Science.gov

Sample records for isotope abundance measurements

  1. Raman scattering method and apparatus for measuring isotope ratios and isotopic abundances

    DOEpatents

    Harney, Robert C.; Bloom, Stewart D.

    1978-01-01

    Raman scattering is used to measure isotope ratios and/or isotopic abundances. A beam of quasi-monochromatic photons is directed onto the sample to be analyzed, and the resulting Raman-scattered photons are detected and counted for each isotopic species of interest. These photon counts are treated mathematically to yield the desired isotope ratios or isotopic abundances.

  2. LITERATURE SURVEY ON ISOTOPIC ABUNDANCE RATIO MEASUREMENTS - 2001-2005

    SciTech Connect

    HOLDEN, N.E.

    2005-08-13

    Along with my usual weekly review of the published literature for new nuclear data, I also search for new candidates for best measurements of isotopic abundances from a single source. Most of the published articles, that I previously had found in the Research Library at the Brookhaven Lab, have already been sent to the members of the Atomic Weights Commission, by either Michael Berglund or Thomas Walczyk. In the last few days, I checked the published literature for any other articles in the areas of natural variations in isotopic abundance ratios, measurements of isotopic abundance ratios on samples of extra-terrestrial material and isotopic abundance ratio measurements performed using ICPMS instruments. Hopefully this information will be of interest to members of the Commission, the sub-committee on isotopic abundance measurements (SIAM), members of the former sub-committee on natural isotopic fractionation (SNIF), the sub-committee on extra-terrestrial isotope ratios (SETIR), the RTCE Task Group and the Guidelines Task Group, who are dealing with ICPMS and TIMS comparisons. In the following report, I categorize the publications in one of four areas. Measurements performed using either positive or negative ions with Thermal Ionization Mass Spectrometer, TIMS, instruments; measurements performed on Inductively Coupled Plasma Mass Spectrometer, ICPMS, instruments; measurements of natural variations of the isotopic abundance ratios; and finally measurements on extra-terrestrial samples with instrumentation of either type. There is overlap in these areas. I selected out variations and ET results first and then categorized the rest of the papers by TIMS and ICPMS.

  3. Mass Spectrometric Measurement of Martian Krypton and Xenon Isotopic Abundance

    NASA Technical Reports Server (NTRS)

    Mahaffy, P.; Mauersberger, K.

    1993-01-01

    The Viking gas chromatograph mass spectrometer experiment provided significant data on the atmospheric composition at the surface of Mars, including measurements of several isotope ratios. However, the limited dynamic range of this mass spectrometer resulted in marginal measurements for the important Kr and Xe isotopic abundance. The Xe-129 to Xe-132 ratio was measured with an uncertainty of 70%, but none of the other isotope ratios for these species were obtained. Accurate measurement of the Xe and Kr isotopic abundance in this atmosphere provides an important data point in testing theories of planetary formation and atmospheric evolution. The measurement is also essential for a stringent test for the Martian origin of the SNC meteorites, since the Kr and Xe fractionation pattern seen in gas trapped in glassy nodules of an SNC (EETA 79001) is unlike any other known solar system resevoir. Current flight mass spectrometer designs combined with the new technology of a high-performance vacuum pumping system show promise for a substantial increase in gas throughput and the dynamic range required to accurately measure these trace species. Various aspects of this new technology are discussed.

  4. Resonance ionization mass spectrometry for isotopic abundance measurements

    NASA Technical Reports Server (NTRS)

    Miller, C. M.

    1986-01-01

    Resonance ionization mass spectrometry (RIMS) is a relatively new laser-based technique for the determination of isotopic abundances. The resonance ionization process depends upon the stepwise absorption of photons from the laser, promoting atoms of the element of interest through progressively higher electronic states until an ion is formed. Sensitivity arises from the efficiency of the resonant absorption process when coupled with the power available from commercial laser sources. Selectivity derives naturally from the distinct electronic structure of different elements. This isobaric discrimination has provided the major impetus for development of the technique. Resonance ionization mass spectrometry was used for analysis of the isotopic abundances of the rare earth lutetium. Isobaric interferences from ytterbium severely effect the ability to measure small amounts of the neutron-deficient Lu isotopes by conventional mass spectrometric techniques. Resonance ionization for lutetium is performed using a continuous-wave laser operating at 452 nm, through a sequential two-photon process, with one photon exciting the intermediate resonance and the second photon causing ionization. Ion yields for microgram-sized quantities of lutetium lie between 10(6) and 10(7) ions per second, at overall ionization efficiencies approaching 10(-4). Discrimination factors against ytterbium greater than 10(6) have been measured. Resonance ionization for technetium is also being explored, again in response to an isobaric interference, molybdenum. Because of the relatively high ionization potential for Tc, three-photon, two-color RIMS processes are being developed.

  5. Measurement of isotope abundance variations in nature by gravimetric spiking isotope dilution analysis (GS-IDA).

    PubMed

    Chew, Gina; Walczyk, Thomas

    2013-04-02

    Subtle variations in the isotopic composition of elements carry unique information about physical and chemical processes in nature and are now exploited widely in diverse areas of research. Reliable measurement of natural isotope abundance variations is among the biggest challenges in inorganic mass spectrometry as they are highly sensitive to methodological bias. For decades, double spiking of the sample with a mix of two stable isotopes has been considered the reference technique for measuring such variations both by multicollector-inductively coupled plasma mass spectrometry (MC-ICPMS) and multicollector-thermal ionization mass spectrometry (MC-TIMS). However, this technique can only be applied to elements having at least four stable isotopes. Here we present a novel approach that requires measurement of three isotope signals only and which is more robust than the conventional double spiking technique. This became possible by gravimetric mixing of the sample with an isotopic spike in different proportions and by applying principles of isotope dilution for data analysis (GS-IDA). The potential and principle use of the technique is demonstrated for Mg in human urine using MC-TIMS for isotopic analysis. Mg is an element inaccessible to double spiking methods as it consists of three stable isotopes only and shows great potential for metabolically induced isotope effects waiting to be explored.

  6. An investigation of techniques for the measurement and interpretation of cosmic ray isotopic abundances. Ph.D. Thesis

    NASA Technical Reports Server (NTRS)

    Wiedenbeck, M. E.

    1977-01-01

    An instrument, the Caltech High Energy Isotope Spectrometer Telescope was developed to measure isotopic abundances of cosmic ray nuclei by employing an energy loss - residual energy technique. A detailed analysis was made of the mass resolution capabilities of this instrument. A formalism, based on the leaky box model of cosmic ray propagation, was developed for obtaining isotopic abundance ratios at the cosmic ray sources from abundances measured in local interstellar space for elements having three or more stable isotopes, one of which is believed to be absent at the cosmic ray sources. It was shown that the dominant sources of uncertainty in the derived source ratios are uncorrelated errors in the fragmentation cross sections and statistical uncertainties in measuring local interstellar abundances. These results were applied to estimate the extent to which uncertainties must be reduced in order to distinguish between cosmic ray production in a solar-like environment and in various environments with greater neutron enrichments.

  7. High Spatial Resolution Isotopic Abundance Measurements by Secondary Ion Mass Spectrometry: Status and Prospects

    NASA Astrophysics Data System (ADS)

    McKeegan, K. D.

    2007-12-01

    Secondary Ion Mass Spectrometry, SIMS or ion microprobe analysis, has become an important tool for geochemistry because of its ability study the distributions of elemental and isotopic abundances in situ on polished samples with high (typically a few microns to sub-micron) spatial resolution. In addition, SIMS exhibits high sensitivity for a wide range of elements (H to Pu) so that isotope analyses can sometimes be performed for elements that comprise only trace quantities of some mineral phase (e.g., Pb in zircon) or on major and/or minor elements in very small samples (e.g., presolar dust grains). Offsetting these positive attributes are analytical difficulties due to the complexity of the sputtering source of analyte ions: (1) relatively efficient production of molecular ion species (especially from a complex matrix such as most natural minerals) that cause interferences at the same nominal mass as atomic ions of interest, and (2) quantitation problems caused by variations in the ionization efficiencies of different elements and/or isotopes depending upon the chemical state of the sample surface during sputtering--the so-called "matrix effects". Despite the availability of high mass resolution instruments (e.g., SHRIMP II/RG, CAMECA 1270/1280/NanoSIMS), the molecular ion interferences effectively limit the region of the mass table that can be investigated in most samples to isotope systems at Ni or lighter or at Os or heavier. The matrix effects and the sensitivity of instrumental mass discrimination to the physical state of the sample surface can hamper reproducibility and have contributed to a view that SIMS analyses, especially for so- called stable isotopes, are most appropriate for extraterrestrial samples which are often small, rare, and can exhibit large magnitude isotopic effects. Recent improvements in instrumentation and technique have extended the scope of SIMS isotopic analyses and applications now range from geochronology to paleoclimatology to

  8. Study on strontium isotope abundance-ratio measurements by using a 13-MeV proton beam

    NASA Astrophysics Data System (ADS)

    Jeong, Cheol-Ki; Jang, Han; Lee, Goung-Jin

    2016-09-01

    The Rb-Sr dating method is used in dating Paleozoic and Precambrian rocks. This method measures the 87Rb and the 87Sr concentrations by using thermal ionization mass spectrometry (TIMS) [J. Hefne et al., Inter. J. Phys. Sci. 3(1), 28 (2008)]. In addition, it calculates the initial 87Sr/86Sr ratio to increase the reliability of Rb-Sr dating. In this study, the 87Sr/86Sr ratio was measured by using a 13-MeV proton accelerator. Proton kinetic energies are in the range of tens of megaelectronvolts, and protons have large absorption cross-sections for ( p, n) reactions with most substances. After absorbing a proton with such a high kinetic energy, an element is converted into a nuclide with its atomic number increased by one via nuclear transmutation. These nuclides usually have short half-lives and return to the original state through radioactive decay. When a strontium sample is irradiated with protons, nuclear transmutation occurs; thus, the strontium isotope present in the sample changes to a yttrium isotope, which is an activated radioisotope. Based on this, the 87Sr/86Sr ratio was calculated by analyzing the gamma-rays emitted by each yttrium isotope. The KIRAMS-13 cyclotron at the Cyclotron Center of Chosun University, where 13-MeV protons can be extracted, was utilized in our experiment. The 87Sr/86Sr isotope ratio was computed for samples irradiated with these protons, and the result was similar to the isotope ratio for the Standard Reference Material, i.e., 98.2 ± 3.4%. As part of the analysis, proton activation analyses were performed using 13-MeV protons, and the experimental results of this research suggest a possible approach for measuring the strontium-isotope abundance ratio of samples.

  9. Determination of the natural abundance δ15N of taurine by gas chromatography-isotope ratio measurement mass spectrometry.

    PubMed

    Tea, Illa; Antheaume, Ingrid; Besnard, Jorick; Robins, Richard J

    2010-12-15

    The measurement of the nitrogen isotope ratio of taurine (2-aminoethanesulphonic acid) in biological samples has a large number of potential applications. Taurine is a small water-soluble molecule which is notoriously difficult to analyze due to its polarity and functionality. A method is described which allows the determination of the natural abundance δ(15)N values of taurine and structural analogues, such as 3-amino-1-propanesulphonic acid (APSA), by isotope ratio mass spectrometry interfaced to gas chromatography (GC-irm-MS). The one-step protocol exploits the simultaneous derivatization of both functionalities of these aminosulphonic acids by reaction with triethylorthoacetate (TEOA). Conditions have been established which ensure quantitative reaction thus avoiding any nitrogen isotope fractionation during derivatization and workup. The differences in the δ(15)N values of derivatized and non-derivatized taurine and APSA all fall within the working range of 0.4‰ (-0.02 to 0.39‰). When applied to four sources of taurine with various δ(15)N values, the method achieved excellent reproducibility and accuracy. The optimized method enables the determination of the natural abundance δ(15)N values of taurine over the concentration range 1.5-7.84 µmol.mL(-1) in samples of biological origin.

  10. THE ATOMIC WEIGHTS COMMISSION AND ISOTOPIC ABUNDANCE RATIO DETERMINATIONS.

    SciTech Connect

    HOLDEN, N.E.

    2005-08-07

    Following Thomson's discovery of stable isotopes in non-radioactive chemical elements, the derivation of atomic weight values from mass spectrometric measurements of isotopic abundance ratios moved very slowly. Forty years later, only 3 1/2 % of the recommended values were based on mass spectrometric measurements and only 38% in the first half century. It might be noted that two chemical elements (tellurium and mercury) are still based on chemical measurements, where the atomic weight value calculated from the relative isotopic abundance measurement either agrees with the value from the chemical measurement or the atomic weight value calculated from the relative isotopic abundance measurement falls within the uncertainty of the chemical measurement of the atomic weight. Of the 19 chemical elements, whose atomic weight is based on non-corrected relative isotopic abundance measurements, five of these are two isotope systems (indium, iridium, lanthanum, lutetium and tantalum) and one is a three-isotope system (oxygen).

  11. Symbiotic nitrogen fixation in a tropical rainforest: 15N natural abundance measurements supported by experimental isotopic enrichment.

    PubMed

    Pons, Thijs L; Perreijn, Kristel; van Kessel, Chris; Werger, Marinus J A

    2007-01-01

    * Leguminous trees are very common in the tropical rainforests of Guyana. Here, species-specific differences in N(2) fixation capability among nodulating legumes growing on different soils and a possible limitation of N(2) fixation by a relatively high nitrogen (N) and low phosphorus (P) availability in the forest were investigated. * Leaves of 17 nodulating species and 17 non-nodulating reference trees were sampled and their delta(15)N values measured. Estimates of N(2) fixation rates were calculated using the (15)N natural abundance method. Pot experiments were conducted on the effect of N and P availability on N(2) fixation using the (15)N-enriched isotope dilution method. * Nine species showed estimates of > 33% leaf N derived from N(2) fixation, while the others had low or undetectable N(2) fixation rates. High N and low P availability reduced N(2) fixation substantially. * The results suggest that a high N and low P availability in the forest limit N(2) fixation. At the forest ecosystem level, N(2) fixation was estimated at c. 6% of total N uptake by the tree community. We conclude that symbiotic N(2) fixation plays an important role in maintaining high amounts of soil available N in undisturbed forest.

  12. Novel concept for the mass spectrometric determination of absolute isotopic abundances with improved measurement uncertainty: Part 1 - theoretical derivation and feasibility study

    NASA Astrophysics Data System (ADS)

    Rienitz, Olaf; Pramann, Axel; Schiel, Detlef

    2010-01-01

    The development of a new method for the experimental determination of absolute isotopic abundances using a modified isotope dilution mass spectrometry (IDMS) technique is described. The intention and thus main application will be the quantification of molar masses M of highly enriched materials with improved measurement uncertainty (Urel(M) [approximate] 10-8 with k = 2). In part 1 of the current work, the theoretical foundation of the new method and its mathematical derivation is shown in detail, while part 2 will cover the experiments based on the new method described. Its core idea is the introduction of a virtual element (VE) consisting of all isotopes but the one having the largest or smallest abundance. IDMS is used to determine the mass fraction of this VE in its matrix, namely the element itself. A new set of equations serve to calculate all isotopic abundances (even the large one omitted with the introduction of the VE) merely from the mass fraction of the VE. A comprehensive uncertainty budget according to the Guide to the Expression of Uncertainty in Measurement (GUM) was set up in order to discuss and validate the novel concept. The hypothetical input data of the uncertainty budget were estimated to resemble a silicon material highly enriched with respect to 28Si used in the context of the international Avogadro Project. Considering the calculated results, the experimental determination of the molar mass of the above mentioned silicon seems very promising. As far as the authors know, this will be the first time IDMS was applied to determine a molar mass.

  13. Literature survey of isotopic abundance data for 1987-1989

    SciTech Connect

    Holden, N.E. )

    1989-08-09

    I have compiled all of the data on isotopic abundance measurements and their variation in nature for the time period since the last General Assembly. Most of the data deals with the variations in the abundances as given by per mil deviations from some standard. As such, they are not of major interest to the Atomic Weights Commission. However, there were some measurements which are of general interest in this list.

  14. Evaluation of accurate mass and relative isotopic abundance measurements in the LTQ-orbitrap mass spectrometer for further metabolomics database building.

    PubMed

    Xu, Ying; Heilier, Jean-François; Madalinski, Geoffrey; Genin, Eric; Ezan, Eric; Tabet, Jean-Claude; Junot, Christophe

    2010-07-01

    Recently, high-resolution mass spectrometry has been largely employed for compound identification, thanks to accurate mass measurements. As additional information, relative isotope abundance (RIA) is often needed to reduce the number of candidates prior to tandem MS(n). Here, we report on the evaluation of the LTQ-Orbitrap, in terms of accurate mass and RIA measurements for building further metabolomics spectral databases. Accurate mass measurements were achieved in the ppm range, using external calibration within 24 h, and remained at <5 ppm over a one-week period. The experimental relative abundances of (M+1) isotopic ions were evaluated in different data sets. First of all, 137 solutions of commercial compounds were analyzed by flow injection analysis in both the positive and negative ion modes. It was found that the ion abundance was the main factor impacting the accuracy of RIA measurements. It was possible to define some intensity thresholds above which errors were systematically <20% of their theoretical values. The same type of results were obtained with analyses from two biological media. Otherwise, no significant effect of ion transmission between the LTQ ion trap and the Orbitrap analyzer on RIA measurement errors was found, whereas the reliability of RIA measurements was dramatically improved by reducing the mass detection window. It was also observed that the signal integration method had a significant impact on RIA measurement errors, with the most-reliable results being obtained with peak height integrations. Finally, automatic integrations using the data preprocessing software XCMS and MZmine gave results similar to those obtained by manual integration, suggesting that it is relevant to use the RIA information in automatic elemental composition determination software from metabolomic peak tables.

  15. Helium isotopic abundance variation in nature

    SciTech Connect

    Holden, N.E.

    1993-08-01

    The isotopic abundance of helium in nature has been reviewed. This atomic weight value is based on the value of helium in the atmosphere, which is invariant around the world and up to a distance of 100,000 feet. Helium does vary in natural gas, volcanic rocks and gases, ocean floor sediments, waters of various types and in radioactive minerals and ores due to {alpha} particle decay of radioactive nuclides.

  16. The abundance and isotopic composition of water in eucrites

    NASA Astrophysics Data System (ADS)

    Barrett, T. J.; Barnes, J. J.; TartèSe, R.; Anand, M.; Franchi, I. A.; Greenwood, R. C.; Charlier, B. L. A.; Grady, M. M.

    2016-06-01

    Volatile elements play a key role in the dynamics of planetary evolution. Extensive work has been carried out to determine the abundance, distribution, and source(s) of volatiles in planetary bodies such as the Earth, Moon, and Mars. A recent study showed that the water in apatite from eucrites has similar hydrogen isotopic compositions compared to water in terrestrial rocks and carbonaceous chondrites, suggesting that water accreted very early in the inner solar system given the ancient crystallization ages (~4.5 Ga) of eucrites. Here, the measurements of water (reported as equivalent H2O abundances) and the hydrogen isotopic composition (δD) of apatite from five basaltic eucrites and one cumulate eucrite are reported. Apatite H2O abundances range from ~30 to ~3500 ppm and are associated with a weighted average δD value of -34 ± 67‰. No systematic variations or correlations are observed in H2O abundance or δD value with eucrite geochemical trend or metamorphic grade. These results extend the range of previously published hydrogen isotope data for eucrites and confirm the striking homogeneity in the H-isotopic composition of water in eucrites, which is consistent with a common source for water in the inner solar system.

  17. Isotopic abundance in atom trap trace analysis

    SciTech Connect

    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.

  18. The Abundance and Isotopic Composition of Hg in Extraterrestrial Materials

    NASA Technical Reports Server (NTRS)

    Lauretta, D. S.

    2004-01-01

    During the past three year grant period we made excellent progress in our study of the abundances and isotopic compositions of Hg and other volatile trace elements in extraterrestrial materials. As part of my startup package I received funds to construct a state-of-the-art experimental facility to study gas-solid reaction kinetics. Much of our effort was spent developing the methodology to measure the abundance and isotopic composition of Hg at ultratrace levels in solid materials. In our first study, the abundance and isotopic composition of Hg was determined in bulk samples of the Murchison (CM) and Allende (CV) carbonaceous chondrites. We have continued our study of mercury in primitive meteorites and expanded the suite of meteorites to include other members of the CM and CV chondrite group as well as CI and CO chondrites. Samples of the CI chondrite Orgueil, the CM chondrites Murray, Nogoya, and Cold Bokkeveld, the CO chondrites Kainsaz, Omans, and Isna, and the CV chondrites Vigarano, Mokoia, and Grosnaja were tested. We have developed a thermal analysis ICP-MS technique and applied it to the study of a suite of thermally labile elements (Zn, As, Se, Cd, In, Sn, Sb, Te, Hg, Au, Tl, Pb, and Bi) in geologic materials as well.

  19. Anatomy of a cluster IDP. Part 2: Noble gas abundances, trace element geochemistry, isotopic abundances, and trace organic chemistry of several fragments from L2008#5

    NASA Technical Reports Server (NTRS)

    Thomas, K. L.; Clemett, S. J.; Flynn, G. J.; Keller, L. P.; Mckay, David S.; Messenger, S.; Nier, A. O.; Schlutter, D. J.; Sutton, S. R.; Walker, R. M.

    1994-01-01

    The topics discussed include the following: noble gas content and release temperatures; trace element abundances; heating summary of cluster fragments; isotopic measurements; and trace organic chemistry.

  20. Measuring Solar Abundances with Seismology

    NASA Astrophysics Data System (ADS)

    Mussack, K.; Gough, D.

    2009-12-01

    The revision of the photospheric abundances proferred by Asplund et al. (2005) has rendered opacity theory inconsistent with the seismologically determined opacity through the Sun. This highlights the need for a direct seismological measurement of solar abundances. Here we describe the technique used to measure abundances with seismology, examine our ability to detect differences between solar models using this technique, and discuss its application in the Sun.

  1. Study of the Role of Terrestrial Processes in the Carbon Cycle Based on Measurements of the Abundance and Isotopic Composition of Atmospheric CO2

    SciTech Connect

    Piper, Stephen C; Keeling, Ralph F

    2012-01-03

    The main objective of this project was to continue research to develop carbon cycle relationships related to the land biosphere based on remote measurements of atmospheric CO2 concentration and its isotopic ratios 13C/12C, 18O/16O, and 14C/12C. The project continued time-series observations of atmospheric carbon dioxide and isotopic composition begun by Charles D. Keeling at remote sites, including Mauna Loa, the South Pole, and eight other sites. Using models of varying complexity, the concentration and isotopic measurements were used to study long-term change in the interhemispheric gradients in CO2 and 13C/12C to assess the magnitude and evolution of the northern terrestrial carbon sink, to study the increase in amplitude of the seasonal cycle of CO2, to use isotopic data to refine constraints on large scale changes in isotopic fractionation which may be related to changes in stomatal conductance, and to motivate improvements in terrestrial carbon cycle models. The original proposal called for a continuation of the new time series of 14C measurements but subsequent descoping to meet budgetary constraints required termination of measurements in 2007.

  2. A measurement of the energy spectra and relative abundance of the cosmic-ray H and He isotopes over a broad energy range

    NASA Technical Reports Server (NTRS)

    Webber, W. R.; Yushak, S. M.

    1983-01-01

    The measurements reported of these isotopes were made using two sets of detectors during the same minimum modulation period in 1977. One measurement was made with a balloon-borne telescope, the other with telescopes on the Voyager spacecraft. It is noted that together they provide the widest energy range yet available for studying these isotopes: 14-150 MeV per nucleon for H2 and 10-290 MeV per nucleon for He-3. The simultaneous helium isotope observations are used to give a mutually consistent picture of galactic propagation and solar modulation. The data define the form of the interstellar H-1 and He-4 spectra, an interstellar matter path length for both H-1 and He-4, and a total residual modulation for He-4. The H-2 observations suggest a picture that is very similar for the galactic propagation of H-1 and He-4.

  3. The new face of isotopic NMR at natural abundance.

    PubMed

    Jézéquel, Tangi; Joubert, Valentin; Giraudeau, Patrick; Remaud, Gérald S; Akoka, Serge

    2017-02-01

    The most widely used method for isotope analysis at natural abundance is isotope ratio monitoring by Mass Spectrometry (irm-MS) which provides bulk isotopic composition in (2) H, (13) C, (15) N, (18) O or (34) S. However, in the 1980s, the direct access to Site-specific Natural Isotope Fractionation by Nuclear Magnetic Resonance (SNIF-NMR(TM) ) was immediately recognized as a powerful technique to authenticate the origin of natural or synthetic products. The initial - and still most popular - application consisted in detecting the chaptalization of wines by irm-(2) H NMR. The approach has been extended to a wide range of methodologies over the last decade, paving the way to a wide range of applications, not only in the field of authentication but also to study metabolism. In particular, the emerging irm-(13) C NMR approach delivers direct access to position-specific (13) C isotope content at natural abundance. After highlighting the application scope of irm-NMR ((2) H and (13) C), this article describes the major improvements which made possible to reach the required accuracy of 1‰ (0.1%) in irm-(13) C NMR. The last part of the manuscript summarizes the different steps to perform isotope analysis as a function of the sample properties (concentration, peak overlap) and the kind of targeted isotopic information (authentication, affiliation). Copyright © 2016 John Wiley & Sons, Ltd.

  4. Isotope-abundance variations of selected elements (IUPAC technical report)

    USGS Publications Warehouse

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

    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 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.

  5. Cometary Isotopic Measurements

    NASA Astrophysics Data System (ADS)

    Bockelée-Morvan, Dominique; Calmonte, Ursina; Charnley, Steven; Duprat, Jean; Engrand, Cécile; Gicquel, Adeline; Hässig, Myrtha; Jehin, Emmanuël; Kawakita, Hideyo; Marty, Bernard; Milam, Stefanie; Morse, Andrew; Rousselot, Philippe; Sheridan, Simon; Wirström, Eva

    2015-12-01

    Isotopic ratios in comets provide keys for the understanding of the origin of cometary material, and the physical and chemical conditions in the early Solar Nebula. We review here measurements acquired on the D/H, 14N/15N, 16O/18O, 12C/13C, and 32S/34S ratios in cometary grains and gases, and discuss their cosmogonic implications. The review includes analyses of potential cometary material available in collections on Earth, recent measurements achieved with the Herschel Space Observatory, large optical telescopes, and Rosetta, as well as recent results obtained from models of chemical-dynamical deuterium fractionation in the early solar nebula. Prospects for future measurements are presented.

  6. Natural abundances of carbon isotopes in acetate from a coastal marine sediment

    NASA Technical Reports Server (NTRS)

    Blair, N. E.; Martens, C. S.; Des Marais, D. J.

    1987-01-01

    Measurements of the natural abundances of carbon isotopes were made in acetate samples isolated from the anoxic marine sediment of Cape Lookout Bight, North Carolina. The typical value of the total acetate carbon isotope ratio (delta 13C) was -16.1 +/- 0.2 per mil. The methyl and carboxyl groups were determined to be -26.4 +/- 0.3 and -6.0 +/- 0.3 per mil, respectively, for one sample. The isotopic composition of the acetate is thought to have resulted from isotopic discriminations that occurred during the cycling of that molecule. Measurements of this type, which have not been made previously in the natural environment, may provide information about the dominant microbial pathways in anoxic sediments as well as the processes that influence the carbon isotopic composition of biogenic methane from many sources.

  7. Natural abundance variations in stable isotopes and their potential uses in animal physiological ecology.

    PubMed

    Gannes, L Z; Martínez del Rio, C; Koch, P

    1998-03-01

    Chemical, biological, and physical processes lead to distinctive "isotopic signatures" in biological materials that allow tracing of the origins of organic substances. Isotopic variation has been extensively used by plant physiological ecologists and by paleontologists, and recently ecologists have adopted the use of stable isotopes to measure ecosystem patterns and processes. To date, animal physiological ecologists have made minimal use of naturally occurring stable isotopes as tracers. Here we provide a review of the current and potential uses of naturally occurring stable isotopes in animal physiological ecology. We outline the physical and biological processes that lead to variation in isotopic abundance in plants and animals. We summarize current uses in animal physiological ecology (diet reconstruction and animal movement patterns), and suggest areas of research where the use of stable isotopes can be fruitful (protein balance and turnover and the allocation of dietary nutrients). We argue that animal physiological ecologists can benefit from including the measurement of naturally occurring stable isotopes in their battery of techniques. We also argue that animal physiologists can make an important contribution to the emerging field of stable isotopes in biology by testing experimentally the plethora of assumptions upon which the techniques rely.

  8. Developing Model Constraints on Northern Extra-Tropical Carbon Cycling Based on measurements of the Abundance and Isotopic Composition of Atmospheric CO2

    SciTech Connect

    Keeling, Ralph

    2014-12-12

    The objective of this project was to perform CO2 data syntheses and modeling activities to address two central questions: 1) how much has the seasonal cycle in atmospheric CO2 at northern high latitudes changed since the 1960s, and 2) how well do prognostic biospheric models represent these changes. This project also supported the continuation of the Scripps time series of CO2 isotopes and concentration at ten baseline stations distributed globally.

  9. The Abundance and Isotopic Composition of Hg in Extraterrestrial Materials

    NASA Technical Reports Server (NTRS)

    Blum, J. D.; Klaue, Bjorn

    2005-01-01

    During the three year grant period we made excellent progress in our study of the abundances and isotopic compositions of Hg and other volatile trace elements in extraterrestrial materials. At the time the grant started, our collaborating PI, Dante Lauretts, was a postdoctoral research associate working with Peter Buseck at Arizona State University. The work on chondritic Hg was done in collaboration with Dante Lauretta and Peter Buseck and this study was published in Lauretta et a1 (2001a). In July, 2001 Dante Lauretta accepted a position as an Assistant Professor in the Lunar and Planetary Laboratory at the University of Arizona. His funding was transferred and this grant has supported much of his research activities during his first two years at the U of A. Several other papers are in preparation and will be published soon. We presented papers on this topic at Goldschmidt Conferences, the Lunar and Planetary Science Conferences, and the Annual Meetings of the Meteoritical Society. The work done under this grant has spurred several new directions of inquiry, which we are still pursuing. Included in this paper are the studies of bulk abundances and isotopic compositions of metreoritic Mercury, and the development of a thermal analysis ICP-MS technique applied to thermally liable elements.

  10. Isotopic ratio measurements with ICP-MS

    SciTech Connect

    Russ, G.P. III; Bazan, J.M.

    1986-06-03

    An inductively-coupled-plasma source mass spectrometer (ICP-MS) has been used to measure the isotopic composition of U, Pb, Os, and B standards. Particular emphasis has been placed on uranium because of its nuclear and environmental interest and because of the availability of a well-characterized set of standards with a wide range of isotopic compositions. The precision and accuracy obtainable in isotope ratio measurements by ICP-MS depend on many factors including background, interferences, dead time, mass fractionation (bias), abundance sensitivity, and counting statistics. Which, if any, of these factors controls accuracy and precision depends on the type of sample being analyzed and the characteristics of the mass spectrometer. These issues are discussed in detail.

  11. Elemental and isotopic abundances in the solar wind

    NASA Technical Reports Server (NTRS)

    Geiss, J.

    1972-01-01

    The use of collecting foils and lunar material to assay the isotopic composition of the solar wind is reviewed. Arguments are given to show that lunar surface correlated gases are likely to be most useful in studying the history of the solar wind, though the isotopic abundances are thought to give a good approximation to the solar wind composition. The results of the analysis of Surveyor material are also given. The conditions leading to a significant component of the interstellar gas entering the inner solar system are reviewed and suggestions made for experimental searches for this fraction. A critical discussion is given of the different ways in which the basic solar composition could be modified by fractionation taking place between the sun's surface and points of observation such as on the Moon or in interplanetary space. An extended review is made of the relation of isotopic and elemental composition of the interplanetary gas to the dynamic behavior of the solar corona, especially processes leading to fractionation. Lastly, connection is made between the subject of composition, nucleosynthesis and the convective zone of the sun, and processes leading to modification of initial accretion of certain gases on the Earth and Moon.

  12. Ion Mobility Mass Spectrometry Direct Isotope Abundance Analysis

    SciTech Connect

    Manuel J. Manard, Stephan Weeks, Kevin Kyle

    2010-05-27

    The nuclear forensics community is currently engaged in the analysis of illicit nuclear or radioactive material for the purposes of non-proliferations and attribution. One technique commonly employed for gathering nuclear forensics information is isotope analysis. At present, the state-of-the-art methodology for obtaining isotopic distributions is thermal ionization mass spectrometry (TIMS). Although TIMS is highly accurate at determining isotope distributions, the technique requires an elementally pure sample to perform the measurement. The required radiochemical separations give rise to sample preparation times that can be in excess of one to two weeks. Clearly, the nuclear forensics community is in need of instrumentation and methods that can expedite their decision making process in the event of a radiological release or nuclear detonation. Accordingly, we are developing instrumentation that couples a high resolution IM drift cell to the front end of a MS. The IM cell provides a means of separating ions based upon their collision cross-section and mass-to-charge ratio (m/z). Two analytes with the same m/z, but with different collision cross-sections (shapes) would exit the cell at different times, essentially enabling the cell to function in a similar manner to a gas chromatography (GC) column. Thus, molecular and atomic isobaric interferences can be effectively removed from the ion beam. The mobility selected chemical species could then be introduced to a MS for high-resolution mass analysis to generate isotopic distributions of the target analytes. The outcome would be an IM/MS system capable of accurately measuring isotopic distributions while concurrently eliminating isobaric interferences and laboratory radiochemical sample preparation. The overall objective of this project is developing instrumentation and methods to produce near real-time isotope distributions with a modular mass spectrometric system that performs the required gas-phase chemistry and

  13. Abundance measurements in stellar environments

    SciTech Connect

    Leone, F.

    2014-05-09

    Most of what we know about stars, and systems of stars, is derived from the analysis of their electromagnetic radiation. This lesson is an attempt to describe to Physicists, without any Astrophysical background, the framework to understand the present status of abundance determination in stellar environments and its limit. These notes are dedicated to the recently passed, November 21, 2013, Prof. Dimitri Mihalas who spent his life confuting the 19th century positivist philosopher Auguste Comte who stated that we shall not at all be able to determine the chemical composition of stars.

  14. Abundance measurements in stellar environments

    NASA Astrophysics Data System (ADS)

    Leone, F.

    2014-05-01

    Most of what we know about stars, and systems of stars, is derived from the analysis of their electromagnetic radiation. This lesson is an attempt to describe to Physicists, without any Astrophysical background, the framework to understand the present status of abundance determination in stellar environments and its limit. These notes are dedicated to the recently passed, November 21, 2013, Prof. Dimitri Mihalas who spent his life confuting the 19th century positivist philosopher Auguste Comte who stated that we shall not at all be able to determine the chemical composition of stars.

  15. Short course on St-02 applications of isotope dilutions and isotopic measurements

    SciTech Connect

    Miller, P.

    1998-01-05

    This short course includes information on these topics and subtopics: (I) Nuclear Properties: (A) Historic roots; (B) Nomenclature; (C) Nuclear Stability and abundance; (D) Uses of isotopic techniques; (II) Instrumentation: (A) Sources; (B) Mass resolving elements; (C) Detectors; (III) Making Isotopic Measurements by ICP-MS: (A) Deadtime Correction; (B) Mass Discrimination; (C) Signal /Noise considerations; (IV) Applications and examples: (A) Isotope dilution; (B) Double Spike; (C) Biological Application; (D) Environmental Application; (E) Geological.

  16. Isotopic abundances - Inferences on solar system and planetary evolution

    NASA Astrophysics Data System (ADS)

    Wasserburg, G. J.

    1987-12-01

    For matter that has been removed from a region of nucleosynthetic activity and the effects of interactions with nuclear active particles, the only changes in nuclear abundances that can occur in an isolated system derive from the decay of radioactive nuclei of an element to yield the nucleus of another element. These two related nuclei furnish the absolute chronometers of geologic and cosmic time, through the decay of spontaneously radioactive parent nuclei and the accumulation of daughter nuclei. For systems related to such cosmic processes as the formation of the solar system from the precursor interstellar medium, and involving the very early evolution of the sun, there may arise considerable complexity, due to the intrinsic isotopic heterogeneity of the medium and the presence of short-lived nuclei.

  17. s-process studies - Xenon and krypton isotopic abundances

    NASA Technical Reports Server (NTRS)

    Clayton, D. D.; Ward, R. A.

    1978-01-01

    We propose an analysis of the s-process contributions to the isotopes of xenon and krypton. The object is to aid studies of the possibility that meteorites may contain gas that was carried in presolar grains that were grown in stellar ejecta and that were not degassed prior to incorporation into parent bodies. That model suggests routine interstellar fractionation of s-isotopes from r-isotopes owing to differential incorporation into dust. We show that a deficiency of s-process nuclei cannot yield details of Xe-X, but the gross similarities are strong enough to lead one to think that such a deficiency may play a role in a more complicated explanation. We predict the existence of an s-rich complement somewhere if fractional separation of this type has played a role in Xe-X. We show that the analogous decomposition of krypton is more uncertain, and we call for measurements of neutron-capture cross sections to alleviate these uncertainties.

  18. Absolute isotopic composition of molybdenum and the solar abundances of the p-process nuclides Mo92,94

    NASA Astrophysics Data System (ADS)

    Wieser, M. E.; de Laeter, J. R.

    2007-05-01

    The isotopic composition of molybdenum has been measured with high precision using a thermal ionization mass spectrometer, the linearity of which has been verified by measuring the isotopically-certified reference material for strontium (NIST 987). The abundance sensitivity of the mass spectrometer in the vicinity of the molybdenum ion beams has been carefully examined to ensure the absence of tailing effects. Particular care was given to ensuring that potential isobaric interferences from zirconium and ruthenium did not affect the measurement of the isotopic composition of molybdenum. Gravimetric mixtures of two isotopically enriched isotopes, Mo92 and Mo98, were analyzed mass spectrometrically to calibrate the mass spectrometer, in order to establish the isotope fractionation of the spectrometer for the molybdenum isotopes. This enabled the “absolute” isotopic composition of molybdenum to be determined. An accurate determination of the isotopic composition is required in order to calculate the atomic weight of molybdenum, which is one of the least accurately known values of all the elements. The absolute isotope abundances (in atom %) of molybdenum measured in this experiment are as follows: Mo92=14.5246±0.0015; Mo94=9.1514±0.0074; Mo95=15.8375±0.0098; Mo96=16.672±0.019; Mo97=9.5991±0.0073; Mo98=24.391±0.018; and Mo100=9.824±0.050, with uncertainties at the 1s level. These values enable an atomic weight Ar(Mo) of 95.9602±0.0023 (1s) to be calculated, which is slightly higher than the current Standard Atomic Weight Ar(Mo) =95.94±0.02 and with a much improved uncertainty interval. These “absolute” isotope abundances also enable the Solar System abundances of molybdenum to be calculated for astrophysical purposes. Of particular interest are the Solar System abundances of the two p-process nuclides—Mo92 and Mo94, which are present in far greater abundance than p-process theory suggests. The Solar System abundances for Mo92 and Mo94 of 0.364±0

  19. Mercury Abundances and Isotopic Compositions in the Murchison (CM) and Allende (CV)Carbonaceous Chondrites

    NASA Technical Reports Server (NTRS)

    Lauretta, D. S.; Klaue, B.; Blum, J. D.; Buseck, P. R.

    2001-01-01

    The abundance and isotopic composition of Hg was determined in bulk samples of both the Murchison (CM) and Allende (CV) carbonaceous chondrites using single- and multi-collector inductively coupled plasma mass spectrometry (ICP-MS). The bulk abundances of Hg are 294 6 15 ng/g in Murchison and 30.0 6 1.5 ng/g in Allende. These values are within the range of previous measurements of bulk Hg abundances by neutron activation analysis (NAA). Prior studies suggested that both meteorites contain isotopically anomalous Hg, with d l 96/202Hg values for the anomalous, thermal-release components from bulk samples ranging from 2260 %o to 1440 9/00 in Murchison and from 2620 9/00 to 1540 9/00 in Allende (Jovanovic and Reed, 1976a; 1976b; Kumar and Goel, 1992). Our multi-collector ICP-MS measurements suggest that the relative abundances of all seven stable Hg isotopes in both meteorites are identical to terrestrial values within 0.2 to 0.5 9/00m. On-line thermal-release experiments were performed by coupling a programmable oven with the singlecollector ICP-MS. Powdered aliquots of each meteorite were linearly heated from room temperature to 900 C over twenty-five minutes under an Ar atmosphere to measure the isotopic composition of Hg released fiom the meteorites as a h c t i o n of temperature. In separate experiments, the release profiles of S and Se were determined simultaneously with Hg to constrain the Hg distribution within the meteorites and to evaluate the possibility of Se interferences in previous NAA studies. The Hg-release patterns differ between Allende and Murchison. The Hg-release profile for Allende contains two distinct peaks, at 225" and 343"C, whereas the profile for Murchison has only one peak, at 344 C. No isotopically anomalous Hg was detected in the thermal-release experiments at a precision level of 5 to 30 9/00, depending on the isotope ratio. In both meteorites the Hg peak at ;340"C correlates with a peak in the S-release profile. This correlation

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

    SciTech Connect

    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 attempt 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.

  1. Measurement of the Abundance of Radioactive Be-10 and Other Light Isotopes in Cosmic Radiation Up to 2 GeV /Nucleon with the Balloon-Borne Instrument Isomax

    NASA Technical Reports Server (NTRS)

    Hams, T.; Barbier, L. M.; Bremerich, M.; Christian, E. R.; deNolfo, G. A.; Geier, S.; Goebel, H.; Gupta, S. K.; Hof, M.; Menn, W.

    2004-01-01

    The Isotope Magnet Experiment (ISOMAX), a balloon-borne superconducting magnet spectrometer, was designed to measure the isotopic composition of the light isotopes (3 les than or = Z less than or = 8) of cosmic radiation up to 4 GeV/nucleon with a mass resolution of better than 0.25 amu by using the velocity versus rigidity technique. To achieve this stringent mass resolution, ISOMAX was composed of three major detector systems: a magnetic rigidity spectrometer with a precision drift chamber tracker in conjunction with a three-layer time-of-flight system, and two silica-aerogel Cerenkov counters for velocity determination. A special emphasis of the ISOMAX program was the accurate measurement of radioactive Be-10 with respect to its stable neighbor isotope Be-9, which provides important constraints on the age of cosmic rays in the Galaxy. ISOMAX had its first balloon flight on 1998 August 4-5 from Lynn Lake, Manitoba, Canada. Thirteen hours of data were recorded during this flight at a residual atmosphere of less than 5 g/sq cm. The isotopic ratio at the top of the atmosphere for Be-10/Be-9 was measured to be 0.195 +/- 0.036 (statistical) +/- 0.039 (systematic) between 0.26 and 1.03 GeV/nucleon and 0.317 +/- 0.109(statistical) +/- 0.042(systematic) between 1.13 and 2.03 GeV/nucleon. This is the first measurement of its kind above l GeV/nucleon. ISOMAX results tend to be higher than predictions from current propagation models. In addition to the beryllium results, we report the isotopic ratios of neighboring lithium and boron in the energy range of the time-of-flight system (up to approx. 1 GeV/nucleon). The lithium and boron ratios agree well with existing data and model predictions at similar energies.

  2. RELATIVE ABUNDANCE MEASUREMENTS IN PLUMES AND INTERPLUMES

    SciTech Connect

    Guennou, C.; Hahn, M.; Savin, D. W.

    2015-07-10

    We present measurements of relative elemental abundances in plumes and interplumes. Plumes are bright, narrow structures in coronal holes that extend along open magnetic field lines far out into the corona. Previous work has found that in some coronal structures the abundances of elements with a low first ionization potential (FIP) <10 eV are enhanced relative to their photospheric abundances. This coronal-to-photospheric abundance ratio, commonly called the FIP bias, is typically 1 for elements with a high-FIP (>10 eV). We have used Extreme Ultraviolet Imaging Spectrometer observations made on 2007 March 13 and 14 over a ≈24 hr period to characterize abundance variations in plumes and interplumes. To assess their elemental composition, we used a differential emission measure analysis, which accounts for the thermal structure of the observed plasma. We used lines from ions of iron, silicon, and sulfur. From these we estimated the ratio of the iron and silicon FIP bias relative to that for sulfur. From the results, we have created FIP-bias-ratio maps. We find that the FIP-bias ratio is sometimes higher in plumes than in interplumes and that this enhancement can be time dependent. These results may help to identify whether plumes or interplumes contribute to the fast solar wind observed in situ and may also provide constraints on the formation and heating mechanisms of plumes.

  3. Coupling a high-temperature catalytic oxidation total organic carbon analyzer to an isotope ratio mass spectrometer to measure natural-abundance delta13C-dissolved organic carbon in marine and freshwater samples.

    PubMed

    Panetta, Robert J; Ibrahim, Mina; Gélinas, Yves

    2008-07-01

    The stable isotope composition of dissolved organic carbon (delta(13)C-DOC) provides powerful information toward understanding carbon sources and cycling, but analytical limitations have precluded its routine measurement in natural samples. Recent interfacing of wet oxidation-based dissolved organic carbon analyzers and isotope ratio mass spectrometers has simplified the measurement of delta(13)C-DOC in freshwaters, but the analysis of salty estuarine/marine samples still proves difficult. Here we describe the coupling of the more widespread high-temperature catalytic oxidation-based total organic carbon analyzer to an isotope ratio mass spectrometer (HTC-IRMS) through cryogenic trapping of analyte gases exiting the HTC analyzer for routine analysis of delta(13)C-DOC in aquatic and marine samples. Targeted elimination of major sources of background CO2 originating from the HTC analyzer allows for the routine measurement of samples over the natural range of DOC concentrations (from 40 microM to over 2000 microM), and salinities (<0.1-36 g/kg). Because consensus reference natural samples for delta(13)C-DOC do not exist, method validation was carried out with water-soluble stable isotope standards as well as previously measured natural samples (IAEA sucrose, Suwannee River Fulvic Acids, Deep Sargasso Sea consensus reference material, and St. Lawrence River water) and result in excellent delta(13)C-DOC accuracy (+/-0.2 per thousand) and precision (+/-0.3 per thousand).

  4. OH vertical column abundance - Tropical measurements

    NASA Astrophysics Data System (ADS)

    Burnett, Clyde R.; Minschwaner, Kenneth R.; Burnett, Elizabeth B.

    1990-09-01

    Measurements of the vertical column abundance of atmospheric hydroxyl (OH) have been made during the period 1987-1989 at the National Weather Service (NWS) station at Moen, Truk, Federated States of Micronesia (7 deg N, 152 deg E). A total of 384 independent data sets was obtained. Tropical OH abundance levels average about 22 percent above corresponding mid-latitude values, with OH levels during late winter and early spring up to 50 percent above those observed at 40 deg N. Stratospheric wind and temperature data obtained from the daily NWS radiosonde data are examined for correlations with the OH results.

  5. OH vertical column abundance - Tropical measurements

    NASA Technical Reports Server (NTRS)

    Burnett, Clyde R.; Minschwaner, Kenneth R.; Burnett, Elizabeth B.

    1990-01-01

    Measurements of the vertical column abundance of atmospheric hydroxyl (OH) have been made during the period 1987-1989 at the National Weather Service (NWS) station at Moen, Truk, Federated States of Micronesia (7 deg N, 152 deg E). A total of 384 independent data sets was obtained. Tropical OH abundance levels average about 22 percent above corresponding mid-latitude values, with OH levels during late winter and early spring up to 50 percent above those observed at 40 deg N. Stratospheric wind and temperature data obtained from the daily NWS radiosonde data are examined for correlations with the OH results.

  6. Measuring Abundance Ratios from Integrated Light

    NASA Astrophysics Data System (ADS)

    Worthey, G.

    2010-06-01

    Age, overall abundance, and detailed, element-by-element abundances can be extracted from the integrated light of distant galaxies. The method, at its most basic, is merely the comparison of observed spectra with appropriate models. The relative ratios of elements C, N, O, Na, Mg, Ca, Sc, Ti, Cr, Mn, Fe, Co, Ni, Sr, and Ba can be determined to scientifically useful precision. Cases of interest that are borderline because they suffer internal degeneracies (although plenty of signal is present) are Al and the trio C, N, and O. The elements S, K, Cu, Eu, and the noble gases are too difficult to measure, and V is borderline. Changing the relative abundance ratios, even at fixed heavy-element content, changes the temperatures, luminosities, and number densities of the underlying stellar evolution, as well as more direct changes in the spectra of the stars present. The latter effects dominate the spectral shape, while the former effects render age estimation quite difficult.

  7. Studies of Isotopic Abundances through Gamma-Ray Lines

    NASA Astrophysics Data System (ADS)

    Diehl, Roland

    2006-07-01

    Cosmic gamma-ray lines convey isotopic information from sites of nucleosynthesis and from their surrounding interstellar medium. With recent space-borne gamma-ray spectrometers of high resolution (INTEGRAL, RHESSI), new results have been obtained for 44Ti from the Cas A core-collapse supernova, from long-lived radioactive 26Al and 60Fe, and from positron annihilation in our Galaxy: 44Ti ejection from Cas A may be on the low side of previously-reported values, and/or at velocities >7000 km s-1. 26Al sources apparently share the Galactic rotation in the inner Galaxy, and thus allow to estimate a total mass of 26Al in the Galaxy of 2.8 Msolar from the measured flux. The 60Fe production in massive stars appears lower than predicted by standard models, as constrained by the recent, though marginal, 60Fe detections. Positron annihilation in the Galaxy shows a remarkable bulge component, which is difficult to understand in terms of nucleosynthetic production of the positrons.

  8. Sims Analysis of Water Abundance and Hydrogen Isotope in Lunar Highland Plagioclase

    NASA Technical Reports Server (NTRS)

    Hui, Hejiu; Guan, Yunbin; Chen, Yang; Peslier, Anne H.; Zhang, Youxue; Liu, Yang; Rossman, George R.; Eiler, John M.; Neal, Clive R.

    2015-01-01

    The detection of indigenous water in mare basaltic glass beads has challenged the view established since the Apollo era of a "dry" Moon. Since this discovery, measurements of water in lunar apatite, olivine-hosted melt inclusions, agglutinates, and nominally anhydrous minerals have confirmed that lunar igneous materials contain water, implying that some parts of lunar mantle may have as much water as Earth's upper mantle. The interpretation of hydrogen (H) isotopes in lunar samples, however, is controversial. The large variation of H isotope ratios in lunar apatite (delta Deuterium = -202 to +1010 per mille) has been taken as evidence that water in the lunar interior comes from the lunar mantle, solar wind protons, and/or comets. The very low deuterium/H ratios in lunar agglutinates indicate that solar wind protons have contributed to their hydrogen content. Conversely, H isotopes in lunar volcanic glass beads and olivine-hosted melt inclusions being similar to those of common terrestrial igneous rocks, suggest a common origin for water in both Earth and Moon. Lunar water could be inherited from carbonaceous chondrites, consistent with the model of late accretion of chondrite-type materials to the Moon as proposed by. One complication about the sources of lunar water, is that geologic processes (e.g., late accretion and magmatic degassing) may have modified the H isotope signatures of lunar materials. Recent FTIR analyses have shown that plagioclases in lunar ferroan anorthosite contain approximately 6 ppm H2O. So far, ferroan anorthosite is the only available lithology that is believed to be a primary product of the lunar magma ocean (LMO). A possible consequence is that the LMO could have contained up to approximately 320 ppm H2O. Here we examine the possible sources of water in the LMO through measurements of water abundances and H isotopes in plagioclase of two ferroan anorthosites and one troctolite from lunar highlands.

  9. On the volatile inventory of Titan from isotopic abundances in nitrogen and methane.

    PubMed

    Lunine, J I; Yung, Y L; Lorenz, R D

    1999-01-01

    We analyze recently published nitrogen and hydrogen isotopic data to constrain the initial volatile abundances on Saturn's giant moon Titan. The nitrogen data are interpreted in terms of a model of non-thermal escape processes that lead to enhancement in the heavier isotope. We show that these data do not, in fact, strongly constrain the abundance of nitrogen present in Titan's early atmosphere, and that a wide range of initial atmospheric masses (all larger than the present value) can yield the measured enhancement. The enrichment in deuterated methane is now much better determined than it was when Pinto et al. (1986. Nature 319, 388-390) first proposed a photochemical mechanism to preferentially retain the deuterium. We develop a simple linear theory to provide a more reliable estimate of the relative dissociation rates of normal and deuterated methane. We utilize the improved data and models to compute initial methane reservoirs consistent with the observed enhancement. The result of this analysis agrees with an independent estimate for the initial methane abundance based solely on the present-day rate of photolysis and an assumption of steady state. This consistency in reservoir size is necessary but not sufficient to infer that methane photolysis has proceeded steadily over the age of the solar system to produce large quantities of less volatile organics. Our analysis indicates an epoch of early atmospheric escape of nitrogen, followed by a later addition of methane by outgassing from the interior. The results also suggest that Titan's volatile inventory came in part or largely from a circum-Saturnian disk of material more reducing than the surrounding solar nebula. Many of the ambiguities inherent in the present analysis can be resolved through Cassini-Huygens data and a program of laboratory studies on isotopic and molecular exchange processes. The value of, and interest in, the Cassini-Huygens data can be greatly enhanced if such a program were undertaken

  10. 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.

  11. Laser spectroscopic measurement of helium isotope ratios.

    SciTech Connect

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

    2003-06-13

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

  12. Purdue Rare Isotope Measurement Laboratory

    NASA Astrophysics Data System (ADS)

    Caffee, M.; Elmore, D.; Granger, D.; Muzikar, P.

    2002-12-01

    The Purdue Rare Isotope Measurement Laboratory (PRIME Lab) is a dedicated research and service facility for accelerator mass spectrometry. AMS is an ultra-sensitive analytical technique used to measure low levels of long-lived cosmic-ray-produced and anthropogenic radionuclides, and rare trace elements. We measure 10Be (T1/2 = 1.5 My), 26Al (.702 My), 36Cl (.301 My), and 129I (16 My), in geologic samples. Applications include dating the cosmic-ray-exposure time of rocks on Earth's surface, determining rock and sediment burial ages, measuring the erosion rates of rocks and soils, and tracing and dating ground water. We perform sample preparation and separation chemistries for these radio-nuclides for our internal research activities and for those external researchers not possessing this capability. Our chemical preparation laboratories also serve as training sites for members of the geoscience community developing these techniques at their institutions. Research at Purdue involves collaborators among members of the Purdue Departments of Physics, Earth and Atmospheric Sciences, Chemistry, Agronomy, and Anthropology. We also collaborate and serve numerous scientists from other institutions. We are currently in the process of modernizing the facility with the goals of higher precision for routinely measured radio-nuclides, increased sample throughput, and the development of new measurement capabilities for the geoscience community.

  13. The abundance of the radioactive isotope Al-26 in galactic cosmic rays

    NASA Technical Reports Server (NTRS)

    Wiedenbeck, M. E.

    1983-01-01

    Satellite observations of the isotopic composition of aluminum in low energy cosmic rays (E/M = 200 MeV/amu) have been used to determine the abundance of the unstable isotope Al-26 (T1/2 = 0.87 Myr). The observed abundance ratio, Al-26/Al-27 = 0.036 (+0.037, -0.022), is in good agreement with previous balloon observations and yields a cosmic ray confinement time consistent with values based on the abundance of Be-10.

  14. Absolute Abundance Measurements in Solar Flares

    NASA Astrophysics Data System (ADS)

    Warren, Harry

    2014-06-01

    We present measurements of elemental abundances in solar flares with EVE/SDO and EIS/Hinode. EVE observes both high temperature Fe emission lines Fe XV-XXIV and continuum emission from thermal bremsstrahlung that is proportional to the abundance of H. By comparing the relative intensities of line and continuum emission it is possible to determine the enrichment of the flare plasma relative to the composition of the photosphere. This is the first ionization potential or FIP bias (F). Since thermal bremsstrahlung at EUV wavelengths is relatively insensitive to the electron temperature it is important to account for the distribution of electron temperatures in the emitting plasma. We accomplish this by using the observed spectra to infer the differential emission measure distribution and FIP bias simultaneously. In each of the 21 flares that we analyze we find that the observed composition is close to photospheric. The mean FIP bias in our sample is F=1.17+-0.22. Furthermore, we have compared the EVE measurements with corresponding flare observations of intermediate temperature S, Ar, Ca, and Fe emission lines taken with EIS. Our initial calculations also indicate a photospheric composition for these observations. This analysis suggests that the bulk of the plasma evaporated during a flare comes from deep in the chromosphere, below the region where elemental fractionation in the non-flaring corona occurs.

  15. Isotopic abundances of magnesium in five G and K dwarfs

    NASA Astrophysics Data System (ADS)

    Tomkin, J.; Lambert, D. L.

    1980-02-01

    The paper reports on an analysis of high-resolution low-noise Reticon observations of MgH lines in the spectra of Mu Cas, Epsilon Eri, 61 Cyg A and B, and Gmb 1830 by spectrum synthesis. It is shown that the mixtures of the isotopes in Mu Cas, Epsilon Eri, and 61 Cyg A and B are not significantly different from the terrestrial mixture. Attention is also given to a nonterrestrial mixture which is found in Gmb 1830.

  16. Atmospheric Trace Gas Abundances and Stable Isotope Ratios via IR-LIF

    NASA Technical Reports Server (NTRS)

    Blake, Geoffrey A.

    2004-01-01

    We propose to develop new technologies with support provided by PIDDP that will enable the in situ measurements of abundances and stable isotope ratios in important radiatively and biogenically active gases such as carbon dioxide, carbon monoxide, water, methane, nitrous oxide, and hydrogen sulfide to very high precision (0.1 per mil or better for the isotopic ratios, for example). Such measurements, impossible at present, could provide pivotal new constraints on the global (bio)geochemical budgets of these critical species, and could also be used to examine the dynamics of atmospheric transport on Mars, Titan, and other solar system bodies. We believe the combination of solid state light sources with imaging of the IR laser induced fluorescence (IR-LIF) via newly available detector arrays will make such in situ measurements possible for the first time. Even under ambient terrestrial conditions, the LIF yield from vibrational excitation of species such as water and carbon dioxide should produce emission measures well in excess of ten billion photons/sec from samples volumes of order 1 c.c. These count rates can, in principle, yield detection limits into the sub-ppt range that are required for the in situ isotopic study of atmospheric trace gases. While promising, such technologies are relatively immature, but developing rapidly, and there are a great many uncertainties regarding their applicability to in situ IR-LIF planetary studies. We therefore feel PIDDP support will be critical to developing these new tools, and propose a three-year program to combine microchip near-IR lasers with low background detection axes and state-of-the-art HgCdTe detectors developed for astronomical spectroscopy to investigate the sensitivity of IR-LIF under realistic planetary conditions, to optimize the optical pumping and filtering schemes for important species, and to apply the spectrometer to the non-destructive measurement of stable isotopes in a variety of test samples. These

  17. Abundances in red giant stars - Nitrogen isotopes in carbon-rich molecular envelopes

    NASA Technical Reports Server (NTRS)

    Wannier, P. G.; Andersson, B.-G.; Olofsson, H.; Ukita, N.; Young, K.

    1991-01-01

    Results are presented of millimeter- and submillimeter-wave observations of HCN and HCCCN that were made of the circmustellar envelopes of eight carbon stars, including the two protoplanetary nebulae CRL 618 and CRL 2688. The observations yield a measure of the double ratio (N-14)(C-13)/(N-15)(C-12). Measured C-12/C-13 ratios are used to estimate the N-14/N-15 abundance ratio, with the resulting lower limits in all eight envelopes and possible direct determinations in two envelopes. The two determinations and four of the remaining six lower limits are found to be in excess of the terrestrial value of N-14/N-15 = 272, indicating an evolution of the nitrogen isotope ratio, which is consistent with stellar CNO processing. Observations of thermal SiO (v = 0, J = 2-1) emission show that the Si-29/Si-28 ratio can be determined in carbon stars, and further observations are indicated.

  18. Measurements of Absolute Abundances in Solar Flares

    NASA Astrophysics Data System (ADS)

    Warren, Harry P.

    2014-05-01

    We present measurements of elemental abundances in solar flares with the EUV Variability Experiment (EVE) on the Solar Dynamics Observatory. EVE observes both high temperature Fe emission lines (Fe XV-Fe XXIV) and continuum emission from thermal bremsstrahlung that is proportional to the abundance of H. By comparing the relative intensities of line and continuum emission it is possible to determine the enrichment of the flare plasma relative to the composition of the photosphere. This is the first ionization potential or FIP bias (f). Since thermal bremsstrahlung at EUV wavelengths is relatively insensitive to the electron temperature, it is important to account for the distribution of electron temperatures in the emitting plasma. We accomplish this by using the observed spectra to infer the differential emission measure distribution and FIP bias simultaneously. In each of the 21 flares that we analyze we find that the observed composition is close to photospheric. The mean FIP bias in our sample is f = 1.17 ± 0.22. This analysis suggests that the bulk of the plasma evaporated during a flare comes from deep in the chromosphere, below the region where elemental fractionation occurs.

  19. MEASUREMENTS OF ABSOLUTE ABUNDANCES IN SOLAR FLARES

    SciTech Connect

    Warren, Harry P.

    2014-05-01

    We present measurements of elemental abundances in solar flares with the EUV Variability Experiment (EVE) on the Solar Dynamics Observatory. EVE observes both high temperature Fe emission lines (Fe XV-Fe XXIV) and continuum emission from thermal bremsstrahlung that is proportional to the abundance of H. By comparing the relative intensities of line and continuum emission it is possible to determine the enrichment of the flare plasma relative to the composition of the photosphere. This is the first ionization potential or FIP bias (f). Since thermal bremsstrahlung at EUV wavelengths is relatively insensitive to the electron temperature, it is important to account for the distribution of electron temperatures in the emitting plasma. We accomplish this by using the observed spectra to infer the differential emission measure distribution and FIP bias simultaneously. In each of the 21 flares that we analyze we find that the observed composition is close to photospheric. The mean FIP bias in our sample is f = 1.17 ± 0.22. This analysis suggests that the bulk of the plasma evaporated during a flare comes from deep in the chromosphere, below the region where elemental fractionation occurs.

  20. Multiple linear regression for isotopic measurements

    NASA Astrophysics Data System (ADS)

    Garcia Alonso, J. I.

    2012-04-01

    There are two typical applications of isotopic measurements: the detection of natural variations in isotopic systems and the detection man-made variations using enriched isotopes as indicators. For both type of measurements accurate and precise isotope ratio measurements are required. For the so-called non-traditional stable isotopes, multicollector ICP-MS instruments are usually applied. In many cases, chemical separation procedures are required before accurate isotope measurements can be performed. The off-line separation of Rb and Sr or Nd and Sm is the classical procedure employed to eliminate isobaric interferences before multicollector ICP-MS measurement of Sr and Nd isotope ratios. Also, this procedure allows matrix separation for precise and accurate Sr and Nd isotope ratios to be obtained. In our laboratory we have evaluated the separation of Rb-Sr and Nd-Sm isobars by liquid chromatography and on-line multicollector ICP-MS detection. The combination of this chromatographic procedure with multiple linear regression of the raw chromatographic data resulted in Sr and Nd isotope ratios with precisions and accuracies typical of off-line sample preparation procedures. On the other hand, methods for the labelling of individual organisms (such as a given plant, fish or animal) are required for population studies. We have developed a dual isotope labelling procedure which can be unique for a given individual, can be inherited in living organisms and it is stable. The detection of the isotopic signature is based also on multiple linear regression. The labelling of fish and its detection in otoliths by Laser Ablation ICP-MS will be discussed using trout and salmon as examples. As a conclusion, isotope measurement procedures based on multiple linear regression can be a viable alternative in multicollector ICP-MS measurements.

  1. Measuring SNM Isotopic Distributions using FRAM

    SciTech Connect

    Geist, William H.

    2015-12-02

    The first group of slides provides background information on the isotopic composition of plutonium. It is shown that 240Pu is the critical isotope in neutron coincidence/multiplicity counting. Next, response function analysis to determine isotopic composition is discussed. The isotopic composition can be determined by measuring the net peak counts from each isotope and then taking the ratio of the counts for each isotope relative to the total counts for the element. Then FRAM (Fixed energy Response function Analysis with Multiple efficiencies) is explained. FRAM can control data acquisition, automatically analyze newly acquired data, analyze previously acquired data, provide information on the quality of the analysis, and facilitate analysis in unusual situations (non-standard energy calibrations, gamma rays from non-SNM isotopes, poor spectra (within limits)).

  2. Empirical Solar Abundance Scaling Laws of Supernova {gamma} Process Isotopes

    SciTech Connect

    Hayakawa, Takehito; Iwamoto, Nobuyuki; Kajino, Toshitaka; Shizum, Toshiyuki; Umeda, Hideyuki; Nomoto, Ken'Ichi

    2008-11-11

    Analyzing the solar system abundances, we have found two empirical abundance scaling laws concerning the p- and s-nuclei with the same atomic number. They are evidence that the 27 p-nuclei are synthesized by the supernova {gamma}-process. The scalings lead to a novel concept of 'universality of {gamma}-process' that the s/p and p/p ratios of nuclei produced by individual {gamma}-processes are almost constant, respectively. We have calculated the ratios of materials produced by the {gamma}-process based on core-collapse supernova explosion models under various astrophysical conditions and found that the scalings hold for individual {gamma}-processes independent of the conditions assumed. The results further suggest an extended universality that the s/p ratios in the {gamma}-process layers are not only constant but also centered on a specific value of 3. With this specific value and the scaling of the s/p ratios, we estimate that the ratios of the s-process abundance contributions from the AGB stars to the massive stars are almost 6.7 for the s-nuclei of A>90 in the solar system.

  3. Isotope-abundance variations and atomic weights of selected elements: 2016 (IUPAC Technical Report)

    USGS Publications Warehouse

    Coplen, Tyler B.; Shrestha, Yesha

    2016-01-01

    There are 63 chemical elements that have two or more isotopes that are used to determine their standard atomic weights. The isotopic abundances and atomic weights of these elements can vary in normal materials due to physical and chemical fractionation processes (not due to radioactive decay). These variations are well known for 12 elements (hydrogen, lithium, boron, carbon, nitrogen, oxygen, magnesium, silicon, sulfur, chlorine, bromine, and thallium), and the standard atomic weight of each of these elements is given by IUPAC as an interval with lower and upper bounds. Graphical plots of selected materials and compounds of each of these elements have been published previously. Herein and at the URL http://dx.doi.org/10.5066/F7GF0RN2, we provide isotopic abundances, isotope-delta values, and atomic weights for each of the upper and lower bounds of these materials and compounds.

  4. Carbon and nitrogen biogeochemistry in the ocean: A study using stable isotope natural abundance

    NASA Technical Reports Server (NTRS)

    Rau, G. H.; Desmarais, David J.

    1985-01-01

    Determining the biogeochemical pathways traveled by carbon and nitrogen in the ocean is fundamental to the understanding of how the ocean participates in the cycling of these elements within the biosphere. Because biological production, metabolism, and respiration can significantly alter the natural abundance of C-13 and N-15, these abundances can provide important information about the nature of these biological processes and their variability in the marine environment. The research initially seeks to characterize the spatial and temporal patterns of stable isotope abundances in organic matter, and to relate these abundances to C and N biogeochemical processes within selected areas of the northeastern Pacific Ocean.

  5. Element distribution and noble gas isotopic abundances in lunar meteorite Allan Hills A81005

    NASA Technical Reports Server (NTRS)

    Kraehenbuehl, U.; Eugster, O.; Niedermann, S.

    1986-01-01

    Antarctic meteorite ALLAN HILLS A81005, an anorthositic breccia, is recognized to be of lunar origin. The noble gases in this meteorite were analyzed and found to be solar-wind implanted gases, whose absolute and relative concentrations are quite similar to those in lunar regolith samples. A sample of this meteorite was obtained for the analysis of the noble gas isotopes, including Kr(81), and for the determination of the elemental abundances. In order to better determine the volume derived from the surface correlated gases, grain size fractions were prepared. The results of the instrumental measurements of the gamma radiation are listed. From the amounts of cosmic ray produced noble gases and respective production rates, the lunar surface residence times were calculated. It was concluded that the lunar surface time is about half a billion years.

  6. On krypton isotopic abundances in the sun and in the solar wind

    NASA Technical Reports Server (NTRS)

    Marti, K.

    1980-01-01

    The Kr isotopic systematics in the meteorite Pesyanoe which is known to contain solar-type gases, are reported. Discrepancies in the isotopic data of fractions released at stepwise increasing temperatures cannot be reconciled with spallation Kr components, although spallation effects are significant. Fractionation mechanisms on the parent body and in the solar wind source region are considered and the implications for solar abundances discussed.

  7. The source charge and isotopic abundances of cosmic rays with Z = 9-16 - A study using new fragmentation cross sections

    NASA Technical Reports Server (NTRS)

    Webber, W. R.; Gupta, M.; Soutoul, A.; Ferrando, P.

    1990-01-01

    The cosmic ray source charge and isotopic abundances for charges with Z = 9-16 are reexamined using newly measured fragmentation cross sections in a standard Galactic propagation model. Compared with earlier studies, the cosmic-ray data are now consistent with no excess of Si-29 and Si-30 in the source relative to the solar coronal abundances. The excess of Mg-25 and Mg-26 is now about 1 sigma or less relative to solar coronal isotopic abundances, leaving Ne-22 as the only clearly established neutron-rich isotopic excess in the cosmic ray source. Better estimates of the source abundances of elements obtained using the new cross sections permit the conclusion that high first ionization potential (FIP) elements have a wide spread of compositional differences in the cosmic-ray source relative to solar coronal abundances, whereas elements with a low FIP have a composition similar to the solar corona.

  8. Feasibility of Isotopic Measurements: Graphite Isotopic Ratio Method

    SciTech Connect

    Wood, Thomas W.; Gerlach, David C.; Reid, Bruce D.; Morgan, W. C.

    2001-04-30

    This report addresses the feasibility of the laboratory measurements of isotopic ratios for selected trace constituents in irradiated nuclear-grade graphite, based on the results of a proof-of-principal experiment completed at Pacific Northwest National Laboratory (PNNL) in 1994. The estimation of graphite fluence through measurement of isotopic ratio changes in the impurity elements in the nuclear-grade graphite is referred to as the Graphite Isotope Ratio Method (GIRM). Combined with reactor core and fuel information, GIRM measurements can be employed to estimate cumulative materials production in graphite moderated reactors. This report documents the laboratory procedures and results from the initial measurements of irradiated graphite samples. The irradiated graphite samples were obtained from the C Reactor (one of several production reactors at Hanford) and from the French G-2 Reactor located at Marcoule. Analysis of the irradiated graphite samples indicated that replicable measurements of isotope ratios could be obtained from the fluence sensitive elements of Ti, Ca, Sr, and Ba. While these impurity elements are present in the nuclear-grade graphite in very low concentrations, measurement precision was typically on the order of a few tenths of a percent to just over 1 percent. Replicability of the measurements was also very good with measured values differing by less than 0.5 percent. The overall results of this initial proof-of-principal experiment are sufficiently encouraging that a demonstration of GIRM on a reactor scale basis is planned for FY-95.

  9. A robust method for ammonium nitrogen isotopic analysis in freshwater and seawater at natural abundance levels

    NASA Astrophysics Data System (ADS)

    Zhang, L.; Altabet, M. A.; Wu, T.; Hadas, O.

    2006-12-01

    Natural ammonium N isotopic abundance has been increasingly used in studies of marine and freshwater biogeochemistry. However, current methods are time-consuming, subject to interference from DON, and not reliable at low concentrations. Our new method for determining the δ15N of ammonium overcomes these difficulties by employing the oxidation of ammonium to nitrite followed by conversion of nitrite to nitrous oxide. In the first step, ammonium is quantitatively oxidized by hypobromite at pH~12. After the addition of sodium arsenite to consume excess hypobromite, yield is verified by colorimetric NO2-measurement using sulfanilamide and naphthyl ethylenediamine (NED). Nitrite is further reduced to N2O by a 1:1 sodium azide and acetic acid buffer solution using previously established procedures. Buffer concentration can be varied according to sample matrix to ensure that a reaction pH between 2 and 4 is reached. The product nitrous oxide is then isotopically analyzed using a continuous flow purge and cryogenic trap system coupled to an isotope ratio mass spectrometer. Reliable δ15N values (±0.31‰) are obtained over a concentration range of 0.5 μM to 20 μM using 20 ml volumes of either fresh or seawater samples. Reagent blanks are very low, about 0.05 μM. There is no interference from any of the nitrogen containing compounds tested except short chain aliphatic amino acid (i.e. glycine) which typically are not present at sufficiently high environmental concentrations to pose a problem.

  10. Line formation in solar granulation. VII. CO lines and the solar C and O isotopic abundances

    NASA Astrophysics Data System (ADS)

    Scott, P. C.; Asplund, M.; Grevesse, N.; Sauval, A. J.

    2006-09-01

    CO spectral line formation in the Sun has long been a source of consternation for solar physicists, as have the elemental abundances it seems to imply. We modelled solar CO line formation using a realistic, ab initio, time-dependent 3D radiative-hydrodynamic model atmosphere. Results were compared with space-based observations from the ATMOS space shuttle experiment. We employed weak 12C16O, 13C16O and 12C18O lines from the fundamental (Δ v = 1) and first overtone (Δ v = 2) bands to determine the solar carbon abundance, as well as the 12C/13C and 16O/18O isotopic ratios. A weighted solar carbon abundance of logɛ_C=8.39 ± 0.05 was found. We note with satisfaction that the derived abundance is identical to our recent 3D determination based on C i, [C i], C2 and CH lines, increasing our confidence in the accuracy of both results. Identical calculations were carried out using 1D models, but only the 3D model was able to produce abundance agreement between different CO lines and the other atomic and molecular diagnostics. Solar 12C/13C and 16O/18O ratios were measured as 86.8+3.9-3.7 (δ13C = 30+46-44) and 479+29-28 (δ18O = 41+67-59), respectively. These values may require current theories of solar system formation, such as the CO self-shielding hypothesis, to be revised. Excellent agreement was seen between observed and predicted weak CO line shapes, without invoking micro- or macroturbulence. Agreement breaks down for the strongest CO lines however, which are formed in very high atmospheric layers. Whilst the line asymmetries (bisectors) were reasonably well reproduced, line strengths predicted on the basis of C and O abundances from other diagnostics were weaker than observed. The simplest explanation is that temperatures are overestimated in the highest layers of the 3D simulation. Thus, our analysis supports the presence of a COmosphere above the traditional photospheric temperature minimum, with an average temperature of less than 4000 K. This shortcoming of

  11. ANALYSIS OF RICIN TOXIN PREPARATIONS FOR CARBOHYDRATE AND FATTY ACID ABUNDANCE AND ISOTOPE RATIO INFORMATION

    SciTech Connect

    Wunschel, David S.; Kreuzer-Martin, Helen W.; Antolick, Kathryn C.; Colburn, Heather A.; Moran, James J.; Melville, Angela M.

    2009-12-01

    employing a quadrupole MS system for compound identification and an isotope ratio MS for measuring the stable isotope ratios of deuterium and hydrogen (D/H) in fatty acids. Finally, the method for analyzing the compound abundance data is included. This study indicates that removal of ricinoleic acid is a conserved consequence of each processing step we tested. Furthermore, the stable isotope D/H ratio of ricinoleic acid distinguished between two of the three castor seed sources. Concentrations of arabinose, xylose, mannose, glucosamine and myo-inositol differentiated between crude or acetone extracted samples and samples produced by protein precipitation. Taken together these data illustrate the ability to distinguish between processes used to purify a ricin sample as well as potentially the source seeds.

  12. Isotopic abundances of Hg in mercury stars inferred from the Hg II line at 3984 A

    NASA Technical Reports Server (NTRS)

    White, R. E.; Vaughan, A. H., Jr.; Preston, G. W.; Swings, J. P.

    1976-01-01

    Wavelengths of the Hg II absorption feature at 3984 A in 30 Hg stars are distributed uniformly from the value for the terrestrial mix to a value that corresponds to nearly pure Hg-204. The wavelengths are correlated loosely with effective temperatures inferred from Q(UBV). Relative isotopic abundances derived from partially resolved profiles of the 3984-A line in iota CrB, chi Lup, and HR 4072 suggest that mass-dependent fractionation has occurred in all three stars. It is supposed that such fractionation occurs in all Hg stars, and a scheme whereby isotopic compositions can be inferred from a comparison of stellar wavelengths and equivalent widths with those calculated for a family of fractionated isotopic mixes. Theoretical profiles calculated for the derived isotopic composition agree well with high-resolution interferometric profiles obtained for three of the stars.

  13. Electrolytic recovery of mercury enriched in isotopic abundance

    DOEpatents

    Grossman, Mark W.

    1991-01-01

    The present invention is directed to a method of electrolytically extracting liquid mercury from HgO or Hg.sub.2 Cl.sub.2. Additionally there are disclosed two related techniques associated with the present invention, namely (1) a technique for selectively removing product from different regions of a long photochemical reactor (photoreactor) and (2) a method of accurately measuring the total quantity of mercury formed as either HgO or Hg.sub.2 Cl.sub.2.

  14. Plant abundance: the measurement and relationship with seed size

    USGS Publications Warehouse

    Guo, Q.

    2003-01-01

    There are many inconsistencies in early reports describing the relationships between plant abundance and other biotic (e.g., seed size) or abiotic variables (e.g., precipitation). It has been difficult to generalize such relationships when abundance is measured differently (e.g., density, biomass, cover). This article suggests using abundance in two broad categories: numerical abundance (e.g., number of individuals, density) and mass abundance (e.g., biomass, cover). Collective evidence indicates that when abundance is measured the same way, the observed patterns may actually be more consistent.

  15. The Oxygen Isotopic Composition of MIL 090001: A CR2 Chondrite with Abundant Refractory Inclusions

    NASA Technical Reports Server (NTRS)

    Keller, Lindsay P.; McKeegan, K. D.; Sharp, Z. D.

    2012-01-01

    MIL 090001 is a large (>6 kg) carbonaceous chondrite that was classified as a member of the CV reduced subgroup (CVred) that was recovered during the 2009-2010 ANSMET field season [1]. Based on the abundance of refractory inclusions and the extent of aqueous alteration, Keller [2] suggested a CV2 classification. Here we report additional mineralogical and petrographic data for MIL 090001, its whole-rock oxygen isotopic composition and ion microprobe analyses of individual phases. The whole rock oxygen isotopic analyses show that MIL 090001 should be classified as a CR chondrite.

  16. Absolute Isotopic Abundance Ratios and Atomic Weight of a Reference Sample of Nickel

    PubMed Central

    Gramlich, J. W.; Machlan, L. A.; Barnes, I. L.; Paulsen, P. J.

    1989-01-01

    Absolute values have been obtained for the isotopic abundance ratios of a reference sample of nickel (Standard Reference Material 986), using thermal ionization mass spectrometry. Samples of known isotopic composition, prepared from nearly isotopically pure separated nickel isotopes, were used to calibrate the mass spectrometers. The resulting absolute isotopic ratios are: 58Ni/60Ni=2.596061±0.000728, 61Ni/60Ni=0.043469±0.000015,62Ni/60Ni=0.138600±0.000045, and 64Ni/60Ni=0.035295±0.000024, which yield atom percents of 58Ni=68.076886 ±0.005919, 60Ni = 26.223146±0.005144,61Ni=1.139894±0.000433, 62Ni =3.634528±0.001142, and 64Ni =0.925546±0.000599. The atomic weight calculated from this isotopic composition is 58.693353 ±0.000147. The indicated uncertainties are overall limits of error based on two standard deviations of the mean and allowances for the effects of known sources of possible systematic error. PMID:28053421

  17. Lithium isotopes and light lithophile element abundances in shergottites: Evidence for both magmatic degassing and subsolidus diffusion

    NASA Astrophysics Data System (ADS)

    Udry, Arya; McSween, Harry Y.; Hervig, Richard L.; Taylor, Lawrence A.

    2016-01-01

    Degassed magmatic water was potentially the major source of surficial water on Mars. We measured Li, B, and Be abundances and Li isotope profiles in pyroxenes, olivines, and maskelynite from four compositionally different shergottites—Shergotty, QUE 94201, LAR 06319, and Tissint—using secondary ion mass spectrometry (SIMS). All three light lithophile elements (LLE) are incompatible: Li and B are soluble in H2O-rich fluids, whereas Be is insoluble. In the analyzed shergottites, Li concentration decreases and Be concentration increases from cores to rims in pyroxenes. However, B concentrations do not vary consistently with Li and Be abundances, except in QUE 94201 pyroxenes. Additionally, abundances of these three elements in olivines show a normal igneous-fractionation trend consistent with the crystallization of olivine before magma ascent and degassing. We expect that kinetic effects would lead to fractionation of 6Li in the vapor phase compared to 7Li during degassing. The Li isotope profiles, with increasing δ7Li from cores to rims, as well as Li and B profiles indicate possible degassing of hydrous fluids only for the depleted shergottite QUE 94201, as also supported by degassing models. Conversely, Shergotty, LAR 06319, and Tissint appear to have been affected by postcrystallization diffusion, based on their LLE and Li isotope profiles, accompanied by diffusion models. This process may represent an overlay on a degassing pattern. The LLE profiles and isotope profiles in QUE 94201 support the hypothesis that degassing of some basaltic shergottite magmas provided water to the Martian surface, although evidence may be obscured by subsolidus diffusion processes.

  18. Carbon, hydrogen and nitrogen in carbonaceous chondrites Abundances and isotopic compositions in bulk samples

    NASA Technical Reports Server (NTRS)

    Kerridge, J. F.

    1985-01-01

    Whole-rock samples of 25 carbonaceous chondrites were analyzed for contents of C, H and N and delta C-13, delta D and delta N-15. Inhomogeneous distribution of these isotopes within individual meteorites is pronounced in several cases. Few systematic intermeteorite trends were observed; N data are suggestive of isotopic inhomogeneity in the early solar system. Several chondrites revealed unusual compositions which would repay further, more detailed study. The data are also useful for classification of carbonaceous chondrites; N abundance and isotopic compositions can differentiate existing taxonomic groups with close to 100 percent reliability; Al Rais and Renazzo clearly constitute a discrete 'grouplet', and there are hints that both CI and CM groups may each be divisible into two subgroups.

  19. Interpretation of the carbon abundance in Saturn measured by Cassini

    NASA Astrophysics Data System (ADS)

    Hersant, Franck; Gautier, Daniel; Tobie, Gabriel; Lunine, Jonathan I.

    2008-06-01

    Spectral observations of Saturn from the far infrared spectrometer aboard the Cassini spacecraft [Flasar, F.M., et al., 2005. Temperatures, winds, and composition in the Saturnian system. Science 307, 1247-1251] have revealed that the C/H ratio in the planet is in fact about twice higher than previously derived from ground based observations and in agreement with the C/H value derived from Voyager IRIS by Courtin et al. [1984. The composition of Saturn's atmosphere at northern temperate latitudes from Voyager IRIS spectra - NH 3, PH 3, C 2H 2, C 2H 6, CH 3D, CH 4, and the Saturnian D/H isotopic ratio. Astrophys. J. 287, 899-916] . The implications of this measurement are reanalyzed in the present report on the basis that volatiles observed in cometary atmospheres, namely CO2, CH4, NH3 and H2S may have been trapped as solids in the feeding zone of the planet. CH4 and H2S may have been in the form of clathrate hydrates while CO2 presumably condensed in the cooling solar nebula. Carbon may also have been incorporated in organics. Conditions of temperature and pressure ease the hydratation of NH3. Such icy grains were included in planetesimals which subsequently collapsed into the hydrogen envelope of the planet, then resulting in C, N and S enrichments with respect to the solar abundance. Our calculations are consistent, within error bars, with observed elemental abundances on Saturn provided that the carbon trapped in planetesimals was mainly in the form of CH4 clathrate and CO2 ice (and maybe as organics) while nitrogen was in the form of NH3 hydrate. Our approach has implications on the possible pattern of noble gases in Saturn, since we predict that contrary to what is observed in Jupiter, Ar and Kr should be in solar abundance while Xe might be strongly oversolar. The only way to verify this scenario is to send a probe making in situ mass spectrometer measurements. Our scenario also predicts that the 14N/ 15N ratio should be somewhat smaller in Saturn than

  20. Can heavy isotopes increase lifespan? Studies of relative abundance in various organisms reveal chemical perspectives on aging

    PubMed Central

    2016-01-01

    Stable heavy isotopes co‐exist with their lighter counterparts in all elements commonly found in biology. These heavy isotopes represent a low natural abundance in isotopic composition but impose great retardation effects in chemical reactions because of kinetic isotopic effects (KIEs). Previous isotope analyses have recorded pervasive enrichment or depletion of heavy isotopes in various organisms, strongly supporting the capability of biological systems to distinguish different isotopes. This capability has recently been found to lead to general decline of heavy isotopes in metabolites during yeast aging. Conversely, supplementing heavy isotopes in growth medium promotes longevity. Whether this observation prevails in other organisms is not known, but it potentially bears promise in promoting human longevity. PMID:27554342

  1. Boron abundances and isotopic ratios of olivine grains on Itokawa returned by the Hayabusa spacecraft

    NASA Astrophysics Data System (ADS)

    Fujiya, Wataru; Hoppe, Peter; Ott, Ulrich

    2016-09-01

    We report the B abundances and isotopic ratios of two olivine grains from the S-type asteroid Itokawa sampled by the Hayabusa spacecraft. Olivine grains from the Dar al Gani (DaG) 989 LL6 chondrite were used as a reference. Since we analyzed polished thin sections in both cases, we expect the contribution from the solar wind B (rich in 10B) to be minimal because the solar wind was implanted only within very thin layers of the grain surface. The Itokawa and DaG 989 olivine grains have homogeneous B abundances (~400 ppb) and 11B/10B ratios compatible with the terrestrial standard and bulk chondrites. The observed homogeneous B abundances and isotopic ratios of the Itokawa olivine grains are likely the result of thermal metamorphism which occurred in the parent asteroid of Itokawa, which had a similar composition as LL chondrites. The chondritic B isotopic ratios of the Itokawa samples suggest that they contain little cosmogenic B (from cosmic-ray spallation reactions) rich in 10B. This observation is consistent with the short cosmic-ray exposure ages of Itokawa samples inferred from the small concentrations of cosmogenic 21Ne. If other Itokawa samples have little cosmogenic B as well, the enrichment in 10B found previously on the surface of another Itokawa particle (as opposed to the bulk grain study here) may be attributed to implanted solar wind B.

  2. Determination of the abundance and carbon isotope composition of elemental carbon in sediments

    NASA Astrophysics Data System (ADS)

    Bird, Michael I.; Gröcke, Darren R.

    1997-08-01

    We report measurements of the susceptibility of a variety of elemental and organic carbon samples to oxidative degradation using both acid dichromate and basic peroxide reagents. Organic carbon is rapidly oxidized using either reagent, or both reagents sequentially. Elemental carbon exhibits a wide range of susceptibilities to oxidation related both to the degree to which the precursor plant material was carbonized during pyrolysis and to the surface area available for oxidation. Despite a range of susceptibilities, a component of oxidation-resistant elemental carbon has been identified which can be reproducibly separated from organic contaminants. The carbon isotope composition (δ 13C value) of the precursor plant materials underwent a 0-1.6‰ decrease during the production of the elemental carbon by pyrolysis, while the subsequent oxidative degradation of the samples resulted in only small (generally < 0.5%o) changes in the δ 13C value of the remaining elemental carbon. The results suggest that the technique can be used to obtain records of elemental carbon abundance in marine sediment cores, and thus a record of the intensity of biomass burning on adjacent continental land masses in the geologic past. In addition, the δ 13C value of the elemental carbon can provide an indication of the type of vegetation being burnt.

  3. MGA: A gamma-ray spectrum analysis code for determining plutonium isotopic abundances. Volume 3, FORTRAN listing of the GA code

    SciTech Connect

    Gunnink, R

    1991-09-01

    Nondestructive measurements of x-ray and gamma-ray emissions can be used to determine the abundances of various actinides in a sample. Volume 1 of this report describes the methods and algorithms we have developed to determine the relative isotopic abundances of actinides in a sample, by analyzing gamma-ray spectra obtained using germanium detector systems. Volume 2 is a guide to using the MGA (Multiple Group Analysis) computer program we have written to perform plutonium isotopic analyses. This report contains a listing of the FORTRAN instructions of the code.

  4. Lunar Elemental Abundances from Gamma-Ray and Neutron Measurements

    NASA Astrophysics Data System (ADS)

    Reedy, R. C.; Vaniman, D. T.

    1999-01-01

    % , with Ti and Fe emitting more fast neutrons than light elements like O and Si. Most elements moderate neutrons to thermal energies at similar rates. The main exception is when neutrons scatter from H, in which case neutrons can be rapidly thermalized. The cross sections for the absorption of thermal neutrons can vary widely among elements, with major elements like Ti and Fe having high-capture cross sections. Some trace elements, such as Sm and Gd, have such large neutron-absorption cross sections that, despite their low abundances, can absorb significant amounts of thermal neutrons in the Moon. Because the processes affecting neutrons are complicated, good modeling is needed to properly extract elemental information from measured neutron fluxes. The LAHET Code System (LCS) can be use to calculate neutron fluxes from GCR interactions in the Moon. Lunar Gamma-Ray Spectroscopy: The main sources of planetary gamma-rays are the decay of the naturally occurring radioactive isotopes of K, Th, and U and the interactions of GCRs with atomic nuclei in the planet's surface. Most "cosmogenic" gamma-rays are produced by fast and thermal neutrons made in the planet's surface by GCRs, and their production rates can vary with time. Over 300 gamma-ray lines have been identified that can be emitted from planetary surfaces by a variety of production mechanisms. There exist nuclear databases that can be used to identify and quantify other gamma-ray lines. Use will be made of gamma-rays from major elements, particularly those from Si and O, that have not been routinely used in the past. The fluxes of gamma-rays from a given element can vary depending on many factors besides the concentration of that element. For example, the fluxes of neutron-capture gamma-rays in the planetary region of interest depend on (1) the total cross section for elements to absorb thermalized neutrons and (2) the H content of the top meter of the surface. The fluxes of the fast neutrons that induce inelastic

  5. Mercury (Hg) in meteorites: Variations in abundance, thermal release profile, mass-dependent and mass-independent isotopic fractionation

    NASA Astrophysics Data System (ADS)

    Meier, Matthias M. M.; Cloquet, Christophe; Marty, Bernard

    2016-06-01

    We have measured the concentration, isotopic composition and thermal release profiles of Mercury (Hg) in a suite of meteorites, including both chondrites and achondrites. We find large variations in Hg concentration between different meteorites (ca. 10 ppb to 14,000 ppb), with the highest concentration orders of magnitude above the expected bulk solar system silicates value. From the presence of several different Hg carrier phases in thermal release profiles (150-650 °C), we argue that these variations are unlikely to be mainly due to terrestrial contamination. The Hg abundance of meteorites shows no correlation with petrographic type, or mass-dependent fractionation of Hg isotopes. Most carbonaceous chondrites show mass-independent enrichments in the odd-numbered isotopes 199Hg and 201Hg. We show that the enrichments are not nucleosynthetic, as we do not find corresponding nucleosynthetic deficits of 196Hg. Instead, they can partially be explained by Hg evaporation and redeposition during heating of asteroids from primordial radionuclides and late-stage impact heating. Non-carbonaceous chondrites, most achondrites and the Earth do not show these enrichments in vapor-phase Hg. All meteorites studied here have however isotopically light Hg (δ202Hg = ∼-7 to -1) relative to the Earth's average crustal values, which could suggest that the Earth has lost a significant fraction of its primordial Hg. However, the late accretion of carbonaceous chondritic material on the order of ∼2%, which has been suggested to account for the water, carbon, nitrogen and noble gas inventories of the Earth, can also contribute most or all of the Earth's current Hg budget. In this case, the isotopically heavy Hg of the Earth's crust would have to be the result of isotopic fractionation between surface and deep-Earth reservoirs.

  6. 13C and 15N natural isotope abundance reflects breast cancer cell metabolism

    NASA Astrophysics Data System (ADS)

    Tea, Illa; Martineau, Estelle; Antheaume, Ingrid; Lalande, Julie; Mauve, Caroline; Gilard, Francoise; Barillé-Nion, Sophie; Blackburn, Anneke C.; Tcherkez, Guillaume

    2016-09-01

    Breast cancer is the most common cancer in women worldwide. Despite the information provided by anatomopathological assessment and molecular markers (such as receptor expression ER, PR, HER2), breast cancer therapies and prognostics depend on the metabolic properties of tumor cells. However, metabolomics have not provided a robust and congruent biomarker yet, likely because individual metabolite contents are insufficient to encapsulate all of the alterations in metabolic fluxes. Here, we took advantage of natural 13C and 15N isotope abundance to show there are isotopic differences between healthy and cancer biopsy tissues or between healthy and malignant cultured cell lines. Isotope mass balance further suggests that these differences are mostly related to lipid metabolism, anaplerosis and urea cycle, three pathways known to be impacted in malignant cells. Our results demonstrate that the isotope signature is a good descriptor of metabolism since it integrates modifications in C partitioning and N excretion altogether. Our present study is thus a starting point to possible clinical applications such as patient screening and biopsy characterization in every cancer that is associated with metabolic changes.

  7. 13C and 15N natural isotope abundance reflects breast cancer cell metabolism

    PubMed Central

    Tea, Illa; Martineau, Estelle; Antheaume, Ingrid; Lalande, Julie; Mauve, Caroline; Gilard, Francoise; Barillé-Nion, Sophie; Blackburn, Anneke C.; Tcherkez, Guillaume

    2016-01-01

    Breast cancer is the most common cancer in women worldwide. Despite the information provided by anatomopathological assessment and molecular markers (such as receptor expression ER, PR, HER2), breast cancer therapies and prognostics depend on the metabolic properties of tumor cells. However, metabolomics have not provided a robust and congruent biomarker yet, likely because individual metabolite contents are insufficient to encapsulate all of the alterations in metabolic fluxes. Here, we took advantage of natural 13C and 15N isotope abundance to show there are isotopic differences between healthy and cancer biopsy tissues or between healthy and malignant cultured cell lines. Isotope mass balance further suggests that these differences are mostly related to lipid metabolism, anaplerosis and urea cycle, three pathways known to be impacted in malignant cells. Our results demonstrate that the isotope signature is a good descriptor of metabolism since it integrates modifications in C partitioning and N excretion altogether. Our present study is thus a starting point to possible clinical applications such as patient screening and biopsy characterization in every cancer that is associated with metabolic changes. PMID:27678172

  8. Isotopic Measurements of Organic Sulfonates From The Murchison Meteorite

    NASA Technical Reports Server (NTRS)

    Cooper, G. W.; Chang, S.; DeVincenzi, Donald L. (Technical Monitor)

    1995-01-01

    Organic sulfonates and phosphonates have been extracted from the Murchison meteorite for stable isotope measurements. Preliminary stable isotope measurements of individual alkyl sulfonates, R-SO3H (R=C(sub n)H(sub 2n+l)), are shown. These compounds were found in aqueous extracts of Murchison. Both groups show trends similar to other homologous series of organic compounds indigenous to Murchison. Molecular abundances decrease with increasing carbon number, and all possible isomers at each carbon number (through C-4) are present. Carbon isotope measurements of the sulfonates show a decrease in the C-13/C-12 ratio with increasing carbon number. The overall objectives of this project are to obtain dime element carbon, hydrogen, and sulfur - intramolecular isotopic analyses of individual sulfonates, and isotopic measurement of carbon and hydrogen of the phosphonates as a group. The Murchison meteorite is the best characterized carbonaceous chondrite with respect to organic chemistry. The finding of organic sulfonates and phosphonates in Murchison is of interest because they are the first well-characterized series of sulfur and phosphorus containing organic compounds found in meteorites. Also, meteorites, comets, and interplanetary dust particles may have been involved in chemical evolution on the early Earth. Because of the critical role of organic phosphorus and sulfur in all living systems, it is particularly interesting to see examples of abiotic syntheses of these classes of compounds. The study of the isotopic composition of the sulfonates and phosphonates can yield insight into their possible interstellar origin as well as their mechanisms of synthesis in the early solar system. Previous isotopic analyses of other classes of organic compounds indigenous to meteorites, e.g., amino acids, carboxylic acids, and hydrocarbons indicate the possibility that interstellar molecules were incorporated into meteorite parent bodies. In these compounds the ratios of heavy to

  9. Nonlinearity of Argon Isotope Measurements for Samples of Different Sizes

    NASA Astrophysics Data System (ADS)

    Cox, S. E.; Hemming, S. R.; Turrin, B. D.; Swisher, C. C.

    2010-12-01

    Uncertainty in isotope ratio linearity is not propagated into the final uncertainty of high-precision Ar-Ar analyses. Nonlinearity is assumed to be negligible compared to other sources of error, so mass discrimination is calculated using air pipettes of a single size similar to typical unknowns. The calculated discrimination factor is applied to all measured isotopes regardless of the difference in relative isotope abundance or the difference in gas pressure between the sample and the air pipette. We measured 40Ar/36Ar ratios of different size air samples created using up to twenty pipette shots on two different mass spectrometers with automated air pipette systems (a VG5400 and an MAP 215-50) in order to test the assumption that the measured isotope ratios are consistent at different gas pressures. We typically obtain reproducibility < 0.5% on the 40Ar/36Ar of similar size air standards, but we measured 40Ar/36Ar ratios for aliquots 0.5 to 20 times the typical volume from the same reservoir that varied by as much as 10% (Figure 1). In sets VG1, VG2, and MAP, 40Ar/36Ar ratios increased with gas pressure (expressed as number of air pipette shots; R2 > 0.9). Several months later, we performed the same measurements on the VG5400 with a new filament and different tuning parameters and obtained a different result (Set VG3). In this case, the 40Ar/36Ar ratios still varied with gas pressure, but less drastically (R2 > 0.3), and the slope was reversed--40Ar/36Ar ratios decreased with gas pressure. We conclude that isotope ratio nonlinearity is a common phenomenon that has the potential to affect monitor standard and timescale age calculations at the 0.1% level of significance defined by EARTHTIME. We propose that argon labs incorporate air pipettes of varying size and isotopic compositions to allow for routine calibration of isotope ratio nonlinearity in the course of high-precision analyses. Figure 1: Measured 40Ar/36Ar vs. number of air pipettes. Sets VG1, VG2, and MAP

  10. MGA (Multi-Group Analysis): A gamma-ray spectrum analysis code for determining plutonium isotopic abundances

    SciTech Connect

    Gunnink, R

    1990-04-03

    Nondestructive measurements of x-ray and gamma-ray emissions can be used to analyze a sample for plutonium. This report describes the methods and algorithms we have developed for analyzing gamma-ray spectra obtained by using a germanium detector system to accurately determine the relative abundances of various actinide isotopes in a sample. Our methodology requires no calibrations and can be used to measure virtually any size and type of plutonium sample. Measurement times can be as short as a few minutes; measurements are frequently accurate to within 1%. Our methods have been programmed into a computerized analysis code called MGA (Multi-Group Analysis). Our current versions can be run on personal computers (IBM type) and on the DEC VAX microcomputer. Spectral analysis times are usually far less than a minute. 28 refs., 26 figs., 1 tab.

  11. Biosynthesis of gallic acid in Rhus typhina: discrimination between alternative pathways from natural oxygen isotope abundance.

    PubMed

    Werner, Roland A; Rossmann, Andreas; Schwarz, Christine; Bacher, Adelbert; Schmidt, Hanns-Ludwig; Eisenreich, Wolfgang

    2004-10-01

    The biosynthetic pathway of gallic acid in leaves of Rhus typhina is studied by oxygen isotope ratio mass spectrometry at natural oxygen isotope abundance. The observed delta18O-values of gallic acid indicate an 18O-enrichment of the phenolic oxygen atoms of more than 30 per thousand above that of the leaf water. This enrichment implies biogenetical equivalence with oxygen atoms of carbohydrates but not with oxygen atoms introduced by monooxygenase activation of molecular oxygen. It can be concluded that all phenolic oxygen atoms of gallic acid are retained from the carbohydrate-derived precursor 5-dehydroshikimate. This supports that gallic acid is synthesized entirely or predominantly by dehydrogenation of 5-dehydroshikimate.

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

    NASA Technical Reports Server (NTRS)

    Wannier, P. G.; Sahai, R.

    1987-01-01

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

  13. Quantifying nitrogen process rates in a constructed wetland using natural abundance stable isotope signatures and stable isotope amendment experiments.

    PubMed

    Erler, Dirk V; Eyre, Bradley D

    2010-01-01

    This study describes the spatial variability in nitrogen (N) transformation within a constructed wetland (CW) treating domestic effluent. Nitrogen cycling within the CW was driven by settlement and mineralization of particulate organic nitrogen and uptake of NO3-. The concentration of NO3- was found to decrease, as the delta15N-NO3- signature increased, as water flowed through the CW, allowing denitrification rates to be estimated on the basis of the degree of fractionation of delta15N-NO3-. Estimates of denitrification hinged on the determination of a net isotope effect (eta), which was influenced byprocesses that enrich or deplete 15NO3- (e.g., nitrification), as well as the rate constants associated with the different processes involved in denitrification (i.e., diffusion and enzyme activity). The influence of nitrification on eta was quantified; however, it remained unclear how eta varied due to variability in denitrification rate constants. A series of stable isotope amendment experiments was used to further constrain the value of eta and calculate rates of denitrification, and nitrification, within the wetland. The maximum calculated rate of denitrification was 956 +/- 187 micromol N m(-2) h(-1), and the maximum rate of nitrification was 182 +/- 28.9 micromol N m(-2) h(-1). Uptake of NO3- was quantitatively more important than denitrification throughoutthe wetland. Rates of N cycling varied spatially within thewetland, with denitrification dominating in the downstream deoxygenated region of the wetland. Studies that use fractionation of N to derive rate estimates must exercise caution when interpreting the net isotope effect. We suggest a sampling procedure for future natural abundance studies that may help improve the accuracy of N cycling rate estimates.

  14. Specific activity and isotope abundances of strontium in purified strontium-82

    SciTech Connect

    Fitzsimmons, J. M.; Medvedev, D. G.; Mausner, L. F.

    2015-11-12

    A linear accelerator was used to irradiate a rubidium chloride target with protons to produce strontium-82 (Sr-82), and the Sr-82 was purified by ion exchange chromatography. The amount of strontium associated with the purified Sr-82 was determined by either: ICP-OES or method B which consisted of a summation of strontium quantified by gamma spectroscopy and ICP-MS. The summation method agreed within 10% to the ICP-OES for the total mass of strontium and the subsequent specific activities were determined to be 0.25–0.52 TBq mg-1. Method B was used to determine the isotope abundances by weight% of the purified Sr-82, and the abundances were: Sr-82 (10–20.7%), Sr-83 (0–0.05%), Sr-84 (35–48.5%), Sr-85 (16–25%), Sr-86 (12.5–23%), Sr-87 (0%), and Sr-88 (0–10%). The purified strontium contained mass amounts of Sr-82, Sr-84, Sr-85, Sr-86, and Sr-88 in abundances not associated with natural abundance, and 90% of the strontium was produced by the proton irradiation. A comparison of ICP-OES and method B for the analysis of Sr-82 indicated analysis by ICP-OES would be easier to determine total mass of strontium and comply with regulatory requirements. An ICP-OES analytical method for Sr-82 analysis was established and validated according to regulatory guidelines.

  15. BENCHMARKING ORTEC ISOTOPIC MEASUREMENTS AND CALCULATIONS

    SciTech Connect

    Dewberry, R; Raymond Sigg, R; Vito Casella, V; Nitin Bhatt, N

    2008-09-29

    This report represents a description of compiled benchmark tests conducted to probe and to demonstrate the extensive utility of the Ortec ISOTOPIC {gamma}-ray analysis computer program. The ISOTOPIC program performs analyses of {gamma}-ray spectra applied to specific acquisition configurations in order to apply finite-geometry correction factors and sample-matrix-container photon absorption correction factors. The analysis program provides an extensive set of preset acquisition configurations to which the user can add relevant parameters in order to build the geometry and absorption correction factors that the program determines from calculus and from nuclear g-ray absorption and scatter data. The Analytical Development Section field nuclear measurement group of the Savannah River National Laboratory uses the Ortec ISOTOPIC analysis program extensively for analyses of solid waste and process holdup applied to passive {gamma}-ray acquisitions. Frequently the results of these {gamma}-ray acquisitions and analyses are to determine compliance with facility criticality safety guidelines. Another use of results is to designate 55-gallon drum solid waste as qualified TRU waste3 or as low-level waste. Other examples of the application of the ISOTOPIC analysis technique to passive {gamma}-ray acquisitions include analyses of standard waste box items and unique solid waste configurations. In many passive {gamma}-ray acquisition circumstances the container and sample have sufficient density that the calculated energy-dependent transmission correction factors have intrinsic uncertainties in the range 15%-100%. This is frequently the case when assaying 55-gallon drums of solid waste with masses of up to 400 kg and when assaying solid waste in extensive unique containers. Often an accurate assay of the transuranic content of these containers is not required, but rather a good defensible designation as >100 nCi/g (TRU waste) or <100 nCi/g (low level solid waste) is required. In

  16. Construction of confidence regions for isotopic abundance patterns in LC/MS data sets for rigorous determination of molecular formulas.

    PubMed

    Ipsen, Andreas; Want, Elizabeth J; Ebbels, Timothy M D

    2010-09-01

    It has long been recognized that estimates of isotopic abundance patterns may be instrumental in identifying the many unknown compounds encountered when conducting untargeted metabolic profiling using liquid chromatography/mass spectrometry. While numerous methods have been developed for assigning heuristic scores to rank the degree of fit of the observed abundance patterns with theoretical ones, little work has been done to quantify the errors that are associated with the measurements made. Thus, it is generally not possible to determine, in a statistically meaningful manner, whether a given chemical formula would likely be capable of producing the observed data. In this paper, we present a method for constructing confidence regions for the isotopic abundance patterns based on the fundamental distribution of the ion arrivals. Moreover, we develop a method for doing so that makes use of the information pooled together from the measurements obtained across an entire chromatographic peak, as well as from any adducts, dimers, and fragments observed in the mass spectra. This greatly increases the statistical power, thus enabling the analyst to rule out a potentially much larger number of candidate formulas while explicitly guarding against false positives. In practice, small departures from the model assumptions are possible due to detector saturation and interferences between adjacent isotopologues. While these factors form impediments to statistical rigor, they can to a large extent be overcome by restricting the analysis to moderate ion counts and by applying robust statistical methods. Using real metabolic data, we demonstrate that the method is capable of reducing the number of candidate formulas by a substantial amount, even when no bromine or chlorine atoms are present. We argue that further developments in our ability to characterize the data mathematically could enable much more powerful statistical analyses.

  17. Stable isotope natural abundance of nitrous oxide emitted from Antarctic tundra soils: effects of sea animal excrement depositions.

    PubMed

    Zhu, Renbin; Liu, Yashu; Li, Xianglan; Sun, Jianjun; Xu, Hua; Sun, Liguang

    2008-11-01

    Nitrous oxide (N2O), a greenhouse gas, is mainly emitted from soils during the nitrification and denitrification processes. N2O stable isotope investigations can help to characterize the N2O sources and N2O production mechanisms. N2O isotope measurements have been conducted for different types of global terrestrial ecosystems. However, no isotopic data of N2O emitted from Antarctic tundra ecosystems have been reported although the coastal ice-free tundra around Antarctic continent is the largest sea animal colony on the global scale. Here, we report for the first time stable isotope composition of N2O emitted from Antarctic sea animal colonies (including penguin, seal and skua colonies) and normal tundra soils using in situ field observations and laboratory incubations, and we have analyzed the effects of sea animal excrement depositions on stable isotope natural abundance of N2O. For all the field sites, the soil-emitted N2O was 15N- and 18O-depleted compared with N2O in local ambient air. The mean delta values of the soil-emitted N2O were delta15N = -13.5 +/- 3.2 per thousand and delta18O = 26.2 +/- 1.4 per thousand for the penguin colony, delta15N = -11.5 +/- 5.1 per thousand and delta18O = 26.4 +/- 3.5 per thousand for the skua colony and delta15N = -18.9 +/- 0.7 per thousand and delta18O = 28.8 +/- 1.3 per thousand for the seal colony. In the soil incubations, the isotopic composition of N2O was measured under N2 and under ambient air conditions. The soils incubated under the ambient air emitted very little N2O (2.93 microg N2O--N kg(-1)). Under N2 conditions, much more N2O was formed (9.74 microg N2O--N kg(-1)), and the mean delta15N and delta18O values of N2O were -19.1 +/- 8.0 per thousand and 21.3 +/- 4.3 per thousand, respectively, from penguin colony soils, and -17.0 +/- 4.2 per thousand and 20.6 +/- 3.5 per thousand, respectively, from seal colony soils. The data from in situ field observations and laboratory experiments point to denitrification as the

  18. Natural isotope correction of MS/MS measurements for metabolomics and (13)C fluxomics.

    PubMed

    Niedenführ, Sebastian; ten Pierick, Angela; van Dam, Patricia T N; Suarez-Mendez, Camilo A; Nöh, Katharina; Wahl, S Aljoscha

    2016-05-01

    Fluxomics and metabolomics are crucial tools for metabolic engineering and biomedical analysis to determine the in vivo cellular state. Especially, the application of (13)C isotopes allows comprehensive insights into the functional operation of cellular metabolism. Compared to single MS, tandem mass spectrometry (MS/MS) provides more detailed and accurate measurements of the metabolite enrichment patterns (tandem mass isotopomers), increasing the accuracy of metabolite concentration measurements and metabolic flux estimation. MS-type data from isotope labeling experiments is biased by naturally occurring stable isotopes (C, H, N, O, etc.). In particular, GC-MS(/MS) requires derivatization for the usually non-volatile intracellular metabolites introducing additional natural isotopes leading to measurements that do not directly represent the carbon labeling distribution. To make full use of LC- and GC-MS/MS mass isotopomer measurements, the influence of natural isotopes has to be eliminated (corrected). Our correction approach is analyzed for the two most common applications; (13)C fluxomics and isotope dilution mass spectrometry (IDMS) based metabolomics. Natural isotopes can have an impact on the calculated flux distribution which strongly depends on the substrate labeling and the actual flux distribution. Second, we show that in IDMS based metabolomics natural isotopes lead to underestimated concentrations that can and should be corrected with a nonlinear calibration. Our simulations indicate that the correction for natural abundance in isotope based fluxomics and quantitative metabolomics is essential for correct data interpretation.

  19. Measurement of Plutonium Isotopic Composition - MGA

    SciTech Connect

    Vo, Duc Ta

    2015-08-21

    In this module, we will use the Canberra InSpector-2000 Multichannel Analyzer with a high-purity germanium detector (HPGe) and the MGA isotopic anlysis software to assay a variety of plutonium samples. The module provides an understanding of the MGA method, its attributes and limitations. You will assess the system performance by measuring a range of materials similar to those you may assay in your work. During the final verification exercise, the results from MGA will be combined with the 240Pueff results from neutron coincidence or multiplicity counters so that measurements of the plutonium mass can be compared with the operator-declared (certified) values.

  20. Abundance, distribution, and isotopic composition of particulate black carbon in the northern Gulf of Mexico

    NASA Astrophysics Data System (ADS)

    Yang, Weifeng; Guo, Laodong

    2014-11-01

    There exists increasing evidence supporting the important role of black carbon in global carbon cycles. Particulate black carbon (PBC) is allochthonous and has distinct reactivities compared to the bulk particulate organic carbon (tot-POC) in marine environments. However, the abundance, geochemical behavior of PBC and its importance in oceanic carbon budget remain poorly understood. Here we report the abundance, distribution, and stable isotopic signatures of BC derived from the chemo-thermal oxidation (CTO-375) method (BCCTO) in the Gulf of Mexico. Our results show that BCCTO abundance decreased from shelf to basin, and more than a half of riverine BCCTO could be removed over the shelf. Moreover, BCCTO is much more refractory compared to the tot-POC and has δ13C values lower than those of BC-excluded POC. These results highlight the significance of PBC in marine carbon cycles and potentially suggest the need for a new end-member term in quantifying POC sources in the ocean.

  1. Mass spectrometric measurements of the isotopic anatomies of molecules (Invited)

    NASA Astrophysics Data System (ADS)

    Eiler, J. M.; Krumwiede, D.; Schlueter, H.

    2013-12-01

    Site-specific and multiple isotopic substitutions in molecular structures potentially provide an extraordinarily rich set of constraints on their sources, conditions of formation, reaction and transport histories, and perhaps other issues. Examples include carbonate ';clumped isotope' thermometry, clumped isotope measurements of CO2, O2, and, recently, methane, ethane and N2O; site-specific 15N measurements in N2O and 13C and D analyses of fatty acids, sugars, cellulose, food products, and, recently, n-alkanes. Extension of the principles behind these tools to the very large number of isotopologues of complex molecules could potentially lead to new uses of isotope chemistry, similar to proteomics, metabolomics and genomics in their complexity and depth of detail (';isotomics'?). Several technologies are potentially useful for this field, including ';SNIF-NMR', gas source mass spectrometry and IR absorption spectroscopy. However, all well established methods have restrictive limits in the sizes of samples, types of analyzes, and the sorts of isotopologues that can be measured with useful precision. We will present an overview of several emerging instruments and techniques of high-resolution gas source mass spectrometry that may enable study of a large proportion of the isotopologues of a wide range of volatile and semi-volatile compounds, including many organics, with precisions and sample sizes suitable for a range of applications. A variety of isotopologues can be measured by combining information from the Thermo 253 Ultra (a new high resolution, multi-collector gas source mass spectrometer) and the Thermo DFS (a very high resolution single collector, but used here on a novel mode to achieve ~per mil precision ratio measurements), sometimes supplemented by conventional bulk isotopic measurements. It is possible to design methods in which no one of these sources of data meaningfully constrain abundances of specific isotopologues, but their combination fully and

  2. DANCEing with the Stars: Measuring Neutron Capture on Unstable Isotopes with DANCE

    NASA Astrophysics Data System (ADS)

    Couture, A.; Agvaanluvsan, U.; Baker, J. D.; Bayarbadrahk, B.; Becker, J. A.; Bond, E.; Bredeweg, T. A.; Chyzh, A.; Dashdorj, D.; Fowler, M.; Haight, R. C.; Jandel, M.; Keksis, A. L.; O'Donnell, J. M.; Reifarth, R.; Rundberg, R.; Ullmann, J. L.; Vieira, D. J.; Wouters, J. M.

    2009-03-01

    Isotopes heavier than iron are known to be produced in stars through neutron capture processes. Two major processes, the slow (s) and rapid (r) processes are each responsible for 50% of the abundances of the heavy isotopes. The neutron capture cross sections of the isotopes on the s process path reveal information about the expected abundances of the elements as well as stellar conditions and dynamics. Until recently, measurements on unstable isotopes, which are most important for determining stellar temperatures and reaction flow, have not been experimentally feasible. The Detector for Advance Neutron Capture Experiments (DANCE) located at the Los Alamos Neutron Science Center (LANSCE) was designed to perform time-of-flight neutron capture measurements on unstable isotopes for nuclear astrophysics, stockpile stewardship, and reactor development. DANCE is a 4-π BaF2 scintillator array which can perform measurements on sub-milligram samples of isotopes with half-lives as short as a few hundred days. These cross sections are critical for advancing our understanding of the production of the heavy isotopes.

  3. DANCEing with the Stars: Measuring Neutron Capture on Unstable Isotopes with DANCE

    SciTech Connect

    Couture, A.; Bond, E.; Bredeweg, T. A.; Fowler, M.; Haight, R. C.; Jandel, M.; Keksis, A. L.; O'Donnell, J. M.; Rundberg, R.; Ullmann, J. L.; Vieira, D. J.; Wouters, J. M.; Agvaanluvsan, U.; Becker, J. A.; Baker, J. D.; Bayarbadrahk, B.; Chyzh, A.; Dashdorj, D.; Reifarth, R.

    2009-03-10

    Isotopes heavier than iron are known to be produced in stars through neutron capture processes. Two major processes, the slow (s) and rapid (r) processes are each responsible for 50% of the abundances of the heavy isotopes. The neutron capture cross sections of the isotopes on the s process path reveal information about the expected abundances of the elements as well as stellar conditions and dynamics. Until recently, measurements on unstable isotopes, which are most important for determining stellar temperatures and reaction flow, have not been experimentally feasible. The Detector for Advance Neutron Capture Experiments (DANCE) located at the Los Alamos Neutron Science Center (LANSCE) was designed to perform time-of-flight neutron capture measurements on unstable isotopes for nuclear astrophysics, stockpile stewardship, and reactor development. DANCE is a 4-{pi}BaF{sub 2} scintillator array which can perform measurements on sub-milligram samples of isotopes with half-lives as short as a few hundred days. These cross sections are critical for advancing our understanding of the production of the heavy isotopes.

  4. A novel sample decomposition technique at atmospheric pressure for the determination of Os abundances in iron meteorites using isotope dilution inductively coupled plasma-mass spectrometry.

    PubMed

    Hattori, M; Hirata, T

    2001-06-01

    A safe and reliable analytical technique for the determination of Os abundances in ten iron meteorites of various chemical groups was developed using isotope dilution inductively coupled plasma-mass spectrometry coupled with a sample decomposition technique. A major advantage of the sample decomposition technique developed here is that the pressure inside the reaction flask is not increased through the decomposition reaction because the flask is a fully opened system, obviating the risk of explosion of the glass apparatus. Another advantage is that there is no restriction in the sample size being decomposed. In this study, about 2 g of metallic sample were decomposed safely, and this sample size, > 10 times larger than that typically used for the Carius tube technique, allows one to obtain more reliable Os data for heterogeneous samples. The metallic samples were decomposed in a glass flask purged with Ar. Since the O2 was purged from the reaction flask, Os was not oxidised to volatile OsO4, thereby preventing significant evaporation loss of Os. The typical recovery of Os throughout the sample decomposition and separation processes was > 80%, and the total Os blank through the decomposition of a 1 g amount of sample was less than 20 pg. Os abundances were determined by means of stable isotope dilution mass spectrometry using a 190Os-enriched isotopic tracer. Except for Sikhote-Alin, the measured Os abundances in almost all the iron meteorites exhibited a good agreement with the previously published Os abundance data, within the analytical uncertainty achieved in this study (2-5%). For the Sikhote-Alin meteorite, on the basis of a better correlation between Os and Ir abundances, we believe that our Os abundance data should be more reliable. The Os abundance data obtained in this work clearly demonstrated the suitability of the newly developed sample decomposition procedure for low level Os determinations.

  5. The Abundance and Isotopic Composition of Water in Howardite-Eucrite-Diogenite Meteorites

    NASA Astrophysics Data System (ADS)

    Barrett, T. J.; Tartèse, R.; Anand, M.; Franchi, I. A.; Grady, M. M.; Greenwood, R. C.; Charlier, B. L. A.

    2014-09-01

    Using SIMs techniques we measure OH abundances and D/H ratios in apatite grains from two Eucrites (DaG 945, DaG 844).The average δD values of these two samples are also similar to carbonaceous chondrites, the Earth and the Moon.

  6. Abundance and isotopic composition of gases in the martian atmosphere from the Curiosity rover.

    PubMed

    Mahaffy, Paul R; Webster, Christopher R; Atreya, Sushil K; Franz, Heather; Wong, Michael; Conrad, Pamela G; Harpold, Dan; Jones, John J; Leshin, Laurie A; Manning, Heidi; Owen, Tobias; Pepin, Robert O; Squyres, Steven; Trainer, Melissa

    2013-07-19

    Volume mixing and isotope ratios secured with repeated atmospheric measurements taken with the Sample Analysis at Mars instrument suite on the Curiosity rover are: carbon dioxide (CO2), 0.960(±0.007); argon-40 ((40)Ar), 0.0193(±0.0001); nitrogen (N2), 0.0189(±0.0003); oxygen, 1.45(±0.09) × 10(-3); carbon monoxide, < 1.0 × 10(-3); and (40)Ar/(36)Ar, 1.9(±0.3) × 10(3). The (40)Ar/N2 ratio is 1.7 times greater and the (40)Ar/(36)Ar ratio 1.6 times lower than values reported by the Viking Lander mass spectrometer in 1976, whereas other values are generally consistent with Viking and remote sensing observations. The (40)Ar/(36)Ar ratio is consistent with martian meteoritic values, which provides additional strong support for a martian origin of these rocks. The isotopic signature δ(13)C from CO2 of ~45 per mil is independently measured with two instruments. This heavy isotope enrichment in carbon supports the hypothesis of substantial atmospheric loss.

  7. A Comparison of Stellar Elemental Abundance Techniques and Measurements

    NASA Astrophysics Data System (ADS)

    Hinkel, Natalie R.; Young, Patrick A.; Pagano, Michael D.; Desch, Steven J.; Anbar, Ariel D.; Adibekyan, Vardan; Blanco-Cuaresma, Sergi; Carlberg, Joleen K.; Delgado Mena, Elisa; Liu, Fan; Nordlander, Thomas; Sousa, Sergio G.; Korn, Andreas; Gruyters, Pieter; Heiter, Ulrike; Jofré, Paula; Santos, Nuno C.; Soubiran, Caroline

    2016-09-01

    Stellar elemental abundances are important for understanding the fundamental properties of a star or stellar group, such as age and evolutionary history, as well as the composition of an orbiting planet. However, as abundance measurement techniques have progressed, there has been little standardization between individual methods and their comparisons. As a result, different stellar abundance procedures determine measurements that vary beyond the quoted error for the same elements within the same stars. The purpose of this paper is to better understand the systematic variations between methods and offer recommendations for producing more accurate results in the future. We invited a number of participants from around the world (Australia, Portugal, Sweden, Switzerland, and the United States) to calculate 10 element abundances (C, O, Na, Mg, Al, Si, Fe, Ni, Ba, and Eu) using the same stellar spectra for four stars (HD 361, HD 10700, HD 121504, and HD 202206). Each group produced measurements for each star using (1) their own autonomous techniques, (2) standardized stellar parameters, (3) a standardized line list, and (4) both standardized parameters and a line list. We present the resulting stellar parameters, absolute abundances, and a metric of data similarity that quantifies the homogeneity of the data. We conclude that standardization of some kind, particularly stellar parameters, improves the consistency between methods. However, because results did not converge as more free parameters were standardized, it is clear there are inherent issues within the techniques that need to be reconciled. Therefore, we encourage more conversation and transparency within the community such that stellar abundance determinations can be reproducible as well as accurate and precise.

  8. Nickel isotope abundances of type I deep-sea spheres and of iron-nickel spherules from sediments in Alberta, Canada

    NASA Astrophysics Data System (ADS)

    Xue, S.; Herzog, G. F.; Hall, G. S.; Bi, D.; Brownlee, D. E.

    1995-12-01

    Nickel isotope abundances were measured by ICP-MS in twenty-one whole, type I deep-sea spheres, in Ni-rich cores and oxide shells separated from three others, and in Fe-Ni alloy spherules from Alberta, Canada. The nickel isotopes in the whole deep-sea spheres are mass fractionated from 0.4 to 2.4%/ AMU. These: values correspond to open system vaporization losses of Ni as high as 94% (relative). The degree of mass fractionation correlates well with bulk nickel content in most cases. Taken together with published iron isotope data, the nickel isotope results indicate a pre-loss Fe/Ni ratio of about 12 for many spheres. Similar ratios are observed in the following types of meteoritic material: EL-chondrite metal; IA, IIE, IIIA, and IVA iron meteorites; and metal from pallasites and mesosiderites. Metal cores separated from three deep-sea spheres contain between 40 and 52% Ni, with mass fractionations ranging from undetectable to a high of 0.8%/AMU. Within experimental error, the degree of Ni mass fractionation in each oxide shell was the same as that in the corresponding core. No mass-dependent isotopic fractionation of nickel was observed in Ni-rich spherules recovered from Alberta sands of Pleistocene age. In general, Ni-rich samples have low degrees of isotopic fractionation which suggests that the most rapid vaporization of Ni occurs when both Fe and Ni have been oxidized.

  9. ICP-MS for isotope ratio measurement

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The use of stable isotopes in mineral nutrition research has become a fundamental aspect of conducting this research. A gradual transition has occurred, now virtually complete, from radioactive isotope studies to those using stable isotopes. Although primarily used in human research, mineral stable ...

  10. Isotope shift measurements in titanium I

    NASA Astrophysics Data System (ADS)

    Azaroual, E. M.; Luc, P.; Vetter, R.

    1992-06-01

    The use of an effusive beam of titanium atoms crossed with a CW single-mode tunable dye laser has allowed the high-resolution, Doppler-free study of the isotope shifts between50Ti,48Ti and46Ti, for seven 3 d 2 4 s 2 a3 F J → 3 d 2 4 s 4 p z 5 D J , visible transitions of Ti I. The measurements show without ambiguity the existence of a non-negligible field shift. Using the values of the nuclear radii of titanium (coming from muonic X-ray measurements), it is possible to determine the respective values of the field and mass shifts.

  11. Penning trap mass measurements on nobelium isotopes

    SciTech Connect

    Dworschak, M.; Block, M.; Ackermann, D.; Herfurth, F.; Hessberger, F. P.; Hofmann, S.; Vorobyev, G. K.; Audi, G.; Blaum, K.; Droese, C.; Marx, G.; Schweikhard, L.; Eliseev, S.; Ketter, J.; Fleckenstein, T.; Haettner, E.; Plass, W. R.; Scheidenberger, C.; Ketelaer, J.; Kluge, H.-J.

    2010-06-15

    The Penning trap mass spectrometer SHIPTRAP at GSI Darmstadt allows accurate mass measurements of radionuclides, produced in fusion-evaporation reactions and separated by the velocity filter SHIP from the primary beam. Recently, the masses of the three nobelium isotopes {sup 252-254}No were determined. These are the first direct mass measurements of transuranium elements, which provide new anchor points in this region. The heavy nuclides were produced in cold-fusion reactions by irradiating a PbS target with a {sup 48}Ca beam, resulting in production rates of the nuclei of interest of about one atom per second. In combination with data from decay spectroscopy our results are used to perform a new atomic-mass evaluation in this region.

  12. Determining Mineral Types and Abundances from Reflectance Measurements

    NASA Technical Reports Server (NTRS)

    Smith, M. O.; Adams, J. B.

    1985-01-01

    Mineral types and their abundances were quantitatively determined from laboratory reflectance spectra using principal components analysis (PCA). PCA reduced the measured spectral dimensionality and allowed testing the uniqueness and validity of spectral mixing models. In addition to interpreting absorption bands, in this new approach we interpreted variations in the overall spectral curves in terms of physical processes, namely changes in mixtures of minerals, in particle size and in illumination geometry. Application of this approach to reflectances of planetary surfaces allows interpretation to be extended to quantitative determinations of mineral types and abundances.

  13. Helium Isotopes and Noble Gas Abundances of Cave Dripping Water in Three Caves in East Asia

    NASA Astrophysics Data System (ADS)

    Chen, A. T.; Shen, C. C.; Tan, M.; Li, T.; Uemura, R.; Asami, R.

    2015-12-01

    Paleo-temperature recorded in nature archives is a critical parameter to understand climate change in the past. With advantages of unique inert chemical characteristics and sensitive solubilities with temperature, dissolved noble gases in speleothem inclusion water were recently proposed to retrieve terrestrial temperature history. In order to accurately apply this newly-developed speleothem noble gas temperature (NGT) as a reliable proxy, a fundamental issue about behaviors of noble gases in the karst should be first clarified. In this study, we measured noble gas contents in air and dripping water to evaluate any ratio deviation between noble gases. Cave dripping water samples was collected from three selected caves, Shihua Cave in northern China, Furong Cave in southwestern, and Gyukusen Cave in an island located in the western Pacific. For these caves are characterized by a thorough mixing and long-term storage of waters in a karst aquifer by the absence of seasonal oxygen isotope shifts. Ratios of dripping water noble gases are statistically insignificant from air data. Helium isotopic ratios in the dripping water samples match air value. The results indicate that elemental and isotopic signatures of noble gases from air can be frankly preserved in the epikarst and support the fidelity of NGT techniques.

  14. The Determination of the Natural Abundance of the Isotopes of Chlorine: An Introductory Experiment in Mass Spectrometry.

    ERIC Educational Resources Information Center

    O'Malley, Rebecca M.

    1982-01-01

    Describes a laboratory experiment which introduces basic principles and experimental techniques of mass spectrometry for fourth year undergraduate (B.Sc.) students. Laboratory procedures, background information, and discussion of results are provided for the experiment in which the natural isotopic abundance of chlorine is determined. (Author/JN)

  15. Siderophile and chalcophile element abundances in oceanic basalts, Pb isotope evolution and growth of the earth's core

    NASA Technical Reports Server (NTRS)

    Newsom, H. E.; White, W. M.; Jochum, K. P.; Hofmann, A. W.

    1986-01-01

    The hypothesis that the mantle Pb isotope ratios reflect continued extraction of Pb into the earth's core over geologic time is evaluated by studying the depeletion of chalcophile and siderophile elements in the mantle. Oceanic basalt samples are analyzed in order to determine the Pb, Sr, and Nd isotropic compositions and the abundances of siderophile and chalcophile elements and incompatible lithophile elements. The data reveal that there is no systematic variation of siderophile or chalcophile element abundances relative to abundances of lithophile elements and the Pb/Ce ratio of the mantle is constant. It is suggested that the crust formation involves nonmagmatic and magmatic processes.

  16. The origin of aubrites: Evidence from lithophile trace element abundances and oxygen isotope compositions

    NASA Astrophysics Data System (ADS)

    Barrat, J. A.; Greenwood, R. C.; Keil, K.; Rouget, M. L.; Boesenberg, J. S.; Zanda, B.; Franchi, I. A.

    2016-11-01

    We report the abundances of a selected set of ;lithophile; trace elements (including lanthanides, actinides and high field strength elements) and high-precision oxygen isotope analyses of a comprehensive suite of aubrites. Two distinct groups of aubrites can be distinguished: (a) the main-group aubrites display flat or light-REE depleted REE patterns with variable Eu and Y anomalies; their pyroxenes are light-REE depleted and show marked negative Eu anomalies; (b) the Mount Egerton enstatites and the silicate fraction from Larned display distinctive light-REE enrichments, and high Th/Sm ratios; Mount Egerton pyroxenes have much less pronounced negative Eu anomalies than pyroxenes from the main-group aubrites. Leaching experiments were undertaken to investigate the contribution of sulfides to the whole rock budget of the main-group aubrites. Sulfides contain in most cases at least 50% of the REEs and of the actinides. Among the elements we have analyzed, those displaying the strongest lithophile behaviors are Rb, Ba, Sr and Sc. The homogeneity of the Δ17O values obtained for main-group aubrite falls [Δ17O = +0.009 ± 0.010‰ (2σ)] suggests that they originated from a single parent body whose differentiation involved an early phase of large-scale melting that may have led to the development of a magma ocean. This interpretation is at first glance in agreement with the limited variability of the shapes of the REE patterns of these aubrites. However, the trace element concentrations of their phases cannot be used to discuss this hypothesis, because their igneous trace-element signatures have been modified by subsolidus exchange. Finally, despite similar O isotopic compositions, the marked light-REE enrichments displayed by Mount Egerton and Larned suggest that they are unrelated to the main-group aubrites and probably originated from a distinct parent body.

  17. Preliminary CALET Ultra Heavy Cosmic Ray Abundance Measurements

    NASA Astrophysics Data System (ADS)

    Rauch, Brian; CALET Collaboration

    2017-01-01

    The CALorimetric Electron Telescope (CALET) on the International Space Station (ISS) was launched August 19, 2015 and has been returning excellent data for over a year. The main calorimeter (CAL) on CALET measures the fluxes of high-energy electrons, nuclei and gamma rays. In addition to measuring the energy spectra of the more abundant cosmic-ray nuclei through 26Fe, CAL has the dynamic range to measure the abundances of the ultra-heavy (UH) cosmic-ray nuclei through 40Zr. In an anticipated 5 year mission on the ISS CALET will collect a UH data set with statistics comparable to that achieved with the first flight of the SuperTIGER balloon-borne instrument. The CALET space-based measurement has the advantage of not requiring corrections for atmospheric losses, and unlike other UH measurements the abundances of all nuclei from 1H through 40Zr are observed with the same instrument. We present preliminary CALET UH analysis results from the first year of operation. This research was supported by NASA at Washington University under Grant Number NNX11AE02G.

  18. Measurements of Volatile Circumstellar Isotopes: Effects of Fractionation vs. Nucleosynthesis

    NASA Astrophysics Data System (ADS)

    Milam, Stefanie

    The origin, evolution, and fate of our Universe and/or Galaxy have puzzled humankind for centuries. One approach to answering this question is to gain further understanding of stellar evolution, since stars are fundamental in galaxy development and evolution. A compilation of stellar composition can reveal the age, dynamics, and possibly the evolutionary state of a galaxy. In particular the volatile isotope ratios carry an imprint of stellar evolution and nucleosynthesis. Primitive materials, such as meteorites and IDPs, have revealed a component of ``atypical" isotopic signatures of these fundamental elements denoting a possible stellar origin. Understanding the processes by which these elements derive is essential for astrophysics on cosmochemical, galactic, stellar, and planetary scales. We propose to analyze data obtained from the Herschel Space Observatory of circumstellar envelopes to definitively measure C, N, and O isotope ratios and test current models of photo-selective isotope fractionation vs. nucleosynthetically determined values. This proposal augments data from the Herschel Space Observatory, primarily from the HIFISTARS program and MESS, though the entire Herschel archive will be searched for relevant data. The broader implications for this study include fundamental data necessary for furthering our current understanding of stellar nucleosynthesis, circumstellar chemistry, Galactic chemical evolution, and the origin of presolar grains found in primitive materials. We will focus on isotopologues of species formed in thermochemical equilibrium and trace their natal, nucleosynthetic isotope ratios. We will analyze Herschel data obtained for a survey of evolved stars with varying degrees of nuclear processing, evolutionary states, and envelope chemistry (e.g. oxygen-rich vs. carbon-rich). A full circumstellar model will be developed for each source to address specific affects that may influence either the ratios or chemistry. The isotope ratios of 12C

  19. Scale-dependent linkages between nitrate isotopes and denitrification in surface soils: implications for isotope measurements and models.

    PubMed

    Hall, Steven J; Weintraub, Samantha R; Bowling, David R

    2016-08-01

    Natural abundance nitrate (NO3 (-)) isotopes represent a powerful tool for assessing denitrification, yet the scale and context dependence of relationships between isotopes and denitrification have received little attention, especially in surface soils. We measured the NO3 (-) isotope compositions in soil extractions and lysimeter water from a semi-arid meadow and lawn during snowmelt, along with the denitrification potential, bulk O2, and a proxy for anaerobic microsites. Denitrification potential varied by three orders of magnitude and the slope of δ(18)O/δ(15)N in soil-extracted NO3 (-) from all samples measured 1.04 ± 0.12 (R (2) = 0.64, p < 0.0001), consistent with fractionation from denitrification. However, δ(15)N of extracted NO3 (-) was often lower than bulk soil δ(15)N (by up to 24 ‰), indicative of fractionation during nitrification that was partially overprinted by denitrification. Mean NO3 (-) isotopes in lysimeter water differed from soil extractions by up to 19 ‰ in δ(18)O and 12 ‰ in δ(15)N, indicating distinct biogeochemical processing in relatively mobile water versus soil microsites. This implies that NO3 (-) isotopes in streams, which are predominantly fed by mobile water, do not fully reflect terrestrial soil N cycling. Relationships between potential denitrification and δ(15)N of extracted NO3 (-) showed a strong threshold effect culminating in a null relationship at high denitrification rates. Our observations of (1) competing fractionation from nitrification and denitrification in redox-heterogeneous surface soils, (2) large NO3 (-) isotopic differences between relatively immobile and mobile water pools, (3) and the spatial dependence of δ(18)O/δ(15)N relationships suggest caution in using NO3 (-) isotopes to infer site or watershed-scale patterns in denitrification.

  20. Importance of regression processes in evaluating analytical errors in argon isotope measurements

    NASA Astrophysics Data System (ADS)

    Min, K.; Powell, L.

    2003-04-01

    For 40Ar/39Ar dating, it is required to measure five argon isotopes of 36Ar ~ 40Ar with high precision. The process involves isolating the purified gas in an analytical volume and cyclically measuring the abundance of each Ar isotope using an electron multiplier to minimize detector calibration and sensitivity errors. Each cycle is composed of maximum several tens of fundamental digital voltmeter (DVM) readings per isotope. Since the abundance of each isotope varies over analytical time, it is necessary to statistically treat the data to obtain most probable estimates. The readings on one mass from one cycle are commonly averaged to be treated as a single data point for regression. The y-intercept derived from the regression is assumed to represent an initial isotopic abundance at the time (t0) when the gas was introduced to the analytical volume. This procedure is repeated for each Ar isotope. About 0.2 % precision is often claimed for 40Ar and 39Ar measurements for properly irradiated, K-rich samples. The uncertainty of the calculated y-intercept varies depending on the distribution of the averaged DVM readings as well as the model equation used in regression. The “internal error” associated with the distribution of individual DVM readings in the group average are, however, commonly ignored in the regression procedure probably due to complex weighting processes. Including the internal error may significantly increase the uncertainties of 40Ar/39Ar ages especially for young samples because the analytical errors (from isotopic ratio measurements) are more dominant than the systematic errors (from decay constant, age of neutron flux monitor, etc). Alternative way to include the internal error is to regress all of the DVM readings with a single equation, then propagate the regression error into y-intercept calculation. In any case, it is necessary to propagate uncertainties derived from fundamental readings to properly estimate analytical errors in 40Ar/39Ar age

  1. Achievements in testing of the MGA and FRAM isotopic software codes under the DOE/NNSA-IRSN cooperation of gamma-ray isotopic measurement systems

    SciTech Connect

    Vo, Duc; Wang, Tzu - Fang; Funk, Pierre; Weber, Anne - Laure; Pepin, Nicolas; Karcher, Anna

    2009-01-01

    DOE/NNSA and IRSN collaborated on a study of gamma-ray instruments and analysis methods used to perform isotopic measurements of special nuclear materials. The two agencies agreed to collaborate on the project in response to inconsistencies that were found in the various versions of software and hardware used to determine the isotopic abundances of uranium and plutonium. IRSN used software developed internally to test the MGA and FRAM isotopic analysis codes for criteria used to stop data acquisition. The stop-criterion test revealed several unusual behaviors in both the MGA and FRAM software codes.

  2. 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.

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

    SciTech Connect

    Fahey, Albert J.; Perea, Daniel E.; Bartrand, Jonah AG; Arey, Bruce W.; Thevuthasan, Suntharampillai

    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 the 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.

  4. Measurement of the J = 0-1 rotational transitions of three isotopes of ArD(+)

    NASA Technical Reports Server (NTRS)

    Bowman, W. C.; Plummer, G. M.; Herbst, E.; De Lucia, F. C.

    1983-01-01

    The rotational transitions of all three isotopic species of ArD(+) in samples containing the Ar isotopes in their natural abundances have been measured by means of millimeter and submillimeter techniques that employ a magnetically enhanced abnormal glow discharge. All three transition frequency measurements were made from digitally averaged signals detected through a lock-in amplifier with a 10-msec time constant. The Ar-4OD(+) transition was easily visible in real time on an oscilloscope with SNR of about 15. It is noted that the observed transition of Ar-38D(+) is more than five orders of magnitude weaker than that due to HCO(+).

  5. {sup 39}Ar Detection at the 10{sup -16} Isotopic Abundance Level with Atom Trap Trace Analysis

    SciTech Connect

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

    2011-03-11

    Atom trap trace analysis, a laser-based atom counting method, has been applied to analyze atmospheric {sup 39}Ar (half-life=269 yr), a cosmogenic isotope with an isotopic abundance of 8x10{sup -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.

  6. Further carbon isotope measurements of LEW 88516

    NASA Technical Reports Server (NTRS)

    Wright, I. P.; Douglas, C.; Pillinger, C. T.

    1993-01-01

    Douglas et al. have previously analyzed the carbon content and isotopic composition of a crushed sample (sub-sample 13) of the shergottite, LEW 88516. The powder, which was from a relatively large portion of the meteorite in order to obtain a representative sample, was distributed amongst the scientific community. However, it is probable that the preparation procedure was not optimized for the purposes of carbon measurements. Indeed, it was found that LEW 88516,13 contained over 1200 ppm carbon, a concentration which is greater than that present in any other SNC meteorite. That a close relative, ALH A77005, contains only 141 ppm carbon seems to implicate the preparation procedure as being responsible for the apparently high carbon content of LEW 88516. However, it may also be the nature of the fine powder which has resulted in contamination. The observation of high carbon content in LEW 88516,13 highlights the extreme difficulty of trying to obtain representative samples of whole meteorites for this kind of investigation. Presented herein are some further measurements of LEW 88516 which should serve to clarify some of the issues raised by the previous investigation.

  7. MeV He3/He4 isotope abundances in solar energetic particle events: SOHO/COSTEP observations

    NASA Astrophysics Data System (ADS)

    Bothmer, V.:; Sierks, H.; Böhm, E.; Kunow, H.

    2001-08-01

    We present first results based on a systematic survey of 4-41 MeV/N 3He/4He isotope abundances with ratios >0.01 detected by the COmprehensive SupraThermal and Energetic Particle analyzer (COSTEP) onboard the SOHO (SOlar and Heliospheric Observatory) spacecraft. More than about 25% of the identified events showed 3He/4He ratios in the range 0.1-1. For events with sufficiently high detector count rates the atomic mass plots can be resolved up to a time resolution of about 1 hour. These events are most suitable for comparisons with in situ solar wind plasma and magnetic field measurements and SOHO's optical white-light and extreme ultraviolet (EUV) observations of the Sun. The correlations show an association with passages of shock associated coronal mass ejections (CMEs) in the solar wind that inhibit high He/H plasma overabundances. It is likely that the CMEs have been released in strong magnetic reconfiguration processes at the solar source sites. Here we present a brief overview of such an event detected on October 30, 2000. 1. Introduction The SOHO/COSTEP instrument measures solar energetic particles (SEPs) at MeV energies in the interplanetary medium. The solid state detectors are capable to detect 3 He/4 He-enrichments at these energies (Müller-Mellin et al., 1995). Usually, the 3 He/4 He-ratio in the solar wind is at the order of 10-4 , but occasionally ratios up to about values of ~1 or even above have been observed in SEP events (e.g., Mason et al., 1999). The origin of these isotope abundances has commonly been attributed to impulsive solar flares and wave-particle interaction mechanisms (Temerin and Roth, 1992). However, fully satisfying physical explanations are still lacking. Here we present first results of a systematic survey of the He-measurements taken by COSTEP since launch in 1995 until the end of the year 2000. 2. Data For this study we have analyzed SOHO/COSTEP measurements of 4.3-40.9 MeV/N helium particles as well as COSTEP data covering

  8. Measuring β-diversity with species abundance data.

    PubMed

    Barwell, Louise J; Isaac, Nick J B; Kunin, William E

    2015-07-01

    Baselga R turn , βBaselga B-C turn and βsim measured purely species turnover and were independent of nestedness. Among the other metrics, sensitivity to nestedness varied >4-fold. Our results indicate large amounts of redundancy among existing β-diversity metrics, whilst the estimation of unseen shared and unshared species is lacking and should be addressed in the design of new abundance-based metrics.

  9. Isotopic CO2 Instrumentation for UAV Measurements

    NASA Astrophysics Data System (ADS)

    Gomez, A.; Silver, J.

    2013-12-01

    Carbon dioxide is the largest component of anthroprogenic green house gas emissions. Knowing atmospheric 13CO2/12CO2 ratios precisely is important for understanding biogenic and anthroprogenic sources and sinks for carbon. Instrumentation mounted on UAV aircraft would enable important spatial isotopic CO2 information. However, current isotopic CO2 instrumentation have unfavorable attributes for UAV use, such as high power requirements, high cost, high weight, and large size. Here we present the early development of a compact isotopic CO2 instrument that is designed to nullify effects of pressure, temperature and moisture, and will ultimately be suitable for UAV deployment.

  10. Measurement of isotope shifts in Fe II

    NASA Astrophysics Data System (ADS)

    Ascoli, Marco; Kawall, David; Eyler, Edward; Demille, David

    2006-05-01

    We describe absorption spectra of singly ionized iron (Fe II) obtained with a compact ion source and a high-resolution UV laser. Using a Nd:YAG laser ablation source and buffer gas cooling with room-temperature argon, Fe II ions are produced in a cold plasma. Grating spectroscopy is used to determine conditions favorable parameters providing good cooling and ion yield. This novel technique allows us to study the Fe II transition a ^6D9->z^6D^o9 with Doppler widths about 3 GHz, by measuring the absorption of a frequency-tripled pulse-amplified cw Ti:Sapphire laser. The isotope shift of this transition is important to the analysis of astronomical data on the cosmological evolution of the fine-structure constant α [1]. We will discus the design of the ion source and laser system, and present preliminary results. This study was funded by the National Science Foundation. 12 pt [1] J.K Webb,M.T. Murphy, V.V. Flambaum, V.A. Dzuba, J.D. Barrow, C.W. Churchill, J.X. Prochaska, and A.M. Wolfe, Phys. Rev. Lett. 87, 091301 (2001).

  11. 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.

  12. Isotopic Resonance Hypothesis: Experimental Verification by Escherichia coli Growth Measurements

    NASA Astrophysics Data System (ADS)

    Xie, Xueshu; Zubarev, Roman A.

    2015-03-01

    Isotopic composition of reactants affects the rates of chemical and biochemical reactions. As a rule, enrichment of heavy stable isotopes leads to progressively slower reactions. But the recent isotopic resonance hypothesis suggests that the dependence of the reaction rate upon the enrichment degree is not monotonous. Instead, at some ``resonance'' isotopic compositions, the kinetics increases, while at ``off-resonance'' compositions the same reactions progress slower. To test the predictions of this hypothesis for the elements C, H, N and O, we designed a precise (standard error +/-0.05%) experiment that measures the parameters of bacterial growth in minimal media with varying isotopic composition. A number of predicted resonance conditions were tested, with significant enhancements in kinetics discovered at these conditions. The combined statistics extremely strongly supports the validity of the isotopic resonance phenomenon (p << 10-15). This phenomenon has numerous implications for the origin of life studies and astrobiology, and possible applications in agriculture, biotechnology, medicine, chemistry and other areas.

  13. Neutron Capture Measurements on Tl-isotopes at DANCE

    NASA Astrophysics Data System (ADS)

    Couture, A.; Bredeweg, T. A.; Esch, E.-I.; Jandel, M.; Haight, R. C.; O'Donnell, J. M.; Reifarth, R.; Rundberg, R. S.; Ullmann, J. L.; Vieira, D. J.; Wouters, J. M.

    2006-10-01

    The thallium isotopes play an important role in the s-process nucleosynthesis at the s-process endpoint. Furthermore, ^204Tl is one of few branch point isotopes in the endpoint region. The understanding of branch point isotopes provides modeling constraints on the temperatures during which the process takes place. The production of s-only ^204Pb is controlled entirely by ^204Tl. Measurements of the capture cross-sections of the stable Tl isotopes have recently been made using the DANCE 4-π array at LANSCE. This provides needed resonance information in the region as well as preparing the way for measurements of as yet unmeasured capture cross-section of the unstable ^204Tl. The neutron capture data for the stable isotopes as well as the plan for future measurements will be discussed.

  14. Carbon Isotopic Measurements of Amino Acids in Stardust-Returned Samples

    NASA Technical Reports Server (NTRS)

    Elsila, Jamie

    2009-01-01

    NASA's Stardust spacecraft returned to Earth samples from comet 81P/Wild 2 in January 2006. Preliminary examinations revealed the presence of a suite of organic compounds including several amines and amino acids, but the origin of these compounds could not be identified. Here, we present the carbon isotopic ratios of glycine and e-aminocaproic acid (EACA), the two most abundant amino acids, in Stardust-returned foil samples measured by gas chromatography-combustion-isotope ratio mass spectrometry coupled with quadrupole mass spectrometry (GC-CAMS/IRMS).

  15. Ground-based column abundance measurements of atmospheric hydroxyl

    NASA Astrophysics Data System (ADS)

    Burnett, Clyde R.

    1988-04-01

    The preliminary results of ground-based OH column abundance measurements from Truk, Federated States of Micronesia, are contained. These are the first OH column measurements from the tropics, and constitute a signficcant contribution to the OH data base. Comparisons of tropical OH behavior with the extensive mid-latitude observations serve as a critical test of the current understanding of the HO (sub x) photochemistry and its relationship to the other major chemical families. The quasi-biennial oscillation (QBO) in tropical stratospheric winds exerts a major influence on the Hadley cell vertical transport. Related QBOs in total O3 and in stratospheric H2O were identified, but QBO effects on other stratospheric species are still unknown. The solar tide in the tropics produces a diurnal surface pressure variation of 2 to 3 mb; its effect on OH photochemistry in the stratosphere may be significant.

  16. Ground-based column abundance measurements of atmospheric hydroxyl

    NASA Technical Reports Server (NTRS)

    Burnett, Clyde R.

    1988-01-01

    The preliminary results of ground-based OH column abundance measurements from Truk, Federated States of Micronesia, are contained. These are the first OH column measurements from the tropics, and constitute a signficcant contribution to the OH data base. Comparisons of tropical OH behavior with the extensive mid-latitude observations serve as a critical test of the current understanding of the HO (sub x) photochemistry and its relationship to the other major chemical families. The quasi-biennial oscillation (QBO) in tropical stratospheric winds exerts a major influence on the Hadley cell vertical transport. Related QBOs in total O3 and in stratospheric H2O were identified, but QBO effects on other stratospheric species are still unknown. The solar tide in the tropics produces a diurnal surface pressure variation of 2 to 3 mb; its effect on OH photochemistry in the stratosphere may be significant.

  17. On strontium isotopic anomalies and odd-A p-process abundances. [in solar system

    NASA Technical Reports Server (NTRS)

    Clayton, D. D.

    1978-01-01

    Several aspects of the nucleosynthesis of Sr isotopes are considered in an attempt to shed light on the problem of the Sr isotopic anomalies discovered in an inclusion of the Allende meteorite. Decomposition of the Sr isotopes into average r-, s-, and p-process nucleosynthetic classes is performed. It is suggested that the Allende inclusion most likely has an excess of s-process Sr and that the initial Sr-87/Sr-86 isotopic ratio is probably slightly more primitive than basaltic achondrites. The results also show that Sn-115 is mostly due to the r-process and that odd-A yields are very small. It is concluded that if the Sr anomaly in the inclusion is an average s enhancement, it argues somewhat in favor of a model of gas/dust fractionation of s and r isotopes during accumulation of the inclusion parent in the protosolar cloud.

  18. Measurements of CFC Isotope Changes in Firn, Stratospheric and Tropospheric Air

    NASA Astrophysics Data System (ADS)

    Allin, S.; Laube, J.; Witrant, E.; Kaiser, J.; McKenna, E.; Dennis, P.; Mulvaney, R.; Capron, E.; Martinerie, P.; Blunier, T.; Schwander, J.; Fraser, P. J.; Sturges, W. T.

    2014-12-01

    The degradation of chlorofluorocarbons (CFCs) releases chlorine, which is a major contributor to the destruction of stratospheric ozone. Recent studies of CFC-12 (CCl2F2) have reported strong chlorine and carbon isotope fractionations in stratospheric and tropospheric samples, respectively. The δ(37Cl) variations were attributed to isotope dependent sink reactions, similar to effects seen in nitrous oxide (N2O), whereas adjustments to manufacturing processes were used to explain the δ(13C) changes. Using air archives to measure chlorine and carbon isotope ratios in CFCs could help to identify and quantify their sources and sinks. We analyse the three most abundant CFCs and show that CFC-11 (CCl3F) and CFC-113 (CClF2CCl2F) exhibit significant chlorine isotope fractionation in the stratosphere, in common with CFC-12. We then use a 2-box model to estimate the expected tropospheric isotope signature of these gases, based on their emissions and transport history, as well as their measured stratospheric isotope fractionation constants (ɛapp). We also present long-term δ(37Cl) and δ(13C) trends of all three CFCs, determined from background tropospheric samples from the Cape Grim air archive (1978 - 2010) and firn air samples from the Arctic (NEEM, Greenland) and Antarctica (Fletcher Promontory). These measurements are compared to our model trends, leading to an evaluation of long-term chlorine and carbon isotope changes. This study also extends the novel approach to measuring trace gas isotope ratios in small air volumes, using a single-detector gas chromatography-mass spectrometry system.

  19. A large detector for cosmic ray abundance and energy measurements

    NASA Astrophysics Data System (ADS)

    Alsop, C.

    A large aperture, balloon borne cosmic ray detector was designed to measure the energy spectra of individual cosmic ray species with Z greater than 8 in the energy range 0.3GeV/N to 400GeV/N. The energy dependence of the abundance spectrum extending up to such high energies will provide valuable data for determining the nature of the origin and propagation of cosmic rays in the Galaxy. The properties of cosmic ray nuclei and the interpretation of the energy dependence of the abundance spectrum are discussed. The design and response of the BUGS IV cosmic ray detector are described. The measurement techniques used are gas scintillation, gas proportional scintillation and Cerenkov radiation from both gases and solids. The light collection properties of the detector and several experimental investigations of the light collection efficiency of the drift chamber region are described. The expected signals from the gas scintillation and gas Cerenkov emissions are predicted and the choice of a suitable scintillating gas mixture for minimizing the uncertainty in the charge and energy measurements is considered. The theoretical aspects of electron drift and diffusion in gases and several experimental investigations on the electron drift in the BUGS IV drift chamber are given. Also some preliminary results from a uniform field drift chamber are included which demonstrate the sensitivity of the electron drift velocity in inert gas mixtures to water vapor contamination. The expected overall performance of BUGS IV and the results of an experimental simulation of the parachute landing of the detector are given.

  20. A measurement of cosmic-ray beryllium isotopes from 200 to 1500 MeV per nucleon

    NASA Technical Reports Server (NTRS)

    Buffington, A.; Orth, C. D.; Mast, T. S.

    1978-01-01

    A balloon-borne superconducting magnetic spectrometer was used in the measurement of cosmic-ray isotopic abundances from lithium through oxygen in the energy range 200-1500 MeV per nucleon. Except for Be-7 all isotopic composition is essentially energy-independent. Be-10 is nearly absent, indicating a mean cosmic-ray age of 6(-3, +10) x 10 to the 6th years. Above about 500 MeV per nucleon, Be-7 drops dramatically in abundance relative to Be-9 and C. By 1500 MeV per nucleon, the relative abundance of Be-7 has become one-half of its lower-energy value. Since Be-7 is the only isotope measured which decays by electron capture, this result is interpreted as indicating that higher-energy Be-7 had an appreciable probability of not being stripped of all its electrons before entering interstellar space where electron pickup is negligible.

  1. Isotope shift measurements on the D1 line in francium isotopes at TRIUMF

    NASA Astrophysics Data System (ADS)

    Collister, R.; Tandecki, M.; Gwinner, G.; Behr, J. A.; Pearson, M. R.; Gomez, E.; Aubin, S.; Zhang, J.; Orozco, L. A.

    2013-05-01

    Francium is the heaviest alkali and has no stable isotopes. The longest-lived among them, with half-lives from seconds to a few minutes, are now available in the new Francium Trapping Facility at TRIUMF, Canada, for future weak interaction studies. We present isotope shift measurements on the 7S1 / 2 --> 7P1 / 2 (D 1) transition on three isotopes, 206, 207 and 213 in a magneto-optical trap. The shifts are measured using a c.w. Ti:sapphire laser locked to a stabilized cavity at the mid-point between two hyperfine transitions of the reference isotope 209Fr. Scanning tunable microwave sidebands locate transitions in the other isotopes. In combination with the D 2 isotope shifts, analysis can provide a separation of the field shift, due to a changing nuclear charge radius, and specific mass shift, due to changing electron correlations, in these isotopes. Work supported by NSERC and NRC from Canada, NSF and DOE from USA, CONYACT from Mexico.

  2. Oxygen isotopic abundances in calcium- aluminum-rich inclusions from ordinary chondrites: implications for nebular heterogeneity.

    PubMed

    McKeegan, K D; Leshin, L A; Russell, S S; MacPherson, G J

    1998-04-17

    The oxygen isotopic compositions of two calcium-aluminum-rich inclusions (CAIs) from the unequilibrated ordinary chondrite meteorites Quinyambie and Semarkona are enriched in 16O by an amount similar to that in CAIs from carbonaceous chondrites. This may indicate that most CAIs formed in a restricted region of the solar nebula and were then unevenly distributed throughout the various chondrite accretion regions. The Semarkona CAI is isotopically homogeneous and contains highly 16O-enriched melilite, supporting the hypothesis that all CAI minerals were originally 16O-rich, but that in most carbonaceous chondrite inclusions some minerals exchanged oxygen isotopes with an external reservoir following crystallization.

  3. Precision Measures of the Primordial Abundance of Deuterium

    NASA Astrophysics Data System (ADS)

    Cooke, Ryan J.; Pettini, Max; Jorgenson, Regina A.; Murphy, Michael T.; Steidel, Charles C.

    2014-01-01

    We report the discovery of deuterium absorption in the very metal-poor ([Fe/H] = -2.88) damped Lyα system at z abs = 3.06726 toward the QSO SDSS J1358+6522. On the basis of 13 resolved D I absorption lines and the damping wings of the H I Lyα transition, we have obtained a new, precise measure of the primordial abundance of deuterium. Furthermore, to bolster the present statistics of precision D/H measures, we have reanalyzed all of the known deuterium absorption-line systems that satisfy a set of strict criteria. We have adopted a blind analysis strategy (to remove human bias) and developed a software package that is specifically designed for precision D/H abundance measurements. For this reanalyzed sample of systems, we obtain a weighted mean of (D/H)p = (2.53 ± 0.04) × 10-5, corresponding to a universal baryon density 100 Ωb, 0 h 2 = 2.202 ± 0.046 for the standard model of big bang nucleosynthesis (BBN). By combining our measure of (D/H)p with observations of the cosmic microwave background (CMB), we derive the effective number of light fermion species, N eff = 3.28 ± 0.28. We therefore rule out the existence of an additional (sterile) neutrino (i.e., N eff = 4.046) at 99.3% confidence (2.7σ), provided that the values of N eff and of the baryon-to-photon ratio (η10) did not change between BBN and recombination. We also place a strong bound on the neutrino degeneracy parameter, independent of the 4He primordial mass fraction, Y P: ξD = +0.05 ± 0.13 based only on the CMB+(D/H)p observations. Combining this value of ξD with the current best literature measure of Y P, we find a 2σ upper bound on the neutrino degeneracy parameter, |ξ| <= +0.062. Based on observations collected at the European Organisation for Astronomical Research in the Southern Hemisphere, Chile (VLT program IDs: 68.B-0115(A), 70.A-0425(C), 078.A-0185(A), 085.A-0109(A)), and at the W. M. Keck Observatory, which is operated as a scientific partnership among the California Institute of

  4. Precision measures of the primordial abundance of deuterium

    SciTech Connect

    Cooke, Ryan J.; Jorgenson, Regina A.; Murphy, Michael T.; Steidel, Charles C.

    2014-01-20

    We report the discovery of deuterium absorption in the very metal-poor ([Fe/H] = –2.88) damped Lyα system at z {sub abs} = 3.06726 toward the QSO SDSS J1358+6522. On the basis of 13 resolved D I absorption lines and the damping wings of the H I Lyα transition, we have obtained a new, precise measure of the primordial abundance of deuterium. Furthermore, to bolster the present statistics of precision D/H measures, we have reanalyzed all of the known deuterium absorption-line systems that satisfy a set of strict criteria. We have adopted a blind analysis strategy (to remove human bias) and developed a software package that is specifically designed for precision D/H abundance measurements. For this reanalyzed sample of systems, we obtain a weighted mean of (D/H){sub p} = (2.53 ± 0.04) × 10{sup –5}, corresponding to a universal baryon density 100 Ω{sub b,} {sub 0} h {sup 2} = 2.202 ± 0.046 for the standard model of big bang nucleosynthesis (BBN). By combining our measure of (D/H){sub p} with observations of the cosmic microwave background (CMB), we derive the effective number of light fermion species, N {sub eff} = 3.28 ± 0.28. We therefore rule out the existence of an additional (sterile) neutrino (i.e., N {sub eff} = 4.046) at 99.3% confidence (2.7σ), provided that the values of N {sub eff} and of the baryon-to-photon ratio (η{sub 10}) did not change between BBN and recombination. We also place a strong bound on the neutrino degeneracy parameter, independent of the {sup 4}He primordial mass fraction, Y {sub P}: ξ{sub D} = +0.05 ± 0.13 based only on the CMB+(D/H){sub p} observations. Combining this value of ξ{sub D} with the current best literature measure of Y {sub P}, we find a 2σ upper bound on the neutrino degeneracy parameter, |ξ| ≤ +0.062.

  5. Cumulative fission yields of short-lived isotopes under natural-abundance-boron-carbide-moderated neutron spectrum

    SciTech Connect

    Finn, Erin C.; Metz, Lori A.; Greenwood, Lawrence R.; Pierson, Bruce; Wittman, Richard S.; Friese, Judah I.; Kephart, Rosara F.

    2015-04-09

    The availability of gamma spectroscopy data on samples containing mixed fission products at short times after irradiation is limited. Due to this limitation, data interpretation methods for gamma spectra of mixed fission product samples, where the individual fission products have not been chemically isolated from interferences, are not well-developed. The limitation is particularly pronounced for fast pooled neutron spectra because of the lack of available fast reactors in the United States. Samples containing the actinide isotopes 233, 235, 238U, 237Np, and 239Pu individually were subjected to a 2$ pulse in the Washington State University 1 MW TRIGA reactor. To achieve a fission-energy neutron spectrum, the spectrum was tailored using a natural abundance boron carbide capsule to absorb neutrons in the thermal and epithermal region of the spectrum. Our tailored neutron spectrum is unique to the WSU reactor facility, consisting of a soft fission spectrum that contains some measurable flux in the resonance region. This results in a neutron spectrum at greater than 0.1 keV with an average energy of 70 keV, similar to fast reactor spectra and approaching that of 235U fission. Unique fission product gamma spectra were collected from 4 minutes to 1 week after fission using single-crystal high purity germanium detectors. Cumulative fission product yields measured in the current work generally agree with published fast pooled fission product yield values from ENDF/B-VII, though a bias was noted for 239Pu. The present work contributes to the compilation of energy-resolved fission product yield nuclear data for nuclear forensic purposes.

  6. Temporal variation in mycorrhizal diversity and carbon and nitrogen stable isotope abundance in the wintergreen meadow orchid Anacamptis morio.

    PubMed

    Ercole, Enrico; Adamo, Martino; Rodda, Michele; Gebauer, Gerhard; Girlanda, Mariangela; Perotto, Silvia

    2015-02-01

    Many adult orchids, especially photoautotrophic species, associate with a diverse range of mycorrhizal fungi, but little is known about the temporal changes that might occur in the diversity and functioning of orchid mycorrhiza during vegetative and reproductive plant growth. Temporal variations in the spectrum of mycorrhizal fungi and in stable isotope natural abundance were investigated in adult plants of Anacamptis morio, a wintergreen meadow orchid. Anacamptis morio associated with mycorrhizal fungi belonging to Tulasnella, Ceratobasidium and a clade of Pezizaceae (Ascomycetes). When a complete growing season was investigated, multivariate analyses indicated significant differences in the mycorrhizal fungal community. Among fungi identified from manually isolated pelotons, Tulasnella was more common in autumn and winter, the pezizacean clade was very frequent in spring, and Ceratobasidium was more frequent in summer. By contrast, relatively small variations were found in carbon (C) and nitrogen (N) stable isotope natural abundance, A. morio samples showing similar (15)N enrichment and (13)C depletion at the different sampling times. These observations suggest that, irrespective of differences in the seasonal environmental conditions, the plant phenological stages and the associated fungi, the isotopic content in mycorrhizal A. morio remains fairly constant over time.

  7. Measuring Isotope Ratios Across the Solar System

    NASA Technical Reports Server (NTRS)

    Webster, Chris R.; Mahaffy, Paul R.

    2012-01-01

    Stable isotope ratios in C, H, N, O and S are powerful indicators of a wide variety of planetary geophysical processes that can identify origin, transport, temperature history, radiation exposure, atmospheric escape, environmental habitability and biology [1]. For the Allan Hills 84001 meteorite, for example, the (sup 1)(sup 3)C/(sup 1)(sup 2)C ratio identifies it as a Mars (SNC) meteorite; the ??K/??Ar ratio tells us the last time the rock cooled to solid, namely 4 Gya; isotope ratios in (sup 3)He, (sup 2)(sup 1)Ne and (sup 3)?Ar show it was in space (cosmic ray exposure) for 10-20 million years; (sup 1)?C dating that it sat in Antarctica for 13,000 years before discovery; and clumped isotope analysis of (sup 1)?O(sup 1)(sup 3)C(sup 1)?O in its carbonate that it was formed at 18+/-4 ?C in a near-surface aqueous environment [2]. Solar System Formation

  8. Natural-abundance stable carbon isotopes of small-subunit ribosomal RNA (SSU rRNA) from Guaymas Basin (Mexico)

    NASA Astrophysics Data System (ADS)

    MacGregor, B. J.; Mendlovitz, H.; Albert, D.; Teske, A. P.

    2012-12-01

    Small-subunit ribosomal RNA (SSU rRNA) is a phylogenetically informative molecule found in all species. Because it is poorly preserved in most environments, it is a useful marker for active microbial populations. We are using the natural-abundance stable carbon isotopic composition of specific microbial groups to help identify the carbon substrates contributing to microbial biomass in a variety of marine environments. At Guaymas Basin, hydrothermal fluids interact with abundant sedimentary organic carbon to produce natural gas and petroleum. Where this reaches the sediment surface, it can support dense patches of seafloor life, including Beggiatoa mats. We report here on the stable carbon isotopic composition of SSU rRNA from a Beggiatoa mat transect, a cold background site, a warm site with high oil concentration, and a second Beggiatoa mat. The central part of the transect mat overlay the steepest temperature gradient, and was visually dominated by orange Beggiatoa. This was fringed by white Beggiatoa mat and bare, but still warm, sediment. Methane concentrations were saturating beneath the orange and white mats and at the oily site, lower beneath bare sediment, and below detection at the background site. Our initial hypotheses were that rRNA isotopic composition would be strongly influenced by methane supply, and that archaeal rRNA might be lighter than bacterial due to contributions from methanogens and anaerobic methane oxidizers. We used biotin-labeled oligonucleotides to capture Bacterial and Archaeal SSU rRNA for isotopic determination. Background-site rRNA was isotopically heaviest, and bacterial RNA from below 2 cm at the oily site was lightest, consistent with control by methane. Within the transect mat, however, the pattern was more complicated; at some sediment depths, rRNA from the mat periphery was isotopically lightest. Part of this may be due to the spatially and temporally variable paths followed by hydrothermal fluid, which can include horizontal

  9. An automated method for 'clumped-isotope' measurements on small carbonate samples.

    PubMed

    Schmid, Thomas W; Bernasconi, Stefano M

    2010-07-30

    Clumped-isotope geochemistry deals with the state of ordering of rare isotopes in molecules, in particular with their tendency to form bonds with other rare isotopes rather than with the most abundant ones. Among its possible applications, carbonate clumped-isotope thermometry is the one that has gained most attention because of the wide potential of applications in many disciplines of earth sciences. Clumped-isotope thermometry allows reconstructing the temperature of formation of carbonate minerals without knowing the isotopic composition of the water from which they were formed. This feature enables new approaches in paleothermometry. The currently published method is, however, limited by sample weight requirements of 10-15 mg and because measurements are performed manually. In this paper we present a new method using an automated sample preparation device coupled to an isotope ratio mass spectrometer. The method is based on the repeated analysis (n = 6-8) of 200 microg aliquots of sample material and completely automated measurements. In addition, we propose to use precisely calibrated carbonates spanning a wide range in Delta(47) instead of heated gases to correct for isotope effects caused by the source of the mass spectrometer, following the principle of equal treatment of the samples and standards. We present data for international standards (NBS 19 and LSVEC) and different carbonates formed at temperatures exceeding 600 degrees C to show that precisions in the range of 10 to 15 ppm (1 SE) can be reached for repeated analyses of a single sample. Finally, we discuss and validate the correction procedure based on high-temperature carbonates instead of heated gases.

  10. A stable isotope dilution method for measuring bioavailability of organic contaminants

    PubMed Central

    Delgado-Moreno, Laura; Gan, Jay

    2014-01-01

    Methods for determining bioavailability of organic contaminants suffer various operational limitations. We explored the use of stable isotope labeled references in developing an isotope dilution method (IDM) to measure the exchangeable pool (E) of pyrene and bifenthrin as an approximation of their bioavailability in sediments. The exchange of deuterated bifenthrin or pyrene with its native counterpart was completed within 48 h. The derived E was 38–82% for pyrene and 28–59% for bifenthrin. Regression between E and the sum of rapid and slow desorption fractions obtained from sequential desorption showed a slope close to 1.0. The ability of IDM to predict bioavailability was further shown from a strong relationship (r2 > 0.93) between E and bioaccumulation into Chironomus tentans. Given the abundance of stable isotope labeled references and their relatively easy analysis, the IDM has the potential to become a readily adoptable tool for estimating organic contaminants bioaccessibility in various matrices. PMID:23434573

  11. Stable platinum isotope measurements in presolar nanodiamonds by TEAMS

    PubMed Central

    Wallner, A.; Melber, K.; Merchel, S.; Ott, U.; Forstner, O.; Golser, R.; Kutschera, W.; Priller, A.; Steier, P.

    2013-01-01

    Nanodiamonds are stardust grains commonly found in primitive meteorites. They survived the formation of the solar system and kept their own individuality. Measurements of trace-element isotopic signatures in these grains will help understanding heavy element nucleosynthesis in massive stars and dust formation from their ejecta. We have continued previous attempts to search for stable Pt isotope anomalies in nanodiamonds via trace element accelerator mass spectrometry (TEAMS). The installation of a new injector beam line at the VERA facility allowed studying low traces of stable elements in different materials. Moreover, recent experiments showed that VERA provides the required measurement precision together with a low Pt machine background. Here, we observed for the first time an indication for enhancements of 198Pt/195Pt isotope ratios in two diamond residues prepared by different chemical separation techniques from the Allende meteorite. Variations in other isotopic ratios were within analytical uncertainty, and no anomaly was identified in a third diamond fraction. PMID:23565017

  12. Stable platinum isotope measurements in presolar nanodiamonds by TEAMS

    NASA Astrophysics Data System (ADS)

    Wallner, A.; Melber, K.; Merchel, S.; Ott, U.; Forstner, O.; Golser, R.; Kutschera, W.; Priller, A.; Steier, P.

    2013-01-01

    Nanodiamonds are stardust grains commonly found in primitive meteorites. They survived the formation of the solar system and kept their own individuality. Measurements of trace-element isotopic signatures in these grains will help understanding heavy element nucleosynthesis in massive stars and dust formation from their ejecta. We have continued previous attempts to search for stable Pt isotope anomalies in nanodiamonds via trace element accelerator mass spectrometry (TEAMS). The installation of a new injector beam line at the VERA facility allowed studying low traces of stable elements in different materials. Moreover, recent experiments showed that VERA provides the required measurement precision together with a low Pt machine background. Here, we observed for the first time an indication for enhancements of 198Pt/195Pt isotope ratios in two diamond residues prepared by different chemical separation techniques from the Allende meteorite. Variations in other isotopic ratios were within analytical uncertainty, and no anomaly was identified in a third diamond fraction.

  13. Abundances and isotopic compositions of rhenium and osmium in pyrite samples from the Huaibei coalfield, Anhui, China

    USGS Publications Warehouse

    Liu, Gaisheng; Chou, C.-L.; Peng, Z.; Yang, G.

    2008-01-01

    Two pyrite samples from the Shihezi Formation (Lower Permian), Huaibei coalfield, Anhui, China, have been analyzed for abundances and isotopic compositions of rhenium and osmium using negative thermal ion mass spectrometry. The Re-Os ages of the pyrites are 64.4 and 226 Ma, which are younger than the formation age of the coal seam. The pyrite samples may consist of pyrite formed at various stages during the history of coal formation. The ??Osvalues of the two pyrite samples are +17 and +18, respectively. Such high ??Osvalues are reported for the first time for recycles crustal materials from a sedimentary basin. ?? Springer-Verlag 2007.

  14. MG Isotopic Measurement of FIB-Isolated Presolar Silicate Grains

    NASA Technical Reports Server (NTRS)

    Messenger, Scott R.; Nguyen, A.; Ito, M.; Rahman, Z.

    2010-01-01

    The majority of presolar oxide and silicate grains are ascribed to origins in low-mass red giant and asymptotic giant branch (AGB) stars based on their O isotopic ratios. However, a minor population of these grains (< 10%) has O isotopic ratios incompatible with these sources. Two principle alternative sources are higher-than-solar metallicity (Z) stars or, more likely, supernovae (SN) [1-3]. These rare (Group 4) grains [3] are characterized by enrichments in O-18, and typically also enrichments in O-17. An even rarer subset of grains with extremely large enrichments in O-17 and smaller depletions in O-18 were suggested to come from binary star systems [2]. To establish the origins of these isotopically unusual grains, it is necessary to examine isotopic systems in addition to O. Presolar silicates offer several elements diagnostic of their stellar sources and nuclear processes, including O, Si, Mg, Fe and Ca. However, the database for minor element isotopic compositions in silicates is seriously lacking. To date only two silicate grains have been analyzed for Mg [4] or Fe [5]. One major complicating factor is their small size (average 230 nm), which greatly limits the number of measurements that can be performed on any one grain and makes it more difficult to obtain statistically relevant data. This problem is compounded because the grains are identified among isotopically solar silicates, which contribute a diluting signal in isotopic measurements [1]. Thus, relatively small isotopic anomalies are missed due to this dilution effect. By applying focused ion beam (FIB) milling, we obtain undiluted Mg isotopic ratios of isolated rare presolar silicate grains to investigate their sources.

  15. Silver isotope variations in chondrites: Volatile depletion and the initial 107Pd abundance of the solar system

    NASA Astrophysics Data System (ADS)

    Schönbächler, M.; Carlson, R. W.; Horan, M. F.; Mock, T. D.; Hauri, E. H.

    2008-11-01

    The extinct radionuclide 107Pd decays to 107Ag (half-life of 6.5 Ma) and is an early solar system chronometer with outstanding potential to study volatile depletion in the early solar system. Here, a comprehensive Ag isotope study of carbonaceous and ordinary chondrites is presented. Carbonaceous chondrites show limited variations ( ɛ107Ag = -2.1 to +0.8) in Ag isotopic composition that correlate with the Pd/Ag ratios. Assuming a strictly radiogenic origin of these variations, a new initial 107Pd/ 108Pd of 5.9 (±2.2) × 10 -5 for the solar system can be deduced. Comparing the Pd-Ag and Mn-Cr data for carbonaceous chondrites suggests that Mn-Cr and Pd-Ag fractionation took place close to the time of calcium-aluminium-rich inclusion (CAI) and chondrule formation ˜4568 Ma ago. Using the new value for the initial 107Pd abundance, the revised ages for the iron-rich meteorites Gibeon (IVA, 8.5 +3.2/-4.6 Ma), Grant (IIIAB, 13.0 +3.5/-4.9 Ma) and Canyon Diablo (IA, 19.5 +24.1/-10.4 Ma) are consistent with cooling rates and the closure temperature of the Pd-Ag system. In contrast to carbonaceous chondrites, ordinary chondrites show large stable isotope fractionation of order of 1 permil for 107Ag/ 109Ag. This indicates that different mechanisms of volatile depletion were active in carbonaceous and ordinary chondrites. Nebular processes and accretion, as experienced by carbonaceous chondrites, did not led to significant Ag isotope fractionation, while the significant Ag isotope variations in ordinary chondrites are most likely inflicted by open system parent body metamorphism.

  16. Production of highly-enriched 134Ba for a reference material for isotope dilution mass spectrometry measurements

    DOE PAGES

    Horkley, J. J.; Carney, K. P.; Gantz, E. M.; ...

    2015-03-17

    Isotope dilution mass spectrometry (IDMS) is an analytical technique capable of providing accurate and precise quantitation of trace isotope abundance and assay providing measurement uncertainties below 1 %. To achieve these low uncertainties, the IDMS method ideally utilizes chemically pure “spike” solutions that consist of a single highly enriched isotope that is well-characterized relating to the abundance of companion isotopes and concentration in solution. To address a current demand for accurate 137Cs/137Ba ratio measurements for “age” determination of radioactive 137Cs sources, Idaho National Laboratory (INL) is producing enriched 134Ba isotopes that are tobe used for IDMS spikes to accurately determinemore » 137Ba accumulation from the decay of 137Cs. The final objective of this work it to provide a homogenous set of reference materials that the National Institute of Standards and Technology can certify as standard reference materials used for IDMS. The process that was developed at INL for the separation and isolation of Ba isotopes, chemical purification of the isotopes in solution, and the encapsulation of the materials will be described.« less

  17. Production of highly-enriched 134Ba for a reference material for isotope dilution mass spectrometry measurements

    SciTech Connect

    J.J. Horkley; K.P E.M. Gantz; J.E. Davis; R.R. Lewis; J.P. Crow; C.A. Poole; T.S. Grimes; J.J. Giglio

    2015-03-01

    t Isotope dilution mass spectrometry (IDMS) is an analytical technique capable of providing accurate and precise quantitation of trace isotope abundance and assay providing measurement uncertainties below 1 %. To achieve these low uncertainties, the IDMS method ideally utilizes chemically pure ‘‘spike’’ solutions that consist of a single highly enriched isotope that is well-characterized relating to the abundance of companion isotopes and concentration in solution. To address a current demand for accurate 137Cs/137Ba ratio measurements for ‘‘age’’ determination of radioactive 137Cs sources, Idaho National Laboratory (INL) is producing enriched 134Ba isotopes that are tobe used for IDMS spikes to accurately determine 137Ba accumulation from the decay of 137Cs. The final objective of this work it to provide a homogenous set of reference materials that the National Institute of Standards and Technology can certify as standard reference materials used for IDMS. The process that was developed at INL for the separation and isolation of Ba isotopes, chemical purification of the isotopes in solution,

  18. Production of highly-enriched 134Ba for a reference material for isotope dilution mass spectrometry measurements

    SciTech Connect

    Horkley, J. J.; Carney, K. P.; Gantz, E. M.; Davies, J. E.; Lewis, R. R.; Crow, J. P.; Poole, C. A.; Grimes, T. S.; Giglio, J. J.

    2015-03-17

    Isotope dilution mass spectrometry (IDMS) is an analytical technique capable of providing accurate and precise quantitation of trace isotope abundance and assay providing measurement uncertainties below 1 %. To achieve these low uncertainties, the IDMS method ideally utilizes chemically pure “spike” solutions that consist of a single highly enriched isotope that is well-characterized relating to the abundance of companion isotopes and concentration in solution. To address a current demand for accurate 137Cs/137Ba ratio measurements for “age” determination of radioactive 137Cs sources, Idaho National Laboratory (INL) is producing enriched 134Ba isotopes that are tobe used for IDMS spikes to accurately determine 137Ba accumulation from the decay of 137Cs. The final objective of this work it to provide a homogenous set of reference materials that the National Institute of Standards and Technology can certify as standard reference materials used for IDMS. The process that was developed at INL for the separation and isolation of Ba isotopes, chemical purification of the isotopes in solution, and the encapsulation of the materials will be described.

  19. ISOTOPIC RATIOS IN TITAN's METHANE: MEASUREMENTS AND MODELING

    SciTech Connect

    Nixon, C. A.; Achterberg, R. K.; Temelso, B.; Vinatier, S.; Bezard, B.; Coustenis, A.; Teanby, N. A.; Mandt, K. E.; Sherrill, C. D.; Irwin, P. G. J.; Jennings, D. E.; Romani, P. N.; Flasar, F. M.

    2012-04-20

    The existence of methane in Titan's atmosphere ({approx}6% level at the surface) presents a unique enigma, as photochemical models predict that the current inventory will be entirely depleted by photochemistry in a timescale of {approx}20 Myr. In this paper, we examine the clues available from isotopic ratios ({sup 12}C/{sup 13}C and D/H) in Titan's methane as to the past atmosphere history of this species. We first analyze recent infrared spectra of CH{sub 4} collected by the Cassini Composite Infrared Spectrometer, measuring simultaneously for the first time the abundances of all three detected minor isotopologues: {sup 13}CH{sub 4}, {sup 12}CH{sub 3}D, and {sup 13}CH{sub 3}D. From these we compute estimates of {sup 12}C/{sup 13}C = 86.5 {+-} 8.2 and D/H = (1.59 {+-} 0.33) Multiplication-Sign 10{sup -4}, in agreement with recent results from the Huygens GCMS and Cassini INMS instruments. We also use the transition state theory to estimate the fractionation that occurs in carbon and hydrogen during a critical reaction that plays a key role in the chemical depletion of Titan's methane: CH{sub 4} + C{sub 2}H {yields} CH{sub 3} + C{sub 2}H{sub 2}. Using these new measurements and predictions we proceed to model the time evolution of {sup 12}C/{sup 13}C and D/H in Titan's methane under several prototypical replenishment scenarios. In our Model 1 (no resupply of CH{sub 4}), we find that the present-day {sup 12}C/{sup 13}C implies that the CH{sub 4} entered the atmosphere 60-1600 Myr ago if methane is depleted by chemistry and photolysis alone, but much more recently-most likely less than 10 Myr ago-if hydrodynamic escape is also occurring. On the other hand, if methane has been continuously supplied at the replenishment rate then the isotopic ratios provide no constraints, and likewise for the case where atmospheric methane is increasing. We conclude by discussing how these findings may be combined with other evidence to constrain the overall history of the atmospheric

  20. Isotopic Ratios in Titan's Methane: Measurements and Modeling

    NASA Technical Reports Server (NTRS)

    Nixon, C. A.; Temelso, B.; Vinatier, S.; Teanby, N. A.; Bezard, B.; Achterberg, R. K.; Mandt, K. E.; Sherrill, C. D.; Irwin, P. G.; Jennings, D. E.; Romani, P. N.; Coustenis, A.; Flasar, F. M.

    2012-01-01

    The existence of methane in Titan's atmosphere (approx. 6% level at the surface) presents a unique enigma, as photochemical models predict that the current inventory will be entirely depleted by photochemistry in a timescale of approx 20 Myr. In this paper, we examine the clues available from isotopic ratios (C-12/C-13 and D/H) in Titan's methane as to the past atmosphere history of this species. We first analyze recent infrared spectra of CH4 collected by the Cassini Composite Infrared Spectrometer, measuring simultaneously for the first time the abundances of all three detected minor isotopologues: (13)CH4, (12)CH3D, and (13)CH3D. From these we compute estimates of C-12/C-13 = 86.5 +/- 8.2 and D/H = (1.59 +/- 0.33) x 10(exp -4) , in agreement with recent results from the Huygens GCMS and Cassini INMS instruments. We also use the transition state theory to estimate the fractionation that occurs in carbon and hydrogen during a critical reaction that plays a key role in the chemical depletion of Titan's methane: CH4 + C2H yields CH3 + C2H2. Using these new measurements and predictions we proceed to model the time evolution of C-12/C-13 and D/H in Titan's methane under several prototypical replenishment scenarios. In our Model 1 (no resupply of CH4), we find that the present-day C-12/C-13 implies that the CH4 entered the atmosphere 60-1600 Myr ago if methane is depleted by chemistry and photolysis alone, but much more recently-most likely less than 10 Myr ago-if hydrodynamic escape is also occurring. On the other hand, if methane has been continuously supplied at the replenishment rate then the isotopic ratios provide no constraints, and likewise for the case where atmospheric methane is increasing, We conclude by discussing how these findings may be combined with other evidence to constrain the overall history of the atmospheric methane.

  1. Non-Gaussian error distribution of 7Li abundance measurements

    NASA Astrophysics Data System (ADS)

    Crandall, Sara; Houston, Stephen; Ratra, Bharat

    2015-07-01

    We construct the error distribution of 7Li abundance measurements for 66 observations (with error bars) used by Spite et al. (2012) that give A(Li) = 2.21 ± 0.065 (median and 1σ symmetrized error). This error distribution is somewhat non-Gaussian, with larger probability in the tails than is predicted by a Gaussian distribution. The 95.4% confidence limits are 3.0σ in terms of the quoted errors. We fit the data to four commonly used distributions: Gaussian, Cauchy, Student’s t and double exponential with the center of the distribution found with both weighted mean and median statistics. It is reasonably well described by a widened n = 8 Student’s t distribution. Assuming Gaussianity, the observed A(Li) is 6.5σ away from that expected from standard Big Bang Nucleosynthesis (BBN) given the Planck observations. Accounting for the non-Gaussianity of the observed A(Li) error distribution reduces the discrepancy to 4.9σ, which is still significant.

  2. Use of Isotope Abundance of 15NO3-N in a Nitrate Rich Stream Below a Wastewater Treatment Plant to Evaluate Denitrification

    NASA Astrophysics Data System (ADS)

    Lofton, D.; Hershey, A. E.

    2005-05-01

    Using natural isotope abundances of nitrate-nitrogen, in conjunction with nitrate concentrations along a stream transect, can provide information about nitrate input versus downstream export and losses due to denitrification. Given that denitrifying microbes prefer the lighter isotope, isotopic fractionation should occur in nitrate rich streams resulting in enrichment of 15NO3-N if denitrification is an important process resulting in an inverse relationship between nitrate and δ 15NO3-N. Conversely, if the relationship between 15NO3-N and δ 15N is not inversely proportional, denitrification is likely of minor importance in the reach. Variable nonlinear patterns could be indicative of 15NO3-N rich input from groundwater, tributaries or concentrations in excess of microbial demand leading to massive downstream export. We measured stream 15NO3-N concentrations in an urban stream receiving high nitrogen inputs from a wastewater treatment plant. Although observed NO3-N concentrations varied from 3-6 mg L-1 in the stream reach, the relationship between ln NO3 and δ 15NO3-N was very weak, suggesting limited importance of denitrification.

  3. Measurement of stable carbon isotope ratios of non-methane hydrocarbons and halocarbons

    NASA Astrophysics Data System (ADS)

    Zuiderweg, A. T.

    2012-09-01

    Within the realm of volatile organic compounds, hydrocarbons and halocarbons form a sizable proportion of carbon input to the atmosphere. Within these compound categories, the light non-methane hydrocarbons (NMHC, two to seven carbon atoms) and monocarbon halocarbons have a special place as these have strong, if not exclusive, anthropogenic (human-caused) sources. With common atmospheric molar mixing ratios in the parts-per-trillion (10-12 mole/mole) to parts-per-billion (10-9 mole/mole) range, these trace gases, though decidedly minor constituants of the atmosphere, have diverse consequences due to their atmospheric presence and their removal processes. Effects range from causing ground level air pollution and resulting hazards to health, to contributing to anthropogenic climate change and the destruction of the ozone layer in the stratosphere, among many others. The existance of stable isotopes (otherwise identical atoms with varying amounts of neutrons that do not spontaneously disintegrate) in several elements relevant to atmospheric chemistry and physics is a boon to research. Their presence in molecules is detectable by mass and cause small intra- and intermolecular property changes. These changes range from the physical (e.g. boiling point variation) to the chemical (reaction rate variation) and can influence external interactions as well. The measurement of the ratio of a minor stable isotope of an element to the major one (the stable isotope ratio) can be used to establish source fingerprints, trace the interaction dynamics, and refine the understanding of the relative contribution of sources and sinks to the atmosphere as a whole. The stable minor stable isotope of carbon, 13C, has a natural abundance of approximately 1.1 %. It has a sufficient fractional mass difference from its major isotope as to cause significant effects, making it ideal for measuring the ratios and properties of hydro- and halocarbons. In order to enable a better understanding of the

  4. Guide to plutonium isotopic measurements using gamma-ray spectrometry

    SciTech Connect

    Lemming, J.F.; Rakel, D.A.

    1982-08-26

    Purpose of this guide is to assist those responsible for plutonium isotopic measurements in the application of gamma-ray spectrometry. Objectives are to promote an understanding of the measurement process, including its limitations and applicability, by reviewing the general features of a plutonium spectrum and identifying the quantities which must be extracted from the data; to introduce state-of-the-art analysis techniques by reviewing four isotopic analysis packages and identifying their differences; to establish the basis for measurement control and assurance by discussing means of authenticating the performance of a measurement system; and to prepare for some specific problems encountered in plutonium isotopic analyses by providing solutions from the practical experiences of several laboratories. 29 references, 12 figures, 17 tables.

  5. Tracing the source of cooking oils with an integrated approach of using stable carbon isotope and fatty acid abundance.

    PubMed

    Liu, Weiguo; Yang, Hong; Wang, Zheng; Liu, Jinzhao

    2012-08-15

    We report a new approach to identify swill-cooked oils that are recycled from tainted food and livestock waste from commercial vegetable and animal oils by means of carbon isotope values and relative abundance of fatty acids. We test this method using 40 cooking oil samples of different types with known sources. We found significant differences in both total organic carbon isotope as well as compound-specific isotope values and fatty acid C(14)/C(18) ratios between commercial vegetable oils refined from C(3) plants (from -35.7 to -27.0‰ and from 0 to 0.15) and animal oils (from -28.3 to -14.3‰ and from 0.1 to 0.6). Tested swill-cooked oils, which were generally refined by mixing with animal waste illegally, fall into a narrow δ(13)C/fatty acid ratio distribution: from -25.9 to -24.1‰ and from 0.1 to 0.2. Our data demonstrate that the index of a cross-plotting between fatty acid δ(13)C values and C(14)/C(18) ratios can be used to distinguish clean commercial cooking oils from illegal swill-cooked oils.

  6. Development of Novel Instrumentation to Measure All Nitrous Oxide Mono-Substituted Rare Isotopic Species

    NASA Astrophysics Data System (ADS)

    Du, X.; Leen, J. B.; Gupta, M.; Baer, D. S.

    2015-12-01

    Analysis of isotopic ratios is of great importance to study the sources and sinks of nitrous oxide (N2O) in atmosphere. N2O has four mono-substituted rare isotopic species - 14N15N16O, 15N14N16O, 14N218O, and 14N217O. Here we report on the development of novel instrumentation which is capable of measuring all four N2O isotopic species and therefore enables a complete characterization of abundance variations of these species. This instrument, which employs cavity enhanced absorption technology and a mid-infrared laser, has been developed for simultaneous measurements of all four isotopic species in either a continuous flow mode or a batch mode. A precision of better than 1 per mil for 14N217O has been achieved with samples of 10 ppm N2O in 300 seconds of measurement time. In addition, a precision of better than 1 per mil for 14N15N16O and 15N14N16O and 2 per mil for 14N218O has been achieved with samples of 300 ppb N2O or higher in 300 seconds of measurement time.

  7. Defining uncertainty and error in planktic foraminiferal oxygen isotope measurements

    NASA Astrophysics Data System (ADS)

    Fraass, A. J.; Lowery, C. M.

    2017-02-01

    Foraminifera are the backbone of paleoceanography. Planktic foraminifera are one of the leading tools for reconstructing water column structure. However, there are unconstrained variables when dealing with uncertainty in the reproducibility of oxygen isotope measurements. This study presents the first results from a simple model of foraminiferal calcification (Foraminiferal Isotope Reproducibility Model; FIRM), designed to estimate uncertainty in oxygen isotope measurements. FIRM uses parameters including location, depth habitat, season, number of individuals included in measurement, diagenesis, misidentification, size variation, and vital effects to produce synthetic isotope data in a manner reflecting natural processes. Reproducibility is then tested using Monte Carlo simulations. Importantly, this is not an attempt to fully model the entire complicated process of foraminiferal calcification; instead, we are trying to include only enough parameters to estimate the uncertainty in foraminiferal δ18O records. Two well-constrained empirical data sets are simulated successfully, demonstrating the validity of our model. The results from a series of experiments with the model show that reproducibility is not only largely controlled by the number of individuals in each measurement but also strongly a function of local oceanography if the number of individuals is held constant. Parameters like diagenesis or misidentification have an impact on both the precision and the accuracy of the data. FIRM is a tool to estimate isotopic uncertainty values and to explore the impact of myriad factors on the fidelity of paleoceanographic records, particularly for the Holocene.

  8. Theoretical effect of diffusion on isotopic abundance ratios in rocks and associated fluids

    USGS Publications Warehouse

    Senftle, F.E.; Bracken, J.T.

    1955-01-01

    Diffusion is considered as a possible process of isotope fractionation taking place throughout geologic time. Both diffusion in solids and diffusion in liquids are taken as possible mechanisms, the latter being more important. Arguments are presented to show that if significant fractionation takes place within a crystal by outward diffusion under solid-state conditions, enrichment will be evident only in elements of minor concentration. Similar conclusions are inferred for solid-state diffusion across a boundary or for diffusion in liquids. No isotopic enrichment can be expected in relatively large bodies of diffusion transported material. Although the necessary data to confirm these conclusions are scanty, it seems worth while to undertake further work in this direction. ?? 1955.

  9. Continuous on-line water vapor isotope measurements in Antarctica

    NASA Astrophysics Data System (ADS)

    Landsberg, Janek; Romanini, Daniele; Holmen, Kim; Isaksson, Elisabeth; Meijer, Harro; Kerstel, Erik

    2010-05-01

    In the context of a globally warming climate it is crucial to study the climate variability in the past and to understand the underlying mechanisms (1). Precipitation deposited on the polar ice caps provides a means to retrieve information on temperature changes (through the paleo-temperature dependence of the isotopic composition of the ice) and atmospheric composition (of gas stored in bubbles in the ice) on time scales from one to almost one million years, with sub-annual resolution in the most recent centuries. However, it is now widely recognized that the calibration of the paleo-thermometer is highly problematic. For this reason attempts to model the global water cycle, including the isotope signals, are ongoing with the aim of providing a more physical basis of the isotope - temperature relation. Currently, there is a large divergence in the results obtained by different modeling strategies. The missing link in these model studies is their forcing by experimental data on the pre-deposition isotopic composition of the vapor phase compartment of the hydrological cycle. We propose to measure the isotopic composition of moisture carried towards and deposited on Antarctica, in order to constrain the numerical models. In this context we are developing a modified, more sensitive and precise, version of a laser water vapor isotope spectrometer, originally designed for stratospheric studies (2, 3). This instrument, which will first be operated at the Norwegian station of Troll in Queen Maud Land, will enable the continuous, online measurement of all three stable isotope ratios of atmospheric water vapor. So far, such data is non-existent. Our data should improve the validity of the models and improve the understanding of the physical mechanisms at the basis of the isotope thermometer. This in turn will lead to an increased confidence in the predictions of (general circulation) models concerning climate variability. (1) International Panel on Climate Change (IPCC), 4

  10. First Results on Kr and Xe Abundances in the Bulk Solar Wind Measured in Silicon Targets exposed on GENESIS

    NASA Astrophysics Data System (ADS)

    Heber, V. S.; Baur, H.; Wieler, R.; Vogel, N.; Wiens, R. C.; Burnett, D. S.

    2008-12-01

    The solar wind (SW) Kr and Xe elemental and isotopic composition is one of the primary objectives of the GENESIS mission. Solar Kr and Xe abundances cannot be analyzed insitu in the present-day SW due to their low abundances nor can they be measured in the solar photosphere due to the lack of suitable spectral lines. Thus, solar data have been exclusively derived from SW-irradiated regolith samples. Here we present first results on bulk SW Kr and Xe abundances, as well as selected isotope ratios, from captured SW returned by GENESIS. Five aliquot analyses were done by UV laser ablation from Si targets (rastered areas are between 10 and 50mm2). Measured SW fluences (atoms/cm2) are 2.97(4)E+10 36Ar, 1.22(6)E+7 84Kr and 1.4(2)E+6 132Xe. The measured 86Kr/84Kr of 0.3035(36) is in good agreement with SW- Kr obtained from lunar regoliths. The same is true for 129Xe/132Xe of 1.043(25). Our preliminary Kr and Xe elemental abundances are in fair agreement with earlier values derived from lunar soils, although the Genesis SW 36Ar/84Kr of 2390(150) is 30% larger than the lunar value, presumed to be representative for the solar wind in the last 100 Ma. The GENESIS 84Kr/132Xe of 8.2(1.5) is within 10% of the value derived from relatively recently irradiated lunar soils. The understanding of fractionation processes in the SW is important to finally deduce solar abundances for noble gases (and other elements) from SW data. Former investigations showed that Kr and Xe are enriched in the SW relative to Ar and solar abundances. This fractionation process operates upon ionization of SW particles and affects mainly the elemental composition of the SW. However, adopting the recently strongly reduced solar Ne and Ar abundances at constant Kr and Xe would now question this fractionation model for Kr and Xe. We reassess models of fractionation processes in the light of the modified solar abundances and also compare the GENESIS Ar, Kr and Xe data with current estimates of solar abundances.

  11. Models of earth structure inferred from neodymium and strontium isotopic abundances

    PubMed Central

    Wasserburg, G. J.; DePaolo, D. J.

    1979-01-01

    A simplified model of earth structure based on the Nd and Sr isotopic characteristics of oceanic and continental tholeiitic flood basalts is presented, taking into account the motion of crustal plates and a chemical balance for trace elements. The resulting structure that is inferred consists of a lower mantle that is still essentially undifferentiated, overlain by an upper mantle that is the residue of the original source from which the continents were derived. PMID:16592688

  12. CNO abundances and carbon isotope ratios in evolved stars of the open clusters NGC 2324, NGC 2477, and NGC 3960

    NASA Astrophysics Data System (ADS)

    Tautvaišienė, Gražina; Drazdauskas, Arnas; Bragaglia, Angela; Randich, Sofia; Ženovienė, Renata

    2016-10-01

    Aims: Our main aim is to determine carbon-to-nitrogen and carbon isotope ratios for evolved giants in the open clusters NGC 2324, NGC 2477, and NGC 3960, which have turn-off masses of about 2 M⊙, and to compare them with predictions of theoretical models. Methods: High-resolution spectra were analysed using a differential synthetic spectrum method. Abundances of carbon were derived using the C2 Swan (0, 1) band heads at 5135 and 5635.5 Å. The wavelength interval 7940-8130 Å with strong CN features was analysed to determine nitrogen abundances and carbon isotope ratios. The oxygen abundances were determined from the [O i] line at 6300 Å. Results: The mean values of the CNO abundances are [C/Fe] = -0.35 ± 0.06 (s.d.), [N/Fe] = 0.28 ± 0.05, and [O/Fe] = -0.02 ± 0.10 in seven stars of NGC 2324; [C/Fe] = -0.26 ± 0.02, [N/Fe] = 0.39 ± 0.04, and [O/Fe] = -0.11 ± 0.06 in six stars of NGC 2477; and [C/Fe] = -0.39 ± 0.04, [N/Fe] = 0.32 ± 0.05, and [O/Fe] = -0.19 ± 0.06 in six stars of NGC 3960. The mean C/N ratio is equal to 0.92 ± 0.12, 0.91 ± 0.09, and 0.80 ± 0.13, respectively. The mean 12C /13C ratio is equal to 21 ± 1, 20 ± 1, and 16 ± 4, respectively. The 12C /13C and C/N ratios of stars in the investigated open clusters were compared with the ratios predicted by stellar evolution models. Conclusions: The mean values of the 12C /13C and C/N ratios in NGC 2324 and NGC 2477 agree well with the first dredge-up and thermohaline-induced extra-mixing models, which are similar for intermediate turn-off mass stars. The 12C /13C ratios in the investigated clump stars of NGC 3960 span from 10 to 20. The mean carbon isotope and C/N ratios in NGC 3960 are close to predictions of the model in which the thermohaline- and rotation-induced (if rotation velocity at the zero-age main sequence was 30% of the critical velocity) extra-mixing act together. Based on observations collected at ESO telescopes under programmes 072.D-0550 and 074.D-0571.

  13. Determining the isotopic abundance of a labeled compound by mass spectrometry and how correcting for natural abundance distribution using analogous data from the unlabeled compound leads to a systematic error.

    PubMed

    Schenk, David J; Lockley, William J S; Elmore, Charles S; Hesk, Dave; Roberts, Drew

    2016-04-01

    When the isotopic abundance or specific activity of a labeled compound is determined by mass spectrometry (MS), it is necessary to correct the raw MS data to eliminate ion intensity contributions, which arise from the presence of heavy isotopes at natural abundance (e.g., a typical carbon compound contains ~1.1% (13) C per carbon atom). The most common approach is to employ a correction in which the mass-to-charge distribution of the corresponding unlabeled compound is used to subtract the natural abundance contributions from the raw mass-to-charge distribution pattern of the labeled compound. Following this correction, the residual intensities should be due to the presence of the newly introduced labeled atoms only. However, this will only be the case when the natural abundance mass isotopomer distribution of the unlabeled compound is the same as that of the labeled species. Although this may be a good approximation, it cannot be accurate in all cases. The implications of this approximation for the determination of isotopic abundance and specific activity have been examined in practice. Isotopically mixed stable-atom labeled valine batches were produced, and both these and [(14) C6 ]carbamazepine were analyzed by MS to determine the extent of the error introduced by the approach. Our studies revealed that significant errors are possible for small highly-labeled compounds, such as valine, under some circumstances. In the case with [(14) C6 ]carbamazepine, the errors introduced were minor but could be significant for (14) C-labeled compounds with particular isotopic distributions. This source of systematic error can be minimized, although not eliminated, by the selection of an appropriate isotopic correction pattern or by the use of a program that varies the natural abundance distribution throughout the correction.

  14. Isotopic Resonance Hypothesis: Experimental Verification by Escherichia coli Growth Measurements

    PubMed Central

    Zubarev, Roman A.

    2015-01-01

    Isotopic composition of reactants affects the rates of chemical and biochemical reactions. As a rule, enrichment of heavy stable isotopes leads to progressively slower reactions. But the recent isotopic resonance hypothesis suggests that the dependence of the reaction rate upon the enrichment degree is not monotonous. Instead, at some “resonance” isotopic compositions, the kinetics increases, while at “off-resonance” compositions the same reactions progress slower. To test the predictions of this hypothesis for the elements C, H, N and O, we designed a precise (standard error ±0.05%) experiment that measures the parameters of bacterial growth in minimal media with varying isotopic composition. A number of predicted resonance conditions were tested, with significant enhancements in kinetics discovered at these conditions. The combined statistics extremely strongly supports the validity of the isotopic resonance phenomenon (p ≪ 10−15). This phenomenon has numerous implications for the origin of life studies and astrobiology, and possible applications in agriculture, biotechnology, medicine, chemistry and other areas. PMID:25782666

  15. Trace Element Abundance Measurements on Cosmic Dust Particles

    NASA Technical Reports Server (NTRS)

    Flynn, George

    1996-01-01

    The X-Ray Microprobe on beamline X-26A at the National Synchrotron Light Source (NSLS) at Brookhaven National Laboratory was used to determine the abundances of elements from Cr through Sr in individual interplanetary dust particles (IDPs) collected from the Earth's stratosphere and the Scanning Transmission X-ray Microscope (STXM) on beamline X-1A at the NSLS was used to determine the carbon abundances and spatial distributions in IDPs. In addition, modeling was performed in an attempt to associate particular types of IDPs with specific types of parent bodies, and thus to infer the chemistry, mineralogy, and structural properties of those parent bodies.

  16. A chart of cosmic ray isotopes. [showing radioactive decay, abundance and nucleosynthesis

    NASA Technical Reports Server (NTRS)

    Waddington, C. J.

    1975-01-01

    A chart has been prepared that lists some of the properties relevant to cosmic ray studies of all the significant nuclides between lithium and nickel. On this chart there are shown all the possible decays that might be of interest in the unique conditions experienced by cosmic ray nuclei, various abundance figures and the probable nucleosynthesis processes of origin.

  17. A Portable, Field-Deployable Analyzer for Isotopic Water Measurements

    NASA Astrophysics Data System (ADS)

    Berman, E. S.; Gupta, M.; Huang, Y. W.; Lacelle, D.; McKay, C. P.; Fortson, S.

    2015-12-01

    Water stable isotopes have for many years been used to study the hydrological cycle, catchment hydrology, and polar climate among other applications. Typically, discrete water samples are collected and transported to a laboratory for isotope analysis. Due to the expense and labor associated with such sampling, isotope studies have generally been limited in scope and time-resolution. Field sampling of water isotopes has been shown in recent years to provide dense data sets with the increased time resolution illuminating substantially greater short term variability than is generally observed during discrete sampling. A truly portable instrument also opens the possibility to utilize the instrument as a tool for identifying which water samples would be particularly interesting for further laboratory investigation. To make possible such field measurements of liquid water isotopes, Los Gatos Research has developed a miniaturized, field-deployable liquid water isotope analyzer. The prototype miniature liquid water isotope analyzer (mini-LWIA) uses LGR's patented Off-Axis ICOS (Integrated Cavity Output Spectroscopy) technology in a rugged, Pelican case housing for easy transport and field operations. The analyzer simultaneously measures both δ2H and δ18O from liquid water, with both manual and automatic water introduction options. The laboratory precision for δ2H is 0.6 ‰, and for δ18O is 0.3 ‰. The mini-LWIA was deployed in the high Arctic during the summer of 2015 at Inuvik in the Canadian Northwest Territories. Samples were collected from Sachs Harbor, on the southwest coast of Banks Island, including buried basal ice from the Lurentide Ice Sheet, some ice wedges, and other types of ground ice. Methodology and water analysis results from this extreme field deployment will be presented.

  18. Radioactive halos and ion microprobe measurement of Pb isotope ratios

    NASA Technical Reports Server (NTRS)

    Gentry, R. V.

    1974-01-01

    This investigation was to obtain, if possible, the Pb isotope ratios of both lunar and meteoritic troilite grains by utilizing ion microprobe techniques. Such direct in situ measurement of Pb isotope ratios would eliminate contamination problems inherent in wet chemistry separation procedures, and conceivably determine whether lunar troilite grains were of meteoritic origin. For comparison purposes two samples of meteoritic troilite were selected (one from Canyon Diablo) for analysis along with two very small lunar troilite grains (approximately 50-100 microns). It was concluded that the ion microprobe as presently operating, does not permit the in situ measurement of Pb isotope ratios in lunar or meteoritic troilite. On the basis of these experiments no conclusions could be drawn as to the origin of the lunar troilite grains.

  19. Precise measurement of chromium isotopes by MC-ICPMS

    PubMed Central

    Schiller, Martin; Van Kooten, Elishevah; Holst, Jesper C.; Olsen, Mia B.; Bizzarro, Martin

    2014-01-01

    We report novel analytical procedures allowing for the concurrent determination of the stable and mass-independent Cr isotopic composition of silicate materials by multiple collector inductively coupled mass spectrometry (MC-ICPMS). In particular, we focus on improved precision of the measurement of the neutron-rich isotope 54Cr. Because nitride and oxide interferences are a major obstacle to precise and accurate 54Cr measurements by MC-ICPMS, our approach is designed to minimize these interferences. Based on repeat measurements of standards, we show that the mass-independent 53Cr and 54Cr compositions can be routinely determined with an external reproducibility better than 2.5 and 5.8 ppm (2 sd), respectively. This represents at least a two-fold improvement compared to previous studies. Although this approach uses significantly more Cr (30–60 μg) than analysis by thermal ionization mass spectrometry (TIMS), our result indicate that it is possible to obtain an external reproducibility of 19 ppm for the μ54Cr when consuming amounts similar to that typically analyzed by TIMS (1 μg). In addition, the amount of time required for analysis by MC-ICPMS is much shorter thereby enabling a higher sample throughput. As a result of the improved analytical precision, we identified small apparent mass-independent differences between different synthetic Cr standards and bulk silicate Earth (BSE) when using the kinetic law for the mass bias correction. These differences are attributed to the Cr loss by equilibrium processes during production of the synthetic standards. The stable isotope data concurrently obtained have a precision of 0.05‰ Da −1, which is comparable to earlier studies. Comparison of the measured isotopic composition of four meteorites with published data indicates that Cr isotope data measured by the technique described here are accurate to stated uncertainties. The stable Cr composition of the Bilanga and NWA 2999 achondrites suggests that the

  20. Abundance and Isotopic Composition of Gases in the Martian Atmosphere: First Results from the Mars Curiosity Rover

    NASA Technical Reports Server (NTRS)

    Mahaffy, Paul; Webster, Chris R.; Atreya, Sushil K.; Franz, Heather; Wong, Michael; Conrad, Pamela G.; Harpold, Dan; Jones, John J.; Leshin, Laurie, A.; Manning, Heidi; Owen, Tobias; Pepin, Robert O.; Squyres, Steven; Trainer, Melissa

    2013-01-01

    Repeated measurements of the composition of the Mars atmosphere from Curiosity Rover yield a (40)Ar/N2 ratio 1.7 times greater and the (40)Ar/(36)Ar ratio 1.6 times smaller than the Viking Lander values in 1976. The unexpected change in (40)Ar/N2 ratio probably results from different instrument characteristics although we cannot yet rule out some unknown atmospheric process. The new (40)Ar/(36)Ar ratio is more aligned with Martian meteoritic values. Besides Ar and N2 the Sample Analysis at Mars instrument suite on the Curiosity Rover has measured the other principal components of the atmosphere and the isotopes. The resulting volume mixing ratios are: CO2 0.960(+/- 0.007); (40)Ar 0.0193(+/- 0.0001); N2 0.0189(+/- 0.0003); O2 1.45(+/- 0.09) x 10(exp -3); and CO 5.45(+/- 3.62) x 10(exp 4); and the isotopes (40)Ar/(36)Ar 1.9(+/- 0.3) x 10(exp 3), and delta (13)C and delta (18)O from CO2 that are both several tens of per mil more positive than the terrestrial averages. Heavy isotope enrichments support the hypothesis of large atmospheric loss. Moreover, the data are consistent with values measured in Martian meteorites, providing additional strong support for a Martian origin for these rocks.

  1. Hydrogen isotope abundances in the solar system. Part II: Meteorites with terrestrial-like D / H ratio

    NASA Astrophysics Data System (ADS)

    Robert, François; Javoy, Marc; Halbout, Jérôme; Dimon, Bernard; Merlivat, Liliane

    1987-07-01

    Hydrogen isotopic compositions were determined by progressive pyrolysis in type 6 to type 3 ordinary chondrites. A marked decrease in the isotopic composition patterns was observed at intermediate temperatures (250-300°C) and results from the pyrolysis of a D-depleted component. A δD value of-400‰ for this component can be inferred from a mathematical treatment of the H concentration release pattern. At higher temperatures (600 to 900°C) the bimodal δD pattern was observed in Hedjaz (L3-L6) with negative δD values, suggesting the presence of a carbonaceous chondrite-like organic polymer in this meteorite. A peak in the δD pattern was observed at high temperature in all the analyzed samples, suggesting that D-rich H is widespread among meteorites. A minimum of 50% of the total H is concentrated in the fine-grained particles (the "holy smoke") of equilibrated chondrites, reinforcing the idea that H is associated with the C. An internal correlation between the bulk isotopic composition of HT H 2 and the maximum measured D/H ratio is interpreted as the result of either the mixing of two components (Model 1), namely a D-depleted H at -400‰ and a D-rich H at +5000‰, or a progressive isotopic fractionation of a D-depleted reservoir (Model 2). The first model (the favored one) implies that the two components were present in different proportions at the time of the formation of each meteorite, and that metamorphism has homogeneized the two phases. The uniqueness of the two isotopic end-members for all meteorites is not demonstrated. The second model relates the isotopic fractionation of the D-rich phase to the degree of equilibration of chondrites. All the isotopic variations reported in this work for ordinary chondrites can be explained quantitatively by either one of these two models. The upper and lower limits for the D/Hratios of the D-rich and of the D-depleted H in meteorites are calculated to be 1.1 × 10 -3 and 9 × 10 -5, respectively.

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

    NASA Astrophysics Data System (ADS)

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

    2013-10-01

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

  3. Paleodietary reconstruction using stable isotopes and abundance analysis of bovids from the Shungura Formation of South Omo, Ethiopia.

    PubMed

    Negash, Enquye W; Alemseged, Zeresenay; Wynn, Jonathan G; Bedaso, Zelalem K

    2015-11-01

    Preservation of the stable carbon isotopic composition of fossil tooth enamel enables us to estimate the relative proportion of C3 versus C4 vegetation in an animal's diet, which, combined with analysis of faunal abundance, may provide complementary methods of paleoenvironmental reconstruction. To this end, we analyzed stable carbon isotopic composition (δ(13)C values) of tooth enamel from four bovid tribes (Tragelaphini, Aepycerotini, Reduncini, and Alcelaphini) derived from six members of the Shungura Formation (Members B, C, D, F, G, and L; ages from ca. 2.90-1.05 Ma (millions of years ago) in the Lower Omo Valley of southwestern Ethiopia. The bovids show a wide range of δ(13)C values within taxa and stratigraphic members, as well as temporal changes in the feeding strategies of taxa analyzed throughout the middle to late Pliocene and early Pleistocene. Such variation suggests that the use of actualistic approaches for paleoenvironmental reconstruction may not always be warranted. Alcelaphini was the only taxon analyzed that retained a consistent dietary preference throughout the sequence, with entirely C4-dominated diets. Reduncini had a mixed C3/C4 to C4-dominated diet prior to 2.4 Ma, after which this taxon shifted to a largely C4-dominated diet. Aepycerotini generally showed a mixed C3/C4 diet, with a period of increased C4 diet from 2.5 to 2.3 Ma. Tragelaphini showed a range of mixed C3/C4 diets, with a median value that was briefly nearer the C4 end member from 2.9 to 2.4 Ma but was otherwise towards the C3 end member. These isotopic results, combined with relative abundance data for these bovids, imply that the environment of the Lower Omo Valley consisted of a mosaic of closed woodlands, with riverine forests and open grasslands. However, our data also signify that the overall environment gradually became more open, and that C4 grasses became more dominant. Finally, these results help document the range and extent of environments and potential diets

  4. Vadose Zone Infiltration Rates from Sr isotope Measurements

    NASA Astrophysics Data System (ADS)

    Maher, K.; Maher, K.; DePaolo, D. J.; DePaolo, D. J.; Conrad, M.

    2001-12-01

    Predicting infiltration rates and recharge through the vadose zone in arid regions is difficult and hence developing methods for the measurement of infiltration rates is important. We have been investigating the use of Sr isotope measurements for determining infiltration at the 200 Area plateau on the Hanford reservation in central Washington. In this context, infiltration affects the transport of contaminants to the water table as well as recharge of the groundwater system. Using Sr isotopes for this purpose requires drill core and water samples from the vadose zone, although leaches of the cores can substitute for water samples. Complementary information, including some constraints on regional recharge, can also be obtained using water samples from groundwater monitoring wells. The VZ method is based on the fact that the Sr isotope ratio of soil water just below the surface is often set by dissolution of aeolian material including carbonate, and this ratio is different from the average value in the deeper underlying vadose zone rock matrix. As water infiltrates, the Sr isotopic composition of the water changes toward the rock values as a result of Sr released from the rocks by weathering reactions. The rate of change with depth of the Sr isotope ratio of the vadose zone water is a function ultimately of q/R; the ratio of the infiltration flux (q) to the bulk rock weathering rate (R). Where it is possible to evaluate R, q can be estimated. As data accumulate it may be possible to improve the calibration of the method. At Hanford the vadose zone rock material is mostly unconsolidated sand, silt, and gravel of broadly granitic composition, which constitute the Hanford and Ringold formations. Annual precipitation is about 160 mm/yr. Drilling and coring of a ca. 70m hole to the water table in 1999 as part of the Hanford groundwater monitoring program, in a relatively undisturbed area of the site, allowed us to generate a unique Sr isotope data set. The Sr isotope

  5. Continental-Scale Stable Isotope Measurements at NEON to Address Ecological Processes Across Systems

    NASA Astrophysics Data System (ADS)

    Luo, H.; Goodman, K. J.; Hinckley, E. S.; West, J. B.; Williams, D. G.; Bowen, G. J.

    2013-12-01

    The National Ecological Observatory Network (NEON) is a national-scale research platform. The overarching goal of NEON is to enable understanding and forecasting of the impacts of climate change, land use change, and invasive species on aspects of continental-scale ecology (such as biodiversity, biogeochemistry, infectious diseases, ecohydrology, etc.). NEON focuses explicitly on questions that relate to grand challenges in environmental science, are relevant to large regions, and would otherwise be very difficult to address with traditional ecological approaches. The use of stable isotope approaches in ecological research has grown steadily during the last two decades. Stable isotopes at natural abundances in the environment trace and integrate the interaction between abiotic and biotic components across temporal and spatial scales. In this poster, we will present the NEON data products that incorporate stable isotope measurements in atmospheric, terrestrial, and aquatic ecosystems in North America. We further outline current questions in the natural sciences community and how these data products can be used to address continental-scale ecological questions, such as the ecological impacts of climate change, terrestrial-aquatic system linkages, land-atmosphere exchange, landscape ecohydrological processes, and linking biogeochemical cycles across systems. Specifically, we focus on the use of stable isotopes to evaluate water availability and residence times in terrestrial systems, as well as nutrient sources to terrestrial systems, and cycling across ecosystem boundaries.

  6. Measurements of isotope effects in the photoionization of N2 and implications for Titan's atmosphere

    SciTech Connect

    Croteau, Philip; Randazzo, John B.; Kostko, Oleg; Ahmed, Musahid; Liang, Mao-Chang; Yung, Yuk L.; Boering, Kristie A.

    2010-12-30

    Isotope effects in the non-dissociative photoionization of molecular nitrogen (N2 + h nu -> N2+ + e-) may play a role in determining the relative abundances of isotopic species containing nitrogen in interstellar clouds and planetary atmospheres but have not been previously measured. Measurements of the photoionization efficiency spectra of 14N2, 15N14N, and 15N2 from 15.5 to 18.9 eV (65.6-80.0 nm) using the Advanced Light Source at Lawrence Berkeley National Laboratory show large differences in peak energies and intensities, with the ratio of the energy-dependent photoionization cross-sections, sigma(14N2)/sigma(15N14N), ranging from 0.4 to 3.5. Convolving the cross-sections with the solar flux and integrating over the energies measured, the ratios of photoionization rate coefficients are J(15N14N)/J(14N2)=1.00+-0.02 and J(15N2)/J(14N2)=1.00+-0.02, suggesting that isotopic fractionation between N2 and N2+ should be small under such conditions. In contrast, in a one-dimensional model of Titan's atmosphere, isotopic self-shielding of 14N2 leads to values of J(15N14N)/J(14N2) as large as ~;;1.17, larger than under optically thin conditions but still much smaller than values as high as ~;;29 predicted for N2 photodissociation. Since modeled photodissociation isotope effects overpredict the HC15N/HC14N ratio in Titan's atmosphere, and since both N atoms and N2+ ions may ultimately lead to the formation of HCN, estimates of the potential of including N2 photoionization to contribute to a more quantitative explanation of 15N/14N for HCN in Titan's atmosphere are explored.

  7. Accurate and precise zinc isotope ratio measurements in urban aerosols.

    PubMed

    Gioia, Simone; Weiss, Dominik; Coles, Barry; Arnold, Tim; Babinski, Marly

    2008-12-15

    We developed an analytical method and constrained procedural boundary conditions that enable accurate and precise Zn isotope ratio measurements in urban aerosols. We also demonstrate the potential of this new isotope system for air pollutant source tracing. The procedural blank is around 5 ng and significantly lower than published methods due to a tailored ion chromatographic separation. Accurate mass bias correction using external correction with Cu is limited to Zn sample content of approximately 50 ng due to the combined effect of blank contribution of Cu and Zn from the ion exchange procedure and the need to maintain a Cu/Zn ratio of approximately 1. Mass bias is corrected for by applying the common analyte internal standardization method approach. Comparison with other mass bias correction methods demonstrates the accuracy of the method. The average precision of delta(66)Zn determinations in aerosols is around 0.05 per thousand per atomic mass unit. The method was tested on aerosols collected in Sao Paulo City, Brazil. The measurements reveal significant variations in delta(66)Zn(Imperial) ranging between -0.96 and -0.37 per thousand in coarse and between -1.04 and 0.02 per thousand in fine particular matter. This variability suggests that Zn isotopic compositions distinguish atmospheric sources. The isotopic light signature suggests traffic as the main source. We present further delta(66)Zn(Imperial) data for the standard reference material NIST SRM 2783 (delta(66)Zn(Imperial) = 0.26 +/- 0.10 per thousand).

  8. Abundant climatic information in water stable isotope record from a maritime glacier on southeastern Tibetan Plateau

    NASA Astrophysics Data System (ADS)

    Zhao, Huabiao; Xu, Baiqing; Li, Zhen; Wang, Mo; Li, Jiule; Zhang, Xiaolong

    2017-02-01

    Climatic significance of ice core stable isotope record in the Himalayas and southern Tibetan Plateau (TP), where the climate is alternately influenced by Indian summer monsoon and mid-latitude westerlies, is still debated. A newly drilled Zuoqiupu ice core from a temperate maritime glacier on the southeastern TP covering 1942-2011 is investigated in terms of the relationships between δ18O and climate parameters. Distinct seasonal variation of δ18O is observed due to high precipitation amount in this area. Thus the monsoon (June to September) and non-monsoon (October to May) δ18O records are reconstructed, respectively. The temperature effect is identified in the annual δ18O record, which is predominantly contributed by temperature control on the non-monsoon precipitation δ18O record. Conversely, the negative correlation between annual δ18O record and precipitation amount over part of Northeast India is mostly contributed by the monsoon precipitation δ18O record. The variation of monsoon δ18O record is greatly impacted by the Indian summer monsoon strength, while that of non-monsoon δ18O record is potentially associated with the mid-latitude westerly activity. The relationship between Zuoqiupu δ18O record and Sea Surface Temperature (SST) is found to be inconsistent before and after the climate shift of 1976/1977. In summer monsoon season, the role of SST in the monsoon δ18O record is more important in eastern equatorial Pacific Ocean and tropical Indian Ocean before and after the shift, respectively. In non-monsoon season, however, the Atlantic Multidecadal Oscillation has a negative impact before but positive impact after the climate shift on the non-monsoon δ18O record.

  9. A natural abundance stable isotope tracer experiment to define SO2 oxidation pathways and their fractionation during heterogeneous oxidation

    NASA Astrophysics Data System (ADS)

    Amiri, N.; Norman, A. L.

    2015-12-01

    Sulfate aerosols have crucial direct and indirect effects on climate from radiative cooling to modifying clouds by formation of cloud condensation nuclei. Secondary sulfate aerosols are formed by oxidation of SO2 and subsequent nucleation and growth and the characteristics of primary aerosol sulfate can be modified by oxidation of SO2. There are several known oxidation pathways for SO2; gaseous phase OH oxidation and aqueous phase H2O2, O3 and transition metal oxides oxidation. The SO2 oxidation pathway affects the characteristics of the aerosols formed. Stable isotope techniques are useful in determining the oxidation pathway of SO2 due to unique fractionation patterns (Harris et al., 2012). However, there are still gaps in our understanding of the oxidation pathways and fractionations affecting SO2 and secondary sulfate. A tracer experiment to investigate the oxidation of SO2 and fractionation using size segregated aerosols in the presence of different compounds is described. Two high volume samplers situated to measure background sulfate upwind, and the results of a tracer experiment, downwind, is described. After sufficient size segregated aerosol sulfate has been collected, a source of SO2 with known isotopic composition is introduced to the second high volume sampler. Changes in the isotopic composition for size segregated aerosol sulfate in comparison to the first high volume sampler are investigated. The amount of fractionation during heterogeneous oxidation of SO2 on pre-existing aerosols is calculated using the concentrations and known isotopic composition and compared to data from laboratory and field experiments. The experiment is performed downwind of sources of organic compounds such as pine forests, and characterized using co-located canister samples, to determine the effects of SO2 oxidation on secondary aerosol sulfate.

  10. Measurements of stable isotope ratios in milk samples from a farm placed in the mountains of Transylvania

    SciTech Connect

    Magdas, D. A. Cristea, G. Bot, A.; Puscas, R.; Radu, S.; Mirel, V.; Cordea, D. V.; Mihaiu, M.

    2013-11-13

    Product origin is of great importance for consumers especially because its association in consumer's perception with food quality, freedom from disease or pollution. Stable isotope ratio analysis is a powerful technique in food authenticity and traceability control which has been introduced within the European wine industry to ensure authenticity of wine provenance and to detect adulteration. Isotopic ratios measurements have also been successfully to other food commodities like: fruit juices, honey and dairy foods. The δ{sup 18}O and δ{sup 2}H content in milk water reflects the isotope composition of the ground water drunk by animals. Seasonal effects are also very important: in summer, milk water contains higher δ{sup 18}O and δ{sup 2}H values due to the fresh plants that are ate by animals. Relative carbon stable isotope abundances in total milk reflect the isotopic composition of the diet fed to the dairy cows. In this study the hydrogen, oxygen and carbon isotopic composition of 15 milk samples coming from a unit placed in the mountains of Transylvania was investigated. The distribution of the obtained isotopic values was than discussed taking into account that all the animals were feed with the same type of forage and consumed water was taken from the same source.

  11. Measurements of stable isotope ratios in milk samples from a farm placed in the mountains of Transylvania

    NASA Astrophysics Data System (ADS)

    Magdas, D. A.; Cristea, G.; Cordea, D. V.; Bot, A.; Puscas, R.; Radu, S.; Mirel, V.; Mihaiu, M.

    2013-11-01

    Product origin is of great importance for consumers especially because its association in consumer's perception with food quality, freedom from disease or pollution. Stable isotope ratio analysis is a powerful technique in food authenticity and traceability control which has been introduced within the European wine industry to ensure authenticity of wine provenance and to detect adulteration. Isotopic ratios measurements have also been successfully to other food commodities like: fruit juices, honey and dairy foods. The δ18O and δ2H content in milk water reflects the isotope composition of the ground water drunk by animals. Seasonal effects are also very important: in summer, milk water contains higher δ18O and δ2H values due to the fresh plants that are ate by animals. Relative carbon stable isotope abundances in total milk reflect the isotopic composition of the diet fed to the dairy cows. In this study the hydrogen, oxygen and carbon isotopic composition of 15 milk samples coming from a unit placed in the mountains of Transylvania was investigated. The distribution of the obtained isotopic values was than discussed taking into account that all the animals were feed with the same type of forage and consumed water was taken from the same source.

  12. 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

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

    SciTech Connect

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

    2015-12-07

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

  14. Pooled versus separate measurements of tree-ring stable isotopes.

    PubMed

    Dorado Liñán, Isabel; Gutiérrez, Emilia; Helle, Gerhard; Heinrich, Ingo; Andreu-Hayles, Laia; Planells, Octavi; Leuenberger, Markus; Bürger, Carmen; Schleser, Gerhard

    2011-05-01

    δ(13)C and δ(18)O of tree rings contain time integrated information about the environmental conditions weighted by seasonal growth dynamics and are well established as sources of palaeoclimatic and ecophysiological data. Annually resolved isotope chronologies are frequently produced by pooling dated growth rings from several trees prior to the isotopic analyses. This procedure has the advantage of saving time and resources, but precludes from defining the isotopic error or statistical uncertainty related to the inter-tree variability. Up to now only a few studies have compared isotope series from pooled tree rings with isotopic measurements from individual trees. We tested whether or not the δ(13)C and the δ(18)O chronologies derived from pooled and from individual tree rings display significant differences at two locations from the Iberian Peninsula to assess advantages and constraints of both methodologies. The comparisons along the period 1900-2003 reveal a good agreement between pooled chronologies and the two mean master series which were created by averaging raw individual values (Mean) or by generating a mass calibrated mean (MassC). In most of the cases, pooled chronologies show high synchronicity with averaged individual samples at interannual scale but some differences also show up especially when comparing δ(18)O decadal to multi-decadal variations. Moreover, differences in the first order autocorrelation among individuals may be obscured by pooling strategies. The lack of replication of pooled chronologies prevents detection of a bias due to a higher mass contribution of one sample but uncertainties associated with the analytical process itself, as sample inhomogeneity, seems to account for the observed differences.

  15. On the accuracy of gamma spectrometric isotope ratio measurements of uranium

    NASA Astrophysics Data System (ADS)

    Ramebäck, H.; Lagerkvist, P.; Holmgren, S.; Jonsson, S.; Sandström, B.; Tovedal, A.; Vesterlund, A.; Vidmar, T.; Kastlander, J.

    2016-04-01

    The isotopic composition of uranium was measured using high resolution gamma spectrometry. Two acid solutions and two samples in the form of UO2 pellets were measured. The measurements were done in close geometries, i.e. directly on the endcap of the high purity germanium detector (HPGe). Applying no corrections for count losses due to true coincidence summing (TCS) resulted in up to about 40% deviation in the abundance of 235U from the results obtained with mass spectrometry. However, after correction for TCS, excellent agreement was achieved between the results obtained using two different measurement methods, or a certified value. Moreover, after corrections, the fitted relative response curves correlated excellently with simulated responses, for the different geometries, of the HPGe detector.

  16. Millimeter-scale variations of stable isotope abundances in carbonates from banded iron-formations in the Hamersley Group of Western Australia

    NASA Technical Reports Server (NTRS)

    Baur, M. E.; Hayes, J. M.; Studley, S. A.; Walter, M. R.

    1985-01-01

    Several diamond drill cores from formations within the Hamersley Group of Western Australia have been studied for evidence of short-range variations in the isotopic compositions of the carbonates. For a set of 32 adjacent microbands analyzed in a specimen from the Marra Mamba Iron Formation, carbon isotope compositions of individual microbands ranged from -2.8 to -19.8 per mil compared to PDB and oxygen isotope compositions ranged from 10.2 to 20.8 per mil compared to SMOW. A pattern of alternating abundances was present, with the average isotopic contrasts between adjacent microbands being 3.0 per mil for carbon and 3.1 per mil for oxygen. Similar results were obtained for a suite of 34 microbands (in four groups) from the Bruno's Band unit of the Mount Sylvia Formation. Difficulties were experienced in preparing samples of single microbands from the Dales Gorge Member of the Brockman Iron Formation, but overall isotopic compositions were in good agreement with values reported by previous authors. Chemical analyses showed that isotopically light carbon and oxygen were correlated with increased concentrations of iron. The preservation of these millimeter-scale variations in isotopic abundances is interpreted as inconsistent with a metamorphic origin for the isotopically light carbon in the BIF carbonates. A biological origin is favored for the correlated variations in 13C and Fe, and it is suggested that the 13C-depleted carbonates may derive either from fermentative metabolism or from anaerobic respiration. A model is presented in which these processes occur near the sediment-water interface and are coupled with an initial oxidative precipitation of the iron.

  17. Potassium Stable Isotopic Compositions Measured by High-Resolution MC-ICP-MS

    NASA Technical Reports Server (NTRS)

    Morgan, Leah E.; Lloyd, Nicholas S.; Ellam, Robert M.; Simon, Justin I.

    2012-01-01

    Potassium isotopic (K-41/K-39) compositions are notoriously difficult to measure. TIMS measurements are hindered by variable fractionation patterns throughout individual runs and too few isotopes to apply an internal spike method for instrumental mass fractionation corrections. Internal fractionation corrections via the K-40/K-39 ratio can provide precise values but assume identical K-40/K-39 ratios (e.g. 0.05% (1sigma) in [1]); this is appropriate in some cases (e.g. identifying excess K-41) but not others (e.g., determining mass fractionation effects and metrologically traceable isotopic abundances). SIMS analyses have yielded measurements with 0.25% precisions (1sigma) [2]. ICP-MS analyses are significantly affected by interferences from molecular species such as Ar-38H(+) and Ar-40H(+) and instrument mass bias. Single collector ICP-MS instruments in "cold plasma" mode have yielded uncertainties as low as 2% (1sigma, e.g. [3]). Although these precisions may be acceptable for some concentration determinations, they do not resolve isotopic variation in terrestrial materials. Here we present data from a series of measurements made on the Thermo Scientific NEPTUNE Plus multi-collector ICP-MS that demonstrate the ability to make K-41/K-39 ratio measurements with 0.07% precisions (1sigma). These data, collected on NIST K standards, indicate the potential for MC-ICP-MS measurements to look for K isotopic variations at the sub-permil level. The NEPTUNE Plus can sufficiently resolve 39K and 41K from the interfering 38ArH+ and 40ArH+ peaks in wet cold plasma and high-resolution mode. Measurements were made on small but flat, interference-free, plateaus (ca. 50 ppm by mass width for K-41). Although ICP-MS does not yield accurate K-41/K-39 values due to significant instrumental mass fractionation (ca. 6%), this bias can be sufficiently stable over the time required for several measurements so that relative K-41/K-39 values can be precisely determined via sample

  18. Evaluating Nitrogen Isotope Measurements in Unconventional Hydrocarbon Reservoirs

    NASA Astrophysics Data System (ADS)

    Quan, T. M.; Rivera, K.; Adigwe, E.; Riedinger, N.; Puckette, J.

    2014-12-01

    Nitrogen isotope (δ15N) measurements from core samples taken from unconventional hydrocarbon reservoirs may provide important information on depositional environment, reservoir characterization, and post-depositional processes. In order to evaluate the potential of nitrogen isotopes as geochemical proxies for resource evaluation, we measured δ15Nbulk values for six Woodford Shale (Late Devonian-Early Mississippian) cores and three Caney Shale (Early Mississippian) cores and compared the profiles with other geochemical, lithological, maturation, and well-log data. The strongest correlation is between δ15Nbulk and redox-sensitive trace metals and other redox proxies, as predicted by previous research into δ15Nbulk values. This indicates that δ15Nbulk can be used in unconventional reservoirs as a proxy for depositional redox conditions. Unlike other redox proxies, δ15Nbulk reflects the redox state of the deep-water column, rather than that of the deposited sediment, providing a representation of water column processes during deposition. The δ15Nbulk proxy also appears not to be overprinted by catagenic processes. Associations of δ15Nbulk with thermal maturity, gamma ray response, and catagenesis and diagenesis proxies were found to be minimal. The δ15Nbulk profiles do not appear to be overprinted during catagenesis and therefore are not a reliable record of post-depositional processes. Including nitrogen isotope analyses in a geochemical assessment can provide valuable information about the original redox state of the reservoir unit, and assist in characterizing depositional environment.

  19. Isotope shift and hyperfine structure measurements in titanium I

    NASA Astrophysics Data System (ADS)

    Luc, P.; Vetter, R.; Bauche-Arnoult, C.; Bauche, J.

    1994-09-01

    High accuracy measurements of hyperfine structure due to47Ti and49Ti in the 3 d 2 4 s 2 a 3 F 2-3 d 2 4 s4 p z 5 D 1 absorption line at σ=18482.772 cm-1 have been performed by use of a Doppler-free experiment, where a beam of titanium atoms is crossed by a CW single mode tunable dye laser. They have allowed for the determination of isotope shifts between46Ti,47Ti,48Ti,49Ti and50Ti. By use of accurate values of mean square nuclear charge radii for the even isotopes, it has been possible to separate mass shifts from field shifts and to determine accurate values for the mean square nuclear charge radii of47Ti and49Ti. The field shift presents a marked odd-even staggering.

  20. Cross-Section Measurements with the Radioactive Isotope Accelerator (RIA)

    SciTech Connect

    Stoyer, M A; Moody, K J; Wild, J F; Patin, J B; Shaughnessy, D A; Stoyer, N J; Harris, L J

    2002-11-19

    RIA will produce beams of exotic nuclei of unprecedented luminosity. Preliminary studies of the feasibility of measuring cross-sections of interest to the science based stockpile stewardship (SBSS) program will be presented, and several experimental techniques will be discussed. Cross-section modeling attempts for the A = 95 mass region will be shown. In addition, several radioactive isotopes could be collected for target production or medical isotope purposes while the main in-beam experiments are running. The inclusion of a broad range mass analyzer (BRAMA) capability at RIA will enable more effective utilization of the facility, enabling the performance of multiple experiments at the same time. This option will be briefly discussed.

  1. In situ measurements of Li isotopes in foraminifera

    NASA Astrophysics Data System (ADS)

    Vigier, Nathalie; Rollion-Bard, Claire; Spezzaferri, Silvia; Brunet, Fabrice

    2007-01-01

    In situ measurement of Li isotope ratios in foraminifera has been developed using a Cameca ims 1270 ion microprobe. In situ δ7Li analyses have been performed in biogenic calcite of planktonic foraminifera from various locations. Results show that for west Pacific mixed Globigerinoides and Globorotalia (22°S161°E), the isotopic variability between tests and within a single test, respectively, is not significantly greater than estimated analytical uncertainty (˜1.5‰). Mean δ7Li for several planktonic foraminifera tests corresponds to the seawater value, strongly suggesting negligible Li isotope fractionation relative to seawater, as previously inferred by Hall et al. (2005) using thermo-ionization mass spectrometer and multicollector-inductively coupled plasma-mass spectrometry techniques. Combined with scanning electron microscopy and ion microprobe imaging, micron-sized grains, enriched in lithium, silica and aluminum have been found in the foraminifera calcite matrix. A simple mixing model shows that 0.3-2 wt % of marine clays incorporated within the analyzed calcite would lower the foraminifera δ7Li value, by 3‰ to 10‰ relative to the isotopic composition of the pure calcite. By comparison, no such grains have been detected in corals. The presence of micron-sized silicate grains embedded within the foraminifera calcite is consistent with the Erez (2003) biomineralization model, involving calcite precipitation from seawater vacuoles. By contrast, coral calcium carbonate is instead precipitated from ions, which have been pumped or diffused through several membranes, impermeable to micrometric grains. Ion microprobe in situ δ7Li measurements in biogenic calcite present new methods for investigating both biomineralization processes and the past record of the ocean composition by exploring geochemical variations at a scale that is smaller in space and in time.

  2. The use of reference materials in isotope measurements (Invited)

    NASA Astrophysics Data System (ADS)

    Kessel, R.

    2009-12-01

    Over the last few decades, mass spectrometry has emerged as one of the most important tools for chemical analysis. Isotope measurements on modern mass spectrometers have achieved unprecedented repeatability due to the semi-automated nature and stability. As a consequence of these high precisions, one of the most important factors for improving the total uncertainty of the measurement results is associated with the reference materials used for calibration. Different metrological concepts have been developed to deal with this problem. This talk will examine the impact of these concepts involving reference materials on the uncertainty budget, traceability and comparability of the results.

  3. Abundance and isotope systematics of carbon in subglacial basalts, geothermal gases and fluids from Iceland's rift zones

    NASA Astrophysics Data System (ADS)

    Barry, P. H.; Hilton, D. R.; Fueri, E.; Halldorsson, S. A.; Fischer, T. P.; Gronvold, K.

    2010-12-01

    P. H. BARRY1*, D. R. HILTON1, E. FÜRI1, S.A. HALLDÓRSON1, T.P. FISCHER2, K. GRONVOLD3 1 Scripps Institution of Oceanography, UCSD, La Jolla, California 92093, USA (*Correspondence: pbarry@ucsd.edu). 2University of New Mexico, Albuquerque, NM 87131, USA. 3University of Iceland, Askja, Sturlugata 7, IS-101, Reykjavik, Iceland Carbon dioxide (CO2) is the dominant non-aqueous volatile species found in oceanic basalts and geothermal fluids and serves as the carrier gas for trace volatiles such as He and other noble gases. The aim of this study is to identify the superimposed effects of degassing and crustal contamination on the CO2 systematics of the Icelandic hotspot in order to reveal and characterize the carbon abundance and isotopic features of the underlying mantle source. Our approach involves coupling CO2 with He, utilizing the sensitivity of 3He/4He ratios to reveal mantle and crustal inputs. We report new C-isotope (δ13C) and abundance characteristics for a suite of 47 subglacial basalts and 50 geothermal gases and fluids from Iceland. CO2 contents in hyaloclastite glasses are extremely low (10-100 ppm) and likely residual following extensive degassing whereas geothermal fluids are dominated by CO2 (>90 %). C-isotopes range from -27.2 to -3.6 ‰ (vs. PDB) for basalts and from -18.8 to 2.86 ‰ (vs. PDB) for geothermal samples (mean = -4.2 ± 3.6 ‰). CO2/3He ratios range from 108 to 1012 for basalts and from 105 to 1012 for geothermal samples: In both cases, our results extend He-CO2 relationships over a much broader range than reported previously [1]. Taken together, these data suggest that several processes including mixing, degassing, and/or syn- or post-eruptive crustal contamination may act to modify CO2 source characteristics. Equilibrium degassing models are compatible with ~75 % of the basalt data, and preliminary results indicate that initial Icelandic source characteristics are ~500 ppm CO2 and δ13C ~ -5 ‰ (vs. PDB). These values are high

  4. Major and trace element abundances, and Sr and Nd isotopic composition of Carbonatites from Amba Dongar, Gujarat, India

    NASA Astrophysics Data System (ADS)

    Chandra, Jyoti; Paul, Debajyoti; Viladkar, Shrinivas G.; Sensarma, Sarajit

    2015-04-01

    Despite significant progress during the last decade, the petrogenesis of carbonatites is still highly debated regarding the exact mechanism of carbonatite magma generation (fractional crystallization of carbonated-silicate magmas, liquid immiscibility of carbonated-silicate magmas, partial melting of carbonated mantle peridotite or carbonated lherzolitic mantle) and its evolution. The Amba Dongar carbonatite complex in Chhota Udaipur district, Gujarat is the youngest Indian carbonatite complex, which intruded into the ~ 90 Ma Bagh sandstones and limestone and 68-65 Ma Deccan flood basalts. The emplacement age (40Ar/39Ar age of 65±0.3 Ma; Ray and Pande, 1999) coincides with the age of main pulse of Deccan flood basalts at ca. 65 Ma. We report new geochemical data (major oxide and trace element abundances, and Sr and Nd isotopic ratios) on 23 carbonatite samples from Amba Dongar. The Amba Dongar carbonatite complex consists of carbonatite (sövite, and ankerite), and associated nephelinite, phonolite, and both pre- and post-carbonatite basalts. Detailed minerology of carbonatite include dominant calcite along with pyrochlore, apatite, magnetite, aegirine-augite and accessory phases. Apatite crystals are observed in carbonatite as well as in nephelinite. In sövites, apatite occur in various forms including cumulus, clusters and scattered within and along the boundary of calcite crystals. Two generation of apatite crystals are commonly observed in sövite and nephelinite; textural changes suggest presence of different five pulses of sövitic magma during the emplacement of the sövite ring dike. Bulk major oxides and trace element (including REEs) compositions of carbonatites and associated silicate rocks are determined by WD-XRF and ICP-MS, respectively. Major oxides abundances are consistent with the already available data on the Amba Dongar carbonatite complex. Trace element concentrations for the sövite reveals high concentrations of Sr (929-7476 ppm), Ba (344

  5. Abundance-weighted phylogenetic diversity measures distinguish microbial community states and are robust to sampling depth.

    PubMed

    McCoy, Connor O; Matsen, Frederick A

    2013-01-01

    In microbial ecology studies, the most commonly used ways of investigating alpha (within-sample) diversity are either to apply non-phylogenetic measures such as Simpson's index to Operational Taxonomic Unit (OTU) groupings, or to use classical phylogenetic diversity (PD), which is not abundance-weighted. Although alpha diversity measures that use abundance information in a phylogenetic framework do exist, they are not widely used within the microbial ecology community. The performance of abundance-weighted phylogenetic diversity measures compared to classical discrete measures has not been explored, and the behavior of these measures under rarefaction (sub-sampling) is not yet clear. In this paper we compare the ability of various alpha diversity measures to distinguish between different community states in the human microbiome for three different datasets. We also present and compare a novel one-parameter family of alpha diversity measures, BWPDθ, that interpolates between classical phylogenetic diversity (PD) and an abundance-weighted extension of PD. Additionally, we examine the sensitivity of these phylogenetic diversity measures to sampling, via computational experiments and by deriving a closed form solution for the expectation of phylogenetic quadratic entropy under re-sampling. On the three datasets, a phylogenetic measure always performed best, and two abundance-weighted phylogenetic diversity measures were the only measures ranking in the top four across all datasets. OTU-based measures, on the other hand, are less effective in distinguishing community types. In addition, abundance-weighted phylogenetic diversity measures are less sensitive to differing sampling intensity than their unweighted counterparts. Based on these results we encourage the use of abundance-weighted phylogenetic diversity measures, especially for cases such as microbial ecology where species delimitation is difficult.

  6. Beta Decay Measurements of Neutron Deficient Cesium Isotopes.

    NASA Astrophysics Data System (ADS)

    Parry, Roger Franklin

    The study of nuclei far from beta stability provides information on nuclear binding energies and nuclear structure. However, as one progresses away from the valley of stability, the associated half-lives and production cross sections decrease with increasing interference from the decays of adjacent nuclei. An experimental solution to these problems was the use of the He-jet fed on-line mass separator, RAMA. This instrument provided a fast and selective technique for the mass separation necessary for the investigation of exotic nuclei. Using this device, a beta decay Q-value study of the neutron deficient cesium isotopes, ('119-123)Cs, was conducted. Beta decay endpoint energy measurements of the neutron deficient cesium isotopes were done using an energy spectrum shape fitting technique. This was a departure from the typical method of endpoint energy analysis, the Fermi-Kurie plot. A discussion of the shape fitting procedure and its improved features are discussed. These beta endpoint measurements have led to total decay energies (Q(,EC)) of the neutron deficient ('119 -123)Cs isotopes. The total decay energies of ('122m)Cs (Q(,EC) = 6.95 (+OR-) 0.25 MeV) and ('119)Cs (Q(,EC) = 6.26 (+OR-) 0.29 MeV) were new measurements. The total decay energies of ('123)Cs (Q(,EC) = 4.05 (+OR-) 0.18 MeV), ('122g)Cs (Q(,EC) = 7.05 (+OR-) 0.18 MeV), ('121)Cs (Q(,EC) = 5.21 (+OR-) 0.22 MeV), and ('120)Cs (Q(,EC) = 7.38 (+OR -) 0.23 MeV) were measurements with significantly improved uncertainties as compared to the literature. Further, a combination of the energy levels derived from previous literature gamma-gamma coincident measurements and the experimental beta-coincident gamma decay energies has supported an improved level scheme for ('121)Xe and the proposal of three new energy levels in ('119)Xe. Comparison of the experimental cesium mass excesses (determined with our Q(,EC) values and known xenon mass excesses) with both the literature and theoretical predicted values showed

  7. Isotopic measurements of N2O in a hypersaline pond

    NASA Astrophysics Data System (ADS)

    Peters, B. D.; Casciotti, K.; Samarkin, V.; Joye, S. B.; Madigan, M.; Schutte, C.

    2012-12-01

    Production of nitrous oxide (N2O) in aquatic environments has often been attributed to biological processes. However, reports of abiotic mechanisms of N2O production have suggested that such processes may be substantial in Antarctic Dry Valley soils. It has been proposed that the reduction of nitrate (NO3-) and nitrite (NO2-) coupled to Fe (II) oxidation can produce N2O with a characteristic site preference (SP), where SP is defined as the difference in nitrogen isotope ratio between the center and outside nitrogen atoms in the linear N2O molecule. The current study uses isotopic measurements of N2O, NO2-, and NO3- to examine N2O production mechanisms in Don Juan Pond (DJP), a hypersaline pond in the McMurdo Dry Valleys, Antarctica. [NO3-] and [NO2-] in DJP brine were quite high, ranging from 6,238 to 7,719μM and 23 to 36μM, respectively. N2O samples from pond water (brine) yielded δ15Nbulk of -38±1‰, δ18O of +60±2‰, and SP of +1±7‰. Gas collected from soil had similar N2O isotope ratios, with δ15Nbulk of -45±4‰, δ18O of +56±3‰, and SP of +6±1‰. These field measurements were interpreted using a two end member mixing model, in which the measured N2O was assumed to be a mixture between atmospheric N2O and N2O from a local source. Using the three isotope systems (δ15Nbulk, δ18O, and SP), a series of four equations were constructed with five unknowns: δ15Nbulk, δ18O, and SP of the source, and the fractional contributions of the local source and atmospheric N2O. Solving the equations required an assumption about one of the five unknowns. To do this, we used data from laboratory experiments carried out with sterile brine and DJP soil in order to provide an estimate of the N2O isotope signature of the abiotic source. DJP brine and soil measurements gave similar model results, and thus only results using DJP soil measurements are reported here. Assuming δ18O of the unknown local source is near +82‰(from abiotic laboratory experiments), then

  8. Mobile measurement of methane: plumes, isotopes and inventory verification

    NASA Astrophysics Data System (ADS)

    Lowry, D.; Zazzeri, G.; Fisher, R. E.; France, J.; Al-Shalaan, A.; Lanoisellé, M.; Nisbet, E. G.

    2015-12-01

    Since 2013 the RHUL group has been identifying methane plumes from major UK sources using a Picarro 2301 coupled to the A0941 mobile module. Once identified the plumes have been sampled by filling Tedlar or Flexfoil bags for later carbon isotopic analysis by high-precision IRMS. This method has ben successfully deployed to isotopically characterize the main anthropogenic methane emitters in the UK (natural gas, coal, landfill, wastewater treatment, cattle; Zazzeri et al., 2015) and during overseas campaigns in eastern Australia (coal, cattle, legacy gas wells) and Kuwait (landfill, wastewater treatment, oil refineries, cattle, camels). This has identified strong similarities of isotopic signature for some sources (landfill, cattle), but large variations for others (natural gas, coal), which must be isotopically resolved at regional scale. Both landfill and natural gas emissions in SE England have tightly-constrained δ13C signatures, averaging -58 ± 3‰ and -36 ± 2‰, respectively, the latter being characteristic of homogenised North Sea gas supply. In contrast, signatures for coal mines in England and Wales fall in a range of 51.2 ± 0.3‰ to 30.9 ± 1.4‰, but can be tightly constrained by region. On a local scale in west London, repeat surveys in the boroughs of Hounslow and Runnymede have been made for comparison with the latest 1x1 km grid UK inventories for 2009 and 2012, which are subdivided by UNECE categories. An excess methane map can be derived for comparison with inventory emissions maps by identifying daily background and binning the excess values from mobile measurements by grid-square. This shows that the spatial distribution of emissions in the UK 2012 inventory is a big improvement on that of 2009. It also suggests that there is an overestimation of emissions from old landfills (closed before 2000 and reliant on a topsoil cap for oxidation), and an underestimation on emissions from currently active landfill cells. Zazzeri, G. et al. (2015

  9. Measurement of picosecond lifetimes in neutron-rich Xe isotopes

    NASA Astrophysics Data System (ADS)

    Ilieva, S.; Kröll, Th.; Régis, J.-M.; Saed-Samii, N.; Blanc, A.; Bruce, A. M.; Fraile, L. M.; de France, G.; Hartig, A.-L.; Henrich, C.; Ignatov, A.; Jentschel, M.; Jolie, J.; Korten, W.; Köster, U.; Lalkovski, S.; Lozeva, R.; Mach, H.; Mǎrginean, N.; Mutti, P.; Paziy, V.; Regan, P. H.; Simpson, G. S.; Soldner, T.; Thürauf, M.; Ur, C. A.; Urban, W.; Warr, N.

    2016-09-01

    Background: Lifetimes of nuclear excited states in fission fragments have been studied in the past following isotope separation, thus giving access mainly to the fragments' daughters and only to long-lived isomeric states in the primary fragments. For the first time now, short-lived excited states in the primary fragments, produced in neutron-induced prompt fission of 235U and 241Pu, were studied within the EXILL&FATIMA campaign at the intense neutron-beam facility of the Institute Laue-Langevin in Grenoble. Purpose: We aim to investigate the quadrupole collective properties of neutron-rich even-even 138,140,142Xe isotopes lying between the double shell closure N =82 and Z =50 and a deformed region with octupole collectivity. Method: The γ rays emitted from the excited fragments were detected with a mixed array consisting of 8 HPGe EXOGAM Clover detectors (EXILL) and 16 LaBr3(Ce) fast scintillators (FATIMA). The detector system has the unique ability to select the interesting fragment making use of the high resolution of the HPGe detectors and determine subnanosecond lifetimes using the fast scintillators. For the analysis the generalized centroid difference method was used. Results: We show that quadrupole collectivity increases smoothly with increasing neutron number above the closed N =82 neutron shell. Our measurements are complemented by state-of-the-art theory calculations based on shell-model descriptions. Conclusions: The observed smooth increase in quadrupole collectivity is similar to the evolution seen in the measured masses of the xenon isotopic chain and is well reproduced by theory. This behavior is in contrast to higher Z even-even nuclei where abrupt change in deformation occurs around N =90 .

  10. Rb, Sr and strontium isotopic composition, K/Ar age and large ion lithophile trace element abundances in rocks and glasses from the Wanapitei Lake impact structure

    NASA Technical Reports Server (NTRS)

    Winzer, S. R.; Lum, R. K. L.; Schuhmann, S.

    1976-01-01

    Shock metamorphosed rocks and shock-produced melt glasses from the Wanapitei Lake impact structure have been examined petrographically and by electron microprobe. Eleven clasts exhibiting varying degrees of shock metamorphism and eight impact-produced glasses have been analyzed for Rb, Sr and Sr isotopic composition. Five clasts and one glass have also been analyzed for large ion lithophile (LIL) trace element abundances including Li, Rb, Sr, and Ba and the REE's. The impact event forming the Wanapitei Lake structure occurred 37 m.y. ago based on K/Ar dating of glass and glassy whole-rock samples. Rb/Sr isotopic dating failed to provide a meaningful whole-rock or internal isochron. The isotopic composition of the glasses can be explained by impact-produced mixing and melting of metasediments.

  11. Iron and Nickel Isotopic Compositions of Presolar Silicon Carbide Grains from AGB Stars Measured with CHILI

    NASA Astrophysics Data System (ADS)

    Trappitsch, R.; Stephan, T.; Davis, A. M.; Pellin, M. J.; Savina, M. R.; Gyngard, F.; Bisterzo, S.; Gallino, R.; Dauphas, N.

    2016-08-01

    Simultaneous iron and nickel isotopic studies in presolar SiC mainstream grains measured on CHILI show the expected AGB star anomalies in the neutron-rich isotopes. Neutron-poor isotopes are dominated by GCE and show clear correlations with silicon.

  12. Determining the geochemical structure of the mantle from surface isotope distribution patterns? Insights from Ne and He isotopes and abundance ratios

    NASA Astrophysics Data System (ADS)

    Stroncik, N.; Niedermann, S.; Schnabel, E.; Erzinger, J.

    2011-12-01

    It is a common procedure among geochemists to use surface distribution patterns of e.g. Sr, Nd, Pb or He isotopes of lavas erupted at oceanic islands to map the geochemical structure of the Earth's mantle. Advances in noble gas mass spectrometry within the last decade resulting in an increasing availability of Ne isotope data sets allow us to test the strength of this approach. 4He and 21Ne are coupled through the same parent nuclides and therefore should show analogous isotope distribution patterns. Here we present He and Ne fusion data of fresh olivines derived from Big Island, Hawaii, together with He and Ne fusion data of fresh glasses from the Easter Seamount Chain (ESC), indicating that the observed isotope distribution patterns are mainly controlled by melting and shallow mixing processes. He isotopic ratios of the investigated olivines vary from MORB-like (8 ± 1 RA) to ratios more typical for a primitive mantle source (up to 20 and 26 RA for Hawaii and the ESC, respectively; RA = atmospheric 3He/4He ratio of 1.39 x 10-6). In contrast, all Ne isotope data plot within error limits along the Loihi-Kilauea line in a Ne three-isotope diagram. The Loihi-Kilauea line is regarded to be typical for a primitive mantle source. Thus, the Ne isotope data are inconsistent with any kind of zoned plume model or even a heterogeneous mantle source. The combined He and Ne data show that these He and Ne isotope systematics are produced by a pre-degassing fractionation process and subsequent melt mixing. Basically, this process causes a He deficit in melts generated by the plume, as shown by 3He/22NeS below current estimates of solar or planetary composition and 4He/21Ne* lower than the production ratio, making the He isotopic composition more susceptible to changes than the Ne isotopic composition. This can best be explained by a model in which He is fractionated from Ne during formation of melts from a plume (or enriched parts of a plume) at low melting degrees, which

  13. Evolution, Abundance and Biocalcification of Calcareous Nannoplankton During the Aptian (Early Cretaceous): Causes and Consequences for C Isotopic Anomalies, Climate Changes and the Carbon Cycle.

    NASA Astrophysics Data System (ADS)

    Erba, E.

    2005-12-01

    The mid Cretaceous is marked by extreme greenhouse conditions, coeval with emplacement of large igneous provinces, C isotopic anomalies, major changes in structure and composition of the oceans, and accelerated rates in the evolutionary history of calcareous plankton. The Aptian is a crucial interval to decipher links between biotic evolution and environmental pressure: it is appealing for understanding nannofloral biocalcification and feedbacks in the carbonate system and in the global carbon cycle. Ontong Java, Manihiki and Kerguelen Plateaus formed in the Aptian affecting the ocean-atmosphere system with excess CO2, changes in Ca2+ and Mg2+ concentrations, and varying nutrient cycling. Two large C isotopic anomalies are associated with episodes of prolonged high primary productivity, changes in alkality, global warming and cooling, anoxia, speciations and extinctions in planktonic communities. Nannofossil diversity, abundance and biocalcification are quantified in continuous, complete, pelagic sections to derive biosphere-geosphere interactions at short and long time scales. The early Aptian C isotopic anomaly interrupts a speciation episode in calcareous nannoplankton paralleled by a drastic reduction in nannofossil paleofluxes culminating in the nannoconid crisis preceding the Oceanic Anoxic Event 1a and the negative C isotopic spike linked to clathrate melting presumably triggered by the thermal maximum at the onset of the mid Cretaceous greenhouse climate. No extinctions are recorded. In the early late Aptian resumption of nannoconid production and appearance of several taxa are coeval with a return to normal C isotopic values. The occurrence of calpionellids and diversified planktonic foraminifers indicate successful biocalcification and restoration of the thermocline. In the late Aptian a drop in nannofossil abundance and accelerated extinction rates are associated with another C isotopic excursion under cool conditions possibly due to a prolonged volcanic

  14. Beta-decay measurements of neutron-deficient cesium isotopes

    SciTech Connect

    Parry, R.F.

    1983-03-01

    Beta decay endpoint energy measurements of the neutron deficient cesium isotopes were done using an energy spectrum shape fitting technique. This was a departure from the typical method of endpoint energy analysis, the Fermi-Kurie plot. A discussion of the shape fitting procedure and its improved features are discussed. These beta endpoint measurements have led to total decay energies (Q/sub EC/) of the neutron deficient /sup 119/ /sup 123/Cs isotopes. The total decay energies of /sup 122m/Cs (Q/sub EC/ = 6.95 +- 0.25 MeV) and /sup 119/Cs (Q/sub EC/ = 6.26 +- 0.29 MeV) were new measurements. The total decay energies of /sup 123/Cs (Q/sub EC/ = 4.05 +- 0.18 MeV), /sup 122g/Cs (Q/sub EC/ = 7.05 +- 0.18 MeV), /sup 121/Cs (Q/sub EC/ = 5.21 +- 0.22 MeV), and /sup 120/Cs (Q/sub EC/ = 7.38 +- 0.23 MeV) were measurements with significantly improved uncertainties as compared to the literature. Further, a combination of the energy levels derived from previous literature gamma-gamma coincident measurements and the experimental beta-coincident gamma decay energies has supported an improved level scheme for /sup 121/Xe and the proposal of three new energy levels in /sup 119/Xe. Comparison of the experimental cesium mass excesses (determined with our Q/sub EC/ values and known xenon mass excesses) with both the literature and theoretical predicted values showed general agreement except for /sup 120/Cs. Possible explanations for this deviation are discussed.

  15. Silicon isotope ratio measurements by inductively coupled plasma tandem mass spectrometry for alteration studies of nuclear waste glasses.

    PubMed

    Gourgiotis, Alkiviadis; Ducasse, Thomas; Barker, Evelyne; Jollivet, Patrick; Gin, Stéphane; Bassot, Sylvain; Cazala, Charlotte

    2017-02-15

    High-level, long-lived nuclear waste arising from spent fuel reprocessing is vitrified in silicate glasses for final disposal in deep geologic formations. In order to better understand the mechanisms driving glass dissolution, glass alteration studies, based on silicon isotope ratio monitoring of (29)Si-doped aqueous solutions, were carried out in laboratories. This work explores the capabilities of the new type of quadrupole-based ICP-MS, the Agilent 8800 tandem quadrupole ICP-MS/MS, for accurate silicon isotope ratio determination for alteration studies of nuclear waste glasses. In order to avoid silicon polyatomic interferences, a new analytical method was developed using O2 as the reaction gas in the Octopole Reaction System (ORS), and silicon isotopes were measured in mass-shift mode. A careful analysis of the potential polyatomic interferences on SiO(+) and SiO2(+) ion species was performed, and we found that SiO(+) ion species suffer from important polyatomic interferences coming from the matrix of sample and standard solutions (0.5M HNO3). For SiO2(+), no interferences were detected, and thus, these ion species were chosen for silicon isotope ratio determination. A number of key settings for accurate isotope ratio analysis like, detector dead time, integration time, number of sweeps, wait time offset, memory blank and instrumental mass fractionation, were considered and optimized. Particular attention was paid to the optimization of abundance sensitivity of the quadrupole mass filter before the ORS. We showed that poor abundance sensitivity leads to a significant shift of the data away from the Exponential Mass Fractionation Law (EMFL) due to the spectral overlaps of silicon isotopes combined with different oxygen isotopes (i.e. (28)Si(16)O(18)O(+), (30)Si(16)O(16)O(+)). The developed method was validated by measuring a series of reference solutions with different (29)Si enrichment. Isotope ratio trueness, uncertainty and repeatability were found to be <0

  16. Strong Coupling of Shoot Assimilation and Soil Respiration during Drought and Recovery Periods in Beech As Indicated by Natural Abundance δ(13)C Measurements.

    PubMed

    Blessing, Carola H; Barthel, Matti; Gentsch, Lydia; Buchmann, Nina

    2016-01-01

    Drought down-regulates above- and belowground carbon fluxes, however, the resilience of trees to drought will also depend on the speed and magnitude of recovery of these above- and belowground fluxes after re-wetting. Carbon isotope composition of above- and belowground carbon fluxes at natural abundance provides a methodological approach to study the coupling between photosynthesis and soil respiration (SR) under conditions (such as drought) that influence photosynthetic carbon isotope discrimination. In turn, the direct supply of root respiration with recent photoassimilates will impact on the carbon isotope composition of soil-respired CO2. We independently measured shoot and soil CO2 fluxes of beech saplings (Fagus sylvatica L.) and their respective δ(13)C continuously with laser spectroscopy at natural abundance. We quantified the speed of recovery of drought stressed trees after re-watering and traced photosynthetic carbon isotope signal in the carbon isotope composition of soil-respired CO2. Stomatal conductance responded strongly to the moderate drought (-65%), induced by reduced soil moisture content as well as increased vapor pressure deficit. Simultaneously, carbon isotope discrimination decreased by 8‰, which in turn caused a significant increase in δ(13)C of recent metabolites (1.5-2.5‰) and in δ(13)C of SR (1-1.5‰). Generally, shoot and soil CO2 fluxes and their δ(13)C were in alignment during drought and subsequent stress release, clearly demonstrating a permanent dependence of root respiration on recently fixed photoassimilates, rather than on older reserves. After re-watering, the drought signal persisted longer in δ(13)C of the water soluble fraction that integrates multiple metabolites (soluble sugars, amino acids, organic acids) than in the neutral fraction which represents most recently assimilated sugars or in the δ(13)C of SR. Nevertheless, full recovery of all aboveground physiological variables was reached within 4 days - and

  17. Simultaneous measurements of stable water isotopes in near-surface vapor and precipitation to constrain below-cloud processes

    NASA Astrophysics Data System (ADS)

    Graf, Pascal; Sodemann, Harald; Pfahl, Stephan; Schneebeli, Marc; Ventura, Jordi Figueras i.; Leuenberger, Andreas; Grazioli, Jacopo; Raupach, Tim; Berne, Alexis; Wernli, Heini

    2016-04-01

    Present-day observations of stable water isotopes (SWI) in precipitation on monthly time scales are abundant and the processes governing the variation of SWI on these time scales have been investigated by many studies. However, also on much shorter time scales of hours mesoscale meteorological processes lead to significant variations of SWIs, which are important to understand. There are only few studies investigating the variations of SWI on this short time scale, for which, e.g., frontal dynamics, convection and cloud microphysics play an essential role. In particular, the isotopic composition of both near-surface vapor and precipitation is significantly influenced by below-cloud processes that include precipitation evaporation and isotopic exchange between falling precipitation and surrounding vapor. In this study, simultaneous measurements of SWI in near-surface vapor and precipitation with high (sub-hourly) temporal resolution in combination with observational data from radars, disdrometers, radiosondes and standard meteorological instruments are used for a detailed analysis of the relative importance of below-cloud and in-cloud (i.e., precipitation formation) processes during the course of three rain events in Switzerland in spring 2014. Periods are identified when the isotopic composition of near-surface vapor and equilibrium vapor above liquid rain drops agree and when they differ due to either evaporation of precipitation or incomplete equilibration of precipitation with surrounding vapor. These findings are verified by the supporting observational data. In addition, calculations with a simple rain-shaft model fed with observational data are compared to the actual isotopic composition of precipitation. This combination of isotope measurements and model calculations allows us to test the sensitivity of the precipitation isotope signal to rain intensity, drop-size distribution and temperature and humidity profiles.

  18. 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.

  19. 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 A r(E) and its uncertainty U[Ar(E)] recommended by CAWIA in 2001. ?? 2005 American Institute of Physics.

  20. Evidence from carbon isotope measurements for diverse origins of sedimentary hydrocarbons

    NASA Technical Reports Server (NTRS)

    Freeman, K. H.; Hayes, J. M.; Trendel, J. M.; Albrecht, P.

    1990-01-01

    The organic matter found in sedimentary rocks must derive from many sources; not only from ancient primary producers but also from consumers and secondary producers. In all of these organisms, isotope effects can affect the abundance and distribution of 13C in metabolites. Here, by using an improved form of a previously described technique in which the effluent of a gas chromatograph is continuously analysed isotopically, we report evidence of the diverse origins of sedimentary organic matter. The record of 13C abundances in sedimentary carbonate and total organic carbon can be interpreted in terms of variations in the global carbon cycle. Our results demonstrate, however, that isotope variations within sedimentary organic mixtures substantially exceed those observed between samples of total organic carbon. Resolution of isotope variations at the molecular level offers a new and convenient means of refining views both of localized palaeoenvironments and of control mechanisms within the global carbon cycle.

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

    NASA Technical Reports Server (NTRS)

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

    2011-01-01

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

  2. Determining the Local Abundance of Martian Methane and its 13-C/l2-C and D/H Isotopic Ratios for Comparison with Related Gas and Soil Analysis on the 2011 Mars Science Laboratory (MSL) Mission

    NASA Technical Reports Server (NTRS)

    Webster, Christopher R.; Mahaffy, Paul R.

    2011-01-01

    Understanding the origin of Martian methane will require numerous complementary measurements from both in situ and remote sensing investigations and laboratory work to correlate planetary surface geophysics with atmospheric dynamics and chemistry. Three instruments (Quadrupole Mass Spectrometer (QMS), Gas Chromatograph (GC) and Tunable Laser Spectrometer (TLS)) with sophisticated sample handling and processing capability make up the Sample Analysis at Mars (SAM) analytical chemistry suite on NASA s 2011 Mars Science Laboratory (MSL) Mission. Leveraging off the SAM sample and gas processing capability that includes methane enrichment, TLS has unprecedented sensitivity for measuring absolute methane (parts-per-trillion), water, and carbon dioxide abundances in both the Martian atmosphere and evolved from heated soil samples. In concert with a wide variety of associated trace gases (e.g. SO2, H2S, NH3, higher hydrocarbons, organics, etc.) and other isotope ratios measured by SAM, TLS will focus on determining the absolute abundances of methane, water and carbon dioxide, and their isotope ratios: 13C/12C and D/H in methane; 13C/12C and 18O/17O/16O in carbon dioxide; and 18O/17O/16O and D/H in water. Measurements near the MSL landing site will be correlated with satellite (Mars Express, Mars 2016) and ground-based observations.

  3. New Half-lives of r-process Zn and Ga Isotopes Measured with Electromagnetic Separation

    SciTech Connect

    Madurga, M; Surman, Rebecca; Borzov, Ivan N; Grzywacz, R.; Rykaczewski, Krzysztof Piotr; Gross, Carl J; Miller, D; Stracener, Daniel W; Batchelder, Jon Charles; Brewer, N.T.; Cartegni, L.; Hamilton, J. H.; Hwang, J. K.; Liu, S. H.; Ilyushkin, S.; Karny, M.; Korgul, A.; Krolas, W.; Kuzniak, A.; Mazzocchi, C.; Mendez, II, Anthony J; Miernik, K.; Padgett, Stephen; Paulauskas, S.; Ramayya, A. V.; Winger, J. A.; Wolinska-Cichocka, Marzena; Zganjar, E. F.

    2012-01-01

    The {beta} decays of neutron-rich nuclei near the doubly magic {sup 78}Ni were studied at the Holifield Radioactive Ion Beam Facility using an electromagnetic isobar separator. The half-lives of {sup 82}Zn (228 {+-} 10 ms), {sup 83}Zn (117 {+-} 20 ms), and {sup 85}Ga (93 {+-} 7 ms) were determined for the first time. These half-lives were found to be very different from the predictions of the global model used in astrophysical simulations. A new calculation was developed using the density functional model, which properly reproduced the new experimental values. The robustness of the new model in the {sup 78}Ni region allowed us to extrapolate data for more neutron-rich isotopes. The revised analysis of the rapid neutron capture process in low entropy environments with our new set of measured and calculated half-lives shows a significant redistribution of predicted isobaric abundances strengthening the yield of A > 140 nuclei.

  4. Evaluating microbial carbon sources in Athabasca oil sands tailings ponds using natural abundance stable and radiocarbon isotopes

    NASA Astrophysics Data System (ADS)

    Ahad, J. M.; Pakdel, H.

    2013-12-01

    Natural abundance stable (δ13C) and radiocarbon (Δ14C) isotopes of phospholipid fatty acids (PLFAs) were used to evaluate the carbon sources utilized by the active microbial populations in surface sediments from Athabasca oil sands tailings ponds. The absence of algal-specific PLFAs at three of the four sites investigated, in conjunction with δ13C signatures for PLFAs that were generally within ~3‰ of that reported for oil sands bitumen (~ -30‰), indicated that the microbial communities growing on petroleum constituents were dominated by aerobic heterotrophs. The Δ14C values of PLFAs ranged from -906 to -586‰ and pointed to a significant uptake of fossil carbon (up to ~90% of microbial carbon derived from petroleum), particularly in PLFAs (e.g., cy17:0 and cy19:0) often associated with petroleum hydrocarbon degrading bacteria. The comparatively higher levels of 14C in other, less specific PLFAs (e.g., 16:0) indicated the preferential uptake of younger organic matter by the general microbial population (~50-80% of microbial carbon derived from petroleum). Since the main carbon pools in tailings sediment were essentially 'radiocarbon dead' (i.e., no detectable 14C), the principal source for this modern carbon is considered to be the Athabasca River, which provides the bulk of the water used in the bitumen extraction process. The preferential uptake of the minor amount of young and presumably more biodegradable material present in systems otherwise dominated by recalcitrant petroleum constituents has important implications for remediation strategies. On the one hand, it implies that mining-related organic contaminants could persist in the environment long after tailings pond reclamation has begun. Alternatively, it may be that the young, labile organic matter provided by the Athabasca River plays an important role in stimulating or supporting the microbial utilization of petroleum carbon in oil sands tailings ponds via co-metabolism or priming processes

  5. A century of progress in the sciences due to atomic weight and isotopic composition measurements.

    PubMed

    De Laeter, J R; Peiser, H S

    2003-01-01

    Even before the 20th century, a consistent set of internationally accepted atomic weights was an important objective of the scientific community because of the fundamental importance of these values to science, technology and trade. As the 20th century progressed, physicists, geoscientists, and metrologists collaborated with chemists to revolutionize the science of atomic weights. At the beginning of the century, atomic weights were determined from mass relationships between chemical reactants and products of known stoichiometry. They are now derived from the measured isotopic composition of elements and the atomic masses of the isotopes. Accuracy in measuring atomic weights has improved continually, leading to the revelation of small but significant variations in the isotope abundances of many elements in their normal terrestrial occurrences caused by radioactivity and a variety of physicochemical and biochemical fractionation mechanisms. This atomic-weight variability has now been recognized as providing new scientific insights into and knowledge of the history of materials. Atomic weights, except those of the monoisotopic elements, are thus no longer regarded as "constants of nature". At the beginning of the 20th century, two scales for atomic weights were in common use: that based on the atomic weight of hydrogen being 1 and that based on the atomic weight of oxygen being 16. Atomic weights are now scaled to (12)C, which has the value 12 exactly. Accurate atomic weights of silicon, silver, and argon, have enabled the values of the Avogadro, Faraday and Universal Gas constants, respectively, to be established, with consequent effects on other fundamental constants.

  6. Nitrate dynamics in natural plants: insights based on the concentration and natural isotope abundances of tissue nitrate

    PubMed Central

    Liu, Xue-Yan; Koba, Keisuke; Makabe, Akiko; Liu, Cong-Qiang

    2014-01-01

    The dynamics of nitrate (NO−3), a major nitrogen (N) source for natural plants, has been studied mostly through experimental N addition, enzymatic assay, isotope labeling, and genetic expression. However, artificial N supply may not reasonably reflect the N strategies in natural plants because NO−3 uptake and reduction may vary with external N availability. Due to abrupt application and short operation time, field N addition, and isotopic labeling hinder the elucidation of in situ NO−3-use mechanisms. The concentration and natural isotopes of tissue NO−3 can offer insights into the plant NO−3 sources and dynamics in a natural context. Furthermore, they facilitate the exploration of plant NO−3 utilization and its interaction with N pollution and ecosystem N cycles without disturbing the N pools. The present study was conducted to review the application of the denitrifier method for concentration and isotope analyses of NO−3 in plants. Moreover, this study highlights the utility and advantages of these parameters in interpreting NO−3 sources and dynamics in natural plants. We summarize the major sources and reduction processes of NO−3 in plants, and discuss the implications of NO−3 concentration in plant tissues based on existing data. Particular emphasis was laid on the regulation of soil NO−3 and plant ecophysiological functions in interspecific and intra-plant NO−3 variations. We introduce N and O isotope systematics of NO−3 in plants and discuss the principles and feasibilities of using isotopic enrichment and fractionation factors; the correlation between concentration and isotopes (N and O isotopes: δ18O and Δ17O); and isotope mass-balance calculations to constrain sources and reduction of NO−3 in possible scenarios for natural plants are deliberated. Finally, we offer a preliminary framework of intraplant δ18O-NO−3 variation, and summarize the uncertainties in using tissue NO−3 parameters to interpret plant NO−3 utilization

  7. Nitrate dynamics in natural plants: insights based on the concentration and natural isotope abundances of tissue nitrate.

    PubMed

    Liu, Xue-Yan; Koba, Keisuke; Makabe, Akiko; Liu, Cong-Qiang

    2014-01-01

    The dynamics of nitrate (NO(-) 3), a major nitrogen (N) source for natural plants, has been studied mostly through experimental N addition, enzymatic assay, isotope labeling, and genetic expression. However, artificial N supply may not reasonably reflect the N strategies in natural plants because NO(-) 3 uptake and reduction may vary with external N availability. Due to abrupt application and short operation time, field N addition, and isotopic labeling hinder the elucidation of in situ NO(-) 3-use mechanisms. The concentration and natural isotopes of tissue NO(-) 3 can offer insights into the plant NO(-) 3 sources and dynamics in a natural context. Furthermore, they facilitate the exploration of plant NO(-) 3 utilization and its interaction with N pollution and ecosystem N cycles without disturbing the N pools. The present study was conducted to review the application of the denitrifier method for concentration and isotope analyses of NO(-) 3 in plants. Moreover, this study highlights the utility and advantages of these parameters in interpreting NO(-) 3 sources and dynamics in natural plants. We summarize the major sources and reduction processes of NO(-) 3 in plants, and discuss the implications of NO(-) 3 concentration in plant tissues based on existing data. Particular emphasis was laid on the regulation of soil NO(-) 3 and plant ecophysiological functions in interspecific and intra-plant NO(-) 3 variations. We introduce N and O isotope systematics of NO(-) 3 in plants and discuss the principles and feasibilities of using isotopic enrichment and fractionation factors; the correlation between concentration and isotopes (N and O isotopes: δ(18)O and Δ(17)O); and isotope mass-balance calculations to constrain sources and reduction of NO(-) 3 in possible scenarios for natural plants are deliberated. Finally, we offer a preliminary framework of intraplant δ(18)O-NO(-) 3 variation, and summarize the uncertainties in using tissue NO(-) 3 parameters to interpret

  8. Measurements of the Fe-group abundance in energetic solar particles

    NASA Technical Reports Server (NTRS)

    Bertsch, D. L.; Fichtel, C. E.; Pellerin, C. J.; Reames, D. V.

    1972-01-01

    The abundance of Fe-group nuclei in the energetic solar particles was measured twice in the 24 January 1971 event and once in the 2 September 1971 event. Including earlier results from the 2 September 1966 event, the Fe-group abundance was found to be in the range from 3% to 6% of the oxygen nuclei in the energy interval from 21 to 50 MeV/nucleon, in those events where the Fe-group abundance could be measured. Fe-nuclei have a different charge-to-mass ratio from that of the C, N, O nuclei, so small variations in the Fe abundance in solar particles are expected. In the three exposures where the statistics were adequate to construct an energy spectrum, the Fe-group nuclei were seen to have an energy/nucleon spectrum similar to that of the C, N, O nuclei; however, the energy/nucleon range was limited. The abundance for the Fe-group nuclei is consistent with the present solar spectroscopic abundance estimates.

  9. Actinide abundances in ordinary chondrites

    NASA Technical Reports Server (NTRS)

    Hagee, B.; Bernatowicz, T. J.; Podosek, F. A.; Johnson, M. L.; Burnett, D. S.

    1990-01-01

    Measurements of actinide and light REE (LREE) abundances and of phosphate abundances in equilibrated ordinary chondrites were obtained and were used to define the Pu abundance in the solar system and to determine the degree of variation of actinide and LREE abundances. The results were also used to compare directly the Pu/U ratio with the earlier obtained ratio determined indirectly, as (Pu/Nd)x(Nd/U), assuming that Pu behaves chemically as a LREE. The data, combined with high-accuracy isotope-dilution data from the literature, show that the degree of gram-scale variability of the Th, U, and LREE abundances for equilibrated ordinary chondrites is a factor of 2-3 for absolute abundances and up to 50 percent for relative abundances. The observed variations are interpreted as reflecting the differences in the compositions and/or proportions of solar nebula components accreted to ordinary chondrite parent bodies.

  10. Nicotine, acetanilide and urea multi-level 2H-, 13C- and 15N-abundance reference materials for continuous-flow isotope ratio mass spectrometry.

    PubMed

    Schimmelmann, Arndt; Albertino, Andrea; Sauer, Peter E; Qi, Haiping; Molinie, Roland; Mesnard, François

    2009-11-01

    Accurate determinations of stable isotope ratios require a calibration using at least two reference materials with different isotopic compositions to anchor the isotopic scale and compensate for differences in machine slope. Ideally, the delta values of these reference materials should bracket the isotopic range of samples with unknown delta values. While the practice of analyzing two isotopically distinct reference materials is common for water (VSMOW-SLAP) and carbonates (NBS 19 and L-SVEC), the lack of widely available organic reference materials with distinct isotopic composition has hindered the practice when analyzing organic materials by elemental analysis/isotope ratio mass spectrometry (EA-IRMS). At present only L-glutamic acids USGS40 and USGS41 satisfy these requirements for delta13C and delta15N, with the limitation that L-glutamic acid is not suitable for analysis by gas chromatography (GC). We describe the development and quality testing of (i) four nicotine laboratory reference materials for on-line (i.e. continuous flow) hydrogen reductive gas chromatography-isotope ratio mass-spectrometry (GC-IRMS), (ii) five nicotines for oxidative C, N gas chromatography-combustion-isotope ratio mass-spectrometry (GC-C-IRMS, or GC-IRMS), and (iii) also three acetanilide and three urea reference materials for on-line oxidative EA-IRMS for C and N. Isotopic off-line calibration against international stable isotope measurement standards at Indiana University adhered to the 'principle of identical treatment'. The new reference materials cover the following isotopic ranges: delta2H(nicotine) -162 to -45 per thousand, delta13C(nicotine) -30.05 to +7.72 per thousand, delta15N(nicotine) -6.03 to +33.62 per thousand; delta15N(acetanilide) +1.18 to +40.57 per thousand; delta13C(urea) -34.13 to +11.71 per thousand, delta15N(urea) +0.26 to +40.61 per thousand (recommended delta values refer to calibration with NBS 19, L-SVEC, IAEA-N-1, and IAEA-N-2). Nicotines fill a gap as

  11. Nicotine, acetanilide and urea multi-level2H-,13C- and15N-abundance reference materials for continuous-flow isotope ratio mass spectrometry

    USGS Publications Warehouse

    Schimmelmann, A.; Albertino, A.; Sauer, P.E.; Qi, H.; Molinie, R.; Mesnard, F.

    2009-01-01

    Accurate determinations of stable isotope ratios require a calibration using at least two reference materials with different isotopic compositions to anchor the isotopic scale and compensate for differences in machine slope. Ideally, the S values of these reference materials should bracket the isotopic range of samples with unknown S values. While the practice of analyzing two isotopically distinct reference materials is common for water (VSMOW-SLAP) and carbonates (NBS 19 and L-SVEC), the lack of widely available organic reference materials with distinct isotopic composition has hindered the practice when analyzing organic materials by elemental analysis/isotope ratio mass spectrometry (EA-IRMS). At present only L-glutamic acids USGS40 and USGS41 satisfy these requirements for ??13C and ??13N, with the limitation that L-glutamic acid is not suitable for analysis by gas chromatography (GC). We describe the development and quality testing of (i) four nicotine laboratory reference materials for on-line (i.e. continuous flow) hydrogen reductive gas chromatography-isotope ratio mass-spectrometry (GC-IRMS), (ii) five nicotines for oxidative C, N gas chromatography-combustion-isotope ratio mass-spectrometry (GC-C-IRMS, or GC-IRMS), and (iii) also three acetanilide and three urea reference materials for on-line oxidative EA-IRMS for C and N. Isotopic off-line calibration against international stable isotope measurement standards at Indiana University adhered to the 'principle of identical treatment'. The new reference materials cover the following isotopic ranges: ??2Hnicotine -162 to -45%o, ??13Cnicotine -30.05 to +7.72%, ?? 15Nnicotine -6.03 to +33.62%; ??15N acetanilide +1-18 to +40.57%; ??13Curea -34.13 to +11.71%, ??15Nurea +0.26 to +40.61% (recommended ?? values refer to calibration with NBS 19, L-SVEC, IAEA-N-1, and IAEA-N-2). Nicotines fill a gap as the first organic nitrogen stable isotope reference materials for GC-IRMS that are available with different ??13N

  12. Attogram measurement of rare isotopes by CW resonance ionization mass spectrometry

    SciTech Connect

    Bushaw, B.A.

    1992-05-01

    Three-color double-resonance ionization mass spectrometry, using two single-frequency cw dye lasers and a cw carbon dioxide laser, has been applied to the detection of attogram quantities of rare radionuclides. {sup 210}Pb has been measured in human hair and brain tissue samples to assess indoor radon exposure. Measurements on {sup 90}Sr have shown overall isotopic selectivity of greater than 10{sup 9} despite unfavorable isotope shifts relative to the major stable isotope, {sup 88}Sr.

  13. Using continuous underway isotope measurements to map water residence time in hydrodynamically complex tidal environments

    USGS Publications Warehouse

    Downing, Bryan D.; Bergamaschi, Brian; Kendall, Carol; Kraus, Tamara; Dennis, Kate J.; Carter, Jeffery A.; von Dessonneck, Travis

    2016-01-01

    Stable isotopes present in water (δ2H, δ18O) have been used extensively to evaluate hydrological processes on the basis of parameters such as evaporation, precipitation, mixing, and residence time. In estuarine aquatic habitats, residence time (τ) is a major driver of biogeochemical processes, affecting trophic subsidies and conditions in fish-spawning habitats. But τ is highly variable in estuaries, owing to constant changes in river inflows, tides, wind, and water height, all of which combine to affect τ in unpredictable ways. It recently became feasible to measure δ2H and δ18O continuously, at a high sampling frequency (1 Hz), using diffusion sample introduction into a cavity ring-down spectrometer. To better understand the relationship of τ to biogeochemical processes in a dynamic estuarine system, we continuously measured δ2H and δ18O, nitrate and water quality parameters, on board a small, high-speed boat (5 to >10 m s–1) fitted with a hull-mounted underwater intake. We then calculated τ as is classically done using the isotopic signals of evaporation. The result was high-resolution (∼10 m) maps of residence time, nitrate, and other parameters that showed strong spatial gradients corresponding to geomorphic attributes of the different channels in the area. The mean measured value of τ was 30.5 d, with a range of 0–50 d. We used the measured spatial gradients in both τ and nitrate to calculate whole-ecosystem uptake rates, and the values ranged from 0.006 to 0.039 d–1. The capability to measure residence time over single tidal cycles in estuaries will be useful for evaluating and further understanding drivers of phytoplankton abundance, resolving differences attributable to mixing and water sources, explicitly calculating biogeochemical rates, and exploring the complex linkages among time-dependent biogeochemical processes in hydrodynamically complex environments such as estuaries.

  14. Measurement of labile Cu in soil using stable isotope dilution and isotope ratio analysis by ICP-MS.

    PubMed

    Nolan, Annette L; Ma, Yibing; Lombi, Enzo; McLaughlin, Mike J

    2004-11-01

    Isotope dilution is a useful technique to measure the labile metal pool, which is the amount of metal in soil in rapid equilibrium (<7 days) with the soil solution. This is normally performed by equilibrating soil with a metal isotope, and sampling the labile metal pool by using an extraction (E value), or by growing plants (L value). For Cu, this procedure is problematic for E values, and impossible for L values, due to the short half-life of the 64Cu radioisotope (12.4 h), which makes access and handling very difficult. We therefore developed a technique using enriched 65Cu stable isotope and measurement of 63Cu/65Cu ratios by quadrupole inductively coupled plasma mass spectrometry (ICP-MS) to measure labile pools of Cu in soils using E value techniques. Mass spectral interferences in detection of 63Cu/65Cu ratios in soil extracts were found to be minimal. Isotope ratios determined by quadrupole ICP-MS compared well to those determined by high-resolution (magnetic sector) ICP-MS. E values determined using the stable isotope technique compared well to those determined using the radioisotope for both uncontaminated and Cu-contaminated soils.

  15. Ice core measurements of the isotopic composition of nitrate: new results and interpretation

    NASA Astrophysics Data System (ADS)

    Steig, E. J.; Hastings, M. G.; Alexander, B.; Jarvis, J. C.; Kunasek, S. C.

    2006-12-01

    Several fundamental questions about the magnitude of natural variability in the global nitrogen cycle, and the impact of human activities in the last century, remain open. For example, lakes around the world show significant declines in organic nitrogen isotope ratios but it remains unclear to what extent this reflects changed nitrate sources or in situ changes in lake biogeochemistry. It also remains unknown whether atmospheric NOx mixing ratios were significantly different during the last glacial period; because atmospheric NOx abundances influence methane oxidation chemistry, this may have implications for closure of the global methane budget. While ice core measurements of nitrate concentration demonstrate that human activity has at least doubled the concentration of nitrogen oxides in the atmosphere in the last century, more quantitative use of such data has proven difficult due to the variety of possible nitrate sources, the complex atmospheric chemistry, and the potential for post-depositional change. The utility of ice cores in elucidating past changes in the global nitrogen cycle may be greatly enhanced through the analysis of nitrate isotope ratios. Our work on ice cores is coupled with direct atmospheric measurements of gas-phase HNO3 and its precursors, and global modeling of isotope variations in reactive nitrogen species, reported elsewhere at this meeting. Here, we report on our ongoing analyses of nitrogen and oxygen isotope ratios from ice cores at South Pole, the WAIS Divide (site of the new US drilling effort in West Antarctica), GISP2, and a new 100-meter core from Summit, Greenland. Snow pit data demonstrate that changes in oxygen isotope ratios (δ18O and Δ17O [= δ17O -0.52*δ18O]) in nitrate can be related directly to changes in the ratio of gas phase ("daytime") vs. aqueous phase ("nighttime") chemistry in the production of nitrate in the atmosphere. Nitrogen isotope ratios (δ15N) are also affected by photochemistry, but variations in

  16. Measurements of the isotopic composition of solar energetic particles with the MAST instrument aboard the SAMPEX spacecraft

    NASA Astrophysics Data System (ADS)

    Williams, Daniel Leroy

    which occurred during periods of low to moderate counting rates, the probability of such coincidences could be reduced, and these tails could be effectively removed. The elemental composition was used to find and correct for the bias introduced by these restrictions.The energy spectra of the elements in each SEP event could be fit with exponentials in energy per nucleon, with a single, characteristic e-folding energy for each event. Such well-behaved spectra allowed elemental abundances to be calculated. These abundances exhibited a fractionation due to acceleration and propagation of the SEP source material, which could be ordered as a function of the charge to mass ratio of each element. The SEP source abundances exhibited a depletion of elements with a high first-ionization potential as compared to the composition of the solar photosphere, a phenomena which has been well-observed in SEP composition for many years. The depletion factor varied by a factor of ~2 between the two SEP events.The isotopic ratios of [...], [...], [...], [...] and [...] were found to be in generally good agreement with the solar system values of isotopic composition as tabulated by Anders and Grevesse (1989) based on terrestrial and meteoritic measurements. Earlier measurements of SEP isotopes found a [...] ratio which was ~80% higher than the [...] ratio measured in the solar wind, but close to the neon-A component found in meteorites, which had been adopted as the solar system standard by Cameron (1982). Our measurements of [...], however, are consistent with the [...] ratio found in the solar wind. This leads us to conclude that the underlying isotopic composition of the SEP source material is closer to that of the solar wind.There are only two cases in which the measured isotope ratios differ significantly from the Anders and Grevesse (1989) values, the [...] and the [...] ratio in the second SEP event, both of which are a factor of ~2 higher than the solar system value. There is no

  17. Determination of carbon isotopic measurement conditions for ceramide in skin using gas chromatography-combustion-isotope ratio mass spectrometry.

    PubMed

    Haraguchi, Hiroyuki; Yamada, Keita; Miyashita, Rumiko; Aida, Kazuhiko; Ohnishi, Masao; Gilbert, Alexis; Yoshida, Naohiro

    2014-01-01

    The ceramide (Cer) content of skin and glucosylceramide (GlcCer) intake affect skin moisture conditions, but their mutual relation in skin remains unclear. For clarification of that mutual relation, carbon stable isotopes ((12)C and (13)C) are useful as a tracer. However, carbon isotopic measurement has not been applied to the study of clarifying their skin moisturizing effects. Therefore, we used gas chromatography / combustion / isotope ratio mass spectrometry (GC-C-IRMS) to ascertain the appropriate conditions for carbon isotopic measurements using synthesized Cer (SCer) in substitution for very low concentrations of Cer in skin. SCer was derivatized to trimethylsilylated SCer (TMS-SCer) quantitatively using N-trimethylsilylimidazole (TMSI) depending on the amount of SCer. The derivatization rates were 75-85%. Excess TMSI was removed using three cycles of hexane-water distribution. Under these conditions, carbon isotopic measurements of TMS-SCer conducted using GC-C-IRMS showed high repeatability and good inter-day variation (S.D. < 0.3‰). The carbon stable isotope ratio value (δ(13)C) of SCer calculated using a mass balance equation was compared with δ(13)C of underivatized SCer, which was regarded as the actual δ(13)C of SCer obtained using sealed tube combustion method. The difference between the calculated δ(13)C of SCer and δ(13)C of the underivatized SCer depended on the TMSI reagent supplier and on the number of hydroxyl groups to be derivatized in SCer. For accurate δ(13)C of Cer in skin using GC-C-IRMS, the measured δ(13)C of a target TMS-Cer must be calculated using a correction factor representing the difference in δ(13)C of underivatized standard SCer from that of TMS-standard SCer having a structure resembling that of the target Cer in skin. In addition, we show that the same lot of TMSI reagent from a specific supplier must be used throughout the experiments.

  18. Continuous measurements of isotopic composition of water vapour on the East Antarctic Plateau

    NASA Astrophysics Data System (ADS)

    Casado, Mathieu; Landais, Amaelle; Masson-Delmotte, Valérie; Genthon, Christophe; Kerstel, Erik; Kassi, Samir; Arnaud, Laurent; Picard, Ghislain; Prie, Frederic; Cattani, Olivier; Steen-Larsen, Hans-Christian; Vignon, Etienne; Cermak, Peter

    2016-07-01

    Water stable isotopes in central Antarctic ice cores are critical to quantify past temperature changes. Accurate temperature reconstructions require one to understand the processes controlling surface snow isotopic composition. Isotopic fractionation processes occurring in the atmosphere and controlling snowfall isotopic composition are well understood theoretically and implemented in atmospheric models. However, post-deposition processes are poorly documented and understood. To quantitatively interpret the isotopic composition of water archived in ice cores, it is thus essential to study the continuum between surface water vapour, precipitation, surface snow and buried snow. Here, we target the isotopic composition of water vapour at Concordia Station, where the oldest EPICA Dome C ice cores have been retrieved. While snowfall and surface snow sampling is routinely performed, accurate measurements of surface water vapour are challenging in such cold and dry conditions. New developments in infrared spectroscopy enable now the measurement of isotopic composition in water vapour traces. Two infrared spectrometers have been deployed at Concordia, allowing continuous, in situ measurements for 1 month in December 2014-January 2015. Comparison of the results from infrared spectroscopy with laboratory measurements of discrete samples trapped using cryogenic sampling validates the relevance of the method to measure isotopic composition in dry conditions. We observe very large diurnal cycles in isotopic composition well correlated with temperature diurnal cycles. Identification of different behaviours of isotopic composition in the water vapour associated with turbulent or stratified regime indicates a strong impact of meteorological processes in local vapour/snow interaction. Even if the vapour isotopic composition seems to be, at least part of the time, at equilibrium with the local snow, the slope of δD against δ18O prevents us from identifying a unique origin leading

  19. The relative abundances of resolved l2CH2D2 and 13CH3D and mechanisms controlling isotopic bond ordering in abiotic and biotic methane gases

    NASA Astrophysics Data System (ADS)

    Young, E. D.; Kohl, I. E.; Lollar, B. Sherwood; Etiope, G.; Rumble, D.; Li (李姝宁), S.; Haghnegahdar, M. A.; Schauble, E. A.; McCain, K. A.; Foustoukos, D. I.; Sutclife, C.; Warr, O.; Ballentine, C. J.; Onstott, T. C.; Hosgormez, H.; Neubeck, A.; Marques, J. M.; Pérez-Rodríguez, I.; Rowe, A. R.; LaRowe, D. E.; Magnabosco, C.; Yeung, L. Y.; Ash, J. L.; Bryndzia, L. T.

    2017-04-01

    We report measurements of resolved 12CH2D2 and 13CH3D at natural abundances in a variety of methane gases produced naturally and in the laboratory. The ability to resolve 12CH2D2 from 13CH3D provides unprecedented insights into the origin and evolution of CH4. The results identify conditions under which either isotopic bond order disequilibrium or equilibrium are expected. Where equilibrium obtains, concordant Δ12CH2D2 and Δ13CH3D temperatures can be used reliably for thermometry. We find that concordant temperatures do not always match previous hypotheses based on indirect estimates of temperature of formation nor temperatures derived from CH4/H2 D/H exchange, underscoring the importance of reliable thermometry based on the CH4 molecules themselves. Where Δ12CH2D2 and Δ13CH3D values are inconsistent with thermodynamic equilibrium, temperatures of formation derived from these species are spurious. In such situations, while formation temperatures are unavailable, disequilibrium isotopologue ratios nonetheless provide novel information about the formation mechanism of the gas and the presence or absence of multiple sources or sinks. In particular, disequilibrium isotopologue ratios may provide the means for differentiating between methane produced by abiotic synthesis vs. biological processes. Deficits in 12CH2D2 compared with equilibrium values in CH4 gas made by surface-catalyzed abiotic reactions are so large as to point towards a quantum tunneling origin. Tunneling also accounts for the more moderate depletions in 13CH3D that accompany the low 12CH2D2 abundances produced by abiotic reactions. The tunneling signature may prove to be an important tracer of abiotic methane formation, especially where it is preserved by dissolution of gas in cool hydrothermal systems (e.g., Mars). Isotopologue signatures of abiotic methane production can be erased by infiltration of microbial communities, and Δ12CH2D2 values are a key tracer of microbial recycling.

  20. A solvent extraction technique for the isotopic measurement of dissolved copper in seawater.

    PubMed

    Thompson, Claire M; Ellwood, Michael J; Wille, Martin

    2013-05-02

    Stable copper (Cu) isotope geochemistry provides a new perspective for investigating and understanding Cu speciation and biogeochemical Cu cycling in seawater. In this work, sample preparation for isotopic analysis employed solvent-extraction with amino pyrollidine dithiocarbamate/diethyl dithiocarbamate (APDC/DDC), coupled with a nitric acid back-extraction, to concentrate Cu from seawater. This was followed by Cu-purification using anion-exchange. This straightforward technique is high yielding and fractionation free for Cu and allows precise measurement of the seawater Cu isotopic composition using multi-collector inductively coupled plasma mass-spectrometry. A deep-sea profile measured in the oligotrophic north Tasman Sea shows fractionation in the Cu isotopic signature in the photic zone but is relatively homogenised at depth. A minima in the Cu isotopic profile correlates with the chlorophyll a maximum at the site. These results indicate that a range of processes are likely to fractionate stable Cu isotopes in seawater.

  1. Isotopic composition of atmospheric moisture from pan water evaporation measurements.

    PubMed

    Devi, Pooja; Jain, Ashok Kumar; Rao, M Someshwer; Kumar, Bhishm

    2015-01-01

    A continuous and reliable time series data of the stable isotopic composition of atmospheric moisture is an important requirement for the wider applicability of isotope mass balance methods in atmospheric and water balance studies. This requires routine sampling of atmospheric moisture by an appropriate technique and analysis of moisture for its isotopic composition. We have, therefore, used a much simpler method based on an isotope mass balance approach to derive the isotopic composition of atmospheric moisture using a class-A drying evaporation pan. We have carried out the study by collecting water samples from a class-A drying evaporation pan and also by collecting atmospheric moisture using the cryogenic trap method at the National Institute of Hydrology, Roorkee, India, during a pre-monsoon period. We compared the isotopic composition of atmospheric moisture obtained by using the class-A drying evaporation pan method with the cryogenic trap method. The results obtained from the evaporation pan water compare well with the cryogenic based method. Thus, the study establishes a cost-effective means of maintaining time series data of the isotopic composition of atmospheric moisture at meteorological observatories. The conclusions drawn in the present study are based on experiments conducted at Roorkee, India, and may be examined at other regions for its general applicability.

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

    NASA Astrophysics Data System (ADS)

    Kerstel, E.; Gianfrani, L.

    2008-09-01

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

  3. Monte Carlo method for calculating oxygen abundances and their uncertainties from strong-line flux measurements

    NASA Astrophysics Data System (ADS)

    Bianco, F. B.; Modjaz, M.; Oh, S. M.; Fierroz, D.; Liu, Y. Q.; Kewley, L.; Graur, O.

    2016-07-01

    We present the open-source Python code pyMCZ that determines oxygen abundance and its distribution from strong emission lines in the standard metallicity calibrators, based on the original IDL code of Kewley and Dopita (2002) with updates from Kewley and Ellison (2008), and expanded to include more recently developed calibrators. The standard strong-line diagnostics have been used to estimate the oxygen abundance in the interstellar medium through various emission line ratios (referred to as indicators) in many areas of astrophysics, including galaxy evolution and supernova host galaxy studies. We introduce a Python implementation of these methods that, through Monte Carlo sampling, better characterizes the statistical oxygen abundance confidence region including the effect due to the propagation of observational uncertainties. These uncertainties are likely to dominate the error budget in the case of distant galaxies, hosts of cosmic explosions. Given line flux measurements and their uncertainties, our code produces synthetic distributions for the oxygen abundance in up to 15 metallicity calibrators simultaneously, as well as for E(B- V) , and estimates their median values and their 68% confidence regions. We provide the option of outputting the full Monte Carlo distributions, and their Kernel Density estimates. We test our code on emission line measurements from a sample of nearby supernova host galaxies (z < 0.15) and compare our metallicity results with those from previous methods. We show that our metallicity estimates are consistent with previous methods but yield smaller statistical uncertainties. It should be noted that systematic uncertainties are not taken into account. We also offer visualization tools to assess the spread of the oxygen abundance in the different calibrators, as well as the shape of the estimated oxygen abundance distribution in each calibrator, and develop robust metrics for determining the appropriate Monte Carlo sample size. The code

  4. Heavy Atom Labeled Nucleotides for Measurement of Kinetic Isotope Effects

    PubMed Central

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

    2015-01-01

    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. 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 site-specifically enriched for heavy oxygen and nitrogen and their application in heavy atom isotope effect studies. PMID:25828952

  5. The Effect of Isotopic Composition on the Uncertainty of Routine Metal Mass Concentration Measurements in Ambient Air

    PubMed Central

    Brown, Richard J. C.; Goddard, Sharon L.; Brown, Andrew S.; Yardley, Rachel E.

    2008-01-01

    The main sources of uncertainty encountered during the analysis of the mass concentration of metals in ambient air as part of the operation of the UK Heavy Metals Monitoring Network are presented. It is observed that the uncertainty contribution from possible variation in the isotopic composition of the sample depends on the element in question, but can be significant (e.g., for Pb, Cd, and Hg). The working curve method for the ICP-MS analysis of metals in solution, with a low resolution, high throughput instrument measuring at one m/z ratio per element, relies on the relative abundance of the isotopes under consideration being the same in both the sample and the calibration solution. Calculation of the uncertainty in this analysis assumes that the isotopic composition variation within the sample and calibration solution is limited to a defined range. Therefore, in order to confirm the validity of this quantification methodology and its uncertainty budget, the isotopic composition of the calibration standards used for quantification has been determined. The results of this analysis are presented here. PMID:19223968

  6. Precision Oxygen Isotope Measurements of Two C-Rich Hydrated Interplanetary Dust Particles

    NASA Technical Reports Server (NTRS)

    Snead, C. J.; Keller, L. P.; McKeegan, K. D.; Messenger, S.

    2016-01-01

    SMOW (minus 33 plus or minus 19 per mille, 1 plus or minus 14 per mille 1 sigma), several delta D-rich hotspots were also identified, reaching 2000 per mille. As shown in Fig. 1, these hotspots are clearly associated with discrete carbonaceous inclusions that are akin to nanoglobules found in many meteorites and other IDPs. Oxygen Isotopes. Results of the oxygen isotope measurements are shown in Figure 1. The oxygen isotope composition for L2079C35 was delta 18O equals plus11.6 plus or minus 1.9per mille, delta 17O equals plus 7.9 plus or minus 1.9per mille (2 standard errors). The oxygen isotope composition for L2083D46 was delta 18O equals minus 8.1 plus or minus 1.9 per mille, delta 17O equals minus 6.4 plus or minus 3.1 per mille (2 standard errors). The oxygen isotope composition for L2083E46 was delta 18O equals plus 12.0 plus or minus 1.9 per mille, delta 17O equals plus 9.2 plus or minus 2.0 per mille (2 standard errors). Discussion: Despite mineralogical similarities to highly aqueously altered carbonaceous chondrites, the hydrated IDPs we analyzed have oxygen isotopic compositions that are distinct from matrix materials in the CI, CM, and CR chondrites. The IDPs plot along the Young-Russell line, with delta 17O values for C35 and E46 suggestive of interaction with a 16O-poor reservoir. However, we have thus far not observed evidence of extreme 16O-poor reservoirs expected from self-shielding models and observed in Acfer 094 simplectite. The high carbon contents of the IDPs also set them apart from known meteoritic samples. The lack of atmospheric entry heating effects are consistent with low encounter velocities and suggest either an asteroidal source, or a low inclination, low eccentricity cometary origin. Conclusions: The unusual oxygen isotopic compositions, high carbon contents, and the abundance of Drich nanoglobules, together, suggest that the high-carbon, hydrated IDPs are derived from a primitive source that is not yet represent ed in meteorite

  7. Can measures of prey availability improve our ability to predict the abundance of large marine predators?

    PubMed

    Wirsing, Aaron J; Heithaus, Michael R; Dill, Lawrence M

    2007-09-01

    Apex marine predators can structure marine communities, so factors underlying their abundance are of broad interest. However, such data are almost completely lacking for large sharks. We assessed the relationship between tiger shark abundance, water temperature, and the availability of a variety of known prey over 5 years in Western Australia. Abundance of sharks in four size categories and the density of prey (cormorants, dugongs, sea snakes, sea turtles) were indexed using daily catch rates and transects, respectively. Across all sizes, thermal conditions were a determinant of abundance, with numerical peaks coinciding with periods of high water temperature. However, for sharks exceeding 300 cm total length, the inclusion of dugong density significantly improved temperature-based models, suggesting that use of particular areas by large tiger sharks is influenced by availability of this sirenian. We conclude that large marine predator population models may benefit from the inclusion of measures of prey availability, but only if such measures consider prey types separately and account for ontogenetic shifts in the diet of the predator in question.

  8. Hydrogen Isotope Measurements of Organic Acids and Alcohols by Pyrolysis-GC-MS-TC-IRMS

    NASA Technical Reports Server (NTRS)

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

    2011-01-01

    One possible process responsible for methane generation on Mars is abiotic formation by Fischer-Tropsch-type (FTT) synthesis during serpentinization reactions. Measurement of carbon and hydrogen isotopes of intermediary organic compounds can help constrain the origin of this methane by tracing the geochemical pathway during formation. Of particular interest within the context of this work is the isotopic composition of organic intermediaries produced on the surfaces of mineral catalysts (i.e. magnetite) during hydrothermal experiments, and the ability to make meaningful and reproducible hydrogen isotope measurements. Reported here are results of experiments to characterize the hydrogen isotope composition of low molecular weight organic acids and alcohols. The presence of these organic compounds has been suggested by others as intermeadiary products made during mineral surface catalyzed reactions. This work compliments our previous study characterizing the carbon isotope composition of similar low molecular weight intermediary organic compounds (Socki, et al, American Geophysical Union Fall meeting, Abstr. #V51B-2189, Dec., 2010). Our hydrogen isotope measurements utilize a unique analytical technique combining Pyrolysis-Gas Chromatograph-Mass Spectrometry-High Temperature Conversion-Isotope Ratio Mass Spectrometry (Py-GC-MS-TC-IRMS). Our technique is unique in that it carries a split of the pyrolyzed GC-separated product to a Thermo DSQ-II? quadrupole mass spectrometer as a means of making qualitative and semi-quantitative compositional measurements of separated organic compounds, therefore both chemical and isotopic measurements can be carried out simultaneously on the same sample.

  9. Variations in Os- and Mo-isotope compositions and trace element abundances across the Permo-Triassic boundary, Meishan, China: Proxy evidence for large-scale oceanic anoxia?

    NASA Astrophysics Data System (ADS)

    Cohen, A. S.; Saunders, A.; Zhang, H.; Li, J.

    2009-12-01

    We have carried out Os-isotope analyses, and major and trace element determinations, on samples from the Permo-Triassic section at Meishan B sections, adjacent to the GSSP, China, to assess environmental change at the P-Tr boundary (Bed 27) and the underlying main extinction horizon (Bed 25). Major and trace element abundances were determined by XRF on 38 samples from a 2.3-metre interval of limestone, shale and dolomitic marl from Bed 24a to Bed 32. Re, Os and Mo abundances, and Os-isotope compositions, were determined on a subset of 26 samples, predominantly dark-coloured mudrocks; new Mo-isotope data will be presented. Initial 187Os/188Os(t=250Ma) ranges from 0.3 to 2, with no obvious pattern of change up-section. The data thus provide no unambiguous evidence at Meishan for major perturbation of seawater 187Os/188Os in this region of Palaeotethys, at least at the scale of the sampling. This is unlike early Jurassic and end-Cretaceous boundary sections, and mid-Cretaceous OAE intervals, which record substantial shifts in seawater 187Os/188Os that clearly reflect the influence of LIP emplacement. Major changes in elemental abundances occur between Beds 24 and Bed 27, accompanying the documented excursion in d13C. Redox- and biologically-sensitive elements such as Cu, Ni, P, V and Zn show strong fluctuations in abundance throughout Bed 24, even when abundances are normalised using Al2O3 to minimise the effects of carbonate dilution. In the lower part of Bed 27, however, the Al2O3-normalised concentrations of these elements decrease by an order of magnitude, and remain consistently low in the overlying Triassic marls. The relative decreases in Re and Os abundances throughout Bed 27 are even more substantial. Whilst these decreases are partly an artefact of Al-normalisation, the changes are accompanied by large increases in ratios involving lithogenous elements such as REE, Nb, Zr, Th and Ti. The data thus record a dramatic change in the marine depositional

  10. Mantle in the Manihiki Plateau source with ultra-depleted incompatible element abundances but FOZO-like isotopic signature

    NASA Astrophysics Data System (ADS)

    Golowin, R.; Hoernle, K.; Portnyagin, M.; Hauff, F.; Gurenko, A.; Garbe-Schoenberg, C. D.; Werner, R.

    2014-12-01

    The ~120Ma Manihiki Plateau basement consists of high-Ti tholeiitic basalts with EM-I type isotopic signatures, similar to the Singgalo basalts at Ontong Java, and low-Ti tholeiitic basalts with FOZO (Kwaimbaita/Kroenke) to HIMU-type isotopic compositions, similar to late stage volcanism on Hikurangi and Manihiki Plateaus (Hoernle et al. 2010; Timm et al. 2011). The low-Ti basalts have affinities to boninites and have been interpreted to be derived from residual mantle wedge mantle (Ingle et al. 2007). New major, volatile and trace element and radiogenic isotope data have been generated from fresh low-Ti glass samples recovered during R/V Sonne cruises SO193 and SO225. The low-Ti samples have distinctly lower Ti/V ratios compared to lavas from Ontong Java Plateau (Kwaimbaita-Kroenke and Singgalo), but similar to boninitic rocks. Glasses and melt inclusions in olivine have low volatile contents (0.12-0.25 wt% H2O). Olivine chemistry points to derivation from peridotite source. Therefore we interpret the low-Ti lavas to have formed through melting of dry and depleted peridotite at high temperatures, consistent with Timm et al (2011). The low-Ti group is characterized by U-shaped trace element patterns. The glass samples form linear mixing arrays on radiogenic isotope diagrams, pointing to the involvement of two components: 1) a component ultra-depleted in highly incompatible elements (UDC) but with intermediate Pb, Sr and Nd isotopic compositions, being similar to Kwaimbaita/Kroenke lavas from Ontong Java, and 2) an enriched component with HIMU-type incompatible element and isotopic characteristics, similar to late-stage volcanism on Manihiki, Hikurangi and Ontong Java (e.g. Hoernle et al. 2010). The ultra-depleted, FOZO-like mantle component could represent second stage melting of FOZO type mantle or re-melting of young recycled oceanic lithosphere within the plume head. Enrichment with HIMU type melts is required to explain the enrichment in the most incompatible

  11. A balloon measurement of the isotopic composition of galactic cosmic ray boron, carbon and nitrogen. Ph.D. Thesis

    NASA Technical Reports Server (NTRS)

    Zumberge, J. F.

    1981-01-01

    The isotopic compositions of galactic cosmic ray boron, carbon, and nitrogen were measured at energies near 300 MeV amu, using a balloon-borne instrument at an atmospheric depth of approximately 5 g/sq cm. The calibrations of the detectors comprising the instrument are described. The saturation properties of the cesium iodide scintillators used for measurement of particle energy are studied in the context of analyzing the data for mass. The achieved rms mass resolution varies from approximately 0.3 amu at boron to approximately 0.5 amu at nitrogen, consistent with a theoretical analysis of the contributing factors. Corrected for detector interactions and the effects of the residual atmosphere the results are B-10/B=0.33 (+0.17, -0.11), C-13/C=0.06 (+0.13, -0.11), and N-15/N=0.42 (+0.19, -0.17). A model of galactic propagation and solar modulation is described. Assuming a cosmic ray source composition of solar-like isotopic abundances, the model predicts abundances near Earth consistent with the measurements.

  12. The {sup 13}C-pocket structure in AGB models: constraints from zirconium isotope abundances in single mainstream SiC grains

    SciTech Connect

    Liu, Nan; Davis, Andrew M.; Pellin, Michael J.; Gallino, Roberto; Bisterzo, Sara; Savina, Michael R.

    2014-06-20

    We present postprocess asymptotic giant branch (AGB) nucleosynthesis models with different {sup 13}C-pocket internal structures to better explain zirconium isotope measurements in mainstream presolar SiC grains by Nicolussi et al. and Barzyk et al. We show that higher-than-solar {sup 92}Zr/{sup 94}Zr ratios can be predicted by adopting a {sup 13}C-pocket with a flat {sup 13}C profile, instead of the previous decreasing-with-depth {sup 13}C profile. The improved agreement between grain data for zirconium isotopes and AGB models provides additional support for a recent proposal of a flat {sup 13}C profile based on barium isotopes in mainstream SiC grains by Liu et al.

  13. Correction for the 17O interference in δ(13C) measurements when analyzing CO2 with stable isotope mass spectrometry

    USGS Publications Warehouse

    Coplen, Tyler B.; Brand, Willi A.; Assonov, Sergey S.

    2010-01-01

    Measurements of δ(13C) determined on CO2 with an isotope-ratio mass spectrometer (IRMS) must be corrected for the amount of 17O in the CO2. For data consistency, this must be done using identical methods by different laboratories. This report aims at unifying data treatment for CO2 IRMS by proposing (i) a unified set of numerical values, and (ii) a unified correction algorithm, based on a simple, linear approximation formula. Because the oxygen of natural CO2 is derived mostly from the global water pool, it is recommended that a value of 0.528 be employed for the factor λ, which relates differences in 17O and 18O abundances. With the currently accepted N(13C)/N(12C) of 0.011 180(28) in VPDB (Vienna Peedee belemnite) reevaluation of data yields a value of 0.000 393(1) for the oxygen isotope ratio N(17O)/N(16O) of the evolved CO2. The ratio of these quantities, a ratio of isotope ratios, is essential for the 17O abundance correction: [N(17O)/N(16O)]/[N(13C)/N(12C)] = 0.035 16(8). The equation [δ(13C) ≈ 45δVPDB-CO2 + 2 17R/13R (45δVPDB-CO2 – λ46δVPDB-CO2)] closely approximates δ(13C) values with less than 0.010 ‰ deviation for normal oxygen-bearing materials and no more than 0.026 ‰ in extreme cases. Other materials containing oxygen of non-mass-dependent isotope composition require a more specific data treatment. A similar linear approximation is also suggested for δ(18O). The linear approximations are easy to implement in a data spreadsheet, and also help in generating a simplified uncertainty budget.

  14. On the Measurement of Elemental Abundance Ratios in Inner Galaxy H II Regions

    NASA Astrophysics Data System (ADS)

    Simpson, Janet P.; Rubin, Robert H.; Colgan, Sean W. J.; Erickson, Edwin F.; Haas, Michael R.

    2004-08-01

    Although variations in elemental abundance ratios in the Milky Way certainly exist, details remain uncertain, particularly in the inner Galaxy, where stars and H II regions in the Galactic plane are obscured optically. In this paper we revisit two previously studied, inner Galaxy H II regions: G333.6-0.2 and W43. We observed three new positions in G333.6-0.2 with the Kuiper Airborne Observatory and reobserved the central position with the Infrared Space Observatory's Long Wavelength Spectrometer in far-infrared lines of S++, N++, N+, and O++. We also added the N+ lines at 122 and 205 μm to the suite of lines measured in W43 by Simpson and coworkers. The measured electron densities range from ~40 to over 4000 cm-3 in a single H II region, indicating that abundance analyses must consider density variations, since the critical densities of the observed lines range from 40 to 9000 cm-3. We propose a method to handle density variations and make new estimates of the S/H and N/H abundance ratios. We find that our sulfur abundance estimates for G333.6-0.2 and W43 agree with the S/H abundance ratios expected for the S/H abundance gradient previously reported by Simpson and coworkers, with the S/H values revised to be smaller as a result of changes in collisional excitation cross sections. The estimated N/H, S/H, and N/S ratios are the most reliable because of their small corrections for unseen ionization states (<~10%). The estimated N/S ratios for the two sources are smaller than what would be calculated from the N/H and S/H ratios in our previous paper. We compute models of the two H II regions to estimate corrections for the other unseen ionization states. We find, with large uncertainties, that oxygen does not have a high abundance, with the result that the N/O ratio is as high (~0.35) as previously reported. The reasons for the uncertainty in the ionization corrections for oxygen are both the nonuniqueness of the H II region models and the sensitivity of these models

  15. Coronal abundances in solar active regions measured by the Solar Maximum Mission flat crystal spectrometer

    NASA Technical Reports Server (NTRS)

    Saba, Julia L. R.; Strong, Keith T.

    1992-01-01

    High resolution soft X-ray spectra acquired by the Flat Crystal Spectrometer (FCS) on solar Maximum Mission provide an excellent data base to study the relative abundances of O, Ne, Mg, and Fe in solar active regions. The FCS data show significant variability for all combinations of these elements. The largest variation occurs for Fe:Ne, which shows region to region changes of up to a factor of 7, and frequent factor of 2 variations in day to day samples of a given region. The atomic data and the ionization balance calculations used to interpret the line ratios affect the actual abundance values obtained, but have little effect on the magnitude of the total range of variation inferred. Resonance scattering of Fe XVII could cause a systematic offset in the abundances determined, but cannot be responsbile for the bulk of the observed variability. While abundance variability complicates the derivation of plasma parameters from spectroscopic measurements, it should offer exciting new clues to the processes which form and heat the corona.

  16. The use of Molecular Beacons to Directly Measure Bacterial mRNA Abundances and Transcript Degradation

    PubMed Central

    Kuechenmeister, Lisa J.; Anderson, Kelsi L.; Morrison, John M.; Dunman, Paul M.

    2009-01-01

    The regulation of mRNA turnover is a dynamic means by which bacteria regulate gene expression. Although current methodologies allow characterization of the stability of individual transcripts, procedures designed to measure alterations in transcript abundance/turnover on a high throughput scale are lacking. In the current report, we describe the development of a rapid and simplified molecular beacon-based procedure to directly measure the mRNA abundances and mRNA degradation properties of well-characterized Staphylococcus aureus pathogenicity factors. This method does not require any PCR-based amplification, can monitor the abundances of multiple transcripts within a single RNA sample, and was successfully implemented into a high throughput screen of transposon mutant library members to detect isolates with altered mRNA turnover properties. It is expected that the described methodology will provide great utility in characterizing components of bacterial RNA degradation processes and can be used to directly measure the mRNA levels of virtually any bacterial transcript. PMID:18992285

  17. THE SuperTIGER Instrument: Measurement of Elemental Abundances of Ultra-Heavy Galactic Cosmic Rays

    NASA Technical Reports Server (NTRS)

    Binns, W. R.; Bose, R. G.; Braun, D. L.; Brandt, T. J.; Daniels, W. M.; DowKonnt, P. F.; Fitzsimmons, S. P.; Hahne, D. J.; Hams, T.; Israel, M. H.; Klemic, J.; Labrador, A. W.; Link, J. T.; Mewaldt, R. A.; Mitchell, J. W.; Moore, P.; Murphy, R. P.; Olevitch, M. A.; Rauch, B. F.; Sakai, K.; San Sebastian, F.; Sasaki, M.; Simburger, G. E.; Stone, E. C.; Waddington, C. J.; Ward, J. E.; Wiedenbeck, M. E.

    2014-01-01

    The SuperTIGER (Super Trans-Iron Galactic Element Recorder) instrument was developed to measure the abundances of galactic cosmic-ray elements from Ne-10 to Zr-40 with individual element resolution and the high statistics needed to test models of cosmic-ray origins. SuperTIGER also makes exploratory measurements of the abundances of elements with 40 < Z < or = 60 and measures the energy spectra of the more abundant elements for Z < or = 30 from about 0.8 to 10 GeV/nucleon. This instrument is an enlarged and higher resolution version of the earlier TIGER instrument. It was designed to provide the largest geometric acceptance possible and to reach as high an altitude as possible, flying on a standard long-duration 1.11 million cu m balloon. SuperTIGER was launched from Williams Field, McMurdo Station, Antarctica, on 2012 December 8, and made about 2.7 revolutions around the South Pole in 55 days of flight, returning data on over 50 x 10(exp 6) cosmic-ray nuclei with Z > or = 10, including approx.1300 with Z > 29 and approx.60 with Z > 49. Here, we describe the instrument, the methods of charge identification employed, the SuperTIGER balloon flight, and the instrument performance.

  18. The superTIGER instrument: Measurement of elemental abundances of ultra-heavy galactic cosmic rays

    SciTech Connect

    Binns, W. R.; Bose, R. G.; Braun, D. L.; Dowkontt, P. F.; Israel, M. H.; Moore, P.; Murphy, R. P.; Olevitch, M. A.; Rauch, B. F.; Brandt, T. J.; Daniels, W. M.; Fitzsimmons, S. P.; Hahne, D. J.; Hams, T.; Link, J. T.; Mitchell, J. W.; Sakai, K.; and others

    2014-06-10

    The SuperTIGER (Super Trans-Iron Galactic Element Recorder) instrument was developed to measure the abundances of galactic cosmic-ray elements from {sub 10}Ne to {sub 40}Zr with individual element resolution and the high statistics needed to test models of cosmic-ray origins. SuperTIGER also makes exploratory measurements of the abundances of elements with 40 < Z ≤ 60 and measures the energy spectra of the more abundant elements for Z ≤ 30 from about 0.8 to 10 GeV/nucleon. This instrument is an enlarged and higher resolution version of the earlier TIGER instrument. It was designed to provide the largest geometric acceptance possible and to reach as high an altitude as possible, flying on a standard long-duration 1.11 million m{sup 3} balloon. SuperTIGER was launched from Williams Field, McMurdo Station, Antarctica, on 2012 December 8, and made about 2.7 revolutions around the South Pole in 55 days of flight, returning data on over 50 × 10{sup 6} cosmic-ray nuclei with Z ≥ 10, including ∼1300 with Z > 29 and ∼60 with Z > 49. Here, we describe the instrument, the methods of charge identification employed, the SuperTIGER balloon flight, and the instrument performance.

  19. Abundance, stable isotopic composition, and export fluxes of DOC, POC, and DIC from the Lower Mississippi River during 2006-2008

    NASA Astrophysics Data System (ADS)

    Cai, Yihua; Guo, Laodong; Wang, Xuri; Aiken, George

    2015-11-01

    Sources, abundance, isotopic compositions, and export fluxes of dissolved inorganic carbon (DIC), dissolved and colloidal organic carbon (DOC and COC), and particulate organic carbon (POC), and their response to hydrologic regimes were examined through monthly sampling from the Lower Mississippi River during 2006-2008. DIC was the most abundant carbon species, followed by POC and DOC. Concentration and δ13C of DIC decreased with increasing river discharge, while those of DOC remained fairly stable. COC comprised 61 ± 3% of the bulk DOC with similar δ13C abundances but higher percentages of hydrophobic organic acids than DOC, suggesting its aromatic and diagenetically younger status. POC showed peak concentrations during medium flooding events and at the rising limb of large flooding events. While δ13C-POC increased, δ15N of particulate nitrogen decreased with increasing discharge. Overall, the differences in δ13C between DOC or DIC and POC show an inverse correlation with river discharge. The higher input of soil organic matter and respired CO2 during wet seasons was likely the main driver for the convergence of δ13C between DIC and DOC or POC, whereas enhanced in situ primary production and respiration during dry seasons might be responsible for their isotopic divergence. Carbon export fluxes from the Mississippi River were estimated to be 13.6 Tg C yr-1 for DIC, 1.88 Tg C yr-1 for DOC, and 2.30 Tg C yr-1 for POC during 2006-2008. The discharge-normalized DIC yield decreased during wet seasons, while those of POC and DOC increased and remained constant, respectively, implying variable responses in carbon export to the increasing discharge.

  20. Abundance, stable isotopic composition, and export fluxes of DOC, POC, and DIC from the Lower Mississippi River during 2006–2008

    USGS Publications Warehouse

    Cai, Yihua; Guo, Laodong; Wang, Xuri; Aiken, George R.

    2015-01-01

    Sources, abundance, isotopic compositions, and export fluxes of dissolved inorganic carbon (DIC), dissolved and colloidal organic carbon (DOC and COC), and particulate organic carbon (POC), and their response to hydrologic regimes were examined through monthly sampling from the Lower Mississippi River during 2006–2008. DIC was the most abundant carbon species, followed by POC and DOC. Concentration and δ13C of DIC decreased with increasing river discharge, while those of DOC remained fairly stable. COC comprised 61 ± 3% of the bulk DOC with similar δ13C abundances but higher percentages of hydrophobic organic acids than DOC, suggesting its aromatic and diagenetically younger status. POC showed peak concentrations during medium flooding events and at the rising limb of large flooding events. While δ13C-POC increased, δ15N of particulate nitrogen decreased with increasing discharge. Overall, the differences in δ13C between DOC or DIC and POC show an inverse correlation with river discharge. The higher input of soil organic matter and respired CO2 during wet seasons was likely the main driver for the convergence of δ13C between DIC and DOC or POC, whereas enhanced in situ primary production and respiration during dry seasons might be responsible for their isotopic divergence. Carbon export fluxes from the Mississippi River were estimated to be 13.6 Tg C yr−1 for DIC, 1.88 Tg C yr−1 for DOC, and 2.30 Tg C yr−1 for POC during 2006–2008. The discharge-normalized DIC yield decreased during wet seasons, while those of POC and DOC increased and remained constant, respectively, implying variable responses in carbon export to the increasing discharge.

  1. Stable Isotope Measurements of Carbon Dioxide, Methane, and Hydrogen Sulfide Gas Using Frequency Modulation Spectroscopy

    NASA Astrophysics Data System (ADS)

    Nowak-Lovato, K.

    2014-12-01

    Seepage from enhanced oil recovery, carbon storage, and natural gas sites can emit trace gases such as carbon dioxide, methane, and hydrogen sulfide. Trace gas emission at these locations demonstrate unique light stable isotope signatures that provide information to enable source identification of the material. Light stable isotope detection through surface monitoring, offers the ability to distinguish between trace gases emitted from sources such as, biological (fertilizers and wastes), mineral (coal or seams), or liquid organic systems (oil and gas reservoirs). To make light stable isotope measurements, we employ the ultra-sensitive technique, frequency modulation spectroscopy (FMS). FMS is an absorption technique with sensitivity enhancements approximately 100-1000x more than standard absorption spectroscopy with the advantage of providing stable isotope signature information. We have developed an integrated in situ (point source) system that measures carbon dioxide, methane and hydrogen sulfide with isotopic resolution and enhanced sensitivity. The in situ instrument involves the continuous collection of air and records the stable isotope ratio for the gas being detected. We have included in-line flask collection points to obtain gas samples for validation of isotopic concentrations using our in-house isotope ratio mass spectroscopy (IRMS). We present calibration curves for each species addressed above to demonstrate the sensitivity and accuracy of the system. We also show field deployment data demonstrating the capabilities of the system in making live dynamic measurements from an active source.

  2. New method for the measurement of osmium isotopes applied to a New Zealand Cretaceous/Tertiary boundary shale

    USGS Publications Warehouse

    Lichte, F.E.; Wilson, S.M.; Brooks, R.R.; Reeves, R.D.; Holzbecher, J.; Ryan, D.E.

    1986-01-01

    The determination of osmium content and isotopic abundances in geological materials has received increasing attention in recent years following the proposal of Alvarez et al.1 that mass extinctions at the end of the Cretaceous period were caused by the impact of a large (???10km) meteorite which left anomalously high iridium levels as a geochemical signature in the boundary shales. Here we report a new and simple method for measuring osmium in geological materials, involving fusion of the sample with sodium peroxide, distillation of the osmium as the tetroxide using perchloric acid, extraction into chloroform, and absorption of the chloroform extract onto graphite powder before instrumental neutron activation analysis. In a variant of this technique, the chloroform extract is back-extracted into an aqueous phase and the osmium isotopes are determined by plasma-source mass spectrometry (ICPMS). We have used this method on the Woodside Creek (New Zealand) Cretaceous/Tertiary boundary clay and have obtained the first osmium content (6g ng g-1) for this material. The 187Os/186Os ratio is 1.12??0.16, showing a typical non-crustal signature. This combined distillation-extraction- ICPMS method will prove to be useful for measuring osmium isotopes in other geological materials. ?? 1986 Nature Publishing Group.

  3. Carbon-13 isotopic abundance and concentration of atmospheric methane for background air in the Southern and Northern Hemispheres from 1978 to 1989

    SciTech Connect

    Stevens, C.M.; Sepanski; Morris, L.J.

    1995-03-01

    Atmospheric methane (CH{sub 4}) may become an increasingly important contributor to global warming in future years. Its atmospheric concentration has risen, doubling over the past several hundred years, and additional methane is thought to have a much greater effect on climate, on a per molecule basis, than additional C0{sub 2} at present day concentrations (Shine et al. 1990). The causes of the increase of atmospheric CH{sub 4} have been difficult to ascertain because of a lack of quantitative knowledge of the fluxes (i.e., net emissions) from the numerous anthropogenic and natural sources. The goal of CH{sub 4} isotopic studies is to provide a constraint (and so reduce the uncertainties) in estimating the relative fluxes from the various isotopically distinct sources, whose combined fluxes must result in the measured atmospheric isotopic composition, after the fractionating effect of the atmospheric removal process is considered. In addition, knowledge of the spatial and temporal changes in the isotopic composition of atmospheric CH{sub 4}, along with estimates of the fluxes from some of the major sources, makes it possible to calculate growth rates for sources whose temporal emissions trends would be difficult to measure directly.

  4. Oxygen Isotope Measurements of a Rare Murchison Type A CAI and Its Rim

    NASA Technical Reports Server (NTRS)

    Matzel, J. E. P.; Simon, J. I.; Hutcheon, I. D.; Jacobsen, B.; Simon, S. B.; Grossman, L.

    2013-01-01

    Ca-, Al-rich inclusions (CAIs) from CV chondrites commonly show oxygen isotope heterogeneity among different mineral phases within individual inclusions reflecting the complex history of CAIs in both the solar nebula and/or parent bodies. The degree of isotopic exchange is typically mineral-specific, yielding O-16-rich spinel, hibonite and pyroxene and O-16-depleted melilite and anorthite. Recent work demonstrated large and systematic variations in oxygen isotope composition within the margin and Wark-Lovering rim of an Allende Type A CAI. These variations suggest that some CV CAIs formed from several oxygen reservoirs and may reflect transport between distinct regions of the solar nebula or varying gas composition near the proto-Sun. Oxygen isotope compositions of CAIs from other, less-altered chondrites show less intra-CAI variability and 16O-rich compositions. The record of intra-CAI oxygen isotope variability in CM chondrites, which commonly show evidence for low-temperature aqueous alteration, is less clear, in part because the most common CAIs found in CM chondrites are mineralogically simple (hibonite +/- spinel or spinel +/- pyroxene) and are composed of minerals less susceptible to O-isotopic exchange. No measurements of the oxygen isotope compositions of rims on CAIs in CM chondrites have been reported. Here, we present oxygen isotope data from a rare, Type A CAI from the Murchison meteorite, MUM-1. The data were collected from melilite, hibonite, perovskite and spinel in a traverse into the interior of the CAI and from pyroxene, melilite, anorthite, and spinel in the Wark-Lovering rim. Our objectives were to (1) document any evidence for intra-CAI oxygen isotope variability; (2) determine the isotopic composition of the rim minerals and compare their composition(s) to the CAI interior; and (3) compare the MUM-1 data to oxygen isotope zoning profiles measured from CAIs in other chondrites.

  5. Airborne Measurements of Atmospheric Methane Column Abundance Made Using a Pulsed IPDA Lidar

    NASA Technical Reports Server (NTRS)

    Riris, Haris; Numata, Kenji; Li, Steve; Wu, Stewart; Ramanathan, Anamd; Dawsey, Martha; Mao, Jianping; Kawa, Randolph; Abshire, James B.

    2012-01-01

    We report airborne measurements of the column abundance of atmospheric methane made over an altitude range of 3-11 km using a direct detection IPDA lidar with a pulsed laser emitting at 1651 nm. The laser transmitter was a tunable, seeded optical parametric amplifier (OPA) pumped by a Nd:YAG laser and the receiver used a photomultiplier detector and photon counting electronics. The results follow the expected changes with aircraft altitude and the measured line shapes and optical depths show good agreement with theoretical calculations.

  6. The measurement of elemental abundances above 10 sup 15 eV at a lunar base

    SciTech Connect

    Swordy, S.P. )

    1990-03-15

    At {approx}10{sup 15} eV the slope of the energy spectrum of cosmic rays becomes significantly steeper than at lower energies. The measurement of relative elemental abundances at these energies is expected to provide a means to resolve the origin of this feature and greatly contribute to the understanding of the sources of cosmic rays. We describe a moon based detector for making well resolved elemental measurements at these energies using hadronic calorimetry. This detector is particularly well suited for a site on the lunar surface because there is no overlying layer of atmosphere and the large mass required can be provided by the lunar regolith.

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

    NASA Astrophysics Data System (ADS)

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

    2012-04-01

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

  8. Using antibody arrays to measure protein abundance and glycosylation: considerations for optimal performance.

    PubMed

    Haab, Brian B; Partyka, Katie; Cao, Zheng

    2013-09-24

    Antibody arrays provide a valuable method for obtaining multiple protein measurements from small volumes of biological samples. Antibody arrays can be designed to target not only core protein abundances (relative or absolute abundances, depending on the availability of standards for calibration), but also posttranslational modifications, provided antibodies or other affinity reagents are available to detect them. Glycosylation is a common modification that has important and diverse functions in both normal and disease biology. Significant progress has been made in developing methods for measuring glycan levels on multiple specific proteins using antibody arrays and glycan-binding reagents. This unit describes practical approaches for developing, optimizing, and using antibody array assays to determine both protein abundance and glycosylation state. Low-volume arrays can be used to reduce sample consumption, and a new way to improve the binding strength of particular glycan-binding reagents through multimerization is discussed. These methods can be useful for a wide range of biological studies in which glycosylation may change and/or affect protein function.

  9. A PRECISE WATER ABUNDANCE MEASUREMENT FOR THE HOT JUPITER WASP-43b

    SciTech Connect

    Kreidberg, Laura; Bean, Jacob L.; Stevenson, Kevin B.; Désert, Jean-Michel; Line, Michael R.; Fortney, Jonathan J.; Madhusudhan, Nikku; Showman, Adam P.; Kataria, Tiffany; Charbonneau, David; McCullough, Peter R.; Seager, Sara; Burrows, Adam; Henry, Gregory W.; Williamson, Michael; Homeier, Derek

    2014-10-01

    The water abundance in a planetary atmosphere provides a key constraint on the planet's primordial origins because water ice is expected to play an important role in the core accretion model of planet formation. However, the water content of the solar system giant planets is not well known because water is sequestered in clouds deep in their atmospheres. By contrast, short-period exoplanets have such high temperatures that their atmospheres have water in the gas phase, making it possible to measure the water abundance for these objects. We present a precise determination of the water abundance in the atmosphere of the 2 M {sub Jup} short-period exoplanet WASP-43b based on thermal emission and transmission spectroscopy measurements obtained with the Hubble Space Telescope. We find the water content is consistent with the value expected in a solar composition gas at planetary temperatures (0.4-3.5 × solar at 1σ confidence). The metallicity of WASP-43b's atmosphere suggested by this result extends the trend observed in the solar system of lower metal enrichment for higher planet masses.

  10. Using antibody arrays to measure protein abundance and glycosylation: considerations for optimal performance

    PubMed Central

    Haab, Brian B.; Partyka, Katie; Cao, Zheng

    2013-01-01

    Antibody arrays provide a valuable method of obtaining multiple protein measurements from low volumes of biological samples. Antibody arrays can be designed to target not only core protein abundances (relative or absolute abundances, depending on the availability of standards for calibration), but also protein post-translational modifications, provided antibodies or other affinity reagents are available to detect the modifications. Glycosylation is a common modification that has important and diverse functions, both in normal and disease biology. The methods for measuring glycan levels on multiple, specific proteins using antibody arrays and glycan-binding reagents have made significant progress. Here we describe practical approaches to develop, optimize and use antibody array assays to determine both protein abundances and glycosylation states. We cover the use of low-volume arrays to reduce sample consumption and a new way to improve the binding strength of particular glycan-binding reagents through multimerization. These methods could be useful for a wide range of biological studies in which glycosylation may be changing or affect protein function. PMID:24510592

  11. Strong Coupling of Shoot Assimilation and Soil Respiration during Drought and Recovery Periods in Beech As Indicated by Natural Abundance δ13C Measurements

    PubMed Central

    Blessing, Carola H.; Barthel, Matti; Gentsch, Lydia; Buchmann, Nina

    2016-01-01

    Drought down-regulates above- and belowground carbon fluxes, however, the resilience of trees to drought will also depend on the speed and magnitude of recovery of these above- and belowground fluxes after re-wetting. Carbon isotope composition of above- and belowground carbon fluxes at natural abundance provides a methodological approach to study the coupling between photosynthesis and soil respiration (SR) under conditions (such as drought) that influence photosynthetic carbon isotope discrimination. In turn, the direct supply of root respiration with recent photoassimilates will impact on the carbon isotope composition of soil-respired CO2. We independently measured shoot and soil CO2 fluxes of beech saplings (Fagus sylvatica L.) and their respective δ13C continuously with laser spectroscopy at natural abundance. We quantified the speed of recovery of drought stressed trees after re-watering and traced photosynthetic carbon isotope signal in the carbon isotope composition of soil-respired CO2. Stomatal conductance responded strongly to the moderate drought (-65%), induced by reduced soil moisture content as well as increased vapor pressure deficit. Simultaneously, carbon isotope discrimination decreased by 8‰, which in turn caused a significant increase in δ13C of recent metabolites (1.5–2.5‰) and in δ13C of SR (1–1.5‰). Generally, shoot and soil CO2 fluxes and their δ13C were in alignment during drought and subsequent stress release, clearly demonstrating a permanent dependence of root respiration on recently fixed photoassimilates, rather than on older reserves. After re-watering, the drought signal persisted longer in δ13C of the water soluble fraction that integrates multiple metabolites (soluble sugars, amino acids, organic acids) than in the neutral fraction which represents most recently assimilated sugars or in the δ13C of SR. Nevertheless, full recovery of all aboveground physiological variables was reached within 4 days – and within 7

  12. Abundance Anomaly of the 13C Isotopic Species of c-C3H2 in the Low-mass Star Formation Region L1527

    NASA Astrophysics Data System (ADS)

    Yoshida, Kento; Sakai, Nami; Tokudome, Tomoya; López-Sepulcre, Ana; Watanabe, Yoshimasa; Takano, Shuro; Lefloch, Bertrand; Ceccarelli, Cecilia; Bachiller, Rafael; Caux, Emmanuel; Vastel, Charlotte; Yamamoto, Satoshi

    2015-07-01

    The rotational spectral lines of c-C3H2 and two kinds of the 13C isotopic species, c-{}13{{CCCH}}2 ({C}2v symmetry) and c-{{CC}}13{{CH}}2 (Cs symmetry), have been observed in the 1-3 mm band toward the low-mass star-forming region L1527. We have detected 7, 3, and 6 lines of c-C3H2, c-{}13{{CCCH}}2, and c-{{CC}}13{{CH}}2, respectively, with the Nobeyama 45 m telescope and 34, 6, and 13 lines, respectively, with the IRAM 30 m telescope, where seven, two, and two transitions, respectively, are observed with both telescopes. With these data, we have evaluated the column densities of the normal and 13C isotopic species. The [c-C3H2]/[c-{}13{{CCCH}}2] ratio is determined to be 310 ± 80, while the [c-C3H2]/[c-{{CC}}13{{CH}}2] ratio is determined to be 61 ± 11. The [c-C3H2]/[c-{}13{{CCCH}}2] and [c-C3H2]/[c-{{CC}}13{{CH}}2] ratios expected from the elemental 12C/13C ratio are 60-70 and 30-35, respectively, where the latter takes into account the statistical factor of 2 for the two equivalent carbon atoms in c-C3H2. Hence, this observation further confirms the dilution of the 13C species in carbon-chain molecules and their related molecules, which are thought to originate from the dilution of 13C+ in the gas-phase C+ due to the isotope exchange reaction: {}13{{{C}}}++{CO}\\to {}13{CO}+{{{C}}}+. Moreover, the abundances of the two 13C isotopic species are different from each other. The ratio of c-{}13{{CCCH}}2 species relative to c-{{CC}}13{{CH}}2 is determined to be 0.20 ± 0.05. If 13C were randomly substituted for the three carbon atoms, the [c-{}13{{CCCH}}2]/[c-{{CC}}13{{CH}}2] ratio would be 0.5. Hence, the observed ratio indicates that c-{{CC}}13{{CH}}2 exists more favorably. Possible origins of the different abundances are discussed. Based on observations carried out with the IRAM 30 m Telescope and the NRO 45 m Telescope. IRAM is supported by INSU/CNRS (France), MPG (Germany), and IGN (Spain). NRO is a branch of the National Astronomical Observatory of Japan

  13. Experimental measurement of boron isotope fractionation in seawater

    NASA Astrophysics Data System (ADS)

    Klochko, Kateryna; Kaufman, Alan J.; Yao, Wengsheng; Byrne, Robert H.; Tossell, John A.

    2006-08-01

    The boron isotopic composition of marine carbonates is considered to be a tracer of seawater pH. Use of this proxy benefits from an intimate understanding of chemical kinetics and thermodynamic isotope exchange reactions between the two dominant boron-bearing species in seawater: boric acid B(OH) 3 and borate ion B(OH) 4-. However, because of our inability to quantitatively separate these species in solution, the degree of boron isotope exchange has only been known through theoretical estimates. In this study, we present results of a spectrophotometric procedure wherein the boron isotope equilibrium constant ( 11-10KB) is determined empirically from the difference in the dissociation constants of 11B(OH) 3 and 10B(OH) 3 in pure water, 0.6 mol kg - 1 H 2O KCl and artificial seawater. Within experimental uncertainty, our results show no dependence of 11-10KB on temperature, but 11-10KB at 25 °C in pure water was statistically different than results obtained in solutions at high ionic strength. 11-10KB of the seawater ( S = 35, B T = 0.01 mol kg - 1 H 2O) at 25 °C is 1.0272 ± 0.0006. This result is significantly larger than the theoretical value used in numerous paleo-pH studies ( 11-10KB = 1.0194).

  14. Measuring and predicting abundance and dynamics of habitat for piping plovers on a large reservoir

    USGS Publications Warehouse

    Anteau, Michael J.; Wiltermuth, Mark T.; Sherfy, Mark H.; Shaffer, Terry L.

    2014-01-01

    Measuring habitat and understanding habitat dynamics have become increasingly important for wildlife conservation. Using remotely-sensed data, we developed procedures to measure breeding habitat abundance for the federally listed piping plover (Charadrius melodus) at Lake Sakakawea, North Dakota, USA. We also developed a model to predict habitat abundance based on past and projected water levels, vegetation colonization rates, and topography. Previous studies define plover habitat as flat areas (30% bare-substrate obstruction) were 76% correct and omission and commission errors were equal. Due to water level fluctuations, habitat abundance varied markedly among years (1986–2009) ranging from 9 to 5195 ha. The proportion bare substrate declined with the number of years since a contour was inundated until 5 years (β = -0.65, SE = 0.05), then it stabilized near zero, and the decline varied by shoreline segment (5, 50, and 95 percentile were β = -0.19, SE = 0.05, β = -0.63, SE = 0.05, and β = -0.91, SE = 0.05, respectively). Years since inundated predicted habitat abundance well at shoreline segments (R2 = 0.77), but it predicted better for the whole lake (R2 = 0.86). The vastness and dynamics of plover habitat on Lake Sakakawea suggest that this is a key area for conservation of this species. Model-based habitat predictions can benefit resource conservation because they can (1) form the basis for a sampling stratification, (2) help allocate monitoring efforts among areas, and (3) help inform management through simulations or what-if scenarios.

  15. New Oxygen Isotope Measurements of Four Stardust Impact Crater Residues Show IDP-Like Compositions

    NASA Astrophysics Data System (ADS)

    Snead, C. J.; McKeegan, K. D.

    2015-07-01

    We have measured the oxygen isotope compositions of four Stardust impact crater residues. These analyses reveal compositions that are similar to those found in interplanetary dust particles, antarctic micrometeorites and CI chondrite components.

  16. ROSINA/DFMS capabilities to measure isotopic ratios in water at comet 67P/Churyumov-Gerasimenko

    NASA Astrophysics Data System (ADS)

    Hässig, M.; Altwegg, K.; Balsiger, H.; Berthelier, J. J.; Calmonte, U.; Combi, M.; De Keyser, J.; Fiethe, B.; Fuselier, S. A.; Rubin, M.

    2013-08-01

    The likelihood that comets may have delivered part of the water to Earth has been reinforced by the recent observation of the earth-like D/H ratio in Jupiter-family comet 103P/Hartley 2 by Hartogh et al. (2012). Prior to this observation, results from several Oort cloud comets indicated a factor of 2 enrichment of deuterium relative to the abundance at Earth. The European Space Agency's Rosetta spacecraft will encounter comet 67P/Churyumov-Gerasimenko, another Jupiter-family comet of likely Kuiper belt origin, in 2014 and accompany it from almost aphelion to and past perihelion. Onboard Rosetta is the Rosetta Orbiter Spectrometer for Ion and Neutral Analysis (ROSINA) which consists of two mass spectrometers and a pressure sensor (Balsiger et al., 2007). With its unprecedented mass resolution, for a space-borne instrument, the Double Focusing Mass Spectrometer (DFMS), one of the major subsystems of ROSINA, will be able to obtain unambiguously the ratios of the isotopes in water from in situ measurements in the coma around the comet. In this paper we discuss the performance of this sensor on the basis of measurements of the terrestrial hydrogen and oxygen isotopic ratios performed with the flight spare instrument in the lab. We also show that the instrument on Rosetta is capable of measuring the D/H and the oxygen isotopic ratios even in the very low density water background released by the spacecraft. This capability demonstrates that ROSINA should obtain very accurate isotopic ratios in the cometary environment.

  17. Infrared measurements of column abundances of several trace gases in the Antarctic atmosphere

    NASA Technical Reports Server (NTRS)

    Murcray, F. J.; Murcray, F. H.; Murcray, D. G.

    1988-01-01

    Atmospheric emission measurements were made in 1978 from an LC 130 aircraft from Point Mugu, CA, to McMurdo Station, Antarctica, and from McMurdo over the Antarctic continent on several different flights. These included a number of flights over the South Pole. In December 1980, infrared solar spectra were obtained from the ground at South Pole Station. Infrared solar spectra were also obtained from South Pole during late November and early December of 1986. These latter measurements were extended to cover additional spectral regions to obtain column densities of a number of additional constituents. The results obtained from these measurement series are reviewed and, where measurements were made during both periods, compared. Spectral absorption or emission features due to HNO3, NO, NO2, HCl, (H-16)2O, (H-18)2O, HDO, CH4, and N2O were used to obtain data on the total column abundances for these compounds.

  18. A hydrogen gas-water equilibration method produces accurate and precise stable hydrogen isotope ratio measurements in nutrition studies

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Stable hydrogen isotope methodology is used in nutrition studies to measure growth, breast milk intake, and energy requirement. Isotope ratio MS is the best instrumentation to measure the stable hydrogen isotope ratios in physiological fluids. Conventional methods to convert physiological fluids to ...

  19. The Application of Methane Clumped Isotope Measurements to Determine the Source of Large Methane Seeps in Alaskan Lakes

    NASA Astrophysics Data System (ADS)

    Douglas, P. M.; Stolper, D. A.; Eiler, J. M.; Sessions, A. L.; Walter Anthony, K. M.

    2014-12-01

    Natural methane emissions from the Arctic present an important potential feedback to global warming. Arctic methane emissions may come from either active microbial sources or from deep fossil reservoirs released by the thawing of permafrost and melting of glaciers. It is often difficult to distinguish between and quantify contributions from these methane sources based on stable isotope data. Analyses of methane clumped isotopes (isotopologues with two or more rare isotopes such as 13CH3D) can complement traditional stable isotope-based classifications of methane sources. This is because clumped isotope abundances (for isotopically equilibrated systems) are a function of temperature and can be used to identify pathways of methane generation. Additionally, distinctive effects of mixing on clumped isotope abundances make this analysis valuable for determining the origins of mixed gasses. We find large variability in clumped isotope compositions of methane from seeps in several lakes, including thermokarst lakes, across Alaska. At Lake Sukok in northern Alaska we observe the emission of dominantly thermogenic methane, with a formation temperature of at least 100° C. At several other lakes we find evidence for mixing between thermogenic methane and biogenic methane that forms in low-temperature isotopic equilibrium. For example, at Eyak Lake in southeastern Alaska, analysis of three methane samples results in a distinctive isotopic mixing line between a high-temperature end-member that formed between 100-170° C, and a biogenic end-member that formed in isotopic equilibrium between 0-20° C. In this respect, biogenic methane in these lakes resembles observations from marine gas seeps, oil degradation, and sub-surface aquifers. Interestingly, at Goldstream Lake in interior Alaska, methane with strongly depleted clumped-isotope abundances, indicative of disequilibrium gas formation, is found, similar to observations from methanogen culture experiments.

  20. High Precision Ti stable Isotope Measurement of Terrestrial Rocks

    NASA Astrophysics Data System (ADS)

    Millet, M. A.; Dauphas, N.; Williams, H. M.; Burton, K. W.; Nowell, G. M.

    2014-12-01

    Advances in multi-collection plasma source mass spectrometry have allowed the determination of stable isotope composition of transition metals to address questions relevant to both high and low temperature geochemistry. However, titanium has received only very limited attention. Here we present a new technique allowing the determination of the stable isotope composition of titanium in geological samples (d49Ti or deviation of the 49Ti/47Ti ratio from the OL-Ti in-house standard of reference) using double-spike methodology and high-resolution MC-ICP-MS. We have carried out a range analytical tests for a wide spectrum of samples matrices to demonstrate a external reproducibility of ±0.02‰ on the d49Ti while using as little as 150ng of natural Ti for a single analysis. We have analysed a comprehensive selection of mantle-derived samples covering a range of geodynamic contexts (MORB, IAB, OIB, adakites, eclogites, serpentines) and geographical distribution (MORB: Mid-Atlantic Ridge, Southwest Indian Ridge and Eastern Pacific Ridge; IAB: New Britain reference suite and Marianas Arc). The samples show a very limited range from -0.06‰ to +0.04‰ with a main mode at +0.004‰ relative to the OL-Ti standard. Average values for MORB, IAB and eclogites are similar within uncertainty and thus argue for limited mobility of Ti during subduction zone processes and homogeneity of the Ti stable isotope composition of the upper mantle. However, preliminary data for more evolved igneous rocks suggest that they display heavier Ti stable isotope compositions, which may reflect the removal of isotopically light Ti as a function of Fe-Ti oxide crystallisation. This is in good agreement with Ti being present in 5-fold and 6-fold coordination in basaltic melts and preferential uptake of 6-folded Ti by Ti-bearing oxides [1]. This dataset will be complemented by analysis of abyssal peridotites to confirm the homogeneity of the mantle as well as data for a range of ferromanganese crusts

  1. Pseudomonas stutzeri Nitrite Reductase Gene Abundance in Environmental Samples Measured by Real-Time PCR

    PubMed Central

    Grüntzig, Verónica; Nold, Stephen C.; Zhou, Jizhong; Tiedje, James M.

    2001-01-01

    We used real-time PCR to quantify the denitrifying nitrite reductase gene (nirS), a functional gene of biogeochemical significance. The assay was tested in vitro and applied to environmental samples. The primer-probe set selected was specific for nirS sequences that corresponded approximately to the Pseudomonas stutzeri species. The assay was linear from 1 to 106 gene copies (r2 = 0.999). Variability at low gene concentrations did not allow detection of twofold differences in gene copy number at less than 100 copies. DNA spiking and cell-addition experiments gave predicted results, suggesting that this assay provides an accurate measure of P. stutzeri nirS abundance in environmental samples. Although P. stutzeri abundance was high in lake sediment and groundwater samples, we detected low or no abundance of this species in marine sediment samples from Puget Sound (Wash.) and from the Washington ocean margin. These results suggest that P. stutzeri may not be a dominant marine denitrifier. PMID:11157241

  2. Distribution, abundance and carbon isotopic composition of gaseous hydrocarbons in Big Soda Lake, Nevada - An alkaline, meromictic lake

    NASA Technical Reports Server (NTRS)

    Oremland, R. S.; Des Marais, D. J.

    1983-01-01

    The study of the distribution and isotopic composition of low molecular weight hydrocarbon gases at the Big Soda Lake, Nevada, has shown that while neither ethylene nor propylene were found in the lake, ethane, propane, isobutane and n-butane concentrations all increased with water column depth. It is concluded that methane has a biogenic origin in both the sediments and the anoxic water column, and that C2-C4 alkanes have biogenic origins in the monimolimnion water and shallow sediments. The changes observed in delta C-13/CH4/ and CH4/(C2H6 + C3H8) with depth in the water column and sedimeents are probably due to bacterial processes, which may include anaerobic methane oxidation and different rates of methanogenesis, and C2-to-C4 alkane production by microorganisms.

  3. Measuring the IMF and Detailed Abundance Patterns from the Integrated Light of Old Stellar Systems

    NASA Astrophysics Data System (ADS)

    Conroy, Charlie

    The spectral energy distributions (SEDs) of unresolved stellar systems holds key information regarding the detailed abundance pattern, star formation history, dust properties, and initial mass function (IMF) of the underlying stellar population(s). This information can only be extracted with the aid of stellar population synthesis (SPS) models. Such models have been employed to estimate basic properties such as the star formation rate, metallicity (Z, and in certain contexts, alpha-enhancement), and total stellar mass (assuming an IMF). However, much more information is available in the SED than can be extracted by the current generation of SPS models because existing models are plagued by incomplete and poorly calibrated ingredients. The proposers request funds to develop a next generation SPS model capable of measuring the IMF and detailed abundance patterns from the SEDs of composite stellar systems. In particular, we intend to develop an SPS model that makes accurate predictions for the SEDs (from 0.1-3mu m at a resolving power of ~5,000) of composite systems as a function of the IMF, stellar age, metallicity, and individual elemental abundances (including C, N, O, Na, Mg, Ca, Ti, Cr, Mn, Fe, Sr, and Ba). This will require the construction of a new synthetic stellar spectral library and a new isochrone library. This new model will be the first to make predictions for the full SED shape as a function of individual abundance ratios, age, and the IMF. We will extensively calibrate the model predictions against data on individual stars and globular clusters. The new model will be essential for interpreting optical-NIR spectra obtained from the James Webb Space Telescope as well as both present and future ground-based facilities.

  4. Measuring and Extrapolating the Chemical Abundances of Normal and Superluminous Core-Collapse Supernovae

    NASA Astrophysics Data System (ADS)

    Stoll, R. A.

    2013-10-01

    stars that are the progenitors of core-collapse supernovae, and because iron enrichment lags oxygen enrichment, we find a general conversion from oxygen abundance to iron abundance. The distributions we present here are the best yet observational standard of comparison for evaluating how different classes of supernovae depend on progenitor metallicity. We spectroscopically measure the gas-phase oxygen abundance near a representative subsample of the hosts of type II supernovae from the first-year Palomar Transient Factory (PTF) supernova search. The median metallicity is 12+log(O/H) = 8.65 and the median host galaxy stellar mass from fits to SDSS photometry is 109.9 M⊙. They do not show a systematic offset in metallicity or mass from a redshift-matched sample of the MPA/JHU value-added catalog. In contrast to previous supernova host metallicity studies, this sample is drawn from a single survey. It is also drawn from an areal rather than a targeted survey, so supernovae in the lowest-mass galaxies are not excluded. Indeed, the PTF supernova search has a slight bias towards following up transients in low mass galaxies. The progenitor region metallicity distribution we find is statistically indistinguishable from the metallicity distribution of type II supernova hosts found by targeted surveys and by samples from multiple surveys with different selection functions. Using the relationship between iron and oxygen abundances found for Milky Way disk, bulge, and halo stars, we translate our distribution of type II SN environments as a function of oxygen abundance into an estimate of the iron abundance, since iron varies more steeply than oxygen. We find that though this sample spans only 0.65 dex in oxygen abundance, the gap between the iron and oxygen abundance is 50% wider at the low-metallicity end of our sample than at the high-metallicity end. We compare the host metallicity distribution of core-collapse supernovae (CCSNe) with peak absolute magnitudes brighter than

  5. Volatile abundances and oxygen isotopes in basaltic to dacitic lavas on mid-ocean ridges: The role of assimilation at spreading centers

    USGS Publications Warehouse

    Wanless, V.D.; Perfit, M.R.; Ridley, W.I.; Wallace, P.J.; Grimes, Craig B.; Klein, E.M.

    2011-01-01

    Most geochemical variability in MOR basalts is consistent with low- to moderate-pressure fractional crystallization of various mantle-derived parental melts. However, our geochemical data from MOR high-silica glasses, including new volatile and oxygen isotope data, suggest that assimilation of altered crustal material plays a significant role in the petrogenesis of dacites and may be important in the formation of basaltic lavas at MOR in general. MOR high-silica andesites and dacites from diverse areas show remarkably similar major element trends, incompatible trace element enrichments, and isotopic signatures suggesting similar processes control their chemistry. In particular, very high Cl and elevated H2O concentrations and relatively light oxygen isotope ratios (~ 5.8‰ vs. expected values of ~ 6.8‰) in fresh dacite glasses can be explained by contamination of magmas from a component of ocean crust altered by hydrothermal fluids. Crystallization of silicate phases and Fe-oxides causes an increase in δ18O in residual magma, but assimilation of material initially altered at high temperatures results in lower δ18O values. The observed geochemical signatures can be explained by extreme fractional crystallization of a MOR basalt parent combined with partial melting and assimilation (AFC) of amphibole-bearing altered oceanic crust. The MOR dacitic lavas do not appear to be simply the extrusive equivalent of oceanic plagiogranites. The combination of partial melting and assimilation produces a distinct geochemical signature that includes higher incompatible trace element abundances and distinct trace element ratios relative to those observed in plagiogranites.

  6. Calcium isotope analysis by mass spectrometry.

    PubMed

    Boulyga, Sergei F

    2010-01-01

    The variations in the isotopic composition of calcium caused by fractionation in heterogeneous systems and by nuclear reactions can provide insight into numerous biological, geological, and cosmic processes, and therefore isotopic analysis finds a wide spectrum of applications in cosmo- and geochemistry, paleoclimatic, nutritional, and biomedical studies. The measurement of calcium isotopic abundances in natural samples has challenged the analysts for more than three decades. Practically all Ca isotopes suffer from significant isobaric interferences, whereas low-abundant isotopes can be particularly affected by neighboring major isotopes. The extent of natural variations of stable isotopes appears to be relatively limited, and highly precise techniques are required to resolve isotopic effects. Isotope fractionation during sample preparation and measurements and instrumental mass bias can significantly exceed small isotope abundance variations in samples, which have to be investigated. Not surprisingly, a TIMS procedure developed by Russell et al. (Russell et al., 1978. Geochim Cosmochim Acta 42: 1075-1090) for Ca isotope measurements was considered as revolutionary for isotopic measurements in general, and that approach is used nowadays (with small modifications) for practically all isotopic systems and with different mass spectrometric techniques. Nevertheless, despite several decades of calcium research and corresponding development of mass spectrometers, the available precision and accuracy is still not always sufficient to achieve the challenging goals. The present article discusses figures of merits of presently used analytical methods and instrumentation, and attempts to critically assess their limitations. In Sections 2 and 3, mass spectrometric methods applied to precise stable isotope analysis and to the determination of (41)Ca are described. Section 4 contains a short summary of selected applications, and includes tracer experiments and the potential use

  7. Precise determination of the absolute isotopic abundance ratio and the atomic weight of chlorine in three international reference materials by the positive thermal ionization mass spectrometer-Cs2Cl+-graphite method.

    PubMed

    Wei, Hai-Zhen; Jiang, Shao-Yong; Xiao, Ying-Kai; Wang, Jun; Lu, Hai; Wu, Bin; Wu, He-Pin; Li, Qing; Luo, Chong-Guang

    2012-12-04

    Because the variation in chlorine isotopic abundances of naturally occurring chlorine bearing substances is significant, the IUPAC Inorganic Chemistry Division, Commission on Isotopic Abundances and Atomic Weights (CIAAW-IUPAC) decided that the uncertainty of atomic weight of chlorine (A(r)(Cl)) should be increased so that the implied range was related to terrestrial variability in 1999 (Coplen, T. B. Atomic weights of the elements 1999 (IUPAC Technical Report), Pure Appl. Chem.2001, 73(4), 667-683; and then, it emphasized that the standard atomic weights of ten elements including chlorine were not constants of nature but depend upon the physical, chemical, and nuclear history of the materials in 2009 (Wieser, M. E.; Coplen, T. B. Pure Appl. Chem.2011, 83(2), 359-396). According to the agreement by CIAAW that an atomic weight could be defined for one specified sample of terrestrial origin (Wieser, M. E.; Coplen, T. B. Pure Appl. Chem.2011, 83(2), 359-396), the absolute isotope ratios and atomic weight of chlorine in standard reference materials (NIST 975, NIST 975a, ISL 354) were accurately determined using the high-precision positive thermal ionization mass spectrometer (PTIMS)-Cs(2)Cl(+)-graphite method. After eliminating the weighing error caused from evaporation by designing a special weighing container and accurately determining the chlorine contents in two highly enriched Na(37)Cl and Na(35)Cl salts by the current constant coulometric titration, one series of gravimetric synthetic mixtures prepared from two highly enriched Na(37)Cl and Na(35)Cl salts was used to calibrate two thermal ionization mass spectrometers in two individual laboratories. The correction factors (i.e., K(37/35) = R(37/35meas)/R(37/35calc)) were obtained from five cycles of iterative calculations on the basis of calculated and determined R((37)Cl/(35)Cl) values in gravimetric synthetic mixtures. The absolute R((37)Cl/(35)Cl) ratios for NIST SRM 975, NIST 975a, and ISL 354 by the precise

  8. Relative elemental abundance and heating constraints determined for the solar corona from SERTS measurements

    NASA Technical Reports Server (NTRS)

    Falconer, David A.

    1994-01-01

    Intensities of EUV spectral lines were measured as a function of radius off the solar limb by two flights of Goddard's Solar EUV Rocket Telescope and Spectrograph (SERTS) for three quiet sun regions. The density scale height, line-ratio densities, line-ratio temperatures, and emission measures were determined. The line-ratio temperature determined from the ionization balances of Arnaud and Rothenflug (1985) were more self-consistent than the line-ratio temperatures obtained from the values of Arnaud and Raymond (1992). Limits on the filling factor were determined from the emission measure and the line-ratio densities for all three regions. The relative abundances of silicon, aluminum, and chromium to iron were determined. Results did agree with standard coronal relative elemental abundances for one observation, but did not agree for another. Aluminum was overabundant while silicon was underabundant. Heating was required above 1.15 solar radii for all three regions studied. For two regions, local nonconductive heating is needed for any filling factor, and in all three regions for filling factor of 0.1.

  9. On the Measurement of Elemental Abundance Ratios in Inner Galaxy H II Regions

    NASA Technical Reports Server (NTRS)

    Simpson, Janet P.; Rubin, Robert H.; Colgan, Sean W. J.; Erickson, Edwin F.; Haas, Michael R.

    2004-01-01

    Although abundance gradients in the Milky Way Galaxy certainly exist, details remain uncertain, particularly in the inner Galaxy, where stars and H II regions in the Galactic plane are obscured optically. In this paper we revisit two previously studied, inner Galaxy H II regions: G333.6-0.2 and W43. We observed three new positions in G333.6-0.2 with the Kuiper Airborne Observatory and reobserved the central position with the Infrared Space Observatory's Long Wavelength Spectrometer in far-infrared lines of S++, N++, N+, and O++. We also added the N+ lines at 122 and 205 microns to the suite of lines measured in W43 by Simpson et al.. The measured electron densities range from approx. 40 to over 4000 per cu cm in a single HII region, indicating that abundance analyses must consider density variations, since the critical densities of the observed lines range from 40 to 9000 per cu cm. We propose a method to handle density variations and make new estimates of the S/H and N/H abundance ratios. We find that our sulfur abundance estimates for G333.6-0.2 and W43 agree with the S/H abundance ratios expected for the gradient previously reported by Simpson et al., with the S/H values revised to be smaller owing to changes in collisional excitation cross sections. The estimated N/H, S/H, and N/S ratios are the most reliable because of their small corrections for unseen ionization states (< or approx. 10%). The estimated N/S ratios for the two sources are smaller than what would be calculated from the N/H and S/H ratios in our previous paper. If all low excitation H II regions had similar changes to their N/S ratios as a result of adding measurements of N+ to previous measurements of N++, there would be no or only a very small gradient in N/S. This is interesting because nitrogen is considered to be a secondary element and sulfur is a primary element in galactic chemical evolution calculations. We compute models of the two H II regions to estimate corrections for the other

  10. Earthworm eco-physiological characteristics and quantification of earthworm feeding in vermifiltration system for sewage sludge stabilization using stable isotopic natural abundance.

    PubMed

    Li, Xiaowei; Xing, Meiyan; Yang, Jian; Dai, Xiaohu

    2014-07-15

    Previous studies showed that the presence of earthworm improves treatment performance of vermifilter (VF) for sewage sludge stabilization, but earthworm eco-physiological characteristics and effects in VF were not fully investigated. In this study, earthworm population, enzymatic activity, gut microbial community and stable isotopic abundance were investigated in the VF. Results showed that biomass, average weight, number and alkaline phosphatase activity of the earthworms tended to decrease, while protein content and activities of peroxidase and catalase had an increasing tendency as the VF depth. Earthworm gut microbial communities were dominated by Gammaproteobacteria, and the percentages arrived to 76-92% of the microbial species detected. (15)N and (13)C natural abundance of the earthworms decreased with operation time, and increased as the VF depth. Quantitative analysis using δ(15)N showed that earthworm feeding and earthworm-microorganism interaction were responsible for approximately 21% and 79%, respectively, of the enhanced volatile suspended solid reduction due to the presence of earthworm. The finding provides a quantitative insight into how earthworms influence on sewage sludge stabilization in vermifiltration system.

  11. Measurement error associated with surveys of fish abundance in Lake Michigan

    USGS Publications Warehouse

    Krause, Ann E.; Hayes, Daniel B.; Bence, James R.; Madenjian, Charles P.; Stedman, Ralph M.

    2002-01-01

    In fisheries, imprecise measurements in catch data from surveys adds uncertainty to the results of fishery stock assessments. The USGS Great Lakes Science Center (GLSC) began to survey the fall fish community of Lake Michigan in 1962 with bottom trawls. The measurement error was evaluated at the level of individual tows for nine fish species collected in this survey by applying a measurement-error regression model to replicated trawl data. It was found that the estimates of measurement-error variance ranged from 0.37 (deepwater sculpin, Myoxocephalus thompsoni) to 1.23 (alewife, Alosa pseudoharengus) on a logarithmic scale corresponding to a coefficient of variation = 66% to 156%. The estimates appeared to increase with the range of temperature occupied by the fish species. This association may be a result of the variability in the fall thermal structure of the lake. The estimates may also be influenced by other factors, such as pelagic behavior and schooling. Measurement error might be reduced by surveying the fish community during other seasons and/or by using additional technologies, such as acoustics. Measurement-error estimates should be considered when interpreting results of assessments that use abundance information from USGS-GLSC surveys of Lake Michigan and could be used if the survey design was altered. This study is the first to report estimates of measurement-error variance associated with this survey.

  12. Preliminary Figures of Merit for Isotope Ratio Measurements: The Liquid Sampling-Atmospheric Pressure Glow Discharge Microplasma Ionization Source Coupled to an Orbitrap Mass Analyzer

    SciTech Connect

    Hoegg, Edward D.; Barinaga, Charles J.; Hager, George J.; Hart, Garret L.; Koppenaal, David W.; Marcus, R. Kenneth

    2016-04-14

    ABSTRACT In order to meet a growing need for fieldable mass spectrometer systems for precise elemental and isotopic analyses, the liquid sampling-atmospheric pressure glow discharge (LS-APGD) has a number of very promising characteristics. One key set of attributes that await validation deals with the performance characteristics relative to isotope ratio precision and accuracy. Due to its availability and prior experience with this research team, the initial evaluation of isotope ratio (IR) performance was performed on a Thermo Scientific Exactive Orbitrap instrument. While the mass accuracy and resolution performance for orbitrap analyzers are very well documented, no detailed evaluations of the IR performance have been published. Efforts described here involve two variables: the inherent IR precision and accuracy delivered by the LSAPGD microplasma and the inherent IR measurement qualities of orbitrap analyzers. Important to the IR performance, the various operating parameters of the orbitrap sampling interface, HCD dissociation stage, and ion injection/data acquisition have been evaluated. The IR performance for a range of other elements, including natural, depleted, and enriched uranium isotopes was determined. In all cases the precision and accuracy are degraded when measuring low abundance (<0.1% isotope fractions). In the best case, IR precision on the order of 0.1 %RSD can be achieved, with values of 1-3 %RSD observed for low-abundance species. The results suggest that the LSAPGD is a very good candidate for field deployable MS analysis and that the high resolving powers of the orbitrap may be complemented with a here-to-fore unknown capacity to deliver high-precision isotope ratios.

  13. The Abundance and Isotopic Signature of Chlorine in UrKREEP: Implications for the Early Degassing of the Moon

    NASA Technical Reports Server (NTRS)

    Boyce, J. W.; Kanee, S.; McCubbin, F. M.; Barnes, J. J.; Bricker, H.; Treiman. A. H.

    2017-01-01

    Initally, the elevated delta-37 Cl values of lunar materials were attributed to volcanic degassing[1]. However, chlorine isotope ratios of apatite in lunarmare basalts appear to reflect mixing between two reservoirs.One component, with elevated delta-37 Cl is greater than or equal to + (25%) ([2] may represent the urKREEP--the final product of the crystallization of the lunar magma ocean. The second component, with delta-37 Cl is approximately (0%), is inferred to represent either a mare basalt reservoir or meteoritic materials. The idea that high delta-37 Cl is related to urKREEP suggest a global enrichment that occurred earlier in the lunar history [2,3]. Here we test this urKREEP-mixing hypothesis more rigorously, and report the observed limits of the model. We then use the results to calculate the Cl content of the urKREEP component and use those results to update estimates of the bulk Cl content of the Moon. This allows us to speculate on the mechanisms of loss of Cl from the lunar magma ocean.

  14. Measurements of Cosmic-Ray Hydrogen and Helium Isotopes with the PAMELA Experiment

    NASA Astrophysics Data System (ADS)

    Adriani, O.; Barbarino, G. C.; Bazilevskaya, G. A.; Bellotti, R.; Boezio, M.; Bogomolov, E. A.; Bongi, M.; Bonvicini, V.; Bottai, S.; Bruno, A.; Cafagna, F.; Campana, D.; Carlson, P.; Casolino, M.; Castellini, G.; De Donato, C.; De Santis, C.; De Simone, N.; Di Felice, V.; Formato, V.; Galper, A. M.; Karelin, A. V.; Koldashov, S. V.; Koldobskiy, S.; Krutkov, S. Y.; Kvashnin, A. N.; Leonov, A.; Malakhov, V.; Marcelli, L.; Martucci, M.; Mayorov, A. G.; Menn, W.; Mergè, M.; Mikhailov, V. V.; Mocchiutti, E.; Monaco, A.; Mori, N.; Munini, R.; Osteria, G.; Palma, F.; Panico, B.; Papini, P.; Pearce, M.; Picozza, P.; Ricci, M.; Ricciarini, S. B.; Sarkar, R.; Scotti, V.; Simon, M.; Sparvoli, R.; Spillantini, P.; Stozhkov, Y. I.; Vacchi, A.; Vannuccini, E.; Vasilyev, G.; Voronov, S. A.; Yurkin, Y. T.; Zampa, G.; Zampa, N.

    2016-02-01

    The cosmic-ray hydrogen and helium (1H, 2H, 3He, 4He) isotopic composition has been measured with the satellite-borne experiment PAMELA, which was launched into low-Earth orbit on board the Resurs-DK1 satellite on 2006 June 15. The rare isotopes 2H and 3He in cosmic rays are believed to originate mainly from the interaction of high-energy protons and helium with the galactic interstellar medium. The isotopic composition was measured between 100 and 1100 MeV/n for hydrogen and between 100 and 1400 MeV/n for helium isotopes using two different detector systems over the 23rd solar minimum from 2006 July to 2007 December.

  15. MEASUREMENTS OF COSMIC-RAY HYDROGEN AND HELIUM ISOTOPES WITH THE PAMELA EXPERIMENT

    SciTech Connect

    Adriani, O.; Bongi, M.; Barbarino, G. C.; Bazilevskaya, G. A.; Bellotti, R.; Bruno, A.; Boezio, M.; Bonvicini, V.; Formato, V.; Bogomolov, E. A.; Bottai, S.; Cafagna, F.; Campana, D.; Carlson, P.; Casolino, M.; Santis, C. De; Castellini, G.; Donato, C. De; Simone, N. De; Felice, V. Di; and others

    2016-02-10

    The cosmic-ray hydrogen and helium ({sup 1}H, {sup 2}H, {sup 3}He, {sup 4}He) isotopic composition has been measured with the satellite-borne experiment PAMELA, which was launched into low-Earth orbit on board the Resurs-DK1 satellite on 2006 June 15. The rare isotopes {sup 2}H and {sup 3}He in cosmic rays are believed to originate mainly from the interaction of high-energy protons and helium with the galactic interstellar medium. The isotopic composition was measured between 100 and 1100 MeV/n for hydrogen and between 100 and 1400 MeV/n for helium isotopes using two different detector systems over the 23rd solar minimum from 2006 July to 2007 December.

  16. Comparison of multifrequency acoustic and in situ measurements of zooplankton abundances in Knight Inlet, British Columbia.

    PubMed

    Trevorrow, Mark V; Mackas, David L; Benfield, Mark C

    2005-06-01

    An investigation of midwater zooplankton aggregations in a coastal fjord was conducted in November 2002. This study focused on quantitative comparisons between a calibrated, three-frequency (38, 120, and 200 kHz) vessel-based echo-sounder, a multinet towed zooplankton sampler (BIONESS), and a high-resolution underwater camera (ZOOVIS). Daytime layers of euphausiids and amphipods near 70-90-m depth were observed in lower parts of the inlet, especially concentrated by tidal flows around a sill. Quantitative backscatter measurements of euphausiids and amphipods, combined with in situ size and abundance estimates, and using an assumed tilt-angle distribution, were in agreement with averaged fluid-cylinder scattering models produced by Stanton and Chu [ICES J. Mar. Sci. 57, 793-807, (2000)]. Acoustic measurements of physonect siphonophores in the upper inlet were found to have a strong 38-kHz scattering strength, in agreement with a damped bubble scattering model using a diameter of 0.4 mm. In relatively dense euphausiid layers, ZOOVIS abundance estimates were found to be a factor of 2 to 4 higher than the acoustic estimates, potentially due to deviations from assumed euphausiid orientation. Nocturnal near-surface euphausiid scattering exhibited a strong (15 dB) and rapid (seconds) sensitivity to vessel lights, interpreted as due to changing animal orientation.

  17. A Low Abundance of 135Cs in the Early Solar System from Barium Isotopic Signatures of Volatile-depleted Meteorites

    NASA Astrophysics Data System (ADS)

    Brennecka, Gregory A.; Kleine, Thorsten

    2017-03-01

    Precise knowledge of the abundances of short-lived radionuclides at the start of the solar system leads to fundamental information about the stellar environment of solar system formation. Previous investigations of the short-lived {}135{Cs} \\to {}135{Ba} system (t 1/2 = 2.3 Ma) have resulted in a range of calculated initial amounts of 135Cs, with most estimates elevated to a level that requires extraneous input of material to the protoplanetary disk. Such an array of proposed 135Cs/133Cs initial solar system values has severely restricted the system’s use as both a possible chronometer and as an informant about supernovae input. However, if 135Cs was as abundant in the early solar system as previously proposed, the resulting deficits in its daughter product 135Ba would be easily detectable in volatile-depleted parent bodies (i.e., having sub-chondritic Cs/Ba) from the very early solar system. In this work, we show that angrites and eucrites, which were volatile-depleted within ∼1 million years of the start of the solar system, do not possess deficits in 135Ba compared to other planetary bodies. From this, we calculate an upper limit for the initial 135Cs/133Cs of 2.8 × 10‑6, well below previous estimates. This significantly lower initial 135Cs/133Cs ratio now suggests that all of the 135Cs present in the early solar system was inherited simply from galactic chemical evolution and no longer requires an addition from an external stellar source such as an asymptotic giant branch star or SN II, corroborating evidence from several other short-lived radionuclides.

  18. Micron-scale coupled carbon isotope and nitrogen abundance variations in diamonds: Evidence for episodic diamond formation beneath the Siberian Craton

    NASA Astrophysics Data System (ADS)

    Wiggers de Vries, D. F.; Bulanova, G. P.; De Corte, K.; Pearson, D. G.; Craven, J. A.; Davies, G. R.

    2013-01-01

    The internal structure and growth history of six macro-diamonds from kimberlite pipes in Yakutia (Russia) were investigated with cathodoluminescence imaging and coupled carbon isotope and nitrogen abundance analyses along detailed core to rim traverses. The diamonds are characterised by octahedral zonation with layer-by-layer growth. High spatial resolution SIMS profiles establish that there is no exchange of the carbon isotope composition across growth boundaries at the μm scale and that isotopic variations observed between (sub)zones within the diamonds are primary. The macro-diamonds have δ13C values that vary within 2‰ of -5.3‰ and their nitrogen contents range between 0-1334 at. ppm. There are markedly different nitrogen aggregation states between major growth zones within individual diamonds that demonstrate Yakutian diamonds grew in multiple growth events. Growth intervals were punctuated by stages of dissolution now associated with <10 μm wide zones of nitrogen absent type II diamond. Across these resorption interfaces carbon isotope ratios and nitrogen contents record shifts between 0.5-2.3‰ and up to 407 at. ppm, respectively. Co-variation in δ13C value-nitrogen content suggests that parts of individual diamonds precipitated in a Rayleigh process from either oxidised or reduced fluids/melts, with two single diamonds showing evidence of both fluid types. Modelling the co-variation establishes that nitrogen is a compatible element in diamond relative to its growth medium and that the nitrogen partition coefficient is different between oxidised (3-4.1) and reduced (3) sources. The reduced sources have δ13C values between -7.3‰ and -4.6‰, while the oxidised sources have higher δ13C values between -5.8‰ and -1.8‰ (if grown from carbonatitic media) or between -3.8‰ and +0.2‰ (if grown from CO2-rich media). It is therefore concluded that individual Yakutian diamonds originate from distinct fluids/melts of variable compositions. The

  19. Accurate measurement of silver isotopic compositions in geological materials including low Pd/Ag meteorites

    NASA Astrophysics Data System (ADS)

    Woodland, S. J.; Rehkämper, M.; Halliday, A. N.; Lee, D.-C.; Hattendorf, B.; Günther, D.

    2005-04-01

    Very precise silver (Ag) isotopic compositions have been determined for a number of terrestrial rocks, and high and low Pd/Ag meteorites by utilizing multicollector inductively coupled plasma mass spectrometry (MC-ICPMS). The meteorites include primitive chondrites, the Group IAB iron meteorites Canyon Diablo and Toluca, and the Group IIIAB iron meteorite Grant. Silver isotopic measurements are primarily of interest because 107Ag was produced by decay of the short-lived radionuclide 107Pd during the formation of the solar system and hence the Pd-Ag chronometer has set constraints on the timing of early planetesimal formation. A 2σ precision of ±0.05‰ can be obtained for analyses of standard solutions when Ag isotopic ratios are normalized to Pd, to correct for instrumental mass discrimination, and to bracketing standards. Caution must be exercised when making Ag isotopic measurements because isotopic artifacts can be generated in the laboratory and during mass spectrometry. The external reproducibility for geological samples based on replicate analyses of rocks is ±0.2‰ (2σ). All chondrites analyzed have similar Ag isotopic compositions that do not differ significantly (>0.3‰) from the 'terrestrial' value of the NIST SRM 978a Ag isotope standard. Hence, they show no evidence of excess 107Ag derived from 107Pd decay or, of stable Ag isotope fractionation associated with volatile element depletion within the accretion disk or from parent body metamorphism. The Group IAB iron meteorite samples analyzed show evidence of complex behavior and disturbance of Ag isotope systematics. Therefore, care must be taken when using this group of iron meteorites to obtain chronological information based on the Pd-Ag decay scheme.

  20. An isotopic approach to measuring nitrogen balance in caribou

    USGS Publications Warehouse

    Gustine, D.D.; Barboza, P.S.; Adams, L.G.; Farnell, R.G.; Parker, K.L.

    2011-01-01

    Nutritional restrictions in winter may reduce the availability of protein for reproduction and survival in northern ungulates. We refined a technique that uses recently voided excreta on snow to assess protein status in wild caribou (Rangifer tarandus) in late winter. Our study was the first application of this non-invasive, isotopic approach to assess protein status of wild caribou by determining dietary and endogenous contributions of nitrogen (N) to urinary urea. We used isotopic ratios of N (??15N) in urine and fecal samples to estimate the proportion of urea N derived from body N (p-UN) in pregnant, adult females of the Chisana Herd, a small population that ranged across the Alaska-Yukon border. We took advantage of a predator-exclosure project to examine N status of penned caribou in April 2006. Lichens were the primary forage (>40%) consumed by caribou in the pen and ?? 15N of fiber tracked the major forages in their diets. The ??15N of urinary urea for females in the pen was depleted relative (-1.3 ?? 1.0 parts per thousand [??], x?? ?? SD) to the ??15N of body N (2.7 ?? 0.7??). A similar proportion of animals in the exclosure lost core body mass (excluding estimates of fetal and uterine tissues; 55%) and body protein (estimated by isotope ratios; 54%). This non-invasive technique could be applied at various spatial and temporal scales to assess trends in protein status of free-ranging populations of northern ungulates. Intra- and inter-annual estimates of protein status could help managers monitor effects of foraging conditions on nutritional constraints in ungulates, increase the efficiency and efficacy of management actions, and help prepare stakeholders for potential changes in population trends. ?? 2010 The Wildlife Society.

  1. Non-destructive measurement of carbonic anhydrase activity and the oxygen isotope composition of soil water

    NASA Astrophysics Data System (ADS)

    Jones, Sam; Sauze, Joana; Ogée, Jérôme; Wohl, Steven; Bosc, Alexandre; Wingate, Lisa

    2016-04-01

    oxygen isotope composition of ambient CO2. This non-destructive approach was tested through laboratory incubations of air-dried soils that were re-wetted with water of known isotopic composition. Performance was assessed by comparing estimates of the soil water oxygen isotope composition derived from open chamber flux measurements with those measured in the irrigation water and soil water extracted following incubations. The influence of soil pH and bovine carbonic anhydrase additions on these estimates was also investigated. Coherent values were found between the soil water composition estimates obtained from the dual steady state approach and those measured for irrigation waters. Estimates of carbonic anhydrase activity made using this approach also reflected well artificial increases to the concentration of carbonic anhydrase and indicated that this activity was sensitive to soil pH.

  2. Satellite measurements of the isotopic composition of galactic cosmic rays

    NASA Technical Reports Server (NTRS)

    Mewaldt, R. A.; Spalding, J. D.; Stone, E. C.; Vogt, R. E.

    1979-01-01

    The individual isotopes of galactic cosmic ray Ne, Mg, and Si at 100 MeV/nucleon were clearly resolved with an rms mass resolution of 0.20 amu. The results suggest the cosmic ray source is enriched in Ne-22, Mg-25, and Mg-26 when compared to the solar system. The ratio of (Mg-25)+(Mg-26) to Mg-24, which is approximately 0.49 compared to the solar system value of 0.27, suggest that the cosmic ray source and solar system material were synthesized under different conditions.

  3. Chlorine and carbon isotope measurements can help assessing the effectivenes of a zero valent iron barrier

    NASA Astrophysics Data System (ADS)

    Cretnik, S.; Audi, C.; Bernstein, A.; Palau, J.; Soler, A.; Elsner, M.

    2012-04-01

    Chlorinated aliphatic hydrocarbons (CAH's) such as trichloroethene (TCE), cis-dichloroethene (cis-DCE) and vinylchloride (VC) are extensively used in industrial applications. One of the most promising remediation techniques for CAH's in groundwater is their removal via abiotic reductive dechlorination using Zero Valent Iron (ZVI). This is applied for the treatment of contaminated sites by installing permeable reactive barriers (PRB). In this study, isotope fractionation of chlorinated ethylenes in transformation by cast iron has been investigated, because such types of iron are commonly used in PRBs. Batch experiments have been carried out in closed flasks, containing cast iron with aqueous solutions of TCE, cDCE and VC. These substrates and their respective products have been monitored by headspace samplings for their concentration (by GC-FID) and isotope fractionation of carbon and chlorine (by GC-IRMS). A decreasing reactivity trend was observed when compounds contain less chlorine atoms, with differences in rate constants of about one order of magnitude between each of the substances TCE > cDCE > VC. This resulted in the accumulation of products with fewer chlorine atoms. Therefore a similar observation can be expected if degradation in the field is incomplete, for example in the case of aged or improperly designed PRB. Pronounced carbon and chlorine isotope fractionation was measured for each of the compounds, and characteristic dual isotope plots (C, Cl) were obtained for TCE and cDCE. These results may serve as an important reference for the interpretation of isotope data from field sites, since stable isotope fractionation is widely recognized as robust indicator for such pollutant transformations. However, carbon isotope fractionation in a given parent compound may be caused by either abiotic or biotic degradation. In the field, it can therefore be difficult to delineate the contribution of abiotic transformation by PRB in the presence of ongoing

  4. Evaluation of the combined measurement uncertainty in isotope dilution by MC-ICP-MS.

    PubMed

    Fortunato, G; Wunderli, S

    2003-09-01

    The combination of metrological weighing, the measurement of isotope amount ratios by a multicollector inductively coupled plasma mass spectrometer (MC-ICP-MS) and the use of high-purity reference materials are the cornerstones to achieve improved results for the amount content of lead in wine by the reversed isotope dilution technique. Isotope dilution mass spectrometry (IDMS) and reversed IDMS have the potential to be a so-called primary method, with which close comparability and well-stated combined measurement uncertainties can be obtained. This work describes the detailed uncertainty budget determination using the ISO-GUM approach. The traces of lead in wine were separated from the matrix by ion exchange chromatography after HNO(3)/H(2)O(2) microwave digestion. The thallium isotope amount ratio ( n((205)Tl)/ n((203)Tl)) was used to correct for mass discrimination using an exponential model approach. The corrected lead isotope amount ratio n((206)Pb)/ n((208)Pb) for the isotopic standard SRM 981 measured in our laboratory was compared with ratio values considered to be the least uncertain. The result has been compared in a so-called pilot study "lead in wine" organised by the CCQM (Comité Consultatif pour la Quantité de Matière, BIPM, Paris; the highest measurement authority for analytical chemical measurements). The result for the lead amount content k(Pb) and the corresponding expanded uncertainty U given by our laboratory was:k(Pb)=1.329 x 10-10mol g-1 (amount content of lead in wine)U[k(Pb)]=1.0 x 10-12mol g-1 (expanded uncertainty U=kxuc, k=2)The uncertainty of the main influence parameter of the combined measurement uncertainty was determined to be the isotope amount ratio R(206,B) of the blend between the enriched spike and the sample.

  5. Ab initio calculations of the Fe(II) and Fe(III) isotopic effects in citrates, nicotianamine, and phytosiderophore, and new Fe isotopic measurements in higher plants

    NASA Astrophysics Data System (ADS)

    Moynier, Frédéric; Fujii, Toshiyuki; Wang, Kun; Foriel, Julien

    2013-05-01

    Iron is one of the most abundant transition metal in higher plants and variations in its isotopic compositions can be used to trace its utilization. In order to better understand the effect of plant-induced isotopic fractionation on the global Fe cycling, we have estimated by quantum chemical calculations the magnitude of the isotopic fractionation between different Fe species relevant to the transport and storage of Fe in higher plants: Fe(II)-citrate, Fe(III)-citrate, Fe(II)-nicotianamine, and Fe(III)-phytosiderophore. The ab initio calculations show firstly, that Fe(II)-nicotianamine is ˜3‰ (56Fe/54Fe) isotopically lighter than Fe(III)-phytosiderophore; secondly, even in the absence of redox changes of Fe, change in the speciation alone can create up to ˜1.5‰ isotopic fractionation. For example, Fe(III)-phytosiderophore is up to 1.5‰ heavier than Fe(III)-citrate2 and Fe(II)-nicotianamine is up to 1‰ heavier than Fe(II)-citrate. In addition, in order to better understand the Fe isotopic fractionation between different plant components, we have analyzed the iron isotopic composition of different organs (roots, seeds, germinated seeds, leaves and stems) from six species of higher plants: the dicot lentil (Lens culinaris), and the graminaceous monocots Virginia wild rye (Elymus virginicus), Johnsongrass (Sorghum halepense), Kentucky bluegrass (Poa pratensis), river oat (Uniola latifolia), and Indian goosegrass (Eleusine indica). The calculations may explain that the roots of strategy-II plants (Fe(III)-phytosiderophore) are isotopically heavier (by about 1‰ for the δ56Fe) than the upper parts of the plants (Fe transported as Fe(III)-citrate in the xylem or Fe(II)-nicotianamine in the phloem). In addition, we suggest that the isotopic variations observed between younger and older leaves could be explained by mixing of Fe received from the xylem and the phloem.

  6. Distribution, abundance and carbon isotopic composition of gaseous hydrocarbons in Big Soda Lake, Nevada: An alkaline, meromictic lake

    USGS Publications Warehouse

    Oremland, R.S.; Des Marais, D.J.

    1983-01-01

    Distribution and isotopic composition (??13C) of low molecular weight hydrocarbon gases were studied in Big Soda Lake (depth = 64 m), an alkaline, meromictic lake with permanently anoxic bottom waters. Methane increased with depth in the anoxic mixolimnion (depth = 20-35 m), reached uniform concentrations (55 ??M/l) in the monimolimnion (35-64 m) and again increased with depth in monimolimnion bottom sediments (>400 ??M/kg below 1 m sub-bottom depth). The ??13C[CH4] values in bottom sediment below 1 m sub-bottom depth (<-70 per mil) increased with vertical distance up the core (??13C[CH4] = -55 per mil at sediment surface). Monimolimnion ??13C[CH4] values (-55 to -61 per mil) were greater than most ??13C[CH4] values found in the anoxic mixolimnion (92% of samples had ??13C[CH4] values between -20 and -48 per mil). No significant concentrations of ethylene or propylene were found in the lake. However ethane, propane, isobutane and n-butane concentrations all increased with water column depth, with respective maximum concentrations of 260, 80, 23 and 22 nM/l encountered between 50-60 m depth. Concentrations of ethane, propane and butanes decreased with depth in the bottom sediments. Ratios of CH4 [C2H6 + C3H8] were high (250-620) in the anoxic mixolimnion, decreased to ~161 in the monimolimnion and increased with depth in the sediment to values as high as 1736. We concluded that methane has a biogenic origin in both the sediments and the anoxic water column and that C2-C4 alkanes have biogenic origins in the monimolimnion water and shallow sediments. The changes observed in ??13C[CH4] and CH4 (C2H6 + C3H8) with depth in the water column and sediments are probably caused by bacteria] processes. These might include anaerobic methane oxidation and different rates of methanogenesis and C2 to C4 alkane production by microorganisms. ?? 1983.

  7. PC/FRAM: New capabilities for the gamma-ray spectrometry measurement of plutonium isotopic composition

    SciTech Connect

    Sampson, T.E.; Kelley, T.A.; Cremers, T.L.; Konkel, T.R.; Friar, R.J.

    1995-10-01

    We describe the new capability of and.present measurement results from the PC/FRAM plutonium isotopic analysis code. This new code allows data acquisition from a single coaxial germanium detector and analysis over an energy range from 120 keV to above I MeV. For the first time we demonstrate a complete isotopic analysis using only gamma rays greater than 200 keV in energy. This new capability allows the measurement of the plutonium isotopic composition of items inside shielded or heavy-walled containers without having to remove the items from the container. This greatly enhances worker safety by reducing handling and the resultant radiation exposure. Another application allows international inspectors to verify the contents of items inside sealed, long-term storage containers that may not be opened for national security or treaty compliance reasons. We present measurement results for traditional planar germanium detectors as well as coaxial detectors measuring shielded and unshielded samples.

  8. High sensitivity measurement of amino acid isotope enrichment using liquid chromatography-mass spectrometry.

    PubMed

    van Eijk, Hans M H; Wijnands, Karolina A P; Bessems, Babs A F M; Olde Damink, Steven W; Dejong, Cornelis H C; Poeze, Martijn

    2012-09-15

    Measurement of the incorporation or conversion of infused stable isotope enriched metabolites in vivo such as amino acids plays a key role in metabolic research. Specific routes are frequently probed in knockout mouse models limiting the available amount of sample. Although less precise as compared to combustion-isotope ratio mass spectrometry (C-IRMS), gas chromatography-mass spectrometry (GC-MS) or liquid chromatography-mass spectrometry (LC-MS) techniques are therefore often the method of choice to measure isotopic enrichment of target metabolites. However, under conditions of metabolic depletion, the precision of these systems becomes limiting. In this paper, studies were performed to enhance the sensitivity and precision of isotope enrichment measurements using LC-MS. Ion-statistics and resolution were identified as critical factors for this application when using a linear trap mass spectrometer. The combination with an automated pre-column derivatization and a carefully selected solvent mix allowed us to measure isotopic enrichments down to 0.005% at plasma concentrations as low as 5 μmol/l, an improvement by a factor of 100 compared to alternative methods. The resulting method now allowed measurement of the in vivo conversion of the amino acid arginine into citrulline as a marker for the production of nitric oxide in an in vivo murine endotoxemia model with depleted plasma levels of arginine and citrulline.

  9. Isotope composition of sulphate in acid mine drainage as measure of bacterial oxidation

    USGS Publications Warehouse

    Taylor, B.E.; Wheeler, M.C.; Nordstrom, D.K.

    1984-01-01

    The formation of acid waters by oxidation of pyrite-bearing ore deposits, mine tailing piles, and coal measures is a complex biogeochemical process and is a serious environmental problem. We have studied the oxygen and sulphur isotope geochemistry of sulphides, sulphur, sulphate and water in the field and in experiments to identify sources of oxygen and reaction mechanisms of sulphate formation. Here we report that the oxygen isotope composition of sulphate in acid mine drainage shows a large variation due to differing proportions of atmospheric- and water-derived oxygen from both chemical and bacterially-mediated oxidation. 18O-enrichment of sulphate results from pyrite oxidation facilitated by Thiobacillus ferrooxidans in aerated environments. Oxygen isotope analysis may therefore be useful in monitoring the effectiveness of abatement programmes designed to inhibit bacterial oxidation. Sulphur isotopes show no significant fractionation between pyrite and sulphate, indicating the quantitative insignificance of intermediate oxidation states of sulphur under acid conditions. ?? 1984 Nature Publishing Group.

  10. The capabilities of ROSINA/DFMS to measure argon isotopes at comet 67P/Churyumov-Gerasimenko

    NASA Astrophysics Data System (ADS)

    Hässig, M.; Altwegg, K.; Berthelier, J. J.; Calmonte, U.; De Keyser, J.; Fiethe, B.; Fuselier, S. A.; Gombosi, T. I.; Le Roy, L.; Owen, T.; Rubin, M.

    2015-01-01

    Little is known about the noble gas abundances in comets. These highly volatile atoms are possible tracers of the history of cometary matter including the thermal evolution. They can help quantify the contribution of cometary impacts to terrestrial oceans and help elucidate on the formation history of comets and their role in the formation and evolution of planetary atmospheres. This paper focuses on argon and the capabilities to measure this noble gas with in situ mass spectrometry at comet 67P/Churyumov-Gerasimenko, the target of the European Space Agency's spacecraft Rosetta. Argon may have been detected by remote sensing in a single Oort cloud comet but to date nothing is known about the isotopic abundances of argon in comets. Furthermore, no detection of argon in a Jupiter-family comet has been reported. Comet 67P/Churyumov-Gerasimenko belongs to the group of Jupiter-family comets and originates most likely in the Kuiper belt. Onboard Rosetta is ROSINA/DFMS (Rosetta Orbiter Spectrometer for Ion and Neutral Analysis/Double Focusing Mass Spectrometer). DFMS has unprecedented mass resolution and high sensitivity and is designed to measure isotopic ratios including argon (Balsiger et al., 2007). Argon measurements using the DFMS lab model (identical to the flight model) demonstrate this capability. At very least, this mass spectrometer has the resolution and sensitivity to reduce the upper limit on the argon outgassing rate relative to water by more than three orders of magnitude (for 38Ar). Most likely, ROSINA/DFMS will provide the first detection of argon in a Jupiter-family comet together with the first determination of the 36Ar/38Ar ratio at a comet.

  11. Application of lead and strontium isotope ratio measurements for the origin assessment of uranium ore concentrates.

    PubMed

    Varga, Zsolt; Wallenius, Maria; Mayer, Klaus; Keegan, Elizabeth; Millet, Sylvain

    2009-10-15

    Lead and strontium isotope ratios were used for the origin assessment of uranium ore concentrates (yellow cakes) for nuclear forensic purposes. A simple and low-background sample preparation method was developed for the simultaneous separation of the analytes followed by the measurement of the isotope ratios by multicollector inductively coupled plasma mass spectrometry (MC-ICPMS). The lead isotopic composition of the ore concentrates suggests applicability for the verification of the source of the nuclear material and by the use of the radiogenic (207)Pb/(206)Pb ratio the age of the raw ore material can be calculated. However, during data interpretation, the relatively high variation of the lead isotopic composition within the mine site and the generally high contribution of natural lead as technological contamination have to be carefully taken into account. The (87)Sr/(86)Sr isotope ratio is less prone to the variation within one mine site and less affected by the production process, thus it was found to be a more purposeful indicator for the origin assessment and source verification than the lead. The lead and strontium isotope ratios measured and the methodology developed provide information on the initial raw uranium ore used, and thus they can be used for source attribution of the uranium ore concentrates.

  12. Constraints on nitrogen cycling at the subtropical North Pacific Station ALOHA from isotopic measurements of nitrate and particulate nitrogen

    NASA Astrophysics Data System (ADS)

    Casciotti, K. L.; Trull, T. W.; Glover, D. M.; Davies, D.

    2008-07-01

    Nitrogen supply to surface waters can play an important role in the productivity and ecology of subtropical ecosystems. As part of the Vertical Transport in the Global Ocean (VERTIGO) program, we examined the fluxes of nitrogen into and out of the euphotic zone at station ALOHA in the North Pacific Subtropical Gyre using natural abundance stable isotopic measurements of nitrate ( δN and δO), as well as sinking and suspended particulate nitrogen (δ 15N PN). Paralleling the steep gradient in nitrate concentration in the upper thermocline at ALOHA, we observed a steep gradient in δN, decreasing from a maximum of +7.1‰ at 500 meters (m) to +1.5-2.4‰ at 150 m. δO values also decreased from +3.0‰ at 300 m to +0.7-0.9‰ at 150 m. The decreases in both δN and δO require inputs of isotopically "light" nitrate to balance the upward flux of nitrate with high δN (and δO). We conclude that both nitrogen fixation and diagenetic alteration of the sinking flux contribute to the decrease in δN and δO in the upper thermocline at station ALOHA. While nitrogen fixation is required to explain the nitrogen isotope patterns, the rates of nitrogen fixation may be lower than previously estimated. By including high-resolution nitrate isotope measurements in the nitrogen isotope budget for the euphotic zone at ALOHA, we estimate that approximately 25%, rather than 50%, of export production was fueled by N 2 fixation during our study. On the other hand, this input of N 2-derived production accumulates in the upper thermocline over time, playing a significant role in subtropical nutrient cycling through maintenance of the subsurface nitrate pool. An increase in sinking δ 15N PN between 150 and 300 m, also suggests that fractionation during remineralization contributed to the low δN values observed in this depth range by introducing a subsurface nitrate source that is 0.5‰ lower in δ 15N than the particle flux exported from the euphotic zone. While the time scale of these

  13. Reporting and measurement of mass-dependent and mass-independent fractionation of mercury isotopes

    NASA Astrophysics Data System (ADS)

    Bergquist, B. A.; Blum, J. D.

    2007-12-01

    Hg isotope analysis by MC-ICP-MS is an important new approach for fingerprinting Hg sources and monitoring Hg redox reactions and bioaccumulation, especially with the recent discovery of mass independent Hg isotope fractionation. Unfortunately research groups have adopted different standards, definitions of delta values, and methods of isotopic measurement. We suggest that a single standard, NIST SRM 3133, be adopted for reporting the isotopic variability of Hg isotopes. Isotope ratios should be determined by sample-standard bracketing (SSB) during analysis and reported as permil (‰) deviation from SRM 3133. For the highest precision and accuracy, a Tl internal standard along with SSB should be used to correct instrumental mass bias. Measurement routines should also include on-peak zero corrections and matching of concentration and matrix between the samples and bracketing standard. For samples that display mass-dependent fractionation (MDF), only one delta value needs to be reported (δ202/198Hg). Mass-independent fractionation (MIF) (Jackson et al., 2006; Bergquist et al., 2006; Bergquist and Blum, submitted) requires additional nomenclature, and we suggest reporting MIF as the deviation in isotope ratios from the theoretical mass dependent kinetic isotope fractionation (Δxxx/198Hg)¬. External reproducibility should be monitored by analysis of secondary standards. For studies of MDF, we use an in-house secondary standard solution made from metallic Hg mined from Almaden Spain and obtain a δ202Hg of -0.55 ±0.06‰ (2SD). For studies of MIF, we use NRCC CRM DORM-2 (dogfish muscle) and obtain a mean value of δ202Hg of +0.19 ±0.13‰ (2SD), Δ201Hg of +0.89 ±0.07‰ (2SD) , and Δ199Hg of +1.07 ±0.08‰ (2SD).

  14. Site-selective nitrogen isotopic ratio measurement of nitrous oxide using a TE-cooled CW-RT-QCL based spectrometer.

    PubMed

    Li, Jingsong; Zhang, Lizhu; Yu, Benli

    2014-12-10

    The feasibility of laser spectroscopic isotopic composition measurements of atmospheric N2O was demonstrated, although making them useful will require further improvements. The system relies on a thermoelectrically (TE) cooled continuous-wave (CW) room temperature (RT) quantum cascade laser source emitting wavelength of around 4.6μm, where strong fundamental absorption bands occur for the considered specie and its isotopomers. The analysis technique is based on wavelength modulation spectroscopy with second-harmonic detection and the combination of long-path absorption cell. Primary laboratory tests have been performed to estimate the achievable detection limits and the signal reproducibility levels in view of possible measurements of (15)N/(14)N and (18)O/(16)O isotope ratios. The experiment results showed that the site-selective (15)N/(14)N ratio can be measured with a precision of 3‰ with 90s averaging time using natural-abundance N2O sample of 12.7ppm.

  15. Influence of relative abundance of isotopes on depth resolution for depth profiling of metal coatings by laser ablation inductively coupled plasma mass spectrometry.

    PubMed

    Fariñas, Juan C; Coedo, Aurora G; Dorado, Teresa

    2010-04-15

    A systematic study on the influence of relative abundance of isotopes of elements in the coating (A(c)) and in the substrate (A(s)) on both shape of time-resolved signals and depth resolution (Delta z) was performed for depth profile analysis of metal coatings on metal substrates by ultraviolet (266 nm) nanosecond laser ablation inductively coupled plasma quadrupole mass spectrometry. Five coated samples with coating thicknesses of the same order of magnitude (20-30 microm) were tested: nickel coating on aluminium, chromium and copper, and steel coated with copper and zinc. A laser repetition rate of 1 Hz and a laser fluence of 21 J cm(-2) were used. Five different depth profile types were established, which showed a clear dependence on A(c)/A(s) ratio. In general, depth profiles obtained for ratios above 1-10 could not be used to determine Delta z. We found that Delta z increased non-linearly with A(c)/A(s) ratio. The best depth profile types, leading to highest depth resolution and reproducibility, were attained in all cases by using the isotopes with low/medium A(c) values and with the highest A(s) values. In these conditions, an improvement of up to 4 times in Delta z values was achieved. The average ablation rates were in the range from 0.55 microm pulse(-1) for copper coating on steel to 0.83 microm pulse(-1) for zinc coating on steel, and the Delta z values were between 2.74 microm for nickel coating on chromium and 5.91 microm for nickel coating on copper, with RSD values about 5-8%.

  16. Tracing magma sources in an arc-arc collision zone: Helium and carbon isotope and relative abundance systematics of the Sangihe Arc, Indonesia

    NASA Astrophysics Data System (ADS)

    Jaffe, Lillie A.; Hilton, David R.; Fischer, Tobias P.; Hartono, Udi

    2004-04-01

    The Sangihe Arc is presently colliding with the Halmahera Arc in northeastern Indonesia, forming the world's only extant example of an arc-arc collision zone. We report the first helium and carbon isotopic and relative abundance data from the Sangihe Arc volcanoes as a means to trace magma origins in this complicated tectonic region. Results of this study define a north-south trend in 3He/4He, CO2/3He, and δ13C, suggesting that there are variations in primary magma source characteristics along the strike of the arc. The northernmost volcanoes (Awu and Karangetang) have higher CO2/3He and δ13C (up to 179 × 109 and -0.4‰, respectively) and lower 3He/4He (˜5.4 RA) than the southernmost volcanoes (Ruang, Lokon, and Mahawu). Resolving the arc CO2 into component structures (mantle-derived, plus slab-derived organic and carbonate CO2), the northern volcanoes contain an unusually high (>90%) contribution of CO2 derived from isotopically heavy carbonate associated with the subducting slab (sediment and altered oceanic basement). Furthermore, the overall slab contribution (CO2 of carbonate and organic origin) relative to carbon of mantle wedge origin is significantly enhanced in the northern segment of the arc. These observations may be caused by greater volumes of sediment subduction in the northern arc, along-strike variability in subducted sediment composition, or enhanced slab-derived fluid/melt production resulting from the superheating of the slab as collision progresses southward.

  17. Chlorine Abundances in Cool Stars

    NASA Astrophysics Data System (ADS)

    Maas, Z. G.; Pilachowski, C. A.; Hinkle, K.

    2016-12-01

    Chlorine abundances are reported in 15 evolved giants and 1 M dwarf in the solar neighborhood. The Cl abundance was measured using the vibration-rotation 1-0 P8 line of H35Cl at 3.69851 μm. The high-resolution L-band spectra were observed using the Phoenix infrared spectrometer on the Kitt Peak Mayall 4 m telescope. The average [35Cl/Fe] abundance in stars with -0.72 < [Fe/H] < 0.20 is [35Cl/Fe] = (-0.10 ± 0.15) dex. The mean difference between the [35Cl/Fe] ratios measured in our stars and chemical evolution model values is (0.16 ± 0.15) dex. The [35Cl/Ca] ratio has an offset of ˜0.35 dex above model predictions, suggesting that chemical evolution models are underproducing Cl at the high metallicity range. Abundances of C, N, O, Si, and Ca were also measured in our spectral region and are consistent with F and G dwarfs. The Cl versus O abundances from our sample match Cl abundances measured in planetary nebula and H ii regions. In one star where both H35Cl and H37Cl could be measured, a 35Cl/37Cl isotope ratio of 2.2 ± 0.4 was found, consistent with values found in the Galactic ISM and predicted chemical evolution models.

  18. Evapotranspiration partitioning through in-situ oxygen isotope measurements in an oasis cropland

    NASA Astrophysics Data System (ADS)

    Wen, Xue-Fa

    2016-04-01

    The oxygen isotope compositions of ecosystem water pools and fluxes are useful tracers in the water cycle. As part of the Heihe Watershed Allied Telemetry Experimental Research (HiWATER) program, high-frequency and near-continuous in situ measurements of 18O composition of atmospheric vapor (δv) and of evapotranspiration (δET) were made with the flux-gradient method using a cavity ring-down spectroscopy water vapor isotope analyzer. At the sub-daily scale, we found, in conjunction with intensive isotopic measurements of other ecosystem water pools, that the differences between 18O composition of transpiration (δT) and of xylem water (δx) were negligible in early afternoon (13:00-15:00 Beijing time) when ET approached the daytime maximum, indicating isotopic steady state. At the daily scale, for the purpose of flux partitioning, δT was approximated by δx at early afternoon hours, and the 18O composition of soil evaporation (δE) was obtained from the Craig-Gordon model with a moisture-dependent soil resistance. The relative contribution of transpiration to evapotranspiration ranged from 0.71 to 0.96 with a mean of 0.87 ± 0.052 for the growing season according to the isotopic labeling, which was good agreement with soil lysimeter measurements showing a mean transpiration fraction of 0.86 ± 0.058. At the growing season scale, the predicted18O composition of runoff water was within the range of precipitation and irrigation water according to the isotopic mass conservation. The 18O mass conservation requires that the decreased δ18O of ET should be balanced by enhanced δ18O of runoff water. (Wen, XF*, Yang, B, Sun, XM, Lee, X. 2015. Evapotranspiration partitioning through in-situ oxygen isotope measurements in an oasis cropland. Agricultural and Forest Meteorology , doi:10.1016/j.agrformet.2015.12.003).

  19. Separation of copper, iron, and zinc from complex aqueous solutions for isotopic measurement

    USGS Publications Warehouse

    Borrok, D.M.; Wanty, R.B.; Ridley, W.I.; Wolf, R.; Lamothe, P.J.; Adams, M.

    2007-01-01

    The measurement of Cu, Fe, and Zn isotopes in natural samples may provide valuable information about biogeochemical processes in the environment. However, the widespread application of stable Cu, Fe, and Zn isotope chemistry to natural water systems remains limited by our ability to efficiently separate these trace elements from the greater concentrations of matrix elements. In this study, we present a new method for the isolation of Cu, Fe, and Zn from complex aqueous solutions using a single anion-exchange column with hydrochloric acid media. Using this method we are able to quantitatively separate Cu, Fe, and Zn from each other and from matrix elements in a single column elution. Elution of the elements of interest, as well as all other elements, through the anion-exchange column is a function of the speciation of each element in the various concentrations of HCl. We highlight the column chemistry by comparing our observations with published studies that have investigated the speciation of Cu, Fe, and Zn in chloride solutions. The functionality of the column procedure was tested by measuring Cu, Fe, and Zn isotopes in a variety of stream water samples impacted by acid mine drainage. The accuracy and precision of Zn isotopic measurements was tested by doping Zn-free stream water with the Zn isotopic standard. The reproducibility of the entire column separation process and the overall precision of the isotopic measurements were also evaluated. The isotopic results demonstrate that the Cu, Fe, and Zn column separates from the tested stream waters are of sufficient purity to be analyzed directly using a multicollector inductively coupled plasma mass spectrometer (MC-ICP-MS), and that the measurements are fully-reproducible, accurate, and precise. Although limited in scope, these isotopic measurements reveal significant variations in ??65Cu (- 1.41 to + 0.30???), ??56Fe (- 0.56 to + 0.34???), and ??66Zn (0.31 to 0.49???) among samples collected from different

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

    NASA Astrophysics Data System (ADS)

    Dong, F.; Baer, D. S.

    2010-12-01

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

  1. High-precision measurements of seawater Pb isotope compositions by double spike thermal ionization mass spectrometry.

    PubMed

    Paul, Maxence; Bridgestock, Luke; Rehkämper, Mark; van DeFlierdt, Tina; Weiss, Dominik

    2015-03-10

    A new method for the determination of seawater Pb isotope compositions and concentrations was developed, which combines and optimizes previously published protocols for the separation and isotopic analysis of this element. For isotopic analysis, the procedure involves initial separation of Pb from 1 to 2L of seawater by co-precipitation with Mg hydroxide and further purification by a two stage anion exchange procedure. The Pb isotope measurements are subsequently carried out by thermal ionization mass spectrometry using a (207)Pb-(204)Pb double spike for correction of instrumental mass fractionation. These methods are associated with a total procedural Pb blank of 28±21 pg (1sd) and typical Pb recoveries of 40-60%. The Pb concentrations are determined by isotope dilution (ID) on 50 mL of seawater, using a simplified version of above methods. Analyses of multiple aliquots of six seawater samples yield a reproducibility of about ±1 to ±10% (1sd) for Pb concentrations of between 7 and 50 pmol/kg, where precision was primarily limited by the uncertainty of the blank correction (12±4 pg; 1sd). For the Pb isotope analyses, typical reproducibilities (±2sd) of 700-1500 ppm and 1000-2000 ppm were achieved for (207)Pb/(206)Pb, (208)Pb/(206)Pb and (206)Pb/(204)Pb, (207)Pb/(204)Pb, (208)Pb/(204)Pb, respectively. These results are superior to literature data that were obtained using plasma source mass spectrometry and they are at least a factor of five more precise for ratios involving the minor (204)Pb isotope. Both Pb concentration and isotope data, furthermore, show good agreement with published results for two seawater intercomparison samples of the GEOTRACES program. Finally, the new methods were applied to a seawater depth profile from the eastern South Atlantic. Both Pb contents and isotope compositions display a smooth evolution with depth, and no obvious outliers. Compared to previous Pb isotope data for seawater, the (206)Pb/(204)Pb ratios are well correlated

  2. Calcium-aluminum-rich inclusions with fractionation and unidentified nuclear effects (FUN CAIs): II. Heterogeneities of magnesium isotopes and 26Al in the early Solar System inferred from in situ high-precision magnesium-isotope measurements

    NASA Astrophysics Data System (ADS)

    Park, Changkun; Nagashima, Kazuhide; Krot, Alexander N.; Huss, Gary R.; Davis, Andrew M.; Bizzarro, Martin

    2017-03-01

    Calcium-aluminum-rich inclusions with isotopic mass fractionation effects and unidentified nuclear isotopic anomalies (FUN CAIs) have been studied for more than 40 years, but their origins remain enigmatic. Here we report in situ high precision measurements of aluminum-magnesium isotope systematics of FUN CAIs by secondary ion mass spectrometry (SIMS). Individual minerals were analyzed in six FUN CAIs from the oxidized CV3 carbonaceous chondrites Axtell (compact Type A CAI Axtell 2271) and Allende (Type B CAIs C1 and EK1-4-1, and forsterite-bearing Type B CAIs BG82DH8, CG-14, and TE). Most of these CAIs show evidence for excess 26Mg due to the decay of 26Al. The inferred initial 26Al/27Al ratios [(26Al/27Al)0] and the initial magnesium isotopic compositions (δ26Mg0) calculated using an exponential law with an exponent β of 0.5128 are (3.1 ± 1.6) × 10-6 and 0.60 ± 0.10‰ (Axtell 2271), (3.7 ± 1.5) × 10-6 and -0.20 ± 0.05‰ (BG82DH8), (2.2 ± 1.1) × 10-6 and -0.18 ± 0.05‰ (C1), (2.3 ± 2.4) × 10-5 and -2.23 ± 0.37‰ (EK1-4-1), (1.5 ± 1.1) × 10-5 and -0.42 ± 0.08‰ (CG-14), and (5.3 ± 0.9) × 10-5 and -0.05 ± 0.08‰ (TE) with 2σ uncertainties. We infer that FUN CAIs recorded heterogeneities of magnesium isotopes and 26Al in the CAI-forming region(s). Comparison of 26Al-26Mg systematics, stable isotope (oxygen, magnesium, calcium, and titanium) and trace element studies of FUN and non-FUN igneous CAIs indicates that there is a continuum among these CAI types. Based on these observations and evaporation experiments on CAI-like melts, we propose a generic scenario for the origin of igneous (FUN and non-FUN) CAIs: (i) condensation of isotopically normal solids in an 16O-rich gas of approximately solar composition; (ii) formation of CAI precursors by aggregation of these solids together with variable abundances of isotopically anomalous grains-possible carriers of unidentified nuclear (UN) effects; and (iii) melt evaporation of these precursors

  3. VAPOR PRESSURE ISOTOPE EFFECTS IN THE MEASUREMENT OF ENVIRONMENTAL TRITIUM SAMPLES.

    SciTech Connect

    Kuhne, W.

    2012-12-03

    Standard procedures for the measurement of tritium in water samples often require distillation of an appropriate sample aliquot. This distillation process may result in a fractionation of tritiated water and regular light water due to the vapor pressure isotope effect, introducing either a bias or an additional contribution to the total tritium measurement uncertainty. The magnitude of the vapor pressure isotope effect is characterized as functions of the amount of water distilled from the sample aliquot and the heat settings for the distillation process. The tritium concentration in the distillate is higher than the tritium concentration in the sample early in the distillation process, it then sharply decreases due to the vapor pressure isotope effect and becomes lower than the tritium concentration in the sample, until the high tritium concentration retained in the boiling flask is evaporated at the end of the process. At that time, the tritium concentration in the distillate again overestimates the sample tritium concentration. The vapor pressure isotope effect is more pronounced the slower the evaporation and distillation process is conducted; a lower heat setting during the evaporation of the sample results in a larger bias in the tritium measurement. The experimental setup used and the fact that the current study allowed for an investigation of the relative change in vapor pressure isotope effect in the course of the distillation process distinguish it from and extend previously published measurements. The separation factor as a quantitative measure of the vapor pressure isotope effect is found to assume values of 1.034 {+-} 0.033, 1.052 {+-} 0.025, and 1.066 {+-} 0.037, depending on the vigor of the boiling process during distillation of the sample. A lower heat setting in the experimental setup, and therefore a less vigorous boiling process, results in a larger value for the separation factor. For a tritium measurement in water samples, this implies that

  4. Carbon and Hydrogen Isotope Measurements of Alcohols and Organic Acids by Online Pyroprobe-GC-IRMS

    NASA Technical Reports Server (NTRS)

    Socki, Richard A.; Fu, Qi; Niles, Paul B.; Gibson, Everett K., Jr.

    2012-01-01

    The detection of methane in the atmosphere of Mars, combined with evidence showing widespread water-rock interaction during martian history, suggests that the production of methane on Mars may be the result of mineral surface-catalyzed CO2 and or CO reduction during Fisher-Tropsch Type (FTT) reactions. A better understanding of these reaction pathways and corresponding C and H isotope fractionations is critical to deciphering the synthesis of organic compounds produced under abiotic hydrothermal conditions. Described here is a technique for the extraction and analysis of both C and H isotopes from alcohols (C1-C4) and organic acids (C1-C6). This work is meant to provide a "proof of concept" for making meaningful isotope measurements on complex mixtures of solid-phase hydrocarbons and other intermediary products produced during high-temperature and high-pressure synthesis on mineral-catalyzed surfaces. These analyses are conducted entirely "on-line" utilizing a CDS model 5000 Pyroprobe connected to a Thermo Trace GC Ultra that is interfaced with a Thermo MAT 253 isotope ratio mass spectrometer operating in continuous flow mode. Also, this technique is designed to carry a split of the GC-separated product to a DSQ II quadrupole mass spectrometer as a means of making semi-quantitative compositional measurements. Therefore, both chemical and isotopic measurements can be carried out on the same sample.

  5. Epiphyte Density and Diversity on Halimeda incrassata and the Affect on Bulk Isotopic Measurements

    NASA Astrophysics Data System (ADS)

    Drayer, C. L.; Katz, D. A.; Devlin, Q. B.; Swart, P. K.; Evans, S. L.

    2008-12-01

    Epiphytic density and diversity, organic and inorganic δ13C and organic δ15N were determined for the green calcifying benthic macroalgae, Halimeda incrassata, from Biscayne Bay, a subtropical coastal lagoon located off the southeastern coast of Florida. Cocconeis and Bacteriastrum were determined to be the two most dominant diatomaceous epiphytes living on the Halimeda tissue but an unidentified bacteria proved to be the overall most abundant epiphyte. Cocconeis and the bacteria reached maximum densities mid-strand while Bacteriastrum reached a bimodal peak density at the top and bottom of the strand. Organic δ13C are consistently lighter towards the top of the strand while inorganic δ13C shows the opposite pattern. These results indicate that photosynthetic rates are higher at the top of the strand where metabolic processes are able to preferentially uptake 12C . δ13C values can vary as much as 3 ‰ by algal segment and inorganic values tend to approach equilibrium with the surrounding seawater in the lower algal segments, which are the oldest parts of the thallus. Organic δ15N shows no definite independent trend but increases in δ15N appear to correlate with increased density of the Cocconeis diatom. Organic δ15N can vary as much 9 ‰ by algal segment. This work questions the validity of using bulk isotopic measurements of the algae as a proxy for the origin of nitrogen. Future work should address quantification of epiphytic and Halimeda sp. biomass, the possible presence of other bacteria within the algal tissue and skeletal structure, the relationship between the bacteria and algal host (symbiotic vs. parasitic), and determine how epiphytic communities vary over time (seasons) and space (location within the Bay).

  6. Preliminary Figures of Merit for Isotope Ratio Measurements: The Liquid Sampling-Atmospheric Pressure Glow Discharge Microplasma Ionization Source Coupled to an Orbitrap Mass Analyzer.

    PubMed

    Hoegg, Edward D; Barinaga, Charles J; Hager, George J; Hart, Garret L; Koppenaal, David W; Marcus, R Kenneth

    2016-08-01

    In order to meet a growing need for fieldable mass spectrometer systems for precise elemental and isotopic analyses, the liquid sampling-atmospheric pressure glow discharge (LS-APGD) has a number of very promising characteristics. One key set of attributes that await validation deals with the performance characteristics relative to isotope ratio precision and accuracy. Owing to its availability and prior experience with this research team, the initial evaluation of isotope ratio (IR) performance was performed on a Thermo Scientific Exactive Orbitrap instrument. While the mass accuracy and resolution performance for Orbitrap analyzers are well-documented, no detailed evaluations of the IR performance have been published. Efforts described here involve two variables: the inherent IR precision and accuracy delivered by the LS-APGD microplasma and the inherent IR measurement qualities of Orbitrap analyzers. Important to the IR performance, the various operating parameters of the Orbitrap sampling interface, high-energy collisional dissociation (HCD) stage, and ion injection/data acquisition have been evaluated. The IR performance for a range of other elements, including natural, depleted, and enriched uranium isotopes was determined. In all cases, the precision and accuracy are degraded when measuring low abundance (<0.1% isotope fractions). In the best case, IR precision on the order of 0.1% RSD can be achieved, with values of 1%-3% RSD observed for low-abundance species. The results suggest that the LS-APGD is a promising candidate for field deployable MS analysis and that the high resolving powers of the Orbitrap may be complemented with a here-to-fore unknown capacity to deliver high-precision IRs. Graphical Abstract ᅟ.

  7. Preliminary Figures of Merit for Isotope Ratio Measurements: The Liquid Sampling-Atmospheric Pressure Glow Discharge Microplasma Ionization Source Coupled to an Orbitrap Mass Analyzer

    NASA Astrophysics Data System (ADS)

    Hoegg, Edward D.; Barinaga, Charles J.; Hager, George J.; Hart, Garret L.; Koppenaal, David W.; Marcus, R. Kenneth

    2016-08-01

    In order to meet a growing need for fieldable mass spectrometer systems for precise elemental and isotopic analyses, the liquid sampling-atmospheric pressure glow discharge (LS-APGD) has a number of very promising characteristics. One key set of attributes that await validation deals with the performance characteristics relative to isotope ratio precision and accuracy. Owing to its availability and prior experience with this research team, the initial evaluation of isotope ratio (IR) performance was performed on a Thermo Scientific Exactive Orbitrap instrument. While the mass accuracy and resolution performance for Orbitrap analyzers are well-documented, no detailed evaluations of the IR performance have been published. Efforts described here involve two variables: the inherent IR precision and accuracy delivered by the LS-APGD microplasma and the inherent IR measurement qualities of Orbitrap analyzers. Important to the IR performance, the various operating parameters of the Orbitrap sampling interface, high-energy collisional dissociation (HCD) stage, and ion injection/data acquisition have been evaluated. The IR performance for a range of other elements, including natural, depleted, and enriched uranium isotopes was determined. In all cases, the precision and accuracy are degraded when measuring low abundance (<0.1% isotope fractions). In the best case, IR precision on the order of 0.1% RSD can be achieved, with values of 1%-3% RSD observed for low-abundance species. The results suggest that the LS-APGD is a promising candidate for field deployable MS analysis and that the high resolving powers of the Orbitrap may be complemented with a here-to-fore unknown capacity to deliver high-precision IRs.

  8. Precipitation water stable isotope measurements and analyses in Middle and Polar Ural

    NASA Astrophysics Data System (ADS)

    Stukova, Olga; Gribanov, Konstantin; Zakharov, Vyacheslav; Cattani, Olivier; Jouzel, Jean

    2015-11-01

    In this paper, we present results of precipitation (rain, snow) water stable isotope measurements, which were collected on two places. Measuring was made on laser spectroscopy analyzer PICARRO L2130-i equipped with liquid auto sampler. We describe method of sample collecting, preparing, measuring and continuing analysis of experimental data. Stored data include results of 177 samples measuring from Kourovka collected from November 2012 to March 2014 and 73 samples from Labytnangi collected from March 2013 to December 2013.

  9. Hydroacoustic measures of Mysis relicta abundance and distribution in Lake Ontario

    USGS Publications Warehouse

    Rudstam, L. G.; Schaner, T.; Gal, G.; Boscarino, B.T.; O'Gorman, R.; Warner, D.M.; Johannsson, O.E.; Bowen, K.L.

    2008-01-01

    Mysis relicta can be observed on echograms as a sound scattering layer when they migrate into the water column at night to feed on zooplankton. However, quantitative measures of mysid abundance with hydroacoustics requires knowledge of mysid target strength (TS), a method of removing fish echoes and contribution from noise, and an understanding of the effect of range on the ability of hydroacoustics to detect mysids (the detection limit). Comparisons of paired net data and acoustics data from July 7, 2005 yielded a mysid TS of -86.3 dB (9 mm animal) and a biomass TS of -58.4 dB (g dry wt)-1. With ambient noise levels (Sv of -125 dB at 1 m depth) and this TS, we can detect a mysid density of 1 m-3 at 60 m depth with a signal to noise ratio of 3 dB. We present a method to remove backscattering from both noise and fish and apply this method and the new TS data to whole lake acoustic data from Lake Ontario collected in July 25-31, 2005 with a 120 kHz echosounder as part of the annual standard fish survey in that lake. Mysis abundance was strongly depth dependent, with highest densities in areas with bottom depth > 100 m, and few mysids in areas with bottom depth 100 m, 100-75 m, 75-50 m, 50-30 m, < 30 m), the whole-lake average mysid density was 118 m-2 (CV 21%) and the whole-lake average mysid biomass was 0.19 g dry wt m-2 (CV 22%) in July 2005. The CVs of these densities also account for uncertainty in the TS estimates. This is comparable to whole-lake density estimates using vertical net tows in November, 2005 (93 m-2, CV 16%). Copyright ?? 2008 AEHMS.

  10. Solar photospheric and coronal abundances from solar energetic particle measurements. Ph.D. Thesis

    NASA Technical Reports Server (NTRS)

    Breneman, H.

    1985-01-01

    Observations of solar energetic particles (SEP) from 22 solar flares in the 1977 to 1982 time period are reported. SEP abundances were obtained for all elements with 3 approximately less than Z approximately less than 30 except Li, Be, B, F, Sc, v, Co and Cu for which upper limits were obtained. Statistically meaningful abundances of several rare elements (P, Cl, K, Ti, and Mn) were determined for the first time, and the average abundance of the more abundant elements were determined with improved precision.

  11. Interchange for Joint Research Entitled: Measurement of Stable Nitrogen and Sulfur Isotopes

    NASA Technical Reports Server (NTRS)

    Becker, Joseph F.; Valentin, Jose

    1997-01-01

    Viking measurements of the Martian atmosphere indicate a value of N-15/N-14 which is markedly greater than that found in Earth's atmosphere. These isotopic measurements provide a powerful diagnostic tool which may be used to derive valuable information regarding the past history of Mars and they have been used to place important constraints on the evolution of Mars' atmosphere. Initial partial pressures of nitrogen, outgassing rates, and integrated deposition of nitrogen into minerals have been calculated from this important atmospheric data (McElroy et al., 1976 and 1977; Fox and Dalgarno, 1983). The greater precision obtained in laser spectrometer isotopic measurements compared to the Viking data will greatly improve these calculated values. It has also been proposed that the N-15/N-14 value in Mars' atmosphere has increased monotonically over time (McElroy et al., 1977; Fox and Dalgarno, 1983; Wallis, 1989) owing to preferential escape of atmospheric 14N to space. Nitrogen isotopic ratios might be used to identify relatively ancient crustal rocks (R. Mancinelli, personal communication), and perhaps determine relative aces of surface samples. As a first step in successfully measuring nitrogen isotopes optically we have demonstrated the measurement of 15NI14N to a precision of 0.1% (See Figures 1-4) using a tunable diode laser and an available gas (N-,O) with spectral lines in the 2188 cm-1 region. The sample and reference gas cells contained gases of identical isotopic composition so that the 15NI14N absorption ratio determined from the sample cell, when divided by the 15NI14N absorption ratio determined from the reference cell, should yield an ideal value of unity. The average measured value of this "ratio of ratios" was 0.9983 with a standard deviation (20 values) of 0.0010. This corresponds to a precision of 0.1% (1 per mil) for nitrogen isotopes, a value sufficiently precise to provide important isotopic data of interest to exobiologists. The precision

  12. 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.

  13. Measurement of Relative Abundances of Ultra-Heavy Cosmic Rays with CALET on the ISS

    NASA Astrophysics Data System (ADS)

    Rauch, Brian; Calet Collaboration

    2016-03-01

    The CALorimetric Electron Telescope (CALET) is a Japanese-Italian-US astroparticle observatory that was launched from the Tanegashima Space Center on the H-IIB Launch Vehicle No.5 (H-IIB F5) aboard the KOUNOTORI5 (HTV5 cargo transfer vehicle) to the International Space Station (ISS) on August 19, 2015. The HTV5 arrived at the ISS on August 24, and CALET was installed on port 9 of the Japanese Experiment Module ``Kibo'' Exposed Facility (JEM-EF), where CALET underwent the planned turn on and checkout procedures. CALET has completed its commissioning phase and its main calorimeter (CAL) is observing the highest energy cosmic electrons from 1 GeV to 20 TeV, along with cosmic ray nuclei through iron up to 1,000 TeV and gamma-rays above 10 GeV. In a five-year mission CALET will also have the exposure to measure the relative abundances of the ultra-heavy (UH) cosmic rays with ~4 × the statistics of the TIGER instrument for the full CAL acceptance. Rigidity cutoffs based on the earth's geomagnetic field in the 51.6° inclination ISS orbit can provide an energy independent UH measurement with expanded acceptance with ~10 × the TIGER statistics. An overview of the anticipated performance and preliminary CALET UH analysis data will be presented. This research was supported by NASA at Washington University under Grant Number NNX11AE02G.

  14. Stratospheric NO and NO2 Abundances from ATMOS Solar-Occultation Measurements

    NASA Technical Reports Server (NTRS)

    Newchurch, M. J.; Allen, M.; Gunson, M. R.; Salawitch, R. J.; Collins, G. B.; Huston, K. H.; Abbas, M. M.; Abrams, M. C.; Chang, A. Y.; Fahey, D. W.; Gao, R. S.; Irion, F. W.; Lowenstein, M.; Manney, G. L.; Michelsen, H. A.; Podolske, J. R.; Rinsland, C. P.; Zander, R.

    1996-01-01

    Using results from a time-dependent photochemical model to calculate the diurnal variation of NO and NO2, we have corrected Atmospheric Trace MOlecule Spectroscopy (ATMOS) solar-occultation retrievals of the NO and NO2 abundances at 90' solar zenith angle. Neglecting to adjust for the rapid variation of these gases across the terminator results in potential errors in retrieved profiles of approximately 20% for NO2 and greater than 100% for NC at altitudes below 25 km. Sensitivity analysis indicates that knowledge of the local 03 and temperature profiles, rather than zonal mean or climatological conditions of these quantities, is required to obtain reliable retrievals of NO and NO2 in the lower stratosphere. Extremely inaccurate 03 or temperature values at 20 km can result in 50% errors in retrieved NO or NO2. Mixing ratios of NO in the mid-latitude, lower stratosphere measured by ATMOS during the November 1994 ATLAS-3 mission compare favorably with in situ ER-2 observations, providing strong corroboration of the reliability of the adjusted space-borne measurements.

  15. D/H Isotope Ratio Measurements of Atmospheric Volatile Organic Compounds

    NASA Astrophysics Data System (ADS)

    Meisehen, Thomas; Bühler, Fred; Koppmann, Ralf; Krebsbach, Marc

    2015-04-01

    Analysis of isotope ratios in atmospheric volatile organic compounds (VOC) is a reliable method to allocate their sources, to estimate atmospheric residence times and investigate physical and chemical processes on various temporal and spatial scales. Most investigations yet focus on carbon isotope ratios. Certainly more detailed information can be gained by the ratio of deuterium (D) to hydrogen (H) in VOC, especially due to the high mass ratio. Combining measurements of carbon and hydrogen isotopes could lead to considerable improvement in our understanding of atmospheric processes. For this purpose we set up and thoroughly characterised a gas chromatograph pyrolysis isotope ratio mass spectrometer to measure the D/H ratio in atmospheric VOC. From a custom-made gas standard mixture VOC were adsorbed on Tenax®TA which has the advantage that CO2 is not preconcentrated when measuring ambient air samples. Our results show that the pyrolysis method has significant impact on the D/H ratios. A pyrolysis temperature of at least 1723 K and conditioning of the ceramic tube on a regular basis is essential to obtain reproducible D/H isotope ratios. For an independent comparison D/H ratios of the pure VOC used in the gas standard were determined using elemental analysis by Agroisolab (Jülich, Germany). Comparisons of 10 VOC show perfect agreement within the standard deviations of our measurements and the errors given by Agroisolab, e.g. for n-pentane, toluene, 4-methyl-2-pentanone and n-octane. A slight mean difference of 5.1 o was obtained for n-heptane while significant mean differences of 15.5 o and 20.3 o arose for 1,2,4-trimethylbenzene and isoprene, respectively. We further demonstrate the stability of our system and show that the sample preparation does not affect the isotope ratios. Moreover the applicability of our system to ambient air samples is demonstrated.

  16. Carbon and Sulfur Isotopic Composition of Yellowknife Bay Sediments: Measurements by the Sample Analysis at Mars (SAM) Quadrupole Mass Spectrometer

    NASA Technical Reports Server (NTRS)

    Franz, H. B.; Mahaffy, P. R.; Stern, J. C.; Eigenbrode, J. L.; Steele, A.; Ming, D. W.; McAdam, A. C.; Freissinet, C.; Glavin, D. P.; Archer, P. D.; Brunner, A. E.; Grotzinger,J. P.; Jones, J. H.; Leshin, L. A.; Miller, K.; Morris, R. V.; Navarro-Gonzalez, R.; Niles, P. B.; Owen, T. C.; Summons, R. E.; Sutter, B.; Webster, C. R.

    2014-01-01

    Since landing at Gale Crater in Au-gust 2012, the Sample Analysis at Mars (SAM) instru-ment suite on the Mars Science Laboratory (MSL) “Curiosity” rover has analyzed solid samples from the martian regolith in three locations, beginning with a scoop of aeolian deposits from the Rocknest (RN) sand shadow. Curiosity subsequently traveled to Yellowknife Bay, where SAM analyzed samples from two separate holes drilled into the Sheepbed Mudstone, designated John Klein (JK) and Cumberland (CB). Evolved gas analysis (EGA) of all samples revealed the presence of H2O as well as O-, C- and S-bearing phas-es, in most cases at abundances below the detection limit of the CheMin instrument. In the absence of definitive mineralogical identification by CheMin, SAM EGA data can help provide clues to the mineralogy of volatile-bearing phases through examination of tem-peratures at which gases are evolved from solid sam-ples. In addition, the isotopic composition of these gas-es may be used to identify possible formation scenarios and relationships between phases. Here we report C and S isotope ratios for CO2 and SO2 evolved from the JK and CB mudstone samples as measured with SAM’s quadrupole mass spectrometer (QMS) and draw com-parisons to RN.

  17. Tracing the dispersion of contaminated sediment with plutonium isotope measurements in coastal catchments of Fukushima Prefecture

    NASA Astrophysics Data System (ADS)

    Evrard, Olivier; Pointurier, Fabien; Onda, Yuichi; Chartin, Caroline; Hubert, Amélie; Lepage, Hugo; Pottin, Anne-Claire; Lefèvre, Irène; Bonté, Philippe; Laceby, J. Patrick; Ayrault, Sophie

    2015-04-01

    The Fukushima Dai-ichi Nuclear Power Plant (FDNPP) accident led to important releases of radionuclides into the environment, and trace levels of plutonium (Pu) were detected in northeastern Japan. However, measurement of Pu isotopic atom and activity ratios is required to differentiate between the contributions of global nuclear test fallout and FDNPP emissions. In this study, we measured Pu isotopic ratios in recently deposited sediments along rivers draining the most contaminated part of the inland radioactive plume. To this end, we carried out a thorough chemical purification and concentration of Pu from sediment samples (5 g dry material) and precise isotopic measurements using a double-focusing sector field ICP-MS. Results showed that the entire range of measured Pu isotopes (i.e., 239Pu, 240Pu, 241Pu, and 242Pu) were detected in all samples, although in extremely low concentrations. The 241Pu/239Pu atom ratios measured in sediment deposits (0.0017-0.0884) were significantly higher than the corresponding values attributed to the global fallout (0.00113±0.00008 on average in the Northern Hemisphere between 31°-71°N). The results indicated the presence of Pu from FDNPP, in slight excess compared to the Pu background from global fallout, representing up to ca. 60% of Pu in the analyzed samples. These results demonstrate that this radionuclide has been transported relatively long distances (45 km) from FDNPP and deposited in rivers representing a potential source of Pu to the ocean.

  18. Fast Scanning Single Collector ICP-MS for Low Level Isotope Ratio Measurements

    NASA Astrophysics Data System (ADS)

    Newman, K.; Georg, B.

    2010-12-01

    Multiple collector (MC)-ICP-MS is recognized as a workhorse in the field of isotope ratio measurements. With its unrivalled precision, high sample throughput and multi-element coverage, MC-ICPMS has opened up new areas of study in earth, environmental and biological sciences. However, SC-ICP-MS is fit for purpose for many applications where sample amount is limited and fractionations are relatively large. To compensate for the inherent ion beam instability associated with the ICP ion source, fast scanning magnetic sector instruments are used. Here, we describe and discuss the use of the Nu Attom SC-ICP-MS for low level isotope ratio measurements. The Nu Attom is a double focusing magnetic sector mass spectrometer with unique fast scanning capabilities. Deflectors located at the entrance and exit of the flight tube are used to alter the effective magnet radius by changing the ion trajectory. This enables a fast electrostatic scan over a mass range of approximately 40%. In contrast to other fast scanning magnetic sector instruments, there is no change in the ion energy which may introduce additional mass bias effects. The Nu Attom also has fully adjustable source and collector slits. This facilitates measurements in medium mass resolution (R=1500-2500), whilst maintaining a flat topped peak necessary for precise isotope ratio measurements. The potential applications of the Nu Attom in isotope ratio measurements will be explored.

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

    PubMed

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

    2007-12-15

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

  20. Capabilities to measure isotopic ratios in water at comet 67P/Churyumov-Gerasimenko with ROSINA/DFMS

    NASA Astrophysics Data System (ADS)

    Hässig, Myrtha; Altwegg, K.; Balsiger, H.; Berthelier, J.; Calmonte, U.; Combi, M. R.; De Keyser, J.; Fiethe, B.; Fuselier, S. A.; Rubin, M.; ROSINA-Team

    2013-10-01

    The likelihood that comets may have delivered part of the water to Earth has been reinforced by the recent observation of the earth-like D/H ratio in Jupiter-family comet 103P/Hartley 2 by Hartogh et al. (2011). Prior to this observation, results from several Oort cloud comets indicated a factor of 2 enrichment of deuterium relative to the abundance at Earth. The European Space Agency’s Rosetta spacecraft will encounter comet 67P/Churyumov-Gerasimenko, another Jupiter-family comet of likely Kuiper belt origin, in 2014 and accompany it from almost aphelion to and past perihelion. Onboard Rosetta is the Rosetta Orbiter Spectrometer for Ion and Neutral Analysis (ROSINA) which consists of two mass spectrometers and a pressure sensor [Balsiger et al. 2007]. With its unprecedented mass resolution, for a space-borne instrument, the Double Focusing Mass Spectrometer (DFMS), one of the major subsystems of ROSINA, will be able to obtain unambiguously the ratios of the isotopes in water from in situ measurements in the coma around the comet. We will discuss the performance of this sensor on the basis of measurements of the terrestrial hydrogen and oxygen isotopic ratios performed with the flight spare instrument in the lab. We also show that the instrument on Rosetta is capable of measuring the D/H even in the very low density water background released by the spacecraft. This capability demonstrates that ROSINA should obtain very sensitive measurements of these ratios in the cometary environment. These measurements will allow detection of fractionation as function of the distance from the nucleus as well as fractionation due to mechanisms that are correlated with heliocentric distance. References: H. Balsiger et al., Space Sci. Rev., 128, 745-801 P. Hartogh et al., Nature, 478, 218-220, 2011 M. Hässig et al., PSS, 84, 148-152, 2013

  1. The stability and calibration of water vapor isotope ratio measurements during long-term deployments

    NASA Astrophysics Data System (ADS)

    Bailey, A.; Noone, D.; Berkelhammer, M.; Steen-Larsen, H. C.; Sato, P.

    2015-10-01

    With the recent advent of commercial laser absorption spectrometers, field studies measuring stable isotope ratios of hydrogen and oxygen in water vapor have proliferated. These pioneering analyses have provided invaluable feedback about best strategies for optimizing instrumental accuracy, yet questions still remain about instrument performance and calibration approaches for multi-year field deployments. With clear scientific potential for using these instruments to carry out monitoring of the hydrological cycle, this study examines the long-term stability of the isotopic biases associated with three cavity-enhanced laser absorption spectrometers - calibrated with different systems and approaches - at two remote field sites: Mauna Loa Observatory, Hawaii, USA, and Greenland Environmental Observatory, Summit, Greenland. The analysis pays particular attention to the stability of measurement dependencies on water vapor concentration and also evaluates whether these so-called concentration dependences are sensitive to statistical curve-fitting choices or measurement hysteresis. The results suggest evidence of monthly-to-seasonal concentration-dependence variability - which likely stems from low signal-to-noise at the humidity-range extremes - but no long-term directional drift. At Mauna Loa, where the isotopic analyzer is calibrated by injection of liquid water standards into a vaporizer, the largest source of inaccuracy in characterizing the concentration dependence stems from an insufficient density of calibration points at low water vapor volume mixing ratios. In comparison, at Summit, the largest source of inaccuracy is measurement hysteresis associated with interactions between the reference vapor, generated by a custom dew point generator, and the sample tubing. Nevertheless, prediction errors associated with correcting the concentration dependence are small compared to total measurement uncertainty. At both sites, changes in measurement repeatability that are

  2. On the cross-sensitivity between water vapor mixing ratio and stable isotope measurements of in-situ analyzers

    NASA Astrophysics Data System (ADS)

    Parkes, Stephen; Wang, Lixin; McCabe, Matthew

    2015-04-01

    In recent years there has been an increasing amount of water vapor stable isotope data collected using in-situ instrumentation. A number of papers have characterized the performance of these in-situ analyzers and suggested methods for calibrating raw measurements. The cross-sensitivity of the isotopic measurements on the mixing ratio has been shown to be a major uncertainty and a variety of techniques have been suggested to characterize this inaccuracy. However, most of these are based on relating isotopic ratios to water vapor mixing ratios from in-situ analyzers when the mixing ratio is varied and the isotopic composition kept constant. An additional correction for the span of the isotopic ratio scale is then applied by measuring different isotopic standards. Here we argue that the water vapor cross-sensitivity arises from different instrument responses (span and offset) of the parent H2O isotope and the heavier isotopes, rather than spectral overlap that could cause a true variation in the isotopic ratio with mixing ratio. This is especially relevant for commercial laser optical instruments where absorption lines are well resolved. Thus, the cross-sensitivity determined using more conventional techniques is dependent on the isotopic ratio of the standard used for the characterization, although errors are expected to be small. Consequently, the cross-sensitivity should be determined by characterizing the span and zero offset of each isotope mixing ratio. In fact, this technique makes the span correction for the isotopic ratio redundant. In this work we model the impact of changes in the span and offset of the heavy and light isotopes and illustrate the impact on the cross-sensitivity of the isotopic ratios on water vapor. This clearly shows the importance of determining the zero offset for the two isotopes. The cross-sensitivity of the isotopic ratios on water vapor is then characterized by determining the instrument response for the individual isotopes for a

  3. Homo- and Heteronuclear Multiple-Quantum Filters for Measurement of NMR Isotope Shifts

    NASA Astrophysics Data System (ADS)

    Wooten, E. W.; Dua, R. K.; Dotson, G. D.; Woodard, R. W.

    The measurement of NMR isotope shifts as mechanistic probes can be complicated by mixtures of isotopomers. Homo- and heteronuclear NMR techniques based on multiple-quantum filtration are presented and shown to be a useful aid in measuring such shifts. The effects of 1H/ 2H substitution and 16O/ 18O substitution on the nuclear shielding of 1H, 13C, and 31P in a multiply labeled phosphoenolpyruvate are measured and interpreted qualitatively in terms of their rovibrational origins.

  4. Improved ground-based FTS measurement for column abundance CO2 retrievals(Conference Presentation)

    NASA Astrophysics Data System (ADS)

    Goo, Tae-Young

    2016-10-01

    The National Institute of Meteorological Sciences has operated a ground-based Fourier Transform Spectrometer (FTS) at Anmyeondo, Korea since December 2012. Anmyeondo FTS site is a designated operational station of Total Carbon Column Observing Network (TCCON) and belongs to regional Global Atmosphere Watch observatory. A Bruker IFS-125HR model, which has a significantly high spectral resolution by 0.02 cm-1, is employed and instrument specification is almost same as the TCCON configuration. such as a spectrum range of 3,800 16,000 cm-1, a resolution of 1 cm-1, InGaAs and Si-Diode detectors and CaF2 beam splitter. It is found that measured spectra have a good agreement with simulated spectra. In order to improve the spectral accuracy and stability, The Operational Automatic System for Intensity of Sunray (OASIS) has been developed. The OASIS can provide consistent photon energy optimized to detector range by controlling the diameter of solar beam reflected from the mirror of suntracker. As a result, monthly modulation efficiency (ME), which indicates the spectral accuracy of FTS measurement, has been recorded the vicinity of 99.9% since Feb 2015. The ME of 98% is regarded as the error of 0.1% in the ground-based in-situ CO2 measurement. Total column abundances of CO2 and CH4 during 2015 are estimated by using GGG v14 and compared with ground-based in-situ CO2 and CH4 measurements at the height of 86 m above sea level. The seasonality of CO2 is well captured by both FTS and in-situ measurements while there is considerable difference on the amplitude of CO2 seasonal variation due to the insensitivity of column CO2 to the surface carbon cycle dynamics in nature as well as anthropogenic sources. Total column CO2 and CH4 approximately vary from 395 ppm to 405 ppm and from 1.82 ppm to 1.88 ppm, respectively. It should be noted that few measurements obtained in July to August because of a lot of cloud and fog. It is found that enhancement of CH4 from the FTS at Anmyeondo

  5. The Ins and Outs of U and Th Isotopic Measurements Using a Nu Plasma 1700 MC-ICP- MS

    NASA Astrophysics Data System (ADS)

    Pietruszka, A. J.; Rooney, T. O.

    2007-12-01

    The Nu Plasma 1700 is a relatively new type of large-geometry MC-ICP-MS that offers the potential to improve the accuracy and precision of U and Th isotopic measurements compared to previous instruments (e.g., the Plasma 54-30, or P54-30). The higher resolution of the Nu Plasma 1700 translates to more than a factor of 6 improvement in the abundance sensitivity at high mass (compared to the P54-30), and virtually eliminates the necessity of a tail correction on 230Th during the measurement of 232Th/230Th ratios (the major source of uncertainty using the P54-30). However, the Nu Plasma 1700 uses a discrete dynode secondary electron multiplier for ion-counting, which has a smaller dynamic range than the Daly detector used by the P54- 30. This prevents the placement of a relatively large 235U signal on the ion-counter, and thus, requires alternative methods to correct for the effects of instrumental mass bias. Initial efforts in our laboratory have focused on the development of standard-sample bracketing (SSB) techniques to correct for mass bias, with a careful evaluation of possible instrumental artifacts such as matrix effects, drift in the bias between the Faraday collectors and the ion-counting detector (Faraday/IC bias), and non-linearity of both the ion-counting detector and the retardation lens. Experiments with solution standards suggest that the major source of uncertainty on U and Th isotopic measurements using the Nu Plasma 1700 in SSB mode is drift in the Faraday/IC bias. Nevertheless, SSB analyses for U and Th solution standards are reproducible to 0.3% for 238U/234U and 0.4% for 232Th/230Th (±2σ), which is similar to the results obtained on the Plasma 54-30 (Luo et al., 1997; Pietruszka et al., 2002). So far, accuracy has been evaluated by repeatedly analyzing the UCSC Th isotopic standard against a previously characterized in-house Th isotopic standard in SSB mode. The result agrees within error of previous determinations for UCSC Th using the Plasma

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

    NASA Astrophysics Data System (ADS)

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

    2014-03-01

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

  7. Iron and Nickel Isotope Measurements on SiC X Grains with CHILI

    NASA Astrophysics Data System (ADS)

    Kodolányi, J.; Stephan, T.; Trappitsch, R.; Hoppe, P.; Pignatari, M.; Davis, A. M.; Pellin, M. J.

    2016-08-01

    New measurements with CHILI on SiC X grains provide more detailed Fe and Ni isotope data than previous NanoSIMS analyses. The new data suggest that Fe-Ni fractionation may occur in supernova ejecta before SiC condensation.

  8. Deriving Plasma Densities and Elemental Abundances from SERTS Differential Emission Measure Analysis

    NASA Technical Reports Server (NTRS)

    Schmelz, J. T.; Kimble, J. A.; Saba, J. L. R.

    2012-01-01

    We use high-resolution spectral emission line data obtained by the SERTS instrument during three rocket flights to demonstrate a new approach for constraining electron densities of solar active region plasma.We apply differential emission measure (DEM) forward-fitting techniques to characterize the multithermal solar plasma producing the observed EUV spectra, with constraints on the high-temperature plasma from the Yohkoh Soft X-ray Telescope. In this iterative process, we compare line intensities predicted by an input source distribution to observed line intensities for multiple iron ion species, and search a broad range of densities to optimize chi-square simultaneously for the many available density-sensitive lines. This produces a density weighted by the DEM, which appears to be useful for characterizing the bulk of the emitting plasma over a significant range of temperature. This "DEM-weighted density" technique is complementary to the use of density-sensitive line ratios and less affected by uncertainties in atomic data and ionization fraction for any specific line. Once the DEM shape and the DEM-weighted density have been established from the iron lines, the relative elemental abundances can be determined for other lines in the spectrum. We have also identified spectral lines in the SERTS wavelength range that may be problematic

  9. DERIVING PLASMA DENSITIES AND ELEMENTAL ABUNDANCES FROM SERTS DIFFERENTIAL EMISSION MEASURE ANALYSIS

    SciTech Connect

    Schmelz, J. T.; Kimble, J. A.; Saba, J. L. R.

    2012-09-20

    We use high-resolution spectral emission line data obtained by the SERTS instrument during three rocket flights to demonstrate a new approach for constraining electron densities of solar active region plasma. We apply differential emission measure (DEM) forward-fitting techniques to characterize the multithermal solar plasma producing the observed EUV spectra, with constraints on the high-temperature plasma from the Yohkoh Soft X-ray Telescope. In this iterative process, we compare line intensities predicted by an input source distribution to observed line intensities for multiple iron ion species, and search a broad range of densities to optimize {chi}{sup 2} simultaneously for the many available density-sensitive lines. This produces a density weighted by the DEM, which appears to be useful for characterizing the bulk of the emitting plasma over a significant range of temperature. This 'DEM-weighted density' technique is complementary to the use of density-sensitive line ratios and less affected by uncertainties in atomic data and ionization fraction for any specific line. Once the DEM shape and the DEM-weighted density have been established from the iron lines, the relative elemental abundances can be determined for other lines in the spectrum. We have also identified spectral lines in the SERTS wavelength range that may be problematic.

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

    NASA Astrophysics Data System (ADS)

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

    2005-12-01

    We present results and speculative interpretation of leaf-level carbon isotope discrimination and ecosystem respired carbon and oxygen isotope ratios from a semi-arid, C3/C4 woodland located in northern New Mexico, USA. Overstory leaf area index (LAI) is dominated by live juniper (Juniperus monosperma) trees with an LAI value of approximately 1.0 m2 per m2 ground area, and has a seasonally dynamic understory of mixed C3 forbs and C4 grasses and cacti, with a maximum LAI of 0.30 m2 per m2 ground area. Ecosystem respired carbon isotope ratios showed values characteristic of C3 dominated photosynthesis (Keeling plot intercepts of -35 to -22 per mil). Seasonal variation was typical of that found in wetter, C3 dominated forests, as was the dependence on climate (e.g. relationships with vapor pressure deficit, soil water content, and canopy conductance). Leaf-level carbon isotope discrimination of the junipers, measured by coupling a Li-Cor 6400 photosynthesis system to the TDL, provided discrimination-Ci and discrimination-vpd relationships consistent with measured ecosystem respired carbon isotope ratios. The oxygen isotope ratio of ecosystem respiration was dependent on rain water isotope composition, but was correlated with soil water content during rain-free periods. The cumulative effect of vapor pressure deficit after a rain event was tightly correlated with the oxygen isotope ratio of ecosystem respiration, suggesting the primary drivers are evaporative enrichment of soil water and perhaps nocturnal leaf enrichment. Instrument precision for carbon and oxygen isotope ratios of carbon dioxide is 0.06 to 0.18 per mil; however, overall precision is somewhat lower due to pressure and sampling effects.

  11. Progress in AMS measurement of U isotope ratios in nanogram U samples

    NASA Astrophysics Data System (ADS)

    Dong, Kejun; He, Ming; Wang, Chen; Zhao, Xinhong; Li, Lili; Zhao, Yonggang; Wang, Xianggao; Shen, Hongtao; Wang, Xiaoming; Pang, Fangfang; Xu, Yongning; Zhao, Qingzhang; Dou, Liang; Yang, Xuran; Wu, Shaoyong; Lin, Deyu; Li, Kangning; You, Qubo; Bao, Yiwen; Hu, Yueming; Xia, Qingliang; Yin, Xinyi; Jiang, Shan

    2015-10-01

    The determination of uranium isotopic composition in ultra-trace U samples is very important in different fields, especially for the nuclear forensics. A new Accelerator Mass Spectrometry (AMS) technique has been developed for the measurement of uranium isotopic ratios in ng level uranium samples at China Institute of Atomic Energy (CIAE). Recently, the method was further optimized and developed by using a series of blank and standard samples. The results show that the 236U at the femtogram level can be determined in nanogram U samples by the newly developed AMS technique at CIAE. The experimental setup, performances and results will be detailed in this contribution.

  12. Towards high precision measurements of nuclear g-factors for the Be isotopes

    NASA Astrophysics Data System (ADS)

    Takamine, A.; Wada, M.; Okada, K.; Ito, Y.; Schury, P.; Arai, F.; Katayama, I.; Imamura, K.; Ichikawa, Y.; Ueno, H.; Wollnik, H.; Schuessler, H. A.

    2016-06-01

    We describe the present status of future high-precision measurements of nuclear g-factors utilizing laser-microwave double and laser-microwave-rf triple resonance methods for online-trapped, laser-cooled radioactive beryllium isotope ions. These methods have applicability to other suitably chosen isotopes and for beryllium show promise in deducing the hyperfine anomaly of 11Be with a sufficiently high precision to study the nuclear magnetization distribution of this one-neutron halo nucleus in a nuclear-model-independent manner.

  13. Reconciling the Differences between the Measurements of CO2 Isotopes by the Phoenix and MSL Landers

    NASA Technical Reports Server (NTRS)

    Niles, P. B.; Mahaffy, P. R.; Atreya, S.; Pavlov, A. A.; Trainer, M.; Webster, C. R.; Wong, M.

    2014-01-01

    Precise stable isotope measurements of the CO2 in the martian atmosphere have the potential to provide important constraints for our understanding of the history of volatiles, the carbon cycle, current atmospheric processes, and the degree of water/rock interaction on Mars. There have been several different measurements by landers and Earth based systems performed in recent years that have not been in agreement. In particular, measurements of the isotopic composition of martian atmospheric CO2 by the Thermal and Evolved Gas Analyzer (TEGA) instrument on the Mars Phoenix Lander and the Sample Analysis at Mars (SAM) instrument on the Mars Science Laboratory (MSL) are in stark disagreement. This work attempts to use measurements of mass 45 and mass 46 of martian atmospheric CO2 by the SAM and TEGA instruments to search for agreement as a first step towards reaching a consensus measurement that might be supported by data from both instruments.

  14. Technical note: Consistent calculation of aquatic gross production from oxygen triple isotope measurements

    NASA Astrophysics Data System (ADS)

    Kaiser, J.

    2011-07-01

    Oxygen triple isotope measurements can be used to calculate aquatic gross oxygen production rates. Past studies have emphasised the appropriate definition of the 17O excess and often used an approximation to derive production rates from the 17O excess. Here, I show that the calculation can be phrased more consistently and without any approximations using the relative 17O/16O and 18O/16O isotope ratio differences (delta values) directly. I call this the "dual delta method". The 17O excess is merely a mathematical construct and the derived production rate is independent of its definition, provided all calculations are performed with a consistent definition. I focus on the mixed layer, but also show how time series of triple isotope measurements below the mixed layer can be used to derive gross production. In the calculation of mixed layer productivity, I explicitly include isotopic fractionation during gas invasion and evasion, which requires the oxygen supersaturation s to be measured as well. I also suggest how bubble injection could be considered in the same mathematical framework. I distinguish between concentration steady state and isotopic steady state and show that only the latter needs to be assumed in the calculation. It is even possible to derive an estimate of the net production rate in the mixed layer that is independent of the assumption of concentration steady state. I review measurements of the parameters required for the calculation of gross production rates and show how their systematic uncertainties as well as the use of different published calculation methods can cause large variations in the production rates for the same underlying isotope ratios. In particular, the 17O excess of dissolved O2 in equilibrium with atmospheric O2 and the 17O excess of photosynthetic O2 need to be re-measured. Because of these uncertainties, all calculation parameters should always be fully documented and the measured relative isotope ratio differences as well as the

  15. Measurement of the intramolecular isotope effect on aliphatic hydroxylation by Chromobacterium violaceum phenylalanine hydroxylase.

    PubMed

    Panay, Aram J; Fitzpatrick, Paul F

    2010-04-28

    The non-heme iron enzyme phenylalanine hydroxylase from Chromobacterium violaceum has previously been shown to catalyze the hydroxylation of benzylic and aliphatic carbons in addition to the normal aromatic hydroxylation reaction. The intrinsic isotope effect for hydroxylation of 3-cyclochexylalanine by the enzyme was determined in order to gain insight into the reactivity of the iron center. With 3-[(2)H(11)-cyclohexyl]alanine as the substrate, the isotope effect on the k(cat) value was 1, consistent with an additional step in the overall reaction being significantly slower than hydroxylation. Consequently, the isotope effect was determined as an intramolecular effect by measuring the amount of deuterium lost in the hydroxylation of 3-[1,2,3,4,5,6-(2)H(6)-cyclohexyl]alanine. The ratio of 4-HO-cyclohexylalanine that retained deuterium to that which lost one deuterium atom was 2.8. This gave a calculated value of 12.6 for the ratio of the primary deuterium kinetic isotope effect to the secondary isotope effect. This value is consistent with hydrogen atom abstraction by an electrophilic Fe(O) center and a contribution of quantum-mechanical tunneling to the reaction.

  16. Measurement of helium isotopes in soil gas as an indicator of tritium groundwater contamination.

    PubMed

    Olsen, Khris B; Dresel, P Evan; Evans, John C; McMahon, William J; Poreda, Robert

    2006-05-01

    The focus of this study was to define the shape and extent of tritium groundwater contamination emanating from a legacy burial ground and to identify vadose zone sources of tritium using helium isotopes (3He and 4He) in soil gas. Helium isotopes were measured in soil-gas samples collected from 70 sampling points around the perimeter and downgradient of a burial ground that contains buried radioactive solid waste. The soil-gas samples were analyzed for helium isotopes using rare gas mass spectrometry. 3He/4He ratios, reported as normalized to the air ratio (RA), were used to locate the tritium groundwater plume emanating from the burial ground. The 3He (excess) suggested that the general location of the tritium source is within the burial ground. This study clearly demonstrated the efficacy of the 3He method for application to similar sites elsewhere within the DOE weapons complex.

  17. Carbon and Oxygen Stable Isotope Measurements of Martian Atmospheric CO2 by the Phoenix Lander

    NASA Technical Reports Server (NTRS)

    Niles, Paul B.; Boynton, W. V.; Hoffman, J. H.; Ming, D. W.; Hamara, D.

    2010-01-01

    Precise stable isotope measurements of the CO2 in the martian atmosphere have the potential to provide important constraints for our understanding of the history of volatiles, the carbon cycle, current atmospheric processes, and the degree of water/rock interaction on Mars [1]. The isotopic composition of the martian atmosphere has been measured using a number of different methods (Table 1), however a precise value (<1%) has yet to be achieved. Given the elevated Delta(sup 13)C values measured in carbonates in martian meteorites [2-4] it has been proposed that the martian atmosphere was enriched in 13C [8]. This was supported by measurements of trapped CO2 gas in EETA 79001[2] which showed elevated Delta(sup 13)C values (Table 1). More recently, Earth-based spectroscopic measurements of the martian atmosphere have measured the martian CO2 to be depleted in C-13 relative to CO2 in the terrestrial atmosphere[ 7, 9-11]. The Thermal and Evolved Gas Analyzer (TEGA) instrument on the Mars Phoenix Lander [12] included a magnetic-sector mass spectrometer (EGA) [13] which had the goal of measuring the isotopic composition of martian atmospheric CO2 to within 0.5%. The mass spectrometer is a miniature instrument intended to measure both the martian atmosphere as well as gases evolved from heating martian soils.

  18. Equation of State measurements of hydrogen isotopes on Nova

    SciTech Connect

    Collins, G. W., LLNL

    1997-11-01

    High intensity lasers can be used to perform measurements of materials at extremely high pressures if certain experimental issues can be overcome. We have addressed those issues and used the Nova laser to shock-compress liquid deuterium and obtain measurements of density and pressure on the principal Hugoniot at pressures from 300 kbar to more than 2 Mbar. The data are compared with a number of equation of state models. The data indicate that the effect of molecular dissociation of the deuterium into a monatomic phase may have a significant impact on the equation of state near 1 Mbar.

  19. Application of neodymium isotope ratio measurements for the origin assessment of uranium ore concentrates.

    PubMed

    Krajkó, Judit; Varga, Zsolt; Yalcintas, Ezgi; Wallenius, Maria; Mayer, Klaus

    2014-11-01

    A novel procedure has been developed for the measurement of (143)Nd/(144)Nd isotope ratio in various uranium-bearing materials, such as uranium ores and ore concentrates (UOC) in order to evaluate the usefulness and applicability of variations of (143)Nd/(144)Nd isotope ratio for provenance assessment in nuclear forensics. Neodymium was separated and pre-concentrated by extraction chromatography and then the isotope ratios were measured by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). The method was validated by the measurement of standard reference materials (La Jolla, JB-2 and BCR-2) and the applicability of the procedure was demonstrated by the analysis of uranium samples of world-wide origin. The investigated samples show distinct (143)Nd/(144)Nd ratio depending on the ore type, deposit age and Sm/Nd ratio. Together with other characteristics of the material in question, the Nd isotope ratio is a promising signature for nuclear forensics and suggests being indicative of the source material, the uranium ore.

  20. The cosmic ray abundances of the platinum-lead elements as measured on HEAO-3

    NASA Technical Reports Server (NTRS)

    Fixsen, D. J.; Waddington, C. J.; Binns, W. R.; Israel, M. H.; Klarmann, J.; Garrard, T. L.; Newport, B. J.; Stone, E. C.

    1983-01-01

    The relative abundances of elements in the charge ranges of Z = 75-79 (platinum) and Z = 80-83 (lead) should be a sensitive indication of the contributions of the r- and s-processes in nucleosynthesis. Data from the HEAO 3 Heavy Nuclei Experiment are used to establish abundances, relative to iron, of these elements in the cosmic radiation, as well as the ratio of 'secondary' elements, in the Z = 62-74 range, to the primary lead-platinum elements. These results appear to suggest that either the source abundances are deficient in s-process elements or that they are not organized solely by first ionization potential. In addition, present propagation models can adequately represent the relative abundances of primary and secondary elements.

  1. Aragonite-Calcite Inversion During Biogenic Carbonate Sampling: Considerations for Interpreting Isotopic Measurements in Paleoclimate Studies

    NASA Astrophysics Data System (ADS)

    Waite, A. J.; Swart, P. K.

    2011-12-01

    As aragonite is the metastable polymorph of calcium carbonate, it lends itself to monotropic inversion to the more stable polymorph, calcite. This inversion is possible through an increase in the temperature and pressure conditions to which the sample is exposed and, although first noted nearly a century ago, has been primarily discussed in the context of sample roasting prior to analyses in paleoclimatological studies. Over the last several decades, however, researchers have found evidence to suggest that the friction associated with the sampling of biogenic carbonates via milling/drilling also induces inversion. Furthermore, this inversion may be associated with a shift in measured oxygen isotopic values and ultimately have significant implications for the interpretation of paleoclimatic reconstructions. Despite this, the isotopic heterogeneity of biogenic aragonite skeletons makes the effects of inversion challenging to test and the subject remains underrepresented in the literature. Here we present a first order study into the effects of milling on both the mineralogy and isotopic compositions measured in sclerosponges, corals, and molluscs. X-Ray diffraction analysis of samples hand ground with a mortar and pestle reveal 100% aragonitic skeletons. Conversely, samples milled with a computerized micromill show measurable inversion to calcite. On average, percent inversion of aragonite to calcite for individual specimens was 15% for sclerosponges, 16% for corals, and 9% for molluscs. Isotopic data from these specimens show that the higher the percentage of aragonite inverted to calcite, the more depleted the measured oxygen isotopic values. In the largest of the datasets (sclerosponges), it is evident that the range of oxygen isotope values from milled samples (-0.02 to +0.84%) exceeds the range in values for those samples which were hand ground and showed no inversion (+0.53 to +0.90%). This, coupled with the strong correlation between the two variables

  2. Simultaneous measurement of CO2 concentration and isotopic ratios in gas samples using IRMS

    NASA Astrophysics Data System (ADS)

    Yu, Eun-Ji; Lee, Dongho; Bong, Yeon-Sik; Lee, Kwang-Sik

    2014-05-01

    Isotopic methods are indispensable tools for studies on atmosphere-biosphere exchanges of CO2 and environmental monitoring such as CO2 leakage detection from subsurface carbon storages. CO2 concentration is an important variable in interpreting isotopic composition of CO2 especially in atmospheric applications (e.g., 'Keeling plot'). Optical methods such as CRDS (Cavity Ring Down Spectroscopy) are gaining attention recently because of its capability to simultaneously measure CO2 concentration and isotopic ratios with a short measurement interval (up to 1 sec.). On the other hand, IRMS (Isotope Ratio Mass Spectrometer) has been used only for isotopic measurements. In this study, we propose a method to measure CO2 concentration from gas samples along with isotopic ratios using conventional IRMS system. The system consists of Delta V Plus IRMS interfaced with GasBench II (Thermo Scientific, Germany). 12-mL vials with open top screw cap and rubber septum were used for both gas sampling and analysis. For isotopic analysis, gases in the vials were transferred into GasBench II by He carrier flow and CO2 was trapped by a single cryotrap (-180 ºC) after passing a water trap (Mg(ClO4)2). Upon release of the cryotrap, liberated CO2 was separated from N2O using gas chromatography column inside the GasBench II and introduced online into the IRMS. Isotopic ratios were measured for the masses of 44, 45 and 46, and the peak intensity (mV of mass 44 and peak area) was recorded for the concentration calculation. For the determination of CO2 concentration, a calibration curve relating the peak intensity with molar concentration of CO2 was constructed. By dissolving NaHCO3 in de-ionized water, solutions containing 0.05, 0.1, 0.25 and 0.5 µmol of inorganic carbon were prepared in 12 mL vials. Phosphoric acid was injected through rubber septum of the vials to acidify the solution and released CO2 was analyzed for the isotopic ratios and the corresponding peak intensity was recorded

  3. High Frequency Measurements of Methane Concentrations and Carbon Isotopes at a Marsh and Landfill

    NASA Astrophysics Data System (ADS)

    Mortazavi, B.; Wilson, B.; Chanton, J.; Eller, K.; Dong, F.; Baer, D. S.; Gupta, M.; Dzwonkowski, B.

    2012-12-01

    High frequency measurements of methane concentrations and carbon isotopes can help constrain the source strengths of methane emitted to the atmosphere. We report here methane concentrations and 13C values measured at 0.5 Hz with cavity enhanced laser absorption spectrometers (Los Gatos Research) deployed at a saltmarsh in Alabama and a landfill in Florida. Methane concentrations and 13C at the saltmarsh were monitored over a 2.5 day time period at 2 m, 0.5 m above the ground as well as from the outflow of a flow-through (2 L) chamber placed on the Spartina alterniflora dominated marsh. A typical measurement cycle included regular samples from two tanks of known methane concentrations and isotopic values and from ambient air samples. Over the 2.5-day measurement period methane concentrations and isotopic ratios at 2 m averaged 1.85 ppm and -43.57‰ (±0.34, 1 SE), respectively. The concentration and isotopic values from the chamber outflow varied from 1.92 to 5.81 ppm and -38.5 to -59.3‰, respectively. Methane flux from the marsh ranged from undetectable to 3.6 mgC m-2hr-1, with high fluxes measured during low tide. The 13δCH4 of the emitted CH4 from the marsh, determined from a mass balance equation using the chamber inflow and outflow concentration and isotopic values ranged from -62.1 to -93.9‰ and averaged -77‰ (±1.25, 1SE). At the landfill ambient methane concentrations and 13C ratios measured over multiple days varied from 4.25 to 11.91 ppm and from -58.81 to -45.12‰, respectively. At higher methane concentrations the δ13C of CH4 was more depleted consistent with previously observed relationship at this site made by more traditional techniques. Over a 30-minute measurement period CH4 concentrations at the landfill could vary by as much as 15 ppm. The high frequency continuous optical measurements with field-deployed instruments provide us with an unprecedented temporal resolution of CH4 concentrations and isotopic ratios. These measurements will

  4. Neutron multiplicity measurements of Cf and Fm isotopes

    SciTech Connect

    Hoffman, D.C.; Ford, G.P.; Balagna, J.P.; Veeser, L.R.

    1980-02-01

    Prompt neutrons in coincidence with the fission fragments from the spontaneous fission of /sup 250,252,254/Cf and /sup 257/Fm were measured inside a 75-cm-diameter, Gd-loaded liquid scintillation counter having a neutron-detection efficiency of about 78%. Measurements for /sup 256/Fm were done just outside the counter with an efficiency of 31%. The kinetic energies of both fission fragments and the number of neutrons for each fission event were recorded. From these data, the fragment kinetic energies and masses and the neutron multiplicity distributions were determined for /sup 250,252,254/Cf and /sup 257/Fm. Variances of neutron multiplicity distributions as a function of total fragment kinetic energy and the ratio of fragment masses have been calculated and are presented for all the nuclides studied.

  5. Spectral contaminant identifier for off-axis integrated cavity output spectroscopy measurements of liquid water isotopes

    SciTech Connect

    Brian Leen, J.; Berman, Elena S. F.; Gupta, Manish; Liebson, Lindsay

    2012-04-15

    Developments in cavity-enhanced absorption spectrometry have made it possible to measure water isotopes using faster, more cost-effective field-deployable instrumentation. Several groups have attempted to extend this technology to measure water extracted from plants and found that other extracted organics absorb light at frequencies similar to that absorbed by the water isotopomers, leading to {delta}{sup 2}H and {delta}{sup 18}O measurement errors ({Delta}{delta}{sup 2}H and {Delta}{delta}{sup 18}O). In this note, the off-axis integrated cavity output spectroscopy (ICOS) spectra of stable isotopes in liquid water is analyzed to determine the presence of interfering absorbers that lead to erroneous isotope measurements. The baseline offset of the spectra is used to calculate a broadband spectral metric, m{sub BB}, and the mean subtracted fit residuals in two regions of interest are used to determine a narrowband metric, m{sub NB}. These metrics are used to correct for {Delta}{delta}{sup 2}H and {Delta}{delta}{sup 18}O. The method was tested on 14 instruments and {Delta}{delta}{sup 18}O was found to scale linearly with contaminant concentration for both narrowband (e.g., methanol) and broadband (e.g., ethanol) absorbers, while {Delta}{delta}{sup 2}H scaled linearly with narrowband and as a polynomial with broadband absorbers. Additionally, the isotope errors scaled logarithmically with m{sub NB}. Using the isotope error versus m{sub NB} and m{sub BB} curves, {Delta}{delta}{sup 2}H and {Delta}{delta}{sup 18}O resulting from methanol contamination were corrected to a maximum mean absolute error of 0.93 per mille and 0.25 per mille respectively, while {Delta}{delta}{sup 2}H and {Delta}{delta}{sup 18}O from ethanol contamination were corrected to a maximum mean absolute error of 1.22 per mille and 0.22 per mille . Large variation between instruments indicates that the sensitivities must be calibrated for each individual isotope analyzer. These results suggest that the

  6. Spectral contaminant identifier for off-axis integrated cavity output spectroscopy measurements of liquid water isotopes

    NASA Astrophysics Data System (ADS)

    Brian Leen, J.; Berman, Elena S. F.; Liebson, Lindsay; Gupta, Manish

    2012-04-01

    Developments in cavity-enhanced absorption spectrometry have made it possible to measure water isotopes using faster, more cost-effective field-deployable instrumentation. Several groups have attempted to extend this technology to measure water extracted from plants and found that other extracted organics absorb light at frequencies similar to that absorbed by the water isotopomers, leading to δ2H and δ18O measurement errors (Δδ2H and Δδ18O). In this note, the off-axis integrated cavity output spectroscopy (ICOS) spectra of stable isotopes in liquid water is analyzed to determine the presence of interfering absorbers that lead to erroneous isotope measurements. The baseline offset of the spectra is used to calculate a broadband spectral metric, mBB, and the mean subtracted fit residuals in two regions of interest are used to determine a narrowband metric, mNB. These metrics are used to correct for Δδ2H and Δδ18O. The method was tested on 14 instruments and Δδ18O was found to scale linearly with contaminant concentration for both narrowband (e.g., methanol) and broadband (e.g., ethanol) absorbers, while Δδ2H scaled linearly with narrowband and as a polynomial with broadband absorbers. Additionally, the isotope errors scaled logarithmically with mNB. Using the isotope error versus mNB and mBB curves, Δδ2H and Δδ18O resulting from methanol contamination were corrected to a maximum mean absolute error of 0.93 ‰ and 0.25 ‰ respectively, while Δδ2H and Δδ18O from ethanol contamination were corrected to a maximum mean absolute error of 1.22 ‰ and 0.22 ‰. Large variation between instruments indicates that the sensitivities must be calibrated for each individual isotope analyzer. These results suggest that the properly calibrated interference metrics can be used to correct for polluted samples and extend off-axis ICOS measurements of liquid water to include plant waters, soil extracts, wastewater, and alcoholic beverages. The general technique

  7. Strong anion exchange liquid chromatographic separation of protein amino acids for natural 13C-abundance determination by isotope ratio mass spectrometry.

    PubMed

    Abaye, Daniel A; Morrison, Douglas J; Preston, Tom

    2011-02-15

    Amino acids are the building blocks of proteins and the analysis of their (13)C abundances is greatly simplified by the use of liquid chromatography (LC) systems coupled with isotope ratio mass spectrometry (IRMS) compared with gas chromatography (GC)-based methods. To date, various cation exchange chromatography columns have been employed for amino acid separation. Here, we report strong anion exchange chromatography (SAX) coupled to IRMS with a Liquiface interface for amino acid δ(13)C determination. Mixtures of underivatised amino acids (0.1-0.5 mM) and hydrolysates of representative proteins (prawns and bovine serum albumin) were resolved by LC/IRMS using a SAX column and inorganic eluents. Background inorganic carbon content was minimised through careful preparation of alkaline reagents and use of a pre-injector on-line carbonate removal device. SAX chromatography completely resolved 11 of the 16 expected protein amino acids following acid hydrolysis in underivatised form. Basic and neutral amino acids were resolved with 35 mM NaOH in isocratic mode. Elution of the aromatic and acidic amino acids required a higher hydroxide concentration (180 mM) and a counterion (NO 3-, 5-25 mM). The total run time was 70 min. The average δ(13)C precision of baseline-resolved peaks was 0.75‰ (range 0.04 to 1.06‰). SAX is a viable alternative to cation chromatography, especially where analysis of basic amino acids is important. The technology shows promise for (13)C amino acid analysis in ecology, archaeology, forensic science, nutrition and protein metabolism.

  8. High-temperature pyrolysis/gas chromatography/isotope ratio mass spectrometry: simultaneous measurement of the stable isotopes of oxygen and carbon in cellulose.

    PubMed

    Woodley, Ewan J; Loader, Neil J; McCarroll, Danny; Young, Giles H F; Robertson, Iain; Heaton, Timothy H E; Gagen, Mary H; Warham, Joseph O

    2012-01-30

    Stable isotope analysis of cellulose is an increasingly important aspect of ecological and palaeoenvironmental research. Since these techniques are very costly, any methodological development which can provide simultaneous measurement of stable carbon and oxygen isotope ratios in cellulose deserves further exploration. A large number (3074) of tree-ring α-cellulose samples are used to compare the stable carbon isotope ratios (δ(13)C) produced by high-temperature (1400°C) pyrolysis/gas chromatography (GC)/isotope ratio mass spectrometry (IRMS) with those produced by combustion GC/IRMS. Although the two data sets are very strongly correlated, the pyrolysis results display reduced variance and are strongly biased towards the mean. The low carbon isotope ratios of tree-ring cellulose during the last century, reflecting anthropogenic disturbance of atmospheric carbon dioxide, are thus overestimated. The likely explanation is that a proportion of the oxygen atoms are bonding with residual carbon in the reaction chamber to form carbon monoxide. The 'pyrolysis adjustment', proposed here, is based on combusting a stratified sub-sample of the pyrolysis results, across the full range of carbon isotope ratios, and using the paired results to define a regression equation that can be used to adjust all the pyrolysis measurements. In this study, subsamples of 30 combustion measurements produced adjusted chronologies statistically indistinguishable from those produced by combusting every sample. This methodology allows simultaneous measurement of the stable isotopes of carbon and oxygen using high-temperature pyrolysis, reducing the amount of sample required and the analytical costs of measuring them separately.

  9. Tropospheric chlorine isotope measurements in CFC-11, CFC-12 and CFC-113

    NASA Astrophysics Data System (ADS)

    Allin, Sam; Kaiser, Jan; Laube, Johannes; Sturges, Bill

    2014-05-01

    In 2010, we reported the first measurements of chlorine isotope fractionation in stratospheric dichlorodifluoromethane (CF2Cl2, CFC-12) (Laube et al., Science 329:1167, 2010). We found an increase in the isotope delta, δ(37Cl), with altitude and a tight correlation between ln[1 + δ(37Cl)] and ln(mixing ratio). The derived apparent isotope fractionation was ɛapp = (-12 ± 2) o. The stratospheric isotopic fractionation should lead to a continuous increase of the tropospheric chlorine isotope delta while CFC-12 is still emitted into the atmosphere. Provided the source signature has not changed, we predict a 2.5 to 3 o increase since when CFC emissions started in the 1930s until 2010, with the strongest increase in recent years (about 1 o per decade since the mid-1990s). We have now measured the chlorine isotope delta of CFC-12 as well as CFC-11 (trichlorofluoromethane, CFCl3) and CFC-113 (1,1,2-trichloro-1,2,2-trifluoroethane, C2F3Cl3) in the Cape Grim Air Archive (1978 to 2010) and Arctic (NEEM, Greenland) and Antarctic firn samples (Fletcher, West Antarctica). The deepest firn samples include a significant proportion of older air from before 1978. The repeatability for individual samples was ±2.6o for CFC-12 and ±2.7o for CFC-11 and ±3.7o for CFC-113. The results show no significant trends in δ(37Cl) over the whole time period; however, there is a small positive trend for the latter period of the samples of (0.3 ± 0.1) o per decade for CFC-12 since 1997, which explains at third of the predicted trend. The discrepancy between observed and predicted trends may be due to offsetting changes in the source isotope signature: If the there was decrease in the isotope delta of the emissions over time, this would reduce the predicted increase caused by downward transport of 37Cl-enriched stratospheric air.

  10. Isotope 18 O 16 O Ratio Measurements of Water Vapor by use of Photoacoustic Spectroscopy

    NASA Astrophysics Data System (ADS)

    Matsumi, Yutaka; Kishigami, Masahiro; Tanaka, Noriyuki; Kawasaki, Masahiro; Inoue, Gen

    1998-09-01

    We applied a photoacoustic spectroscopy technique to isotope ratio measurements of 16 O and 18 O in water-vapor samples, using a pulsed tunable dye laser pumped by a Nd:YAG laser. The fourth overtone bands (4 OH ) of water molecules near 720 nm were investigated. We identified the absorption lines of H 2 16 O and H 2 18 O in the photoacoustic spectra that we measured by using an 18 O-enriched water sample and the HITRAN database. We measured the difference in the 18 O 16 O isotope ratios for normal distilled water and Antarctic ice, using the photoacoustic method. The value obtained for the difference between the two samples is 18 O 32 16 , where the indicated deviation was a 1 value among 240-s measurements, whereas the value measured with a conventional isotope mass spectrometer was 18 O 28 2 . This method is demonstrated to have the potential of a transportable system for in situ and quick measurements of the H 2 18 O H 2 16 O ratio in the environment.

  11. Mars Atmospheric Composition and Stable Isotope Ratios in H, C and O Measured by the SAM Instrument Suite on the Curiosity Rover

    NASA Astrophysics Data System (ADS)

    Webster, Christopher; Mahaffy, Paul; Stern, Jen; Franz, Heather; Flesch, Greg; Leshin, Laurie; Atreya, Sushil; Wong, Michael; Farley, Ken; MSL Science Team

    2013-04-01

    From the Curiosity Rover sampling the near-surface Martian atmosphere in the vicinity of Gale Crater, volume mixing ratios of the five major constituents (CO2, Ar, N2, O2 and CO) have been made using the Quadrupole Mass Spectrometer (QMS) of the Sample Analysis at Mars (SAM) suite that has additionally measured the isotope ratios of 40Ar/36Ar, and δ13C and δ18O in CO2. A second SAM instrument, the Tunable Laser Spectrometer (TLS) has made a sensitive search for Martian methane, measured water abundances in the vicinity of the rover, and isotope ratios of δ13C, δ18O, δ17O and δ13C18O in CO2; and δD and δ18O in H2O. These atmospheric composition and isotope ratio measurements represent the most precise made in situ to date on any planetary surface and record Mars atmospheric escape and atmosphere-surface interactions. Updated values and error bars will be given for these measurements that provide a baseline for discussion and interpretation of SAM analysis of soil and rock samples [Mahaffy et al., EGU 2013]. Acknowledgement: The research described here was carried out at the Jet Propulsion Laboratory, California Institute of Technology, under a contract with the National Aeronautics and Space Administration (NASA).

  12. Stable carbon isotope measurements of atmospheric organic acids in Los Angeles, California

    SciTech Connect

    Sakugawa, H.; Kaplan, I.R.

    1995-06-15

    Atmospheric organic acids are ubiquitous constituents of urban smog and haze and are also present in the atmospheres of rural and largely uninhabited areas (e.g., the Amazon Rain Forest Basin). The authors report here source characterization of atmospheric organic acids in Los Angeles by measurements of their stable carbon isotopic ratios, e.g., {sup 13}C/{sup 12}C({delta}{sup 13}C). The study was performed by separating formic and acetic acids using ion chromatography exclusion (ICE) and isolating milligram quantities of individual organic acids from atmospheric rain samples. Authentic reference samples of formic and acetic acids were used to determine that only a negligible isotope fractionation of {delta}{sup 13}C value occurs after the ICE separation. During 1991-1992, rainwaters were collected in Los Angeles to isolate formic and acetic acids for the isotope measurements. Results presented in this paper demonstrate a significant isotopic difference between the mean {delta}{sup 13}C value for acetic acid ({minus}20.5{per_thousand}) and formic acid ({minus}30.1{per_thousand}). The authors conclude from these results that the formic acid is derived from mixing of formic acid from direct emissions with the acid formed by secondary oxidation processes in the atmosphere, most probably from aldehydes, whereas acetic acid originates only from direct source emissions. 26 refs., 1 fig., 2 tabs.

  13. Stable carbon isotope measurements of atmospheric organic acids in Los Angeles, California

    NASA Astrophysics Data System (ADS)

    Sakugawa, Hiroshi; Kaplan, Isaac R.

    Atmospheric organic acids are ubiquitous constituents of urban smog and haze and are also present in the atmospheres of rural and largely uninhabited areas (e.g., the Amazon Rain Forest Basin). We report here source characterization of atmospheric organic acids in Los Angeles by measurements of their stable carbon isotopic ratios, e.g., 13C/12C(δ13C). The study was performed by separating formic and acetic acids using ion chromatography exclusion (ICE) and isolating milligram quantities of individual organic acids from atmospheric rain samples. Authentic reference samples of formic and acetic acids were used to determine that only a negligible isotope fractionation of δ13C value occurs after the ICE separation. During 1991-1992, rainwaters were collected in Los Angeles to isolate formic and acetic acids for the isotope measurements. Results presented in this paper demonstrate a significant isotopic difference between the mean δ13C value for acetic acid (-20.5‰) and formic acid (-30.1‰). We conclude from these results that the formic acid is derived from mixing of formic acid from direct emissions with the acid formed by secondary oxidation processes in the atmosphere, most probably from aldehydes, whereas acetic acid originates only from direct source emissions.

  14. Stable isotope and high precision concentration measurements confirm that all humans produce and exhale methane.

    PubMed

    Keppler, Frank; Schiller, Amanda; Ehehalt, Robert; Greule, Markus; Hartmann, Jan; Polag, Daniela

    2016-01-29

    Mammalian formation of methane (methanogenesis) is widely considered to occur exclusively by anaerobic microbial activity in the gastrointestinal tract. Approximately one third of humans, depending on colonization of the gut by methanogenic archaea, are considered methane producers based on the classification terminology of high and low emitters. In this study laser absorption spectroscopy was used to precisely measure concentrations and stable carbon isotope signatures of exhaled methane in breath samples from 112 volunteers with an age range from 1 to 80 years. Here we provide analytical evidence that volunteers exhaled methane levels were significantly above background (inhaled) air. Furthermore, stable carbon isotope values of the exhaled methane unambiguously confirmed that this gas was produced by all of the human subjects studied. Based on the emission and stable carbon isotope patterns of various age groups we hypothesize that next to microbial sources in the gastrointestinal tracts there might be other, as yet unidentified, processes involved in methane formation supporting the idea that humans might also produce methane endogenously in cells. Finally we suggest that stable isotope measurements of volatile organic compounds such as methane might become a useful tool in future medical research diagnostic programs.

  15. Measurements of CO2 Carbon Stable Isotopes at Artificial and Natural Analog Sites

    NASA Astrophysics Data System (ADS)

    Humphries, S. D.; Clegg, S. M.; Rahn, T.; Fessenden, J. E.; Dobeck, L.; Spangler, L.; McLing, T. L.

    2010-12-01

    Carbon storage in geologic formations is one method to prevent carbon dioxide (CO2), produced by fossil fuel combustion, from entering the Earth's atmosphere. The monitoring, verification and accounting (MVA) of geologically sequestered CO2 is critical to the operation of a geologic storage site. Surface MVA techniques need to identify seepage from the sequestration reservoir at or below ambient CO2 concentrations. The CO2 carbon stable isotope ratio of is a sensitive diagnostic signature that can distinguish between anthropogenic and natural sources of CO2. Frequency Modulated spectroscopy (FMS) is an ultra-sensitive version of absorption spectroscopy that is capable of detecting the CO2 carbon stable isotope ratios. The technique involves phase modulation of the laser such that two side bands, spaced wider than the absorption feature of interest (in this case +/-2 GHz) are created. The signal is mixed with the local oscillator yielding a signal proportional to the species concentration. This FMS signature is recorded at multiple wavelengths to obtain the CO2 carbon isotope ratio.Two instruments using the FMS technique have been built and tested at LANL. One instrument draws ambient air into a multi-pass cell for a measurement, point source measurements. The other instrument uses an open-air path, tested up to 160 m (round trip), to measure the CO2 carbon isotopic ratio along the beam path, column average measurements. In this paper, results from multiple field deployments of one or both of the instruments will be presented. The Zero Emissions Research & Technology (ZERT) group at Montana State University established a field test site where controlled amounts of CO2 are released to test the performance of CO2 detection instruments and measurement techniques. The field site allows a controlled flow rate of CO2 to be released into the near surface through a 100 m long horizontal pipe. In July of 2009, a release was conducted, with a uniform flow rate of 0.2 tons per

  16. Consistent calculation of aquatic gross production from oxygen triple isotope measurements

    NASA Astrophysics Data System (ADS)

    Kaiser, J.

    2011-04-01

    Oxygen triple isotope measurements can be used to calculate aquatic gross oxygen production rates. Past studies have emphasised the appropriate definition of the 17O excess and often used an approximation to derive production rates from the 17O excess. Here, I show that the calculation can be phrased more consistently and without any approximations using the relative 17O/16O and 18O/16O isotope ratio differences directly. The 17O excess is merely a mathematical construct and the derived production rate is independent of its definition, provided all calculations are performed with a consistent definition. I focus on the mixed layer, but also show how time series of triple oxygen measurements below the mixed layer can be used to derive gross production. In the calculation of mixed layer productivity, I explicitly include isotopic fractionation during gas invasion and evasion, which requires the oxygen supersaturation s to be measured as well. I also suggest how bubble injection could be considered in the same mathematical framework. I distinguish between concentration steady state and isotopic steady state and show that only the latter needs to be assumed in the calculation. It is even possible to derive an estimate of the net production rate in the mixed layer that is independent of the assumption of concentration steady state. I review measurements of the parameters required for the calculation of gross production rates and show how their systematic uncertainties as well as the use of different published calculation methods can cause large variations in the production rates for the same underlying isotope ratios. In particular, the 17O excess of dissolved O2 in equilibrium with atmospheric O2 and the 17O excess of photosynthetic O2 need to be re-measured. Because of these uncertainties, all calculation parameters should always be fully documented and the measured isotope ratio differences as well as the oxygen supersaturation should be permanently archived, so that

  17. Ca isotope variations in Allende

    NASA Technical Reports Server (NTRS)

    Jungck, M. H. A.; Shimamura, T.; Lugmair, G. W.

    1984-01-01

    Ca-isotope measurements of Allende Ca-Al-rich inclusions (CAIs), together with those on an apatite-enriched fraction from Orgueil, indicate the existence of widespread excesses on the neutron-rich isotope Ca-48. Isotopic anomalies are noted in 7 out of 11 CAIs analyzed. This abundance of isotopic excesses places Ca alongside Ti and O, although no clear correlation has yet been found between Ca-48 and Ti-50, which are thought to be coproduced by neutron-rich nucleosynthetic processes within stars. It is suggested that the higher volatility of Ca, by comparison with Ti compounds, led to a variable dilution with isotopically normal Ca in vaporization and recondensation processes in stellar envelopes, the interstellar medium, and/or the solar nebula.

  18. Standardization for oxygen isotope ratio measurement - still an unsolved problem.

    PubMed

    Kornexl; Werner; Gehre

    1999-07-01

    Numerous organic and inorganic laboratory standards were gathered from nine European and North American laboratories and were analyzed for their delta(18)O values with a new on-line high temperature pyrolysis system that was calibrated using Vienna standard mean ocean water (VSMOW) and standard light Antartic precipitation (SLAP) internationally distributed reference water samples. Especially for organic materials, discrepancies between reported and measured values were high, ranging up to 2 per thousand. The reasons for these discrepancies are discussed and the need for an exact and reliable calibration of existing reference materials, as well as for the establishment of additional organic and inorganic reference materials is stressed. Copyright 1999 John Wiley & Sons, Ltd.

  19. Simultaneous measurement of denitrification and nitrogen fixation using isotope pairing with membrane inlet mass spectrometry analysis.

    PubMed

    An, S; Gardner, W S; Kana, T

    2001-03-01

    A method for estimating denitrification and nitrogen fixation simultaneously in coastal sediments was developed. An isotope-pairing technique was applied to dissolved gas measurements with a membrane inlet mass spectrometer (MIMS). The relative fluxes of three N(2) gas species ((28)N(2), (29)N(2), and (30)N(2)) were monitored during incubation experiments after the addition of (15)NO(3)(-). Formulas were developed to estimate the production (denitrification) and consumption (N(2) fixation) of N(2) gas from the fluxes of the different isotopic forms of N(2). Proportions of the three isotopic forms produced from (15)NO(3)(-) and (14)NO(3)(-) agreed with expectations in a sediment slurry incubation experiment designed to optimize conditions for denitrification. Nitrogen fixation rates from an algal mat measured with intact sediment cores ranged from 32 to 390 microg-atoms of N m(-2) h(-1). They were enhanced by light and organic matter enrichment. In this environment of high nitrogen fixation, low N(2) production rates due to denitrification could be separated from high N(2) consumption rates due to nitrogen fixation. Denitrification and nitrogen fixation rates were estimated in April 2000 on sediments from a Texas sea grass bed (Laguna Madre). Denitrification rates (average, 20 microg-atoms of N m(-2) h(-1)) were lower than nitrogen fixation rates (average, 60 microg-atoms of N m(-2) h(-1)). The developed method benefits from simple and accurate dissolved-gas measurement by the MIMS system. By adding the N(2) isotope capability, it was possible to do isotope-pairing experiments with the MIMS system.

  20. Fossil Fuel Combustion Fingerprint in High-Resolution Urban Water Vapor Isotope Measurements

    NASA Astrophysics Data System (ADS)

    Gorski, G.; Good, S. P.; Bowen, G. J.

    2014-12-01

    Increasing energy consumption and rapid urbanization have many important and poorly understood consequences for the hydrologic cycle in urban and suburban areas. Wide use of fossil fuels for transportation and heating releases isotopically distinctive water vapor that contributes to the overall water vapor budget in varying, usually unknown, concentrations. The use of long term, high resolution isotopic measurements can help determine different sources and proportions of water vapor at various time scales. We present two months of high-resolution water vapor isotope measurements coupled with CO2 concentrations and co-located meteorological observations from December 2013 - January 2014 in Salt Lake City, UT. Periods of atmospheric stagnation (cold-air inversions) show a buildup of CO2 from baseline values of 420 ppm to as high as 600 ppm and an associated decrease in water vapor deuterium-excess values from a baseline of approx. 10‰ to values as low as -10‰ (where d = δ2H - 8*δ18O, in per mil units). We suggest that the strong relationship between CO2and d during inversion periods is driven by the build-up of fossil fuel combustion-derived water vapor with very low d values (≤ -150‰). Based on our measurements of its isotopic composition, combustion-derived water vapor could contribute as much as 15% to the total water vapor budget during inversion periods. We present evidence of this effect at both the multi-day scale and the diurnal scale, where periods of increased automobile use and home heating can be identified. This study provides the first isotopic evidence that accumulation of water of combustion can be identified in boundary layer water vapor, suggests that an appreciable fraction of boundary layer vapor can be derived from combustion under certain atmospheric conditions, and indicates that the distinctive d values of combustion-derived vapor may be a useful tracer for this component of the atmospheric water budget in other urban regions.

  1. Size-Based Hydroacoustic Measures of Within-Season Fish Abundance in a Boreal Freshwater Ecosystem

    PubMed Central

    Pollom, Riley A.; Rose, George A.

    2015-01-01

    Eleven sequential size-based hydroacoustic surveys conducted with a 200 kHz split-beam transducer during the summers of 2011 and 2012 were used to quantify seasonal declines in fish abundance in a boreal reservoir in Manitoba, Canada. Fish densities were sufficiently low to enable single target resolution and tracking. Target strengths converted to log2-based size-classes indicated that smaller fish were consistently more abundant than larger fish by a factor of approximately 3 for each halving of length. For all size classes, in both years, abundance (natural log) declined linearly over the summer at rates that varied from -0.067.day-1 for the smallest fish to -0.016.day-1 for the largest (R2 = 0.24–0.97). Inter-annual comparisons of size-based abundance suggested that for larger fish (>16 cm), mean winter decline rates were an order of magnitude lower (-0.001.day-1) and overall survival higher (71%) than in the main summer fishing season (mean loss rate -0.038.day-1; survival 33%). We conclude that size-based acoustic survey methods have the potential to assess within-season fish abundance dynamics, and may prove useful in long-term monitoring of productivity and hence management of boreal aquatic ecosystems. PMID:25875467

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

    PubMed

    Seltzer, Michael D

    2003-09-01

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

  3. Ion microprobe measurement of strontium isotopes in calcium carbonate with application to salmon otoliths

    USGS Publications Warehouse

    Weber, P.K.; Bacon, C.R.; Hutcheon, I.D.; Ingram, B.L.; Wooden, J.L.

    2005-01-01

    The ion microprobe has the capability to generate high resolution, high precision isotopic measurements, but analysis of the isotopic composition of strontium, as measured by the 87Sr/ 86Sr ratio, has been hindered by isobaric interferences. Here we report the first high precision measurements of 87Sr/ 86Sr by ion microprobe in calcium carbonate samples with moderate Sr concentrations. We use the high mass resolving power (7000 to 9000 M.R.P.) of the SHRIMP-RG ion microprobe in combination with its high transmission to reduce the number of interfering species while maintaining sufficiently high count rates for precise isotopic measurements. The isobaric interferences are characterized by peak modeling and repeated analyses of standards. We demonstrate that by sample-standard bracketing, 87Sr/86Sr ratios can be measured in inorganic and biogenic carbonates with Sr concentrations between 400 and 1500 ppm with ???2??? external precision (2??) for a single analysis, and subpermil external precision with repeated analyses. Explicit correction for isobaric interferences (peak-stripping) is found to be less accurate and precise than sample-standard bracketing. Spatial resolution is ???25 ??m laterally and 2 ??m deep for a single analysis, consuming on the order of 2 ng of material. The method is tested on otoliths from salmon to demonstrate its accuracy and utility. In these growth-banded aragonitic structures, one-week temporal resolution can be achieved. The analytical method should be applicable to other calcium carbonate samples with similar Sr concentrations. Copyright ?? 2005 Elsevier Ltd.

  4. Neutron-Induced Fission Cross Section Measurements for Uranium Isotopes and Other Actinides at LANSCE

    SciTech Connect

    Laptev, Alexander B.; Tovesson, Fredrik K.; Hill, Tony S.

    2012-08-16

    A well established program of neutron-induced fission cross section measurement at Los Alamos Neutron Science Center (LANSCE) is supporting the Fuel Cycle Research program (FC R&D). The incident neutron energy range spans from sub-thermal up to 200 MeV by combining two LANSCE facilities, the Lujan Center and the Weapons Neutron Research center (WNR). The time-of-flight method is implemented to measure the incident neutron energy. A parallel-plate fission ionization chamber was used as a fission fragment detector. The event rate ratio between the investigated foil and a standard {sup 235}U foil is translated into a fission cross section ratio. Thin actinide targets with deposits of <200 {micro}g/cm{sup 2} on stainless steel backing were loaded into a fission chamber. In addition to previously measured data for {sup 237}Np, {sup 239-242}Pu, {sup 243}Am, new measurements include the recently completed {sup 233,238}U isotopes, {sup 236}U data which is being analyzed, and {sup 234}U data acquired in the 2011-2012 LANSCE run cycle. The new data complete the full suite of Uranium isotopes which were investigated with this experimental approach. When analysis of the new measured data is completed, data will be delivered to evaluators. Having data for multiple Uranium isotopes will support theoretical modeling capabilities and strengthens nuclear data evaluation.

  5. 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

  6. Ptolemy an Instrument to Measure Stable Isotopic Ratios of Key Volatiles on a Cometary Nucleus

    NASA Astrophysics Data System (ADS)

    Wright, I. P.; Barber, S. J.; Morgan, G. H.; Morse, A. D.; Sheridan, S.; Andrews, D. J.; Maynard, J.; Yau, D.; Evans, S. T.; Leese, M. R.; Zarnecki, J. C.; Kent, B. J.; Waltham, N. R.; Whalley, M. S.; Heys, S.; Drummond, D. L.; Edeson, R. L.; Sawyer, E. C.; Turner, R. F.; Pillinger, C. T.

    2007-02-01

    A fundamental goal of cometary studies is to determine the exact relationship between these bodies and the Solar System the question(s) can be summarised as follows: did comets originate during the same events that spawned the Sun and planets, are they more primitive bodies that record a pre-solar history, or are they interstellar materials collected in relatively more recent times? Now, whatever the origin of comets, it is entirely possible that they could, in part, contain interstellar or pre-solar components indeed, it seems rather likely in light of the fact that primitive meteorites contain such entities. These particular components are likely to be refractory (dust, macromolecular organic complexes, etc.). Of more relevance to the issues above are the volatile constituents, which make up the bulk of a comet's mass. Since these materials, by their very nature, volatilise during perihelion passage of a comet they can, in some instances, be detected and measured spectroscopically. Perhaps the most useful species for isotopic investigations are C2, HCN and CN. Unfortunately, spectroscopic measurements can only currently be made with accuracies of ±10 to ±20%. As such it is very often not practical to conclude anything further than the fact that isotopic measurements are compatible with ‘`solar’' values, which tends to imply an origin from the margins of the solar accretion disk. But there is another problem with the spectroscopic measurements since these are made on gaseous species in the coma (and relatively minor species at that) it is impossible to be certain that these represent the true nuclear values. In other words, if the processes of sublimation, active jetting, and photochemistry in the coma impart isotopic fractionation, the spectroscopic measurements could give a false impression of the true isotope ratios. What is required is an experiment capable of measuring isotopic ratios at the very surface of a comet. Herein we describe the Ptolemy

  7. The exchange of acetaldehyde between plants and the atmosphere: Stable carbon isotope and flux measurements

    NASA Astrophysics Data System (ADS)

    Jardine, Kolby Jeremiah

    The exchange of acetaldehyde between plant canopies and the atmosphere may significantly influence regional atmospheric chemistry and plant metabolism. While plants are known to both produce and consume acetaldehyde, the exchange of this compound with forested ecosystems is complicated by physical, biological, and chemical processes that range from being poorly understood to completely unknown. This precludes a quantitative understanding of acetaldehyde exchange rates between the atmosphere and the biosphere. In this study, the processes controlling the exchange of acetaldehyde with plant canopies was investigated using concentration, flux, and natural abundance 13C measurements of gas phase acetaldehyde from individual plants, soils, and entire ecosystems. Although previously only considered important in anoxic tissues, it was discovered that acetaldehyde is produced and consumed in leaves through ethanolic fermentation coupled to the pyruvate dehydrogenase bypass system under normal aerobic conditions. These coupled pathways determine the acetaldehyde compensation point, a major factor controlling its exchange with the atmosphere. Carbon isotope analysis suggests a new pathway for acetaldehyde production from plants under stress involving the peroxidation of membrane fatty acids. This pathway may be a major source of acetaldehyde to the atmosphere from plants under biotic and abiotic stresses. Plant stomata were found to be the dominant pathway for the exchange of acetaldehyde with the atmosphere with stomatal conductance influencing both emission and uptake fluxes. In addition, increasing temperature and solar radiation was found to increase the compensation point by increasing the rates of acetaldehyde production relative to consumption. Under ambient conditions, bare soil was neutral to the exchange of acetaldehyde while senescing and decaying leaves were found to be strong source of acetaldehyde to the atmosphere due to increased decomposition processes and

  8. Measurement of CO{sub 2} and N{sub 2}O at nanomolar amounts using continuous-flow isotope-ratio mass spectrometry (CF-IRMS)

    SciTech Connect

    Patel, A; Downie, S.; Webster, E.; Hopkins, D.W.; Rennie, M.J.

    1994-12-01

    We are currently developing methods using Continuous Flow Isotope Ratio Mass Spectrometry (CF-IRMS) in conjunction with a thermal desorption purification unit to measure nanomolar levels of C0{sub 2} and N{sub 2}0. Samples of the pure gases diluted in He/air and transferred to septum capped Exetainers (Labco) provided a simple means to investigate the technique. We analyzed C0{sub 2} at natural abundance in the concentration range 50 to 5 nmoles and N{sub 2}0 at two concentrations between 25 and 5 nmoles. The technique was then used to measure C0{sub 2} (natural abundance and {sup 13}C-labeled) generated from the ninhydrin reaction. The results are summarized in a table; values are expressed in delta {sup 13}C notation relative to Pee Dee Belemnite. The data show that, provided care is taken to minimize or eliminate sources of contamination (air leaks, etc.), CF-IRMS coupled with a thermal desorption unit permits measurement of {sup 13}C enrichment in much smaller amounts of isolated amino acids than has been possible until now. The new methodology, including thermal desorption, should allow stable-isotope investigations on much smaller samples than are possible with other currently available techniques-while maintaining high precision.

  9. Fractionation in position-specific isotope composition during vaporization of environmental pollutants measured with isotope ratio monitoring by ¹³C nuclear magnetic resonance spectrometry.

    PubMed

    Julien, Maxime; Parinet, Julien; Nun, Pierrick; Bayle, Kevin; Höhener, Patrick; Robins, Richard J; Remaud, Gérald S

    2015-10-01

    Isotopic fractionation of pollutants in terrestrial or aqueous environments is a well-recognized means by which to track different processes during remediation. As a complement to the common practice of measuring the change in isotope ratio for the whole molecule using isotope ratio monitoring by mass spectrometry (irm-MS), position-specific isotope analysis (PSIA) can provide further information that can be exploited to investigate source and remediation of soil and water pollutants. Position-specific fractionation originates from either degradative or partitioning processes. We show that isotope ratio monitoring by (13)C NMR (irm-(13)C NMR) spectrometry can be effectively applied to methyl tert-butylether, toluene, ethanol and trichloroethene to obtain this position-specific data for partitioning. It is found that each compound exhibits characteristic position-specific isotope fractionation patterns, and that these are modulated by the type of evaporative process occurring. Such data should help refine models of how remediation is taking place, hence back-tracking to identify pollutant sources.

  10. Laboratory and Field Measurements of the Nitrogen Isotopic Composition of NOx

    NASA Astrophysics Data System (ADS)

    Fibiger, D. L.; Miller, D. J.; Dahal, B. R.; Lew, A. F.; Peltier, R.; Hastings, M. G.

    2014-12-01

    The nitrogen isotopic composition of nitrogen oxides (NOx = NO + NO2) has been measured from several NOx emissions sources in prior studies. These measurements have utilized a variety of methods for collecting the NOx as nitrate or nitrite for isotopic analysis, but none of these methods have been verified for complete conversion of NOx. Less than 100% conversion can result in isotopic fractionations. We present a method for accurately measuring the nitrogen isotopic composition of NOx using a .25 M KMnO4 and 0.5 M NaOH solution. Based on laboratory tests, this technique has been found to collect all NOx passed through under a variety of conditions (e.g., air flow rate, NOx concentration, temperature, humidity), allowing for diagnosis of δ15N-NOx without correction for fractionation. The precision across the entire analytic technique is 1.5‰. This active collection method is advantageous for collecting NOx over short time scales in environments with highly variable NOx sources and concentrations. The major drawback of the NaOH/KMnO4 method is a significant nitrate background found in the KMnO4, but this background is consistent and can be easily accounted for. We aim to use this method to provide more robust constraints on the isotopic signatures of NOx emissions from different sources. Initial results will be presented from lab- and field-based collections of NOx emissions. Emissions from a diesel engine were measured in a laboratory smog chamber and yielded δ15N values with a mean of -18.0‰ (n = 5, 1σ = 0.97‰). Measurements of δ15N-NOx were also made on a rooftop between two highways in Providence, RI. The values ranged from -7.7 to -0.63‰ for different time periods sampled, with excellent reproducibility in side-by-side collections. Additionally, the NaOH/KMnO4 was deployed in a laboratory study of biomass burning (FLAME4) to analyze the nitrogen isotopic composition of NOx produced from the burning of variety of materials (e.g. trees, agricultural

  11. 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

  12. The stability and calibration of water vapor isotope ratio measurements during long-term deployments

    NASA Astrophysics Data System (ADS)

    Bailey, A.; Noone, D.; Berkelhammer, M.; Steen-Larsen, H. C.; Sato, P.

    2015-05-01

    With the recent advent of commercial laser absorption spectrometers, field studies measuring stable isotope ratios of hydrogen and oxygen in water vapor have proliferated. These pioneering analyses have provided invaluable feedback about best strategies for optimizing instrumental accuracy, yet questions still remain about instrument performance and calibration approaches for multi-year field deployments. With clear scientific potential for using these instruments to carry out long-term monitoring of the hydrological cycle, this study examines the long-term stability of the isotopic biases associated with three cavity-enhanced laser absorption spectrometers - calibrated with different systems and approaches - at two remote field sites: Mauna Loa Observatory, Hawaii, USA, and Greenland Environmental Observatory, Summit, Greenland. The analysis pays particular attention to the stability of measurement dependencies on water vapor concentration and also evaluates whether these so-called concentration-dependences are sensitive to statistical curve-fitting choices or measurement hysteresis. The results suggest evidence of monthly-to-seasonal concentration-dependence variability - which likely stems from low signal-to-noise at the humidity-range extremes - but no long-term directional drift. At Mauna Loa, where the isotopic analyzer is calibrated by injection of liquid water standards into a vaporizer, the largest source of inaccuracy in characterizing the concentration-dependence stems from an insufficient density of calibration points at low humidity. In comparison, at Greenland, the largest source of inaccuracy is measurement hysteresis associated with interactions between the reference vapor, generated by a custom dew point generator (DPG), and the sample tubing. Nevertheless, prediction errors associated with correcting the concentration-dependence are small compared to total measurement uncertainty. At both sites, a dominant source of uncertainty is instrumental

  13. MEASUREMENTS OF THE RELATIVE ABUNDANCES OF HIGH-ENERGY COSMIC-RAY NUCLEI IN THE TeV/NUCLEON REGION

    SciTech Connect

    Ahn, H. S.; Ganel, O.; Han, J. H.; Kim, K. C.; Lee, M. H.; Malinin, A.; Allison, P. S.; Beatty, J. J.; Brandt, T. J.; Bagliesi, M. G.; Bigongiari, G.; Maestro, P.; Marrocchesi, P. S.; Barbier, L.; Childers, J. T.; DuVernois, M. A.; Conklin, N. B.; Coutu, S.; Jeon, J. A.; Lee, J.

    2010-06-01

    We present measurements of the relative abundances of cosmic-ray nuclei in the energy range of 500-3980 GeV/nucleon from the second flight of the Cosmic Ray Energetics And Mass balloon-borne experiment. Particle energy was determined using a sampling tungsten/scintillating-fiber calorimeter, while particle charge was identified precisely with a dual-layer silicon charge detector installed for this flight. The resulting element ratios C/O, N/O, Ne/O, Mg/O, Si/O, and Fe/O at the top of atmosphere are 0.919 {+-} 0.123{sup stat} {+-} 0.030{sup syst}, 0.076 {+-} 0.019{sup stat} {+-} 0.013{sup syst}, 0.115 {+-} 0.031{sup stat} {+-} 0.004{sup syst}, 0.153 {+-} 0.039{sup stat} {+-} 0.005{sup syst}, 0.180 {+-} 0.045{sup stat} {+-} 0.006{sup syst}, and 0.139 {+-} 0.043{sup stat} {+-} 0.005{sup syst}, respectively, which agree with measurements at lower energies. The source abundance of N/O is found to be 0.054 {+-} 0.013{sup stat} {+-} 0.009{sup syst+0.010esc} {sub -0.017}. The cosmic-ray source abundances are compared to local Galactic (LG) abundances as a function of first ionization potential and as a function of condensation temperature. At high energies the trend that the cosmic-ray source abundances at large ionization potential or low condensation temperature are suppressed compared to their LG abundances continues. Therefore, the injection mechanism must be the same at TeV/nucleon energies as at the lower energies measured by HEAO-3, CRN, and TRACER. Furthermore, the cosmic-ray source abundances are compared to a mixture of 80% solar system abundances and 20% massive stellar outflow (MSO) as a function of atomic mass. The good agreement with TIGER measurements at lower energies confirms the existence of a substantial fraction of MSO material required in the {approx}TeV per nucleon region.

  14. Measuring technique for thermal ionisation mass spectrometry of human tracer kinetic study with stable cerium isotopes.

    PubMed

    Keiser, Teresa; Höllriegl, Vera; Giussani, Augusto; Oeh, Uwe

    2011-06-01

    Thermal ionisation mass spectrometry (TIMS) method has been developed for the simultaneous detection of different cerium isotopes in biological samples (i.e., blood and urine) at very low concentrations. The work has been done in the frame of a biokinetic study, where different stable cerium isotopes have been administered orally and intravenously as tracers to the human body. In order to develop an appropriate detection method for the tracers in the biological samples, an optimum sample preparation technique has been set and adapted to the specific requirements of the analysis technique used, i.e., TIMS. For sample evaporation and ionisation, the double tantalum filament technique showed the best results. The ions produced were simultaneously collected on a secondary electron multiplier so that the isotopic ratios of the cerium isotopes in the biological samples could be measured. The technique has been optimised for the determination of cerium down to 1 ng loaded on the evaporation filament corresponding to cerium concentrations of down to 1 ng ml(-1) in the blood or urine samples. It has been shown that the technique is reliable in application and enables studies on cerium metabolism and biokinetics in humans without employing radioactive tracers.

  15. Separation Of Uranium And Plutonium Isotopes For Measurement By Multi Collector Inductively Coupled Plasma Mass Spectroscopy

    SciTech Connect

    Martinelli, R E; Hamilton, T F; Williams, R W; Kehl, S R

    2009-03-29

    Uranium (U) and plutonium (Pu) isotopes in coral soils, contaminated by nuclear weapons testing in the northern Marshall Islands, were isolated by ion-exchange chromatography and analyzed by mass spectrometry. The soil samples were spiked with {sup 233}U and {sup 242}Pu tracers, dissolved in minerals acids, and U and Pu isotopes isolated and purified on commercially available ion-exchange columns. The ion-exchange technique employed a TEVA{reg_sign} column coupled to a UTEVA{reg_sign} column. U and Pu isotope fractions were then further isolated using separate elution schemes, and the purified fractions containing U and Pu isotopes analyzed sequentially using multi-collector inductively coupled plasma mass spectrometer (MCICP-MS). High precision measurements of {sup 234}U/{sup 235}U, {sup 238}U/{sup 235}U, {sup 236}U/{sup 235}U, and {sup 240}Pu/{sup 239}Pu in soil samples were attained using the described methodology and instrumentation, and provide a basis for conducting more detailed assessments of the behavior and transfer of uranium and plutonium in the environment.

  16. Spectroscopic measurements of element abundances in the solar corona: Variations on the FIP theme

    NASA Technical Reports Server (NTRS)

    Saba, J. L. R.

    1995-01-01

    Solar wind and solar energetic particle (SEP) data yield systematic differences between elemental abundances in the corona and in the photosphere related to the first ionization potential (FIP) of the elements: low-FIP elements are preferentially enhanced relative to high-FIP elements by about a factor of four. Spectroscopic studies of the inner corona show that such a pattern may apply on average but not in detail for coronal loops: substantial abundance differences occur between different types of coronal structures, and variations have been found from flare to flare, from one active region to another, and over time in the same region; further, in some flares, anomalies such as enhanced Ne:O ratios, distinctly at odds with the FIP pattern, show that a competing element selection mechanism sometimes operates. Details of the observed abundance variability -- such as the magnitude of the variations, the relevant temporal and spatial scales, and correlations with other properties of the given coronal structure -- may give important clues to the processes which supply and heat the corona, or they may reflect the changing physical conditions or locations where those processes take place. However, many such details remain to be established definitively. At present, abundance variability is primarily a major complication to data analysis and interpretation. However, once it is better understood, it may provide a new diagnostic tool for probing the lower layers of the solar atmosphere.

  17. Advances in Methane Isotope Measurements via Direct Absorption Spectroscopy with Applications to Oil and Gas Source Characterization

    NASA Astrophysics Data System (ADS)

    Yacovitch, T. I.; Herndon, S. C.; Roscioli, J. R.; Petron, G.; Shorter, J. H.; Jervis, D.; McManus, J. B.; Nelson, D. D.; Zahniser, M. S.; Kolb, C. E., Jr.

    2015-12-01

    Instrumental developments in the measurement of multiple isotopes of methane (12CH4, 13CH4 and 12CH3D) are presented. A first generation 8-micron instrument quantifies 12CH4 and 13CH4 at a 1-second rate via tunable infrared direct absorption spectroscopy (TILDAS). A second generation instrument uses two 3-micron intraband cascade lasers in an Aerodyne dual laser chassis for simultaneous measurement of 12CH4, 13CH4 and 12CH3D. Sensitivity and noise performance improvements are examined. The isotopic signature of methane provides valuable information for emission source identification of this greenhouse gas. A first generation spectrometer has been deployed in the field on a mobile laboratory along with a sophisticated 4-tank calibration system. Calibrations are done on an agressive schedule, allowing for the correction of measured isotope ratios to an absolute isotope scale. Distinct isotopic signatures are found for a number of emission sources in the Denver-Julesburg Basin: oil and gas gathering stations, compressor stations and processing plants; a municipal landfill, and dairy/cattle operations. The isotopic signatures are compared with measured ethane/methane ratios. These direct absorption measurements have larger uncertainties than samples measured via gas chromatography-mass spectrometry, but have several advantages over canister sampling methods: individual sources of short duration are easier to isolate; calibrated isotope ratio results are available immediately; replicate measurements on a single source are easily performed; and the number of sources sampled is not limited by canister availability and processing time.

  18. A review and interpretation of recent cosmic ray beryllium isotope measurements

    NASA Technical Reports Server (NTRS)

    Buffington, A.

    1978-01-01

    Beryllium-10 is of interest for cosmic ray propagation, because its radioactive decay half-life is well matched to the expected cosmic ray age. Recent beryllium isotope measurements from satellites and balloon covered an energy range from about 30 to 300 MeV/nucleon. At the lowest energies, most of the Be-10 is absent, indicating a cosmic ray lifetime of order 2 x 10 to the 7th power years and the rather low average density of 0.2 atoms/cc traversed by the cosmic rays. At higher energies, a greater propagation of Be-10 is observed, indicating a somewhat shorter lifetime. These experiments will be reviewed and then compared with a new experiment covering from 100 to 1000 MeV/nucleon. Although improved experiments will be necessary to realize the full potential of cosmic ray beryllium isotope measurements, these first results are already disclosing interesting and unexpected facts about cosmic ray acceleration and propagation.

  19. Rn-222 tracing and stable isotope measurements of biogenic gas fluxes from methane saturated sediments

    NASA Technical Reports Server (NTRS)

    Martens, Christopher S.; Green, C. D.; Blair, Neal; Chanton, J. P.

    1985-01-01

    Transport of reduced biogenic gases from anoxic sediments and soils to the atmosphere can be quantitatively studied through measurement of radon-222/radium-226 disequilibrium. In previous work, seasonal variations in biogenic gas transport mechanisms, net fluxes and overall composition were documented. Now presented are direct field measurements of radon-222 activity in gases exiting organic rich sediments which show their usefulness for tracing of the stripping of dissolved biogenic gases from within the sediment column and transport via bubble ebullition. Methane is depleted in deuterium during the summer as compared with winter months and is in general lighter than in most marine sediments signaling the probable importance of acetate as an important precursor molecule. The significant seasonal isotopic variations observed illustrate the importance of understanding mechanisms and rates of biogenic gas production in order to interpret observed tropospheric isotopic data.

  20. BESS-Polar II Hydrogen and Helium Isotope Measurements to Constrain Cosmic-Ray Propagation Models

    NASA Astrophysics Data System (ADS)

    Picot-Clemente, Nicolas; BESS-Polar Collaboration

    2017-01-01

    The Balloon-borne Experiment with Superconducting Spectrometer BESS-Polar II flew over Antarctica for 24.5 days from December 2007 through January 2008, during the 23rd solar cycle minimum. The instrument is made of complementary particle detectors which allow to precisely measure the charge, velocity and rigidity of incoming cosmic rays. It can accurately separate cosmic-ray hydrogen and helium isotopes from 0.2 to 1.5 GeV/nucleon. Flux and secondary-to-primary ratios of these particles can bring important information to better understand the cosmic-ray propagation history in the Galaxy. BESS-Polar II provides the most precise isotope measurements to date between 0.2 and 1.5 GeV/nucleon. These data will be reported and constraints on cosmic-ray propagation models, using the GALPROP program, will be discussed.

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

    PubMed

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

    2011-03-15

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

  2. Study for Nuclear Structures of 22-35Na Isotopes via Measurements of Reaction Cross Sections

    NASA Astrophysics Data System (ADS)

    Suzuki, Shinji

    2014-09-01

    T. Ohtsubo, M. Nagashima, T. Ogura, Y. Shimbara (Grad. Sch. of Sc., Niigata Univ.), M.Takechi, H. Geissel, M. Winkler (GSI), D. Nishimura, T. Sumikama (Dept. of Phys., Tokyo Univ. of Sc.), M. Fukuda, M. Mihara, H. Uenishi (Dept. of Phys., Osaka Univ.), T. Kuboki, T. Suzuki, T. Yamaguchi, H. Furuki, C. S. Lee, K. Sato (Dept. of Phys., Saitama Univ.), A. Ozawa, H. Ohnishi, T. Moriguchi, S. Fukuda, Y. Ishibashi, D. Nagae, R. Nishikiori, T. Niwa (Inst. of Phys., Univ. of Tsukuba), N. Aoi (RCNP), Rui-Jiu Chen, N. Inabe, D. Kameda, T. Kubo, M. Lantz, T. Ohnishi, K. Okumura, H. Sakurai, H. Suzuki, H. Takeda, S. Takeuchi, K. Tanaka, Y. Yanagisawa (RIKEN), De-Qing Fang, Yu-Gang Ma (SINAP), T. Izumikawa (RI Ctr., Niigata Univ.), and S. Momota (Fac. of Engn., Kochi Univ. of Tech.) Reaction cross sections (σR) for 22-35Na isotopes have been measured at around 240 MeV/nucleon. The σR for 22-35Na were measured for the first time. Enhancement in cross sections is clearly observed from the systematics for stable nuclei, for isotopes with large mass numbers. These enhancement can be mainly ascribed to the nuclear deformation. We will discuss the nuclear structure (neutron skin, nuclear shell structure) for neutron-excess Na isotopes. T. Ohtsubo, M. Nagashima, T. Ogura, Y. Shimbara (Grad. Sch. of Sc., Niigata Univ.), M.Takechi, H. Geissel, M. Winkler (GSI), D. Nishimura, T. Sumikama (Dept. of Phys., Tokyo Univ. of Sc.), M. Fukuda, M. Mihara, H. Uenishi (Dept. of Phys., Osaka Univ.), T. Kuboki, T. Suzuki, T. Yamaguchi, H. Furuki, C. S. Lee, K. Sato (Dept. of Phys., Saitama Univ.), A. Ozawa, H. Ohnishi, T. Moriguchi, S. Fukuda, Y. Ishibashi, D. Nagae, R. Nishikiori, T. Niwa (Inst. of Phys., Univ. of Tsukuba), N. Aoi (RCNP), Rui-Jiu Chen, N. Inabe, D. Kameda, T. Kubo, M. Lantz, T. Ohnishi, K. Okumura, H. Sakurai, H. Suzuki, H. Takeda, S. Takeuchi, K. Tanaka, Y. Yanagisawa (RIKEN), De-Qing Fang, Yu-Gang Ma (SINAP), T. Izumikawa (RI Ctr., Niigata Univ.), and S. Momota (Fac. of Engn

  3. Data reduction framework for standard atomic weights and isotopic compositions of the elements

    NASA Astrophysics Data System (ADS)

    Meija, Juris; Possolo, Antonio

    2017-04-01

    We outline a general framework to compute consensus reference values of standard atomic weights, isotope ratios, and isotopic abundances, and to evaluate associated uncertainties using modern statistical methods for consensus building that can handle mutually inconsistent measurement results. The multivariate meta-regression approach presented here is directly relevant to the work of the IUPAC Commission on Isotopic Abundances and atomic weights (CIAAW), and we illustrate the proposed method in meta-analyses of the isotopic abundances and atomic weights of zinc, platinum, antimony, and iridium.

  4. Combining metal and nonmetal isotopic measurements in barite to identify mode of formation

    NASA Astrophysics Data System (ADS)

    Griffith, E. M.; Paytan, A.; Eisenhauer, A.; Scher, H. D.; Wortmann, U.

    2014-12-01

    Barite (BaSO4) is a highly stable and widely-distributed mineral found in magmatic, metamorphic, and sedimentary rocks (of all ages), as well as in soils, aerosol dust, and extraterrestrial material. Today, barite can form in a variety of settings in the oceans (hydrothermal, cold seeps, water column, sediments) and on the continents - where supersaturation and precipitation of barite typically occurs from the mixing of fluids - one containing Ba and another containing sulfate. Sulfur (δ34S) and oxygen (δ18O) isotopes together with 87Sr/86Sr and stable Sr-isotopic signatures (δ88/86Sr) of modern authigenic continental barite are compared to modern pelagic marine barite and marine hydrothermal and cold seep barite to investigate the potential for their combined use to indicate mode of barite formation. The 87Sr/86Sr in barite cleary identifies the source of fluid for any particular type of barite (as previously noted, see Paytan et al., 2002). The highest (most radiogenic) 87Sr/86Sr values are measured in continental barite samples. There is no unique δ88/86Sr signature for any particular type of barite, but coretop marine (pelagic) barite has a consistent value measured from samples collected in different ocean basins. The highest and lowest δ88/86Sr values were measured in continental barite samples. The combination of isotopic systems result in unique δ88/86Sr and δ18O relationships and distinct δ88/86Sr and δ34S relationships for different types of barites investigated. Data suggest that the combined use of these metal and nonmetal isotopic measurements in barite could be useful as a new geochemical proxy to identify mode of barite mineralization for use in earth science applications including understanding ancient barite deposits.

  5. Isotope ratio measurements by secondary ion mass spectrometry (SIMS) and glow discharge mass spectrometry (GDMS)

    NASA Astrophysics Data System (ADS)

    Betti, Maria

    2005-04-01

    The basic principles of secondary ion mass spectrometry and glow discharge mass spectrometry have been shortly revisited. The applications of both techniques as exploited for the isotope ratio measurements in several matrices have been reviewed. Emphasis has been given to research fields in expansions such as solar system studies, medicine, biology, environment and nuclear forensic. The characteristics of the two techniques are discussed in terms of sensitivity and methodology of quantification. Considerations on the different detection possibilities in SIMS are also presented.

  6. On-line systems for continuous water and gas isotope ratio measurements.

    PubMed

    Huber, Christof; Leuenberger, Markus

    2005-09-01

    New continuous on-line techniques for water and air extracted from ice cores are developed. Water isotope ratio determination on any of the water phases (water vapour, water, ice) is of great relevance in different research fields, such as climate and paleoclimate studies, geological surveys, and hydrological studies. The conventional techniques for water isotopes are available in different layouts but all of them are rather time-consuming. Here we report new fast on-line techniques that process water as well as ice samples. The analysis time is only approximately 5 min per sample which includes equilibration and processing. Measurement precision and accuracy are better than 0.1 per thousand and 1 per thousand for delta18O and deltaD, respectively, comparable to conventional techniques. The new on-line techniques are able to analyze a wide range of aqueous samples. This allows, for the first time, to make continuous isotope measurements on ice cores. Similarly, continuous and fast analysis of aqueous samples can be of great value for hydrological, geological and perhaps medical applications.Furthermore, a new technique for the on-line analysis of air isotopes extracted from ice cores is developed. This technique allows rapid analyses with high resolution of the main air components nitrogen, oxygen, and argon. Measurement precision is comparable to precisions obtained by conventional techniques. It is now possible to measure delta15N and delta18O(atm) over entire ice cores helping to synchronize chronologies, to assess gas age-ice age differences, and to calibrate the paleothermometry for rapid temperature changes. This new on-line air extraction and analyzing technique complements the water methods in an ideal way as it separates the air from the melt-water of an ice sample. The remaining water waste flux can directly be analyzed by the water methods.

  7. High Precision Osmium Isotope Measurements Using New Generation Thermal Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Brandon, A.

    2006-12-01

    The technique for measuring Os isotopes to high precision (e.g. +/-30-50 ppm on the 186/188 ratio, 2 sigma) via negative thermal ionization mass spectrometry (NTIMS) was established a decade ago at the University of Maryland. Recent technical advances have resulted in the production of a new generation of TIMS that allows isotopic measurements with substantial improvement in accuracy and precision. Because of the improved capability, the new generation TIMS holds great potential to examine a variety of problems in geochemistry and cosmochemistry. Over the past 5 years, I have refined the technique for higher precision measurements of Os isotopes using the Triton TIMS from Thermo Electron. The measurements are made in static mode using 7 Faraday collectors. 70 or more nanograms of Os is loaded onto a Pt filament with barium hydroxide, the latter is an electron emitter that promotes efficient production of Os trioxide. Oxygen is bled into the source at constant pressures. Signal intensities of 120-180 mV 186Os trioxide are generated and measured as negative ions. Oxygen corrections to the raw data are made using the oxygen isotopic composition obtained for 2 ng loads of Re tetroxide measured on the Faraday cups. Multiple runs over the course of 3 years for the same lecture bottle used to bleed in oxygen to the source showed no change in the oxygen isotopic composition. Oxygen corrections are followed by instrumental mass fractionation corrections using 189/188, 192/189, or 192/188 using the exponential law. Both the internal and external precision for standard and unknown data are best when using 192/188, by a factor of 1.4 over 189/188, and 1.8 over 192/189. Replicate runs on 100 ng standard loads of a single filament shows no change in corrected values within external precision for all Os isotopic ratios over a wide range of fractionation, confirming adherence to the exponential law during emission. 39 runs for a standard solution gave +/-14 ppm (2 sigma) on the

  8. Cosmic ray isotope measurements with a new Cerenkov X total energy telescope

    NASA Technical Reports Server (NTRS)

    Webber, W. R.; Kish, J. C.; Schrier, D. A.

    1985-01-01

    Measurements of the isotopic composition of cosmic nuclei with Z = 7-20 are reported. These measurements were made with a new version of a Cerenkov x total E telescope. Path length and uniformity corrections are made to all counters to a RMS level 1%. Since the Cerenkov counter is crucial to mass measurements using the C x E technique - special care was taken to optimize the resolution of the 2.4 cm thick Pilot 425 Cerenkov counter. This counter exhibited a beta = 1 muon equivalent LED resolution of 24%, corresponding to a total of 90 p.e. collected at the 1st dynodes of the photomultiplier tubes.

  9. MEASUREMENT OF THE ISOTOPIC COMPOSITION OF HYDROGEN AND HELIUM NUCLEI IN COSMIC RAYS WITH THE PAMELA EXPERIMENT

    SciTech Connect

    Adriani, O.; Bongi, M.; Barbarino, G. C.; Bazilevskaya, G. A.; Bellotti, R.; Bruno, A.; Boezio, M.; Bonvicini, V.; Carbone, R.; Bogomolov, E. A.; Borisov, S.; Casolino, M.; De Pascale, M. P.; Bottai, S.; Cafagna, F.; Campana, D.; Carlson, P.; Castellini, G.; Danilchenko, I. A.; De Santis, C.; and others

    2013-06-10

    The satellite-borne experiment PAMELA has been used to make new measurements of cosmic ray H and He isotopes. The isotopic composition was measured between 100 and 600 MeV/n for hydrogen and between 100 and 900 MeV/n for helium isotopes over the 23rd solar minimum from 2006 July to 2007 December. The energy spectrum of these components carries fundamental information regarding the propagation of cosmic rays in the galaxy which are competitive with those obtained from other secondary to primary measurements such as B/C.

  10. Preparation of the anapole moment measurement in a chain of isotopes

    NASA Astrophysics Data System (ADS)

    Sheng, Dong; Hood, Jonathan; Orozco, Luis

    2010-02-01

    We present the current status of the experimental effort towards the measurement of the anapole moment in different isotopes of francium. The anapole is a parity violating, time reversal conserving nuclear moment that arises from the weak interaction among nucleons, and should be sensitive to the changes in the nuclear structure configuration among the isotopes. The anapole is a unique probe of the weak interaction in the presence of the strong interaction. The system is currently being tested with rubidium and we have analyzed the sensitivity to measurements with a chain of Rb isotopes. Our experimental scheme involves a collection of cold atoms in a blue-detuned dipole trap located at the anti-node of a microwave cavity. The standing wave would drive a parity forbidden E1 transition between hyperfine ground states, interfering with an allowed transition. The rate of transitions depends on the positive or negative handedness of the apparatus and the measurement of their difference is proportional to the anapole moment. The experiment will use of the ISAC radioactive beam facility at TRIUMF. )

  11. Measurements of Hydrogen and Helium Isotopes with the BESS-Polar II Instrument

    NASA Astrophysics Data System (ADS)

    Picot-Clemente, Nicolas; BESS-Polar Collaboration

    2015-04-01

    The Balloon-Borne Experiment with a Superconducting Spectrometer (BESS-Polar II) flew successfully over Antarctica for 24.5 days in December 2007 through January 2008 during a period of minimum Solar activity. BESS-Polar II is configured with a solenoidal superconducting magnet and a suite of precision particle detectors. It can accurately identify hydrogen and helium isotopes among the incoming cosmic-ray nuclei with energies from 0.2 up to about 1.5 GeV/n. The long duration of the flight, and the good stability of the detectors increased the number of cosmic-ray events previously recorded with BESS-Polar I by a factor of 5, reaching about 4.7 billion collected particles. This allows to study and measure energy spectrum of hydrogen and helium isotope fluxes with unprecedented precision. The isotope flux and ratio measurements with BESS-Polar II will be presented and compared to previous measurements and theoretical predictions. They provide essential information to constrain cosmic-ray propagation models.

  12. Tracking nitrous oxide emission processes at a suburban site with semicontinuous, in situ measurements of isotopic composition

    NASA Astrophysics Data System (ADS)

    Harris, Eliza; Henne, Stephan; Hüglin, Christoph; Zellweger, Christoph; Tuzson, Béla; Ibraim, Erkan; Emmenegger, Lukas; Mohn, Joachim

    2017-02-01

    The isotopic composition of atmospheric nitrous oxide (N2O) was measured semicontinuously, at ˜35 min frequency in intermittent periods of 1-6 days over one and a half years, using preconcentration coupled to a quantum cascade laser spectrometer at the suburban site of Dübendorf, Switzerland. The achieved measurement repeatability was 0.08‰, 0.11‰, and 0.10‰ for δ18O, site preference, and δ15Nbulk respectively, which is better than or equal to standard flask sampling-based isotope ratio mass spectrometry performance. The observed mean diurnal cycle reflected the buildup of N2O from isotopically light sources on an isotopically heavy tropospheric background. The measurements were used to determine the source isotopic composition, which varied significantly compared to chemical and meteorological parameters monitored at the site. FLEXPART-COSMO transport modeling in combination with modified Emissions Database for Global Atmospheric Research inventory emissions was used to model N2O mole fractions at the site. Additionally, isotopic signatures were estimated for different source categories using literature data and used to simulate N2O isotopic composition over the measurement period. The model was able to capture variability in N2O mole fraction well, but simulations of isotopic composition showed little agreement with observations. In particular, measured source isotopic composition exhibited one magnitude larger variability than simulated, clearly indicating that the range of isotopic source signatures estimated from literature significantly underestimates true variability of source signatures. Source δ18O signature was found to be the most sensitive tracer for urban/industry versus agricultural N2O. δ15Nbulk and site preference may provide more insight into microbial and chemical emission processes than partitioning of anthropogenic source categories.

  13. Potential phytoavailability of anthropogenic cobalt in soils as measured by isotope dilution techniques.

    PubMed

    Bakkaus, Estelle; Collins, Richard N; Morel, Jean-Louis; Gouget, Barbara

    2008-11-15

    Isotope dilution is a useful technique to determine the potential phytoavailability of an element in soil. This method involves equilibrating an isotope with soil and then sampling the labile metal pool by analysis of the soil solution (E value) or plants growing in the soil (L value). The work reported here was conducted to evaluate the distribution coefficient (Kd), and the potential phytoavailability (E value) of cobalt (Co) in eight soils subjected to the atmospheric deposition of anthropogenic Co. Multiple regression analyses demonstrated that the K(d) of isotopically exchangeable Co in these soils was best modelled with two parameters: soil pH and organic carbon (OC) content (log Kd=0.85(pH)+1.1(logOC)-5.0, R2=0.94, p<0.01). Cobalt E values ranged from 1.5 to 37% of total soil Co concentrations. No evidence was obtained to suggest that Co(III), if present, was isotopically exchangeable in these soils and it was concluded that the Co E values consisted solely of Co(II). Cobalt L values, measured with Triticum aestivum L. (46 days), of two of these soils (varying in soil pH, e.g. 5.0 and 7.2) were statistically (p<0.05) different to E values. However, when changes of bulk soil pH on Co E values were considered, the two values were statistically (p<0.05) similar indicating that processes affecting soil pH during plant growth can alter isotopically exchangeable concentrations of Co.

  14. Ground based mobile isotopic methane measurements in the Front Range, Colorado

    NASA Astrophysics Data System (ADS)

    Vaughn, B. H.; Rella, C.; Petron, G.; Sherwood, O.; Mielke-Maday, I.; Schwietzke, S.

    2014-12-01

    Increased development of unconventional oil and gas resources in North America has given rise to attempts to monitor and quantify fugitive emissions of methane from the industry. Emission estimates of methane from oil and gas basins can vary significantly from one study to another as well as from EPA or State estimates. New efforts are aimed at reconciling bottom-up, or inventory-based, emission estimates of methane with top-down estimates based on atmospheric measurements from aircraft, towers, mobile ground-based vehicles, and atmospheric models. Attributing airborne measurements of regional methane fluxes to specific sources is informed by ground-based measurements of methane. Stable isotopic measurements (δ13C) of methane help distinguish between emissions from the O&G industry, Confined Animal Feed Operations (CAFO), and landfills, but analytical challenges typically limit meaningful isotopic measurements to individual point sampling. We are developing a toolbox to use δ13CH4 measurements to assess the partitioning of methane emissions for regions with multiple methane sources. The method was applied to the Denver-Julesberg Basin. Here we present data from continuous isotopic measurements obtained over a wide geographic area by using MegaCore, a 1500 ft. tube that is constantly filled with sample air while driving, then subsequently analyzed at slower rates using cavity ring down spectroscopy (CRDS). Pressure, flow and calibration are tightly controlled allowing precise attribution of methane enhancements to their point of collection. Comparisons with point measurements are needed to confirm regional values and further constrain flux estimates and models. This effort was made in conjunction with several major field campaigns in the Colorado Front Range in July-August 2014, including FRAPPÉ (Front Range Air Pollution and Photochemistry Experiment), DISCOVER-AQ, and the Air Water Gas NSF Sustainability Research Network at the University of Colorado.

  15. Radon isotope measurements as a monitoring tool for CO2 leakage in geological storage

    NASA Astrophysics Data System (ADS)

    Grandia, F.; Mazadiego, L. F.; de Elío, J.; Ortega, M.; Bruno, J.

    2011-12-01

    Early detection of the failure of the seal integrity is fundamental in the monitoring plan of a deep geological CO2 storage. A number of methods of leakage control are based on changes in fluid geochemistry (shallow water, soil gases) providing valuable indicators. Among them, the measurement of CO2 fluxes in the soil-atmosphere interface is commonly used since it can be easily done using portable infra-red analyzers (i.e., accumulation chambers). However, initial emission of CO2 from storage horizon could be masked by fluxes from biological activity, limiting its applicability as an early alarm system. The measurement of fluxes of trace gas (Rn, He, VOC) that are virtually absent in the pre-injection baseline turns out a promising complementary method. The measurement of radon isotopes has been long used for the observation of mass transport from deep reservoirs to surface despite the flux of 222Rn and 220Rn is usually very limited in sedimentary basins due to the short half-life of these isotopes. The enhanced transport of radon in CO2 fluxes has been reported from natural systems, resulting in concentration in air up to several thousands of Bq/m3. In the frame of the Compostilla pilot plant project in Spain, a number of methodologies to measure radon emission are being tested in natural systems to select of the most reliable and cost-effective method to be used in leakage control. These methods are (1) Scintillation detector EDA RD-200, (2) Track Etch °, (3) Ionization Chamber and (4) alpha spectroscopy SARAD RTM 200. Some of them are capable of measuring the isotopes separately (SARAD) whereas others just detect the bulk radon concentration. Also, these methods follow distinct procedures and acquisition times. The studied natural sites are located in central and NE Spain (Campo de Calatrava and La Selva basins), and in central Italy (Arezzo basin). Apparently, radon isotopes (up 200000 Bq/m3) are measured far from parent isotopes, and they are coupled to

  16. Symbiotic nitrogen fixation in an arid ecosystem measured by sup 15 N natural abundance

    SciTech Connect

    Johnson, G.V. )

    1990-05-01

    Plants dependent on nitrogen fixation have an {sup 15}N abundance similar to the atmosphere, while non-nitrogen fixing plants usually are enriched in {sup 15}N and are similar to soil nitrogen values. The natural abundance of {sup 15}N in leaf tissues and soils was determined to evaluate symbiotic nitrogen fixation by several legumes and actinorhizal species in the Sevilleta Long-term Ecological Research area in central New Mexico. Comparison of {delta}{sup 15}N values for the legume Prosopis glandulosa (mesquite) to adjacent Atriplex canascens (fourwing saltbush) indicated that P. glandulosa obtained 66% of its nitrogen by fixation. The legume Hoffmanseggia jamesii was found to be utilizing soil nitrogen. The {delta}{sup 15}N values for the actinorhizal plants, Elaeagnus angustifolia and Cercocarpus montanus, while below values for soil nitrogen, did not differ from associated non-fixing plants.

  17. Sulfur abundances in the solar wind measured by SWICS on Ulysses. [Solar Wind Ion Composition Spectrometer

    NASA Technical Reports Server (NTRS)

    Shafer, C. M.; Gloeckler, G.; Galvin, A. B.; Ipavich, F. M.; Geiss, J.; Von Steiger, R.; Ogilvie, K.

    1993-01-01

    One of the nine experiments on Ulysses (launched October, 1990), the Solar Wind Ion Composition Spectrometer, utilizes an energy per charge deflection system along with time of flight technology to uniquely determine the mass and mass per charge of solar wind particles. Thus the composition of various solar wind types can be analyzed. Using the SWICS data accumulated during the in-ecliptic phase of the mission, we have determined the sulfur abundance, relative to silicon, in two different types of solar wind: transient and coronal hole associated flows. Sulfur is of extreme interest because it is one of the few elements that lies in the transitional region of the FIP-dependent relative abundance enrichment function, observed for solar energetic particles and some types of solar wind flows.

  18. Measuring marine fish biodiversity: temporal changes in abundance, life history and demography

    PubMed Central

    Hutchings, Jeffrey A; Baum, Julia K

    2005-01-01

    Patterns in marine fish biodiversity can be assessed by quantifying temporal variation in rate of population change, abundance, life history and demography concomitant with long-term reductions in abundance. Based on data for 177 populations (62 species) from four north-temperate oceanic regions (Northeast Atlantic and Pacific, Northwest Atlantic, North mid-Atlantic), 81% of the populations in decline prior to 1992 experienced reductions in their rate of loss thereafter; species whose rate of population decline accelerated after 1992 were predominantly top predators such as Atlantic cod (Gadus morhua), sole (Solea solea) and pelagic sharks. Combining population data across regions and species, marine fish have declined 35% since 1978 and are currently less than 70% of recorded maxima; demersal species are generally at historic lows, pelagic species are generally stable or increasing in abundance. Declines by demersal species have been associated with substantive increases in pelagic species, a pattern consistent with the hypothesis that increases in the latter may be attributable to reduced predation mortality. There is a need to determine the consequences to population growth effected by the reductions in age (21%) and size (13%) at maturity and in mean age (5%) and size (18%) of spawners, concomitant with population decline. We conclude that reductions in the rate of population decline, in the absence of targets for population increase, will be insufficient to effect a recovery of marine fish biodiversity, and that great care must be exercised when interpreting multi-species patterns in abundance. Of fundamental importance is the need to explain the geographical, species-specific and habitat biases that pervade patterns of marine fish recovery and biodiversity. PMID:15814348

  19. Measurements of the interstellar C-12H+/C-13H+ abundance

    NASA Astrophysics Data System (ADS)

    vanden, P. A.; Snell, R. L.

    1980-03-01

    Detections have been made of the interstellar 13CH+ satellite lines of λ4232 in high-resolution spectra of 20 Tau, ξ Per, and ζ Oph and of λ3957 in ζ Oph that were taken using a Reticon detector. These detections lead to 12CH+/113CH+ abundance ratios of 49( + 12, -8), 59( +24, - 13), and 77( + 17, -12) for the 20 Tau, ξ Per, and ζ Oph clouds, respectively.

  20. Chlorine Stable Isotope Measurements by SIMS: a Calibration with IRMS Technique.

    NASA Astrophysics Data System (ADS)

    Godon, A. V.; Webster, J. D.; Layne, G. D.; Jendrzejewski, N.; Pineau, F.; Mathez, E.; Javoy, M.

    2001-12-01

    Chlorine isotope distribution is not uniform in nature and the few chlorine isotope data reported in the literature cover a large range of δ 37Cl values (from -14 to +10 permil versus SMOC). Deep Earth reservoirs are isotopically distinct compared to seawater and other surficial reservoirs. Physio-chemical processes, such as diffusion or ion filtration can produce important isotopic variations. Data and experimental studies on chlorine isotope fractionation are needed to understand the origin of such fractionations and to constrain the global chlorine geochemical cycle, and this requires new analytical tools. Accordingly, we have conducted a calibration of Secondary Ion Mass Spectrometry (SIMS) using the gaseous Isotope Ratio Mass Spectrometry (IRMS) technique as the standard comparison method. Homogeneous silicate glasses, for use as SIMS chlorine-isotope standards, were prepared with an internally heated pressure vessel at the American Museum of Natural History. Rock powders ranging in composition from basalt to rhyolite were fused in Au and Au-Pd capsules, with Cl added as PtCl2 and other chloride salts, at 2 to 4 kilobars and 1000 to 1170° C. The purpose of these glasses is to determine the potential influence of composition on the mass fractionation factors for Cl isotope analysis by SIMS. The chemical homogeneity of the glass was checked by electron microprobe. In Paris GIS Lab., the chlorine was extracted from the glasses by NaOH alkali fusion at 500° C. After acidification at pH 2.2 and addition of KNO3 to adjust the ionic strength, AgCl was precipitated and recovered by filtration at 0.7 μ m. In a sealed capsule under vacuum, an excess of ICH3 was added to AgCl to produce ClCH3. This ClCH3 was then purified by gas chromatography. δ 37Cl measurements were performed with a gaseous dual inlet mass spectrometer on ClCH3+, with a precision better than 0.1 permil on 30 μ mol of Cl. SIMS measurements, using the IMS 1270 at Woods Hole Oceanographic

  1. Carbon Reservoir History of Mars Constrained by Atmospheric Isotopic Measurements and Carbonate Remote Sensing

    NASA Astrophysics Data System (ADS)

    Hu, R.; Kass, D. M.; Ehlmann, B. L.; Yung, Y. L.

    2015-12-01

    The evolution of the atmosphere on Mars is one of the most intriguing problems in the exploration of the Solar System, and the climate of Mars may have evolved from a warmer, wetter early state to the cold, dry current state. Because CO2 is the major constituent of Mars's atmosphere, its isotopic signatures offer a unique window to trace the evolution of climate on Mars. We derive new quantitative constraints on the amount of carbonate deposition and the atmospheric pressure of Mars through time, extending into the Noachian, ~3.8 Gyr before present. This determination is based on recent Mars Science Laboratory (MSL) isotopic measurements of Mars's atmosphere, recent orbiter, lander, and rover measurements of Mars's surface, and a newly identified mechanism (photodissociation of CO) that efficiently enriches the heavy carbon isotope. In particular, we find that escape via CO photodissociation on Mars has a fractionation factor of 0.6 and hence, photochemical escape processes can effectively enrich 13C in the Mars's atmosphere during the Amazonian. This enrichment is partially compensated by moderate carbonate precipitation during the late Noachian and/or Hesperian. The current atmospheric 13C/12C and rock and soil carbonate measurements indicate an early atmosphere with a surface pressure less than 1 bar. Only scenarios with large amounts of carbonate formation in open lakes permit higher values up to 1.8 bars. The evolutionary scenarios are fully testable with data from the MAVEN mission and further studies of the isotopic composition of carbonate in the Martian rock record through time.

  2. Controls on the stable isotope compositions of travertine from hyperalkaline springs in Oman: Insights from clumped isotope measurements

    NASA Astrophysics Data System (ADS)

    Falk, E. S.; Guo, W.; Paukert, A. N.; Matter, J. M.; Mervine, E. M.; Kelemen, P. B.

    2016-11-01

    Carbonate formation at hyperalkaline springs is typical of serpentinization in peridotite massifs worldwide. These travertines have long been known to exhibit large variations in their carbon and oxygen isotope compositions, extending from apparent equilibrium values to highly depleted values. However, the exact causes of these variations are not well constrained. We analyzed a suite of well-characterized fresh carbonate precipitates and travertines associated with hyperalkaline springs in the peridotite section of the Samail ophiolite, Sultanate of Oman, and found their clumped isotope compositions vary systematically with formation environments. Based on these findings, we identified four main processes controlling the stable isotope compositions of these carbonates. These include hydroxylation of CO2, partial isotope equilibration of dissolved inorganic carbon, mixing between isotopically distinct carbonate end-members, and post-depositional recrystallization. Most notably, in fresh crystalline films on the surface of hyperalkaline springs and in some fresh carbonate precipitates from the bottom of hyperalkaline pools, we observed large enrichments in Δ47 (up to ∼0.2‰ above expected equilibrium values) which accompany depletions in δ18O and δ13C, yielding about 0.01‰ increase in Δ47 and 1.1‰ decrease in δ13C for every 1‰ decrease in δ18O, relative to expected equilibrium values. This disequilibrium trend, also reflected in preserved travertines ranging in age from modern to ∼40,000 years old, is interpreted to arise mainly from the isotope effects associated with the hydroxylation of CO2 in high-pH fluids and agrees with our first-order theoretical estimation. In addition, in some fresh carbonate precipitates from the bottom of hyperalkaline pools and in subsamples of one preserved travertine terrace, we observed additional enrichments in Δ47 at intermediate δ13C and δ18O, consistent with mixing between isotopically distinct carbonate end

  3. Analytical Validation of Accelerator Mass Spectrometry for Pharmaceutical Development: the Measurement of Carbon-14 Isotope Ratio.

    SciTech Connect

    Keck, B D; Ognibene, T; Vogel, J S

    2010-02-05

    Accelerator mass spectrometry (AMS) is an isotope based measurement technology that utilizes carbon-14 labeled compounds in the pharmaceutical development process to measure compounds at very low concentrations, empowers microdosing as an investigational tool, and extends the utility of {sup 14}C labeled compounds to dramatically lower levels. It is a form of isotope ratio mass spectrometry that can provide either measurements of total compound equivalents or, when coupled to separation technology such as chromatography, quantitation of specific compounds. The properties of AMS as a measurement technique are investigated here, and the parameters of method validation are shown. AMS, independent of any separation technique to which it may be coupled, is shown to be accurate, linear, precise, and robust. As the sensitivity and universality of AMS is constantly being explored and expanded, this work underpins many areas of pharmaceutical development including drug metabolism as well as absorption, distribution and excretion of pharmaceutical compounds as a fundamental step in drug development. The validation parameters for pharmaceutical analyses were examined for the accelerator mass spectrometry measurement of {sup 14}C/C ratio, independent of chemical separation procedures. The isotope ratio measurement was specific (owing to the {sup 14}C label), stable across samples storage conditions for at least one year, linear over 4 orders of magnitude with an analytical range from one tenth Modern to at least 2000 Modern (instrument specific). Further, accuracy was excellent between 1 and 3 percent while precision expressed as coefficient of variation is between 1 and 6% determined primarily by radiocarbon content and the time spent analyzing a sample. Sensitivity, expressed as LOD and LLOQ was 1 and 10 attomoles of carbon-14 (which can be expressed as compound equivalents) and for a typical small molecule labeled at 10% incorporated with {sup 14}C corresponds to 30 fg

  4. Monitoring great ape and elephant abundance at large spatial scales: measuring effectiveness of a conservation landscape.

    PubMed

    Stokes, Emma J; Strindberg, Samantha; Bakabana, Parfait C; Elkan, Paul W; Iyenguet, Fortuné C; Madzoké, Bola; Malanda, Guy Aimé F; Mowawa, Brice S; Moukoumbou, Calixte; Ouakabadio, Franck K; Rainey, Hugo J

    2010-04-23

    Protected areas are fundamental to biodiversity conservation, but there is growing recognition of the need to extend beyond protected areas to meet the ecological requirements of species at larger scales. Landscape-scale conservation requires an evaluation of management impact on biodiversity under different land-use strategies; this is challenging and there exist few empirical studies. In a conservation landscape in northern Republic of Congo we demonstrate the application of a large-scale monitoring program designed to evaluate the impact of conservation interventions on three globally threatened species: western gorillas, chimpanzees and forest elephants, under three land-use types: integral protection, commercial logging, and community-based natural resource management. We applied distance-sampling methods to examine species abundance across different land-use types under varying degrees of management and human disturbance. We found no clear trends in abundance between land-use types. However, units with interventions designed to reduce poaching and protect habitats--irrespective of land-use type--harboured all three species at consistently higher abundance than a neighbouring logging concession undergoing no wildlife management. We applied Generalized-Additive Models to evaluate a priori predictions of species response to different landscape processes. Our results indicate that, given adequate protection from poaching, elephants and gorillas can profit from herbaceous vegetation in recently logged forests and maintain access to ecologically important resources located outside of protected areas. However, proximity to the single integrally protected area in the landscape maintained an overriding positive influence on elephant abundance, and logging roads--even subject to anti-poaching controls--were exploited by elephant poachers and had a major negative influence on elephant distribution. Chimpanzees show a clear preference for unlogged or more mature forests

  5. Water stable isotope measurements of Antarctic samples by means of IRMS and WS-CRDS techniques

    NASA Astrophysics Data System (ADS)

    Michelini, Marzia; Bonazza, Mattia; Braida, Martina; Flora, Onelio; Dreossi, Giuliano; Stenni, Barbara

    2010-05-01

    In the last years in the scientific community there has been an increasing interest for the application of stable isotope techniques to several environmental problems such as drinking water safeguarding, groundwater management, climate change, soils and paleoclimate studies etc. For example, the water stable isotopes, being natural tracers of the hydrological cycle, have been extensively used as tools to characterize regional aquifers and to reconstruct past temperature changes from polar ice cores. Here the need for improvements in analytical techniques: the high request for information calls for technologies that can offer a great quantity of analyses in short times and with low costs. Furthermore, sometimes it is difficult to obtain big amount of samples (as is the case for Antarctic ice cores or interstitial water) preventing the possibility to replicate the analyses. Here, we present oxygen and hydrogen measurements performed on water samples covering a big range of isotopic values (from very negative antarctic precipitation to mid-latitude precipitation values) carried out with both the conventional Isotope Ratio Mass Spectrometry (IRMS) technique and with a new method based on laser absorption techniques, the Wavelenght Scanned Cavity Ringdown Spectroscopy (WS-CRDS). This study is focusing on improving the precision of the measurements carried out with WS-CRDS in order to extensively apply this method to Antarctic ice core paleoclimate studies. The WS-CRDS is a variation of the CRDS developed in 1988 by O'Keef and Deacon. In CRDS a pulse of light goes through a box with high reflective inner surfaces; when there is no sample in the box the light beam doesn't find any obstacle in its path, but the reflectivity of the walls is not perfect so eventually there will be an absorption of the light beam; when the sample is injected in the box there is absorption and the difference between the time of absorption without and with sample is proportional to the quantity

  6. Stable isotope ratios of atmospheric CO_{2} and CH_{4} over Siberia measured at ZOTTO

    NASA Astrophysics Data System (ADS)

    Timokhina, Anastasiya; Prokushkin, Anatily; Lavric, Jost; Heimann, Martin

    2016-04-01

    The boreal and arctic zones of Siberia housing the large amounts of carbon stored in the living biomass of forests and wetlands, as well as in soils and specifically permafrost, play a crucial role in earth's global carbon cycle. The long-term studies of greenhouse gases (GHG) concentrations are important instruments to analyze the response of these systems to climate warming. In parallel to GHG observations, the measurements of their stable isotopic composition can provide useful information for distinguishing contribution of individual GHG source to their atmospheric variations, since each source has its own isotopic signature. In this study we report first results of laboratory analyses of the CO2 and CH4 concentrations, the stable isotope ratio of δ13C-CO2, δ18O-CO2, δ13C-CH4, δD-CH4 measured in one-liter glass flasks which were obtained from 301 height of ZOTTO (Zotino Tall Tower Observatory, near 60° N, 90° E, about 20 km west of the Yenisei River) during 2008 - 2013 and 2010 - 2013 for stable isotope composition of CO2 and CH4. The magnitudes of δ13C-CO2 and δ18O-CO2 in a seasonal cycle are -1.4±0.1‰ (-7.6 - -9.0‰) and -2.2±0.2‰ (-0.1 - -2.3‰), respectively. The δ13C-CO2 seasonal pattern opposes the CO2 concentrations, with a gradual enrichment in heavy isotope occurring during May - July, reflecting its discrimination in photosynthesis, and further depletion in August - September as photosynthetic activity decreases comparatively to ecosystem respiration. Relationship between the CO2 concentrations and respective δ13C-CO2 (Keeling plot) reveals isotopic source signature for growing season (May - September) -27.3±1.4‰ and -30.4±2.5‰ for winter (January - March). The behavior of δ18O-CO2 associated with both high photosynthetic rate in the June (enrichment of atmospheric CO2 by 18O as consequence of CO2 equilibrium with "heavy" leaf water) and respiratory activity of forest floor in June - October (depletion of respired CO2 by 18O

  7. Accuracy of delta 18O isotope ratio measurements on the same sample by continuous-flow isotope-ratio mass spectrometry

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The doubly labeled water method is considered the reference method to measure energy expenditure. Conventional mass spectrometry requires a separate aliquot of the same sample to be prepared and analyzed separately. With continuous-flow isotope-ratio mass spectrometry, the same sample could be analy...

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

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

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

  9. Comparisons of HELIOS Calculated Isotope Concentrations to Measured Values for Several Reactor Systems

    SciTech Connect

    Charlton, W.S.; Perry, R.T.; Fearey, B.L.; Parish, T.A.

    1998-10-21

    Heavy metal and fission product noble gas concentrations in spent fuel from two different PWR'S were calculated using HELIOS and compared to measured results from the literature. It was found that for the U-235/U-238 and Pu-240/Pu-239 isotopic ratios, the HELIOS calculation agreed to within the experimental uncertainty. For the Xe-131/Xe-134 isotopic ratios, HELIOS tended to overestimate the result by up to 4%. Conversely for the Xe-132/Xe-134 ratios, HELIOS underestimated the result by a slight amount ({approximately}1%). This suggests that either the fission product yields for Xe-131 and Xe-132 should be slightly altered or that the absorption cross-section for Xe-131 should be slightly increased. More analysis is necessary to determine which of these two alternatives is more appropriate. This work has shown that the accuracy of HELIOS (within 2% for heavy metals and within 4% for fission noble gases) is sufficient for most analyses.

  10. System and method for high precision isotope ratio destructive analysis

    DOEpatents

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

    2013-07-02

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

  11. Precision Measurement of the Hydrogen-Deuterium 1S-2S Isotope Shift

    SciTech Connect

    Parthey, Christian G.; Matveev, Arthur; Alnis, Janis; Pohl, Randolf; Udem, Thomas; Kolachevsky, Nikolai; Haensch, Theodor W.; Jentschura, Ulrich D.

    2010-06-11

    Measuring the hydrogen-deuterium isotope shift via two-photon spectroscopy of the 1S-2S transition, we obtain 670 994 334 606(15) Hz. This is a 10-times improvement over the previous best measurement [A. Huber et al., Phys. Rev. Lett. 80, 468 (1998)] confirming its frequency value. A calculation of the difference of the mean square charge radii of deuterium and hydrogen results in {sub d}-{sub p}=3.820 07(65) fm{sup 2}, a more than twofold improvement compared to the former value.

  12. New lifetime measurements in the stable semimagic Sn isotopes using the Doppler-shift attenuation technique

    NASA Astrophysics Data System (ADS)

    Jungclaus, A.; Walker, J.; Leske, J.; Speidel, K.-H.; Stuchbery, A. E.; East, M.; Boutachkov, P.; Cederkäll, J.; Doornenbal, P.; Egido, J. L.; Ekström, A.; Gerl, J.; Gernhäuser, R.; Goel, N.; Górska, M.; Kojouharov, I.; Maier-Komor, P.; Modamio, V.; Naqvi, F.; Pietralla, N.; Pietri, S.; Prokopowicz, W.; Schaffner, H.; Schwengner, R.; Wollersheim, H.-J.

    2011-09-01

    Precise measurements of lifetimes in the picosecond range of excited states in the stable even-A Sn isotopes 112,114,116,122Sn have been performed using the Doppler shift attenuation technique. For the first excited 2+ states in 112Sn, 114Sn and 116Sn the E2 transition strengths deduced from the measured lifetimes are in disagreement with the previously adopted values. They indicate a shallow minimum at N = 66 in contrast to the maximum at mid-shell predicted by modern shell model calculations.

  13. First Measurement of Several β -Delayed Neutron Emitting Isotopes Beyond N =126

    NASA Astrophysics Data System (ADS)

    Caballero-Folch, R.; Domingo-Pardo, C.; Agramunt, J.; Algora, A.; Ameil, F.; Arcones, A.; Ayyad, Y.; Benlliure, J.; Borzov, I. N.; Bowry, M.; Calviño, F.; Cano-Ott, D.; Cortés, G.; Davinson, T.; Dillmann, I.; Estrade, A.; Evdokimov, A.; Faestermann, T.; Farinon, F.; Galaviz, D.; García, A. R.; Geissel, H.; Gelletly, W.; Gernhäuser, R.; Gómez-Hornillos, M. B.; Guerrero, C.; Heil, M.; Hinke, C.; Knöbel, R.; Kojouharov, I.; Kurcewicz, J.; Kurz, N.; Litvinov, Yu. A.; Maier, L.; Marganiec, J.; Marketin, T.; Marta, M.; Martínez, T.; Martínez-Pinedo, G.; Montes, F.; Mukha, I.; Napoli, D. R.; Nociforo, C.; Paradela, C.; Pietri, S.; Podolyák, Zs.; Prochazka, A.; Rice, S.; Riego, A.; Rubio, B.; Schaffner, H.; Scheidenberger, Ch.; Smith, K.; Sokol, E.; Steiger, K.; Sun, B.; Taín, J. L.; Takechi, M.; Testov, D.; Weick, H.; Wilson, E.; Winfield, J. S.; Wood, R.; Woods, P.; Yeremin, A.

    2016-07-01

    The β -delayed neutron emission probabilities of neutron rich Hg and Tl nuclei have been measured together with β -decay half-lives for 20 isotopes of Au, Hg, Tl, Pb, and Bi in the mass region N ≳126 . These are the heaviest species where neutron emission has been observed so far. These measurements provide key information to evaluate the performance of nuclear microscopic and phenomenological models in reproducing the high-energy part of the β -decay strength distribution. This provides important constraints on global theoretical models currently used in r -process nucleosynthesis.

  14. Measurement of long-lived isotopes and helium production in fusion materials

    SciTech Connect

    Greenwood, L.R.

    1989-01-01

    Results are summarized for measurements of the production rates for long-lived radioisotopes and helium in fusion reactor materials. Measurements have been performed at T(d,n) generators, near 14 MeV; at broad-spectrum Be(d,n) accelerator-based neutron fields; and in various fission reactors. These activation data are used to predict the production of these isotopes in fusion reactor materials for the simulation of fusion materials damage in fission reactor irradiations and as a stable product dosimeter. Nuclear data needs and future plans are discussed. 20 refs., 5 figs., 4 tabs.

  15. Hydrogen Atom Collision Processes in Cool Stellar Atmospheres: Effects on Spectral Line Strengths and Measured Chemical Abundances in Old Stars

    NASA Astrophysics Data System (ADS)

    Barklem, Paul S.

    2012-12-01

    The precise measurement of the chemical composition of stars is a fundamental problem relevant to many areas of astrophysics. State-of-the-art approaches attempt to unite accurate descriptions of microphysics, non-local thermodynamic equilibrium (non-LTE) line formation and 3D hydrodynamical model atmospheres. In this paper I review progress in understanding inelastic collisions of hydrogen atoms with other species and their influence on spectral line formation and derived abundances in stellar atmospheres. These collisions are a major source of uncertainty in non-LTE modelling of spectral lines and abundance determinations, especially for old, metal-poor stars, which are unique tracers of the early evolution of our galaxy. Full quantum scattering calculations of direct excitation processes X(nl) + H leftrightarrow X(n'l') + H and charge transfer processes X(nl) + H leftrightarrow X+ + H- have been done for Li, Na and Mg [1,2,3] based on detailed quantum chemical data, e.g. [4]. Rate coefficients have been calculated and applied to non-LTE modelling of spectral lines in stellar atmospheres [5,6,7,8,9]. In all cases we find that charge transfer processes from the first excited S-state are very important, and the processes affect measured abundances for Li, Na and Mg in some stars by as much as 60%. Effects vary with stellar parameters (e.g. temperature, luminosity, metal content) and so these processes are important not only for accurate absolute abundances, but also for relative abundances among dissimilar stars.

  16. The abundance of the actinides in the cosmic radiation as measured on HEAO 3

    NASA Technical Reports Server (NTRS)

    Binns, W. R.; Israel, M. H.; Klarmann, J.; Fickle, R. K.; Waddington, C. J.; Garrard, T. L.; Stone, E. C.

    1982-01-01

    The HEAO 3 detector of heavy cosmic-ray nuclei has observed one possible actinide nucleus and some 100 nuclei of the platinum-lead group of elements. The resulting upper limit of 3% for the abundance ratio of actinides to platinum-lead nuclides is significantly lower than previous results from other observations. This new limit is inconsistent with freshly synthesized, pure r-process sources for cosmic-ray nuclei in this charge interval but is consistent with a source having a composition similar to the solar system, or to aged r-process material. We observe no events with a charge greater than 96.

  17. Continuous-flow water sampler for real-time isotopic water measurements

    NASA Astrophysics Data System (ADS)

    Carter, J.; Dennis, K.

    2013-12-01

    Measuring the stable isotopes of liquid water (δ18O and δD) is a tool familiar to many Earth scientists, but most current techniques require discrete sampling. For example, isotope ratio mass spectrometry requires the collection of aliquots of water that are then converted to CO2, CO or H2 for analysis. Similarly, laser-based techniques, such as Cavity Ring-Down Spectroscopy (CRDS) convert discrete samples (typically < 2μL) of liquid water to water vapor using a flash vaporization process. By requiring the use of discrete samples fine-scale spatial and temporal studies of changes in δ18O and δD are limited. Here we present a continuous-flow water sampler that will enable scientists to probe isotopic changes in real-time, with applications including, but not limited to, quantification of the 'amount effect' (Dansgaard, 1964) during an individual precipitation event or storm track, real-time mixing of water in river systems, and shipboard continuous water measurements (Munksgaard et al., 2012). Due to the inherent ability of CRDS to measure a continuous flow of water vapor it is an ideal candidate for interfacing with a continuous water sampling system. Here we present results from the first commercially available continuous-flow water sampler, developed by engineers at Picarro. This peripheral device is compatible with Picarro CRDS isotopic water analyzers, allowing real-time, continuous isotopic measurements of liquid water. The new device, which expands upon the design of Munskgaard et al. (2011), utilizes expanded polytetrafluoroethylene (ePTFE) membrane technology to continuously generate gas-phase water, while liquid water is pumped through the system. The water vapor subsequently travels to the CRDS analyzer where the isotopic ratios are measured and recorded. The generation of water vapor using membrane technology is sensitive to environmental conditions, which if not actively control, lead to sustainable experimental noise and drift. Consequently, our

  18. Environmental isotope investigation of groundwater flow in the Honey Lake Basin, California and Nevada

    SciTech Connect

    Rose, T.P.; Davisson, M.L.; Hudson, G.B.; Varian, A.R.

    1997-07-01

    The hydrology of Honey Lake Basin was studied using environmental isotope measurements of approximately 130 water samples collected during 1995 and 1996. The principal analytical methods included hydrogen, oxygen and carbon stable isotope ratio measurements, radiocarbon and tritium dating, and measurements of dissolved noble gas abundances.

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

    USGS Publications Warehouse

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

    2014-01-01

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

  20. Measuring the expressed abundance of the three phases of water with an imaging spectrometer over melting snow

    NASA Astrophysics Data System (ADS)

    Green, Robert O.; Painter, Thomas H.; Roberts, Dar A.; Dozier, Jeff

    2006-10-01

    From imaging spectrometer data, we simultaneously estimate the abundance of the three phases of water in an environment that includes melting snow, basing the analysis on the spectral shift in the absorption coefficient between water vapor, liquid water, and ice at 940, 980, and 1030 nm respectively. We apply a spectral fitting algorithm that measures the expressed abundance of the three phases of water to a data set acquired by the Airborne Visible/Infrared Imaging Spectrometer (AVIRIS) over Mount Rainier, Washington, on 14 June 1996. Precipitable water vapor varies from 1 mm over the summit of Mount Rainier to 10 mm over the lower valleys to the northwest. Equivalent path absorption of liquid water varies from 0 to 13 mm, with the zero values over rocky areas and high-elevation snow and the high values associated with liquid water held in vegetation canopies and in melting snow. Ice abundance varies from 0 to 30 mm equivalent path absorption in the snow- and glacier-covered portions of Mount Rainier. The water and ice abundances are related to the amount of liquid water and the sizes of the ice grains in the near-surface layer. Precision of the estimates, calculated over locally homogeneous areas, indicates an uncertainty of better than 1.5% for all three phases, except for liquid water in vegetation, where an optimally homogeneous site was not found. The analysis supports new strategies for hydrological research and applications as imaging spectrometers become more available.

  1. The abundance of ice nuclei during airborne measurements over Germany and the Caribbean

    NASA Astrophysics Data System (ADS)

    Danielczok, A..; Bingemer, H.; Curtius, J.; DeMott, P. J.

    2012-04-01

    The tropospheric abundance of ice nuclei (IN) acting at -8 to -18 °C in the deposition and condensation nucleation modes was investigated during series of research flights on board a Learjet over northern Germany in June 2011 and on board of the NSF/NCAR C-130 during the ICE IN CLOUDS EXPERIMENT - TROPICAL (ICE-T) over the Caribbean in July 2011. Ice nuclei were collected from the air by electrostatic precipitation of aerosol onto silicon substrates. Samples were subsequently analyzed in the laboratory by the isothermal static vapor diffusion chamber FRIDGE (FRankfurt Ice Nuclei Deposition FreezinG Experiment). IN abundance in the free and upper troposphere varied between < 1 and 50 IN L-1 in the upper troposphere over Germany, and between < 1 to 40 IN L-1 in the lower and middle troposphere in the Caribbean. A few dust layers were encountered. The results will be presented and discussed in the light of trajectory analysis and other supporting information.

  2. Rapid U separation and its precise isotopic measurements using ICP-QMS

    NASA Astrophysics Data System (ADS)

    Douville, E.; Salle, E.; Gourgiotis, A.; Ayrault, S.; Frank, N.

    2007-12-01

    Here we present a largely simplified analytical separation technique for U from marin carbonates and sediments and U isotopic measurements obtained by inductively coupled plasma-source quadrupole mass spectrometer (ICP-QMS) Xseries II - Thermo Scientific. The separation of U is done from dissolved carbonates and sediments using a single ion exchange column packed with ~500 μg of UTEVA resin from EICHROM industries. The column is pre-cleaned and loaded by several rinses of MilliQ water and 3N HNO3. Then earth alkali, transition metals and lanthanides are eluted quantitatively using 3N HNO3. Pure Th and U solutions are then successively extracted from the column using 3N HCl and 1N HCl at ~100% yield. U solutions at ~25-50 ppb were injected into the ICP-QMS at conventional sample flow rates of approximately 1ml/minute, without particular injection systems such as a desolvator or μ - nebuliser. 30 scans with 180 sweeps and a dwell time of 50 ms per isotope were used to collect 233U, 234U, 235U and 236U on an electron multiplier. Baseline sensitivity was followed on mass 228 with <1cps at ~ 1000cps on mass 234. Then, mass discrimination was corrected using the 233U/236U spike of known isotopic ratio and HU1 reference solutions were used to test the reproducibility and to correct drifts using standard - sample bracketing. Overall ICPMS analyses yield a stunning reproducibility of <0.4 % at 2 σ, which is close to the one obtained by conventional TIMS instruments ~0.2-0.4 %. We have applied this technique to organic rich sediments and marine carbonate samples previously measured by TIMS and found a perfect agreement for both U concentration and its isotopic composition. This rapid and effective chemical purification and isotopic measurement of U allows to process more than 20 samples a day allowing to investigate large numbers of natural samples for weathering, tracer and geochronological studies.

  3. Ion Microprobe U-Pb Dating and Sr Isotope Measurement of Conodont

    NASA Astrophysics Data System (ADS)

    Sano, Y.; Ishida, A.; Kagoshima, T.; Takahata, N.

    2014-12-01

    We have developed a method of in situ ion microprobe U-Pb dating and Sr isotope measurement of biogenic apatite using NanoSIMS. This was applied to a protoconodont, an early Cambrian phosphate microfossil [1]. On a single fragment of a fossil derived from a sedimentary layer in the Meishucunian Yuhucun Formation, southern China [2], 23 spots provide a 238U/206Pb isochron age of 547 ± 43 Ma (2sigma), which is consistent with the depositional age, 536.5 ± 2.5 Ma estimated using zircon U-Pb dating of interbedded tuffs [3]. However, five spots on a small region in the same protoconodont yield an isochron age of 417 ± 74 Ma (2sigma), apparently younger than the formation age. The younger age might be attributable to a later hydrothermal event, perhaps associated with Caledonian orogenic activity recorded in younger zircon with an age of 420-440 Ma [4]. We measured Sr isotopic ratios of the protoconodont by NanoSIMS. In the older domain, 19 spots give the ratio of 0.71032 ± 0.00023 (2sigma), although seven spots on the younger region provide the ratio of 0.70862 ± 0.00045; which is significantly less radiogenic than the older domain. We also measured U-Pb age and Sr isotopes of a Carboniferous conodont derived from the Kinderhookian stage from the Illinois Basin region in North America. 20 spots yield a 238U/206Pb isochron age of 291 ± 56 Ma (2sigma), which is markedly younger than the depositional age of the fossil of 350-363 Ma. On the other hand, 9 spots give a Sr isotopic ratio of 0.70784 ± 0.00030, less radiogenic than the older domain of protoconodont. These data together with other isotopes such as Cl may provide a constraint on the model for chemical evolution of seawater. [1] Sano et al. (2014) J. Asian Earth Sci. 92, 10-17. [2] Condon et al. (2005) Science 308, 95-98. [3] Sawaki et al. (2008) Gondwana Res. 14, 148-158. [4] Guo et al. (2009) Geochem. J. 43, 101-122.

  4. Measurement of the Isotopic Signatures of Water on Mars: Implications for Studying Methane

    NASA Technical Reports Server (NTRS)

    Novak, R. E.; Mumma, M. J.; Villanueva, G. L.

    2010-01-01

    The recent discovery of methane on Mars has led to much discussion concerning its origin. On Earth, the isotopic signatures of methane vary with the nature of its production. Specifically, the ratios among 12CH4, 13CH4, and 12CH3D differ for biotic and abiotic origins. On Mars, measuring these ratios would provide insights into the origins of methane and measurements of water isotopologues co-released with methane would assist in testing their chemical relationship. Since 1997, we have been measuring HDO and H2O in Mars atmosphere and comparing their ratio to that in Earth s oceans. We recently incorporated a line-by-line radiative transfer model (LBLRTM) into our analysis. Here, we present a map for [HDO]/[H2O] along the central meridian (1541W) for Ls 501. From these results, we constructed models to determine the observational conditions needed to quantify the isotopic ratios of methane in Mars atmosphere. Current ground-based instruments lack the spectral resolution and sensitivity needed to make these measurements. Measurements of the isotopologues of methane will likely require in situ sampling.

  5. Improved isotope ratio measurement performance in liquid chromatography/isotope ratio mass spectrometry by removing excess oxygen.

    PubMed

    Hettmann, Elena; Brand, Willi A; Gleixner, Gerd

    2007-01-01

    A low dead volume oxygen scrubbing system was introduced in a commercially available liquid chromatography/isotope ratio mass spectrometry (LC/IRMS) interface to enhance the analytical capability of the system. In the LC/IRMS interface carbon from organic samples is converted into CO(2) inside the mobile phase by wet chemical oxidation using peroxodisulfate (Na(2)S(2)O(8)). After passing the hot reaction zone, surplus oxygen (O(2)) remains dissolved in the liquid phase. Both CO(2) and O(2) diffuse through a transfer membrane into the helium carrier and are transferred to the mass spectrometer. The presence of O(2) in the ion source may have detrimental effects on measurement accuracy and precision as well as on filament lifetime. As a remedy, a new on-line O(2)-removing device has been incorporated into the system. The new O(2) scrubber consists of two parallel hot copper reduction reactors (0.8 mm i.d., active length 120 mm) and a switch-over valve between them. One reactor is regenerated using He/H(2) while the other is actively scavenging O(2) from the gas stream. The capacity of each reduction reactor, expressed as usage time, is between 40 and 50 min. This is sufficient for a single LC run for sugars and organic acids. A further increase of the reduction capacity is accompanied by a peak broadening of about 100%. After switching to a freshly reduced reactor the oxygen background and the delta(13)C values of the reference gas need up to 500 s to stabilize. For repeated injections the delta(13)C values of sucrose remain constant (+/-0.1 per thousand) for about 3000 s. The long-term stability for measurements of sucrose was 0.11 per thousand without the reduction oven and improved slightly to 0.08 per thousand with the reduction oven. The filament lifetime improved by more than 600%, thereby improving the long-term system stability and analytical efficiency. In addition the costs per analysis were reduced considerably.

  6. Radiogenic Isotopes As Paleoceanographic Tracers in Deep-Sea Corals: Advances in TIMS Measurements of Pb Isotopes and Application to Southern Ocean Corals

    NASA Astrophysics Data System (ADS)

    Wilson, D. J.; van de Flierdt, T.; Bridgestock, L. J.; Paul, M.; Rehkamper, M.; Robinson, L. F.; Adkins, J. F.

    2014-12-01

    Deep-sea corals have emerged as a valuable archive of deep ocean paleoceanographic change, with uranium-series dating providing absolute ages and the potential for centennial resolution. In combination with measurements of radiocarbon, neodymium isotopes and clumped isotopes, this archive has recently been exploited to reconstruct changes in ventilation, water mass sourcing and temperature in relation to millennial climate change. Lead (Pb) isotopes in both corals and seawater have also been used to track anthropogenic inputs through space and time and to trace transport pathways within the oceans. Better understanding of the oceanic Pb cycle is emerging from the GEOTRACES programme. However, while Pb isotopes have been widely used in environmental studies, their full potential as a (pre-anthropogenic) paleoceanographic tracer remains to be exploited. In deep-sea corals, challenges exist from low Pb concentrations in aragonite in comparison to secondary coatings, the potential for contamination, and the efficient elemental separation required for measurement by thermal ionisation mass spectrometry (TIMS). Here we discuss progress in measuring Pb isotopes in coral aragonite using a 207Pb-204Pb double spike on a ThermoFinnigan Triton TIMS. For a 2 ng NIST-981 Pb standard, the long term reproducibility (using 1011 Ω resistors) is ~1000 ppm (2 s.d.) on 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb ratios. We now show that using a new 1012 Ω resistor to measure the small 204Pb beam improves the internal precision on these ratios from ~500 ppm (2 s.e.) to ~250 ppm (2 s.e.) and we envisage a potential improvement in the long term reproducibility as a consequence. We further assess the internal precision and external reproducibility of our method using a BCR-2 rock standard and an in-house coral standard. Preliminary evidence on the application of this method to natural samples is derived from cleaning experiments and replication tests on deep-sea corals from the Southern

  7. A fast switching electrostatic deflector system for actinide isotopic ratio measurements

    NASA Astrophysics Data System (ADS)

    Zorko, Benjamin; Child, D. P.; Hotchkis, M. A. C.

    2010-04-01

    We have implemented a fast switching electrostatic system on the actinides beamline on the ANTARES accelerator at ANSTO, to improve the precision of analyses by accelerator mass spectrometry. This high-energy bouncing system is based on a pair of deflector plates, deflecting in the orbit plane, set at the entrance and exit of the analysing magnet. The design of deflector plates is unique, and it was modelled by SIMION in order to minimize field inhomogenity and fringe field effects. The pair of deflector plates are supplied by a high-voltage amplifier driven by an EPICS-enabled control unit, with two 4 W power supplies providing up to ±10 kV modulation. The high-energy bouncing system is synchronized with the existing low-energy bouncing system. To measure the isotopic ratio with the new system, the magnetic fields of the injector and analysing magnets are set to transmit selected isotopes along the beam line with zero voltage applied. The other isotopes of interest are transmitted by keeping the magnetic fields constant and modulating the voltages on the injector magnet chamber and on the high-energy deflector plates.

  8. Biological Oxygen Productivity Over The Last Glacial Termination From Triple Oxygen Isotope Measurements

    NASA Astrophysics Data System (ADS)

    Blunier, T.; Bender, M. L.; Hendricks, M. B.

    The atmospheric oxygen isotope signature of O2 is linked to the oxygen signature of seawater through photosynthesis and respiration. Fractionation during these pro- cesses is mass dependent affecting 17O about half as much as 18O. A mass indepen- dent fractionation process takes place during isotope exchange between O2 and CO2 in the stratosphere (Thiemens, 1999; Luz et al., 1999). The magnitude of the mass- independent anomaly in the triple isotope composition of O2 depends on relative rates of biological O2 cycling and photochemical reactions in the stratosphere. Variations of this anomaly thus allows us to estimate changes of mass dependent O2 production by photosynthesis versus mass independent O2-CO2 exchange in the stratosphere. We reconstruct total oxygen productivity for the past from 17O and 18O measure- ments of O2 trapped in ice cores. With a box model we estimate that the total biogenic productivity was only 76-83 % of today for the glacial and was probably still lower than today during the glacial-interglacial transition and the early Holocene. In principle we can calculate the oxygen flux from the ocean biosphere if we know the oxygen flux from the land biosphere. Calculated ocean production is very sensitive to the estimate of land biosphere production. The latter term remains uncertain, however, and we can presently only constrain glacial ocean production to 88 to 140 % of the present value.

  9. Stable isotope measurements of martian atmospheric CO2 at the Phoenix landing site.

    PubMed

    Niles, Paul B; Boynton, William V; Hoffman, John H; Ming, Douglas W; Hamara, Dave

    2010-09-10

    Carbon dioxide is a primary component of the martian atmosphere and reacts readily with water and silicate rocks. Thus, the stable isotopic composition of CO2 can reveal much about the history of volatiles on the planet. The Mars Phoenix spacecraft measurements of carbon isotopes [referenced to the Vienna Pee Dee belemnite (VPDB)] [delta13C(VPDB) = -2.5 +/- 4.3 per mil (per thousand)] and oxygen isotopes [referenced to the Vienna standard mean ocean water (VSMOW)] (delta18O(VSMOW) = 31.0 +/- 5.7 per thousand), reported here, indicate that CO2 is heavily influenced by modern volcanic degassing and equilibration with liquid water. When combined with data from the martian meteorites, a general model can be constructed that constrains the history of water, volcanism, atmospheric evolution, and weathering on Mars. This suggests that low-temperature water-rock interaction has been dominant throughout martian history, carbonate formation is active and ongoing, and recent volcanic degassing has played a substantial role in the composition of the modern atmosphere.

  10. Measurement of the turnover of glycogen phosphorylase by GC/MS using stable isotope derivatives of pyridoxine (vitamin B6).

    PubMed Central

    Beynon, R J; Leyland, D M; Evershed, R P; Edwards, R H; Coburn, S P

    1996-01-01

    The majority of vitamin B6 in the body is in skeletal muscle, bound as the cofactor pyridoxal 5'-phosphate to one abundant protein, glycogen phosphorylase. Previous work has established that radiolabelled vitamin B6 can be used as a turnover label for glycogen phosphorylase. In this study, a stable isotope derivative of pyridoxine ¿dideuterated pyridoxine; 3-hydroxy-4-(hydroxymethyl) -5-[hydroxymethyl-2H2]-2-methylpyridine¿ ([2H2]PN) has been used as a metabolic tracer to study the kinetics of labelling of the body pools of vitamin B6 in mice. A non-invasive method was developed in which the isotope abundance of the urinary excretory product of vitamin B6 metabolism, 4-pyridoxic acid, was analysed by GC/MS. The change in isotope abundance of urinary 4-pyridoxic acid following administration of [2H2]PN reflects the kinetics of labelling of the body pools of vitamin B6, and yields, non-invasively, the rate of degradation of glycogen phosphorylase. PMID:8713093

  11. Physical and Mathematical Methods for Removing Organic Interference from Optical Isotope Measurements

    NASA Astrophysics Data System (ADS)

    Hsiao, G.; Chappellet-Volini, L.; Vu, D.

    2012-12-01

    Portable high precision isotope analyzers using CRDS technology have greatly increased the use of stable isotopes in hydrological, oceanographic, and ecological studies over the past five years. However studies of some water samples yielded incorrect isotopic values indicating some form of spectroscopic interference. Subsequent work has shown that waters derived from some plants containing interfering alcohols but meteoric waters are not affected. The initial approach to handling such samples was to use spectroscopic anomalies to identify and flag affected samples for later analysis by non-optical methods. This presentation will examine the approaches developed within the past year to allow for accurate analysis of such samples by optical methods. The first approach uses an advanced spectroscopic model to identify and quantify alcohols present in the sample. The alcohol signal is incorporated into the overall fit of the measure spectra to calculate the concentration of the individual isotopes. It was found that the δ18O value could be calculated with high accuracy, the result for the δ2H value was sufficient for many applications. The second approach uses physical treatment of the sample to break down the organic molecules into non-interfering species. The liquid sample is injected into a flash vaporizer then the vapor travels through a cartridge for physical treatment prior to analysis by CRDS. Inside the cartridge the organic molecules undergo oxidation at high temperature in the air carrier gas when exposed to the catalyst. This approach is highly effective for ethanol solutions as high as 5% as well as for the complex mixtures of alcohols found in plants. Comparison of the results of both of these methods will be compared with tertiary techniques such as IRMS where possible.

  12. MULTI-ELEMENT ABUNDANCE MEASUREMENTS FROM MEDIUM-RESOLUTION SPECTRA. II. CATALOG OF STARS IN MILKY WAY DWARF SATELLITE GALAXIES

    SciTech Connect

    Kirby, Evan N.; Cohen, Judith G.; Guhathakurta, Puragra; Rockosi, Constance M.; Geha, Marla C.; Sneden, Christopher; Sohn, Sangmo Tony; Majewski, Steven R.; Siegel, Michael

    2010-12-15

    We present a catalog of Fe, Mg, Si, Ca, and Ti abundances for 2961 stars in eight dwarf satellite galaxies of the Milky Way (MW): Sculptor, Fornax, Leo I, Sextans, Leo II, Canes Venatici I, Ursa Minor, and Draco. For the purposes of validating our measurements, we also observed 445 red giants in MW globular clusters and 21 field red giants in the MW halo. The measurements are based on Keck/DEIMOS medium-resolution spectroscopy (MRS) combined with spectral synthesis. We estimate uncertainties in [Fe/H] by quantifying the dispersion of [Fe/H] measurements in a sample of stars in monometallic globular clusters (GCs). We estimate uncertainties in Mg, Si, Ca, and Ti abundances by comparing to high-resolution spectroscopic abundances of the same stars. For this purpose, a sample of 132 stars with published high-resolution spectroscopy in GCs, the MW halo field, and dwarf galaxies has been observed with MRS. The standard deviations of the differences in [Fe/H] and ([{alpha}/Fe]) (the average of [Mg/Fe], [Si/Fe], [Ca/Fe], and [Ti/Fe]) between the two samples is 0.15 and 0.16, respectively. This catalog represents the largest sample of multi-element abundances in dwarf galaxies to date. The next papers in this series draw conclusions on the chemical evolution, gas dynamics, and star formation histories from the catalog presented here. The wide range of dwarf galaxy luminosity reveals the dependence of dwarf galaxy chemical evolution on galaxy stellar mass.

  13. Uranium and Calcium Isotope Ratio Measurements using the Modified Total Evaporation Method in TIMS

    NASA Astrophysics Data System (ADS)

    Richter, S.; Kuehn, H.; Berglund, M.; Hennessy, C.

    2010-12-01

    A new version of the "modified total evaporation" (MTE) method for isotopic analysis by multi-collector thermal ionization mass spectrometry (TIMS), with high analytical performance and designed in a more user-friendly and routinely applicable way, is described in detail. It is mainly being used for nuclear safeguards measurements of U and Pu and nuclear metrology, but can readily be applied to other scientific tasks in geochemistry, e.g. for Sr, Nd and Ca, as well. The development of the MTE method was organized in collaboration of several "key nuclear mass spectrometry laboratories", namely the New Brunswick Laboratory (NBL), the Institute for Transuranium Elements (ITU), the Safeguards Analytical Laboratory (now Safeguards Analytical Services, SGAS) of the International Atomic Energy Agency (IAEA) and the Institute for Reference Materials and Measurements (IRMM), with IRMM taking the leading role. The manufacturer of the TRITON TIMS instrument, Thermo Fisher Scientific, integrated this method into the software of the instrument. The development has now reached its goal to become a user-friendly and routinely useable method for uranium isotope ratio measurements with high precision and accuracy. Due to the use of the “total evaporation” (TE) method the measurement of the "major" uranium isotope ratio 235U/238U is routinely being performed with a precision of 0.01% to 0.02%. The use of a (certified) reference material measured under comparable conditions is emphasized to achieve an accuracy at a level of 0.02% - depending on the stated uncertainty of the certified value of the reference material. In contrast to the total evaporation method (TE), in the MTE method the total evaporation sequence is interrupted on a regular basis to allow for correction for background from peak tailing, internal calibration of a secondary electron multiplier (SEM) detector versus the Faraday cups, and ion source re-focusing. Therefore, the most significant improvement using the

  14. Cosmic-ray abundances of Sn, Te, Xe, and Ba nuclei measured on HEAO 3

    NASA Technical Reports Server (NTRS)

    Binns, W. R.; Israel, M. H.; Klarmann, J.; Fickle, R. K.; Waddington, C. J.; Garrard, T. L.; Krombel, K. E.; Stone, E. C.

    1983-01-01

    The results of an analysis of HEAO 3 Heavy Nuclei Experimental data covering 440 days of observations of Sn-Ba nuclei in cosmic rays are reported. The particles were detected by a Cernkov counter, and a Z-squared ceiling was calculated to normalize the histograms produced. The observed large abundance of Sn and Ba relative to other elements in the region of interest indicated a predominance of the s-process in the source of the particles. When account was taken of first ionization potential effects, the data indicated that the material could be solar system in origin. A source dominated by the r-process nucleosynthesis was ruled out at the 0.93 confidence level.

  15. Near Real-Time Isotopic Measurements of Carbon Dioxide from Outgassing Volcanoes

    NASA Astrophysics Data System (ADS)

    Stix, J.; Lucic, G.; Malowany, K.

    2014-12-01

    For the past several years we have been using a Picarro G1101-i isotopic mass analyzer to study the behavior of carbon dioxide emanating from active volcanoes. Because of its portability (it weighs about 30 kg), the instrument accompanies us on our field campaigns. Typically, we collect gas samples during the day and analyze them in the evening. The result is near-real-time isotopic measurements of CO2, and we are thus able to plan and adjust our field campaigns according to the results that we obtain on a continual basis. This is the primary advantage of the instrument. The G1101-i requires about 350 watts of power, typically provided by wall current with an uninterruptible power supply between the wall and instrument to deal with power fluctuations and outages. We calibrate the instrument every 2-5 days with a series of four well-characterized gas standards which we bring with us into the field in evacuated glass containers. Calibrations are typically robust and highly linear, with sub per mil precision. We also normally obtain a few samples which we analyze both by the G1101-i and later by mass spectrometry, in order to provide an independent means of checking our accuracy. Standards and samples are typically analyzed at similar CO2 concentrations to minimize any concentration-dependent effects on the isotopic analysis, even though these are generally small to negligible. Our applications so far have been focused at one caldera system and one subduction-related stratovolcano. We have analyzed soil gases at Long Valley caldera, California, to study the interplay of volcanic and tectonic controls upon diffuse CO2 release. We have analyzed CO2 in the the plume of Turrialba volcano, Costa Rica, to identify the volcanic isotopic signal and understand the mixing of the plume with surrounding atmosphere. At both localities, with appropriate dilutions as needed, we have been able to analyze the isotopic signal for CO2 concentrations ranging from atmospheric (400 ppm) to

  16. High Precision Measurement of Isotope Effects on Noncovalent Host-Guest Interactions

    SciTech Connect

    Mugridge, Jeffrey S.; Bergman, Robert G.; Raymond, Kenneth N.

    2009-06-23

    Isotope effects (IEs) are a powerful tool for examining the reactivity of, and interactions between, molecules. Recently, secondary IEs have been used to probe the nature of noncovalent interactions between guest and host molecules in supramolecular systems. While these studies can provide valuable insight into the specific interactions governing guest recognition and binding properties, IEs on noncovalent interactions are often very small and difficult to measure precisely. The Perrin group has developed an NMR titration method capable of determining ratios of equilibrium constants with remarkable precision. They have used this technique to study small, secondary equilibrium isotope effects (EIEs) on the acidity of carboxylic acids and phenols and on the basicity of amines, measuring differences down to thousandths of a pK{sub a} unit. It occurred to us that this titration method can in principle measure relative equilibrium constants for any process which is fast on the NMR timescale and for which the species under comparison are distinguishable by NMR. Here we report the application of this method to measure very small EIEs on noncovalent host-guest interactions in a supramolecular system.

  17. The abundances of H-3 and C-14 in the solar wind. [measured by lunar soil analysis

    NASA Technical Reports Server (NTRS)

    Fireman, E. L.; Defelice, J.; Damico, J.

    1976-01-01

    Tritium is measured as a function of depth in a Surveyor 3 sample. The upper limit for solar-wind-implanted tritium gives a H-3/H-1 limit for the solar wind of 1 part in one hundred billion. The temperature release patterns of C-14 from lunar soils are measured. The C-14 release patterns from surface soils differ from a trench-bottom soil and give evidence for the presence of C-14 in the solar wind with a C-14/H-1 ratio of approximately 4 parts in one hundred billion. The implications of these radionuclide abundances in the solar wind are discussed.

  18. Origin of water and mantle-crust interactions on Mars inferred from hydrogen isotopes and volatile element abundances of olivine-hosted melt inclusions of primitive shergottites

    NASA Astrophysics Data System (ADS)

    Usui, Tomohiro; Alexander, Conel M. O'D.; Wang, Jianhua; Simon, Justin I.; Jones, John H.

    2012-12-01

    Volatile elements have influenced the differentiation and eruptive behavior of Martian magmas and played an important role in the evolution of Martian climate and near-surface environments. However, the abundances of volatiles, and in particular the amount of water in the Martian interior, are disputed. A record of volatile reservoirs is contained in primitive Martian basalts (shergottites). Olivine-hosted melt inclusions from a geochemically depleted shergottite (Yamato 980459, representing a very primitive Martian melt) possess undegassed water with a chondritic and Earth-like D/H ratio (δD≤275‰). Based on volatile measurements in these inclusions, the water content of the depleted shergottite mantle is calculated to be 15-47 ppm, which is consistent with the dry mantle hypothesis. In contrast to D/H in the depleted shergottite, melt from an enriched shergottite (Larkman Nunatak 06319), which either formed by melting of an enriched mantle or by assimilation of crust, exhibits an extreme δD of ˜5000‰, indicative of a surface reservoir (e.g., the Martian atmosphere or crustal hydrosphere). These data provide strong evidence that the Martian mantle had retained the primordial low-δD component until at least the time of shergottite formation, and that young Martian basalts assimilated old Martian crust.

  19. Selected isotope ratio measurements of light metallic elements (Li, Mg, Ca, and Cu) by multiple collector ICP-MS

    PubMed Central

    Platzner, Thomas I.; Segal, Irina

    2007-01-01

    The unique capabilities of multiple collector inductively coupled mass spectrometry (MC-ICP-MS) for high precision isotope ratio measurements in light elements as Li, Mg, Ca, and Cu are reviewed in this paper. These elements have been intensively studied at the Geological Survey of Israel (GSI) and other laboratories over the past few years, and the methods used to obtain high precision isotope analyses are discussed in detail. The scientific study of isotopic fractionation of these elements is significant for achieving a better understanding of geochemical and biochemical processes in nature and the environment. PMID:17962922

  20. Preparing the measurement of anapole moment in a chain of francium isotopes

    NASA Astrophysics Data System (ADS)

    Sheng, Dong

    This thesis presents the current status of the experimental efforts towards the measurement of the anapole moment in francium. The anapole moment is a parity violating, time-reversal conserving nuclear moment that arises from the weak interaction among nucleons. It is nuclear spin dependent and sensitive to the configuration of nuclear structure. Our experimental scheme is to perform a direct measurement of the anapole moment, by driving a parity forbidden E1 transition between ground hyperfine states in a series of francium isotopes inside a blue detuned dipole trap at the electric anti-node of a microwave cavity. We explore the tests using rubidium isotopes. The francium experiment will be moved to the ISAC radioactive beam facility of TRIUMF, Canada. During the preparation of the apparatus, we test the coherent control of the ground states via microwave and Raman beams, characterize the performance of a blue detuned dipole trap and study the atomic dynamics inside it using both classical and quantum methods. We also measure the lifetime of excited 5d states in Rb, with less than 1% uncertainty, to test and help to improve the current atomic structure theories.

  1. The Bremen mass spectrometric facility for the measurement of helium isotopes, neon, and tritium in water.

    PubMed

    Sültenfuss, Jürgen; Roether, Wolfgang; Rhein, Monika

    2009-06-01

    We describe the mass spectrometric facility for measuring helium isotopes, neon, and tritium that has been operative at this institute since 1989, and also the sampling and sample preparation steps that precede the mass spectrometric analysis. For water samples in a near-equilibrium with atmospheric air, the facility achieves precision for (3)He/(4)He ratios of+/-0.4% or better, and+/-0.8 % or better for helium and neon concentrations. Tritium precision is typically+/-3 % and the detection limit 10 mTU ( approximately 1.2.10(-3) Bq/kg of pure water). Sample throughputs can reach some thousands per year. These achievements are enabled, among other features, by automation of the measurement procedure and by elaborate calibration, assisted by continual development in detail. To date, we have measured more than 15,000 samples for tritium and 23,000 for helium isotopes and neon, mostly in the context of oceanographic and hydrologic work. Some results of such work are outlined. Even when atmospheric tritium concentrations have become rather uniform, tritium provides water ages if (3)He data are taken concurrently. The technique can resolve tritium concentrations in waters of the pre-nuclear era.

  2. Position measurements for the isotope production facility and the switchyard kicker upgrade projects

    SciTech Connect

    Gilpatrick, J. D.; Barr, D. S.; O'Hara, J. F.; Shurter, R. B.; Stettler, M. W.; Martinez, D. G.

    2003-01-01

    The Los Alamos Neutron Science Center (LANSCE) is installing two beam lines to both improve operational tuning and provide new capabilities within the facility. The Isotope Production Facility (IPF) will provide isotopes for medical purposes by using the H' beam spur at 100 MeV and the Switchyard Kicker Upgrade (SYK) will allow the LANSCE 800-MeV H beam to be rapidly switched between various beam lines within the facility. The beam position measurements for both of these beam lines uses a standard micro-stripline beam position monitor (BPM) with both a 50-mm and 75-mm radius. The cable plant is unique in that it unambiguously provides a method of verifying the operation of the complete position measurement. The processing electronics module uses a log ratio technique with error corrections such that it has a dynamic range of -12 dBm to -85 dBm with errors less than 0.15 dB within this range. This paper will describe the primary components of these measurement systems and provide initial data of their o