Unstable Nuclei' of Volume 19 `Nuclear States from Charged Particle Reactions' of Landolt-Börnstein - Group I `Elementary Particles, Nuclei and Atoms'. It provides energy levels for atomic nuclei of the isotope Ac-212 (actinium, atomic number Z = 89, mass number A = 212).

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

Characterizing fallout material using Cs and Pu atom ratios in environmental samples from the FDNPP fallout zone

NASA Astrophysics Data System (ADS)

Richards, David; Dunne, James; Martin, Peter; Scott, Tom; Yamashiki, Yosuke; Coath, Chris; Chen, Hart

2017-04-01

Here we report the use of combined of Cs and Pu isotope measurements to investigate the extensive plumes of radioactive fallout from the disaster at Fukishima Daiichi nuclear power plant (FNDPP) in March 2011. Among the aims of our study are improved assessment of the physico-chemical nature and changing distribution of land-based fallout. 135Cs/137Cs and 134Cs/137Cs atom ratios are indicative of conditions that relate to the nuclear fission reactions responsible for producing the respective radiocaesium isotopes, and offer much more in terms of forensic and chronological analysis than monitoring 137Cs alone. We briefly present methods to quantify the atom ratios of Cs and Pu isotopes in soil, lichen and moss samples from FDNPP catchment using mass spectrometry (ThermoTRITON for Cs and ThermoNEPTUNE for Pu). High precision data from Fukushima are presented (e.g decay corrected 135Cs/137Cs atom ratio = 0.384 ± 0.001 (n = 5) for roadside dust from Iitate region), and these are in agreement with prelimary estimates by others. We also confirm results for IAEA-330, a spinach sample collected from Polesskoe, Ukraine and subject to contamination from the Chernobyl accident. In addition to Cs isotopes, we adopt Pu isotopes to add a further dimension to the forensic analysis. We discuss the corrections required for background levels prior to the disaster, possibility for multiple components of fallout and complicating factors associated with remobilisation during the clean-up operation. In parallel with this work on digests and leaches from bulk environmental samples, we are refining methods for particle identification, isolation and characterisation using a complementary sequence of cutting-edge materials and manipulation techniques, including combined electron microscopy, focused ion beam techniques (Dualbeam), nano/micro manipulators and nano-scale imaging x-ray photoelectron spectroscopy (NanoESCA) and microCT.

Competition H(D) Kinetic Isotope Effects in the Autoxidation of Hydrocarbons

PubMed Central

Muchalski, Hubert; Levonyak, Alexander J.; Xu, Libin; Ingold, Keith U.; Porter, Ned A.

2016-01-01

Hydrogen atom transfer is central to many important radical chain sequences. We report here a method for determination of both the primary and secondary isotope effects for symmetrical substrates by the use of NMR. Intramolecular competition reactions were carried out on substrates having an increasing number of deuterium atoms at symmetry-related sites. Products that arise from peroxyl radical abstraction at each position of the various substrates reflect the competition rates for H(D) abstraction. The primary KIE for autoxidation of tetralin was determined to be 15.9 ± 1.4, a value that exceeds the maximum predicted by differences in H(D) zero-point energies (~7) and strongly suggests that H atom abstraction by the peroxyl radical occurs with substantial quantum mechanical tunneling. PMID:25533605

Competition H(D) kinetic isotope effects in the autoxidation of hydrocarbons.

PubMed

Muchalski, Hubert; Levonyak, Alexander J; Xu, Libin; Ingold, Keith U; Porter, Ned A

2015-01-14

Hydrogen atom transfer is central to many important radical chain sequences. We report here a method for determination of both the primary and secondary isotope effects for symmetrical substrates by the use of NMR. Intramolecular competition reactions were carried out on substrates having an increasing number of deuterium atoms at symmetry-related sites. Products that arise from peroxyl radical abstraction at each position of the various substrates reflect the competition rates for H(D) abstraction. The primary KIE for autoxidation of tetralin was determined to be 15.9 ± 1.4, a value that exceeds the maximum predicted by differences in H(D) zero-point energies (∼7) and strongly suggests that H atom abstraction by the peroxyl radical occurs with substantial quantum mechanical tunneling.

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.

STANDARD ATOMIC WEIGHTS TABLES 2007 ABRIDGED TO FOUR AND FIVE SIGNIFICANT FIGURES.

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

HOLDEN,N.E.

2007-08-01

In response to a recommendation to the Commission on Isotopic Abundances and Atomic Weights (CIAAW) that abridged versions of the Table on Standard Atomic Weights be prepared and published, this report has been prepared. A brief history is presented of such Atomic Weight tables that have been abridged to four significant figures and to five significant figures are noted. Tables of Standard Atomic Weight values abridged to four places and five places from the official 2007 Table of Atomic Weights approved by CIAAW are included.

Atomic Mass and Nuclear Binding Energy for U-287 (Uranium)

NASA Astrophysics Data System (ADS)

Sukhoruchkin, S. I.; Soroko, Z. N.

This document is part of the Supplement containing the complete sets of data of Subvolume B `Nuclei with Z = 55 - 100' of Volume 22 `Nuclear Binding Energies and Atomic Masses' of Landolt-Börnstein - Group I `Elementary Particles, Nuclei and Atoms', and additionally including data for nuclei with Z = 101 - 130. It provides atomic mass, mass excess, nuclear binding energy, nucleon separation energies, Q-values, and nucleon residual interaction parameters for atomic nuclei of the isotope U-287 (Uranium, atomic number Z = 92, mass number A = 287).

Atomic Mass and Nuclear Binding Energy for Ac-212 (Actinium)

NASA Astrophysics Data System (ADS)

Sukhoruchkin, S. I.; Soroko, Z. N.

This document is part of the Supplement containing the complete sets of data of Subvolume B `Nuclei with Z = 55 - 100' of Volume 22 `Nuclear Binding Energies and Atomic Masses' of Landolt-Börnstein - Group I `Elementary Particles, Nuclei and Atoms', and additionally including data for nuclei with Z = 101 - 130. It provides atomic mass, mass excess, nuclear binding energy, nucleon separation energies, Q-values, and nucleon residual interaction parameters for atomic nuclei of the isotope Ac-212 (Actinium, atomic number Z = 89, mass number A = 212).

Quantum Theory of an Atom Near Partially Reflecting Walls

DTIC Science & Technology

1987-06-15

rotating - wave approximations . Jaynes and Cummings5 but they are damped by the factor e -Y, where y is the , showed that the same sort of "Rabi...equation describing renewed interest in the Jaynes - Cummings model by the coupling of the atoms of the (dielectric) mirror to the describing certain... Jaynes - Cummings model in which one begins a priori way. DISTR1UTION ffATDi0I A 35 5081 @1987 The American Physical Society Approvd for pubWi MIM D19bi

The pressure dependence of oxygen-isotope-exchange rates between solution and apical oxygens on the UO 2(OH) 4 2- ion

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

Harley, Steven J.; Ohlin, C. Andre; Johnson, Rene L.

2011-04-06

The pressure dependence of isotope exchange rate was determined for apical oxygen atoms in the UO 2(OH) 4 2-(aq) ion. The results can be interpreted to indicate an associative character of the reaction.

Miniature Dual-Mode Absolute Scalar Magnetometer Based on the Rubidium Isotope 87Rb

NASA Astrophysics Data System (ADS)

Korth, H.; Strohbehn, K.; Kitching, J.

2016-10-01

Miniaturized absolute scalar magnetometer based on the rubidium isotope 87Rb takes advantage of recent breakthroughs in micro-fabricated atomic devices, has a total mass of 210 g and uses <1 W of power, and maintains a sensitivity of 0.1 nT rms.

Visualization of Radioisotope Detectability Over Time.

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

Huynh, Brady

A radioactive isotope is an atom that has an unstable nucleus. The isotope can undergo radioactive decay, the process in which excessive nuclear energy is emitted from the nucleus in many different forms, such as gamma radiation, alpha particles, or beta particles. The important thing to note is that these emissions act as a signature for the isotope. Each radioisotope has a particular emission spectrum, emitting radiation at different energies and at different rates.

The NO+O3 reaction: a triple oxygen isotope perspective on the reaction dynamics and atmospheric implications for the transfer of the ozone isotope anomaly.

PubMed

Savarino, J; Bhattacharya, S K; Morin, S; Baroni, M; Doussin, J-F

2008-05-21

Atmospheric nitrate shows a large oxygen isotope anomaly (Delta 17 O), characterized by an excess enrichment of 17 O over 18 O, similar to the ozone molecule. Modeling and observations assign this specific isotopic composition mainly to the photochemical steady state that exists in the atmosphere between ozone and nitrate precursors, namely, the nitrogen oxides (NOx=NO+NO2). However, this transfer is poorly quantified and is built on unverified assumptions about which oxygen atoms of ozone are transferred to NO(x), greatly weakening any interpretation of the nitrate oxygen isotopic composition in terms of chemical reaction pathways and the oxidation state of the atmosphere. With the aim to improve our understanding and quantify how nitrate inherits this unusual isotopic composition, we have carried out a triple isotope study of the reaction NO+O3. Using ozone intramolecular isotope distributions available in the literature, we have found that the central atom of the ozone is abstracted by NO with a probability of (8+/-5)%(+/-2 sigma) at room temperature. This result is at least qualitatively supported by dynamical reaction experiments, the non-Arrhenius behavior of the kinetic rate of this reaction, and the kinetic isotope fractionation factor. Finally, we have established the transfer function of the isotope anomaly of O3 to NO2, which is described by the linear relationship Delta 17 O(NO2)=A x Delta 17 O(O3)+B, with A=1.18+/-0.07(+/-1 sigma) and B=(6.6+/-1.5)[per thousand](+/-1 sigma). Such a relationship can be easily incorporated into models dealing with the propagation of the ozone isotope anomaly among oxygen-bearing species in the atmosphere and should help to better interpret the oxygen isotope anomaly of atmospheric nitrate in terms of its formation reaction pathways.

Changes in the mean square charge radii and electromagnetic moments of neutron-deficient Bi isotopes

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

Barzakh, A. E., E-mail: barzakh@mail.ru; Batist, L. Kh.; Fedorov, D. V.

In-source laser spectroscopy experiments for neutron deficient bismuth isotopes at the 306.77 nm atomic transition were carried out at the IRIS (Investigation of Radioactive Isotopes on Synchrocyclotron) facility of Petersburg Nuclear Physics Institute (PNPI). New data on isotope shifts and hyperfine structure for {sup 189–198,} {sup 211}Bi isotopes and isomers were obtained. The changes in the mean-square charge radii and the magnetic moment values were deduced. Marked deviation from the nearly spherical behavior for ground states of bismuth isotopes at N < 109 is demonstrated, in contrast to the lead and thallium isotopic chains. The big isomer shift between Imore » = 1/2 (intruder) and I = 9/2 (normal) states for odd Bi isotopes (A = 193, 195, 197) was found.« less

Inner- and outer-wall sorting of double-walled carbon nanotubes

NASA Astrophysics Data System (ADS)

Li, Han; Gordeev, Georgy; Wasserroth, Sören; Chakravadhanula, Venkata Sai Kiran; Neelakandhan, Shyam Kumar Chethala; Hennrich, Frank; Jorio, Ado; Reich, Stephanie; Krupke, Ralph; Flavel, Benjamin Scott

2017-12-01

Double-walled carbon nanotubes (DWCNTs) consist of two coaxially aligned single-walled carbon nanotubes (SWCNTs), and previous sorting methods only achieved outer-wall electronic-type selectivity. Here, a separation technique capable of sorting DWCNTs by semiconducting (S) or metallic (M) inner- and outer-wall electronic type is presented. Electronic coupling between the inner and outer wall is used to alter the surfactant coating around each of the DWCNT types, and aqueous gel permeation is used to separate them. Aqueous methods are used to remove SWCNT species from the raw material and prepare enriched DWCNT fractions. The enriched DWCNT fractions are then transferred into either chlorobenzene or toluene using the copolymer PFO-BPy to yield the four inner@outer combinations of M@M, M@S, S@M and S@S. The high purity of the resulting fractions is verified by absorption measurements, transmission electron microscopy, atomic force microscopy, resonance Raman mapping and high-density field-effect transistor devices.

Inner- and outer-wall sorting of double-walled carbon nanotubes.

PubMed

Li, Han; Gordeev, Georgy; Wasserroth, Sören; Chakravadhanula, Venkata Sai Kiran; Neelakandhan, Shyam Kumar Chethala; Hennrich, Frank; Jorio, Ado; Reich, Stephanie; Krupke, Ralph; Flavel, Benjamin Scott

2017-12-01

Double-walled carbon nanotubes (DWCNTs) consist of two coaxially aligned single-walled carbon nanotubes (SWCNTs), and previous sorting methods only achieved outer-wall electronic-type selectivity. Here, a separation technique capable of sorting DWCNTs by semiconducting (S) or metallic (M) inner- and outer-wall electronic type is presented. Electronic coupling between the inner and outer wall is used to alter the surfactant coating around each of the DWCNT types, and aqueous gel permeation is used to separate them. Aqueous methods are used to remove SWCNT species from the raw material and prepare enriched DWCNT fractions. The enriched DWCNT fractions are then transferred into either chlorobenzene or toluene using the copolymer PFO-BPy to yield the four inner@outer combinations of M@M, M@S, S@M and S@S. The high purity of the resulting fractions is verified by absorption measurements, transmission electron microscopy, atomic force microscopy, resonance Raman mapping and high-density field-effect transistor devices.

Counting individual sulfur atoms in a protein by ultrahighresolution Fourier transform ion cyclotron resonance mass spectrometry: Experimental resolution of isotopic fine structure in proteins

PubMed Central

Shi, Stone D.-H.; Hendrickson, Christopher L.; Marshall, Alan G.

1998-01-01

A typical molecular ion mass spectrum consists of a sum of signals from species of various possible isotopic compositions. Only the monoisotopic peak (e.g., all carbons are 12C; all nitrogens are 14N, etc.) has a unique elemental composition. Every other isotope peak at approximately integer multiples of ∼1 Da higher in nominal mass represents a sum of contributions from isotope combinations differing by a few mDa (e.g., two 13C vs. two 15N vs. one 13C and one 15N vs. 34S, vs. 18O, etc., at ∼2 Da higher in mass than the monoisotopic mass). At sufficiently high mass resolving power, each of these nominal-mass peaks resolves into its isotopic fine structure. Here, we report resolution of the isotopic fine structure of proteins up to 15.8 kDa (isotopic 13C,15N doubly depleted tumor suppressor protein, p16), made possible by electrospray ionization followed by ultrahigh-resolution Fourier transform ion cyclotron resonance mass analysis at 9.4 tesla. Further, a resolving power of m/Δm50% ≈8,000,000 has been achieved on bovine ubiquitin (8.6 kDa). These results represent a 10-fold increase in the highest mass at which isotopic fine structure previously had been observed. Finally, because isotopic fine structure reveals elemental composition directly, it can be used to confirm or determine molecular formula. For p16, for example, we were able to determine (5.1 ± 0.3) the correct number (five) of sulfur atoms solely from the abundance ratio of the resolved 34S peak to the monoisotopic peak. PMID:9751700

Sedimentary processes on the Mekong subaqueous delta: Clay mineral and geochemical analysis

NASA Astrophysics Data System (ADS)

Xue, Zuo; Paul Liu, J.; DeMaster, Dave; Leithold, Elana L.; Wan, Shiming; Ge, Qian; Nguyen, Van Lap; Ta, Thi Kim Oanh

2014-01-01

Sedimentary processes on the inner Mekong Shelf were investigated by examining the characteristics of sediments sampled in gravity cores at 15 locations, including grain size, clay mineralogy, sediment accumulation rates, and the elemental and stable carbon isotopic composition of organic matter (atomic C/N ratios and δ13C). Deltaic deposits exhibit contrasting characteristics along different sides of the delta plain (South China Sea, SCS hereafter, to the east and Gulf of Thailand, GOT hereafter, to the west) as well as on and off the subaqueous deltaic system. On one hand, cores recovered from the subaqueous delta in the SCS/GOT are consisted of poorly/well sorted sediments with similar/different clay mineral assemblage with/from Mekong sediments. Excess 210Pb profiles, supported by 14C chronologies, indicate either "non-steady" (SCS side) or "rapid accumulation" (GOT side) processes on the subaqueous delta. The δ13C and C/N ratio indicate a mixture of terrestrial and marine-sourced organic matter in the deltaic sediment. On the other hand, cores recovered from areas with no deltaic deposits or seaward of the subaqueous delta show excess 210Pb profiles indicating "steady-state" accumulation with a greater proportion of marine-sourced organic matter. Core analysis's relevance with local depositional environment and previous acoustic profiling are discussed.

The New Element Curium (Atomic Number 96)

DOE R&D Accomplishments Database

Seaborg, G. T.; James, R. A.; Ghiorso, A.

1948-01-01

Two isotopes of the element with atomic number 96 have been produced by the helium-ion bombardment of plutonium. The name curium, symbol Cm, is proposed for element 96. The chemical experiments indicate that the most stable oxidation state of curium is the III state.

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.

Environmental site description for a Uranium Atomic Vapor Laser Isotope Separation (U-AVLIS) production plant at the Paducah Gaseous Diffusion Plant site

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

Marmer, G.J.; Dunn, C.P.; Moeller, K.L.

Uranium enrichment in the United States has utilized a diffusion process to preferentially enrich the U-235 isotope in the uranium product. The U-AVLIS process is based on electrostatic extraction of photoionized U-235 atoms from an atomic vapor stream created by electron-beam vaporization of uranium metal alloy. The U-235 atoms are ionized when precisely tuned laser light -- of appropriate power, spectral, and temporal characteristics -- illuminates the uranium vapor and selectively photoionizes the U-235 isotope. A programmatic document for use in screening DOE site to locate a U-AVLIS production plant was developed and implemented in two parts. The first partmore » consisted of a series of screening analyses, based on exclusionary and other criteria, that identified a reasonable number of candidate sites. These sites were subjected to a more rigorous and detailed comparative analysis for the purpose of developing a short list of reasonable alternative sites for later environmental examination. This environmental site description (ESD) provides a detailed description of the PGDP site and vicinity suitable for use in an environmental impact statement (EIS). The report is based on existing literature, data collected at the site, and information collected by Argonne National Laboratory (ANL) staff during a site visit. 65 refs., 15 tabs.« less

Gold and isotopically enriched platinium targets for the production of radioactive beams of francium

NASA Astrophysics Data System (ADS)

Lipski, A. R.; Orozco, L. A.; Pearson, M. R.; Simsarian, J. E.; Sprouse, G. D.; Zhao, W. Z.

1999-12-01

Au and isotopically enriched Pt targets are discussed for the production of radioactive Fr beams. Target foils, serving also as ionizers, have to be heated in order to enhance the diffusion of atoms to the surface for further extraction and injection into the electrostatic transport system.

Nuclear spectroscopy of r-process nuclei around N = 126 using KISS

NASA Astrophysics Data System (ADS)

Hirayama, Y.; Watanabe, Y. X.; Miyatake, H.; Schury, P.; Wada, M.; Oyaizu, M.; Kakiguchi, Y.; Mukai, M.; Kimura, S.; Ahmed, M.; Jeong, S. C.; Moon, J. Y.; Park, J. H.

2017-09-01

The beta-decay properties and atomic mass of nuclei with neutron magic number of N = 126 are considered critical for understanding the production of heavy elements such as gold and platinum at astrophysical sites. We will produce and measure the half-lives and masses of the nuclei with Z = 74-77 around N = 126 by using the multinucleon transfer (MNT) reaction of ^{136} Xe/ ^{238} U beams and ^{198} Pt target system. For this purpose, we have constructed the KEK Isotope Separation System (KISS) at RIKEN RIBF facility. KISS consists of an argon gas cell based laser ion source (atomic number selection) and an isotope separation on-line (ISOL) (mass number selection), to produce pure low-energy beams of neutron-rich isotopes around N = 126 . We performed the on-line tests to study the basic properties of the KISS and, successfully extracted laser-ionized nuclei around N = 126.

Stable-isotope analysis of a deep-sea benthic-fish assemblage: evidence of an enriched benthic food web.

PubMed

Boyle, M D; Ebert, D A; Cailliet, G M

2012-04-01

In this study, fishes and invertebrates collected from the continental slope (1000 m) of the eastern North Pacific Ocean were analysed using stable-isotope analysis (SIA). Resulting trophic positions (T(P) ) were compared to known diets and habitats from the literature. Dual isotope plots indicated that most species groups (invertebrates and fishes) sorted as expected along the carbon and nitrogen axes, with less intraspecific variability than interspecific variability. Results also indicated an isotopically distinct benthic and pelagic food web, as the benthic food web was more enriched in both nitrogen and carbon isotopes. Trophic positions from SIA supported this finding, resulting in the assignment of fishes to different trophic positions from those expected based on published dietary information. These differences can be explained largely by the habitat of the prey and the percentage of the diet that was scavenged. A mixing model estimated dietary contributions of prey similar to those of the known diet of Bathyraja trachura from stomach-content analysis (SCA). Linear regressions indicated that trophic positions calculated from SIA and SCA, when plotted against B. trachura total length for 32 individuals, exhibited similar variation and patterns. Only the T(P) from SCA yielded significant results (stomach content: P < 0·05, stable isotope: P > 0·05). © 2012 The Authors. Journal of Fish Biology © 2012 The Fisheries Society of the British Isles.

Neutral atom analyzers for diagnosing hot plasmas: A review of research at the ioffe physicotechnical institute

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

Kislyakov, A. I.; Petrov, M. P.

2009-07-15

Research on neutral particle diagnostics of thermonuclear plasmas that has been carried out in recent years at the Ioffe Physicotechnical Institute of the Russian Academy of Sciences (St. Petersburg, Russia) is reviewed. Work on the creation and improvement of neutral atom analyzers was done in two directions: for potential applications (in particular, on the International Thermonuclear Experimental Reactor, which is now under construction at Cadarache in France) and for investigation of the ion plasma component in various devices (in particular, in the largest tokamaks, such as JET, TFTR, and JT-60). Neutral atom analyzers are the main tool for studying themore » behavior of hydrogen ions and isotopes in magnetic confinement systems. They make it possible to determine energy spectra, to perform the isotope analysis of atom fluxes from the plasma, to measure the absolute intensity of the fluxes, and to record how these parameters vary with time. A comparative description of the analyzers developed in recent years at the Ioffe Institute is given. These are ACORD-12/24 analyzers for recording 0.2-100-keV hydrogen and deuterium atoms with a tunable range of simultaneously measured energies, CNPA compact analyzers for a fixed energy gain in the ranges 80-1000 eV and 0.8-100 keV, an ISEP analyzer for simultaneously recording the atoms of all the three hydrogen isotopes (H, D, and T) in the energy range 5-700 keV, and GEMMA analyzers for recording atom fluxes of hydrogen and helium isotopes in the range 0.1-4 MeV. The scintillating detectors of the ISEP and GEMMA analyzers have a lowered sensitivity to neutrons and thus can operate without additional shielding in neutron fields of up to 10{sup 9} n/(cm{sup 2} s). These two types of analyzers, intended to operate under deuterium-tritium plasma conditions, are prototypes of atom analyzers created at the Ioffe Institute for use in the International Thermonuclear Experimental Reactor. With these analyzers, a number of new results have been obtained in recent years in various devices. Some results are presented from investigation of ions in the Globus-M spherical tokamak, the W7-AS stellarator, and the JET tokamak by means of the analyzers developed at the Ioffe Institute. Challenges and opportunities for applying these diagnostics in the International Thermonuclear Experimental Reactor project are discussed.« less

HYPERFINE STRUCTURES AND NUCLEAR MOMENTS OF Lu$sup 176$m, Br$sup 80$, Br$sup 80$m, AND I$sup 132$ (thesis)

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

White, M.B.

1962-09-01

The method of atomic-beam radiofrequency spectroscopy was used to determine some nuclear and atomic properties of Lu/sup 176m/, Br/sup 80/, Br/sup 80m/, and I/sup 132/. Hyperfine structure me asurements were raade to determine the magnetic dipole interaction constants and the electric quadrupole interaction constants of all these isotopes. Also the nuclear spin and the electronic g/sub J/ factor were measured for Lu/sup 176m/, and the nuclear magnetic dipole moments and the electric quadrupole moments for the isotopes were calculated. All results are listed. 62 references. (auth)

Neutron scattering at the high flux isotope reactor at Oak Ridge National Laboratory

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

Yethiraj, M.; Fernandez-Baca, J.A.

Since its beginnings in Oak Ridge and Argonne in the late 1940`s, neutron scattering has been established as the premier tool to study matter in its various states. Since the thermal neutron wavelength is of the same order of magnitude as typical atomic spacings and because they have comparable energies to those of atomic excitations in solids, both structure and dynamics of matter can be studied via neutron scattering. The High Flux Isotope Reactor (HFIR) provides an intense source of neutrons with which to carry out these measurements. This paper summarizes the available neutron scattering facilities at the HFIR.

The New Element Berkelium (Atomic Number 97)

DOE R&D Accomplishments Database

Seaborg, G. T.; Thompson, S. G.; Ghiorso, A.

1950-04-26

An isotope of the element with atomic number 97 has been discovered as a product of the helium-ion bombardment of americium. The name berkelium, symbol Bk, is proposed for element 97. The chemical separation of element 97 from the target material and other reaction products was made by combinations of precipitation and ion exchange adsorption methods making use of its anticipated (III) and (IV) oxidation states and its position as a member of the actinide transition series. The distinctive chemical properties made use of in its separation and the equally distinctive decay properties of the particular isotope constitute the principal evidence for the new element.

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

Orozco, Luis A

This is a report of the construction of a Francium Trapping Facility (FTF) at the Isotope Separator and Accelerator (ISAC) of TRIUMF in Vancouver, Canada, where the Francium Parity Non Conservation (FrPNC) international collaboration has its home. This facility will be used to study fundamental symmetries with high-resolution atomic spectroscopy. The primary scientific objective of the program is a measurement of the anapole moment of francium in a chain of isotopes by observing the parity violation induced by the weak interaction. The anapole moment of francium and associated signal are expected to be ten times larger than in cesium, themore » only element in which an anapole moment has been observed. The measurement will provide crucial information for better understanding weak hadronic interactions in the context of Quantum Chromodynamics (QCD). The methodology combines nuclear and particle physics techniques for the production of francium with precision measurements based on laser cooling and trapping and microwave spectroscopy. The program builds on an initial series of atomic spectroscopy measurements of the nuclear structure of francium, based on isotope shifts and hyperfine anomalies, before conducting the anapole moment measurements, these measurements performed during commissioning runs help understand the atomic and nuclear structure of Fr.« less

Spectroscopy of Lithium Atoms and Molecules on Helium Nanodroplets

PubMed Central

2013-01-01

We report on the spectroscopic investigation of lithium atoms and lithium dimers in their triplet manifold on the surface of helium nanodroplets (HeN). We present the excitation spectrum of the 3p ← 2s and 3d ← 2s two-photon transitions for single Li atoms on HeN. The atoms are excited from the 2S(Σ) ground state into Δ, Π, and Σ pseudodiatomic molecular substates. Excitation spectra are recorded by resonance enhanced multiphoton ionization time-of-flight (REMPI-TOF) mass spectroscopy, which allows an investigation of the exciplex (Li*–Hem, m = 1–3) formation process in the Li–HeN system. Electronic states are shifted and broadened with respect to free atom states, which is explained within the pseudodiatomic model. The assignment is assisted by theoretical calculations, which are based on the Orsay–Trento density functional where the interaction between the helium droplet and the lithium atom is introduced by a pairwise additive approach. When a droplet is doped with more than one alkali atom, the fragility of the alkali–HeN systems leads preferably to the formation of high-spin molecules on the droplets. We use this property of helium nanodroplets for the preparation of Li dimers in their triplet ground state (13Σu+). The excitation spectrum of the 23Πg(ν′ = 0–11) ← 13Σu+(ν″ = 0) transition is presented. The interaction between the molecule and the droplet manifests in a broadening of the transitions with a characteristic asymmetric form. The broadening extends to the blue side of each vibronic level, which is caused by the simultaneous excitation of the molecule and vibrations of the droplet (phonons). The two isotopes of Li form 6Li2 and 7Li2 as well as isotope mixed 6Li7Li molecules on the droplet surface. By using REMPI-TOF mass spectroscopy, isotope-dependent effects could be studied. PMID:23895106

Atom exchange between aqueous Fe(II) and structural Fe in clay minerals.

PubMed

Neumann, Anke; Wu, Lingling; Li, Weiqiang; Beard, Brian L; Johnson, Clark M; Rosso, Kevin M; Frierdich, Andrew J; Scherer, Michelle M

2015-03-03

Due to their stability toward reductive dissolution, Fe-bearing clay minerals are viewed as a renewable source of Fe redox activity in diverse environments. Recent findings of interfacial electron transfer between aqueous Fe(II) and structural Fe in clay minerals and electron conduction in octahedral sheets of nontronite, however, raise the question whether Fe interaction with clay minerals is more dynamic than previously thought. Here, we use an enriched isotope tracer approach to simultaneously trace Fe atom movement from the aqueous phase to the solid ((57)Fe) and from the solid into the aqueous phase ((56)Fe). Over 6 months, we observed a significant decrease in aqueous (57)Fe isotope fraction, with a fast initial decrease which slowed after 3 days and stabilized after about 50 days. For the aqueous (56)Fe isotope fraction, we observed a similar but opposite trend, indicating that Fe atom movement had occurred in both directions: from the aqueous phase into the solid and from the solid into aqueous phase. We calculated that 5-20% of structural Fe in clay minerals NAu-1, NAu-2, and SWa-1 exchanged with aqueous Fe(II), which significantly exceeds the Fe atom layer exposed directly to solution. Calculations based on electron-hopping rates in nontronite suggest that the bulk conduction mechanism previously demonstrated for hematite1 and suggested as an explanation for the significant Fe atom exchange observed in goethite2 may be a plausible mechanism for Fe atom exchange in Fe-bearing clay minerals. Our finding of 5-20% Fe atom exchange in clay minerals indicates that we need to rethink how Fe mobility affects the macroscopic properties of Fe-bearing phyllosilicates and its role in Fe biogeochemical cycling, as well as its use in a variety of engineered applications, such as landfill liners and nuclear repositories.

Preservation Methods Alter Carbon and Nitrogen Stable Isotope Values in Crickets (Orthoptera: Grylloidea)

PubMed Central

Jesus, Fabiene Maria; Pereira, Marcelo Ribeiro; Rosa, Cassiano Sousa; Moreira, Marcelo Zacharias; Sperber, Carlos Frankl

2015-01-01

Stable isotope analysis (SIA) is an important tool for investigation of animal dietary habits for determination of feeding niche. Ideally, fresh samples should be used for isotopic analysis, but logistics frequently demands preservation of organisms for analysis at a later time. The goal of this study was to establish the best methodology for preserving forest litter-dwelling crickets for later SIA analysis without altering results. We collected two cricket species, Phoremia sp. and Mellopsis doucasae, from which we prepared 70 samples per species, divided among seven treatments: (i) freshly processed (control); preserved in fuel ethanol for (ii) 15 and (iii) 60 days; preserved in commercial ethanol for (iv) 15 and (v) 60 days; fresh material frozen for (vi) 15 and (vii) 60 days. After oven drying, samples were analyzed for δ 15N, δ 13C values, N(%), C(%) and C/N atomic values using continuous flow isotope ratio mass spectrometry. All preservation methods tested, significantly impacted δ 13C and δ 15N and C/N atomic values. Chemical preservatives caused δ 13C enrichment as great as 1.5‰, and δ 15N enrichment as great as 0.9‰; the one exception was M. doucasae stored in ethanol for 15 days, which had δ 15N depletion up to 1.8‰. Freezing depleted δ 13C and δ 15N by up to 0.7 and 2.2‰, respectively. C/N atomic values decreased when stored in ethanol, and increased when frozen for 60 days for both cricket species. Our results indicate that all preservation methods tested in this study altered at least one of the tested isotope values when compared to fresh material (controls). We conclude that only freshly processed material provides adequate SIA results for litter-dwelling crickets. PMID:26390400

Preservation Methods Alter Carbon and Nitrogen Stable Isotope Values in Crickets (Orthoptera: Grylloidea).

PubMed

Jesus, Fabiene Maria; Pereira, Marcelo Ribeiro; Rosa, Cassiano Sousa; Moreira, Marcelo Zacharias; Sperber, Carlos Frankl

2015-01-01

Stable isotope analysis (SIA) is an important tool for investigation of animal dietary habits for determination of feeding niche. Ideally, fresh samples should be used for isotopic analysis, but logistics frequently demands preservation of organisms for analysis at a later time. The goal of this study was to establish the best methodology for preserving forest litter-dwelling crickets for later SIA analysis without altering results. We collected two cricket species, Phoremia sp. and Mellopsis doucasae, from which we prepared 70 samples per species, divided among seven treatments: (i) freshly processed (control); preserved in fuel ethanol for (ii) 15 and (iii) 60 days; preserved in commercial ethanol for (iv) 15 and (v) 60 days; fresh material frozen for (vi) 15 and (vii) 60 days. After oven drying, samples were analyzed for δ15N, δ13C values, N(%), C(%) and C/N atomic values using continuous flow isotope ratio mass spectrometry. All preservation methods tested, significantly impacted δ13C and δ15N and C/N atomic values. Chemical preservatives caused δ13C enrichment as great as 1.5‰, and δ15N enrichment as great as 0.9‰; the one exception was M. doucasae stored in ethanol for 15 days, which had δ15N depletion up to 1.8‰. Freezing depleted δ13C and δ15N by up to 0.7 and 2.2‰, respectively. C/N atomic values decreased when stored in ethanol, and increased when frozen for 60 days for both cricket species. Our results indicate that all preservation methods tested in this study altered at least one of the tested isotope values when compared to fresh material (controls). We conclude that only freshly processed material provides adequate SIA results for litter-dwelling crickets.

Amino Acid Selective 13C Labeling and 13C Scrambling Profile Analysis of Protein α and Side-Chain Carbons in Escherichia coli Utilized for Protein Nuclear Magnetic Resonance.

PubMed

Sugiki, Toshihiko; Furuita, Kyoko; Fujiwara, Toshimichi; Kojima, Chojiro

2018-06-20

Amino acid selective isotope labeling is an important nuclear magnetic resonance technique, especially for larger proteins, providing strong bases for the unambiguous resonance assignments and information concerning the structure, dynamics, and intermolecular interactions. Amino acid selective 15 N labeling suffers from isotope dilution caused by metabolic interconversion of the amino acids, resulting in isotope scrambling within the target protein. Carbonyl 13 C atoms experience less isotope scrambling than the main-chain 15 N atoms do. However, little is known about the side-chain 13 C atoms. Here, the 13 C scrambling profiles of the Cα and side-chain carbons were investigated for 15 N scrambling-prone amino acids, such as Leu, Ile, Tyr, Phe, Thr, Val, and Ala. The level of isotope scrambling was substantially lower in 13 Cα and 13 C side-chain labeling than in 15 N labeling. We utilized this reduced scrambling-prone character of 13 C as a simple and efficient method for amino acid selective 13 C labeling using an Escherichia coli cold-shock expression system and high-cell density fermentation. Using this method, the 13 C labeling efficiency was >80% for Leu and Ile, ∼60% for Tyr and Phe, ∼50% for Thr, ∼40% for Val, and 30-40% for Ala. 1 H- 15 N heteronuclear single-quantum coherence signals of the 15 N scrambling-prone amino acid were also easily filtered using 15 N-{ 13 Cα} spin-echo difference experiments. Our method could be applied to the assignment of the 55 kDa protein.

ATTA-3: a State-of-the-Art Instrument for Radio-Krypton Dating

NASA Astrophysics Data System (ADS)

Jiang, W.; Zappala, J. C.; Bailey, K.; Lu, Z.; Müller, P.; O'Connor, T. P.

2013-12-01

The ATTA-3 instrument at Argonne has recently enabled routine Kr-81 dating. The instrument is based on Atom Trap Trace Analysis (ATTA), a novel laser based atom counting technique that allows detection of long lived noble gas radioisotopes (Kr-81, Kr-85 and Ar-39) with extremely low abundance (1E-16 to 1E-10). At the center of the instrument is a magneto-optical trap (MOT), which traps and counts only the atoms of the desired isotope. This unique feature makes ATTA free of interference from any other isotopes or molecular species. For Kr-81 dating in the age range of 150 - 1,500 kyr, the required sample size is 5 - 10 micro-L STP of krypton gas, which can be extracted from approximately 100 - 200 kg of water or 40 - 80 kg of ice. Several recent developments in our lab may lead to further improvements to the current ATTA-3 apparatus: 1) The isotopic abundance ratio between the unknown, rare isotope (either Kr-81 or Kr-85) and the stable, abundant isotope (Kr-83) is measured. Here the stable isotope serves as a control isotope. A new method has been developed that allows more accurate measurements of the control isotope Kr-83. Combined with the ability to measure the rare Kr-81 and Kr-85 isotopes, this scheme allows ATTA-3 to directly determine 81Kr/Kr and 85Kr/Kr ratios without other supplemental measurements, to reduce the overall uncertainties of the measured isotope ratios, and also to improve the long term stability of the system. 2) The current capacity of the ATTA-3 instrument is about 120 samples per year. The throughput is mainly limited by the so called 'memory effect', which is caused by the residual samples trapped in the system after each measurement. These residual samples are gradually released in subsequent measurements, causing cross-sample contaminations. In order to mitigate this problem, we wash the system with a xenon discharge for about 36 hours between measurements. This practice limits the overall sample processing speed. Preliminary investigations of the memory effect indicate that it can be reduced and the wash time between measurements shortened. This will increase the number of samples that the ATTA-3 instrument can handle annually in the future. This work is supported by DOE, Office of Nuclear Physics, under contract DE-AC02-06CH11357.

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.

Research on the properties and interactions of simple atomic and ionic systems

NASA Technical Reports Server (NTRS)

Novick, R.

1972-01-01

Simple ionic systems were studied, such as metastable autoionizing states of the negative He ion, two-photon decay spectrum of metastable He ion, optical excitation with low energy ions, and lifetime measurements of singly ionized Li and metastable He ion. Simple atomic systems were also investigated. Metastable autoionizing atomic energy levels in alkali elements were included, along with lifetime measurements of Cr-53, group 2A isotopes, and alkali metal atoms using level crossing and optical double resonance spectroscopy.

Synthesis of isotopically labeled R- or S-[.sup.13C, .sup.2H] glycerols

DOEpatents

Martinez, Rodolfo A [Santa Fe, NM; Unkefer, Clifford J [Los Alamos, NM; Alvarez, Marc A [Santa Fe, NM

2008-01-22

The present invention is directed to asymmetric chiral labeled glycerols including at least one chiral atom, from one to two .sup.13C atoms and from zero to four deuterium atoms bonded directly to a carbon atom, e.g., (2S) [1,2-.sup.13C.sub.2]glycerol and (2R) [1,2-.sup.13C.sub.2]glycerol, and to the use of such chiral glycerols in the preparation of labeled amino acids.

Carbon cycling in terrestrial environments: Chapter 17

USGS Publications Warehouse

Wang, Yang; Huntington, Thomas G.; Osher, Laurie J.; Wassenaar, Leonard I; Trumbore, Susan E.; Amundson, Ronald; Harden, Jennifer W.; McKnight, Diane M.; Schiff, Sherry L.; Aiken, George R.; Lyons, W. Berry; Aravena, Ramon O.; Baron, Jill S.

1998-01-01

This chapter reviews a number of applications of isotopic techniques for the investigation of carbon cycling processes. Carbon dioxide (C02) is an important greenhouse gas. Its concentration in the atmosphere has increased from an estimated 270 ppm at the beginning of the industrial revolution to ∼ 360 ppm at present. Climatic conditions and atmospheric C02 concentration also influence isotopic discrimination during photosynthesis. Natural and anthropogenically induced variations in the carbon isotopic abundance can be exploited to investigate carbon transformations between pools on various time scales. It also discusses one of the isotopes of carbon, the 14C, that is produced in the atmosphere by interactions of cosmic-ray produced neutrons with stable isotopes of nitrogen (N), oxygen (O), and carbon (C), and has a natural abundance in the atmosphere of ∼1 atom 14 C per 1012 atoms 12C. The most important factor affecting the measured 14C ages of soil organic matter is the rate of organic carbon cycling in soils. Differences in the dynamics of soil carbon among different soils or soil horizons will result in different soil organic 14C signatures. As a result, the deviation of the measured 14C age from the true age could differ significantly among different soils or soil horizons.

Can the waiting-point nucleus 78Ni be studied at an on-line mass-separator?

NASA Astrophysics Data System (ADS)

Wöhr, A.; Andreyev, A.; Bijnens, N.; Breitenbach, J.; Franchoo, S.; Huyse, M.; Kudryavtsev, Y. A.; Piechaczek, A.; Raabe, R. R.; Reusen, I.; Vermeeren, L.; Van Duppen, P.

1997-02-01

Short-lived nickel isotopes have been studied using a chemically selective Ion Guide Laser Ion Source (IGLIS) based on resonance ionisation of atoms at the Leuven Isotope Separator On-Line (LISOL) separator. The decay properties of different Ni isotopes have been studied using β-γ-coincidences. Experimental production rates of proton induced fission of 238U are obtained for 69,71Ni. These numbers are in a strong disagreement with Silberg-Tsao calculations.

Barium isotopes in Allende meteorite - Evidence against an extinct superheavy element

NASA Technical Reports Server (NTRS)

Lewis, R. S.; Anders, E.; Shimamura, T.; Lugmair, G. W.

1983-01-01

Carbon and chromite fractions from the Allende meteorite that contain isotopically anomalous xenon-131 to xenon-136 (carbonaceous chondrite fission or CCF xenon) at up to 5 x 10 to the 11th atoms per gram show no detectable isotopic anomalies in barium-130 to barium-138. This rules out the possibility that the CCF xenon was formed by in situ fission of an extinct superheavy element. Apparently the CCF xenon and its carbonaceous carrier are relics from stellar nucleosynthesis.

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.

Measurement of the 17O-excess (Δ17O) of tropospheric ozone using a nitrite-coated filter.

PubMed

Vicars, William C; Bhattacharya, S K; Erbland, Joseph; Savarino, Joël

2012-05-30

The (17)O-excess (Δ(17)O) of tropospheric ozone (O(3)) serves as a useful marker in studies of atmospheric oxidation pathways; however, due to the complexity and expense of currently available analytical techniques, no systematic sampling campaign has yet been undertaken and natural variations in Δ(17)O(O(3)) are therefore not well constrained. The nitrite-coated filter method is a new technique for O(3) isotope analysis that employs the aqueous phase NO(2)(-) + O(3) → NO(3)(-) + O(2) reaction to obtain quantitative information on O(3) via the oxygen atom transfer to nitrate (NO(3)(-)). The triple-oxygen isotope analysis of the NO(3)(-) produced during this reaction, achieved in this study using the bacterial denitrifier method followed by isotope-ratio mass spectrometry (IRMS), directly yields the Δ(17)O value transferred from O(3). This isotope transfer process was investigated in a series of vacuum-line experiments, which were conducted by exposing coated filters to O(3) of various known Δ(17)O values and then determining the isotopic composition of the NO(3)(-) produced on the filter. The isotope transfer experiments revealed a strong linear correlation between the Δ(17)O of the O(3) produced and that of the oxygen atom transferred to NO(3)(-), with a slope of 1.55 for samples with bulk Δ(17)O(O(3)) values in the atmospheric range (20-40‰). This finding is in agreement with theoretical postulates that place the (17) O-excess on only the terminal oxygen atoms of ozone. Ambient measurements yield average Δ(17)O(O(3))(bulk) values in agreement with previous studies (22.9 ± 1.9‰). The nitrite-coated filter technique is a sufficiently robust, field-deployable method for the determination of the triple-oxygen isotopic composition of tropospheric O(3). Further ambient measurements will undoubtedly lead to an improved quantitative view of natural Δ(17)O(O(3)) variation and transfer in the atmosphere. Copyright © 2012 John Wiley & Sons, Ltd.

Kankan diamonds (Guinea) III: δ13C and nitrogen characteristics of deep diamonds

NASA Astrophysics Data System (ADS)

Stachel, T.; Harris, J. W.; Aulbach, S.; Deines, P.

Diamonds from the Kankan area in Guinea formed over a large depth profile beginning within the cratonic mantle lithosphere and extending through the asthenosphere and transition zone into the lower mantle. The carbon isotopic composition, the concentration of nitrogen impurities and the nitrogen aggregation level of diamonds representing this entire depth range have been determined. Peridotitic and eclogitic diamonds of lithospheric origin from Kankan have carbon isotopic compositions (δ13C: peridotitic -5.4 to -2.2‰ eclogitic -19.7 to -0.7‰) and nitrogen characteristics (N: peridotitic 17-648 atomic ppm; eclogitic 0-1,313 atomic ppm; aggregation from IaA to IaB) which are generally typical for diamonds of these two suites worldwide. Geothermobarometry of peridotitic and eclogitic inclusion parageneses (worldwide sources) indicates that both suites formed under very similar conditions within the cratonic lithosphere, which is not consistent with a derivation of diamonds with light carbon isotopic composition from subducted organic matter within subducting oceanic slabs. Diamonds containing majorite garnet inclusions fall to the isotopically heavy side (δ13C: -3.1‰ to +0.9‰) of the worldwide diamond population. Nitrogen contents are low (0-126 atomic ppm) and one of the two nitrogen-bearing diamonds shows such a low level of nitrogen aggregation (30% B-centre) that it cannot have been exposed to ambient temperatures of the transition zone (>=1,400 °C) for more than 0.2 Ma. This suggests rapid upward transport and formation of some Kankan diamonds pene-contemporaneous to Cretaceous kimberlite activity. Similar to these diamonds from the asthenosphere and the transition zone, lower mantle diamonds show a small shift towards isotopic heavy compositions (-6.6 to -0.5‰, mode at -3.5‰). As already observed for other mines, the nitrogen contents of lower mantle diamonds were below detection (using FTIRS). The mutual shift of sublithospheric diamonds towards isotopic heavier compositions suggests a common carbon source, which may have inherited an isotopic heavy composition from a component consisting of subducted carbonates.

Kankan diamonds (Guinea) III: δ13C and nitrogen characteristics of deep diamonds

NASA Astrophysics Data System (ADS)

Stachel, T.; Harris, J. W.; Aulbach, S.; Deines, P.

2001-08-01

Diamonds from the Kankan area in Guinea formed over a large depth profile beginning within the cratonic mantle lithosphere and extending through the asthenosphere and transition zone into the lower mantle. The carbon isotopic composition, the concentration of nitrogen impurities and the nitrogen aggregation level of diamonds representing this entire depth range have been determined. Peridotitic and eclogitic diamonds of lithospheric origin from Kankan have carbon isotopic compositions (δ13C: peridotitic -5.4 to -2.2‰ eclogitic -19.7 to -0.7‰) and nitrogen characteristics (N: peridotitic 17-648 atomic ppm; eclogitic 0-1,313 atomic ppm; aggregation from IaA to IaB) which are generally typical for diamonds of these two suites worldwide. Geothermobarometry of peridotitic and eclogitic inclusion parageneses (worldwide sources) indicates that both suites formed under very similar conditions within the cratonic lithosphere, which is not consistent with a derivation of diamonds with light carbon isotopic composition from subducted organic matter within subducting oceanic slabs. Diamonds containing majorite garnet inclusions fall to the isotopically heavy side (δ13C: -3.1‰ to +0.9‰) of the worldwide diamond population. Nitrogen contents are low (0-126 atomic ppm) and one of the two nitrogen-bearing diamonds shows such a low level of nitrogen aggregation (30% B-centre) that it cannot have been exposed to ambient temperatures of the transition zone (>=1,400 °C) for more than 0.2 Ma. This suggests rapid upward transport and formation of some Kankan diamonds pene-contemporaneous to Cretaceous kimberlite activity. Similar to these diamonds from the asthenosphere and the transition zone, lower mantle diamonds show a small shift towards isotopic heavy compositions (-6.6 to -0.5‰, mode at -3.5‰). As already observed for other mines, the nitrogen contents of lower mantle diamonds were below detection (using FTIRS). The mutual shift of sublithospheric diamonds towards isotopic heavier compositions suggests a common carbon source, which may have inherited an isotopic heavy composition from a component consisting of subducted carbonates.

Calculation of individual isotope equilibrium constants for geochemical reactions

USGS Publications Warehouse

Thorstenson, D.C.; Parkhurst, D.L.

2004-01-01

Theory is derived from the work of Urey (Urey H. C. [1947] The thermodynamic properties of isotopic substances. J. Chem. Soc. 562-581) to calculate equilibrium constants commonly used in geochemical equilibrium and reaction-transport models for reactions of individual isotopic species. Urey showed that equilibrium constants of isotope exchange reactions for molecules that contain two or more atoms of the same element in equivalent positions are related to isotope fractionation factors by ?? = (Kex)1/n, where n is the number of atoms exchanged. This relation is extended to include species containing multiple isotopes, for example 13C16O18O and 1H2H18O. The equilibrium constants of the isotope exchange reactions can be expressed as ratios of individual isotope equilibrium constants for geochemical reactions. Knowledge of the equilibrium constant for the dominant isotopic species can then be used to calculate the individual isotope equilibrium constants. Individual isotope equilibrium constants are calculated for the reaction CO2g = CO2aq for all species that can be formed from 12C, 13C, 16O, and 18O; for the reaction between 12C18 O2aq and 1H218Ol; and among the various 1H, 2H, 16O, and 18O species of H2O. This is a subset of a larger number of equilibrium constants calculated elsewhere (Thorstenson D. C. and Parkhurst D. L. [2002] Calculation of individual isotope equilibrium constants for implementation in geochemical models. Water-Resources Investigation Report 02-4172. U.S. Geological Survey). Activity coefficients, activity-concentration conventions for the isotopic variants of H2O in the solvent 1H216Ol, and salt effects on isotope fractionation have been included in the derivations. The effects of nonideality are small because of the chemical similarity of different isotopic species of the same molecule or ion. The temperature dependence of the individual isotope equilibrium constants can be calculated from the temperature dependence of the fractionation factors. The derivations can be extended to calculation of individual isotope equilibrium constants for ion pairs and equilibrium constants for isotopic species of other chemical elements. The individual isotope approach calculates the same phase isotopic compositions as existing methods, but also provides concentrations of individual species, which are needed in calculations of mass-dependent effects in transport processes. The equilibrium constants derived in this paper are used to calculate the example of gas-water equilibrium for CO2 in an acidic aqueous solution. ?? 2004 Elsevier Ltd.

Nuclear field shift in natural environments

NASA Astrophysics Data System (ADS)

Moynier, Frédéric; Fujii, Toshiyuki; Brennecka, Gregory A.; Nielsen, Sune G.

2013-03-01

The nuclear field shift (NFS) is an isotope shift in atomic energy levels caused by a combination of differences in nuclear size and shape and electron densities at the nucleus. The effect of NFS in isotope fractionation was theoretically established by Bigeleisen in 1996 [Bigeleisen J. (1996) J. Am. Chem. Soc. 118:3676-3680] and has been analytically measured in laboratory chemical exchange reactions. More recently, some isotopic variations of heavy elements (Hg, Tl, U) measured in natural systems as well as isotopic anomalies measured for lower-mass elements in meteorites have been attributed to the NFS effect. These isotopic variations open up new and exciting fields of investigations in Earth sciences. In this paper, we review the different natural systems in which NFS has been proposed to be the origin of isotopic variations.

Product ion isotopologue pattern: A tool to improve the reliability of elemental composition elucidations of unknown compounds in complex matrices.

PubMed

Kaufmann, A; Walker, S; Mol, G

2016-04-15

Elucidation of the elemental compositions of unknown compounds (e.g., in metabolomics) generally relies on the availability of accurate masses and isotopic ratios. This study focuses on the information provided by the abundance ratio within a product ion pair (monoisotopic versus the first isotopic peak) when isolating and fragmenting the first isotopic ion (first isotopic mass spectrum) of the precursor. This process relies on the capability of the quadrupole within the Q Orbitrap instrument to isolate a very narrow mass window. Selecting only the first isotopic peak (first isotopic mass spectrum) leads to the observation of a unique product ion pair. The lighter ion within such an isotopologue pair is monoisotopic, while the heavier ion contains a single carbon isotope. The observed abundance ratio is governed by the percentage of carbon atoms lost during the fragmentation and can be described by a hypergeometric distribution. The observed carbon isotopologue abundance ratio (product ion isotopologue pattern) gives reliable information regarding the percentage of carbon atoms lost in the fragmentation process. It therefore facilitates the elucidation of the involved precursor and product ions. Unlike conventional isotopic abundances, the product ion isotopologue pattern is hardly affected by isobaric interferences. Furthermore, the appearance of these pairs greatly aids in cleaning up a 'matrix-contaminated' product ion spectrum. The product ion isotopologue pattern is a valuable tool for structural elucidation. It increases confidence in results and permits structural elucidations for heavier ions. This tool is also very useful in elucidating the elemental composition of product ions. Such information is highly valued in the field of multi-residue analysis, where the accurate mass of product ions is required for the confirmation process. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Magnetic isotope effect and theory of atomic orbital hybridization to predict a mechanism of chemical exchange reactions.

PubMed

Epov, Vladimir N

2011-08-07

A novel approach is suggested to investigate the mechanisms of chemical complexation reactions based on the results of Fujii with co-workers; they have experimentally observed that several metals and metalloids demonstrate mass-independent isotope fractionation during the reactions with the DC18C6 crown ether using solvent-solvent extraction. In this manuscript, the isotope fractionation caused by the magnetic isotope effect is used to understand the mechanisms of chemical exchange reactions. Due to the rule that reactions are allowed for certain electron spin states, and forbidden for others, magnetic isotopes show chemical anomalies during these reactions. Mass-independent fractionation is suggested to take place due to the hyperfine interaction of the nuclear spin with the electron spin of the intermediate product. Moreover, the sign of the mass-independent fractionation is found to be dependent on the element and its species, which is also explained by the magnetic isotope effect. For example, highly negative mass-independent isotope fractionation of magnetic isotopes was observed for reactions of DC18C6 with SnCl(2) species and with several Ru(III) chloro-species, and highly positive for reactions of this ether with TeCl(6)(2-), and with several Cd(II) and Pd(II) species. The atomic radius of an element is also a critical parameter for the reaction with crown ether, particularly the element ions with [Kr]4d(n)5s(m) electron shell fits the best with the DC18C6 crown ring. It is demonstrated that the magnetic isotope effect in combination with the theory of orbital hybridization can help to understand the mechanism of complexation reactions. The suggested approach is also applied to explain previously published mass-independent fractionation of Hg isotopes in other types of chemical exchange reactions. This journal is © the Owner Societies 2011

Effects of surface structural disorder and surface coverage on isotopic fractionation during Zn(II) adsorption onto quartz and amorphous silica surfaces

DOE PAGES

Nelson, Joey; Wasylenki, Laura; Bargar, John R.; ...

2017-08-05

Metal ion-mineral surface interactions and the attendant isotopic fractionation depend on the properties of the mineral surface and the local atomic-level chemical environment. Furthermore, these factors have not been systematically examined for phases of the same composition with different levels of surface disorder.

Effects of surface structural disorder and surface coverage on isotopic fractionation during Zn(II) adsorption onto quartz and amorphous silica surfaces

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

Nelson, Joey; Wasylenki, Laura; Bargar, John R.

Metal ion-mineral surface interactions and the attendant isotopic fractionation depend on the properties of the mineral surface and the local atomic-level chemical environment. Furthermore, these factors have not been systematically examined for phases of the same composition with different levels of surface disorder.

Source Water Identification and Chemical Typing for Nitrogen at the Kissimmee River, Pool C, Florida--Preliminary Assessment

DTIC Science & Technology

2002-01-01

and the mass-spectrometric measurement techniques, in J.R. Gat and R. Gonfiantini, eds., Stable isotope hydrology: Deuterium and oxygen-18 in the water ... cycle , chap. 4, p. 35-84, International Atomic Energy Agency, Vienna, Austria. Heaton, T.H.E., 1986, Isotopic studies of nitrogen pollution in the

Determination of 13C isotopic enrichment of valine and threonine by GC-C-IRMS after formation of the N(O,S)-ethoxycarbonyl ethyl ester derivatives of the amino acids.

PubMed

Godin, Jean-Philippe; Faure, Magali; Breuille, Denis; Hopfgartner, Gérard; Fay, Laurent-Bernard

2007-06-01

We describe a new method of assessing, in a single run, (13)C isotopic enrichment of both Val and Thr by gas chromatography-combustion-isotope-ratio mass spectrometry (GC-C-IRMS). This method characterised by a rapid one-step derivatisation procedure performed at room temperature to form the N(O,S)-ethoxycarbonyl ethyl ester derivatives, and a polar column for GC. The suitability of this method for Val and Thr in in-vivo samples (mucosal hydrolysate) was demonstrated by studying protein metabolism with two tracers ((13)C-valine or (13)C-threonine). The intra-day and inter-day repeatability were both assessed either with standards or with in-vivo samples at natural abundance and at low (13)C isotopic enrichment. For inter-day repeatability CVs were between 0.8 and 1.5% at natural abundance and lower than 5.5% at 0.112 and 0.190 atom% enrichment for Val and Thr, respectively. Overall isotopic precision was studied for eleven standard amino acid derivatives (those of Val, Ala, Leu, Iso, Gly, Pro, Asp, Thr, Ser, Met, and Phe) and was assessed at 0.32 per thousand. The (13)C isotopic measurement was then extended to the other amino acids (Ala, Val, Leu, Iso, Gly, Pro, Thr, and Phe) at natural abundance for in-vivo samples. The isotopic precision was better than 0.002 atom% per amino acid (for n = 4 rats). This analytical method was finally applied to an animal study to measure Thr utilization in protein synthesis.

Non-statistical 13C Fractionation Distinguishes Co-incident and Divergent Steps in the Biosynthesis of the Alkaloids Nicotine and Tropine.

PubMed

Romek, Katarzyna M; Remaud, Gérald S; Silvestre, Virginie; Paneth, Piotr; Robins, Richard J

2016-08-05

During the biosynthesis of natural products, isotopic fractionation occurs due to the selectivity of enzymes for the heavier or lighter isotopomers. As only some of the positions in the molecule are implicated in a given reaction mechanism, position-specific fractionation occurs, leading to a non-statistical distribution of isotopes. This can be accessed by isotope ratio monitoring (13)C NMR spectrometry. The solanaceous alkaloids S-(-)-nicotine and hyoscyamine (atropine) are related in having a common intermediate, but downstream enzymatic steps diverge, providing a relevant test case to: (a) elucidate the isotopic affiliation between carbon atoms in the alkaloids and those in the precursors; (b) obtain information about the kinetic isotope effects of as yet undescribed enzymes, thus to make predictions as to their possible mechanism(s). We show that the position-specific (13)C/(12)C ratios in the different moieties of these compounds can satisfactorily be related to their known precursors and to the known kinetic isotope effects of enzymes involved in their biosynthesis, or to similar reaction mechanisms. Thus, the pathway to the common intermediate, N-methyl-Δ(1)-pyrrolinium, is seen to introduce similar isotope distribution patterns in the two alkaloids independent of plant species, whereas the remaining atoms of each target compound, which are of different origins, reflect their specific metabolic ancestry. We further demonstrate that the measured (13)C distribution pattern can be used to deduce aspects of the reaction mechanism of enzymes still to be identified. © 2016 by The American Society for Biochemistry and Molecular Biology, Inc.

Non-statistical 13C Fractionation Distinguishes Co-incident and Divergent Steps in the Biosynthesis of the Alkaloids Nicotine and Tropine*

PubMed Central

Romek, Katarzyna M.; Remaud, Gérald S.; Silvestre, Virginie; Paneth, Piotr; Robins, Richard J.

2016-01-01

During the biosynthesis of natural products, isotopic fractionation occurs due to the selectivity of enzymes for the heavier or lighter isotopomers. As only some of the positions in the molecule are implicated in a given reaction mechanism, position-specific fractionation occurs, leading to a non-statistical distribution of isotopes. This can be accessed by isotope ratio monitoring 13C NMR spectrometry. The solanaceous alkaloids S-(−)-nicotine and hyoscyamine (atropine) are related in having a common intermediate, but downstream enzymatic steps diverge, providing a relevant test case to: (a) elucidate the isotopic affiliation between carbon atoms in the alkaloids and those in the precursors; (b) obtain information about the kinetic isotope effects of as yet undescribed enzymes, thus to make predictions as to their possible mechanism(s). We show that the position-specific 13C/12C ratios in the different moieties of these compounds can satisfactorily be related to their known precursors and to the known kinetic isotope effects of enzymes involved in their biosynthesis, or to similar reaction mechanisms. Thus, the pathway to the common intermediate, N-methyl-Δ1-pyrrolinium, is seen to introduce similar isotope distribution patterns in the two alkaloids independent of plant species, whereas the remaining atoms of each target compound, which are of different origins, reflect their specific metabolic ancestry. We further demonstrate that the measured 13C distribution pattern can be used to deduce aspects of the reaction mechanism of enzymes still to be identified. PMID:27288405

Reaction rates and kinetic isotope effects of H{sub 2} + OH → H{sub 2}O + H

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

Meisner, Jan; Kästner, Johannes, E-mail: kaestner@theochem.uni-stuttgart.de

2016-05-07

We calculated reaction rate constants including atom tunneling of the reaction of dihydrogen with the hydroxy radical down to a temperature of 50 K. Instanton theory and canonical variational theory with microcanonical optimized multidimensional tunneling were applied using a fitted potential energy surface [J. Chen et al., J. Chem. Phys. 138, 154301 (2013)]. All possible protium/deuterium isotopologues were considered. Atom tunneling increases at about 250 K (200 K for deuterium transfer). Even at 50 K the rate constants of all isotopologues remain in the interval 4 ⋅ 10{sup −20} to 4 ⋅ 10{sup −17} cm{sup 3} s{sup −1}, demonstrating thatmore » even deuterated versions of the title reaction are possibly relevant to astrochemical processes in molecular clouds. The transferred hydrogen atom dominates the kinetic isotope effect at all temperatures.« less

Isotope effect of mercury diffusion in air

PubMed Central

Koster van Groos, Paul G.; Esser, Bradley K.; Williams, Ross W.; Hunt, James R.

2014-01-01

Identifying and reducing impacts from mercury sources in the environment remains a considerable challenge and requires process based models to quantify mercury stocks and flows. The stable isotope composition of mercury in environmental samples can help address this challenge by serving as a tracer of specific sources and processes. Mercury isotope variations are small and result only from isotope fractionation during transport, equilibrium, and transformation processes. Because these processes occur in both industrial and environmental settings, knowledge of their associated isotope effects is required to interpret mercury isotope data. To improve the mechanistic modeling of mercury isotope effects during gas phase diffusion, an experimental program tested the applicability of kinetic gas theory. Gas-phase elemental mercury diffusion through small bore needles from finite sources demonstrated mass dependent diffusivities leading to isotope fractionation described by a Rayleigh distillation model. The measured relative atomic diffusivities among mercury isotopes in air are large and in agreement with kinetic gas theory. Mercury diffusion in air offers a reasonable explanation of recent field results reported in the literature. PMID:24364380

Isotope effect of mercury diffusion in air.

PubMed

Koster van Groos, Paul G; Esser, Bradley K; Williams, Ross W; Hunt, James R

2014-01-01

Identifying and reducing impacts from mercury sources in the environment remains a considerable challenge and requires process based models to quantify mercury stocks and flows. The stable isotope composition of mercury in environmental samples can help address this challenge by serving as a tracer of specific sources and processes. Mercury isotope variations are small and result only from isotope fractionation during transport, equilibrium, and transformation processes. Because these processes occur in both industrial and environmental settings, knowledge of their associated isotope effects is required to interpret mercury isotope data. To improve the mechanistic modeling of mercury isotope effects during gas phase diffusion, an experimental program tested the applicability of kinetic gas theory. Gas-phase elemental mercury diffusion through small bore needles from finite sources demonstrated mass dependent diffusivities leading to isotope fractionation described by a Rayleigh distillation model. The measured relative atomic diffusivities among mercury isotopes in air are large and in agreement with kinetic gas theory. Mercury diffusion in air offers a reasonable explanation of recent field results reported in the literature.

Kinetics of the reaction of the heaviest hydrogen atom with H2, the 4Heμ + H2 → 4HeμH + H reaction: Experiments, accurate quantal calculations, and variational transition state theory, including kinetic isotope effects for a factor of 36.1 in isotopic mass

NASA Astrophysics Data System (ADS)

Fleming, Donald G.; Arseneau, Donald J.; Sukhorukov, Oleksandr; Brewer, Jess H.; Mielke, Steven L.; Truhlar, Donald G.; Schatz, George C.; Garrett, Bruce C.; Peterson, Kirk A.

2011-11-01

The neutral muonic helium atom 4Heμ, in which one of the electrons of He is replaced by a negative muon, may be effectively regarded as the heaviest isotope of the hydrogen atom, with a mass of 4.115 amu. We report details of the first muon spin rotation (μSR) measurements of the chemical reaction rate constant of 4Heμ with molecular hydrogen, 4Heμ + H2 → 4HeμH + H, at temperatures of 295.5, 405, and 500 K, as well as a μSR measurement of the hyperfine coupling constant of muonic He at high pressures. The experimental rate constants, kHeμ, are compared with the predictions of accurate quantum mechanical (QM) dynamics calculations carried out on a well converged Born-Huang (BH) potential energy surface, based on complete configuration interaction calculations and including a Born-Oppenheimer diagonal correction. At the two highest measured temperatures the agreement between the quantum theory and experiment is good to excellent, well within experimental uncertainties that include an estimate of possible systematic error, but at 295.5 K the quantum calculations for kHeμ are below the experimental value by 2.1 times the experimental uncertainty estimates. Possible reasons for this discrepancy are discussed. Variational transition state theory calculations with multidimensional tunneling have also been carried out for kHeμ on the BH surface, and they agree with the accurate QM rate constants to within 30% over a wider temperature range of 200-1000 K. Comparisons between theory and experiment are also presented for the rate constants for both the D + H2 and Mu + H2 reactions in a novel study of kinetic isotope effects for the H + H2 reactions over a factor of 36.1 in isotopic mass of the atomic reactant.

Synthesis of l-cysteine derivatives containing stable sulfur isotopes and application of this synthesis to reactive sulfur metabolome.

PubMed

Ono, Katsuhiko; Jung, Minkyung; Zhang, Tianli; Tsutsuki, Hiroyasu; Sezaki, Hiroshi; Ihara, Hideshi; Wei, Fan-Yan; Tomizawa, Kazuhito; Akaike, Takaaki; Sawa, Tomohiro

2017-05-01

Cysteine persulfide is an L-cysteine derivative having one additional sulfur atom bound to a cysteinyl thiol group, and it serves as a reactive sulfur species that regulates redox homeostasis in cells. Here, we describe a rapid and efficient method of synthesis of L-cysteine derivatives containing isotopic sulfur atoms and application of this method to a reactive sulfur metabolome. We used bacterial cysteine syntheses to incorporate isotopic sulfur atoms into the sulfhydryl moiety of L-cysteine. We cloned three cysteine synthases-CysE, CysK, and CysM-from the Gram-negative bacterium Salmonella enterica serovar Typhimurium LT2, and we generated their recombinant enzymes. We synthesized 34 S-labeled L-cysteine from O-acetyl-L-serine and 34 S-labeled sodium sulfide as substrates for the CysK or CysM reactions. Isotopic labeling of L-cysteine at both sulfur ( 34 S) and nitrogen ( 15 N) atoms was also achieved by performing enzyme reactions with 15 N-labeled L-serine, acetyl-CoA, and 34 S-labeled sodium sulfide in the presence of CysE and CysK. The present enzyme systems can be applied to syntheses of a series of L-cysteine derivatives including L-cystine, L-cystine persulfide, S-sulfo-L-cysteine, L-cysteine sulfonate, and L-selenocystine. We also prepared 34 S-labeled N-acetyl-L-cysteine (NAC) by incubating 34 S-labeled L-cysteine with acetyl coenzyme A in test tubes. Tandem mass spectrometric identification of low-molecular-weight thiols after monobromobimane derivatization revealed the endogenous occurrence of NAC in the cultured mammalian cells such as HeLa cells and J774.1 cells. Furthermore, we successfully demonstrated, by using 34 S-labeled NAC, metabolic conversion of NAC to glutathione and its persulfide, via intermediate formation of L-cysteine, in the cells. The approach using isotopic sulfur labeling combined with mass spectrometry may thus contribute to greater understanding of reactive sulfur metabolome and redox biology. Copyright © 2017 Elsevier Inc. All rights reserved.

High speed acquisition of multiparameter data using a Macintosh IIcx

NASA Astrophysics Data System (ADS)

Berno, Anthony; Vogel, John S.; Caffee, Marc

1991-05-01

Accelerator mass spectrometry systems based on > 3 MV tandem accelerators often use multianode ionization detectors and/or time-of-flight detectors to identify individual isotopes through multiparameter analysis. A Macintosh IIcx has been programmed to collect AMS data from a CAMAC-implemented analyzer and to display the histogrammed individual parameters and a doubleparameter array. The computer-CAMAC connection is through a NuBus to CAMAC dataway interface which allows direct addressing to all functions and registers in the crate. Asynchronous data from the rare isotope are sorted into a CAMAC memory module by a list sequence controller. Isotope switching is controlled by a one-cycle timing generator. A rate-dependent amount of time is used to transfer the data from the memory module at the end of each timing cycle. The present configuration uses 10-75 ms for rates of 500-10000 cps. Parameter analysis occurs during the rest of the 520 ms data collection cycle. Completed measurements of the isotope concentrations of each sample are written to files which are compatible with standard Macintosh databases or other processing programs. The system is inexpensive and operates at speeds comparable to those obtainable using larger computers.

Edwin M. McMillan

Science.gov Websites

mixture. The separation of the different components in these compound earths has been no easy task, since terbium and dysprosium in the lanthanides. By irradiating different sorts of heavy atoms with neutrons Berkeley Lab Search Submit Web People Close About the Lab Leadership/Organization Calendar News Center

Use of a Card Sort Task to Assess Students' Ability to Coordinate Three Levels of Representation in Chemistry

ERIC Educational Resources Information Center

Irby, Stefan M.; Phu, Andy L.; Borda, Emily J.; Haskell, Todd R.; Steed, Nicole; Meyer, Zachary

2016-01-01

There is much agreement among chemical education researchers that expertise in chemistry depends in part on the ability to coordinate understanding of phenomena on three levels: macroscopic (observable), sub-microscopic (atoms, molecules, and ions) and symbolic (chemical equations, graphs, etc.). We hypothesize this "level-coordination…

Icosahedral and decagonal quasicrystals of intermetallic compounds are multiple twins of cubic or orthorhombic crystals composed of very large atomic complexes with icosahedral point-group symmetry in cubic close packing or body-centered packing: Structure of decagonal Al6Pd

PubMed Central

Pauling, Linus

1989-01-01

A doubly icosahedral complex involves roughly spherical clusters of atoms with icosahedral point-group symmetry, which are themselves, in parallel orientation, icosahedrally packed. These complexes may form cubic crystallites; three structures of this sort have been identified. Analysis of electron diffraction photographs of the decagonal quasicrystal Al6Pd has led to its description as involving pentagonal twinning of an orthorhombic crystal with a = 51.6 Å, b = 37.6 Å, and c = 33.24 Å, with about 4202 atoms in the unit, comprising two 1980-atom doubly icosahedral complexes, each involving icosahedral packing of 45 44-atom icosahedral complexes (at 0 0 0 and 1/2 1/2 1/2) and 242 interstitial atoms. The complexes and clusters are oriented with one of their fivefold axes in the c-axis direction. Images PMID:16594092

Icosahedral and decagonal quasicrystals of intermetallic compounds are multiple twins of cubic or orthorhombic crystals composed of very large atomic complexes with icosahedral point-group symmetry in cubic close packing or body-centered packing: Structure of decagonal Al(6)Pd.

PubMed

Pauling, L

1989-12-01

A doubly icosahedral complex involves roughly spherical clusters of atoms with icosahedral point-group symmetry, which are themselves, in parallel orientation, icosahedrally packed. These complexes may form cubic crystallites; three structures of this sort have been identified. Analysis of electron diffraction photographs of the decagonal quasicrystal Al(6)Pd has led to its description as involving pentagonal twinning of an orthorhombic crystal with a = 51.6 A, b = 37.6 A, and c = 33.24 A, with about 4202 atoms in the unit, comprising two 1980-atom doubly icosahedral complexes, each involving icosahedral packing of 45 44-atom icosahedral complexes (at 0 0 0 and 1/2 1/2 1/2) and 242 interstitial atoms. The complexes and clusters are oriented with one of their fivefold axes in the c-axis direction.

Low energy collisions of spin-polarized metastable argon atoms with ground state argon atoms

NASA Astrophysics Data System (ADS)

Taillandier-Loize, T.; Perales, F.; Baudon, J.; Hamamda, M.; Bocvarski, V.; Ducloy, M.; Correia, F.; Fabre, N.; Dutier, G.

2018-04-01

The collision between a spin-polarized metastable argon atom in Ar* (3p54s, 3P2, M = +2) state slightly decelerated by the Zeeman slower-laser technique and a co-propagating thermal ground state argon atom Ar (3p6, 1S0), both merged from the same supersonic beam, but coming through adjacent slots of a rotating disk, is investigated at the center of mass energies ranging from 1 to 10 meV. The duration of the laser pulse synchronised with the disk allows the tuning of the relative velocity and thus the collision energy. At these sub-thermal energies, the ‘resonant metastability transfer’ signal is too small to be evidenced. The explored energy range requires using indiscernibility amplitudes for identical isotopes to have a correct interpretation of the experimental results. Nevertheless, excitation transfers are expected to increase significantly at much lower energies as suggested by previous theoretical predictions of potentials 2g(3P2) and 2u(3P2). Limits at ultra-low collisional energies of the order of 1 mK (0.086 μeV) or less, where gigantic elastic cross sections are expected, will also be discussed. The experimental method is versatile and could be applied using different isotopes of Argon like 36Ar combined with 40Ar, as well as other rare gases among which Krypton should be of great interest thanks to the available numerous isotopes present in a natural gas mixture.

Development of particle induced gamma-ray emission methods for nondestructive determination of isotopic composition of boron and its total concentration in natural and enriched samples.

PubMed

Chhillar, Sumit; Acharya, Raghunath; Sodaye, Suparna; Pujari, Pradeep K

2014-11-18

We report simple particle induced gamma-ray emission (PIGE) methods using a 4 MeV proton beam for simultaneous and nondestructive determination of the isotopic composition of boron ((10)B/(11)B atom ratio) and total boron concentrations in various solid samples with natural isotopic composition and enriched with (10)B. It involves measurement of prompt gamma-rays at 429, 718, and 2125 keV from (10)B(p,αγ)(7)Be, (10)B(p, p'γ)(10)B, and (11)B(p, p'γ)(11)B reactions, respectively. The isotopic composition of boron in natural and enriched samples was determined by comparing peak area ratios corresponding to (10)B and (11)B of samples to natural boric acid standard. An in situ current normalized PIGE method, using F or Al, was standardized for total B concentration determination. The methods were validated by analyzing stoichiometric boron compounds and applied to samples such as boron carbide, boric acid, carborane, and borosilicate glass. Isotopic compositions of boron in the range of 0.247-2.0 corresponding to (10)B in the range of 19.8-67.0 atom % and total B concentrations in the range of 5-78 wt % were determined. It has been demonstrated that PIGE offers a simple and alternate method for total boron as well as isotopic composition determination in boron based solid samples, including neutron absorbers that are important in nuclear technology.

Partitioning Tungsten between Matrix Precursors and Chondrule Precursors through Relative Settling

NASA Astrophysics Data System (ADS)

Hubbard, Alexander

2016-08-01

Recent studies of chondrites have found a tungsten isotopic anomaly between chondrules and matrix. Given the refractory nature of tungsten, this implies that W was carried into the solar nebula by at least two distinct families of pre-solar grains. The observed chondrule/matrix split requires that the distinct families were kept separate during the dust coagulation process, and that the two families of grain interacted with the chondrule formation mechanism differently. We take the co-existence of different families of solids in the same general orbital region at the chondrule-precursor size as given, and explore the requirements for them to have interacted with the chondrule formation process at significantly different rates. We show that this sorting of families of solids into chondrule- and matrix-destined dust had to have been at least as powerful a sorting mechanism as the relative settling of aerodynamically distinct grains at least two scale heights above the midplane. The requirement that the chondrule formation mechanism was correlated in some fashion with a dust-grain sorting mechanism argues strongly for spatially localized chondrule formation mechanisms such as turbulent dissipation in non-thermally ionized disk surface layers, and argues against volume-filling mechanisms such as planetesimal bow shocks.

Compact hydrogen/helium isotope mass spectrometer

DOEpatents

Funsten, Herbert O.; McComas, David J.; Scime, Earl E.

1996-01-01

The compact hydrogen and helium isotope mass spectrometer of the present invention combines low mass-resolution ion mass spectrometry and beam-foil interaction technology to unambiguously detect and quantify deuterium (D), tritium (T), hydrogen molecule (H.sub.2, HD, D.sub.2, HT, DT, and T.sub.2), .sup.3 He, and .sup.4 He concentrations and concentration variations. The spectrometer provides real-time, high sensitivity, and high accuracy measurements. Currently, no fieldable D or molecular speciation detectors exist. Furthermore, the present spectrometer has a significant advantage over traditional T detectors: no confusion of the measurements by other beta-emitters, and complete separation of atomic and molecular species of equivalent atomic mass (e.g., HD and .sup.3 He).

Characterization of D-glucaric acid using NMR, x-ray crystal structure, and MM3 molecular modeling analyses

USDA-ARS?s Scientific Manuscript database

D-glucaric acid was characterized in solution by comparing NMR spectra from the isotopically unlabeled molecule with those from D-glucaric acid labeled with deuterium or carbon-13 atoms. The NMR studies provided unequivocal assignments for all carbon atoms and non-hydroxyl protons of the molecule. ...

Atomic power in space: A history

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

Not Available

1987-03-01

''Atomic Power in Space,'' a history of the Space Isotope Power Program of the United States, covers the period from the program's inception in the mid-1950s through 1982. Written in non-technical language, the history is addressed to both the general public and those more specialized in nuclear and space technologies. 19 figs., 3 tabs.

In-situ Isotopic Analysis at Nanoscale using Parallel Ion Electron Spectrometry: A Powerful New Paradigm for Correlative Microscopy

NASA Astrophysics Data System (ADS)

Yedra, Lluís; Eswara, Santhana; Dowsett, David; Wirtz, Tom

2016-06-01

Isotopic analysis is of paramount importance across the entire gamut of scientific research. To advance the frontiers of knowledge, a technique for nanoscale isotopic analysis is indispensable. Secondary Ion Mass Spectrometry (SIMS) is a well-established technique for analyzing isotopes, but its spatial-resolution is fundamentally limited. Transmission Electron Microscopy (TEM) is a well-known method for high-resolution imaging down to the atomic scale. However, isotopic analysis in TEM is not possible. Here, we introduce a powerful new paradigm for in-situ correlative microscopy called the Parallel Ion Electron Spectrometry by synergizing SIMS with TEM. We demonstrate this technique by distinguishing lithium carbonate nanoparticles according to the isotopic label of lithium, viz. 6Li and 7Li and imaging them at high-resolution by TEM, adding a new dimension to correlative microscopy.

Unexpectedly large difference of the electron density at the nucleus in the 4p ^2{P}_{{1}/{2},{3}/{2}} fine-structure doublet of Ca^+

NASA Astrophysics Data System (ADS)

Shi, C.; Gebert, F.; Gorges, C.; Kaufmann, S.; Nörtershäuser, W.; Sahoo, B. K.; Surzhykov, A.; Yerokhin, V. A.; Berengut, J. C.; Wolf, F.; Heip, J. C.; Schmidt, P. O.

2017-01-01

We measured the isotope shift in the ^2{S}_{{1}/{2}} → ^2{P}_{{3}/{2}} (D2) transition in singly ionized calcium ions using photon recoil spectroscopy. The high accuracy of the technique enables us to compare the difference between the isotope shifts of this transition to the previously measured isotopic shifts of the ^2{S}_{{1}/{2}} → ^2{P}_{{1}/{2}} (D1) line. This so-called splitting isotope shift is extracted and exhibits a clear signature of field shift contributions. From the data, we were able to extract the small difference of the field shift coefficient and mass shifts between the two transitions with high accuracy. This J-dependence is of relativistic origin and can be used to benchmark atomic structure calculations. As a first step, we use several ab initio atomic structure calculation methods to provide more accurate values for the field shift constants and their ratio. Remarkably, the high-accuracy value for the ratio of the field shift constants extracted from the experimental data is larger than all available theoretical predictions.

Sr and Pb isotopic geochemistry of feldspars and implications for the growth of megacrysts in plutonic settings.

NASA Astrophysics Data System (ADS)

Munnikhuis, J.; Glazner, A. F.; Coleman, D. S.; Mills, R. D.

2015-12-01

Why megacrystic textures develop in silicic igneous rocks is still unknown. One hypothesis is that these crystals nucleate early in a magma chamber with a high liquid content. A supportive observation of this hypothesis is areas in plutons with high concentrations of megacrysts suggesting flow sorting. Another group of hypotheses suggest megacrystic textures form during protracted late-stage coarsening in a low-melt, interlocked matrix due to either thermal oscillations from incremental pluton emplacement, or Ostwald ripening. Isotopic analyses of large, euhedral K-feldspar megacrysts from the Cretaceous intrusive suites of the Sierra Nevada batholith (SNB) provide new insight into their origin. Megacrysts from the SNB reach the decimeter scale, are Or rich (85-90%), are perthitic, and host mineral inclusions of nearly all phases in the host rock. In-situ micro-drilling of transects, from core to rim, of the alkali feldspars provides material for Sr and Pb isotopic analyses by thermal ionization mass spectrometry (TIMS). Preliminary 87Sr/86Sr(i) isotopic data from samples from the Cathedral Peak Granodiorite, of the Tuolumne Intrusive Suite range from 0.706337 to 0.706452 (~1.6ɛSr) near the cores, whereas a sawtooth pattern with larger variability, 0.706179 to 0.706533 (~5ɛSr), occurs nears the rims. We interpret these preliminary data to indicate that the late portion of growth (i.e. crystal rim) was dominated by either cannibalism of small K-feldspar crystals with isotopic variability, or by addition of isotopically diverse late components to the magma. By comparing the Sr and Pb isotopic stratigraphy of megacrysts from a variety of rock matrices and different granitoids in the SNB isotopic trends can be evaluated to determine if crystals sizes are dependent on disequilibrium processes or grow at a steady state.

High-resolution quantitative imaging of mammalian and bacterial cells using stable isotope mass spectrometry.

PubMed

Lechene, Claude; Hillion, Francois; McMahon, Greg; Benson, Douglas; Kleinfeld, Alan M; Kampf, J Patrick; Distel, Daniel; Luyten, Yvette; Bonventre, Joseph; Hentschel, Dirk; Park, Kwon Moo; Ito, Susumu; Schwartz, Martin; Benichou, Gilles; Slodzian, Georges

2006-01-01

Secondary-ion mass spectrometry (SIMS) is an important tool for investigating isotopic composition in the chemical and materials sciences, but its use in biology has been limited by technical considerations. Multi-isotope imaging mass spectrometry (MIMS), which combines a new generation of SIMS instrument with sophisticated ion optics, labeling with stable isotopes, and quantitative image-analysis software, was developed to study biological materials. The new instrument allows the production of mass images of high lateral resolution (down to 33 nm), as well as the counting or imaging of several isotopes simultaneously. As MIMS can distinguish between ions of very similar mass, such as 12C15N- and 13C14N-, it enables the precise and reproducible measurement of isotope ratios, and thus of the levels of enrichment in specific isotopic labels, within volumes of less than a cubic micrometer. The sensitivity of MIMS is at least 1,000 times that of 14C autoradiography. The depth resolution can be smaller than 1 nm because only a few atomic layers are needed to create an atomic mass image. We illustrate the use of MIMS to image unlabeled mammalian cultured cells and tissue sections; to analyze fatty-acid transport in adipocyte lipid droplets using 13C-oleic acid; to examine nitrogen fixation in bacteria using 15N gaseous nitrogen; to measure levels of protein renewal in the cochlea and in post-ischemic kidney cells using 15N-leucine; to study DNA and RNA co-distribution and uridine incorporation in the nucleolus using 15N-uridine and 81Br of bromodeoxyuridine or 14C-thymidine; to reveal domains in cultured endothelial cells using the native isotopes 12C, 16O, 14N and 31P; and to track a few 15N-labeled donor spleen cells in the lymph nodes of the host mouse. MIMS makes it possible for the first time to both image and quantify molecules labeled with stable or radioactive isotopes within subcellular compartments.

Selective deuteration illuminates the importance of tunneling in the unimolecular decay of Criegee intermediates to hydroxyl radical products

DOE PAGES

Green, Amy M.; Barber, Victoria P.; Fang, Yi; ...

2017-11-06

Ozonolysis of alkenes, an important nonphotolytic source of hydroxyl (OH) radicals in the atmosphere, proceeds through unimolecular decay of Criegee intermediates. Here, we report a large kinetic isotope effect associated with the rate-limiting hydrogen-transfer step that releases OH radicals for a prototypical Criegee intermediate, CH 3CHOO. IR excitation of selectively deuterated syn-CD 3CHOO is shown to result in deuterium atom transfer and release OD radical products. Vibrational activation of syn-CD 3CHOO is coupled with direct time-resolved detection of OD products to measure a 10-fold slower rate of unimolecular decay upon deuteration in the vicinity of the transition state barrier, whichmore » is confirmed by microcanonical statistical theory that incorporates quantum mechanical tunneling. The corresponding kinetic isotope effect of ~10 is attributed primarily to the decreased probability of D-atom vs. H-atom transfer arising from tunneling. Master equation modeling is utilized to compute the thermal unimolecular decay rates for selectively and fully deuterated syn methyl-substituted Criegee intermediates under atmospheric conditions. Lastly, at 298 K (1 atm), tunneling is predicted to enhance the thermal decay rate of syn-CH 3CHOO compared with the deuterated species, giving rise to a significant kinetic isotope effect of ~50.« less

Selective deuteration illuminates the importance of tunneling in the unimolecular decay of Criegee intermediates to hydroxyl radical products

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

Green, Amy M.; Barber, Victoria P.; Fang, Yi

Ozonolysis of alkenes, an important nonphotolytic source of hydroxyl (OH) radicals in the atmosphere, proceeds through unimolecular decay of Criegee intermediates. Here, we report a large kinetic isotope effect associated with the rate-limiting hydrogen-transfer step that releases OH radicals for a prototypical Criegee intermediate, CH 3CHOO. IR excitation of selectively deuterated syn-CD 3CHOO is shown to result in deuterium atom transfer and release OD radical products. Vibrational activation of syn-CD 3CHOO is coupled with direct time-resolved detection of OD products to measure a 10-fold slower rate of unimolecular decay upon deuteration in the vicinity of the transition state barrier, whichmore » is confirmed by microcanonical statistical theory that incorporates quantum mechanical tunneling. The corresponding kinetic isotope effect of ~10 is attributed primarily to the decreased probability of D-atom vs. H-atom transfer arising from tunneling. Master equation modeling is utilized to compute the thermal unimolecular decay rates for selectively and fully deuterated syn methyl-substituted Criegee intermediates under atmospheric conditions. Lastly, at 298 K (1 atm), tunneling is predicted to enhance the thermal decay rate of syn-CH 3CHOO compared with the deuterated species, giving rise to a significant kinetic isotope effect of ~50.« less

Selective deuteration illuminates the importance of tunneling in the unimolecular decay of Criegee intermediates to hydroxyl radical products.

PubMed

Green, Amy M; Barber, Victoria P; Fang, Yi; Klippenstein, Stephen J; Lester, Marsha I

2017-11-21

Ozonolysis of alkenes, an important nonphotolytic source of hydroxyl (OH) radicals in the atmosphere, proceeds through unimolecular decay of Criegee intermediates. Here, we report a large kinetic isotope effect associated with the rate-limiting hydrogen-transfer step that releases OH radicals for a prototypical Criegee intermediate, CH 3 CHOO. IR excitation of selectively deuterated syn -CD 3 CHOO is shown to result in deuterium atom transfer and release OD radical products. Vibrational activation of syn -CD 3 CHOO is coupled with direct time-resolved detection of OD products to measure a 10-fold slower rate of unimolecular decay upon deuteration in the vicinity of the transition state barrier, which is confirmed by microcanonical statistical theory that incorporates quantum mechanical tunneling. The corresponding kinetic isotope effect of ∼10 is attributed primarily to the decreased probability of D-atom vs. H-atom transfer arising from tunneling. Master equation modeling is utilized to compute the thermal unimolecular decay rates for selectively and fully deuterated syn methyl-substituted Criegee intermediates under atmospheric conditions. At 298 K (1 atm), tunneling is predicted to enhance the thermal decay rate of syn -CH 3 CHOO compared with the deuterated species, giving rise to a significant kinetic isotope effect of ∼50.

Selective deuteration illuminates the importance of tunneling in the unimolecular decay of Criegee intermediates to hydroxyl radical products

PubMed Central

Green, Amy M.; Barber, Victoria P.; Fang, Yi; Klippenstein, Stephen J.; Lester, Marsha I.

2017-01-01

Ozonolysis of alkenes, an important nonphotolytic source of hydroxyl (OH) radicals in the atmosphere, proceeds through unimolecular decay of Criegee intermediates. Here, we report a large kinetic isotope effect associated with the rate-limiting hydrogen-transfer step that releases OH radicals for a prototypical Criegee intermediate, CH3CHOO. IR excitation of selectively deuterated syn-CD3CHOO is shown to result in deuterium atom transfer and release OD radical products. Vibrational activation of syn-CD3CHOO is coupled with direct time-resolved detection of OD products to measure a 10-fold slower rate of unimolecular decay upon deuteration in the vicinity of the transition state barrier, which is confirmed by microcanonical statistical theory that incorporates quantum mechanical tunneling. The corresponding kinetic isotope effect of ∼10 is attributed primarily to the decreased probability of D-atom vs. H-atom transfer arising from tunneling. Master equation modeling is utilized to compute the thermal unimolecular decay rates for selectively and fully deuterated syn methyl-substituted Criegee intermediates under atmospheric conditions. At 298 K (1 atm), tunneling is predicted to enhance the thermal decay rate of syn-CH3CHOO compared with the deuterated species, giving rise to a significant kinetic isotope effect of ∼50. PMID:29109292

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

Garcia Ruiz, R. F.; Bissell, M. L.; Blaum, K.

Here, despite being a complex many-body system, the atomic nucleus exhibits simple structures for certain ‘magic’ numbers of protons and neutrons. The calcium chain in particular is both unique and puzzling: evidence of doubly magic features are known in 40,48Ca, and recently suggested in two radioactive isotopes, 52,54Ca. Although many properties of experimentally known calcium isotopes have been successfully described by nuclear theory, it is still a challenge to predict the evolution of their charge radii. Here we present the first measurements of the charge radii of 49,51,52Ca, obtained from laser spectroscopy experiments at ISOLDE, CERN. The experimental results aremore » complemented by state-of-the-art theoretical calculations. The large and unexpected increase of the size of the neutron-rich calcium isotopes beyond N = 28 challenges the doubly magic nature of 52Ca and opens new intriguing questions on the evolution of nuclear sizes away from stability, which are of importance for our understanding of neutron-rich atomic nuclei.« less

Investigations of interhydrogen bond dynamical coupling effects in the polarized IR spectra of acetanilide crystals.

PubMed

Flakus, Henryk T; Michta, Anna

2010-02-04

This Article presents the investigation results of the polarized IR spectra of the hydrogen bond in acetanilide (ACN) crystals measured in the frequency range of the proton and deuteron stretching vibration bands, nu(N-H) and nu(N-D). The basic spectral properties of the crystals were interpreted quantitatively in terms of the "strong-coupling" theory. The model of the centrosymmetric dimer of hydrogen bonds postulated by us facilitated the explanation of the well-developed, two-branch structure of the nu(N-H) and nu(N-D) bands as well as the isotopic dilution effects in the spectra. On the basis of the linear dichroic and temperature effects in the polarized IR spectra of ACN crystals, the H/D isotopic "self-organization" effects were revealed. A nonrandom distribution of hydrogen isotope atoms (H or D) in the lattice was deduced from the spectra of isotopically diluted ACN crystals. It was also determined that identical hydrogen isotope atoms occupy both hydrogen bonds in the dimeric systems, where each hydrogen bond belongs to a different chain. A more complex fine structure pattern of nu(N-H) and nu(N-D) bands in ACN spectra in comparison with the spectra of other secondary amides (e.g., N-methylacetamide) can be explained in terms of the "relaxation" theory of the IR spectra of hydrogen-bonded systems.

Charge radii and electromagnetic moments of At-211195

NASA Astrophysics Data System (ADS)

Cubiss, J. G.; Barzakh, A. E.; Seliverstov, M. D.; Andreyev, A. N.; Andel, B.; Antalic, S.; Ascher, P.; Atanasov, D.; Beck, D.; Bieroń, J.; Blaum, K.; Borgmann, Ch.; Breitenfeldt, M.; Capponi, L.; Cocolios, T. E.; Day Goodacre, T.; Derkx, X.; De Witte, H.; Elseviers, J.; Fedorov, D. V.; Fedosseev, V. N.; Fritzsche, S.; Gaffney, L. P.; George, S.; Ghys, L.; Heßberger, F. P.; Huyse, M.; Imai, N.; Kalaninová, Z.; Kisler, D.; Köster, U.; Kowalska, M.; Kreim, S.; Lane, J. F. W.; Liberati, V.; Lunney, D.; Lynch, K. M.; Manea, V.; Marsh, B. A.; Mitsuoka, S.; Molkanov, P. L.; Nagame, Y.; Neidherr, D.; Nishio, K.; Ota, S.; Pauwels, D.; Popescu, L.; Radulov, D.; Rapisarda, E.; Revill, J. P.; Rosenbusch, M.; Rossel, R. E.; Rothe, S.; Sandhu, K.; Schweikhard, L.; Sels, S.; Truesdale, V. L.; Van Beveren, C.; Van den Bergh, P.; Wakabayashi, Y.; Van Duppen, P.; Wendt, K. D. A.; Wienholtz, F.; Whitmore, B. W.; Wilson, G. L.; Wolf, R. N.; Zuber, K.

2018-05-01

Hyperfine-structure parameters and isotope shifts of At-211195 have been measured for the first time at CERN-ISOLDE, using the in-source resonance-ionization spectroscopy method. The hyperfine structures of isotopes were recorded using a triad of experimental techniques for monitoring the photo-ion current. The Multi-Reflection Time-of-Flight Mass Spectrometer, in connection with a high-resolution electron multiplier, was used as an ion-counting setup for isotopes that either were affected by strong isobaric contamination or possessed a long half-life; the ISOLDE Faraday cups were used for cases with high-intensity beams; and the Windmill decay station was used for short-lived, predominantly α -decaying nuclei. The electromagnetic moments and changes in the mean-square charge radii of the astatine nuclei have been extracted from the measured hyperfine-structure constants and isotope shifts. This was only made possible by dedicated state-of-the-art large-scale atomic computations of the electronic factors and the specific mass shift of atomic transitions in astatine that are needed for these extractions. By comparison with systematics, it was possible to assess the reliability of the results of these calculations and their ascribed uncertainties. A strong deviation in the ground-state mean-square charge radii of the lightest astatine isotopes, from the trend of the (spherical) lead isotopes, is interpreted as the result of an onset of deformation. This behavior bears a resemblance to the deviation observed in the isotonic polonium isotopes. Cases for shape coexistence have been identified in At,199197, for which a significant difference in the charge radii for ground (9 /2- ) and isomeric (1 /2+ ) states has been observed.

Hydroxylation of p-substituted phenols by tyrosinase: Further insight into the mechanism of tyrosinase activity

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

Munoz-Munoz, Jose Luis; Berna, Jose; Garcia-Molina, Maria del Mar

2012-07-27

Highlights: Black-Right-Pointing-Pointer The action the copper complexes and tyrosinase on phenols is equivalent. Black-Right-Pointing-Pointer Isotope effect showed that nucleophilic attack to copper atom may be the slower step. Black-Right-Pointing-Pointer The value of {rho} (Hammett constant) supports an electrophilic aromatic substitution. Black-Right-Pointing-Pointer Data obtained in steady state pH 7 conditions support the mechanism of Scheme 1SM. -- Abstract: A study of the monophenolase activity of tyrosinase by measuring the steady state rate with a group of p-substituted monophenols provides the following kinetic information: k{sub cat}{sup m} and the Michaelis constant, K{sub M}{sup m}. Analysis of these data taking into account chemicalmore » shifts of the carbon atom supporting the hydroxyl group ({delta}) and {sigma}{sub p}{sup +}, enables a mechanism to be proposed for the transformation of monophenols into o-diphenols, in which the first step is a nucleophilic attack on the copper atom on the form E{sub ox} (attack of the oxygen of the hydroxyl group of C-1 on the copper atom) followed by an electrophilic attack (attack of the hydroperoxide group on the ortho position with respect to the hydroxyl group of the benzene ring, electrophilic aromatic substitution with a reaction constant {rho} of -1.75). These steps show the same dependency on the electronic effect of the substituent groups in C-4. Furthermore, a study of a solvent deuterium isotope effect on the oxidation of monophenols by tyrosinase points to an appreciable isotopic effect. In a proton inventory study with a series of p-substituted phenols, the representation of k{sub cat}{sup f{sub n}}/k{sub cat}{sup f{sub 0}} against n (atom fractions of deuterium), where k{sub cat}{sup f{sub n}} is the catalytic constant for a molar fraction of deuterium (n) and k{sub cat}{sup f{sub 0}} is the corresponding kinetic parameter in a water solution, was linear for all substrates. These results indicate that only one of the proton transfer processes from the hydroxyl groups involved the catalytic cycle is responsible for the isotope effects. We suggest that this step is the proton transfer from the hydroxyl group of C-1 to the peroxide of the oxytyrosinase form (E{sub ox}). After the nucleophilic attack, the incorporation of the oxygen in the benzene ring occurs by means of an electrophilic aromatic substitution mechanism in which there is no isotopic effect.« less

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

Taylor, Sandra D.; Liu, Jia; Arey, Bruce W.

The distribution of iron resulting from the autocatalytic interaction of aqueous Fe(II) with the hematite (001) surface was directly mapped in three dimensions (3D) for the first time, using iron isotopic labelling and atom probe tomography (APT). Analyses of the mass spectrum showed that natural abundance ratios in 56Fe-dominant hematite are recovered at depth with good accuracy, whereas at the relict interface with 57Fe(II) solution evidence for hematite growth by oxidative adsorption of Fe(II) was found. 3D reconstructions of the isotope positions along the surface normal direction showed a zone enriched in 57Fe, which was consistent with an average netmore » adsorption of 3.2 – 4.3 57Fe atoms nm–2. Statistical analyses utilizing grid-based frequency distribution analyses show a heterogeneous, non-random distribution of oxidized Fe on the (001) surface, consistent with Volmer-Weber-like island growth. The unique 3D nature of the APT data provides an unprecedented means to quantify the atomic-scale distribution of sorbed 57Fe atoms and the extent of segregation on the hematite surface. This new ability to spatially map growth on single crystal faces at the atomic scale will enable resolution to long-standing unanswered questions about the underlying mechanisms for electron and atom exchange involved in a wide variety of redox-catalyzed processes at this archetypal and broadly relevant interface.« less

Tracking heavy water (D2O) incorporation for identifying and sorting active microbial cells

PubMed Central

Berry, David; Mader, Esther; Lee, Tae Kwon; Woebken, Dagmar; Wang, Yun; Zhu, Di; Palatinszky, Marton; Schintlmeister, Arno; Schmid, Markus C.; Hanson, Buck T.; Shterzer, Naama; Mizrahi, Itzhak; Rauch, Isabella; Decker, Thomas; Bocklitz, Thomas; Popp, Jürgen; Gibson, Christopher M.; Fowler, Patrick W.; Huang, Wei E.; Wagner, Michael

2015-01-01

Microbial communities are essential to the function of virtually all ecosystems and eukaryotes, including humans. However, it is still a major challenge to identify microbial cells active under natural conditions in complex systems. In this study, we developed a new method to identify and sort active microbes on the single-cell level in complex samples using stable isotope probing with heavy water (D2O) combined with Raman microspectroscopy. Incorporation of D2O-derived D into the biomass of autotrophic and heterotrophic bacteria and archaea could be unambiguously detected via C-D signature peaks in single-cell Raman spectra, and the obtained labeling pattern was confirmed by nanoscale-resolution secondary ion MS. In fast-growing Escherichia coli cells, label detection was already possible after 20 min. For functional analyses of microbial communities, the detection of D incorporation from D2O in individual microbial cells via Raman microspectroscopy can be directly combined with FISH for the identification of active microbes. Applying this approach to mouse cecal microbiota revealed that the host-compound foragers Akkermansia muciniphila and Bacteroides acidifaciens exhibited distinctive response patterns to amendments of mucin and sugars. By Raman-based cell sorting of active (deuterated) cells with optical tweezers and subsequent multiple displacement amplification and DNA sequencing, novel cecal microbes stimulated by mucin and/or glucosamine were identified, demonstrating the potential of the nondestructive D2O-Raman approach for targeted sorting of microbial cells with defined functional properties for single-cell genomics. PMID:25550518

Extended atmospheres of outer planet satellites and comets

NASA Technical Reports Server (NTRS)

Smyth, W. H.; Combi, M. R.

1985-01-01

Collisions between neutral hydrogen atoms in the interstellar medium and those in the so-called Titan hydrogen torus may provide an additional lifetime sink for atoms in the Saturn environment. Progress toward re-sorting the Voyager UVS scans of neutral hydrogen in the Saturn system to enable both a factor of two increase in the amount of data to be analyzed as well as to help identify near-Titan hydrogen is discussed. Progress toward development of the cometary carbon and oxygen models is also discussed and a preliminary model run for the H2O source of cometary oxygen is presented.

Liquid and gas chromatography coupled to isotope ratio mass spectrometry for the determination of 13C-valine isotopic ratios in complex biological samples.

PubMed

Godin, Jean-Philippe; Breuillé, Denis; Obled, Christiane; Papet, Isabelle; Schierbeek, Henk; Hopfgartner, Gérard; Fay, Laurent-Bernard

2008-10-01

On-line gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS) is commonly used to measure isotopic ratios at natural abundance as well as for tracer studies in nutritional and medical research. However, high-precision (13)C isotopic enrichment can also be measured by liquid chromatography-isotope ratio mass spectrometry (LC-IRMS). Indeed, LC-IRMS can be used, as shown by the new method reported here, to obtain a baseline separation and to measure (13)C isotopic enrichment of underivatised amino acids (Asp, Thr-Ser, Glu, Pro, Gly, Ala, Cys and Val). In case of Val, at natural abundance, the SD(delta(13)C) reported with this method was found to be below 1 per thousand . Another key feature of the new LC-IRMS method reported in this paper is the comparison of the LC-IRMS approach with the conventional GC-C-IRMS determination. To perform this comparative study, isotopic enrichments were measured from underivatised Val and its N(O, S)-ethoxycarbonyl ethyl ester derivative. Between 0.0 and 1.0 molar percent excess (MPE) (delta(13)C= -12.3 to 150.8 per thousand), the calculated root-mean-square (rms) of SD was 0.38 and 0.46 per thousand and the calculated rms of accuracy was 0.023 and 0.005 MPE, respectively, for GC-C-IRMS and LC-IRMS. Both systems measured accurately low isotopic enrichments (0.002 atom percent excess (APE)) with an SD (APE) of 0.0004. To correlate the relative (delta(13)C) and absolute (atom%, APE and MPE) isotopic enrichment of Val measured by the GC-C-IRMS and LC-IRMS devices, mathematical equations showing the slope and intercept of the curves were established and validated with experimental data between 0.0 to 2.3 MPE. Finally, both GC-C-IRMS and LC-IRMS instruments were also used to assess isotopic enrichment of protein-bound (13)C-Val in tibial epiphysis in a tracer study performed in rats. Isotopic enrichments measured by LC-IRMS and GC-C-IRMS were not statistically different (p>0.05). The results of this work indicate that the LC-IRMS was successful for high-precision (13)C isotopic measurements in tracer studies giving (13)C isotopic enrichment similar to the GC-C-IRMS but without the step of GC derivatisation. Therefore, for clinical studies requiring high-precision isotopic measurement, the LC-IRMS is the method of choice to measure the isotopic ratio.

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

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

Metal isotope and density functional study of the tetracarboxylatodicopper(II) core vibrations

NASA Astrophysics Data System (ADS)

Drożdżewski, Piotr; Brożyna, Anna

2005-11-01

Vibrational spectra of tetrakis(acetato)diaquadicopper(II) complex have been deeply examined in order to provide a detailed description of dynamics of [Cu 2O 8C 4] core being a typical structural unit of most copper(II) carboxylates. Low frequency bands related to significant motions of metal atoms were detected by metal isotope substitution. Observed spectra and isotope shifts were reproduced in DFT calculations. For clear presentation of computed normal vibrations, a D 4h symmetry approximation was successfully applied. Basing on observed isotope shifts and calculation results, all skeletal vibrations have been analyzed including normal mode with the largest Cu ⋯Cu stretching amplitude assigned to Raman band at 178 cm -1.

Constraining new physics models with isotope shift spectroscopy

NASA Astrophysics Data System (ADS)

Frugiuele, Claudia; Fuchs, Elina; Perez, Gilad; Schlaffer, Matthias

2017-07-01

Isotope shifts of transition frequencies in atoms constrain generic long- and intermediate-range interactions. We focus on new physics scenarios that can be most strongly constrained by King linearity violation such as models with B -L vector bosons, the Higgs portal, and chameleon models. With the anticipated precision, King linearity violation has the potential to set the strongest laboratory bounds on these models in some regions of parameter space. Furthermore, we show that this method can probe the couplings relevant for the protophobic interpretation of the recently reported Be anomaly. We extend the formalism to include an arbitrary number of transitions and isotope pairs and fit the new physics coupling to the currently available isotope shift measurements.

Microwave-assisted deuterium exchange: the convenient preparation of isotopically labelled analogues for stable isotope dilution analysis of volatile wine phenols.

PubMed

Crump, Anna M; Sefton, Mark A; Wilkinson, Kerry L

2014-11-01

This study reports the convenient, low cost, one-step synthesis of labelled analogues of six volatile phenols, guaiacol, 4-methylguaiacol, 4-ethylguaiacol, 4-ethylphenol, eugenol and vanillin, using microwave-assisted deuterium exchange, for use as internal standards for stable isotope dilution analysis. The current method improves on previous strategies in that it enables incorporation of deuterium atoms on the aromatic ring, thereby ensuring retention of the isotope label during mass spectrometry fragmentation. When used as standards for SIDA, these labelled volatile phenols will improve the accuracy and reproducibility of quantitative food and beverage analysis. Copyright © 2014 Elsevier Ltd. All rights reserved.

Diode laser based resonance ionization mass spectrometric measurement of strontium-90

NASA Astrophysics Data System (ADS)

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

1997-10-01

A diode laser based scheme for the isotopically selective excitation and ionization of strontium is presented. The double-resonance excitation 5s 21S 0→5s5p 3P 1→5s6s 3S 1 is followed by photoionization at 488 nm. The isotope shifts and hyperfine structure in the resonance transitions have been accurately measured for the stable isotopes and 90Sr, with the measurement of the 90Sr shifts using sub-pg samples. Analytical tests, using graphite crucible atomization, demonstrated 90Sr detection limits of 0.8 fg and overall (optical+mass spectrometer) isotopic selectivity of >10 10 against stable strontium.

The reaction efficiency of thermal energy oxygen atoms with polymeric materials

NASA Technical Reports Server (NTRS)

Koontz, S. L.; Nordine, Paul

1990-01-01

The reaction efficiency of several polymeric materials with thermal-energy (0.04 eV translational energy), ground-state (O3P) oxygen atoms was determined by exposing the materials to a room temperature gas containing a known concentration of atomic oxygen. The reaction efficiency measurements were conducted in two flowing afterglow systems of different configuration. Atomic oxygen concentration measurements, flow, transport and surface dose analysis is presented in this paper. The measured reaction efficiencies of Kapton, Mylar, polyethylene, D4-polyethylene and Tedlar are .001 to .0001 those determined with high-energy ground-state oxygen atoms in low earth orbit or in a high-velocity atom beam. D4-polyethylene exhibits a large kinetic isotope effect with atomic oxygen at thermal but not hyperthermal atom energies.

Observation of the 162Dy-164Dy Isotope Shift for the 0 → 16 717.79 cm-1 Optical Transition.

PubMed

Nardin Barreta, Luiz Felipe; Victor, Alessandro Rogério; Bueno, Patrícia; Dos Santos, Jhonatha Ricardo; da Silveira, Carlos Alberto Barbosa; Neri, José Wilson; Neto, Jonas Jakutis; Sbampato, Maria Esther; Destro, Marcelo Geraldo

2017-08-01

In this work, we report a newly observed isotope shift between 162 Dy and 164 Dy isotopes for the 0 → 16 717.79 cm -1 (598.003 nm) optical transition. We compared the newly observed results against two other lines (597.452 nm and 598.859 nm), which we measured in this work, and were already reported in the literature. The newly observed 162-164 Dy isotope shift, shows at least a 20% larger isotope shift than the isotope shifts for the other two lines investigated. The larger 162-164 isotope shift observed for the 598.003 nm line could lead to an increased isotope selectivity for atomic vapor laser isotope separation (AVLIS). Hence, this line could be a good choice for application in AVLIS. Experimental data available in the literature for the 597.452 nm and 598.859 nm lines, enabled us to perform simulations of spectra for both lines, in order to confirm the accuracy of our experimental measurements.

Ion-Beam-Induced Atomic Mixing in Ge, Si, and SiGe, Studied by Means of Isotope Multilayer Structures

PubMed Central

Radek, Manuel; Liedke, Bartosz; Schmidt, Bernd; Voelskow, Matthias; Bischoff, Lothar; Lundsgaard Hansen, John; Nylandsted Larsen, Arne; Bougeard, Dominique; Böttger, Roman; Prucnal, Slawomir; Posselt, Matthias; Bracht, Hartmut

2017-01-01

Crystalline and preamorphized isotope multilayers are utilized to investigate the dependence of ion beam mixing in silicon (Si), germanium (Ge), and silicon germanium (SiGe) on the atomic structure of the sample, temperature, ion flux, and electrical doping by the implanted ions. The magnitude of mixing is determined by secondary ion mass spectrometry. Rutherford backscattering spectrometry in channeling geometry, Raman spectroscopy, and transmission electron microscopy provide information about the structural state after ion irradiation. Different temperature regimes with characteristic mixing properties are identified. A disparity in atomic mixing of Si and Ge becomes evident while SiGe shows an intermediate behavior. Overall, atomic mixing increases with temperature, and it is stronger in the amorphous than in the crystalline state. Ion-beam-induced mixing in Ge shows no dependence on doping by the implanted ions. In contrast, a doping effect is found in Si at higher temperature. Molecular dynamics simulations clearly show that ion beam mixing in Ge is mainly determined by the thermal spike mechanism. In the case of Si thermal spike, mixing prevails at low temperature whereas ion beam-induced enhanced self-diffusion dominates the atomic mixing at high temperature. The latter process is attributed to highly mobile Si di-interstitials formed under irradiation and during damage annealing. PMID:28773172

Ion-Beam-Induced Atomic Mixing in Ge, Si, and SiGe, Studied by Means of Isotope Multilayer Structures.

PubMed

Radek, Manuel; Liedke, Bartosz; Schmidt, Bernd; Voelskow, Matthias; Bischoff, Lothar; Hansen, John Lundsgaard; Larsen, Arne Nylandsted; Bougeard, Dominique; Böttger, Roman; Prucnal, Slawomir; Posselt, Matthias; Bracht, Hartmut

2017-07-17

Crystalline and preamorphized isotope multilayers are utilized to investigate the dependence of ion beam mixing in silicon (Si), germanium (Ge), and silicon germanium (SiGe) on the atomic structure of the sample, temperature, ion flux, and electrical doping by the implanted ions. The magnitude of mixing is determined by secondary ion mass spectrometry. Rutherford backscattering spectrometry in channeling geometry, Raman spectroscopy, and transmission electron microscopy provide information about the structural state after ion irradiation. Different temperature regimes with characteristic mixing properties are identified. A disparity in atomic mixing of Si and Ge becomes evident while SiGe shows an intermediate behavior. Overall, atomic mixing increases with temperature, and it is stronger in the amorphous than in the crystalline state. Ion-beam-induced mixing in Ge shows no dependence on doping by the implanted ions. In contrast, a doping effect is found in Si at higher temperature. Molecular dynamics simulations clearly show that ion beam mixing in Ge is mainly determined by the thermal spike mechanism. In the case of Si thermal spike, mixing prevails at low temperature whereas ion beam-induced enhanced self-diffusion dominates the atomic mixing at high temperature. The latter process is attributed to highly mobile Si di-interstitials formed under irradiation and during damage annealing.

Method and means of reducing erosion of components of plasma devices exposed to helium and hydrogen isotope radiation

DOEpatents

Kaminsky, Manfred S.; Das, Santosh K.; Rossing, Thomas D.

1977-01-25

Surfaces of components of plasma devices exposed to radiation by atoms or ions of helium or isotopes of hydrogen can be protected from damage due to blistering by shielding the surfaces with a structure formed by sintering a powder of aluminum or beryllium and its oxide or by coating the surfaces with such a sintered metal powder.

A Short History of the Discovery of Isotopes (and Some of Their Uses)

ERIC Educational Resources Information Center

Scott, Dave

2013-01-01

This article looks at the events that led to the discovery of isotopes in the early part of the 20th century. It is difficult to claim that the discovery was a single event. A number of famous scientists worked independently to provide the evidence, and the understanding of the need to think differently about atoms gradually emerged. Four varied…

Monte Carlo isotopic inventory analysis for complex nuclear systems

NASA Astrophysics Data System (ADS)

Phruksarojanakun, Phiphat

Monte Carlo Inventory Simulation Engine (MCise) is a newly developed method for calculating isotopic inventory of materials. It offers the promise of modeling materials with complex processes and irradiation histories, which pose challenges for current, deterministic tools, and has strong analogies to Monte Carlo (MC) neutral particle transport. The analog method, including considerations for simple, complex and loop flows, is fully developed. In addition, six variance reduction tools provide unique capabilities of MCise to improve statistical precision of MC simulations. Forced Reaction forces an atom to undergo a desired number of reactions in a given irradiation environment. Biased Reaction Branching primarily focuses on improving statistical results of the isotopes that are produced from rare reaction pathways. Biased Source Sampling aims at increasing frequencies of sampling rare initial isotopes as the starting particles. Reaction Path Splitting increases the population by splitting the atom at each reaction point, creating one new atom for each decay or transmutation product. Delta Tracking is recommended for high-frequency pulsing to reduce the computing time. Lastly, Weight Window is introduced as a strategy to decrease large deviations of weight due to the uses of variance reduction techniques. A figure of merit is necessary to compare the efficiency of different variance reduction techniques. A number of possibilities for figure of merit are explored, two of which are robust and subsequently used. One is based on the relative error of a known target isotope (1/R 2T) and the other on the overall detection limit corrected by the relative error (1/DkR 2T). An automated Adaptive Variance-reduction Adjustment (AVA) tool is developed to iteratively define parameters for some variance reduction techniques in a problem with a target isotope. Sample problems demonstrate that AVA improves both precision and accuracy of a target result in an efficient manner. Potential applications of MCise include molten salt fueled reactors and liquid breeders in fusion blankets. As an example, the inventory analysis of a liquid actinide fuel in the In-Zinerator, a sub-critical power reactor driven by a fusion source, is examined. The result reassures MCise as a reliable tool for inventory analysis of complex nuclear systems.

The ATTA-Hefei Instrument for Radioactive Noble-gas Dating

NASA Astrophysics Data System (ADS)

Hu, S.; Cheng, C.; Cheng, G.; Sun, Y. R.; Tu, L.; Yang, G.

2013-12-01

Long-lived noble-gas isotopes 85Kr (10.8 y), 39Ar (269 y) and 81Kr (229 ky) are ideal tracers for dating environmental samples such as groundwater and ice. Together with 14C, these nuclides can be used to cover the whole range of 100-106 y. Atom Trap Trace Analysis (ATTA) is an emerging method for the analysis of these isotopes at an isotopic abundance level as low as 10^-16 [1,2]. The ATTA instrument built in Hefei, China, can determine the isotopic abundances of 85Kr and 81Kr with typically 5-10% accuracy using krypton gas samples of a few micro-liters (STP) krypton gas [3]. The krypton gas sample can be extracted from several liters of air using a distillation-chromatograph setup with a typical efficiency of 85%, while the air sample can be extracted from groundwater or ices. The typical sample size for ATTA measurement is 100L groundwater or 40Kg ices. One such ATTA beamline can handle about 100 samples per year. [1] Chen, C. Y. et al. Ultrasensitive isotope trace analyses with a magneto-optical trap. Science 286, 1139-1141 (1999). [2] Jiang, W. et al. 39Ar detection at the 10-16 isotopic abundance level with atom trap trace analysis. Phys. Rev. Lett. 106, 103001 (2011). [3] Yang, G. -M. et al. Analysis of 85Kr: a comparison at the 10-14 level using micro-liter samples, Sci. Rep. 3, 1596 (2013). Relative uncertainty of the determined 85Kr abundance by the ATTA-Hefei instrument.

Isotope shift, nonlinearity of King plots, and the search for new particles

NASA Astrophysics Data System (ADS)

Flambaum, V. V.; Geddes, A. J.; Viatkina, A. V.

2018-03-01

We derive a mean-field relativistic formula for the isotope shift of an electronic energy level for arbitrary angular momentum; we then use it to predict the spectra of superheavy metastable neutron-rich isotopes belonging to the hypothetical island of stability. Our results may be applied to the search for superheavy atoms in astrophysical spectra using the known values of the transition frequencies for the neutron-deficient isotopes produced in the laboratory. An example of a relevant astrophysical system may be the spectra of the Przybylski's star where superheavy elements up to Z =99 have been possibly identified. In addition, it has been recently suggested to use the measurements of King plot nonlinearity in a search for hypothetical new light bosons. On the other hand, one can find the nonlinear corrections to the King plot arising already in the standard model framework. We investigate contributions to the nonlinearity arising from relativistic effects in the isotope field shift, the nuclear polarizability, and many-body effects. It is found that the nuclear polarizability contribution can lead to the significant deviation of the King plot from linearity. Therefore, the measurements of the nonlinearity of King plots may be applied to obtain the nuclear polarizability change between individual isotopes. We then proceed with providing a rough analytical estimate of the nonlinearity arising solely from the effect of a hypothetical scalar boson. Our predictions give theoretical limitations on the sensitivity of the search for new interactions and should help to identify the most suitable atoms for corresponding experiments.

Oxygen Isotope Signatures of Biogenic Manganese(III/IV) Oxides

NASA Astrophysics Data System (ADS)

Sutherland, K. M.; Hansel, C. M.; Wankel, S. D.

2015-12-01

Manganese (Mn) oxide minerals are pervasive throughout a number of surface earth environments as rock varnishes, ferromanganese nodules, crusts around deep-sea vents, and cave deposits among many other marine, freshwater, and terrestrial deposits. Mn(III,IV) oxides are also among the strongest sorbents and oxidants in surface earth environments and are crucial to understanding the fate of organic matter in sedimentary environments. The precipitation of Mn oxide minerals proceeds via both abiotic and biotic oxidation pathways, the latter due to the indirect or direct activity of Mn(II)- oxidizing microorganisms, including bacteria and fungi. Although the precipitation of Mn oxides is believed to be primarily controlled by Mn(II)-oxidizing organisms in most surface earth environments, confirmation of this generally held notion has remained illusive and limits our understanding of their formation on Earth and beyond (e.g., Mars). Previous work provided evidence that O atom incorporation by specific Mn oxidation pathways may exhibit unique and predictable isotopic fractionation. In this study, we expand upon this evidence by measuring the oxygen isotope signature of several biogenic and abiogenic Mn oxide minerals synthesized under a range of oxygen-18 labeled water. These results allow us to determine the relative amount oxygen atoms derived from water and molecular oxygen that are incorporated in the oxide and shed light on corresponding isotope fractionation factors. Additionally, we show that, once precipitated, Mn oxide isotope signatures are robust with respect to aqueous oxygen isotope exchange. The study provides a foundation on which to study and interpret Mn oxides in natural environments and determine which environmental controls may govern Mn(II) oxidation.

Linking protein structure and dynamics to catalysis: the role of hydrogen tunnelling

PubMed Central

Klinman, Judith P

2006-01-01

Early studies of enzyme-catalysed hydride transfer reactions indicated kinetic anomalies that were initially interpreted in the context of a ‘tunnelling correction’. An alternate model for tunnelling emerged following studies of the hydrogen atom transfer catalysed by the enzyme soybean lipoxygenase. This invokes full tunnelling of all isotopes of hydrogen, with reaction barriers reflecting the heavy atom, environmental reorganization terms. Using the latter approach, we offer an integration of the aggregate data implicating hydrogen tunnelling in enzymes (i.e. deviations from Swain–Schaad relationships and the semi-classical temperature dependence of the hydrogen isotope effect). The impact of site-specific mutations of enzymes plays a critical role in our understanding of the factors that control tunnelling in enzyme reactions. PMID:16873120

Laser Ablation Molecular Isotopic Spectrometry for Molecules Formation Chemistry in Femtosecond-Laser Ablated Plasmas.

PubMed

Hou, Huaming; Mao, Xianglei; Zorba, Vassilia; Russo, Richard E

2017-07-18

Recently, laser ablated molecular isotopic spectrometry (LAMIS) has expanded its capability to explore molecules formation mechanism in laser-induced plasma in addition to isotope analysis. LAMIS is a powerful tool for tracking the origination of atoms that is involved in formation of investigated molecules by labeling atoms with their isotopic substitution. The evolutionary formation pathways of organic molecules, especially of C 2 dimers and CN radicals, were frequently reported. However, very little is known about the formation pathways for metallic radicals and heterodimers in laser ablated plasma. This research focuses on elucidating the formation pathways of AlO radicals in femtosecond laser ablated plasma from 18 O-labeled Al 2 O 3 pellet. Plasmas expanding with strong forward bias in the direction normal to the sample surface were generated in the wake of a weakly ionized channel created by a femtosecond laser. The formation mechanism of AlO and influence of air were investigated with multiple plasma diagnostic methods such as monochromatic fast gating imaging, spatiotemporal resolved optical emission spectroscopy, and LAMIS. An advanced LAMIS fitting procedure was used to deduce the spatiotemporal distributions of Al 18 O and Al 16 O number densities and also their ratios. We found that the Al 16 O/Al 18 O number density ratio is higher for plasma portion closer to the sample surface, which suggests that chemical reactions between the plasma plume and ambient air are more intense at the tail of the plasma. The results also reveals that direct association of free Al and O atoms is the main mechanism for the formation of AlO at the early stage of the plasma. To the contrast, chemical reactions between plasma materials and ambient oxygen molecules and the isotope exchange effect are the dominant mechanisms of the formation of AlO and evolution of Al 16 O/Al 18 O number density ratio at the late stage of the plasma.

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 Exotic Beams at ISOLDE: A Laboratory Portrait special issue.

Plutonium isotopes in the Hungarian environment.

PubMed

Varga, Beata; Tarján, Sandor; Vajda, Nora

2008-04-01

More than 50 soil samples were analysed from different parts of the country, the activity concentration of 239+240Pu was in the range of 0.01-0.84 Bq/kg dry soil with the average of 0.10 Bq/kg. 238Pu could be detected only in few moss samples and 238Pu/239+240Pu ratio determines the origin of plutonium. 241Pu was determined by liquid scintillation spectrometry. The activity concentration of this isotope in the soil is between 0.04 and 3.74 Bq/kg with the average of 0.82 Bq/kg, while in the moss is also similar 0.01-2.07 Bq/kg fresh mass with the average of 0.43 Bq/kg. Significant difference could not be observed between the different types of soils occurring in the country, but the results could be sorted according to the sampling carried out on undisturbed or cultivated area. The isotope ratios 241Pu/239+240Pu prove that the origin of the plutonium in Hungary is the global fallout determined by the atmospheric nuclear weapon tests.

Charge exchange collisions of slow C6 + with atomic and molecular H

NASA Astrophysics Data System (ADS)

Saha, Bidhan C.; Guevara, Nicolais L.; Sabin, John R.; Deumens, Erik; Öhrn, Yngve

2016-04-01

Charge exchange in collisions of C6+ ions with H and H2 is investigated theoretically at projectile energies 0.1 < E < 10 keV/amu, using electron nuclear dynamics (END) - a semi-classical approximation which not only includes electron translation factors for avoiding spurious couplings but also employs full dynamical trajectories to treat nuclear motions. Both the total and partial cross sections are reported for the collision of C6+ ions with atomic and molecular hydrogen. A comparison with other theoretical and experimental results shows, in general good agreement except at very low energy, considered here. For H2, the one- and two-electron charge exchange cross sections are calculated and compared with other theoretical and experimental results. Small but non-negligible isotope effects are found at the lowest energy studied in the charge transfer of C6+ with H. In low energy region, it is observed that H2 has larger isotope effects than H atom due to the polarizability effect which is larger than the mass effect.

Neutral atom traps of rare isotopes

NASA Astrophysics Data System (ADS)

Mueller, Peter

2016-09-01

Laser cooling and trapping techniques offer exquisite control of an atom's external and internal degrees of freedom. The species of interest can be selectively captured, cooled close to absolute zero temperatures, and observed with high signal-to-noise ratio. Moreover, the atom's electronic and magnetic state populations can be precisely manipulated and interrogated. Applied in nuclear physics, these techniques are ideal for precision measurements in the fields of fundamental interactions and symmetries, nuclear structure studies, and isotopic trace analysis. In particular, they offer unique opportunities in the quest for physics beyond the standard model. I will shortly review the basics of this approach and the state of the field and then cover in more details recent results from two such efforts: the search for a permanent electric dipole moment in 225Ra and the beta-neutrino angular correlation measurement with laser trapped 6He. This work is supported by the U.S. DOE, Office of Science, Office of Nuclear Physics, under Contract DE-AC02-06CH11357.

Miniature atomic scalar magnetometer for space based on the rubidium isotope 87Rb.

PubMed

Korth, Haje; Strohbehn, Kim; Tejada, Francisco; Andreou, Andreas G; Kitching, John; Knappe, Svenja; Lehtonen, S John; London, Shaughn M; Kafel, Matiwos

2016-08-01

A miniature atomic scalar magnetometer based on the rubidium isotope 87 Rb was developed for operation in space. The instrument design implements both M x and M z mode operation and leverages a novel microelectromechanical system (MEMS) fabricated vapor cell and a custom silicon-on-sapphire (SOS) complementary metal-oxide-semiconductor (CMOS) integrated circuit. The vapor cell has a volume of only 1 mm 3 so that it can be efficiently heated to its operating temperature by a specially designed, low-magnetic-field-generating resistive heater implemented in multiple metal layers of the transparent sapphire substrate of the SOS-CMOS chips. The SOS-CMOS chip also hosts the Helmholtz coil and associated circuitry to stimulate the magnetically sensitive atomic resonance and temperature sensors. The prototype instrument has a total mass of fewer than 500 g and uses less than 1 W of power, while maintaining a sensitivity of 15 pT/√Hz at 1 Hz, comparable to present state-of-the-art absolute magnetometers.

Atomic weights: no longer constants of nature

USGS Publications Warehouse

Coplen, Tyler B.; Holden, Norman E.

2011-01-01

Many of us were taught that the standard atomic weights we found in the back of our chemistry textbooks or on the Periodic Table of the Chemical Elements hanging on the wall of our chemistry classroom are constants of nature. This was common knowledge for more than a century and a half, but not anymore. The following text explains how advances in chemical instrumentation and isotopic analysis have changed the way we view atomic weights and why they are no longer constants of nature

A Water Geochemistry Study of Indian Wells Valley, Inyo and Kern Counties, California. Supplement. Isotope Geochemistry and Appendix H.

DTIC Science & Technology

1990-09-01

accuracy by Carl F. Austin, NWC; James Moore, California Energy Co.; and Robert 0. Fournier, Unites States Geological Survey. Approved by Under authority...protons, electrons , and neutrons. The electrical charge of protons is positive, and that of electrons is negative. Neutrons have no electrical charge...The number of protons determines what element an atom is and gives it its atomic number. In a neutral or nonionized atom the number of electrons

Hunting a Black Swan: Policy Options for America’s Police in Preventing Radiological/Nuclear Terrorism

DTIC Science & Technology

2012-09-01

patrol vehicles. The Department’s Counter-Terror Operations Unit serves as the program coordinator and as the archetypical NIMS Type I Team. The...is defined by Title I of the Atomic Energy Act of 1954 as plutonium, uranium-233, or uranium enriched in the isotopes uranium-233 or uranium...end of World War II. Radioactive Materials—materials that contain radioactive atoms . Radioactive atoms are unstable; that is, they have too much

Magnesium isotopic composition of the mantle

NASA Astrophysics Data System (ADS)

Teng, F.; Li, W.; Ke, S.; Marty, B.; Huang, S.; Dauphas, N.; Wu, F.; Helz, R. L.

2009-12-01

Studies of Mg isotopic composition of the Earth not only are important for understanding its geochemistry but also can shed light on the accretion history of the Earth as well as the evolution of the Earth-Moon system. However, to date, the Mg isotopic composition of the Earth is still poorly constrained and highly debated. There is uncertainty in the magnitude of Mg isotope fractionation at mantle temperatures and whether the Earth has a chondritic Mg isotopic composition or not. To constrain further the Mg isotopic composition of the mantle and investigate the behavior of Mg isotopes during igneous differentiation, we report >200 high-precision (δ26Mg < 0.1‰, 2SD) analyses of Mg isotopes on 1) global mid-ocean ridge basalts covering major ridge segments of the world and spanning a broad range in latitudes, chemical and radiogenic isotopic compositions; 2) ocean island basalts from Hawaiian (Koolau, Kilauea and Loihi) and French Polynesian volcanoes (Society island and Cook Austral chain); 3) olivine grains from Hawaiian volcanoes (Kilauea, Koolau and Loihi) and 4) peridotite xenoliths from Australia, China, France, Tanzania and USA. Global oceanic basalts and peridotite xenoliths have a limited (<0.2 ‰) variation in Mg isotopic composition, with an average δ26Mg = -0.25 relative to DSM3. Olivines from Hawaiian lavas have δ26Mg ranging from -0.43 to +0.03, with most having compositions identical to basalts and peridotites. Therefore, the mantle’s δ26Mg value is estimated to be ~ -0.25 ± 0.1 (2SD), different from that reported by Wiechert and Halliday (2007; δ26Mg = ~ 0) but similar to more recent studies (δ26Mg = -0.27 to -0.33) (Teng et al. 2007; Handler et al. 2009; Yang et al., 2009). Moreover, we suggest the Earth, as represented by the mantle, has a Mg isotopic composition similar to chondrites (δ26Mg = ~-0.33). The need for a model such as that of Wiechert and Halliday (2007) that involves sorting of chondrules and calcium-aluminum-rich inclusions in the proto planetary disc is thus not required to explain the Mg isotopic composition of the Earth.

Tracking niche variation over millennial timescales in sympatric killer whale lineages

PubMed Central

Foote, Andrew D.; Newton, Jason; Ávila-Arcos, María C.; Kampmann, Marie-Louise; Samaniego, Jose A.; Post, Klaas; Rosing-Asvid, Aqqalu; Sinding, Mikkel-Holger S.; Gilbert, M. Thomas P.

2013-01-01

Niche variation owing to individual differences in ecology has been hypothesized to be an early stage of sympatric speciation. Yet to date, no study has tracked niche width over more than a few generations. In this study, we show the presence of isotopic niche variation over millennial timescales and investigate the evolutionary outcomes. Isotopic ratios were measured from tissue samples of sympatric killer whale Orcinus orca lineages from the North Sea, spanning over 10 000 years. Isotopic ratios spanned a range similar to the difference in isotopic values of two known prey items, herring Clupea harengus and harbour seal Phoca vitulina. Two proxies of the stage of speciation, lineage sorting of mitogenomes and genotypic clustering, were both weak to intermediate indicating that speciation has made little progress. Thus, our study confirms that even with the necessary ecological conditions, i.e. among-individual variation in ecology, it is difficult for sympatric speciation to progress in the face of gene flow. In contrast to some theoretical models, our empirical results suggest that sympatric speciation driven by among-individual differences in ecological niche is a slow process and may not reach completion. We argue that sympatric speciation is constrained in this system owing to the plastic nature of the behavioural traits under selection when hunting either mammals or fish. PMID:23945688

Tracking niche variation over millennial timescales in sympatric killer whale lineages.

PubMed

Foote, Andrew D; Newton, Jason; Ávila-Arcos, María C; Kampmann, Marie-Louise; Samaniego, Jose A; Post, Klaas; Rosing-Asvid, Aqqalu; Sinding, Mikkel-Holger S; Gilbert, M Thomas P

2013-10-07

Niche variation owing to individual differences in ecology has been hypothesized to be an early stage of sympatric speciation. Yet to date, no study has tracked niche width over more than a few generations. In this study, we show the presence of isotopic niche variation over millennial timescales and investigate the evolutionary outcomes. Isotopic ratios were measured from tissue samples of sympatric killer whale Orcinus orca lineages from the North Sea, spanning over 10 000 years. Isotopic ratios spanned a range similar to the difference in isotopic values of two known prey items, herring Clupea harengus and harbour seal Phoca vitulina. Two proxies of the stage of speciation, lineage sorting of mitogenomes and genotypic clustering, were both weak to intermediate indicating that speciation has made little progress. Thus, our study confirms that even with the necessary ecological conditions, i.e. among-individual variation in ecology, it is difficult for sympatric speciation to progress in the face of gene flow. In contrast to some theoretical models, our empirical results suggest that sympatric speciation driven by among-individual differences in ecological niche is a slow process and may not reach completion. We argue that sympatric speciation is constrained in this system owing to the plastic nature of the behavioural traits under selection when hunting either mammals or fish.

A beachhead on the island of stability

DOE PAGES

Oganessian, Yuri Ts.; Rykaczewski, Krzysztof P.

2015-01-01

Remember learning the periodic table of elements in high school? Our chemistry teachers explained that the chemical properties of elements come from the electronic shell structure of atoms. Furthermore, our physics teachers enriched that picture of the atomic world by introducing us to isotopes and the Segrè chart of nuclides, which arranges them by proton number Z and neutron number N.

Organic chemistry of Murchison meteorite: Carbon isotopic fractionation

NASA Technical Reports Server (NTRS)

Yuen, G. U.; Blair, N. E.; Desmarais, D. J.; Cronin, J. R.; Chang, S.

1986-01-01

The carbon isotopic composition of individual organic compounds of meteoritic origin remains unknown, as most reported carbon isotopic ratios are for bulk carbon or solvent extractable fractions. The researchers managed to determine the carbon isotopic ratios for individual hydrocarbons and monocarboxylic acids isolated from a Murchison sample by a freeze-thaw-ultrasonication technique. The abundances of monocarboxylic acids and saturated hydrocarbons decreased with increasing carbon number and the acids are more abundant than the hydrocarbon with the same carbon number. For both classes of compounds, the C-13 to C-12 ratios decreased with increasing carbon number in a roughly parallel manner, and each carboxylic acid exhibits a higher isotopic number than the hydrocarbon containing the same number of carbon atoms. These trends are consistent with a kinetically controlled synthesis of higher homologues for lower ones.

A UHV compatible source for a highly polarized thermal atomic beam of radioactive 8Li

NASA Astrophysics Data System (ADS)

Jänsch, H. J.; Kirchner, G.; Kühlert, O.; Lisowski, M.; Paggel, J. J.; Platzer, R.; Schillinger, R.; Tilsner, H.; Weindel, C.; Winnefeld, H.; Fick, D.

2000-12-01

A beam of the radioactive isotope 8Li is prepared at thermal velocities. The nuclei are highly spin polarized by transverse optical pumping of the thermal beam. The installation is ultra-high vacuum (UHV) compatible in a non-UHV accelerator environment. Since the atomic beam is used in a surface science experiment, where contamination must be avoided, special emphasis is given to the vacuum coupling of the accelerator/ 8Li production/surface experimental areas. The atomic beam is produced by stopping the nuclear reaction products and evaporating them again from high-temperature graphite. To enhance the atomic beam, a novel tubular thermalizer is applied. The thermal polarized atomic beam intensity is approximately 5×10 8 atoms/s sr.

Mapping the subcellular distribution of biomolecules at the ultrastructural level by ion microscopy.

PubMed

Galle, P; Escaig, F; Dantin, F; Zhang, L

1996-05-01

Analytical ion microscopy, a method proposed and developed in 1960 by Casting and Slodzian at the Orsay University (France), makes it possible to obtain easily and rapidly analytical images representing the distribution in a tissue section of elements or isotopes (beginning from the three isotopes of hydrogen until to transuranic elements), even when these elements or isotopes are at a trace concentration of 1 ppm or less. This method has been applied to study the subcellular distribution of different varieties of biomolecules. The subcellular location of these molecules can be easily determined when the molecules contain in their structures a specific atom such as fluorine, iodine, bromine or platinum, what is the case of many pharmaceutical drugs. In this situation, the distribution of these specific atoms can be considered as representative of the distribution of the corresponding molecule. In other cases, the molecules must be labelled with an isotope which may be either radioactive or stable. Recent developments in ion microscopy allow the obtention of their chemical images at ultra structural level. In this paper we present the results obtained with the prototype of a new Scanning Ion Microscope used for the study of the intracellular distribution of different varieties of molecules: glucocorticoids, estrogens, pharmaceutical drugs and pyrimidine analogues.

Theoretical study of the hyperfine-interaction constants and the isotope-shift factors for the 3 s21S0-3 s 3 p 3,1P1o transitions in Al+

NASA Astrophysics Data System (ADS)

Zhang, Tingxian; Xie, Luyou; Li, Jiguang; Lu, Zehuang

2017-07-01

We calculated the magnetic dipole and the electric quadrupole hyperfine interaction constants of 3 s 3 p 3,1P1o states and the isotope shift, including mass and field shift, factors for transitions from these two states to the ground state 3 s 2 1S0 in Al+ ions using the multiconfiguration Dirac-Hartree-Fock method. The effects of the electron correlations and the Breit interaction on these physical quantities were investigated in detail based on the active space approach. It is found that the core-core and the higher order correlations are considerable for evaluating the uncertainties of the atomic parameters concerned. The uncertainties of the hyperfine interaction constants in this work are less than 1.6%. Although the isotope shift factors are highly sensitive to the electron correlations, reasonable uncertainties were obtained by exploring the effects of the electron correlations. Moreover, we found that the relativistic nuclear recoil corrections to the mass shift factors are very small and insensitive to the electron correlations for Al+. These atomic parameters present in this work are valuable for extracting the nuclear electric quadrupole moments and the mean-square charge radii of Al isotopes.

The Geologic Time Spiral - A Path to the Past

USGS Publications Warehouse

Graham, Joseph; Newman, William; Stacy, John

2008-01-01

The Earth is very old - 4.5 billion years or more according to scientific estimates. Most of the evidence for an ancient Earth is contained in the rocks that form the Earth's crust. The rock layers themselves - like pages in a long and complicated history - record the events of the past, and buried within them are the remains of life - the plants and animals that evolved from organic structures that existed 3 billion years ago. Also contained in rocks once molten are radioactive elements whose isotopes provide Earth with an atomic clock. Within these rocks, 'parent' isotopes decay at a predictable rate to form 'daughter' isotopes. By determining the relative amounts of parent and daughter isotopes, the age of these rocks can be calculated. Thus, the scientific evidence from rock layers, from fossils, and from the ages of rocks as measured by atomic clocks attests to a very old Earth. See USGS Fact Sheet 2007-3015 at http://pubs.usgs.gov/fs/2007/3015/ for ages of geologic time periods. Ages in the spiral have been rounded from the age estimates in the Fact Sheet. B.Y., billion years; M.Y., million years. For more information, see the booklet on Geologic Time at http://pubs.usgs.gov/gip/geotime/. The Geologic Time Spiral poster is available for purchase from the USGS Store.

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.

Mass-Dependent and -Independent Fractionation of Mercury Isotope during Gas-Phase Oxidation of Elemental Mercury Vapor by Atomic Cl and Br.

PubMed

Sun, Guangyi; Sommar, Jonas; Feng, Xinbin; Lin, Che-Jen; Ge, Maofa; Wang, Weigang; Yin, Runsheng; Fu, Xuewu; Shang, Lihai

2016-09-06

This study presents the first measurement of Hg stable isotope fractionation during gas-phase oxidation of Hg(0) vapor by halogen atoms (Cl(•), Br(•)) in the laboratory at 750 ± 1 Torr and 298 ± 3 K. Using a relative rate technique, the rate coefficients for Hg(0)+Cl(•) and Hg(0)+Br(•) reactions are determined to be (1.8 ± 0.5) × 10(-11) and (1.6 ± 0.8) × 10(-12) cm(3) molecule(-1) s(-1), respectively. Results show that heavier isotopes are preferentially enriched in the remaining Hg(0) during Cl(•) initiated oxidation, whereas being enriched in the product during oxidation by Br(•). The fractionation factors for (202)Hg/(198)Hg during the Cl(•) and Br(•) initiated oxidations are α(202/198) = 0.99941 ± 0.00006 (2σ) and 1.00074 ± 0.00014 (2σ), respectively. A Δ(199)Hg/Δ(201)Hg ratio of 1.64 ± 0.30 (2σ) during oxidation of Hg(0) by Br atoms suggests that Hg-MIF is introduced by the nuclear volume effect (NVE). In contrast, the Hg(0) + Cl(•) reaction produces a Δ(199)Hg/Δ(201)Hg-slope of 1.89 ± 0.18 (2σ), which in addition to a high degree of odd-mass-number isotope MIF suggests impacts from MIF effects other than NVE. This reaction also exhibits significant MIF of (200)Hg (Δ(200)Hg, up to -0.17‰ in the reactant) and is the first physicochemical process identified to trigger (200)Hg anomalies that are frequently detected in atmospheric samples.

Nanogeochronology of discordant zircon measured by atom probe microscopy of Pb-enriched dislocation loops

PubMed Central

Peterman, Emily M.; Reddy, Steven M.; Saxey, David W.; Snoeyenbos, David R.; Rickard, William D. A.; Fougerouse, Denis; Kylander-Clark, Andrew R. C.

2016-01-01

Isotopic discordance is a common feature in zircon that can lead to an erroneous age determination, and it is attributed to the mobilization and escape of radiogenic Pb during its post-crystallization geological evolution. The degree of isotopic discordance measured at analytical scales of ~10 μm often differs among adjacent analysis locations, indicating heterogeneous distributions of Pb at shorter length scales. We use atom probe microscopy to establish the nature of these sites and the mechanisms by which they form. We show that the nanoscale distribution of Pb in a ~2.1 billion year old discordant zircon that was metamorphosed c. 150 million years ago is defined by two distinct Pb reservoirs. Despite overall Pb loss during peak metamorphic conditions, the atom probe data indicate that a component of radiogenic Pb was trapped in 10-nm dislocation loops that formed during the annealing of radiation damage associated with the metamorphic event. A second Pb component, found outside the dislocation loops, represents homogeneous accumulation of radiogenic Pb in the zircon matrix after metamorphism. The 207Pb/206Pb ratios measured from eight dislocation loops are equivalent within uncertainty and yield an age consistent with the original crystallization age of the zircon, as determined by laser ablation spot analysis. Our results provide a specific mechanism for the trapping and retention of radiogenic Pb during metamorphism and confirm that isotopic discordance in this zircon is characterized by discrete nanoscale reservoirs of Pb that record different isotopic compositions and yield age data consistent with distinct geological events. These data may provide a framework for interpreting discordance in zircon as the heterogeneous distribution of discrete radiogenic Pb populations, each yielding geologically meaningful ages. PMID:27617295

The electrooxidation mechanism of formic acid on platinum and on lead ad-atoms modified platinum studied with the kinetic isotope effect

NASA Astrophysics Data System (ADS)

Bełtowska-Brzezinska, M.; Łuczak, T.; Stelmach, J.; Holze, R.

2014-04-01

Kinetics and mechanism of formic acid (FA) oxidation on platinum and upd-lead ad-atoms modified platinum electrodes have been studied using unlabelled and deuterated compounds. Poisoning of the electrode surface by CO-like species was prevented by suppression of dissociative chemisorption of FA due to a fast competitive underpotential deposition of lead ad-atoms on the Pt surface from an acidic solution containing Pb2+ cations. Modification of the Pt electrode with upd lead induced a catalytic effect in the direct electrooxidation of physisorbed FA to CO2. With increasing degree of H/D substitution, the rate of this reaction decreased in the order: HCOOH > DCOOH ≥ HCOOD > DCOOD. HCOOH was oxidized 8.5-times faster on a Pt/Pb electrode than DCOOD. This primary kinetic isotope effect proves that the C-H- and O-H-bonds are simultaneously cleaved in the rate determining step. A secondary kinetic isotope effect was found in the dissociative chemisorption of FA in the hydrogen adsorption-desorption range on a bare Pt electrode after H/D exchange in the C-H bond, wherein the influence of deuterium substitution in the O-H group was negligibly small. Thus the C-H bond cleavage is accompanied by the C-OH and not the O-H bond split in the FA decomposition, producing CO-like species on the Pt surface sites.

Carbon Exchange and Loss Processes on Mars

NASA Image and Video Library

2015-11-24

This graphic depicts paths by which carbon has been exchanged between Martian interior, surface rocks, polar caps, waters and atmosphere, and also depicts a mechanism by which carbon is lost from the atmosphere with a strong effect on isotope ratio. Carbon dioxide (CO2) to generate the Martian atmosphere originated in the planet's mantle and has been released directly through volcanoes or trapped in rocks crystallized from magmas and released later. Once in the atmosphere, the CO2 can exchange with the polar caps, passing from gas to ice and back to gas again. The CO2 can also dissolve into waters, which can then precipitate out solid carbonates, either in lakes at the surface or in shallow aquifers. Carbon dioxide gas in the atmosphere is continually lost to space at a rate controlled in part by the sun's activity. One loss mechanism is called ultraviolet photodissociation. It occurs when ultraviolet radiation (indicated on the graphic as "hv") encounters a CO2 molecule, breaking the bonds to first form carbon monoxide (CO) molecules and then carbon (C) atoms. The ratio of carbon isotopes remaining in the atmosphere is affected as these carbon atoms are lost to space, because the lighter carbon-12 (12C) isotope is more easily removed than the heavier carbon-13 (13C) isotope. This fractionation, the preferential loss of carbon-12 to space, leaves a fingerprint: enrichment of the heavy carbon-13 isotope, measured in the atmosphere of Mars today. http://photojournal.jpl.nasa.gov/catalog/PIA20163

PARTITIONING TUNGSTEN BETWEEN MATRIX PRECURSORS AND CHONDRULE PRECURSORS THROUGH RELATIVE SETTLING

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

Hubbard, Alexander, E-mail: ahubbard@amnh.org

2016-08-01

Recent studies of chondrites have found a tungsten isotopic anomaly between chondrules and matrix. Given the refractory nature of tungsten, this implies that W was carried into the solar nebula by at least two distinct families of pre-solar grains. The observed chondrule/matrix split requires that the distinct families were kept separate during the dust coagulation process, and that the two families of grain interacted with the chondrule formation mechanism differently. We take the co-existence of different families of solids in the same general orbital region at the chondrule-precursor size as given, and explore the requirements for them to have interactedmore » with the chondrule formation process at significantly different rates. We show that this sorting of families of solids into chondrule- and matrix-destined dust had to have been at least as powerful a sorting mechanism as the relative settling of aerodynamically distinct grains at least two scale heights above the midplane. The requirement that the chondrule formation mechanism was correlated in some fashion with a dust-grain sorting mechanism argues strongly for spatially localized chondrule formation mechanisms such as turbulent dissipation in non-thermally ionized disk surface layers, and argues against volume-filling mechanisms such as planetesimal bow shocks.« less

Method for the determination of cobalt from biological products with graphite furnace atomic absorption spectrometer

NASA Astrophysics Data System (ADS)

Zamfir, Oana-Liliana; Ionicǎ, Mihai; Caragea, Genica; Radu, Simona; Vlǎdescu, Marian

2016-12-01

Cobalt is a chemical element with symbol Co and atomic number 27 and atomic weight 58.93. 59 Co is the only stable cobalt isotope and the only isotope to exist naturally on Earth. Cobalt is the active center of coenzymes called cobalamin or cyanocobalamin the most common example of which is vitamin B12. Vitamin B12 deficiency can potentially cause severe and irreversible damage, especially to the brain and nervous system in the form of fatigue, depression and poor memory or even mania and psychosis. In order to study the degree of deficiency of the population with Co or the correctness of treatment with vitamin B12, a modern optoelectronic method for the determination of metals and metalloids from biological samples has been developed, Graphite Furnace - Atomic Absorption Spectrometer (GF- AAS) method is recommended. The technique is based on the fact that free atoms will absorb light at wavelengths characteristic of the element of interest. Free atoms of the chemical element can be produced from samples by the application of high temperatures. The system GF-AAS Varian used as biological samples, blood or urine that followed the digest of the organic matrix. For the investigations was used a high - performance GF-AAS with D2 - background correction system and a transversely heated graphite atomizer. As result of the use of the method are presented the concentration of Co in the blood or urine of a group of patient in Bucharest. The method is sensitive, reproducible relatively easy to apply, with a moderately costs.

Updated atomic weights: Time to review our table

USGS Publications Warehouse

Coplen, Tyler B.; Meyers, Fabienne; Holden, Norman E.

2016-01-01

Despite common belief, atomic weights are not necessarily constants of nature. Scientists’ ability to measure these values is regularly improving, so one would expect that the accuracy of these values should be improving with time. It is the task of the IUPAC (International Union of Pure and Applied Chemistry) Commission on Isotopic Abundances and Atomic Weights (CIAAW) to regularly review atomic-weight determinations and release updated values.According to an evaluation published in Pure and Applied Chemistry [1], even the most simplified table abridged to four significant digits needs to be updated for the elements selenium and molybdenum. According to the most recent 2015 release of "Atomic Weights of the Elements" [2], another update is needed for ytterbium.

Sr-87/Sr-86 isotopic age determination of upper Cretaceous Santonian, Campanian and Maastrichtian chondrichthyan teeth of the Atlantic and Eastern Gulf Coastal Plains: Implications for sea level cyclicity and macrofossil time-averaging in depositional sequence lag deposits

NASA Astrophysics Data System (ADS)

Becker, Martin Andrew

1997-11-01

Unconformities and fossil rich layers are common elements in the stratigraphic architecture of upper Cretaceous sediments exposed on both the Atlantic and Eastern Gulf Coastal Plains. Contacts between the Eutaw Formation and Tombigbee Sands Member in Alabama, the Blufftown Formation and Cusseta Sands in Georgia and the Wenonah- Mt. Laurel and Navesink Formations in New Jersey are marked by erosional surfaces with overlying blankets and lenses of macrofossil residuum. These contacts correspond to bounding unconformities and transgressive lags separating Santonian-Campanian, lower Campanian-upper Campanian and Campanian-Maastrichtian depositional sequences. Regression and subsequent transgression of sea level at the top of these depositional sequences resulted in hydrodynamic sorting of sediments and fossils that had previously accumulated in shelf and lower shoreface paleoenvironments. Remobilization of sediments by shoreface retreat reworked fossil hard-parts which became concentrated above erosional surfaces as sea level rose. Because of the abundance of chondrichthyan, pelecypod and ammonite fossils, these lags have great biostratigraphic significance and provide a basis for examining time averaging in macrofossil zonation. Chondrichthyan teeth are composed of extremely durable and highly insoluble, biogenic apatite. This tooth apatite accurately records the Sr87/Sr86 isotopic signature of seawater, from which the numerical age of the teeth can be calculated using published age/concentration data. Teeth (e.g. Squalicorax kaupi, Scapanorhynchus texanus) from Santonian-Campanian lag deposits at the contact of the Eutaw Formation and Tombigbee Sands Member in Alabama yield approximate ages of 85-81 Ma. Teeth from lower-upper Campanian lag deposits at the contact of the Blufftown Formation and Cusseta Sands in Georgia yield approximate ages of 83-75 Ma. Teeth from Campanian-Maastrichtian lag deposits at the contact of the Wenonah-Mt. Laurel and Navesink Formations in New Jersey yield approximate ages of 80-76 Ma. Isotopic age determination from these chondrichthyan teeth indicate average hiatus of approximately 3-7 million years occur during the development of lag accumulations and transgressive unconformities. Santonian, Campanian and Maastrichtian macrofossils analyzed in this study are hydrodynamically stable components representing time-averaged fossil assemblages sorted together by physical processes and are not life cohorts. Abrupt appearance and disappearance of organisms found in upper Cretaceous lag deposits of the Atlantic and Eastern Gulf Coastal Plains are artifacts of a physical sorting processes associated with sea-level cyclicity.

Carnivore specific bone bioapatite and collagen carbon isotope fractionations: Case studies of modern and fossil grey wolf populations

NASA Astrophysics Data System (ADS)

Fox-Dobbs, K.; Wheatley, P. V.; Koch, P. L.

2006-12-01

Stable isotope analyses of modern and fossil biogenic tissues are routinely used to reconstruct present and past vertebrate foodwebs. Accurate isotopic dietary reconstructions require a consumer and tissue specific understanding of how isotopes are sorted, or fractionated, between trophic levels. In this project we address the need for carnivore specific isotope variables derived from populations that are ecologically well- characterized. Specifically, we investigate the trophic difference in carbon isotope values between mammalian carnivore (wolf) bone bioapatite and herbivore (prey) bone bioapatite. We also compare bone bioapatite and collagen carbon isotope values collected from the same individuals. We analyzed bone specimens from two modern North American grey wolf (Canis lupus) populations (Isle Royale National Park, Michigan and Yellowstone National Park, Wyoming), and the ungulate herbivores that are their primary prey (moose and elk, respectively). Because the diets of both wolf populations are essentially restricted to a single prey species, there were no confounding effects due to carnivore diet variability. We measured a trophic difference of approximately -1.3 permil between carnivore (lower value) and herbivore (higher value) bone bioapatite carbon isotope values, and an average inter-tissue difference of 5.1 permil between carnivore bone collagen (lower value) and bioapatite (higher value) carbon isotope values. Both of these isotopic differences differ from previous estimates derived from a suite of African carnivores; our carnivore-herbivore bone bioapatite carbon isotope spacing is smaller (-1.3 vs. -4.0 permil), and our carnivore collagen-bioapatite carbon difference is larger (5.1 vs. 3.0 permil). These discrepancies likely result from comparing values measured from a single hypercarnivore (wolf) to average values calculated from several carnivore species, some of which are insectivorous or partly omnivorous. The trophic and inter-tissue differences we measured for wolves are applicable to future isotopic studies of consumers with purely carnivorous diets. For example, we collected bone bioapatite and collagen carbon isotope data from late Pleistocene grey wolf fossils from eastern Beringia (Fairbanks, Alaska), and used the modern inter-tissue difference presented here to verify bioapatite preservation. We then compared the wolves to herbivores (horse and caribou) from the same locality, and found the difference in their bone bioapatite carbon isotope values corresponded to the modern carnivore-herbivore trophic spacing given above. We therefore were able to conclude that horse and caribou were part of Beringian wolf diet.

Envelope: interactive software for modeling and fitting complex isotope distributions.

PubMed

Sykes, Michael T; Williamson, James R

2008-10-20

An important aspect of proteomic mass spectrometry involves quantifying and interpreting the isotope distributions arising from mixtures of macromolecules with different isotope labeling patterns. These patterns can be quite complex, in particular with in vivo metabolic labeling experiments producing fractional atomic labeling or fractional residue labeling of peptides or other macromolecules. In general, it can be difficult to distinguish the contributions of species with different labeling patterns to an experimental spectrum and difficult to calculate a theoretical isotope distribution to fit such data. There is a need for interactive and user-friendly software that can calculate and fit the entire isotope distribution of a complex mixture while comparing these calculations with experimental data and extracting the contributions from the differently labeled species. Envelope has been developed to be user-friendly while still being as flexible and powerful as possible. Envelope can simultaneously calculate the isotope distributions for any number of different labeling patterns for a given peptide or oligonucleotide, while automatically summing these into a single overall isotope distribution. Envelope can handle fractional or complete atom or residue-based labeling, and the contribution from each different user-defined labeling pattern is clearly illustrated in the interactive display and is individually adjustable. At present, Envelope supports labeling with 2H, 13C, and 15N, and supports adjustments for baseline correction, an instrument accuracy offset in the m/z domain, and peak width. Furthermore, Envelope can display experimental data superimposed on calculated isotope distributions, and calculate a least-squares goodness of fit between the two. All of this information is displayed on the screen in a single graphical user interface. Envelope supports high-quality output of experimental and calculated distributions in PNG or PDF format. Beyond simply comparing calculated distributions to experimental data, Envelope is useful for planning or designing metabolic labeling experiments, by visualizing hypothetical isotope distributions in order to evaluate the feasibility of a labeling strategy. Envelope is also useful as a teaching tool, with its real-time display capabilities providing a straightforward way to illustrate the key variable factors that contribute to an observed isotope distribution. Envelope is a powerful tool for the interactive calculation and visualization of complex isotope distributions for comparison to experimental data. It is available under the GNU General Public License from http://williamson.scripps.edu/envelope/.

Probing New Long-Range Interactions by Isotope Shift Spectroscopy

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

Berengut, Julian C.; Budker, Dmitry; Delaunay, Cédric

We explore a method to probe new long- and intermediate-range interactions using precision atomic isotope shift spectroscopy. We develop a formalism to interpret linear King plots as bounds on new physics with minimal theory inputs. We focus only on bounding the new physics contributions that can be calculated independently of the standard model nuclear effects. We apply our method to existing Ca + data and project its sensitivity to conjectured new bosons with spin-independent couplings to the electron and the neutron using narrow transitions in other atoms and ions, specifically, Sr and Yb. Future measurements are expected to improve themore » relative precision by 5 orders of magnitude, and they can potentially lead to an unprecedented sensitivity for bosons within the 0.3 to 10 MeV mass range.« less

Probing New Long-Range Interactions by Isotope Shift Spectroscopy.

PubMed

Berengut, Julian C; Budker, Dmitry; Delaunay, Cédric; Flambaum, Victor V; Frugiuele, Claudia; Fuchs, Elina; Grojean, Christophe; Harnik, Roni; Ozeri, Roee; Perez, Gilad; Soreq, Yotam

2018-03-02

We explore a method to probe new long- and intermediate-range interactions using precision atomic isotope shift spectroscopy. We develop a formalism to interpret linear King plots as bounds on new physics with minimal theory inputs. We focus only on bounding the new physics contributions that can be calculated independently of the standard model nuclear effects. We apply our method to existing Ca^{+} data and project its sensitivity to conjectured new bosons with spin-independent couplings to the electron and the neutron using narrow transitions in other atoms and ions, specifically, Sr and Yb. Future measurements are expected to improve the relative precision by 5 orders of magnitude, and they can potentially lead to an unprecedented sensitivity for bosons within the 0.3 to 10 MeV mass range.

Heaviest Nuclei: New Element with Atomic Number 117

ScienceCinema

Oganessian, Yuri

2018-01-24

One of the fundamental outcomes of the nuclear shell model is the prediction of the 'stability islands' in the domain of the hypothetical super heavy elements. The talk is devoted to the experimental verification of these predictions - the synthesis and study of both the decay and chemical properties of the super heavy elements. The discovery of a new chemical element with atomic number Z=117 is reported. The isotopes 293117 and 294117 were produced in fusion reactions between 48Ca and 249Bk. Decay chains involving 11 new nuclei were identified by means of the Dubna gas-filled recoil separator. The measured decay properties show a strong rise of stability for heavier isotopes with Z =111, validating the concept of the long sought island of enhanced stability for heaviest nuclei.

Probing New Long-Range Interactions by Isotope Shift Spectroscopy

DOE PAGES

Berengut, Julian C.; Budker, Dmitry; Delaunay, Cédric; ...

2018-02-26

We explore a method to probe new long- and intermediate-range interactions using precision atomic isotope shift spectroscopy. We develop a formalism to interpret linear King plots as bounds on new physics with minimal theory inputs. We focus only on bounding the new physics contributions that can be calculated independently of the standard model nuclear effects. We apply our method to existing Ca + data and project its sensitivity to conjectured new bosons with spin-independent couplings to the electron and the neutron using narrow transitions in other atoms and ions, specifically, Sr and Yb. Future measurements are expected to improve themore » relative precision by 5 orders of magnitude, and they can potentially lead to an unprecedented sensitivity for bosons within the 0.3 to 10 MeV mass range.« less

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.

Temporal and spatial distribution of isotopes in river water in Central Europe: 50 years experience with the Austrian network of isotopes in rivers.

PubMed

Rank, Dieter; Wyhlidal, Stefan; Schott, Katharina; Weigand, Silvia; Oblin, Armin

2018-05-01

The Austrian network of isotopes in rivers comprises about 15 sampling locations and has been operated since 1976. The Danube isotope time series goes back to 1963. The isotopic composition of river water in Central Europe is mainly governed by the isotopic composition of precipitation in the catchment area; evaporation effects play only a minor role. Short-term and long-term isotope signals in precipitation are thus transmitted through the whole catchment. The influence of climatic changes has become observable in the long-term stable isotope time series of precipitation and surface waters. Environmental 3 H values were around 8 TU in 2015, short-term 3 H pulses up to about 80 TU in the rivers Danube and March were a consequence of releases from nuclear power plants. The complete isotope data series of this network will be included in the Global Network of Isotopes in Rivers database of the International Atomic Energy Agency (IAEA) in 2017. This article comprises a review of 50 years isotope monitoring on rivers and is also intended to provide base information on the (isotope-)hydrological conditions in Central Europe specifically for the end-users of these data, e.g. for modelling hydrological processes. Furthermore, this paper includes the 2006-2015 supplement adding to the Danube isotope set published earlier.

Alteration of the Carbon and Nitrogen Isotopic Composition in the Martian Surface Rocks Due to Cosmic Ray Exposure

NASA Technical Reports Server (NTRS)

Pavlov, A. A.; Pavlov, A. K.; Ostryakov, V. M.; Vasilyev, G. I.; Mahaffy, P.; Steele, A.

2014-01-01

C-13/C-12 and N-15/N-14 isotopic ratios are pivotal for our understanding of the Martian carbon cycle, history of the Martian atmospheric escape, and origin of the organic compounds on Mars. Here we demonstrate that the carbon and nitrogen isotopic composition of the surface rocks on Mars can be significantly altered by the continuous exposure of Martian surface to cosmic rays. Cosmic rays can effectively produce C-13 and N-15 isotopes via spallation nuclear reactions on oxygen atoms in various Martian rocks. We calculate that in the top meter of the Martian rocks, the rates of production of both C-13 and N-15 due to galactic cosmic rays (GCRs) exposure can vary within 1.5-6 atoms/cm3/s depending on rocks' depth and chemical composition. We also find that the average solar cosmic rays can produce carbon and nitrogen isotopes at a rate comparable to GCRs in the top 5-10 cm of the Martian rocks. We demonstrate that if the total carbon content in a surface Martian rock is <10 ppm, then the "light," potentially "biological" C-13/C-12 ratio would be effectively erased by cosmic rays over 3.5 billion years of exposure. We found that for the rocks with relatively short exposure ages (e.g., 100 million years), cosmogenic changes in N-15/N-14 ratio are still very significant. We also show that a short exposure to cosmic rays of Allan Hills 84001 while on Mars can explain its high-temperature heavy nitrogen isotopic composition (N-15/N-14). Applications to Martian meteorites and the current Mars Science Laboratory mission are discussed.

Matrix effects of calcium on high-precision sulfur isotope measurement by multiple-collector inductively coupled plasma mass spectrometry.

PubMed

Liu, Chenhui; Bian, Xiao-Peng; Yang, Tao; Lin, An-Jun; Jiang, Shao-Yong

2016-05-01

Multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) has been successfully applied in the rapid and high-precision measurement for sulfur isotope ratios in recent years. During the measurement, the presence of matrix elements would affect the instrumental mass bias for sulfur and these matrix-induced effects have aroused a lot of researchers' interest. However, these studies have placed more weight on highlighting the necessity for their proposed correction protocols (e.g., chemical purification and matrix-matching) while less attention on the key property of the matrix element gives rise to the matrix effects. In this study, four groups of sulfate solutions, which have different concentrations of sulfur (0.05-0.60mM) but a constant sequence of atomic calcium/sulfur ratios (0.1-50), are investigated under wet (solution) and dry (desolvation) plasma conditions to make a detailed evaluation on the matrix effects from calcium on sulfur isotope measurement. Based on a series of comparative analyses, we indicated that, the matrix effects of calcium on both measured sulfur isotope ratios and detected (32)S signal intensities are dependent mainly on the absolute calcium concentration rather than its relative concentration ratio to sulfur (i.e., atomic calcium/sulfur ratio). Also, for the same group of samples, the matrix effects of calcium under dry plasma condition are much more significant than that of wet plasma. This research affords the opportunity to realize direct and relatively precise sulfur isotope measurement for evaporite gypsum, and further provides some suggestions with regard to sulfur isotope analytical protocols for sedimentary pore water. Copyright © 2016 Elsevier B.V. All rights reserved.

Calibrated sulfur isotope abundance ratios of three IAEA sulfur isotope reference materials and V-CDT with a reassessment of the atomic weight of sulfur

NASA Astrophysics Data System (ADS)

Ding, T.; Valkiers, S.; Kipphardt, H.; De Bièvre, P.; Taylor, P. D. P.; Gonfiantini, R.; Krouse, R.

2001-08-01

Calibrated values have been obtained for sulfur isotope abundance ratios of sulfur isotope reference materials distributed by the IAEA (Vienna). For the calibration of the measurements, a set of synthetic isotope mixtures were prepared gravimetrically from high purity Ag2S materials enriched in32S, 33S, and 34S. All materials were converted into SF6 gas and subsequently, their sulfur isotope ratios were measured on the SF5+ species using a special gas source mass spectrometer equipped with a molecular flow inlet system (IRMM's Avogadro II amount comparator). Values for the 32S/34S abundance ratios are 22.650 4(20), 22.142 4(20), and 23.393 3(17) for IAEA-S-1, IAEA-S-2, and IAEA-S-3, respectively. The calculated 32S/34S abundance ratio for V-CDT is 22.643 6(20), which is very close to the calibrated ratio obtained by Ding et al. (1999). In this way, the zero point of the VCDT scale is anchored firmly to the international system of units SI. The 32S/33S abundance ratios are 126.942(47), 125.473(55), 129.072(32), and 126.948(47) for IAEA-S-1, IAEA-S-2, IAEA-S-3, and V-CDT, respectively. In this way, the linearity of the V-CDT scale is improved over this range. The values of the sulfur molar mass for IAEA-S-1 and V-CDT were calculated to be 32.063 877(56) and 32.063 911(56), respectively, the values with the smallest combined uncertainty ever reported for the sulfur molar masses (atomic weights).

A 220Rn source for the calibration of low-background experiments

NASA Astrophysics Data System (ADS)

Lang, R. F.; Brown, A.; Brown, E.; Cervantes, M.; Macmullin, S.; Masson, D.; Schreiner, J.; Simgen, H.

2016-04-01

We characterize two 40 kBq sources of electrodeposited 228Th for use in low-background experiments. The sources efficiently emanate 220Rn, a noble gas that can diffuse in a detector volume. 220Rn and its daughter isotopes produce α-, β-, and γ-radiation, which may used to calibrate a variety of detector responses and features, before decaying completely in only a few days. We perform various tests to place limits on the release of other long-lived isotopes. In particular, we find an emanation of < 0.008 atoms/min/kBq (90% CL) for 228Th and (1.53 ± 0.04) atoms/min/kBq for 224Ra. The sources lend themselves in particular to the calibration of detectors employing liquid noble elements such as argon and xenon. With the source mounted in a noble gas system, we demonstrate that filters are highly efficient in reducing the activity of these longer-lived isotopes further. We thus confirm the suitability of these sources even for use in next-generation experiments, such as XENON1T/XENONnT, LZ, and nEXO.

A Geant4-based Simulation to Evaluate the Feasibility of Using Nuclear Resonance Fluorescence (NRF) in Determining Atomic Compositions of Body Tissue in Cancer Diagnostics and Irradiation

NASA Astrophysics Data System (ADS)

Gilbo, Yekaterina; Wijesooriya, Krishni; Liyanage, Nilanga

2017-01-01

Customarily applied in homeland security for identifying concealed explosives and chemical weapons, NRF (Nuclear Resonance Fluorescence) may have high potential in determining atomic compositions of body tissue. High energy photons incident on a target excite the target nuclei causing characteristic re-emission of resonance photons. As the nuclei of each isotope have well-defined excitation energies, NRF uniquely indicates the isotopic content of the target. NRF radiation corresponding to nuclear isotopes present in the human body is emitted during radiotherapy based on Bremsstrahlung photons generated in a linear electron accelerator. We have developed a Geant4 simulation in order to help assess NRF capabilities in detecting, mapping, and characterizing tumors. We have imported a digital phantom into the simulation using anatomical data linked to known chemical compositions of various tissues. Work is ongoing to implement the University of Virginia's cancer center treatment setup and patient geometry, and to collect and analyze the simulation's physics quantities to evaluate the potential of NRF for medical imaging applications. Preliminary results will be presented.

Fission fragment yields from heavy-ion-induced reactions measured with a fragment separator

NASA Astrophysics Data System (ADS)

Tarasov, O. B.; Delaune, O.; Farget, F.; Morrissey, D. J.; Amthor, A. M.; Bastin, B.; Bazin, D.; Blank, B.; Cacéres, L.; Chbihi, A.; Fernández-Dominguez, B.; Grévy, S.; Kamalou, O.; Lukyanov, S. M.; Mittig, W.; Pereira, J.; Perrot, L.; Saint-Laurent, M.-G.; Savajols, H.; Sherrill, B. M.; Stodel, C.; Thomas, J. C.; Villari, A. C.

2018-04-01

The systematic study of fission fragment yields under different initial conditions has provided valuable experimental data for benchmarking models of fission product yields. Nuclear reactions using inverse kinematics coupled to the use of a high-resolution spectrometer with good fragment identification are shown here to be a powerful tool to measure the inclusive isotopic yields of fission fragments. In-flight fusion-fission was used in this work to produce secondary beams of neutron-rich isotopes in the collisions of a 238U beam at 24 MeV/u with 9Be and 12C targets at GANIL using the LISE3 fragment separator. Unique identification of the A, Z, and atomic charge state, q, of fission products was attained with the Δ E- TKE-B ρ- ToF measurement technique. Mass, and atomic number distributions are reported for the two reactions. The results show the importance of different reaction mechanisms in the two cases. The optimal target material for higher yields of neutron-rich high- Z isotopes produced in fusion-fission reactions as a function of projectile energy is discussed.

Towards laser spectroscopy of the proton-halo candidate boron-8

NASA Astrophysics Data System (ADS)

Maaß, Bernhard; Müller, Peter; Nörtershäuser, Wilfried; Clark, Jason; Gorges, Christian; Kaufmann, Simon; König, Kristian; Krämer, Jörg; Levand, Anthony; Orford, Rodney; Sánchez, Rodolfo; Savard, Guy; Sommer, Felix

2017-11-01

We propose to determine the nuclear charge radius of 8B by high-resolution laser spectroscopy. 8B (t 1/2 = 770 ms) is perhaps the best candidate of a nucleus exhibiting an extended proton wave-function or "one-proton-halo" in a more descriptive picture. Laser spectroscopic measurements of the isotope shift will be used to probe the change in nuclear charge radius along the three boron isotopes 8B, 10B and 11B. The change in nuclear charge radius directly correlates with the extent of the proton wave function. In-flight production and preparation of sufficient yields of 8B ions at low energies is provided by the Argonne Tandem Linac Accelerator System (ATLAS) at Argonne National Laboratory (ANL) in Chicago, IL, USA. Subsequently, the ions will be guided through a charge exchange cell for neutralization and the fluorescence signal of the atoms which interact with the resonant laser light will be detected. The charge radius can then be extracted from the measured isotope shift by employing highly accurate atomic theory calculations of this five-electron system which are carried out presently.

Natural Isotope Abundance in Metabolites: Techniques and Kinetic Isotope Effect Measurement in Plant, Animal, and Human Tissues.

PubMed

Tea, Illa; Tcherkez, Guillaume

2017-01-01

The natural isotope abundance in bulk organic matter or tissues is not a sufficient base to investigate physiological properties, biosynthetic mechanisms, and nutrition sources of biological systems. In fact, isotope effects in metabolism lead to a heterogeneous distribution of 2 H, 18 O, 13 C, and 15 N isotopes in metabolites. Therefore, compound-specific isotopic analysis (CSIA) is crucial to biological and medical applications of stable isotopes. Here, we review methods to implement CSIA for 15 N and 13 C from plant, animal, and human samples and discuss technical solutions that have been used for the conversion to CO 2 and N 2 for IRMS analysis, derivatization and isotope effect measurements. It appears that despite the flexibility of instruments used for CSIA, there is no universal method simply because the chemical nature of metabolites of interest varies considerably. Also, CSIA methods are often limited by isotope effects in sample preparation or the addition of atoms from the derivatizing reagents, and this implies that corrections must be made to calculate a proper δ-value. Therefore, CSIA has an enormous potential for biomedical applications, but its utilization requires precautions for its successful application. © 2017 Elsevier Inc. All rights reserved.

Tracking heavy water (D 2O) incorporation for identifying and sorting active microbial cells

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

Berry, David; Mader, Esther; Lee, Tae Kwon

Here, microbial communities are essential to the function of virtually all ecosystems and eukaryotes, including humans. However, it is still a major challenge to identify microbial cells active under natural conditions in complex systems. Here in this study, we developed a new method to identify and sort active microbes on the single-cell level in complex samples using stable isotope probing with heavy water (D 2O) combined with Raman microspectroscopy. Incorporation of D 2O-derived D into the biomass of autotrophic and heterotrophic bacteria and archaea could be unambiguously detected via C-D signature peaks in single-cell Raman spectra, and the obtained labelingmore » pattern was confirmed by nanoscale-resolution secondary ion MS. In fast-growing Escherichia coli cells, label detection was already possible after 20 min. For functional analyses of microbial communities, the detection of D incorporation from D 2O in individual microbial cells via Raman microspectroscopy can be directly combined with FISH for the identification of active microbes. Applying this approach to mouse cecal microbiota revealed that the host-compound foragers Akkermansia muciniphila and Bacteroides acidifaciens exhibited distinctive response patterns to amendments of mucin and sugars. By Raman-based cell sorting of active (deuterated) cells with optical tweezers and subsequent multiple displacement amplification and DNA sequencing, novel cecal microbes stimulated by mucin and/or glucosamine were identified, demonstrating the potential of the nondestructive D 2O-Raman approach for targeted sorting of microbial cells with defined functional properties for single-cell genomics.« less

Tracking heavy water (D 2O) incorporation for identifying and sorting active microbial cells

DOE PAGES

Berry, David; Mader, Esther; Lee, Tae Kwon; ...

2014-12-30

Here, microbial communities are essential to the function of virtually all ecosystems and eukaryotes, including humans. However, it is still a major challenge to identify microbial cells active under natural conditions in complex systems. Here in this study, we developed a new method to identify and sort active microbes on the single-cell level in complex samples using stable isotope probing with heavy water (D 2O) combined with Raman microspectroscopy. Incorporation of D 2O-derived D into the biomass of autotrophic and heterotrophic bacteria and archaea could be unambiguously detected via C-D signature peaks in single-cell Raman spectra, and the obtained labelingmore » pattern was confirmed by nanoscale-resolution secondary ion MS. In fast-growing Escherichia coli cells, label detection was already possible after 20 min. For functional analyses of microbial communities, the detection of D incorporation from D 2O in individual microbial cells via Raman microspectroscopy can be directly combined with FISH for the identification of active microbes. Applying this approach to mouse cecal microbiota revealed that the host-compound foragers Akkermansia muciniphila and Bacteroides acidifaciens exhibited distinctive response patterns to amendments of mucin and sugars. By Raman-based cell sorting of active (deuterated) cells with optical tweezers and subsequent multiple displacement amplification and DNA sequencing, novel cecal microbes stimulated by mucin and/or glucosamine were identified, demonstrating the potential of the nondestructive D 2O-Raman approach for targeted sorting of microbial cells with defined functional properties for single-cell genomics.« less

A Tale of Two Gases: Isotope Effects Associated with the Enzymatic Production of H2 and N2O

NASA Astrophysics Data System (ADS)

Yang, H.; Gandhi, H.; Kreuzer, H. W.; Moran, J.; Hill, E. A.; McQuarters, A.; Lehnert, N.; Ostrom, N. E.; Hegg, E. L.

2014-12-01

Stable isotopes can provide considerable insight into enzymatic mechanisms and fluxes in various biological processes. In our studies, we used stable isotopes to characterize both enzyme-catalyzed H2 and N2O production. H2 is a potential alternative clean energy source and also a key metabolite in many microbial communities. Biological H2 production is generally catalyzed by hydrogenases, enzymes that combine protons and electrons to produce H2 under anaerobic conditions. In our study, H isotopes and fractionation factors (α) were used to characterize two types of hydrogenases: [FeFe]- and [NiFe]-hydrogenases. Due to differences in the active site, the α associated with H2 production for [FeFe]- and [NiFe]-hydrogenases separated into two distinct clusters (αFeFe > αNiFe). The calculated kinetic isotope effects indicate that hydrogenase-catalyzed H2 production has a preference for light isotopes, consistent with the relative bond strengths of O-H and H-H bonds. Interestingly, the isotope effects associated with H2 consumption and H2-H2O exchange reactions were also characterized, but in this case no specific difference was observed between the different enzymes. N2O is a potent greenhouse gas with a global warming potential 300 times that of CO2, and the concentration of N2O is currently increasing at a rate of ~0.25% per year. Thus far, bacterial and fungal denitrification processes have been identified as two of the major sources of biologically generated N2O. In this study, we measured the δ15N, δ18O, δ15Nα (central N atom in N2O), and δ15Nβ (terminal N atom in N2O) of N2O generated by purified fungal P450 nitric oxide reductase (P450nor) from Histoplasma capsulatum. We observed normal isotope effects for δ18O and δ15Nα, and inverse isotope effects for bulk δ15N (the average of Nα and Nβ) and δ15Nβ. The observed isotope effects have been used in conjunction with DFT calculations to provide important insight into the mechanism of P450nor. Similar experiments were performed with bacterial nitric oxide reductase from Paracoccus denitrificans (cNOR). In this case both Nα and Nβ exhibited inverse isotope effects, while O had a normal isotope effect. Together, these data highlight the utility in using stable isotopes as both tracers and mechanistic probes when studying metabolic processes.

Vertical distribution of 236U in the North Pacific Ocean.

PubMed

Eigl, R; Steier, P; Sakata, K; Sakaguchi, A

2017-04-01

The first extensive study on 236 U in the North Pacific Ocean has been conducted. The vertical distribution of 236 U/ 238 U isotopic ratios and the 236 U concentrations were analysed on seven depth profiles, and large variations with depth were found. The range of 236 U/ 238 U isotopic ratios was from (0.09 ± 0.03) × 10 -10 to (14.1 ± 2.2) × 10 -10 , which corresponds to 236 U concentrations of (0.69 ± 0.24) × 10 5 atoms/kg and (119 ± 21) × 10 5 atoms/kg, respectively. The variations in 236 U concentrations could mainly be attributed to the different water masses in the North Pacific Ocean and their formation processes. Uranium-236 inventories on the water column of each sampling station were calculated and varied between (3.89 ± 0.08) × 10 12 atoms/m 2 and (7.03 ± 0.50) × 10 12 atoms/m 2 , which is lower than in former studies on comparable latitudes in the North Atlantic Ocean and the Sea of Japan. The low inventories of 236 U found for the North Pacific Ocean in this study can be explained by the lack of additional input sources of artificial radionuclides, apart from global and regional/local fallout. This study expands the use of 236 U as oceanographic circulation tracer to yet another ocean basin and shows that this isotope can be used for tracing circulation patterns of water masses in the Pacific Ocean. Copyright © 2016 Elsevier Ltd. All rights reserved.

Dual isotope notch observer for isotope identification, assay and imaging with mono-energetic gamma-ray sources

DOEpatents

Barty, Christopher P.J.

2013-02-05

A dual isotope notch observer for isotope identification, assay and imaging with mono-energetic gamma-ray sources includes a detector arrangement consists of three detectors downstream from the object under observation. The latter detector, which operates as a beam monitor, is an integrating detector that monitors the total beam power arriving at its surface. The first detector and the middle detector each include an integrating detector surrounding a foil. The foils of these two detectors are made of the same atomic material, but each foil is a different isotope, e.g., the first foil may comprise U235 and second foil may comprise U238. The integrating detectors surrounding these pieces of foil measure the total power scattered from the foil and can be similar in composition to the final beam monitor. Non-resonant photons will, after calibration, scatter equally from both foils.

The study of trace metal absoption using stable isotopes and mass spectrometry

NASA Astrophysics Data System (ADS)

Fennessey, P. V.; Lloyd-Kindstrand, L.; Hambidge, K. M.

1991-12-01

The absorption and excretion of zinc stable isotopes have been followed in more than 120 human subjects. The isotope enrichment determinations were made using a standard VG 7070E HF mass spectrometer. A fast atom gun (FAB) was used to form the ions from a dry residue on a pure silver probe tip. Isotope ratio measurements were found to have a precision of better than 2% (relative standard deviation) and required a sample size of 1-5 [mu]g. The average true absorption of zinc was found to be 73 ± 12% (2[sigma]) when the metal was taken in a fasting state. This absorption figure was corrected for tracer that had been absorbed and secreted into the gastrointestinal (GI) tract over the time course of the study. The average time for a majority of the stable isotope tracer to pass through the GI tract was 4.7 ± 1.9 (2[sigma]) days.

High-resolution studies of tropolone in the S0 and S1 electronic states: isotope driven dynamics in the zero-point energy levels.

PubMed

Keske, John C; Lin, Wei; Pringle, Wallace C; Novick, Stewart E; Blake, Thomas A; Plusquellic, David F

2006-02-21

Rotationally resolved microwave (MW) and ultraviolet (UV) spectra of jet-cooled tropolone have been obtained in S(0) and S(1) electronic states using Fourier-transform microwave and UV-laser/molecular-beam spectrometers. In the ground electronic state, the MW spectra of all heavy-atom isotopomers including one (18)O and four (13)C isotopomers were observed in natural abundance. The OD isotopomer was obtained from isotopically enriched samples. The two lowest tunneling states of each isotopomer except (18)O have been assigned. The observed inversion splitting for the OD isotopomer is 1523.227(5) MHz. For the asymmetric (13)C structures, the magnitudes of tunneling-rotation interactions are found to diminish with decreasing distance between the heavy atom and the tunneling proton. In the limit of closest approach, the 0(+) state of (18)O was well fitted to an asymmetric rotor Hamiltonian, reflecting significant changes in the tautomerization dynamics. Comparisons of the substituted atom coordinates with theoretical predictions at the MP2/aug-cc-pVTZ level of theory suggest the localized 0(+) and 0(-) wave functions of the heavier isotopes favor the C-OH and C=O forms of tropolone, respectively. The only exception occurs for the (13)C-OH and (13)C[Double Bond]O structures which correlate to the 0(-) and 0(+) states, respectively. These preferences reflect kinetic isotope effects as quantitatively verified by the calculated zero-point energy differences between members of the asymmetric atom pairs. From rotationally resolved data of the 0(+) <--0(+) and 0(-) <--0(-) bands in S(1), line-shape fits have yielded Lorentzian linewidths that differ by 12.2(16) MHz over the 19.88(4) cm(-1) interval in S(1). The fluorescence decay rates together with previously reported quantum yield data give nonradiative decay rates of 7.7(5) x 10(8) and 8.5(5) x 10(8) s(-1) for the 0(+) and 0(-) levels of the S(1) state of tropolone.

U, Pu, and Am nuclear signatures of the Thule hydrogen bomb debris.

PubMed

Eriksson, Mats; Lindahl, Patric; Roos, Per; Dahlgaard, Henning; Holm, Elis

2008-07-01

This study concerns an arctic marine environment that was contaminated by actinide elements after a nuclear accident in 1968, the so-called Thule accident In this study we have analyzed five isolated hot particles as well as sediment samples containing particles from the weapon material for the determination of the nuclear fingerprint of the accident. We report that the fissile material in the hydrogen weapons involved in the Thule accident was a mixture of highly enriched uranium and weapon-grade plutonium and that the main fissile material was 235U (about 4 times more than the mass of 239Pu). In the five hot particles examined, the measured uranium atomic ratio was 235U/238U = 1.02 +/- 0.16 and the Pu-isotopic ratios were as follows: 24Pu/239Pu = 0.0551 +/- 0.0008 (atom ratio), 238Pu/239+240Pu = 0.0161 +/- 0.0005 (activity ratio), 241Pu/239+240Pu = 0.87 +/- 0.12 (activity ratio), and 241Am/ 239+240Pu = 0.169 +/- 0.005 (activity ratio) (reference date 2001-10-01). From the activity ratios of 241Pu/241Am, we estimated the time of production of this weapon material to be from the late 1950s to the early 1960s. The results from reanalyzed bulk sediment samples showed the presence of more than one Pu source involved in the accident, confirming earlier studies. The 238Pu/239+240PU activity ratio and the 240Pu/ 239Pu atomic ratio were divided into at least two Pu-isotopic ratio groups. For both Pu-isotopic ratios, one ratio group had identical ratios as the five hot particles described above and for the other groups the Pu isotopic ratios were lower (238Pu/ 239+240PU activity ratio approximately 0.01 and the 240Pu/P239Pu atomic ratio 0.03). On the studied particles we observed that the U/Pu ratio decreased as a function of the time these particles were present in the sediment. We hypothesis that the decrease in the ratio is due to a preferential leaching of U relative to Pu from the particle matrix.

The quantum life

NASA Astrophysics Data System (ADS)

Davies, Paul

2009-07-01

To a physicist, life seems little short of miraculous-all those stupid atoms getting together to perform such clever tricks! For centuries, living organisms were regarded as some sort of magic matter. Today, we know that no special "life force" is at work in biology; there is just ordinary matter doing extraordinary things, all the while obeying the familiar laws of physics. What, then, is the secret of life's remarkable properties?

Characterization of wines according the geographical origin by analysis of isotopes and minerals and the influence of harvest on the isotope values.

PubMed

Dutra, S V; Adami, L; Marcon, A R; Carnieli, G J; Roani, C A; Spinelli, F R; Leonardelli, S; Vanderlinde, R

2013-12-01

We studied Brazilian wines produced by microvinification from Cabernet Sauvignon and Merlot grapes, vintages 2007 and 2008, from the Serra Gaúcha, Campanha and Serra do Sudeste regions, in order to differentiate them according to geographical origin by using isotope and mineral element analyses. In addition, the influence of vintage production in isotope values was verified. Isotope analysis was performed by isotope ratio mass spectrometry (IRMS), and the determination of minerals was by flame atomic absorption (FAA). The best parameters to classify the wines in the 2008 vintage were Rb and Li. The results of the δ(13)C of wine ethanol, Rb and Li showed a significant difference between the varieties regardless of the region studied. The δ(18)O values of water and δ(13)C of ethanol showed significant differences, regardless of the variety. Discriminant analysis of isotope and minerals values allowed to classify approximately 80% of the wines from the three regions studied. Copyright © 2013 Elsevier Ltd. All rights reserved.

Transition from single-jump type to highly cooperative diffusion during structural relaxation of a metallic glass

NASA Astrophysics Data System (ADS)

Rätzke, K.; Hüppe, P. W.; Faupel, F.

1992-04-01

The isotope effect E=(Dα/Dβ-1)/[(mβ/mα)1/2-1] of cobalt diffusion has been measured in melt-spun amorphous Co76.7Fe2Nb14.3B7 ribbon at different stages of structural relaxation. A drastic drop of the isotope effect from E>0.5 in the as-quenched glass to E=0.1 in the relaxed state wass observed. While the latter value relflects highly cooperative diffusion, the large isotope effect in the as-quenched ribbon points to the prevalence of single-atom jumps and vacancylike holes of excess volume.

Restoring defect structures in 3C-SiC/Si (001) from spherical aberration-corrected high-resolution transmission electron microscope images by means of deconvolution processing.

PubMed

Wen, C; Wan, W; Li, F H; Tang, D

2015-04-01

The [110] cross-sectional samples of 3C-SiC/Si (001) were observed with a spherical aberration-corrected 300 kV high-resolution transmission electron microscope. Two images taken not close to the Scherzer focus condition and not representing the projected structures intuitively were utilized for performing the deconvolution. The principle and procedure of image deconvolution and atomic sort recognition are summarized. The defect structure restoration together with the recognition of Si and C atoms from the experimental images has been illustrated. The structure maps of an intrinsic stacking fault in the area of SiC, and of Lomer and 60° shuffle dislocations at the interface have been obtained at atomic level. Copyright © 2015 Elsevier Ltd. All rights reserved.

Towards phasing using high X-ray intensity

DOE PAGES

Galli, Lorenzo; Son, Sang -Kil; Barends, Thomas R. M.; ...

2015-09-30

X-ray free-electron lasers (XFELs) show great promise for macromolecular structure determination from sub-micrometre-sized crystals, using the emerging method of serial femtosecond crystallography. The extreme brightness of the XFEL radiation can multiply ionize most, if not all, atoms in a protein, causing their scattering factors to change during the pulse, with a preferential `bleaching' of heavy atoms. This paper investigates the effects of electronic damage on experimental data collected from a Gd derivative of lysozyme microcrystals at different X-ray intensities, and the degree of ionization of Gd atoms is quantified from phased difference Fourier maps. In conclusion, a pattern sorting schememore » is proposed to maximize the ionization contrast and the way in which the local electronic damage can be used for a new experimental phasing method is discussed.« less

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.

Testing atomic mass models with radioactive beams

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

Haustein, P.E.

1989-01-01

Significantly increased yields of new or poorly characterized exotic isotopes that lie far from beta-decay stability can be expected when radioactive beams are used to produce these nuclides. Measurements of the masses of these new species are very important. Such measurements are motivated by the general tendency of mass models to diverge from one another upon excursions from the line of beta-stability. Therefore in these regions (where atomic mass data are presently nonexistent or sparse) the models can be tested rigorously to highlight the features that affect the quality of their short-range and long-range extrapolation properties. Selection of systems tomore » study can be guided, in part, by a desire to probe those mass regions where distinctions among mass models are most apparent and where yields of exotic isotopes, produced via radioactive beams, can be optimized. Identification of models in such regions that have good predictive properties will aid materially in guiding the selection of additional experiments which ultimately will provide expansion of the atomic mass database for further refinement of the mass models. 6 refs., 5 figs.« less

Atom interferometry in space: Thermal management and magnetic shielding

NASA Astrophysics Data System (ADS)

Milke, Alexander; Kubelka-Lange, André; Gürlebeck, Norman; Rievers, Benny; Herrmann, Sven; Schuldt, Thilo; Braxmaier, Claus

2014-08-01

Atom interferometry is an exciting tool to probe fundamental physics. It is considered especially apt to test the universality of free fall by using two different sorts of atoms. The increasing sensitivity required for this kind of experiment sets severe requirements on its environments, instrument control, and systematic effects. This can partially be mitigated by going to space as was proposed, for example, in the Spacetime Explorer and Quantum Equivalence Principle Space Test (STE-QUEST) mission. However, the requirements on the instrument are still very challenging. For example, the specifications of the STE-QUEST mission imply that the Feshbach coils of the atom interferometer are allowed to change their radius only by about 260 nm or 2.6 × 10-4 % due to thermal expansion although they consume an average power of 22 W. Also Earth's magnetic field has to be suppressed by a factor of 105. We show in this article that with the right design such thermal and magnetic requirements can indeed be met and that these are not an impediment for the exciting physics possible with atom interferometers in space.

Fractionation of carbon (13C/12C) isotopes in glycine decarboxylase reaction.

PubMed

Ivlev, A A; Bykova, N V; Igamberdiev, A U

1996-05-20

Fractionation of carbon isotopes (13C/12C) by glycine decarboxylase (GDC) was investigated in mitochondrial preparations isolated from photosynthetic tissues of different plants (Pisum, Medicago, Triticum, Hordeum, Spinacia, Brassica, Wolffia). 20 mM glycine was supplied to mitochondria, and the CO2 formed was absorbed and analyzed for isotopic content. CO2 evolved by mitochondria of Pisum was enriched up to 8% in 12C compared to the carboxylic atom of glycine. CO2 evolved by mitochondria of the other plants investigated was enriched by 5-16% in 13C. Carbon isotope effects were sensitive to reaction conditions (pH and the presence of GDC cofactors). Theoretical treatment of the reaction mechanism enabled us to conclude that the value and even the sign of the carbon isotope effect in glycine decarboxylation depend on the contribution of the enzyme-substrate binding step and of the decarboxylation step itself to the overall reaction rate. Therefore, the fractionation of carbon isotopes in GDC reaction was revealed which provides essential isotopic effects in plants in addition to the well-known effect of carbon isotope fractionation by the central photosynthetic enzyme, ribulose-1,5-biphosphate carboxylase.

Reduction of chemical formulas from the isotopic peak distributions of high-resolution mass spectra.

PubMed

Roussis, Stilianos G; Proulx, Richard

2003-03-15

A method has been developed for the reduction of the chemical formulas of compounds in complex mixtures from the isotopic peak distributions of high-resolution mass spectra. The method is based on the principle that the observed isotopic peak distribution of a mixture of compounds is a linear combination of the isotopic peak distributions of the individual compounds in the mixture. All possible chemical formulas that meet specific criteria (e.g., type and number of atoms in structure, limits of unsaturation, etc.) are enumerated, and theoretical isotopic peak distributions are generated for each formula. The relative amount of each formula is obtained from the accurately measured isotopic peak distribution and the calculated isotopic peak distributions of all candidate formulas. The formulas of compounds in simple spectra, where peak components are fully resolved, are rapidly determined by direct comparison of the calculated and experimental isotopic peak distributions. The singular value decomposition linear algebra method is used to determine the contributions of compounds in complex spectra containing unresolved peak components. The principles of the approach and typical application examples are presented. The method is most useful for the characterization of complex spectra containing partially resolved peaks and structures with multiisotopic elements.

Stable isotope-resolved metabolomics and applications for drug development

PubMed Central

Fan, Teresa W-M.; Lorkiewicz, Pawel; Sellers, Katherine; Moseley, Hunter N.B.; Higashi, Richard M.; Lane, Andrew N.

2012-01-01

Advances in analytical methodologies, principally nuclear magnetic resonance spectroscopy (NMR) and mass spectrometry (MS), during the last decade have made large-scale analysis of the human metabolome a reality. This is leading to the reawakening of the importance of metabolism in human diseases, particularly cancer. The metabolome is the functional readout of the genome, functional genome, and proteome; it is also an integral partner in molecular regulations for homeostasis. The interrogation of the metabolome, or metabolomics, is now being applied to numerous diseases, largely by metabolite profiling for biomarker discovery, but also in pharmacology and therapeutics. Recent advances in stable isotope tracer-based metabolomic approaches enable unambiguous tracking of individual atoms through compartmentalized metabolic networks directly in human subjects, which promises to decipher the complexity of the human metabolome at an unprecedented pace. This knowledge will revolutionize our understanding of complex human diseases, clinical diagnostics, as well as individualized therapeutics and drug response. In this review, we focus on the use of stable isotope tracers with metabolomics technologies for understanding metabolic network dynamics in both model systems and in clinical applications. Atom-resolved isotope tracing via the two major analytical platforms, NMR and MS, has the power to determine novel metabolic reprogramming in diseases, discover new drug targets, and facilitates ADME studies. We also illustrate new metabolic tracer-based imaging technologies, which enable direct visualization of metabolic processes in vivo. We further outline current practices and future requirements for biochemoinformatics development, which is an integral part of translating stable isotope-resolved metabolomics into clinical reality. PMID:22212615

Carbon Kinetic Isotope Effects in the Oxidation of Atmospheric Alkane and Aromatic Hydrocarbons by Hydroxyl Radicals

NASA Astrophysics Data System (ADS)

Anderson, R. S.; Thompson, A. E.; Rudolph, J.; Huang, L.

2001-12-01

To interpret measurements of stable carbon isotope ratios of ambient NMHC, we need to understand the isotopic composition of the emissions, and the isotope fractionation associated with the removal of NMHC from the atmosphere. Oxidation by OH-radicals is by far the most important atmospheric process for removal of NMHC. In this presentation measurements of the kinetic isotope effects (KIEs) for the reactions of hydroxyl radicals with several C5-C8 alkanes, including cyclic, branched and straight-chain alkanes, as well as C6-C9 aromatics are presented. All KIEs are positive: compounds containing only 12C atoms react faster than 13C labelled compounds. KIEs for light n-alkanes are typically between 1.5-4‰ and are larger than mass dependent collision frequencies, deviating from the collision frequency as carbon number increases. For n-alkanes there is no statistically significant difference between the KIEs of structural isomers. KIEs for the reactions of light alkenes and aromatics with OH-radicals are considerably higher than for alkane reactions, ranging from 3-18‰ . The KIEs for the aromatic reactions can be described by a 33.3+/-2.0‰ fractionation for the addition of an OH-radical to the aromatic ring and an inverse dependency on the number of carbon atoms, added to the mass dependent collision frequency. There are indications for minor structure specific effects, however the deviations from the idealised inverse carbon number dependence is relatively small and the limited number of studied alkyl benzenes does not yet allow the identification of systematic dependencies.

Atomic Power in Space: A History

DOE R&D Accomplishments Database

1987-03-01

"Atomic Power in Space," a history of the Space Isotope Power Program of the United States, covers the period from the program's inception in the mid-1950s through 1982. Written in non-technical language, the history is addressed to both the general public and those more specialized in nuclear and space technologies. Interplanetary space exploration successes and achievements have been made possible by this technology, for which there is no known substitue.

Plutonium isotopes and 241Am in the atmosphere of Lithuania: A comparison of different source terms

NASA Astrophysics Data System (ADS)

Lujanienė, G.; Valiulis, D.; Byčenkienė, S.; Šakalys, J.; Povinec, P. P.

2012-12-01

137Cs, 241Am and Pu isotopes collected in aerosol samples during 1994-2011 were analyzed with special emphasis on better understanding of Pu and Am behavior in the atmosphere. The results from long-term measurements of 240Pu/239Pu atom ratios showed a bimodal frequency distribution with median values of 0.195 and 0.253, indicating two main sources contributing to the Pu activities at the Vilnius sampling station. The low Pu atom ratio of 0.141 could be attributed to the weapon-grade plutonium derived from the nuclear weapon test sites. The frequency of air masses arriving from the North-West and North-East correlated with the Pu atom ratio indicating the input from the sources located in these regions (the Novaya Zemlya test site, Siberian nuclear plants), while no correlation with the Chernobyl region was observed. Measurements carried out during the Fukushima accident showed a negligible impact of this source with Pu activities by four orders of magnitude lower as compared to the Chernobyl accident. The activity concentration of actinides measured in the integrated sample collected in March-April, 2011 showed a small contribution of Pu with unusual activity and atom ratios indicating the presence of the spent fuel of different origin than that of the Chernobyl accident.

Gadolinium photoionization process

DOEpatents

Paisner, J.A.; Comaskey, B.J.; Haynam, C.A.; Eggert, J.H.

1993-04-13

A method is provided for selective photoionization of the odd-numbered atomic mass gadolinium isotopes 155 and 157. The selective photoionization is accomplished by circular or linear parallel polarized laser beam energy effecting a three-step photoionization pathway.

Gadolinium photoionization process

DOEpatents

Paisner, Jeffrey A.; Comaskey, Brian J.; Haynam, Christopher A.; Eggert, Jon H.

1993-01-01

A method is provided for selective photoionization of the odd-numbered atomic mass gadolinium isotopes 155 and 157. The selective photoionization is accomplished by circular or linear parallel polarized laser beam energy effecting a three-step photoionization pathway.

The table of isotopes-8th edition and beyond

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

Firestone, R.B.

A new edition of the Table of Isotopes has been published this year by John Wiley and Sons, Inc. This edition is the eighth in a series started by Glenn T. Seaborg in 1940. The two-volume, 3168-page, cloth-bound edition is twice the size of the previous edition published in 1978. It contains nuclear structure and decay data, based mainly on the Evaluated Nuclear Structure Data File (ENSDF), for >3100 isotopes and isomers. Approximately 24000 references are cited, and the appendices have been updated and extended. The book is packaged with an interactive CD-ROM that contains the Table of Isotopes inmore » Adobe Acrobat Portable Document Format for convenient viewing on personal computer (PC) and UNIX workstations. The CD-ROM version contains a chart of the nuclides graphical index and separate indices organized for radioisotope users and nuclear structure physicists. More than 100000 hypertext links are provided to move the user quickly through related information free from the limitations of page size. Complete references with keyword abstracts are provided. The CD-ROM also contains the Table of Super-deformed Nuclear Bands and Fission Isomers; Tables of Atoms, Atomic Nuclei, and Subatomic Particles by Ivan P. Selinov; the ENSDF and nuclear structure reference (NSR) databases; the ENSDF manual by Jagdish K. Tuli; and Abode Acrobat Reader software.« less

Method of synthesizing enriched decaborane for use in generating boron neutron capture therapy pharmaceuticals

DOEpatents

Cowan, Robert L.; Ginosar, Daniel M.; Dunks, Gary B.

2000-01-01

A method is described for synthesizing decaborane wherein at least about 90% of the boron atoms in the decaborane are the .sup.10 B isotope, comprising the steps of: (a) reacting boric acid with a C.sub.1 to C.sub.10 alkanol to form a .sup.10 B-alkyl borate wherein at least about 90% of the boron atoms in the boric acid are the .sup.10 B isotope; (b) reducing the .sup.10 B-alkyl borate to form an alkali metal .sup.10 B-borohydride; (c) converting the alkali metal .sup.10 B-borohydride to a .sup.10 B-tetradecahydroundecaborate ion; and (d) converting the .sup.10 B-tetradecahydroundecaborate ion to .sup.10 B-decaborane. Methods of preparing tetradecahydroundecaborate ions and decaborane from alkali metal borohydrides are also described.

Probing the interface of doped isotopically mixed helium droplets by the directional anisotropy of interatomic Coulombic decay.

PubMed

Kryzhevoi, Nikolai V; Mateo, David; Pi, Martí; Barranco, Manuel; Cederbaum, Lorenz S

2013-11-07

Interatomic Coulombic decay (ICD) represents an efficient electronic relaxation mechanism of an ionized or an excited system embedded in an environment. The type of this environment and its size have a great impact on the ICD performance. It is stressed that ICD is sensitive to the arrangement of neighboring atoms when the initially created vacancy has a polarization direction. This is demonstrated in the present paper for the case of a 3p-ionized Ca surrounded by He atoms. Useful explicit expressions are derived for the ICD widths which show that the neighbors located along the polarization direction of the ionized orbital have the largest contribution to the ICD rate. By comparison with ab initio results for small clusters, we also show that in a helium environment, the pairwise approximation represents a reliable approach for computing ICD widths. Using this approximation and the density distribution of the helium atoms obtained within density functional theory, we explore ICD in large isotopically mixed helium droplets doped with Ca. A special emphasis is given to the difference between the ICD widths for the Ca3p orbitals directed perpendicular and parallel to the droplet surface. Depending on the size and isotopic composition of the droplet, Ca resides in the interfacial layer between the (4)He core and the (3)He outer shell. Hence, ICD studies in these droplets may provide valuable information on the properties of this interface.

Quantum trajectories in elastic atom-surface scattering: threshold and selective adsorption resonances.

PubMed

Sanz, A S; Miret-Artés, S

2005-01-01

The elastic resonant scattering of He atoms off the Cu(117) surface is fully described with the formalism of quantum trajectories provided by Bohmian mechanics. Within this theory of quantum motion, the concept of trapping is widely studied and discussed. Classically, atoms undergo impulsive collisions with the surface, and then the trapped motion takes place covering at least two consecutive unit cells. However, from a Bohmian viewpoint, atom trajectories can smoothly adjust to the equipotential energy surface profile in a sort of sliding motion; thus the trapping process could eventually occur within one single unit cell. In particular, both threshold and selective adsorption resonances are explained by means of this quantum trapping considering different space and time scales. Furthermore, a mapping between each region of the (initial) incoming plane wave and the different parts of the diffraction and resonance patterns can be easily established, an important issue only provided by a quantum trajectory formalism. (c) 2005 American Institute of Physics.

Investigation of Kp- and Kd-atom formation and their collisional processes with hydrogen and deuterium targets by the classical-trajectory Monte Carlo method

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

Raeisi, G. M.; Department of Physics, Shahrekord University, Shahrekord 115; Kalantari, S. Z.

The classical-trajectory Monte Carlo method has been used to study the capture of negative kaons by hydrogen and deuterium atoms; subsequently, the elastic scattering, Stark mixing, and Coulomb deexcitation cross sections of Kp and Kd atoms have been determined. The results for kaonic atom formation confirm the initial conditions that have been parametrically applied by most atomic cascade models. Our results show that Coulomb deexcitation in Kp and Kd atoms with {Delta}n>1 is important in addition to n=1. We have shown that the contribution of molecular structure effects to the cross sections of the collisional processes is larger than themore » isotopic effects of the targets. We have also compared our results with the semiclassical approaches.« less

Use of Hilbert Curves in Parallelized CUDA code: Interaction of Interstellar Atoms with the Heliosphere

NASA Astrophysics Data System (ADS)

Destefano, Anthony; Heerikhuisen, Jacob

2015-04-01

Fully 3D particle simulations can be a computationally and memory expensive task, especially when high resolution grid cells are required. The problem becomes further complicated when parallelization is needed. In this work we focus on computational methods to solve these difficulties. Hilbert curves are used to map the 3D particle space to the 1D contiguous memory space. This method of organization allows for minimized cache misses on the GPU as well as a sorted structure that is equivalent to an octal tree data structure. This type of sorted structure is attractive for uses in adaptive mesh implementations due to the logarithm search time. Implementations using the Message Passing Interface (MPI) library and NVIDIA's parallel computing platform CUDA will be compared, as MPI is commonly used on server nodes with many CPU's. We will also compare static grid structures with those of adaptive mesh structures. The physical test bed will be simulating heavy interstellar atoms interacting with a background plasma, the heliosphere, simulated from fully consistent coupled MHD/kinetic particle code. It is known that charge exchange is an important factor in space plasmas, specifically it modifies the structure of the heliosphere itself. We would like to thank the Alabama Supercomputer Authority for the use of their computational resources.

Deuterium enrichment by selective photo-induced dissociation of an organic carbonyl compound

DOEpatents

Marling, John B.

1981-01-01

A method for producing a deuterium enriched material by photoinduced dissociation which uses as the working material a gas phase photolytically dissociable organic carbonyl compound containing at least one hydrogen atom bonded to an atom which is adjacent to a carbonyl group and consisting of molecules wherein said hydrogen atom is present as deuterium and molecules wherein said hydrogen atom is present as another isotope of hydrogen. The organic carbonyl compound is subjected to intense infrared radiation at a preselected wavelength to selectively excite and thereby induce dissociation of the deuterium containing species to yield a deuterium enriched stable molecular product. Undissociated carbonyl compound, depleted in deuterium, is preferably redeuterated for reuse.

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.

Distinguishing sources of ground water recharge by using δ2H and δ18O

USGS Publications Warehouse

Blasch, Kyle W.; Bryson, Jeannie R.

2007-01-01

Stable isotope values of hydrogen and oxygen from precipitation and ground water samples were compared by using a volumetrically based mixing equation and stable isotope gradient to estimate the season and location of recharge in four basins. Stable isotopes were sampled at 11 precipitation sites of differing elevation during a 2-year period to quantify seasonal stable isotope contributions as a function of elevation. Supplemental stable isotope data collected by the International Atomic Energy Association during a 14-year period were used to reduce annual variability of the mean seasonal stable isotope data. The stable isotope elevation relationships and local precipitation elevation relationships were combined by using a digital elevation model to calculate the total volumetric contribution of water and stable isotope values as a function of elevation within the basins. The results of these precipitation calculations were compared to measured ground water stable isotope values at the major discharge points near the terminus of the basins. Volumetric precipitation contributions to recharge were adjusted to isolate contributing elevations. This procedure provides an improved representation of recharge contributions within the basins over conventional stable isotope methods. Stable isotope values from wells and springs at the terminus of each basin were used to infer the elevations of precipitation important for recharge of the regional ground water flow system. Ancillary climatic, geologic, and stable isotope values were used to further constrain the location where precipitation is entering the ground water flow system.

Sediment Fingerprinting Using Carbon and Nitrogen Stable Isotopes in the Upper Palouse Watershed, Northwestern Idaho

NASA Astrophysics Data System (ADS)

Fox, J. F.; Papanicolaou, A. T.

2003-12-01

Unwarranted soil erosion creates detrimental problems for watershed users and for habitats and human infrastructure that experience increased suspended sediment in surface water. Identification and mitigation of erosion prone uplands relies on the realization that land uses (i.e. agriculture, forest, industrial, pasture, etc.) "produce sediment differently" at the watershed scale. Quantification of sediment production from various land uses is deemed feasible by using sediment-particle fingerprinting. This technique utilizes vegetative derived carbon (C) and nitrogen (N) stable isotopes and the carbon/nitrogen (C/N) atomic ratio of sediments to identify sediment producing land uses. Past research has established differences between C and N isotopic signatures and C/N ratios for soils under forest vs. agriculture (i.e. grasses and wheat) land cover. The current research rigorously examines these distinct signatures through isotopic analysis of field soils from the Palouse River Watershed of Northwestern Idaho preceded with statistical analyses to establish soil uniqueness. In addition, stream sediments are preliminarily analyzed to identify their origin with the goal of establishing a blueprint methodology for estimating sediment source and erosion rates within the watershed. Prior to field sampling of source soils, a statistical-experimental design was established with the intent to capture spatial and temporal variations and random errors of C and N isotopic signatures and C/N ratios within the forest and agriculture land uses. Factors including, elevation, slope topography, and season, were assessed by excavating over 300 samples during 4 seasons (i.e. May 2002, August 2002, November 2002, and March 2003) and at numerous locations throughout the watershed. Atomic analyses was performed at the University of Idaho Natural Resources Stable Isotope Laboratory using a Costech 4010 Elemental Combustion System connected with a continuous flow inlet system to the Finnigan MAT Delta Plus isotope ratio mass spectrometer. The statistical analysis of variance (ANOVA) with C and N isotopic signatures and C/N ratios as three independent response variables was administered to identify the agriculture and forested uniqueness, and discriminant analysis was used to create an organic fingerprint parameter which weights the contribution of C and N isotopic signatures and C/N ratios to the land cover separation. Results indicate uniqueness of the N isotope C/N ratio for the forest and agriculture sediment sources and little distinction possible for the C isotope signature. The organic fingerprint parameter was then calculated and coupled with in-stream sediment isotopic data using a simple end-member model. Preliminary results indicate that C and N isotopic signatures and C/N ratios will serve as a useful technique in quantifying erosive source rates and understanding upland erosion processes.

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

NASA Technical Reports Server (NTRS)

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

1984-01-01

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

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.

UV-spektra från Hubble-teleskopet avslöjar en stjärna i Vargen som lagrar tunga isotoper av mycket tunga grundämnen.

NASA Astrophysics Data System (ADS)

Johansson, S. E.; Leckrone, D. S.; Wahlgren, G. M.

1994-09-01

UV spectra from the Hubble Space Telescope reveal a star that stores heavy isotopes of very heavy elements. Atomic and plasma physics arguments for UV spectroscopy from space borne observatories are given. As an example, the authors discuss the analysis of high resolution spectra of the chemically peculiar star χ Lupi, obtained with the Hubble Space Telescope, in terms of identification of spectral lines of very heavy elements.

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.

Light-Shifts of an Integrated Filter-Cell Rubidium Atomic Clock

DTIC Science & Technology

2015-05-25

the light-shift coefficient for two different rf- discharge lamps (i.e., a pure 87Rb lamp and a lamp filled with the natural Rb isotope abundance...for the Galileo Rb clock under the assumption of a natural (or 85Rb isotopically enriched) rf- discharge lamp for the Galileo clock. I...satellites [14]. 6.8347… GHz 85Rb Filter Cell Cell Resonance Photodiode Microwave Cavity 87Rb Discharge Lamp 87Rb & N2 Rb & Xe, Kr Optical Pumping 87Rb

Mass spectrometric measurement of hydrogen isotope fractionation for the reactions of chloromethane with OH and Cl

NASA Astrophysics Data System (ADS)

Keppler, Frank; Bahlmann, Enno; Greule, Markus; Schöler, Heinz Friedrich; Wittmer, Julian; Zetzsch, Cornelius

2018-05-01

Chloromethane (CH3Cl) is an important provider of chlorine to the stratosphere but detailed knowledge of its budget is missing. Stable isotope analysis is a potentially powerful tool to constrain CH3Cl flux estimates. The largest degree of isotope fractionation is expected to occur for deuterium in CH3Cl in the hydrogen abstraction reactions with its main sink reactant tropospheric OH and its minor sink reactant Cl atoms. We determined the isotope fractionation by stable hydrogen isotope analysis of the fraction of CH3Cl remaining after reaction with hydroxyl and chlorine radicals in a 3.5 m3 Teflon smog chamber at 293 ± 1 K. We measured the stable hydrogen isotope values of the unreacted CH3Cl using compound-specific thermal conversion isotope ratio mass spectrometry. The isotope fractionations of CH3Cl for the reactions with hydroxyl and chlorine radicals were found to be -264±45 and -280±11 ‰, respectively. For comparison, we performed similar experiments using methane (CH4) as the target compound with OH and obtained a fractionation constant of -205±6 ‰ which is in good agreement with values previously reported. The observed large kinetic isotope effects are helpful when employing isotopic analyses of CH3Cl in the atmosphere to improve our knowledge of its atmospheric budget.

Interpretation of atomic mass systematics in terms of the valence shells and a simple scheme for predicting masses

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

Haustein, P.E.; Brenner, D.S.; Casten, R.F.

1988-07-01

A new semiempirical method that significantly simplifies atomic mass systematics and which provides a method for making mass predictions by linear interpolation is discussed in the context of the nuclear valence space. In certain regions complicated patterns of mass systematics in traditional plots versus Z, N, or isospin are consolidated and transformed into linear ones extending over long isotopic and isotonic sequences.

Charge Radii of Neutron Deficient Fe,5352 Produced by Projectile Fragmentation

NASA Astrophysics Data System (ADS)

Minamisono, K.; Rossi, D. M.; Beerwerth, R.; Fritzsche, S.; Garand, D.; Klose, A.; Liu, Y.; Maaß, B.; Mantica, P. F.; Miller, A. J.; Müller, P.; Nazarewicz, W.; Nörtershäuser, W.; Olsen, E.; Pearson, M. R.; Reinhard, P.-G.; Saperstein, E. E.; Sumithrarachchi, C.; Tolokonnikov, S. V.

2016-12-01

Bunched-beam collinear laser spectroscopy is performed on neutron deficient Fe,5352 prepared through in-flight separation followed by a gas stopping. This novel scheme is a major step to reach nuclides far from the stability line in laser spectroscopy. Differential mean-square charge radii δ ⟨r2⟩ of Fe,5352 are determined relative to stable 56Fe as δ ⟨r2⟩56 ,52=-0.034 (13 ) fm2 and δ ⟨r2⟩56 ,53=-0.218 (13 ) fm2 , respectively, from the isotope shift of atomic hyperfine structures. The multiconfiguration Dirac-Fock method is used to calculate atomic factors to deduce δ ⟨r2⟩. The values of δ ⟨r2⟩ exhibit a minimum at the N =28 neutron shell closure. The nuclear density functional theory with Fayans and Skyrme energy density functionals is used to interpret the data. The trend of δ ⟨r2⟩ along the Fe isotopic chain results from an interplay between single-particle shell structure, pairing, and polarization effects and provides important data for understanding the intricate trend in the δ ⟨r2⟩ of closed-shell Ca isotopes.

Order-disorder antiferroelectric phase transition in a hybrid inorganic-organic framework with the perovskite architecture.

PubMed

Jain, Prashant; Dalal, Naresh S; Toby, Brian H; Kroto, Harold W; Cheetham, Anthony K

2008-08-13

[(CH3)2NH2]Zn(HCOO)3, 1, adopts a structure that is analogous to that of a traditional perovskite, ABX3, with A = [(CH3)2NH2], B = Zn, and X = HCOO. The hydrogen atoms of the dimethyl ammonium cation, which hydrogen bond to oxygen atoms of the formate framework, are disordered at room temperature. X-ray powder diffraction, dielectric constant, and specific heat data show that 1 undergoes an order-disorder phase transition on cooling below 156 K. We present evidence that this is a classical paraelectric to antiferroelectric phase transition that is driven by ordering of the hydrogen atoms. This sort of electrical ordering associated with order-disorder phase transition is unprecedented in hybrid frameworks and opens up an exciting new direction in rational synthetic strategies to create extended hybrid networks for applications in ferroic-related fields.

Compound-specific isotope analysis as a tool to characterize biodegradation of ethylbenzene.

PubMed

Dorer, Conrad; Vogt, Carsten; Kleinsteuber, Sabine; Stams, Alfons J M; Richnow, Hans-Hermann

2014-08-19

This study applied one- and two-dimensional compound-specific isotope analysis (CSIA) for the elements carbon and hydrogen to assess different means of microbial ethylbenzene activation. Cultures incubated under nitrate-reducing conditions showed significant carbon and highly pronounced hydrogen isotope fractionation of comparable magnitudes, leading to nearly identical slopes in dual-isotope plots. The results imply that Georgfuchsia toluolica G5G6 and an enrichment culture dominated by an Azoarcus species activate ethylbenzene by anaerobic hydroxylation catalyzed by ethylbenzene dehydrogenase, similar to Aromatoleum aromaticum EbN1. The isotope enrichment pattern in dual plots from two strictly anaerobic enrichment cultures differed considerably from those for benzylic hydroxylation, indicating an alternative anaerobic activation step, most likely fumarate addition. Large hydrogen fractionation was quantified using a recently developed Rayleigh-based approach considering hydrogen atoms at reactive sites. Data from nine investigated microbial cultures clearly suggest that two-dimensional CSIA in combination with the magnitude of hydrogen isotope fractionation is a valuable tool to distinguish ethylbenzene degradation and may be of practical use for monitoring natural or technological remediation processes at field sites.

Development of fast-release solid catchers for rare isotopes

NASA Astrophysics Data System (ADS)

Nolen, Jerry; Greene, John; Elam, Jeffrey; Mane, Anil; Sampathkumaran, Uma; Winter, Raymond; Hess, David; Mushfiq, Mohammad; Stracener, Daniel; Wiendenhoever, Ingo

2015-04-01

Porous solid catchers of rare isotopes are being developed for use at high power heavy ion accelerator facilities such as RIKEN, FRIB, and RISP. Compact solid catchers are complementary to helium gas catchers for parasitic harvesting of rare isotopes in the in-flight separators. They are useful for short lived isotopes for basic nuclear physics research and longer-lived isotopes for off-line applications. Solid catchers can operate effectively with high intensity secondary beams, e.g. >> 1E10 atoms/s with release times as short as 10-100 milliseconds. A new method using a very sensitive and efficient RGA has been commissioned off-line at Argonne and is currently being shipped to Florida State University for in-beam measurements of the release curves using stable beams. The same porous solid catcher technology is also being evaluated for use in targets for the production of medical isotopes such as 211-At. Research supported by the U.S. DOE Office of Nuclear Physics under the SBIR Program and Contract # DE-AC02-06CH11357 and a University of Chicago Comprehensive Cancer Center/ANL Pilot Project.

The Potential of Isotope Ratio Mass Spectrometry (IRMS) and Gas Chromatography-IRMS Analysis of Triacetone Triperoxide in Forensic Explosives Investigations.

PubMed

Bezemer, Karlijn D B; Koeberg, Mattijs; van der Heijden, Antoine E D M; van Driel, Chris A; Blaga, Cornelia; Bruinsma, Jildert; van Asten, Arian C

2016-09-01

Studying links between triacetone triperoxide (TATP) samples from crime scenes and suspects can assist in criminal investigations. Isotope ratio mass spectrometry (IRMS) and gas chromatography (GC)-IRMS were used to measure the isotopic compositions of TATP and its precursors acetone and hydrogen peroxide. In total, 31 TATP samples were synthesized with different raw material combinations and reaction conditions. For carbon, a good differentiation and a linear relationship were observed for acetone-TATP combinations. The extent of negative (δ(13) C) fractionation depended on the reaction yield. Limited enrichment was observed for the hydrogen isotope (δ(2) H) values of the TATP samples probably due to a constant exchange of hydrogen atoms in aqueous solution. For oxygen (δ(18) O), the small isotopic range and excess of water in hydrogen peroxide resulted in poor differentiation. GC-IRMS and IRMS data were comparable except for one TATP sample prepared with high acid concentration demonstrating the potential of compound-specific isotope analysis. Carbon IRMS has practical use in forensic TATP investigations. © 2016 American Academy of Forensic Sciences.

Isotope engineering of van der Waals interactions in hexagonal boron nitride

NASA Astrophysics Data System (ADS)

Vuong, T. Q. P.; Liu, S.; van der Lee, A.; Cuscó, R.; Artús, L.; Michel, T.; Valvin, P.; Edgar, J. H.; Cassabois, G.; Gil, B.

2018-02-01

Hexagonal boron nitride is a model lamellar compound where weak, non-local van der Waals interactions ensure the vertical stacking of two-dimensional honeycomb lattices made of strongly bound boron and nitrogen atoms. We study the isotope engineering of lamellar compounds by synthesizing hexagonal boron nitride crystals with nearly pure boron isotopes (10B and 11B) compared to those with the natural distribution of boron (20 at% 10B and 80 at% 11B). On the one hand, as with standard semiconductors, both the phonon energy and electronic bandgap varied with the boron isotope mass, the latter due to the quantum effect of zero-point renormalization. On the other hand, temperature-dependent experiments focusing on the shear and breathing motions of adjacent layers revealed the specificity of isotope engineering in a layered material, with a modification of the van der Waals interactions upon isotope purification. The electron density distribution is more diffuse between adjacent layers in 10BN than in 11BN crystals. Our results open perspectives in understanding and controlling van der Waals bonding in layered materials.

Isotope engineering of van der Waals interactions in hexagonal boron nitride.

PubMed

Vuong, T Q P; Liu, S; Van der Lee, A; Cuscó, R; Artús, L; Michel, T; Valvin, P; Edgar, J H; Cassabois, G; Gil, B

2018-02-01

Hexagonal boron nitride is a model lamellar compound where weak, non-local van der Waals interactions ensure the vertical stacking of two-dimensional honeycomb lattices made of strongly bound boron and nitrogen atoms. We study the isotope engineering of lamellar compounds by synthesizing hexagonal boron nitride crystals with nearly pure boron isotopes ( 10 B and 11 B) compared to those with the natural distribution of boron (20 at% 10 B and 80 at% 11 B). On the one hand, as with standard semiconductors, both the phonon energy and electronic bandgap varied with the boron isotope mass, the latter due to the quantum effect of zero-point renormalization. On the other hand, temperature-dependent experiments focusing on the shear and breathing motions of adjacent layers revealed the specificity of isotope engineering in a layered material, with a modification of the van der Waals interactions upon isotope purification. The electron density distribution is more diffuse between adjacent layers in 10 BN than in 11 BN crystals. Our results open perspectives in understanding and controlling van der Waals bonding in layered materials.

SELF-REACTIVATING NEUTRON SOURCE FOR A NEUTRONIC REACTOR

DOEpatents

Newson, H.W.

1959-02-01

Reactors of the type employing beryllium in a reflector region around the active portion and to a neutron source for use therewith are discussed. The neutron source is comprised or a quantity of antimony permanently incorporated in, and as an integral part of, the reactor in or near the beryllium reflector region. During operation of the reactor the natural occurring antimony isotope of atomic weight 123 absorbs neutrons and is thereby transformed to the antimony isotope of atomic weight 124, which is radioactive and emits gamma rays. The gamma rays react with the beryllium to produce neutrons. The beryllium and antimony thus cooperate to produce a built in neutron source which is automatically reactivated by the operation of the reactor itself and which is of sufficient strength to maintain the slow neutron flux at a sufficiently high level to be reliably measured during periods when the reactor is shut down.

The production and certification of a plutonium equal-atom reference material: NBL CRM 128

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

Crawford, D.W.; Gradle, C.G.; Soriano, M.D.

This report describes the design, production, and certification of the New Brunswick Laboratory plutonium equal-atom certified reference material (CRM), NBL CRM 128. The primary use of this CRM is for the determination of bias corrections encountered in the operation of a mass spectrometer. This reference material is available to the US Department of Energy contractor-operated and government-operated laboratories, as well as to the international nuclear safeguards community. The absolute, or unbiased, certified value for the CRM's Pu-242/Pu-239 ratio is 1.00063 {plus minus} 0.00026 (95% confidence interval) as of October 1, 1984. This value was obtained through the quantitative blending ofmore » high-purity, chemically and isotopically characterized separated isotopes, as well as through intercomparisons of CRM samples with calibration mixtures using thermal ionization mass spectrometry. 32 tabs.« less

Hydrogen isotope fractionation during lipid biosynthesis by Haloarcula marismortui

NASA Astrophysics Data System (ADS)

Dirghangi, Sitindra S.; Pagani, Mark

2013-10-01

We studied the controls on the fractionation of hydrogen isotopes during lipid biosynthesis by Haloarcula marismortui, a halophilic archaea, in pure culture experiments by varying organic substrate, the hydrogen isotope composition (D/H) of water, temperature, and salinity. Cultures were grown on three substrates: succinate, pyruvate and glycerol with known hydrogen isotope compositions, and in water with different hydrogen isotopic compositions. All culture series grown on a particular substrate show strong correlations between δDarchaeol and δDwater. However, correlations are distinctly different for cultures grown on different substrates. Our results indicate that the metabolic pathway of substrate exerts a fundamental influence on the δD value of lipids, likely by influencing the D/H composition of NADPH (nicotinamide adenine dinucleotide phosphate), the reducing agent that contributes hydrogen to carbon atoms during lipid biosynthesis. Temperature and salinity have smaller, but similar effects on δDlipid, primarily due to the way temperature and salinity influence growth rate, as well as temperature effects on the activity of enzymes.

Physics overview of AVLIS

NASA Astrophysics Data System (ADS)

Solarz, R. W.

1985-02-01

Atomic vapor laster isotope separation (AVLIS) represents the largest-scale potential application of tunable lasers that has received serious attention. The underlying physical principles were identified and optimized, the major technology components were developed, and the integrated enrichment performance of the process was tested. The central physical processes are outlined, progress to date on the technology elements is reviewed, and scaling laws are fomulated. Two primary applications are the production of light-water reactor fuel and the conversion of fuel-grade plutonium to weapons-grade material. A variety of applications exist that all potentially use a common base of AVLIS technology. These include missions such as the enrichment of mercury isotopes to improve fluorescent lamp efficiency, the enrichment of iodine isotopes for medical isotope use, and the cleanup of strontium from defense waste for recovering strontium isotopes for radiothermal mechanical generators. The ability to radidly assess the economic and technical feasibility of each mission is derived from the general applicability of AVLIS physics and AVLIS technology.

SU-C-204-03: DFT Calculations of the Stability of DOTA-Based-Radiopharmaceuticals

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

Khabibullin, A.R.; Woods, L.M.; Karolak, A.

2016-06-15

Purpose: Application of the density function theory (DFT) to investigate the structural stability of complexes applied in cancer therapy consisting of the 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) chelated to Ac225, Fr221, At217, Bi213, and Gd68 radio-nuclei. Methods: The possibility to deliver a toxic payload directly to tumor cells is a highly desirable aim in targeted alpha particle therapy. The estimation of bond stability between radioactive atoms and the DOTA chelating agent is the key element in understanding the foundations of this delivery process. Thus, we adapted the Vienna Ab-initio Simulation Package (VASP) with the projector-augmented wave method and a plane-wave basis setmore » in order to study the stability and electronic properties of DOTA ligand chelated to radioactive isotopes. In order to count for the relativistic effect of radioactive isotopes we included Spin-Orbit Coupling (SOC) in the DFT calculations. Five DOTA complex structures were represented as unit cells, each containing 58 atoms. The energy optimization was performed for all structures prior to calculations of electronic properties. Binding energies, electron localization functions as well as bond lengths between atoms were estimated. Results: Calculated binding energies for DOTA-radioactive atom systems were −17.792, −5.784, −8.872, −13.305, −18.467 eV for Ac, Fr, At, Bi and Gd complexes respectively. The displacements of isotopes in DOTA cages were estimated from the variations in bond lengths, which were within 2.32–3.75 angstroms. The detailed representation of chemical bonding in all complexes was obtained with the Electron Localization Function (ELF). Conclusion: DOTA-Gd, DOTA-Ac and DOTA-Bi were the most stable structures in the group. Inclusion of SOC had a significant role in the improvement of DFT calculation accuracy for heavy radioactive atoms. Our approach is found to be proper for the investigation of structures with DOTA-based-radiopharmaceuticals and will enhance our understanding of processes occurring at subatomic levels.« less

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

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

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

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

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

PubMed Central

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

2017-01-01

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

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

DOE PAGES

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

2017-03-08

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

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

NASA Astrophysics Data System (ADS)

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

2017-03-01

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

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.

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.

Iron(II)-Catalyzed Iron Atom Exchange and Mineralogical Changes in Iron-rich Organic Freshwater Flocs: An Iron Isotope Tracer Study.

PubMed

ThomasArrigo, Laurel K; Mikutta, Christian; Byrne, James; Kappler, Andreas; Kretzschmar, Ruben

2017-06-20

In freshwater wetlands, organic flocs are often found enriched in trace metal(loid)s associated with poorly crystalline Fe(III)-(oxyhydr)oxides. Under reducing conditions, flocs may become exposed to aqueous Fe(II), triggering Fe(II)-catalyzed mineral transformations and trace metal(loid) release. In this study, pure ferrihydrite, a synthetic ferrihydrite-polygalacturonic acid coprecipitate (16.7 wt % C), and As- (1280 and 1230 mg/kg) and organic matter (OM)-rich (18.1 and 21.8 wt % C) freshwater flocs dominated by ferrihydrite and nanocrystalline lepidocrocite were reacted with an isotopically enriched 57 Fe(II) solution (0.1 or 1.0 mM Fe(II)) at pH 5.5 and 7. Using a combination of wet chemistry, Fe isotope analysis, X-ray absorption spectroscopy (XAS), 57 Fe Mössbauer spectroscopy and X-ray diffraction, we followed the Fe atom exchange kinetics and secondary mineral formation over 1 week. When reacted with Fe(II) at pH 7, pure ferrihydrite exhibited rapid Fe atom exchange at both Fe(II) concentrations, reaching 76 and 89% atom exchange in experiments with 0.1 and 1 mM Fe(II), respectively. XAS data revealed that it transformed into goethite (21%) at the lower Fe(II) concentration and into lepidocrocite (73%) and goethite (27%) at the higher Fe(II) concentration. Despite smaller Fe mineral particles in the coprecipitate and flocs as compared to pure ferrihydrite (inferred from Mössbauer-derived blocking temperatures), these samples showed reduced Fe atom exchange (9-30% at pH 7) and inhibited secondary mineral formation. No release of As was recorded for Fe(II)-reacted flocs. Our findings indicate that carbohydrate-rich OM in flocs stabilizes poorly crystalline Fe minerals against Fe(II)-catalyzed transformation by surface-site blockage and/or organic Fe(II) complexation. This hinders the extent of Fe atom exchange at mineral surfaces and secondary mineral formation, which may consequently impair Fe(II)-activated trace metal(loid) release. Thus, under short-term Fe(III)-reducing conditions facilitating the fast attainment of solid-solution equilibria (e.g., in stagnant waters), Fe-rich freshwater flocs are expected to remain an effective sink for trace elements.

The Stark Effect on the Wave Function of Tritium in Relativistic Condition

NASA Astrophysics Data System (ADS)

Supriadi, B.; Prastowo, S. H. B.; Bahri, S.; Ridlo, Z. R.; Prihandono, T.

2018-03-01

Tritium Atom is one of the isotopes of Hydrogen that has two Neutrons in the nucleus and an electron that surrounds the nucleus. The Stark Effect is an effect of a shift or polarization of the atomic spectrum caused by the external electrostatic field. The interaction between the electrons and the external electric field can be reviewed using an approximation method of perturbation theory. The perturbation theory used is a time Independent non-degenerate perturbation and reviewed to second order to obtain correction of Tritium Atomic wave function. The condition that used in the system is a relativistic condition by reviewing the movement of electrons within the Atom. The effects of relativity also affect the correction of the wave function of Atom Tritium in the ground state. Tritium is radioactive material that is still relatively safe, and one of the applications of Tritium Atom is on the battery of betavoltaics (Nano Tritium Battery).

Isotopic Shift of Atom-Dimer Efimov Resonances in K-Rb Mixtures: Critical Effect of Multichannel Feshbach Physics.

PubMed

Kato, K; Wang, Yujun; Kobayashi, J; Julienne, P S; Inouye, S

2017-04-21

Multichannel Efimov physics is investigated in ultracold heteronuclear admixtures of K and Rb atoms. We observe a shift in the scattering length where the first atom-dimer resonance appears in the ^{41}K-^{87}Rb system relative to the position of the previously observed atom-dimer resonance in the ^{40}K-^{87}Rb system. This shift is well explained by our calculations with a three-body model including van der Waals interactions, and, more importantly, multichannel spinor physics. With only minor differences in the atomic masses of the admixtures, the shift in the atom-dimer resonance positions can be cleanly ascribed to the isolated and overlapping Feshbach resonances in the ^{40}K-^{87}Rb and ^{41}K-^{87}Rb systems, respectively. Our study demonstrates the role of multichannel Feshbach physics in determining Efimov resonances in heteronuclear three-body systems.

Determination of ultra-low level plutonium isotopes (239Pu, 240Pu) in environmental samples with high uranium.

PubMed

Xing, Shan; Zhang, Weichao; Qiao, Jixin; Hou, Xiaolin

2018-09-01

In order to measure trace plutonium and its isotopes ratio ( 240 Pu/ 239 Pu) in environmental samples with a high uranium, an analytical method was developed using radiochemical separation for separation of plutonium from matrix and interfering elements including most of uranium and ICP-MS for measurement of plutonium isotopes. A novel measurement method was established for extensively removing the isobaric interference from uranium ( 238 U 1 H and 238 UH 2 + ) and tailing of 238 U, but significantly improving the measurement sensitivity of plutonium isotopes by employing NH 3 /He as collision/reaction cell gases and MS/MS system in the triple quadrupole ICP-MS instrument. The results show that removal efficiency of uranium interference was improved by more than 15 times, and the sensitivity of plutonium isotopes was increased by a factor of more than 3 compared to the conventional ICP-MS. The mechanism on the effective suppress of 238 U interference for 239 Pu measurement using NH 3 -He reaction gases was explored to be the formation of UNH + and UNH 2 + in the reactions of UH + and U + with NH 3 , while no reaction between NH 3 and Pu + . The detection limits of this method were estimated to be 0.55 fg mL -1 for 239 Pu, 0.09 fg mL -1 for 240 Pu. The analytical precision and accuracy of the method for Pu isotopes concentration and 240 Pu/ 239 Pu atomic ratio were evaluated by analysis of sediment reference materials (IAEA-385 and IAEA-412) with different levels of plutonium and uranium. The developed method were successfully applied to determine 239 Pu and 240 Pu concentrations and 240 Pu/ 239 Pu atomic ratios in soil samples collected in coastal areas of eastern China. Copyright © 2018 Elsevier B.V. All rights reserved.

Segregation of Calcium Isotopes in the Atmospheres of CP Stars as a Consequence of Light-Induced Drift

NASA Astrophysics Data System (ADS)

Parkhomenko, A. I.; Shalagin, A. M.

2018-06-01

A mechanism for the segregation of calcium isotopes in the atmospheres of chemically peculiar (CP) stars due to light-induced drift (LID) of singly charged 48Ca+ ions is discussed. One peculiarity of Ca+ is that an adequate description of the effect of LID requires taking into account several energy levels of Ca+, and thus several pairs of relative differences ( ν i - ν k )/ ν i for the transport frequencies for collisions of levels i and k with neutral atoms (hydrogen, helium). The known real (calculated ab initio) interaction potentials are used to numerically calculate the factors ( ν i - ν k )/ ν i for several states of Ca+ for collisions with H and He atoms. These computations show that, at the temperatures characteristic of the atmospheres of CP stars, T = 6600-12 000 K, fairly high values are obtained for Ca+ ions, ( ν i - ν k )/ ν i ≈ 0.4-0.6. Simple, transparent computations demonstrate that the LID rates of Ca+ ions in the atmospheres of cool CP stars ( T eff = 6600 K) exceed the drift rate due to light pressure by two orders of magnitude. The LID is directed upward in the stellar atmosphere, and the heavy isotope 48Ca is pushed into upper layers of the atmosphere. This can explain the observed predominance of the heavy isotope 48Ca in the upper atmospheric layers of CP stars; according to the radiative-diffusion theory, the action of light pressure alone (in the absence of LID) would lead to sinking of the isotope 48Ca deeper into stellar atmosphere, following the lighter main isotope 40Ca. The 48Ca+ LIDrate decreases and its drift rate due to light pressure increases with growth of the effective temperatures in the atmospheres of CP stars. The manifestations of LID and light pressure are roughly comparable in the atmospheres of CP stars with effective temperatures near T eff = 9500 K.

Rolf Landauer and Charles H. Bennett Award Talk: Experimental development of spin qubits in silicon

NASA Astrophysics Data System (ADS)

Morello, Andrea

The modern information era is built on silicon nanoelectronic devices. The future quantum information era might be built on silicon too, if we succeed in controlling the interactions between individual spins hosted in silicon nanostructures. Spins in silicon constitute excellent solid-state qubits, because of the weak spin-orbit coupling and the possibility to remove nuclear spins from the environment through 28Si isotopic enrichment. Substitutional 31P atoms in silicon behave approximately like hydrogen in vacuum, providing two spin 1/2 qubits - the donor-bound electron and the 31P nucleus - that can be coherently controlled, read out in single-shot, and are naturally coupled through the hyperfine interaction. In isotopically-enriched 28Si, these single-atom qubits have demonstrated outstanding coherence times, up to 35 seconds for the nuclear spin, and 1-qubit gate fidelities well above 99.9% for both the electron and the nucleus. The hyperfine coupling provides a built-in interaction to entangle the two qubits within one atom. The combined initialization, control and readout fidelities result in a violation of Bell's inequality with S = 2 . 70 , a record value for solid-state qubits. Despite being identical atomic systems, 31P atoms can be addressed individually by locally modifying the hyperfine interaction through electrostatic gating. Multi-qubit logic gates can be mediated either by the exchange interaction or by electric dipole coupling. Scaling up beyond a single atom presents formidable challenges, but provides a pathway to building quantum processors that are compatible with standard semiconductor fabrication, and retain a nanometric footprint, important for truly large-scale quantum computers. Work supported by US Army Research Office (W911NF-13-1-0024) and Australian Research Council (CE110001027).

Metabolic response of Candida albicans to phenylethyl alcohol under hyphae-inducing conditions.

PubMed

Han, Ting-Li; Tumanov, Sergey; Cannon, Richard D; Villas-Boas, Silas G

2013-01-01

Phenylethyl alcohol was one of the first quorum sensing molecules (QSMs) identified in C. albicans. This extracellular signalling molecule inhibits the hyphal formation of C. albicans at high cell density. Little is known, however, about the underlying mechanisms by which this QSM regulates the morphological switches of C. albicans. Therefore, we have applied metabolomics and isotope labelling experiments to investigate the metabolic changes that occur in C. albicans in response to phenylethyl alcohol under defined hyphae-inducing conditions. Our results showed a global upregulation of central carbon metabolism when hyphal development was suppressed by phenylethyl alcohol. By comparing the metabolic changes in response to phenylethyl alcohol to our previous metabolomic studies, we were able to short-list 7 metabolic pathways from central carbon metabolism that appear to be associated with C. albicans morphogenesis. Furthermore, isotope-labelling data showed that phenylethyl alcohol is indeed taken up and catabolised by yeast cells. Isotope-labelled carbon atoms were found in the majority of amino acids as well as in lactate and glyoxylate. However, isotope-labelled carbon atoms from phenylethyl alcohol accumulated mainly in the pyridine ring of NAD(+)/NADH and NADP(-/)NADPH molecules, showing that these nucleotides were the main products of phenylethyl alcohol catabolism. Interestingly, two metabolic pathways where these nucleotides play an important role, nitrogen metabolism and nicotinate/nicotinamide metabolism, were also short-listed through our previous metabolomics works as metabolic pathways likely to be closely associated with C. albicans morphogenesis.

Lead concentrations and isotope ratios in street dust determined by electrothermal atomic absorption spectrometry and inductively coupled plasma mass spectrometry.

PubMed

Nageotte, S M; Day, J P

1998-01-01

A major source of environmental lead, particularly in urban areas, has been from the combustion of leaded petrol. Street dust has previously been used to assess urban lead contamination, and the dust itself can also be a potential source of lead ingestion, particularly to children. The progressive reduction of lead in petrol, in recent years, would be expected to have been reflected in a reduction of lead in urban dust. We have tested this hypothesis by repeating an earlier survey of Manchester street dust and carrying out a comparable survey in Paris. Samples were collected from streets and parks, lead was extracted by digestion with concentrated nitric acid and determined by electrothermal atomic absorption spectrometry. Lead isotope ratios were measured by inductively coupled plasma mass spectrometry. Results for Manchester show that lead concentrations have fallen by about 40% (street dust averages, 941 micrograms g-1 (ppm) in 1975 down to 569 ppm in 1997). In Paris, the lead levels in street dust are much higher and significant differences were observed between types of street (not seen in Manchester). Additionally, lead levels in parks were much lower than in Manchester. Samples collected under the Eiffel Tower had very high concentrations and lead isotope ratios showed that this was unlikely to be fallout from motor vehicles but could be due to the paint used on the tower. Isotope ratios measurements also revealed that lead additives used in France and the UK come from different sources.

Depth profile of 236U/238U in soil samples in La Palma, Canary Islands

PubMed Central

Srncik, M.; Steier, P.; Wallner, G.

2011-01-01

The vertical distribution of the 236U/238U isotopic ratio was investigated in soil samples from three different locations on La Palma (one of the seven Canary Islands, Spain). Additionally the 240Pu/239Pu atomic ratio, as it is a well establish tool for the source identification, was determined. The radiochemical procedure consisted of a U separation step by extraction chromatography using UTEVA® Resin (Eichrom Technologies, Inc.). Afterwards Pu was separated from Th and Np by anion exchange using Dowex 1x2 (Dow Chemical Co.). Furthermore a new chemical procedure with tandem columns to separate Pu and U from the matrix was tested. For the determination of the uranium and plutonium isotopes by alpha spectrometry thin sources were prepared by microprecipitation techniques. Additionally these fractions separated from the soil samples were measured by Accelerator Mass Spectrometry (AMS) to get information on the isotopic ratios 236U/238U, 240Pu/239Pu and 236U/239Pu, respectively. The 236U concentrations [atoms/g] in each surface layer (∼2 cm) were surprisingly high compared to deeper layers where values around two orders of magnitude smaller were found. Since the isotopic ratio 240Pu/239Pu indicated a global fallout signature we assume the same origin as the probable source for 236U. Our measured 236U/239Pu value of around 0.2 is within the expected range for this contamination source. PMID:21481502

Voyager measurements of the isotopic composition of cosmic-ray aluminum and implications for the propagation of cosmic rays

NASA Technical Reports Server (NTRS)

Lukasiak, A.; Mcdonald, F. B.; Webber, W. R.

1994-01-01

We report a new measurement of the cosmic-ray isotopic composition of aluminum in the low-energy range form 75 to 206 MeV per nucleon.This measurement was made using the high-energy telescope of the CRS experiment on the Voyager 1 and 2 spacecraft during the time period from 1977 to 1993 with an average solar modulation level about 497 MV, roughly the same as at Earth near sunspot minimum. We obtain approximately 430 Al events of which approximately 35 are Al-26 and 395 are Al-27. The Al isotopes were separated with an average mass resolution sigma of 0.35 amu. Our interpretation of the isotopic composition of cosmic-ray aluminum is based on a standard Leaky-Box model for the interstellar propagation of cosmic-ray nuclei using the latest cross sections of the New Mexico-Saclay collaboration as well as a disk-halo diffusion model. From our observed ratio Al-26/Al-27 of 8.3 +/- 2.4 % we deduce an average interstellar density of about 0.52 (+0.26, -0.2) atoms per cu cm. This density is larger than the value of 0.28 (+0.14, -0.11) atoms per cu cm we found from an analysis of the observed abundance of the longer lived Be-10 made using data from the Voyager detectors over almost the same time interval and using essentially the same propagation program.

Determination of U isotope ratios in sediments using ICP-QMS after sample cleanup with anion-exchange and extraction chromatography.

PubMed

Zheng, Jian; Yamada, Masatoshi

2006-01-15

The determination of uranium is important for environmental radioactivity monitoring, which investigates the releases of uranium from nuclear facilities and of naturally occurring radioactive materials by the coal, oil, natural gas, mineral, ore refining and phosphate fertilizer industries, and it is also important for studies on the biogeochemical behavior of uranium in the environment. In this paper, we describe a quadrupole ICP-MS (ICP-QMS)-based analytical procedure for the accurate determination of U isotope ratios ((235)U/(238)U atom ratio and (234)U/(238)U activity ratio) in sediment samples. A two-stage sample cleanup using anion-exchange and TEVA extraction chromatography was employed in order to obtain accurate and precise (234)U/(238)U activity ratios. The factors that affect the accuracy and precision of U isotope ratio analysis, such as detector dead time, abundance sensitivity, dwell time and mass bias were carefully evaluated and corrected. With natural U, a precision lower than 0.5% R.S.D. for (235)U/(238)U atom ratio and lower than 2.0% R.S.D. for (234)U/(238)U activity ratio was obtained with less than 90 ng uranium. The developed analytical method was validated using an ocean sediment reference material and applied to an investigation into the uranium isotopic compositions in a sediment core in a brackish lake in the vicinity of U-related nuclear facilities in Japan.

Development of Optical Crystals for High Power and Tunable Visible and Infrared Light Generation

DTIC Science & Technology

2015-02-11

ultra high chemical purity (5N), 95% isotopically enriched 6Li was purified in a multi-stage vacuum distillation process previously reported by...enriched 6Li was purified in a multi-stage vacuum distillation process previously reported by Stowe et al.[4]. 6LiIn alloy was synthesized in a... quantum mechanics, it has been determined that atoms, molecules, ions have discrete energy levels. Therefore there exists allowed atomic transitions

Precision mass measurements of magnesium isotopes and implications for the validity of the isobaric mass multiplet equation

DOE PAGES

Brodeur, M.; Kwiatkowski, A. A.; Drozdowski, O. M.; ...

2017-09-18

If the mass excess of neutron-deficient nuclei and their neutron-rich mirror partners are both known, it can be shown that deviations of the isobaric mass multiplet equation (IMME) in the form of a cubic term can be probed. Such a cubic term was probed by using the atomic mass of neutron-rich magnesium isotopes measured using the TITAN Penning trap and the recently measured proton-separation energies of 29Cl and 30Ar. The atomic mass of 27Mg was found to be within 1.6σ of the value stated in the Atomic Mass Evaluation. The atomic masses of 28,29Mg were measured to be both withinmore » 1σ, while being 7 and 33 times more precise, respectively. Using the 29Mg mass excess and previous measurements of 29Cl, we uncovered a cubic coefficient of d = 28(7)keV, which is the largest known cubic coefficient of the IMME. This departure, however, could also be caused by experimental data with unknown systematic errors. Hence there is a need to confirm the mass excess of 28S and the one-neutron separation energy of 29Cl, which have both come from a single measurement. Lastly, our results were compared with ab initio calculations from the valence-space in-medium similarity renormalization group, resulting in a good agreement.« less

RBS, SY-XRF, INAA and ICP-IDMS of antimony implanted in silicon - A multi-method approach to characterize and certify a reference material

NASA Astrophysics Data System (ADS)

Ecker, K. H.; Wätjen, U.; Berger, A.; Persson, L.; Pritzkow, W.; Radtke, M.; Riesemeier, H.

2002-04-01

A layer of Sb atoms, implanted with an energy of 400 keV and a nominal dose of 5×10 16 atoms/cm 2 into a high purity silicon wafer, was certified for its areal density (atoms/cm 2) using Rutherford backscattering spectrometry (RBS), instrumental neutron activation analysis (INAA) and inductively coupled plasma isotope dilution mass spectrometry (ICP-IDMS) and for its isotope ratio using INAA and ICP-IDMS. Excellent agreement between the results of the different independent methods was found. In the present work, the measurements of the homogeneity of the areal density of Sb, previously determined with RBS in spots having 1 mm diameter, are improved with synchrotron X-ray fluorescence analysis: Higher precision in even smaller sample spots allows to estimate a reduced inhomogeneity of the whole batch of samples of the order of only 0.4%. Thus the uncertainty of the certified value can further be reduced. Down to fractions of a chip with 0.3×0.4 mm 2 area, the areal density is now certified as (4.81±0.06)×10 16 Sb atoms/cm 2, where the expanded uncertainty 0.06 (coverage factor k=2) corresponds to only 1.2%. The relative merits of the different analytical methods are discussed.

Precision mass measurements of magnesium isotopes and implications for the validity of the isobaric mass multiplet equation

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

Brodeur, M.; Kwiatkowski, A. A.; Drozdowski, O. M.

If the mass excess of neutron-deficient nuclei and their neutron-rich mirror partners are both known, it can be shown that deviations of the isobaric mass multiplet equation (IMME) in the form of a cubic term can be probed. Such a cubic term was probed by using the atomic mass of neutron-rich magnesium isotopes measured using the TITAN Penning trap and the recently measured proton-separation energies of 29Cl and 30Ar. The atomic mass of 27Mg was found to be within 1.6σ of the value stated in the Atomic Mass Evaluation. The atomic masses of 28,29Mg were measured to be both withinmore » 1σ, while being 7 and 33 times more precise, respectively. Using the 29Mg mass excess and previous measurements of 29Cl, we uncovered a cubic coefficient of d = 28(7)keV, which is the largest known cubic coefficient of the IMME. This departure, however, could also be caused by experimental data with unknown systematic errors. Hence there is a need to confirm the mass excess of 28S and the one-neutron separation energy of 29Cl, which have both come from a single measurement. Lastly, our results were compared with ab initio calculations from the valence-space in-medium similarity renormalization group, resulting in a good agreement.« less

Small changes in Cu redox state and speciation generate large isotope fractionation during adsorption and incorporation of Cu by a phototrophic biofilm

NASA Astrophysics Data System (ADS)

Coutaud, Margot; Méheut, Merlin; Glatzel, Pieter; Pokrovski, Gleb S.; Viers, Jérôme; Rols, Jean-Luc; Pokrovsky, Oleg S.

2018-01-01

Despite the importance of phototrophic biofilms in metal cycling in freshwater systems, metal isotope fractionation linked to metal adsorption and uptake by biofilm remains very poorly constrained. Here, copper isotope fractionation by a mature phototrophic biofilm during Cu surface adsorption and incorporation was studied in batch reactor (BR) and open drip flow reactor (DFR) systems at ambient conditions. X-ray Absorption Spectroscopy (both Near Edge Structure, XANES, and Extended Fine Structure, EXAFS) at Cu K-edge of the biofilm after its interaction with Cu in BR experiments allowed characterizing the molecular structure of assimilated Cu and quantifying the degree of CuII to CuI reduction linked to Cu assimilation. For both BR and DFR experiments, Cu adsorption caused enrichment in heavy isotope at the surface of the biofilm relative to the aqueous solution, with an apparent enrichment factor for the adsorption process, ε65Cuads, of +1.1 ± 0.3‰. In contrast, the isotope enrichment factor during copper incorporation into the biofilm (ε65Cuinc) was highly variable, ranging from -0.6 to +0.8‰. This variability of the ε65Cuinc value was likely controlled by Cu cellular uptake via different transport pathways resulting in contrasting fractionation. Specifically, the CuII storage induced enrichment in heavy isotope, whereas the toxicity response of the biofilm to Cu exposure resulted in reduction of CuII to CuI, thus yielding the biofilm enrichment in light isotope. EXAFS analyses suggested that a major part of the Cu assimilated by the biofilm is bound to 5.1 ± 0.3 oxygen or nitrogen atoms, with a small proportion of Cu linked to sulfur atoms (NS < 0.6) of sulfhydryl groups. XANES analyses showed that the proportion of CuIIvs CuI, compared to the initial CuII/CuI ratio, decreased by 14% after the first hour of reaction and by 6% after 96 h of reaction. The value of ε65Cuinc of the biofilm exhibited a similar trend over time of exposure. Our study demonstrates the complexity of biological processes associated with live phototrophic biofilms, which produce large and contrasting isotope fractionations following rather small Cu redox and speciation changes during uptake, storage or release of the metal, i.e., favoring heavy isotopes during complexation with carboxylate ligands and light isotopes during reduction of CuII-O/N to CuI-sulfhydryl moieties.

Safety of stable isotope use.

PubMed

Koletzko, B; Sauerwald, T; Demmelmair, H

1997-08-01

The increased employment of stable isotope tracers for diagnostic and research purposes frequently raises questions on potential risks associated with their use, which is of particular importance in the paediatric age group. Biological effects and the potential of adverse events has been evaluated in a large number of animal and, in part, also human studies. Possible differences in physical, chemical and biochemical behaviour resulting in kinetic and thermodynamic isotope effects between stable isotopes of the same element are related to the relative differences in atomic weight. Deuterium (2H), which differs markedly in mass from the predominant hydrogen isotope 1H, may induce serious side-effects at high concentrations in body fluids. The threshold dose for the occurrence of side-effects lies well above the usual tracer dosages for clinical use. In contrast to deuterium, heavier stable isotopes such as 13C, 15N or 18O that differ relatively little in mass from the predominant isotopes such as 12C, does not show any adverse biological effects even at highest enrichments. The doses of stable isotope tracer substances that are used for clinical diagnostic and research purposes appear safe and without any adverse effects. Stable isotope tracers should only be used in children if the trace is safe at the doses applied, and tracer is chemically pure and stable. In the case of intravenous application, the tracer preparation must also be sterile and pyrogen free.

Effect of atomic noise on optical squeezing via polarization self-rotation in a thermal vapor cell

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

Hsu, M. T. L.; Hetet, G.; Peng, A.

2006-02-15

The traversal of an elliptically polarized optical field through a thermal vapor cell can give rise to a rotation of its polarization axis. This process, known as polarization self-rotation (PSR), has been suggested as a mechanism for producing squeezed light at atomic transition wavelengths. We show results of the characterization of PSR in isotopically enhanced rubidium-87 cells, performed in two independent laboratories. We observed that, contrary to earlier work, the presence of atomic noise in the thermal vapor overwhelms the observation of squeezing. We present a theory that contains atomic noise terms and show that a null result in squeezingmore » is consistent with this theory.« less

Experimental determination of barium isotope fractionation during diffusion and adsorption processes at low temperatures

NASA Astrophysics Data System (ADS)

van Zuilen, Kirsten; Müller, Thomas; Nägler, Thomas F.; Dietzel, Martin; Küsters, Tim

2016-08-01

Variations in barium (Ba) stable isotope abundances measured in low and high temperature environments have recently received increasing attention. The actual processes controlling Ba isotope fractionation, however, remain mostly elusive. In this study, we present the first experimental approach to quantify the contribution of diffusion and adsorption on mass-dependent Ba isotope fractionation during transport of aqueous Ba2+ ions through a porous medium. Experiments have been carried out in which a BaCl2 solution of known isotopic composition diffused through u-shaped glass tubes filled with silica hydrogel at 10 °C and 25 °C for up to 201 days. The diffused Ba was highly fractionated by up to -2.15‰ in δ137/134Ba, despite the low relative difference in atomic mass. The time-dependent isotope fractionation can be successfully reproduced by a diffusive transport model accounting for mass-dependent differences in the effective diffusivities of the Ba isotope species (D137Ba /D134Ba =(m134 /m137) β). Values of β extracted from the transport model were in the range of 0.010-0.011. Independently conducted batch experiments revealed that adsorption of Ba onto the surface of silica hydrogel favoured the heavier Ba isotopes (α = 1.00015 ± 0.00008). The contribution of adsorption on the overall isotope fractionation in the diffusion experiments, however, was found to be small. Our results contribute to the understanding of Ba isotope fractionation processes, which is crucial for interpreting natural isotope variations and the assessment of Ba isotope ratios as geochemical proxies.

High-precision Penning trap mass measurements of 9,10Be and the one-neutron halo nuclide 11Be

NASA Astrophysics Data System (ADS)

Ringle, R.; Brodeur, M.; Brunner, T.; Ettenauer, S.; Smith, M.; Lapierre, A.; Ryjkov, V. L.; Delheij, P.; Drake, G. W. F.; Lassen, J.; Lunney, D.; Dilling, J.

2009-05-01

Penning trap mass measurements of 9Be, 10Be (t1 / 2 = 1.51 My), and the one-neutron halo nuclide 11Be (t1 / 2 = 13.8 s) have been performed using TITAN at TRIUMF. The resulting 11Be mass excess (ME = 20 177.60 (58) keV) is in agreement with the current Atomic Mass Evaluation (AME03) [G. Audi, et al., Nucl. Phys. A 729 (2003) 337] value, but is over an order of magnitude more precise. The precision of the mass values of 9,10Be have been improved by about a factor of four and reveal a ≈ 2 σ deviation from the AME mass values. Results of new atomic physics calculations are presented for the isotope shift of 11Be relative to 9Be, and it is shown that the new mass values essentially remove atomic mass uncertainties as a contributing factor in determining the relative nuclear charge radius from the isotope shift. The new mass values of 10,11Be also allow for a more precise determination of the single-neutron binding energy of the halo neutron in 11Be.

New limits on variation of the fine-structure constant using atomic dysprosium.

PubMed

Leefer, N; Weber, C T M; Cingöz, A; Torgerson, J R; Budker, D

2013-08-09

We report on the spectroscopy of radio-frequency transitions between nearly degenerate, opposite-parity excited states in atomic dysprosium (Dy). Theoretical calculations predict that these states are very sensitive to variation of the fine-structure constant α owing to large relativistic corrections of opposite sign for the opposite-parity levels. The near degeneracy reduces the relative precision necessary to place constraints on variation of α, competitive with results obtained from the best atomic clocks in the world. Additionally, the existence of several abundant isotopes of Dy allows isotopic comparisons that suppress common-mode systematic errors. The frequencies of the 754-MHz transition in 164Dy and 235-MHz transition in 162Dy are measured over the span of two years. The linear variation of α is α·/α=(-5.8±6.9([1σ]))×10(-17)  yr(-1), consistent with zero. The same data are used to constrain the dimensionless parameter kα characterizing a possible coupling of α to a changing gravitational potential. We find that kα=(-5.5±5.2([1σ]))×10(-7), essentially consistent with zero and the best constraint to date.

Electron transfer and atom exchange between aqueous Fe(II) and structural Fe(III) in clays. Role in U and Hg(II) transformations

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

Scherer, Michelle

2016-08-31

During this project, we investigated Fe electron transfer and atom exchange between aqueous Fe(II) and structural Fe(III) in clay minerals. We used selective chemical extractions, enriched Fe isotope tracer experiments, computational molecular modeling, and Mössbauer spectroscopy. Our findings indicate that structural Fe(III) in clay minerals is reduced by aqueous Fe(II) and that electron transfer occurs when Fe(II) is sorbed to either basal planes and edge OH-groups of clay mineral. Findings from highly enriched isotope experiments suggest that up to 30 % of the Fe atoms in the structure of some clay minerals exhanges with aqueous Fe(II). First principles calculations usingmore » a small polaron hopping approach suggest surprisingly fast electron mobility at room temperature in a nontronite clay mineral and are consistent with temperature dependent Mössbauer data Fast electron mobility suggests that electrons may be able to conduct through the mineral fast enough to enable exchange of Fe between the aqueous phase and clay mineral structure. over the time periods we observed. Our findings suggest that Fe in clay minerals is not as stable as previously thought.« less

β-decay half-lives of new neutron-rich rare-earth isotopes 159Pm,162Sm, and 166Gd

NASA Astrophysics Data System (ADS)

Ichikawa, S.; Asai, M.; Tsukada, K.; Haba, H.; Nagame, Y.; Shibata, M.; Sakama, M.; Kojima, Y.

2005-06-01

The new neutron-rich rare-earth isotopes 159Pm, 162Sm, and 166Gd produced in the proton-induced fission of 238U were identified using the JAERI on-line isotope separator (JAERI-ISOL) coupled to a gas-jet transport system. The half-lives of 159Pm, 162Sm, and 166Gd were determined to be 1.5 ± 0.2, 2.4 ± 0.5, and 4.8 ± 1.0 s respectively. The partial decay scheme of 166Gd was constructed from γγ-coincidence data. A more accurate half-life value of 25.6 ± 2.2 s was obtained for the previously identified isotope 166Tb. The half-lives measured in the present study are in good agreement with the theoretical predictions calculated by the second generation of the gross theory with the atomic masses evaluated by Audi and Wapstra.

Constraints on Galactic Cosmic-Ray Origins from Elemental and Isotopic Composition Measurements

NASA Technical Reports Server (NTRS)

Binns, W. R.; Christian, E. R.; Cummings, A. C.; deNolfo, G. A.; Israel, M. H.; Leske, R. A.; Mewaldt, R. A,; Stone, E. C.; vonRosevinge, T. T.; Wiedenbeck, M. E.

2013-01-01

The most recent measurements by the Cosmic Ray Isotope Spectrometer (CRIS) aboard the Advanced Composition Explorer (ACE) satellite of ultra-heavy cosmic ray isotopic and elemental abundances will be presented. A range of isotope and element ratios, most importantly Ne-22/Ne-20, Fe-58/Fe-56, and Ga-31/Ge -32 show that the composition is consistent with source material that is a mix of approx 80% ISM (with Solar System abundances) and 20% outflow/ejecta from massive stars. In addition, our data show that the ordering of refractory and volatile elements with atomic mass is greatly improved when compared to an approx 80%/20% mix rather than pure ISM, that the refractory and volatile elements have similar slopes, and that refractory elements are preferentially accelerated by a factor of approx 4. We conclude that these data are consistent with an OB association origin of GCRs.

The oxygen isotope composition of phosphate released from phytic acid by the activity of wheat and Aspergillus niger phytase

NASA Astrophysics Data System (ADS)

von Sperber, C.; Tamburini, F.; Brunner, B.; Bernasconi, S. M.; Frossard, E.

2015-07-01

Phosphorus (P) is an essential nutrient for living organisms. Under P-limiting conditions plants and microorganisms can exude extracellular phosphatases that release inorganic phosphate (Pi) from organic phosphorus compounds (Porg). Phytic acid (myo-inositol hexakisphosphate, IP6) is an important form of Porg in many soils. The enzymatic hydrolysis of IP6 by phytase yields available Pi and less phosphorylated inositol derivates as products. The hydrolysis of organic P compounds by phosphatases leaves an isotopic imprint on the oxygen isotope composition (δ18O) of released Pi, which might be used to trace P in the environment. This study aims at determining the effect of phytase on the oxygen isotope composition of released Pi. For this purpose, enzymatic assays with histidine acid phytases from wheat and Aspergillus niger were prepared using IP6, adenosine 5'-monophosphate (AMP) and glycerophosphate (GPO4) as substrates. For a comparison to the δ18O of Pi released by other extracellular enzymes, enzymatic assays with acid phosphatases from potato and wheat germ with IP6 as a substrate were prepared. During the hydrolysis of IP6 by phytase, four of the six Pi were released, and one oxygen atom from water was incorporated into each Pi. This incorporation of oxygen from water into Pi was subject to an apparent inverse isotopic fractionation (ϵ ~ 6 to 10 ‰), which was similar to that imparted by acid phosphatase from potato during the hydrolysis of IP6 (ϵ ~ 7 ‰), where less than three Pi were released. The incorporation of oxygen from water into Pi during the hydrolysis of AMP and GPO4 by phytase yielded a normal isotopic fractionation (ϵ ~ -12 ‰), similar to values reported for acid phosphatases from potato and wheat germ. We attribute this similarity in ϵ to the same amino acid sequence motif (RHGXRXP) at the active site of these enzymes, which leads to similar reaction mechanisms. We suggest that the striking substrate dependency of the isotopic fractionation could be attributed to a difference in the δ18O values of the C-O-P bridging and non-bridging oxygen atoms in organic phosphate compounds.

The oxygen isotope composition of phosphate released from phytic acid by the activity of wheat and Aspergillus niger phytase

NASA Astrophysics Data System (ADS)

Sperber, C. v.; Tamburini, F.; Brunner, B.; Bernasconi, S. M.; Frossard, E.

2015-03-01

Phosphorus (P) is an essential nutrient for living organisms. Under P-limiting conditions plants and microorganisms can exude extracellular phosphatases that release inorganic phosphate (Pi) from organic phosphorus compounds (Porg). Phytic acid (IP6) is an important form of Porg in many soils. The enzymatic hydrolysis of IP6 by phytase yields plant available inorganic phosphate (Pi) and less phosphorylated inositol derivates as products. The hydrolysis of organic P-compounds by phosphatases leaves an isotopic imprint on the oxygen isotope composition (δ18O) of released Pi, which might be used to trace P in the environment. This study aims at determining the effect of phytase on the oxygen isotope composition of released Pi. For this purpose, enzymatic assays with histidine acid phytases from wheat and Aspergillus niger were prepared using IP6, adenosine 5'monophosphate (AMP) and glycerophosphate (GPO4) as substrates. For a comparison to the δ18O of Pi released by other extracellular enzymes, enzymatic assays with acid phosphatases from potato and wheat germ with IP6 as substrate were prepared. During the hydrolysis of IP6 by phytase, four Pi are released, and one oxygen atom from water is incorporated into each Pi. This incorporation of oxygen from water into Pi is subject to an apparent inverse isotopic fractionation (ϵ ∼ 6 to 10‰), which is similar to that imparted by acid phosphatase from potato during the hydrolysis of IP6 (ϵ ∼ 7‰) where less than three Pi are released. The incorporation of oxygen from water into Pi during the hydrolysis of AMP and GPO4 by phytase yielded a normal isotopic fractionation (ϵ ∼ -12‰), again similar to values reported for acid phosphatases from potato and wheat germ. We attribute this similarity in ɛ to the same amino acid sequence motif (RHGXRXP) at the active site of these enzymes, which leads to similar reaction mechanisms. We suggest that the striking substrate-dependency of the isotopic fractionation could be attributed to a difference in the δ18O-values of the C-O-P bridging and non-bridging oxygen atoms in organic phosphate compounds.

Atom interferometry in space: Thermal management and magnetic shielding

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

Milke, Alexander; Kubelka-Lange, André; Gürlebeck, Norman, E-mail: norman.guerlebeck@zarm.uni-bremen.de

2014-08-15

Atom interferometry is an exciting tool to probe fundamental physics. It is considered especially apt to test the universality of free fall by using two different sorts of atoms. The increasing sensitivity required for this kind of experiment sets severe requirements on its environments, instrument control, and systematic effects. This can partially be mitigated by going to space as was proposed, for example, in the Spacetime Explorer and Quantum Equivalence Principle Space Test (STE-QUEST) mission. However, the requirements on the instrument are still very challenging. For example, the specifications of the STE-QUEST mission imply that the Feshbach coils of themore » atom interferometer are allowed to change their radius only by about 260 nm or 2.6 × 10{sup −4} % due to thermal expansion although they consume an average power of 22 W. Also Earth's magnetic field has to be suppressed by a factor of 10{sup 5}. We show in this article that with the right design such thermal and magnetic requirements can indeed be met and that these are not an impediment for the exciting physics possible with atom interferometers in space.« less

Strong Inter-channel Effects in Dipole Photoionization of d-subshells of Xe, Cs, and Ba Atoms

NASA Astrophysics Data System (ADS)

Manson, S.; Amusia, M.; Baltenkov, A.; Chernysheva, L.; Felfli, Z.; Msezane, A.

2003-05-01

In the framework of a specially modified Random Phase Approximation with Exchange approach (SPRPAE) developed for half-filled atomic subshells the dipole angular anisotropy parameters β(ω) for the 3d-photoionization of Xe, Cs and Ba atoms have been calculated. The main point of this approach is that we consider the 3d electrons of these atoms as belonging to two semi-filled atomic levels that contain two different sorts of electrons, namely that six electrons form the 3d_5/2 subshell (called "up"), while the other four electrons form the 3d_3/2 subshell (called "down"). This permits to apply straightforwardly the RPAE for these semi-filled subshells. We show that the interaction between "up" and "down" electrons results in a qualitative alteration of the frequency (ω) dependence of β_5/2(ω) and β_3/2(ω) that define the photoelectron angular distribution from the 3d_5/2 and 3d_3/2 levels. In all these atoms the effect of 3d_3/2 upon 3d_5/2 leads to the creation of an additional maximum near the photoionization thresholds, while the effect for 3d_3/2 is rather weak. Work supported by CRDF (No ZP1- 2449-TA-02), ISTC grant 1358 and NSF

Phonon interference control of atomic-scale metamirrors, meta-absorbers, and heat transfer through crystal interfaces

NASA Astrophysics Data System (ADS)

Kosevich, Yu. A.; Potyomina, L. G.; Darinskii, A. N.; Strelnikov, I. A.

2018-03-01

The paper theoretically studies the possibility of using the effects of phonon interference between paths through different interatomic bonds for the control of phonon heat transfer through internal crystal interfaces and for the design of phonon metamirrors and meta-absorbers. These metamirrors and meta-absorbers are considered to be defect nanolayers of atomic-scale thicknesses embedded in a crystal. Several analytically solvable three-dimensional lattice-dynamics models of the phonon metamirrors and meta-absorbers at the internal crystal planes are described. It is shown that due to destructive interference in the two or more phonon paths, the internal crystal planes, fully or partially filled with weakly bound or heavy-isotope defect atoms, can completely reflect or completely absorb phonons at the transmission antiresonances, whose wavelengths are larger than the effective thickness of the metamirror or meta-absorber. Due to cooperative superradiant effect, the spectral widths of the two-path interference antiresonances for the plane waves are given by the square of partial filling fraction in the defect crystal plane. Our analysis reveals that the presence of two or more phonon paths plays the dominant role in the emergence of the transmission antiresonances in phonon scattering at the defect crystal planes and in reduction of the thermal interface conductance in comparison with the Fano-resonance concept. We study analytically phonon transmission through internal crystal plane in a model cubic lattice of Si-like atoms, partially filled with Ge-like defect atoms. Such a plane can serve as interference phonon metamirror with the transmission antiresonances in the vicinities of eigenmode frequencies of Ge-like defect atoms in the terahertz frequency range. We predict the extraordinary phonon transmission induced by the two-path constructive interference of the lattice waves in resonance with the vibrations of rare host atoms, periodically distributed in the crystal plane almost completely filled with heavy-isotope defects. We show that the phonon-interference-induced transparency can be produced by the defect nanolayer with the non-nearest-neighbor interactions, filled with two types of isotopes with relatively small difference in masses or binding force constants. In this case, relatively broad transmission antiresonance is accompanied by the narrow transmission peak close to the antiresonance frequency. We describe the softening of the flexural surface acoustic wave, localized at the embedded defect nanolayer, caused by negative surface stress in the layer. The surface wave softening results in spatially periodic static bending deformation of the embedded nanolayer with the definite wave number. The latter effect is estimated for graphene monolayer embedded in a strained matrix of polyethylene. We analyze the effect of nonlinearity in the dynamics of defect atoms on the one- and two-path phonon interference and show that the interference transmission resonances and antiresonances are shifted in frequencies but not completely suppressed by rather strong anharmonicity of interatomic bonds. The reduction of the Kapitza thermal interface conductance caused by the destructive phonon interference in a defect monolayer is described. We show that the additional relatively weak non-nearest-neighbor interactions through the defect crystal plane filled with heavy isotopes substantially reduces the interface thermal conductance, and this effect is stronger in the three-dimensional system than in the quasi-one-dimensional systems studied previously.

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

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

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

Conversion of deuterium gas to heavy water by catalytic isotopic exchange using wetproof catalyst

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

Quaiattini, R.J.; McGauley, M.P.; Burns, D.L.

The invention at Chalk River Nuclear Laboratories of a simple method of wetproofing platinum catalysts allows them to retain their activity in liquid water. High performance catalysts for the hydrogen-water isotope exchange reaction that remain active for years can now be routinely produced. The first commercial application using the ordered-bed-type wetproofed isotope exchange catalyst developed and patented by Atomic Energy of Canada Ltd. has been successfully completed. Approximately 9100 m/sup 3/ of deuterium gas stored at Brookhaven National Laboratory was converted to high grade heavy water. Conversion efficiency exceeded 99.8%. The product D/sub 2/O concentration was 6.7 percentage points highermore » than the feed D/sub 2/ gas.« less

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.

Development of procedure for measurement of Pb isotope ratios in seawater by application of seaFAST sample pre-treatment system and Sector Field Inductively Coupled Plasma Mass Spectrometry

NASA Astrophysics Data System (ADS)

Vassileva, Emilia; Wysocka, Irena

2016-12-01

Anthropogenic Pb in the oceans, derived from high-temperature industrial processes, fuel combustion and incineration can have an isotopic signature distinct from naturally occurring Pb, supplied by rock weathering. To identify the different pollution sources accurately and to quantify their relative contributions, Pb isotope ratios are widely used. Due to the high salt content (approximately 3.5% of total dissolved solids) and very low levels of Pb (typically from 1 to 100 ng L- 1) in seawater the determination of Pb isotope ratios requires preliminary matrix separation and analyte preconcentration. An analytical protocol for the measurements of Pb isotope ratios in seawater combining seaFAST sample pre-treatment system and Sector Field Inductively Coupled Plasma Mass Spectrometry (SF ICP-MS) was developed. The application of seaFAST system was advantageous, because of its completely closed working cycle and small volumes of chemicals introduced in pre-treatment step, resulting in very low detection limits and procedural blanks. The preconcentration/matrix separation step was also of crucial importance for minimizing the isobaric and matrix interferences, coming from the seawater. In order to differentiate between anthropogenic and natural Pb sources, particular attention was paid to the determination of 204Pb isotope because of its implication in some geological interpretations. The validation of the analytical procedure was effectuated according to the recommendations of the ISO/IEC 17025 standard. The method was validated by processing the common Pb isotope reference material NIST SRM 981. All major sources of uncertainty were identified and propagated together following the ISO/GUM guidelines. The estimation of the total uncertainty associated to each measurement result was fundamental tool for sorting the main sources of possible biases. The developed analytical procedure was applied to the coastal and open seawater samples, collected in different regions of the world and revealed that the procedure is applicable for the measurement of Pb isotope ratios in seawater with combined uncertainty adequate to discuss the origin of Pb pollution in the ocean.

Theory of long-range interactions for Rydberg states attached to hyperfine-split cores

NASA Astrophysics Data System (ADS)

Robicheaux, F.; Booth, D. W.; Saffman, M.

2018-02-01

The theory is developed for one- and two-atom interactions when the atom has a Rydberg electron attached to a hyperfine-split core state. This situation is relevant for some of the rare-earth and alkaline-earth atoms that have been proposed for experiments on Rydberg-Rydberg interactions. For the rare-earth atoms, the core electrons can have a very substantial total angular momentum J and a nonzero nuclear spin I . In the alkaline-earth atoms there is a single (s ) core electron whose spin can couple to a nonzero nuclear spin for odd isotopes. The resulting hyperfine splitting of the core state can lead to substantial mixing between the Rydberg series attached to different thresholds. Compared to the unperturbed Rydberg series of the alkali-metal atoms, the series perturbations and near degeneracies from the different parity states could lead to qualitatively different behavior for single-atom Rydberg properties (polarizability, Zeeman mixing and splitting, etc.) as well as Rydberg-Rydberg interactions (C5 and C6 matrices).

Algorithm for quantum-mechanical finite-nuclear-mass variational calculations of atoms with two p electrons using all-electron explicitly correlated Gaussian basis functions

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

Sharkey, Keeper L.; Pavanello, Michele; Bubin, Sergiy

2009-12-15

A new algorithm for calculating the Hamiltonian matrix elements with all-electron explicitly correlated Gaussian functions for quantum-mechanical calculations of atoms with two p electrons or a single d electron have been derived and implemented. The Hamiltonian used in the approach was obtained by rigorously separating the center-of-mass motion and it explicitly depends on the finite mass of the nucleus. The approach was employed to perform test calculations on the isotopes of the carbon atom in their ground electronic states and to determine the finite-nuclear-mass corrections for these states.

The nuclear size and mass effects on muonic hydrogen-like atoms embedded in Debye plasma

NASA Astrophysics Data System (ADS)

Poszwa, A.; Bahar, M. K.; Soylu, A.

2016-10-01

Effects of finite nuclear size and finite nuclear mass are investigated for muonic atoms and muonic ions embedded in the Debye plasma. Both nuclear charge radii and nuclear masses are taken into account with experimentally determined values. In particular, isotope shifts of bound state energies, radial probability densities, transition energies, and binding energies for several atoms are studied as functions of Debye length. The theoretical model based on semianalytical calculations, the Sturmian expansion method, and the perturbative approach has been constructed, in the nonrelativistic frame. For some limiting cases, the comparison with previous most accurate literature results has been made.

Diffraction pattern simulation of cellulose fibrils using distributed and quantized pair distances

DOE PAGES

Zhang, Yan; Inouye, Hideyo; Crowley, Michael; ...

2016-10-14

Intensity simulation of X-ray scattering from large twisted cellulose molecular fibrils is important in understanding the impact of chemical or physical treatments on structural properties such as twisting or coiling. This paper describes a highly efficient method for the simulation of X-ray diffraction patterns from complex fibrils using atom-type-specific pair-distance quantization. Pair distances are sorted into arrays which are labelled by atom type. Histograms of pair distances in each array are computed and binned and the resulting population distributions are used to represent the whole pair-distance data set. These quantized pair-distance arrays are used with a modified and vectorized Debyemore » formula to simulate diffraction patterns. This approach utilizes fewer pair distances in each iteration, and atomic scattering factors are moved outside the iteration since the arrays are labelled by atom type. As a result, this algorithm significantly reduces the computation time while maintaining the accuracy of diffraction pattern simulation, making possible the simulation of diffraction patterns from large twisted fibrils in a relatively short period of time, as is required for model testing and refinement.« less

Diffraction pattern simulation of cellulose fibrils using distributed and quantized pair distances

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

Zhang, Yan; Inouye, Hideyo; Crowley, Michael

Intensity simulation of X-ray scattering from large twisted cellulose molecular fibrils is important in understanding the impact of chemical or physical treatments on structural properties such as twisting or coiling. This paper describes a highly efficient method for the simulation of X-ray diffraction patterns from complex fibrils using atom-type-specific pair-distance quantization. Pair distances are sorted into arrays which are labelled by atom type. Histograms of pair distances in each array are computed and binned and the resulting population distributions are used to represent the whole pair-distance data set. These quantized pair-distance arrays are used with a modified and vectorized Debyemore » formula to simulate diffraction patterns. This approach utilizes fewer pair distances in each iteration, and atomic scattering factors are moved outside the iteration since the arrays are labelled by atom type. This algorithm significantly reduces the computation time while maintaining the accuracy of diffraction pattern simulation, making possible the simulation of diffraction patterns from large twisted fibrils in a relatively short period of time, as is required for model testing and refinement.« less

Diffraction pattern simulation of cellulose fibrils using distributed and quantized pair distances

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

Zhang, Yan; Inouye, Hideyo; Crowley, Michael

Intensity simulation of X-ray scattering from large twisted cellulose molecular fibrils is important in understanding the impact of chemical or physical treatments on structural properties such as twisting or coiling. This paper describes a highly efficient method for the simulation of X-ray diffraction patterns from complex fibrils using atom-type-specific pair-distance quantization. Pair distances are sorted into arrays which are labelled by atom type. Histograms of pair distances in each array are computed and binned and the resulting population distributions are used to represent the whole pair-distance data set. These quantized pair-distance arrays are used with a modified and vectorized Debyemore » formula to simulate diffraction patterns. This approach utilizes fewer pair distances in each iteration, and atomic scattering factors are moved outside the iteration since the arrays are labelled by atom type. As a result, this algorithm significantly reduces the computation time while maintaining the accuracy of diffraction pattern simulation, making possible the simulation of diffraction patterns from large twisted fibrils in a relatively short period of time, as is required for model testing and refinement.« less

A Distinct Magnetic Isotope Effect Measured in Atmospheric Mercury in Epiphytes

NASA Astrophysics Data System (ADS)

Ghosh, S.; Odom, A. L.

2007-12-01

Due to the importance of Mercury as an environmental contaminant, mercury cycling in the atmosphere has been extensively studied. However, there still remain uncertainties in the relative amounts of natural and anthropogenic emissions, atmospheric deposition rates as well as the spatial variation of atmospheric mercury. Part of a study to determine the isotopic composition of mercury deposited from the atmosphere has involved the use of epiphytes as monitors. The greatest advantage of such natural monitors is that a widespread, high-density network is possible at low cost. One of the disadvantages at present is that these monitors likely contain different mercury species (for example both gaseous, elemental mercury trapped by adsorption and Hg (II) by wet deposition). The project began with the understanding that biochemical reactions involving metallothioneins within the epiphytes might have produced an isotopic effect. One such regional network was composed of samples of Tillandsia usenoides (common name: Spanish moss) collected along the eastern Coastal Plain of the U.S. from northern Florida to North Carolina. The isotopic composition of a sample is expressed as permil deviations from a standard. The deviations are defined as δAHg = \\left(\\frac{Rsample}{Rstd}-1 \\right)1000 ‰ , where A represents the atomic mass number. R=\\frac{AHg}{202Hg} were measured for the isotopes 198Hg, 199Hg, 200Hg, 201Hg, 202Hg and 204Hg relative to the mercury standard SRM NIST 3133, by a standard-sample bracketing technique. For all samples, the delta values of the even-N plotted against atomic mass numbers define a linear curve. For the odd-N isotopes, δ199Hg and δ201Hg deviate from this mass-dependent fractionation (MDF) relationship and indicate a mass-independent fractionation (MIF) effect and a negative anomaly, i.e. a depletion in 199Hg and 201Hg relative to the even-N isotopes. These deviations are expressed as Δ199Hg = δ199Hgtotal - δ199HgMDF. A Δ201Hg/Δ199Hg ratio of 1.11 is predicted by isotope fractionation due to the Magnetic Isotope Effect (MIE), because 1.11 is the ratio of the magnetic moments of the two odd-N isotopes. A plot of Δ199Hg versus Δ201Hg values obtained reveals a striking pattern. All samples plot well within analytical uncertainly along a straight line passing through zero and having a slope of 1.11. Based on thermodynamic principles, some have argued that nuclear spin effects are quite insignificant in producing isotopic fractionation. However the MIE is a kinetic one in which those isotopes with non-zero magnetic moments effect the rates of recombination of free radical pairs by nuclear-electron hyperfine interaction and can become enriched or depleted in either reactants or products. In the samples studied here, the nuclear spin is far more important than either nuclear mass or nuclear volume in effecting isotopic fractionation of Mercury.

Method and apparatus for transmutation of atomic nuclei

DOEpatents

Maenchen, John Eric; Ruiz, Carlos Leon

1998-01-01

Insuring a constant supply of radioisotopes is of great importance to medicine and industry. This invention addresses this problem, and helps to solve it by introducing a new apparatus for transmutation of isotopes which enables swift and flexible production on demand.

Abiologic silicon isotope fractionation between aqueous Si and Fe(III)-Si gel in simulated Archean seawater: Implications for Si isotope records in Precambrian sedimentary rocks

NASA Astrophysics Data System (ADS)

Zheng, Xin-Yuan; Beard, Brian L.; Reddy, Thiruchelvi R.; Roden, Eric E.; Johnson, Clark M.

2016-08-01

Precambrian Si-rich sedimentary rocks, including cherts and banded iron formations (BIFs), record a >7‰ spread in 30Si/28Si ratios (δ30Si values), yet interpretation of this large variability has been hindered by the paucity of data on Si isotope exchange kinetics and equilibrium fractionation factors in systems that are pertinent to Precambrian marine conditions. Using the three-isotope method and an enriched 29Si tracer, a series of experiments were conducted to constrain Si isotope exchange kinetics and fractionation factors between amorphous Fe(III)-Si gel, a likely precursor to Precambrian jaspers and BIFs, and aqueous Si in artificial Archean seawater under anoxic conditions. Experiments were conducted at room temperature, and in the presence and absence of aqueous Fe(II) (Fe(II)aq). Results of this study demonstrate that Si solubility is significantly lower for Fe-Si gel than that of amorphous Si, indicating that seawater Si concentrations in the Precambrian may have been lower than previous estimates. The experiments reached ∼70-90% Si isotope exchange after a period of 53-126 days, and the highest extents of exchange were obtained where Fe(II)aq was present, suggesting that Fe(II)-Fe(III) electron-transfer and atom-exchange reactions catalyze Si isotope exchange through breakage of Fe-Si bonds. All experiments except one showed little change in the instantaneous solid-aqueous Si isotope fractionation factor with time, allowing extraction of equilibrium Si isotope fractionation factors through extrapolation to 100% isotope exchange. The equilibrium 30Si/28Si fractionation between Fe(III)-Si gel and aqueous Si (Δ30Sigel-aqueous) is -2.30 ± 0.25‰ (2σ) in the absence of Fe(II)aq. In the case where Fe(II)aq was present, which resulted in addition of ∼10% Fe(II) in the final solid, creating a mixed Fe(II)-Fe(III) Si gel, the equilibrium fractionation between Fe(II)-Fe(III)-Si gel and aqueous Si (Δ30Sigel-aqueous) is -3.23 ± 0.37‰ (2σ). Equilibrium Si isotope fractionation for Fe-Si gel systems is significantly larger in magnitude than estimates of a near-zero solid-aqueous fractionation factor between pure Si gel and aqueous Si, indicating a major influence of Fe atoms on Si-O bonds, and hence the isotopic properties, of Fe-Si gel. Larger Si isotope fractionation in the Fe(II)-bearing systems may be caused by incorporation of Fe(II) into the solid structure, which may further weaken Fe-Si bonds and thus change the Si isotope fractionation factor. The relatively large Si isotope fractionation for Fe-Si gel, relative to pure Si gel, provides a new explanation for the observed contrast in δ30Si values in the Precambrian BIFs and cherts, as well as an explanation for the relatively negative δ30Si values in BIFs, in contrast to previous proposals that the more negative δ30Si values in BIFs reflect hydrothermal sources of Si or sorption to Fe oxides/hydroxides.

Advances in the Metrology of Absolute Value Assignments to Isotopic Reference Materials: Consequences from the Avogadro Project

NASA Astrophysics Data System (ADS)

Vocke, Robert; Rabb, Savelas

2015-04-01

All isotope amount ratios (hereafter referred to as isotope ratios) produced and measured on any mass spectrometer are biased. This unfortunate situation results mainly from the physical processes in the source area where ions are produced. Because the ionized atoms in poly-isotopic elements have different masses, such processes are typically mass dependent and lead to what is commonly referred to as mass fractionation (for thermal ionization and electron impact sources) and mass bias (for inductively coupled plasma sources.) This biasing process produces a measured isotope ratio that is either larger or smaller than the "true" ratio in the sample. This has led to the development of numerous fractionation "laws" that seek to correct for these effects, many of which are not based on the physical processes giving rise to the biases. The search for tighter and reproducible precisions has led to two isotope ratio measurement systems that exist side-by-side. One still seeks to measure "absolute" isotope ratios while the other utilizes an artifact based measurement system called a delta-scale. The common element between these two measurement systems is the utilization of isotope reference materials (iRMs). These iRMs are used to validate a fractionation "law" in the former case and function as a scale anchor in the latter. Many value assignments of iRMs are based on "best measurements" by the original groups producing the reference material, a not entirely satisfactory approach. Other iRMs, with absolute isotope ratio values, have been produced by calibrated measurements following the Atomic Weight approach (AW) pioneered by NBS nearly 50 years ago. Unfortunately, the AW is not capable of calibrating the new generation of iRMs to sufficient precision. So how do we get iRMs with isotope ratios of sufficient precision and without bias? Such a focus is not to denigrate the extremely precise delta-scale measurements presently being made on non-traditional and tradition stable isotope systems. But even absolute isotope ratio measurements have an important role to play in delta-scale schemes. Highly precise and unbiased measurements of the artifact anchor for any scale facilitates the replacement of that scale's anchor once the initial supply of the iRM is exhausted. Absolute isotope ratio measurements of artifacts at the positive and negative extremes of a delta-scale will allow the appropriate assignment of delta-values to these normalizing iRMs, thereby minimizing any scale contractions or expansions to either side of the anchor artifact. And finally, absolute values for critical iRMs with also allow delta-scale results to be used in other scientific disciplines that employ other units of measure. Precise absolute isotope ratios of Si has been one of the consequences of the Avogadro Project (an international effort to replace the original kilogram artifact with a natural constant, the Planck constant.) We will present the results of applying such measurements to the principal iRMs for the Si isotope system (SRM 990, Big Batch and Diatomite) and its consequences for their delta-Si29 and delta-Si30 values.

Assessment of Non-Traditional Isotopic Ratios by Mass Spectrometry for Analysis of Nuclear Activities

DTIC Science & Technology

2016-03-01

Assessment of Non-traditional Isotopic Ratios by Mass Spectrometry for Analysis of Nuclear Activities Distribution Statement A. Approved for pubic...cubic meter (m 3 ) cubic foot (ft 3 ) 2.831 685 × 10 –2 cubic meter (m 3 ) Mass /Density pound (lb) 4.535 924 × 10 –1 kilogram (kg) unified...atomic mass unit (amu) 1.660 539 × 10 –27 kilogram (kg) pound- mass per cubic foot (lb ft –3 ) 1.601 846 × 10 1 kilogram per cubic meter (kg m –3

Structural requirements and reaction pathways in dimethyl ether combustion catalyzed by supported Pt clusters.

PubMed

Ishikawa, Akio; Neurock, Matthew; Iglesia, Enrique

2007-10-31

The identity and reversibility of the elementary steps required for catalytic combustion of dimethyl ether (DME) on Pt clusters were determined by combining isotopic and kinetic analyses with density functional theory estimates of reaction energies and activation barriers to probe the lowest energy paths. Reaction rates are limited by C-H bond activation in DME molecules adsorbed on surfaces of Pt clusters containing chemisorbed oxygen atoms at near-saturation coverages. Reaction energies and activation barriers for C-H bond activation in DME to form methoxymethyl and hydroxyl surface intermediates show that this step is more favorable than the activation of C-O bonds to form two methoxides, consistent with measured rates and kinetic isotope effects. This kinetic preference is driven by the greater stability of the CH3OCH2* and OH* intermediates relative to chemisorbed methoxides. Experimental activation barriers on Pt clusters agree with density functional theory (DFT)-derived barriers on oxygen-covered Pt(111). Measured DME turnover rates increased with increasing DME pressure, but decreased as the O2 pressure increased, because vacancies (*) on Pt surfaces nearly saturated with chemisorbed oxygen are required for DME chemisorption. DFT calculations show that although these surface vacancies are required, higher oxygen coverages lead to lower C-H activation barriers, because the basicity of oxygen adatoms increases with coverage and they become more effective in hydrogen abstraction from DME. Water inhibits reaction rates via quasi-equilibrated adsorption on vacancy sites, consistent with DFT results indicating that water binds more strongly than DME on vacancies. These conclusions are consistent with the measured kinetic response of combustion rates to DME, O2, and H2O, with H/D kinetic isotope effects, and with the absence of isotopic scrambling in reactants containing isotopic mixtures of 18O2-16O2 or 12CH3O12CH3-13CH3O13CH3. Turnover rates increased with Pt cluster size, because small clusters, with more coordinatively unsaturated surface atoms, bind oxygen atoms more strongly than larger clusters and exhibit lower steady-state vacancy concentrations and a consequently smaller number of adsorbed DME intermediates involved in kinetically relevant steps. These effects of cluster size and metal-oxygen bond energies on reactivity are ubiquitous in oxidation reactions requiring vacancies on surfaces nearly saturated with intermediates derived from O2.

Organic nitrogen chemistry during low-grade metamorphism

USGS Publications Warehouse

Boudou, J.-P.; Schimmelmann, A.; Ader, M.; Mastalerz, Maria; Sebilo, M.; Gengembre, L.

2008-01-01

Most of the organic nitrogen (Norg) on Earth is disseminated in crustal sediments and rocks in the form of fossil nitrogen-containing organic matter. The chemical speciation of fossil Norg within the overall molecular structure of organic matter changes with time and heating during burial. Progressive thermal evolution of organic matter involves phases of enhanced elimination of Norg and ultimately produces graphite containing only traces of nitrogen. Long-term chemical and thermal instability makes the chemical speciation of Norg a valuable tracer to constrain the history of sub-surface metamorphism and to shed light on the subsurface biogeochemical nitrogen cycle and its participating organic and inorganic nitrogen pools. This study documents the evolutionary path of Norg speciation, transformation and elimination before and during metamorphism and advocates the use of X-ray photoelectron spectroscopy (XPS) to monitor changes in Norg speciation as a diagnostic tool for organic metamorphism. Our multidisciplinary evidence from XPS, stable isotopes, traditional quantitative coal analyses, and other analytical approaches shows that at the metamorphic onset Norg is dominantly present as pyrrolic and pyridinic nitrogen. The relative abundance of nitrogen substituting for carbon in condensed, partially aromatic systems (where N is covalently bonded to three C atoms) increases exponentially with increasing metamorphic grade, at the expense of pyridinic and pyrrolic nitrogen. At the same time, much Norg is eliminated without significant nitrogen isotope fractionation. The apparent absence of Rayleigh-type nitrogen isotopic fractionation suggests that direct thermal loss of nitrogen from an organic matrix does not serve as a major pathway for Norg elimination. Instead, we propose that hot H, O-containing fluids or some of their components gradually penetrate into the carbonaceous matrix and eliminate Norg along a progressing reaction front, without causing nitrogen isotope fractionation in the residual Norg in the unreacted core of the carbonaceous matrix. Before the reaction front can reach the core, an increasing part of core Norg chemically stabilizes in the form of nitrogen atoms substituting for carbon in condensed, partially aromatic systems forming graphite-like structural domains with delocalized ??-electron systems (nitrogen atoms substituting for "graphitic" carbon in natural metamorphic organic matter). Thus, this nitrogen species with a conservative isotopic composition is the dominant form of residual nitrogen at higher metamorphic grade. ?? 2007 Elsevier Ltd. All rights reserved.

Non-Evaporative Cooling via Inelastic Collisions in an Optical Trap

DTIC Science & Technology

2013-02-28

Simultaneous loading of 85 Rb and 87 Rb into an optical trap from a Magneto - optic Trap (MOT) As was mentioned in the previous section, when both...potential in an 85 Rb magneto - optical trap , Phys. Rev. A 83, 033419 (2011) I.D Ultracold plasma response to few-cycle rf pulses As will be detailed in...ultracold atoms of each isotope were cooled into overlapping Magneto - optic Traps (MOTs). From there, the atoms were then loaded into a Far-off

A new form of strange matter and new hope for finding it

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

Flam, F.

Deep in the dense cores of collapsed stars even atoms don't survive. The force of gravity crushes them into particle mushes weighing megatons per teaspoon. But even these alien forms of matter don't hold a candle to another possible end product of a collapsing star: something physicists justifiably call strange matter. This strangeness comes from an exotic particle not associated with ordinary matter: the strange quark. It belongs to a six-member quark family, along with up, down, charm, top, and bottom, each of which carries a different combination of charge and mass. The only ones that make up matter asmore » we know it are up and down quarks, but in theory, matter could form out of strange quarks as well. In nature, it would turn up most probably in interiors of collapsed stars. Scientists originally imagined strange matter as a sort of disorganized mixed bag of strange quarks, but this summer a group proposed that the quarks could form a sort of mutant atomic nucleus that could conceivably grow to the size of a star. For the moment this is speculation, but it may not be theoretical musing for long. Physicists are preparing to try making strange matter here on Earth, in experiments at Brookhaven National Laboratory in New York and Switzerland's CERN, next summer.« less

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

Charge radii of neutron deficient Fe 52 , 53 produced by projectile fragmentation

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

Minamisono, K.; Rossi, D. M.; Beerwerth, R.

Bunched-beam collinear laser spectroscopy is performed on neutron deficient 52,53Fe prepared through in-flight separation followed by a gas stopping. This novel scheme is a major step to reach nuclides far from the stability line in laser spectroscopy. Differential mean-square charge radii δmore » $$\\langle$$r 2$$\\rangle$$ of 52,53Fe are determined relative to stable 56Fe as δ$$\\langle$$r2$$\\rangle$$ 56,52=$-$0.034(13) fm 2 and δ$$\\langle$$r 2$$\\rangle$$56,53=$-$0.218(13) fm 2, respectively, from the isotope shift of atomic hyperfine structures. The multiconfiguration Dirac-Fock method is used to calculate atomic factors to deduce δ$$\\langle$$r 2$$\\rangle$$. The values of δ$$\\langle$$r 2$$\\rangle$$ exhibit a minimum at the N=28 neutron shell closure. The nuclear density functional theory with Fayans and Skyrme energy density functionals is used to interpret the data. As a result, the trend of δ$$\\langle$$r 2$$\\rangle$$ along the Fe isotopic chain results from an interplay between single-particle shell structure, pairing, and polarization effects and provides important data for understanding the intricate trend in the δ$$\\langle$$r 2$$\\rangle$$ of closed-shell Ca isotopes« less

Quantum tunneling observed without its characteristic large kinetic isotope effects.

PubMed

Hama, Tetsuya; Ueta, Hirokazu; Kouchi, Akira; Watanabe, Naoki

2015-06-16

Classical transition-state theory is fundamental to describing chemical kinetics; however, quantum tunneling is also important in explaining the unexpectedly large reaction efficiencies observed in many chemical systems. Tunneling is often indicated by anomalously large kinetic isotope effects (KIEs), because a particle's ability to tunnel decreases significantly with its increasing mass. Here we experimentally demonstrate that cold hydrogen (H) and deuterium (D) atoms can add to solid benzene by tunneling; however, the observed H/D KIE was very small (1-1.5) despite the large intrinsic H/D KIE of tunneling (≳ 100). This strong reduction is due to the chemical kinetics being controlled not by tunneling but by the surface diffusion of the H/D atoms, a process not greatly affected by the isotope type. Because tunneling need not be accompanied by a large KIE in surface and interfacial chemical systems, it might be overlooked in other systems such as aerosols or enzymes. Our results suggest that surface tunneling reactions on interstellar dust may contribute to the deuteration of interstellar aromatic and aliphatic hydrocarbons, which could represent a major source of the deuterium enrichment observed in carbonaceous meteorites and interplanetary dust particles. These findings could improve our understanding of interstellar physicochemical processes, including those during the formation of the solar system.

Quantum tunneling observed without its characteristic large kinetic isotope effects

PubMed Central

Hama, Tetsuya; Ueta, Hirokazu; Kouchi, Akira; Watanabe, Naoki

2015-01-01

Classical transition-state theory is fundamental to describing chemical kinetics; however, quantum tunneling is also important in explaining the unexpectedly large reaction efficiencies observed in many chemical systems. Tunneling is often indicated by anomalously large kinetic isotope effects (KIEs), because a particle’s ability to tunnel decreases significantly with its increasing mass. Here we experimentally demonstrate that cold hydrogen (H) and deuterium (D) atoms can add to solid benzene by tunneling; however, the observed H/D KIE was very small (1–1.5) despite the large intrinsic H/D KIE of tunneling (≳100). This strong reduction is due to the chemical kinetics being controlled not by tunneling but by the surface diffusion of the H/D atoms, a process not greatly affected by the isotope type. Because tunneling need not be accompanied by a large KIE in surface and interfacial chemical systems, it might be overlooked in other systems such as aerosols or enzymes. Our results suggest that surface tunneling reactions on interstellar dust may contribute to the deuteration of interstellar aromatic and aliphatic hydrocarbons, which could represent a major source of the deuterium enrichment observed in carbonaceous meteorites and interplanetary dust particles. These findings could improve our understanding of interstellar physicochemical processes, including those during the formation of the solar system. PMID:26034285

Charge radii of neutron deficient Fe 52 , 53 produced by projectile fragmentation

DOE PAGES

Minamisono, K.; Rossi, D. M.; Beerwerth, R.; ...

2016-12-15

Bunched-beam collinear laser spectroscopy is performed on neutron deficient 52,53Fe prepared through in-flight separation followed by a gas stopping. This novel scheme is a major step to reach nuclides far from the stability line in laser spectroscopy. Differential mean-square charge radii δmore » $$\\langle$$r 2$$\\rangle$$ of 52,53Fe are determined relative to stable 56Fe as δ$$\\langle$$r2$$\\rangle$$ 56,52=$-$0.034(13) fm 2 and δ$$\\langle$$r 2$$\\rangle$$56,53=$-$0.218(13) fm 2, respectively, from the isotope shift of atomic hyperfine structures. The multiconfiguration Dirac-Fock method is used to calculate atomic factors to deduce δ$$\\langle$$r 2$$\\rangle$$. The values of δ$$\\langle$$r 2$$\\rangle$$ exhibit a minimum at the N=28 neutron shell closure. The nuclear density functional theory with Fayans and Skyrme energy density functionals is used to interpret the data. As a result, the trend of δ$$\\langle$$r 2$$\\rangle$$ along the Fe isotopic chain results from an interplay between single-particle shell structure, pairing, and polarization effects and provides important data for understanding the intricate trend in the δ$$\\langle$$r 2$$\\rangle$$ of closed-shell Ca isotopes« less

Theoretical description of quantum mechanical permeation of graphene membranes by charged hydrogen isotopes

NASA Astrophysics Data System (ADS)

Mazzuca, James W.; Haut, Nathaniel K.

2018-06-01

It has been recently shown that in the presence of an applied voltage, hydrogen and deuterium nuclei can be separated from one another using graphene membranes as a nuclear sieve, resulting in a 10-fold enhancement in the concentration of the lighter isotope. While previous studies, both experimental and theoretical, have attributed this effect mostly to differences in vibrational zero point energy (ZPE) of the various isotopes near the membrane surface, we propose that multi-dimensional quantum mechanical tunneling of nuclei through the graphene membrane influences this proton permeation process in a fundamental way. We perform ring polymer molecular dynamics calculations in which we include both ZPE and tunneling effects of various hydrogen isotopes as they permeate the graphene membrane and compute rate constants across a range of temperatures near 300 K. While capturing the experimentally observed separation factor, our calculations indicate that the transverse motion of the various isotopes across the surface of the graphene membrane is an essential part of this sieving mechanism. An understanding of the multi-dimensional quantum mechanical nature of this process could serve to guide the design of other such isotopic enrichment processes for a variety of atomic and molecular species of interest.

Theoretical description of quantum mechanical permeation of graphene membranes by charged hydrogen isotopes.

PubMed

Mazzuca, James W; Haut, Nathaniel K

2018-06-14

It has been recently shown that in the presence of an applied voltage, hydrogen and deuterium nuclei can be separated from one another using graphene membranes as a nuclear sieve, resulting in a 10-fold enhancement in the concentration of the lighter isotope. While previous studies, both experimental and theoretical, have attributed this effect mostly to differences in vibrational zero point energy (ZPE) of the various isotopes near the membrane surface, we propose that multi-dimensional quantum mechanical tunneling of nuclei through the graphene membrane influences this proton permeation process in a fundamental way. We perform ring polymer molecular dynamics calculations in which we include both ZPE and tunneling effects of various hydrogen isotopes as they permeate the graphene membrane and compute rate constants across a range of temperatures near 300 K. While capturing the experimentally observed separation factor, our calculations indicate that the transverse motion of the various isotopes across the surface of the graphene membrane is an essential part of this sieving mechanism. An understanding of the multi-dimensional quantum mechanical nature of this process could serve to guide the design of other such isotopic enrichment processes for a variety of atomic and molecular species of interest.

Method and apparatus for transmutation of atomic nuclei

DOEpatents

Maenchen, J.E.; Ruiz, C.L.

1998-12-08

Insuring a constant supply of radioisotopes is of great importance to medicine and industry. This invention addresses this problem, and helps to solve it by introducing a new apparatus for transmutation of isotopes which enables swift and flexible production on demand. 9 figs.

Method and apparatus for transmutation of atomic nuclei

DOEpatents

Maenchen, J.E.; Ruiz, C.L.

1998-06-09

Insuring a constant supply of radioisotopes is of great importance to medicine and industry. This invention addresses this problem, and helps to solve it by introducing a new apparatus for transmutation of isotopes which enables swift and flexible production on demand. 9 figs.

Radioisotope Dating with Accelerators.

ERIC Educational Resources Information Center

Muller, Richard A.

1979-01-01

Explains a new method of detecting radioactive isotopes by counting their accelerated ions rather than the atoms that decay during the counting period. This method increases the sensitivity by several orders of magnitude, and allows one to find the ages of much older and smaller samples. (GA)

Hydrogen and oxygen in brine shrimp chitin reflect environmental water and dietary isotopic composition

NASA Astrophysics Data System (ADS)

Nielson, Kristine E.; Bowen, Gabriel J.

2010-03-01

Hydrogen and oxygen isotope ratios of the common structural biopolymer chitin are a potential recorder of ecological and environmental information, but our understanding of the mechanisms of incorporation of H and O from environmental substrates into chitin is limited. We report the results of a set of experiments in which the isotopic compositions of environmental water and diet were varied independently in order to assess the contribution of these variables to the H and O isotopic composition of Artemia franciscana chitin. Hydrogen isotope ratios of chitin were strongly linearly correlated with both food and water, with approximately 26% of the hydrogen signal reflecting food and approximately 38% reflecting water. Oxygen isotopes were also strongly correlated with the isotopic composition of water and food, but whereas 69% of oxygen in chitin exchanged with environmental water, only 10% was derived from food. We propose that these observations reflect the position-specific, partial exchange of H and O atoms with brine shrimp body water during the processes of digestion and chitin biosynthesis. Comparison of culture experiments with a set of natural samples collected from the Great Salt Lake, UT in 2006 shows that, with some exceptions, oxygen isotope compositions of chitin track those of water, whereas hydrogen isotopes vary inversely with those of lake water. The different behavior of the two isotopic systems can be explained in terms of a dietary shift from allochthonous particulate matter with relatively higher δ 2H values in the early spring to autochthonous particulate matter with significantly lower δ 2H values in the late summer to autumn. These results suggest oxygen in chitin may be a valuable proxy for the oxygen isotopic composition of environmental water, whereas hydrogen isotope values from the same molecule may reveal ecological and biogeochemical changes within lakes.

The isotope mass effect on chlorine diffusion in dacite melt, with implications for fractionation during bubble growth

NASA Astrophysics Data System (ADS)

Fortin, Marc-Antoine; Watson, E. Bruce; Stern, Richard

2017-12-01

Previous experimental studies have revealed that the difference in diffusivity of two isotopes can be significant in some media and can lead to an observable fractionation effect in silicate melts based on isotope mass. Here, we report the first characterization of the difference in diffusivities of stable isotopes of Cl (35Cl and 37Cl). Using a piston-cylinder apparatus, we generated quenched melts of dacitic composition enriched in Cl; from these we fabricated diffusion couples in which Cl atoms were induced to diffuse in a chemical gradient at 1200 to 1350 °C and 1 GPa. We analyzed the run products by secondary ion mass spectrometry (SIMS) for their isotopic compositions along the diffusion profiles, and we report a diffusivity ratio for 37Cl/35Cl of 0.995 ± 0.001 (β = 0.09 ± 0.02). No significant effect of temperature on the diffusivity ratio was discernable over the 150 °C range covered by our experiments. The observed 0.5% difference in diffusivity of the two isotopes could affect our interpretation of isotopic measurements of Cl isotopes in bubble-bearing or degassed magmas, because bubble growth is regulated in part by the diffusive supply of volatiles to the bubble from the surrounding melt. Through numerical simulations, we constrain the extent of Cl isotopic fractionation between bubble and host melt during this process. Bubble growth rates vary widely in nature-which implies a substantial range in the expected magnitude of isotopic fractionation-but plausible growth scenarios lead to Cl isotopic fractionations up to about 5‰ enrichment of 35Cl relative to 37Cl in the bubble. This effect should be considered when interpreting Cl isotopic measurements of systems that have experienced vapor exsolution.

Annual Report to Congress of the Atomic Energy Commission for 1969

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

Seaborg, Glenn T.

1970-01-31

The document represents the 1969 Annual Report of the Atomic Energy Commission (AEC) to Congress. The report opens with ''An Introduction to the Atomic Energy Programs during 1969'' followed by 17 Chapters, 8 appendices and an index. Chapters are as follows: (1) Source, Special, and Byproduct Nuclear Materials; (2) Nuclear Materials Safeguards; (3) The Nuclear Defense Effort; (4) Naval Propulsion Reactors; (5) Reactor Development and Technology; (6) Licensing and Regulating the Atom; (7) Operational and Public Safety; (8) Space Nuclear Propulsion; (9) Specialized Nuclear Power; (10) Isotopic Radiation Applications; (11) Peaceful Nuclear Explosives; (12) International Affairs and Cooperation; (13) Informationalmore » and Related Activities; (14) Nuclear Education and Training; (15) Biomedical and Physical Research; (16) Industrial Participation Aspects; and, (17) Administrative and Management Matters.« less

Annual Report to Congress of the Atomic Energy Commission for 1968

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

Seaborg, Glenn T.

1969-01-31

The document represents the 1968 Annual Report of the Atomic Energy Commission (AEC) to Congress. The report opens with ''An Introduction to the Atomic Energy Programs during 1968'' followed by 17 Chapters, 8 appendices and an index. Chapters are as follows: (1) Source, Special, and Nuclear Byproduct Materials; (2) Nuclear Materials Safeguards; (3) The Nuclear Defense Effort; (4) Naval Propulsion Reactors; (5) Reactor Development and Technology; (6) Licensing and Regulating the Atom; (7) Operational and Public Safety; (8) Nuclear Rocket Propulsion; (9) Specialized Nuclear Power; (10) Isotopic Radiation Applications; (11) Peaceful Nuclear Explosives; (12) International Affairs and Cooperation; (13) Informationalmore » and Related Activities; (14) Nuclear Education and Training; (15) Biomedical and Physical Research; (16) Industrial Participation Aspects; and, (17) Administrative and Management Matters.« less

Isotope analysis of diamond-surface passivation effect of high-temperature H{sub 2}O-grown atomic layer deposition-Al{sub 2}O{sub 3} films

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

Hiraiwa, Atsushi, E-mail: hiraiwa@aoni.waseda.jp, E-mail: qs4a-hriw@asahi-net.or.jp; Saito, Tatsuya; Matsumura, Daisuke

2015-06-07

The Al{sub 2}O{sub 3} film formed using an atomic layer deposition (ALD) method with trimethylaluminum as Al precursor and H{sub 2}O as oxidant at a high temperature (450 °C) effectively passivates the p-type surface conduction (SC) layer specific to a hydrogen-terminated diamond surface, leading to a successful operation of diamond SC field-effect transistors at 400 °C. In order to investigate this excellent passivation effect, we carried out an isotope analysis using D{sub 2}O instead of H{sub 2}O in the ALD and found that the Al{sub 2}O{sub 3} film formed at a conventional temperature (100 °C) incorporates 50 times more CH{sub 3} groups thanmore » the high-temperature film. This CH{sub 3} is supposed to dissociate from the film when heated afterwards at a higher temperature (550 °C) and causes peeling patterns on the H-terminated surface. The high-temperature film is free from this problem and has the largest mass density and dielectric constant among those investigated in this study. The isotope analysis also unveiled a relatively active H-exchange reaction between the diamond H-termination and H{sub 2}O oxidant during the high-temperature ALD, the SC still being kept intact. This dynamic and yet steady H termination is realized by the suppressed oxidation due to the endothermic reaction with H{sub 2}O. Additionally, we not only observed the kinetic isotope effect in the form of reduced growth rate of D{sub 2}O-oxidant ALD but found that the mass density and dielectric constant of D{sub 2}O-grown Al{sub 2}O{sub 3} films are smaller than those of H{sub 2}O-grown films. This is a new type of isotope effect, which is not caused by the presence of isotopes in the films unlike the traditional isotope effects that originate from the presence of isotopes itself. Hence, the high-temperature ALD is very effective in forming Al{sub 2}O{sub 3} films as a passivation and/or gate-insulation layer of high-temperature-operation diamond SC devices, and the knowledge of the aforementioned new isotope effect will be a basis for further enhancing ALD technologies in general.« less

1986-87 atomic mass predictions

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

Haustein, P.E.

A project to perform a comprehensive update of the atomic mass predictions has recently been concluded and will be published shortly in Atomic Data and Nuclear Data Tables. The project evolved from an ongoing comparison between available mass predictions and reports of newly measured masses of isotopes throughout the mass surface. These comparisons have highlighted a variety of features in current mass models which are responsible for predictions that diverge from masses determined experimentally. The need for a comprehensive update of the atomic mass predictions was therefore apparent and the project was organized and began at the last mass conferencemore » (AMCO-VII). Project participants included: Pape and Anthony; Dussel, Caurier and Zuker; Moeller and Nix; Moeller, Myers, Swiatecki and Treiner; Comay, Kelson, and Zidon; Satpathy and Nayak; Tachibana, Uno, Yamada and Yamada; Spanier and Johansson; Jaenecke and Masson; and Wapstra, Audi and Hoekstra. An overview of the new atomic mass predictions may be obtained by written request.« less

The 1986-87 atomic mass predictions

NASA Astrophysics Data System (ADS)

Haustein, P. E.

1987-12-01

A project to perform a comprehensive update of the atomic mass predictions has recently been concluded and will be published shortly in Atomic Data and Nuclear Data Tables. The project evolved from an ongoing comparison between available mass predictions and reports of newly measured masses of isotopes throughout the mass surface. These comparisons have highlighted a variety of features in current mass models which are responsible for predictions that diverge from masses determined experimentally. The need for a comprehensive update of the atomic mass predictions was therefore apparent and the project was organized and began at the last mass conference (AMCO-VII). Project participants included: Pape and Anthony; Dussel, Caurier and Zuker; Möller and Nix; Möller, Myers, Swiatecki and Treiner; Comay, Kelson, and Zidon; Satpathy and Nayak; Tachibana, Uno, Yamada and Yamada; Spanier and Johansson; Jänecke and Masson; and Wapstra, Audi and Hoekstra. An overview of the new atomic mass predictions may be obtained by written request.

Experimental studies of electron impact depopulation of excited states of atoms: applications to laser development for fusion and isotope separation. Final report, 1 January 1977-30 June 1979

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

Lubell, M.S.

1980-06-01

Motivated by the need for measurements of metastable depopulation mechanisms of Ar and Kr in the KrF rare-gas monohalide excimer laser, an ultra-high vacuum triple crossed-beams apparatus has been designed, fabricated, and assembled for the purpose of studying electron scattering from excited states of Ar and Kr atoms. A beam of metastable rare gas atoms, produced by near-resonant charge transfer of rare gas ions with alkali neutral atoms, is crossed by an electron beam and a far-red laser beam along mutually orthogonal axes. A hemispherical electron monochromator-spectrometer pair is used to measure the cross section for electron scattering from themore » 2p/sub 9/ excited state of the rare gas atom. Testing of parts of the assembled apparatus has been completed.« less

2015 Progress Report/July 2016: Iron Oxide Redox Transformation Pathways: The Bulk Electrical Conduction Mechanism

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

Scherer, Michelle M.; Rosso, Kevin M.

Despite decades of research on the reactivity and stable isotope properties of Fe oxides, the ability to describe the redox behavior of Fe oxides in the environment is still quite limited. This is due, in large part, to the analytical and spatial complexities associated with studying microscopic processes at the Fe oxide-water interface. This project had the long-term vision of filling this gap by developing a detailed understanding of the relationship between interfacial ET processes, surface structure and charge, and mineral semiconducting properties. We focused on the Fe(III)-oxides and oxyhydroxides because of their geochemical preponderance, versatility in synthesis of compositionally,more » structurally, and morphologically tailored phases, and because they are amenable to a wide range of surface and bulk properties characterization. In particular, reductive transformation of phases such as hematite (α-Fe 2O 3) and goethite (α-FeOOH) in aqueous solution can serve as excellent model systems for studies of electron conduction processes, as well as provide valuable insights into effect of nanoscale conductive materials on contaminant fate at DOE sites. More specifically, the goal of the Iowa component of this project was to use stable Fe isotope measurements to simultaneously measure isotope specific oxidation states and concentrations of Fe at the hematite-water and goethite-water interface. This work builds on our previous work where we used an innovative combination of 57Fe Mössbauer spectroscopy and high precision isotope ratio measurements (MC-ICP-MS) to probe the dynamics of the reaction of aqueous Fe(II) with goethite. Mössbauer spectroscopy detects 57Fe only among all other Fe isotopes and we have capitalized on this to spectroscopically demonstrate Fe(II)-Fe(III) electron transfer between sorbed Fe(II) and Fe(III) oxides (Handler, et al., 2009; Gorski, et al. 2010; Rosso et al., 2010). By combining the Mössbauer spectroscopy and stable isotopes measurements, we have been able to simultaneously track the oxidation state and isotope concentration of the bulk Fe oxide and aqueous Fe. One of our most compelling findings is that despite the apparent stability of the Fe(II)-goethite system, there is actually a tremendous amount of Fe atom cycling occurring between the aqueous phase and the bulk goethite as indicated by the isotopic composition of both phases approaching the mass balance average (Handler et al., 2009). How such extensive re-crystallization and Fe atom exchange can occur with no significant morphological change is a fascinating question. Based on previous work from PI Rosso’s group showing that a potential gradient across hematite crystal faces leads to conduction through hematite and growth and dissolution at separate crystal faces we proposed that a redox-driven recrystallization could be occurring that would explain the extensive mixing observed with the isotope data. From our previous studies utilizing Mössbauer spectroscopy, we know that sorption of Fe(II) onto goethite results in electron transfer between the sorbed Fe(II) and the structural Fe(III) in goethite. Oxidation of the sorbed Fe(II) produces growth of goethite on goethite (i.e., homoepitaxy), as well as injection of an electron into goethite. It is possible that electron transfer from sorbed Fe(II) occurs across a potential gradient, and that Fe(II) atoms are dissolved at a different location on the goethite surface. These newly-reduced Fe(II) atoms could then dissolve into the aqueous phase, exposing fresh Fe(III) goethite to the aqueous phase. Through a repeated series of these five steps of sorption–electron transfer–crystal growth–conduction– dissolution, a redox-driven conveyor belt, could be established that would allow all of the goethite to be eventually exposed to the aqueous phase and exchanged. This surface-mediated recrystallization process would result in similar Fe isotope distributions in the aqueous phase and goethite particle, as we have observed here. It would also result in a stable aqueous Fe(II) concentration, if there were equal rates of goethite growth and dissolution.« less

High resolution isotopic analysis of U-bearing particles via fusion of SIMS and EDS images

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

Tarolli, Jay G.; Naes, Benjamin E.; Garcia, Benjamin J.

Image fusion of secondary ion mass spectrometry (SIMS) images and X-ray elemental maps from energy-dispersive spectroscopy (EDS) was performed to facilitate the isolation and re-analysis of isotopically unique U-bearing particles where the highest precision SIMS measurements are required. Image registration, image fusion and particle micromanipulation were performed on a subset of SIMS images obtained from a large area pre-screen of a particle distribution from a sample containing several certified reference materials (CRM) U129A, U015, U150, U500 and U850, as well as a standard reference material (SRM) 8704 (Buffalo River Sediment) to simulate particles collected on swipes during routine inspections ofmore » declared uranium enrichment facilities by the International Atomic Energy Agency (IAEA). In total, fourteen particles, ranging in size from 5 – 15 µm, were isolated and re-analyzed by SIMS in multi-collector mode identifying nine particles of CRM U129A, one of U150, one of U500 and three of U850. These identifications were made within a few percent errors from the National Institute of Standards and Technology (NIST) certified atom percent values for 234U, 235U and 238U for the corresponding CRMs. This work represents the first use of image fusion to enhance the accuracy and precision of isotope ratio measurements for isotopically unique U-bearing particles for nuclear safeguards applications. Implementation of image fusion is essential for the identification of particles of interests that fall below the spatial resolution of the SIMS images.« less

Super-chondritic Sm/Nd ratios in Mars, the Earth and the Moon.

PubMed

Caro, Guillaume; Bourdon, Bernard; Halliday, Alex N; Quitté, Ghylaine

2008-03-20

Small isotopic differences in the atomic abundance of neodymium-142 (142Nd) in silicate rocks represent the time-averaged effect of decay of formerly live samarium-146 (146Sm) and provide constraints on the timescales and mechanisms by which planetary mantles first differentiated. This chronology, however, assumes that the composition of the total planet is identical to that of primitive undifferentiated meteorites called chondrites. The difference in the 142Nd/144Nd ratio between chondrites and terrestrial samples may therefore indicate very early isolation (<30 Myr from the formation of the Solar System) of the upper mantle or a slightly non-chondritic bulk Earth composition. Here we present high-precision 142Nd data for 16 martian meteorites and show that Mars also has a non-chondritic composition. Meteorites belonging to the shergottite subgroup define a planetary isochron yielding an age of differentiation of 40 +/- 18 Myr for the martian mantle. This isochron does not pass through the chondritic reference value (100 x epsilon(142)Nd = -21 +/- 3; 147Sm/144Nd = 0.1966). The Earth, Moon and Mars all seem to have accreted in a portion of the inner Solar System with approximately 5 per cent higher Sm/Nd ratios than material accreted in the asteroid belt. Such chemical heterogeneities may have arisen from sorting of nebular solids or from impact erosion of crustal reservoirs in planetary precursors. The 143Nd composition of the primitive mantle so defined by 142Nd is strikingly similar to the putative endmember component 'FOZO' characterized by high 3He/4He ratios.

Calcium induced ATP synthesis: Isotope effect, magnetic parameters and mechanism

NASA Astrophysics Data System (ADS)

Buchachenko, A. L.; Kuznetsov, D. A.; Breslavskaya, N. N.; Shchegoleva, L. N.; Arkhangelsky, S. E.

2011-03-01

ATP synthesis by creatine kinase with calcium ions is accompanied by 43Ca/ 40Ca isotope effect: the enzyme with 43Ca 2+ was found to be 2.0 ± 0.3 times more active than enzymes, in which Ca 2+ ions have nonmagnetic nuclei 40Ca. The effect demonstrates that primary reaction in ATP synthesis is electron transfer between reaction partners, Сa( HO)n2+ ( n ⩽ 3) and Ca 2+(ADP) 3-. It generates ion-radical pair, in which spin conversion results in the isotope effect. Magnetic parameters (g-factors and HFC constants a( 43Ca) and a( 31P)) confirm that namely terminal oxygen atom of the ADP ligand in the complex Ca 2+(ADP) 3- donates electron to the Ca( HO)n2+ ion.

Hydrogen atoms can be located accurately and precisely by x-ray crystallography.

PubMed

Woińska, Magdalena; Grabowsky, Simon; Dominiak, Paulina M; Woźniak, Krzysztof; Jayatilaka, Dylan

2016-05-01

Precise and accurate structural information on hydrogen atoms is crucial to the study of energies of interactions important for crystal engineering, materials science, medicine, and pharmacy, and to the estimation of physical and chemical properties in solids. However, hydrogen atoms only scatter x-radiation weakly, so x-rays have not been used routinely to locate them accurately. Textbooks and teaching classes still emphasize that hydrogen atoms cannot be located with x-rays close to heavy elements; instead, neutron diffraction is needed. We show that, contrary to widespread expectation, hydrogen atoms can be located very accurately using x-ray diffraction, yielding bond lengths involving hydrogen atoms (A-H) that are in agreement with results from neutron diffraction mostly within a single standard deviation. The precision of the determination is also comparable between x-ray and neutron diffraction results. This has been achieved at resolutions as low as 0.8 Å using Hirshfeld atom refinement (HAR). We have applied HAR to 81 crystal structures of organic molecules and compared the A-H bond lengths with those from neutron measurements for A-H bonds sorted into bonds of the same class. We further show in a selection of inorganic compounds that hydrogen atoms can be located in bridging positions and close to heavy transition metals accurately and precisely. We anticipate that, in the future, conventional x-radiation sources at in-house diffractometers can be used routinely for locating hydrogen atoms in small molecules accurately instead of large-scale facilities such as spallation sources or nuclear reactors.

Hydrogen atoms can be located accurately and precisely by x-ray crystallography

PubMed Central

Woińska, Magdalena; Grabowsky, Simon; Dominiak, Paulina M.; Woźniak, Krzysztof; Jayatilaka, Dylan

2016-01-01

Precise and accurate structural information on hydrogen atoms is crucial to the study of energies of interactions important for crystal engineering, materials science, medicine, and pharmacy, and to the estimation of physical and chemical properties in solids. However, hydrogen atoms only scatter x-radiation weakly, so x-rays have not been used routinely to locate them accurately. Textbooks and teaching classes still emphasize that hydrogen atoms cannot be located with x-rays close to heavy elements; instead, neutron diffraction is needed. We show that, contrary to widespread expectation, hydrogen atoms can be located very accurately using x-ray diffraction, yielding bond lengths involving hydrogen atoms (A–H) that are in agreement with results from neutron diffraction mostly within a single standard deviation. The precision of the determination is also comparable between x-ray and neutron diffraction results. This has been achieved at resolutions as low as 0.8 Å using Hirshfeld atom refinement (HAR). We have applied HAR to 81 crystal structures of organic molecules and compared the A–H bond lengths with those from neutron measurements for A–H bonds sorted into bonds of the same class. We further show in a selection of inorganic compounds that hydrogen atoms can be located in bridging positions and close to heavy transition metals accurately and precisely. We anticipate that, in the future, conventional x-radiation sources at in-house diffractometers can be used routinely for locating hydrogen atoms in small molecules accurately instead of large-scale facilities such as spallation sources or nuclear reactors. PMID:27386545

Our Two Cents Worth.

ERIC Educational Resources Information Center

Corcoran, Tim; Allen, Bill

1991-01-01

Described is an activity in which students determine the percent composition of zinc and copper in pennies minted before and after 1982. Students also use pennies to show the natural relative abundance of isotopes and to explain how the weighted atomic mass of the elements is determined. (KR)

Paleodiet characterisation of an Etrurian population of Pontecagnano (Italy) by Isotope Ratio Mass Spectrometry (IRMS) and Atomic Absorption Spectrometry (AAS)(#).

PubMed

Scarabino, Carla; Lubritto, Carmine; Proto, Antonio; Rubino, Mauro; Fiengo, Gilda; Marzaioli, Fabio; Passariello, Isabella; Busiello, Gaetano; Fortunato, Antonietta; Alfano, Davide; Sabbarese, Carlo; Rogalla, Detlef; De Cesare, Nicola; d'Onofrio, Antonio; Terrasi, Filippo

2006-06-01

Human bones recovered from the archaeological site of Pontecagnano (Salerno, Italy) have been studied to reconstruct the diet of an Etrurian population. Two different areas were investigated, named Library and Sant' Antonio, with a total of 44 tombs containing human skeletal remains, ranging in age from the 8th to the 3rd century B.C. This time span was confirmed by 14C dating obtained using Accelerator Mass Spectrometry (AMS) on one bone sample from each site. Atomic Absorption Spectrometry (AAS) was used to extract information about the concentration of Sr, Zn, Ca elements in the bone inorganic fraction, whilst stable isotope ratio measurements (IRMS) were carried out on bone collagen to obtain the delta13C and delta15N. A reliable technique has been used to extract and separate the inorganic and organic fractions of the bone remains. Both IRMS and AAS results suggest a mixed diet including C3 plant food and herbivore animals, consistent with archaeological indications.

Temporal variation of cesium isotope concentrations and atom ratios in zooplankton in the Pacific off the east coast of Japan.

PubMed

Ikenoue, Takahito; Takata, Hyoe; Kusakabe, Masashi; Kudo, Natsumi; Hasegawa, Kazuyuki; Ishimaru, Takashi

2017-01-04

After the Fukushima Daiichi Nuclear Power Plant accident in March 2011, concentrations of cesium isotopes ( 133 Cs, 134 Cs, and 137 Cs) were measured in zooplankton collected in the Pacific off the east coast of Japan from May 2012 to February 2015. The time series of the data exhibited sporadic 137 Cs concentration peaks in zooplankton. In addition, the atom ratio of 137 Cs/ 133 Cs in zooplankton was consistently high compared to that in ambient seawater throughout the sampling period. These phenomena cannot be explained fully by the bioaccumulation of 137 Cs in zooplankton via ambient seawater intake, the inclusion of resuspended sediment in the plankton sample, or the taxonomic composition of the plankton. Autoradiography revealed highly radioactive particles within zooplankton samples, which could be the main factor underlying the sporadic appearance of high 137 Cs concentrations in zooplankton as well as the higher ratio of 137 Cs/ 133 Cs in zooplankton than in seawater.

Temporal variation of cesium isotope concentrations and atom ratios in zooplankton in the Pacific off the east coast of Japan

PubMed Central

Ikenoue, Takahito; Takata, Hyoe; Kusakabe, Masashi; Kudo, Natsumi; Hasegawa, Kazuyuki; Ishimaru, Takashi

2017-01-01

After the Fukushima Daiichi Nuclear Power Plant accident in March 2011, concentrations of cesium isotopes (133Cs, 134Cs, and 137Cs) were measured in zooplankton collected in the Pacific off the east coast of Japan from May 2012 to February 2015. The time series of the data exhibited sporadic 137Cs concentration peaks in zooplankton. In addition, the atom ratio of 137Cs/133Cs in zooplankton was consistently high compared to that in ambient seawater throughout the sampling period. These phenomena cannot be explained fully by the bioaccumulation of 137Cs in zooplankton via ambient seawater intake, the inclusion of resuspended sediment in the plankton sample, or the taxonomic composition of the plankton. Autoradiography revealed highly radioactive particles within zooplankton samples, which could be the main factor underlying the sporadic appearance of high 137Cs concentrations in zooplankton as well as the higher ratio of 137Cs/133Cs in zooplankton than in seawater. PMID:28051136

Nuclear quantum effects of light and heavy water studied by all-electron first principles path integral simulations

NASA Astrophysics Data System (ADS)

Machida, Masahiko; Kato, Koichiro; Shiga, Motoyuki

2018-03-01

The isotopologs of liquid water, H2O, D2O, and T2O, are studied systematically by first principles PIMD simulations, in which the whole entity of the electrons and nuclei are treated quantum mechanically. The simulation results are in reasonable agreement with available experimental data on isotope effects, in particular, on the peak shift in the radial distributions of H2O and D2O and the shift in the evaporation energies. It is found that, due to differences in nuclear quantum effects, the H atoms in the OH bonds more easily access the dissociative region up to the hydrogen bond center than the D (T) atoms in the OD (OT) bonds. The accuracy and limitation in the use of the current density-functional-theory-based first principles PIMD simulations are also discussed. It is argued that the inclusion of the dispersion correction or relevant improvements in the density functionals are required for the quantitative estimation of isotope effects.

Pu isotopes in soils collected downwind from Lop Nor: regional fallout vs. global fallout.

PubMed

Bu, Wenting; Ni, Youyi; Guo, Qiuju; Zheng, Jian; Uchida, Shigeo

2015-07-17

For the first time, soil core samples from the Jiuquan region have been analyzed for Pu isotopes for radioactive source identification and radiological assessment. The Jiuquan region is in downwind from the Lop Nor Chinese nuclear test (CNT) site. The high Pu inventories (13 to 546 Bq/m(2)) in most of the sampling locations revealed that this region was heterogeneously contaminated by the regional fallout Pu from the CNTs. The contributions of the CNTs to the total Pu in soils were estimated to be more than 40% in most cases. The (240)Pu/(239)Pu atom ratios in the soils ranged from 0.059 to 0.186 with an inventory-weighted average of 0.158, slightly lower than that of global fallout. This atom ratio could be considered as a mixed fingerprint of Pu from the CNTs. In addition, Pu in soils of Jiuquan region had a faster downward migration rate compared with other investigated places in China.

Pu isotopes in soils collected downwind from Lop Nor: regional fallout vs. global fallout

PubMed Central

Bu, Wenting; Ni, Youyi; Guo, Qiuju; Zheng, Jian; Uchida, Shigeo

2015-01-01

For the first time, soil core samples from the Jiuquan region have been analyzed for Pu isotopes for radioactive source identification and radiological assessment. The Jiuquan region is in downwind from the Lop Nor Chinese nuclear test (CNT) site. The high Pu inventories (13 to 546 Bq/m2) in most of the sampling locations revealed that this region was heterogeneously contaminated by the regional fallout Pu from the CNTs. The contributions of the CNTs to the total Pu in soils were estimated to be more than 40% in most cases. The 240Pu/239Pu atom ratios in the soils ranged from 0.059 to 0.186 with an inventory-weighted average of 0.158, slightly lower than that of global fallout. This atom ratio could be considered as a mixed fingerprint of Pu from the CNTs. In addition, Pu in soils of Jiuquan region had a faster downward migration rate compared with other investigated places in China. PMID:26184740

Research in Knowledge Representation for Natural Language Understanding

DTIC Science & Technology

1981-11-01

interpretation would not be too bad if one were to believe that a frame "is intended to represent a ’ stereotypical situation’" ( [24], p. 48). We...natural kind-like concepts - some form of definitional structuring is necessary. The internal structure of non atomic concepts (e.g., proximate genus ...types of beer, bottles of wine, etc.; <x> need not be any sort of Onatural genus .’ For example, in Dll the definite pronoun Othem" is not meant to I

Resolving mass spectral overlaps in atom probe tomography by isotopic substitutions - case of TiSi15N.

PubMed

Engberg, David L J; Johnson, Lars J S; Jensen, Jens; Thuvander, Mattias; Hultman, Lars

2018-01-01

Mass spectral overlaps in atom probe tomography (APT) analyses of complex compounds typically limit the identification of elements and microstructural analysis of a material. This study concerns the TiSiN system, chosen because of severe mass-to-charge-state ratio overlaps of the 14 N + and 28 Si 2+ peaks as well as the 14 N 2 + and 28 Si + peaks. By substituting 14 N with 15 N, mass spectrum peaks generated by ions composed of one or more N atoms will be shifted toward higher mass-to-charge-state ratios, thereby enabling the separation of N from the predominant Si isotope. We thus resolve thermodynamically driven Si segregation on the nanometer scale in cubic phase Ti 1- x Si x 15 N thin films for Si contents 0.08 ≤ x ≤ 0.19 by APT, as corroborated by transmission electron microscopy. The APT analysis yields a composition determination that is in good agreement with energy dispersive X-ray spectroscopy and elastic recoil detection analyses. Additionally, a method for determining good voxel sizes for visualizing small-scale fluctuations is presented and demonstrated for the TiSiN system. Copyright © 2017 Elsevier B.V. All rights reserved.

Nano is the next big thing: Revealing geochemical processes with atom probe microscopy

NASA Astrophysics Data System (ADS)

Reddy, Steven; Saxey, David; Rickard, William; Fougerouse, Denis; Peterman, Emily; van Riessen, Arie; Johnson, Tim

2017-04-01

Characterizing compositional variations in minerals at the nanometre scale has the potential to yield fundamental insights into a range of geological processes associated with nucleation and mineral growth and the subsequent modification of mineral compositions by processes such as diffusion, deformation and recrystallization. However, there are few techniques that allow the quantitative measurement of low abundance trace elements and isotopes signatures at the nanometre scale. Atom probe microscopy is one such technique that has been widely used in the study of metals and, in the last decade, semiconductors. However, the development and application of atom probe microscopy to minerals is in its infancy and only a handful of published studies exist in the literature. Here, we provide an introduction to atom probe microscopy and its potential use in geological studies using two examples from both undeformed and deformed zircon (ZrSiO4). In the first example, we use atom probe microscopy to show that discordant data from the core of an undeformed 2.1 Ga zircon, metamorphosed at granulite facies conditions 150 Myr ago, contains distinct Pb reservoirs that represent both the crystallisation and metamorphic 207Pb/206Pb ages. Crystallisation ages are preserved within ˜10 nm diameter dislocation loops that formed during annealing of radiation-damaged zircon during the prograde path of the metamorphic event. The results highlight the potential for resolving the chronology of multiple, distinct Pb reservoirs within isotopically complex zircon and provide an explanation for varying amounts of discordance within individual zircon grains. In the second example, we illustrate complex trace element distributions associated with near-instantaneous deformation of a shocked zircon during the ˜1.17 Ga Stac Fada bolide impact. Substitutional and interstitial ions show correlated segregation, indicating coupling between different mobility mechanisms associated with the rapid formation and migration of oxygen vacancies and dislocations into low energy configurations. The results of these two studies show how quantification of elemental and isotopic variations at the nanoscale may reveal fundamental new insights into geochemical processes that underpin the interpretation of geochemical data collected at the microscale. Furthermore, these new data highlight the important role of crystal defects, even in undeformed zircon, in the chemical modification of zircon, and allow the interplay amongst radiation damage, recrystallization and deformation to be assessed.

{beta}-decay half-lives of new neutron-rich rare-earth isotopes {sup 159}Pm,{sup 162}Sm, and {sup 166}Gd

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

Ichikawa, S.; Asai, M.; Tsukada, K.

The new neutron-rich rare-earth isotopes {sup 159}Pm, {sup 162}Sm, and {sup 166}Gd produced in the proton-induced fission of {sup 238}U were identified using the JAERI on-line isotope separator (JAERI-ISOL) coupled to a gas-jet transport system. The half-lives of {sup 159}Pm, {sup 162}Sm, and {sup 166}Gd were determined to be 1.5 {+-} 0.2, 2.4 {+-} 0.5, and 4.8 {+-} 1.0 s respectively. The partial decay scheme of {sup 166}Gd was constructed from {gamma}{gamma}-coincidence data. A more accurate half-life value of 25.6 {+-} 2.2 s was obtained for the previously identified isotope {sup 166}Tb. The half-lives measured in the present study aremore » in good agreement with the theoretical predictions calculated by the second generation of the gross theory with the atomic masses evaluated by Audi and Wapstra.« less

Isotope-Labeled Composition B for Tracing Detonation Signatures

NASA Astrophysics Data System (ADS)

Manner, Virginia; Podlesak, David; Huber, Rachel; Amato, Ronald; Giambra, Anna; Bowden, Patrick; Hartline, Ernest; Dattelbaum, Dana

2017-06-01

To better understand how solid carbon forms and evolves during detonation, we have prepared Composition B with 13 C and 15 N-labeled 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX) and 2,4,6-trinitrotoluene (TNT) in order to trace the formation of soot from the carbon and nitrogen atoms in these explosives. Isotope-labeling of explosives has been performed in the recent past for a variety of reasons, including environmental remediation and reaction mechanism studies. Because it is expensive and time consuming to prepare these materials, and our detection equipment only requires trace amounts of isotopes, we have prepared fully-labeled materials and substituted them into unlabeled RDX and TNT at less than the 1% level. We will discuss the preparation and full characterization of this labeled Composition B, the detonation tests performed, along with the results of the post-detonation soot analysis. Various detonation models predict differing amounts and forms of carbon and nitrogen; these isotopically-labeled precursors have allowed these models to be tested.

Why new neutron detector materials must replace helium-3

NASA Astrophysics Data System (ADS)

Hurd, Alan J.; Kouzes, Richard T.

2014-10-01

Helium-3 has such unique physical and nuclear properties that to a physicist it seems appalling the isotope was once indiscriminately released to the atmosphere as a waste gas. Not gravitationally bound to our planet, a He-3 atom is effectively lost to the human race once released. Consequently, when a confluence of independent factors in national security and research in the last decade created a "custody battle" over this scarce isotope, an intense search for substitutes and alternative technologies ensued for various applications. This Focus Point of EPJ Plus is dedicated to neutron detector alternatives.

A precise few-nucleon size difference by isotope shift measurements of helium

NASA Astrophysics Data System (ADS)

Rezaeian, Nima Hassan

We perform high precision measurements of an isotope shift between the two stable isotopes of helium. We use laser excitation of the 23 S1 -- 23P0 transition at 1083 .... in a metastable beam of 3He and 4He atoms. A newly developed tunable laser frequency selector along with our previous electro-optic frequency modulation technique provides extremely reliable, adaptable, and precise frequency and intensity control. The intensity control contributes negligibly to overall experimental uncertainty by selecting (t selection < 50 ) and stabilizing the intensity of the required sideband and eliminating (˜10-5) the unwanted frequencies generated during the modulation of 1083 nm laser carrier frequency. The selection technique uses a MEMS based fiber switch (tswitch ≈ 10 ms) and several temperature stabilized narrow band (˜3 GHz) fiber gratings. A fiber based optical circulator and an inline fiber amplifier provide the desired isolation and the net gain for the selected frequency. Also rapid (˜2 sec.) alternating measurements of the 23 S1 -- 23P0 interval for both species of helium is achieved with a custom fiber laser for simultaneous optical pumping. A servo-controlled retro-reflected laser beam eliminates residual Doppler effects during the isotope shift measurement. An improved detection design and software control makes negligible subtle potential biases in the data collection. With these advances, combined with new internal and external consistency checks, we are able to obtain results consistent with the best previous measurements, but with substantially improved precision. Our measurement of the 23S 1 -- 23P0 isotope shift between 3He and 4He is 31 097 535.2 (5)kHz. The most recent theoretic calculation combined with this measuremen. yields a new determination for nuclear size differences between 3He and 4He: Deltarc = 0.292 6 (1)exp (8)th(52)expfm, with a precision of less than a part in 104 coming from the experimental uncertainty (first parenthesis), and a part in 10 3 coming from theory. This value is consistent with electron scattering measurement, but a factor of 10 more precise. It is inconsistent (4 sigma) with a recent isotope shift measurement on another helium transition (2 1S0 -- 23 S1). Comparisons with ongoing muonic helium measurements may provide clues to the origin of what is currently called the proton puzzle: electronic and muonic measurements of the proton size do not agree. In the future, the experimental improvements described here can be used for higher precision tests of atomic theory and quantum electrodynamics, as well as an important atomic physics source of the fine structure constant.

10 CFR 140.3 - Definitions.

Code of Federal Regulations, 2010 CFR

2010-01-01

... atomic weapon, designed or used to sustain nuclear fission in a self-supporting chain reaction. (g... experiments; or (ii) A liquid fuel loading; or (iii) An experimental facility in the core in excess of 16... in the isotope 235, except laboratory scale facilities designed or used for experimental or...

10 CFR 140.3 - Definitions.

Code of Federal Regulations, 2011 CFR

2011-01-01

... in the isotope 235, except laboratory scale facilities designed or used for experimental or... atomic weapon, designed or used to sustain nuclear fission in a self-supporting chain reaction. (g... experiments; or (ii) A liquid fuel loading; or (iii) An experimental facility in the core in excess of 16...

10 CFR 140.3 - Definitions.

Code of Federal Regulations, 2012 CFR

2012-01-01

... in the isotope 235, except laboratory scale facilities designed or used for experimental or... atomic weapon, designed or used to sustain nuclear fission in a self-supporting chain reaction. (g... experiments; or (ii) A liquid fuel loading; or (iii) An experimental facility in the core in excess of 16...

Position-specific isotope analysis by on-line pyrolysis coupled to IRMS

NASA Astrophysics Data System (ADS)

Gilbert, A.; Suda, K.; Yamada, K.; Ueno, Y.; Yoshida, N.

2016-12-01

Position-specific isotopic analyses (PSIA) provide unique information regarding the sources, sinks and processes related to natural molecules. For instance, PSIA of short-chain hydrocarbons could lead to temperature of formation and maturity of natural gas reservoirs [1][2]. In the last decade, quantitative Nuclear Magnetic Resonance (NMR) specrometry has been used for PSIA of organic molecules such as glucose or n-alkanes [3][4]. However, due to its low sensitivity, application to low amount geochemical samples remains challenging. In 1997, Corso & Brenna proposed to adapt a pyrolysis furnace to an isotope ratio mass spectrometer, making it possible the thermal degradation of the target molecule and the subsequent analysis of the d13C values of the fragments formed [5]. Starting from fatty acid methyl esters they demonstrated the absence of rearrangement during pyrolytic degradation and could determine the d13C value of carboxyl C-atom position. We adapted the system for the full characterization of position-specific isotope composition of small molecules (ethanol, acetic acid, alanine, propane). Nanomole amount of sample can be analyzed with a precision on intramolecular d13C values of 1‰ or lower [2]. We recently analyzed abiotic and thermogenic propane samples both from the field and from lab simulations. PSIA of propane shows systematic differences of position-specific isotope composition between thermogenic and abiotic samples. While the former show 13C-depletion on the terminal C-atom position - consistent with thermal cracking kinetic models [6] - abiotic samples show little or no preference for terminal or central 13C-isotopomer. These results emphasize the potential of PSIA to trace the the processes associated with organic molecules production. [1] Piasecki et al. 2016 GCA 188, 58 [2] Gilbert et al. 2016 GCA 177, 205 [3] Gilbert et al. 2012 PNAS, 109, 18204 [4] Gilbert et al. 2013 Org. Geochem, 62, 56 [5] Corso & Brenna 1997 PNAS, 94, 1049 [6] Tang et al., 2000 GCA 64, 2673

Investigating Pu and U isotopic compositions in sediments: a case study in Lake Obuchi, Rokkasho Village, Japan using sector-field ICP-MS and ICP-QMS.

PubMed

Zheng, Jian; Yamada, Masatoshi

2005-08-01

The objectives of the present work were to study isotope ratios and the inventory of plutonium and uranium isotope compositions in sediments from Lake Obuchi, which is in the vicinity of several nuclear fuel facilities in Rokkasho, Japan. Pu and its isotopes were determined using sector-field ICP-MS and U and its isotopes were determined with ICP-QMS after separation and purification with a combination of ion-exchange and extraction chromatography. The observed (240)Pu/(239)Pu atom ratio (0.186 +/- 0.016) was similar to that of global fallout, indicating that the possible early tropospheric fallout Pu did not deliver Pu from the Pacific Proving Ground to areas above 40 degrees N. The previously reported higher Pu inventory in the deep water area of Lake Obuchi could be attributed to the lateral transportation of Pu deposited in the shallow area which resulted from the migration of deposited global fallout Pu from the land into the lake by river runoff and from the Pacific Ocean by tide movement and sea water scavenging, as well as from direct soil input by winds. The (235)U/(238)U atom ratios ranged from 0.00723 to 0.00732, indicating the natural origin of U in the sediments. The average (234)U/(238)U activity ratio of 1.11 in a sediment core indicated a significant sea water U contribution. No evidence was found for the release of U containing wastes from the nearby nuclear facilities. These results will serve as a reference baseline on the levels of Pu and U in the studied site so that any further contamination from the spent nuclear fuel reprocessing plants, the radioactive waste disposal and storage facilities, and the uranium enrichment plant can be identified, and the impact of future release can be rapidly assessed.

Organic molecules, ions, and rare isotopologues in the remnant of the stellar-merger candidate, CK Vulpeculae (Nova 1670)

NASA Astrophysics Data System (ADS)

Kamiński, T.; Menten, K. M.; Tylenda, R.; Karakas, A.; Belloche, A.; Patel, N. A.

2017-11-01

Context. CK Vulpeculae (CK Vul) is an enigmatic star whose outburst was observed in 1670-72. A stellar-merger event was proposed to explain its ancient eruption. Aims: We aim to investigate the composition of the molecular gas recently discovered in the remnant of CK Vul. Deriving the chemical, elemental, and isotopic composition is crucial for identifying the nature of the object and obtaining clues on its progenitor(s). Methods: We observed millimeter and submillimeter-wave spectra of CK Vul using the IRAM 30 m and APEX telescopes. Radiative-transfer modeling of the observed molecular features was performed to yield isotopic ratios for various elements. Results: The spectra of CK Vul reveal a very rich molecular environment of low excitation (Tex ≲ 12 K). Atomic carbon and twenty-seven different molecules, including two ions, were identified. They range from simple diatomic to complex polyatomic species of up to seven atoms large. The chemical composition of the molecular gas is indicative of carbon and nitrogen-driven chemistry but oxides are also present. Additionally, the abundance of fluorine may be enhanced. The spectra are rich in isotopologues that are very rare in most known sources. All stable isotopes of C, N, O, Si, and S are observed and their isotopic ratios are derived. Conclusions: The composition of the remnant's molecular gas is most peculiar and gives rise to a very unique millimeter and submillimeter spectrum. The observation of ions and complex molecules suggests the presence of a photoionizing source but its nature (a central star or shocks) remains unknown. The elemental and isotopic composition of the gas cannot be easily reconciled with standard stellar nucleosynthesis but processing in hot CNO cycles and partial helium burning can explain most of the chemical peculiarities. The isotopic ratios of CK Vul are remarkably close to those of presolar "nova grains" but the link of Nova 1670 to objects responsible for these grains is unclear. The accuracy of isotopic ratios can be improved by future observations at higher angular resolutions and with realistic models of the kinematical structure of the remnant. The reduced spectra are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/607/A78

A table of polyatomic interferences in ICP-MS

USGS Publications Warehouse

May, Thomas W.; Wiedmeyer, Ray H.

1998-01-01

Spectroscopic interferences are probably the largest class of interferences in ICP-MS and are caused by atomic or molecular ions that have the same mass-to-charge as analytes of interest. Current ICP-MS instrumental software corrects for all known atomic “isobaric” interferences, or those caused by overlapping isotopes of different elements, but does not correct for most polyatomic interferences. Such interferences are caused by polyatomic ions that are formed from precursors having numerous sources, such as the sample matrix, reagents used for preparation, plasma gases, and entrained atmospheric gases.

Hepatoblastoma Biology Using Isotope Ratio Mass Spectrometry: Utility of a Unique Technique for the Analysis of Oncological Specimens.

PubMed

Taran, Katarzyna; Frączek, Tomasz; Sitkiewicz, Anna; Sikora-Szubert, Anita; Kobos, Józef; Paneth, Piotr

2016-07-07

Hepatoblastoma is the most common primary liver tumor in children. However, it occurs rarely, with an incidence of 0.5-1.5 cases per million children. There is no clear explanation of the relationship between clinicopathologic features, therapy, and outcome in hepatoblastoma cases, so far. One of the most widely accepted prognostic factors in hepatoblastoma is histology of the tumor. The aim of the study was to determine the potential differences in biology of hepatoblastoma histological subtypes at the atomic level using the unique method of isotope ratio mass spectrometry, which is especially valuable in examination of small groups of biological samples. Twenty-four measurements of nitrogen stable isotope ratio, carbon stable isotope ratio and total carbon to nitrogen mass ratio in fetal and embryonal hepatoblastoma tissue were performed using a Sercon 20-22 Continuous Flow Isotope Ratio Mass Spectrometer (CF-IRMS) coupled with a Sercon SL elemental analyzer for simultaneous carbon-nitrogen-sulfur (NCS) analysis. A difference of about 1.781‰ in stable nitrogen isotope 15N/14N ratio was found between examined hepatoblastoma histological subtypes. The prognosis in liver tumors cases in children may be challenging particularly because of the lack of versatile methods of its evaluation. Isotope ratio mass spectrometry allows one to determine the difference between hepatoblastoma histological subtypes and clearly indicates the cases with the best outcome.

Polarization IR spectra of hydrogen bonded pyrazole crystals: self-organization effects in proton and deuteron mixture systems. Long-range H/D isotopic effects

NASA Astrophysics Data System (ADS)

Flakus, Henryk T.; Machelska, Aleksandra

2002-02-01

This paper deals with experimental studies of the polarization IR spectra of solid-state pyrazole H1345, as well as of its H1D345, D1H345 and D1345 deuterium derivatives. Spectra were measured for the νNH and νND band frequency ranges at temperatures of 298 and 77 K. The spectra were found to strongly change their intensity distribution and their polarization properties with the decrease of temperature. These effects were ascribed to some temperature-induced conformational changes in the hydrogen bond lattices. The studies reported allowed the finding of new kind of isotopic effects H/D in the open-chain hydrogen bond systems, i.e. the self-organization effects. It was found that the spectrally active aggregates of hydrogen bonds remain unchanged despite the growing isotope H/D exchange rate. This statement was supported by analysis of the residual polarized νNH and νND band properties, measured for the isotopically diluted crystalline samples. Analysis of the band shapes of the four hydrogen isotope derivative crystals proved the existence of another kind of H/D isotopic effect, i.e. the long-range isotopic effect. It depends on an influence of the pyrazole ring hydrogen atoms onto the νNH and νND band widths and onto the band fine structures.

Quantitative Fissile Assay In Used Fuel Using LSDS System

NASA Astrophysics Data System (ADS)

Lee, YongDeok; Jeon, Ju Young; Park, Chang-Je

2017-09-01

A quantitative assay of isotopic fissile materials (U235, Pu239, Pu241) was done at Korea Atomic Energy Research Institute (KAERI), using lead slowing down spectrometer (LSDS). The optimum design of LSDS was performed based on economics, easy maintenance and assay effectiveness. LSDS system consists of spectrometer, neutron source, detection and control. LSDS system induces fissile fission and fast neutrons are collected at fission chamber. The detected signal has a direct relation to the mass of existing fissile isotopes. Many current commercial assay technologies have a limitation in direct application on isotopic fissile assay of spent fuel, except chemical analysis. In the designed system, the fissile assay model was setup and the correction factor for self-shield was obtained. The isotopic fissile content assay was performed by changing the content of Pu239. Based on the fuel rod, the isotopic content was consistent with 2% uncertainty for Pu239. By applying the covering (neutron absorber), the effective shielding was obtained and the activation was calculated on the target. From the assay evaluation, LSDS technique is very powerful and direct to analyze the isotopic fissile content. LSDS is applicable for nuclear fuel cycle and spent fuel management for safety and economics. Additionally, an accurate fissile content will contribute to the international transparency and credibility on spent fuel.

New developments of the in-source spectroscopy method at RILIS/ISOLDE

NASA Astrophysics Data System (ADS)

Marsh, B. A.; Andel, B.; Andreyev, A. N.; Antalic, S.; Atanasov, D.; Barzakh, A. E.; Bastin, B.; Borgmann, Ch.; Capponi, L.; Cocolios, T. E.; Day Goodacre, T.; Dehairs, M.; Derkx, X.; De Witte, H.; Fedorov, D. V.; Fedosseev, V. N.; Focker, G. J.; Fink, D. A.; Flanagan, K. T.; Franchoo, S.; Ghys, L.; Huyse, M.; Imai, N.; Kalaninova, Z.; Köster, U.; Kreim, S.; Kesteloot, N.; Kudryavtsev, Yu.; Lane, J.; Lecesne, N.; Liberati, V.; Lunney, D.; Lynch, K. M.; Manea, V.; Molkanov, P. L.; Nicol, T.; Pauwels, D.; Popescu, L.; Radulov, D.; Rapisarda, E.; Rosenbusch, M.; Rossel, R. E.; Rothe, S.; Schweikhard, L.; Seliverstov, M. D.; Sels, S.; Sjödin, A. M.; Truesdale, V.; Van Beveren, C.; Van Duppen, P.; Wendt, K.; Wienholtz, F.; Wolf, R. N.; Zemlyanoy, S. G.

2013-12-01

At the CERN ISOLDE facility, long isotope chains of many elements are produced by proton-induced reactions in target materials such as uranium carbide. The Resonance Ionization Laser Ion Source (RILIS) is an efficient and selective means of ionizing the reaction products to produce an ion beam of a chosen isotope. Coupling the RILIS with modern ion detection techniques enables highly sensitive studies of nuclear properties (spins, electromagnetic moments and charge radii) along an isotope chain, provided that the isotope shifts and hyperfine structure splitting of the atomic transitions can be resolved. At ISOLDE the campaign to measure the systematics of isotopes in the lead region (Pb, Bi, Tl and Po) has been extended to include the gold and astatine isotope chains. Several developments were specifically required for the feasibility of the most recent measurements: new ionization schemes (Po, At); a remote controlled narrow line-width mode of operation for the RILIS Ti:sapphire laser (At, Au, Po); isobar free ionization using the Laser Ion Source Trap, LIST (Po); isobar selective particle identification using the multi-reflection time-of-flight mass separator (MR-ToF MS) of ISOLTRAP (Au, At). These are summarized as part of an overview of the current status of the in-source resonance ionization spectroscopy setup at ISOLDE.

[Determination of deuterium concentration in foods and influence of water with modified isotopic composition on oxidation parameters and heavy hydrogen isotopes content in experimental animals].

PubMed

Basov, A A; Bykov, I M; Baryshev, M G; Dzhimak, S S; Bykov, M I

2014-01-01

The article presents the results of the study of the deuterium (D) content in food products as well as the influence of deuterium depleted water (DDW) on the concentration of heavy hydrogen isotopes in the blood and lyophilized tissues of rats. The most significant difference in the content of D was found between potato and pork fat, which indexes the standard delta notation (δ) D in promille, related to the international standard SMOW (Standard Mean Ocean of Water) amounted to -83,2 per thousand and -250,7 per thousand, respectively (p<0,05). Among the investigated samples of water deuterium concentration ranged from -75,5 per thousand (Narzan) to +72,1 per thousand (Kubai), that indicates the ability of some food products to increase the concentration of heavy hydrogen atoms in the body. The data obtained in the experimental modeling of the diet of male Wistar rats in the age of 5-6 mo (weight 235 ± 16 g) using DDW (δD = -743,2 per thousand) instead of drinking water (δD = -37,0 per thousand) with identical mineral composition showed that after 2 weeks significant (p <0,05) formation of isotopic (deuterium-protium, D/H) gradient in the body is possible. Changing the direction of isotopic D/H gradient in laboratory animals in comparison with its physiological indicators (72-127 per thousand, "plasma>tissue") is due to different rates ofisotopic exchange reactions in plasma and tissues (liver, kidney, heart), which can be explained by entering into the composition of a modified diet of organic substrates with more than DDW concentration D, which are involved in the construction of cellular structures and eventually lead to a redistribution of D and change direction of D/H gradient "plasma

Sodium Atoms in the Lunar Exotail: Observed Velocity and Spatial Distributions

NASA Technical Reports Server (NTRS)

Line, Michael R.; Mierkiewicz, E. J.; Oliversen, R. J.; Wilson, J. K.; Haffner, L. M.; Roesler, F. L.

2011-01-01

The lunar sodium tail extends long distances due to radiation pressure on sodium atoms in the lunar exosphere. Our earlier observations determined the average radial velocity of sodium atoms moving down the lunar tail beyond Earth along the Sun-Moon-Earth line (i.e., the anti-lunar point) to be 12.4 km/s. Here we use the Wisconsin H-alpha Mapper to obtain the first kinematically resolved maps of the intensity and velocity distribution of this emission over a 15 x times 15 deg region on the sky near the anti-lunar point. We present both spatially and spectrally resolved observations obtained over four nights around new moon in October 2007. The spatial distribution of the sodium atoms is elongated along the ecliptic with the location of the peak intensity drifting 3 degrees east along the ecliptic per night. Preliminary modeling results suggest that the spatial and velocity distributions in the sodium exotail are sensitive to the near surface lunar sodium velocity distribution and that observations of this sort along with detailed modeling offer new opportunities to describe the time history of lunar surface sputtering over several days.

Update and evaluation of decay data for spent nuclear fuel analyses

NASA Astrophysics Data System (ADS)

Simeonov, Teodosi; Wemple, Charles

2017-09-01

Studsvik's approach to spent nuclear fuel analyses combines isotopic concentrations and multi-group cross-sections, calculated by the CASMO5 or HELIOS2 lattice transport codes, with core irradiation history data from the SIMULATE5 reactor core simulator and tabulated isotopic decay data. These data sources are used and processed by the code SNF to predict spent nuclear fuel characteristics. Recent advances in the generation procedure for the SNF decay data are presented. The SNF decay data includes basic data, such as decay constants, atomic masses and nuclide transmutation chains; radiation emission spectra for photons from radioactive decay, alpha-n reactions, bremsstrahlung, and spontaneous fission, electrons and alpha particles from radioactive decay, and neutrons from radioactive decay, spontaneous fission, and alpha-n reactions; decay heat production; and electro-atomic interaction data for bremsstrahlung production. These data are compiled from fundamental (ENDF, ENSDF, TENDL) and processed (ESTAR) sources for nearly 3700 nuclides. A rigorous evaluation procedure of internal consistency checks and comparisons to measurements and benchmarks, and code-to-code verifications is performed at the individual isotope level and using integral characteristics on a fuel assembly level (e.g., decay heat, radioactivity, neutron and gamma sources). Significant challenges are presented by the scope and complexity of the data processing, a dearth of relevant detailed measurements, and reliance on theoretical models for some data.

Path Integral Simulation of the H/D Kinetic Isotope Effect in Monoamine Oxidase B Catalyzed Decomposition of Dopamine.

PubMed

Mavri, Janez; Matute, Ricardo A; Chu, Zhen T; Vianello, Robert

2016-04-14

Brain monoamines regulate many centrally mediated body functions, and can cause adverse symptoms when they are out of balance. A starting point to address challenges raised by the increasing burden of brain diseases is to understand, at atomistic level, the catalytic mechanism of an essential amine metabolic enzyme-monoamine oxidase B (MAO B). Recently, we demonstrated that the rate-limiting step of MAO B catalyzed conversion of amines into imines represents the hydride anion transfer from the substrate α-CH2 group to the N5 atom of the flavin cofactor moiety. In this article we simulated for MAO B catalyzed dopamine decomposition the effects of nuclear tunneling by the calculation of the H/D kinetic isotope effect. We applied path integral quantization of the nuclear motion for the methylene group and the N5 atom of the flavin moiety in conjunction with the QM/MM treatment on the empirical valence bond (EVB) level for the rest of the enzyme. The calculated H/D kinetic isotope effect of 12.8 ± 0.3 is in a reasonable agreement with the available experimental data for closely related biogenic amines, which gives strong support for the proposed hydride mechanism. The results are discussed in the context of tunneling in enzyme centers and advent of deuterated drugs into clinical practice.

Energy transfer in O collisions with He isotopes and helium escape from Mars

NASA Astrophysics Data System (ADS)

Bovino, S.; Zhang, P.; Kharchenko, V.; Dalgarno, A.

2010-12-01

Helium is one of the dominant constituents in the upper atmosphere of Mars [1]. Thermal (Jeans’) escape of He is negligible on Mars [2] and major mechanism of escape is related to the collisional ejection of He atoms by energetic oxygen. Collisional ejection dominates over ion-related mechanisms [3] and evaluation of the escape flux of neutral He becomes an important issue. The dissociative recombination of O2+ is considered to be the major source of energetic oxygen atoms [4]. We report accurate data on energy-transfer collisions between hot oxygen atoms and the atmospheric helium gas. Angular dependent scattering cross sections for elastic collisions of O(3P) and O(1D) atoms with helium gas have been calculated quantum mechanically and found to be surprisingly similar. Cross sections, computed for collisions with both helium isotopes, 3He and 4He, have been used to construct the kernel of the Boltzmann equation, describing the energy relaxation of hot oxygen atoms. Computed rates of energy transfer in O + He collisions have been used to evaluate the flux of He atoms escaping from the Mars atmosphere at different solar conditions. We have identified atmospheric layers mostly responsible for production of the He escape flux. Our results are consistent with recent data from Monte Carlo simulations of the escape of O atoms: strong angular anisotropy of atomic cross sections leads to an increased transparency of the upper atmosphere for escaping O flux [5] and stimulate the collisional ejection of He atoms. References [1] Krasnopolsky, V. A., and G. R. Gladstone (2005), Helium on Mars and Venus: EUVE observations and modeling, Icarus, 176, 395. [2] Chassefiere E. and F. Leblanc (2004), Mars atmospheric escape and evolution; interaction with the solar wind, Planetary and Space Science, 52, 1039 [3] Krasnopolsky, V. (2010), Solar activity variations of thermospheric temperatures on Mars and a problem of CO in the lower atmoshpere, Icarus, 207, 638. [4] Fox, J. L. (1995), On the escape of oxygen and hydrogen from Mars, Geophy. Rev. Lett., 20, 1847. [5] Krestyanikova, M. A. and V. I. Shematovich (2006), Stochastic models of hot planetary and satellite coronas: a hot oxygen corona of Mars, Solar System Research, 40, 384.

DETERMINING ION COMPOSITIONS USING AN ACCURATE MASS, TRIPLE QUADRUPOLE MASS SPECTROMETER

EPA Science Inventory

For the past decade, we have used double focusing mass spectrometers to determine
compositions of ions observed in mass spectra produced from compounds introduced by GC
based on measured exact masses of the ions and their +1 and +2 isotopic profiles arising from atoms of ...

78 FR 46829 - Assistance to Foreign Atomic Energy Activities

Federal Register 2010, 2011, 2012, 2013, 2014

2013-08-02

... Departments of Commerce and State Approved Activities 9. Medical Isotope Production 10. Activities Carried Out... production of special nuclear material (SNM). Proposed Sec. 810.2(c) would identify exempt activities, some... activities do not involve the production or use of special nuclear material; Production or extraction of...

Learning Activity Package, Physical Science. LAP Numbers 1, 2, 3, and 4.

ERIC Educational Resources Information Center

Williams, G. J.

These four units of the Learning Activity Packages (LAPs) for individualized instruction in physical science cover measuring techniques, operations of instruments, metric system heat, matter, energy, elements, atomic numbers, isotopes, molecules, mixtures, compounds, physical and chemical properties, liquids, solids, and gases. Each unit contains…

Fast Steering Mirror systems for the U-AVLIS program at LLNL

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

Watson, J.; Avicola, K.; Payne, A.

1994-07-01

We have successfully deployed several fast steering mirror systems in the Uranium Atomic Vapor Isotope Separation (U-AVLIS) facility at LLNL. These systems employ 2 mm to 150 mm optics and piezoelectric actuators to achieve microradian pointing accuracy with disturbance rejection bandwidths to a few hundred hertz.

Mobility of nitrogen-15-labeled nitrate and sulfur-34-labeled sulfate during snowmelt

Treesearch

John L. Campbell; Myron J. Mitchell; Bernhard Mayer; Peter M. Groffman; Lynn M. Christenson

2007-01-01

The objective of this study was to investigate the winter dynamics of SO42− and NO3− in a forested soil to better understand controls on these acidifying anions during snowmelt. In February 2004, a stable isotopic tracer solution with 93 atom% 34...

A sputtering derived atomic oxygen source for studying fast atom reactions

NASA Technical Reports Server (NTRS)

Ferrieri, Richard A.; Yung, Y. Chu; Wolf, Alfred P.

1987-01-01

A technique for the generation of fast atomic oxygen was developed. These atoms are created by ion beam sputtering from metal oxide surfaces. Mass resolved ion beams at energies up to 60 KeV are produced for this purpose using a 150 cm isotope separator. Studies have shown that particles sputtered with 40 KeV Ar(+) on Ta2O5 were dominantly neutral and exclusively atomic. The atomic oxygen also resided exclusively in its 3P ground state. The translational energy distribution for these atoms peaked at ca 7 eV (the metal-oxygen bond energy). Additional measurements on V2O5 yielded a bimodal distribution with the lower energy peak at ca 5 eV coinciding reasonably well with the metal-oxygen bond energy. The 7 eV source was used to investigate fast oxygen atom reactions with the 2-butene stereoisomers. Relative excitation functions for H-abstraction and pi-bond reaction were measured with trans-2-butene. The abstraction channel, although of minor relative importance at thermal energy, becomes comparable to the addition channel at 0.9 eV and dominates the high-energy regime. Structural effects on the specific channels were also found to be important at high energy.

Growth of continental crust: Clues from Nd isotopes and Nb-Th relationships in mantle-derived magmas

NASA Astrophysics Data System (ADS)

Arndt, N. T.; Chauvel, C.; Jochum, K.-P.; Gruau, G.; Hofmann, A. W.

Isotope and trace element geochemistry of Precambrian mantle derived rocks and implications for the formation of the continental crust is discussed. Epsilon Nd values of Archean komatiites are variable, but range up to at least +5, suggesting that the Archean mantle was heterogeneous and, in part, very depleted as far back as 3.4 to 3.5 Ga. This may be taken as evidence for separation of continental crust very early in Earth history. If these komatiite sources were allowed to evolve in a closed system, they would produce modern day reservoirs with much higher epsilon Nd values than is observed. This implies recycling of some sort of enriched material, perhaps subducted sediments, although other possibilities exist. Archean volcanics show lower Nb/Th than modern volcanics, suggesting a more primitive mantle source than that observed nowadays. However, Cretaceous komatiites from Gorgona island have similar Nb/Th to Archean volcanics, indicating either the Archean mantle source was indeed more primitive, or Archean magmas were derived from a deep ocean island source like that proposed for Gorgona.

Growth of continental crust: Clues from Nd isotopes and Nb-Th relationships in mantle-derived magmas

NASA Technical Reports Server (NTRS)

Arndt, N. T.; Chauvel, C.; Jochum, K.-P.; Gruau, G.; Hofmann, A. W.

1988-01-01

Isotope and trace element geochemistry of Precambrian mantle derived rocks and implications for the formation of the continental crust is discussed. Epsilon Nd values of Archean komatiites are variable, but range up to at least +5, suggesting that the Archean mantle was heterogeneous and, in part, very depleted as far back as 3.4 to 3.5 Ga. This may be taken as evidence for separation of continental crust very early in Earth history. If these komatiite sources were allowed to evolve in a closed system, they would produce modern day reservoirs with much higher epsilon Nd values than is observed. This implies recycling of some sort of enriched material, perhaps subducted sediments, although other possibilities exist. Archean volcanics show lower Nb/Th than modern volcanics, suggesting a more primitive mantle source than that observed nowadays. However, Cretaceous komatiites from Gorgona island have similar Nb/Th to Archean volcanics, indicating either the Archean mantle source was indeed more primitive, or Archean magmas were derived from a deep ocean island source like that proposed for Gorgona.

Quality assurance and quality control in light stable isotope laboratories: A case study of Rio Grande, Texas, water samples

USGS Publications Warehouse

Coplen, T.B.; Qi, H.

2009-01-01

New isotope laboratories can achieve the goal of reporting the same isotopic composition within analytical uncertainty for the same material analysed decades apart by (1) writing their own acceptance testing procedures and putting them into their mass spectrometric or laser-based isotope-ratio equipment procurement contract, (2) requiring a manufacturer to demonstrate acceptable performance using all sample ports provided with the instrumentation, (3) for each medium to be analysed, prepare two local reference materials substantially different in isotopic composition to encompass the range in isotopic composition expected in the laboratory and calibrated them with isotopic reference materials available from the International Atomic Energy Agency (IAEA) or the US National Institute of Standards and Technology (NIST), (4) using the optimum storage containers (for water samples, sealing in glass ampoules that are sterilised after sealing is satisfactory), (5) interspersing among sample unknowns local laboratory isotopic reference materials daily (internationally distributed isotopic reference materials can be ordered at three-year intervals, and can be used for elemental analyser analyses and other analyses that consume less than 1 mg of material) - this process applies to H, C, N, O, and S isotope ratios, (6) calculating isotopic compositions of unknowns by normalising isotopic data to that of local reference materials, which have been calibrated to internationally distributed isotopic reference materials, (7) reporting results on scales normalised to internationally distributed isotopic reference materials (where they are available) and providing to sample submitters the isotopic compositions of internationally distributed isotopic reference materials of the same substance had they been analysed with unknowns, (8) providing an audit trail in the laboratory for analytical results - this trail commonly will be in electronic format and might include a laboratory information management system, (9) making at regular intervals a complete backup of laboratory analytical data (both of samples logged into the laboratory and of mass spectrometric analyses), being sure to store one copy of this backup offsite, and (10) participating in interlaboratory comparison exercises sponsored by the IAEA and other agencies at regular intervals. ?? Taylor & Francis.

Uranium isotope separation from 1941 to the present

NASA Astrophysics Data System (ADS)

Maier-Komor, Peter

2010-02-01

Uranium isotope separation was the key development for the preparation of highly enriched isotopes in general and thus became the seed for target development and preparation for nuclear and applied physics. In 1941 (year of birth of the author) large-scale development for uranium isotope separation was started after the US authorities were warned that NAZI Germany had started its program for enrichment of uranium and might have confiscated all uranium and uranium mines in their sphere of influence. Within the framework of the Manhattan Projects the first electromagnetic mass separators (Calutrons) were installed and further developed for high throughput. The military aim of the Navy Department was to develop nuclear propulsion for submarines with practically unlimited range. Parallel to this the army worked on the development of the atomic bomb. Also in 1941 plutonium was discovered and the production of 239Pu was included into the atomic bomb program. 235U enrichment starting with natural uranium was performed in two steps with different techniques of mass separation in Oak Ridge. The first step was gas diffusion which was limited to low enrichment. The second step for high enrichment was performed with electromagnetic mass spectrometers (Calutrons). The theory for the much more effective enrichment with centrifugal separation was developed also during the Second World War, but technical problems e.g. development of high speed ball and needle bearings could not be solved before the end of the war. Spying accelerated the development of uranium separation in the Soviet Union, but also later in China, India, Pakistan, Iran and Iraq. In this paper, the physical and chemical procedures are outlined which lead to the success of the project. Some security aspects and Non-Proliferation measures are discussed.

Rate constants for the slow Mu + propane abstraction reaction at 300 K by diamagnetic RF resonance.

PubMed

Fleming, Donald G; Cottrell, Stephen P; McKenzie, Iain; Ghandi, Khashayar

2015-08-14

The study of kinetic isotope effects for H-atom abstraction rates by incident H-atoms from the homologous series of lower mass alkanes (CH4, C2H6 and, here, C3H8) provides important tests of reaction rate theory on polyatomic systems. With a mass of only 0.114 amu, the most sensitive test is provided by the rates of the Mu atom. Abstraction of H by Mu can be highly endoergic, due to the large zero-point energy shift in the MuH bond formed, which also gives rise to high activation energies from similar zero-point energy corrections at the transition state. Rates are then far too slow near 300 K to be measured by conventional TF-μSR techniques that follow the disappearance of the spin-polarised Mu atom with time. Reported here is the first measurement of a slow Mu reaction rate in the gas phase by the technique of diamagnetic radio frequency (RF) resonance, where the amplitude of the MuH product formed in the Mu + C3H8 reaction is followed with time. The measured rate constant, kMu = (6.8 ± 0.5) × 10(-16) cm(3) s(-1) at 300 K, is surprisingly only about a factor of three slower than that expected for H + C3H8, indicating a dominant contribution from quantum tunneling in the Mu reaction, consistent with elementary transition state theory calculations of the kMu/kH kinetic isotope effect.

Importance of a serine proximal to the C(4a) and N(5) flavin atoms for hydride transfer in choline oxidase.

PubMed

Yuan, Hongling; Gadda, Giovanni

2011-02-08

Choline oxidase catalyzes the flavin-dependent, two-step oxidation of choline to glycine betaine with the formation of an aldehyde intermediate. In the first oxidation reaction, the alcohol substrate is initially activated to its alkoxide via proton abstraction. The substrate is oxidized via transfer of a hydride from the alkoxide α-carbon to the N(5) atom of the enzyme-bound flavin. In the wild-type enzyme, proton and hydride transfers are mechanistically and kinetically uncoupled. In this study, we have mutagenized an active site serine proximal to the C(4a) and N(5) atoms of the flavin and investigated the reactions of proton and hydride transfers by using substrate and solvent kinetic isotope effects. Replacement of Ser101 with threonine, alanine, cysteine, or valine resulted in biphasic traces in anaerobic reductions of the flavin with choline investigated in a stopped-flow spectrophotometer. Kinetic isotope effects established that the kinetic phases correspond to the proton and hydride transfer reactions catalyzed by the enzyme. Upon removal of Ser101, there is an at least 15-fold decrease in the rate constants for proton abstraction, irrespective of whether threonine, alanine, valine, or cysteine is present in the mutant enzyme. A logarithmic decrease spanning 4 orders of magnitude is seen in the rate constants for hydride transfer with increasing hydrophobicity of the side chain at position 101. This study shows that the hydrophilic character of a serine residue proximal to the C(4a) and N(5) flavin atoms is important for efficient hydride transfer.

Observation of coherent backscattering of light in ultracold ^85Rb

NASA Astrophysics Data System (ADS)

Kulatunga, P.; Sukenik, C. I.; Havey, M. D.; Kupriyanov, D. V.; Sokolov, I. M.

2002-05-01

We report investigation of multiple coherent light scattering from ^85Rb atoms confined in a magneto-optic trap. In experimental studies, measurements are made of coherent backscattering of a low-intensity probe beam tuned near the F = 3 - F' = 4 transition in ^85Rb atoms. Polarization of backscattered light is determined by a backscattering polarimeter; the spatial distribution of light intensity is measured by a liquid-nitrogen cooled CCD camera set in the focal plane of the analyzing optics. The instrument has angular resolution of about 100 micro-radians, and a polarization analyzing power of roughly 1000. In this paper we describe the instrument details, including calibration procedures, and our measurements of atomic coherent backscattering. In a theoretical study of intensity enhancement of near-resonant backscattered light from cold ^85,87Rb atoms, we consider scattering orders up to 8 and a Gaussian atom distribution in the MOT. Enhancement factors are calculated for all D1 and D2 hyperfine components and for both isotopes.

Multiple coherent light scattering in ultracold rubidium

NASA Astrophysics Data System (ADS)

Kulatunga, P.; Sukenik, C. I.; Havey, M. D.; Kupriyanov, D. V.; Sokolov, I. M.

2001-11-01

We report investigation of multiple coherent light scattering from ^85Rb atoms confined in a magneto-optic trap. In a theoretical study of intensity enhancement of near-resonant backscattered light from cold ^85,87Rb atoms, we consider the dominant mode of double scattering only. Enhancement factors are calculated for all D1 and D2 hyperfine components and for both isotopes. In experimental studies, measurements are made of coherent backscattering of a low-intensity probe beam tuned near the F = 3 - F' = 4 transition in ^85Rb atoms. Polarization of backscattered light is determined by a backscattering polarimeter; the spatial distribution of light intensity is measured by a liquid-nitrogen cooled CCD camera set in the focal plane of the analyzing optics. The instrument has angular resolution of about 100 micro-radians, and a polarization analyzing power of roughly 1000. In this paper we describe the instrument details, including calibration procedures, and progress towards observation of atomic coherent backscattering.

Multiple coherent light scattering in ultracold rubidium

NASA Astrophysics Data System (ADS)

Havey, M. D.; Sukenik, C. I.; Kulatunga, P.; Kupriyanov, D. V.; Sokolov, I. M.

2001-05-01

We report investigation of multiple coherent light scattering from ^85Rb atoms confined in a magneto-optic trap. In a theoretical study of intensity enhancement of near-resonant backscattered light from cold ^85,87Rb atoms, we consider the dominant mode of double scattering only. Enhancement factors are calculated for all D1 and D2 hyperfine components and for both isotopes. In experimental studies, measurements are made of coherent backscattering of a low-intensity probe beam tuned near the F = 3 - F' = 4 transition in ^85Rb atoms. Polarization of backscattered light is determined by a backscattering polarimeter; the spatial distribution of light intensity is measured by a liquid-nitrogen cooled CCD camera set in the focal plane of the analyzing optics. The instrument has angular resolution of about 100 micro-radians, and a polarization analyzing power of roughly 1000. In this paper we describe the instrument details, including calibration procedures, and progress towards observation of atomic coherent backscattering.

Hydrogen isotopic substitution of solid methylamine through atomic surface reactions at low temperatures: A potential contribution to the D/H ratio of methylamine in molecular clouds

NASA Astrophysics Data System (ADS)

Oba, Yasuhiro; Chigai, Takeshi; Osamura, Yoshihiro; Watanabe, Naoki; Kouchi, Akira

2014-01-01

We experimentally studied hydrogen (H)-deuterium (D) substitution reactions of solid methylamine (CH3NH2) under astrophysically relevant conditions. We also calculated the potential energy surface for the H-D substitution reactions of methylamine isotopologues using quantum chemical methods. Despite the relatively large energy barrier of more than 18 kJ mol-1, CH3NH2 reacted with D atoms to yield deuterated methylamines at 10 K, suggesting that the H-D substitution reaction proceeds through quantum tunneling. Deuterated methylamines reacted with H atoms as well. On the basis of present results, we propose that methylamine has potential for D enrichment through atomic surface reactions on interstellar grains at very low temperatures in molecular clouds. D enrichment would occur in particular in the methyl group of methylamine.

Chemical experiments with superheavy elements.

PubMed

Türler, Andreas

2010-01-01

Unnoticed by many chemists, the Periodic Table of the Elements has been extended significantly in the last couple of years and the 7th period has very recently been completed with eka-Rn (element 118) currently being the heaviest element whose synthesis has been reported. These 'superheavy' elements (also called transactinides with atomic number > or = 104 (Rf)) have been artificially synthesized in fusion reactions at accelerators in minute quantities of a few single atoms. In addition, all isotopes of the transactinide elements are radioactive and decay with rather short half-lives. Nevertheless, it has been possible in some cases to investigate experimentally chemical properties of transactinide elements and even synthesize simple compounds. The experimental investigation of superheavy elements is especially intriguing, since theoretical calculations predict significant deviations from periodic trends due to the influence of strong relativistic effects. In this contribution first experiments with hassium (Hs, atomic number 108), copernicium (Cn, atomic number 112) and element 114 (eka-Pb) are reviewed.

Investigation of mass dependence effects for the accurate determination of molybdenum isotope amount ratios by MC-ICP-MS using synthetic isotope mixtures.

PubMed

Malinovsky, Dmitry; Dunn, Philip J H; Petrov, Panayot; Goenaga-Infante, Heidi

2015-01-01

Methodology for absolute Mo isotope amount ratio measurements by multicollector inductively coupled plasma-mass spectrometry (MC-ICP-MS) using calibration with synthetic isotope mixtures (SIMs) is presented. For the first time, synthetic isotope mixtures prepared from seven commercially available isotopically enriched molybdenum metal powders ((92)Mo, (94)Mo, (95)Mo, (96)Mo, (97)Mo, (98)Mo, and (100)Mo) are used to investigate whether instrumental mass discrimination of Mo isotopes in MC-ICP-MS is consistent with mass-dependent isotope distribution. The parent materials were dissolved and mixed as solutions to obtain mixtures with accurately known isotope amount ratios. The level of elemental impurities in the isotopically enriched molybdenum metal powders was quantified by ICP-MS by using both high-resolution and reaction cell instruments to completely resolve spectral interferences. The Mo isotope amount ratio values with expanded uncertainty (k = 2), determined by MC-ICP-MS for a high-purity Mo rod from Johnson Matthey, were as follows: (92)Mo/(95)Mo = 0.9235(9), (94)Mo/(95)Mo = 0.5785(8), (96)Mo/(95)Mo = 1.0503(9), (97)Mo/(95)Mo = 0.6033(6), (98)Mo/(95)Mo = 1.5291(20), and (100)Mo/(95)Mo = 0.6130(7). A full uncertainty budget for the measurements is presented which shows that the largest contribution to the uncertainty budget comes from correction for elemental impurities (∼51%), followed by the contribution from weighing operations (∼26 %). The atomic weight of molybdenum was calculated to be 95.947(2); the uncertainty in parentheses is expanded uncertainty with the coverage factor of 2. A particular advantage of the developed method is that calibration factors for all six Mo isotope amount ratios, involving the (95)Mo isotope, were experimentally determined. This allows avoiding any assumption on mass-dependent isotope fractions in MC-ICP-MS, inherent to the method of double spike previously used for Mo isotope amount ratio measurements. However, data obtained in this study show that instrumental mass discrimination in MC-ICP-MS is consistent with mass-dependent Mo isotope fractionation. This was demonstrated by a good agreement between experimentally obtained and theoretically expected values of the exponent of isotope fractionation, β, for each triad of Mo isotopes.

Isotope shifts in the 7 s →8 s transition of francium: Measurements and comparison to ab initio theory

NASA Astrophysics Data System (ADS)

Kalita, M. R.; Behr, J. A.; Gorelov, A.; Pearson, M. R.; DeHart, A. C.; Gwinner, G.; Kossin, M. J.; Orozco, L. A.; Aubin, S.; Gomez, E.; Safronova, M. S.; Dzuba, V. A.; Flambaum, V. V.

2018-04-01

We observe the electric-dipole forbidden 7 s →8 s transition in the francium isotopes Fr-211208 and 213Fr using a two-photon excitation scheme. We collect the atoms online from an accelerator and confine them in a magneto-optical trap for the measurements. In combination with previous measurements of the 7 s →7 p1 /2 transition we perform a King plot analysis. We compare the thus-determined ratio of the field shift constants (1.228 ± 0.019) to results obtained from new ab initio calculations (1.234 ± 0.010).

Calorimetric Study of the Activation of Hydrogen by Tris(pentafluorophenyl)borane and Trimesitylphosphine

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

Houghton, Adrian Y.; Autrey, Tom

The mechanism of H2 activation by B(C6F5)3 and P(mes)3 was investigated by isothermal reaction calorimetry, and the heat curves generated were modelled in Berkeley Madonna. The reaction is treated as a single, termolecular step, and an Eyring analysis gave activation parameters of ΔH‡ = 13.6(9) kJ mol-1 and ΔS‡ = -204(85) J K-1 mol-1. The enthalpy of the reaction was found to be -141 kJ mol-1. The kinetic isotope effect was measured as 1.1, consistent with a four-center transition state containing two isotopically exchangeable atoms.

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.

Simultaneous determination of iron, cadmium, zinc, copper, nickel, lead, and uranium in seawater by stable isotope dilution spark source mass spectrometry

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

Mykytiuk, A.P.; Russell, D.S.; Sturgeon, R.E.

Trace concentrations (ng/mL) of Fe, Cd, Zn, Cu, Ni, Pb, U, and Co have been determined in seawater by stable isotope dilution spark source mass spectrometry. The seawater samples were preconcentrated on the ion exchanger Chelex-100 and the concentrate was evaporated on a graphite or silver electrode. The results are compared with those obtained by graphite furnace atomic absorption spectrometry and inductively coupled plasma emission spectrometry. The technique avoids the use of calibration standards and is capable of producing results in cases where the analyte is only partially recovered. 2 tables.

HFS and isotope shift in the atomic spectrum of205Pb

NASA Astrophysics Data System (ADS)

Barboza-Flores, M.; Redi, O.; Schönberger, P.; Stroke, H. H.; Naumann, R. A.

1987-06-01

The hfs of205Pb in the 283.3-nm resonance line and its isotope shift (IS) have been measured in absorption with the use of dispersive spectroscopy. A new method for calibration and analysis, when internal standards are not available is described. The results are: hfs interaction constants A=70.3(5)×10-3 cm-1, B=-0.6(1.1)×10-3 cm-1,205Pb-208Pb IS=-123.9(2.0)×10-3 cm-1. The derived nuclear magnetic dipole moment, μ=0.704(5) μ N is in good agreement with values calculated with a nuclear configuration mixing model.

Oxygen Isotope Composition of Nitrate Produced by Freshwater Nitrification

NASA Astrophysics Data System (ADS)

Boshers, D.; Granger, J.; Bohlke, J. K.

2016-12-01

Measurements of the naturally occurring nitrogen and oxygen stable isotope ratios of nitrate (NO3-), δ15N and δ18O, can be used to determine the source, dispersal, and fate of natural and contaminant NO3- in aquatic environments. To this end, it is necessary to know the extent to which NO3- isotopologues are modified by biological reactions, as heavy and light isotopes have different reaction rates. The purpose of this study was to determine the influence of the δ18O of ambient water on the isotope composition of NO3- produced during nitrification, the biological oxidation of ammonium (NH4+) to nitrite (NO2-) and then NO3-, which is poorly constrained in freshwater systems. To determine the δ18O of NO3- produced by nitrification in freshwater, we collected water from a stream in New England, which we amended with NH4+ and with increments of 18O-enriched water, to monitor the isotope composition of NO3- produced by a natural consortium of nitrifiers. Added NH4+ was completely oxidized to NO3- over 26 days. The final δ18O of nitrified NO3- revealed sensitivity to the δ18O of water mediated by (a) isotopic equilibration between water and NO2- and (b) kinetic isotope fractionation during O-atom incorporation from water into NO2- and NO3-. Our results concur with nitrifying culture experiments that have demonstrated analogous sensitivity of the δ18O of nitrified NO3- to equilibrium and kinetic O isotope effects (Buchwald et al. 2012), as well as show that these dynamics need to be considered to interpret NO3- isotope distribution in freshwater environments.

Image segmentation for uranium isotopic analysis by SIMS: Combined adaptive thresholding and marker controlled watershed approach

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

Willingham, David G.; Naes, Benjamin E.; Heasler, Patrick G.

A novel approach to particle identification and particle isotope ratio determination has been developed for nuclear safeguard applications. This particle search approach combines an adaptive thresholding algorithm and marker-controlled watershed segmentation (MCWS) transform, which improves the secondary ion mass spectrometry (SIMS) isotopic analysis of uranium containing particle populations for nuclear safeguards applications. The Niblack assisted MCWS approach (a.k.a. SEEKER) developed for this work has improved the identification of isotopically unique uranium particles under conditions that have historically presented significant challenges for SIMS image data processing techniques. Particles obtained from five NIST uranium certified reference materials (CRM U129A, U015, U150, U500more » and U850) were successfully identified in regions of SIMS image data 1) where a high variability in image intensity existed, 2) where particles were touching or were in close proximity to one another and/or 3) where the magnitude of ion signal for a given region was count limited. Analysis of the isotopic distributions of uranium containing particles identified by SEEKER showed four distinct, accurately identified 235U enrichment distributions, corresponding to the NIST certified 235U/238U isotope ratios for CRM U129A/U015 (not statistically differentiated), U150, U500 and U850. Additionally, comparison of the minor uranium isotope (234U, 235U and 236U) atom percent values verified that, even in the absence of high precision isotope ratio measurements, SEEKER could be used to segment isotopically unique uranium particles from SIMS image data. Although demonstrated specifically for SIMS analysis of uranium containing particles for nuclear safeguards, SEEKER has application in addressing a broad set of image processing challenges.« less

Pu isotopes in the western North Pacific Ocean before the accident at Fukushima Dai-ichi Nuclear Power Station

NASA Astrophysics Data System (ADS)

Yamada, M.; Zheng, J.; Aono, T.

2011-12-01

Anthropogenic radionuclides such as Pu-239 (half-life: 24100 yr), Pu-240 (half-life: 6560 yr) and Pu-241 (half-life: 14.325 yr) mainly have been released into the environment as the result of atmospheric nuclear weapons testing. In the North Pacific Ocean, two distinct sources of Pu isotopes can be identified; i.e., the global stratospheric fallout and close-in tropospheric fallout from nuclear weapons testing at the Pacific Proving Grounds in the Marshall Islands. The atom ratio of Pu-240/Pu-239 is a powerful fingerprint to identify the sources of Pu in the ocean. The Pu-240/Pu-239 atom ratios in seawater and marine sediment samples collected in the western North Pacific before the accident at Fukushima Dai-ichi Nuclear Power Station will provide useful background data for understanding the process controlling Pu transport and for distinguishing future Pu sources. The atom ratios of Pu-240/Pu-239 in water columns from the Yamato and Tsushima Basins in the Japan Sea were significantly higher than the mean global fallout ratio of 0.18; however, there were no temporal variation of atom ratios during the period from 1984 to 1993 in the Japan Sea. The total Pu-239+240 inventories in the whole water columns were approximately doubled during the period from 1984 to 1993 in the two basins. The atom ratio of Pu-240/Pu-239 in surface water from Sagami Bay, western North Pacific Ocean, was 0.224 and showed no notable variation from the surface to the bottom with the mean atom ratio being 0.234. The atom ratios for the Pacific coast, near the Rokkasho nuclear fuel reprocessing plant, were approximately the same as the 0.224 ratio obtained from Sagami Bay, western North Pacific margin. The atom ratios in the surficial sediments from Sagami Bay ranged from 0.229 to 0.247. The mean atom ratio in the sediment columns in the East China Sea ranged from 0.248 for the Changjiang estuary to 0.268 for the shelf edge. The observed atom ratios were significantly higher than the mean global fallout ratio of 0.180, proving the existence of close-in fallout Pu originating from the Pacific Proving Grounds. The North Equatorial Current and Kuroshio Current were proposed as pathways for transporting Pacific Proving Grounds-origin Pu to the western North Pacific Ocean.

New perspectives on the Li isotopic composition of the upper continental crust and its weathering signature

NASA Astrophysics Data System (ADS)

Sauzéat, Lucie; Rudnick, Roberta L.; Chauvel, Catherine; Garçon, Marion; Tang, Ming

2015-10-01

Lithium isotopes are increasingly used to trace both present-day and past weathering processes at the surface of the Earth, and could potentially be used to evaluate the average degree of past weathering recorded by the upper continental crust (UCC). Yet the previous estimate of average δ7Li of the UCC has a rather large uncertainty, hindering the use of Li isotopes for this purpose. New δ7Li for desert and periglacial loess deposits (windblown dust) from several parts of the world (Europe, Argentina, China and Tajikistan) demonstrate that the former are more homogeneous than the latter, and may therefore serve as excellent proxies of the average composition of large tracts of the UCC. The Li isotopic compositions and concentrations of desert loess samples are controlled by eolian sorting that can be quantified by a binary mixing between a weathered, fine-grained end-member, dominated by phyllosilicates and having low δ7Li, and an unweathered, coarse-grained end-member, that is a mixture of quartz and plagioclase having higher δ7Li. We use correlations between insoluble elements (REE, Nd/Hf and Fe2O3/SiO2), Li concentrations (henceforth referred as [Li]), and δ7Li to estimate a new, more precise, average Li isotopic composition and concentration for the UCC: [ Li ] = 30.5 ± 3.6 (2 σ) ppm, and δ7Li = + 0.6 ± 0.6 (2 σ). The δ7Li for desert loess deposits is anti-correlated with the chemical index of alteration (CIA). Using this relationship, along with our average δ7Li, we infer that (1) the present-day CIA of the average UCC is 61-2+4 (2 σ), higher than the common reference value of 53, and (2) the average proportion of chemically weathered components is as high as 37-10+17 (2 σ)% at the surface of the Earth.

What Is a Chemical Element?

ERIC Educational Resources Information Center

ten Hoor, Marten J.

2017-01-01

Contrary to current IUPAC recommendations, the chemical element X should be defined as the nucleus of the X atom. Consequently, different isotopes with their different nuclei belong to different elements, each one with its own physical and chemical properties. This view leads to the conclusion that we no longer have a periodic table of the…

Atomic spectrometry update - atomic mass spectrometry.

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

Bacon, J.; Crain, J. S.; McMahon, A. W.

The MS and XRF updates have been published together since their introduction in 1988. In the last few years, however, the two sections have been prepared independently of each other and it therefore seemed appropriate to publish the two sections separately. With effect from this issue, the MS Update will appear in the October issue of JAAS and the XRF Update in the November issue. The format used for the MS section is broadly similar to that used last year, with some additional sub-headings. This Update is intended to cover all atomic and stable isotopic MS techniques, but not thosemore » used in studies of fundamental nuclear physics and exotic nuclei far from stability. Also excluded are those reports in which MS is used as a tool in the study of molecular processes and of gaseous components. the review is based on critical selection of developments in instrumentation and methodology, notable for their innovation, originality or achievement of significant advances, and is not intended to be comprehensive in its coverage. Conference papers are only included if they contain enough information to show they meet these criteria, and our policy in general remains one of waiting for a development to appear in a full paper before inclusion in the review. a similar policy applies to foreign language papers unlikely to reach a wide audience. Routine applications of atomic MS are not included in this Update and the reader is referred to the Updates on Industrial Analysis: Metals, Chemicals and Advanced Materials (96/416), Environmental Analysis (96/1444) and Clinical and Biological Materials, Food and Beverages (96/2479). Also excluded are those applications, even if not routine, which use atomic spectroscopy as a tool for the study of a non-atomic property, for example, the use of stable isotope labeling of carbon or nitrogen in biomolecules in metabolic studies. There have been few general reviews on atomic MS of note in the period covered by this update. That of Colodner et al.(95/3890) gave a general review of ion sources, in particular GDMS, ICP-MS, SIMS and TIMS, and that of Blades (95/2568 and 95/3077) was a very general overview of some of the techniques covered in this Update. The review of the literature in the period covered by this Update reveals strong advances in all areas, with a continuing push to achieve better analyses on smaller samples and in less time. Most advances generally require more sophisticated instrumentation, improved sample preparation methods or new methods of sample introduction. This is typified by advances in ICP-MS, which see considerable emphasis on sample introduction techniques and a move towards magnetic sector instruments. Most applications of ICP-MS are now highly routine. There is still, however, a desire to achieve affordable analysis with simplified and cost-effective instruments, as illustrated by the development of mobile, in-situ isotope MS for environmental studies.« less

Neutron protein crystallography: A complementary tool for locating hydrogens in proteins.

PubMed

O'Dell, William B; Bodenheimer, Annette M; Meilleur, Flora

2016-07-15

Neutron protein crystallography is a powerful tool for investigating protein chemistry because it directly locates hydrogen atom positions in a protein structure. The visibility of hydrogen and deuterium atoms arises from the strong interaction of neutrons with the nuclei of these isotopes. Positions can be unambiguously assigned from diffraction at resolutions typical of protein crystals. Neutrons have the additional benefit to structural biology of not inducing radiation damage in protein crystals. The same crystal could be measured multiple times for parametric studies. Here, we review the basic principles of neutron protein crystallography. The information that can be gained from a neutron structure is presented in balance with practical considerations. Methods to produce isotopically-substituted proteins and to grow large crystals are provided in the context of neutron structures reported in the literature. Available instruments for data collection and software for data processing and structure refinement are described along with technique-specific strategies including joint X-ray/neutron structure refinement. Examples are given to illustrate, ultimately, the unique scientific value of neutron protein crystal structures. Copyright © 2015 Elsevier Inc. All rights reserved.

Charge transfer in low-energy collisions of H with He+ and H+ with He in excited states

NASA Astrophysics Data System (ADS)

Loreau, J.; Ryabchenko, S.; Muñoz Burgos, J. M.; Vaeck, N.

2018-04-01

The charge transfer process in collisions of excited (n = 2, 3) hydrogen atoms with He+ and in collisions of excited helium atoms with H+ is studied theoretically. A combination of a fully quantum-mechanical method and a semi-classical approach is employed to calculate the charge-exchange cross sections at collision energies from 0.1 eV u‑1 up to 1 keV u‑1. These methods are based on accurate ab initio potential energy curves and non-adiabatic couplings for the molecular ion HeH+. Charge transfer can occur either in singlet or in triplet states, and the differences between the singlet and triplet spin manifolds are discussed. The dependence of the cross section on the quantum numbers n and l of the initial state is demonstrated. The isotope effect on the charge transfer cross sections, arising at low collision energy when H is substituted by D or T, is investigated. Rate coefficients are calculated for all isotopes up to 106 K. Finally, the impact of the present calculations on models of laboratory plasmas is discussed.

High Useful Yield and Isotopic Analysis of Uranium by Resonance Ionization Mass Spectrometry

DOE PAGES

Savina, Michael R.; Isselhardt, Brett H.; Kucher, Andrew; ...

2017-05-09

Useful yields from resonance ionization mass spectrometry can be extremely high compared to other mass spectrometry techniques, but uranium analysis shows strong matrix effects arising from the tendency of uranium to form strongly bound oxide molecules that do not dissociate appreciably on energetic ion bombardment. Here, we demonstrate a useful yield of 24% for metallic uranium. Modeling the laser ionization and ion transmission processes shows that the high useful yield is attributable to a high ion fraction achieved by resonance ionization. We quantify the reduction of uranium oxide surface layers by Ar + and Ga + sputtering. The useful yieldmore » for uranium atoms from a uranium dioxide matrix is 0.4% and rises to 2% when the surface is in sputter equilibrium with the ion beam. The lower useful yield from the oxide is almost entirely due to uranium oxide molecules reducing the neutral atom content of the sputtered flux. We also demonstrate rapid isotopic analysis of solid uranium oxide at a precision of <0.5% relative standard deviation using relatively broadband lasers to mitigate spectroscopic fractionation.« less