Science.gov

Sample records for isotopic mass chain

  1. Isotope dilution mass spectrometry

    NASA Astrophysics Data System (ADS)

    Heumann, Klaus G.

    1992-09-01

    In the past isotope dilution mass spectrometry (IDMS) has usually been applied using the formation of positive thermal ions of metals. Especially in calibrating other analytical methods and for the certification of standard reference materials this type of IDMS became a routine method. Today, the progress in this field lies in the determination of ultra trace amounts of elements, e.g. of heavy metals in Antarctic ice and in aerosols in remote areas down to the sub-pg g-1 and sub-pg m-3 levels respectively, in the analysis of uranium and thorium at concentrations of a few pg g-1 in sputter targets for the production of micro- electronic devices or in the determination of sub-picogram amounts of230Th in corals for geochemical age determinations and of226Ra in rock samples. During the last few years negative thermal ionization IDMS has become a frequently used method. The determination of very small amounts of selenium and technetium as well as of other transition metals such as vanadium, chromium, molybdenum and tungsten are important examples in this field. Also the measurement of silicon in connection with a re-determination of Avogadro's number and osmium analyses for geological age determinations by the Re/Os method are of special interest. Inductively-coupled plasma mass spectrometry is increasingly being used for multi-element analyses by the isotope dilution technique. Determinations of heavy metals in samples of marine origin are representative examples for this type of multi-element analysis by IDMS. Gas chromatography-mass spectrometry systems have also been successfully applied after chelation of metals (for example Pt determination in clinical samples) or for the determination of volatile element species in the environment, e.g. dimethyl sulfide. However, IDMS--specially at low concentration levels in the environment--seems likely to be one of the most powerful analytical methods for speciation in the future. This has been shown, up to now, for species of

  2. Mass-independent isotope effects.

    PubMed

    Buchachenko, Anatoly L

    2013-02-28

    Three fundamental properties of atomic nuclei-mass, spin (and related magnetic moment), and volume-are the source of isotope effects. The mostly deserved and popular, with almost hundred-year history, is the mass-dependent isotope effect. The first mass-independent isotope effect which chemically discriminates isotopes by their nuclear spins and nuclear magnetic moments rather than by their masses was detected in 1976. It was named as the magnetic isotope effect because it is controlled by magnetic interaction, i.e., electron-nuclear hyperfine coupling in the paramagnetic species, the reaction intermediates. The effect follows from the universal physical property of chemical reactions to conserve angular momentum (spin) of electrons and nuclei. It is now detected for oxygen, silicon, sulfur, germanium, tin, mercury, magnesium, calcium, zinc, and uranium in a great variety of chemical and biochemical reactions including those of medical and ecological importance. Another mass-independent isotope effect was detected in 1983 as a deviation of isotopic distribution in reaction products from that which would be expected from the mass-dependent isotope effect. On the physical basis, it is in fact a mass-dependent effect, but it surprisingly results in isotope fractionation which is incompatible with that predicted by traditional mass-dependent effects. It is supposed to be a function of dynamic parameters of reaction and energy relaxation in excited states of products. The third, nuclear volume mass-independent isotope effect is detected in the high-resolution atomic and molecular spectra and in the extraction processes, but there are no unambiguous indications of its importance as an isotope fractionation factor in chemical reactions. PMID:23301791

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

    PubMed

    Gilbert, Alexis; Yamada, Keita; Yoshida, Naohiro

    2016-06-01

    We measured (13)C intramolecular isotopic composition of commercially available short-chain hydrocarbons (n-C6-n-C12) using (13)C-NMR. Results show that the main variation is between the terminal and the sub-terminal C-atom positions. Site-preference (difference in δ(13)C values between terminal and sub-terminal C-atom positions) among all the samples varies between -12.2‰ and +8.4‰. Comparison of these results with those obtained using on-line pyrolysis coupled with GC-C-IRMS show that the thermal cracking of hydrocarbons occurs with a good isotopic fidelity between terminal and sub-terminal C-atom positions of the starting material and the related pyrolysis products (methane and ethylene). On-line pyrolysis coupled with GC-C-IRMS can thus be used for tracing hydrocarbons biogeochemical processes. PMID:27130103

  4. Advanced Mass Spectrometers for Hydrogen Isotope Analyses

    SciTech Connect

    Chastagner, P.

    2001-08-01

    This report is a summary of the results of a joint Savannah River Laboratory (SRL) - Savannah River Plant (SRP) ''Hydrogen Isotope Mass Spectrometer Evaluation Program''. The program was undertaken to evaluate two prototype hydrogen isotope mass spectrometers and obtain sufficient data to permit SRP personnel to specify the mass spectrometers to replace obsolete instruments.

  5. Mass Chain Evaluation for A=95

    SciTech Connect

    Basu, S.K.; Sonzogni, A.; Basu, Swapan Kr.; Mukherjee, Gopal; Sonzogni, A. A.

    2011-08-01

    A full evaluation of the mass chain A = 95 has been done in the ENSDF format taking into account all the available data until June 2009. Excited states populated by in-beam nuclear reactions and by radioactive decay have been considered. The 'evp' editor, developed at the NNDC, has been used for the evaluation. This mass chain was last evaluated in 1993. Many new and improved data were reported since then. A total of 13 nuclei have been evaluated.

  6. High-precision lead isotopes and stripy plumes: Revisiting the Society chain in French Polynesia

    NASA Astrophysics Data System (ADS)

    Cordier, Carole; Chauvel, Catherine; Hémond, Christophe

    2016-09-01

    An increasing number of geochemical studies looked for spatial organization of the isotopic variations along Pacific volcanic island chains (e.g., Hawaii, Marquesas, Samoa and Society Islands) in order to discuss the possible zoning of the plume conduits. Here, we reexamine the occurrence of isotopic stripes in the Society archipelago in French Polynesia, using new Sr-Nd-Hf-Pb isotope ratios of sixty-six lavas from six islands (Mehetia, Moorea, Maupiti, Huahine, Raiatea, Bora-Bora). We demonstrate that the Pb isotope variability observed using literature data is an analytical artifact related to the poor control of mass fractionation during Pb measurements by conventional TIMS technique. New MC-ICP-MS Pb data demonstrate that the isotopic stripes as previously defined disappear. They rather show that individual islands cover a significant part of the entire isotopic range of the chain. We suggest, therefore, that the dominant characteristic of the Society plume is small-scale heterogeneities, evenly distributed within the plume conduit. At a global scale, we show that some ocean island chains with similar geochemical and isotopic characteristics, such as Samoa and Society Islands, define different arrays when variations of Nd with high-precision Pb isotopes are considered. We proposed that this puzzling observation might record differences in recycling age of the basalt + sediment mixture subducted into the mantle and sampled by mantle plume.

  7. Mass measurement of radioactive isotopes

    NASA Astrophysics Data System (ADS)

    Kluge, H.-J.; Blaum, K.; Scheidenberger, C.

    2004-10-01

    The highest precision in mass measurements on short-lived radionuclides is obtained using trapping and cooling techniques. Here, the experimental storage ring (ESR) at GSI/Darmstadt and the tandem Penning trap mass spectrometer ISOLTRAP at ISOLDE/CERN play an important role. Status and recent results on mass measurements of radioactive nuclides with ESR and ISOLTRAP are summarized.

  8. Mass Fractionation Laws, Mass-Independent Effects, and Isotopic Anomalies

    NASA Astrophysics Data System (ADS)

    Dauphas, Nicolas; Schauble, Edwin A.

    2016-06-01

    Isotopic variations usually follow mass-dependent fractionation, meaning that the relative variations in isotopic ratios scale with the difference in mass of the isotopes involved (e.g., δ17O ≈ 0.5×δ18O). In detail, however, the mass dependence of isotopic variations is not always the same, and different natural processes can define distinct slopes in three-isotope diagrams. These variations are subtle, but improvements in analytical capabilities now allow precise measurement of these effects and make it possible to draw inferences about the natural processes that caused them (e.g., reaction kinetics versus equilibrium isotope exchange). Some elements, in some sample types, do not conform to the regularities of mass-dependent fractionation. Oxygen and sulfur display a rich phenomenology of mass-independent fractionation, documented in the laboratory, in the rock record, and in the modern atmosphere. Oxygen in meteorites shows isotopic variations that follow a slope-one line (δ17O ≈ δ18O) whose origin may be associated with CO photodissociation. Sulfur mass-independent fractionation in ancient sediments provides the tightest constraint on the oxygen partial pressure in the Archean and the timing of Earth's surface oxygenation. Heavier elements also show departures from mass fractionation that can be ascribed to exotic effects associated with chemical reactions such as magnetic effects (e.g., Hg) or the nuclear field shift effect (e.g., U or Tl). Some isotopic variations in meteorites and their constituents cannot be related to the terrestrial composition by any known process, including radiogenic, nucleogenic, and cosmogenic effects. Those variations have a nucleosynthetic origin, reflecting the fact that the products of stellar nucleosynthesis were not fully homogenized when the Solar System formed. Those anomalies are found at all scales, from nanometer-sized presolar grains to bulk terrestrial planets. They can be used to learn about stellar

  9. Extending the isotopically resolved mass range of Orbitrap mass spectrometers.

    PubMed

    Shaw, Jared B; Brodbelt, Jennifer S

    2013-09-01

    The routine analysis of large biomolecules (greater than 30 kDa) has been a challenge for Orbitrap mass spectrometers due to the relatively high kinetic energy of ions entering and within the Orbitrap mass analyzer. This characteristic results in rapid signal decay for large biomolecules due to energetic collisions with background gas molecules. Here, we report a method to significantly enhance the analysis of large biomolecules in an Orbitrap mass spectrometer. The combination of reduced C-trap and higher energy collisional dissociation (HCD) cell bath gas pressures, using helium as the bath gas and trapping ions in the HCD cell prior to mass analysis, greatly increased sensitivity and reduced signal decay for large protein ions. As a result, isotopic resolution of monoclonal immunoglobulin G was achieved, and we have established a new high-mass record for which accurate mass measurement and isotopic resolution have been achieved. PMID:23909473

  10. Iron, copper and zinc isotopic fractionation up mammal trophic chains

    NASA Astrophysics Data System (ADS)

    Jaouen, Klervia; Pons, Marie-Laure; Balter, Vincent

    2013-07-01

    There is a growing body of evidence that some non-traditional elements exhibit stable isotope compositions that are distinct in botanical and animal products, providing potential new tracers for diet reconstructions. Here, we present data for iron (Fe), copper (Cu) and zinc (Zn) stable isotope compositions in plants and bones of herbivores and carnivores. The samples come from trophic chains located in the Western Cape area and in the Kruger National Park in South Africa. The Fe, Cu and Zn isotope systematics are similar in both parks. However, local Cu, and possibly Zn, isotopic values of soils influence that of plants and of higher trophic levels. Between plants and bones of herbivores, the Zn isotope compositions are 66Zn-enriched by about 0.8‰ whereas no significant trophic enrichment is observed for Fe and Cu. Between bones of herbivores and bones of carnivores, the Fe isotope compositions are 56Fe-depleted by about 0.6‰, the Cu isotope compositions are 65Cu-enriched by about 1.0‰, and the Zn isotope compositions are slightly 66Zn-depleted by about 0.2‰. The isotopic distributions of the metals in the body partly explain the observed trophic isotopic systematics. However, it is also necessary to invoke differential intestinal metal absorption between herbivores and carnivores to account for the observed results. Further studies are necessary to fully understand how the Fe, Cu and Zn isotope values are regulated within the ecosystem's trophic levels, but the data already suggests significant potential as new paleodietary and paleoecological proxies.

  11. Linear-chain structure of alpha clusters in Carbon isotopes

    NASA Astrophysics Data System (ADS)

    Baba, Tomoyuki; Chiba, Yohei; Kimura, Masaaki

    2014-09-01

    The linear-chain structure of 12C in which three alpha particles are linearly aligned has long been interested and investigated since its proposal by Morinaga, but nowadays, its existence is doubt, because its instability was shown by fill-microscopic nuclear models. However, the possible existence of linear-chains in neutron-rich carbon isotopes assisted by the valence neutrons was recently suggested based on the cluster model. Therefore, it is of importance and interest to examine their stability and investigate the stabilization mechanism based on full-microscopic model. In this presentation, we will discuss the alpha cluster states of carbon isotopes including the linear-chains based on the antisymmetrized molecular dynamics (AMD) model. For, example, we will demonstrate two different types of the alpha cluster states, that are, triangular and linear-chain configurations. Four valence neutrons occupy the molecular-orbit surrounding the cluster cores, in particular, their orbits of the linear-chain structure are π-orbit and σ-orbit as suggested by the cluster calculation. In addition, we predict the excitation energies of two structures. We will show that the linear-chain states have very large moment of inertia and they appear near the 6He+10Be threshold energy.

  12. 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.

  13. Mass Distributions of Linear Chain Polymers

    PubMed Central

    Hubler, Shane L.; Craciun, Gheorghe

    2012-01-01

    Biochemistry has many examples of linear chain polymers, i.e., molecules formed from a sequence of units from a finite set of possibilities; examples include proteins, RNA, single-stranded DNA, and paired DNA. In the field of mass spectrometry, it is useful to consider the idea of weighted alphabets, with a word inheriting weight from its letters. We describe the distribution of the mass of these words in terms of a simple recurrence relation, the general solution to that relation, and a canonical form that explicitly describes both the exponential form of this distribution and its periodic features, thus explaining a wave pattern that has been observed in protein mass databases. Further, we show that a pure exponential term dominates the distribution and that there is exactly one such purely exponential term. Finally, we illustrate the use of this theorem by describing a formula for the integer mass distribution of peptides and we compare our theoretical results with mass distributions of human and yeast peptides. PMID:23024448

  14. Compact hydrogen/helium isotope mass spectrometer

    DOEpatents

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

    1996-01-01

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

  15. Comparison of aquatic food chains using nitrogen isotopes.

    PubMed Central

    Cabana, G; Rasmussen, J B

    1996-01-01

    Recent studies have shown the utility of delta(15)N to model trophic structure and contaminant bioaccumulation in aquatic food webs. However, cross-system comparisons in delta(15)N can be complicated by differences in delta(15)N at the base of the food chain. Such baseline variation in delta(15)N is difficult to resolve using plankton because of the large temporal variability in the delta(15)N of small organisms that have fast nitrogen turnover. Comparisons using large primary consumers, which have stable tissue isotopic signatures because of their slower nitrogen turnover, show that delta(15)N increases markedly with the human population density in the lake watershed. This shift in delta(15)N likely reflects the high delta(15)N of human sewage. Correcting for this baseline variation in delta(15)N, we report that, contrary to expectations based on previous food-web analysis, the food chains leading up to fish varied by about only one trophic level among the 40 lakes studied. Our results also suggest that the delta(15)N signatures of nitrogen at the base of the food chain will provide a useful tool in the assessment of anthropogenic nutrient inputs. Images Fig. 4 PMID:8855268

  16. Experimental investigation of mass-dependent and mass-independent fractionation of mercury isotopes

    NASA Astrophysics Data System (ADS)

    Bergquist, B. A.; Blum, J. D.; Marcus, J. W.; Biswas, A.

    2006-12-01

    Mercury is a globally distributed and highly toxic pollutant, the mobility and bioaccumulation of which is highly dependent on its redox cycling. With seven isotopes (including two odd-mass isotopes) and a relative mass difference of 4%, stable isotope fractionation of Hg could be a powerful tool to track and understand Hg cycling in the environment. Ongoing studies of natural mercury isotope variations in ore deposits, hydrothermal fluids, sediments, soils, fish tissues and bacterial cultures have documented a measurable range in Hg isotopes of up to ~5‰ in the ^{202}Hg/^{198}Hg ratio with most samples displaying mass-dependent fractionation. A small, but growing, body of data also suggests that natural samples display mass-independent fractionation of Hg isotopes. In this study, we explore mechanisms that lead to both mass- dependent and mass-independent fractionation of Hg isotopes. Isotope ratios were measured by continuous- flow cold-vapor generation coupled to MC-ICPMS with an external precision of ±0.1‰ (2SD). We observe three distinct types of isotope fractionation for Hg: (1) mass-dependent fractionation, (2) mass- independent fractionation of odd isotopes concurrent with mass-dependent fractionation of even isotopes, and (3) mass-independent fractionation of all Hg isotopes. Reduction of Hg species to Hg(0) vapor is an important mechanism for removal of Hg from aqueous systems into the atmosphere. Reduction of Hg occurs through numerous pathways including photoreduction, abiotic organic reduction, and biological reduction. We find that photoreduction of Hg(II) by natural sunlight leads to mass-independent fractionation of the odd isotopes (^{201}Hg, ^{199}Hg) with several permil deviations from predicted mass dependence, and mass- dependent fractionation of the even isotopes. In contrast, both biological reduction (Kritee et al., 2006) and dark abiotic organically mediated reduction follow mass-dependent fractionation of even and odd isotopes

  17. The Mass-Dependence of Cadmium Isotope Fractionation During Evaporation

    NASA Astrophysics Data System (ADS)

    Rehkamper, M.; Wombacher, F.; Mezger, K.; Wiechert, U.

    2002-12-01

    Isotope fractionation laws relate the isotope fractionation factor αA of one isotope ratio to the fractionation factor αB of a second isotope ratio of the same element with a fractionation exponent β, such that αA = αBβ. In a recent paper, Young et al. (GCA 66, 1095-1104 (2002)) inferred that kinetic and equilibrium isotope fractionations are characterized by different mass functions, such that βkin is not equal to βeq. As a consequence, kinetic isotope fractionation is expected to produce fractionation lines in three isotope space that are different from those generated by equilibrium fractionation processes. Young et al. furthermore stated that the variability in mass-dependent fractionation laws may be sufficient to account for the negative Δ17O of tropospheric O2 and the Δ17O anomalies of minerals in SNC meteorites. Such variations have otherwise been interpreted as evidence of non-mass dependant isotope fractionations (Luz et al., Nature 400, 547-550 (1999); Farquhar et al., Science 280, 1589-1582 (1998)). In the present study, we investigated the mass-dependence of isotope fractionation by evaluating the results of evaporation experiments that produced very large differences in Cd isotope compositions (up to about 100‰ ). In these experiments, liquid Cd was evaporated into a vacuum at a temperature of about 200°C. The metal residues remaining after evaporation were analyzed for their Cd isotope composition by multiple-collector inductively coupled plasma-mass spectrometry (MC-ICPMS) relative to the unfractionated starting material. The precision of the measurements is sufficient to clearly distinguish between different fractionation mechanisms. In linearized three-isotope space, the residual Cd metals plot on fractionation lines (e.g., with a slope β = 2.049 +/- 2 for 106}Cd/{114Cd vs. 110}Cd/{114Cd) that are intermediate between the kinetic (β = 2.036) and the equilibrium (β = 2.075) fractionation lines. This can be explained by an

  18. SILEC: a protocol for generating and using isotopically labeled coenzyme A mass spectrometry standards

    PubMed Central

    Basu, Sankha S; Blair, Ian A

    2013-01-01

    Stable isotope labeling by essential nutrients in cell culture (SILEC) was recently developed to generate isotopically labeled coenzyme A (CoA) and short-chain acyl-CoA thioesters. This was accomplished by modifying the widely used technique of stable isotope labeling by amino acids in cell culture to include [13C315N]-pantothenate (vitamin B5), a CoA precursor, instead of the isotopically labeled amino acids. The lack of a de novo pantothenate synthesis pathway allowed for efficient and near-complete labeling of the measured CoA species. This protocol provides a step-by-step approach for generating stable isotope-labeled short-chain acyl-CoA internal standards in mammalian and insect cells as well as instructions on how to use them in stable isotope dilution mass spectrometric-based analyses. Troubleshooting guidelines, as well as a list of unlabeled and labeled CoA species, are also included. This protocol represents a prototype for generating stable isotope internal standards from labeled essential nutrients such as pantothenate. The generation and use of SILEC standards takes approximately 2–3 weeks. PMID:22157971

  19. Computer Analysis of Isotope Clusters in Mass Spectrometry

    ERIC Educational Resources Information Center

    Bell, Harold M.

    1974-01-01

    Describes the application of a computer program designed to produce a formula determination simultaneously accounting for both elemental composition and probable isotopic species for a measured ion mass. (SLH)

  20. The isotopic composition of Nd in different ocean masses

    NASA Technical Reports Server (NTRS)

    Piepgras, D. J.; Wasserburg, G. J.; Dasch, E. J.

    1979-01-01

    The paper examines the isotopic composition of Nd in marine environments. The Sm-Nd data for authigenic ferromanganese sediments indicate that the Atlantic, Pacific, and Indian Oceans have a distinct range in Nd isotopic composition characteristics of each ocean basin and reflect the dissolved load of Nd in the water mass. Measurements of the Nd isotopic seawater composition of seawater indicate that the rare earth elements (REE) in ferromanganese sediments are derived by direct precipitation of these elements out of seawater. It is believed that the Nd isotopic variations in these sediments represent true variations in the dissolved Nd isotopic composition which reflect the age and (Sm-147)/(Nd-144) ratios of the continental masses sampled believed to be the major source of REE in seawater.

  1. A carbon isotope mass balance for an anoxic marine sediment: Isotopic signatures of diagenesis

    NASA Technical Reports Server (NTRS)

    Boehme, Susan E.

    1993-01-01

    A carbon isotope mass balance was determined for the sediments of Cape Lookout Bight, NC to constrain the carbon budgets published previously. The diffusive, ebullitive and burial fluxes of sigma CO2 and CH4, as well as the carbon isotope signatures of these fluxes, were measured. The flux-weighted isotopic signature of the remineralized carbon (-18.9 plus or minus 2.7 per mil) agreed with the isotopic composition of the remineralized organic carbon determined from the particulate organic carbon (POC) delta(C-13) profiles (-19.2 plus or minus 0.2), verifying the flux and isotopic signature estimates. The measured delta(C-13) values of the sigma CO2 and CH4 diffusive fluxes were significantly different from those calculated from porewater gradients. The differences appear to be influenced by methane oxidation at the sediment-water interface, although other potential processes cannot be excluded. The isotope mass balance provides important information concerning the locations of potential diagenetic isotope effects. Specifically, the absence of downcore change in the delta(C-13) value of the POC fraction and the identical isotopic composition of the POC and the products of remineralization indicate that no isotopic fractionation is expressed during the initial breakdown of the POC, despite its isotopically heterogeneous composition.

  2. Microbeam titanium isotopic analysis by resonance ionization mass spectrometry

    SciTech Connect

    Spiegel, D.R.; Davis, A.M.; Clayton, R.N. . Enrico Fermi Inst.); Pellin, M.J.; Calaway, W.F.; Burnett, J.W.; Coon, S.R.; Young, C.E.; Gruen, D.M. )

    1991-01-01

    The importance of isotopic anomalies in refractory inclusions in meteorites is well established. Measurements of the anomalies using conventional mass spectrometry are often rendered difficult, however, by isobarically interfering isotopes: for example, {sup 48}Ti and {sup 48}Ca. Resonance ionization mass spectrometry (RIMS) can substantially reduce isobaric interferences in a number of systems. We have employed RIMS for the in situ detection of Ti atoms sputtered from pure Ti metal and from several terrestrial oxides containing both Ti and Ca. Tunable lasers were employed to resonantly ionize neutral Ti atoms. We have chosen Ti specifically because of the importance of Ti isotopic anomalies in cosmochemistry.

  3. Isotopic mass-dependence of noble gas diffusion coefficients inwater

    SciTech Connect

    Bourg, I.C.; Sposito, G.

    2007-06-25

    Noble gas isotopes are used extensively as tracers inhydrologic and paleoclimatic studies. These applications requireknowledge of the isotopic mass (m) dependence of noble gas diffusioncoefficients in water (D), which has not been measured but is estimatedusing experimental D-values for the major isotopes along with an untestedrelationship from kinetic theory, D prop m-0.5. We applied moleculardynamics methods to determine the mass dependence of D for four noblegases at 298 K, finding that D prop m-beta with beta<0.2, whichrefutes the kinetic theory model underlying all currentapplications.

  4. Analytical techniques in biomedical stable isotope applications: (isotope ratio) mass spectrometry or infrared spectrometry?

    PubMed

    Stellaard, Frans; Elzinga, Henk

    2005-12-01

    An overview is presented of biomedical applications of stable isotopes in general, but mainly focused on the activities of the Center for Liver, Digestive and Metabolic Diseases of the University Medical Center Groningen. The aims of metabolic studies in the areas of glucose, fat, cholesterol and protein metabolism are briefly explained, as well as the principle of breath testing and the techniques to study body composition and energy expenditure. Much attention is paid to the analytical considerations based upon metabolite concentrations, sample size restrictions, the availability of stable isotope labelled substrates and dose requirements in relation to compound-specific isotope analysis. The instrumental advantages and limitations of the generally used techniques gas chromatography/reaction/isotope ratio mass spectrometry and gas chromatography/mass spectrometry are described as well as the novelties of the recently commercialised liquid chromatography/combustion/isotope ratio mass spectrometry. The present use and future perspective of infrared (IR) spectrometry for clinical and biomedical stable isotope applications are reviewed. In this respect, the analytical demands on IR spectrometry are discussed to enable replacement of isotope ratio mass spectrometry by IR spectrometry, in particular, for the purpose of compound-specific isotope ratio analysis in biological matrices. PMID:16543190

  5. Exploring Mass Perception with Markov Chain Monte Carlo

    ERIC Educational Resources Information Center

    Cohen, Andrew L.; Ross, Michael G.

    2009-01-01

    Several previous studies have examined the ability to judge the relative mass of objects in idealized collisions. With a newly developed technique of psychological Markov chain Monte Carlo sampling (A. N. Sanborn & T. L. Griffiths, 2008), this work explores participants; perceptions of different collision mass ratios. The results reveal…

  6. High Resolution Double-Focusing Isotope Ratio Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Radke, J.; Deerberg, M.; Hilkert, A.; Schlüter, H.-J.; Schwieters, J.

    2012-04-01

    In recent years isotope ratio mass spectrometry has extended to the capability of quantifying very small isotope signatures related with low abundances and simultaneously detecting molecular masses such as isotopomers and isotopologues containing clumped isotopes. Some of those applications are limited by molecular interferences like different gas molecules with the same nominal mass, e.g. Ar/O2, adducts of the same molecule or of different molecules, and very small isotope abundances. The Thermo Scientific MAT 253 ULTRA is the next generation of high precision gas isotope ratio mass spectrometry, which combines a 10 KV gas ionization source (Thermo Scientific MAT 253) with a double focusing multi-collector mass analyzer (Thermo Scientific Neptune) and reduces those limitations by measuring isotope ratios on a larger dynamic range with high precision. Small ion beam requirements and high sensitivity are achieved by signal-to-noise improvements through enhanced ion beam amplification in faraday cups and ion counters. Interfering backgrounds, e.g. interfering isotopologues or isobaric ions of contaminants, are dramatically decreased by a dynamic range increase combined with high evacuation leading to undisturbed ion transmission through the double-focusing analyser. Furthermore, automated gain calibration for mathematical baseline corrections, switchable detector arrays, ion source control, analyser focusing and full data export is controlled under Isodat data control. New reference/sample strategies are under investigation besides incorporation of the continuous-flow technique and its versatile inlet devices. We are presenting first results and applications of the MAT 253 Ultra.

  7. An isotopic mass effect on the intermolecular potential

    NASA Astrophysics Data System (ADS)

    Herman, Michael F.; Currier, Robert P.; Clegg, Samuel M.

    2015-10-01

    The impact of isotopic variation on the electronic energy and intermolecular potentials is often suppressed when calculating isotopologue thermodynamics. Intramolecular potential energy surfaces for distinct isotopologues are in fact equivalent under the Born-Oppenheimer approximation, which is sometimes used to imply that the intermolecular interactions are independent of isotopic mass. In this communication, the intermolecular dipole-dipole interaction between hetero-nuclear diatomic molecules is considered. It is shown that the intermolecular potential contains mass-dependent terms even though each nucleus moves on a Born-Oppenheimer surface. The analysis suggests that mass dependent variations in intermolecular potentials should be included in comprehensive descriptions of isotopologue thermodynamics.

  8. Diagnosis of medium chain acyl-CoA dehydrogenase deficiency by stable isotope dilution analysis of urinary acylglycines: Retrospective and prospective studies, and comparison of its accuracy to acylcarnitine identification by FAB/mass spectrometry

    SciTech Connect

    Rinaldo, P.; O'Shea, J.J.; Welch, R.D.; Tanaka, K. )

    1990-01-01

    In summary, we have demonstrated that the accurate quantitation of urinary HG and PPG by stable isotope dilution analysis is currently the most reliable method for the diagnosis of MCAD deficiency. This method is particularly useful for testing random samples from asymptomatic patients without any provocative test, and it is suitable to widely survey a fairly large population, such as patients with episodic manifestations and families with a history of SIDS.

  9. Isotope ratio mass spectrometry - history and terminology in brief.

    PubMed

    Flenker, Ulrich

    2012-12-01

    The history of isotope ratio mass spectrometry (IRMS) is briefly described. It is shown that the fundamental design of isotope ratio mass spectrometers has not changed since the 1940s. The basic findings concerning the natural variation of isotope abundances even date back to the 1930s. Recent improvements in the methodology mainly concern online coupling and analytical peripherals. The nature of isotopic scales necessitates a specific terminology which is unfamiliar to many analysts. However, corresponding guidelines exist that should be adopted by the anti-doping community. Currently, steroids represent the only group of compounds routinely analyzed by IRMS in doping-control. Suggestions are made in respect to a harmonized terminology concerning the nature and origins of steroids. PMID:22972693

  10. Evaluating chlorine isotope effects from isotope ratios and mass spectra of polychlorinated molecules.

    PubMed

    Elsner, Martin; Hunkeler, Daniel

    2008-06-15

    Compound-specific chlorine isotope analysis receives much interest to assess the fate of chlorinated hydrocarbons in contaminated environments. This paper provides a theoretical basis to calculate isotope ratios and quantify isotope fractionation from ion-current ratios of molecular- and fragment-ion multiplets. Because both (35)Cl and (37)Cl are of high abundance, polychlorinated hydrocarbons consist of molecules containing different numbers of (37)Cl denoted as isotopologues. We show that, during reactions, the changes in isotopologue ratios are proportional to changes in the isotope ratio assuming a nonselective isotope distribution in the initial compound. This proportionality extents even to fragments formed in the ion source of a mass spectrometer such as C 2Cl 2 (double dechlorinated fragment of perchloroethylene, PCE). Fractionation factors and kinetic isotope effects (KIE) may, therefore, be evaluated from isotope, isotopologue or even fragment ratios according to conventional simple equations. The proportionality is exact with symmetric molecules such as dichloroethylene (DCE) and PCE, whereas it is approximately true with molecules containing nonreactive positions such as trichloroethylene (TCE). If in the latter case isotope ratios are derived from dechlorinated fragments, e.g., C 2HCl 2, it is important that fragmentation in the ion source affect all molecular positions alike, as otherwise isotopic changes in reactive positions may be underrepresented. PMID:18484745

  11. Mono-isotope Prediction for Mass Spectra Using Bayes Network

    PubMed Central

    Li, Hui; Rwebangira, Mugizi Robert; Burge, Legand

    2015-01-01

    Mass spectrometry is one of the widely utilized important methods to study protein functions and components. The challenge of mono-isotope pattern recognition from large scale protein mass spectral data needs computational algorithms and tools to speed up the analysis and improve the analytic results. We utilized naïve Bayes network as the classifier with the assumption that the selected features are independent to predict mono-isotope pattern from mass spectrometry. Mono-isotopes detected from validated theoretical spectra were used as prior information in the Bayes method. Three main features extracted from the dataset were employed as independent variables in our model. The application of the proposed algorithm to publicMo dataset demonstrates that our naïve Bayes classifier is advantageous over existing methods in both accuracy and sensitivity. PMID:25620856

  12. Mass distributions for induced fission of different Hg isotopes

    NASA Astrophysics Data System (ADS)

    Andreev, A. V.; Adamian, G. G.; Antonenko, N. V.

    2012-10-01

    With the improved scission-point model mass distributions are calculated for induced fission of different Hg isotopes with even mass numbers A=180, 184, 188, 192, 196, and 198. The calculated mass distribution and mean total kinetic energy of fission fragments are in good agreement with the existing experimental data. The asymmetric mass distribution of fission fragments of 180Hg observed in the recent experiment is explained. The change in the shape of the mass distribution from asymmetric to more symmetric is revealed with increasing A of the fissioning AHg nucleus, and reactions are proposed to verify this prediction experimentally.

  13. Traveling Waves for the Mass in Mass Model of Granular Chains

    NASA Astrophysics Data System (ADS)

    Kevrekidis, Panayotis G.; Stefanov, Atanas G.; Xu, Haitao

    2016-06-01

    In the present work, we consider the mass in mass (or mass with mass) system of granular chains, namely, a granular chain involving additionally an internal (or, respectively, external) resonator. For these chains, we rigorously establish that under suitable "anti-resonance" conditions connecting the mass of the resonator and the speed of the wave, bell-shaped traveling-wave solutions continue to exist in the system, in a way reminiscent of the results proven for the standard granular chain of elastic Hertzian contacts. We also numerically touch upon settings, where the conditions do not hold, illustrating, in line also with recent experimental work, that non-monotonic waves bearing non-vanishing tails may exist in the latter case.

  14. Traveling waves for the mass in mass model of granular chains

    DOE PAGESBeta

    Kevrekidis, Panayotis G.; Stefanov, Atanas G.; Xu, Haitao

    2016-08-01

    In this work, we consider the mass in mass (or mass with mass) system of granular chains, namely, a granular chain involving additionally an internal (or, respectively, external) resonator. For these chains, we rigorously establish that under suitable “anti-resonance” conditions connecting the mass of the resonator and the speed of the wave, bell-shaped traveling-wave solutions continue to exist in the system, in a way reminiscent of the results proven for the standard granular chain of elastic Hertzian contacts. Finally, we also numerically touch upon settings, where the conditions do not hold, illustrating, in line also with recent experimental work, thatmore » non-monotonic waves bearing non-vanishing tails may exist in the latter case.« less

  15. Traveling Waves for the Mass in Mass Model of Granular Chains

    NASA Astrophysics Data System (ADS)

    Kevrekidis, Panayotis G.; Stefanov, Atanas G.; Xu, Haitao

    2016-08-01

    In the present work, we consider the mass in mass (or mass with mass) system of granular chains, namely, a granular chain involving additionally an internal (or, respectively, external) resonator. For these chains, we rigorously establish that under suitable "anti-resonance" conditions connecting the mass of the resonator and the speed of the wave, bell-shaped traveling-wave solutions continue to exist in the system, in a way reminiscent of the results proven for the standard granular chain of elastic Hertzian contacts. We also numerically touch upon settings, where the conditions do not hold, illustrating, in line also with recent experimental work, that non-monotonic waves bearing non-vanishing tails may exist in the latter case.

  16. Chiral three-nucleon forces and the evolution of correlations along the oxygen isotopic chain

    NASA Astrophysics Data System (ADS)

    Cipollone, A.; Barbieri, C.; Navrátil, P.

    2015-07-01

    Background: Three-nucleon forces (3NFs) have nontrivial implications on the evolution of correlations at extreme proton-neutron asymmetries. Recent ab initio calculations show that leading-order chiral interactions are crucial to obtain the correct binding energies and neutron driplines along the O, N, and F chains [A. Cipollone, C. Barbieri, and P. Navrátil, Phys. Rev. Lett. 111, 062501 (2013), 10.1103/PhysRevLett.111.062501]. Purpose: Here we discuss the impact of 3NFs along the oxygen chain for other quantities of interest, such has the spectral distribution for attachment and removal of a nucleon, spectroscopic factors, and radii. The objective is to better delineate the general effects of 3NFs on nuclear correlations. Methods: We employ self-consistent Green's function (SCGF) theory which allows a comprehensive calculation of the single-particle spectral function. For the closed subshell isotopes, 14O, 16O, 22O, 24O, and 28O, we perform calculations with the Dyson-ADC(3) method, which is fully nonperturbative and is the state of the art for both nuclear physics and quantum chemistry applications. The remaining open-shell isotopes are studied using the newly developed Gorkov-SCGF formalism up to second order. Results: We produce complete plots for the spectral distributions. The spectroscopic factors for the dominant quasiparticle peaks are found to depend very little on the leading-order (NNLO) chiral 3NFs. The latter have small impact on the calculated matter radii, which, however, are consistently obtained smaller than experiment. Similarly, single-particle spectra tend to be too spread with respect to the experiment. This effect might hinder, to some extent, the onset of correlations and screen the quenching of calculated spectroscopic factors. The most important effect of 3NFs is thus the fine tuning of the energies for the dominant quasiparticle states, which governs the shell evolution and the position of driplines. Conclusions: Although present chiral

  17. Isotope Ratio Monitoring Gas Chromatography Mass Spectrometry (IRM-GCMS)

    NASA Technical Reports Server (NTRS)

    Freeman, K. H.; Ricci, S. A.; Studley, A.; Hayes, J. M.

    1989-01-01

    On Earth, the C-13 content of organic compounds is depleted by roughly 13 to 23 permil from atmospheric carbon dioxide. This difference is largely due to isotope effects associated with the fixation of inorganic carbon by photosynthetic organisms. If life once existed on Mars, then it is reasonable to expect to observe a similar fractionation. Although the strongly oxidizing conditions on the surface of Mars make preservation of ancient organic material unlikely, carbon-isotope evidence for the existence of life on Mars may still be preserved. Carbon depleted in C-13 could be preserved either in organic compounds within buried sediments, or in carbonate minerals produced by the oxidation of organic material. A technique is introduced for rapid and precise measurement of the C-13 contents of individual organic compounds. A gas chromatograph is coupled to an isotope-ratio mass spectrometer through a combustion interface, enabling on-line isotopic analysis of isolated compounds. The isotope ratios are determined by integration of ion currents over the course of each chromatographic peak. Software incorporates automatic peak determination, corrections for background, and deconvolution of overlapped peaks. Overall performance of the instrument was evaluated by the analysis of a mixture of high purity n-alkanes of know isotopic composition. Isotopic values measured via IRM-GCMS averaged withing 0.55 permil of their conventionally measured values.

  18. Mass measurements on radioactive isotopes with a Penning trap mass spectrometer

    SciTech Connect

    Bollen, G.; Ames, F.; Schark, E.; Audi, G.; Lunney, D.; Saint Simon, M. de; Beck, D.; Herfurth, F.; Kluge, H.-J.; Kohl, A.; Schwarz, S.; Moore, R. B.; Szerypo, J.

    1999-01-15

    Penning trap mass measurements on short-lived isotopes are performed with the ISOLTRAP mass spectrometer at the radioactive beam facility ISOLDE/CERN. In the last years the applicability of the spectrometer has been considerably extended by the installation of an RFQ trap ion beam buncher and a new cooler Penning trap, which is operated as an isobar separator. These improvements allowed for the first time measurements on isotopes of rare earth elements and on isotopes with Z=80-85. In all cases an accuracy of {delta}m/m{approx_equal}1{center_dot}10{sup -7} was achieved.

  19. 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

  20. Stable isotope mass balance of lakes: a contemporary perspective (Invited)

    NASA Astrophysics Data System (ADS)

    Gibson, J. J.; Birks, S. J.; YI, Y.; Jasechko, S.

    2013-12-01

    Stable isotopes are widely used in paleoclimate studies of lakes to reconstruct water balance and/or climatic conditions, but there are a variety of assumptions that are often made to simplify and operationalize the isotope transfer functions. Based on recent studies conducted on a wide range of lakes across North America, as well as a comprehensive compilation of existing data from around the globe, we present contemporary examples of stable-isotope mass-balance studies based on site-specific to regional lake datasets. We illustrate the need in most cases to understand and characterize the local climate and hydrological setting to accurately model the observed isotopic enrichment, as well as the importance of amount-weighting liquid fluxes and evaporation-flux-weighting vapour fluxes. Potential complications due to atmospheric feedback are also explored by presenting a new analysis of the Laurentian Great Lakes where we apply a model that considers the timing of evaporation, which occurs mainly in the winter, and accounts for downwind lake effects, humidity and isotopic build-up in the boundary layer. One future opportunity of lake-based paleoclimate research may be to develop controlled studies that allow for specific atmospheric or water-balance processes to be targeted and reconstructed. We also show relationships between selected water quality indicators and isotope-based water balance indicators that should, in principle, be preserved in the lake sediment record.

  1. Fe and Cu isotope mass balances in the human body

    NASA Astrophysics Data System (ADS)

    Balter, V.; Albarede, F.; Jaouen, K.

    2011-12-01

    The ranges of the Fe and Cu isotope compositions in the human body are large, i.e. ~3% and ~2%, respectively. Both isotopic fractionations appear to be mainly controlled by redox conditions. The Fe and Cu isotope compositions of the tissues analyzed so far plot on a mixing hyperbolae between a reduced and an oxidized metals pools. The reduced metals pool is composed by erythrocytes, where Fe is bounded to hemoglobin as Fe(II) and Cu to superoxide-dismutase as Cu(I). The oxidized metals pool is composed by hepatocytes, where Fe and Cu are stored as Fe(III) ferritin and as Cu(II) ceruloplasmine, respectively. The position of each biological component in the δ56Fe-δ65Cu diagram therefore reflects the oxidation state of Fe and Cu of the predominant metal carrier protein and allows to quantify Fe and Cu fluxes between organs using mass balance calculations. For instance, serum and clot Fe and Cu isotope compositions show that current biological models of erythropoiesis violates mass conservation requirements, and suggest hidden Fe and Cu pathways during red blood cells synthesis. The results also show that a coupled Fe-Cu strong gender isotopic effect is observed in various organs. The isotopic difference between men and women is unlikely to be due to differential dietary uptake or endometrium loss, but rather reflects the effect of menstrual losses and a correlative solicitation of hepatic stores. We speculate that thorough studies of the metabolism of stable isotopes in normal conditions is a prerequisite for the understanding of the pathological dysregulations.

  2. Quantitative imaging of subcellular metabolism with stable isotopes and multi-isotope imaging mass spectrometry

    PubMed Central

    Steinhauser, Matthew L.; Lechene, Claude P.

    2014-01-01

    Multi-isotope imaging mass spectrometry (MIMS) is the quantitative imaging of stable isotope labels in cells with a new type of secondary ion mass spectrometer (NanoSIMS). The power of the methodology is attributable to (i) the immense advantage of using non-toxic stable isotope labels, (ii) high resolution imaging that approaches the resolution of usual transmission electron microscopy and (iii) the precise quantification of label down to 1 part-per-million and spanning several orders of magnitude. Here we review the basic elements of MIMS and describe new applications of MIMS to the quantitative study of metabolic processes including protein and nucleic acid synthesis in model organisms ranging from microbes to humans. PMID:23660233

  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. Mass Independent Isotopic Compositions of Aerosol Sulfate and Nitrates

    NASA Astrophysics Data System (ADS)

    Thiemens, M. H.

    2001-12-01

    For nearly a half-century stable isotope ratio measurements have been utilized as a tool to understand sources, fates, and transformation mechanisms of atmospheric molecules. Carbon and oxygen (δ 13C and δ 18O) measurements of CO2 have been instrumental in providing specific details of the carbon cycle. Without these measurements, understanding of the carbon cycle and transfer rates between reservoirs would be considerably diminished. Deuterium and oxygen isotopic measurements of atmospheric water has similarly enhanced the ability to model the atmospheric and geochemical recycling of the hydrologic cycle. Other molecules investigated include, for example, CO, CH4, N2O, SO4, NH, and Cl. The ability to interpret these high precision isotope ratio measurements relies upon a fundamental understanding of the basic physical-chemical processes which produce the alteration of the stable isotope ratio. Such processes typically include thermodynamics (viz a viz isotope exchange), kinetics, and evaporation-condensation. Though the mechanism by which these alterations occur, they all depend in some fashion upon mass differences in the isotopically substituted atoms. In 1983, Thiemens and Heidenreich (1) demonstrated that a chemical process is capable of producing an alteration of stable isotopes which was independent of mass. Subsequent to that time, it has been shown that measurements of mass independent isotopic compositions provide a new view of atmospheric process which may not be derived from single isotope ratio measurements (reviews by (2), (3)). In the past few years, mass independent isotopic compositions have been utilized to understand ancient atmospheres on both Earth and Mars (review by (4)). It has been known for decades that atmospheric sulfate is an extraordinary species. It participates in climate change in its capacity as a cloud condensation nuclei and it is a human and environmental health hazard. By the same token, aerosol nitrate is an environmental

  5. 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).

  6. Stable isotope, site-specific mass tagging for protein identification

    DOEpatents

    Chen, Xian

    2006-10-24

    Proteolytic peptide mass mapping as measured by mass spectrometry provides an important method for the identification of proteins, which are usually identified by matching the measured and calculated m/z values of the proteolytic peptides. A unique identification is, however, heavily dependent upon the mass accuracy and sequence coverage of the fragment ions generated by peptide ionization. The present invention describes a method for increasing the specificity, accuracy and efficiency of the assignments of particular proteolytic peptides and consequent protein identification, by the incorporation of selected amino acid residue(s) enriched with stable isotope(s) into the protein sequence without the need for ultrahigh instrumental accuracy. Selected amino acid(s) are labeled with .sup.13C/.sup.15N/.sup.2H and incorporated into proteins in a sequence-specific manner during cell culturing. Each of these labeled amino acids carries a defined mass change encoded in its monoisotopic distribution pattern. Through their characteristic patterns, the peptides with mass tag(s) can then be readily distinguished from other peptides in mass spectra. The present method of identifying unique proteins can also be extended to protein complexes and will significantly increase data search specificity, efficiency and accuracy for protein identifications.

  7. Multi-collector Isotope Ratio Mass Spectrometer -- Operational Performance Report

    SciTech Connect

    Appelhans, Anthony D; Olson, John E; Watrous, Matthew G; Ward, Michael B.; Dahl, David A.

    2010-12-01

    This report describes the operational testing of a new magnetic sector mass spectrometer that utilizes seven full-sized discrete dynode electron multipliers operating simultaneously. The instrument includes a newly developed ion dispersion lens that enables the mass dispersed individual isotope beams to be separated sufficiently to allow a full-sized discrete dynode pulse counting multiplier to be used to measure each isotope beam. The performance of the instrument was measured using SRM 996 (244Pu spike) at loadings of 2.4 and 12 fg on resin beads and with SRM 4350B Columbia River Sediment samples. The measured limit of detection (3s) for 240Pu was 3.4 attograms for SRM 996. The limit of quantitation (LOQ), defined as 10 s, was 11.2 attograms. The measured concentration of 239Pu in the CRS standard was 152 ± 6 fg/g.

  8. Mass and isotopic effects in the Li-Li+ collision

    NASA Astrophysics Data System (ADS)

    Bouledroua, Moncef; Bouchelaghem, Fouzia

    2011-10-01

    We suggest in this work to deal with the ion-atom collision. More precisely, the transport coefficients, the temperature-dependant mobilities, and the charge-transfer phenomena are examined quatum-mechanically. Also is examined the mass and isotopic effects and their behaviour with temperature. To do so, the interatomic potentials are constructed and then injected in the radial wave equation to determine the phase shifts.

  9. 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.

  10. Calcium isotope constraints on the end-Permian mass extinction

    PubMed Central

    Payne, Jonathan L.; Turchyn, Alexandra V.; Paytan, Adina; DePaolo, Donald J.; Lehrmann, Daniel J.; Yu, Meiyi; Wei, Jiayong

    2010-01-01

    The end-Permian mass extinction horizon is marked by an abrupt shift in style of carbonate sedimentation and a negative excursion in the carbon isotope (δ13C) composition of carbonate minerals. Several extinction scenarios consistent with these observations have been put forward. Secular variation in the calcium isotope (δ44/40Ca) composition of marine sediments provides a tool for distinguishing among these possibilities and thereby constraining the causes of mass extinction. Here we report δ44/40Ca across the Permian-Triassic boundary from marine limestone in south China. The δ44/40Ca exhibits a transient negative excursion of ∼0.3‰ over a few hundred thousand years or less, which we interpret to reflect a change in the global δ44/40Ca composition of seawater. CO2-driven ocean acidification best explains the coincidence of the δ44/40Ca excursion with negative excursions in the δ13C of carbonates and organic matter and the preferential extinction of heavily calcified marine animals. Calcium isotope constraints on carbon cycle calculations suggest that the average δ13C of CO2 released was heavier than -28‰ and more likely near -15‰; these values indicate a source containing substantial amounts of mantle- or carbonate-derived carbon. Collectively, the results point toward Siberian Trap volcanism as the trigger of mass extinction. PMID:20421502

  11. Raman spectroscopic and mass spectrometric investigations of the hydrogen isotopes and isotopically labelled methane

    SciTech Connect

    Jewett, J.R., Fluor Daniel Hanford

    1997-02-24

    Suitable analytical methods must be tested and developed for monitoring the individual process steps within the fuel cycle of a fusion reactor and for tritium accountability. The utility of laser-Raman spectroscopy accompanied by mass spectrometry with an Omegatron was investigated using the analysis of all hydrogen isotopes and isotopically labeled methanes as an example. The Omegatron is useful for analyzing all hydrogen isotopes mixed with the stable helium isotopes. The application of this mass spectrometer were demonstrated by analyzing mixtures of deuterated methanes. In addition, it was employed to study the radiochemical Witzbach exchange reaction between tritium and methanes. A laser-Raman spectrometer was designed for analysis of tritium-containing gases and was built from individual components. A tritium-compatible, metal-sealed Raman cuvette having windows with good optical properties and additional means for measuring the stray light was first used successfully in this work. The Raman spectra of the hydrogen isotopes were acquired in the pure rotation mode and in the rotation-vibration mode and were used for on. The deuterated methanes were measured by Raman spectroscopy, the wavenumbers determined were assigned to the corresponding vibrations, and the wavenumbers for the rotational fine-structure were summarized in tables. The fundamental Vibrations of the deuterated methanes produced Witzbach reactions were detected and assigned. The fundamental vibrations of the molecules were obtained with Raman spectroscopy for the first time in this work. The @-Raman spectrometer assembled is well suited for the analysis of tritium- containing gases and is practical in combination with mass spectrometry using an Omegatron, for studying gases used in fusion.

  12. Chemical and Isotopic Thresholds in Charring: Implications for the Interpretation of Charcoal Mass and Isotopic Data.

    PubMed

    Pyle, Lacey A; Hockaday, William C; Boutton, Thomas; Zygourakis, Kyriacos; Kinney, Timothy J; Masiello, Caroline A

    2015-12-15

    Charcoal plays a significant role in the long-term carbon cycle, and its use as a soil amendment is promoted as a C sequestration strategy (biochar). One challenge in this research area is understanding the heterogeneity of charcoal properties. Although the maximum reaction temperature is often used as a gauge of pyrolysis conditions, pyrolysis duration also changes charcoal physicochemical qualities. Here, we introduce a formal definition of charring intensity (CI) to more accurately characterize pyrolysis, and we document variation in charcoal chemical properties with variation in CI. We find two types of responses to CI: either linear or threshold relationships. Mass yield decreases linearly with CI, while a threshold exists across which % C, % N, and δ(15)N exhibit large changes. This CI threshold co-occurs with an increase in charcoal aromaticity. C isotopes do not change from original biomass values, supporting the use of charcoal δ(13)C signatures to infer paleoecological conditions. Fractionation of N isotopes indicates that fire may be enriching soils in (15)N through pyrolytic N isotope fractionation. This influx of "black N" could have a significant impact on soil N isotopes, which we show theoretically using a simple mass-balance model. PMID:26523420

  13. Stable isotope mass balance of lakes: a contemporary perspective

    NASA Astrophysics Data System (ADS)

    Gibson, J. J.; Birks, S. J.; Yi, Y.

    2016-01-01

    The theoretical basis for application of stable isotope mass balance of lakes is described for a range of climatic situations including low latitude, high latitude, high altitude, continental and coastal systems, as well as cases where the atmospheric boundary layer is significantly modified by the lake evaporation process. The effects of seasonality on isotopic offset between precipitation and atmospheric vapour and the slope of the local evaporation line are described. Atmospheric feedback and its role in labelling the isotopic composition of the Laurentian Great Lakes and tropical lakes is discussed. Several important considerations are suggested to improve parameterization of quantitative paleoclimatic reconstructions including use of assumptions that are appropriate for the climatic setting, for the atmospheric feedback situation, for salinity, and headwater setting. Potential for use of dual-isotopes to trace past changes in seasonality and input, and a dual-lake index method that can potentially be used to trace connectivity of lakes are presented. In cases where modern or paleo-evaporation systems may be under-defined there are inherent limitations in the degree of quantification that can be attained.

  14. Oxygen and hydrogen isotope signatures of Northeast Atlantic water masses

    NASA Astrophysics Data System (ADS)

    Voelker, Antje H. L.; Colman, Albert; Olack, Gerard; Waniek, Joanna J.; Hodell, David

    2015-06-01

    Only a few studies have examined the variation of oxygen and hydrogen isotopes of seawater in NE Atlantic water masses, and data are especially sparse for intermediate and deep-water masses. The current study greatly expands this record with 527 δ18O values from 47 stations located throughout the mid- to low-latitude NE Atlantic. In addition, δD was analyzed in the 192 samples collected along the GEOTRACES North Atlantic Transect GA03 (GA03_e=KN199-4) and the 115 Iberia-Forams cruise samples from the western and southern Iberian margin. An intercomparison study between the two stable isotope measurement techniques (cavity ring-down laser spectroscopy and magnetic-sector isotope ratio mass spectrometry) used to analyze GA03_e samples reveals relatively good agreement for both hydrogen and oxygen isotope ratios. The surface (0-100 m) and central (100-500 m) water isotope data show the typical, evaporation related trend of increasing values equatorward with the exception for the zonal transect off Cape Blanc, NW Africa. Off Cape Blanc, surface water isotope signatures are modified by the upwelling of fresher Antarctic Intermediate Water (AAIW) that generally has isotopic values of 0.0 to 0.5‰ for δ18O and 0 to 2‰ for δD. Along the Iberian margin the Mediterranean Outflow Water (MOW) is clearly distinguished by its high δ18O (0.5-1.1‰) and δD (3-6‰) values that can be traced into the open Atlantic. Isotopic values in the NE Atlantic Deep Water (NEADW) are relatively low (δ18O: -0.1 to 0.5‰; δD: -1 to 4‰) and show a broader range than observed previously in the northern and southern convection areas. The NEADW is best observed at GA03_e Stations 5 and 7 in the central NE Atlantic basin. Antarctic Bottom Water isotope values are relatively high indicating modification of the original Antarctic source water along the flow path. The reconstructed δ18O-salinity relationship for the complete data set has a slope of 0.51, i.e., slightly steeper than the 0

  15. Protein stable isotope fingerprinting: multidimensional protein chromatography coupled to stable isotope-ratio mass spectrometry.

    PubMed

    Mohr, Wiebke; Tang, Tiantian; Sattin, Sarah R; Bovee, Roderick J; Pearson, Ann

    2014-09-01

    Protein stable isotope fingerprinting (P-SIF) is a method to measure the carbon isotope ratios of whole proteins separated from complex mixtures, including cultures and environmental samples. The goal of P-SIF is to expose the links between taxonomic identity and metabolic function in microbial ecosystems. To accomplish this, two dimensions of chromatography are used in sequence to resolve a sample containing ca. 5-10 mg of mixed proteins into 960 fractions. Each fraction then is split in two aliquots: The first is digested with trypsin for peptide sequencing, while the second has its ratio of (13)C/(12)C (value of δ(13)C) measured in triplicate using an isotope-ratio mass spectrometer interfaced with a spooling wire microcombustion device. Data from cultured species show that bacteria have a narrow distribution of protein δ(13)C values within individual taxa (±0.7-1.2‰, 1σ). This is moderately larger than the mean precision of the triplicate isotope measurements (±0.5‰, 1σ) and may reflect heterogeneous distribution of (13)C among the amino acids. When cells from different species are mixed together prior to protein extraction and separation, the results can predict accurately (to within ±1σ) the δ(13)C values of the original taxa. The number of data points required for this endmember prediction is ≥20/taxon, yielding a theoretical resolution of ca. 10 taxonomic units/sample. Such resolution should be useful to determine the overall trophic breadth of mixed microbial ecosystems. Although we utilize P-SIF to measure natural isotope ratios, it also could be combined with experiments that incorporate stable isotope labeling. PMID:25121924

  16. Mass measurements of neutron-rich Rb and Sr isotopes

    NASA Astrophysics Data System (ADS)

    Klawitter, R.; Bader, A.; Brodeur, M.; Chowdhury, U.; Chaudhuri, A.; Fallis, J.; Gallant, A. T.; Grossheim, A.; Kwiatkowski, A. A.; Lascar, D.; Leach, K. G.; Lennarz, A.; Macdonald, T. D.; Pearkes, J.; Seeraji, S.; Simon, M. C.; Simon, V. V.; Schultz, B. E.; Dilling, J.

    2016-04-01

    We report on the mass measurements of several neutron-rich Rb and Sr isotopes in the A ≈100 region with the TITAN Penning-trap mass spectrometer. By using highly charged ions in the charge state q =10 + , the masses of Rb,9998 and Sr-10098 have been determined with a precision of 6-12 keV, making their uncertainty negligible for r -process nucleosynthesis network calculations. The mass of 101Sr has been determined directly for the first time with a precision eight times higher than the previous indirect measurement and a deviation of 3 σ when compared to the Atomic Mass Evaluation. We also confirm the mass of 100Rb from a previous measurement. Furthermore, our data indicate the existence of a low-lying isomer with 80 keV excitation energy in 98Rb. We show that our updated mass values lead to minor changes in the r process by calculating fractional abundances in the A ≈100 region of the nuclear chart.

  17. 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

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

    NASA Astrophysics Data System (ADS)

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

    2013-04-01

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

  19. Using isotope dilution mass spectrometry to determine aqueous trichloroacetic acid

    SciTech Connect

    Norwood, D.L.; Christman, R.F.; Johnson, J.D.; Hass, J.R.

    1986-01-01

    The development, verification, and application of a method based on isotope-dilution gas chromatography-mass spectrometry to determine aqueous trichloroacetic acid (TCAA) at the micrograms per litre level are described. The simultaneous determination of aqueous chloroform is also demonstrated. Trichloroacetic acid is shown to be a significant by-product of the chlorination of raw waters in the laboratory and to constitute a large fraction of the total organic halide (TOX) formed. Analysis of finished-water samples indicated that TCAA, like trihalomethanes is ubiquitous. Positive correlations exist between the levels of TCAA in laboratory-chlorinated raw waters and in finished waters and measured TOX.

  20. Nonenzymatic assembly of natural polyubiquitin chains of any linkage composition and isotopic labeling scheme.

    PubMed

    Castañeda, Carlos; Liu, Jia; Chaturvedi, Apurva; Nowicka, Urszula; Cropp, T Ashton; Fushman, David

    2011-11-01

    Polymeric chains made of a small protein ubiquitin act as molecular signals regulating a variety of cellular processes controlling essentially all aspects of eukaryotic biology. Uncovering the mechanisms that allow differently linked polyubiquitin chains to serve as distinct molecular signals requires the ability to make these chains with the native connectivity, defined length, linkage composition, and in sufficient quantities. This, however, has been a major impediment in the ubiquitin field. Here, we present a robust, efficient, and widely accessible method for controlled iterative nonenzymatic assembly of polyubiquitin chains using recombinant ubiquitin monomers as the primary building blocks. This method uses silver-mediated condensation reaction between the C-terminal thioester of one ubiquitin and the ε-amine of a specific lysine on the other ubiquitin. We augment the nonenzymatic approaches developed recently by using removable orthogonal amine-protecting groups, Alloc and Boc. The use of bacterially expressed ubiquitins allows cost-effective isotopic enrichment of any individual monomer in the chain. We demonstrate that our method yields completely natural polyubiquitin chains (free of mutations and linked through native isopeptide bonds) of essentially any desired length, linkage composition, and isotopic labeling scheme, and in milligram quantities. Specifically, we successfully made Lys11-linked di-, tri-, and tetra-ubiquitins, Lys33-linked diubiquitin, and a mixed-linkage Lys33,Lys11-linked triubiquitin. We also demonstrate the ability to obtain, by high-resolution NMR, residue-specific information on ubiquitin units at any desired position in such chains. This method opens up essentially endless possibilities for rigorous structural and functional studies of polyubiquitin signals. PMID:21962295

  1. Low-lying dipole excitations in vibrational nuclei: The Cd isotopic chain studied in photon scattering experiments

    SciTech Connect

    Kohstall, C.; Belic, D.; Kneissl, U.; Nord, A.; Pitz, H.H.; Scheck, M.; Stedile, F.; Brentano, P. von; Fransen, C.; Gade, A.; Herzberg, R.-D.; Jolie, J.; Linnemann, A.; Pietralla, N.; Werner, V.; Yates, S.W.

    2005-09-01

    High-resolution nuclear resonance fluorescence experiments (NRF) were performed on {sup 110,111,112,114,116}Cd at the bremsstrahlung facility of the 4.3-MV Dynamitron accelerator in Stuttgart to study the low-lying dipole strength distributions in these vibrational nuclei. Numerous excited states, most of them previously unknown, were observed in the excitation energy range up to 4 MeV. Detailed spectroscopic information has been obtained on excitation energies, spins, decay widths, decay branchings, and transition probabilities. For states in the even-even isotopes {sup 110,112,114,116}Cd, parities could be assigned from linear polarization measurements. Together with our previous results for {sup 108,112,113,114}Cd from NRF studies without polarization measurements, systematics was established for the dipole strength distributions of the stable nuclei within the Cd isotopic chain. The results are discussed with respect to the systematics of E1 two-phonon excitations and mixed-symmetry states in even-even nuclei near the Z=50 shell closure and the fragmentation of these excitation modes in the odd-mass Cd isotopes.

  2. Mechanisms of Mass-independent Fractionation of Sulfur Isotopes

    NASA Astrophysics Data System (ADS)

    Lyons, J. R.

    2006-05-01

    Sulfur mass-independent fractionation (MIF) is believed to arise from gas-phase atmospheric reactions involving SO2 and H2S [1]. However, a quantitative understanding of the mechanisms remains elusive. Here I will discuss two MIF mechanisms for sulfur isotopes, and use existing laboratory data to place constraints on these mechanisms. The relevant laboratory data includes the following: 1) Photolysis of H2S [2]; 2) spark discharge of SO2 [3]; 3) SO2 photolysis from 190-210 nm [3]; 4) SO2 photolysis at wavelengths > 220 nm [4]. Experiments 1 and 2 yielded elemental sulfur (Sel) that exhibited primarily mass-dependent fractionation, while experiment 3 produced Sel with a large MIF signature, and experiment 4 yielded sulfate with a smaller MIF signature. One likely MIF mechanism is intramolecular disequilibrium (or non-RRKM) effects, as proposed for O + O2 -- > O3 [5]. The isoelectronic sulfur reaction, S + S2 --> S3, may also exhibit non-RRKM effects, but for several reasons that I will discuss such effects may either be reduced in magnitude or of negligible importance. A second possible source of MIF is isotope-selective photodissociation during predissociation. This process is likely in SO and SH, may occur in SO2, and unlikely in H2S, but in all cases depends on wavelength. SO2 dissociation is also likely to depend on the oxygen isotopes present, because an O isotope substitution will change SO2 symmetry. Although this may produce a MIF signature in oxygen isotopes, it's not clear that this would be accompanied by a MIF effect in S. I will present kinetics simulations of the above H2S and SO2 photolysis experiments, and show how it is possible to use the results of these experiments to constrain the mechanism of MIF for atmospheric sulfur species. For example, simulations of Sel formation by H2S photolysis predict little MIF in experiments, but possible MIF in the atmosphere. [1] J. Farquhar et al. (2000) Science 289 756-758. [2] J. Farquhar et al. (2000) Nature

  3. Seven Channel Multi-collector Isotope Ratio Mass Spectrometer

    SciTech Connect

    Anthony D. Appelhans

    2008-07-01

    A new magnetic sector mass spectrometer that utilizes seven full-sized discrete dynode electron multipliers operating simultaneously has been designed, constructed and is in preliminary testing. The instrument utilizes a newly developed ion dispersion lens that enables the mass dispersed individual isotope beams to be separated sufficiently (35 mm) to allow a full-sized discrete dynode pulse counting multiplier to be used for each beam. The ion dispersion lens is a two element electrostatic 90 degree sector device that causes the beam-to-beam dispersion to increase faster than the intra-beam dispersion. Each multiplier is contained in an isolated case with a deflector/condenser lens at the entrance. A 9-sample filament cartridge is mounted on a micro-manipulator two-axis stage that enables adjustment of the filament position with 10 micron resolution within the ion lens. Results of initial testing with actinides will be presented.

  4. Accurate mass determination of short-lived isotopes by a tandem Penning-trap mass spectrometer

    SciTech Connect

    Stolzenberg, H.; Becker, S.; Bollen, G.; Kern, F.; Kluge, H.; Otto, T.; Savard, G.; Schweikhard, L. ); Audi, G. ); Moore, R.B. ); The ISOLDE Collaboration

    1990-12-17

    A mass spectrometer consisting of two Penning traps has been set up for short-lived isotopes at the on-line mass separator ISOLDE at CERN. The ion beam is collected and cooled in the first trap. After delivery to the second trap, high-accuracy direct mass measurements are made by determining the cyclotron frequency of the stored ions. Measurements have been performed for {sup 118}Cs--{sup 137}Cs. A resolving power of over 10{sup 6} and an accuracy of 1.4{times}10{sup {minus}7} have been achieved, corresponding to about 20 keV.

  5. High-precision masses of neutron-deficient rubidium isotopes using a Penning trap mass spectrometer

    SciTech Connect

    Kellerbauer, A.; Audi, G.; Guenaut, C.; Lunney, D.; Beck, D.; Herfurth, F.; Kluge, H.-J.; Weber, C.; Yazidjian, C.; Blaum, K.; Bollen, G.; Schwarz, S.; Herlert, A.; Schweikhard, L.

    2007-10-15

    The atomic masses of the neutron-deficient radioactive rubidium isotopes {sup 74-77,79,80,83}Rb have been measured with the Penning trap mass spectrometer ISOLTRAP. Using the time-of-flight cyclotron resonance technique, relative mass uncertainties ranging from 1.6x10{sup -8} to 5.6x10{sup -8} were achieved. In all cases, the mass precision was significantly improved as compared with the prior Atomic-Mass Evaluation; no significant deviations from the literature values were observed. The exotic nuclide {sup 74}Rb, with a half-life of only 65 ms, is the shortest-lived nuclide on which a high-precision mass measurement in a Penning trap has been carried out. The significance of these measurements for a check of the conserved-vector-current hypothesis of the weak interaction and the unitarity of the Cabibbo-Kobayashi-Maskawa matrix is discussed.

  6. A New Multi Collector Isotope Ratio Mass Spectrometer

    NASA Astrophysics Data System (ADS)

    Appelhans, A. D.; Olson, J. E.; Ward, M. B.; Dahl, D. A.

    2007-12-01

    With the goal of improving the sensitivity of isotope ratio measurements, particularly for actinides, a new magnetic sector mass spectrometer that utilizes up to seven full-sized discrete dynode electron multipliers operating simultaneously has been designed, constructed and is in the early stages of testing. The design is based on a newly developed ion dispersion lens that enables the mass dispersed individual isotope beams to be separated by 35 mm; this allows a full-sized discrete dynode pulse counting multiplier to be used for each beam. The ion dispersion lens (US patents 6,297,501 and pending) is a two element electrostatic 90 degree sector device that causes the beam-to-beam dispersion to increase faster than the intra-beam dispersion. Each of the multipliers is housed in an isolated case and is equipped with a deflector/condenser lens at the entrance to optimize pulse generation. The instrument includes a 9-sample filament cartridge mounted on a micro-manipulator X-Y stage that enables adjustment of the filament position with 10 micron resolution within the ion lens. Initial testing has shown that the instrument is performing as predicted by the ion optics model of the design.

  7. Mass Independent Fractionation of Hg Isotopes Preserved in the Precambrian

    NASA Astrophysics Data System (ADS)

    Thibodeau, A. M.; Bergquist, B. A.; Kah, L. C.; Ono, S.; Ghosh, S.; Hazen, R. M.

    2013-12-01

    Mercury (Hg) is a photochemically active, redox-sensitive, chalcophilic metal with complex biogeochemistry that displays a wide range of mass-dependent (MDF) and mass-independent (MIF) stable isotopic fractionation. In the past decade, Hg isotopes have emerged as important tracers of both the sources and cycling of Hg in the modern environment. However, their utility as environmental proxies in ancient rocks remains largely unexplored. The potential of Hg isotopes to inform Precambrian environments derives from the observation that Hg isotopes with odd atomic mass numbers (199Hg and 201Hg) undergo large MIF by the magnetic isotope effect (MIE) and smaller MIF through the nuclear volume effect (NVE). Small MIF produced via NVE has been observed for numerous transformations and is characterized by MIF ratios (Δ199Hg/Δ201Hg) of about 1.6. Large Hg-MIF driven by MIE has been observed during photochemical transformations and is characterized by Δ199Hg/Δ201Hg ratios between 1 and 1.3. This MIF signal is sensitive to a range of environmental conditions, including the amount and type of solar radiation, the presence and type of complexing organic ligands, and the Hg/dissolved organic carbon (DOC) ratio. Thus, it is hoped that Hg-MIF signals may indirectly record changes in atmospheric composition or seawater chemistry if preserved in marine sedimentary records. Previous work has clearly demonstrated that Hg-MIF signals are preserved in Archean and Paleoproterozoic marine shales and massive sulfide deposits. Here, we present evidence that such signals are also preserved in marine shales of mid-Proterozoic age, including the ~1.3 Ga Sulky formation (Dismal Lakes Group, NW Arctic), the ~1.45 Ga Greyson Shale (Belt Basin, Montana), and the ~1.5 Ga Katalsy formation (Kypry Group, Eastern European Platform). We observe that the Greyson shale and shales within the Sulky formation yield negative Hg-MIF with Δ199Hg/Δ201Hg ratios close to 1 and that Kaltasy group sediments

  8. Mass Dependence of Iron Isotope Fractionation in Fe(II)-Fe(III) Electron Exchange Equilibration

    NASA Astrophysics Data System (ADS)

    Fujii, Yasuhiko; Kim, Sang-Ho; Nomura, Masao; Kawakami, Fumiaki

    2013-02-01

    A one hundred meter long ion-exchange chromatograph was used to establish rigorously the mass effects in the iron isotope fractionation in the Fe(II)-Fe(III) electron exchange equilibration.We used a highly porous, strongly basic anion exchange resin packed in glass columns. The abundance ratios of all natural iron isotopes, 54Fe, 56Fe, 57Fe, and 58Fe, in the effluent at the iron adsorption band boundary were measured with a mass spectrometer. The enrichment correlations among these isotopes were analyzed by three-isotope plots. The results clearly showed that the isotope fractionation of Fe(II)-Fe(III) is governed by the normal mass effect; the iron isotope fractionation is not proportional to the nuclear size, but proportional to the reduced mass difference of the pair of iron isotopes.

  9. Cooling of radioactive isotopes for Schottky mass spectrometry

    SciTech Connect

    Steck, M.; Beckert, K.; Eickhoff, H.; Franzke, B.; Nolden, F.; Reich, H.; Schlitt, B.; Winkler, T.

    1999-01-15

    Nuclear masses of radioactive isotopes can be determined by measurement of their revolution frequency relative to the revolution frequency of reference ions with well-known masses. The resolution of neighboring frequency lines and the accuracy of the mass measurement is dependent on the achievable minimum longitudinal momentum spread of the ion beam. Electron cooling allows an increase of the phase space density by several orders of magnitude. For high intensity beams Coulomb scattering in the dense ion beam limits the beam quality. For low intensity beams a regime exists in which the diffusion due to intrabeam scattering is not dominating any more. The minimum momentum spread {delta}p/p=5x10{sup -7} which is observed by Schottky noise analysis is considerably higher than the value expected from the longitudinal electron temperature. The measured frequency spread results from fluctuations of the magnetic field in the storage ring magnets. Systematic mass measurements have started and can be presently used for ions with half-lives of some ten seconds. For shorter-lived nuclei a stochastic precooling system is in preparation.

  10. Quantitative measurement of immunoglobulins and free light chains using mass spectrometry.

    PubMed

    VanDuijn, Martijn M; Jacobs, Joannes F M; Wevers, Ron A; Engelke, Udo F; Joosten, Irma; Luider, Theo M

    2015-08-18

    Serum free light chain (sFLC) assays are well established in the diagnosis and monitoring of plasma cell disorders. However, current FLC immunoassays are subject to several analytical issues, which results in a lack of harmonized results. To facilitate sFLC standardization, we investigated the strengths and limitations of mass spectrometry as a novel technological platform for sFLC quantification. Stable isotope labeled reference peptides are added to serum samples for quantitation by selected reaction monitoring (SRM). The use of redundant peptide sets allows for quality control measures during data analysis. Measurements on serum provide information on intact immunoglobulins, but depletion of these intact molecules from the sera during sample processing permits the quantitation of sFLC. sFLC concentrations measured with SRM were comparable to those obtained by nephelometry and showed excellent linearity (r(2) > 0.99). In samples with high levels of sFLC, SRM data was more consistent with serum protein electrophoresis than nephelometric data and SRM is unaffected by antigen excess. The lower limits of quantitation were 3.8 and 2.7 mg/L for κ and λ sFLC. Errors due to polymorphic sequences were prevented by comparison of redundant peptide pairs. The application of stable isotope labeling combined with SRM can overcome many of the current potential analytical issues of sFLC analysis. We describe which hurdles still need to be taken to make SRM a robust and more accurate method for sFLC measurements. PMID:26168337

  11. Nitrogen isotopic analyses by isotope-ratio-monitoring gas chromatography/mass spectrometry

    NASA Technical Reports Server (NTRS)

    Merritt, D. A.; Hayes, J. M.

    1994-01-01

    Amino acids containing natural-abundance levels of 15N were derivatized and analyzed isotopically using a technique in which individual compounds are separated by gas chromatography, combusted on-line, and the product stream sent directly to an isotope-ratio mass spectrometer. For samples of N2 gas, standard deviations of ratio measurement were better than 0.1% (Units for delta are parts per thousand or per million (%).) for samples larger than 400 pmol and better than 0.5% for samples larger than 25 pmol (0.1% 15N is equivalent to 0.00004 atom % 15N). Results duplicated those of conventional, batchwise analyses to within 0.05%. For combustion of organic compounds yielding CO2/N2 ratios between 14 and 28, in particular for N-acetyl n-propyl derivatives of amino acids, delta values were within 0.25% of results obtained using conventional techniques and standard deviations were better than 0.35%. Pooled data for measurements of all amino acids produced an accuracy and precision of 0.04 and 0.23%, respectively, when 2 nmol of each amino acid was injected on column and 20% of the stream of combustion products was delivered to the mass spectrometer.

  12. Stable nitrogen isotope ratios and accumulation of various HOCs in northern Baltic aquatic food chains

    SciTech Connect

    Broman, D.; Axelman, J.; Bergqvist, P.A.; Naef, C.; Rolff, C.; Zebuehr, Y.

    1995-12-31

    Ratios of naturally occurring stable isotopes of nitrogen ({delta}{sup 15}N) can be used to numerically classify trophic levels of organisms in food chains. By combining analyses results of various HOCs (e.g. PCDD/Fs, PCBs, DDTs, HCHs and some other pesticides) the biomagnification of these substances can be quantitatively estimated. In this paper different pelagic and benthic northern Baltic food chains were studied. The {delta}{sup 15}N-data gave food chain descriptions qualitatively consistent with previous conceptions of trophic arrangements in the food chains. The different HOCs concentrations were plotted versus the {delta}{sup 15}N-values for the different trophic levels and an exponential model of the form e{sup (A+B*{delta}N)} was fitted to the data. The estimates of the constant B in the model allows for an estimation of a biomagnification power (B) of different singular, or groups of, contaminants. A B-value around zero indicates that a substance is flowing through the food chain without being magnified, whereas a value > 0 indicates that a substance is biomagnified. Negative B-values indicate that a substance is not taken up or is metabolized. The A-term of the expression is only a scaling factor depending on the background level of the contaminant.

  13. Microbial mass-dependent fractionation of chromium isotopes

    USGS Publications Warehouse

    Sikora, E.R.; Johnson, T.M.; Bullen, T.D.

    2008-01-01

    Mass-dependent fractionation of Cr isotopes occurs during dissimilatory Cr(VI) reduction by Shewanella oneidensis strain MR-1. Cells suspended in a simple buffer solution, with various concentrations of lactate or formate added as electron donor, reduced 5 or 10 ??M Cr(VI) to Cr(III) over days to weeks. In all nine batch experiments, 53Cr/52Cr ratios of the unreacted Cr(VI) increased as reduction proceeded. In eight experiments covering a range of added donor concentrations up to 100 ??M, isotopic fractionation factors were nearly invariant, ranging from 1.0040 to 1.0045, with a mean value somewhat larger than that previously reported for abiotic Cr(VI) reduction (1.0034). One experiment containing much greater donor concentration (10 mM lactate) reduced Cr(VI) much faster and exhibited a lesser fractionation factor (1.0018). These results indicate that 53Cr/52Cr measurements should be effective as indicators of Cr(VI) reduction, either bacterial or abiotic. However, variability in the fractionation factor is poorly constrained and should be studied for a variety of microbial and abiotic reduction pathways. ?? 2008 Elsevier Ltd.

  14. Isotopic mass and alpha heating effects in TFTR DT plasmas

    SciTech Connect

    Budny, R.V.; Bell, M.G.; Mansfield, D.K.

    1994-09-01

    Sets of similar TFTR discharges with varying amounts of D and T are compared. The T content is altered by varying the mix of D and T NBI at approximately constant total NBI power. The total plasma current, toroidal field, central Z{sub eff}, and wall conditions are very similar in each set. The electron density profiles are approximately similar. The sets contain pairs of discharges with D-only and DT-NBI. Several sets also contain discharges with T-only NBI. The discharges are analyzed using the TRANSP plasma analysis code. Good agreement with measured parameters is achieved. Profiles are computed for the isotopic mass of the hydrogenic thermal species A, and for the hydrogenic thermal plus beam species A{sub tot}. Their volume averages increase approximately linearly as the fraction of T-NBI power increases, and they are slightly peaked for DT and T-only NBI discharges. The total energy and the total energy confinement time increase approximately linearly with A{sub tot} up to 30%. The beam fraction of the total energy at 0.5 sec of NBI remains relatively constant, {approx} 40--50% as A{sub tot} varies. The thermal ion fraction increases slightly, and the electron fraction decreases. The isotopic and alpha heating effects contribute in roughly equal amounts to the increase in central T{sub e}.

  15. Isotope mass and charge effects in tokamak plasmas

    SciTech Connect

    Pusztai, I.; Candy, J.; Gohil, P.

    2011-12-15

    The effect of primary ion species of differing charge and mass - specifically, deuterium, hydrogen, and helium - on instabilities and transport is studied in DIII-D plasmas through gyrokinetic simulations with gyro [J. Candy and E. Belli, General Atomics Technical Report No. GA-A26818, 2010]. In linear simulations under imposed similarity of the profiles, there is an isomorphism between the linear growth rates of hydrogen isotopes, but the growth rates are higher for Z > 1 main ions due to the appearance of the charge in the Poisson equation. On ion scales the most significant effect of the different electron-to-ion mass ratio appears through collisions stabilizing trapped electron modes. In nonlinear simulations, significant favorable deviations from pure gyro-Bohm scaling are found due to electron-to-ion mass ratio effects and collisions. The presence of any non-trace impurity species cannot be neglected in a comprehensive simulation of the transport; including carbon impurity in the simulations caused a dramatic reduction of energy fluxes. The transport in the analyzed deuterium and helium discharges could be well reproduced in gyrokinetic and gyrofluid simulations while the significant hydrogen discrepancy is the subject of ongoing investigation.

  16. First observation of a mass independent isotopic fractionation in a condensation reaction

    NASA Technical Reports Server (NTRS)

    Thiemens, M. H.; Nelson, R.; Dong, Q. W.; Nuth, Joseph A., III

    1994-01-01

    Thiemens and Heidenreich (1983) first demonstrated that a chemically produced mass independent isotopic fractionation process could produce an isotopic composition which is identical to that observed in Allende inclusions. This raised the possibility that the meteoritic components could be produced by chemical, rather than nuclear processes. In order to develop a mechanistic model of the early solar system, it is important that relevant reactions be studied, particularly, those which may occur in the earliest condensation reactions. The isotopic results for isotopic fractionations associated with condensation processes are reported. A large mass independent isotopic fractionation is observed in one of the experiments.

  17. Secondary ionization mass spectrometric analysis of impurity element isotope ratios in nuclear reactor materials

    NASA Astrophysics Data System (ADS)

    Gerlach, D. C.; Cliff, J. B.; Hurley, D. E.; Reid, B. D.; Little, W. W.; Meriwether, G. H.; Wickham, A. J.; Simmons, T. A.

    2006-07-01

    During reactor operations and fuel burn up, some isotopic abundances change due to nuclear reactions and provide sensitive indicators of neutron fluence and fuel burnup. Secondary ion mass spectrometry (SIMS) analysis has been used to measure isotope ratios of selected impurity elements in irradiated nuclear reactor graphite. Direct SIMS measurements were made in graphite samples, following shaping and surface cleaning. Models predicting local fuel burnup based on isotopic measurements of B and Li isotopes by SIMS agreed well with U and Pu isotopic measurements obtained by thermal ionization mass spectrometry (TIMS).

  18. Isospin dependence of mass-distribution shape of fission fragments of Hg isotopes

    NASA Astrophysics Data System (ADS)

    Andreev, A. V.; Adamian, G. G.; Antonenko, N. V.; Andreyev, A. N.

    2013-10-01

    Using an improved scission-point model, the mass distributions are calculated for induced fission of even Hg isotopes with mass numbers A=174to196. With increasing A of a fissioning AHg nucleus the mass distribution evolves from symmetric for 174Hg, to asymmetric for isotopes close to 180Hg, and back to more symmetric for 192,194,196Hg. In the fissioning Hg isotopes their excitation energy weakly influences the shape of the mass distribution. In 180,184Hg, the mass distributions of fission fragments remain asymmetric even at high excitation energies.

  19. Introduction to Chemistry and Applications in Nature of Mass Independent Isotope Effects Special Feature

    PubMed Central

    Thiemens, Mark H.

    2013-01-01

    Stable isotope ratio variations are regulated by physical and chemical laws. These rules depend on a relation with mass differences between isotopes. New classes of isotope variation effects that deviate from mass dependent laws, termed mass independent isotope effects, were discovered in 1983 and have a wide range of applications in basic chemistry and nature. In this special edition, new applications of these effects to physical chemistry, solar system origin models, terrestrial atmospheric and biogenic evolution, polar paleo climatology, snowball earth geology, and present day atmospheric sciences are presented. PMID:24167299

  20. Mass-Dependent and -Independent Fractionation of Hg Isotopes by Photoreduction in Aquatic Systems

    NASA Astrophysics Data System (ADS)

    Bergquist, Bridget A.; Blum, Joel D.

    2007-10-01

    Mercury (Hg) isotopes can be used as tracers of Hg biogeochemical pathways in the environment. The photochemical reduction of aqueous Hg species by natural sunlight leads to both mass-dependent fractionation (MDF) of Hg isotopes and mass-independent fractionation (MIF) of the odd-mass isotopes, with the relation between the MIF for the two odd isotopes being distinct for different photoreduction pathways. Large variations in MDF and MIF are observed in fish and provide new insights into the sources and bioaccumulation of Hg in food webs. MIF in fish can also be used to estimate the loss of methylmercury via photoreduction in aquatic ecosytems.

  1. Introduction to chemistry and applications in nature of mass independent isotope effects special feature.

    PubMed

    Thiemens, Mark H

    2013-10-29

    Stable isotope ratio variations are regulated by physical and chemical laws. These rules depend on a relation with mass differences between isotopes. New classes of isotope variation effects that deviate from mass dependent laws, termed mass independent isotope effects, were discovered in 1983 and have a wide range of applications in basic chemistry and nature. In this special edition, new applications of these effects to physical chemistry, solar system origin models, terrestrial atmospheric and biogenic evolution, polar paleo climatology, snowball earth geology, and present day atmospheric sciences are presented. PMID:24167299

  2. Iron-Isotopic Fractionation Studies Using Multiple Collector Inductively Coupled Plasma Mass Spectrometry

    NASA Technical Reports Server (NTRS)

    Anbar, A. D.; Zhang, C.; Barling, J.; Roe, J. E.; Nealson, K. H.

    1999-01-01

    The importance of Fe biogeochemistry has stimulated interest in Fe isotope fractionation. Recent studies using thermal ionization mass spectrometry (TIMS) and a "double spike" demonstrate the existence of biogenic Fe isotope effects. Here, we assess the utility of multiple-collector inductively-coupled plasma mass spectrometry(MC-ICP-MS) with a desolvating sample introduction system for Fe isotope studies, and present data on Fe biominerals produced by a thermophilic bacterium. Additional information is contained in the original extended abstract.

  3. Using Punnett Squares to Facilitate Students' Understanding of Isotopic Distributions in Mass Spectrometry

    ERIC Educational Resources Information Center

    Sein, Lawrence T., Jr.

    2006-01-01

    The isotopic distribution in mass spectroscopy is described for identifying pure compounds, being able to distinguish molecular fragments by masses. Punnett squares are familiar, easy to compute, and often graphical which makes helpful to students and the relative distribution of isotopic combination is easily generated for even isotopic…

  4. Carbon isotopic analysis of atmospheric methane by isotope-ratio-monitoring gas chromatography-mass spectrometry

    NASA Technical Reports Server (NTRS)

    Merritt, Dawn A.; Hayes, J. M.; Des Marais, David J.

    1995-01-01

    Less than 15 min are required for the determination of delta C(sub PDB)-13 with a precision of 0.2 ppt(1 sigma, single measurement) in 5-mL samples of air containing CH4 at natural levels (1.7 ppm). An analytical system including a sample-introduction unit incorporating a preparative gas chromatograph (GC) column for separation of CH4 from N2, O2, and Ar is described. The 15-min procedure includes time for operation of that system, high-resolution chromatographic separation of the CH4, on-line combustion and purification of the products, and isotopic calibration. Analyses of standards demonstrate that systematic errors are absent and that there is no dependence of observed values of delta on sample size. For samples containing 100 ppm or more CH4, preconcentration is not required and the analysis time is less than 5 min. The system utilizes a commercially available, high-sensitivity isotope-ratio mass spectrometer. For optimal conditions of smaple handling and combustion, performance of the system is within a factor of 2 of the shot-noise limit. The potential exists therefore for analysis of samples as small as 15 pmol CH4 with a standard deviation of less than 1 ppt.

  5. Isotope mass and charge effects in tokamak plasmas

    NASA Astrophysics Data System (ADS)

    Pusztai, I.; Candy, J.; Gohil, P.

    2011-12-01

    The effect of primary ion species of differing charge and mass—specifically, deuterium, hydrogen, and helium—on instabilities and transport is studied in DIII-D plasmas through gyrokinetic simulations with gyro [J. Candy and E. Belli, General Atomics Technical Report No. GA-A26818, 2010]. In linear simulations under imposed similarity of the profiles, there is an isomorphism between the linear growth rates of hydrogen isotopes, but the growth rates are higher for Z > 1 main ions due to the appearance of the charge in the Poisson equation. On ion scales the most significant effect of the different electron-to-ion mass ratio appears through collisions stabilizing trapped electron modes. In nonlinear simulations, significant favorable deviations from pure gyro-Bohm scaling are found due to electron-to-ion mass ratio effects and collisions. The presence of any non-trace impurity species cannot be neglected in a comprehensive simulation of the transport; including carbon impurity in the simulations caused a dramatic reduction of energy fluxes. The transport in the analyzed deuterium and helium discharges could be well reproduced in gyrokinetic and gyrofluid simulations while the significant hydrogen discrepancy is the subject of ongoing investigation.

  6. Quantitation of DNA adducts by stable isotope dilution mass spectrometry

    PubMed Central

    Tretyakova, Natalia; Goggin, Melissa; Janis, Gregory

    2012-01-01

    Exposure to endogenous and exogenous chemicals can lead to the formation of structurally modified DNA bases (DNA adducts). If not repaired, these nucleobase lesions can cause polymerase errors during DNA replication, leading to heritable mutations potentially contributing to the development of cancer. Due to their critical role in cancer initiation, DNA adducts represent mechanism-based biomarkers of carcinogen exposure, and their quantitation is particularly useful for cancer risk assessment. DNA adducts are also valuable in mechanistic studies linking tumorigenic effects of environmental and industrial carcinogens to specific electrophilic species generated from their metabolism. While multiple experimental methodologies have been developed for DNA adduct analysis in biological samples – including immunoassay, HPLC, and 32P-postlabeling – isotope dilution high performance liquid chromatography-electrospray ionization-tandem mass spectrometry (HPLC-ESI-MS/MS) generally has superior selectivity, sensitivity, accuracy, and reproducibility. As typical DNA adducts concentrations in biological samples are between 0.01 – 10 adducts per 108 normal nucleotides, ultrasensitive HPLC-ESI-MS/MS methodologies are required for their analysis. Recent developments in analytical separations and biological mass spectrometry – especially nanoflow HPLC, nanospray ionization MS, chip-MS, and high resolution MS – have pushed the limits of analytical HPLC-ESI-MS/MS methodologies for DNA adducts, allowing researchers to accurately measure their concentrations in biological samples from patients treated with DNA alkylating drugs and in populations exposed to carcinogens from urban air, drinking water, cooked food, alcohol, and cigarette smoke. PMID:22827593

  7. Reduction of determinate errors in mass bias-corrected isotope ratios measured using a multi-collector plasma mass spectrometer

    NASA Astrophysics Data System (ADS)

    Doherty, W.

    2015-05-01

    A nebulizer-centric instrument response function model of the plasma mass spectrometer was combined with a signal drift model, and the result was used to identify the causes of the non-spectroscopic determinate errors remaining in mass bias-corrected Pb isotope ratios (Tl as internal standard) measured using a multi-collector plasma mass spectrometer. Model calculations, confirmed by measurement, show that the detectable time-dependent errors are a result of the combined effect of signal drift and differences in the coordinates of the Pb and Tl response function maxima (horizontal offset effect). If there are no horizontal offsets, then the mass bias-corrected isotope ratios are approximately constant in time. In the absence of signal drift, the response surface curvature and horizontal offset effects are responsible for proportional errors in the mass bias-corrected isotope ratios. The proportional errors will be different for different analyte isotope ratios and different at every instrument operating point. Consequently, mass bias coefficients calculated using different isotope ratios are not necessarily equal. The error analysis based on the combined model provides strong justification for recommending a three step correction procedure (mass bias correction, drift correction and a proportional error correction, in that order) for isotope ratio measurements using a multi-collector plasma mass spectrometer.

  8. Comparison of thermal ionization mass spectrometry and Multiple Collector Inductively Coupled Plasma Mass Spectrometry for cesium isotope ratio measurements

    NASA Astrophysics Data System (ADS)

    Isnard, H.; Granet, M.; Caussignac, C.; Ducarme, E.; Nonell, A.; Tran, B.; Chartier, F.

    2009-11-01

    In the nuclear domain, precise and accurate isotopic composition determination of elements in spent nuclear fuels is mandatory to validate neutron calculation codes and for nuclear waste disposal. The present study presents the results obtained on Cs isotope ratio by mass spectrometric measurements. Natural cesium is monoisotopic ( 133Cs) whereas cesium in spent fuels has 4 isotopes ( 133Cs, 134Cs, 135Cs, and 137Cs). As no standard reference material is available to evaluate the accuracy of Cs isotopic measurements, a comparison of cesium isotopic composition in spent nuclear fuels has been performed between Thermal Ionization Mass Spectrometry (TIMS) and a new method involving Multiple Collector Inductively Coupled Plasma Mass Spectrometry (MC-ICPMS) measurements. For TIMS measurements, isotopic fractionation has been evaluated by studying the behavior of cesium isotope ratios ( 133Cs/ 137Cs and 135Cs/ 137Cs) during the analyses. For MC-ICPMS measurements, the mass bias effects have been corrected with an external mass bias correction using elements (Eu and Sb) close to cesium masses. The results obtained by the two techniques show good agreement: relative difference on 133Cs/ 137Cs and 135Cs/ 137Cs ratios for two nuclear samples, analyzed after chemical separation, ranges from 0.2% to 0.5% depending on the choice of reference value for mass bias correction by MC-ICPMS. Finally the quantification of the 135Cs/ 238U ratio by the isotope dilution technique is presented in the case of a MOx (mixed oxide) spent fuel sample. Evaluation of the global uncertainties shows that this ratio could be defined at an uncertainty of 0.5% ( k = 2). The intercomparison between two independent mass spectrometric techniques is fundamental for the evaluation of uncertainty when no isotopic standard is available.

  9. Mass dependent stable isotope fractionation of mercury during mer mediated microbial degradation of monomethylmercury

    NASA Astrophysics Data System (ADS)

    Kritee, K.; Barkay, Tamar; Blum, Joel D.

    2009-03-01

    Controlling bioaccumulation of toxic monomethylmercury (MMHg) in aquatic food chains requires differentiation between biotic and abiotic pathways that lead to its production and degradation. Recent mercury (Hg) stable isotope measurements of natural samples suggest that Hg isotope ratios can be a powerful proxy for tracing dominant Hg transforming pathways in aquatic ecosystems. Specifically, it has been shown that photo-degradation of MMHg causes both mass dependent (MDF) and mass independent fractionation (MIF) of Hg isotopes. Because the extent of MDF and MIF observed in natural samples (e.g., fish, soil and sediments) can potentially be used to determine the relative importance of pathways leading to MMHg accumulation, it is important to determine the potential role of microbial pathways in contributing to the fractionation, especially MIF, observed in these samples. This study reports the extent of fractionation of Hg stable isotopes during degradation of MMHg to volatile elemental Hg and methane via the microbial Hg resistance ( mer) pathway in Escherichia coli carrying a mercury resistance ( mer) genetic system on a multi-copy plasmid. During experimental microbial degradation of MMHg, MMHg remaining in reactors became progressively heavier (increasing δ202Hg) with time and underwent mass dependent Rayleigh fractionation with a fractionation factor α202/198 = 1.0004 ± 0.0002 (2SD). However, MIF was not observed in any of the microbial MMHg degradation experiments indicating that the isotopic signature left by mer mediated MMHg degradation is significantly different from fractionation observed during DOC mediated photo-degradation of MMHg. Additionally, a clear suppression of Hg isotope fractionation, both during reduction of Hg(II) and degradation of MMHg, was observed when the cell densities increased, possibly due to a reduction in substrate bioavailability. We propose a multi-step framework for understanding the extent of fractionation seen in our MMHg

  10. High-accuracy mass measurements of neutron-rich Kr isotopes

    SciTech Connect

    Delahaye, P.; Kellerbauer, A.; Audi, G.; Lunney, D.; Blaum, K.; George, S.; Carrel, F.; Herfurth, F.; Yazidjian, C.; Herlert, A.; Schweikhard, L.; Kluge, H.-J.

    2006-09-15

    The atomic masses of the neutron-rich krypton isotopes {sup 84,86-95}Kr have been determined with the tandem Penning trap mass spectrometer ISOLTRAP with uncertainties ranging from 20 to 220 ppb. The masses of the short-lived isotopes {sup 94}Kr and {sup 95}Kr were measured for the first time. The masses of the radioactive nuclides {sup 89}Kr and {sup 91}Kr disagree by 4 and 6 standard deviations, respectively, from the present Atomic-Mass Evaluation database. The resulting modification of the mass surface with respect to the two-neutron separation energies as well as implications for mass models and stellar nucleosynthesis are discussed.

  11. 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. )

  12. Phase transition studies of the odd-mass 123‑135Xe isotopes based on SU(1,1) algebra in IBFM

    NASA Astrophysics Data System (ADS)

    Jafarizadeh, M. A.; Fouladi, N.; Ghapanvari, M.; Fathi, H.

    2016-07-01

    In this paper, we have investigated the positive-parity states in the odd-mass transitional 123‑135Xe isotopes within the framework of the interacting boson-fermion model. Two solvable extended transitional Hamiltonians which are based on SU(1,1) algebra are employed to provide an investigation of quantum phase transition (QPT) between the spherical and deformed gamma — unstable shapes along the chain of Xe isotopes. The low-states energy spectra and B(E2) values for these nuclei have been calculated and compared with the experimental data. The predicted excitation energies and B(E2) transition rates of the odd isotopes are found to agree well with the experimental data. We have also analyzed the critical behavior of even-odd Xe isotopes via Catastrophe Theory in combination with a coherent state formalism to generate energy surfaces and special isotopes which are the best candidates for the critical point are identified.

  13. A case for in vivo mass-independent fractionation of mercury isotopes in fish

    NASA Astrophysics Data System (ADS)

    Das, Reshmi; Salters, Vincent J. M.; Odom, A. Leroy

    2009-11-01

    The recent discovery of mass-independent fractionation of mercury isotopes allows new constraints to be placed on the mercury cycle. Here we report new Hg isotopic analyses of zooplankton and fish from different trophic levels of a freshwater lake (Lake Jackson, Florida) bearing systematic mass-independent fractionation of mercury isotopes. Fish muscle tissues show a progressive enrichment in the odd-mass mercury isotopes having odd atomic mass numbers (199 and 201) with increasing trophic level. Trophic level was determined based on nitrogen isotopic composition as well as fish stomach content. Zooplankton in the lake contain mercury with Δ199Hg and Δ201Hg values of +0.43 (±0.07)‰ and +0.44 (±0.07)‰, respectively. The Δ199Hg values increase by ˜1‰ from ˜+0.4‰ in zooplankton, juvenile bluegill, and several other small fishes to Δ199Hg = +1.36‰ for the Florida gar, which is the top predator fish in the lake. Previous observations of odd-mass-number isotope enrichment of mercury have been explained by photoreduction and demethylation of methyl mercury in the water column or as isotope effects related to microbial methylation. However, our data and the data of Jackson et al. (2008) are also consistent with in vivo production of mass-independent fractionation. Considering the alternatives, mass-independent fractionation by metabolic processes is the most straightforward explanation for the mercury isotope data. There are two known mechanisms for mass-independent fractionation of mercury, i.e., the nuclear volume effect and the magnetic isotope effect. While the data are insufficient to serve as proof, the magnitude of the mass-independent effect and the nearly equal enrichment of 199Hg and 201Hg seem most suggestive of a magnetic isotope effect.

  14. Systematics of magnetic dipole strength in the stable even-mass Mo isotopes

    NASA Astrophysics Data System (ADS)

    Rusev, G.; Schwengner, R.; Dönau, F.; Erhard, M.; Frauendorf, S.; Grosse, E.; Junghans, A. R.; Käubler, L.; Kosev, K.; Kostov, L. K.; Mallion, S.; Schilling, K. D.; Wagner, A.; Garrel, H. Von; Kneissl, U.; Kohstall, C.; Kreutz, M.; Pitz, H. H.; Scheck, M.; Stedile, F.; Brentano, P. Von; Fransen, C.; Jolie, J.; Linnemann, A.; Pietralla, N.; Werner, V.

    2006-04-01

    The nuclides Mo92, Mo98, and Mo100 have been studied in photon-scattering experiments by using bremsstrahlung produced at an electron energy of 6 MeV at the ELBE accelerator of the Forschungszentrum Rossendorf and at electron energies from 3.2 to 3.8 MeV at the Dynamitron accelerator at the University of Stuttgart. Six dipole transitions in Mo98 and 19 in Mo100 were observed for the first time in the energy range from 2 to 4 MeV. The experimental results are compared with predictions of the shell model and with predictions of the quasiparticle random-phase approximation (QRPA) in a deformed basis. The latter show significant contributions of isovector-orbital and isovector-spin vibrations. The change of the magnetic dipole strength in the isotopic chain of the even-mass isotopes from Mo92 to Mo100 is discussed. The calculations within the QRPA are extrapolated to the particle-separation energies to estimate the possible influence of M1 strength on the stability of the nuclides against photodissociation in cosmic scenarios.

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

    NASA Astrophysics Data System (ADS)

    Fujii, T.; Moynier, F.; Albarède, F.

    2006-12-01

    The variation of the mean charge distribution in the nucleus with the neutron number of different isotopes induces a tenuous shift of the nuclear field. The mass fractionation induced during phase changes is irregular, notably with 'staggering' between odd and even masses, and becomes increasingly non-linear for neutron-rich isotopes. A strong correlation is observed between the deviation of the isotopic effects from the linear dependence with mass and the corresponding nuclear charge radii. We first demonstrated on a number of elements the existence of such mass-independent isotope fractionation in laboratory experiments of solvent extraction with a macrocyclic compound. The isotope ratios were analyzed by multiple-collector inductively coupled plasma mass spectrometry with a typical precision of <100 ppm. The isotopes of odd and even atomic masses are enriched in the solvent to an extent that closely follows the variation of their nuclear charge radii. The present results fit Bigeleisen's (1996) model, which is the standard mass-dependent theory modified to include a correction term named the nuclear field shift effect. For heavy elements like uranium, the mass-independent effect is important enough to dominate the mass-dependent effect. We subsequently set out to compare the predictions of Bigeleisen's theory with the isotopic anomalies found in meteorites. Some of these anomalies are clearly inconsistent with nucleosynthetic effects (either s- or r-processes). Isotopic variations of Mo and Ru in meteorites, especially in Allende (CV3), show a clear indication of nucleosynthetic components. However, the mass-independent anomaly of Ru observed in Murchison (CM2) is a remarkable exception which cannot be explained by the nucleosynthetic model, but fits the nuclear field shift theory extremely well. The abundances of the even atomic mass Te isotopes in the leachates of carbonaceous chondrites, Allende, Murchison, and Orgueil, fit a mass-dependent law well, but the

  16. The physical chemistry of mass-independent isotope effects and their observation in nature.

    PubMed

    Thiemens, Mark H; Chakraborty, Subrata; Dominguez, Gerardo

    2012-01-01

    Historically, the physical chemistry of isotope effects and precise measurements in samples from nature have provided information on processes that could not have been obtained otherwise. With the discovery of a mass-independent isotopic fractionation during the formation of ozone, a new physical chemical basis for isotope effects required development. Combined theoretical and experimental developments have broadened this understanding and extended the range of chemical systems where these unique effects occur. Simultaneously, the application of mass-independent isotopic measurements to an extensive range of both terrestrial and extraterrestrial systems has furthered the understanding of events such as solar system origin and evolution and planetary atmospheric chemistry, present and past. PMID:22475336

  17. Mass-dependent and -independent fractionation of isotopes in Ni and Pb chelate complex formation reactions

    NASA Astrophysics Data System (ADS)

    Nomura, Masao; Kudo, Takashi; Adachi, Atsuhiko; Aida, Masao; Fujii, Yasuhiko

    2013-11-01

    Mass independent fractionation (MIF) has been a very interesting topic in the field of inorganic isotope chemistry, in particular, geo- and cosmo- chemistry. In the present work, we studied the isotope fractionation of Ni(II) and Pb(II) ions in complex formation with chelating reagent EDTA. To obtain clear results on the mass dependence of the isotope fractionation, we have conducted long-distance ion exchange chromatography of Ni(II) and Pb(II), using chelate complex reagent EDTA. The results apparently show that the isotope fractionation in Ni complex formation system is governed by the mass dependent rule. On the other hand the isotope fractionation in the Pb complex system is governed by the mass independent rule or the nuclear volume effect.

  18. Mass-dependent and -independent fractionation of isotopes in Ni and Pb chelate complex formation reactions

    SciTech Connect

    Nomura, Masao; Kudo, Takashi; Adachi, Atsuhiko; Aida, Masao; Fujii, Yasuhiko

    2013-11-13

    Mass independent fractionation (MIF) has been a very interesting topic in the field of inorganic isotope chemistry, in particular, geo- and cosmo- chemistry. In the present work, we studied the isotope fractionation of Ni(II) and Pb(II) ions in complex formation with chelating reagent EDTA. To obtain clear results on the mass dependence of the isotope fractionation, we have conducted long-distance ion exchange chromatography of Ni(II) and Pb(II), using chelate complex reagent EDTA. The results apparently show that the isotope fractionation in Ni complex formation system is governed by the mass dependent rule. On the other hand the isotope fractionation in the Pb complex system is governed by the mass independent rule or the nuclear volume effect.

  19. Modelling food chain structure and contaminant bioaccumulation using stable nitrogen isotopes

    NASA Astrophysics Data System (ADS)

    Cabana, Gilbert; Rasmussen, Joseph B.

    1994-11-01

    THE nitrogen pools of animals are enriched in 15N relative to their food1, with the top predators having the highest concentrations of this stable isotope2. The use of δ15N to indicate trophic position depends on the degree to which it reflects variation in the underly-ing food-web structure, rather than variable fractionation along the food chain. Here we compare adult lake trout, a top pelagic predator, from a series of lakes, and find that δ15N values vary from 7.5 to 17.5%o, a surprisingly wide range for one species. The length of the food chain can explain this variation, supporting the idea that δ15N is a food-web descriptor. Food-chain length was measured by the presence or absence of two intermediate trophic levels, pelagic forage fish and the macrozooplankter, Mysis relicta, each of which when present contributes about three δ15N units to the trout signature. We find that δ15N can be used as a continuous, integrative measure of trophic position, which is supported by its correlation to mercury levels in lake trout.

  20. Lightning and Mass Independent Oxygen Isotopic Fractionation in Nebular Silicates

    NASA Technical Reports Server (NTRS)

    Nuth, Joseph A.

    2009-01-01

    Lightning has long been postulated as the agent of Chondru|e formation in the solar nebula, but it may have an additional role to play as well. Lightning bolts of almost any scale will both vaporize dust and liberate oxygen atoms that will then interact with both nebular gases as well as the refractory silicate vapor as it re-condenses. Such processes should result in the addition of the heavy oxygen isotopes to the growing silicate grains while the light oxygen-16 becomes part of the gas phase water. This process will proceed to some extent throughout the history of any turbulent nebula and will result in the gradual increase of O-16 in the gas phase and in a much larger relative increase in the O-17 and O-18 content of the nebular dust. Laboratory experiments have demonstrated the production of such "heavy oxygen enriched", non-mass-dependently-fractionated dust grains in a high voltage discharge in a hydrogen rich gas containing small quantities of silane, pentacarbonyl iron and oxygen.

  1. Mass spectrometric analysis of isotope effects in bioconversion of benzene to cyclohexanone

    NASA Astrophysics Data System (ADS)

    Nam, In-Hyun; Murugesan, Kumarasamy; Kim, Young-Mo; Yang, In-Hee; Chang, Yoon-Seok

    2006-06-01

    Pseudomonas veronii strain PH-03 has been shown to convert benzene to cyclohexanone through phenol. Mass spectrometry results revealed that unusual isotopic effects have been occurred in the transformation product, cyclohexanone. The isotopic composition was strongly depends on the compound specific hydrogen or oxygen source. The exchange of labile deuterium atoms has been investigated through electrospray ionization liquid chromatography mass spectrometry. The mass spectrometric analysis of biotransformation products enabled the proposal of a corresponding bioconversion pathway.

  2. Measurement of stable isotopic enrichment and concentration of long-chain fatty acyl-carnitines in tissue by HPLC-MS.

    PubMed

    Sun, Dayong; Cree, Melanie G; Zhang, Xiao-Jun; Bøersheim, Elisabet; Wolfe, Robert R

    2006-02-01

    We have developed a new method for the simultaneous measurements of stable isotopic tracer enrichments and concentrations of individual long-chain fatty acyl-carnitines in muscle tissue using ion-pairing high-performance liquid chromatography-electrospray ionization quadrupole mass spectrometry in the selected ion monitoring (SIM) mode. Long-chain fatty acyl-carnitines were extracted from frozen muscle tissue samples by acetonitrile/methanol. Baseline separation was achieved by reverse-phase HPLC in the presence of the volatile ion-pairing reagent heptafluorobutyric acid. The SIM capability of a single quadrupole mass analyzer allows further separation of the ions of interest from the sample matrixes, providing very clean total and selected ion chromatograms that can be used to calculate the stable isotopic tracer enrichment and concentration of long-chain fatty acyl-carnitines in a single analysis. The combination of these two separation techniques greatly simplifies the sample preparation procedure and increases the detection sensitivity. Applying this protocol to biological muscle samples proves it to be a very sensitive, accurate, and precise analytical tool. PMID:16301738

  3. Chemical and Isotopic Thresholds in Charring: Implications for the Interpretation of Charcoal Mass and Isotopic Data

    NASA Astrophysics Data System (ADS)

    Pyle, L.; Hockaday, W. C.; Boutton, T. W.; Zygourakis, K.; Kinney, T.; Masiello, C. A.

    2014-12-01

    Charcoal plays a significant role in the long-term carbon cycle and its use as a soil amendment is becoming a viable carbon sequestration strategy (biochar). One challenge in this research area has been comparing results between studies in part due to the diversity of lab and field production conditions. Although the highest treatment temperature (HTT) is often used to describe pyrolysis conditions, several studies have shown that length of time at the highest temperature can also cause changes to the physicochemical qualities of charcoal and ignoring this effect may introduce inter-comparison problems. Addressing this issue becomes especially important in the discussion of optimizing biochar for soil remediation and carbon sequestration, and in discussions of charcoal use in reconstructing past fire regimes, as increasing time at temperature may cause changes in charcoal properties similar to the changes caused by increasing HTT. Here we introduce a formal definition of charring intensity (CI) to more accurately characterize pyrolysis, and we document variation in this property with pyrolysis temperature and reaction duration. We found two types of responses to CI: either a linear or a threshold relationship. We show that a threshold exists where %C, %N and δ15N begin exhibiting large changes, and this CI threshold co-occurred with an increase in charcoal aromaticity. Mass yield decreased linearly with charring intensity and carbon isotopes did not change from original biomass values in our controlled laboratory experiments. Analysis of these data shows that pyrolysis parameters should be defined in the literature as a combination of temperature and duration conditions, and that biomass that has undergone pyrolysis may be influencing soil organic nitrogen. Additionally, the lack of alteration in carbon isotopes across our matrix supports the efficacy of using pyrolyzed material for archaeological reconstructions.

  4. A new series of uranium isotope reference materials for investigating the linearity of secondary electron multipliers in isotope mass spectrometry

    NASA Astrophysics Data System (ADS)

    Richter, S.; Alonso, A.; Aregbe, Y.; Eykens, R.; Kehoe, F.; Kühn, He; Kivel, N.; Verbruggen, A.; Wellum, R.; Taylor, P. D. P.

    2009-04-01

    A new series of gravimetrically prepared uranium isotope reference materials, the so-called IRMM-074 series, with the n(235U)/n(238U) isotope ratio held constant at unity and the n(233U)/n(238U) isotope ratios varying from 1.0 to 10-6 has been prepared and certified. This series is suited for calibration of secondary electron multipliers used widely in isotope mass spectrometry, in particular for techniques such as thermal ionization mass spectrometry (TIMS), inductively coupled plasma mass spectrometry (ICPMS), accelerator mass spectrometry (AMS) and resonance ionization mass spectrometry (RIMS). The new IRMM-074 was prepared as a replacement for the already exhausted IRMM-072 predecessor series. Uranium materials with high isotopic enrichments of 233U, 235U and 238U were purified using identical methods involving separation on anion and cation column followed by a precipitation as peroxide. The oxides were calcined to convert them to U3O8 simultaneously, in an oven installed in a glove-box that provided a controlled low-humidity environment. The oxides of 235U and 238U were weighed and mixed with a mole ratio n(235U)/n(238U) = 1.0 and then dissolved. The 233U oxide was dissolved to form a separate solution with the same concentration and 6rom this primary solution three dilutions were made by weighing. A weighed amount of the n(235U)/n(238U) solution and weighed amounts of the 233U solutions were mixed in various proportions in order to achieve n(233U)/n(238U) isotope ratios varying from 1.0 to 10-6. The methods for the preparation, the mixing and the mixing calculations are described. The expanded uncertainties (coverage factor k = 2) of the certified isotope ratios for the IRMM-074 series are 0.015% for the n(235U)/n(238U) ratio and 0.025% for the n(233U)/n(238U) ratios, which constitutes an improvement compared to those of the predecessor IRMM-072 series. In addition, recent observations regarding the linearity response of secondary electron multipliers (SEMs

  5. Chlorine isotope effects from isotope ratio mass spectrometry suggest intramolecular C-Cl bond competition in trichloroethene (TCE) reductive dehalogenation.

    PubMed

    Cretnik, Stefan; Bernstein, Anat; Shouakar-Stash, Orfan; Löffler, Frank; Elsner, Martin

    2014-01-01

    Chlorinated ethenes are prevalent groundwater contaminants. To better constrain (bio)chemical reaction mechanisms of reductive dechlorination, the position-specificity of reductive trichloroethene (TCE) dehalogenation was investigated. Selective biotransformation reactions (i) of tetrachloroethene (PCE) to TCE in cultures of Desulfitobacterium sp. strain Viet1; and (ii) of TCE to cis-1,2-dichloroethene (cis-DCE) in cultures of Geobacter lovleyi strain SZ were investigated. Compound-average carbon isotope effects were -19.0‰ ± 0.9‰ (PCE) and -12.2‰ ± 1.0‰ (TCE) (95% confidence intervals). Using instrumental advances in chlorine isotope analysis by continuous flow isotope ratio mass spectrometry, compound-average chorine isotope effects were measured for PCE (-5.0‰ ± 0.1‰) and TCE (-3.6‰ ± 0.2‰). In addition, position-specific kinetic chlorine isotope effects were determined from fits of reactant and product isotope ratios. In PCE biodegradation, primary chlorine isotope effects were substantially larger (by -16.3‰ ± 1.4‰ (standard error)) than secondary. In TCE biodegradation, in contrast, the product cis-DCE reflected an average isotope effect of -2.4‰ ± 0.3‰ and the product chloride an isotope effect of -6.5‰ ± 2.5‰, in the original positions of TCE from which the products were formed (95% confidence intervals). A greater difference would be expected for a position-specific reaction (chloride would exclusively reflect a primary isotope effect). These results therefore suggest that both vicinal chlorine substituents of TCE were reactive (intramolecular competition). This finding puts new constraints on mechanistic scenarios and favours either nucleophilic addition by Co(I) or single electron transfer as reductive dehalogenation mechanisms. PMID:24853618

  6. Carbon isotope ratio analysis of steroids by high-temperature liquid chromatography-isotope ratio mass spectrometry.

    PubMed

    Zhang, Lijun; Thevis, Mario; Piper, Thomas; Jochmann, Maik A; Wolbert, J Benjamin; Kujawinski, Dorothea M; Wiese, Steffen; Teutenberg, Thorsten; Schmidt, Torsten C

    2014-03-01

    Generally, compound-specific isotope analysis of steroids is carried out by gas chromatography combined with isotope ratio mass spectrometry. Thus, a derivatization of the steroids prior to the measurement is compulsory, and a correction of the isotopic data is often necessary. To overcome this limitation, we present a new approach of high-temperature liquid chromatography coupled with photodiode array detection and isotope ratio mass spectrometry (HT-LC/PDA/IRMS) for the carbon isotope ratio analysis of unconjugated steroids. A steroid mixture containing 19-norandrosterone, testosterone, epitestosterone, androsterone, and 5β-pregnane-3α,17α,20α-triol was fully separated on a C4 column under high-temperature elution with water as the sole eluent. The accuracy for isotope analysis (±0.5 ‰) was around 20 μg g(-1) for testosterone, epitestosterone (79 ng steroid absolute on column), and 30 μg g(-1) for 19-norandrosterone, androsterone, and 5β-pregnane-3α,17α,20α-triol (119 ng steroid absolute on column). The applicability of the method was tested by measuring a pharmaceutical gel containing testosterone. With this work, the scope of LC/IRMS applications has been extended to nonpolar compounds. PMID:24491121

  7. 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.

  8. Simultaneous stable carbon isotopic analysis of wine glycerol and ethanol by liquid chromatography coupled to isotope ratio mass spectrometry.

    PubMed

    Cabañero, Ana I; Recio, Jose L; Rupérez, Mercedes

    2010-01-27

    A novel procedure was established for the simultaneous characterization of wine glycerol and ethanol (13)C/(12)C isotope ratio, using liquid chromatography/isotope ratio mass spectrometry (LC-IRMS). Several parameters influencing separation of glycerol and ethanol from wine matrix were optimized. Results obtained for 35 Spanish samples exposed no significant differences and very strong correlations (r = 0.99) between the glycerol (13)C/(12)C ratios obtained by an alternative method (gas chromatography/isotope ratio mass spectrometry) and the proposed new methodology, and between the ethanol (13)C/(12)C ratios obtained by the official method (elemental analyzer/isotope ratio mass spectrometry) and the proposed new methodology. The accuracy of the proposed method varied from 0.01 to 0.19 per thousand, and the analytical precision was better than 0.25 per thousand. The new developed LC-IRMS method it is the first isotopic method that allows (13)C/(12)C determination of both analytes in the same run directly from a liquid sample with no previous glycerol or ethanol isolation, overcoming technical difficulties associated with complex sample treatment and improving in terms of simplicity and speed. PMID:20025274

  9. Leaf waxes in riparian trees: hydrogen isotopes, concentrations, and chain-length patterns

    NASA Astrophysics Data System (ADS)

    Tipple, B. J.; Ehleringer, J.; Doman, C.; Khachaturyan, S.

    2011-12-01

    The stable hydrogen isotope ratios of epicuticular leaf wax n-alkanes record aspects of a plant's ecophysiological conditions. However, it remains unclear as to whether n-alkane hydrogen isotope values (δ2H) directly reflect environmental water (source water or tissue water) or environmental water in combination with a biochemical fractionation. Furthermore, it is uncertain if leaf n-alkane δ2H values reflect a single time interval during leaf expansion or if n-alkane δ2H values record the combination of inputs throughout the entire lifespan of a leaf. These different possibilities will influence how leaf wax biomarkers are interpreted in both ecological and environmental reconstruction contexts. To address these issues, we sampled leaves/buds, stems, and water sources of five common western U.S. riparian species under natural field conditions throughout the growing season. Riparian species were selected because the input water source is most likely to be nearly constant through the growing season. We found that species in this study demonstrated marked and systematic variations in n-alkane concentration, average chain length, and δ2H values. Intraspecific patterns were consistent: average chain lengths and δ2H values increased from bud opening through full leaf expansion with little variation during the remainder of the sampling interval, while leaf-wax concentration as a fraction of total biomass increased throughout the growing season. These data imply that leaf-wax δ2H values reflect multiple periods of wax growth and that the leaf wax is continually produced throughout a leaf's lifespan.

  10. Analysis of the site-specific carbon isotope composition of propane by gas source isotope ratio mass spectrometer

    NASA Astrophysics Data System (ADS)

    Piasecki, Alison; Sessions, Alex; Lawson, Michael; Ferreira, A. A.; Neto, E. V. Santos; Eiler, John M.

    2016-09-01

    Site-specific isotope ratio measurements potentially provide valuable information about the formation and degradation of complex molecules-information that is lost in conventional bulk isotopic measurements. Here we discuss the background and possible applications of such measurements, and present a technique for studying the site-specific carbon isotope composition of propane at natural abundance based on mass spectrometric analysis of the intact propane molecule and its fragment ions. We demonstrate the feasibility of this approach through measurements of mixtures of natural propane and propane synthesized with site-specific 13C enrichment, and we document the limits of precision of our technique. We show that mass balance calculations of the bulk δ13C of propane based on our site-specific measurements is generally consistent with independent constraints on bulk δ13C. We further demonstrate the accuracy of the technique, and illustrate one of its simpler applications by documenting the site-specific carbon isotope signature associated with gas phase diffusion of propane, confirming that our measurements conform to the predictions of the kinetic theory of gases. This method can be applied to propane samples of moderate size (tens of micromoles) isolated from natural gases. Thus, it provides a means of studying the site-specific stable isotope systematics of propane at natural isotope abundances on sample sizes that are readily recovered from many natural environments. This method may also serve as a model for future techniques that apply high-resolution mass spectrometry to study the site-specific isotopic distributions of larger organic molecules, with potential applications to biosynthesis, forensics and other geochemical subjects.

  11. Stable isotope markers differentiate between mass-reared and wild Lepidoptera in sterile insect technique programs

    Technology Transfer Automated Retrieval System (TEKTRAN)

    In this comprehensive study a number of Sterile Insect Technique (SIT) target moth species were identified and the feasibility was assessed of using isotope signatures to distinguish mass reared from wild moth species as a marking tool. Large natural differences in the isotopic signatures of commer...

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

    PubMed

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

    2014-01-01

    In this paper, we present Molecular Isotopic Distribution Analysis (MIDAs), a new software tool designed to compute molecular isotopic distributions with adjustable accuracies. MIDAs offers two algorithms, one polynomial-based and one Fourier-transform-based, both of which compute molecular isotopic distributions accurately and efficiently. The polynomial-based algorithm contains few novel aspects, whereas the Fourier-transform-based algorithm consists mainly of improvements to other existing Fourier-transform-based algorithms. We have benchmarked the performance of the two algorithms implemented in MIDAs with that of eight software packages (BRAIN, Emass, Mercury, Mercury5, NeutronCluster, Qmass, JFC, IC) using a consensus set of benchmark molecules. Under the proposed evaluation criteria, MIDAs's algorithms, JFC, and Emass compute with comparable accuracy the coarse-grained (low-resolution) isotopic distributions and are more accurate than the other software packages. For fine-grained isotopic distributions, we compared IC, MIDAs's polynomial algorithm, and MIDAs's Fourier transform algorithm. Among the three, IC and MIDAs's polynomial algorithm compute isotopic distributions that better resemble their corresponding exact fine-grained (high-resolution) isotopic distributions. MIDAs can be accessed freely through a user-friendly web-interface at http://www.ncbi.nlm.nih.gov/CBBresearch/Yu/midas/index.html. PMID:24254576

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

    NASA Astrophysics Data System (ADS)

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

    2014-01-01

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

  14. Competition between pairing correlations and deformation from the odd-even mass staggering of francium and radium isotopes

    NASA Astrophysics Data System (ADS)

    Kreim, S.; Beck, D.; Blaum, K.; Borgmann, Ch.; Breitenfeldt, M.; Cocolios, T. E.; Gottberg, A.; Herfurth, F.; Kowalska, M.; Litvinov, Yu. A.; Lunney, D.; Manea, V.; Mendonca, T. M.; Naimi, S.; Neidherr, D.; Rosenbusch, M.; Schweikhard, L.; Stora, Th.; Wienholtz, F.; Wolf, R. N.; Zuber, K.

    2014-08-01

    The masses of Fr222,224,226-233 and Ra233,234 have been determined with the Penning-trap mass spectrometer ISOLTRAP at the ISOLDE facility at CERN, including the previously unknown mass and half-life of Fr233. We study the evolution of the odd-even staggering of binding energies along the francium and radium isotopic chains and of its lowest-order estimator, Δ3(N). An enhancement of the staggering of Δ3(N) is observed towards neutron number N =146, which points to contributions beyond pairing correlations. These contributions are investigated in the Hartree-Fock and Hartree-Fock-Bogoliubov approaches, emphasizing the connections to the single-particle level density and nuclear deformation.

  15. Investigation of bn-44 Peptide Fragments Using High Resolution Mass Spectrometry and Isotope Labeling

    NASA Astrophysics Data System (ADS)

    Wang, Bing; Yu, Jiayi; Wang, Huixin; Wei, Zhonglin; Guo, Xinhua; Xiao, Zhaohui; Zeng, Zhoufang; Kong, Wei

    2014-12-01

    An N-terminal deuterohemin-containing hexapeptide (DhHP-6) was designed as a short peptide cytochrome c (Cyt c) mimetic to study the effect of N-terminal charge on peptide fragmentation pathways. This peptide gave different dissociation patterns than normal tryptic peptides. Upon collision-induced dissociation (CID) with an ion trap mass spectrometer, the singly charged peptide ion containing no added proton generated abundant and characteristic bn-44 ions instead of bn-28 (an) ions. Studies by high resolution mass spectrometry (HRMS) and isotope labeling indicate that elimination of 44 Da fragments from b ions occurs via two different pathways: (1) loss of CH3CHO (44.0262) from a Thr side chain; (2) loss of CO2 (43.9898) from the oxazolone structure in the C-terminus. A series of analogues were designed and analyzed. The experimental results combined with Density Functional Theory (DFT) calculations on the proton affinity of the deuteroporphyrin demonstrate that the production of these novel bn-44 ions is related to the N-terminal charge via a charge-remote rather than radical-directed fragmentation pathway.

  16. Accurate Mass Determinations in Decay Chains with Missing Energy

    SciTech Connect

    Cheng, H.-C; Gunion, John F.; Han Zhenyu; Engelhardt, Dalit; McElrath, Bob

    2008-06-27

    Many beyond the standard model theories include a stable dark matter candidate that yields missing or invisible energy in collider detectors. If observed at the CERN Large Hadron Collider, we must determine if its mass and other properties (and those of its partners) predict the correct dark matter relic density. We give a new procedure for determining its mass with small error.

  17. Accurate mass determinations in decay chains with missing energy.

    PubMed

    Cheng, Hsin-Chia; Engelhardt, Dalit; Gunion, John F; Han, Zhenyu; McElrath, Bob

    2008-06-27

    Many beyond the standard model theories include a stable dark matter candidate that yields missing or invisible energy in collider detectors. If observed at the CERN Large Hadron Collider, we must determine if its mass and other properties (and those of its partners) predict the correct dark matter relic density. We give a new procedure for determining its mass with small error. PMID:18643654

  18. Falling Chains as Variable-Mass Systems: Theoretical Model and Experimental Analysis

    ERIC Educational Resources Information Center

    de Sousa, Celia A.; Gordo, Paulo M.; Costa, Pedro

    2012-01-01

    In this paper, we revisit, theoretically and experimentally, the fall of a folded U-chain and of a pile-chain. The model calculation implies the division of the whole system into two subsystems of variable mass, allowing us to explore the role of tensional contact forces at the boundary of the subsystems. This justifies, for instance, that the…

  19. Quantitative Analysis by Isotopic Dilution Using Mass Spectroscopy: The Determination of Caffeine by GC-MS.

    ERIC Educational Resources Information Center

    Hill, Devon W.; And Others

    1988-01-01

    Describes a laboratory technique for quantitative analysis of caffeine by an isotopic dilution method for coupled gas chromatography-mass spectroscopy. Discusses caffeine analysis and experimental methodology. Lists sample caffeine concentrations found in common products. (MVL)

  20. Chemical and isotopic measurements of micrometeoroids by secondary ion mass spectrometry (A0187-2)

    NASA Technical Reports Server (NTRS)

    Foote, J. H.; Swan, P. D.; Walker, R. M.; Zinner, E. K.; Bahr, D.; Fechtig, H.; Jessberger, E.; Igenbergs, E.; Kreitmayr, U.; Kuczera, H.

    1984-01-01

    The objective of this experiment is to measure the chemical and isotopic composition of interplanetary dust particles of mass greater than 10 to the minus 10 power G for most of thermator elements expected to be present.

  1. Mass-dependent and non-mass-dependent isotope effects in ozone photolysis: Resolving theory and experiments

    SciTech Connect

    Cole, Amanda S.; Boering, Kristie A.

    2006-11-14

    In addition to the anomalous {sup 17}O and {sup 18}O isotope effects in the three-body ozone formation reaction O+O{sub 2}+M, isotope effects in the destruction of ozone by photolysis may also play a role in determining the isotopic composition of ozone and other trace gases in the atmosphere. While previous experiments on ozone photolysis at 254 nm were interpreted as evidence for preferential loss of light ozone that is anomalous (or 'non-mass-dependent'), recent semiempirical theoretical calculations predicted a preferential loss of heavy ozone at that wavelength that is mass dependent. Through photochemical modeling results presented here, we resolve this apparent contradiction between experiment and theory. Specifically, we show that the formation of ozone during the UV photolysis experiments is not negligible, as had been assumed, and that the well-known non-mass-dependent isotope effects in ozone formation can account for the non-mass-dependent enrichment of the heavy isotopologs of ozone observed in the experiment. Thus, no unusual non-mass-dependent fractionation in ozone photolysis must be invoked to explain the experimental results. Furthermore, we show that theoretical predictions of a mass-dependent preferential loss of the heavy isotopologs of ozone during UV photolysis are not inconsistent with the experimental data, particularly if mass-dependent isotope effects in the chemical loss reactions of ozone during the photolysis experiments or experimental artifacts enrich the remaining ozone in {sup 17}O and {sup 18}O. Before the calculated fractionation factors can be quantitatively evaluated, however, further investigation of possible mass-dependent isotope effects in the reactions of ozone with O({sup 1}D), O({sup 3}P), O{sub 2}({sup 1}{delta}), and O{sub 2}({sup 1}{sigma}) is needed through experiments we suggest here.

  2. Experimental investigations of trimer ion contributions in the low resolution mass spectrometry of hydrogen isotope mixtures.

    PubMed

    Bidica, Nicolae

    2012-01-01

    This paper reports on some preliminary experimental results of a work in progress regarding a problem involving the quantitative analysis of hydrogen isotopes by mass spectrometry of low resolution: the triatomic (trimer) ions interferences with the isotopic hydrogen species having the same mass/charge. These results indicate that, in complex mixtures of hydrogen isotopes, trimer ions are strongly affected by the presence of other species, and a new approach that takes into account the destruction mechanism of trimer ions is necessary for a proper determination of their contributions. PMID:23149602

  3. Mass-dependent and -independent signature of Fe isotopes in magnetotactic bacteria.

    PubMed

    Amor, Matthieu; Busigny, Vincent; Louvat, Pascale; Gélabert, Alexandre; Cartigny, Pierre; Durand-Dubief, Mickaël; Ona-Nguema, Georges; Alphandéry, Edouard; Chebbi, Imène; Guyot, François

    2016-05-01

    Magnetotactic bacteria perform biomineralization of intracellular magnetite (Fe3O4) nanoparticles. Although they may be among the earliest microorganisms capable of biomineralization on Earth, identifying their activity in ancient sedimentary rocks remains challenging because of the lack of a reliable biosignature. We determined Fe isotope fractionations by the magnetotactic bacterium Magnetospirillum magneticum AMB-1. The AMB-1 strain produced magnetite strongly depleted in heavy Fe isotopes, by 1.5 to 2.5 per mil relative to the initial growth medium. Moreover, we observed mass-independent isotope fractionations in (57)Fe during magnetite biomineralization but not in even Fe isotopes ((54)Fe, (56)Fe, and (58)Fe), highlighting a magnetic isotope effect. This Fe isotope anomaly provides a potential biosignature for the identification of magnetite produced by magnetotactic bacteria in the geological record. PMID:27151868

  4. Mass-dependent and -independent signature of Fe isotopes in magnetotactic bacteria

    NASA Astrophysics Data System (ADS)

    Amor, Matthieu; Busigny, Vincent; Louvat, Pascale; Gélabert, Alexandre; Cartigny, Pierre; Durand-Dubief, Mickaël; Ona-Nguema, Georges; Alphandéry, Edouard; Chebbi, Imène; Guyot, François

    2016-05-01

    Magnetotactic bacteria perform biomineralization of intracellular magnetite (Fe3O4) nanoparticles. Although they may be among the earliest microorganisms capable of biomineralization on Earth, identifying their activity in ancient sedimentary rocks remains challenging because of the lack of a reliable biosignature. We determined Fe isotope fractionations by the magnetotactic bacterium Magnetospirillum magneticum AMB-1. The AMB-1 strain produced magnetite strongly depleted in heavy Fe isotopes, by 1.5 to 2.5 per mil relative to the initial growth medium. Moreover, we observed mass-independent isotope fractionations in 57Fe during magnetite biomineralization but not in even Fe isotopes (54Fe, 56Fe, and 58Fe), highlighting a magnetic isotope effect. This Fe isotope anomaly provides a potential biosignature for the identification of magnetite produced by magnetotactic bacteria in the geological record.

  5. Mass measurements of short-lived isotopes in a penning trap

    SciTech Connect

    Kern, F.; Egelhof, P.; Hilberath, T.; Kalinowsky, H.; Kluge, H.h.; Kunz, K.; Schweikhard, L.; Stolzenberg, H.; Moore, R.B.; Audi, G.; and others

    1987-12-10

    A mass spectrometer has been set up at the on-line isotope separator ISOLDE at CERN/Geneva. Mass-separated radioactive ions are stored in a Penning trap. Their mass is determined by a measurement of the cyclotron frequency in the magnetic field of a superconducting magnet. A resolving power of up to 300.000 and a precision of some 10 keV were determined in case of mass measurements of neutron-deficient RB and Cs isotopes. The resonance of the isobars /sup 88/Sr and /sup 88/Rb were clearly resolved and evidence was obtained for an isomer in /sup 122/Cs.

  6. A specialized isotope mass spectrometer for noninvasive diagnostics of Helicobacter pylori infection in human beings

    NASA Astrophysics Data System (ADS)

    Blashenkov, N. M.; Sheshenya, E. S.; Solov'ev, S. M.; Sachenko, V. D.; Gall, L. N.; Zarutskii, I. V.; Gall, N. R.

    2013-05-01

    A specialized isotope mass spectrometer for noninvasive diagnostics of Helicobacter pylori infection in human beings based on the carbon-13 isotope breath test has been designed and constructed. Important stages of the work included (i) calculating a low-aberration mass analyzer, (ii) manufacturing and testing special gas inlet system, and (iii) creating a small-size collector of ions. The proposed instrument ensures 13C/12C isotopic ratio measurement to within 1.7‰ (pro mille) accuracy, which corresponds to requirements for a diagnostic tool. Preliminary medical testing showed that the mass spectrometer is applicable to practical diagnostics. The instrument is also capable of measuring isotopic ratios of other light elements, including N, O, B (for BF2+ ions), Ar, Cl, and S.

  7. A gas chromatograph/mass spectrometry method for determining isotopic distributions in organic compounds used in the chemical approach to stable isotope separation

    SciTech Connect

    Martinez, A.M.; Spall, W.D.; Smith, B.F.

    1990-01-01

    A variety of gas chromatograph/mass spectrometry (GC/MS) methods have been developed to resolve benzene, benzophenone, anthracene, fluorenone, and their respective stable isotope analogs from other components by gas chromatography. The ratio of stable isotope-labeled material to natural isotopic abundance compounds is determined from the mass spectra averaged across the chromatographic peak. Both total ion and selective ion chromatographic approaches were used for relative data and comparison. 9 refs., 11 tabs.

  8. Coupled sulfur isotopic and chemical mass transfer modeling: Approach and application to dynamic hydrothermal processes

    SciTech Connect

    Janecky, D.R.

    1988-09-21

    A computational modeling code (EQPSreverse arrowS) has been developed to examine sulfur isotopic distribution pathways coupled with calculations of chemical mass transfer pathways. A post processor approach to EQ6 calculations was chosen so that a variety of isotopic pathways could be examined for each reaction pathway. Two types of major bounding conditions were implemented: (1) equilibrium isotopic exchange between sulfate and sulfide species or exchange only accompanying chemical reduction and oxidation events, and (2) existence or lack of isotopic exchange between solution species and precipitated minerals, parallel to the open and closed chemical system formulations of chemical mass transfer modeling codes. All of the chemical data necessary to explicitly calculate isotopic distribution pathways is generated by most mass transfer modeling codes and can be input to the EQPS code. Routines are built in to directly handle EQ6 tabular files. Chemical reaction models of seafloor hydrothermal vent processes and accompanying sulfur isotopic distribution pathways illustrate the capabilities of coupling EQPSreverse arrowS with EQ6 calculations, including the extent of differences that can exist due to the isotopic bounding condition assumptions described above. 11 refs., 2 figs.

  9. In-Vivo Zinc Metabolism by Isotope Ratio Mass Spectrometry

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The purpose of this chapter is to highlight some of the methodological and technical issues surrounding the in vivo use of stable isotopes and to provide examples of how such studies have advanced our knowledge of human zinc metabolism. The advantages and disadvantages of the currently available in...

  10. Amino and Acetamide Functional Group Effects on the Ionization and Fragmentation of Sugar Chains in Positive-Ion Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Yamagaki, Tohru; Sugahara, Kohtaro; Watanabe, Takehiro

    2014-01-01

    To elucidate the influence of amino (-NH2) and acetamide (-NHCOCH3, -NAc) groups in sugar chains on their ionization and fragmentation, cycloamyloses (cyclodextrins, CyDs) and lacto-oligosaccharide are analyzed by MALDI TOF/TOF and ESI Q-TOF mass spectrometry. CyD derivatives substituted by amino or acetamide groups are ideal analytes to extract the function group effects, which are amino-CyD with one hexosamine (HexNH2) and acetamide-CyD with one N-acetyl hexosamine (HexNAc). Interestingly, the relative ion intensities and isotope-like patterns in their product ion spectra depend on the functional groups and ion forms of sugar chains. Consequently, the results indicate that a proton (H+) localizes on the amino group of the amino sugar, and that the proton (H+) induces their fragmentation. Sodium cation (Na+) attachment is independent from amino group and exerts no influence on their fragmentation patterns in amino group except for mono- and disaccharide fragment ions because there is the possibility of the reducing end effect. In contrast, a sodium cation localizes much more frequently on the acetamide group in acetamide-CyDs because the chemical species with HexNAc are stable. Thus, their ions with HexNAc are abundant. These results are consistent with the fragmentation of lacto-neo- N-tetraose and maltotetraose, suggesting that a sodium cation generally localizes much more frequently on the acetamide group in sugar chains.

  11. Iron and nickel isotopic mass fractionation in deep-sea spherules

    NASA Technical Reports Server (NTRS)

    Davis, Andrew M.; Brownlee, Donald E.

    1993-01-01

    Magnetite-wuestite spherules collected from deep-sea sediments are thought to have originally been Fe-Ni metal particles at the top of the atmosphere that were oxidized and melted during entry into the earth's atmosphere. Some likely sources for the metal particles are Fe-Ni interplanetary dust particles (IDP's) and metal or sulfide from stony IDP's that separated after melting. Davis et al. reported that four of these spherules are enriched in the heavy isotopes of iron, with enrichments of 8-23%/amu. We have developed a technique for analysis of both iron and nickel isotopes on the same ion microprobe spot and have applied this technique to a number of deep-sea spherules in order to better understand the processes leading to isotopic mass fractionation. Eight spherules show iron and nickel isotopic mass fractionation, with iron and nickel enriched in the heavy isotopes by 10-19%/amu and 4-32%/amu, respectively. If the mass fractionations are due to Rayleigh fractionation during evaporation, these spherules lost 76-94% of their original mass. We have analyzed the four magnetite-wuestite spherules for which iron isotopic data were reported by Davis et al. as well as four new spherules.

  12. Differences in the Elemental Isotope Definition May Lead to Errors in Modern Mass-Spectrometry-Based Proteomics.

    PubMed

    Claesen, Jürgen; Lermyte, Frederik; Sobott, Frank; Burzykowski, Tomasz; Valkenborg, Dirk

    2015-11-01

    The elemental isotope definition used to calculate the theoretical masses and isotope distribution of (bio)molecules is considered to be a fixed, universal standard in mass-spectrometry-based proteomics. However, this is an incorrect assumption. In view of the ongoing advances in mass spectrometry technology, and in particular the ever-increasing mass precision, the elemental isotope definition and its variations should be taken into account. We illustrate the effect of the elemental isotope uncertainty on the theoretical and experimental masses with theoretical calculations and examples. PMID:26457653

  13. Further study of α-decay in heavy isotopic chains considering the isospin effect

    NASA Astrophysics Data System (ADS)

    Qian, Yibin; Ren, Zhongzhou

    2016-06-01

    We have enhanced the deformed density-dependent cluster model to improve the quantitative description of α-decay in heavy even–even nuclei with 84≤slant Z≤slant 92. To preliminarily introduce the isospin effect into α-decay, the neutron excess term is added in the establishment of the crucial α-core potential. The proton and neutron density distributions are respectively considered in different parameterized formulas by combining them with available experimental data of both the charge radius and the neutron skin thickness. The calculated α-decay half-lives are found to be in somewhat better agreement with the experimental data as compared with our previous results. Strikingly, it is noted that the relatively large deviation between theory and experiment, along the tail of the isotopic chain, is obviously reduced and smoother. This may indicate the necessity of considering the isospin effect in α-decay, especially for extremely neutron-rich nuclei, which appears to be essential for the extended study of heaviest nuclei as well.

  14. Mass dependent isotope fractionation during impacts induced the Archaean mass-independent fractionation of sulphur: Evidence against Great Oxidation Event

    NASA Astrophysics Data System (ADS)

    Huang, H.

    2010-12-01

    A prevailing hypothesis, low-oxygen level of the Archaean atmosphere, relies strongly on the presence of strong mass-independent fractionation (MIF) of the sulfur isotopes in sulfide- and sulfate-bearing minerals older than 2.4 billion years. Actually, there is “a broad overlap between MIF signals observed within Archaean sedimentary sequences and periods of enhanced asteroid impacts represented by impact ejecta/fallout units”(Glikson 2010) (Fig. 1). Moreover, usually MIF- related sulphur occurs in the Archaean sedimentary rocks as pyrite (FeS2) which has been found in the K-T boundary clay beds and in several identified impact craters, which is an independent argument in favor of pyrites could be the product of impact. Impact processes (vaporization and condensation) are sufficient to explain the MIF signals following the principle: the earlier the condensed material, the more enriched in lighter isotopes (Huang 2010). The nature of the MIF of the sulfur isotopes is that the fractionation of isotope is still mass dependent during impacts, which means the measured nonzero Δ33S values of Archean sulfide- and sulfate-bearing minerals indicate that their different condensation sequences. Another important line of evidence that support the impact-generated MIF of the sulfur isotopes comes from the various iron isotope values of the pyrites especially those with iron isotope heterogeneity at grain scale. Thus, it is clear that the signals are the markers of impact rather than O2 poor atmosphere. Furthermore, this can also account for the lack of MIF-S in several Archaean units before 2.4 billion years. Figure 1 Plot of mass-independent fractionation of sulphur and asteroid impact events with age. Modified from Glikson (2010)

  15. In Vivo Mass-independent Fractionation of Mercury Isotopes in Fish

    NASA Astrophysics Data System (ADS)

    Das, R.; Odom, L. A.

    2008-12-01

    Recent experimental work and analyses of natural samples have revealed both mass-dependent and mass- independent isotope fractionation effects in mercury. These findings portend new avenues toward understanding the global mercury cycle. It has been shown experimentally that photo reduction of Hg+2 and methylmercury in water with concomitant release of the reduced, gaseous species Hg° results in the residual methylmercury possessing a mass-independent isotope effect. This effect is a relative enrichment of isotopes 199Hg and 201Hg over the even mass number isotopes when compared to the mercury standard NIST SRM3133. Large mass independent fractionation (MIF) effects (Δ199Hg values of a few ‰) have been found in mercury in fish and interpreted as isotope effects inherited from the water. To evaluate the possibility that MIF might be produced within the fish, we have analyzed 38 samples that include zooplankton and twelve different species of fish from a single lake collected over a 2-month time period for mercury isotopic compositions. Trophic levels of the same fish specimens had previously been determined from stomach contents and nitrogen isotopes. Zooplankton in the lake contain mercury with Δ199Hg and Δ201Hg values of +0.43 (±0.07) and +0.44 (±0.07) respectively. Among the fish species there is a striking correspondence between trophic level and Δ199Hg and Δ201Hg values for primary, secondary, and tertiary consumers. The Δ199Hg values ranges over ~1‰ from ~+0.4 in zooplankton, juvenile bluegill and several other small fishes to Δ199Hg = + 1.36 for the Florida gar that is the top predator fish in the lake. These observations indicate that the MIF effect, rather than being an artifact of the water column is produced in vivo. Partial separation of 199Hg and 201Hg from isotopes of even neutron number can be achieved by the magnetic isotope effect in reactions involving sufficiently long-lived intermediate free radicals, where nuclear - electron

  16. Quantitative Analysis of Isotope Distributions In Proteomic Mass Spectrometry Using Least-Squares Fourier Transform Convolution

    PubMed Central

    Sperling, Edit; Bunner, Anne E.; Sykes, Michael T.; Williamson, James R.

    2008-01-01

    Quantitative proteomic mass spectrometry involves comparison of the amplitudes of peaks resulting from different isotope labeling patterns, including fractional atomic labeling and fractional residue labeling. We have developed a general and flexible analytical treatment of the complex isotope distributions that arise in these experiments, using Fourier transform convolution to calculate labeled isotope distributions and least-squares for quantitative comparison with experimental peaks. The degree of fractional atomic and fractional residue labeling can be determined from experimental peaks at the same time as the integrated intensity of all of the isotopomers in the isotope distribution. The approach is illustrated using data with fractional 15N-labeling and fractional 13C-isoleucine labeling. The least-squares Fourier transform convolution approach can be applied to many types of quantitive proteomic data, including data from stable isotope labeling by amino acids in cell culture and pulse labeling experiments. PMID:18522437

  17. Quantification of ferritin-bound iron in plant samples by isotope tagging and species-specific isotope dilution mass spectrometry.

    PubMed

    Hoppler, Matthias; Zeder, Christophe; Walczyk, Thomas

    2009-09-01

    Ferritin is nature's predominant iron storage protein. The molecule consists of a hollow protein shell composed of 24 subunits which is capable of storing up to 4500 iron atoms per molecule. Recently, this protein has been identified as a target molecule for increasing iron content in plant staple foods in order to combat dietary iron deficiency, a major public health problem in developing countries. Here, we present a novel technique for quantification of ferritin-bound iron in edible plant seeds using species-specific isotope dilution mass spectrometry (IDMS) by means of a biosynthetically produced (57)Fe-labeled ferritin spike and negative thermal ionization mass spectrometry (NTIMS). Native plant ferritin and added spike ferritin were extracted in 20 mM Tris buffer (pH 7.4) and separated by anion exchange chromatography (DEAE Sepharose), followed by isotopic analysis by thermal ionization mass spectrometry. The chosen IDMS approach was critically evaluated by assessing the (i) efficiency of analyte extraction, (ii) identical behavior of spike and analyte, and (iii) potential iron isotope exchange with natural iron. Repeatabilities that can be achieved are on the order of <5% RSD for quintuplicate analyses at an absolute detection limit of 60 ng of ferritin-bound iron for plant seeds. Studies in six different legumes revealed ferritin-iron contents ranging from 15% of total iron in red kidney beans up to 69% in lentils. PMID:19653660

  18. Consistency of NMR and mass spectrometry determinations of natural-abundance site-specific carbon isotope ratios. The case of glycerol.

    PubMed

    Zhang, B L; Trierweiler, M; Jouitteau, C; Martin, G J

    1999-07-01

    Quantitative determinations of natural-abundance carbon isotope ratios by nuclear magnetic resonance (SNIF-NMR) have been optimized by appropriate selection of the experimental conditions and by signal analysis based on a dedicated algorithm. To check the consistency of the isotopic values obtained by NMR and mass spectrometry (IRMS) the same glycerol samples have been investigated by both techniques. To have access to site-specific isotope ratios by IRMS, the products have been degraded and transformed into two derivatives, one of which contains carbons 1 and 3 and the other carbon 2 of glycerol. The sensitivity of the isotopic parameters determined by IRMS to fractionation effects possibly occurring in the course of the chemical transformations has been investigated, and the repeatability and reproducibility of both analytical chains have been estimated. The good agreement observed between the two series of isotopic results supports the reliability of the two different approaches. SNIF-NMR is therefore a very attractive tool for routine determination, in a single nondestructive experiment, of the carbon isotope distribution in glycerol, and the method can be applied to other compounds. Using this method, the isotopic distributions have been compared for glycerol samples, obtained from plant or animal oils, extracted from fermented media, or prepared by chemical synthesis. Typical behaviors are characterized. PMID:21662780

  19. Application of Uranium Isotope Dilution Mass Spectrometry in the preparation of New Certified Reference Materials

    NASA Astrophysics Data System (ADS)

    Hasözbek, A.; Mathew, K. J.; Orlowicz, G.; Srinivasan, B.; Narayanan, U.

    2012-04-01

    Proven measurement techniques play a critical role in the preparation of Certified Reference Materials (CRMs) - those requiring high accuracy and precision in the measurement results. Isotope Dilution Mass Spectrometry (IDMS) is one such measurement method commonly used in the quantitative analysis of uranium in nuclear safeguards and isotope geology applications. In this project, we evaluated the possibility of using some of the uranium isotopic and assay CRMs made earlier by the New Brunswick laboratory as IDMS spikes to define the uranium mass fraction in future preparations of CRMs. Uranium solutions prepared from CRM 112-A (a highly pure uranium metal assay standard) and CRM 115 (a highly pure uranium oxide isotopic and assay standard) were used as spikes in the determination of uranium. Two different thermal ionization mass spectrometer instruments (MAT 261 and TRITON) were used for the isotopic measurements. Standard IDMS equation was used for data reduction to yield results for uranium mass fraction along with uncertainties, the latter calculated according to GUM. The results show that uranium mass fraction measurements can be made with the required accuracy and precision for defining the uranium concentration in new CRMs as well as in routine samples analyses.

  20. Efficient synthesis of D-branched-chain amino acids and their labeled compounds with stable isotopes using D-amino acid dehydrogenase.

    PubMed

    Akita, Hironaga; Suzuki, Hirokazu; Doi, Katsumi; Ohshima, Toshihisa

    2014-02-01

    D-Branched-chain amino acids (D-BCAAs) such as D-leucine, D-isoleucine, and D-valine are known to be peptide antibiotic intermediates and to exhibit a variety of bioactivities. Consequently, much effort is going into achieving simple stereospecific synthesis of D-BCAAs, especially analogs labeled with stable isotopes. Up to now, however, no effective method has been reported. Here, we report the establishment of an efficient system for enantioselective synthesis of D-BCAAs and production of D-BCAAs labeled with stable isotopes. This system is based on two thermostable enzymes: D-amino acid dehydrogenase, catalyzing NADPH-dependent enantioselective amination of 2-oxo acids to produce the corresponding D-amino acids, and glucose dehydrogenase, catalyzing NADPH regeneration from NADP(+) and D-glucose. After incubation with the enzymes for 2 h at 65°C and pH 10.5, 2-oxo-4-methylvaleric acid was converted to D-leucine with an excellent yield (>99 %) and optical purity (>99 %). Using this system, we produced five different D-BCAAs labeled with stable isotopes: D-[1-(13)C,(15)N]leucine, D-[1-(13)C]leucine, D-[(15)N]leucine, D-[(15)N]isoleucine, and D-[(15)N]valine. The structure of each labeled D-amino acid was confirmed using time-of-flight mass spectrometry and nuclear magnetic resonance analysis. These analyses confirmed that the developed system was highly useful for production of D-BCAAs labeled with stable isotopes, making this the first reported enzymatic production of D-BCAAs labeled with stable isotopes. Our findings facilitate tracer studies investigating D-BCAAs and their derivatives. PMID:23661083

  1. Mass Dependent and Mass Independent Fractionation of Hg Isotopes and Estimation of Photochemical Loss of Hg in Aquatic Systems

    NASA Astrophysics Data System (ADS)

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

    2007-12-01

    Mercury is a globally distributed and highly toxic pollutant, the mobility and bioaccumulation of which is dependent on its redox cycling. Hg isotope analysis is an important new tool for identifying Hg sources and tracking Hg transformations in the environment. Most natural samples analyzed for Hg isotopes display mass-dependent isotope fractionation (MDF), but a small body of data suggests that some natural samples also display mass- independent isotope fractionation (MIF) of the odd Hg isotopes. Here we document MIF of Hg isotopes during an important natural process, constrain the potential mechanism of isotope fractionation, and apply the MIF observed in natural samples to quantify the photochemical reduction of Hg species in the environment. Reduction of Hg species to Hg0 vapor is an important pathway for removal of Hg from aqueous systems into the atmosphere and occurs by abiotic and biotic mechanisms. In laboratory experiments, we find that photochemical reduction Hg species by natural sunlight leads to large MIF of the odd isotopes. Also, the relationship between MIF for the two odd isotopes of Hg is significantly different for different photo-reduction pathways. In contrast, both biological reduction (Kritee et al., 2006) and dark abiotic organically-mediated reduction follow MDF. Natural samples from aquatic ecosystems preserve both MDF and MIF. In fish, MDF increases with the size and Hg concentration of fish suggesting MDF may be useful in understanding Hg bioaccumulation. Fish also display a large range in MIF (4‰), and the relationship between the MIF of the two odd isotopes in fish has a similar slope to the slope found for photo-reduction of CH3Hg+. Since fish bioaccumulate CH3Hg+, fish may be recording the extent to which CH3Hg+ is lost via photochemical reduction in an aquatic ecosystem. Fish populations from different locations have different MIF values, but mostly display similar MIF within a given locale. This suggests that MIF is preserved

  2. Lithium Isotopic Compositions of Lavas From Samoan and Austral Volcanic Chains: Constraints on the Source Components of Mantle Reservoirs

    NASA Astrophysics Data System (ADS)

    Chan, L.; Lassiter, J. C.; Hart, S. R.; Blusztajn, J.; Hauri, E. H.

    2005-12-01

    Radiogenic isotope and trace elemnt studies have revealed a HIMU component, a depleted (DM) component and enriched (EM) components in lavas from Samoan and Cook-Austral volcanic chains. We have determined lithium isotopic compositions of largely fresh basaltic lavas from the Samoan chain and Austral islands (Raivavae and Rapa) to further constrain the origin and sources of the mantle reservoirs in the South Pacific. The DM endmember in Raivavae samples has δ7Li values of 3.2 to 4.2%_0, identical to fresh MORB. δ7Li of HIMU type lavas of Raivavae vary from 4.4 to 5.5%_0. The EM lavas are also enriched in 7Li compared to DM (δ7Li=3.8 to 5.9%_0). Two exceptionally high values are observed in Raivavae (10 and 11.5%_0). Analysis of mineral separates is in progress to determine the origin of these anomalous compositions. Malumalu seamount of the Samoan chain defines the most extreme composition of the EMII mantle. δ7Li values of this mantle endmember have been determined to be 4.8 to 5.6%_0. Available data from other seamount and islands of the chain show a range of δ7Li from 3.2 to 7.7%_0. Thus the south Pacific hot spots display a greater Li isotopic heterogeneity than the Hawaiian plume. Together, the Samoan and Austral samples present systematic relationships between Li and Pb isotope ratios that depict mixing of HIMU and EM materials with a DM component. The HIMU tpe samples display a positive correlation between δ7Li and 206Pb/204Pb, whereas the enriched samples define a generally negative correlation. The heavy Li isotopic composition of the HIMU endmember suggests an origin of recycled altered oceanic crust that has not been greatly depleted by dehydration during subduction. The high δ7Li of the EM member cannot be explained by addition of pelagic sediments which are typically light in Li isotopic composition but may be attributed to mantle wedge manterial that has been metasomatized by 7Li-rich fluids arising from the subductd slab. We have not, however

  3. Mass spectrometric study of the mercury isotopes in the Allende meteorite

    NASA Technical Reports Server (NTRS)

    Nier, A. O.; Schlutter, D. J.

    1986-01-01

    Isotopic abundance ratios for mercury were determined by mass spectrometry in six samples of bulk material and in one sample of chondrules from the Allende meteorite. A primary purpose of the work was to attempt to verify the anomalous ratios reported for Hg-196/Hg-202 by neutron activation. Measurements were made on the mercury released at temperatures of 250, 450, 600 C, and in some cases, higher temperatures. The precision of the measurements was such that if an anomaly of the magnitude reported exists, it should have been seen. The isotopic abundance ratios for the other mercury isotopes were also measured. Within the errors of measurement these agreed with normal terrestrial values.

  4. Mass-independent fractionation of mercury isotopes in compact fluorescent light bulbs

    NASA Astrophysics Data System (ADS)

    Mead, C.; Anbar, A. D.; Lyons, J. R.; Johnson, T. M.

    2010-12-01

    Compact fluorescent lightbulbs (CFLs) are a growing source of Hg pollution. The high-energy environment of the CFLs combined with the known partitioning of Hg into the bulb walls could provide an environment for unusual isotope fractionation that could be used to trace pollution from improper bulb disposal. To investigate this possibility, we analyzed the isotope composition of Hg in CFL glass, phosphor powder, and whole bulbs from CFLs of known ages. We observed large, mass-independent fractionation of Hg isotopes between Hg embedded in the bulb wall and Hg in the liquid and vapor phases, which are the initial reservoir of Hg in the bulb. This fractionation results in the bulb wall showing enrichment of 198Hg, 199Hg, 200Hg, 201Hg, and 204Hg relative to 202Hg, the most abundant isotope. Both the amount of Hg embedded in the glass and the magnitude of the isotope enrichment were found to increase with the number of hours of light bulb use. For a CFL used for 3600 hours (with a rated lifetime of 10,000 hours), the isotopic composition of the Hg in the glass was enriched by 34.5‰, 4.1‰, 6.3‰, 21.1‰, and 12.1‰ for 198Hg/202Hg, 199Hg/202Hg, 200Hg/202Hg, 201Hg/202Hg, and 204Hg/202Hg, respectively, compared to NIST SRM-3133. This pattern of isotope enrichments is not correlated with mass differences for any of the isotope ratios. In contrast, the other mass-independent effects that have recently been observed in Hg isotopes (i.e., the nuclear volume and magnetic isotope effects) resemble mass-dependent fractionation for the even mass isotopes and are anomalous only for the odd mass isotopes, 199Hg and 201Hg. First order theoretical calculations using Hg absorption and emission data for each of the hyperfine components of the 253.7 nm line have shown that similar fractionation can be produced through an optical self-shielding effect. This effect occurs because each Hg isotope has a different degree of optical saturation at their respective absorption wavelength

  5. Caution on the use of liquid nitrogen traps in stable hydrogen isotope-ratio mass spectrometry.

    PubMed

    Coplen, Tyler B; Qi, Haiping

    2010-09-15

    An anomalous stable hydrogen isotopic fractionation of 4 ‰ in gaseous hydrogen has been correlated with the process of adding liquid nitrogen (LN(2)) to top off the dewar of a stainless-steel water trap on a gaseous hydrogen-water platinum equilibration system. Although the cause of this isotopic fractionation is unknown, its effect can be mitigated by (1) increasing the capacity of any dewars so that they do not need to be filled during a daily analytic run, (2) interspersing isotopic reference waters among unknowns, and (3) applying a linear drift correction and linear normalization to isotopic results with a program such as Laboratory Information Management System (LIMS) for Light Stable Isotopes. With adoption of the above guidelines, measurement uncertainty can be substantially improved. For example, the long-term (months to years) δ(2)H reproducibility (1σ standard deviation) of nine local isotopic reference waters analyzed daily improved substantially from about 1 ‰ to 0.58 ‰. This isotopically fractionating mechanism might affect other isotope-ratio mass spectrometers in which LN(2) is used as a moisture trap for gaseous hydrogen. PMID:20718408

  6. Caution on the use of liquid nitrogen traps in stable hydrogen isotope-ratio mass spectrometry

    USGS Publications Warehouse

    Coplen, T.B.; Qi, H.

    2010-01-01

    An anomalous stable hydrogen isotopic fractionation of 4 ??? in gaseous hydrogen has been correlated with the process of adding liquid nitrogen (LN2) to top off the dewar of a stainless-steel water trap on a gaseous hydrogen-water platinum equilibration system. Although the cause of this isotopic fractionation is unknown, its effect can be mitigated by (1) increasing the capacity of any dewars so that they do not need to be filled during a daily analytic run, (2) interspersing isotopic reference waters among unknowns, and (3) applying a linear drift correction and linear normalization to isotopic results with a program such as Laboratory Information Management System (LIMS) for Light Stable Isotopes. With adoption of the above guidelines, measurement uncertainty can be substantially improved. For example, the long-term (months to years) ??2H reproducibility (1?? standard deviation) of nine local isotopic reference waters analyzed daily improved substantially from about 1 ??? to 0.58 ???. This isotopically fractionating mechanism might affect other isotope-ratio mass spectrometers in which LN2 is used as a moisture trap for gaseous hydrogen. ?? This article not subject to U.S. Copyright. Published 2010 by the American Chemical Society.

  7. Caution on the use of liquid nitrogen traps in stable hydrogen isotope-ratio mass spectrometry

    USGS Publications Warehouse

    Coplen, Tyler B.; Qi, Haiping

    2010-01-01

    An anomalous stable hydrogen isotopic fractionation of 4 ‰ in gaseous hydrogen has been correlated with the process of adding liquid nitrogen (LN2) to top off the dewar of a stainless-steel water trap on a gaseous hydrogen-water platinum equilibration system. Although the cause of this isotopic fractionation is unknown, its effect can be mitigated by (1) increasing the capacity of any dewars so that they do not need to be filled during a daily analytic run, (2) interspersing isotopic reference waters among unknowns, and (3) applying a linear drift correction and linear normalization to isotopic results with a program such as Laboratory Information Management System (LIMS) for Light Stable Isotopes. With adoption of the above guidelines, measurement uncertainty can be substantially improved. For example, the long-term (months to years) δ2H reproducibility (1& sigma; standard deviation) of nine local isotopic reference waters analyzed daily improved substantially from about 1‰ to 0.58 ‰. This isotopically fractionating mechanism might affect other isotope-ratio mass spectrometers in which LN2 is used as a moisture trap for gaseous hydrogen

  8. An efficient method for isolating individual long-chain alkenones for compound-specific hydrogen isotope analysis.

    PubMed

    D'Andrea, William J; Liu, Zhonghui; Da Rosa Alexandre, Marcelo; Wattley, Sarah; Herbert, Timothy D; Huang, Yongsong

    2007-05-01

    Hydrogen isotope ratios (2H/H or D/H) of long-chain unsaturated ketones (alkenones) preserved in lake and marine sediments hold great promise for paleoclimate studies. However, compound-specific hydrogen isotope analysis of individual alkenones has not been possible due to chromatographic coelution of alkenones with the same carbon chain length but different numbers of double bonds. Published studies have only reported the deltaD values of the mixture of coeluting alkenones. We developed an efficient procedure to isolate individual alkenones based on double-bond numbers using silica gel impregnated with silver nitrate. The chromatographic procedure is simple, inexpensive, and highly reproducible, offers 87-100% sample recovery, and allows for the first time hydrogen isotopic measurement on individual alkenones. deltaD values of specific di-, tri- and tetraunsaturated C37 alkenones produced by an Emiliania huxleyi culture, as well as those isolated from Greenland lake sediments, differ consecutively by 43-65 per thousand. These findings suggest that alkenones with different numbers of carbon-carbon double bonds express significantly different deltaD values and that coelution of different alkenones may lead to erroneous source water deltaD reconstructions. Our alkenone isolation approach opens a new avenue for paleoclimate reconstructions using hydrogen isotope ratios of individual alkenones. PMID:17391004

  9. Pascal program for mass-spectral isotope-cluster identification. Final report

    SciTech Connect

    Lin, I.J.; Bulpett, D.A.

    1991-09-01

    A new isotope cluster identification program, named Reverse Cluster Search (RCS) is presented in full to assist the mass spectrometrist in the identification of unknowns. Given a clean, complete isotope cluster from a mass spectrum, its empirical formula can be found through the calculations of RCS. RCS was tested on known spectra which fit certain parameters of composition and spectral quality. Correlation between the matches given by RCS and the actual formula was excellent. RCS was written to run on both a DEC VAXStation 3500 and IBM PC compatibles. A companion program is also included which is called Forward Cluster Search (FCS). FCS will calculate theoretical mass spectral isotope clusters from empirical formula data. The purpose of this report is to provide the complete code for a Pascal program which is called Reverse Cluster Search (RCS). The authors goal was to develop a computer program to rapidly identify chemical formulas from mass spectral isotope cluster data requiring minimal disk storage and memory. Relying entirely upon low resolution mass spectral cluster data to predict or confirm empirical formulas is not recommended. High resolution, exact mass data is always preferred when complete confidence is required in the formula assignment; however, the presence of certain isotropic elements must be supported by the cluster data.

  10. Fractionated Mercury Isotopes in Fish: The Effects of Nuclear Mass, Spin, and Volume

    NASA Astrophysics Data System (ADS)

    Das, R.; Odom, A. L.

    2007-12-01

    Mercury is long known as a common environmental contaminant. In methylated form it is even more toxic and the methylation process is facilitated by microbial activities. Methyl mercury easily crosses cell membrane and accumulates in soft tissues of fishes and finally biomagnifies with increasing trophic levels. Natural variations in the isotopic composition of mercury have been reported and such variations have emphasized mass dependent fractionations, while theory and laboratory experiments indicate that mass-independent isotopic fractionation (MIF) effects are likely to be found as well. This study focuses on the MIF of mercury isotopes in the soft tissues of fishes. Samples include both fresh water and marine fish, from different continents and oceans. Approximately 1 gm of fish soft tissue was dissolved in 5 ml of conc. aqua regia for 24 hrs and filtered through a ¬¬¬100 μm filter paper and diluted with DI water. Hg is measured as a gaseous phase generated by reduction of the sample with SnCl2 in a continuous- flow cold-vapor generator connected to a Thermo-Finnigan Neptune MC-ICPMS. To minimize instrumental fractionation isotope ratios were measured by sample standard bracketing and reported as δ‰ relative to NIST SRM 3133 Hg standard where δAHg = [(A Hg/202Hg)sample/(A Hg/202Hg)NIST313] -1 ×1000‰. In this study we have measured the isotope ratios 198Hg/202Hg, 199Hg/202Hg, 200Hg/202Hg, 201Hg/202Hg and 204Hg/202Hg. In all the fish samples δ198Hg, δ200Hg, δ202Hg, δ204Hg define a mass- dependent fractionation sequence, where as the δ199Hg and δ201Hg depart from the mass- dependent fractionation line and indicate an excess of the odd-N isotopes. The magnitude of the deviation (ΔAHg where A=199 or 201) as obtained by difference between the measured δ199Hg and δ201Hg of the samples and the value obtained by linear scaling defined by the even-N isotopes ranges from approximately 0.2 ‰ to 3‰. The ratios of Δ199Hg /Δ201Hg range from 0.8 to 1

  11. Influence of shell effects on mass asymmetry in fission of different Hg isotopes

    NASA Astrophysics Data System (ADS)

    Andreev, A. V.; Adamian, G. G.; Antonenko, N. V.

    2013-12-01

    With the improved scission-point model mass distributions are calculated for induced fission of Hg isotopes with even mass numbers A = 174 - 198. The calculated mass distributions and mean total kinetic energy of fission fragments are in good agreement with the existing experimental data. The asymmetric mass distribution of fission fragments of 180Hg observed in the recent experiment is explained. The change in the shape of the mass distribution with increasing A of the fissioning AHg nucleus from symmetric for 174Hg to asymmetric around 180Hg, and to more symmetric for 192-198Hg is revealed.

  12. Stable isotope ratio mass spectrometry of nanogram quantities of boron and sulfur

    NASA Astrophysics Data System (ADS)

    Wieser, Michael Eugene

    1998-09-01

    Instrumentation and analytical techniques were developed to measure isotope abundances from nanograms of sulfur and boron. Sulfur isotope compositions were determined employing continuous flow isotope ratio mass spectroscopy (CF-IRMS) procedures and AsS+ thermal ionization mass spectrometry techniques (AsS+-TIMS). Boron isotope abundances were determined by BO2/sp--TIMS. CF-IRMS measurements realized δ34S values from 10 μg sulfur with precisions of ±0.3/perthous. To extend sulfur isotope measurements to much smaller samples, a TIMS procedure was developed to measure 75As32S+ and 75As34S+ at masses 108 and 109 from 200 ng S on a Finnigan MAT 262 with an ion counter. This is possibly the smallest amount of sulfur which has been successfully analyzed isotopically. The internal precision of 32S/34S ratios measured by AsS+-TIMS was better than ±0.15 percent. δ34S-values calculated relative to the measured 32S/34S value of an IAEA AG2S standard (S-1) agreed with those determined by CF-IRMS to within ±3/perthous. The increasing sensitivity of S-isotope analyses permits hiterto impossible investigations e.g. sulfur in tree rings and ice cores. Boron isotope abundances were measured as BO2/sp- from 50 ng B using an older thermal ionization mass spectrometer which had been extensively upgraded including the addition of computer control electronics, sensitive ion current amplification and fiber optic data bus. The internal precisions of the measured 11B/10B ratios were ±0.15 percent and the precisions of δ11B values calculated relative to the accepted international standard (SRM-951) were ±3/perthous. Two applications of boron isotope abundance variations were initiated (1) ground waters of Northern Alberta and (2) coffee beans in different regions of the world. In the first it was demonstrated that boron isotopes could be used to trace boron released during steam injection of oil sands into the surrounding environment. Data from the second study suggest that boron

  13. Liquid chromatography combined with mass spectrometry for 13C isotopic analysis in life science research.

    PubMed

    Godin, Jean-Philippe; Fay, Laurent-Bernard; Hopfgartner, Gérard

    2007-01-01

    Among the different disciplines covered by mass spectrometry, measurement of (13)C/(12)C isotopic ratio crosses a large section of disciplines from a tool revealing the origin of compounds to more recent approaches such as metabolomics and proteomics. Isotope ratio mass spectrometry (IRMS) and molecular mass spectrometry (MS) are the two most mature techniques for (13)C isotopic analysis of compounds, respectively, for high and low-isotopic precision. For the sample introduction, the coupling of gas chromatography (GC) to either IRMS or MS is state of the art technique for targeted isotopic analysis of volatile analytes. However, liquid chromatography (LC) also needs to be considered as a tool for the sample introduction into IRMS or MS for (13)C isotopic analyses of non-volatile analytes at natural abundance as well as for (13)C-labeled compounds. This review presents the past and the current processes used to perform (13)C isotopic analysis in combination with LC. It gives particular attention to the combination of LC with IRMS which started in the 1990's with the moving wire transport, then subsequently moved to the chemical reaction interface (CRI) and was made commercially available in 2004 with the wet chemical oxidation interface (LC-IRMS). The LC-IRMS method development is also discussed in this review, including the possible approaches for increasing selectivity and efficiency, for example, using a 100% aqueous mobile phase for the LC separation. In addition, applications for measuring (13)C isotopic enrichments using atmospheric pressure LC-MS instruments with a quadrupole, a time-of-flight, and an ion trap analyzer are also discussed as well as a LC-ICPMS using a prototype instrument with two quadrupoles. PMID:17853432

  14. Characterization of polyubiquitin chain structure by middle-down mass spectrometry.

    PubMed

    Xu, Ping; Peng, Junmin

    2008-05-01

    Ubiquitin (Ub) is a 76 amino acid polypeptide that modifies a wide range of proteins in the types of monomer or polymers, and functional consequence of ubiquitination is modulated by the length and topologies of polyUb chains. Whereas polyUb chains are usually analyzed by fully trypsin digestion and mass spectrometry (MS), we present here a middle-down strategy to characterize the structure of polyUb chains by high-resolution mass spectrometry (MS). Under optimized condition, native folded polyUb is partially trypsinized exclusively at the R74 residue, generating a large Ub fragment (1-74 residues termed UbR74) and its ubiquitinated form with a diglycine tag (UbR74-GG). The molar ratio between UbR74 and UbR74-GG reflects the length of homogeneous polyUb chains (i.e., 1:1 for the dimer, 1:2 for the trimer, 1:3 for the tetramer, and so on). Moreover, lysine residues in ubiquitin used for chain linkages are detectable by MS/MS and MS/MS/MS of large GG-tagged Ub fragments. The strategy was validated using a number of ubiquitin polymers, including K48-linked human di-Ub, K63-linked human tetra-Ub, as well as His-tagged polyUb chains purified from yeast under native condition. The potential of this strategy to analyze polyUb chains with mixed linkages (e.g., forked chains) is also discussed. Together, this middle-down MS strategy provides a novel complementary method for studying the length and linkages of complex polyUb chain structures. PMID:18351785

  15. Advances in Radioactive-Isotope Science from Mass Measurements

    NASA Astrophysics Data System (ADS)

    Lunney, David

    Mass is a fundamental property that is indispensable for the study of nuclear structure, for applications in stellar nucleosynthesis and neutron-star composition, as well as studies of atomic and weak-interaction physics. We briefly review the mass-measurement programs at radioactive-beam facilities worldwide and examine the wealth of new mass data, compare the strengths of the different installations and reflect on the multitude of physics results. The series of ENAM meetings from 1995 to 2008 saw the rise and subsequent dominance of Penning traps in the field of mass spectrometry, which has continued through the new era of the ARIS meetings. As for the ARIS 2011 conference, we attempt a nomination for "Penning trap of the year."

  16. Correlations of experimental isotope shifts with spectroscopic and mass observables

    SciTech Connect

    Cakirli, R. B.; Casten, R. F.; Blaum, K.

    2010-12-15

    Experimental differential observables relating to mean square charge radii, spectroscopic, and mass observables of even-even nuclei are presented for different regions in the nuclear chart. They exhibit remarkable correlations, not heretofore recognized, that provide a new perspective on structural evolution, especially in exotic nuclei. This can also be a guide for future measurements of charge radii, spectroscopic observables, and masses, as well as for future theoretical approaches.

  17. Isotope ratio monitoring of small molecules and macromolecules by liquid chromatography coupled to isotope ratio mass spectrometry.

    PubMed

    Godin, Jean-Philippe; Hau, Jörg; Fay, Laurent-Bernard; Hopfgartner, Gérard

    2005-01-01

    In the field of isotope ratio mass spectrometry, the introduction of an interface allowing the connection of liquid chromatography (LC) and isotope ratio mass spectrometry (IRMS) has opened a range of new perspectives. The LC interface is based on a chemical oxidation, producing CO2 from organic molecules. While first results were obtained from the analysis of low molecular weight compounds, the application of compound-specific isotope analysis by irm-LC/MS to other molecules, in particular biomolecules, is presented here. The influence of the LC flow rate on the CO2 signal and on the observed delta13C values is demonstrated. The limits of quantification for angiotensin III and for leucine were 100 and 38 pmol, respectively, with a standard deviation of the delta13C values better than 0.4 per thousand. Also, accuracy and precision of delta13C values for elemental analyser-IRMS and flow injection analysis-IRMS (FIA-LC/MS) were compared. For compounds with molecular weights ranging from 131 to 66,390 Da, precision was better than 0.3 per thousand, and accuracy varied from 0.1 to 0.7 per thousand. In a second part of the work, a two-dimensional (2D)-LC method for the separation of 15 underivatised amino acids is demonstrated; the precision of delta13C values for several amino acids by irm-LC/MS was better than 0.3 per thousand at natural abundance. For labelled mixtures, the coefficient of variation was between 1% at 0.07 atom % excess (APE) for threonine and alanine, and around 10% at 0.03 APE for valine and phenylalanine. The application of irm-LC/MS to the determination of the isotopic enrichment of 13C-threonine in an extract of rat colon mucosa demonstrated a precision of 0.5 per thousand, or 0.001 atom %. PMID:16124031

  18. Isotope ratio mass spectrometry coupled to liquid and gas chromatography for wine ethanol characterization.

    PubMed

    Cabañero, Ana I; Recio, Jose L; Rupérez, Mercedes

    2008-10-01

    Two new procedures for wine ethanol 13C/12C isotope ratio determination, using high-performance liquid chromatography and gas chromatography isotope ratio mass spectrometry (HPLC/IRMS and GC/IRMS), have been developed to improve isotopic methods dedicated to the study of wine authenticity. Parameters influencing separation of ethanol from wine matrix such as column, temperature, mobile phase, flow rates and injection mode were investigated. Twenty-three wine samples from various origins were analyzed for validation of the procedures. The analytical precision was better than 0.15 per thousand, and no significant isotopic fractionation was observed employing both separative techniques coupled to IRMS. No significant differences and a very strong correlation (r = 0.99) were observed between the 13C/12C ratios obtained by the official method (elemental analyzer/isotope ratio mass spectrometry) and the proposed new methodology. The potential advantages of the developed methods over the traditional one are speed (reducing time required from hours to minutes) and simplicity. In addition, these are the first isotopic methods that allow 13C/12C determination directly from a liquid sample with no previous ethanol isolation, overcoming technical difficulties associated with sample treatment. PMID:18798196

  19. Oxygen isotopic measurements by secondary ion mass spectrometry in uranium oxide microparticles: a nuclear forensic diagnostic.

    PubMed

    Tamborini, G; Phinney, D; Blidstein, O; Betti, M

    2002-12-01

    To exploit oxygen isotopic measurement by SIMS as a diagnostic tool in nuclear forensics, the magnitude and reproducibility of 0-isotope instrumental mass discrimination for O-isotope standards in the SIMS laboratory at the Institute for Transuranium Elements has been evaluated. Tests for matrix-dependent discrimination effects on three different O-isotope standards with substantially different matrix compositions have been performed. The results were checked by an interlaboratory comparison of O-isotope discrimination with those obtained in the SIMS laboratory at the Lawrence Livermore National Laboratory on two standards. The results from the two laboratories are in very good agreement, indicating statistically indistinguishable instrumental mass discrimination factors for 180/160 ratios on the Cameca 6f and 3f, when the analyses are performed under the experimental conditions described. The 2sigma(mean) uncertainties of these factors are in the range of 0.3-0.9%. In accordance with the tested methodology, 0-isotope compositions were measured in three particulate uranium oxide samples of nuclear forensics interest. PMID:12498207

  20. New Short-Lived Isotope 221U and the Mass Surface Near N =126

    NASA Astrophysics Data System (ADS)

    Khuyagbaatar, J.; Yakushev, A.; Düllmann, Ch. E.; Ackermann, D.; Andersson, L.-L.; Block, M.; Brand, H.; Cox, D. M.; Even, J.; Forsberg, U.; Golubev, P.; Hartmann, W.; Herzberg, R.-D.; Heßberger, F. P.; Hoffmann, J.; Hübner, A.; Jäger, E.; Jeppsson, J.; Kindler, B.; Kratz, J. V.; Krier, J.; Kurz, N.; Lommel, B.; Maiti, M.; Minami, S.; Mistry, A. K.; Mrosek, Ch. M.; Pysmenetska, I.; Rudolph, D.; Sarmiento, L. G.; Schaffner, H.; Schädel, M.; Schausten, B.; Steiner, J.; De Heidenreich, T. Torres; Uusitalo, J.; Wegrzecki, M.; Wiehl, N.; Yakusheva, V.

    2015-12-01

    Two short-lived isotopes 221U and 222U were produced as evaporation residues in the fusion reaction 50Ti + 176Yb at the gas-filled recoil separator TASCA. An α decay with an energy of Eα=9.31 (5 ) MeV and half-life T1 /2=4.7 (7 ) μ s was attributed to 222U. The new isotope 221U was identified in α -decay chains starting with Eα=9.71 (5 ) MeV and T1 /2=0.66 (14 ) μ s leading to known daughters. Synthesis and detection of these unstable heavy nuclei and their descendants were achieved thanks to a fast data readout system. The evolution of the N =126 shell closure and its influence on the stability of uranium isotopes are discussed within the framework of α -decay reduced width.

  1. A mass-independent sulfur isotope effect in the nonthermal formation

    NASA Technical Reports Server (NTRS)

    Bains-Sahota, Swroop K.; Thiemens, Mark H.

    1989-01-01

    A nonmass-dependent sulfur isotope effect is present in the rotationally symmetric S2F10 molecule, produced in an electrical discharge through sulfur tetrafluoride. A similar isotopic fractionation was observed in the product S2F10 from the electrodissociation of SF5Cl and in the reaction between fluorine atoms produced by F2 photolysis and SF2, collectively ruling out the SF5 formation process as the source of the mass-independent fractionation. The secondary dissociation of S2F10 as a source of the mass-independent fractionation is ruled out by control S2F10 dissociation experiments which are shown to produce small mass-dependent fractionations. Mass-dependent effects such as sulfur isotopic exchange and secondary dissociation reactions are significant processes for the system under study, and have been quantitatively accounted for. The role of symmetry in nonmass-dependent isotope effects is strengthened by the present experiments, and the search and characterization of mass-independent effects is extended to sulfur-containing molecules.

  2. Separation and Analysis of Boron Isotope in High Plant by Thermal Ionization Mass Spectrometry

    PubMed Central

    Xu, Qingcai; Dong, Yuliang; Zhu, Huayu; Sun, Aide

    2015-01-01

    Knowledge of boron and its isotope in plants is useful to better understand the transposition and translocation of boron within plant, the geochemical behavior in the interface between soil and plant, and the biogeochemical cycle of boron. It is critical to develop a useful method to separate boron from the plant for the geochemical application of boron and its isotope. A method was developed for the extraction of boron in plant sample, whose isotope was determined by thermal ionization mass spectrometry. The results indicated that this method of dry ashing coupled with two-step ion-exchange chromatography is powerful for the separation of boron in plant sample with large amounts of organic matters completely. The ratios of boron isotope composition in those plant tissue samples ranged from −19.45‰ to +28.13‰ (total range: 47.58‰) with a mean value of 2.61 ± 11.76‰ SD. The stem and root isotopic compositions were lower than those in flower and leaf. The molecular mechanism of boron isotope may be responsible for the observed variation of boron isotopic composition and are considered as a useful tool for the better understanding of boron cycling process in the environment and for the signature of living systems. PMID:26819618

  3. Separation and Analysis of Boron Isotope in High Plant by Thermal Ionization Mass Spectrometry.

    PubMed

    Xu, Qingcai; Dong, Yuliang; Zhu, Huayu; Sun, Aide

    2015-01-01

    Knowledge of boron and its isotope in plants is useful to better understand the transposition and translocation of boron within plant, the geochemical behavior in the interface between soil and plant, and the biogeochemical cycle of boron. It is critical to develop a useful method to separate boron from the plant for the geochemical application of boron and its isotope. A method was developed for the extraction of boron in plant sample, whose isotope was determined by thermal ionization mass spectrometry. The results indicated that this method of dry ashing coupled with two-step ion-exchange chromatography is powerful for the separation of boron in plant sample with large amounts of organic matters completely. The ratios of boron isotope composition in those plant tissue samples ranged from -19.45‰ to +28.13‰ (total range: 47.58‰) with a mean value of 2.61 ± 11.76‰ SD. The stem and root isotopic compositions were lower than those in flower and leaf. The molecular mechanism of boron isotope may be responsible for the observed variation of boron isotopic composition and are considered as a useful tool for the better understanding of boron cycling process in the environment and for the signature of living systems. PMID:26819618

  4. Essentials of iron, chromium, and calcium isotope analysis of natural materials by thermal ionization mass spectrometry

    USGS Publications Warehouse

    Fantle, M.S.; Bullen, T.D.

    2009-01-01

    The use of isotopes to understand the behavior of metals in geological, hydrological, and biological systems has rapidly expanded in recent years. One of the mass spectrometric techniques used to analyze metal isotopes is thermal ionization mass spectrometry, or TIMS. While TIMS has been a useful analytical technique for the measurement of isotopic composition for decades and TIMS instruments are widely distributed, there are significant difficulties associated with using TIMS to analyze isotopes of the lighter alkaline earth elements and transition metals. Overcoming these difficulties to produce relatively long-lived and stable ion beams from microgram-sized samples is a non-trivial task. We focus here on TIMS analysis of three geologically and environmentally important elements (Fe, Cr, and Ca) and present an in-depth look at several key aspects that we feel have the greatest potential to trouble new users. Our discussion includes accessible descriptions of different analytical approaches and issues, including filament loading procedures, collector cup configurations, peak shapes and interferences, and the use of isotopic double spikes and related error estimation. Building on previous work, we present quantitative simulations, applied specifically in this study to Fe and Ca, that explore the effects of (1) time-variable evaporation of isotopically homogeneous spots from a filament and (2) interferences on the isotope ratios derived from a double spike subtraction routine. We discuss how and to what extent interferences at spike masses, as well as at other measured masses, affect the double spike-subtracted isotope ratio of interest (44Ca/40Ca in the case presented, though a similar analysis can be used to evaluate 56Fe/54Fe and 53Cr/52Cr). The conclusions of these simulations are neither intuitive nor immediately obvious, making this examination useful for those who are developing new methodologies. While all simulations are carried out in the context of a

  5. Pyrolysis-gas chromatography-isotope ratio mass spectrometry of polyethylene.

    PubMed

    González-Pérez, J A; Jiménez-Morillo, N T; de la Rosa, J M; Almendros, G; González-Vila, F J

    2015-04-01

    Polyethylene is probably the most used plastic material in daily life and its accurate analysis is of importance. In this communication the chemical structure of polyethylenes is studied in detail using conventional analytical pyrolysis (Py-GC/MS), bulk stable isotopic analysis (IRMS) and pyrolysis compound specific stable isotopic analysis (Py-CSIA) to measure stable isotope proportions (δ(13)C, δ(15)N and δD) of polyethylene pyrolysis compounds. Polyethylene pyrolysis yields triplet peaks of n-alkanes, α-alkenes and α,ω-alkanedienes. No differences were found for bulk δ(13)C among different polyethylene types. However, conspicuous differences in δD were evident. It was possible to assign structure δ(13)C and δD values to specific polyethylene pyrolysis products in the range 12-18 carbon chain length. Conspicuous differences were found for the pyrolysis products with unsaturated moieties showing significant higher δD values than saturated chains (alkanes) that were deuterium depleted. In addition, a full isotopic fingerprinting (δ(13)C, δ(15)N and δD) for a dye (o-chloroaniline) contained in a polyethylene is reported. To the best of our knowledge this is the first application Py-CSIA to the study of a synthetic polymer. This hyphenated analytical technique is a promising tool to study synthetic materials, providing not only a fingerprinting, but also allowing the traceability of the polymerization process and the origin of the materials. PMID:25725959

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

    NASA Astrophysics Data System (ADS)

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

    1991-12-01

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

  7. Mass-independent fractionation of oxygen isotopes during thermal decomposition of carbonates

    PubMed Central

    Miller, Martin F.; Franchi, Ian A.; Thiemens, Mark H.; Jackson, Teresa L.; Brack, André; Kurat, Gero; Pillinger, Colin T.

    2002-01-01

    Nearly all chemical processes fractionate 17O and 18O in a mass-dependent way relative to 16O, a major exception being the formation of ozone from diatomic oxygen in the presence of UV radiation or electrical discharge. Investigation of oxygen three-isotope behavior during thermal decomposition of naturally occurring carbonates of calcium and magnesium in vacuo has revealed that, surprisingly, anomalous isotopic compositions are also generated during this process. High-precision measurements of the attendant three-isotope fractionation line, and consequently the magnitude of the isotopic anomaly (Δ17O), demonstrate that the slope of the line is independent of the nature of the carbonate but is controlled by empirical factors relating to the decomposition procedure. For a slope identical to that describing terrestrial silicates and waters (0.5247 ± 0.0007 at the 95% confidence level), solid oxides formed during carbonate pyrolysis fit a parallel line offset by −0.241 ± 0.042‰. The corresponding CO2 is characterized by a positive offset of half this magnitude, confirming the mass-independent nature of the fractionation. Slow, protracted thermolysis produces a fractionation line of shallower slope (0.5198 ± 0.0007). These findings of a 17O anomaly being generated from a solid, and solely by thermal means, provide a further challenge to current understanding of the nature of mass-independent isotopic fractionation. PMID:12167677

  8. 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.

  9. Detection and analysis of polymerase chain reaction products by mass spectrometry

    SciTech Connect

    Hurst, G.B., Doktycz, M.J., Britt, P.F., Vass, A.A., Buchanan, M.V.

    1997-02-01

    This paper describes recent and ongoing efforts to overcome some of the obstacles to more routine and robust application of MALDI-TOF to analysis of polymerase chain reaction products and other information- bearing nucleic acid molecules. Methods for purifying nucleic acid samples are described, as is the application of delayed extraction TOF mass spectrometry to analysis of short oligonucleotides.

  10. Using Theoretical Protein Isotopic Distributions to Parse Small-Mass-Difference Post-Translational Modifications via Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Rhoads, Timothy W.; Williams, Jared R.; Lopez, Nathan I.; Morré, Jeffrey T.; Bradford, C. Samuel; Beckman, Joseph S.

    2013-01-01

    Small-mass-difference modifications to proteins are obscured in mass spectrometry by the natural abundance of stable isotopes such as 13C that broaden the isotopic distribution of an intact protein. Using a ZipTip (Millipore, Billerica, MA, USA) to remove salt from proteins in preparation for high-resolution mass spectrometry, the theoretical isotopic distribution intensities calculated from the protein's empirical formula could be fit to experimentally acquired data and used to differentiate between multiple low-mass modifications to proteins. We could readily distinguish copper from zinc bound to a single-metal superoxide dismutase (SOD1) species; copper and zinc only differ by an average mass of 1.8 Da and have overlapping stable isotope patterns. In addition, proteins could be directly modified while bound to the ZipTip. For example, washing 11 mM S-methyl methanethiosulfonate over the ZipTip allowed the number of free cysteines on proteins to be detected as S-methyl adducts. Alternatively, washing with the sulfhydryl oxidant diamide could quickly reestablish disulfide bridges. Using these methods, we could resolve the relative contributions of copper and zinc binding, as well as disulfide reduction to intact SOD1 protein present from <100 μg of the lumbar spinal cord of a transgenic, SOD1 overexpressing mouse. Although techniques like ICP-MS can measure total metal in solution, this is the first method able to assess the metal-binding and sulfhydryl reduction of SOD1 at the individual subunit level and is applicable to many other proteins.

  11. Stable-hydrogen isotope heterogeneity in keratinous materials: mass spectrometry and migratory wildlife tissue subsampling strategies.

    PubMed

    Wassenaar, Leonard I; Hobson, Keith A

    2006-01-01

    Stable-hydrogen isotope measurements (deltaD) of biological tissues have gained widespread acceptance in wildlife and forensic studies, especially in tracking geographical movements of birds and other species. Continuous-flow isotope-ratio mass spectrometry enables high-throughput deltaD analyses to be conducted on tissue samples as small as 0.15 mg, compared with conventional offline analyses that require 7-10 mg. This reduction in sample size has raised concerns regarding intra-sample hydrogen isotopic variance due to potential biological heterogeneities that could exceed interpretations of geospatial origin. To help resolve this, feathers were obtained from captive birds to examine isotopic variance expected due to sample size, location, and heterogeneity factors, and from selected wild birds to examine isotopic variance due to these and to additional dietary or location changes during feather growth. Captive bird feathers were sub-sampled along the vane on either side of a single feather at masses of 0.25, 0.35, 0.45, 0.6, 1.0 and 2.0 mg, and along the rachis. The results showed consistency of feather deltaD measurements across a wide range of sample masses. Within-feather deltaD isotopic variance for captive and some wild birds was as low as +/-3 per thousand for vane material, which corresponds to a geospatial resolution of about 1 degree of latitude in central North America. Intra-sample variance for the rachis was +/-5 per thousand, with lower deltaD values for both wild and captive birds. However, given the extraordinary intra-feather deltaD variance observed in some wild species, we recommend researchers first carefully assess the degree of intra- and inter-sample hydrogen isotopic variation in the selected tissue growth period for the species of interest before geospatial interpretations of origin are attempted. PMID:16862621

  12. Performance of human mass balance studies with stable isotope-labeled drug and continuous flow-isotope ratio mass spectrometry: a progress report.

    PubMed

    Browne, T R; Szabo, G K; Ajami, A; Browne, D G

    1998-04-01

    We propose performing human mass balance studies by administering stable isotope labeled (13C or 15N) drug and quantitating excess (above background) 13C or 15N in urine, serum, and feces by continuous flow-isotope ratio mass spectrometry (CF-IRMS). Theoretical calculations and empirical data (dynamic range, linearity, sensitivity, precision, accuracy) are presented to establish that commercially available CF-IRMS instruments can quantitate stable isotope labeled (one or two 15N or 13C labels) drug concentrations of 1.0 microg/mL or greater in urine, serum (15N), or feces. More than two 13C labels may be necessary to quantitate 1.0 microg/mL of drug in serum. Three volunteers received 650 mg of 15N13C2-acetaminophen, and urine was collected for 72 hours. Percent of administered label recovered in urine from the three subjects was 97.4, 78.9, and 95.4 for 13C and 90.3, 77.0, and 90.6 for 15N. Fecal recovery of label for one subject was 0.9% (13C2) and 1.1% (15N). Serum pharmacokinetic values obtained by counting 13C or 15N in one subject were as expected for acetaminophen. This method appears to be promising, and further validation is ongoing. PMID:9590457

  13. An Efficient Method to Calculate the Aggregated Isotopic Distribution and Exact Center-Masses

    NASA Astrophysics Data System (ADS)

    Claesen, Jürgen; Dittwald, Piotr; Burzykowski, Tomasz; Valkenborg, Dirk

    2012-04-01

    In this article, we present a computation- and memory-efficient method to calculate the probabilities of occurrence and exact center-masses of the aggregated isotopic distribution of a molecule. The method uses fundamental mathematical properties of polynomials given by the Newton-Girard theorem and Viete's formulae. The calculation is based on the atomic composition of the molecule and the natural abundances of the elemental isotopes in normal terrestrial matter. To evaluate the performance of the proposed method, which we named BRAIN, we compare it with the results obtained from five existing software packages ( IsoPro, Mercury, Emass, NeutronCluster, and IsoDalton) for 10 biomolecules. Additionally, we compare the computed mass centers with the results obtained by calculating, and subsequently aggregating, the fine isotopic distribution for two of the exemplary biomolecules. The algorithm will be made available as a Bioconductor package in R, and is also available upon request.

  14. Recharge Estimation Using Water, Chloride and Isotope Mass Balances

    NASA Astrophysics Data System (ADS)

    Dogramaci, S.; Firmani, G.; Hedley, P.; Skrzypek, G.; Grierson, P. F.

    2014-12-01

    Discharge of surplus mine water into ephemeral streams may elevate groundwater levels and alter the exchange rate between streams and underlying aquifers but it is unclear whether volumes and recharge processes are within the range of natural variability. Here, we present a case study of an ephemeral creek in the semi-arid subtropical Hamersley Basin that has received continuous mine discharge for more than five years. We used a numerical model coupled with repeated measurements of water levels, chloride concentrations and the hydrogen and oxygen stable isotope composition (δ2H and δ18O) to estimate longitudinal evapotranspiration and recharge rates along a 27 km length of Weeli Wolli Creek. We found that chloride increased from 74 to 120 mg/L across this length, while δ18O increased from -8.24‰ to -7.00‰. Groundwater is directly connected to the creek for the first 13 km and recharge rates are negligible. Below this point, the creek flows over a highly permeable aquifer and water loss by recharge increases to a maximum rate of 4.4 mm/d, which accounts for ~ 65% of the total water discharged to the creek. Evapotranspiration losses account for the remaining ~35%. The calculated recharge from continuous flow due to surplus water discharge is similar to that measured for rainfall-driven flood events along the creek. Groundwater under the disconnected section of the creek is characterised by a much lower Cl concentration and more depleted δ18O value than mining discharge water but is similar to flood water generated by large episodic rainfall events. Our results suggest that the impact of recharge from continuous flow on the creek has not extended beyond 27 km from the discharge point. Our approach using a combination of hydrochemical and isotope methods coupled with classical surface flow hydraulic modelling allowed evaluation of components of water budget otherwise not possible in a highly dynamic system that is mainly driven by infrequent but large episodic

  15. 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

  16. Protein N- and C-Termini Identification Using Mass Spectrometry and Isotopic Labeling

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A new method for protein N- and C-terminal analysis using mass spectrometry is introduced. A novel stable isotopic labeling scheme has been developed to identify terminal peptides generated from an enzyme digestion for the determination of both N- and C-termini of the protein. This method works dire...

  17. The use of gas chromatography-mass spectrometry/combustion/isotope ratio mass spectrometry to demonstrate progesterone treatment in bovines.

    PubMed

    Janssens, Geert; Mangelinckx, Sven; Courtheyn, Dirk; De Kimpe, Norbert; Matthijs, Bert; Le Bizec, Bruno

    2016-06-01

    Currently, no analytical method is available to demonstrate progesterone administration in biological samples collected in rearing animals, and therefore, tracking the abuse of this popular growth promoter is arduous. In this study, a method is presented to reveal progesterone (PG) treatment on the basis of carbon isotope measurement of 5β-pregnane-3α, 20α-diol (BAA-PD), a major PG metabolite excreted in bovine urine, by gas chromatography-mass spectrometry/combustion/isotope ratio mass spectrometry (GC-MS/C/IRMS). 5-Androstene-3β,17α-diol (AEdiol) is used as endogenous reference compound. Intermediate precisions (n=11) of 0.56‰ and 0.68‰ have been determined for AEdiol and BAA-PD, respectively. The analytical method was used for the very first time to successfully differentiate urine samples collected in treated and untreated animals. PMID:27157423

  18. Carbon Stable Isotope Analysis of Methylmercury Toxin in Biological Materials by Gas Chromatography Isotope Ratio Mass Spectrometry.

    PubMed

    Masbou, Jeremy; Point, David; Guillou, Gaël; Sonke, Jeroen E; Lebreton, Benoit; Richard, Pierre

    2015-12-01

    A critical component of the biogeochemical cycle of mercury (Hg) is the transformation of inorganic Hg to neurotoxic monomethylmercury (CH3Hg). Humans are exposed to CH3Hg by consuming marine fish, yet the origin of CH3Hg in fish is a topic of debate. The carbon stable isotopic composition (δ(13)C) embedded in the methyl group of CH3Hg remains unexplored. This new isotopic information at the molecular level is thought to represent a new proxy to trace the carbon source at the origin of CH3Hg. Here, we present a compound-specific stable isotope analysis (CSIA) technique for the determination of the δ(13)C value of CH3Hg in biological samples by gas chromatography combustion isotope ratio mass spectrometry analysis (GC-C-IRMS). The method consists first of calibrating a CH3Hg standard solution for δ(13)C CSIA. This was achieved by comparing three independent approaches consisting of the derivatization and halogenation of the CH3Hg standard solution. The determination of δ(13)C(CH3Hg) values on natural biological samples was performed by combining a CH3Hg selective extraction, purification, and halogenation followed by GC-C-IRMS analysis. Reference δ(13)C values were established for a tuna fish certified material (ERM-CE464) originating from the Adriatic Sea (δ(13)C(CH3Hg) = -22.1 ± 1.5‰, ± 2 SD). This value is similar to the δ(13)C value of marine algal-derived particulate organic carbon (δ(13)CPOC = -21‰). PMID:26511394

  19. Performance and limits of liquid chromatography isotope ratio mass spectrometry system for halogenated compounds

    NASA Astrophysics Data System (ADS)

    Gilevska, Tetyana; Gehre, Matthias; Richnow, Hans

    2014-05-01

    Compound Specific Isotope Analysis (CSIA) has been an important step for the assessment of the origin and fate of compounds in environmental science.[1] Biologically or pharmaceutically important compounds often are not amenable for gas chromatographic separation because of high polarity and lacking volatility, thermostability. In 2004 liquid chromatography isotope ratio mass spectrometry (LC-IRMS) became commercially available. LC-IRMS system intent a quantitative conversion of analytes separation into CO2 via wet oxidation with sodium persulfate in the presence of phosphoric acid while analytes are still dissolved in the aqueous liquid phase.[2] The aim of this study is to analyze the oxidation capacity of the interface of the LC-IRMS system and determine which parameters could improve oxidation of compounds which are resistant to persulfate oxidation. Oxidation capacity of the liquid chromatography isotope ratio mass spectrometry system was tested with halogenated acetic acid and a set of aromatic compounds with different substitutes. Acetic acid (AA) was taken as a model compound for complete oxidation and compared to the oxidation of other analytes on a molar basis. Correct values were obtained for di- and mono chlorinated and fluorinated and also for tribrominated acetic acid and for all studied aromatic compounds. Incomplete oxidation for trichloroacetic (TCAA) and trifluoroacetic (TFAA) acid was revealed with lower recovery compared to acetic acid and isotope fractionation leading to depleted carbon isotope composition compared to values obtained with an elementary analyzer connected to an isotope mass spectrometer Several optimization steps were tried in order to improve the oxidation of TCAA and TFAA: (i) increasing the concentration of the oxidizing agent, (ii) variation of flow rate of the oxidizing and acid solution, (iii) variation of flow rate of liquid chromatography pump (iv) addition of a catalyzer. These modifications lead to longer reaction time

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

    PubMed Central

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

    2006-01-01

    Background Secondary-ion mass spectrometry (SIMS) is an important tool for investigating isotopic composition in the chemical and materials sciences, but its use in biology has been limited by technical considerations. Multi-isotope imaging mass spectrometry (MIMS), which combines a new generation of SIMS instrument with sophisticated ion optics, labeling with stable isotopes, and quantitative image-analysis software, was developed to study biological materials. Results The new instrument allows the production of mass images of high lateral resolution (down to 33 nm), as well as the counting or imaging of several isotopes simultaneously. As MIMS can distinguish between ions of very similar mass, such as 12C15N- and 13C14N-, it enables the precise and reproducible measurement of isotope ratios, and thus of the levels of enrichment in specific isotopic labels, within volumes of less than a cubic micrometer. The sensitivity of MIMS is at least 1,000 times that of 14C autoradiography. The depth resolution can be smaller than 1 nm because only a few atomic layers are needed to create an atomic mass image. We illustrate the use of MIMS to image unlabeled mammalian cultured cells and tissue sections; to analyze fatty-acid transport in adipocyte lipid droplets using 13C-oleic acid; to examine nitrogen fixation in bacteria using 15N gaseous nitrogen; to measure levels of protein renewal in the cochlea and in post-ischemic kidney cells using 15N-leucine; to study DNA and RNA co-distribution and uridine incorporation in the nucleolus using 15N-uridine and 81Br of bromodeoxyuridine or 14C-thymidine; to reveal domains in cultured endothelial cells using the native isotopes 12C, 16O, 14N and 31P; and to track a few 15N-labeled donor spleen cells in the lymph nodes of the host mouse. Conclusion MIMS makes it possible for the first time to both image and quantify molecules labeled with stable or radioactive isotopes within subcellular compartments. PMID:17010211

  1. Detailed assessment of isotope ratio infrared spectroscopy and isotope ratio mass spectrometry for the stable isotope analysis of plant and soil waters

    NASA Astrophysics Data System (ADS)

    Zhao, L.; Xiao, H.; Zhou, J.; Wang, L.; Cheng, G.; Zhou, M.; Yin, L.; McCabe, M. F.

    2011-12-01

    As an alternative to isotope ratio mass spectrometry (IRMS) the isotope ratio infrared spectroscopy (IRIS) approach has the advantage of low cost, continuous measurement and capacity for field based application for the analysis of stable water isotopes. Recent studies have indicated that there are potential issues of organic contamination of the spectral signal in the IRIS method, resulting in errant readings for leaf samples. To gain a more thorough understanding of the effects of sample type (e.g., leaf, root, stem and soil), sample species, sampling time and climatic condition (dry vs. wet) on water isotope estimates using IRIS, we collected soil samples and plant components from a number of major species at a fine temporal resolution (every two hours for 24-48 hours) across three locations with different climatic conditions in the Heihe River Basin, China. The hydrogen and oxygen isotopic composition of the extracted water from these samples was measured using both an IRMS and IRIS instrument. Results show that the mean discrepancy between the IRMS and IRIS approach, for δ18O and δD respectively, was: -5.6% and -75.7% for leaf water; -4.0% and -23.3% for stem water; -3.4% and -28.2% for root water; -6.7% and -0.5% for xylem water; -0.06% and -0.3% for xylem flow; and -0.1% and 0.3% for soil water. The order of the discrepancy followed: leaf > stem ≈ root > xylem > xylem flow ≈ soil. In general, species of the same functional types (e.g., woody vs. herbaceous) within similar habitats showed similar deviations. For different functional types, the differences were large. Sampling during the nighttime did not remove the observed deviations.

  2. Detailed assessment of isotope ratio infrared spectroscopy and isotope ratio mass spectrometry for the stable isotope analysis of plant and soil waters.

    PubMed

    Zhao, Liangju; Xiao, Honglang; Zhou, Jian; Wang, Lixin; Cheng, Guodong; Zhou, Maoxian; Yin, Li; McCabe, Matthew F

    2011-10-30

    As an alternative to isotope ratio mass spectrometry (IRMS), the isotope ratio infrared spectroscopy (IRIS) approach has the advantage of low cost, continuous measurement and the capacity for field-based application for the analysis of the stable isotopes of water. Recent studies have indicated that there are potential issues of organic contamination of the spectral signal in the IRIS method, resulting in incorrect results for leaf samples. To gain a more thorough understanding of the effects of sample type (e.g., leaf, root, stem and soil), sample species, sampling time and climatic condition (dry vs. wet) on water isotope estimates using IRIS, we collected soil samples and plant components from a number of major species at a fine temporal resolution (every 2 h for 24-48 h) across three locations with different climatic conditions in the Heihe River Basin, China. The hydrogen and oxygen isotopic compositions of the extracted water from these samples were measured using both an IRMS and an IRIS instrument. The results show that the mean discrepancies between the IRMS and IRIS approaches for δ(18) O and δD, respectively, were: -5.6‰ and -75.7‰ for leaf water; -4.0‰ and -23.3‰ for stem water; -3.4‰ and -28.2‰ for root water; -0.5‰ and -6.7‰ for xylem water; -0.06‰ and -0.3‰ for xylem flow; and -0.1‰ and 0.3‰ for soil water. The order of the discrepancy was: leaf > stem ≈ root > xylem > xylem flow ≈ soil. In general, species of the same functional types (e.g., woody vs. herbaceous) within similar habitats showed similar deviations. For different functional types, the differences were large. Sampling at nighttime did not remove the observed deviations. PMID:21953962

  3. Natural variation of magnesium isotopes in mammal bones and teeth from two South African trophic chains

    NASA Astrophysics Data System (ADS)

    Martin, Jeremy E.; Vance, Derek; Balter, Vincent

    2014-04-01

    Isotopic fractionations accompanying element transfer through terrestrial ecosystems have the potential to shed light on ecological interactions between primary producers and consumers, but with the exception of carbon and nitrogen this potential has barely been exploited. Here, the magnesium stable isotope composition of bones and teeth of extant mammals from Kruger National Park (KNP) and Western Cape (WC), South Africa was measured for the first time. The nature of the geological substrate proves to be a major determinant of the ecosystem isotope baseline, as indicated by the lighter magnesium isotope ratios measured in WC mammals (ranging from -1.58‰ to -0.79‰) compared to those from KNP mammals (ranging from -1.01‰ to -0.04‰). Therefore, comparisons between the isotope signatures of taxa must be restricted to a pre-defined geographic area with a homogeneous substrate. In both parks, Mg shows slight enrichment in heavier isotopes from herbivores to carnivores. Plant remains trapped in the dentition of herbivores provide direct evidence of dietary source and, when available, were measured. In KNP only, δ26Mg of plant remains is systematically lighter than the values for herbivore teeth. These results invite further exploration of the variability of Mg isotopes in vertebrate ecosystems in order to test whether magnesium, a bio-essential element present in relatively large proportions in bone and teeth apatite, may serve as an additional trophic tracer to nitrogen, which is a constituent of collagen that rapidly degrades after burial.

  4. Determination of phenylalanine isotope ratio enrichment by liquid chromatography/time- of-flight mass spectrometry.

    PubMed

    Wu, Zhanpin; Zhang, Xiao-Jun; Cody, Robert B; Wolfe, Robert R

    2004-01-01

    The application of time-of-flight mass spectrometry to isotope ratio measurements has been limited by the relatively low dynamic range of the time-to-digital converter detectors available on commercial LC/ToF-MS systems. Here we report the measurement of phenylalanine isotope ratio enrichment by using a new LC/ToF-MS system with wide dynamic range. Underivatized phenylalanine was injected onto a C18 column directly with 0.1% formic acid/acetonitrile as the mobile phase. The optimal instrument parameters for the time-of-flight mass spectrometer were determined by tuning the instrument with a phenylalanine standard. The accuracy of the isotope enrichment measurement was determined by the injection of standard solutions with known isotope ratios ranging from 0.02% to 9.2%. A plot of the results against the theoretical values gave a linear curve with R2 of 0.9999. The coefficient of variation for the isotope ratio measurement was below 2%. The method is simple, rapid, and accurate and presents an attractive alternative to traditional GC/MS applications. PMID:15531795

  5. Estimating groundwater exchange with lakes: 1. The stable isotope mass balance method

    USGS Publications Warehouse

    Krabbenhoft, David P.; Bowser, Carl J.; Anderson, Mary P.; Valley, John W.

    1990-01-01

    Groundwater inflow and outflow contributions to the hydrologic budget of lakes can be determined using a stable isotope (18O/16O) mass balance method. The stable isotope method provides a way of integrating the spatial and temporal complexities of the flow field around a lake, thereby offering an appealing alternative to the traditional time and labor intensive methods using seepage meters and an extensive piezometer network. In this paper the method is applied to a lake in northern Wisconsin, demonstrating that it can be successfully applied to lakes in the upper midwest where thousands of similar lakes exist. Inflow and outflow rates calculated for the Wisconsin lake using the isotope mass balance method are 29 and 54 cm/yr, respectively, which compare well to estimates, derived independently using a three-dimensional groundwater flow and solute transport model, of 20 and 50 cm/yr. Such a favorable comparison lends confidence to the use of the stable isotope method to estimate groundwater exchange with lakes. In addition, utilization of stable isotopes in studies of groundwater-lake systems lends insight into mixing processes occurring in the unsaturated zone and in the aquifer surrounding the lake and verifies assumed flow paths based on head measurements in piezometers.

  6. Removing costs from the health care supply chain: lessons from mass retail.

    PubMed

    Agwunobi, John; London, Paul A

    2009-01-01

    Improved supply-chain management and high-volume purchasing have benefited other industries. This same approach could also reduce health care costs. Streamlining layers in the supply chain and using purchasing volume to reduce prices can save money and may improve care. Providing access to in-store health clinics and low-cost generic drugs are examples of how this approach is being tested by mass retailers. We examine lessons learned from these and similar initiatives and identify opportunities to cut the costs of generic and name-brand drugs, medical supplies, over-the-counter remedies, and vision care. PMID:19738249

  7. Observations of Carbon Chain Chemistry in the Envelopes of Low-Mass Protostars

    NASA Technical Reports Server (NTRS)

    Cordiner, M.; Charnley, S.; Buckle, J. V.; Walsh, C.; Millar, T. J.

    2012-01-01

    Observational results are reported from our surveys in the Northern Hemisphere (using the Onsala 20 m telescope) and the Southern Hemisphere (using the Mopra 22 m telescope) to search for 3 mm emission lines from carbon-chain-bearing species and other complex molecules in the envelopes of low-mass protostars. Based on a sample of approximately 60 sources, we find that carbon-chain-bearing species including HC3N (and C4H) are highly abundant in the vicinity of more than half of the observed protostars. The origin and evolution of these species, including their likely incorporation into ices in protoplanetary disks will be discussed

  8. The application of isotope ratio mass spectrometry for discrimination and comparison of adhesive tapes.

    PubMed

    Horacek, Micha; Min, Ji-Sook; Heo, Sangcheol; Park, Jongseo; Papesch, Wolfgang

    2008-06-01

    Forensic scientists are frequently requested to differentiate between, or compare, adhesive tapes from a suspect or a crime scene. The most common polymers used to back packaging tape are polypropylene and polyvinyl chloride. Much of the oriented polypropylene (OPP) needed to produce packaging tapes, regardless of the tape brand, is supplied by just a few polymer manufacturers. Consequently, the composition of the backing material varies little. Therefore, the discriminating power of classical methods (physical fit, tape dimensions, colour, morphology, FTIR, PyGC/MS, etc.) is limited. Analysis of stable isotopes using isotope ratio mass spectrometry (IRMS) has been applied in the broad area of forensics and it has been reported that isotope analysis is a valuable tool for the identification of adhesive tapes. We have tested the usefulness of this method by distinguishing different South Korean adhesive tapes produced by just a few manufacturers in the small South Korean market. Korean adhesive tapes were collected and analysed for their isotope signatures. The glue of the tapes was separated from the backing material and these sub-samples were analysed for their H- and C-isotope composition. The result shows the possibility for discriminating most tape samples, even from the same brand. Variations within single rolls have also been investigated, where no variations in H- and C-isotope composition significantly exceeding the standard deviation were found. PMID:18438979

  9. Mass-dependent and mass-independent fractionation of mercury isotopes in precipitation from Guiyang, SW China

    NASA Astrophysics Data System (ADS)

    Wang, Zhuhong; Chen, Jiubin; Feng, Xinbin; Hintelmann, Holger; Yuan, Shengliu; Cai, Hongming; Huang, Qiang; Wang, Shuxiao; Wang, Fengyang

    2015-11-01

    The isotopic composition of mercury (Hg) is increasingly used to constrain the sources and pathways of this metal in the atmosphere. Though China has the highest Hg production, consumption and emission in the world, Hg isotope ratios are rarely reported for Chinese wet deposition. In this study, we examined, for the first time outside North America, both mass-dependent fractionation (MDF, expressed as δ202Hg) and mass-independent fractionation of odd (odd-MIF, Δ199Hg) and even (even-MIF, Δ200Hg) Hg isotopes in 15 precipitation samples collected from September 2012 to August 2013 in Guiyang (SW China). All samples displayed significant negative δ202Hg (-0.44 ∼ -4.27‰), positive Δ199Hg (+0.19 to +1.16‰) and slightly positive Δ200Hg (-0.01‰ to +0.20‰). Potential sources of Hg in precipitation were identified by coupling both MDF and MIF of Hg isotopes with a back-trajectory model. The results showed that local emission from coal-fired power plants and cement plants and western long-range transportation are two main contributing sources, while the contribution of Hg from south wind events would be very limited on an annual basis. The relatively lower Δ200Hg values in Guiyang precipitation may indicate a dilution effect by local sources and/or insignificant even-MIF in the tropopause contribution of this subtropical region. Our study demonstrates the usefulness of isotope fractionation, especially MIF for tracing sources and pathways of Hg in the atmosphere.

  10. Energy and mass dependence of isotopic enrichment in sputtering

    SciTech Connect

    Shutthanandan, V.; Zhang, J.; Ray, Pradosh

    2003-05-01

    When a solid surface containing more than one component is bombarded by energetic particles, the sputtered flux is found to deviated from the stoichiometric composition of the target. This is known as preferential sputtering. Usually the sputtered flux is enriched with the lighter-mass particles, particularly at small emission angles. As the bombardment of the target is continued, the target surface becomes depleted in the particles that are preferentially emitted and a steady state is eventually established, where the ratio of the sputtered particles becomes equal to the natural abundance ratio of the particles in the target.

  11. Profiling thiol redox proteome using isotope tagging mass spectrometry.

    PubMed

    Parker, Jennifer; Zhu, Ning; Zhu, Mengmeng; Chen, Sixue

    2012-01-01

    Pseudomonas syringae pv. tomato strain DC3000 not only causes bacterial speck disease in Solanum lycopersicum but also on Brassica species, as well as on Arabidopsis thaliana, a genetically tractable host plant(1,2). The accumulation of reactive oxygen species (ROS) in cotyledons inoculated with DC3000 indicates a role of ROS in modulating necrotic cell death during bacterial speck disease of tomato(3). Hydrogen peroxide, a component of ROS, is produced after inoculation of tomato plants with Pseudomonas(3). Hydrogen peroxide can be detected using a histochemical stain 3'-3' diaminobenzidine (DAB)(4). DAB staining reacts with hydrogen peroxide to produce a brown stain on the leaf tissue(4). ROS has a regulatory role of the cellular redox environment, which can change the redox status of certain proteins(5). Cysteine is an important amino acid sensitive to redox changes. Under mild oxidation, reversible oxidation of cysteine sulfhydryl groups serves as redox sensors and signal transducers that regulate a variety of physiological processes(6,7). Tandem mass tag (TMT) reagents enable concurrent identification and multiplexed quantitation of proteins in different samples using tandem mass spectrometry(8,9). The cysteine-reactive TMT (cysTMT) reagents enable selective labeling and relative quantitation of cysteine-containing peptides from up to six biological samples. Each isobaric cysTMT tag has the same nominal parent mass and is composed of a sulfhydryl-reactive group, a MS-neutral spacer arm and an MS/MS reporter(10). After labeling, the samples were subject to protease digestion. The cysteine-labeled peptides were enriched using a resin containing anti-TMT antibody. During MS/MS analysis, a series of reporter ions (i.e., 126-131 Da) emerge in the low mass region, providing information on relative quantitation. The workflow is effective for reducing sample complexity, improving dynamic range and studying cysteine modifications. Here we present redox proteomic

  12. Cd Isotopic Composition Measured by Plasma Source Mass Spectrometry on Natural and Anthropogenic Materials. A Preliminary Outline of Cd Isotope Systematics

    NASA Astrophysics Data System (ADS)

    Innocent, C.

    2004-05-01

    Cadmium is a trace metal that is used as a geochemical tracer of natural processes, like biological productivity and paleoproductivity, and also of anthropogenic pollution, as Cd is known to be a toxic heavy metal that has become a major environmental and health concern. For these purposes, an outstanding issue is to determine whether Cd, like a number of metallic elements (e.g. Fe, Cu, Zn, Mo, Tl), may display variable isotopic compositions in natural and/or industrial compounds. It is known that Cd may display variable isotopic composition. Indeed, isotopic fractionation processes have been documented in some meteorites and in lunar soils. Consequently, due to its relatively low boiling point (767\\deg C) and also to the large mass range covered by its isotopes (10 mass units), Cd might fractionate isotopically, for example during the outpouring of acidic volcanic magmas and/or the emplacement of granitoids. On another hand, isotopic fractionation could also occur during human activities like refuse incineration or industrial manufacturing, for instance. Finally, biologically-induced isotopic fractionation should not be ruled out, as it is clearly evidenced for other metals, like Fe. A high precision method has been developed for determining the isotopic composition of Cd by plasma source mass spectrometry (Neptune). This method holds on the standard-bracketing technique, owing to the availability of Cd solutions of known isotopic composition provided by the University of M\\H{u}nster. This allows to correct precisely for mass fractionation that occurs in the plasma source mass spectrometer. It is also critical for the analysis to be possible to work with Cd solutions of very high purity. Chemical isolation of Cd involves 3 steps, and may be also suitable for Cd isotopic measurements using solid source mass spectrometry. Preliminary results suggest that Cd is likely to fractionate during smelting activities, as indicated by measurements on mining waste. The

  13. Re-Os isotope and platinum group elements of a FOcal ZOne mantle source, Louisville Seamounts Chain, Pacific ocean

    NASA Astrophysics Data System (ADS)

    Tejada, Maria Luisa G.; Hanyu, Takeshi; Ishikawa, Akira; Senda, Ryoko; Suzuki, Katsuhiko; Fitton, Godfrey; Williams, Rebecca

    2015-02-01

    The Louisville Seamount Chain (LSC) is, besides the Hawaiian-Emperor Chain, one of the longest-lived hotspot traces. We report here the first Re-Os isotope and platinum group element (PGE) data for Canopus, Rigil, and Burton Guyots along the chain, which were drilled during IODP Expedition 330. The LSC basalts possess (187Os/188Os)i = 0.1245-0.1314 that are remarkably homogeneous and do not vary with age. A Re-Os isochron age of 64.9 ± 3.2 Ma was obtained for Burton seamount (the youngest of the three seamounts drilled), consistent with 40Ar-39Ar data. Isochron-derived initial 187Os/188Os ratio of 0.1272 ± 0.0008, together with data for olivines (0.1271-0.1275), are within the estimated primitive mantle values. This (187Os/188Os)i range is similar to those of Rarotonga (0.124-0.139) and Samoan shield (0.1276-0.1313) basalts and lower than those of Cook-Austral (0.136-0.155) and Hawaiian shield (0.1283-0.1578) basalts, suggesting little or no recycled component in the LSC mantle source. The PGE data of LSC basalts are distinct from those of oceanic lower crust. Variation in PGE patterns can be largely explained by different low degrees of melting under sulfide-saturated conditions of the same relatively fertile mantle source, consistent with their primitive mantle-like Os and primordial Ne isotope signatures. The PGE patterns and the low 187Os/188Os composition of LSC basalts contrast with those of Ontong Java Plateau (OJP) tholeiites. We conclude that the Re-Os isotope and PGE composition of LSC basalts reflect a relatively pure deep-sourced common mantle sampled by some ocean island basalts but is not discernible in the composition of OJP tholeiites.

  14. Coupled effects of temperature and mass transport on the isotope fractionation of zinc during electroplating

    NASA Astrophysics Data System (ADS)

    Black, Jay R.; John, Seth G.; Kavner, Abby

    2014-01-01

    The isotopic composition of zinc metal electrodeposited on a rotating disc electrode from a Zn-citrate aqueous solution was investigated as a function of overpotential (electrochemical driving force), temperature, and rotation rate. Zn metal was measured to be isotopically light with respect to Zn+2 in solution, with observed fractionations varying from Δ66/64Znmetal-aqueous = -1.0‰ to -3.9‰. Fractionation varies continuously as a function of a dimensionless parameter described by the ratio of observed deposition rate to calculated mass-transport limiting rate, where larger fractionations are observed at lower deposition rates, lower temperature, and at faster electrode rotation rates. Thus, the large fractionation and its rate dependence is interpreted as a competition between the two kinetic processes with different effective activation energies: mass-transport-limited (diffusion limited) kinetics with a large activation energy, which creates small fractionations close to the predicted diffusive fractionation; and electrochemical deposition kinetics, with a smaller effective activation energy, which creates large fractionations at low deposition rates and high hydrodynamic fluxes of solute to the electrode. The results provide a framework for predicting isotope fractionation in processes controlled by two competing reactions with different kinetic isotope effects. Light isotopes are electroplated. In all cases light stable isotopes of the metals are preferentially electroplated, with mass-dependent behavior evident where three or more isotopes are measured. Fractionation is time-independent, meaning that the fractionation factor does not vary with the extent of reaction. In most of our experiments, we have controlled the extent of reaction such that only a small amount of metal is deposited from the stock solution, thus avoiding significant evolution of the reservoir composition. In such experiments, the observed isotope fractionation is constant as a

  15. Determination of perchlorate in infant formula by isotope dilution ion chromatography/tandem mass spectrometry

    PubMed Central

    Wang, Z.; Lau, B.P.-Y.; Tague, B.; Sparling, M.; Forsyth, D.

    2011-01-01

    A sensitive and selective isotope dilution ion chromatography/tandem mass spectrometry (ID IC-MS/MS) method was developed and validated for the determination of perchlorate in infant formula. The perchlorate was extracted from infant formula by using 20 ml of methanol and 5 ml of 1% acetic acid. All samples were spiked with 18O4 isotope-labelled perchlorate internal standard prior to extraction. After purification on a graphitised carbon solid-phase extraction column, the extracts were injected into an ion chromatography system equipped with an Ionpac AS20 column for separation of perchlorate from other anions. The presence of perchlorate in samples was quantified by isotope dilution mass spectrometry. Analysis of both perchlorate and its isotope-labelled internal standard was carried out on a Waters Quattro Ultima triple quadrupole mass spectrometer operating in a multiple reaction monitoring (MRM) negative ionisation mode. The method was validated for linearity and range, accuracy, precision, sensitivity, and matrix effects. The limit of quantification (LOQ) was 0.4 μg 1−1 for liquid infant formula and 0.95 μg kg−1 for powdered infant formula. The recovery ranged from 94% to 110% with an average of 98%. This method was used to analyse 39 infant formula, and perchlorate concentrations ranging from

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

    SciTech Connect

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

    2011-03-01

    The use of broad bandwidth lasers with automated feedback control of wavelength was applied to the measurement of {sup 235}U/{sup 238}U ratios by resonance ionization mass spectrometry (RIMS) to decrease laser-induced isotopic fractionation. By broadening the bandwidth of the first laser in a three-color, three-photon ionization process from a bandwidth of 1.8 GHz to about 10 GHz, the variation in sequential relative isotope abundance measurements decreased from 10% to less than 0.5%. This procedure was demonstrated for the direct interrogation of uranium oxide targets with essentially no sample preparation.

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

    NASA Astrophysics Data System (ADS)

    Suen, Timothy Wu

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

  18. Selective isotope determination of lanthanum by diode-laser-initiated resonance-ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Young, J. P.; Shaw, R. W.

    1995-08-01

    A diode-laser step has been incorporated into a resonance-ionization mass spectrometry optical excitation process to enhance the isotopic selectivity of the technique. Lanthanum isotope ratio enhancements as high as 103 were achieved by use of a single-frequency cw diode laser tuned to excite the first step of a three-step excitation-ionization optical process; the subsequent steps were excited by use of a pulsed dye laser. Applying the same optical technique, we measured atomic hyperfine constants for the high-lying even-parity 4D5/2 state of lanthanum at 30354 cm-1 . The general utility of this spectral approach is discussed.

  19. Coupled effects of temperature and mass transport on the isotope fractionation of zinc during electroplating

    NASA Astrophysics Data System (ADS)

    Black, Jay R.; John, Seth G.; Kavner, Abby

    2014-01-01

    The isotopic composition of zinc metal electrodeposited on a rotating disc electrode from a Zn-citrate aqueous solution was investigated as a function of overpotential (electrochemical driving force), temperature, and rotation rate. Zn metal was measured to be isotopically light with respect to Zn+2 in solution, with observed fractionations varying from Δ66/64Znmetal-aqueous = -1.0‰ to -3.9‰. Fractionation varies continuously as a function of a dimensionless parameter described by the ratio of observed deposition rate to calculated mass-transport limiting rate, where larger fractionations are observed at lower deposition rates, lower temperature, and at faster electrode rotation rates. Thus, the large fractionation and its rate dependence is interpreted as a competition between the two kinetic processes with different effective activation energies: mass-transport-limited (diffusion limited) kinetics with a large activation energy, which creates small fractionations close to the predicted diffusive fractionation; and electrochemical deposition kinetics, with a smaller effective activation energy, which creates large fractionations at low deposition rates and high hydrodynamic fluxes of solute to the electrode. The results provide a framework for predicting isotope fractionation in processes controlled by two competing reactions with different kinetic isotope effects. Light isotopes are electroplated. In all cases light stable isotopes of the metals are preferentially electroplated, with mass-dependent behavior evident where three or more isotopes are measured. Fractionation is time-independent, meaning that the fractionation factor does not vary with the extent of reaction. In most of our experiments, we have controlled the extent of reaction such that only a small amount of metal is deposited from the stock solution, thus avoiding significant evolution of the reservoir composition. In such experiments, the observed isotope fractionation is constant as a

  20. Far-infrared and resonance Raman spectroscopy and isotopic substitution studies of halogen-bridged platinum chain solids

    SciTech Connect

    Love, S.P.; Worl, L.A.; Donohoe, R.J.; Huckett, S.C.; Johnson, S.R.; Swanson, B.I.

    1992-12-31

    Here we our most recent results on the vibrational spectroscopy of the MX chain solids [Pt(en){sub 2}][Pt(en){sub 2}X{sub 2}](ClO{sub 4}){sub 4}, (X=Cl, Br or I, and en = C{sub 2}H{sub 8}N{sub 2}), referred to as PtX. Isotopic substitutions are used to clarify the nature of various vibrational modes. For Raman spectroscopy, fundamental phonon frequencies are determined, when possible, by excitation far below the band edge using a Ti:Sapphire laser, thus avoiding defect production, while photo-induced defects are studied specifically after intentional production.

  1. Alternative Filament Loading Solution for Accurate Analysis of Boron Isotopes by Negative Thermal Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Dwyer, G. S.; Vengosh, A.

    2008-12-01

    The negative thermal ionization mass spectrometry technique has become the major tool for investigating boron isotopes in the environment. The high sensitivity of BO2- ionization enables measurements of ng levels of boron. However, B isotope measurement by this technique suffers from two fundamental problems (1) fractionation induced by selective ionization of B isotopes in the mass spectrometer; and (2) CNO- interference on mass 42 that is often present in some load solutions (such as B-free seawater processed through ion-exchange resin). Here we report a potentially improved methodology using an alternative filament loading solution with a recently-installed Thermo Scientific TRITON thermal ionization mass spectrometer. Our initial results suggest that this solution -- prepared by combining high-purity single- element standard solutions of Ca, Mg, Na, and K in proportions similar to those in seawater in a 5% HCl matrix -- may offer significant improvement over some other commonly used load solutions. Total loading blank is around 15pg as determined by isotope dilution (NIST952). Replicate analyses of NIST SRM951 and modern seawater thus far have yielded 11B/10B ratios of 4.0057 (±0.0008, n=14) and 4.1645 (±0.0017, n=7; δ11B=39.6 permil), respectively. Replicate analyses of samples and SRM951 yield an average standard deviation (1 σ) of approximately 0.001 (0.25 permil). Fractionation during analysis (60-90 minutes) has thus far typically been less than 0.002 (0.5 permil). The load solution delivers ionization efficiency similar to directly-loaded seawater and has negligible signal at mass 26 (CN-), a proxy for the common interfering molecular ion (CNO-) on mass 42. Standards and samples loaded with the solution behave fairly predictably during filament heating and analysis, thus allowing for the possibility of fully automated data collection.

  2. Assessment of the effects of cage fish-farming on damselfish-associated food chains using stable-isotope analyses.

    PubMed

    Jan, Rong-Quen; Kao, Shuh-Ji; Dai, Chang-Feng; Ho, Cheng-Tze

    2014-09-15

    To assess the effect of cage fish-farming on the coral reef ecosystem off Xiaoliuchiu Island, southern Taiwan, geographical differences in the food chain of each of two damselfishes, Pomacentrus vaiuli and Chromis margaritifer, were examined using a stable-isotope approach. For each damselfish, individuals were found to consume similar foods at all sites. However, specimens collected at sites near the cage farm (as the experimental sites) exhibited lower δ(13)C and higher δ(15)N signatures compared to those from reference sites. Similar trends also occurred in the zooplankton and detritus, two major food sources for both damselfishes. This finding indicates that particulate organic matter released by the farm may have entered the coral reef ecosystem through the pelagic food chain. Artificial reef emplacement is recommended to provide extra habitats under cage farms to support additional pelagic-feeding fish populations, thereby reducing environmental impacts of cage farming on coral reefs. PMID:25103907

  3. Probing the homogeneity of the isotopic composition and molar mass of the ‘Avogadro’-crystal

    NASA Astrophysics Data System (ADS)

    Pramann, Axel; Lee, Kyoung-Seok; Noordmann, Janine; Rienitz, Olaf

    2015-12-01

    Improved measurements on silicon crystal samples highly enriched in the 28Si isotope (known as ‘Si28’ or AVO28 crystal material) have been carried out at PTB to investigate local isotopic variations in the original crystal. This material was used for the determination of the Avogadro constant NA and therefore plays an important role in the upcoming redefinition of the SI units kilogram and mole, using fundamental constants. Subsamples of the original crystal have been extensively studied over the past few years at the National Research Council (NRC, Canada), the National Metrology Institute of Japan (NMIJ, Japan), the National Institute of Standards and Technology (NIST, USA), the National Institute of Metrology (NIM, People’s Republic of China), and multiple times at PTB. In this study, four to five discrete, but adjacent samples were taken from three distinct axial positions of the crystal to obtain a more systematic and comprehensive understanding of the distribution of the isotopic composition and molar mass throughout the crystal. Moreover, improved state-of-the-art techniques in the experimental measurements as well as the evaluation approach and the determination of the calibration factors were utilized. The average molar mass of the measured samples is M  =  27.976 970 12(12) g mol-1 with a relative combined uncertainty uc,rel(M)  =  4.4 ×10-9. This value is in astounding agreement with the values of single samples measured and published by NIST, NMIJ, and PTB. With respect to the associated uncertainties, no significant variations in the molar mass and the isotopic composition as a function of the sample position in the boule were observed and thus could not be traced back to an inherent property of the crystal. This means that the crystal is not only ‘homogeneous’ with respect to molar mass but also has predominantly homogeneous distribution of the three stable Si isotopes.

  4. Stable isotope composition of waters in the Great Basin, United States 1. Air-mass trajectories

    USGS Publications Warehouse

    Friedman, I.; Harris, J.M.; Smith, G.I.; Johnson, C.A.

    2002-01-01

    Isentropic trajectories, calculated using the NOAA/Climate Monitoring and Diagnostics Laboratory's isentropic transport model, were used to determine air-parcel origins and the influence of air mass trajectories on the isotopic composition of precipitation events that occurred between October 1991 and September 1993 at Cedar City, Utah, and Winnemucca, Nevada. Examination of trajectories that trace the position of air parcels backward in time for 10 days indicated five distinct regions of water vapor origin: (1) Gulf of Alaska and North Pacific, (2) central Pacific, (3) tropical Pacific, (4) Gulf of Mexico, and (5) continental land mass. Deuterium (??D) and oxygen-18 (??18O) analyses were made of precipitation representing 99% of all Cedar City events. Similar analyses were made on precipitation representing 66% of the precipitation falling at Winnemucca during the same period. The average isotopic composition of precipitation derived from each water vapor source was determined. More than half of the precipitation that fell at both sites during the study period originated in the tropical Pacific and traveled northeast to the Great Basin; only a small proportion traversed the Sierra Nevada. The isotopic composition of precipitation is determined by air-mass origin and its track to the collection station, mechanism of droplet formation, reequilibration within clouds, and evaporation during its passage from cloud to ground. The Rayleigh distillation model can explain the changes in isotopic composition of precipitation as an air mass is cooled pseudo-adiabatically during uplift. However, the complicated processes that take place in the rapidly convecting environment of cumulonimbus and other clouds that are common in the Great Basin, especially in summer, require modification of this model because raindrops that form in the lower portion of those clouds undergo isotopic change as they are elevated to upper levels of the clouds from where they eventually drop to the

  5. Stable isotope composition of waters in the Great Basin, United States 1. Air-mass trajectories

    NASA Astrophysics Data System (ADS)

    Friedman, Irving; Harris, Joyce M.; Smith, George I.; Johnson, Craig A.

    2002-10-01

    Isentropic trajectories, calculated using the NOAA/Climate Monitoring and Diagnostics Laboratory's isentropic transport model, were used to determine air-parcel origins and the influence of air mass trajectories on the isotopic composition of precipitation events that occurred between October 1991 and September 1993 at Cedar City, Utah, and Winnemucca, Nevada. Examination of trajectories that trace the position of air parcels backward in time for 10 days indicated five distinct regions of water vapor origin: (1) Gulf of Alaska and North Pacific, (2) central Pacific, (3) tropical Pacific, (4) Gulf of Mexico, and (5) continental land mass. Deuterium (δD) and oxygen-18 (δ18O) analyses were made of precipitation representing 99% of all Cedar City events. Similar analyses were made on precipitation representing 66% of the precipitation falling at Winnemucca during the same period. The average isotopic composition of precipitation derived from each water vapor source was determined. More than half of the precipitation that fell at both sites during the study period originated in the tropical Pacific and traveled northeast to the Great Basin; only a small proportion traversed the Sierra Nevada. The isotopic composition of precipitation is determined by air-mass origin and its track to the collection station, mechanism of droplet formation, reequilibration within clouds, and evaporation during its passage from cloud to ground. The Rayleigh distillation model can explain the changes in isotopic composition of precipitation as an air mass is cooled pseudo-adiabatically during uplift. However, the complicated processes that take place in the rapidly convecting environment of cumulonimbus and other clouds that are common in the Great Basin, especially in summer, require modification of this model because raindrops that form in the lower portion of those clouds undergo isotopic change as they are elevated to upper levels of the clouds from where they eventually drop to the

  6. Asymmetry of fission fragment mass distribution for Po and Ir isotopes

    NASA Astrophysics Data System (ADS)

    Andreev, A. V.; Adamian, G. G.; Antonenko, N. V.

    2016-03-01

    Using the improved scission-point model, the mass distributions are calculated for induced fission of several Po and Ir isotopes. The calculated mass distributions and mean total kinetic energies of fission fragments are compared with the existing experimental data. The revealed coexistence of both symmetric and asymmetric modes in the β -delayed fission of At,196194 is in agreement with the experimental observations. The change of the shape of mass distribution with increasing A of fissioning AIr nucleus from asymmetric for 185Ir to symmetric for 193Ir is found.

  7. Isotope-ratio-monitoring gas chromatography-mass spectrometry: methods for isotopic calibration

    NASA Technical Reports Server (NTRS)

    Merritt, D. A.; Brand, W. A.; Hayes, J. M.

    1994-01-01

    In trial analyses of a series of n-alkanes, precise determinations of 13C contents were based on isotopic standards introduced by five different techniques and results were compared. Specifically, organic-compound standards were coinjected with the analytes and carried through chromatography and combustion with them; or CO2 was supplied from a conventional inlet and mixed with the analyte in the ion source, or CO2 was supplied from an auxiliary mixing volume and transmitted to the source without interruption of the analyte stream. Additionally, two techniques were investigated in which the analyte stream was diverted and CO2 standards were placed on a near-zero background. All methods provided accurate results. Where applicable, methods not involving interruption of the analyte stream provided the highest performance (sigma = 0.00006 at.% 13C or 0.06% for 250 pmol C as CO2 reaching the ion source), but great care was required. Techniques involving diversion of the analyte stream were immune to interference from coeluting sample components and still provided high precision (0.0001 < or = sigma < or = 0.0002 at.% or 0.1 < or = sigma < or = 0.2%).

  8. Osmium isotopic ratio measurements by inductively coupled plasma source mass spectrometry

    SciTech Connect

    Russ, G.P. III; Bazan, J.M.; Date, A.R.

    1987-04-01

    The isotopic composition of nanogram quantities of osmium was measured by using an inductively coupled plasma source mass spectrometer. Sensitivity was enhanced a factor of approx.100 by the use of an osmium tetraoxide vapor generator rather than nebulization of solution. For samples less than or equal to5 ng, the ratios /sup 190/Os//sup 192/Os, /sup 189/Os//sup 192/Os, and /sup 188/Os//sup 192/Os were determined to better than +/- 0.5% (1sigma/sub m/) precision. For the minor isotopes, the ratios /sup 187/Os//sup 192/Os and /sup 186/Os//sup 192/Os were determined to +/-1%, and /sup 184/Os//sup 192/Os (4 x 10/sup -4/) was determined to approx.10%. Isotope ratios for common osmium are reported.

  9. Stable isotope dilution analysis of hydrologic samples by inductively coupled plasma mass spectrometry

    USGS Publications Warehouse

    Garbarino, J.R.; Taylor, H.E.

    1987-01-01

    Inductively coupled plasma mass spectrometry is employed in the determination of Ni, Cu, Sr, Cd, Ba, Ti, and Pb in nonsaline, natural water samples by stable isotope dilution analysis. Hydrologic samples were directly analyzed without any unusual pretreatment. Interference effects related to overlapping isobars, formation of metal oxide and multiply charged ions, and matrix composition were identified and suitable methods of correction evaluated. A comparability study snowed that single-element isotope dilution analysis was only marginally better than sequential multielement isotope dilution analysis. Accuracy and precision of the single-element method were determined on the basis of results obtained for standard reference materials. The instrumental technique was shown to be ideally suited for programs associated with certification of standard reference materials.

  10. Stable nitrogen isotope ratios and accumulation of PCDD/F and PCB in Baltic aquatic food chains

    SciTech Connect

    Broman, D.; Naef, C.; Rolff, C.; Zebuehr, Y.

    1994-12-31

    Ratios of naturally occurring stable isotopes of nitrogen ({delta}{sup 15}N) can be used to numerically classify trophic levels of organisms in food chains. By combining analyses results of PCDD/Fs and non-ortho PCBs the biomagnification of these substances can be quantitatively estimated. The two Baltic food chains studied were one pelagic (phytoplankton -- settling particulate matter (SPM) -- zooplankton -- mysids -- herring -- cod) and one littoral (phytoplankton -- SPM -- blue mussel -- eider duck). The {delta}{sup 15}N-data gave food chain descriptions qualitatively consistent with previous conceptions of trophic arrangements in the food chains. Phytoplankton showed the lowest average {delta}{sup 15}N-value and the juvenile eider duck and the cod showed the highest average {delta}{sup 15}N-values for the littoral and pelagic food chains, respectively. The PCDD/Fs and PCBs concentrations were plotted versus the {delta}{sup 15}N-values for the different trophic levels and an exponential model of the form e{sup (A + B*{delta}N)} was fitted to the data. The estimates of the constant B in the model allows for an estimation of a biomagnification power (B) of different singular, or groups of, contaminants. A B-value around zero indicates that a substance is flowing through the food chain without being magnified, whereas a value > 0 indicates that a substance is biomagnified. Negative B-values indicate that a substance is not taken up or is metabolized. The A-term of the expression is only a scaling factor depending on the background level of the contaminant.

  11. Mass-Dependent and -Independent Fractionation of Mercury Isotopes in Aquatic Systems

    NASA Astrophysics Data System (ADS)

    Bergquist, B. A.; Joel, B. D.; Jude, D. J.

    2008-12-01

    Mercury is a globally distributed and highly toxic pollutant. Although Hg is a proven health risk, much of the natural cycle of Hg is not well understood and new approaches are needed to track Hg and the chemical transformations it undergoes in the environment. Recently, we demonstrated that Hg isotopes exhibit two types of isotope fractionation: (1) mass dependent fractionation (MDF) and (2) mass independent fractionation (MIF) of only the odd isotopes (Bergquist and Blum, 2007). The observation of large MIF of Hg isotopes (up to 5 permil) is exciting because only a few other isotopic systems have been documented to display large MIF, the most notable of which are oxygen and sulfur. In both cases, the application of MIF has proven very useful in a variety of fields including cosmochemistry, paleoclimatology, physical chemistry, atmospheric chemistry, and biogeochemistry. Both MDF and MIF isotopic signatures are observed in natural samples, and together they open the door to a new method for tracing Hg pollution and for investigating Hg behavior in the environment. For example, fish record MDF that appears to be related to size and age. Additionally, fish display MIF signatures that are consistent with the photo-reduction of methylmercury (Bergquist and Blum, 2007). If the MDF and MIF in ecosystems can be understood, the signatures in fish could inform us about the sources and processes transforming Hg and why there are differences in the bioaccumulation of Hg in differing ecosystems and populations of fish. This requires sampling of a variety of ecosystems, the sampling of many components of the ecosystems, and the use of other tracers such as carbon and nitrogen isotopes. We have expanded our studies of aquatic ecosystems to include several lakes in North America. Similar to other isotopic systems used to study food web dynamics and structure (i.e., C and N), the MDF of Hg in fish appears to be related to size and age. The MDF recorded in fish likely reflects

  12. Oxygen isotope analysis of fossil organic matter by secondary ion mass spectrometry

    NASA Astrophysics Data System (ADS)

    Tartèse, Romain; Chaussidon, Marc; Gurenko, Andrey; Delarue, Frédéric; Robert, François

    2016-06-01

    We have developed an analytical procedure for the measurement of oxygen isotope composition of fossil organic matter by secondary ion mass spectrometry (SIMS) at the sub-per mill level, with a spatial resolution of 20-30 μm. The oxygen isotope composition of coal and kerogen samples determined by SIMS are on average consistent with the bulk oxygen isotope compositions determined by temperature conversion elemental analysis - isotope ratio mass spectrometry (TC/EA-IRMS), but display large spreads of δ18O of ∼5-10‰, attributed to mixing of remnants of organic compounds with distinct δ18O signatures. Most of the δ18O values obtained on two kerogen residues extracted from the Eocene Clarno and Early Devonian Rhynie continental chert samples and on two immature coal samples range between ∼10‰ and ∼25‰. Based on the average δ18O values of these samples, and on the O isotope composition of water processed by plants that now constitute the Eocene Clarno kerogen, we estimated δ18Owater values ranging between around -11‰ and -1‰, which overall correspond well within the range of O isotope compositions for present-day continental waters. SIMS analyses of cyanobacteria-derived organic matter from the Silurian Zdanow chert sample yielded δ18O values in the range 12-20‰. Based on the O isotope composition measured on recent cyanobacteria from the hypersaline Lake Natron (Tanzania), and on the O isotope composition of the lake waters in which they lived, we propose that δ18O values of cyanobacteria remnants are enriched by about ∼18 ± 2‰ to 22 ± 2‰ relative to coeval waters. This relationship suggests that deep ocean waters in which the Zdanow cyanobacteria lived during Early Silurian times were characterised by δ18O values of around -5 ± 4‰. This study, establishing the feasibility of micro-analysis of Phanerozoic fossil organic matter samples by SIMS, opens the way for future investigations of kerogens preserved in Archean cherts and of the

  13. Design of a compact permanent magnet Cyclotron Mass Spectrometer for the detection and measurement of trace isotopes

    SciTech Connect

    Young, A.T.; Bertsche, K.J.; Clark, D.J.; Halbach, K.; Kunkel, W.B.; Leung, K.N.; Li, C.Y.

    1992-07-01

    A technique for the detection of trace amounts of rare isotopes, Cyclotron mass Spectrometry (CMS), is described. This technique uses the relationships between particle mass, charge, magnetic field strength and cyclotron orbital frequency to provide high mass resolution. The instrument also has high sensitivity and is capable of measuring isotopes with abundances of < 10{sub {minus} 12}. Improvements now being implemented will lead to further increases in the sensitivity and enhance operating parameters such as cost, portability, and sample throughput.

  14. Discrepancies between isotope ratio infrared spectroscopy and isotope ratio mass spectrometry for the stable isotope analysis of plant and soil waters.

    PubMed

    West, Adam G; Goldsmith, Gregory R; Brooks, Paul D; Dawson, Todd E

    2010-07-30

    The use of isotope ratio infrared spectroscopy (IRIS) for the stable hydrogen and oxygen isotope analysis of water is increasing. While IRIS has many advantages over traditional isotope ratio mass spectrometry (IRMS), it may also be prone to errors that do not impact upon IRMS analyses. Of particular concern is the potential for contaminants in the water sample to interfere with the spectroscopy, thus leading to erroneous stable isotope data. Water extracted from plant and soil samples may often contain organic contaminants. The extent to which contaminants may interfere with IRIS and thus impact upon data quality is presently unknown. We tested the performance of IRIS relative to IRMS for water extracted from 11 plant species and one organic soil horizon. IRIS deviated considerably from IRMS for over half of the samples tested, with deviations as large as 46 per thousand (delta(2)H) and 15.4 per thousand (delta(18)O) being measured. This effect was reduced somewhat by using activated charcoal to remove organics from the water; however, deviations as large as 35 per thousand (delta(2)H) and 11.8 per thousand (delta(18)O) were still measured for these cleaned samples. Interestingly, the use of activated charcoal to clean water samples had less effect than previously thought for IRMS analyses. Our data show that extreme caution is required when using IRIS to analyse water samples that may contain organic contaminants. We suggest that the development of new cleaning techniques for removing organic contaminants together with instrument-based software to flag potentially problematic samples are necessary to ensure accurate plant and soil water analyses using IRIS. PMID:20552579

  15. Isotopic analysis of single uranium and plutonium particles by chemical treatment and mass spectrometry

    NASA Astrophysics Data System (ADS)

    Shinonaga, T.; Esaka, F.; Magara, M.; Klose, D.; Donohue, D.

    2008-11-01

    The isotopic composition of single uranium and plutonium particles was measured with an inductively coupled plasma mass spectrometer (ICP-MS) and a thermal ionization mass spectrometer (TIMS). Particles deposited on a carbon planchet were first analyzed with an energy dispersive X-ray spectrometer (EDX) attached to a scanning electron microscope (SEM) and then transferred on to a silicon wafer using a manipulator. The particle on the silicon wafer was dissolved with nitric acid and the isotopic ratios of U and Pu were measured with ICP-MS and TIMS. The results obtained by both methods for particles of certified reference materials showed good agreement with the certified values within the expected uncertainty. The measurement uncertainties obtained in this study were similar for both mass spectrometric methods. This study was performed to establish the method of particle analysis with SEM, EDX, the particle manipulation and chemical preparation technique, and the measurement of isotopic ratios of U and Pu in a single particle by mass spectrometry.

  16. Pathways for Neoarchean pyrite formation constrained by mass-independent sulfur isotopes

    PubMed Central

    Farquhar, James; Cliff, John; Zerkle, Aubrey L.; Kamyshny, Alexey; Poulton, Simon W.; Claire, Mark; Adams, David; Harms, Brian

    2013-01-01

    It is generally thought that the sulfate reduction metabolism is ancient and would have been established well before the Neoarchean. It is puzzling, therefore, that the sulfur isotope record of the Neoarchean is characterized by a signal of atmospheric mass-independent chemistry rather than a strong overprint by sulfate reducers. Here, we present a study of the four sulfur isotopes obtained using secondary ion MS that seeks to reconcile a number of features seen in the Neoarchean sulfur isotope record. We suggest that Neoarchean ocean basins had two coexisting, significantly sized sulfur pools and that the pathways forming pyrite precursors played an important role in establishing how the isotopic characteristics of each of these pools was transferred to the sedimentary rock record. One of these pools is suggested to be a soluble (sulfate) pool, and the other pool (atmospherically derived elemental sulfur) is suggested to be largely insoluble and unreactive until it reacts with hydrogen sulfide. We suggest that the relative contributions of these pools to the formation of pyrite depend on both the accumulation of the insoluble pool and the rate of sulfide production in the pyrite-forming environments. We also suggest that the existence of a significant nonsulfate pool of reactive sulfur has masked isotopic evidence for the widespread activity of sulfate reducers in the rock record. PMID:23407162

  17. Stable Isotope Analyses of water and Aqueous Solutions by Conventional Dual-inlet Mass Spectrometry

    SciTech Connect

    Horita, Juske; Kendall, C.

    2004-01-01

    The foundation of various analytical methods for the stable isotope composition of water and other aqueous samples (natural abundance, {sup 1}H : {sup 2}H (D) = 99.985 : 0.015 atom%, and {sup 16}O : {sup 17}O : {sup 18}O = 99.762 : 0.038 : 0.200 atom%) was established during the Manhatten Project in the U.S.A., when large amounts of heavy water were produced for nuclear reactors (see Kirshenbaum, 1951, for a detailed account). From early on, there was great interest in the oxygen and hydrogen isotopic compositions of water, because they are the ideal tracers of water sources and reactions. The increased analytical precisions made possible by the subsequent development of modern gas-source isotope-ratio mass spectrometers with dual-inlets and multi-collectors, have caused the proliferation of new analytical methods and applications for the oxygen and hydrogen isotopic compositions of water. These stable isotopes have found wide applications in basic as well as applied sciences (chemistry, geology, hydrology, biology, medical sciences, and food sciences). This is because water is ubiquitous, is an essential and predominant ingredient of living organisms, and is perhaps the most reactive compound in the Earth.

  18. New developments in high-resolution gas source isotope ratio mass spectrometers

    NASA Astrophysics Data System (ADS)

    Clog, M. D.; Ellam, R. M.; Hilkert, A.; Schwieters, J. B.; Hamilton, D.

    2015-12-01

    Gas source isotope ratio mass spectrometry (IRMS) is one of the main tools for the study of the isotopic compositions of light elements, extended in the last 10 years to the measurements of molecules bearing several rare isotopes (e.g., clumped isotopes of CO2) as well as position-specific isotopic substitutions in a few choice analytes (e.g., in N2O). Measuring those low-abundance species creates several technical challenges, with the main one being the presence of numerous isobaric interferences. Those can come either from contaminants (background gases present in the source of the instrument or impurities introduced with the analyte), or unwanted beams created by the analyte itself during the ionization process (for example adducts and fragments). In order to avoid those isobaric species, new high-resolution, double-focusing IRMS have been developed. We present here the capabilities of the production series version of the ThermoFisher Scientific 253 Ultra, which was installed at SUERC in July 2015. The instrument is capable of reaching high mass resolving power (above 40,000) and is similar in design to the Caltech 253 Ultra prototype. The collector array has 9 detector positions, 8 of which are movable. Faraday cups at each detector can be linked to amplifiers with gains ranging from 3.108 to 1012 Ohm (and 1013 Ohm amplifiers being currently developped). There are also 4 ion counters, one of which located behind a retardation lens (RPQ) to limit background noise and improve abundance sensitivity. Additionally, one of the Faraday cup in the new instrument has a very narrow entrance slit, allowing high mass resolving power and high resolution, with a complete separation of the ion beams instead of complex peak shapes corresponding to overlapping ion beams. This will potentially remove the need for adduct lines or peak stripping schemes for analytes like CH4.

  19. Resonance Raman and far-infrared studies of isotopically disordered and mixed-halide halogen-bridged platinum chain solids

    SciTech Connect

    Love, S.P.; Worl, L.A.; Donohoe, R.J.; Huckett, S.C.; Saxena, A.; Huang, X.Z.; Bishop, A.R.; Swanson, B.I.

    1992-12-31

    The MX chain solids [Pt(en){sub 2}][Pt(en){sub 2}X{sub 2}](CIO{sub 4}){sub 4}, (en = C{sub 2}H{sub 8}N{sub 2} and X=Cl, Br), referred to as ``PtX,`` are used to explore some of the surprising spectral consequences of disorder in 1-D systems, first for pure PtCl, where the disorder arises from randomly distributed Cl isotopes, then for the more drastic case of the mixed-halide materials PtCl{sub 1minusx}Br{sub x}. Lattice dynamics and Peierls-Hubbard modelling are used to analyze the observed spectral behavior. In both cases, the complex structure seen in the Raman and IR spectra is found to arise from strongly localized vibrational modes residing on chain segments, defined by sequences of Cl isotopes for PtCl, and by sequences of Cl and Br for PtCl{sub 1minusx}Br{sub x}. 4 figs, 8 refs.

  20. 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.

  1. Neutron unbound resonances cataloged by isotope and invariant mass measurements for nuclei Z = 1-12

    NASA Astrophysics Data System (ADS)

    Havens, Elizabeth; Finck, Joseph; Gueye, Paul; Thoennessen, Michael; MoNA Collaboration

    2015-10-01

    Prior to 2014, no comprehensive study had been undertaken to compile experimental results from neutron unbound spectroscopy using invariant mass measurements, gamma resolutions and half-lives. Through the collaborative efforts of Central Michigan University, Hampton University and the NSCL, a project was initiated to catalog all unbound resonances in light nuclei (Z = 1-12). Unbound resonances were characterized by having a confirmed neutron decay branch and/or an energy level greater than the neutron binding energy listed for that isotope, according to either the NNDC's ENSDF or XUNDL and the referred journals therein. This was initially compiled in July 2014 and presented in October of that year. Recent discoveries and updates to NNDC have added ten isotopes and their resonances. Additionally, various corrections to previously compiled resonances have been made and equivalent evaluated and unevaluated invariant mass measurements have been consolidated into single entries. The neutron separation energy is noted for each isotope. The isotopes in which unbound resonances occur have been identified and, if known, each unbound resonance's gamma resolution, half-life, method of production and journal reference were also determined.

  2. An analytical system for stable isotope analysis on carbon monoxide using continuous-flow isotope-ratio mass spectrometry

    NASA Astrophysics Data System (ADS)

    Pathirana, S. L.; van der Veen, C.; Popa, M. E.; Röckmann, T.

    2015-12-01

    A fully automated system for the determination of δ13C and δ18O in atmospheric CO has been developed. CO is extracted from an air sample and converted into carbon dioxide (CO2) using the Schütze reagent. The isotopic composition is determined with an isotope-ratio mass spectrometer (IRMS) technique. The entire system is continuously flushed with high-purity helium (He), the carrier gas. The blank signal of the Schütze reagent is ~ 4 nmol mol-1, or 1-3 % of the typical sample size. The repeatability is 0.1 ‰ for δ13C and 0.2 ‰ for δ18O. The peak area allows for simultaneous determination of the mole fraction with an analytical repeatability of ~ 0.7 nmol mol-1 for 100 mL of ambient air (185.4 nmol mol-1 of CO). An automated single measurement is performed in only 18 min, and the achieved time efficiency (and small volume of sample air) allows for repetitive measurements practically.

  3. Flow injection analysis-isotope ratio mass spectrometry for bulk carbon stable isotope analysis of alcoholic beverages.

    PubMed

    Jochmann, Maik A; Steinmann, Dirk; Stephan, Manuel; Schmidt, Torsten C

    2009-11-25

    A new method for bulk carbon isotope ratio determination of water-soluble samples is presented that is based on flow injection analysis-isotope ratio mass spectrometry (FIA-IRMS) using an LC IsoLink interface. Advantages of the method are that (i) only very small amounts of sample are required (2-5 microL of the sample for up to 200 possible injections), (ii) it avoids complex sample preparation procedures such as needed for EA-IRMS analysis (only sample dilution and injection,) and (iii) high throughput due to short analysis times is possible (approximately 15 min for five replicates). The method was first tested and evaluated as a fast screening method with industrially produced ethanol samples, and additionally the applicability was tested by the measurement of 81 alcoholic beverages, for example, whiskey, brandy, vodka, tequila, and others. The minimal sample concentration required for precise and reproducible measurements was around 50 microL L(-1) ethanol/water (1.71 mM carbon). The limit of repeatability was determined to be r=0.49%. FIA-IRMS represents a fast screening method for beverage authenticity control. Due to this, samples can be prescreened as a decisive criterion for more detailed investigations by HPLC-IRMS or multielement GC-IRMS measurements for a verification of adulteration. PMID:19856915

  4. Theory of mass-independent fractionation of isotopes, phase space accessibility, and a role of isotopic symmetry

    PubMed Central

    Marcus, Rudolph A.

    2013-01-01

    Key experimental and theoretical features of mass-independent fractionation (MIF) of isotopes, also known as the η-effect, are summarized, including its difference from the exit channel zero-point energy difference effect. The latter exactly cancels in the MIF. One key experimental result is that the MIF for O3 formation is a low-pressure phenomenon and, moreover, that it decreases with increasing pressure of third bodies at pressures far below the “Lindemann fall-off” pressures for three-body recombination of O and O2. A possible origin of the MIF is discussed in terms of a role for isotopologue symmetry in intramolecular energy sharing. An explanation is suggested for the large difference in the fall-off pressure for recombination and the pressure for a large decrease in MIF, in terms of a difference between deactivating collisions and what we term here “symmetry-changing collisions”. It is noted that the theory of the MIF involves four recombination rate constants and an equilibrium constant, for each trace isotope, seven rate constants in all and two equilibrium constants. A conceptual shortcut is noted. Experimental and computational information that may provide added insight into the MIF mechanism and tests is described. PMID:23812747

  5. High-precision Penning-trap mass measurements of heavy xenon isotopes for nuclear structure studies

    SciTech Connect

    Neidherr, D.; Cakirli, R. B.; Audi, G.; Lunney, D.; Minaya-Ramirez, E.; Naimi, S.; Beck, D.; Herfurth, F.; Blaum, K.; Boehm, Ch.; George, S.; Breitenfeldt, M.; Rosenbusch, M.; Schweikhard, L.; Casten, R. F.; Herlert, A.; Kowalska, M.; Kellerbauer, A.; Schwarz, S.

    2009-10-15

    With the double Penning-trap mass spectrometer ISOLTRAP at ISOLDE/CERN the masses of the neutron-rich isotopes {sup 136-146}Xe were measured with a relative uncertainty of the order of 10{sup -8} to 10{sup -7}. In particular, the masses of {sup 144-146}Xe were measured for the first time. These new mass values allow one to extend calculations of the mass surface in this region. Proton-Neutron interaction strength, obtained from double differences of binding energies, relate to subtle structural effects, such as the onset of octupole correlations, the growth of collectivity, and its relation to the underlying shell model levels. In addition, they provide a test of density functional calculations.

  6. 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...

  7. Alleviation of overlap interferences for determination of potassium isotope ratios by inductively coupled plasma mass spectrometry

    SciTech Connect

    Jiang, S.J.; Houk, R.S.; Stevens, M.A.

    1988-06-01

    Positioning the sampling orifice relatively far from the load coil combined with use of low forward power and high aerosol gas flow rate causes the background mass spectrum to become dominated by NO/sup +/. Nearly all the Ar/sup +/ and ArH/sup +/ ions are suppressed under these conditions, which frees m/z 39 and 41 for potassium isotope ratio measurements. The precision is 0.3-0.9% relative standard deviation for potassium concentrations in the range 1-50 mg L/sup -1/. The determined ratios are approx. 9% higher than the accepted value and also vary with the concentration of sodium concomitant, so calibrations and chemical separations are desirable. These observations should permit use of inductively coupled plasma mass spectrometry for rapid isotope ratio determinations of potassium from biological organisms or water sources.

  8. Use of stable carbon and nitrogen isotopes to trace the larval striped bass food chain in the Sacramento-San Joaquin Estuary, California, April to September 1985

    USGS Publications Warehouse

    Rast, Walter; Sutton, J.E.

    1989-01-01

    To assess one potential cause for the decline of the striped bass fishery in the Sacramento-San Joaquin Estuary, stable carbon and nitrogen isotope ratios were used to examine the trophic structures of the larval striped bass food chain, and to trace the flux of these elements through the food chain components. Study results generally confirm a food chain consisting of the elements, phytoplankton/detritus-->zooplankton/Neomysis shrimp-->larval striped bass. The stable isotope ratios generally become more positive as one progresses from the lower to the higher trophic level food chain components, and no unusual trophic structure was found in the food chain. However, the data indicate an unidentified consumer organism occupying an intermediate position between the lower and higher trophic levels of the larval striped bass food chain. Based on expected trophic interactions, this unidentified consumer would have a stable carbon isotope ratio of about 28/mil and a stable nitrogen isotope ratio of about 8/mi. Three possible feeding stages for larval striped bass also were identified, based on their lengths. The smallest length fish seem to subsist on their yolk sac remnants, and the largest length fish subsist on Neomysis shrimp and zooplankton. The intermediate-length fish represent a transition stage between primary food sources and/or use of a mixture of food sources. (USGS)

  9. Development of a dedicated isotope mass spectrometer for the noninvasive diagnostics of humans infected with Helicobacter Pylori

    NASA Astrophysics Data System (ADS)

    Blashenkov, N. M.; Sheshenya, E. S.; Solov'ev, S. M.; Gall', L. N.; Sachenko, V. M.; Zarutskii, I. V.; Gall', N. R.

    2013-06-01

    A dedicated isotope mass spectrometer for the noninvasive diagnostics of humans infected with Helicobacter Pylori using the isotope respiratory test is developed. A low-aberration mass analyzer is calculated, an input system that makes it possible to eliminate the memory effects is developed, and a small-size ion detector is constructed. The mass spectrometer is created, and the tests are performed. The measurement accuracy of the 13C/12C and 16O/18O isotope ratios are 1.7 and 2.2‰, respectively. Preliminary medical tests show that the spectrometer can be employed for the desired diagnostics.

  10. Inductively coupled plasma mass spectrometry for stable isotope metabolic tracer studies of living systems

    SciTech Connect

    Luong, E.

    1999-05-10

    This dissertation focuses on the development of methods for stable isotope metabolic tracer studies in living systems using inductively coupled plasma single and dual quadrupole mass spectrometers. Sub-nanogram per gram levels of molybdenum (Mo) from human blood plasma are isolated by the use of anion exchange alumina microcolumns. Million-fold more concentrated spectral and matrix interferences such as sodium, chloride, sulfate, phosphate, etc. in the blood constituents are removed from the analyte. The recovery of Mo from the alumina column is 82 {+-} 5% (n = 5). Isotope dilution inductively coupled plasma mass spectrometry (ID-ICP-MS) is utilized for the quantitative ultra-trace concentration determination of Mo in bovine and human blood samples. The average Mo concentration in reference bovine serum determined by this method is 10.2 {+-} 0.4 ng/g, while the certified value is 11.5 {+-} 1.1 ng/g (95% confidence interval). The Mo concentration of one pool of human blood plasma from two healthy male donors is 0.5 {+-} 0.1 ng/g. The inductively coupled plasma twin quadrupole mass spectrometer (ICP-TQMS) is used to measure the carbon isotope ratio from non-volatile organic compounds and bio-organic molecules to assess the ability as an alternative analytical method to gas chromatography combustion isotope ratio mass spectrometry (GC-combustion-IRMS). Trytophan, myoglobin, and {beta}-cyclodextrin are chosen for the study, initial observation of spectral interference of {sup 13}C{sup +} with {sup 12}C{sup 1}H{sup +} comes from the incomplete dissociation of myoglobin and/or {beta}-cyclodextrin.

  11. Constraints on continental crustal mass loss via chemical weathering using lithium and its isotopes

    NASA Astrophysics Data System (ADS)

    Rudnick, R. L.; Liu, X. M.

    2012-04-01

    The continental crust has an "intermediate" bulk composition that is distinct from primary melts of peridotitic mantle (basalt or picrite). This mismatch between the "building blocks" and the "edifice" that is the continental crust points to the operation of processes that preferentially remove mafic to ultramafic material from the continents. Such processes include lower crustal recycling (via density foundering or lower crustal subduction - e.g., relamination, Hacker et al., 2011, EPSL), generation of evolved melts via slab melting, and/or chemical weathering. Stable isotope systems point to the influence of chemical weathering on the bulk crust composition: the oxygen isotope composition of the bulk crust is distinctly heavier than that of primary, mantle-derived melts (Simon and Lecuyer, 2005, G-cubed) and the Li isotopic composition of the bulk crust is distinctly lighter than that of mantle-derive melts (Teng et al., 2004, GCA; 2008, Chem. Geol.). Both signatures mark the imprint of chemical weathering on the bulk crust composition. Here, we use a simple mass balance model for lithium inputs and outputs from the continental crust to quantify the mass lost due to chemical weathering. We find that a minimum of 15%, a maximum of 60%, and a best estimate of ~40% of the original juvenile rock mass may have been lost via chemical weathering. The accumulated percentage of mass loss due to chemical weathering leads to an average global chemical weathering rate (CWR) of ~ 1×10^10 to 2×10^10 t/yr since 3.5 Ga, which is about an order of magnitude higher than the minimum estimates based on modern rivers (Gaillardet et al., 1999, Chem. Geol.). While we cannot constrain the exact portion of crustal mass loss via chemical weathering, given the uncertainties of the calculation, we can demonstrate that the weathering flux is non-zero. Therefore, chemical weathering must play a role in the evolution of the composition and mass of the continental crust.

  12. Fluoride sample matrices and reaction cells — new capabilities for isotope measurements in accelerator mass spectrometry

    NASA Astrophysics Data System (ADS)

    Kieser, W. E.; Zhao, X.-L.; Eliades, J.; Litherland, A. E.

    2012-04-01

    Two new techniques, which extend the range of elements that can be analyzed by Accelerator Mass Spectrometry (AMS), and which increase its isobar selection capabilities, have been recently introduced. The first consists of embedding the sample material in a fluoride matrix (e.g. PbF2), which facilitates the production, in the ion source, of fluoride molecular anions that include the isotope of interest. In addition to forming anions with large electron binding energies and thereby increasing the range of analysable elements, in many cases by selection of a molecular form with a particular number of fluorine atoms, some isobar discrimination can be obtained. The second technique, for the significant reduction of atomic isobar interferences, is used following mass selection of the rare isotope. It consists of the deceleration, cooling and reaction of the rare mass beam with a gas, selected so that unwanted isobars are greatly attenuated in comparison with the isotope of interest. Proof of principle measurements for the analysis of 36C1 and 41Ca have provided encouraging results and work is proceeding on the integration of these techniques in a new AMS system planned for installation in late 2012 at the University of Ottawa.

  13. An Update on the Non-Mass-Dependent Isotope Fractionation under Thermal Gradient

    NASA Technical Reports Server (NTRS)

    Sun, Tao; Niles, Paul; Bao, Huiming; Socki, Richard; Liu, Yun

    2013-01-01

    Mass flow and compositional gradient (elemental and isotope separation) occurs when flu-id(s) or gas(es) in an enclosure is subjected to a thermal gradient, and the phenomenon is named thermal diffusion. Gas phase thermal diffusion has been theoretically and experimentally studied for more than a century, although there has not been a satisfactory theory to date. Nevertheless, for isotopic system, the Chapman-Enskog theory predicts that the mass difference is the only term in the thermal diffusion separation factors that differs one isotope pair to another,with the assumptions that the molecules are spherical and systematic (monoatomic-like structure) and the particle collision is elastic. Our previous report indicates factors may be playing a role because the Non-Mass Dependent (NMD) effect is found for both symmetric and asymmetric, linear and spherical polyatomic molecules over a wide range of temperature (-196C to +237C). The observed NMD phenomenon in the simple thermal-diffusion experiments demands quantitative validation and theoretical explanation. Besides the pressure and temperature dependency illustrated in our previous reports, efforts are made in this study to address issues such as the role of convection or molecular structure and whether it is a transient, non-equilibrium effect only.

  14. Acquisition and processing of data for isotope-ratio-monitoring mass spectrometry

    NASA Technical Reports Server (NTRS)

    Ricci, M. P.; Merritt, D. A.; Freeman, K. H.; Hayes, J. M.

    1994-01-01

    Methods are described for continuous monitoring of signals required for precise analyses of 13C, 18O, and 15N in gas streams containing varying quantities of CO2 and N2. The quantitative resolution (i.e. maximum performance in the absence of random errors) of these methods is adequate for determination of isotope ratios with an uncertainty of one part in 10(5); the precision actually obtained is often better than one part in 10(4). This report describes data-processing operations including definition of beginning and ending points of chromatographic peaks and quantitation of background levels, allowance for effects of chromatographic separation of isotopically substituted species, integration of signals related to specific masses, correction for effects of mass discrimination, recognition of drifts in mass spectrometer performance, and calculation of isotopic delta values. Characteristics of a system allowing off-line revision of parameters used in data reduction are described and an algorithm for identification of background levels in complex chromatograms is outlined. Effects of imperfect chromatographic resolution are demonstrated and discussed and an approach to deconvolution of signals from coeluting substances described.

  15. Confirmation of mass-independent Ni isotopic variability in iron meteorites

    NASA Astrophysics Data System (ADS)

    Steele, Robert C. J.; Elliott, Tim; Coath, Christopher D.; Regelous, Marcel

    2011-12-01

    We report high-precision analyses of internally-normalised Ni isotope ratios in 12 bulk iron meteorites. Our measurements of 60Ni/ 61Ni, 62Ni/ 61Ni and 64Ni/ 61Ni normalised to 58Ni/ 61Ni and expressed in parts per ten thousand (‱) relative to NIST SRM 986 as ɛ60Ni,ɛ62Ni and ɛ64Ni, vary by 0.146, 0.228 and 0.687, respectively. The precision on a typical analysis is 0.03‱, 0.05‱ and 0.08‱ for ɛ60Ni, ɛ62Ni and ɛ64Ni, respectively, which is comparable to our sample reproducibility. We show that this 'mass-independent' Ni isotope variability cannot be ascribed to interferences, inaccurate correction of instrumental or natural mass-dependent fractionation, fractionation controlled by nuclear field shift effects, nor the influence of cosmic ray spallation. These results thus document the presence of mass-independent Ni isotopic heterogeneity in bulk meteoritic samples, as previously proposed by Regelous et al. (2008) (EPSL 272, 330-338), but our new analyses are more precise and include determination of 64Ni. Intriguingly, we find that terrestrial materials do not yield homogenous internally-normalised Ni isotope compositions, which, as pointed out by Young et al. (2002) (GCA 66, 1095-1104), may be the expected result of using the exponential (kinetic) law and atomic masses to normalise all fractionation processes. The certified Ni isotope reference material NIST SRM 986 defines zero in this study, while appropriate ratios for the bulk silicate Earth are given by the peridotites JP-1 and DTS-2 and, relative to NIST SRM 986, yield deviations in ɛ60Ni, ɛ62Ni and ɛ64Ni of -0.006‱, 0.036‱ and 0.119‱, respectively. There is a strong positive correlation between ɛ64Ni and ɛ62Ni in iron meteorites analyses, with a slope of 3.03 ± 0.71. The variations of Ni isotope anomalies in iron meteorites are consistent with heterogeneous distribution of a nucleosynthetic component from a type Ia supernova into the proto-solar nebula.

  16. Equilibrium uranium isotope fractionation by nuclear volume and mass-dependent processes

    NASA Astrophysics Data System (ADS)

    Schauble, E. A.

    2006-12-01

    Uranium serves as a geochemical tracer of oxidation near the Earth's surface, and is also the basis for several isotopic geochronometers. It is thus important to understand possible non-radiogenic and non-radioactive isotopic fractionation of uranium in natural systems. This study presents theoretical estimates of equilibrium uranium isotope fractionations in U-bearing molecules and complexes, calculated using first-principles computational chemistry. Ion-exchange experiments (1,2) have indicated that mass-dependent mechanisms, alone, cannot explain 238U/234U and 238U/^{235}U fractionations, so nuclear volume (i.e., field shift) fractionation effects are also considered in theoretical calculations. The results indicate that equilibrium isotopic fractionation is likely when U4+ and U6+ species equilibrate. Nuclear volume fractionation leads to higher 238U/^{235}U in U4+-bearing species, overwhelming a smaller mass- dependent fractionation in the opposite direction. The calculated net fractionation between U(H2O)_94+ and UO2Cl3(H2O)_2^- is approximately 1 per mil at 20-150°C, in agreement with earlier experiments. These results also reproduce the apparent non mass-dependent signature observed in 238U/234U relative to 238U/^{235}U. In addition to redox reactions, significant fractionation is expected between different U6+-bearing uranyl complexes (e.g., UO2(H2O)_52+, UO2(NO3)_3^-, UO2(CO3)(H2O)3). These results suggest that U-isotope composition could be used as a proxy for the oxidation state and speciation of natural waters, and that U-isotope ratios are not constant in materials formed or equilibrated at low temperatures. More generally, nuclear volume fractionations are expected to partially cancel or reverse mass-dependent fractionations caused by redox transitions among the high oxidation states (≥+2) of lanthanides, actinides, and heavy transition elements. References: 1. Nomura, Higuchi and Fujii, 1996, J. Am. Chem. Soc., v. 118, p. 9127-9130. 2. Bigeleisen

  17. Applications of Structural Mass Spectrometry to Metabolomics: Clarifying Bond Specific Spectral Signatures with Isotope Edited Spectroscopy

    NASA Astrophysics Data System (ADS)

    Gorlova, Olga; Wolke, Conrad T.; Fournier, Joseph; Colvin, Sean; Johnson, Mark; Miller, Scott

    2015-06-01

    Comprehensive FTIR, MS/MS and NMR of pharmaceuticals are generally readily available but characterization of their metabolites has been an obstacle. Atorvastatin is a statin drug responsible for the maintenance of cholesterol in the body. Diovan is an angiostensin receptor antagonist used to treat high blood pressure and congestive heart failure. The field of metabolomics, however, is struggling to obtain the identity of their structures. We implement mass spectrometry with cryogenic ion spectroscopy to study gaseous ions of the desired metabolites which, in combination, not only identify the mass of the metabolite but also elucidate their structures through isotope-specific infrared spectroscopy.

  18. Video analysis of sliding chains: A dynamic model based on variable-mass systems

    NASA Astrophysics Data System (ADS)

    Moreno, R.; Page, A.; Riera, J.; Hueso, J. L.

    2015-06-01

    This paper presents an experimental study of the dynamics of a chain sliding off of a table, using video analysis to test a theoretical model. The model consists of two variable-mass subsystems, with friction between the chain and the table and assumes that all links move at the same speed. In order to check the model, the chain position x(t) is obtained using video analysis. The smoothed function x(t) and its derivatives v(t) and a(t) are numerically computed using a local regression algorithm. In this way, the differential equation governing the motion can be directly tested, instead of comparing the position with the solution of the differential equation. Our procedure is very sensitive to deviations between the model and reality, so we can detect the point at which the chain ceases to be in tension and the model is no longer valid. This experiment shows students the limitations of simplified models and offers an opportunity to assess a model's range of validity.

  19. INTERLABORATORY COMPARISON OF MASS SPECTROMETRIC METHODS FOR LEAD ISOTOPES AND TRACE ELEMENTS IN NIST SRM 1400 BONE ASH

    EPA Science Inventory

    The results of an interlaboratory comparison are reported for he lead isotope composition and for trace element concentrations in NIST SRM 1400 Bone Ash obtained using quadrupole and magnetic-sector inductively coupled plasma mass spectrometry (ICP-MS) and (for the Pb isotopes on...

  20. Isotopic mass-dependence of metal cation diffusion coefficients in liquid water

    SciTech Connect

    Bourg, I.C.; Richter, F.M.; Christensen, J.N.; Sposito, G.

    2009-01-11

    Isotope distributions in natural systems can be highly sensitive to the mass (m) dependence of solute diffusion coefficients (D) in liquid water. Isotope geochemistry studies routinely have assumed that this mass dependence either is negligible (as predicted by hydrodynamic theories) or follows a kinetic-theory-like inverse square root relationship (D {proportional_to} m{sup -0.5}). However, our recent experimental results and molecular dynamics (MD) simulations showed that the mass dependence of D is intermediate between hydrodynamic and kinetic theory predictions (D {proportional_to} m{sup -{beta}} with 0 {<=} {beta} < 0.2 for Li{sup +}, Cl{sup -}, Mg{sup 2+}, and the noble gases). In this paper, we present new MD simulations and experimental results for Na{sup +}, K{sup +}, Cs{sup +}, and Ca{sup 2+} that confirm the generality of the inverse power-law relation D {proportional_to} m{sup -{beta}}. Our new findings allow us to develop a general description of the influence of solute valence and radius on the mass dependence of D for monatomic solutes in liquid water. This mass dependence decreases with solute radius and with the magnitude of solute valence. Molecular-scale analysis of our MD simulation results reveals that these trends derive from the exponent {beta} being smallest for those solutes whose motions are most strongly coupled to solvent hydrodynamic modes.

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

    PubMed

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

    2008-10-01

    On-line gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS) is commonly used to measure isotopic ratios at natural abundance as well as for tracer studies in nutritional and medical research. However, high-precision (13)C isotopic enrichment can also be measured by liquid chromatography-isotope ratio mass spectrometry (LC-IRMS). Indeed, LC-IRMS can be used, as shown by the new method reported here, to obtain a baseline separation and to measure (13)C isotopic enrichment of underivatised amino acids (Asp, Thr-Ser, Glu, Pro, Gly, Ala, Cys and Val). In case of Val, at natural abundance, the SD(delta(13)C) reported with this method was found to be below 1 per thousand . Another key feature of the new LC-IRMS method reported in this paper is the comparison of the LC-IRMS approach with the conventional GC-C-IRMS determination. To perform this comparative study, isotopic enrichments were measured from underivatised Val and its N(O, S)-ethoxycarbonyl ethyl ester derivative. Between 0.0 and 1.0 molar percent excess (MPE) (delta(13)C= -12.3 to 150.8 per thousand), the calculated root-mean-square (rms) of SD was 0.38 and 0.46 per thousand and the calculated rms of accuracy was 0.023 and 0.005 MPE, respectively, for GC-C-IRMS and LC-IRMS. Both systems measured accurately low isotopic enrichments (0.002 atom percent excess (APE)) with an SD (APE) of 0.0004. To correlate the relative (delta(13)C) and absolute (atom%, APE and MPE) isotopic enrichment of Val measured by the GC-C-IRMS and LC-IRMS devices, mathematical equations showing the slope and intercept of the curves were established and validated with experimental data between 0.0 to 2.3 MPE. Finally, both GC-C-IRMS and LC-IRMS instruments were also used to assess isotopic enrichment of protein-bound (13)C-Val in tibial epiphysis in a tracer study performed in rats. Isotopic enrichments measured by LC-IRMS and GC-C-IRMS were not statistically different (p>0.05). The results of this work indicate that

  2. Development and Deployment of Retrofit PolarisQ Ion Trap Mass Spectrometer for Isotope Ratio Measurements

    SciTech Connect

    Thompson, Cyril V.; Whitten, William B.

    2015-11-01

    This report describes Oak Ridge National Laboratory’s (ORNL) FY15 progress in support of National Nuclear Security Administration’s (NNSA) Portable Mass Spectrometer project. A retrofit PolarisQ ion trap mass spectrometer (RPMS) has been assembled from components of two PolarisQ ion trap mass spectrometers used in previous isotope ratio programs. The retrofit mass spectrometer includes a custom Hastelloy vacuum chamber which is about ¼ the size of the standard aluminum vacuum chamber and reduces the instrument weight from the original by nine pounds. In addition, the new vacuum chamber can be independently heated to reduce impurities such as water, which reacts with UF6 to produce HF in the vacuum chamber. The analyzer and all components requiring service are mounted on the chamber lid, facilitating quick and easy replacement of consumable components such as the filament and electron multiplier.

  3. Performance and optimization of a combustion interface for isotope ratio monitoring gas chromatography/mass spectrometry.

    PubMed

    Merritt, D A; Freeman, K H; Ricci, M P; Studley, S A; Hayes, J M

    1995-07-15

    Conditions and systems for on-line combustion of effluents from capillary gas chromatographic columns and for removal of water vapor from product streams were tested. Organic carbon in gas chromatographic peaks 15 s wide and containing up to 30 nanomoles of carbon was quantitatively converted to CO2 by tubular combustion reactors, 200 x 0.5 mm, packed with CuO or NiO. No auxiliary source of O2 was required because oxygen was supplied by metal oxides. Spontaneous degradation of CuO limited the life of CuO reactors at T > 850 degrees C. Since NiO does not spontaneously degrade, its use might be favored, but Ni-bound carbon phases form and lead to inaccurate isotopic results at T < 1050 degrees C if gas-phase O2 is not added. For all compounds tested except CH4, equivalent isotopic results are provided by CuO at 850 degrees C, NiO + O2 (gas-phase mole fraction, 10(-3)) at 1050 degrees C and NiO at 1150 degrees C. The combustion interface did not contribute additional analytical uncertainty, thus observed standard deviations of 13C/12C ratios were within a factor of 2 of shot-noise limits. For combustion and isotopic analyses of CH4, in which quantitative combustion required T approximately 950 degrees C, NiO-based systems are preferred, and precision is approximately 2 times lower than that observed for other analytes. Water must be removed from the gas stream transmitted to the mass spectrometer or else protonation of CO2 will lead to inaccuracy in isotopic analyses. Although thresholds for this effect vary between mass spectrometers, differential permeation of H2O through Nafion tubing was effective in both cases tested, but the required length of the Nafion membrane was 4 times greater for the more sensitive mass spectrometer. PMID:11536720

  4. Performance and optimization of a combustion interface for isotope ratio monitoring gas chromatography/mass spectrometry

    NASA Technical Reports Server (NTRS)

    Merritt, D. A.; Freeman, K. H.; Ricci, M. P.; Studley, S. A.; Hayes, J. M.

    1995-01-01

    Conditions and systems for on-line combustion of effluents from capillary gas chromatographic columns and for removal of water vapor from product streams were tested. Organic carbon in gas chromatographic peaks 15 s wide and containing up to 30 nanomoles of carbon was quantitatively converted to CO2 by tubular combustion reactors, 200 x 0.5 mm, packed with CuO or NiO. No auxiliary source of O2 was required because oxygen was supplied by metal oxides. Spontaneous degradation of CuO limited the life of CuO reactors at T > 850 degrees C. Since NiO does not spontaneously degrade, its use might be favored, but Ni-bound carbon phases form and lead to inaccurate isotopic results at T < 1050 degrees C if gas-phase O2 is not added. For all compounds tested except CH4, equivalent isotopic results are provided by CuO at 850 degrees C, NiO + O2 (gas-phase mole fraction, 10(-3)) at 1050 degrees C and NiO at 1150 degrees C. The combustion interface did not contribute additional analytical uncertainty, thus observed standard deviations of 13C/12C ratios were within a factor of 2 of shot-noise limits. For combustion and isotopic analyses of CH4, in which quantitative combustion required T approximately 950 degrees C, NiO-based systems are preferred, and precision is approximately 2 times lower than that observed for other analytes. Water must be removed from the gas stream transmitted to the mass spectrometer or else protonation of CO2 will lead to inaccuracy in isotopic analyses. Although thresholds for this effect vary between mass spectrometers, differential permeation of H2O through Nafion tubing was effective in both cases tested, but the required length of the Nafion membrane was 4 times greater for the more sensitive mass spectrometer.

  5. New Short-Lived Isotope ^{221}U and the Mass Surface Near N=126.

    PubMed

    Khuyagbaatar, J; Yakushev, A; Düllmann, Ch E; Ackermann, D; Andersson, L-L; Block, M; Brand, H; Cox, D M; Even, J; Forsberg, U; Golubev, P; Hartmann, W; Herzberg, R-D; Heßberger, F P; Hoffmann, J; Hübner, A; Jäger, E; Jeppsson, J; Kindler, B; Kratz, J V; Krier, J; Kurz, N; Lommel, B; Maiti, M; Minami, S; Mistry, A K; Mrosek, Ch M; Pysmenetska, I; Rudolph, D; Sarmiento, L G; Schaffner, H; Schädel, M; Schausten, B; Steiner, J; De Heidenreich, T Torres; Uusitalo, J; Wegrzecki, M; Wiehl, N; Yakusheva, V

    2015-12-11

    Two short-lived isotopes ^{221}U and ^{222}U were produced as evaporation residues in the fusion reaction ^{50}Ti+^{176}Yb at the gas-filled recoil separator TASCA. An α decay with an energy of E_{α}=9.31(5)  MeV and half-life T_{1/2}=4.7(7)  μs was attributed to ^{222}U. The new isotope ^{221}U was identified in α-decay chains starting with E_{α}=9.71(5)  MeV and T_{1/2}=0.66(14)  μs leading to known daughters. Synthesis and detection of these unstable heavy nuclei and their descendants were achieved thanks to a fast data readout system. The evolution of the N=126 shell closure and its influence on the stability of uranium isotopes are discussed within the framework of α-decay reduced width. PMID:26705628

  6. Temperature-programmed high-performance liquid chromatography coupled to isotope ratio mass spectrometry.

    PubMed

    Godin, Jean-Philippe; Hopfgartner, Gérard; Fay, Laurent

    2008-09-15

    The utility of liquid chromatography coupled to the isotope ratio mass spectrometry technique (LC-IRMS) has already been established through a variety of successful applications. However, the analytical constraint related to the use of aqueous mobile phases limits the LC separation mechanism. We report here a new strategy for high-precision (13)C isotopic analyses based on temperature-programmed LC-IRMS using aqueous mobile phases. Under these conditions, the isotopic precision and accuracy were studied. On one hand, experiments were carried out with phenolic acids using isothermal LC conditions at high temperature (170 degrees C); on the other hand, several experiments were performed by ramping the temperature, as conventionally used in a gas chromatography-based method with hydrosoluble fatty acids and pulses of CO 2 reference gas. In isothermal conditions at 170 degrees C, despite the increase of the CO 2 background, p-coumaric acid and its glucuronide conjugate gave reliable isotopic ratios compared to flow injection analysis-isotopic ratio mass spectrometry (FIA-IRMS) analyses (isotopic precision and accuracy are lower than 0.3 per thousand). On the opposite, for its sulfate conjugate, the isotopic accuracy is affected by its coelution with p-coumaric acid. Not surprisingly, this study also demonstrates that at high temperature (170 degrees C), a compound eluting with long residence time (i.e., ferulic acid) is degraded, affecting thus the delta (13)C (drift of 3 per thousand) and the peak area (compared to FIA-IRMS analysis at room temperature). Quantitation is also reported in isothermal conditions for p-coumaric acid in the range of 10-400 ng/mL and with benzoic acid as an internal standard. For temperature gradient LC-IRMS, in the area of the LC gradient (set up at 20 degrees C/min), the drift of the background observed produces a nonlinearity of SD (delta (13)C) approximately 0.01 per thousand/mV. To circumvent this drift, which impacts severely the

  7. Variations of the glacio-marine air mass front in West Greenland through water vapor isotopes

    NASA Astrophysics Data System (ADS)

    Kopec, B. G.; Lauder, A. M.; Posmentier, E. S.; Feng, X.

    2012-12-01

    While the isotopic distribution of precipitation has been widely used for research in hydrology, paleoclimatology, and ecology for decades, intensive isotopic studies of atmospheric water vapor has only recently been made possible by spectral-based technology. New instrumentation based on this technology opens up many opportunities to investigate short-term atmospheric dynamics involving the water cycle and moisture transport. We deployed a Los Gatos Water Vapor Isotope Analyzer (WVIA) at Kangerlussuaq, Greenland from July 21 to August 15, and measured the water vapor concentration and its isotopic ratios continuously at 10s intervals. A Danish Meteorological Institute site is located about 1 km from the site of the deployment, and meteorological data is collected at 30 min intervals. During the observation period, the vapor concentration of the ambient air ranges from 5608.4 to 11189.4 ppm; dD and d18O range from -254.5 to -177.7 ‰ and -34.2 to -23.2 ‰, respectively. The vapor content (dew point) and the isotopic ratios are both strongly controlled by the wind direction. The easterly winds are associated with dry, isotopically depleted air masses formed over the glacier, while westerly winds are associated with moist and isotopically enriched air masses from the marine/fjord surface. This region typically experiences katabatic winds off of the ice sheet to the east. However, during some afternoons, the wind shifts 180 degrees, blowing off the fjord to the west. This wind switch marks the onset of a sea breeze, and significant isotopic enrichment results. Enrichment in deuterium is up to 60 ‰ with a mean of 15‰, and oxygen-18 is enriched by 3‰ on average and up to 8 ‰. Other afternoons have no change in wind, and only small changes in humidity and vapor isotopic ratios. The humidity and isotopic variations suggest the local atmosphere circulation is dominated by relatively high-pressure systems above the cold glaciers and cool sea surface, and diurnal

  8. THE GENESIS SOLAR WIND CONCENTRATOR TARGET: MASS FRACTIONATION CHARACTERISED BY NE ISOTOPES

    SciTech Connect

    WIENS, ROGER C.; OLINGER, C.; HEBER, V.S.; REISENFELD, D.B.; BURNETT, D.S.; ALLTON, J.H.; BAUR, H.; WIECHERT, U.; WIELER, R.

    2007-01-02

    The concentrator on Genesis provides samples of increased fluences of solar wind ions for precise determination of the oxygen isotopic composition of the solar wind. The concentration process caused mass fractionation as function of the radial target position. They measured the fractionation using Ne released by UV laser ablation along two arms of the gold cross from the concentrator target to compare measured Ne with modeled Ne. The latter is based on simulations using actual conditions of the solar wind during Genesis operation. Measured Ne abundances and isotopic composition of both arms agree within uncertainties indicating a radial symmetric concentration process. Ne data reveal a maximum concentration factor of {approx} 30% at the target center and a target-wide fractionation of Ne isotopes of 3.8%/amu with monotonously decreasing {sup 20}Ne/{sup 22}Ne ratios towards the center. The experimentally determined data, in particular the isotopic fractionation, differ from the modeled data. They discuss potential reasons and propose future attempts to overcome these disagreements.

  9. Inductively coupled plasma mass spectrometry applied to isotopic analysis of iron in human fecal matter

    SciTech Connect

    Ting, B.T.G.; Janghorbani, M.

    1986-06-01

    Inductively coupled plasma mass spectrometry combined with stable isotope dilution is applied to accurate isotopic analysis of human fecal matter for /sup 54/Fe and /sup 58/Fe. Argon plasma generated interferences are of minor concern. The interference from /sup 54/Cr can be corrected instrumentally, whereas /sup 58/Ni must be removed chemically. The ratio of the stable isotopes of interest can be measured routinely with a relative standard deviation of about 1%. The overall accuracy of the method for quantitative isotopic analyses is evaluated in Standard Reference Material (SRM) 1577a (Bovine Liver), fecal homogenate subsamples, and synthetic solutions of iron. For SRM 1577a, the respective comparisons are (..mu..g/g) 192.2 +/- 2.2 (present method) vs. 194 +/- 20 (certified value). For the fecal matrix, the present method yields (..mu..g/mL) 15.14 +/- 0.36 vs. 15.82 +/- 0.48 based on atomic absorption spectrophotometry. For an iron solution (250 ppm), replicate analyses yield the value of 245.4 +/- 1.5 ppm.

  10. Calibration and Data Processing in Gas Chromatography Combustion Isotope Ratio Mass Spectrometry

    PubMed Central

    Zhang, Ying; Tobias, Herbert J.; Sacks, Gavin L.; Brenna, J. Thomas

    2013-01-01

    Compound-specific isotope analysis (CSIA) by gas chromatography combustion isotope ratio mass spectrometry (GCC-IRMS) is a powerful technique for the sourcing of substances, such as determination of the geographic or chemical origin of drugs and food adulteration, and it is especially invaluable as a confirmatory tool for detection of the use of synthetic steroids in competitive sport. We review here principles and practices for data processing and calibration of GCC-IRMS data with consideration to anti-doping analyses, with a focus on carbon isotopic analysis (13C/12C). After a brief review of peak definition, the isotopologue signal reduction methods of summation, curve-fitting, and linear regression are described and reviewed. Principles for isotopic calibration are considered in the context of the Δ13C = δ13CM – δ13CE difference measurements required for establishing adverse analytical findings for metabolites relative to endogenous reference compounds. Considerations for the anti-doping analyst are reviewed. PMID:22362612

  11. Calibration and data processing in gas chromatography combustion isotope ratio mass spectrometry.

    PubMed

    Zhang, Ying; Tobias, Herbert J; Sacks, Gavin L; Brenna, J Thomas

    2012-12-01

    Compound-specific isotope analysis (CSIA) by gas chromatography combustion isotope ratio mass spectrometry (GCC-IRMS) is a powerful technique for the sourcing of substances, such as determination of the geographic or chemical origin of drugs and food adulteration, and it is especially invaluable as a confirmatory tool for detection of the use of synthetic steroids in competitive sport. We review here principles and practices for data processing and calibration of GCC-IRMS data with consideration to anti-doping analyses, with a focus on carbon isotopic analysis ((13)C/(12)C). After a brief review of peak definition, the isotopologue signal reduction methods of summation, curve-fitting, and linear regression are described and reviewed. Principles for isotopic calibration are considered in the context of the Δ(13)C = δ(13)C(M) - δ(13)C(E) difference measurements required for establishing adverse analytical findings for metabolites (M) relative to endogenous (E) reference compounds. Considerations for the anti-doping analyst are reviewed. PMID:22362612

  12. Compound-specific chlorine isotope analysis: a comparison of gas chromatography/isotope ratio mass spectrometry and gas chromatography/quadrupole mass spectrometry methods in an interlaboratory study.

    PubMed

    Bernstein, Anat; Shouakar-Stash, Orfan; Ebert, Karin; Laskov, Christine; Hunkeler, Daniel; Jeannottat, Simon; Sakaguchi-Söder, Kaori; Laaks, Jens; Jochmann, Maik A; Cretnik, Stefan; Jager, Johannes; Haderlein, Stefan B; Schmidt, Torsten C; Aravena, Ramon; Elsner, Martin

    2011-10-15

    Chlorine isotope analysis of chlorinated hydrocarbons like trichloroethylene (TCE) is of emerging demand because these species are important environmental pollutants. Continuous flow analysis of noncombusted TCE molecules, either by gas chromatography/isotope ratio mass spectrometry (GC/IRMS) or by GC/quadrupole mass spectrometry (GC/qMS), was recently brought forward as innovative analytical solution. Despite early implementations, a benchmark for routine applications has been missing. This study systematically compared the performance of GC/qMS versus GC/IRMS in six laboratories involving eight different instruments (GC/IRMS, Isoprime and Thermo MAT-253; GC/qMS, Agilent 5973N, two Agilent 5975C, two Thermo DSQII, and one Thermo DSQI). Calibrations of (37)Cl/(35)Cl instrument data against the international SMOC scale (Standard Mean Ocean Chloride) deviated between instruments and over time. Therefore, at least two calibration standards are required to obtain true differences between samples. Amount dependency of δ(37)Cl was pronounced for some instruments, but could be eliminated by corrections, or by adjusting amplitudes of standards and samples. Precision decreased in the order GC/IRMS (1σ ≈ 0.1‰), to GC/qMS (1σ ≈ 0.2-0.5‰ for Agilent GC/qMS and 1σ ≈ 0.2-0.9‰ for Thermo GC/qMS). Nonetheless, δ(37)Cl values between laboratories showed good agreement when the same external standards were used. These results lend confidence to the methods and may serve as a benchmark for future applications. PMID:21851081

  13. Advancement and application of gas chromatography isotope ratio mass spectrometry techniques for atmospheric trace gas analysis

    NASA Astrophysics Data System (ADS)

    Giebel, Brian M.

    2011-12-01

    The use of gas chromatography isotope ratio mass spectrometry (GC-IRMS) for compound specific stable isotope analysis is an underutilized technique because of the complexity of the instrumentation and high analytical costs. However stable isotopic data, when coupled with concentration measurements, can provide additional information on a compounds production, transformation, loss, and cycling within the biosphere and atmosphere. A GC-IRMS system was developed to accurately and precisely measure delta13C values for numerous oxygenated volatile organic compounds having natural and anthropogenic sources. The OVOCs include methanol, ethanol, acetone, methyl ethyl ketone, 2-pentanone, and 3-pentanone. Guided by the requirements for analysis of trace components in air, the GC-IRMS system was developed with the goals of increasing sensitivity, reducing dead-volume and peak band broadening, optimizing combustion and water removal, and decreasing the split ratio to the IRMS. The technique relied on a two-stage preconcentration system, a low-volume capillary reactor and water trap, and a balanced reference gas delivery system. Measurements were performed on samples collected from two distinct sources (i.e. biogenic and vehicle emissions) and ambient air collected from downtown Miami and Everglades National Park. However, the instrumentation and the method have the capability to analyze a variety of source and ambient samples. The measured isotopic signatures that were obtained from source and ambient samples provide a new isotopic constraint for atmospheric chemists and can serve as a new way to evaluate their models and budgets for many OVOCs. In almost all cases, OVOCs emitted from fuel combustion were enriched in 13C when compared to the natural emissions of plants. This was particularly true for ethanol gas emitted in vehicle exhaust, which was observed to have a uniquely enriched isotopic signature that was attributed to ethanol's corn origin and use as an alternative

  14. Approaching the N=82 shell closure with mass measurements of Ag and Cd isotopes

    SciTech Connect

    Breitenfeldt, M.; Baruah, S.; Rosenbusch, M.; Schweikhard, L.; Borgmann, Ch.; Boehm, Ch.; George, S.; Audi, G.; Lunney, D.; Minaya-Ramirez, E.; Naimi, S.; Beck, D.; Dworschak, M.; Herfurth, F.; Savreux, R.; Yazidjian, C.; Blaum, K.; Cakirli, R. B.; Casten, R. F.; Delahaye, P.

    2010-03-15

    Mass measurements of neutron-rich Cd and Ag isotopes were performed with the Penning trap mass spectrometer ISOLTRAP. The masses of {sup 112,114-124}Ag and {sup 114,120,122-124,126,128}Cd, determined with relative uncertainties between 2x10{sup -8} and 2x10{sup -7}, resulted in significant corrections and improvements of the mass surface. In particular, the mass of {sup 124}Ag was previously unknown. In addition, other masses that had to be inferred from Q values of nuclear decays and reactions have now been measured directly. The analysis includes various mass differences, namely the two-neutron separation energies, the applicability of the Garvey-Kelson relations, double differences of masses deltaV{sub pn}, which give empirical proton-neutron interaction strengths, as well as a comparison with recent microscopic calculations. The deltaV{sub pn} results reveal that for even-even nuclides around {sup 132}Sn the trends are similar to those in the {sup 208}Pb region.

  15. Detection of counterfeit antiviral drug Heptodin and classification of counterfeits using isotope amount ratio measurements by multicollector inductively coupled plasma mass spectrometry (MC-ICPMS) and isotope ratio mass spectrometry (IRMS).

    PubMed

    Santamaria-Fernandez, Rebeca; Hearn, Ruth; Wolff, Jean-Claude

    2009-06-01

    Isotope ratio mass spectrometry (IRMS) and multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) are highly important techniques that can provide forensic evidence that otherwise would not be available. MC-ICP-MS has proved to be a very powerful tool for measuring high precision and accuracy isotope amount ratios. In this work, the potential of combining isotope amount ratio measurements performed by MC-ICP-MS and IRMS for the detection of counterfeit pharmaceutical tablets has been investigated. An extensive study for the antiviral drug Heptodin has been performed for several isotopic ratios combining MC-ICP-MS and an elemental analyser EA-IRMS for stable isotope amount ratio measurements. The study has been carried out for 139 batches of the antiviral drug and analyses have been performed for C, S, N and Mg isotope ratios. Authenticity ranges have been obtained for each isotopic system and combined to generate a unique multi-isotopic pattern only present in the genuine tablets. Counterfeit tablets have then been identified as those tablets with an isotopic fingerprint outside the genuine isotopic range. The combination of those two techniques has therefore great potential for pharmaceutical counterfeit detection. A much greater power of discrimination is obtained when at least three isotopic systems are combined. The data from these studies could be presented as evidence in court and therefore methods need to be validated to support their credibility. It is also crucial to be able to produce uncertainty values associated to the isotope amount ratio measurements so that significant differences can be identified and the genuineness of a sample can be assessed. PMID:19606588

  16. Isolation and derivatization of plasma taurine for stable isotope analysis by gas chromatography-mass spectrometry

    SciTech Connect

    Irving, C.S.; Klein, P.D.

    1980-09-01

    A method for the isolation and derivatization of plasma taurine is described that allows stable isotope determinations of taurine to be made by gas chromatography-mass spectrometry. The isolation procedure can be applied to 0.1 ml of plasma; the recovery of plasma taurine was 70 to 80%. For gc separation, taurine was converted to its dimethylaminomethylene methyl ester derivative which could not be detected by hydrogen flame ionization, but could be monitored readily by NH/sub 3/ chemical ionization mass spectrometry. The derivatization reaction occurred partially on-column and required optimization of injection conditions. Using stable isotope ratiometry multiple ion detection, (M + 2 + H)/sup +//(M + H)/sup +/ ion ratio of natural abundance taurine was determined with a standard deviation of less than +-0.07% of the ratio. The (1,2-/sup 13/C)taurine/taurine mole ratios of standard mixtures could be accurately determined to 0.001. This stable isotope gc-ms method is suitable for studying the plasma kinetics of (1,2-/sup 13/C)taurine in infants who are at risk with respect to taurine depletion.

  17. Adsorption in gas mass spectrometry. I. Effects on the measurement of individual isotopic species

    NASA Astrophysics Data System (ADS)

    Gonfiantini, Roberto; Valkiers, Staf; Taylor, Philip D. P.; de Bièvre, Paul

    1997-05-01

    The adsorption-desorption process of gas molecules on the walls of the mass spectrometer inlet system was studied in order to assess quantitatively its influence on measurement results. The effects on individual isotopic species in SiF4 measurements required for the re-determination of the Avogadro constant are discussed in this paper, while the effects on isotope amount ratio determinations will be discussed in a companion paper. A model based on the Langmuir adsorption isotherm is developed, which fits well the experimental observations and provides the means to investigate adsorption and desorption kinetics in the inlet system. A parameter called the [`]apparent leak-rate coefficient' is introduced; this represents the relative variation with time of any isotopic species in the inlet system. All the adsorption parameters appearing in the balance equations are derived from the apparent leak-rate coefficient. Application of the model to long mass-spectrometric measurements of SiF4 yields a rate constant of 6.5 × 10-5 s-1 for SiF4 effusion through the molecular leak of the inlet system. Adsorption and desorption rate-constants are equal to 20-25% of the leak rate-constant, and the adsorption sites are about two orders of magnitude lower than the number of Ni and Cu atoms present on the inlet system walls.

  18. Water masses along the OVIDE 2010 section as identified by oxygen and hydrogen stable isotope values

    NASA Astrophysics Data System (ADS)

    Voelker, Antje; Salgueiro, Emilia; Thierry, Virginie

    2016-04-01

    The OVIDE transect between the western Iberian Peninsula and the southern tip of Greenland is one of the hydrographic sections in the North Atlantic that is measured regularly to identify changes in water mass formation and transport and thus to evaluate the state of the Atlantic Meridional Overturning Circulation (Mercier et al., 2015; García-Ibáñez et al., 2015; both in Progr. in Oceanography). During the OVIDE 2010 campaign seawater samples covering the complete water column were collected on the section between Portugal and the Reykjanes ridge for stable isotope analyses. Oxygen (δ18O) and hydrogen (δD) stable isotope values were measured simultaneously by cavity ring-down laser spectroscopy using a L1102-i Picarro water isotope analyser at the Godwin Laboratory for Paleoclimate Research (Univ. Cambridge, UK). Within the upper water column the stable isotope values clearly mark the positions of the Portugal Current (40.3°N 11°W), the North Atlantic Drift (46.2°N 19.4°W) and of the subarctic front (51°N 23.5°W). Up to Station 36 (47.7°N 20.6°W) an upper (around 600 m) and lower (around 1000 m) branch of the Mediterranean Outflow water (MOW) can clearly be distinguished by high oxygen (0.5-0.7‰) and hydrogen (3-5‰) values. At Station 28 (42.3°N 15.1°W) strong MOW influence is also indicated between 1400 and 1600 m. In the west European Basin, lower oxygen isotope values reveal the presence of Labrador Sea Water (LSW) below the MOW (down to 2200 m). Close to and west of the subarctic front this water mass shallows and occupies the complete interval between 1000 and 2000 m water depth. In the Iceland basin, two additional levels with lower oxygen isotope values are observed. The deeper level (2200-3500 m) marks Iceland Scotland Overflow Water (ISOW) that based on its distinct isotopic signature (δ18O ≤ 0.25‰) can be traced as far east as 18.5°W (down to at least 3500 m). Close to the Reykjanes ridge both, the ISOW and LSW, are also

  19. Multiple S-isotopic evidence for episodic shoaling of anoxic water during Late Permian mass extinction

    PubMed Central

    Shen, Yanan; Farquhar, James; Zhang, Hua; Masterson, Andrew; Zhang, Tonggang; Wing, Boswell A.

    2011-01-01

    Global fossil data show that profound biodiversity loss preceded the final catastrophe that killed nearly 90% marine species on a global scale at the end of the Permian. Many hypotheses have been proposed to explain this extinction and yet still remain greatly debated. Here, we report analyses of all four sulphur isotopes (32S, 33S, 34S and 36S) for pyrites in sedimentary rocks from the Meishan section in South China. We observe a sulphur isotope signal (negative δ34S with negative Δ33S) that may have resulted from limitation of sulphate supply, which may be linked to a near shutdown of bioturbation during shoaling of anoxic water. These results indicate that episodic shoaling of anoxic water may have contributed to the profound biodiversity crisis before the final catastrophe. Our data suggest a prolonged deterioration of oceanic environments during the Late Permian mass extinction. PMID:21343928

  20. Multiple S-isotopic evidence for episodic shoaling of anoxic water during Late Permian mass extinction.

    PubMed

    Shen, Yanan; Farquhar, James; Zhang, Hua; Masterson, Andrew; Zhang, Tonggang; Wing, Boswell A

    2011-01-01

    Global fossil data show that profound biodiversity loss preceded the final catastrophe that killed nearly 90% marine species on a global scale at the end of the Permian. Many hypotheses have been proposed to explain this extinction and yet still remain greatly debated. Here, we report analyses of all four sulphur isotopes ((32)S, (33)S, (34)S and (36)S) for pyrites in sedimentary rocks from the Meishan section in South China. We observe a sulphur isotope signal (negative δ(34)S with negative Δ(33)S) that may have resulted from limitation of sulphate supply, which may be linked to a near shutdown of bioturbation during shoaling of anoxic water. These results indicate that episodic shoaling of anoxic water may have contributed to the profound biodiversity crisis before the final catastrophe. Our data suggest a prolonged deterioration of oceanic environments during the Late Permian mass extinction. PMID:21343928

  1. Secondary ion mass spectrometers (SIMS) for calcium isotope measurements as an application to biological samples

    SciTech Connect

    Craven, S.M.; Hoenigman, J.R.; Moddeman, W.E.

    1981-11-20

    The potential use of secondary ion mass spectroscopy (SIMS) to analyze biological samples for calcium isotopes is discussed. Comparison of UTI and Extranuclear based quadrupole systems is made on the basis of the analysis of CaO and calcium metal. The Extranuclear quadrupole based system is superior in resolution and sensitivity to the UTI system and is recommended. For determination of calcium isotopes to within an accuracy of a few percent a high resolution quadrupole, such as the Extranuclear, and signal averaging capability are required. Charge neutralization will be mandated for calcium oxide, calcium nitrate, or calcium oxalate. SIMS is not capable of the high precision and high accuracy results possible by thermal ionization methods, but where faster analysis is desirable with an accuracy of a few percent, SIMS is a viable alternative.

  2. Secondary Ion Mass Spectrometers (SIMS) for calcium isotope measurements as an application to biological samples

    NASA Astrophysics Data System (ADS)

    Craven, S. M.; Hoenigman, J. R.; Moddeman, W. E.

    1981-11-01

    The potential use of secondary ion mass spectroscopy (SIMS) to analyze biological samples for calcium isotopes is discussed. Comparison of UTI and Extranuclear based quadrupole systems is made on the basis of the analysis of CaO and calcium metal. The Extranuclear quadrupole based system is superior in resolution and sensitivity to the UTI system and is recommended. For determination of calcium isotopes to within an accuracy of a few percent a high resolution quadrupole, such as the Extranuclear, and signal averaging capability are required. Charge neutralization will be mandated for calcium oxide, calcium nitrate, or calcium oxalate. SIMS is not capable of the high precision and high accuracy results possible by thermal ionization methods, but where faster analysis is desirable with an accuracy of a few percent, SIMS is a viable alternative.

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

    PubMed

    Seltzer, Michael D

    2003-09-01

    Laser ablation of pressed soil pellets was examined as a means of direct sample introduction to enable inductively coupled plasma mass spectrometry (ICP-MS) screening of soils for residual depleted uranium (DU) contamination. Differentiation between depleted uranium, an anthropogenic contaminant, and naturally occurring uranium was accomplished on the basis of measured 235U/238U isotope ratios. The amount of sample preparation required for laser ablation is considerably less than that typically required for aqueous sample introduction. The amount of hazardous laboratory waste generated is diminished accordingly. During the present investigation, 235U/238U isotope ratios measured for field samples were in good agreement with those derived from gamma spectrometry measurements. However, substantial compensation was required to mitigate the effects of impaired pulse counting attributed to sample inhomogeneity and sporadic introduction of uranium analyte into the plasma. PMID:14611049

  4. Changes in Holocene to LGM water mass stratification near Southern Africa inferred from Nd isotopes

    NASA Astrophysics Data System (ADS)

    Jones, K. M.; Goldstein, S. L.; Hemming, S. R.; Hall, I. R.; Zahn, R.

    2009-12-01

    Global thermohaline circulation (THC) is an important component of the climate system that initiates or amplifies abrupt climate change. A major driver of THC is the formation of North Atlantic Deep Water (NADW), which is sandwiched by northward flowing Southern Ocean water masses as it is advected southward. An important exit route of NADW out of the South Atlantic is through flow around the southern tip of Africa, which makes the South African Margin an excellent location to investigate changes in THC and water mass stratification through time. We measured the Nd isotopes of modern seawater from three depth profiles collected along the South African Margin, which were collected on RSS Charles Darwin Cruise 154. All seawater profiles show a similar pattern with higher ɛNd values at intermediate depths (ɛNd ~ -9.5 at 600-1200m), lower values for the core of NADW (ɛNd ~ -11.5 at 2000-3500m), and higher values in the deepest waters sampled (ɛNd -9.8 at 4150m). This pattern is consistent with conservative mixing of major North Atlantic and Southern Ocean end-member water masses and is not consistent with inputs from, or exchange with margin sediments, for most depths. We also measured the Nd isotopes of multiple sedimentary archives in proximal Holocene coretop sediments collected from depths spanning intermediate to deep/bottom waters. The Nd isotopes of a fish tooth, several foram coating leachates, and multiple bulk sediment Fe-Mn leachates display the same pattern as the local seawater. We had no seawater for comparison with our deepest core (VM19-224; depth ~ 4600m), but the eNd value from it (ɛNd = -8.4) is consistent with Antarctic Bottom Water (ɛNd ~ -8.5). These results suggest: (1) that Nd isotopes of seawater in the region behave conservatively; (2) that the local margin sediments faithfully record the Nd isotope composition of the waters they are bathed in and (3) this “ground-truthing” implies that it is valid to use Nd isotopes as a circulation

  5. Light Isotopes and Trace Organics Analysis of Mars Samples with Mass Spectrometry

    NASA Technical Reports Server (NTRS)

    Mahaffy, P.; Niemann, Hasso (Technical Monitor)

    2001-01-01

    Precision measurement of light isotopes in Mars surface minerals and comparison of this isotopic composition with atmospheric gas and other, well-mixed reservoirs such as surface dust are necessary to understand the history of atmospheric evolution from a possibly warmer and wetter Martian surface to the present state. Atmospheric sources and sinks that set these ratios are volcanism, solar wind sputtering, photochemical processes, and weathering. Measurement of a range of trace organic species with a particular focus on species such as amino acids that are the building blocks of terrestrial life are likewise important to address the questions of prebiotic and present or past biological activity on Mars. The workshop topics "isotopic mineralogy" and "biology and pre-biotic chemistry" will be addressed from the point of view of the capabilities and limitations of insitu mass spectrometry (MS) techniques such as thermally evolved gas analysis (TEGA) and gas chromatography (GC) surface experiments using MS, in both cases, as a final chemical and isotopic composition detector. Insitu experiments using straightforward adaptations of existing space proven hardware can provide a substantial improvement in the precision and accuracy of our present knowledge of isotopic composition both in molecular and atomic species in the atmosphere and those chemically bound in rocks and soils. Likewise, detection of trace organic species with greatly improved sensitivity from the Viking GCMS experiment is possible using gas enrichment techniques. The limits to precision and accuracy of presently feasible insitu techniques compared to laboratory analysis of returned samples will be explored. The insitu techniques are sufficiently powerful that they can provide a high fidelity method of screening samples obtained from a diverse set of surface locations such as the subsurface or the interior of rocks for selection of those that are the most interesting for return to Earth.

  6. Stellar (n ,γ ) cross sections of neutron-rich nuclei: Completing the isotope chains of Yb, Os, Pt, and Hg

    NASA Astrophysics Data System (ADS)

    Marganiec, J.; Dillmann, I.; Domingo-Pardo, C.; Käppeler, F.

    2014-12-01

    The (n ,γ ) cross sections of the most neutron-rich stable isotopes of Yb, Os, Pt, and Hg have been determined in a series of activation measurements at the Karlsruhe 3.7 MV Van de Graaff accelerator, using the quasistellar neutron spectrum for k T =25 keV that can be produced with the 7Li(p ,n ) 7Be reaction. In this way, Maxwellian averaged cross sections could be directly obtained with only minor corrections. After irradiation the induced activities were counted with a HPGe detector via the strongest γ -ray lines. The stellar neutron capture cross sections of Yb,176174, Os,192190, Pt,198196, and Hg,204202, extrapolated to k T =30 keV, were found to be 157 ±6 mb, 114 ±8 mb, 278 ±11 mb, 160 ±7 mb, 171 ±19 mb, 94 ±4 mb, 62 ±2 mb, and 32 ±15 mb, respectively. In the case of 196Pt the partial cross section to the isomeric state at 399.5 keV could be determined as well. With these results the cross section data for long isotopic chains could be completed for a discussion of the predictive power of statistical model calculations towards the neutron-rich and proton-rich sides of the stability valley.

  7. Screening halogenated environmental contaminants in biota based on isotopic pattern and mass defect provided by high resolution mass spectrometry profiling.

    PubMed

    Cariou, Ronan; Omer, Elsa; Léon, Alexis; Dervilly-Pinel, Gaud; Le Bizec, Bruno

    2016-09-14

    In the present work, we addressed the question of global seeking/screening organohalogenated compounds in a large panel of complex biological matrices, with a particular focus on unknown chemicals that may be considered as potential emerging hazards. A fishing strategy was developed based on untargeted profiling among full scan acquisition datasets provided by high resolution mass spectrometry. Since large datasets arise from such profiling, filtering useful information stands as a central question. In this way, we took advantage of the exact mass differences between Cl and Br isotopes. Indeed, our workflow involved an innovative Visual Basic for Applications script aiming at pairing features according to this mass difference, in order to point out potential organohalogenated clusters, preceded by an automated peak picking step based on the centWave function (xcms package of open access R programming environment). Then, H/Cl-scale mass defect plots were used to visualize the datasets before and after filtering. The filtering script was successfully applied to a dataset generated upon liquid chromatography coupled to ESI(-)-HRMS measurement from one eel muscle extract, allowing for realistic manual investigations of filtered clusters. Starting from 9789 initial obtained features, 1994 features were paired in 589 clusters. Hexabromocyclododecane, chlorinated paraffin series and various other compounds have been identified or tentatively identified, allowing thus broad screening of organohalogenated compounds in this extract. Although realistic, manual review of paired clusters remains time consuming and much effort should be devoted to automation. PMID:27566348

  8. Evaluation of meteoric calcite cements as a proxy material for mass-47 clumped isotope thermometry

    NASA Astrophysics Data System (ADS)

    Defliese, William F.; Lohmann, Kyger C.

    2016-01-01

    Meteoric diagenetic cements are ubiquitous throughout geologic history, affecting most carbonate exposures worldwide. They can often be difficult to interpret, as it is usually difficult to separate the influences of water δ18O and temperature on isotopic signals contained within the carbonate rock body. Despite this difficulty in interpretation, meteoric phreatic cements can potentially be a useful proxy material, as they form slowly in equilibrium at mean annual temperature and are not affected by any biogenic effects that can bias other proxy materials. We applied the mass-47 clumped isotope paleothermometer to Pleistocene and Holocene carbonates from Bermuda and Barbados in order to investigate the effects of meteoric diagenesis on Δ47 signals, and to determine their suitability as a paleotemperature proxy. Phreatic calcite cements are found to record the same temperatures as unaltered carbonate sediments, while any sample exhibiting vadose characteristics is biased towards unreasonably hot apparent formation temperatures. Burial heating and re-equilibration are not geologically viable explanations for the anomalously hot temperatures recorded in vadose cements, as neither Bermuda or Barbados has any burial history. Instead, it is likely that precipitation in the vadose zone occurs on timescales quicker than isotopic equilibrium can be achieved, driven by a combination of CO2 degassing and evaporation, which have been previously shown to cause problems in speleothems and pedogenic carbonates. We conclude by suggesting that meteoric phreatic calcites may be an ideal phase for paleotemperature reconstruction, as they accurately record mean annual temperatures and form under equilibrium conditions, while also being resistant to further mineral driven diagenesis. Vadose cements, and any sample likely affected by processes similar to vadose diagenesis, should be avoided for climate reconstructions using the mass-47 clumped isotope thermometer.

  9. Nutrient cycling in the Atlantic basin: The evolution of nitrate isotope signatures in water masses

    NASA Astrophysics Data System (ADS)

    Tuerena, R. E.; Ganeshram, R. S.; Geibert, W.; Fallick, A. E.; Dougans, J.; Tait, A.; Henley, S. F.; Woodward, E. M. S.

    2015-10-01

    A basin-wide transect of nitrate isotopes (δ15NNO3, δ18ONO3), across the UK GEOTRACES 40°S transect in the South Atlantic is presented. This data set is used to investigate Atlantic nutrient cycling and the communication pathways of nitrogen cycling processes in the global ocean. Intermediate waters formed in the subantarctic are enriched in δ15NNO3 and δ18ONO3 from partial utilization of nitrate by phytoplankton and distant denitrification processes, transporting heavy isotope signatures to the subtropical Atlantic. Water mass modification through the Atlantic is investigated by comparing data from 40°S (South Atlantic) and 30°N (North Atlantic). This reveals that nitrate in the upper intermediate waters is regenerated as it transits through the subtropical Atlantic, as evidenced by decreases in δ18ONO3. We document diazotrophy-producing high N:P particle ratios (18-21:1) for remineralization, which is further confirmed by a decrease in δ15NNO3 through the subtropical Atlantic. These modifications influence the isotopic signatures of the North Atlantic Deep Water (NADW) which is subsequently exported from the Atlantic to the Southern Ocean. This study reveals the dominance of recycling processes and diazotrophy on nitrate cycling in the Atlantic. These processes provide a source of low δ15NNO3 to the Southern Ocean via the NADW, to counteract enrichment in δ15NNO3 from water column denitrification in the Indo/Pacific basins. We hence identify the Southern Ocean as a key hub through which denitrification and N2 fixation communicate in the ocean through deepwater masses. Therefore, the balancing of the oceanic N budget and isotopic signatures require time scales of oceanic mixing.

  10. Isotope mass fractionation during evaporation of Mg2SiO4

    NASA Technical Reports Server (NTRS)

    Davis, Andrew M.; Clayton, Robert N.; Mayeda, Toshiko K.; Hashimoto, Akihiko

    1990-01-01

    Synthetic forsterite (Mg2SiO4) was partially evaporated in vacuum for various durations and at different temperatures. The residual charges obtained when molten Mg2SiO4 was evaporated to 12 percent of its initial mass were enriched in heavy isotopes by about 20, 30, and 15 per mil/amu for O, Mg, and Si, respectively, whereas solid forsterite evaporated to a similar residual mass fraction showed negligible fractionations. These results imply that calcium and aluminum-rich refractory inclusions in carbonaceous chondrites must have been at least partially molten in the primordial solar nebula if the observed large mass fractionation effects were caused by evaporation processes in the nebula.

  11. Reformulated 17O correction of mass spectrometric stable isotope measurements in carbon dioxide and a critical appraisal of historic 'absolute' carbon and oxygen isotope ratios

    NASA Astrophysics Data System (ADS)

    Kaiser, Jan

    2008-03-01

    Mass-spectrometric stable isotope measurements of CO 2 use molecular ion currents at mass-to-charge ratios m/ z 44, 45 and 46 to derive the elemental isotope ratios n( 13C)/ n( 12C) and n( 18O)/ n( 16O), abbreviated 13C/ 12C and 18O/ 16O, relative to a reference. The ion currents have to be corrected for the contribution of 17O-bearing isotopologues, the so-called ' 17O correction'. The magnitude of this correction depends on the calibrated isotope ratios of the reference. Isotope ratio calibrations are difficult and are therefore a matter of debate. Here, I provide a comprehensive evaluation of the existing 13C/ 12C ( 13R), 17O/ 16O ( 17R) and 18O/ 16O ( 18R) calibrations of the reference material Vienna Standard Mean Ocean Water (VSMOW) and CO 2 generated from the reference material Vienna Pee Dee Belemnite (VPDB) by reaction with 100% H 3PO 4 at 25 °C (VPDB-CO 2). I find 17R/10-6=382.7-2.1+1.7, 18RVSMOW/10 -6 = 2005.20 ± 0.45, 13R/10-6= 11124 ± 45, 17R/10-6=391.1-2.1+1.7 and 18R/10-6=2088.37±0.90. I also rephrase the calculation scheme for the 17O correction completely in terms of relative isotope ratio differences ( δ values). This reveals that only ratios of isotope ratios (namely, 17R/ 13R and 13R17R/ 18R) are required for the 17O correction. These can be, and have been, measured on conventional stable isotope mass spectrometers. I then show that the remaining error for these ratios of isotope ratios can lead to significant uncertainty in the derived relative 13C/ 12C difference, but not for 18O/ 16O. Even though inter-laboratory differences can be corrected for by a common 'ratio assumption set' and/or normalisation, the ultimate accuracy of the 17O correction is hereby limited. Errors of similar magnitude can be introduced by the assumed mass-dependent relationship between 17O/ 16O and 18O/ 16O isotope ratios. For highest accuracy in the 13C/ 12C ratio, independent triple oxygen isotope measurements are required. Finally, I propose an experiment that

  12. Simultaneous determination of the quantity and isotopic ratios of uranium in individual micro-particles by isotope dilution thermal ionization mass spectrometry (ID-TIMS).

    PubMed

    Park, Jong-Ho; Choi, Eun-Ju

    2016-11-01

    A method to determine the quantity and isotopic ratios of uranium in individual micro-particles simultaneously by isotope dilution thermal ionization mass spectrometry (ID-TIMS) has been developed. This method consists of sequential sample and spike loading, ID-TIMS for isotopic measurement, and application of a series of mathematical procedures to remove the contribution of uranium in the spike. The homogeneity of evaporation and ionization of uranium content was confirmed by the consistent ratio of n((233)U)/n((238)U) determined by TIMS measurements. Verification of the method was performed using U030 solution droplets and U030 particles. Good agreements of resulting uranium quantity, n((235)U)/n((238)U), and n((236)U)/n((238)U) with the estimated or certified values showed the validity of this newly developed method for particle analysis when simultaneous determination of the quantity and isotopic ratios of uranium is required. PMID:27591656

  13. Integration of Stable Isotope and other Mass Spectral Data for Microbial Forensics

    NASA Astrophysics Data System (ADS)

    Kreuzer-Martin, H. W.; Jarman, K. H.

    2008-12-01

    The nascent field of microbial forensics requires the development of diverse signatures as indicators of various aspects of the production environment of microorganisms. We have characterized isotopic relationships between Bacillus subtilis ATCC 6051 spores and their growth environment, using as a database the carbon, nitrogen, oxygen and hydrogen stable isotope ratios of a total of 247 separate cultures of spores produced on a total of 32 different culture media. We have analyzed variation within individual samples, between cultures produced in tandem, and between cultures produced in the same medium but at different times in the context of using stable isotope ratios as a signature for sample matching. We have correlated the stable isotope ratios of carbon, nitrogen, oxygen, and hydrogen of growth medium nutrients or water and spores and show examples of how these relationships can be used to exclude nutrient or water samples as possible growth substrates for specific cultures. The power of stable isotope ratio data can be greatly enhanced by combining it with orthogonal datasets that speak to different aspects of an organism's production environment. We developed a Bayesian network that follows the causal relationship from culture medium recipe to spore elemental content as measured by secondary ion mass spectrometry (SIMS), carbon and nitrogen stable isotope ratios, and to the presence of residual agar by electrospray ionization MS (ESI-MS). The network was developed and tested on data from three replicate cultures of B. subtilis ATCC 49760 in broth and agar-containing versions of four different nutrient media. To test the network, data from SIMS analyses of B. subtilis 49760 produced in a different medium, from approximately 200 ESI MS analyses of B. thuringensis ATCC 58890 and B. anthracis Sterne grown in five additional media, and the stable isotope data from the 247 cultures of B. subtilis 6051 spores were used. This network was able to characterize

  14. Mass-dependent U isotopic variations in altered oceanic crust and volcanic arc magmas

    NASA Astrophysics Data System (ADS)

    Freymuth, H.; Andersen, M. B.; Elliott, T.

    2013-12-01

    We investigate the effect of alteration of the oceanic crust and subduction zone processing on the 238U/235U ratio (typically expressed as δ238U or parts per thousand difference from the CRM 145 standard). This allows us to evaluate the potential of mass-dependent U isotope measurements to trace subduction components in arc magmas and the use of U isotopes as a tracer for deep crustal recycling. It has long been known that U is added to the oceanic crust during both low and high temperature alteration of the oceanic crust, whilst some of the subducted inventory of U is returned to the surface in arc lavas. We have measured the U isotopic compositions of samples from the altered, mafic, oceanic crust (AOC) at ODP site 801 as well as lavas erupted at the volcanic front of the Mariana arc. The former represents a reference site for studying the time-integrated influence of seafloor alteration and the latter constitute a well characterised sample set for which the role of slab-derived ';fluid' and sediment components can be separately recognised. The altered oceanic crust in ODP site 801 is compositionally variable and δ238U in different sections is correlated with indices of alteration such as Rb/Ba. It is similar to seawater in the top ˜100 m and isotopically heavier in deeper parts. These differences are likely to be caused by oxidizing conditions in the top part of the AOC and reducing conditions in deeper parts of the AOC and isotopic fractionation occurring during the alteration of the oceanic crust. The Mariana arc lavas span a range of ˜100 ppm in δ238U and vary systematically between seawater-like compositions in samples that have been previously identified as ';fluid-rich' and heavier values similar to fresh mantle-derived basalts in the more sediment-rich samples. These systematics indicate that either the light U in the upper mafic crust is preferentially lost to the arc lavas or that during slab dehydration of the AOC, U is fractionated to generate an

  15. 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.

  16. Modern Sr isotopic mass balance and Quaternary variation in the Caspian Sea

    NASA Astrophysics Data System (ADS)

    Page, A.; Vance, D.; Fowler, M.; Nisbet, E.

    2003-04-01

    The past chemistry of the Caspian Sea potentially provides a record of palaeoclimatic changes in eastern Europe and central Asia. We report the first Sr isotopic data for the Volga which, together with new data for smaller Caucasian rivers and data in the literature (Clauer et al. 1998), provide a relatively complete Sr mass balance for the modern Caspian. We also present preliminary Sr isotopic data for mollusc shells obtained from Plio-Pleistocene sediments which shed light on the past hydrography of the Caspian Sea. Samples of the modern Caspian Sea give an 87Sr/86Sr ratio of 0.70821, in agreement with published values (Clauer et al. 1998 C.R. Acad. Sci. Paris, 327, 17-24). Data for the Volga are below this value at 0.70802. The rivers draining the Caucusus also have Sr isotope ratios less radiogenic than the Sea, except for the small Terek river in Dagestan. The only significant source of balancing radiogenic Sr is deep fluids, which have been shown to contain large amounts of radiogenic Sr (Clauer et al. 1998). The modern Sr isotopic mass balance requires that around 0.2% of the water and 15-30% of the Sr in the modern Caspian be derived from this source. The modern Sr mass balance suggests that the residence time of Sr in the Caspian Sea is 4-5 kyr, so that Quaternary variations in the discharge rates of riverine water and deep fluids should be reflected in the Sr isotopic composition of the ancient Caspian. 20 kyr mollusc shells have an 87Sr/86Sr ratio of 0.70825 - very close to the value for the modern Caspian. However, Sr from an approximately 100 kyr old shell is more radiogenic, at 0.70842, as are background values in a time-series through latest Pliocene-Early Pleistocene sediments. The time series also exhibits periodic shifts towards much higher values (up to 0.70864). The higher background value for pre-20 kyr samples could be due to a dramatically (4-7 fold) lower river runoff or to order of magnitude higher deep water discharge. More probably, they

  17. IgD Heavy-Chain Deposition Disease: Detection by Laser Microdissection and Mass Spectrometry

    PubMed Central

    Royal, Virginie; Quint, Patrick; Leblanc, Martine; LeBlanc, Richard; Duncanson, Garrett F.; Perrizo, Robert L.; Fervenza, Fernando C.; Kurtin, Paul

    2015-01-01

    Monoclonal Ig deposition disease (MIDD) is a rare complication of monoclonal gammopathy characterized by deposition of monoclonal Ig light chains and/or heavy chains along the glomerular and tubular basement membranes. Here, we describe a unique case of IgD deposition disease. IgD deposition is difficult to diagnose, because routine immunofluorescence does not detect IgD. A 77-year-old man presented with proteinuria and renal failure, and kidney biopsy analysis showed a nodular sclerosing GN with extensive focal global glomerulosclerosis, tubular atrophy, and interstitial fibrosis. Immunofluorescence was negative for Ig deposits, although electron microscopy showed deposits in the glomeruli and along tubular basement membranes. Laser microdissection of glomeruli and mass spectrometry of extracted peptides showed a large spectra number for IgD, and immunohistochemistry showed intense glomerular and tubular staining for IgD. Together, these findings are consistent with IgD deposition disease. Bone marrow biopsy analysis showed 5% plasma cells, which stained for IgD. The patient was treated with bortezomib and dexamethasone, which resulted in improvement of hematologic parameters but no improvement of renal function. The diagnosis of IgD deposition disease underscores the value of laser microdissection and mass spectrometry in further evaluating renal biopsies when routine assessment fails to reach an accurate diagnosis. PMID:25194005

  18. Mass dependence of the activation enthalpy and entropy of unentangled linear alkane chains

    SciTech Connect

    Jeong, Cheol; Douglas, Jack F.

    2015-10-14

    The mass scaling of the self-diffusion coefficient D of polymers in the liquid state, D ∼ M{sup β}, is one of the most basic characteristics of these complex fluids. Although traditional theories such as the Rouse and reptation models of unentangled and entangled polymer melts, respectively, predict that β is constant, this exponent for alkanes has been estimated experimentally to vary from −1.8 to −2.7 upon cooling. Significantly, β changes with temperature T under conditions where the chains are not entangled and at temperatures far above the glass transition temperature T{sub g} where dynamic heterogeneity does not complicate the description of the liquid dynamics. Based on atomistic molecular dynamics simulations on unentangled linear alkanes in the melt, we find that the variation of β with T can be directly attributed to the dependence of the enthalpy ΔH{sub a} and entropy ΔS{sub a} of activation on the number of alkane backbone carbon atoms, n. In addition, we find a sharp change in the melt dynamics near a “critical” chain length, n ≈ 17. A close examination of this phenomenon indicates that a “buckling transition” from rod-like to coiled chain configurations occurs at this characteristic chain length and distinct entropy-enthalpy compensation relations, ΔS{sub a} ∝ ΔH{sub a}, hold on either side of this polymer conformational transition. We conclude that the activation free energy parameters exert a significant influence on the dynamics of polymer melts that is not anticipated by either the Rouse and reptation models. In addition to changes of ΔH{sub a} and ΔS{sub a} with M, we expect changes in these free energy parameters to be crucial for understanding the dynamics of polymer blends, nanocomposites, and confined polymers because of changes of the fluid free energy by interfacial interactions and geometrical confinement.

  19. Mass dependence of the activation enthalpy and entropy of unentangled linear alkane chains

    NASA Astrophysics Data System (ADS)

    Jeong, Cheol; Douglas, Jack F.

    2015-10-01

    The mass scaling of the self-diffusion coefficient D of polymers in the liquid state, D ˜ Mβ, is one of the most basic characteristics of these complex fluids. Although traditional theories such as the Rouse and reptation models of unentangled and entangled polymer melts, respectively, predict that β is constant, this exponent for alkanes has been estimated experimentally to vary from -1.8 to -2.7 upon cooling. Significantly, β changes with temperature T under conditions where the chains are not entangled and at temperatures far above the glass transition temperature Tg where dynamic heterogeneity does not complicate the description of the liquid dynamics. Based on atomistic molecular dynamics simulations on unentangled linear alkanes in the melt, we find that the variation of β with T can be directly attributed to the dependence of the enthalpy ΔHa and entropy ΔSa of activation on the number of alkane backbone carbon atoms, n. In addition, we find a sharp change in the melt dynamics near a "critical" chain length, n ≈ 17. A close examination of this phenomenon indicates that a "buckling transition" from rod-like to coiled chain configurations occurs at this characteristic chain length and distinct entropy-enthalpy compensation relations, ΔSa ∝ ΔHa, hold on either side of this polymer conformational transition. We conclude that the activation free energy parameters exert a significant influence on the dynamics of polymer melts that is not anticipated by either the Rouse and reptation models. In addition to changes of ΔHa and ΔSa with M, we expect changes in these free energy parameters to be crucial for understanding the dynamics of polymer blends, nanocomposites, and confined polymers because of changes of the fluid free energy by interfacial interactions and geometrical confinement.

  20. Validation of New Instrumentation for Isotope Dilution Mass Spectrometric Determination of Organic Serum Analytes

    PubMed Central

    Ellerbe, P.; Phinney, C. S.; Sniegoski, L. T.; Welch, M. J.

    1999-01-01

    A major activity in the 20 year collaboration between the Analytical Chemistry Division at NIST and the College of American Pathologists (CAP) has been the development of highly accurate and precise “definitive” methods for important clinical analytes in human serum. Definitive methods for organic analytes use isotope dilution/gas chromatography/mass spectrometry and require a mass spectrometer capable of making highly precise measurements of the ratio between the ion intensities of a characteristic ion from the analyte of interest and its stable-isotope-labeled analog. Recently, the mass spectrometer used for 20 years for definitive method development and measurements was replaced with a modern instrument capable of automated operation, with accompanying gains in convenience and sample throughput. Switching to the new instrument required modifications of measurement protocols, acceptance criteria, and ratio calculations with background corrections to go along with automated instrument operation. Results demonstrated that the two instruments gave comparable results for measurements of both urea and cholesterol in samples from various serum-based Standard Reference Materials [SRMs] and College of American Pathologists materials.

  1. Determination of total cholesterol in serum by liquid chromatography-isotope dilution mass spectrometry.

    PubMed

    Kock, R; Delvoux, B; Greiling, H

    1997-10-01

    We have developed a liquid chromatography-isotope dilution mass spectrometry procedure to quantify total cholesterol in serum. A particle-beam interface was used for coupling the liquid chromatograph and the mass spectrometer. After electron impact ionization the ions m/z = 386 and m/z = 389 were used for selective ion monitoring of cholesterol and the internal standard [25,26,27-(13)C]cholesterol. The sample preparation steps required for serum materials are alkaline hydrolysis and an extraction of the cholesterol into the cyclohexane phase. Imprecision for the determination of cholesterol in control materials is typically <1.0%. The deviation from the certified reference values was <0.75% for all control materials tested. A method comparison of the results obtained by this method with those obtained by gas chromatography-isotope dilution mass spectrometry for n = 28 pooled human sera derived from samples analyzed in our routine laboratory did not show differences >2.5%. PMID:9342010

  2. 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

  3. Hydroponic isotope labeling of entire plants and high-performance mass spectrometry for quantitative plant proteomics.

    PubMed

    Bindschedler, Laurence V; Mills, Davinia J S; Cramer, Rainer

    2012-01-01

    Hydroponic isotope labeling of entire plants (HILEP) combines hydroponic plant cultivation and metabolic labeling with stable isotopes using (15)N-containing inorganic salts to label whole and mature plants. Employing (15)N salts as the sole nitrogen source for HILEP leads to the production of healthy-looking plants which contain (15)N proteins labeled to nearly 100%. Therefore, HILEP is suitable for quantitative plant proteomic analysis, where plants are grown in either (14)N- or (15)N-hydroponic media and pooled when the biological samples are collected for relative proteome quantitation. The pooled (14)N-/(15)N-protein extracts can be fractionated in any suitable way and digested with a protease for shotgun proteomics, using typically reverse phase liquid chromatography nanoelectrospray ionization tandem mass spectrometry (RPLC-nESI-MS/MS). Best results were obtained with a hybrid ion trap/FT-MS mass spectrometer, combining high mass accuracy and sensitivity for the MS data acquisition with speed and high-throughput MS/MS data acquisition, increasing the number of proteins identified and quantified and improving protein quantitation. Peak processing and picking from raw MS data files, protein identification, and quantitation were performed in a highly automated way using integrated MS data analysis software with minimum manual intervention, thus easing the analytical workflow. In this methodology paper, we describe how to grow Arabidopsis plants hydroponically for isotope labeling using (15)N salts and how to quantitate the resulting proteomes using a convenient workflow that does not require extensive bioinformatics skills. PMID:22665301

  4. Accurate mass measurements of short-lived isotopes with the MISTRAL* rf spectrometer

    SciTech Connect

    Toader, C.; Audi, G.; Doubre, H.; Jacotin, M.; Henry, S.; Kepinski, J.-F.; Le Scornet, G.; Lunney, D.; Monsanglant, C.; Saint Simon, M. de; Thibault, C.; Borcea, C.; Duma, M.; Lebee, G.

    1999-01-15

    The MISTRAL* experiment has measured its first masses at ISOLDE. Installed in May 1997, this radiofrequency transmission spectrometer is to concentrate on nuclides with particularly short half-lives. MISTRAL received its first stable beam in October and first radioactive beam in November 1997. These first tests, with a plasma ion source, resulted in excellent isobaric separation and reasonable transmission. Further testing and development enabled first data taking in July 1998 on neutron-rich Na isotopes having half-lives as short as 31 ms.

  5. New FORTRAN computer programs to acquire and process isotopic mass spectrometric data: Operator`s manual

    SciTech Connect

    Smith, D.H.; McKown, H.S.

    1993-09-01

    This TM is one of a pair that describes ORNL-developed software for acquisition and processing of isotope ratio mass spectral data. This TM is directed at the laboratory analyst. No technical knowledge of the programs and programming is required. It describes how to create and edit files, how to acquire and process data, and how to set up files to obtain the desired results. The aim of this TM is to serve as a utilitarian instruction manual, a {open_quotes}how to{close_quotes} approach rather than a {open_quotes}why?{close_quotes}

  6. The mid-cretaceous water bearer: Isotope mass balance quantification of the Albian hydrologic cycle

    USGS Publications Warehouse

    Ufnar, David F.; Gonzalez, Luis A.; Ludvigson, Greg A.; Brenner, Richard L.; Witzke, B.J.

    2002-01-01

    A latitudinal gradient in meteoric ??18O compositions compiled from paleosol sphaerosiderites throughout the Cretaceous Western Interior Basin (KWIB) (34-75??N paleolatitude) exhibits a steeper, more depleted trend than modern (predicted) values (3.0??? [34??N latitude] to 9.7??? [75??N] lighter). Furthermore, the sphaerosiderite meteoric ??18O latitudinal gradient is significantly steeper and more depleted (5.8??? [34??N] to 13.8??? [75??N] lighter) than a predicted gradient for the warm mid-Cretaceous using modern empirical temperature-??18O precipitation relationships. We have suggested that the steeper and more depleted (relative to the modern theoretical gradient) meteoric sphaerosiderite ??18O latitudinal gradient resulted from increased air mass rainout effects in coastal areas of the KWIB during the mid-Cretaceous. The sphaerosiderite isotopic data have been used to constrain a mass balance model of the hydrologic cycle in the northern hemisphere and to quantify precipitation rates of the equable 'greenhouse' Albian Stage in the KWIB. The mass balance model tracks the evolving isotopic composition of an air mass and its precipitation, and is driven by latitudinal temperature gradients. Our simulations indicate that significant increases in Albian precipitation (34-52%) and evaporation fluxes (76-96%) are required to reproduce the difference between modern and Albian meteoric siderite ??18O latitudinal gradients. Calculations of precipitation rates from model outputs suggest mid-high latitude precipitation rates greatly exceeded modern rates (156-220% greater in mid latitudes [2600-3300 mm/yr], 99% greater at high latitudes [550 mm/yr]). The calculated precipitation rates are significantly different from the precipitation rates predicted by some recent general circulation models (GCMs) for the warm Cretaceous, particularly in the mid to high latitudes. Our mass balance model by no means replaces GCMs. However, it is a simple and effective means of obtaining

  7. An update on the Thermal Gradient Induced Non -Mass-Dependent Isotope Fractionation

    NASA Astrophysics Data System (ADS)

    Sun, T.; Niles, P. B.; Bao, H.; Socki, R. A.

    2012-12-01

    Mass flow and compositional gradient (elemental and isotope separation) occur when fluid(s) or gas(es) in an enclosure is subjected to a thermal gradient, and the phenomenon is named thermal diffusion. Gas phase thermal diffusion has been experimentally and theoretically investigated for more than a century, although there has not been a satisfactory theory to date. Nevertheless, theories predict that when dealing with a multi-isotope system, such as O16-O17-O18, S32-S33-S34-S36, or Ne20-Ne21-Ne22, the mass difference is the only term in the thermal diffusion separation factors that distinguish one isotope pair from another. Thus a mass dependent relationship is expected. For O-bearing molecules the α17O/ α 18O is expected to be at 0.5 to 0.515, and for S-bearing molecules the α33S/ α 34S at 0.5 to 0.508, where α is isotope fractionation factor between cold and warm reservoirs. We recently reported that thermal diffusion generates non-mass dependent (NMD) isotope fractionation for low-pressure O2 and SF6 gases. The observed NMD phenomenon in the simple thermal-diffusion experiments demands quantitative validation and theoretical explanation. It was suggested that additional (not mass related) terms need to be theoretically considered in the order to account for the observations. In addition to the pressure and temperature dependency illustrated in our earlier report, the role of turbulence, batch gas effects, and whether it is only a transient, non-equilibrium effect have been examined in this study. We report here new results on low-pressure O2 gas thermal diffusion. (1) In a purely diffusive vertical two-bulb setting with colder reservoir at lower position, time course experiments showed that the NMD effect persists after the system reaches isotopic steady state between warmer and colder compartments, suggesting that the effect is not a transient one. (2) When the average temperature approaching condensation point for O2, the 17O switches to migrating

  8. Poly(ethylene glycol)-mediated molar mass control of short-chain- and medium-chain-length poly(hydroxyalkanoates) from Pseudomonas oleovorans.

    PubMed

    Ashby, R D; Solaiman, D K Y; Foglia, T A

    2002-10-01

    Three strains of Pseudomonas oleovorans, a well known poly(hydroxyalkanoate) (PHA) producer, were tested for the ability to control PHA molar mass and end group structure by addition of poly(ethylene glycol) (PEG) to the fermentation medium. Each strain of P. oleovorans - NRRL B-14682 (B-14682), NRRL B-14683 (B-14683), and NRRL B-778 (B-778) - synthesized a different type of PHA from oleic acid when cultured under identical growth conditions. Strain B-14682 produced poly(3-hydroxybutyrate) (PHB), while B-14683 synthesized a medium-chain-length PHA ( mcl-PHA) with a repeat unit composition ranging from C4 to C14 and some mono-unsaturation in the C14 alkyl side chains. Strain B-778 synthesized a mixture of PHB (95 mol%) and mcl-PHA (5 mol%). The addition of 0.5% (v/v) PEG (M(n) =200 g/mol, PEG-200) to the fermentation broth of strains B-14682 and B-778 resulted in chain termination through esterification at the carboxyl terminus of the PHB with PEG chain segments, thus reducing the molar mass by 54% and 23%, respectively. The molar mass of the mcl-PHA produced by strains B-14683 and B-778 also showed a 34% and 47% reduction in the presence of PEG-200, respectively, but no evidence of esterification was present. PEG-400 (M(n) =400 g/mol) had a reduced effect on PHA molar mass. In fact, the molar masses of the mcl-PHA derived from strain B-14683 and both the PHB and mcl-PHA from B-778 were unchanged by PEG-400. In contrast, the PHB produced by B-14682 showed a 35% reduction in molar mass in the presence of PEG-400. PMID:12382057

  9. Rapid determination of uranium isotopes in urine by inductively coupled plasma-mass spectrometry.

    PubMed

    Shi, Y; Dai, X; Collins, R; Kramer-Tremblay, S

    2011-08-01

    Following a radiological or nuclear emergency involving uranium exposure, rapid analytical methods are needed to analyze the concentration of uranium isotopes in human urine samples for early dose assessment. The inductively coupled plasma mass spectrometry (ICP-MS) technique, with its high sample throughput and high sensitivity, has advantages over alpha spectrometry for uranium urinalysis after minimum sample preparation. In this work, a rapid sample preparation method using an anion exchange chromatographic column was developed to separate uranium from the urine matrix. A high-resolution sector field ICP-MS instrument, coupled with a high sensitivity desolvation sample introduction inlet, was used to determine uranium isotopes in the samples. The method can analyze up to 24 urine samples in two hours with the limits of detection of 0.0014, 0.10, and 2.0 pg mL(-1) for (234)U, (235)U, and (238)U, respectively, which meet the requirement for isotopic analysis of uranium in a radiation emergency. PMID:21709502

  10. Can stable isotope mass spectrometry replace ‎radiolabelled approaches in metabolic studies?

    PubMed

    Batista Silva, Willian; Daloso, Danilo M; Fernie, Alisdair R; Nunes-Nesi, Adriano; Araújo, Wagner L

    2016-08-01

    Metabolic pathways and the key regulatory points thereof can be deduced using isotopically labelled substrates. One prerequisite is the accurate measurement of the labeling pattern of targeted metabolites. The subsequent estimation of metabolic fluxes following incubation in radiolabelled substrates has been extensively used. Radiolabelling is a sensitive approach and allows determination of total label uptake since the total radiolabel content is easy to detect. However, the incubation of cells, tissues or the whole plant in a stable isotope enriched environment and the use of either mass spectrometry or nuclear magnetic resonance techniques to determine label incorporation within specific metabolites offers the possibility to readily obtain metabolic information with higher resolution. It additionally also offers an important complement to other post-genomic strategies such as metabolite profiling providing insights into the regulation of the metabolic network and thus allowing a more thorough description of plant cellular function. Thus, although safety concerns mean that stable isotope feeding is generally preferred, the techniques are in truth highly complementary and application of both approaches in tandem currently probably provides the best route towards a comprehensive understanding of plant cellular metabolism. PMID:27297990

  11. Subset of Kappa and Lambda Germline Sequences Result in Light Chains with a Higher Molecular Mass Phenotype.

    PubMed

    Barnidge, David R; Lundström, Susanna L; Zhang, Bo; Dasari, Surendra; Murray, David L; Zubarev, Roman A

    2015-12-01

    In our previous work, we showed that electrospray ionization of intact polyclonal kappa and lambda light chains isolated from normal serum generates two distinct, Gaussian-shaped, molecular mass distributions representing the light-chain repertoire. During the analysis of a large (>100) patient sample set, we noticed a low-intensity molecular mass distribution with a mean of approximately 24 250 Da, roughly 800 Da higher than the mean of the typical kappa molecular-mass distribution mean of 23 450 Da. We also observed distinct clones in this region that did not appear to contain any typical post-translational modifications that would account for such a large mass shift. To determine the origin of the high molecular mass clones, we performed de novo bottom-up mass spectrometry on a purified IgM monoclonal light chain that had a calculated molecular mass of 24 275.03 Da. The entire sequence of the monoclonal light chain was determined using multienzyme digestion and de novo sequence-alignment software and was found to belong to the germline allele IGKV2-30. The alignment of kappa germline sequences revealed ten IGKV2 and one IGKV4 sequences that contained additional amino acids in their CDR1 region, creating the high-molecular-mass phenotype. We also performed an alignment of lambda germline sequences, which showed additional amino acids in the CDR2 region, and the FR3 region of functional germline sequences that result in a high-molecular-mass phenotype. The work presented here illustrates the ability of mass spectrometry to provide information on the diversity of light-chain molecular mass phenotypes in circulation, which reflects the germline sequences selected by the immunoglobulin-secreting B-cell population. PMID:26598961

  12. Mass-Independent Fractionation of Oxygen Isotope in Earth Wind: First Principle Calculations for Photodissociation

    NASA Astrophysics Data System (ADS)

    Yamada, A.; Nanbu, S.; Kasai, Y.; Ozima, M.

    2009-12-01

    Mass-independently fractionated oxygen isotope were reported on metal particles extracted from Apollo lunar soils [1, 2], but these origins are still unknown. Since the substantial fraction of Earth-escaping O+ flux (Earth Wind, EW hereafter), comparable to the amount of the anomalous oxygen implanted on the metal particles, could reach the lunar surface [3], Ozima et al. [4] suggested that EW may be responsible to the anomalous oxygen. The purpose is to test this EW hypothesiss, we study oxygen isotopic ratios of O+ at the upper atmosphere. From quantum chemical calculations of photo-dissociation of O2, we show the results in mass-independent isotopic fractionation of oxygen, thereby in conformity with the EW hypothesis. First principles reaction dynamics simulations were performed to compute the photolysis rate for the B3Σu- ← X3Σg- electronic transition, for Schumann-Runge band. With the assumption of the Born-Oppenheimer approximation, we performed the wave-packet dynamics for the nuclei-motion in the potential energy curves determined by the first step calculation. Quantum chemical program package [5] was used for the first step calculation, and the quantum dynamics was carried out by our own program package. Assuming the quantum yield of the corresponding photolysis is unity, the photo-absorption cross section can be correlated with the photolysis rate. Therefore, following the time dependent approach, the autocorrelation function (A(t) = <φ(0)|φ(t)>) was numerically computed by the second step calculation. Finally, the theoretical spectrum as a function of wavelength of excitation light was estimated by the Fourier transform of the autocorrelation function A(t) [6]. Calculated absorption cross sections for C16O showed similar wavelength dependence with experiment [7], although the absolute magnitude was yet to be calibrated for a quantitative comparison. Assuming Boltzmann distribution at 1200 K, we estimated enrichment factors defined as σι(λ)/σ16

  13. A Lie-Theoretic Perspective on O(n) Mass Matrix Inversion for Serial Manipulators and Polypeptide Chains

    PubMed Central

    Lee, Kiju; Wang, Yunfeng; Chirikjian, Gregory S.

    2010-01-01

    Over the past several decades a number of O(n) methods for forward and inverse dynamics computations have been developed in the multi-body dynamics and robotics literature. A method was developed in 1974 by Fixman for O(n) computation of the mass-matrix determinant for a serial polymer chain consisting of point masses. In other recent papers, we extended this method in order to compute the inverse of the mass matrix for serial chains consisting of point masses. In the present paper, we extend these ideas further and address the case of serial chains composed of rigid-bodies. This requires the use of relatively deep mathematics associated with the rotation group, SO(3), and the special Euclidean group, SE(3), and specifically, it requires that one differentiates functions of Lie-group-valued argument. PMID:20165563

  14. Hemoglobin variants as models for investigation of dissociation of intact polypeptide chains by ESI tandem mass spectrometry

    SciTech Connect

    Light, K.J.; Loo, J.A.; Edmonds, C.G.; Smith, R.D.

    1991-06-01

    Electrospray ionization mass spectroscopy (ESI-MS) is rapidly becoming a practical biochemical tool for peptide and protein sequence analysis. The utility of ESI-MS is through use of Collisionally Activated Dissociation (ESI-CAD-MS). Human hemoglobin (Hb, {approximately}62 kDa) consists of four polypeptide chains and a prosthetic heme group. There are over 400 Hb variants, characterized by amino acid substitutions in either the alpha or beta polypeptide chains. We investigated ESI-CAD-MS as a tool for rapidly analyzing amino acid substitutions, using eight Hb beta chain variants. The approximate location of the modification can be deduced from comparison of the CAD mass spectra and observance of the mass shifts of the fragment ion containing the substitution. Fragmentation occurs preferentially at the amino terminus of proline residues. For most substitutions, differences in CAD mass spectra were not seen. 2 figs.

  15. Quantitation of vitamin B6 in biological samples by isotope dilution mass spectrometry

    SciTech Connect

    Hachey, D.L.; Coburn, S.P.; Brown, L.T.; Erbelding, W.F.; DeMark, B.; Klein, P.D.

    1985-11-15

    Methods have been developed for the simultaneous quantitative analysis of vitamin B6 forms in biological samples by isotope dilution mass spectrometry using deuterated forms of pyridoxine, pyridoxal, pyridoxamine, and pyridoxic acid. The biological fluid or tissue sample was homogenized and then treated with a cocktail containing appropriate amounts of each deuterated vitamer, as well as the deuterated, phosphorylated vitamer forms. The individual vitamers were isolated from the homogenate by a complex high-performance liquid chromatographic procedure that provided separate fractions for each of the six vitamers found in biological samples. Aldehydic B6 vitamers were reduced to the alcohol form prior to acetylation and analysis by gas chromatography/mass spectrometry (GC/MS). The three resulting vitamers were analyzed by electron ionization GC/MS using a silicone capillary column. The methods have been applied to analysis of vitamin B6 in liver, milk, urine, and feces at levels as low as 0.02 nmol/ml.

  16. Quantitative Profiling of Long-Chain Bases by Mass Tagging and Parallel Reaction Monitoring

    PubMed Central

    Ejsing, Christer S.; Bilgin, Mesut; Fabregat, Andreu

    2015-01-01

    Long-chain bases (LCBs) are both intermediates in sphingolipid metabolism and potent signaling molecules that control cellular processes. To understand how regulation of sphingolipid metabolism and levels of individual LCB species impinge upon physiological and pathophysiological processes requires sensitive and specific assays for monitoring these molecules. Here we describe a shotgun lipidomics method for quantitative profiling of LCB molecules. The method employs a “mass-tag” strategy where LCBs are chemically derivatized with deuterated methyliodide (CD3I) to produce trimethylated derivatives having a positively charged quaternary amine group. This chemical derivatization minimizes unwanted in-source fragmentation of LCB analytes and prompts a characteristic trimethylaminium fragment ion that enables sensitive and quantitative profiling of LCB molecules by parallel reaction monitoring on a hybrid quadrupole time-of-flight mass spectrometer. Notably, the strategy provides, for the first time, a routine for monitoring endogenous 3-ketosphinganine molecules and distinguishing them from more abundant isomeric sphingosine molecules. To demonstrate the efficacy of the methodology we report an in-depth characterization of the LCB composition of yeast mutants with defective sphingolipid metabolism and the absolute levels of LCBs in mammalian cells. The strategy is generic, applicable to other types of mass spectrometers and can readily be applied as an additional routine in workflows for global lipidome quantification and for functional studies of sphingolipid metabolism. PMID:26660097

  17. Tracing subarctic Pacific water masses with benthic foraminiferal stable isotopes during the LGM and late Pleistocene

    NASA Astrophysics Data System (ADS)

    Cook, Mea S.; Ravelo, A. Christina; Mix, Alan; Nesbitt, Ian M.; Miller, Nari V.

    2016-03-01

    As the largest ocean basin, the Pacific helps to set the global climate state, since its circulation affects mean ocean properties, air-sea partitioning of carbon dioxide, and the distribution of global oceanic poleward heat transport. There is evidence that during the Last Glacial Maximum (LGM) the subarctic Pacific contained a better-ventilated, relatively fresh intermediate water mass above ~2000 m that may have formed locally. The source and spatial extent of this water mass is not known, nor do we know how formation of this water mass varied during Pleistocene glaciations with different orbital and ice sheet boundary conditions. Here we present a 0.5 My multi-species benthic stable isotope record from Site U1345 (1008 m) on the northern Bering slope and a 1.0 My record from U1339 (1868 m) from the Umnak Plateau in the southeastern basin. We find that the relatively well-ventilated low-δ18O intermediate water reaches 1000 m in the Bering Sea during MIS2, but that the hydrographic divide between this water mass and poorly-ventilated deep water was shallower than 1000 m for earlier glaciations. We also compare Bering Sea piston core and IODP Expedition 323 Uvigerina data from the Holocene and LGM with the modern hydrography, and to previously published profiles from the Okhotsk Sea and Emperor Seamounts. We find that the carbon and oxygen stable isotope signatures of well-ventilated water in the Bering and Okhotsk Seas are distinct, suggesting that there may have been intermediate water formation in both basins during the LGM.

  18. Accurate and Efficient Resolution of Overlapping Isotopic Envelopes in Protein Tandem Mass Spectra

    PubMed Central

    Xiao, Kaijie; Yu, Fan; Fang, Houqin; Xue, Bingbing; Liu, Yan; Tian, Zhixin

    2015-01-01

    It has long been an analytical challenge to accurately and efficiently resolve extremely dense overlapping isotopic envelopes (OIEs) in protein tandem mass spectra to confidently identify proteins. Here, we report a computationally efficient method, called OIE_CARE, to resolve OIEs by calculating the relative deviation between the ideal and observed experimental abundance. In the OIE_CARE method, the ideal experimental abundance of a particular overlapping isotopic peak (OIP) is first calculated for all the OIEs sharing this OIP. The relative deviation (RD) of the overall observed experimental abundance of this OIP relative to the summed ideal value is then calculated. The final individual abundance of the OIP for each OIE is the individual ideal experimental abundance multiplied by 1 + RD. Initial studies were performed using higher-energy collisional dissociation tandem mass spectra on myoglobin (with direct infusion) and the intact E. coli proteome (with liquid chromatographic separation). Comprehensive data at the protein and proteome levels, high confidence and good reproducibility were achieved. The resolving method reported here can, in principle, be extended to resolve any envelope-type overlapping data for which the corresponding theoretical reference values are available. PMID:26439836

  19. 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. PMID:20183223

  20. General polytropic self-gravitating cylinder free-fall and accreting mass string with a chain of collapsed objects

    NASA Astrophysics Data System (ADS)

    Lou, Yu-Qing; Hu, Xu-Yao

    2016-06-01

    We present a theoretical model framework for general polytropic (GP) hydrodynamic cylinder under self-gravity of infinite length with axial uniformity and axisymmetry. For self-similar dynamic solutions, we derive valuable integrals, analytic asymptotic solutions, sonic critical curves, shock conditions, and global numerical solutions with or without expansion shocks. Among others, we investigate various dynamic solutions featured with central free-fall asymptotic behaviours, corresponding to a collapsed mass string with a sustained dynamic accretion from a surrounding mass reservoir. Depending on the allowed ranges of a scaling index a < -1, such cylindrical dynamic mass accretion rate could be steady, increasing with time and decreasing with time. Physically, such a collapsed mass string or filament would break up into a sequence of sub-clumps and segments as induced by gravitational Jeans instabilities. Depending on the scales involved, such sub-clumps would evolve into collapsed objects or gravitationally bound systems. In diverse astrophysical and cosmological contexts, such a scenario can be adapted on various temporal, spatial and mass scales to form a chain of collapsed clumps and/or compact objects. Examples include the formation of chains of proto-stars, brown dwarfs and gaseous planets along molecular filaments; the formation of luminous massive stars along magnetized spiral arms and circum-nuclear starburst rings in barred spiral galaxies; the formation of chains of compact stellar objects such as white dwarfs, neutron stars, and black holes along a highly condensed mass string. On cosmological scales, one can perceive the formation of chains of galaxies, chains of galaxy clusters or even chains of supermassive and hypermassive black holes in the Universe including the early Universe. All these chains referred to above include possible binaries.

  1. Ozonolysis of nonmethane hydrocarbons as a source of the observed mass independent oxygen isotope enrichment in tropospheric CO

    NASA Astrophysics Data System (ADS)

    RöCkmann, Thomas; Brenninkmeijer, Carl A. M.; Neeb, Peter; Crutzen, Paul J.

    1998-01-01

    Combined 17O and 18O measurements of tropospheric CO from two northern hemisphere (NH) sites reveal systematically enhanced 17O levels, confirming the existence of significant mass independent oxygen isotope enrichment in this important trace gas. When CO levels increase in the NH winter, the mass independent enrichment decreases proportionally. A possible source of this rare isotope effect in CO is transfer of the mass independent enrichment from O3 to the CO pool via ozonolysis of unsaturated hydrocarbons such as isoprene and terpenes. Laboratory ozonolysis experiments indeed confirm that this process is a potentially important source of mass independently enriched CO. The extra 17O enrichment found in ozonolysis-derived CO is similar to the mass independent fractionation measured on ozone. If ozonolysis is the only source of mass independent enrichment in CO, it is estimated that about 10% of all CO in middle to high latitude winter, at ground level, originates from the ozonolysis of unsaturated hydrocarbons. While the laboratory experiments prove that ozonolysis is a source of mass independent enrichment in CO, a further problem unfolds. Because tropospheric O3 is strongly enriched in 18O as well, this enrichment is also transferred to the CO inventory. When 10% of the CO inventory has the strong 18O enrichment, the measured low 18O abundance of atmospheric CO requires for compensation the existence of a strongly 18O depleted CO source, or a selective isotopic modification due to isotope fractionation. No such source has been identified to date, and thus ozonolysis may not be the only source of mass independent fractionation in atmospheric CO. Because the mass independent isotopic enrichment is by its nature indestructible by common (i.e., mass dependent) fractionation processes, it is an ideal tracer.

  2. Stable Isotope Labeling Strategy for Curcumin Metabolite Study in Human Liver Microsomes by Liquid Chromatography-Tandem Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Gao, Dan; Chen, Xiaowu; Yang, Xiaomei; Wu, Qin; Jin, Feng; Wen, Hongliang; Jiang, Yuyang; Liu, Hongxia

    2015-04-01

    The identification of drug metabolites is very important in drug development. Nowadays, the most widely used methods are isotopes and mass spectrometry. However, the commercial isotopic labeled reagents are usually very expensive, and the rapid and convenient identification of metabolites is still difficult. In this paper, an 18O isotope labeling strategy was developed and the isotopes were used as a tool to identify drug metabolites using mass spectrometry. Curcumin was selected as a model drug to evaluate the established method, and the 18O labeled curcumin was successfully synthesized. The non-labeled and 18O labeled curcumin were simultaneously metabolized in human liver microsomes (HLMs) and analyzed by liquid chromatography/mass spectrometry (LC-MS). The two groups of chromatograms obtained from metabolic reaction mixture with and without cofactors were compared and analyzed using Metabolynx software (Waters Corp., Milford, MA, USA). The mass spectra of the newly appearing chromatographic peaks in the experimental sample were further analyzed to find the metabolite candidates. Their chemical structures were confirmed by tandem mass spectrometry. Three metabolites, including two reduction products and a glucuronide conjugate, were successfully detected under their specific HLMs metabolic conditions, which were in accordance with the literature reported results. The results demonstrated that the developed isotope labeling method, together with post-acquisition data processing using Metabolynx software, could be used for fast identification of new drug metabolites.

  3. Evaluation of the 34S/32S ratio of Soufre de Lacq elemental sulfur isotopic reference material by continuous flow isotope-ratio mass spectrometry

    USGS Publications Warehouse

    Qi, H.P.; Coplen, T.B.

    2003-01-01

    Soufre de Lacq elemental sulfur reference material (IAEA-S-4) isotopically is homogeneous in amounts as small as 41 ??g as determined by continuous flow isotope-ratio mass spectrometry. The ??34S value for this reference material is +16.90 ?? 0.12??? (1??) on a scale (Vienna Can??on Diablo troilite, VCDT) where IAEA-S-1 Ag2S is -0.3??? and IAEA-S-2 Ag2S is +22.67???. Published by Elsevier Science B.V.

  4. Time-of-flight mass measurements of neutron-rich chromium isotopes up to N =40 and implications for the accreted neutron star crust

    NASA Astrophysics Data System (ADS)

    Meisel, Z.; George, S.; Ahn, S.; Bazin, D.; Brown, B. A.; Browne, J.; Carpino, J. F.; Chung, H.; Cyburt, R. H.; Estradé, A.; Famiano, M.; Gade, A.; Langer, C.; Matoš, M.; Mittig, W.; Montes, F.; Morrissey, D. J.; Pereira, J.; Schatz, H.; Schatz, J.; Scott, M.; Shapira, D.; Sieja, K.; Smith, K.; Stevens, J.; Tan, W.; Tarasov, O.; Towers, S.; Wimmer, K.; Winkelbauer, J. R.; Yurkon, J.; Zegers, R. G. T.

    2016-03-01

    We present the mass excesses of Cr-6459, obtained from recent time-of-flight nuclear mass measurements at the National Superconducting Cyclotron Laboratory at Michigan State University. The mass of 64Cr is determined for the first time, with an atomic mass excess of -33.48 (44 ) MeV. We find a significantly different two-neutron separation energy S2 n trend for neutron-rich isotopes of chromium, removing the previously observed enhancement in binding at N =38 . Additionally, we extend the S2 n trend for chromium to N =40 , revealing behavior consistent with the previously identified island of inversion in this region. We compare our results to state-of-the-art shell-model calculations performed with a modified Lenzi-Nowacki-Poves-Sieja interaction in the f p shell, including the g9 /2 and d5 /2 orbits for the neutron valence space. We employ our result for the mass of 64Cr in accreted neutron star crust network calculations and find a reduction in the strength and depth of electron-capture heating from the A =64 isobaric chain, resulting in a cooler than expected accreted neutron star crust. This reduced heating is found to be due to the >1 -MeV reduction in binding for 64Cr with respect to values from commonly used global mass models.

  5. Estimates of Comet Fragment Masses from Impact Crater Chains on Callisto and Ganymede

    NASA Technical Reports Server (NTRS)

    McKinnon, William B.; Schenk, Paul M.

    1995-01-01

    Chains of impact craters, or catenae, have been identified in Voyager images of Callisto and Ganymede. Although these resemble in some respects secondary crater chains, the source craters and basins for the catenae cannot be identified. The best explanation is a phenomenon similar to that displayed by former comet Shoemaker-Levy 9; tidal (or other) breakup close to Jupiter followed by gradual orbital separation of the fragments and collision with a Galilean satellite on the outbound leg of the trajectory. Because the trajectories must pass close to Jupiter, this constrains the impact geometry (velocity and impact angle) of the individual fragments. For the dominant classes of impactors, short period Jupiter-family comets and asteroids, velocities at Callisto and Ganymede are dominated by Jovian gravity and a satellite's orbital motion, and are insensitive to the pre-fragmentation heliocentric velocity; velocities are insensitive to satellite gravity for all impactor classes. Complex crater shapes on Callisto and Ganymede are determined from Voyager images and Schmidt-Holsapple scaling is used to back out individual fragment masses. We find that comet fragment radii are generally less than about 500 m (for ice densities) but can be larger. These estimates can be compared with those for the Shoemaker-Levy 9 impactors.

  6. Global nitrogen cycle: pre-Anthropocene mass and isotope fluxes and effects of human perturbations

    NASA Astrophysics Data System (ADS)

    Joo, Y.; Li, D. D.; Lerman, A.; Mackenzie, F. T.

    2012-12-01

    The size of the largest nitrogen reservoir -- the Earth atmosphere -- and its long residence time of approximately 17 million years suggest that the global N cycle was likely to be balanced at geological time scales. After the industrial revolution, human activities, such as mining, fossil fuel burning, land use change, and artificial fertilization, have resulted in perturbations and numerous flux changes of the N cycle. The effects of human activities on the mass and isotopic composition of the N reservoirs can be predicted using a detailed N cycle model with estimated additions. For the pre-Anthropocene period, a balanced steady-state N cycle model was constructed based on the Redfield ratios and an extensive literature review. The model includes 14 N reservoirs in the domains of the atmosphere, land, and ocean. The biotic reservoirs on land and in the ocean (land plants and marine biota) interact with atmospheric N2 and dissolved inorganic N (DIN) in ocean and soil waters. DIN further interacts with dissolved organic N (DON), particulate organic matter (POM), and ocean sediments. Atmosphere supplies N to land and ocean domains mainly by N fixation, deposition, and dissolution, and these fluxes are balanced by denitrification and volatilization back to atmosphere. Riverine transport of dissolved and particulate N connects land and ocean domains. Once the cycle is mass-balanced, the isotopic composition of reservoir and the size of fractionation accompanying microbial transformations and transfers of N species between the reservoirs were estimated by numerical iteration of the flux equations based on the reported δ15N values and fractionation factors. The calculated fractionation factors tend to be smaller in magnitude than the experimentally measured ones in natural systems, which can be interpreted as an indication of N-limited conditions prevailing in pre-Anthropocene world: a smaller isotope fractionation can be interpreted as an indication of nitrogen

  7. New Precision Mass Measurements of Neutron-Rich Calcium and Potassium Isotopes and Three-Nucleon Forces

    SciTech Connect

    Gallant, A. T.; Bale, J. C.; Chowdhury, U.; Lennarz, A.; Simon, V. V.; Holt, J. D.; Mané, E.; Menéndez, J.; Simon, M. C.; Andreoiu, C.; Delheij, P.; Pearson, M.; Savajols, H.; Schwenk, A.

    2012-01-01

    We present precision Penning trap mass measurements of neutron-rich calcium and potassium isotopes in the vicinity of neutron number N=32. Using the TITAN system, the mass of 51K was measured for the first time, and the precision of the 51,52Ca mass values were improved significantly. The new mass values show a dramatic increase of the binding energy compared to those reported in the atomic mass evaluation. In particular, 52Ca is more bound by 1.74 MeV, and the behavior with neutron number deviates substantially from the tabulated values. An increased binding was predicted recently based on calculations that include three-nucleon (3N) forces. We present a comparison to improved calculations, which agree remarkably with the evolution of masses with neutron number, making neutron-rich calcium isotopes an exciting region to probe 3N forces.

  8. 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. PMID:18041012

  9. Photochemical self-shielding as a source of non-mass-dependent isotope fractionation

    NASA Astrophysics Data System (ADS)

    Lyons, James; Stark, Glenn; Blackie, Doug; Pickering, Juliet; Heays, Alan

    2010-05-01

    Very large isotopic enrichments occur in the photolysis products of molecules that have line-type absorption spectra. Abundance-dependent line saturation, a process termed photochemical self-shielding, yields large non-mass-dependent (NMD) isotope effects, and has been proposed to have occurred in CO in the solar nebula (Clayton 2002) and SO2 in the early Earth atmosphere (Lyons 2007). The NMD signatures derived from photolysis of CO and SO2 are believed to be recorded in primitive meteorites inclusions (CAIs) and in Archean/Paleoproterozoic sulfur sediments, respectively. Comparison of theory and experiment can be used to distinguish self-shielding from other NMD processes. Recent low-resolution (~10 cm^-1) measurements of isotopic SO2 cross sections (Danielache et al. 2008) exhibit NMD effects when included in photoechemical models (Ueno et al. 2009), but not as a result of self-shielding. Higher resolution measurements (1-0.2 cm^-1) of isotopic cross sections are in progress at Imperial College. Inclusion of preliminary 1 cm^-1 resolution cross sections in a photochemical model for Earth's early atmosphere clearly demonstrates that isotopic self-shielding is present, yielding d33S>0 and d34S>0 in photoproduct SO. However, uncertainties in the measured cross sections also introduce NMD signatures. We are presently working to remove these uncertainties. Recent experiments on CO photodissociation at wavelengths ~91-108 nm show very large NMD effects in oxygen (Chakraborty et al. 2008). Because the measured NMD signatures are wavelength dependent, and differ in delta-values (i.e., d17O/d18O not equal unity), Chakraborty et al. claim that their experiments rule out CO self-shielding as the mechanism for the meteorite CAI slope-1 line. Here we show via model simulation of the experiments that the non-unity d17O/d18O values result primarily from self-shielding effects in both C16O and C18O. Also, model results indicate that the non-unity d17O/d18O values only arise for

  10. Determination of Protein Thiol Reduction Potential by Isotope Labeling and Intact Mass Measurement.

    PubMed

    Thurlow, Sophie E; Kilgour, David P; Campopiano, Dominic J; Mackay, C Logan; Langridge-Smith, Pat R R; Clarke, David J; Campbell, Colin J

    2016-03-01

    Oxidation/reduction of thiol residues in proteins is an important type of post-translational modification that is implicated in regulating a range of biological processes. The nature of the modification makes it possible to define a quantifiable electrochemical potential (E(⊕)) for oxidation/reduction that allows cysteine-containing proteins to be ranked based on their propensity to be oxidized. Measuring oxidation of cysteine residues in proteins is difficult using standard electrochemical methods, but top-down mass spectrometry recently has been shown to enable the quantification of E(⊕) for thiol oxidations. In this paper, we demonstrate that mass spectrometry of intact proteins can be used in combination with an isotopic labeling strategy and an automated data analysis algorithm to measure E(⊕) for the thiols in both E. coli Thioredoxin 1 and human Thioredoxin 1. Our methodology relies on accurate mass measurement of proteins using liquid chromatography-mass spectroscopy (LC-MS) analyses and does not necessarily require top-down fragmentation. In addition to analyzing homogeneous protein samples, we also demonstrate that our methodology can be used to determine thiol E(⊕) measurements in samples that contain mixtures of proteins. Thus, the combination of experimential methodology and data analysis regime has the potential to make such measurements in a high-throughput manner and in a manner that is more accessible to a broad community of protein scientists. PMID:26881737

  11. LC-quadrupole/Orbitrap high-resolution mass spectrometry enables stable isotope-resolved simultaneous quantification and ¹³C-isotopic labeling of acyl-coenzyme A thioesters.

    PubMed

    Frey, Alexander J; Feldman, Daniel R; Trefely, Sophie; Worth, Andrew J; Basu, Sankha S; Snyder, Nathaniel W

    2016-05-01

    Acyl-coenzyme A (acyl-CoA) thioesters are evolutionarily conserved, compartmentalized, and energetically activated substrates for biochemical reactions. The ubiquitous involvement of acyl-CoA thioesters in metabolism, including the tricarboxylic acid cycle, fatty acid metabolism, amino acid degradation, and cholesterol metabolism highlights the broad applicability of applied measurements of acyl-CoA thioesters. However, quantitation of acyl-CoA levels provides only one dimension of metabolic information and a more complete description of metabolism requires the relative contribution of different precursors to individual substrates and pathways. Using two distinct stable isotope labeling approaches, acyl-CoA thioesters can be labeled with either a fixed [(13)C3(15)N1] label derived from pantothenate into the CoA moiety or via variable [(13)C] labeling into the acyl chain from metabolic precursors. Liquid chromatography-hybrid quadrupole/Orbitrap high-resolution mass spectrometry using parallel reaction monitoring, but not single ion monitoring, allowed the simultaneous quantitation of acyl-CoA thioesters by stable isotope dilution using the [(13)C3(15)N1] label and measurement of the incorporation of labeled carbon atoms derived from [(13)C6]-glucose, [(13)C5(15)N2]-glutamine, and [(13)C3]-propionate. As a proof of principle, we applied this method to human B cell lymphoma (WSU-DLCL2) cells in culture to precisely describe the relative pool size and enrichment of isotopic tracers into acetyl-, succinyl-, and propionyl-CoA. This method will allow highly precise, multiplexed, and stable isotope-resolved determination of metabolism to refine metabolic models, characterize novel metabolism, and test modulators of metabolic pathways involving acyl-CoA thioesters. PMID:26968563

  12. Mass spectrometric studies of cocaine disposition in animals and humans using stable isotope-labeled analogues.

    PubMed

    Jindal, S P; Lutz, T

    1989-12-01

    Ion cluster technique in conjunction with gas chromatography-mass spectrometry (GC-MS) was used for the identification and quantitation of major metabolites of cocaine (1a) in rat and humans. In a typical experiment, a female rat weighing 250 gm was intraperitoneally administered a 20-mg/kg mixture of 1a, NCD3-cocaine (1b), OCD3-cocaine (1c), and 4T2-cocaine (1d). The urine was collected, extracted with organic solvents, and separated into several fractions using TLC and HPLC techniques. Tritium radioactivity in a metabolically stable position in 1d was useful in the separation of metabolites, while the deuterium labeled 1(b + c), creating an artificial isotopic cluster, provided specific identification of metabolites by mass spectrometric interpretation. Norcocaine (2), benzoylnorecgonine (3), N-hydroxynorcocaine (4), methylecgonidine (5), benzoylecgonine (11), ecgonine methyl ester (9), hydroxycocaine (7), hydroxymethoxycocaine (10), and dimethoxyhydroxycocaine (6) were found to be the major metabolites of 1a in the rat urine as well as in plasma. The whole brain analysis showed significant amounts of unmetabolized 1a and 2, and minor concentrations of 9, 5, 7, and 10, and traces of 6. Some of these metabolites have been reported earlier by us as well as other investigators and are unequivocally confirmed in this work. Unmetabolized 1a, its pharmacologically active metabolite 2, and other major metabolites were quantitated in the rat brain, plasma, and urine using stable isotope-labeled analogues as internal standards and selected ion monitoring (SIM) mass spectrometry. The pharmacokinetic profiles of 1a and 2 indicate half-lives of less than 20 min in the brain and plasma. These data are in good agreement with widely reported short-lived behavioral effects of cocaine.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:2614690

  13. First direct mass measurements of stored neutron-rich 129,130,131Cd isotopes with FRS-ESR

    NASA Astrophysics Data System (ADS)

    Knöbel, R.; Diwisch, M.; Bosch, F.; Boutin, D.; Chen, L.; Dimopoulou, C.; Dolinskii, A.; Franczak, B.; Franzke, B.; Geissel, H.; Hausmann, M.; Kozhuharov, C.; Kurcewicz, J.; Litvinov, S. A.; Martinez-Pinedo, G.; Matoš, M.; Mazzocco, M.; Münzenberg, G.; Nakajima, S.; Nociforo, C.; Nolden, F.; Ohtsubo, T.; Ozawa, A.; Patyk, Z.; Plaß, W. R.; Scheidenberger, C.; Stadlmann, J.; Steck, M.; Sun, B.; Suzuki, T.; Walker, P. M.; Weick, H.; Wu, M.-R.; Winkler, M.; Yamaguchi, T.

    2016-03-01

    A 410 MeV/u 238U projectile beam was used to create cadmium isotopes via abrasion-fission in a beryllium target placed at the entrance of the in-flight separator FRS at GSI. The fission fragments were separated by the FRS and injected into the isochronous storage ring ESR for mass measurements. Isochronous Mass Spectrometry (IMS) was performed under two different experimental conditions, with and without Bρ-tagging at the high-resolution central focal plane of the FRS. In the experiment with Bρ-tagging the magnetic rigidity of the injected fragments was determined with an accuracy of 2 ṡ10-4. A new method of data analysis, which uses a correlation matrix for the combined data set from both experiments, has provided experimental mass values of 25 rare isotopes for the first time. The high sensitivity and selectivity of the method have given access to nuclides detected with a rate of a few atoms per week. In this letter we present for the 129,130,131Cd isotopes mass values directly measured for the first time. The experimental mass values of cadmium as well as for tellurium and tin isotopes show a pronounced shell effect towards and at N = 82. Shell quenching cannot be deduced from a single new mass value, nor by a better agreement with a theoretical model which explicitly takes into account a quenching feature. This is in agreement with the conclusion from γ-ray spectroscopy and confirms modern shell-model calculations.

  14. Assessment of Non-traditional Isotopic Ratios by Mass Spectrometry for Analysis of Nuclear Activities: Annual Report Year 2

    SciTech Connect

    Biegalski, S; Buchholz, B

    2009-08-26

    The objective of this work is to identify isotopic ratios suitable for analysis via mass spectrometry that distinguish between commercial nuclear reactor fuel cycles, fuel cycles for weapons grade plutonium, and products from nuclear weapons explosions. Methods will also be determined to distinguish the above from medical and industrial radionuclide sources. Mass spectrometry systems will be identified that are suitable for field measurement of such isotopes in an expedient manner. Significant progress has been made with this project within the past year: (1) Isotope production from commercial nuclear fuel cycles and nuclear weapons fuel cycles have been modeled with the ORIGEN and MCNPX codes. (2) MCNPX has been utilized to calculate isotopic inventories produced in a short burst fast bare sphere reactor (to approximate the signature of a nuclear weapon). (3) Isotopic ratios have been identified that are good for distinguishing between commercial and military fuel cycles as well as between nuclear weapons and commercial nuclear fuel cycles. (4) Mass spectrometry systems have been assessed for analysis of the fission products of interest. (5) A short-list of forensic ratios have been identified that are well suited for use in portable mass spectrometry systems.

  15. Nuclear Data Evaluation for Mass Chain A=217:Odd-Proton Nuclei

    PubMed Central

    Nafee, Sherif S.; Shaheen, Salem A.; Al-Ramady, Amir M.

    2016-01-01

    Thallium (Tl81217), Bismuth (Bi83217), Astatine (At85217), Francium (Fr87217), Actinium (Ac89217) and Protactinium (Pa91217) are of odd-proton numbers among the mass chain A = 217. In the present work, the half-lives and gamma transitions for the six nuclei have been studied and adopted based on the recently published interactions or unevaluated nuclear data sets XUNDL. The Q (α) has been updated based on the recent published work of the Atomic Mass Evaluation AME2012 as well. Moreover, the total conversion electrons as well as the K-Shell to L-Shell, L-Shell to M-Shell and L-Shell to N-Shell Conversion Electron Ratios have been calculated using BrIcc code v2.3. An updated skeleton decay scheme for each of the above nuclei has been presented here. The decay hindrance factors (HF) calculated using the ALPHAD program, which is available from Brookhaven National Laboratory’s website, have been calculated for the α- decay data sets for 221Fr-, 221Ac- and 221Pa- α-decays. PMID:26761207

  16. Nuclear Data Evaluation for Mass Chain A=217:Odd-Proton Nuclei.

    PubMed

    Nafee, Sherif S; Shaheen, Salem A; Al-Ramady, Amir M

    2016-01-01

    Thallium (81(217)Tl, Bismuth (83(217)Bi), Astatine (85(217)At), Francium (87(217)Fr), Actinium (89(217)Ac) and Protactinium (91(217)Pa) are of odd-proton numbers among the mass chain A = 217. In the present work, the half-lives and gamma transitions for the six nuclei have been studied and adopted based on the recently published interactions or unevaluated nuclear data sets XUNDL. The Q (α) has been updated based on the recent published work of the Atomic Mass Evaluation AME2012 as well. Moreover, the total conversion electrons as well as the K-Shell to L-Shell, L-Shell to M-Shell and L-Shell to N-Shell Conversion Electron Ratios have been calculated using BrIcc code v2.3. An updated skeleton decay scheme for each of the above nuclei has been presented here. The decay hindrance factors (HF) calculated using the ALPHAD program, which is available from Brookhaven National Laboratory's website, have been calculated for the α- decay data sets for (221)Fr-, (221)Ac- and (221)Pa-α-decays. PMID:26761207

  17. Stable isotope model for assessing production of short chain fatty acids from colon-derived sugar: application in pigs.

    PubMed

    Kien, C L; Murray, R D; Ailabouni, A; Powers, P; Kepner, J; Powers, L; Brunengraber, H

    1996-12-01

    Sugar reaching the colon because of intestinal maldigestion or malabsorption may be fermented to acetate and other short-chain fatty acids, resulting in stimulation of colonic water absorption and cell proliferation. To explore this phenomenon in more detail, we have developed a stable isotope model for estimating the fraction of colon-derived glucose or lactose that is fermented to acetate, propionate and butyrate. In an initial application of the model, [d3]-acetate and either [1-(13)C]-glucose or [D-1-(13)C]-lactose were infused into the cecum or colon of piglets, and plateau plasma acetate enrichment was monitored in the carotid artery. In acutely anesthetized piglets, the fractions of glucose and lactose fermented to acetate were 17.0 and 20.0%, respectively. In a chronically catheterized piglet, fermentation was higher (34.2%). When conducted in chronically catheterized animals or via a colostomy or ileostomy in infants, this model may be used to determine how age, previous surgery or antibiotic therapy affects the efficiency of colonic assimilation of carbohydrate. PMID:9001376

  18. Determination of the sulfur isotope ratio in carbonyl sulfide using gas chromatography/isotope ratio mass spectrometry on fragment ions 32S+, 33S+, and 34S+.

    PubMed

    Hattori, Shohei; Toyoda, Akari; Toyoda, Sakae; Ishino, Sakiko; Ueno, Yuichiro; Yoshida, Naohiro

    2015-01-01

    Little is known about the sulfur isotopic composition of carbonyl sulfide (OCS), the most abundant atmospheric sulfur species. We present a promising new analytical method for measuring the stable sulfur isotopic compositions (δ(33)S, δ(34)S, and Δ(33)S) of OCS using nanomole level samples. The direct isotopic analytical technique consists of two parts: a concentration line and online gas chromatography-isotope ratio mass spectrometry (GC-IRMS) using fragmentation ions (32)S(+), (33)S(+), and (34)S(+). The current levels of measurement precision for OCS samples greater than 8 nmol are 0.42‰, 0.62‰, and 0.23‰ for δ(33)S, δ(34)S, and Δ(33)S, respectively. These δ and Δ values show a slight dependence on the amount of injected OCS for volumes smaller than 8 nmol. The isotope values obtained from the GC-IRMS method were calibrated against those measured by a conventional SF6 method. We report the first measurement of the sulfur isotopic composition of OCS in air collected at Kawasaki, Kanagawa, Japan. The δ(34)S value obtained for OCS (4.9 ± 0.3‰) was lower than the previous estimate of 11‰. When the δ(34)S value for OCS from the atmospheric sample is postulated as the global signal, this finding, coupled with isotopic fractionation for OCS sink reactions in the stratosphere, explains the reported δ(34)S for background stratospheric sulfate. This suggests that OCS is a potentially important source for background (nonepisodic or nonvolcanic) stratospheric sulfate aerosols. PMID:25439590

  19. Mass-independent fractionation of mercury isotopes during photochemical reduction in freshwater systems

    NASA Astrophysics Data System (ADS)

    Rose, C. H.; Bergquist, B. A.; Blum, J. D.

    2009-12-01

    Mercury is a globally distributed environmental toxin. Both inorganic and methylated species have severe detrimental effects on humans and animals, but it is methyl mercury (MeHg) that bioaccumulates in food webs and results in significant human exposure via fish consumption. Photochemical reduction of aqueous Hg species to dissolved gaseous Hg(0) can result in a net transfer of Hg from aquatic systems to the atmosphere, making it unavailable for methylation. In addition, photo-reduction of MeHg is an alternative fate to bioaccumulation for this powerful neurotoxin. Both mass-dependent isotope fractionation (MDF) and mass-independent fractionation (MIF) are observed in natural samples. MIF is the deviation in isotope ratios from those predicted by MDF based on 202Hg/198Hg. Bergquist and Blum 2007 showed that aqueous photo-reduction of Hg2+ and MeHg in the presence of dissolved natural organic matter results not only in Rayleigh-type MDF but also significant MIF, with the odd isotopes 199Hg and 201Hg being preferentially retained in the reactant (soluble) phase. Berquist and Blum 2007 also observed that the ratio of the MIF for the odd isotopes was different for each of the photo-reduction pathways (MeHg versus Hg2+) and suggested this ratio could be unique to certain pathways, which might allow identification of photo-reduction among other pathways in natural samples. They also suggested that the magnitude of MIF might relate quantitatively to the amount of photo-reduction Hg undergoes in aqueous systems. To better understand the causes of MIF and its capacity along with MDF as a tool for tracing photo-reduction of Hg, further experiments mimicking the freshwater photo-reduction of Hg2+ and MeHg were carried out. Each species was photo-reduced in the presence of Suwannee River Fulvic Acid with different portions of the electromagnetic spectrum blocked by filters. Bergquist and Blum 2007 suggested the magnetic isotope effect (MIE) as the cause of the MIF they

  20. Dissolved inorganic carbon isotopic composition of the Gulf of Mexico deep-water masses.

    NASA Astrophysics Data System (ADS)

    Quintanilla-Terminel, J. G.; Herguera, J. C.; Ferreira-Bartrina, V.; Hernández-Ayón, J. M.; Camacho-Ibar, V.

    2014-12-01

    This study provides new data for the establishment of a carbon biogeochemical dynamics baseline in the deep Gulf of Mexico (GM) based on carbon isotopes in dissolved inorganic carbon. Water samples from 40 deep-water stations south of 25˚N were collected during XIXIMI-2 cruise, July 2011, aboard BO/Justo Sierra. Vertical profiles of temperature, salinity and dissolved oxygen (DO) were further measured in each station. In the Stable Isotopes Laboratory at CICESE we determined the carbon isotopic composition of the dissolved inorganic carbon (DIC) (δ13CDIC). Remarkably, density, DO and δ13CCID profiles showed a clear difference between the Loop current and the deep-waters of the GM south of 25˚N. We found the following average δ13CCID values in the Loop current and in the deep-waters of the Gulf: subtropical underwater (SUW): 0.73±0.06‰ and 0.86±0.04‰; 18 degree water (18W): 0.76 ± 0.08‰ and 0.58± 0.06‰; North Atlantic central water (NACW): 0.77 ± 0.05‰ and 0.71 ± 0.09‰; South Atlantic central water (SACW): 0.80 ± 0.08‰ and 0.77 ± 0.07‰; Antartic intermediate water (AAIW): 1.00 ± 0.06‰ and 0.90 ± 0.08‰; North Atlantic deep water (NADW): 1.03 ± 0.06‰ and 1.01 ± 0.10‰. We will discuss how the biological component, δ13CCID-BIO, of subsurface water masses match very closely the apparent oxygen utilization relation described by Kroopnick, 1985, with the exception of SUW, and as a consequence the 18W is probably the water mass most affected by organic carbon remineralization processes in the GM south of 25˚N. We further show how these waters seem to store a larger proportion of anthropogenic carbon than the deeper water masses.

  1. Mass-47 clumped isotope thermal history reordering: Example from the Greater Green River basin

    NASA Astrophysics Data System (ADS)

    Lacroix, B.; Niemi, N. A.

    2015-12-01

    During the last several years, many studies have tried to reconstruct the paleoelevations of sedimentary basins and paleosol sequences using the mass-47 clumped isotope thermometer. Ideally, this technique directly preserves the temperature of carbonate formation, avoiding any speculation on the composition of surface or water from which the carbonate precipitated. Recently, however, concerns about post-depositional alteration of the mass-47 isotope signature, due to the effects of burial, O and C volume diffusion, and/or diagenetic alteration have arisen, potentially complicating the application of the clumped thermometer for determining paleo-surface conditions. Here we investigate the effect of burial depth on mass-47 bond reordering. To this purpose we collected samples, from the surface and from drill cores, in two different areas of the Greater Green River basin: the Washakie Basin near Rock Springs, Wyoming and Green River basin near Pinedale, Wyoming. Both basins are filled with a thick Eocene lacustrine series that include numerous limestone beds. The thermal histories of the basins are well documented from petroleum prospecting studies. The Δ47 composition of lacustrine limestones with peak burial depths ranging from 1 to 6 km have been measured and compared to values derived from temperature history reordering models (THRMs). These results show that the THRMs does not predict the observed clumped isotope composition, suggesting than parameters other than temperature are controlling the Δ47 reordering. In order to refine the predictive model, we propose to independently model the best k0 factor of each analyzed sample starting from their final measured Δ47 values and implementing the thermal history from current depth to the period of deposition. Resulting k0 values are surprisingly well correlated with depth, suggesting that pressure and/or depth have a strong influence on the k0factor, and consequently on Δ47 bond reordering. These results suggest

  2. Oxygen Isotope Mass-Balance Constraints on Pliocene Sea Level and East Antarctic Ice Sheet Stability

    NASA Astrophysics Data System (ADS)

    Winnick, M. J.; Caves, J. K.

    2015-12-01

    The mid-Pliocene Warm Period (MPWP, 3.3-2.9 Ma), with reconstructed atmospheric pCO2 of 350-450 ppm, represents a potential analogue for climate change in the near future. Current highly cited estimates place MPWP maximum global mean sea level (GMSL) at 21 ± 10 m above modern, requiring total loss of the Greenland (GIS) and marine West Antarctic Ice Sheets (WAIS) and a substantial loss of the East Antarctic Ice Sheet (EAIS), with only a concurrent 2-3 ºC rise in global temperature. Many estimates of Pliocene GMSL are based on the partitioning of oxygen isotope records from benthic foraminifera (δ18Ob) into changes in deep-sea temperatures and terrestrial ice sheets. These isotopic budgets are underpinned by the assumption that the δ18O of Antarctic ice (δ18Oi) was the same in the Pliocene as it is today, and while the sensitivity of δ18Ob to changing meltwater δ18O has been previously considered, these analyses neglect conservation of 18O/16O in the ocean-ice system. Using well-calibrated δ18O-temperature relationships for Antarctic precipitation along with estimates of Pliocene Antarctic surface temperatures, we argue that the δ18Oi of the Pliocene Antarctic ice sheet was at minimum 1‰-4‰ higher than present. Assuming conservation of 18O/16O in the ocean-ice system, this requires lower Pliocene seawater δ18O (δ18Osw) without a corresponding change in ice sheet mass. This effect alone accounts for 5%-20% of the δ18Ob difference between the MPWP interglacials and the modern. With this amended isotope budget, we suggest that Pliocene GMSL was likely 9-13.5 m and very likely 5-17 m above modern, which suggests the EAIS is less sensitive to radiative forcing than previously inferred from the geologic record.

  3. Can Lightning Produce Significant Levels of Mass-Independent Oxygen Isotopic Fractionation in Nebular Dust?

    NASA Technical Reports Server (NTRS)

    Nuth, Joseph A.; Paquette, John A.; Farquhar, Adam

    2012-01-01

    Based on recent evidence that oxide grains condensed from a plasma will contain oxygen that is mass independently fractionated compared to the initial composition of the vapor, we present a first attempt to evaluate the potential magnitude of this effect on dust in the primitive solar nebula. This assessment relies on previous studies of nebular lightning to provide reasonable ranges of physical parameters to form a very simple model to evaluate the plausibility that lightning could affect a significant fraction of nebular dust and that such effects could cause a significant change in the oxygen isotopic composition of solids in the solar nebula over time. If only a small fraction of the accretion energy is dissipated as lightning over the volume of the inner solar nebula, then a large fraction of nebular dust will be exposed to lightning. If the temperature of such bolts is a few percent of the temperatures measured in terrestrial discharges, then dust will vaporize and recondense in an ionized environment. Finally, if only a small average decrease is assumed in the O-16 content of freshly condensed dust, then over the last 5 million years of nebular accretion the average delta O-17 of the dust could increase by more than 30 per mil. We conclude that it is possible that the measured " slope 1" oxygen isotope line measured in meteorites and their components represents a time-evolution sequence of nebular dust over the last several million years of nebular evolution O-16-rich materials formed first, then escaped further processing as the average isotopic composition of the dust graduaUy became increasingly depleted in O-16 .

  4. Stable isotope labeling - Liquid chromatography/mass spectrometry for quantitative analysis of androgenic and progestagenic steroids.

    PubMed

    Guo, Ning; Liu, Ping; Ding, Jun; Zheng, Shu-Jian; Yuan, Bi-Feng; Feng, Yu-Qi

    2016-01-28

    Steroid hormones play important roles in mammal at very low concentrations and are associated with numerous endocrinology and oncology diseases. Therefore, quantitative analysis of steroid hormones can provide crucial information for uncovering underlying mechanisms of steroid hormones related diseases. In the current study, we developed a sensitive method for the detection of steroid hormones (progesterone, dehydroepiandrosterone, testosterone, pregnenolone, 17-hydroxyprogesterone, androstenedione and 17α-hydroxypregnenolone) in body fluids by stable isotope labeling coupled with liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS/MS) analysis. In this respect, a pair of isotopes labeling reagents, Girard reagent P (GP) and d5-Girard reagent P (d5-GP), were synthesized and utilized to label steroid hormones in follicular fluid samples and steroid hormone standards, respectively. The heavy labeled standards were used as internal standards for quantification to minimize quantitation deviation in MS analysis due to the matrix and ion suppression effects. The ionization efficiencies of steroid hormones were greatly improved by 4-504 folds through the introduction of a permanent charged moiety of quaternary ammonium from GP. Using the developed method, we successfully quantified steroid hormones in human follicular fluid. We found that the contents of testosterone and androstenedione exhibited significant increase while the content of pregnenolone had significant decrease in follicular fluid of polycystic ovarian syndrome (PCOS) patients compared with healthy controls, indicating that these steroid hormones with significant change may contribute to the pathogenesis of PCOS. Taken together, the developed stable isotope labeling coupled LC-ESI-MS/MS analysis demonstrated to be a promising method for the sensitive and accurate determination of steroid hormones, which may facilitate the in-depth investigation of steroid hormones related

  5. Authenticity of carbon dioxide bubbles in French ciders through multiflow-isotope ratio mass spectrometry measurements.

    PubMed

    Gaillard, Laetitia; Guyon, Francois; Salagoïty, Marie-Hélène; Médina, Bernard

    2013-12-01

    A procedure to detect whether carbon dioxide was added to French ciders has been developed. For this purpose, an optimised and simplified method is proposed to determine (13)C/(12)C isotope ratio of carbon dioxide (δ(13)C) in ciders. Three critical steps were checked: (1) influence of atmospheric CO2 remaining in the loaded vial, (2) impact of helium flush, (3) sampling speed. This study showed that atmospheric CO2 does not impact the measurement, that helium flush can lead to isotopic fractionation and finally, that a fractionation occurs only 5h after bottle opening. The method, without any other preparation, consists in sampling 0.2 mL of cold (4 °C) cider in a vial that is passed in an ultrasonic bath for 10 min at room temperature to enhance cider de-carbonation. The headspace CO2 is then analysed using the link Multiflow®-isotope ratio mass spectrometer. Each year, a data bank is developed by fermenting authentic apples juices in order to control cider authenticity. Over a four year span (2008-2011), the CO2 produced during the fermentation step was studied. This set of 61 authentic ciders, from various French production areas, was used to determine a δ(13)C value range of -22.59±0.92‰ for authentic ciders CO2 bubbles. 75 commercial ciders were analysed with this method. Most of the samples analysed present a gas δ(13)C value in the expected range. Nevertheless, some ciders have δ(13)C values outside the 3σ limit, revealing carbonation by technical CO2. This practice is not allowed for organic, "Controlled Appellation of Origin" ciders and ciders specifying natural carbonation on the label. PMID:23870934

  6. Using Lanthanide Nanoparticles as Isotopic Tags for Biomarker Detection by Mass Cytometry

    NASA Astrophysics Data System (ADS)

    Cao, Pengpeng

    The development of robust, versatile, and high-throughput biosensing techniques has widespread implications for early disease detection and accurate diagnosis. An innovative technology, mass cytometry, has been developed to use isotopically-labelled antibodies to simultaneously study multiple parameters of single cells. The current detection sensitivity of mass cytometry is limited by the number of copies of a given isotope that can be attached to a given antibody. This thesis describes research on the synthesis, characterization, and bioconjugation of a new class of nanoparticle-based labelling agents to be employed for the detection of low-abundance biomarkers by mass cytometry. Hydrophobic lanthanide nanoparticles (Ln NPs) have been prepared by the Winnik group. To render the NPs water-soluble for biological applications, we coated the NP surface with a first generation of multidentate poly(ethylene glycol) (PEG)-based ligands via ligand exchange. We measured the size, morphology, and polydispersity of these hydrophilic NPs by transmission electron microscopy (TEM) and dynamic light scattering (DLS). The colloidal stability of the NPs was determined at various pH and in phosphate buffered saline (PBS) solutions. Tetradentate-PEG-coated NPs (Tetra-NPs) exhibited the best stability at pH 3 to 9, and in PBS. However, when cells were treated with Tetra-NPs in preliminary in vitro studies, significant undesirable non-specific binding (NSB) was observed. In order to tackle the NSB issue presented in the Tetra-NPs, we prepared a second generation of polymer-based ligands using ring-opening metathesis polymerization (ROMP). A small library of ROMP polymers was synthesized, characterized, and used to stabilize NPs in aqueous solutions. The ROMP-NPs were found to have significantly reduced NSB to cells by inductively coupled plasma-mass spectrometry (ICP-MS). To further modify the NPs, amine groups were introduced as functional handles to both the tetradentate-PEG and

  7. Estimating ground-water inflow to lakes in central Florida using the isotope mass-balance approach

    USGS Publications Warehouse

    Sacks, Laura A.

    2002-01-01

    The isotope mass-balance approach was used to estimate ground-water inflow to 81 lakes in the central highlands and coastal lowlands of central Florida. The study area is characterized by a subtropical climate and numerous lakes in a mantled karst terrain. Ground-water inflow was computed using both steady-state and transient formulations of the isotope mass-balance equation. More detailed data were collected from two study lakes, including climatic, hydrologic, and isotopic (hydrogen and oxygen isotope ratio) data. For one of these lakes (Lake Starr), ground-water inflow was independently computed from a water-budget study. Climatic and isotopic data collected from the two lakes were similar even though they were in different physiographic settings about 60 miles apart. Isotopic data from all of the study lakes plotted on an evaporation trend line, which had a very similar slope to the theoretical slope computed for Lake Starr. These similarities suggest that data collected from the detailed study lakes can be extrapolated to the rest of the study area. Ground-water inflow computed using the isotope mass-balance approach ranged from 0 to more than 260 inches per year (or 0 to more than 80 percent of total inflows). Steady-state and transient estimates of ground-water inflow were very similar. Computed ground-water inflow was most sensitive to uncertainty in variables used to calculate the isotopic composition of lake evaporate (isotopic compositions of lake water and atmospheric moisture and climatic variables). Transient results were particularly sensitive to changes in the isotopic composition of lake water. Uncertainty in ground-water inflow results is considerably less for lakes with higher ground-water inflow than for lakes with lower ground-water inflow. Because of these uncertainties, the isotope mass-balance approach is better used to distinguish whether ground-water inflow quantities fall within certain ranges of values, rather than for precise

  8. Developing New Isotope-Coded Mass Spectrometry-Cleavable Cross-Linkers for Elucidating Protein Structures

    PubMed Central

    2015-01-01

    Structural characterization of protein complexes is essential for the understanding of their function and regulation. However, it remains challenging due to limitations in existing tools. With recent technological improvements, cross-linking mass spectrometry (XL-MS) has become a powerful strategy to define protein–protein interactions and elucidate structural topologies of protein complexes. To further advance XL-MS studies, we present here the development of new isotope-coded MS-cleavable homobifunctional cross-linkers: d0- and d10-labeled dimethyl disuccinimidyl sulfoxide (DMDSSO). Detailed characterization of DMDSSO cross-linked peptides further demonstrates that sulfoxide-containing MS-cleavable cross-linkers offer robust and predictable MS2 fragmentation of cross-linked peptides, permitting subsequent MS3 analysis for simplified, unambiguous identification. Concurrent usage of these reagents provides a characteristic doublet pattern of DMDSSO cross-linked peptides, thus aiding in the confidence of cross-link identification by MSn analysis. More importantly, the unique isotopic profile permits quantitative analysis of cross-linked peptides and therefore expands the capability of XL-MS strategies to analyze both static and dynamic protein interactions. Together, our work has established a new XL-MS workflow for future studies toward the understanding of structural dynamics of protein complexes. PMID:24471733

  9. Developing new isotope-coded mass spectrometry-cleavable cross-linkers for elucidating protein structures.

    PubMed

    Yu, Clinton; Kandur, Wynne; Kao, Athit; Rychnovsky, Scott; Huang, Lan

    2014-02-18

    Structural characterization of protein complexes is essential for the understanding of their function and regulation. However, it remains challenging due to limitations in existing tools. With recent technological improvements, cross-linking mass spectrometry (XL-MS) has become a powerful strategy to define protein-protein interactions and elucidate structural topologies of protein complexes. To further advance XL-MS studies, we present here the development of new isotope-coded MS-cleavable homobifunctional cross-linkers: d0- and d10-labeled dimethyl disuccinimidyl sulfoxide (DMDSSO). Detailed characterization of DMDSSO cross-linked peptides further demonstrates that sulfoxide-containing MS-cleavable cross-linkers offer robust and predictable MS2 fragmentation of cross-linked peptides, permitting subsequent MS3 analysis for simplified, unambiguous identification. Concurrent usage of these reagents provides a characteristic doublet pattern of DMDSSO cross-linked peptides, thus aiding in the confidence of cross-link identification by MS(n) analysis. More importantly, the unique isotopic profile permits quantitative analysis of cross-linked peptides and therefore expands the capability of XL-MS strategies to analyze both static and dynamic protein interactions. Together, our work has established a new XL-MS workflow for future studies toward the understanding of structural dynamics of protein complexes. PMID:24471733

  10. Determination of Phytochelatins in Rice by Stable Isotope Labeling Coupled with Liquid Chromatography-Mass Spectrometry.

    PubMed

    Liu, Ping; Cai, Wen-Jing; Yu, Lei; Yuan, Bi-Feng; Feng, Yu-Qi

    2015-07-01

    A highly sensitive method was developed for the detection of phytochelatins (PCs) in rice by stable isotope labeling coupled with liquid chromatography-electrospray ionization-tandem mass spectrometry (IL-LC-ESI-MS/MS) analysis. A pair of isotope-labeling reagents [ω-bromoacetonylquinolinium bromide (BQB) and BQB-d(7)] were used to label PCs in plant sample and standard PCs, respectively, and then combined prior to LC/MS analysis. The heavy labeled standards were used as the internal standards for quantitation to minimize the matrix and ion suppression effects in MS analysis. In addition, the ionization efficiency of PCs was greatly enhanced through the introduction of a permanent charged moiety of quaternary ammonium of BQB into PCs. The detection sensitivities of PCs upon BQB labeling improved by 14-750-fold, and therefore, PCs can be quantitated using only 5 mg of plant tissue. Furthermore, under cadmium (Cd) stress, we found that the contents of PCs in rice dramatically increased with the increased concentrations and treatment time of Cd. It was worth noting that PC5 was first identified and quantitated in rice tissues under Cd stress in the current study. Taken together, this IL-LC-ESI-MS/MS method demonstrated to be a promising strategy in detection of PCs in plants with high sensitivity and reliability. PMID:26073168

  11. Carbon and Isotopic Mass Balance Models of Oasis Valley-Fortymile Canyon Groundwater Basin, Southern Nevada

    NASA Astrophysics Data System (ADS)

    White, Art F.; Chuma, Nancy J.

    1987-04-01

    Environmental isotopes and carbon chemistry provide means of differentiating various recharge areas, flow paths, and ages of groundwater in portions of the Nevada Test Site and vicinity. Regional δD/δ18O trends are offset from the present-day meteoric line by a deuterium depletion of 5‰, suggesting paleoclimatic changes. Partial pressures of CO2 and the 18O and 13C data indicate solubility and isotopic equilibrium between the gas and water in the soil zone with progressive exchange with underlying groundwater in the shallow alluvium of Oasis Valley. Application of a closed system CO2 model using the EQ3NR/EQ6 reaction path simulator successfully reproduces chemical compositions observed in the alluvium in the Amargosa Desert and in the deep tuff aquifer beneath Pahute Mesa and Yucca Mountain. Initial PCO2 input to the soil zone during recharge was calculated to range from 0.03 to 0.10 atm, which is comparable to measured soil CO2 pressures in Oasis Valley. Results are compared for 14C ages using the δ13C dilution correction and a mass action correction term relating predicted and calculated ionic activity products of CaCO3. Results are generally comparable with discrepancies attributed to anomalous δ13C values.

  12. Precision mass measurements of some isotopes of tungsten and mercury for an adjustment to the mass table in the region A = 184 to A = 204

    NASA Astrophysics Data System (ADS)

    Barillari, Domenico K.

    This thesis concerns the precise re-measurement of mass values in the region of the mercury isotopes, such that important discrepancies in the high-mass end of the mass table could be resolved. Scope and contents. Four mass spectroscopic doublets involving a comparison between 201Hg, 199Hg and 183W (and using a chlorocarbon reference) are reported from measurements made with the upgraded Manitoba 11 deflection instrument. The measurements address the problem of a mass table mis-adjustment in the region of the valley of β-stability between the tungsten group and the noble metals. The results, forming a well-closed loop of mass differences, support the earlier results of Kozier [Ko(1977)] regarding the (stable) mercury isotope masses and confirm an approximate 20 μu discrepancy in the mass adjustment of Audi et al [Au(1993)]. A local least- square re-adjustment conducted using these and existing mass table data suggests that the error originates with mass differences pertaining to one or more other nuclide pairs, perhaps 193Ir-192Ir. The work on upgrading the precision voltage supply and potentiometry system of the Manitoba II instrument is also reported, as is a new assessment on the data processing method. (Abstract shortened by UMI.)

  13. Results from the NSCL TOF Mass Measurement of Neutron-rich Isotopes of Argon through Iron

    NASA Astrophysics Data System (ADS)

    Meisel, Zachary; George, Sebastian; NSCL TOF Collaboration

    2015-04-01

    A recent experiment at the National Superconducting Cyclotron Laboratory has resulted in an extension of the nuclear mass surface for neutron-rich isotopes of argon through iron. The time-of-flight technique was employed to experimentally determine the masses of several nuclei for the first time. Results include the identification of argon as the lowest even- Z element exhibiting the N = 28 shell closure, as well the uncovering of a relatively small odd-even mass stagger between 56 Ti and 56 Sc. The latter result yields strong Urca cooling when implemented in a state-of-the-art accreted neutron star crust reaction network. A strong 56 Ti-56 Sc Urca neutrino cooling layer makes shallow neutrino cooling in the crust of accreting neutron stars a strong and robust effect due to the copious production of A = 56 material in thermonuclear burning processes that occur at the accreted neutron star surface. This project is funded by the NSF through Grants 247 No. PHY-0822648, PHY-1102511, PHY-1404442, and 248 No. PHY-1430152. S.G. acknowledges support from 249 the DFG under Contracts No. GE2183/1-1 and No. 250 GE2183/2-1.

  14. An interlaboratory study to test instrument performance of hydrogen dual-inlet isotope-ratio mass spectrometers

    USGS Publications Warehouse

    Brand, Willi A.; Coplen, T.B.

    2001-01-01

    An interlaboratory comparison of forty isotope-ratio mass spectrometers of different ages from several vendors has been performed to test 2H/1H performance with hydrogen gases of three different isotopic compositions. The isotope-ratio results (unsufficiently corrected for H3+ contribution to the m/z = 3 collector, uncorrected for valve leakage in the change-over valves, etc.) expressed relative to one of these three gases covered a wide range of values: -630??? to -790??? for the second gas and -368??? to -462??? for the third gas. After normalizing the isotopic abundances of these test gases (linearly adjusting the ?? values so that the gases with the lowest and highest 2H content were identical for all laboratories), the standard deviation of the 40 measurements of the intermediate gas was a remarkably low 0.85???. It is concluded that the use of scaling factors is mandatory for providing accurate internationally comparable isotope-abundance values. Linear scaling for the isotope-ratio scales of gaseous hydrogen mass spectrometers is completely adequate. ?? Springer-Verlag 2001.

  15. 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).

  16. Quantification of four artificial sweeteners in Finnish surface waters with isotope-dilution mass spectrometry.

    PubMed

    Perkola, Noora; Sainio, Pirjo

    2014-01-01

    The artificial sweeteners sucralose (SCL), acesulfame (ACS), saccharin (SAC), and cyclamate (CYC) have been detected in environmental waters in Europe and North America. Higher environmental levels are expected in view of the increasing consumption of these food additives. In this study, an isotope-dilution mass spectrometry (IDMS) LC-MS/MS method was developed and validated for quantifying the four artificial sweeteners in boreal lakes (n = 3) and rivers (n = 12). The highest concentrations of ACS, SAC, CYC and SCL were 9,600, 490, 210 and 1000 ng/L, respectively. ACS and SAC were detected in all studied samples, and CYC and SCL in 98% and 56% of the samples. Seasonal trends of ACS and SAC were observed in some rivers. ACS and SCL concentrations in rivers correlated linearly with population equivalents of the wastewater treatment plants in the catchment areas, whereas SAC and CYC concentrations depend more on the source. PMID:24100049

  17. A study of xenon isotopes in a martian meteorite using the RELAX ultrasensitive mass spectrometer

    SciTech Connect

    Whitby, J A; Gilmour, J D; Turner, G

    1997-01-15

    The Refrigerator Enhanced Analyser for Xenon (RELAX), an ultrasensitive resonance ionization time-of-flight mass spectrometer, has been used with a laser microprobe to investigate the isotopic composition of xenon trapped in the martian meteorite ALH84001. The laser microprobe has a spatial resolution of the order of 100{mu}m thus allowing the in situ analysis of individual mineral grains in a polished section when combined with ultrasensitive, low blank sample analysis. We present results showing that the mineral orthopyroxene in ALH84001 contains a trapped xenon component consistent with a martian origin. Additionally, a cosmic ray exposure age of 15Ma for ALH84001 is obtained from spallation derived xenon trapped within an apatite grain.

  18. Ion exchange separation of chromium from natural water matrix for stable isotope mass spectrometric analysis

    USGS Publications Warehouse

    Ball, J.W.; Bassett, R.L.

    2000-01-01

    A method has been developed for separating the Cr dissolved in natural water from matrix elements and determination of its stable isotope ratios using solid-source thermal-ionization mass spectrometry (TIMS). The separation method takes advantage of the existence of the oxidized form of Cr as an oxyanion to separate it from interfering cations using anion-exchange chromatography, and of the reduced form of Cr as a positively charged ion to separate it from interfering anions such as sulfate. Subsequent processing of the separated sample eliminates residual organic material for application to a solid source filament. Ratios for 53Cr/52Cr for National Institute of Standards and Technology Standard Reference Material 979 can be measured using the silica gel-boric acid technique with a filament-to-filament standard deviation in the mean 53Cr/52Cr ratio for 50 replicates of 0.00005 or less. (C) 2000 Elsevier Science B.V. All rights reserved.

  19. Volcanism, mass extinction, and carbon isotope fluctuations in the Middle Permian of China.

    PubMed

    Wignall, Paul B; Sun, Yadong; Bond, David P G; Izon, Gareth; Newton, Robert J; Védrine, Stéphanie; Widdowson, Mike; Ali, Jason R; Lai, Xulong; Jiang, Haishui; Cope, Helen; Bottrell, Simon H

    2009-05-29

    The 260-million-year-old Emeishan volcanic province of southwest China overlies and is interbedded with Middle Permian carbonates that contain a record of the Guadalupian mass extinction. Sections in the region thus provide an opportunity to directly monitor the relative timing of extinction and volcanism within the same locations. These show that the onset of volcanism was marked by both large phreatomagmatic eruptions and extinctions amongst fusulinacean foraminifers and calcareous algae. The temporal coincidence of these two phenomena supports the idea of a cause-and-effect relationship. The crisis predates the onset of a major negative carbon isotope excursion that points to subsequent severe disturbance of the ocean-atmosphere carbon cycle. PMID:19478179

  20. Volcanism, Mass Extinction, and Carbon Isotope Fluctuations in the Middle Permian of China

    NASA Astrophysics Data System (ADS)

    Wignall, Paul B.; Sun, Yadong; Bond, David P. G.; Izon, Gareth; Newton, Robert J.; Védrine, Stéphanie; Widdowson, Mike; Ali, Jason R.; Lai, Xulong; Jiang, Haishui; Cope, Helen; Bottrell, Simon H.

    2009-05-01

    The 260-million-year-old Emeishan volcanic province of southwest China overlies and is interbedded with Middle Permian carbonates that contain a record of the Guadalupian mass extinction. Sections in the region thus provide an opportunity to directly monitor the relative timing of extinction and volcanism within the same locations. These show that the onset of volcanism was marked by both large phreatomagmatic eruptions and extinctions amongst fusulinacean foraminifers and calcareous algae. The temporal coincidence of these two phenomena supports the idea of a cause-and-effect relationship. The crisis predates the onset of a major negative carbon isotope excursion that points to subsequent severe disturbance of the ocean-atmosphere carbon cycle.

  1. 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.

  2. Biomedical applications of accelerator mass spectrometry-isotope measurements at the level of the atom.

    PubMed

    Barker, J; Garner, R C

    1999-01-01

    Accelerator mass spectrometry (AMS) is a nuclear physics technique developed about twenty years ago, that uses the high energy (several MeV) of a tandem Van de Graaff accelerator to measure very small quantities of rare and long-lived isotopes. Elements that are of interest in biomedicine and environmental sciences can be measured, often to parts per quadrillion sensitivity, i.e. zeptomole to attomole levels (10(-21)-10(-18) mole) from milligram samples. This is several orders of magnitude lower than that achievable by conventional decay counting techniques, such as liquid scintillation counting (LSC). AMS was first applied to geochemical, climatological and archaeological areas, such as for radiocarbon dating (Shroud of Turin), but more recently this technology has been used for bioanalytical applications. In this sphere, most work has been conducted using aluminium, calcium and carbon isotopes. The latter is of special interest in drug metabolism studies, where a Phase 1 adsorption, distribution, metabolism and excretion (ADME) study can be conducted using only 10 nanoCurie (37 Bq or ca. 0.9 microSv) amounts or less of 14C-labelled drugs. In the UK, these amounts of radioactivity are below those necessary to request specific regulatory approval from the Department of Health's Administration of Radioactive Substances Advisory Committee (ARSAC), thus saving on valuable development time and resources. In addition, the disposal of these amounts is much less an environmental issue than that associated with microCurie quantities, which are currently used. Also, AMS should bring an opportunity to conduct "first into man" studies without the need for widespread use of animals. Centre for Biomedical Accelerator Mass Spectrometry (CBAMS) Ltd. is the first fully commercial company in the world to offer analytical services using AMS. With its high throughput and relatively low costs per sample analysis, AMS should be of great benefit to the pharmaceutical and biotechnology

  3. Quantification of ferritin bound iron in human serum using species-specific isotope dilution mass spectrometry.

    PubMed

    Ren, Yao; Walczyk, Thomas

    2014-09-01

    Ferritin is a hollow sphere protein composed of 24 subunits that can store up to 4500 iron atoms in its inner cavity. It is mainly found in the liver and spleen but also in serum at trace levels. Serum ferritin is considered as the best single indicator in assessing body iron stores except liver or bone marrow biopsy. However, it is confounded by other disease conditions. Ferritin bound iron (FBI) and ferritin saturation have been suggested as more robust biomarkers. The current techniques for FBI determination are limited by low antibody specificity, low instrument sensitivity and possible analyte losses during sample preparation. The need for a highly sensitive and reliable method is widely recognized. Here we describe a novel technique to detect serum FBI using species-specific isotope dilution mass spectrometry (SS-IDMS). [(57)Fe]-ferritin was produced by biosynthesis and in vitro labeling with the (57)Fe spike in the form of [(57)Fe]-citrate after cell lysis and heat treatment. [(57)Fe]-ferritin for sample spiking was further purified by fast liquid protein chromatography. Serum ferritin and added [(57)Fe]-ferritin were separated from other iron species by ultrafiltration followed by isotopic analysis of FBI using negative thermal ionization mass spectrometry. Repeatability of our assay is 8% with an absolute detection limit of 18 ng FBI in the sample. As compared to other speciation techniques, SS-IDMS offers maximum control over sample losses and species conversion during analysis. The described technique may therefore serve as a reference technique for clinical applications of FBI as a new biomarker for assessing body iron status. PMID:25008269

  4. Systematic quantification of complex metabolic flux networks using stable isotopes and mass spectrometry.

    PubMed

    Klapa, Maria I; Aon, Juan-Carlos; Stephanopoulos, Gregory

    2003-09-01

    Metabolic fluxes provide a detailed metric of the cellular metabolic phenotype. Fluxes are estimated indirectly from available measurements and various methods have been developed for this purpose. Of particular interest are methods making use of stable isotopic tracers as they enable the estimation of fluxes at a high resolution. In this paper, we present data validating the use of mass spectrometry (MS) for the quantification of complex metabolic flux networks. In the context of the lysine biosynthesis flux network of Corynebacterium glutamicum (ATCC 21799) under glucose limitation in continuous culture, operating at 0.1 x h(-1) after the introduction of 50% [1-13C]glucose, we deploy a bioreaction network analysis methodology for flux determination from mass isotopomer measurements of biomass hydrolysates, while thoroughly addressing the issues of measurement accuracy, flux observability and data reconciliation. The analysis enabled the resolution of the involved anaplerotic activity of the microorganism using only one labeled substrate, the determination of the range of most of the exchange fluxes and the validation of the flux estimates through satisfaction of redundancies. Specifically, we determined that phosphoenolpyruvate carboxykinase and synthase do not carry flux at these experimental conditions and identified a high futile cycle between oxaloacetate and pyruvate, indicating a highly active in vivo oxaloacetate decarboxylase. Both results validated previous in vitro activity measurements. The flux estimates obtained passed the chi2 statistical test. This is a very important result considering that prior flux analyses of extensive metabolic networks from isotopic measurements have failed criteria of statistical consistency. PMID:12919317

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

    DOE PAGESBeta

    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 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

  6. 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,

  7. 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.

  8. Relativistic mean-field study of the properties of Z=117 nuclei and the decay chains of the {sup 293,294}117 isotopes

    SciTech Connect

    Bhuyan, M.; Patra, S. K.; Gupta, Raj K.

    2011-07-15

    We have calculated the binding energy, root-mean-square radius, and quadrupole deformation parameter for the recently synthesized superheavy element Z=117, using the axially deformed relativistic mean-field (RMF) model. The calculation is extended to various isotopes of the Z=117 element, starting from A=286 till A=310. We predict almost spherical structures in the ground state for almost all the isotopes. A shape transition appears at about A=292 from a prolate to an oblate shape structure of the Z=117 nucleus in our mean-field approach. The most stable isotope (largest binding energy per nucleon) is found to be the {sup 288}117 nucleus. Also, the Q{sub {alpha}} values and the half-life T{sub 1/2}{sup {alpha}} for the {alpha}-decay chains of {sup 293}117 and {sup 294}117 are calculated, supporting the magic numbers at N=172 and/or 184.

  9. Inductively Coupled Plasma/Mass Spectrometric Isotopic Determination of Nuclear Wastes Sources Associated with Hanford Tank Leaks

    SciTech Connect

    Evans, John C.; Dresel, P. Evan; Farmer, Orville T.

    2007-11-01

    The subsurface distribution of a nuclear waste tank leak on the U.S. Department of Energy’s Hanford Site was sampled by slant drilling techniques in order to characterize the chemical and radiological characteristics of the leaked material and assess geochemical transport properties of hazardous constituents. Sediment core samples recovered from the borehole were subjected to distilled water and acid leaching procedures with the resulting leachates analyzed for isotopic and chemical signatures. High-sensitivity inductively coupled plasma/mass spectrometry (ICP/MS) techniques were used for determination of isotopic ratios for Cs, I, Mo. Analysis of the isotopic patterns of I and Mo combined with associated chemical data showed evidence for at least two separate intrusions of nuclear waste into the subsurface. Isotopic data for Cs was inconclusive with respect to a source attribution signature.

  10. Compound-specific carbon isotopes from Earth's largest flood basalt eruptions directly linked to the end-Triassic mass extinction.

    PubMed

    Whiteside, Jessica H; Olsen, Paul E; Eglinton, Timothy; Brookfield, Michael E; Sambrotto, Raymond N

    2010-04-13

    A leading hypothesis explaining Phanerozoic mass extinctions and associated carbon isotopic anomalies is the emission of greenhouse, other gases, and aerosols caused by eruptions of continental flood basalt provinces. However, the necessary serial relationship between these eruptions, isotopic excursions, and extinctions has never been tested in geological sections preserving all three records. The end-Triassic extinction (ETE) at 201.4 Ma is among the largest of these extinctions and is tied to a large negative carbon isotope excursion, reflecting perturbations of the carbon cycle including a transient increase in CO(2). The cause of the ETE has been inferred to be the eruption of the giant Central Atlantic magmatic province (CAMP). Here, we show that carbon isotopes of leaf wax derived lipids (n-alkanes), wood, and total organic carbon from two orbitally paced lacustrine sections interbedded with the CAMP in eastern North America show similar excursions to those seen in the mostly marine St. Audrie's Bay section in England. Based on these results, the ETE began synchronously in marine and terrestrial environments slightly before the oldest basalts in eastern North America but simultaneous with the eruption of the oldest flows in Morocco, a CO(2) super greenhouse, and marine biocalcification crisis. Because the temporal relationship between CAMP eruptions, mass extinction, and the carbon isotopic excursions are shown in the same place, this is the strongest case for a volcanic cause of a mass extinction to date. PMID:20308590

  11. Gas-phase Mechanisms of Sulfur Isotope Mass-independent Fractionation

    NASA Astrophysics Data System (ADS)

    Lyons, J. R.

    2006-12-01

    Mass-independent fractionation (MIF) in sulfur isotopes in ancient sulfur-bearing rocks (Farquhar et al. 2000a) is interpreted as evidence for gas-phase MIF processes in the early Earth atmosphere. This interpretation is made by analogy with oxygen isotope MIF in the modern atmosphere (produced during ozone formation), and by laboratory photolysis experiments on SO2 (Farquhar et al. 2001; Wing et al. 2004) that yield both elemental sulfur and sulfate with S MIF signatures at wavelengths above and below the SO2 dissociation limit. What is lacking is a quantitative understanding of the mechanisms of gas-phase S MIF. Quantification is essential in order to extract the full implications of sulfur MIF throughout Earth history, including for bacterial sulfate reduction processes which largely conserve D33S and D36S. Several sulfur MIF mechanisms are possible. The most obvious is the gas-phase thiozone reaction, which is isovalent to the ozone formation reaction. Ozone formation produces a well-known MIF signature in oxygen isotopes (Thiemens and Heidenreich 1983), and a symmetry-dependent non-RRKM mechanism has been proposed as the origin of O MIF (Gao and Marcus 2001). It is possible and perhaps likely that S3 formation also proceeds by a non-RRKM process. Data are lacking on isotopic (an even non-isotopic) rates of S3 formation, so it is not possible to make definitive statements about MIF in S3 at this time. However modeling results suggest that the vapor pressure of S2 is too low for gas-phase S3 formation to be significant. Two additional species that may exhibit a non-RRKM MIF signature are S2O2 and S4. Again, there is a lack of isotopomer-specific kinetic data for these reactions, and gas-phase formation of S4 is likely inconsequential. Perhaps the most obvious mechanism is simply the primary act of SO2 photolysis. The SO2 absorption spectrum is highly structured, with strong vibronic bands above and below the dissociation limit. In contrast H2S, with its mostly

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

    PubMed

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

    2011-09-01

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

  13. Determination of mass-dependent isotopic fractionation of cerium and neodymium in geochemical samples by MC-ICPMS.

    PubMed

    Ohno, Takeshi; Hirata, Takafumi

    2013-01-01

    We have developed a new analytical method to determine the mass-dependent isotopic fractionations on Ce and Nd in geochemical samples. Mass discrimination effects on Ce and Nd were externally corrected by normalizing (149)Sm/(147)Sm and (153)Eu/(151)Eu, being 0.92124 and 1.0916, respectively based on an exponential law. The reproducibility of the isotopic ratio measurements on (142)Ce/(140)Ce, (146)Nd/(144)Nd and (148)Nd/(144)Nd were 0.08‰ (2SD, n = 25), 0.06‰ (2SD, n = 39) and 0.12‰ (2SD, n = 39), respectively. The present technique was applied to determine the variations of the Ce and Nd isotopic ratios for five geochemical reference materials (igneous rocks, JB-1a and JA-2; sedimentary rocks, JMn-1, JCh-1 and JDo-1). The resulting ratios for two igneous rocks (JB-1a and JA-2) and two sedimentary rocks (JMn-1 and JCh-1) did not vary significantly among the samples, whereas the Ce and Nd isotope ratios for the carbonate samples (JDo-1) were significantly higher than those for igneous and sedimentary rock samples. The 1:1 simple correlation between δ(142)Ce and δ(146)Nd indicates that there were no significant difference in the degree of isotopic fractionation between the Ce and Nd. This suggests that the isotopic fractionation for Ce found in the JDo-1 could be induced by geochemical or physicochemical processes without changing the oxidation status of Ce, since the redox-reaction can produce larger isotopic fractionation than the reactions without changing the oxidation state. The variations in the Ce and Nd isotope ratios for geochemical samples could provide new information concerning the physico-chemical processes of the sample formation. PMID:23303084

  14. The confines of triple oxygen isotope exponents in elemental and complex mass-dependent processes

    NASA Astrophysics Data System (ADS)

    Bao, Huiming; Cao, Xiaobin; Hayles, Justin A.

    2015-12-01

    Small differences in triple isotope relationships, or Δ17O in the case of oxygen, have been increasingly used to study a range of problems including hydrological cycles, stratosphere-troposphere exchange, biogeochemical pathways and fluxes, and the Moon's origin in the geochemical and cosmochemical communities. A Δ17O value depends on the triple isotope exponent θ of involved reaction steps. However, the probabilistic distribution of the intrinsic and apparent θ values has not been examined for elemental processes and for processes that are out of equilibrium or bearing reservoir-transport complexities. A lack of knowledge on the confines of θ may hamper our understanding of the subtle differences among mass-dependent processes and may result in mischaracterization of a set of mass-dependent processes as being in violation of mass-dependent rules. Here we advocate a reductionist approach and explore θ confines starting from kinetic isotope effects (KIEs) within the framework of transition state theory (TST). The advantage of our KIE approach is that any elemental or composite, equilibrium or non-equilibrium process can be reduced to a set of KIEs with corresponding θKIE. We establish that the KIE between a reactant and a transition state (TS) is intrinsic. Given a range of KIEs known for Earth processes involving oxygen, we use a Monte Carlo calculation method and a range of oxygen-bonded molecular masses to obtain a distribution of θKIE values and subsequently that of θeq. Next, complexities are examined by looking into expected effects due to reaction progress, unbalanced fluxes, and reference frame. Finally, compounded reservoir-transport effects are examined using two simple processes - Rayleigh Distillation (RD) and Fractional Distillation (FD). Our results show that the apparent θ values between two species or two states of the same evolving species have much broader confines than the commonly used "canonical" confines of 0.51-0.53, particularly

  15. Evolution of nuclear ground-state properties of neutron-deficient isotopes around Z =82 from precision mass measurements

    NASA Astrophysics Data System (ADS)

    Böhm, Ch.; Borgmann, Ch.; Audi, G.; Beck, D.; Blaum, K.; Breitenfeldt, M.; Cakirli, R. B.; Cocolios, T. E.; Eliseev, S.; George, S.; Herfurth, F.; Herlert, A.; Kowalska, M.; Kreim, S.; Lunney, D.; Manea, V.; Minaya Ramirez, E.; Naimi, S.; Neidherr, D.; Rosenbusch, M.; Schweikhard, L.; Stanja, J.; Wang, M.; Wolf, R. N.; Zuber, K.

    2014-10-01

    High-precision mass measurements of neutron-deficient Tl (A =184, 186, 190, 193-195, 198) isotopes as well as Pb (A =202,208), Fr (A =207,208), and Ra (A =224) are performed with the Penning-trap mass spectrometer ISOLTRAP at ISOLDE/CERN. The improved precision of the mass data now allows the study of subtle odd-even effects. The gradual development of collectivity with the removal of protons from the magic Z =82 core is analyzed by combining the new mass results with nuclear charge-radii data and mean-field model predictions.

  16. Synthesis of deuterium-labeled 17-hydroxyprogesterone suitable as an internal standard for isotope dilution mass spectrometry

    SciTech Connect

    Shimizu, K.; Yamaga, N.; Kohara, H.

    1988-03-01

    A synthesis is reported of 17-hydroxyprogesterone, labeled with four atoms of deuterium at ring C and suitable for use as an internal standard for isotope dilution mass spectrometry. Base-catalyzed equilibration of methyl 3 alpha-acetoxy-12-oxo-cholanate (III) with /sup 2/H/sub 2/O, followed by reduction of the 12-oxo group by the modified Wolff-Kisher method using (/sup 2/H)diethylene glycol and (/sup 2/H)hydrazine hydrate afforded (11,11,12,12,23,23(-2)H)lithocholic acid (V). The Meystre-Miescher degradation of the side chain of V yielded 3 alpha-hydroxy-5 beta-(11,11,12,12(-2)H)pregnan-20-one (X). Oxidation of the 3,20-enol-diacetate of X with perbenzoic acid followed by saponification afforded 3 alpha,17-dihydroxy-5 beta-(11,11,12,12(-2)H)pregnan-20-one (XI). Oxidation of XI with N-bromoacetamide yielded 17-hydroxy-5 beta-(11,11,12,12(-2)H)pregnane-3,20-dione (XII). Bromination of XII followed by dehydrobromination yielded 17-hydroxy-(11,11,12,12(-2)H) progesterone (XIV), consisting of 0.3% /sup 2/H0-, 1.1% /sup 2/H/sub 1/-, 8.6% /sup 2/H/sub 2/-, 37.1% /sup 2/H/sub 3/-, 52.1% /sup 2/H/sub 4/-, and 0.8% /sup 2/H/sub 5/-species.

  17. Stable Isotope Peptide Mass Spectrometry To Decipher Amino Acid Metabolism in Dehalococcoides Strain CBDB1

    PubMed Central

    Marco-Urrea, Ernest; Seifert, Jana; von Bergen, Martin

    2012-01-01

    Dehalococcoides species are key players in the anaerobic transformation of halogenated solvents at contaminated sites. Here, we analyze isotopologue distributions in amino acid pools from peptides of Dehalococcoides strain CBDB1 after incubation with 13C-labeled acetate or bicarbonate as a carbon source. The resulting data were interpreted with regard to genome annotations to identify amino acid biosynthesis pathways. In addition to using gas chromatography-mass spectrometry (GC-MS) for analyzing derivatized amino acids after protein hydrolysis, we introduce a second, much milder method, in which we directly analyze peptide masses after tryptic digest and peptide fragments by nano-liquid chromatography-electrospray ionization-tandem mass spectrometry (nano-LC-ESI-MS/MS). With this method, we identify isotope incorporation patterns for 17 proteinaceous amino acids, including proline, cysteine, lysine, and arginine, which escaped previous analyses in Dehalococcoides. Our results confirmed lysine biosynthesis via the α-aminoadipate pathway, precluding lysine formation from aspartate. Similarly, the isotopologue pattern obtained for arginine provided biochemical evidence of its synthesis from glutamate. Direct peptide MS/MS analysis of the labeling patterns of glutamine and asparagine, which were converted to glutamate and aspartate during protein hydrolysis, gave biochemical evidence of their precursors and confirmed glutamate biosynthesis via a Re-specific citrate synthase. By addition of unlabeled free amino acids to labeled cells, we show that in strain CBDB1 none of the 17 tested amino acids was incorporated into cell mass, indicating that they are all synthesized de novo. Our approach is widely applicable and provides a means to analyze amino acid metabolism by studying specific proteins even in mixed consortia. PMID:22661690

  18. Mapping peptide thiol accessibility in membranes using a quaternary ammonium isotope-coded mass tag (ICMT)

    PubMed Central

    Su, Chiao-Yung; London, Erwin; Sampson, Nicole S.

    2013-01-01

    The plasma membrane contains a diverse array of proteins, including receptors, channels, and signaling complexes, that serve as decision-making centers. Investigation of membrane protein topology is important for understanding the function of these types of protein. Here, we report a method to determine protein topology in the membrane that utilizes labeling of cysteine with isotope-coded mass tags. The mass tags contain a thiol reactive moiety, linker, and a quaternary ammonium group to aid ionization in the mass spectrometer and were synthesizes as both light and heavy (deuterated) forms. The probes were found to be membrane impermeable when applied to lipid vesicles. To assess the utility of the probes for mapping peptide thiol topology, we employed a two-step labeling procedure. Vesicles containing α-helical transmembrane peptides were labeled with heavy (or light) probe, solubilized by detergent, and then labeled by an excess of the complementary probe. Peptide for which the cysteine was oriented in the center of the lipid bilayer was not labeled until the lipid vesicles were lysed with detergent, consistent with the membrane impermeability of the probes and reduced ionization of the thiol in the hydrophobic membrane. Peptide for which the cysteine was positioned in the head group zone of the lipid bilayer was labeled rapidly. Peptide for which the cysteine was positioned below the head group abutting the hydrocarbon region was labeled at a reduced rate compared to the fully accessible cysteine. Moreover, the effect of lipid bilayer structure on the kinetics of peptide and lipid flipping in the bilayer was readily measured with our two-step labeling method. The small sample size required, the ease and rapidity of sample preparation, and the amenability of MALDI-TOF mass spectral to analysis in the presence of lipids will enable future facile investigation of membrane proteins in a cellular context. PMID:23725486

  19. (238)U/(235)U isotope ratios of crustal material, rivers and products of hydrothermal alteration: new insights on the oceanic U isotope mass balance.

    PubMed

    Noordmann, Janine; Weyer, Stefan; Georg, R Bastian; Jöns, Svenja; Sharma, Mukul

    2016-01-01

    significantly lower δ(238)U (-0.55 and -0.59 ‰) than seawater (-0.38 ‰). These findings, together with the heavier U isotope composition observed for some altered basalts and carbonate veins support a model, in which redox processes mostly drive U isotope fractionation. This may result in a slightly heavier U isotope composition of U that is removed from seawater during hydrothermal seafloor alteration compared to that of seawater. Using the estimated isotope compositions of rivers and all U sinks from the ocean (of this study and the literature) for modelling of the isotopic U mass balance, this gives reasonable results for recent estimates of the oceanic U budget. It furthermore provides additional constraints on the relative size of the diverse U sinks and respective net isotope fractionation during U removal. PMID:26085006

  20. A combined limit on the neutrino mass from neutrinoless double-beta decay searches in multiple isotopes

    NASA Astrophysics Data System (ADS)

    Guzowski, P.

    2016-05-01

    We set a combined limit on the effective Majorana neutrino mass mββ from experimental searches for neutrinoless double-beta decay of multiple isotopes. The limits on mββ range between 130-310 meV, depending on the choice of nuclear matrix element calculation. The limits on mββ can also be translated into a limit on the neutrino mass and mixing parameters of a fourth sterile neutrino.

  1. 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)

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

    SciTech Connect

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

    2014-08-25

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

  3. Stable isotope dilution method for the determination of guanidinoacetic acid by gas chromatography/mass spectrometry.

    PubMed

    Fingerhut, Ralph

    2003-01-01

    For more than 30 years, guanidinoacetic acid (GAA), together with other guanidino compounds, has been proposed as an important marker for renal failure, in kidney transplantation, and for renal metabolism, especially for the metabolic activity of the renal proximal tubules. Since the discovery of the first patient with guanidinoacetic acid methyltransferase deficiency in 1994 by Stöckler et al. (Pediatr. Res. 1994; 36: 409), GAA has become of great interest for all laboratories involved in the diagnosis of metabolic diseases. In the literature there are several methods described for the determination of GAA, ranging from ion-exchange chromatography with post-column derivatisation, enzymatic methods, gas chromatography/mass spectrometry (GC/MS), to liquid chromatography/atmospheric pressure chemical ionisation mass spectrometry (LC/APCI-MS). Here a stable isotope dilution method for quantitative and accurate determination of GAA in urine, plasma, and cerebrospinal fluid is described. GAA is converted to the bis(trifluoromethyl)pyrimidine di(tert-butyldimethylsilyl) derivative by stepwise derivatisation with hexafluoroacetylacetone and N-(tert-butyldimethylsilyl)-N-methyltrifluoroacetamide (MTBSTFA). Analysis can be performed using a standard benchtop GC/MS system. For quantitative GAA determination with 1,2-(13)C-GAA as internal standard, selected ion monitoring is performed using m/z 460/462, with m/z 432/433 and 375/376 as qualifiers. PMID:12661026

  4. Sulfur-based absolute quantification of proteins using isotope dilution inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Lee, Hyun-Seok; Heun Kim, Sook; Jeong, Ji-Seon; Lee, Yong-Moon; Yim, Yong-Hyeon

    2015-10-01

    An element-based reductive approach provides an effective means of realizing International System of Units (SI) traceability for high-purity biological standards. Here, we develop an absolute protein quantification method using double isotope dilution (ID) inductively coupled plasma mass spectrometry (ICP-MS) combined with microwave-assisted acid digestion for the first time. We validated the method and applied it to certify the candidate protein certified reference material (CRM) of human growth hormone (hGH). The concentration of hGH was determined by analysing the total amount of sulfur in hGH. Next, the size-exclusion chromatography method was used with ICP-MS to characterize and quantify sulfur-containing impurities. By subtracting the contribution of sulfur-containing impurities from the total sulfur content in the hGH CRM, we obtained a SI-traceable certification value. The quantification result obtained with the present method based on sulfur analysis was in excellent agreement with the result determined via a well-established protein quantification method based on amino acid analysis using conventional acid hydrolysis combined with an ID liquid chromatography-tandem mass spectrometry. The element-based protein quantification method developed here can be generally used for SI-traceable absolute quantification of proteins, especially pure-protein standards.

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

    SciTech Connect

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

    1990-02-15

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

  6. Tracing of water masses using a multi isotope approach in the southern Indian Ocean

    NASA Astrophysics Data System (ADS)

    Povinec, P. P.; Breier, R.; Coppola, L.; Groening, M.; Jeandel, C.; Jull, A. J. T.; Kieser, W. E.; Lee, S.-H.; Liong Wee Kwong, L.; Morgenstern, U.; Park, Y.-H.; Top, Z.

    2011-02-01

    Anthropogenic radionuclides (3 H, 14 C, and 129I) stemmed from nuclear weapons tests were found in 1999 to be very abundant in the surface of the southern Indian Ocean, comparable to those in the subtropical Northwest Pacific Ocean. The observed radionuclide variations with latitude/longitude in the southern Indian Ocean are not due to deposition patterns of global fallout, but due to transport of water masses from the western Pacific through the Indonesian seas, and different water fronts present in the Crozet Basin of the Indian Ocean. High radionuclide concentrations observed in the latitudinal belt of 20-40°S are associated with the Indian Ocean Subtropical Gyre which acts as a reservoir of radionuclides, maintaining their high concentrations on a time scale of several decades. 14 C data documents that the southern Indian Ocean is an important for sink of anthropogenic carbon. The isotopic tracers reveal the evidence of the most intense surface gradients and presence of several water masses in the southern Indian Ocean, which makes the region one of the most dynamic places of the World Ocean.

  7. Daily cortisol production rate in man determined by stable isotope dilution/mass spectrometry

    SciTech Connect

    Esteban, N.V.; Loughlin, T.; Yergey, A.L.; Zawadzki, J.K.; Booth, J.D.; Winterer, J.C.; Loriaux, D.L. )

    1991-01-01

    Growth retardation as well as the development of Cushingoid features in adrenally insufficient patients treated with the currently accepted replacement dose of cortisol (33-41 mumol/day.m2; 12-15 mg/m2.day) prompted us to reevaluate the cortisol production rate (FPR) in normal subjects and patients with Cushing's syndrome, using a recently developed thermospray liquid chromatography-mass spectrometry method. The stable isotope (9,12,12-2H3)cortisol was infused continuously for 31 h at about 5% of the anticipated FPR. Blood samples were obtained at 20-min intervals for 24 h, spun, and pooled in 4-h groups. Tracer dilution in plasma was determined by liquid chromatography/mass spectrometry. The method was validated with controlled infusions in 6 patients with adrenal insufficiency. Results from 12 normal volunteers revealed a FPR of 27.3 +/- 7.5 mumol/day (9.9 +/- 2.7 mg/day) or 15.7 mumol/day.m2; 5.7 mg/m2. day. A previously unreported circadian variation in FPR was observed. Patients with Cushing's syndrome demonstrated unequivocal elevation of FPR and cortisol concentration correlated during each sample period in normal volunteers, indicating that cortisol secretion, rather than metabolism, is mainly responsible for changes in plasma cortisol. Our data suggest that the FPR in normal subjects may be lower than previously believed.

  8. Quantitative Metabolome Analysis Based on Chromatographic Peak Reconstruction in Chemical Isotope Labeling Liquid Chromatography Mass Spectrometry.

    PubMed

    Huan, Tao; Li, Liang

    2015-07-21

    Generating precise and accurate quantitative information on metabolomic changes in comparative samples is important for metabolomics research where technical variations in the metabolomic data should be minimized in order to reveal biological changes. We report a method and software program, IsoMS-Quant, for extracting quantitative information from a metabolomic data set generated by chemical isotope labeling (CIL) liquid chromatography mass spectrometry (LC-MS). Unlike previous work of relying on mass spectral peak ratio of the highest intensity peak pair to measure relative quantity difference of a differentially labeled metabolite, this new program reconstructs the chromatographic peaks of the light- and heavy-labeled metabolite pair and then calculates the ratio of their peak areas to represent the relative concentration difference in two comparative samples. Using chromatographic peaks to perform relative quantification is shown to be more precise and accurate. IsoMS-Quant is integrated with IsoMS for picking peak pairs and Zero-fill for retrieving missing peak pairs in the initial peak pairs table generated by IsoMS to form a complete tool for processing CIL LC-MS data. This program can be freely downloaded from the www.MyCompoundID.org web site for noncommercial use. PMID:26086729

  9. Isotopic yield measurement in the heavy mass region for 239Pu thermal neutron induced fission

    NASA Astrophysics Data System (ADS)

    Bail, A.; Serot, O.; Mathieu, L.; Litaize, O.; Materna, T.; Köster, U.; Faust, H.; Letourneau, A.; Panebianco, S.

    2011-09-01

    Despite the huge number of fission yield data available in the different evaluated nuclear data libraries, such as JEFF-3.1.1, ENDF/B-VII.0, and JENDL-4.0, more accurate data are still needed both for nuclear energy applications and for our understanding of the fission process itself. It is within the framework of this that measurements on the recoil mass spectrometer Lohengrin (at the Institut Laue-Langevin, Grenoble, France) was undertaken, to determine isotopic yields for the heavy fission products from the 239Pu(nth,f) reaction. In order to do this, a new experimental method based on γ-ray spectrometry was developed and validated by comparing our results with those performed in the light mass region with completely different setups. Hence, about 65 fission product yields were measured with an uncertainty that has been reduced on average by a factor of 2 compared to that previously available in the nuclear data libraries. In addition, for some fission products, a strongly deformed ionic charge distribution compared to a normal Gaussian shape was found, which was interpreted as being caused by the presence of a nanosecond isomeric state. Finally, a nuclear charge polarization has been observed in agreement, with the one described on other close fissioning systems.

  10. Rapid mass-spectrometric determination of boron isotopic distribution in boron carbide.

    PubMed

    Rein, J E; Abernathey, R M

    1972-07-01

    Boron isotopic ratios are measured in boron carbide by thermionic ionization mass spectrometry with no prior chemical separation. A powder blend of boron carbide and sodium hydroxide is prepared, a small portion is transferred to a tantalum filament, the filament is heated to produce sodium borate, and the filament is transferred to the mass spectrometer where the(11)B/(10)B ratio is measured, using the Na(2)BO(2)(+) ion. Variables investigated for their effect on preferential volatilization of (10)B include the sodium hydroxide-boron carbide ratio and the temperature and duration of filament heating. A series of boron carbide pellets containing natural boron, of the type proposed for the control rods of the Fast Flux Test Facility reactor, were analysed with an apparently unbiased result of 4.0560 for the (11)B/(10)B ratio (standard deviation 0.0087). The pellets contained over 3% metal impurities typically found in this material. Time of analysis is 45 min per sample, with one analyst. PMID:18961131

  11. Asteroid/comet impact clusters, flood basalts and mass extinctions: Significance of isotopic age overlaps

    NASA Astrophysics Data System (ADS)

    Glikson, Andrew

    2005-08-01

    Morgan et al. [J. Phipps Morgan, T.J. Reston, C.R. Ranero. Earth Planet. Sci. Lett. 217 (2004) 263-284.], referring to an overlap between the isotopic ages of volcanic events and four epoch/stage extinction boundaries, suggest a dominant role of Continental Flood Basalts (CFB) and of explosive CO 2-rich volcanic pipes ("Verneshots") as mass extinction triggers. Here I point out that Morgan et al. overlook 3 overlaps between the ages of extraterrestrial impacts, volcanic and mass extinction events, and 3 overlaps between the ages of extraterrestrial impact and volcanic events. These overlaps suggest that both extraterrestrial impacts and volcanism served as extinction triggers separately or in combination. A protracted impact cluster overlaps extinctions at the end-Devonian (˜374-359 Ma) and impact-extinction age overlaps occur in the end-Jurassic (˜145-142 Ma), Aptian (˜125-112 Ma); Cenomanian-Turonian (˜95-94 Ma); K-T boundary (˜65.5 Ma) and mid-Miocene (˜16 Ma) ( Table 1). Morgan et al. appear to question the uniqueness of shock metamorphic and geochemical criteria used to identify asteroid/comet impacts. However, shock pressures at 8-35 GPa, indicated by intra-crystalline planar deformation features (PDF), exceed lithospheric and volcanic explosion pressures by an order of magnitude and are not known to be associated with explosive volcanic diatremes, kimberlites or lamproites. These authors make reference to apparent iridium anomalies of volcanic origin. However, platinum group element (PGE) abundance levels, volatile/refractory PGE ratios, and Cr and Os isotopes of meteoritic materials are clearly distinct from those of terrestrial volcanics. Given a Phanerozoic time-integrated oceanic/continent crustal ratio > 2.5 and the difficulty in identifying oceanic impacts, I suggest the effects of large impacts on thin thermally active oceanic crust-capable of triggering regional to global mafic volcanic events and ensuing environmental effects-provide an

  12. Properties of Z = 120 Nuclei and the α-DECAY Chains of the 292, 304120 Isotopes Using Relativistic and Nonrelativistic Formalisms

    NASA Astrophysics Data System (ADS)

    Ahmad, Shakeb; Bhuyan, M.; Patra, S. K.

    2012-11-01

    The ground state and first intrinsic excited state of superheavy nuclei with Z = 120 and N = 160-204 are investigated using both nonrelativistic Skyrme-Hartree-Fock (SHF) and the axially deformed relativistic mean field (RMF) formalisms. We employ a simple BCS pairing approach for calculating the energy contribution from pairing interaction. The results for isotopic chain of binding energy (BE), quadrupole deformation parameter, two neutron separation energies and some other observables are compared with the finite range droplet model (FRDM) and some recent macroscopic-microscopic calculations. We predict superdeformed ground state solutions for almost all the isotopes. Considering the possibility of magic neutron number, two different modes of α-decay chains 292120 and 304120 are also studied within these frameworks. The Qα-values and the half-life T1/2α for these two different modes of decay chains are compared with FRDM and recent macroscopic-microscopic calculations. The calculation is extended for the α-decay chains of 292120 and 304120 from their excited state configuration to respective configuration, which predicts long half-life T1/2α (in seconds).

  13. Pb, Sr, and Nd isotopes in seamount basalts from the Juan de Fuca Ridge and Kodiak-Bowie seamount chain, northeast Pacific

    USGS Publications Warehouse

    Hegner, E.; Tatsumoto, M.

    1989-01-01

    Pb, Sr, and Nd isotopic ratios and their parent/daughter element concentrations for 28 basalts from 10 hotspot and nonhotspot seamounts are reported. Nd and Sr isotopic compositions (143Nd/144Nd = 0.51325-0.51304; 87Sr/86Sr = 0.70237-0.70275) plot in the envelope for Juan de Fuca-Gorda ridge basalts with tholeiitic basalts showing more depleted sources and a better negative correlation than transitional to alkalic basalts. Pb isotopic ratios in tholeiitic and alkalic basalts overlap (206Pb/204Pb = 18.29-19.44) and display a trend toward more radiogenic Pb in alkalic basalts. The isotopic data for hotspot and nonhotspot basalts are indistinguishable and correlate broadly with rock composition, implying that they are controlled by partial melting. The isotopic variation in the seamount basalts is about 60% (Nd-Sr) to 100% (Pb) of that in East Pacific Rise basalts and is interpreted as a lower limit for the magnitude of mantle heterogeneity in the northeast Pacific. The data indicate absence of a chemically distinct plume component in the linear seamount chains and strongly suggest an origin from mid-ocean ridge basalt-like east Pacific mantle. -Authors

  14. Analyzing Nuclear Fuel Cycles from Isotopic Ratios of Waste Products Applicable to Measurement by Accelerator Mass Spectrometry

    SciTech Connect

    Biegalski, S R; Whitney, S M; Buchholz, B

    2005-08-24

    An extensive study was conducted to determine isotopic ratios of nuclides in spent fuel that may be utilized to reveal historical characteristics of a nuclear reactor cycle. This forensic information is important to determine the origin of unknown nuclear waste. The distribution of isotopes in waste products provides information about a nuclear fuel cycle, even when the isotopes of uranium and plutonium are removed through chemical processing. Several different reactor cycles of the PWR, BWR, CANDU, and LMFBR were simulated for this work with the ORIGEN-ARP and ORIGEN 2.2 codes. The spent fuel nuclide concentrations of these reactors were analyzed to find the most informative isotopic ratios indicative of irradiation cycle length and reactor design. Special focus was given to long-lived and stable fission products that would be present many years after their creation. For such nuclides, mass spectrometry analysis methods often have better detection limits than classic gamma-ray spectroscopy. The isotopic ratios {sup 151}Sm/{sup 146}Sm, {sup 149}Sm/{sup 146}Sm, and {sup 244}Cm/{sup 246}Cm were found to be good indicators of fuel cycle length and are well suited for analysis by accelerator mass spectroscopy.

  15. High-precision measurement of variations in calcium isotope ratios in urine by multiple collector inductively coupled plasma mass spectrometry

    USGS Publications Warehouse

    Morgan, J.L.L.; Gordon, G.W.; Arrua, R.C.; Skulan, J.L.; Anbar, A.D.; Bullen, T.D.

    2011-01-01

    We describe a new chemical separation method to isolate Ca from other matrix elements in biological samples, developed with the long-term goal of making high-precision measurement of natural stable Ca isotope variations a clinically applicable tool to assess bone mineral balance. A new two-column procedure utilizing HBr achieves the purity required to accurately and precisely measure two Ca isotope ratios (44Ca/42Ca and 44Ca/43Ca) on a Neptune multiple collector inductively coupled plasma mass spectrometer (MC-ICPMS) in urine. Purification requirements for Sr, Ti, and K (Ca/Sr > 10000; Ca/Ti > 10000000; and Ca/K > 10) were determined by addition of these elements to Ca standards of known isotopic composition. Accuracy was determined by (1) comparing Ca isotope results for samples and standards to published data obtained using thermal ionization mass spectrometry (TIMS), (2) adding a Ca standard of known isotopic composition to a urine sample purified of Ca, and (3) analyzing mixtures of urine samples and standards in varying proportions. The accuracy and precision of δ44/42Ca measurements of purified samples containing 25 μg of Ca can be determined with typical errors less than ±0.2‰ (2σ).

  16. Automated charge state determination of complex isotope-resolved mass spectra by peak-target Fourier transform.

    PubMed

    Chen, Li; Yap, Yee Leng

    2008-01-01

    This study describes a new algorithm for charge state determination of complex isotope-resolved mass spectra. This algorithm is based on peak-target Fourier transform (PTFT) of isotope packets. It is modified from the widely used Fourier transform method because Fourier transform may give ambiguous charge state assignment for low signal-to-noise ratio (S/N) or overlapping isotopic clusters. The PTFT algorithm applies a novel "folding" strategy to enhance peaks that are symmetrically spaced about the targeted peak before applying the FT. The "folding" strategy multiplies each point to the high-m/z side of the targeted peak by its counterpart on the low-m/z side. A Fourier transform of this "folded" spectrum is thus simplified, emphasizing the charge state of the "chosen" ion, whereas ions of other charge states contribute less to the transformed data. An intensity-dependent technique is also proposed for charge state determination from frequency signals. The performance of PTFT is demonstrated using experimental electrospray ionization Fourier transform ion cyclotron resonance mass spectra. The results show that PTFT is robust for charge state determination of low S/N and overlapping isotopic clusters, and also useful for manual verification of potential hidden isotopic clusters that may be missed by the current analysis algorithms, i.e., AID-MS or THRASH. PMID:18293485

  17. Discovering Mercury Protein Modifications in Whole Proteomes Using Natural Isotope Distributions Observed in Liquid Chromatography-Tandem Mass Spectrometry

    SciTech Connect

    Polacco, Benjamin J.; Purvine, Samuel O.; Zink, Erika M.; LaVoie, Stephen P.; Lipton, Mary S.; Summers, Anne O.; Miller, Susan M.

    2011-08-01

    The identification of peptides that result from post-translational modifications is critical for understanding normal pathways of cellular regulation as well as identifying damage from, or exposures to xenobiotics, i.e. the exposome. However, because of their low abundance in proteomes, effective detection of modified peptides by mass spectrometry (MS) typically requires enrichment to eliminate false identifications. We present a new method for confidently identifying peptides with mercury (Hg)-containing adducts that is based on the influence of mercury’s seven stable isotopes on peptide isotope distributions detected by high-resolution MS. Using a pure protein and E. coli cultures exposed to phenyl mercuric acetate, we show the pattern of peak heights in isotope distributions from primary MS single scans efficiently identified Hg adducts in data from chromatographic separation coupled with tandem mass spectrometry with sensitivity and specificity greater than 90%. Isotope distributions are independent of peptide identifications based on peptide fragmentation (e.g. by SEQUEST), so both methods can be combined to eliminate false positives. Summing peptide isotope distributions across multiple scans improved specificity to 99.4% and sensitivity above 95%, affording identification of an unexpected Hg modification. We also illustrate the theoretical applicability of the method for detection of several less common elements including the essential element, selenium, as selenocysteine in peptides.

  18. Isotope Ratio Mass Spectrometry and Shale Gas - What Is Possible with Current Technology?

    NASA Astrophysics Data System (ADS)

    Barrie, C. D.; Kasson, A.

    2014-12-01

    With ever increasing exploration and exploitation of 'unconventional' hydrocarbon resources, the drive to understand the origins, history and importance of these resources and their effects on the surrounding environment (i.e. ground waters) has never been more important. High-throughput, high-precision isotopic measurements are therefore a key tool in this industry to both understand the gas generated and monitor the development and stability of wells through time. With the advent of cavity ringdown spectroscopy (CRDS) instrumentation, there has been a push in some applications - environmental & atmospheric - to gather more and more data directly at the location of collection or at dedicated field stations. Furthermore, CRDS has resulted in users seeking greater autonomy of instrumentation and so-called black box technology. Traditionally IRMS technology has not met any of these demands, requiring very specific and extensive footprint, power and environmental requirements. This has meant that the 'Oil & Gas' sector, which for natural gases measurements requires GC-IRMS technology - not possible via CRDS - loses time, money and manpower as samples get sent to central facility or contract labs with potentially long lee times. However, recent developments in technology mean that IRMS systems exist which are benchtop, have much lower power requirements, standard power connections and as long as housed in a temperature controlled field stations can be deployed anywhere. Furthermore, with advances in electronics and software IRMS systems are approaching the black box level of newer instrumentation while maintaining the flexibility and abilities of isotope ratio mass spectrometry. This presentation will outline changes in IRMS technology applicable to the Oil & Gas industry, discuss the feasibility of true 'field' deployability and present results from a range of Oil & Gas samples.

  19. Modified ion exchange separation for tungsten isotopic measurements from kimberlite samples using multi-collector inductively coupled plasma mass spectrometry.

    PubMed

    Sahoo, Yu Vin; Nakai, Shun'ichi; Ali, Arshad

    2006-03-01

    Tungsten isotope composition of a sample of deep-seated rock can record the influence of core-mantle interaction of the parent magma. Samples of kimberlite, which is known as a carrier of diamond, from the deep mantle might exhibit effects of core-mantle interaction. Although tungsten isotope anomaly was reported for kimberlites from South Africa, a subsequent investigation did not verify the anomaly. The magnesium-rich and calcium-rich chemical composition of kimberlite might engender difficulty during chemical separation of tungsten for isotope analyses. This paper presents a simple, one-step anion exchange technique for precise and accurate determination of tungsten isotopes in kimberlites using multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). Large quantities of Ca and Mg in kimberlite samples were precipitated and removed with aqueous H(2)SO(4). Highly pure fractions of tungsten for isotopic measurements were obtained following an anion exchange chromatographic procedure involving mixed acids. That procedure enabled efficient removal of high field strength elements (HFSE), such as Hf, Zr and Ti, which are small ions that carry strong charges and develop intense electrostatic fields. The tungsten yields were 85%-95%. Advantages of this system include less time and less use of reagents. Precise and accurate isotopic measurements are possible using fractions of tungsten that are obtained using this method. The accuracy and precision of these measurements were confirmed using various silicate standard rock samples, JB-2, JB-3 and AGV-1. PMID:16496054

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

    SciTech Connect

    Isselhardt, Brett H.

    2011-09-01

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

  1. Analyzing sites of OH radical attack (ring vs. side chain) in oxidation of substituted benzenes via dual stable isotope analysis (δ(13)C and δ(2)H).

    PubMed

    Zhang, Ning; Geronimo, Inacrist; Paneth, Piotr; Schindelka, Janine; Schaefer, Thomas; Herrmann, Hartmut; Vogt, Carsten; Richnow, Hans H

    2016-01-15

    OH radicals generated by the photolysis of H2O2 can degrade aromatic contaminants by either attacking the aromatic ring to form phenolic products or oxidizing the substituent. We characterized these competing pathways by analyzing the carbon and hydrogen isotope fractionation (εC and εH) of various substituted benzenes. For benzene and halobenzenes that only undergo ring addition, low values of εC (-0.7‰ to -1.0‰) were observed compared with theoretical values (-7.2‰ to -8‰), possibly owing to masking effect caused by pre-equilibrium between the substrate and OH radical preceding the rate-limiting step. In contrast, the addition of OH radicals to nitrobenzene ring showed a higher εC (-3.9‰), probably due to the lower reactivity. Xylene isomers, anisole, aniline, N,N-dimethylaniline, and benzonitrile yielded normal εH values (-2.8‰ to -29‰) indicating the occurrence of side-chain reactions, in contrast to the inverse εH (11.7‰ to 30‰) observed for ring addition due to an sp(2) to sp(3) hybridization change at the reacting carbon. Inverse εH values for toluene (14‰) and ethylbenzene (30‰) were observed despite the formation of side-chain oxidation products, suggesting that ring addition has a larger contribution to isotope fractionation. Dual element isotope slopes (∆δ(2)H/∆δ(13)C) therefore allow identification of significant degradation pathways of aromatic compounds by photochemically induced OH radicals. Issues that should be addressed in future studies include quantitative determination of the contribution of each competing pathway to the observed isotope fractionation and characterization of physical processes preceding the reaction that could affect isotope fractionation. PMID:26520272

  2. Top-Down 193-nm Ultraviolet Photodissociation Mass Spectrometry for Simultaneous Determination of Polyubiquitin Chain Length and Topology

    PubMed Central

    2016-01-01

    Protein ubiquitin modifications present a vexing analytical challenge, because of the dynamic changes in the site of modification on the substrate, the number of ubiquitin moieties attached, and the diversity of linkage patterns in which they are attached. Presented here is a method to confidently assign size and linkage type of polyubiquitin modifications. The method combines intact mass measurement to determine the number of ubiquitin moieties in the chain with backbone fragmentation by 193-nm ultraviolet photodissociation (UVPD) to determine the linkage pattern. UVPD fragmentation of proteins leads to reproducible backbone cleavage at almost every inter-residue position, and in polyubiquitin chains, the N-terminally derived fragments from each constituent monomer are identical, up to the site of conjugation. The N-terminal ubiquitin fragment ions are superimposed to create a diagnostic pattern that allows easy recognition of the dominant chain linkages. The method is demonstrated by achieving almost-complete fragmentation of monoubiquitin and then, subsequently, fragmentation of dimeric, tetrameric, and longer Lys48- and Lys63-linked ubiquitin chains. The utility of the method for the analysis of mixed linkage chains is confirmed for mixtures of Lys48 and Lys63 tetramers with known relative concentrations and for an in vitro-formulated ubiquitin chain attached to a substrate protein. PMID:25559986

  3. Two-dimensional electrophoresis of Arenicola marina extracellular hemoglobin: separation of chains with identical molecular mass but different isoelectric point.

    PubMed

    Slitine, F E; Toulmond, A

    1991-01-01

    1. On the basis of their molecular masses, four types of polypeptides (A, B, C, D) were obtained by SDS-PAGE of the extracellular hemoglobin of the polychaete annelid Arenicola marina. 2. On 2-dimensional polyacrylamide gel electrophoresis, the erythrocruorin dissociated into six different types of polypeptide chains; A1, A2, B1, B2, C and D. 3. A1 and B1 migrate in 2-dimensional electrophoresis at the same position as alpha and beta chains of human hemoglobin. PMID:1814687

  4. Quantifying groundwater dependence of a sub-polar lake cluster in Finland using an isotope mass balance approach

    NASA Astrophysics Data System (ADS)

    Isokangas, E.; Rozanski, K.; Rossi, P. M.; Ronkanen, A.-K.; Kløve, B.

    2015-03-01

    A stable isotope study of 67 kettle lakes and ponds situated on an esker aquifer (90 km2) in northern Finland was carried out to determine the role and extent of groundwater inflow in groundwater-dependent lakes. Distinct seasonal fluctuations in the δ18O and δ2H values of lakes are the result of seasonal ice cover prohibiting evaporation during the winter. An iterative isotope mass balance approach was used to calculate the inflow-to-evaporation ratios (ITOT/E) of all 67 lakes during the summer of 2013 when the isotopic compositions of the lakes were approaching a steady-state. The balance calculations were carried out independently for 2H and 18O data. Since evaporation rates were derived independently of any mass balance considerations, it was possible to determine the total inflow (ITOT) and mean turnover time (MTT) of the lakes. Furthermore, the groundwater seepage rates to all studied lakes were calculated. A quantitative measure was introduced for the dependence of a lake on groundwater (G index) that is defined as the percentage contribution of groundwater inflow to the total inflow of water to the given lake. The G index values of the lakes studied ranged from ca. 39 to 98%, revealing generally large groundwater dependency among the studied lakes. This study shows the effectiveness of applying an isotope mass balance approach to quantify the groundwater reliance of lakes situated in a relatively small area with similar climatic conditions.

  5. Direct quantitative determination of cyanamide by stable isotope dilution gas chromatography-mass spectrometry.

    PubMed

    Hiradate, Syuntaro; Kamo, Tsunashi; Nakajima, Eri; Kato, Kenji; Fujii, Yoshiharu

    2005-12-01

    Cyanamide is a multifunctional agrochemical used, for example, as a pesticide, herbicide, and fertilizer. Recent research has revealed that cyanamide is a natural product biosynthesized in a leguminous plant, hairy vetch (Vicia villosa). In the present study, gas chromatography-mass spectrometry (GC-MS) equipped with a capillary column for amines was used for direct quantitative determination of cyanamide. Quantitative signals for ((14)N(2))cyanamide, ((15)N(2))cyanamide (internal standard for stable isotope dilution method), and m-(trifluoromethyl)benzonitrile (internal standard for correcting errors in GC-MS analysis) were recorded as peak areas on mass chromatograms at m/z 42 (A(42)), 44 (A(44)), and 171 (A(IS)), respectively. Total cyanamide content, ((14)N(2))cyanamide plus ((15)N(2))cyanamide, was determined as a function of (A(42)+A(44))/A(IS). Contents of ((14)N(2))cyanamide and ((15)N(2))cyanamide were then calculated by multiplying the total cyanamide content by A(42)/(A(42)+A(44)) and A(44)/(A(42)+A(44)), respectively. The limit of detection for the total cyanamide content by the GC-MS analysis was around 1ng. The molar ratio of ((14)N(2))cyanamide to ((15)N(2))cyanamide in the injected sample was equal to the observed A(42)/A(44) value in the range from 0.1 to 5. It was, therefore, possible to use the stable isotope dilution method to quantify the natural cyanamide content in samples; i.e., the natural cyanamide content was derived by subtracting the A(42)/A(44) ratio of the internal standard from the A(42)/A(44) ratio of sample spiked with internal standard, and then multiplying the resulting difference by the amount of added ((15)N(2))cyanamide (SID-GC-MS method). This method successfully gave a reasonable value for the natural cyanamide content in hairy vetch, concurring with the value obtained by a conventional method in which cyanamide was derivatized to a photometrically active compound 4-cyanimido-1,2-naphthoquinone and analyzed with reversed

  6. Detection of dehydroepiandrosterone misuse by means of gas chromatography- combustion-isotope ratio mass spectrometry.

    PubMed

    Mareck, Ute; Geyer, Hans; Flenker, Ulrich; Piper, Thomas; Thevis, Mario; Schänzer, Wilhelm

    2007-01-01

    According to World Anti-Doping Agency (WADA) rules (WADA Technical Document-TD2004EAAS) urine samples containing dehydroepiandrosterone (DHEA) concentrations greater than 100 ng ML(-1) shall be submitted to isotope ratio mass spectrometry (IRMS) analysis. The threshold concentration is based on the equivalent to the glucuronide, and the DHEA concentrations have to be adjusted for a specific gravity value of 1.020. In 2006, 11,012 doping control urine samples from national and international federations were analyzed in the Cologne doping control laboratory, 100 (0.9%) of them yielding concentrations of DHEA greater than 100 ng mL(-1). Sixty-eight percent of the specimens showed specific gravity values higher than 1.020, 52% originated from soccer players, 95% were taken in competition, 85% were male urines, 99% of the IRMS results did not indicate an application of testosterone or related prohormones. Only one urine sample was reported as an adverse analytical finding having 319 ng mL(-1) DHEA (screening result), more than 10,000 ng mL(-1) androsterone and depleted carbon isotope ratio values for the testosterone metabolites androsterone and etiocholanolone. Statistical evaluation showed significantly different DHEA concentrations between specimens taken in- and out-of- competition, whereas females showed smaller DHEA values than males for both types of control. Also a strong influence of the DHEA excretion on different sport disciplines was detectable. The highest DHEA values were detected for game sports (soccer, basketball, handball, ice hockey), followed by boxing and wrestling. In 2007, 6622 doping control urine samples were analyzed for 3alpha,5-cyclo-5alpha-androstan-6beta-ol-17-one (3alpha,5-cyclo), a DHEA metabolite which was described as a useful gas chromatography-mass spectrometry (GC-MS) screening marker for DHEA abuse. Nineteen urine specimens showed concentrations higher than the suggested threshold of 140 ng mL(-1), six urine samples yielded

  7. Precise ruthenium fission product isotopic analysis using dynamic reaction cell inductively coupled plasma mass spectrometry (DRC-ICP-MS)

    SciTech Connect

    Brown, Christopher F.; Dresel, P. Evan; Geiszler, Keith N.; Farmer, Orville T.

    2006-05-09

    99Tc is a subsurface contaminant of interest at numerous federal, industrial, and international facilities. However, as a mono-isotopic fission product, 99Tc lacks the ability to be used as a signature to differentiate between the different waste disposal pathways that could have contributed to subsurface contamination at these facilities. Ruthenium fission-product isotopes are attractive analogues for the characterization of 99Tc sources because of their direct similarity to technetium with regard to subsurface mobility, and their large fission yields and low natural background concentrations. We developed an inductively coupled plasma mass spectrometry (ICP-MS) method capable of measuring ruthenium isotopes in groundwater samples and extracts of vadose zone sediments. Samples were analyzed directly on a Perkin Elmer ELAN DRC II ICP-MS after a single pass through a 1-ml bed volume of Dowex AG 50W-X8 100-200 mesh cation exchange resin. Precise ruthenium isotopic ratio measurements were achieved using a low-flow Meinhard-type nebulizer and long sample acquisition times (150,000 ms). Relative standard deviations of triplicate replicates were maintained at less than 0.5% when the total ruthenium solution concentration was 0.1 ng/ml or higher. Further work was performed to minimize the impact caused by mass interferences using the dynamic reaction cell (DRC) with O2 as the reaction gas. The aqueous concentrations of 96Mo and 96Zr were reduced by more than 99.7% in the reaction cell prior to injection of the sample into the mass analyzer quadrupole. The DRC was used in combination with stable-mass correction to quantitatively analyze samples containing up to 2-orders of magnitude more zirconium and molybdenum than ruthenium. The analytical approach documented herein provides an efficient and cost-effective way to precisely measure ruthenium isotopes and quantitate total ruthenium (natural vs. fission-product) in aqueous matrixes.

  8. Mass spectrometric methods for studying nutrient mineral and trace element absorption and metabolism in humans using stable isotopes. A review.

    PubMed

    Crews, H M; Ducros, V; Eagles, J; Mellon, F A; Kastenmayer, P; Luten, J B; McGaw, B A

    1994-11-01

    Mass spectrometric methods for determining stable isotopes of nutrient minerals and trace elements in human metabolic studies are described and discussed. The advantages and disadvantages of the techniques of electron ionization, fast atom bombardment, thermal ionization, and inductively coupled plasma and gas chromatography mass spectrometry are evaluated with reference to their accuracy, precision, sensitivity, and convenience, and the demands of human nutrition research. Examples of specific applications are described and the significance of current developments in mass spectrometry are discussed with reference to present and probable future research needs. PMID:7872491

  9. Protein Stable Isotope Fingerprinting (P-SIF): Multidimensional Protein Chromatography Coupled to Stable Isotope-Ratio Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Pearson, A.; Bovee, R. J.; Mohr, W.; Tang, T.

    2012-12-01

    As metagenomics increases our insight into microbial community diversity and metabolic potential, new approaches are required to determine the biogeochemical expression of this potential within ecosystems. Because stable isotopic analysis of the major bioactive elements (C, N) has been used historically to map flows of substrates and energy among macroscopic food webs, similar principles may apply to microbes. To address this challenge, we have developed a new analytical approach called Protein Stable Isotope Fingerprinting (P-SIF). P-SIF generates natural stable isotopic fingerprints of microbial individual or community proteomes. The main advantage of P-SIF is the potential to bridge the gap between diversity and function, thereby providing a window into the "black box" of environmental microbiology and helping to decipher the roles of uncultivated species. Our method implements a three-way, orthogonal scheme to separate mixtures of whole proteins into subfractions dominated by single or closely-related proteins. Protein extracts first are isoelectrically focused in a gel-free technique that yields 12 fractions separated over a gradient of pH 3-10. Each fraction then is separated by size-exclusion chromatography into 20 pools, ranging from >100kD to ~10kD. Finally, each of these pools is subjected to HPLC and collected in 40 time-slices based on protein hydrophobicity. Theoretical calculation reveals that the true chromatographic resolution of the total scheme is 5000, somewhat less than the 9600 resulting fractions. High-yielding fractions are subjected to δ13C analysis by spooling-wire microcombustion irMS (SWiM-irMS) optimized for samples containing 1-5 nmol carbon. Here we will present the method, results for a variety of pure cultures, and preliminary data for a sample of mixed environmental proteins. The data show the promise of this method for unraveling the metabolic complexity hidden within microbial communities.

  10. Development of a portable mass spectrometric system for determination of isotopic composition of solid uranium samples using fluorine volatilization

    NASA Astrophysics Data System (ADS)

    Loge, G.

    1994-09-01

    Using hardware and materials supplied by LANL, a prototype quadrupole mass spectrometer system designed for portable field analysis of isotopic composition of solid uranium samples was assembled and tested. The system contained the capability for fluorine volatilization of solid uranium samples with gas introduction, which was successfully tested and demonstrated using 100 mg samples of U3O8. Determination of precision and accuracy for measuring isotopic composition was performed using isotopic standards. Use with soil samples containing uranium were also attempted. Silicates in the soil forming SiF4 were found to be a kinetic bottleneck to the formation of UF6. This could be avoided by performing some sort of chemical separation as a pre-treatment step, which was demonstrated using nitric acid.

  11. High-resolution isotopic records from corals using ocean temperature and mass-spawning chronometers

    NASA Astrophysics Data System (ADS)

    Gagan, Michael K.; Chivas, Allan R.; Isdale, Peter J.

    1994-02-01

    We present a 6-year-long (1978-1984) delta O-18 and delta C-13 record from a Great Barrier Reef (Pandora Reef) Porites lutea coral based on near-weekly sample intervals. A sampling technique was designed to minimise any smoothing or distortion of the isotopic record due to complex coral growth, calyx architecture, and calcification at depth within the tissue layer. The arrival-time of the mid-winter minimum sea-surface temperature is very consistent (+/- 2 weeks) near Pandora Reef and provides an annual time-marker offering more precision than the traditional density band chronometer. The improved chronology and high-resolution record demonstrate that signal distortion in Porites, due to calcification within the tissue layer and variable intra-annual coral extension, is generally negligible. Also confirmed is that the arrival-time of monsoonal floods is precisely preserved (+/- 1 week) within the skeleton of Porites. The sensitivity of weekly sampling allows the detection of a subtle warm-to-cool sea-surface temperature anomaly which preceded, by more than one year, a similar temperature anomaly associated with the 1982-83 El Nino in the east Pacific. Sharply higher delta C-13 values coincide with the time of the annual coral mass-spawning event in the Great Barrier Reef. Recognition of this mass-spawning signal should simplify the interpretation of coral delta C-13 records and provides an additional, precise time-marker with which to adjust chronologies when intra-annual coral extension is not constant.

  12. Progress of the AVNG System - Attribute Verification System with Information Barriers for Mass Isotopics Measurements.

    SciTech Connect

    Budnikov, D.; Bulatov, M.; Jarikhine, I.; Lebedev, B.; Livke, A.; Modenov, A.; Morkin, A.; Razinkov, S.; Tsaregorodtsev, D.; Vlokh, A.; Yakovleva, S.; Elmont, T. H.; Langner, D. C.; MacArthur, D. W.; Mayo, D. R.; Smith, M. K.; Luke, S. J.

    2005-01-01

    An attribute verification system (AVNG) with information barriers for mass and isotopics measurements has been designed and its fabrication is nearly completed. The AVNG is being built by scientists at the Russian Federal Nuclear Center-VNIIEF, with support of Los Alamos National Laboratory (LANL) and Lawrence Livermore National Laboratory (LLNL). Such a system could be used to verify the presence of several unclassified attributes of classified material with no classified information release. The system is comprised of a neutron multiplicity counter and gamma-spectrometry system based on a high purity germanium gamma detector (nominal relative efficiency @ 1332 keV 50%) and digital gamma-ray spectrometer DSPEC{sup PLUS}. The neutron multiplicity counter is a three ring counter with 164 {sup 3}He tubes. The system was designed to measure prototype containers 491 mm in diameter and 503 mm high. This paper provides a brief history of the project and documents the progress of this effort with drawings and photographs.

  13. Isotopic exchange during derivatization of platelet activating factor for gas chromatography-mass spectrometry

    SciTech Connect

    Haroldsen, P.E.; Gaskell, S.J.; Weintraub, S.T.; Pinckard, R.N. )

    1991-04-01

    One approach to the quantitative analysis of platelet activating factor (PAF, 1-O-alkyl-2-acetyl-sn-glycerol-3-phosphocholine; also referred to as AGEPC, alkyl glyceryl ether phosphocholine) is hydrolytic removal of the phosphocholine group and conversion to an electron-capturing derivative for gas chromatography-negative ion mass spectrometry. (2H3)Acetyl-AGEPC has been commonly employed as an internal standard. When 1-hexadecyl-2-(2H3)acetyl glycerol (obtained by enzymatic hydrolysis of (2H3)-C16:0 AGEPC) is treated with pentafluorobenzoyl chloride at 120 degrees C, the resulting 3-pentafluorobenzoate derivative shows extensive loss of the deuterium label. This exchange is evidently acid-catalyzed since derivatization of 1-hexadecyl-2-acetyl glycerol under the same conditions in the presence of a trace of 2HCl results in the incorporation of up to three deuterium atoms. Isotope exchange can be avoided if the reaction is carried out at low temperature in the presence of base. Direct derivatization of (2H3)-C16:0 AGEPC by treatment with pentafluorobenzoyl chloride or heptafluorobutyric anhydride also results in loss of the deuterium label. The use of (13C2)-C16:0 AGEPC as an internal standard is recommended for rigorous quantitative analysis.

  14. Analysis of acrylamide in coffee and cocoa by isotope dilution liquid chromatography-tandem mass spectrometry.

    PubMed

    Aguas, Patricia C; Fitzhenry, Matthew J; Giannikopoulos, Georgina; Varelis, Peter

    2006-08-01

    An accurate and precise method for the quantification of acrylamide using stable isotope dilution liquid chromatography-tandem mass spectrometry was developed and used to measure acrylamide in coffee and cocoa samples. The sample preparation involved extraction of the analyte and its internal standard, 13C3-acrylamide, into water and subsequent defatting of the aqueous extract with dichloromethane. An aliquot of the resulting aqueous extract was then azeotropically dried under reduced pressure and subsequently purified using an aminopropyl-bonded silica cartridge. The purified extracts were then chromatographed on a 5-microm 2.1 x 150 mm Hypercarb column, the effluent of which was monitored for the analyte and its internal standard using positive-ion APCI-selected reaction monitoring. The intra-laboratory reproducibility of the method, expressed as a relative coefficient of variation (%, n=5), was determined at four levels of concentration (12.3, 42.3, 139.3 and 464.8 microg kg(-1)) and was found to vary between 0.6-2.5%. The accuracy of the method was assessed using a reference sample of coffee. The average result obtained using our method differed from the assigned value of the reference material by less than 1%. An analysis of a cocoa sample revealed that the method is capable of precisely estimating acrylamide in challenging matrices down to a level of at least 12.3 microg kg(-1). PMID:16819634

  15. PROGRESS OF THE AVNG SYSTEM - ATTRIBUTE VERIFICATION SYSTEM WITH INFORMATION BARRIERS FOR MASS AND ISOTOPICS MEASUREMENTS

    SciTech Connect

    Budnikov, D; Bulatov, M; Jarikhine, I; Lebedev, B; Livke, A; Modenov, A; Morkin, A; Razinkov, S; Safronov, S; Tsaregorodtsev, D; Vlokh, A; Yakovleva, S; Elmont, T; Langner, D; MacArthur, D; Mayo, D; Smith, M; Luke, S J

    2005-05-27

    An attribute verification system (AVNG) with information barriers for mass and isotopics measurements has been designed and its fabrication is nearly completed. The AVNG is being built by scientists at the Russian Federal Nuclear Center-VNIIEF, with support of Los Alamos National Laboratory (LANL) and Lawrence Livermore National Laboratory (LLNL). Such a system could be used to verify the presence of several unclassified attributes of classified material with no classified information release. The system is comprised of a neutron multiplicity counter and gamma-spectrometry system based on a high purity germanium gamma detector (nominal relative efficiency {at} 1332 keV 50%) and digital gamma-ray spectrometer DSPEC{sup PLUS}. The neutron multiplicity counter is a three ring counter with 164 {sup 3}He tubes. The system was designed to measure prototype containers 491 mm in diameter and 503 mm high. This paper provides a brief history of the project and documents the progress of this effort with drawings and photographs.

  16. Application of isotope dilution mass spectrometry: determination of ochratoxin A in the Canadian Total Diet Study

    PubMed Central

    Tam, J.; Pantazopoulos, P.; Scott, P.M.; Moisey, J.; Dabeka, R.W.; Richard, I.D.K.

    2011-01-01

    Analytical methods are generally developed and optimized for specific commodities. Total Diet Studies, representing typical food products ‘as consumed’, pose an analytical challenge since every food product is different. In order to address this technical challenge, a selective and sensitive analytical method was developed suitable for the quantitation of ochratoxin A (OTA) in Canadian Total Diet Study composites. The method uses an acidified solvent extraction, an immunoaffinity column (IAC) for clean-up, liquid chromatography-tandem mass spectrometry (LC-MS/MS) for identification and quantification, and a uniformly stable isotope-labelled OTA (U-[13C20]-OTA) as an internal recovery standard. Results are corrected for this standard. The method is accurate (101% average recovery) and precise (5.5% relative standard deviation (RSD)) based on 17 duplicate analysis of various food products over 2 years. A total of 140 diet composites were analysed for OTA as part of the Canadian Total Diet Study. Samples were collected at retail level from two Canadian cities, Quebec City and Calgary, in 2008 and 2009, respectively. The results indicate that 73% (102/140) of the samples had detectable levels of OTA, with some of the highest levels of OTA contamination found in the Canadian bread supply. PMID:21623499

  17. Mass Dependency of Isotope Fractionation of Gases Under Thermal Gradient and Its Possible Implications for Planetary Atmosphere Escaping Process

    NASA Technical Reports Server (NTRS)

    Sun, Tao; Niles, Paul; Bao, Huiming; Socki, Richard

    2014-01-01

    Physical processes that unmix elements/isotopes of gas molecules involve phase changes, diffusion (chemical or thermal), effusion and gravitational settling. Some of those play significant roles for the evolution of chemical and isotopic compositions of gases in planetary bodies which lead to better understanding of surface paleoclimatic conditions, e.g. gas bubbles in Antarctic ice, and planetary evolution, e.g. the solar-wind erosion induced gas escaping from exosphere on terrestrial planets.. A mass dependent relationship is always expected for the kinetic isotope fractionations during these simple physical processes, according to the kinetic theory of gases by Chapman, Enskog and others [3-5]. For O-bearing (O16, -O17, -O18) molecules the alpha O-17/ alpha O-18 is expected at 0.5 to 0.515, and for S-bearing (S32,-S33. -S34, -S36) molecules, the alpha S-33/ alpha S-34 is expected at 0.5 to 0.508, where alpha is the isotope fractionation factor associated with unmixing processes. Thus, one isotope pair is generally proxied to yield all the information for the physical history of the gases. However, we recently] reported the violation of mass law for isotope fractionation among isotope pairs of multiple isotope system during gas diffusion or convection under thermal gradient (Thermal Gradient Induced Non-Mass Dependent effect, TGI-NMD). The mechanism(s) that is responsible to such striking observation remains unanswered. In our past studies, we investigated polyatomic molecules, O2 and SF6, and we suggested that nuclear spin effect could be responsible to the observed NMD effect in a way of changing diffusion coefficients of certain molecules, owing to the fact of negligible delta S-36 anomaly for SF6.. On the other hand, our results also showed that for both diffusion and convection under thermal gradient, this NMD effect is increased by lower gas pressure, bigger temperature gradient and lower average temperature, which indicate that the nuclear spin effect may

  18. Isotopic Signature Transfer and Mass Pattern Prediction (IsoStamp): An Enabling Technique for Chemically-Directed Proteomics

    PubMed Central

    2011-01-01

    Directed proteomics applies mass spectrometry analysis to a subset of information-rich proteins. Here we describe a method for targeting select proteins by chemical modification with a tag that imparts a distinct isotopic signature detectable in a full-scan mass spectrum. Termed isotopic signature transfer and mass pattern prediction (IsoStamp), the technique exploits the perturbing effects of a dibrominated chemical tag on a peptide’s mass envelope, which can be detected with high sensitivity and fidelity using a computational method. Applying IsoStamp, we were able to detect femtomole quantities of a single tagged protein from total mammalian cell lysates at signal-to-noise ratios as low as 2.5:1. To identify a tagged-peptide’s sequence, we performed an inclusion list-driven shotgun proteomics experiment where peptides bearing a recoded mass envelope were targeted for fragmentation, allowing for direct site mapping. Using this approach, femtomole quantities of several targeted peptides were identified in total mammalian cell lysate, while traditional data-dependent methods were unable to identify as many peptides. Additionally, the isotopic signature imparted by the dibromide tag was detectable on a 12-kDa protein, suggesting applications in identifying large peptide fragments, such as those containing multiple or large posttranslational modifications (e.g., glycosylation). IsoStamp has the potential to enhance any proteomics platform that employs chemical labeling for targeted protein identification, including isotope coded affinity tagging, isobaric tagging for relative and absolute quantitation, and chemical tagging strategies for posttranslational modification. PMID:21604797

  19. Mass Accuracy and Isotopic Abundance Measurements for HR-MS Instrumentation: Capabilities for Non-Targeted Analyses

    NASA Astrophysics Data System (ADS)

    Knolhoff, Ann M.; Callahan, John H.; Croley, Timothy R.

    2014-07-01

    The development of automated non-targeted workflows for small molecule analyses is highly desirable in many areas of research and diagnostics. Sufficient mass and chromatographic resolution is necessary for the detectability of compounds and subsequent componentization and interpretation of ions. The mass accuracy and relative isotopic abundance are critical in correct molecular formulae generation for unknown compounds. While high-resolution instrumentation provides accurate mass information, sample complexity can greatly influence data quality and the measurement of compounds of interest. Two high-resolution instruments, an Orbitrap and a Q-TOF, were evaluated for mass accuracy and relative isotopic abundance with various concentrations of a standard mixture in four complex sample matrices. The overall average ± standard deviation of the mass accuracy was 1.06 ± 0.76 ppm and 1.62 ± 1.88 ppm for the Orbitrap and the Q-TOF, respectively; however, individual measurements were ± 5 ppm for the Orbitrap and greater than 10 ppm for the Q-TOF. Relative isotopic abundance measurements for A + 1 were within 5% of the theoretical value if the intensity of the monoisotopic peak was greater than 1E7 for the Orbitrap and 1E5 for the Q-TOF, where an increase in error is observed with a decrease in intensity. Furthermore, complicating factors were found in the data that would impact automated data analysis strategies, including coeluting species that interfere with detectability and relative isotopic abundance measurements. The implications of these findings will be discussed with an emphasis on reasonable expectations from these instruments, guidelines for experimental workflows, data analysis considerations, and software design for non-targeted analyses.

  20. Mass accuracy and isotopic abundance measurements for HR-MS instrumentation: capabilities for non-targeted analyses.

    PubMed

    Knolhoff, Ann M; Callahan, John H; Croley, Timothy R

    2014-07-01

    The development of automated non-targeted workflows for small molecule analyses is highly desirable in many areas of research and diagnostics. Sufficient mass and chromatographic resolution is necessary for the detectability of compounds and subsequent componentization and interpretation of ions. The mass accuracy and relative isotopic abundance are critical in correct molecular formulae generation for unknown compounds. While high-resolution instrumentation provides accurate mass information, sample complexity can greatly influence data quality and the measurement of compounds of interest. Two high-resolution instruments, an Orbitrap and a Q-TOF, were evaluated for mass accuracy and relative isotopic abundance with various concentrations of a standard mixture in four complex sample matrices. The overall average ± standard deviation of the mass accuracy was 1.06 ± 0.76 ppm and 1.62 ± 1.88 ppm for the Orbitrap and the Q-TOF, respectively; however, individual measurements were ± 5 ppm for the Orbitrap and greater than 10 ppm for the Q-TOF. Relative isotopic abundance measurements for A + 1 were within 5% of the theoretical value if the intensity of the monoisotopic peak was greater than 1E7 for the Orbitrap and 1E5 for the Q-TOF, where an increase in error is observed with a decrease in intensity. Furthermore, complicating factors were found in the data that would impact automated data analysis strategies, including coeluting species that interfere with detectability and relative isotopic abundance measurements. The implications of these findings will be discussed with an emphasis on reasonable expectations from these instruments, guidelines for experimental workflows, data analysis considerations, and software design for non-targeted analyses. PMID:24729191

  1. Quantifying precision and accuracy of measurements of dissolved inorganic carbon stable isotopic composition using continuous-flow isotope-ratio mass spectrometry

    PubMed Central

    Waldron, Susan; Marian Scott, E; Vihermaa, Leena E; Newton, Jason

    2014-01-01

    RATIONALE We describe an analytical procedure that allows sample collection and measurement of carbon isotopic composition (δ13CV-PDB value) and dissolved inorganic carbon concentration, [DIC], in aqueous samples without further manipulation post field collection. By comparing outputs from two different mass spectrometers, we quantify with the statistical rigour uncertainty associated with the estimation of an unknown measurement. This is rarely undertaken, but it is needed to understand the significance of field data and to interpret quality assurance exercises. METHODS Immediate acidification of field samples during collection in evacuated, pre-acidified vials removed the need for toxic chemicals to inhibit continued bacterial activity that might compromise isotopic and concentration measurements. Aqueous standards mimicked the sample matrix and avoided headspace fractionation corrections. Samples were analysed using continuous-flow isotope-ratio mass spectrometry, but for low DIC concentration the mass spectrometer response could be non-linear. This had to be corrected for. RESULTS Mass spectrometer non-linearity exists. Rather than estimating precision as the repeat analysis of an internal standard, we have adopted inverse linear calibrations to quantify the precision and 95% confidence intervals (CI) of the δ13CDIC values. The response for [DIC] estimation was always linear. For 0.05–0.5 mM DIC internal standards, however, changes in mass spectrometer linearity resulted in estimations of the precision in the δ13CVPDB value of an unknown ranging from ± 0.44‰ to ± 1.33‰ (mean values) and a mean 95% CI half-width of ±1.1–3.1‰. CONCLUSIONS Mass spectrometer non-linearity should be considered in estimating uncertainty in measurement. Similarly, statistically robust estimates of precision and accuracy should also be adopted. Such estimations do not inhibit research advances: our consideration of small-scale spatial variability at two points on a

  2. Measurement of the stable carbon isotope ratio of atmospheric volatile organic compounds using chromatography, combustion, and isotope ratio mass spectrometry coupled with thermal desorption

    NASA Astrophysics Data System (ADS)

    Kawashima, Hiroto; Murakami, Mai

    2014-06-01

    The isotopic analysis of atmospheric volatile organic compounds (VOCs), and in particular of their stable carbon isotope ratio (δ13C), could potentially be used as an effective tool for identifying the sources of VOCs. However, to date, there have been very few such analyses. In this work, we analyze the δ13C values of VOCs using thermal desorption coupled with chromatography, combustion, and isotope ratio mass spectrometry (TD-GC/C/IRMS). The measured peak shapes were of high quality and 36 compounds in a standard gas containing 58 VOCs (C5-C11) were detected. The measured δ13C varied widely, from -49.7‰ to -22.9‰, while the standard deviation of the δ13C values varied from 0.07‰ to 0.85‰ (n = 5). We then measured samples from two passenger cars in hot and cold modes, three gas stations, roadside air, and ambient air. In comparison with existing studies, the analytical precision for the 36 compounds in this study was reasonable. By comparing the δ13C values obtained from the cars and gas stations, we could identify some degree of the sources of VOCs in the roadside and ambient air samples.

  3. An analytical system for studying the stable isotopes of carbon monoxide using continuous flow-isotope ratio mass spectrometry (CF-IRMS)

    NASA Astrophysics Data System (ADS)

    Pathirana, S. L.; van der Veen, C.; Popa, M. E.; Röckmann, T.

    2015-02-01

    In the atmosphere, carbon monoxide (CO) is the major sink for the hydroxyl radical (OH •), has multiple anthropogenic and natural sources and considerable spatial and seasonal variability. Measurements of CO isotopic composition are useful in constraining the strengths of its individual source and sink processes and thus its global cycle. A fully automated system for δ13C and δ18O analysis has been developed to extract CO from an air sample, convert CO into carbon dioxide (CO2) using the Schütze reagent, and then determine the isotopic composition in an isotope ratio mass spectrometer (IRMS). The entire system is continuously flushed with high-purity helium (He), the carrier gas. The blank signal of the Schütze reagent is only 1-3% of the typical sample size. The repeatability is 0.1‰ for δ13C and 0.2‰ for δ18O. The peak area allows simultaneous determination of the mole fraction with an analytical repeatability of ~0.7 nmol mol-1 for 100 mL of typical ambient air (185.4 nmol mol-1 of CO). A single, automated, measurement is performed in 18 min, so multiple measurements can be combined conveniently to improve precision.

  4. Application of Inductively Coupled Plasma Mass Spectrometry to the determination of uranium isotope ratios in individual particles for nuclear safeguards

    NASA Astrophysics Data System (ADS)

    Zhang, Xiao Zhi; Esaka, Fumitaka; Esaka, Konomi T.; Magara, Masaaki; Sakurai, Satoshi; Usuda, Shigekazu; Watanabe, Kazuo

    2007-10-01

    The capability of inductively coupled plasma mass spectrometry (ICP-MS) for the determination of uranium isotope ratios in individual particles was determined. For this purpose, we developed an experimental procedure including single particle transfer with a manipulator, chemical dissolution and isotope ratio analysis, and applied to the analysis of individual uranium particles in certified reference materials (NBL CRM U050 and U350). As the result, the 235U/ 238U isotope ratio for the particle with the diameter between 0.5 and 3.9 μm was successfully determined with the deviation from the certified ratio within 1.8%. The relative standard deviation (R.S.D.) of the 235U/ 238U isotope ratio was within 4.2%. Although the analysis of 234U/ 238U and 236U/ 238U isotope ratios gave the results with inferior precision, the R.S.D. within 20% was possible for the measurement of the particle with the diameter more than 2.1 μm. The developed procedure was successfully applied to the analysis of a simulated environmental sample prepared from a mixture of indoor dust (NIST SRM 2583) and uranium particles (NBL CRM U050, U350 and U950a). From the results, the proposed procedure was found to be an alternative analytical tool for nuclear safeguards.

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

    SciTech Connect

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

    2015-12-07

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

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

    DOE PAGESBeta

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

    2015-12-07

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

  7. Quantifying groundwater dependence of a sub-polar lake cluster in Finland using an isotope mass balance approach

    NASA Astrophysics Data System (ADS)

    Isokangas, E.; Rozanski, K.; Rossi, P. M.; Ronkanen, A.-K.; Kløve, B.

    2014-08-01

    A stable isotope study of 67 kettle lakes and ponds situated on an esker aquifer (90 km2) in northern Finland was carried out in the summer of 2013 to determine the role of groundwater inflow in groundwater-dependent lakes. Distinct seasonal fluctuations in the δ18O and δ2H values of lakes are the result of seasonal ice cover prohibiting evaporation during the winter. An isotope mass balance approach was used to calculate the inflow-to-evaporation ratios (ITOT/E) of all 67 lakes during the summer of 2013 when the isotopic compositions of the lakes were approaching a steady-state. The normalised relative humidity needed in this approach came from assuming a terminal lake situation for one of the lakes showing the highest isotope enrichment. Since evaporation rates were derived independently of any mass balance considerations, it was possible to determine the total inflow (ITOT) and mean turnover time (MTT) of the lakes. Furthermore, the groundwater seepage rates of those lakes revealing no visible surface inflow were calculated. Here, a quantitative measure was introduced for the dependence of a lake on groundwater (G index) that is defined as the percentage contribution of groundwater inflow to the total inflow of water to the given lake. The G index values of the lakes studied ranged from 27.8-95.0%, revealing large differences in groundwater dependency among the lakes. This study shows the effectiveness of applying an isotope mass balance approach to quantify the groundwater reliance of lakes situated in a relatively small area with similar climatic conditions.

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

    PubMed

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

    2014-12-01

    We report on the determination of trace elements in solid samples by the combination of on-line double isotope dilution and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The proposed method requires the sequential analysis of the sample and a certified natural abundance standard by on-line IDMS using the same isotopically-enriched spike solution. In this way, the mass fraction of the analyte in the sample can be directly referred to the certified standard so the previous characterization of the spike solution is not required. To validate the procedure, Sr, Rb and Pb were determined in certified reference materials with different matrices, including silicate glasses (SRM 610, 612 and 614) and powdered samples (PACS-2, SRM 2710a, SRM 1944, SRM 2702 and SRM 2780). The analysis of powdered samples was carried out both by the preparation of pressed pellets and by lithium borate fusion. Experimental results for the analysis of powdered samples were in agreement with the certified values for all materials. Relative standard deviations in the range of 6-21% for pressed pellets and 3-21% for fused solids were obtained from n=3 independent measurements. Minimal sample preparation, data treatment and consumption of the isotopically-enriched isotopes are the main advantages of the method over previously reported approaches. PMID:25440666

  9. Determination of Polychlorinated Biphenyls in Solid Samples by Isotope Dilution Mass Spectrometry Using ³⁷Cl-Labeled Analogues.

    PubMed

    Somoano-Blanco, Lourdes; Rodriguez-Gonzalez, Pablo; García Fonseca, Sergio; Alonso, J Ignacio Garcia

    2015-08-01

    This work describes the first application of (37)Cl-labeled compounds to isotope dilution mass spectrometry (IDMS). The synthesis of 12 (37)Cl-labeled polychlorinated biphenyls (PCBs) was carried out by the chlorination of biphenyl with isotopically enriched chlorine gas, generated by the direct oxidation of Na(37)Cl with potassium peroxymonosulfate. After an exhaustive purification due to the presence of other congeners, the concentration and the isotopic enrichment of all (37)Cl-labeled PCBs in the mixture was determined. The proposed procedure allows the simultaneous quantification of every isotope diluted PCB congener in a single gas chromatography-tandem mass spectrometry (GC-MS/MS) injection without resorting to a methodological calibration graph. The results obtained here demonstrate that the use of (37)Cl-labeled analogues provides results in agreement with the certified values of three different Certified Reference Materials (marine sediment SRM 1944, fish tissue 1947, and loamy soil CRM 962-50) and analytical figures of merit comparable to those obtained using regular IDMS procedures based on the use of commercially available (13)C-labeled analogues. PMID:26165349

  10. High precision and high accuracy isotopic measurement of uranium using lead and thorium calibration solutions by inductively coupled plasma-multiple collector-mass spectrometry

    SciTech Connect

    Bowen, I.; Walder, A.J.; Hodgson, T.; Parrish, R.R. |

    1998-12-31

    A novel method for the high accuracy and high precision measurement of uranium isotopic composition by Inductively Coupled Plasma-Multiple Collector-Mass Spectrometry is discussed. Uranium isotopic samples are spiked with either thorium or lead for use as internal calibration reference materials. This method eliminates the necessity to periodically measure uranium standards to correct for changing mass bias when samples are measured over long time periods. This technique has generated among the highest levels of analytical precision on both the major and minor isotopes of uranium. Sample throughput has also been demonstrated to exceed Thermal Ionization Mass Spectrometry by a factor of four to five.

  11. A new algorithm to handle finite nuclear mass effects in electronic calculations: the ISOTOPE program.

    PubMed

    Gonçalves, Cristina P; Mohallem, José R

    2004-11-15

    We report the development of a simple algorithm to modify quantum chemistry codes based on the LCAO procedure, to account for the isotope problem in electronic structure calculations. No extra computations are required compared to standard Born-Oppenheimer calculations. An upgrade of the Gamess package called ISOTOPE is presented, and its applicability is demonstrated in some examples. PMID:15362130

  12. SO2 photoexcitation mechanism links mass-independent sulfur isotopic fractionation in cryospheric sulfate to climate impacting volcanism

    PubMed Central

    Hattori, Shohei; Schmidt, Johan A.; Johnson, Matthew S.; Danielache, Sebastian O.; Yamada, Akinori; Ueno, Yuichiro; Yoshida, Naohiro

    2013-01-01

    Natural climate variation, such as that caused by volcanoes, is the basis for identifying anthropogenic climate change. However, knowledge of the history of volcanic activity is inadequate, particularly concerning the explosivity of specific events. Some material is deposited in ice cores, but the concentration of glacial sulfate does not distinguish between tropospheric and stratospheric eruptions. Stable sulfur isotope abundances contain additional information, and recent studies show a correlation between volcanic plumes that reach the stratosphere and mass-independent anomalies in sulfur isotopes in glacial sulfate. We describe a mechanism, photoexcitation of SO2, that links the two, yielding a useful metric of the explosivity of historic volcanic events. A plume model of S(IV) to S(VI) conversion was constructed including photochemistry, entrainment of background air, and sulfate deposition. Isotopologue-specific photoexcitation rates were calculated based on the UV absorption cross-sections of 32SO2, 33SO2, 34SO2, and 36SO2 from 250 to 320 nm. The model shows that UV photoexcitation is enhanced with altitude, whereas mass-dependent oxidation, such as SO2 + OH, is suppressed by in situ plume chemistry, allowing the production and preservation of a mass-independent sulfur isotope anomaly in the sulfate product. The model accounts for the amplitude, phases, and time development of Δ33S/δ34S and Δ36S/Δ33S found in glacial samples. We are able to identify the process controlling mass-independent sulfur isotope anomalies in the modern atmosphere. This mechanism is the basis of identifying the magnitude of historic volcanic events. PMID:23417298

  13. Alternative Methodology for Boron Isotopic Analysis of CaCO3 by Negative Thermal Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Dwyer, G. S.; Vengosh, A.

    2012-12-01

    Negative thermal ionization mass spectrometry (NTIMS) has been a common tool for investigating boron isotopes in CaCO3 and other environmental samples, the high sensitivity of BO2- ionization enabling measurements of ng levels of boron. However, B isotope measurement by this technique suffers from a number of problems, including: (1) fractionation induced by selective ionization of B isotopes in the mass spectrometer; (2) CNO- interference on mass 42 ([10BO2]-) that may be present in some filament load solutions (such as B-free seawater processed through ion-exchange resin), and (3) potential matrix effects due to widely differing chemistry of samples and standards. Here we examine a potentially improved NTIMS methodology that incudes removal of sample-related calcium (and other cations) by ion exchange and uses an alternative filament loading solution prepared from high-purity single-element solutions of Ca, Mg, Na, and K. Initial results suggest that this new method may offer significant improvement over the more traditional NTIMS approach in which digested CaCO3 samples are directly loaded onto filaments in B-free seawater. Replicate analyses of standards and samples yield a typical standard deviation of approximately 0.3‰ δ11B and boron isotopic compositions comparable to reported or consensus values. Fractionation during analysis has thus far typically been less than 0.5‰ δ11B. The method delivers boron ionization efficiency similar to directly-loaded seawater, and negligible signal at mass 26 (CN-), a proxy for the possible interfering molecular CNO- ion. Standards and samples behave similarly and predictably during filament heating and analysis, thus allowing for fully automated data acquisition, which in turn may increase sample throughput and reduce potential analytical inconsistencies associated with operator-controlled heating and analysis.

  14. SO2 photoexcitation mechanism links mass-independent sulfur isotopic fractionation in cryospheric sulfate to climate impacting volcanism.

    PubMed

    Hattori, Shohei; Schmidt, Johan A; Johnson, Matthew S; Danielache, Sebastian O; Yamada, Akinori; Ueno, Yuichiro; Yoshida, Naohiro

    2013-10-29

    Natural climate variation, such as that caused by volcanoes, is the basis for identifying anthropogenic climate change. However, knowledge of the history of volcanic activity is inadequate, particularly concerning the explosivity of specific events. Some material is deposited in ice cores, but the concentration of glacial sulfate does not distinguish between tropospheric and stratospheric eruptions. Stable sulfur isotope abundances contain additional information, and recent studies show a correlation between volcanic plumes that reach the stratosphere and mass-independent anomalies in sulfur isotopes in glacial sulfate. We describe a mechanism, photoexcitation of SO2, that links the two, yielding a useful metric of the explosivity of historic volcanic events. A plume model of S(IV) to S(VI) conversion was constructed including photochemistry, entrainment of background air, and sulfate deposition. Isotopologue-specific photoexcitation rates were calculated based on the UV absorption cross-sections of (32)SO2, (33)SO2, (34)SO2, and (36)SO2 from 250 to 320 nm. The model shows that UV photoexcitation is enhanced with altitude, whereas mass-dependent oxidation, such as SO2 + OH, is suppressed by in situ plume chemistry, allowing the production and preservation of a mass-independent sulfur isotope anomaly in the sulfate product. The model accounts for the amplitude, phases, and time development of Δ(33)S/δ(34)S and Δ(36)S/Δ(33)S found in glacial samples. We are able to identify the process controlling mass-independent sulfur isotope anomalies in the modern atmosphere. This mechanism is the basis of identifying the magnitude of historic volcanic events. PMID:23417298

  15. A universal SI-traceable isotope dilution mass spectrometry method for protein quantitation in a matrix by tandem mass tag technology.

    PubMed

    Li, Jiale; Wu, Liqing; Jin, Youxun; Su, Ping; Yang, Bin; Yang, Yi

    2016-05-01

    Isotope dilution mass spectrometry (IDMS), an important metrological method, is widely used for absolute quantification of peptides and proteins. IDMS employs an isotope-labeled peptide or protein as an internal standard although the use of a protein provides improved accuracy. Generally, the isotope-labeled protein is obtained by stable isotope labeling by amino acids in cell culture (SILAC) technology. However, SILAC is expensive, laborious, and time-consuming. To overcome these drawbacks, a novel universal SI-traceable IDMS method for absolute quantification of proteins in a matrix is described with human transferrin (hTRF). The hTRF and a human serum sample were labeled with different tandem mass tags (TMTs). After mixing the TMT-labeled hTRF and serum sample together followed by digestion, the peptides were separated by nano-liquid chromatography and analyzed by matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS). Using the signature peptides, we calculated the ratios of reporter ions from the TMT-labeled peptides which, in turn, allowed determination of the mass fraction of hTRF. The recovery ranged from 97% to 105% with a CV of 3.9%. The LOD and LOQ were 1.71 × 10(-5) g/g and 5.69 × 10(-5) g/g of hTRF in human serum, respectively, and the relative expanded uncertainty was 4.7% with a mass fraction of 2.08 mg/g. For comparison, an enzyme-linked immunosorbent assay (ELISA) method for hTRF yielded a mass fraction of 2.03 mg/g. This method provides a starting point for establishing IDMS technology to accurately determine the mass fractions of protein biomarkers in a matrix with traceability to SI units. This technology should support the development of a metrological method useful for quantification of a wide variety of proteins. PMID:26942737

  16. Isotope dilution mass spectrometry for quantitative elemental analysis of powdered samples by radiofrequency pulsed glow discharge time of flight mass spectrometry.

    PubMed

    Alvarez-Toral, Aitor; Fernandez, Beatriz; Malherbe, Julien; Claverie, Fanny; Molloy, John L; Pereiro, Rosario; Sanz-Medel, Alfredo

    2013-10-15

    In recent years particular effort is being devoted to the development of pulsed glow discharges (PGDs) for mass spectrometry because this powering operation mode could offer important ionization analytical advantages. However, the capabilities of radiofrequency (RF) PGD coupled to a time of flight mass spectrometry (ToFMS) for accurate isotope ratio measurements have not been demonstrated yet. This work is focused on investigating different time positions along the pulse profile for the accurate measurement of isotope ratios. As a result, a method has been developed for the direct and simultaneous multielement determination of trace elements in powdered geological samples by RF-PGD-ToFMS in combination with isotope dilution mass spectrometry (IDMS) as an absolute measurement method directly traceable to the International System of Units. Optimized operating conditions were 70 W of applied radiofrequency power, 250 Pa of pressure, 2 ms of pulse width and 4 ms of pulse period, being argon the plasma gas used. To homogeneously distribute the added isotopically-enriched standards, lithium borate fusion of powdered solid samples was used as sample preparation approach. In this way, Cu, Zn, Ba and Pb were successfully determined by RF-PGD-ToF(IDMS) in two NIST Standard Reference Materials (SRM 2586 and SRM 2780) representing two different matrices of geological interest (soil and rock samples). Cu, Zn, Ba and Pb concentrations determined by RF-PGD-ToF(IDMS) were well in agreement with the certified values at 95% confidence interval and precisions below 12% relative standard deviation were observed for three independent analyses. Elemental concentrations investigated were in the range of 81-5770 mg/kg, demonstrating the potential of RF-PGD-ToF(IDMS) for a sensitive, accurate and robust analysis of powdered samples. PMID:24054645

  17. Mathematical modeling of the aquatic macrophyte inputs of mid-chain n-alkyl lipids to lake sediments: Implications for interpreting compound specific hydrogen isotopic records

    NASA Astrophysics Data System (ADS)

    Gao, Li; Hou, Juzhi; Toney, Jaime; MacDonald, Dana; Huang, Yongsong

    2011-07-01

    We present a systematic study of chain-length distributions and D/H ratios of n-alkyl lipids (both n-alkanes and n-alkanoic acids) in a wide range of terrestrial and aquatic plants around and in Blood Pond, Massachusetts, USA. The primary goal is to establish a model to quantitatively assess the aquatic plant inputs of the mid-chain length n-alkyl lipids to lake sediments and to determine the average hydrogen isotopic ratios of these lipids in different plants. Our results show that middle-chain n-alkyl lipids (C 21-C 23n-alkanes and C 20-C 24n-alkanoic acids) are exceptionally abundant in floating and submerged aquatic plants, in contrast to the dominance of long-chain n-alkyl lipids (C 27-C 31n-alkanes and C 26-C 32n-alkanoic acids) in other plant types, which are consistent with previously published data from Mountain Kenya and the Tibetan Plateau. Combining available data in different environmental settings allows us to establish statistically robust model distributions of n-alkyl lipids in floating/submerged macrophytes relative to other plant types. Based on the model distributions, we established a multi-source mixing model using a linear algebra approach, in order to quantify the aquatic inputs of mid-chain n-alkyl lipids in lake sediments. The results show that ˜97% of the mid-chain n-alkyl lipids (C 23n-alkane and C 22n-acid (behenic acid)) in Blood Pond sediments are derived from floating and submerged macrophytes. In addition, D/H ratios of C 22n-acid and C 23n-alkane in the floating and submerged plants from Blood Pond display relatively narrow ranges of variation (-161 ± 16‰ and -183 ± 18‰, respectively). Our study demonstrates that mid-chain n-alkyl lipids such as C 23n-alkane and C 22n-acid could be excellent recorders of past lake water isotopic ratios in lakes with abundant floating and submerged macrophyte inputs.

  18. Combination of Silicon and Neodymium Isotopes for a better understanding of past changes in bioproductivity and water mass mixing in the upwelling area off Peru

    NASA Astrophysics Data System (ADS)

    Grasse, P.; Ehlert, C.; Frank, M.; Stramma, L.

    2010-12-01

    The Peru coastal upwelling area is characterized by one of the most pronounced Oxygen Minimum Zones (OMZ). Oxygen concentrations are controlled by consumption through decomposition of organic matter versus ventilation via ocean circulation. Surface productivity is a function of both nutrient supply and upwelling intensity. The isotopic composition of Neodymium (Nd) is a powerful proxy for the reconstruction of past ocean circulation due to its intermediate oceanic residence time and the fact that it is independent of biological fractionation. This is in contrast to Silicon (Si) isotopes, which are fractionated during utilization in a way that the lighter Si isotopes are preferentially incorporated into the diatom frustules. The upwelling area off Peru is mainly influenced by water masses from the Central Pacific, which show more radiogenic values (ɛNd = -2), than water masses from the Northern Pacific (ɛNd = -5 to -3) or water masses from the south, which carry an unradiogenic Nd isotope signature originating from the Southern Ocean (ɛNd = -8 to -9). Upwelled Waters on the shelf are mainly supplied from the Equatorial Under Current (EUC) a strong southward flowing water mass originating in the western pacific. Therefore the δ30Si signal of diatoms is mainly influenced by the isotopic signal of the EUC. Past changes in the hydrography therefore would also influence the Si isotopic signal of this productivity proxy independent of silicic acid utilization. For a better understanding of the influence of water mass mixing on the isotopic signatures in the coastal upwelling area and the OMZ, we directly compare the Nd isotope signatures with dissolved stable Silicon isotope data. The information obtained from the unique combination of the biologically influenced Si isotopes and the Nd isotopes will lead to a better understanding of reconstruction of past ocean circulation and productivity.

  19. Asynchronous evolution of the isotopic composition and amount of precipitation in north China during the Holocene revealed by a record of compound-specific carbon and hydrogen isotopes of long-chain n-alkanes from an alpine lake

    NASA Astrophysics Data System (ADS)

    Rao, Zhiguo; Jia, Guodong; Li, Yunxia; Chen, Jianhui; Xu, Qinghai; Chen, Fahu

    2016-07-01

    Both the timing of the maximum East Asian summer monsoon (EASM) intensity in monsoonal China and the environmental significance of the Chinese stalagmite oxygen isotopic record (δ18O) have been debated. Here, we present a ca. 120-year-resolution compound-specific carbon (δ13C) and hydrogen (δD) isotopes of terrestrial long-chain n-alkanes extracted from a well-dated sediment core from an alpine lake in north China. Our δ13C data, together with previously reported pollen data from a parallel core, demonstrate a humid mid-Holocene from ca. 8-5 ka BP. Assuming that the climatic humidity of north China is an indicator of the EASM intensity, then the maximum EASM intensity occurred in the mid-Holocene. Our δD data reveal a similar long-term trend to the δ18O record from nearby Lianhua Cave, indicating that the synchronous δD and δ18O records faithfully record the δD and δ18O of precipitation, respectively. The most negative δD and δ18O values occur in the early-mid Holocene, from ca. 11-5 ka BP. This contrast in the timing of isotopic variations demonstrates a complex relationship between the isotopic composition of precipitation and precipitation amount, or EASM intensity. Further comparisons indicate a possible linkage between the precipitation amount in north China and the west-east thermal gradient in the equatorial Pacific. In addition, the temperature of the moisture source area may play an important role in determining the isotopic composition of precipitation in monsoonal China.

  20. Determination of lead, uranium, thorium, and thallium in silicate glass standard materials by isotope dilution mass spectrometry

    USGS Publications Warehouse

    Barnes, I.L.; Garner, E.L.; Gramlich, J.W.; Moore, L.J.; Murphy, T.J.; Machlan, L.A.; Shields, W.R.; Tatsumoto, M.; Knight, R.J.

    1973-01-01

    A set of four standard glasses has been prepared which have been doped with 61 different elements at the 500-, 50-, 1-, and 0.02-ppm level. The concentrations of lead, uranium, thorium, and thallium have been determined by isotope dilution mass spectrometry at a number of points in each of the glasses. The results obtained from independent determinations in two laboratories demonstrate the homogeneity of the samples and that precision of the order of 0.5% (95% L.E.) may be obtained by the method even at the 20-ppb level for these elements. The chemical and mass spectrometric procedures necessary are presented.

  1. Energy dependence of mass, charge, isotopic, and energy distributions in neutron-induced fission of 235U and 239Pu

    NASA Astrophysics Data System (ADS)

    Pasca, H.; Andreev, A. V.; Adamian, G. G.; Antonenko, N. V.; Kim, Y.

    2016-05-01

    The mass, charge, isotopic, and kinetic-energy distributions of fission fragments are studied within an improved scission-point statistical model in the reactions 235U+n and 239Pu+n at different energies of the incident neutron. The charge and mass distributions of the electromagnetic- and neutron-induced fission of 214,218Ra, 230,232,238U are also shown. The available experimental data are well reproduced and the energy-dependencies of the observable characteristics of fission are predicted for future experiments.

  2. Ion microscopy with resonant ionization mass spectrometry : time-of-flight depth profiling with improved isotopic precision.

    SciTech Connect

    Pellin, M. J.; Veryovkin, I. V.; Levine, J.; Zinovev, A.; Davis, A. M.; Stephan, T.; Tripa, C. E.; King, B. V.; Savina, M. R.

    2010-01-01

    There are four generally mutually exclusive requirements that plague many mass spectrometric measurements of trace constituents: (1) the small size (limited by the depth probed) of many interesting materials requires high useful yields to simply detect some trace elements, (2) the low concentrations of interesting elements require efficient discrimination from isobaric interferences, (3) it is often necessary to measure the depth distribution of elements with high surface and low bulk contributions, and (4) many applications require precise isotopic analysis. Resonant ionization mass spectrometry has made dramatic progress in addressing these difficulties over the past five years.

  3. Analysis of Atmospheric Nitrogen Inputs to the Forest Through Isotope Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Wright, A. J.; Alexander, B.; Michalski, G. M.; Shepson, P. B.

    2010-12-01

    Understanding the fate of atmospheric nitrogen is essential to understanding the forest nitrogen cycle. Recent studies have indicated that atmospheric nitrogen deposition has an important role in the nitrogen cycle for nitrogen-limited forests. Since most of the forests of the northern hemisphere are nitrogen-limited, wet and dry deposition of atmospheric nitrogen may have a significant impact on carbon sequestration. The current study hypothesizes that a significant fraction of nitrogen that is in the soil is deposited from the atmosphere. In this study, we sampled soil, rainfall, and cloud water in the vicinity of the University of Michigan Biological Station, and determined the value for Δ17O in NO3- from those samples. The average tropospheric Δ17O value for NO3-atm (nitrate aerosol and gaseous HNO3) for the U. S. Midwest region is approximately 23‰ based on recent measurements and modeling considerations. In contrast, nitrate from microbial nitrification of fertilizer or plant matter has Δ17O of zero. This makes Δ17O signals in soil and water nitrate a positive indicator of un-cycled atmospherically-derived nitrate. For this work, the nitrate was extracted, purified, and converted to N2O, which was then separated by GC and detected using a Thermo Delta V continuous flow isotope ratio mass spectrometer. Here we will present and discuss the results of Δ17O measurements for NO3- in these samples, to accurately quantify the proportion of atmospheric nitrate in soils. The dissolved nitrate Δ17O values give both the atmospheric component and the biological component through a two source mixing model. This quantification contributes to the long term effort on improving our understanding of the nature, chemistry, and impact of atmospheric nitrogen on the carbon cycle.

  4. Determination of trace iron in zirconium by isotope dilution-thermal ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Elliot, N. L.; Campbell, M. A.; Green, L. W.

    1995-08-01

    An isotope dilution-thermal ionization mass spectrometry method for the determination of parts-per-million levels of iron in zirconium is required for precise, accurate analyses in studies of the effects of iron on the irradiation deformation of nuclear alloys. A two-stage purification procedure was developed to avoid the signal suppression and interference caused by the zirconium matrix. After sample dissolution and spiking with 54Fe, the bulk of the zirconium is removed by ion exchange chromatography, and the eluted Fe(III) is further purified by micro-solvent extraction into tributyl phosphate-impregnated resin beads. The iron is back-extracted, submicrogram amounts are loaded onto previously outgassed zone-refined Re filaments, and 54/56 ratios are measured at 1170°C. A silica gel/boric acid ionization enhancer is used to obtain stable Fe+ currents as strong as 2 × 10-14. A from nanogram loadings of pure iron. The procedural blank of 20 ± 6 ng is sufficiently low to allow determination of ppm levels of iron in 0.1 g zirconium samples. The analyses of solution standards showed agreement within 2% between measured and expected values, and a good fit, r2 = 0.99997, to a linear regression. The analyses of metal standards exhibited a similar good fit to a linear regression of measured against expected values, and showed good agreement with other methods. The method meets the requirements for zirconium metallurgical studies, and may be extended to other applications.

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

    PubMed

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

    2016-05-01

    Multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) has been successfully applied in the rapid and high-precision measurement for sulfur isotope ratios in recent years. During the measurement, the presence of matrix elements would affect the instrumental mass bias for sulfur and these matrix-induced effects have aroused a lot of researchers' interest. However, these studies have placed more weight on highlighting the necessity for their proposed correction protocols (e.g., chemical purification and matrix-matching) while less attention on the key property of the matrix element gives rise to the matrix effects. In this study, four groups of sulfate solutions, which have different concentrations of sulfur (0.05-0.60mM) but a constant sequence of atomic calcium/sulfur ratios (0.1-50), are investigated under wet (solution) and dry (desolvation) plasma conditions to make a detailed evaluation on the matrix effects from calcium on sulfur isotope measurement. Based on a series of comparative analyses, we indicated that, the matrix effects of calcium on both measured sulfur isotope ratios and detected (32)S signal intensities are dependent mainly on the absolute calcium concentration rather than its relative concentration ratio to sulfur (i.e., atomic calcium/sulfur ratio). Also, for the same group of samples, the matrix effects of calcium under dry plasma condition are much more significant than that of wet plasma. This research affords the opportunity to realize direct and relatively precise sulfur isotope measurement for evaporite gypsum, and further provides some suggestions with regard to sulfur isotope analytical protocols for sedimentary pore water. PMID:26946020

  6. Identification of volatile and semivolatile compounds in chemical ionization GC-MS using a mass-to-structure (MTS) Search Engine with integral isotope pattern ranking.

    PubMed

    Liao, Wenta; Draper, William M

    2013-02-21

    The mass-to-structure or MTS Search Engine is an Access 2010 database containing theoretical molecular mass information for 19,438 compounds assembled from common sources such as the Merck Index, pesticide and pharmaceutical compilations, and chemical catalogues. This database, which contains no experimental mass spectral data, was developed as an aid to identification of compounds in atmospheric pressure ionization (API)-LC-MS. This paper describes a powerful upgrade to this database, a fully integrated utility for filtering or ranking candidates based on isotope ratios and patterns. The new MTS Search Engine is applied here to the identification of volatile and semivolatile compounds including pesticides, nitrosoamines and other pollutants. Methane and isobutane chemical ionization (CI) GC-MS spectra were obtained from unit mass resolution mass spectrometers to determine MH(+) masses and isotope ratios. Isotopes were measured accurately with errors of <4% and <6%, respectively, for A + 1 and A + 2 peaks. Deconvolution of interfering isotope clusters (e.g., M(+) and [M - H](+)) was required for accurate determination of the A + 1 isotope in halogenated compounds. Integrating the isotope data greatly improved the speed and accuracy of the database identifications. The database accurately identified unknowns from isobutane CI spectra in 100% of cases where as many as 40 candidates satisfied the mass tolerance. The paper describes the development and basic operation of the new MTS Search Engine and details performance testing with over 50 model compounds. PMID:23248816

  7. Development of a combined isotopic and mass-balance approach to determine dissolved organic carbon sources in eutrophic reservoirs.

    PubMed

    Pierson-Wickmann, Anne-Catherine; Gruau, Gérard; Jardé, Emilie; Gaury, Nicolas; Brient, Luc; Lengronne, Marion; Crocq, André; Helle, Daniel; Lambert, Thibault

    2011-04-01

    A combined mass-balance and stable isotope approach was set up to identify and quantify dissolved organic carbon (DOC) sources in a DOC-rich (9mgL(-1)) eutrophic reservoir located in Western France and used for drinking water supply (so-called Rophemel reservoir). The mass-balance approach consisted in measuring the flux of allochthonous DOC on a daily basis, and in comparing it with the effective (measured) DOC concentration of the reservoir. The isotopic approach consisted, for its part, in measuring the carbon isotope ratios (δ(13)C values) of both allochthonous and autochthonous DOC sources, and comparing these values with the δ(13)C values of the reservoir DOC. Results from both approaches were consistent pointing out for a DOC of 100% allochthonous origin. In particular, the δ(13)C values of the DOC recovered in the reservoir (-28.5±0.2‰; n=22) during the algal bloom season (May-September) showed no trace of an autochthonous contribution (δ(13)C in algae=-30.1±0.3‰; n=2) being indistinguishable from the δ(13)C values of allochthonous DOC from inflowing rivers (-28.6±0.1‰; n=8). These results demonstrate that eutrophication is not responsible for the high DOC concentrations observed in the Rophemel reservoir and that limiting eutrophication of this reservoir will not reduce the potential formation of disinfection by-products during water treatment. The methodology developed in this study based on a complementary isotopic and mass-balance approach provides a powerful tool, suitable to identify and quantify DOC sources in eutrophic, DOC-contaminated reservoirs. PMID:21190712

  8. Simultaneous Determination of Selected B Vitamins in the NIST SRM 3280 Multivitamin/Multielement Tablets by Liquid Chromatography Isotope Dilution Mass Spectrometry

    Technology Transfer Automated Retrieval System (TEKTRAN)

    There is increased interest in accurately assessing the total dietary intake of vitamins from all sources, including foods and dietary supplements. Isotope dilution mass spectrometry (IDMS) can be a definitive analytical method for very accurate concentration determinations. A liquid chromatographic...

  9. Performance of the wet oxidation unit of the HPLC isotope ratio mass spectrometry system for halogenated compounds.

    PubMed

    Gilevska, Tetyana; Gehre, Matthias; Richnow, Hans Hermann

    2014-08-01

    The performance of liquid chromatography-isotope ratio mass spectrometry (LC-IRMS) for polar halogenated compounds was evaluated. Oxidation capacity of the system was tested with halogenated acetic acids and halogenated aromatic compounds. Acetic acid (AA) was selected as a reference compound for complete oxidation and compared on the molar basis to the oxidation of other analytes. The isotope values were proofed with calibrated δ(13)C values obtained with an elemental analyzer (EA). Correct isotope values were obtained for mono- and dichlorinated, fluorinated, and tribrominated acetic acids and also for aniline, phenol, benzene, bromobenzene, chlorobenzene, 1,2-dichlorobenzene, 2,4,6-trichlorophenol, pentafluorophenol, and nitrobenzene. Incomplete oxidation of trichloroacetic acid (TCA) and trifluoroacetic acid (TFA) resulted in lower recovery compared to AA (37% and 24%, respectively) and in isotopic shift compared to values obtained with EA (TCA Δδ(13)C(EA/LC-IRMS) = 8.8‰, TFA Δδ(13)C(EA/LC-IRMS) = 6.0‰). Improvement of oxidation by longer reaction time in the reactor and increase in the concentration of sulfate radicals did not lead to complete combustion of TCA and TFA needed for δ(13)C analysis. To the best of our knowledge, this is the first time such highly chlorinated compounds were studied with the LC-IRMS system. This work provides information for method development of LC-IRMS methods for halogenated contaminants that are known as potential threats to public health and the environment. PMID:24975492

  10. Determination of total and isotopic uranium and total thorium in soils by inductively coupled plasma-mass spectrometry

    SciTech Connect

    Bolin, R.N.

    1995-12-31

    Inductively coupled plasma-mass spectrometry (ICP-MS), using standard sample introduction by peristaltic pumping, is presented as a method to determine total and isotopic uranium ({sup 234}U, {sup 235}U, {sup 236}U, and {sup 238}U) and thorium ({sup 232}Th) in soil samples. Initial sample preparation consists of oven drying to determine moisture content, and grinding and mixing the soil to make it homogeneous. This is followed by a nitric/hydrofluoric acid digestion to bring the uranium into solution. Bismuth ({sup 209}Bi) is added prior to digestion to monitor for losses due to sample preparation and analysis. An addition digestion, using nitric/perchloric acid is performed if the total thorium concentration is required on the sample. The uranium and thorium content of this solution and the {sup 235}U/{sup 238}U ratio are measured on an initial pass through the ICP-MS. The total uranium measurement is based on the {sup 238}U isotope measurement with correction for the presence of the U isotopes. To determine the concentration of the less abundant {sup 234}U and {sup 236}U isotopes, the digestate is further concentrated by using a solid phase extraction column (TRU.Spec by EiChrom Industries, Inc.) before a second pass through the ICP-MS.

  11. Discrimination of geographical origin of lentils (Lens culinaris Medik.) using isotope ratio mass spectrometry combined with chemometrics.

    PubMed

    Longobardi, F; Casiello, G; Cortese, M; Perini, M; Camin, F; Catucci, L; Agostiano, A

    2015-12-01

    The aim of this study was to predict the geographic origin of lentils by using isotope ratio mass spectrometry (IRMS) in combination with chemometrics. Lentil samples from two origins, i.e. Italy and Canada, were analysed obtaining the stable isotope ratios of δ(13)C, δ(15)N, δ(2)H, δ(18)O, and δ(34)S. A comparison between median values (U-test) highlighted statistically significant differences (p<0.05) for all isotopic parameters between the lentils produced in these two different geographic areas, except for δ(15)N. Applying principal component analysis, grouping of samples was observed on the basis of origin but with overlapping zones; consequently, two supervised discriminant techniques, i.e. partial least squares discriminant analysis and k-nearest neighbours algorithm were used. Both models showed good performances with external prediction abilities of about 93% demonstrating the suitability of the methods developed. Subsequently, isotopic determinations were also performed on the protein and starch fractions and the relevant results are reported. PMID:26041202

  12. Determination of Mineral-Specific Clumped Isotope Acid Digestion Fractionation Factors Using Heating Experiments and Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Henry, D.; Tang, J.; Mosenfelder, J. L.; Eagle, R.; Tripati, A.

    2014-12-01

    Clumped isotope thermometry involves the determination of formation temperatures of carbonates from the fraction of isotopologues containing multiple rare isotopes (oxygen-18 and carbon-13). At high temperatures, the abundance of these isotopologues should be stochastic. At lower temperatures, there is a tendency for heavy isotopes to form bonds with each other. However, spectroscopic determination of isotope ratios with high precision is difficult in solids, and so 13C-18O bond abundance is not measured in the solid phase. Instead, analysis of carbonates is performed using gas source mass spectrometry, by reacting the carbonate samples with phosphoric acid and measuring the evolved CO2 gas. As an oxygen atom is lost during the conversion of CO32- groups to CO2, this reaction is hypothesized to result in mineral and acid digestion temperature-dependent fractionation. In order to quantify this fractionation between CO32- and CO2, this experiment seeks to determine acid fractionation factors for carbonate samples of varying composition by randomizing samples through intense heating and comparing analyte CO2 measured composition to the expected composition for a stochastically distributed sample. From this analysis, future carbonate measurements can be calibrated to account for acid digestion fractionation.

  13. Using Gas Chromatography/Isotope Ratio Mass Spectrometry to Determine the Fractionation Factor for H2 Production by Hydrogenases

    SciTech Connect

    Yang, Hui; Ghandi, H.; Shi, Liang; Kreuzer, Helen W.; Ostrom, Nathaniel; Hegg, Eric L.

    2012-01-15

    Hydrogenases catalyze the reversible formation of H2, and they are key enzymes in the biological cycling of H2. H isotopes should be a very useful tool in quantifying proton trafficking in biological H2 production processes, but there are several obstacles that have thus far limited the use of this tool. In this manuscript, we describe a new method that overcomes some of these barriers and is specifically designed to measure isotopic fractionation during enzyme-catalyzed H2 evolution. A key feature of this technique is that purified hydrogenases are employed, allowing precise control over the reaction conditions and therefore a high level of precision. A custom-designed high-throughput gas chromatography-isotope ratio mass spectrometer is employed to measure the isotope ratio of the H2. Using this method, we determined that the fractionation factor of H2 production by the [NiFe]-hydrogenase from Desulfivibrio fructosovran is 0.27. This result indicates that, as expected, protons are highly favored over deuterons during H2 evolution. Potential applications of this new method are discussed.

  14. Bulk and Compound-Specific Isotope Analysis of Long-Chain, n-alkanes From a 85-kyr Core From Lake Peten Itza, Guatemala

    NASA Astrophysics Data System (ADS)

    Mays, J. L.; Brenner, M.; Bush, M. B.; Correa, A.; Curtis, J. H.; Hodell, D. A.

    2007-12-01

    Drill cores obtained from Lake Petén Itzá, Guatemala, contain a ~85-kyr record of terrestrial climate from lowland Central America. Variations in sediment lithology suggest rapid changes in precipitation during the last glacial and deglacial periods. Previous work in nearby Lake Quexil demonstrated the utility of using the carbon isotopic compositions of leaf wax n-alkanes to infer changes in terrestrial vegetation (Huang et al., 2001). Here we report carbon isotopes of bulk organic and long-chain n-alkanes in 60 samples to reconstruct changes in the relative proportion of C3 and C4 biomass in the watershed under changing climate and atmospheric CO2 conditions during the past 85 kyrs. Compound-specific carbon isotope results are compared directly with pollen analysis from the same samples. Huang, Y., F.A. Street-Perrott, S.E. Metcalfe, M. Brenner, M. Moreland, and K.H. Freeman. 2001. Climate change as the dominant control on glacial-interglacial variations in C3 and C4 plant abundance. Science 293:1647-1651.

  15. GC/MS method for determining carbon isotope enrichment and concentration of underivatized short-chain fatty acids by direct aqueous solution injection of biogas digester samples.

    PubMed

    Mulat, Daniel Girma; Feilberg, Anders

    2015-10-01

    In anaerobic digestion of organic matter, several metabolic pathways are involved during the simultaneous production and consumption of short-chain fatty acids (SCFA) in general and acetate in particular. Understanding the role of each pathway requires both the determination of the concentration and isotope enrichment of intermediates in conjunction with isotope labeled substrates. The objective of this study was to establish a rapid and simple GC/MS method for determining the isotope enrichment of acetate and concentration of underivatized short-chain fatty acids (SCFA) in biogas digester samples by direct liquid injection of acidified aqueous samples. Sample preparation involves only acidification, centrifugation and filtration of the aqueous solution followed by direct injection of the aqueous supernatant solution onto a polar column. With the sample preparation and GC/MS conditions employed, well-resolved and sharp peaks of underivatized SCFA were obtained in a reasonably short time. Good recovery (96.6-102.3%) as well as low detection (4-7 µmol/L) and quantification limits (14-22 µmol/L) were obtained for all the 6 SCFA studied. Good linearity was achieved for both concentration and isotope enrichment measurement with regression coefficients higher than 0.9978 and 0.9996, respectively. The method has a good intra- and inter-day precision with a relative standard deviation (RSD) below 6% for determining the tracer-to-tracee ratio (TTR) of both [2-(13)C]acetate and [U-(13)C]acetate. It has also a good intra- and inter-day precision with a RSD below 6% and 5% for determining the concentration of standard solution and biogas digester samples, respectively. Acidification of biogas digester samples with oxalic acid provided the low pH required for the protonation of SCFA and thus, allows the extraction of SCFA from the complex sample matrix. Moreover, oxalic acid was the source of formic acid which was produced in the injector set at high temperature. The produced

  16. Isotope ratios of uranium using high resolution inductively coupled plasma-mass spectrometry (ICP-MS)

    SciTech Connect

    Hearn, R.; Wildner, H.

    1998-12-31

    Actinide element isotope ratios have been determined in environmental samples using high resolution ICP-MS with ultrasonic nebulization. Precisions as low as 0.1% RSD have been achieved using various methods of acquisition. The methodology has been used for environmental monitoring of uranium isotope ratios as an indicator of nuclear activity. Also, it has been applied to calcite dating studies as a measure of past geochemical disturbances.

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

    PubMed Central

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

    1998-01-01

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

  18. A preliminary report on noble gas isotope analyses using the Helix-MC multi-collector mass spectrometer

    NASA Astrophysics Data System (ADS)

    Honda, M.; Zhang, X.; Phillips, D.; Szczepanski, S.; Deerberg, M.; Hamilton, D.; Krummen, M.; Schwieters, J.

    2013-12-01

    Analyses of noble gas isotopes by multi-collector mass spectrometry substantially improve measurement precision and accuracy, with the potential to revolutionise applications to cosmo-geo-sciences. The Helix-MC noble gas mass spectrometer manufactured by Thermo-Fisher is a 350mm, 120 degree extended geometry, high resolution, multi-collector mass spectrometer for the simultaneous analysis of noble gas isotopes. The detector array includes a fixed axial (Ax) detector, 2 adjustable high mass (H1 and H2) detectors and 2 adjustable low mass (L1 and L2) detectors. Each detector is equipped with a Faraday/ion counting multiplier CFM (Combined Faraday and CDD Multiplier) detector. Mass resolution and mass resolving power on the H2, Ax and L2 detectors of the Helix-MC installed at the Australian National University (ANU) are approximately 1,800 and 8,000, respectively. The noble gas handling system on-line to the Helix-MC consists of: (1) a resistively-heated, double-vacuum, tantalum furnace system, (2) air actuated vacuum crusher, (3) Photon-Machines diode laser heating system, (4) Janis He cryogenic trap assembly, (5) gas purification system and (6) standard gas pipette tanks, which are totally automated and controlled by the Qtegra software platform developed by Thermo-Fisher. Eleven repeat measurements of atmospheric Ar using the H2 Faraday (1E11 ohm resistor) and L2 CDD collectors on the Helix-MC, yield a mean 40Ar/36Ar ratio of 322.09 +- 0.28 (0.089%) with a 4,700 fA 40Ar beam current. This result compares favourably with the precision achieved by the Argus VI at the University of Melbourne (318.12 +- 0.17; 0.052%; n = 10) with a similar beam size of 4,200 fA. The high mass resolution of the L2 collector permits complete separation of the 36Ar and interfering 3 x 12C (required mass resolution (MR) of 1,100) and partial separation of H35Cl (MR = 3,900). This capability enables evaluation of the significance of Ar isotopic interferences related to the correction of

  19. 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

  20. Stable isotope labeling tandem mass spectrometry (SILT): integration with peptide identification and extension to data-dependent scans.

    PubMed

    Elbert, Donald L; Mawuenyega, Kwasi G; Scott, Evan A; Wildsmith, Kristin R; Bateman, Randall J

    2008-10-01

    Quantitation of relative or absolute amounts of proteins by mass spectrometry can be prone to large errors. The use of MS/MS ion intensities and stable isotope labeling, which we term stable isotope labeling tandem mass spectrometry (SILT), decreases the effects of contamination from unrelated compounds. We present a software package (SILTmass) that automates protein identification and quantification by the SILT method. SILTmass has the ability to analyze the kinetics of protein turnover, in addition to relative and absolute protein quantitation. Instead of extracting chromatograms to find elution peaks, SILTmass uses only scans in which a peptide is identified and that meet an ion intensity threshold. Using only scans with identified peptides, the accuracy and precision of SILT is shown to be superior to precursor ion intensities, particularly at high or low dilutions of the isotope labeled compounds or with low amounts of protein. Using example scans, we demonstrate likely reasons for the improvements in quantitation by SILT. The appropriate use of variable modifications in peptide identification is described for measurement of protein turnover kinetics. The combination of identification with SILT facilitates quantitation without peak detection and helps to ensure the appropriate use of variable modifications for kinetics experiments. PMID:18774841

  1. Fission track-secondary ion mass spectrometry as a tool for detecting the isotopic signature of individual uranium containing particles.

    PubMed

    Esaka, Fumitaka; Lee, Chi-Gyu; Magara, Masaaki; Kimura, Takaumi

    2012-04-01

    A fission track technique was used as a sample preparation method for subsequent isotope abundance ratio analysis of individual uranium containing particles with secondary ion mass spectrometry (SIMS) to measure the particles with higher enriched uranium efficiently. A polycarbonate film containing particles was irradiated with thermal neutrons and etched with 6M NaOH solution. Each uranium containing particle was then identified by observing fission tracks created and a portion of the film having a uranium containing particle was cut out and put onto a glassy carbon planchet. The polycarbonate film, which gave the increases of background signals on the uranium mass region in SIMS analysis, was removed by plasma ashing with 200 W for 20 min. In the analysis of swipe samples having particles containing natural (NBL CRM 950a) or low enriched uranium (NBL CRM U100) with the fission track-SIMS method, uranium isotope abundance ratios were successfully determined. This method was then applied to the analysis of a real inspection swipe sample taken at a nuclear facility. As a consequence, the range of (235)U/(238)U isotope abundance ratio between 0.0276 and 0.0438 was obtained, which was higher than that measured by SIMS without using a fission track technique (0.0225 and 0.0341). This indicates that the fission track-SIMS method is a powerful tool to identify the particle with higher enriched uranium in environmental samples efficiently. PMID:22405310

  2. Determination of 237Np and Pu isotopes in large soil samples by inductively coupled plasma mass spectrometry.

    PubMed

    Maxwell, Sherrod L; Culligan, Brian K; Jones, Vernon D; Nichols, Sheldon T; Bernard, Maureen A; Noyes, Gary W

    2010-12-01

    A new method for the determination of (237)Np and Pu isotopes in large soil samples has been developed that provides enhanced uranium removal to facilitate assay by inductively coupled plasma mass spectrometry (ICP-MS). This method allows rapid preconcentration and separation of plutonium and neptunium in large soil samples for the measurement of (237)Np and Pu isotopes by ICP-MS. (238)U can interfere with (239)Pu measurement by ICP-MS as (238)UH(+) mass overlap and (237)Np via (238)U peak tailing. The method provides enhanced removal of uranium by separating Pu and Np initially on TEVA Resin, then transferring Pu to DGA resin for additional purification. The decontamination factor for removal of uranium from plutonium for this method is greater than 1×10(6). Alpha spectrometry can also be applied so that the shorter-lived (238)Pu isotope can be measured successfully. (239) Pu, (242)Pu and (237)Np were measured by ICP-MS, while (236)Pu and (238)Pu were measured by alpha spectrometry. PMID:21056724

  3. DETERMINATION OF 237NP AND PU ISOTOPES IN LARGE SOIL SAMPLES BY INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRY

    SciTech Connect

    Maxwell, S.

    2010-07-26

    A new method for the determination of {sup 237}Np and Pu isotopes in large soil samples has been developed that provides enhanced uranium removal to facilitate assay by inductively coupled plasma mass spectrometry (ICP-MS). This method allows rapid preconcentration and separation of plutonium and neptunium in large soil samples for the measurement of {sup 237}Np and Pu isotopes by ICP-MS. {sup 238}U can interfere with {sup 239}Pu measurement by ICP-MS as {sup 238}UH{sup +} mass overlap and {sup 237}Np via {sup 238}U peak tailing. The method provides enhanced removal of uranium by separating Pu and Np initially on TEVA Resin, then transferring Pu to DGA resin for additional purification. The decontamination factor for removal of uranium from plutonium for this method is greater than 1 x 10{sup 6}. Alpha spectrometry can also be applied so that the shorter-lived {sup 238}Pu isotope can be measured successfully. {sup 239}Pu, {sup 242}Pu and {sup 237}Np were measured by ICP-MS, while {sup 236}Pu and {sup 238}Pu were measured by alpha spectrometry.

  4. Identification of fission-like events in the {sup 16}O + {sup 181}Ta system: Mass and isotopic yield distribution

    SciTech Connect

    Sharma, Vijay R.; Yadav, Abhishek; Singh, Devendra P.; Unnati,; Singh, B. P.; Prasad, R.; Singh, Pushpendra P.; Sharma, Manoj K.; Kumar, R.; Golda, K. S.; Sinha, A. K.

    2011-07-15

    In this paper, nuclear reaction cross sections for 24 fission-like fragments (30{<=}Z{<=}60) have been measured for the 6.5 MeV/A {sup 16}O + {sup 181}Ta system. The recoil-catcher activation technique was employed followed by off-line {gamma} spectroscopy. The isotopic yield distributions for yttrium and indium isotopes have been obtained from the experimental data. The variance of the presently measured isotopic yield distributions have been found to be in agreement with the literature values. However, the variance of the mass distribution of fission residues has found to be narrower as compared to other relatively heavier systems. A self-consistent approach to determining the isobaric charge dispersion parameters has been adopted. The measured fission cross sections at 97 and 100 MeV are satisfactorily described by a statistical model code. An attempt has been made to explain the production cross sections of intermediate mass residues in the fission of heavy residues populated via complete and/or incomplete fusion processes.

  5. QPNM calculation for the ground state magnetic moments of odd-mass deformed nuclei: 157-167Er isotopes

    NASA Astrophysics Data System (ADS)

    Yakut, H.; Guliyev, E.; Guner, M.; Tabar, E.; Zenginerler, Z.

    2012-08-01

    A new microscopic method has been developed in the framework of the Quasiparticle-Phonon Nuclear Model (QPNM) in order to investigate spin polarization effects on the magnetic properties such as magnetic moment, intrinsic magnetic moment and effective gs factor of the ground state of odd-mass 157-167Er isotopes. The calculations were performed using both Tamm-Dancoff Approximation (TDA) and Quasiparticle Random-Phase Approximation (QRPA). Reasonably good agreement has been obtained between the QRPA results and the relevant experimental data. Furthermore the variation of the intrinsic magnetic moment gK values with the mass number A exhibits similar behavior for both theoretical and experimental results. From the compression of the calculated intrinsic magnetic moment values with the experimental data the spin-spin interaction parameter has been found as χ=(30/A) MeV for odd-mass 157-167Er isotopes. Our results clarify the possibility of using this new method to describe the magnetic properties of odd-mass deformed nuclei.

  6. The influence of water mass mixing on the dissolved Si isotope composition in the Eastern Equatorial Pacific

    NASA Astrophysics Data System (ADS)

    Grasse, Patricia; Ehlert, Claudia; Frank, Martin

    2013-10-01

    Silicon isotopes are a powerful tool to investigate the cycling of dissolved silicon (Si). In this study the distribution of the Si isotope composition of dissolved silicic acid (δ30Si(OH)4) was analyzed in the water column of the Eastern Equatorial Pacific (EEP) where one of the globally largest Oxygen Minimum Zones (OMZs) is located. Samples were collected at 7 stations along two meridional transects from the equator to 14°S at 85°50'W and 82°00'W off the Ecuadorian and Peruvian coast. Surface waters show a large range in isotope compositions δ30Si(OH)4 (+2.2‰ to +4.4‰) with the highest values found at the southernmost station at 14°S. This station also revealed the most depleted silicic acid concentrations (0.2 μmol/kg), which is a function of the high degree of Si utilization by diatoms and admixture with waters from highly productive areas. Samples within the upper water column and the OMZ at oxygen concentrations below 10 μmol/kg are characterized by a large range in δ30Si(OH)4, which mainly reflects advection and mixing of different water masses, even though the highly dynamic hydrographic system of the upwelling area off Peru does not allow the identification of clear Si isotope signals for distinct water masses. Therefore we cannot rule out that also dissolution processes have an influence on the δ30Si(OH)4 signature in the subsurface water column. Deep water masses (>2000 m) in the study area show a mean δ30Si(OH)4 of +1.2±0.2‰, which is in agreement with previous studies from the eastern and central Pacific. Comparison of the new deep water data of this study and previously published data from the central Pacific and Southern Ocean reveal substantially higher δ30Si(OH)4 values than deep water signatures from the North Pacific. As there is no clear correlation between δ30Si(OH)4 and silicic acid concentrations in the entire data set the distribution of δ30Si(OH)4 signatures in deep waters of the Pacific is considered to be mainly a

  7. A comparison of lead-isotope measurements on exploration-type samples using inductively coupled plasma and thermal ionization mass spectrometry

    USGS Publications Warehouse

    Gulson, B.L.; Meier, A.L.; Church, S.E.; Mizon, K.J.

    1989-01-01

    Thermal ionization mass spectrometry (TI-MS) has long been the method of choice for Pb-isotope determinations. More recently, however, inductively coupled plasma mass spectrometry (ICP-MS) has been used to determine Pb-isotope ratios for mineral exploration. The ICP-MS technique, although not as precise as TI-MS, may promote a wider application of Ph-isotope ratio methods because it allows individual isotopes to be determined more rapidly, generally without need for chemical separation (e.g., Smith et al., 1984; Hinners et al., 1987). To demonstrate the utility of the ICP-MS method, we have conducted a series of Pb-isotope measurements on several suites of samples using both TI-MS and ICP-MS. ?? 1989.

  8. Development and validation of a liquid chromatography isotope dilution mass spectrometry method for the reliable quantification of alkylphenols in environmental water samples by isotope pattern deconvolution.

    PubMed

    Fabregat-Cabello, Neus; Sancho, Juan V; Vidal, Andreu; González, Florenci V; Roig-Navarro, Antoni Francesc

    2014-02-01

    We present here a new measurement method for the rapid extraction and accurate quantification of technical nonylphenol (NP) and 4-t-octylphenol (OP) in complex matrix water samples by UHPLC-ESI-MS/MS. The extraction of both compounds is achieved in 30min by means of hollow fiber liquid phase microextraction (HF-LPME) using 1-octanol as acceptor phase, which provides an enrichment (preconcentration) factor of 800. On the other hand we have developed a quantification method based on isotope dilution mass spectrometry (IDMS) and singly (13)C1-labeled compounds. To this end the minimal labeled (13)C1-4-(3,6-dimethyl-3-heptyl)-phenol and (13)C1-t-octylphenol isomers were synthesized, which coelute with the natural compounds and allows the compensation of the matrix effect. The quantification was carried out by using isotope pattern deconvolution (IPD), which permits to obtain the concentration of both compounds without the need to build any calibration graph, reducing the total analysis time. The combination of both extraction and determination techniques have allowed to validate for the first time a HF-LPME methodology at the required levels by legislation achieving limits of quantification of 0.1ngmL(-1) and recoveries within 97-109%. Due to the low cost of HF-LPME and total time consumption, this methodology is ready for implementation in routine analytical laboratories. PMID:24423386

  9. A novel liquid chromatography tandem mass spectrometry method for simultaneous determination of branched-chain amino acids and branched-chain α-keto acids in human plasma.

    PubMed

    Li, Ruiting; Liu, Peifang; Liu, Peijia; Tian, Yuan; Hua, Yunfei; Gao, Yiqiao; He, Hua; Chen, Jiaqing; Zhang, Zunjian; Huang, Yin

    2016-06-01

    Branched-chain amino acids (BCAAs) and branched-chain α-keto acids (BCKAs) play significant biological roles as they are involved in protein and neurotransmitter synthesis as well as energy metabolism pathways. To routinely and accurately study the dynamics of BCAAs and BCKAs in human diseases, e.g. cerebral infarction, a novel liquid chromatography-tandem mass spectrometry (LC-MS/MS) method has been developed and validated. The plasma samples were deproteinized with acetonitrile, and then separated on a reversed phase C18 column with a mobile phase of 0.1 % formic acid (solvent A)-methanol (solvent B) using gradient elution. The detection of BCAAs and BCKAs was conducted in multiple reaction monitoring with positive/negative electrospray ionization switching mode. Biologically relevant isomers such as leucine and isoleucine were individually quantified by combining chromatographic separation and fragmentation. Good linearity (R (2) > 0.99) was obtained for all six analytes with the limits of detection from 0.1 to 0.2 µg/mL. The intra-day and inter-day accuracy ranged from 93.7 to 108.4 % and the relative standard deviation (RSD) did not exceed 15.0 %. The recovery was more than 80 % with RSD less than 14.0 %. The main improvements compared to related, state-of-the-art methods included enhanced sensitivity, enhanced separation of isomers, and reduced complexity of sample processing. Finally, the validated method was applied to analyze the plasma samples of healthy volunteers and patients suffering cerebral infarction, and significant differences in the concentration levels of BCAAs and BCKAs were observed. PMID:26984321

  10. Revisiting the metabolism of 19-nortestosterone using isotope ratio and high resolution/high accuracy mass spectrometry.

    PubMed

    Piper, Thomas; Schänzer, Wilhelm; Thevis, Mario

    2016-09-01

    The synthetic anabolic androgenic steroid 19-nortestosterone is prohibited in sports according to the regulations of the World Anti-Doping Agency (WADA) due to its performance-enhancing effects. Today, doping controls focus predominantly on one main urinary metabolite, 19-norandrosterone glucuronide, which offers the required detection windows for an appropriate retrospectivity of sports drug testing programs. As 19-norandrosterone can also be found in urine at low concentrations originating from in situ demethylation of other abundant steroids or from endogenous production, the exogenous source of 19-norandrosterone needs to be verified, which is commonly accomplished by carbon isotope ratio analyses. The aim of this study was to re-investigate the metabolism of 19-nortestosterone in order to probe for additional diagnostic long-term metabolites, which might support the unambiguous attribution of an endo- or exogenous source of detected 19-nortestosterone metabolites. Employing a recently introduced strategy for metabolite identification, threefold deuterated 19-nortestosterone (16,16,17-(2)H3-NT) was administered to one healthy male volunteer and urine samples were collected for 20 days. Samples were prepared with established methods separating unconjugated, glucuronidated and sulfated steroids, and analytes were further purified by means of high-performance liquid chromatography before trimethylsilylation. Deuterated metabolites were identified using gas chromatograph/thermal conversion/isotope ratio mass spectrometer comprising an additional single quadrupole mass spectrometer. Additional structural information was obtained by gas chromatography/time-of-flight mass spectrometry and liquid chromatography/high resolution mass spectrometry. In general, sulfo-conjugated metabolites were excreted for a longer time period than the corresponding glucuronides. Several unexpected losses of the arguably stable isotope labels were observed and characterized, attributed to

  11. Schottky Mass Measurement of the {sup 208}Hg Isotope: Implication for the Proton-Neutron Interaction Strength around Doubly Magic {sup 208}Pb

    SciTech Connect

    Chen, L.; Plass, W. R.; Geissel, H.; Scheidenberger, C.; Litvinov, Yu. A.; Beckert, K.; Beller, P.; Bosch, F.; Caceres, L.; Franzke, B.; Gerl, J.; Gorska, M.; Knoebel, R.; Kozhuharov, C.; Litvinov, S. A.; Mandal, S.; Muenzenberg, G.; Nolden, F.; Saito, N.; Saito, T.

    2009-03-27

    Time-resolved Schottky mass spectrometry has been applied to uranium projectile fragments which yielded the mass value for the {sup 208}Hg (Z=80, N=128) isotope. The mass excess value of ME=-13 265(31) keV has been obtained, which has been used to determine the proton-neutron interaction strength in {sup 210}Pb, as a double difference of atomic masses. The results show a dramatic variation of the strength for lead isotopes when crossing the N=126 neutron shell closure, thus confirming the empirical predictions that this interaction strength is sensitive to the overlap of the wave functions of the last valence neutrons and protons.

  12. Schottky mass measurement of the 208Hg isotope: implication for the proton-neutron interaction strength around doubly magic 208Pb.

    PubMed

    Chen, L; Litvinov, Yu A; Plass, W R; Beckert, K; Beller, P; Bosch, F; Boutin, D; Caceres, L; Cakirli, R B; Carroll, J J; Casten, R F; Chakrawarthy, R S; Cullen, D M; Cullen, I J; Franzke, B; Geissel, H; Gerl, J; Górska, M; Jones, G A; Kishada, A; Knöbel, R; Kozhuharov, C; Litvinov, S A; Liu, Z; Mandal, S; Montes, F; Münzenberg, G; Nolden, F; Ohtsubo, T; Patyk, Z; Podolyák, Zs; Propri, R; Rigby, S; Saito, N; Saito, T; Scheidenberger, C; Shindo, M; Steck, M; Ugorowski, P; Walker, P M; Williams, S; Weick, H; Winkler, M; Wollersheim, H-J; Yamaguchi, T

    2009-03-27

    Time-resolved Schottky mass spectrometry has been applied to uranium projectile fragments which yielded the mass value for the 208Hg (Z=80, N=128) isotope. The mass excess value of ME=-13 265(31) keV has been obtained, which has been used to determine the proton-neutron interaction strength in 210Pb, as a double difference of atomic masses. The results show a dramatic variation of the strength for lead isotopes when crossing the N=126 neutron shell closure, thus confirming the empirical predictions that this interaction strength is sensitive to the overlap of the wave functions of the last valence neutrons and protons. PMID:19392270

  13. Isotope-Ratio-Monitoring Liquid Chromatography Mass Spectrometry (IRM-LCMS): First Results from a Moving Wire Interface System.

    PubMed

    Brand, W A; Dobberstein, P

    1996-08-01

    Abstract A Liquid Chromatography-Combustion (LC-C) Interface, based on a moving wire technique, has been built and tested. The LC effluent is deposited onto a transport wire, which carries the sample through solvent evaporation and combustion ovens. CO(2) from the combustion step is analysed in an isotope ratio mass spectrometer. Performance of the interface was tested by loop injections of sucrose and glucose into a liquid flow of methanol/water (80/20). Accuracy and precision of δ(13)C(PDB) < 1‰ was achieved for sample concentrations > 500 ng/ul (5μl loop), sufficient for studies at natural isotope ratios. In case of (13)C tracer applications the detection limit was determined to be about 20 pg carbon tracer (on wire). PMID:22088119

  14. Measuring the Composition and Stable-Isotope Labeling of Algal Biomass Carbohydrates via Gas Chromatography/Mass Spectrometry.

    PubMed

    McConnell, Brian O; Antoniewicz, Maciek R

    2016-05-01

    We have developed a method to measure carbohydrate composition and stable-isotope labeling in algal biomass using gas chromatography/mass spectrometry (GC/MS). The method consists of two-stage hydrochloric acid hydrolysis, followed by chemical derivatization of the released monomer sugars and quantification by GC/MS. Fully (13)C-labeled sugars are used as internal standards for composition analysis. This convenient, reliable, and accurate single-platform workflow offers advantages over existing methods and opens new opportunities to study carbohydrate metabolism of algae under autotrophic, mixotrophic, and heterotrophic conditions using metabolic flux analysis and isotopic tracers such as (2)H2O and (13)C-glucose. PMID:27042946

  15. Probing Protein 3D Structures and Conformational Changes Using Electrochemistry-Assisted Isotope Labeling Cross-Linking Mass Spectrometry.

    PubMed

    Zheng, Qiuling; Zhang, Hao; Wu, Shiyong; Chen, Hao

    2016-05-01

    This study presents a new chemical cross-linking mass spectrometry (MS) method in combination with electrochemistry and isotope labeling strategy for probing both protein three-dimensional (3D) structures and conformational changes. For the former purpose, the target protein/protein complex is cross-linked with equal mole of premixed light and heavy isotope labeled cross-linkers carrying electrochemically reducible disulfide bonds (i.e., DSP-d0 and DSP-d8 in this study, DSP = dithiobis[succinimidyl propionate]), digested and then electrochemically reduced followed with online MS analysis. Cross-links can be quickly identified because of their reduced intensities upon electrolysis and the presence of doublet isotopic peak characteristics. In addition, electroreduction converts cross-links into linear peptides, facilitating MS/MS analysis to gain increased information about their sequences and modification sites. For the latter purpose of probing protein conformational changes, an altered procedure is adopted, in which the protein in two different conformations is cross-linked using DSP-d0 and DSP-d8 separately, and then the two protein samples are mixed in 1:1 molar ratio. The merged sample is subjected to digestion and electrochemical mass spectrometric analysis. In such a comparative cross-linking experiment, cross-links could still be rapidly recognized based on their responses to electrolysis. More importantly, the ion intensity ratios of light and heavy isotope labeled cross-links reveal the conformational changes of the protein, as exemplified by examining the effect of Ca(2+) on calmodulin conformation alternation. This new cross-linking MS method is fast and would have high value in structural biology. Graphical Abstract ᅟ. PMID:26902947

  16. Probing Protein 3D Structures and Conformational Changes Using Electrochemistry-Assisted Isotope Labeling Cross-Linking Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Zheng, Qiuling; Zhang, Hao; Wu, Shiyong; Chen, Hao

    2016-05-01

    This study presents a new chemical cross-linking mass spectrometry (MS) method in combination with electrochemistry and isotope labeling strategy for probing both protein three-dimensional (3D) structures and conformational changes. For the former purpose, the target protein/protein complex is cross-linked with equal mole of premixed light and heavy isotope labeled cross-linkers carrying electrochemically reducible disulfide bonds (i.e., DSP-d0 and DSP-d8 in this study, DSP = dithiobis[succinimidyl propionate]), digested and then electrochemically reduced followed with online MS analysis. Cross-links can be quickly identified because of their reduced intensities upon electrolysis and the presence of doublet isotopic peak characteristics. In addition, electroreduction converts cross-links into linear peptides, facilitating MS/MS analysis to gain increased information about their sequences and modification sites. For the latter purpose of probing protein conformational changes, an altered procedure is adopted, in which the protein in two different conformations is cross-linked using DSP-d0 and DSP-d8 separately, and then the two protein samples are mixed in 1:1 molar ratio. The merged sample is subjected to digestion and electrochemical mass spectrometric analysis. In such a comparative cross-linking experiment, cross-links could still be rapidly recognized based on their responses to electrolysis. More importantly, the ion intensity ratios of light and heavy isotope labeled cross-links reveal the conformational changes of the protein, as exemplified by examining the effect of Ca2+ on calmodulin conformation alternation. This new cross-linking MS method is fast and would have high value in structural biology.

  17. Probing Protein 3D Structures and Conformational Changes Using Electrochemistry-Assisted Isotope Labeling Cross-Linking Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Zheng, Qiuling; Zhang, Hao; Wu, Shiyong; Chen, Hao

    2016-02-01

    This study presents a new chemical cross-linking mass spectrometry (MS) method in combination with electrochemistry and isotope labeling strategy for probing both protein three-dimensional (3D) structures and conformational changes. For the former purpose, the target protein/protein complex is cross-linked with equal mole of premixed light and heavy isotope labeled cross-linkers carrying electrochemically reducible disulfide bonds (i.e., DSP-d0 and DSP-d8 in this study, DSP = dithiobis[succinimidyl propionate]), digested and then electrochemically reduced followed with online MS analysis. Cross-links can be quickly identified because of their reduced intensities upon electrolysis and the presence of doublet isotopic peak characteristics. In addition, electroreduction converts cross-links into linear peptides, facilitating MS/MS analysis to gain increased information about their sequences and modification sites. For the latter purpose of probing protein conformational changes, an altered procedure is adopted, in which the protein in two different conformations is cross-linked using DSP-d0 and DSP-d8 separately, and then the two protein samples are mixed in 1:1 molar ratio. The merged sample is subjected to digestion and electrochemical mass spectrometric analysis. In such a comparative cross-linking experiment, cross-links could still be rapidly recognized based on their responses to electrolysis. More importantly, the ion intensity ratios of light and heavy isotope labeled cross-links reveal the conformational changes of the protein, as exemplified by examining the effect of Ca2+ on calmodulin conformation alternation. This new cross-linking MS method is fast and would have high value in structural biology.

  18. 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.

  19. Mass-dependent molybdenum isotopes in mid-ocean ridge basalts: A new mantle reference

    NASA Astrophysics Data System (ADS)

    Hibbert, K.; Freymuth, H.; Willbold, M.; Elliott, T.

    2013-12-01

    Molybdenum isotopes have been proposed as a novel tracer for subduction components in arc magmas as well as for recycled crustal components in the source of ocean island basalts. In order to investigate these hypotheses, it is important to establish a reference value for the molybdenum isotope composition of the mantle, which has so far been only poorly constrained and based on continental material and volcanic rocks with large analytical errors [1]. Analysis of samples of basalts from the Mariana arc shows that samples are enriched in Mo relative to Pr, an element with a similar degree of incompatibility during mantle melting. This enrichment correlates with δ98Mo such that the heaviest samples (~+0.16‰ relative to NIST SRM 3134) also have the highest Mo/Pr. The resulting array is interpreted as a result of fluid enrichment of a presumed mantle composition, with isotopically heavy fluids derived from fluid-solid fractionation during slab dehydration [2]. This scenario further implies that the deep recycled, subduction zone processed crust should be isotopically light. There is evidence for this in the Mo isotopic composition of some ocean island basalts (OIBs). Notably, basalts from La Palma, which have radiogenic Pb and Os isotopic compositions proposed to result from a component of recycled mafic oceanic crust, have isotopically light Mo (δ98Mo -0.24 to -0.49‰). Implicit in this apparently self-consistent model is that MORB has a δ98Mo intermediate between the isotopically heavy, fluid-rich arc lavas of the Marianas and the isotopically light basalts of La Palma. The low [Mo] of MORB, coupled with the potential for Fe-Mn coatings to perturb δ98Mo to lower values, has made this a more challenging quest. Here we present new data to constrain this datum for the convecting upper mantle. We have processed up to ~1g of carefully handpicked glasses and obtain values of ~-0.15 to -0.25‰, entirely in keeping with the scenario outlined above. Analysis of

  20. Isotopic Ratio Outlier Analysis of the S. cerevisiae Metabolome Using Accurate Mass Gas Chromatography/Time-of-Flight Mass Spectrometry: A New Method for Discovery.

    PubMed

    Qiu, Yunping; Moir, Robyn; Willis, Ian; Beecher, Chris; Tsai, Yu-Hsuan; Garrett, Timothy J; Yost, Richard A; Kurland, Irwin J

    2016-03-01

    Isotopic ratio outlier analysis (IROA) is a (13)C metabolomics profiling method that eliminates sample to sample variance, discriminates against noise and artifacts, and improves identification of compounds, previously done with accurate mass liquid chromatography/mass spectrometry (LC/MS). This is the first report using IROA technology in combination with accurate mass gas chromatography/time-of-flight mass spectrometry (GC/TOF-MS), here used to examine the S. cerevisiae metabolome. S. cerevisiae was grown in YNB media, containing randomized 95% (13)C, or 5%(13)C glucose as the single carbon source, in order that the isotopomer pattern of all metabolites would mirror the labeled glucose. When these IROA experiments are combined, the abundance of the heavy isotopologues in the 5%(13)C extracts, or light isotopologues in the 95%(13)C extracts, follows the binomial distribution, showing mirrored peak pairs for the molecular ion. The mass difference between the (12)C monoisotopic and the (13)C monoisotopic equals the number of carbons in the molecules. The IROA-GC/MS protocol developed, using both chemical and electron ionization, extends the information acquired from the isotopic peak patterns for formulas generation. The process that can be formulated as an algorithm, in which the number of carbons, as well as the number of methoximations and silylations are used as search constraints. In electron impact (EI/IROA) spectra, the artifactual peaks are identified and easily removed, which has the potential to generate "clean" EI libraries. The combination of chemical ionization (CI) IROA and EI/IROA affords a metabolite identification procedure that enables the identification of coeluting metabolites, and allowed us to characterize 126 metabolites in the current study. PMID:26820234

  1. Illustrating the Concepts of Isotopes and Mass Spectrometry in Introductory Courses: A MALDI-TOF Mass Spectrometry Laboratory Experiment

    ERIC Educational Resources Information Center

    Dopke, Nancy Carter; Lovett, Timothy Neal

    2007-01-01

    Mass spectrometry is a widely used and versatile tool for scientists in many different fields. Soft ionization techniques such as matrix-assisted laser desorption/ionization (MALDI) allow for the analysis of biomolecules, polymers, and clusters. This article describes a MALDI mass spectrometry experiment designed for students in introductory…

  2. Isotope-Encoded Carboxyl Group Footprinting for Mass Spectrometry-Based Protein Conformational Studies

    NASA Astrophysics Data System (ADS)

    Zhang, Hao; Liu, Haijun; Blankenship, Robert E.; Gross, Michael L.

    2016-01-01

    We report an isotope-encoding method coupled with carboxyl-group footprinting to monitor protein conformational changes. The carboxyl groups of aspartic/glutamic acids and of the C-terminus of proteins can serve as reporters for protein conformational changes when labeled with glycine ethyl ester (GEE) mediated by carbodiimide. In the new development, isotope-encoded "heavy" and "light" GEE are used to label separately the two states of the orange carotenoid protein (OCP) from cyanobacteria. Two samples are mixed (1:1 ratio) and analyzed by a single LC-MS/MS experiment. The differences in labeling extent between the two states are represented by the ratio of the "heavy" and "light" peptides, providing information about protein conformational changes. Combining isotope-encoded MS quantitative analysis and carboxyl-group footprinting reduces the time of MS analysis and improves the sensitivity of GEE and other footprinting.

  3. Isotope-Encoded Carboxyl Group Footprinting for Mass Spectrometry-Based Protein Conformational Studies.

    PubMed

    Zhang, Hao; Liu, Haijun; Blankenship, Robert E; Gross, Michael L

    2016-01-01

    We report an isotope-encoding method coupled with carboxyl-group footprinting to monitor protein conformational changes. The carboxyl groups of aspartic/glutamic acids and of the C-terminus of proteins can serve as reporters for protein conformational changes when labeled with glycine ethyl ester (GEE) mediated by carbodiimide. In the new development, isotope-encoded "heavy" and "light" GEE are used to label separately the two states of the orange carotenoid protein (OCP) from cyanobacteria. Two samples are mixed (1:1 ratio) and analyzed by a single LC-MS/MS experiment. The differences in labeling extent between the two states are represented by the ratio of the "heavy" and "light" peptides, providing information about protein conformational changes. Combining isotope-encoded MS quantitative analysis and carboxyl-group footprinting reduces the time of MS analysis and improves the sensitivity of GEE and other footprinting. PMID:26384685

  4. Validation of an isotope dilution gas chromatography-mass spectrometry method for combined analysis of oxysterols and oxyphytosterols in serum samples.

    PubMed

    Schött, Hans-Frieder; Lütjohann, Dieter

    2015-07-01

    We describe the validation of a method for the analysis of oxysterols, i.e. oxycholesterols and oxyphytosterols, in human serum using gas chromatography-mass spectrometry selected ion monitoring (GC-MS-SIM). Concentrations of 7α- and 7β-hydroxy-, and 7oxo-cholesterol, -campesterol, and -sitosterol as well as 4β-hydroxycholesterol and side-chain oxygenated 24S-, 25-, and 27-hydroxycholesterol were determined by isotope dilution methodology. After saponification at room temperature the oxysterols were extracted, separated from their substrates, cholesterol, campesterol, and sitosterol, by solid phase extraction, and subsequently derivatised to their corresponding trimethylsilyl-ethers prior to GC-MS-SIM. In order to prevent artificial autoxidation butylated hydroxytoluene and ethylenediaminetetraacetic acid were added. The validation of the method was performed according to the International Conference on Harmonisation guidance, including limits of detection and quantification, ranges, recovery and precision. Due to improved instrumental settings and work-up procedure, limits of detection and quantification ranged between 8.0-202.0pg/mL and 28.0-674pg/mL, respectively. Recovery data in five calibration points varied between 91.9% and 116.8% and in serum samples between 93.1% and 118.1%. The mean coefficient of variation (CV) for the recovery of all compounds was <10%. Well satisfying CVs for within-day precision (2.1-10.8%) and for between-day precision (2.3-12.1%) were obtained. More than 20 samples could be processed in a single routine day and test series of about 300 samples can be realised without impairment of the validation parameters during a sequence. Comparison of oxysterol and oxyphytosterol content in serum and plasma revealed no difference. A fully validated isotope dilution methodology for the quantification of oxycholesterols and oxyphytosterols from human serum or plasma is presented. PMID:25701095

  5. Momentum autocorrelation function of an impurity in a classical oscillator chain with alternating masses III. Some limiting cases

    NASA Astrophysics Data System (ADS)

    Yu, Ming B.

    2016-04-01

    The momentum autocorrelation function of a mass impurity in a classic diatomic chain is studied using the recurrence relations method. General expressions for the contributions of branch cuts and resonant poles have been derived and illustrated in previous papers I and II, respectively. In the present paper a series of limiting cases that any one of the three masses m0 ,m1 ,m2 approaches to zero or infinity are analyzed. It is found that the cases m0 → 0 and →(2m2)+ are closely related to each other and that the general expressions for the amplitudes are valid also in the limits λ → 0 and ∞. The ergodicity in the case m2 → 0 is studied and the ratio of two specific infinite products is obtained.

  6. An in-depth evaluation of accuracy and precision in Hg isotopic analysis via pneumatic nebulization and cold vapor generation multi-collector ICP-mass spectrometry.

    PubMed

    Rua-Ibarz, Ana; Bolea-Fernandez, Eduardo; Vanhaecke, Frank

    2016-01-01

    Mercury (Hg) isotopic analysis via multi-collector inductively coupled plasma (ICP)-mass spectrometry (MC-ICP-MS) can provide relevant biogeochemical information by revealing sources, pathways, and sinks of this highly toxic metal. In this work, the capabilities and limitations of two different sample introduction systems, based on pneumatic nebulization (PN) and cold vapor generation (CVG), respectively, were evaluated in the context of Hg isotopic analysis via MC-ICP-MS. The effect of (i) instrument settings and acquisition parameters, (ii) concentration of analyte element (Hg), and internal standard (Tl)-used for mass discrimination correction purposes-and (iii) different mass bias correction approaches on the accuracy and precision of Hg isotope ratio results was evaluated. The extent and stability of mass bias were assessed in a long-term study (18 months, n = 250), demonstrating a precision ≤0.006% relative standard deviation (RSD). CVG-MC-ICP-MS showed an approximately 20-fold enhancement in Hg signal intensity compared with PN-MC-ICP-MS. For CVG-MC-ICP-MS, the mass bias induced by instrumental mass discrimination was accurately corrected for by using either external correction in a sample-standard bracketing approach (SSB) or double correction, consisting of the use of Tl as internal standard in a revised version of the Russell law (Baxter approach), followed by SSB. Concomitant matrix elements did not affect CVG-ICP-MS results. Neither with PN, nor with CVG, any evidence for mass-independent discrimination effects in the instrument was observed within the experimental precision obtained. CVG-MC-ICP-MS was finally used for Hg isotopic analysis of reference materials (RMs) of relevant environmental origin. The isotopic composition of Hg in RMs of marine biological origin testified of mass-independent fractionation that affected the odd-numbered Hg isotopes. While older RMs were used for validation purposes, novel Hg isotopic data are provided for the

  7. Geogenic lead isotope signatures from meat products in Great Britain: Potential for use in food authentication and supply chain traceability.

    PubMed

    Evans, Jane A; Pashley, Vanessa; Richards, Gemma J; Brereton, Nicola; Knowles, Toby G

    2015-12-15

    This paper presents lead (Pb) isotope data from samples of farm livestock raised in three areas of Britain that have elevated natural Pb levels: Central Wales, the Mendips and the Derbyshire Peak District. This study highlights three important observations; that the Pb found in modern British meat from these three areas is geogenic and shows no clear evidence of modern tetraethyl anthropogenic Pb contribution; that the generally excellent match between the biological samples and the ore field data, particularly for the Mendip and Welsh data, suggests that this technique might be used to provenance biological products to specific ore sites, under favourable conditions; and that modern systems reflect the same process of biosphere averaging that is analogous to cultural focusing in human archaeological studies that is the process of biological averaging leading to an homogenised isotope signature with increasing Pb concentration. PMID:26282777

  8. Mass spectrometric methods for the direct elemental and isotopic analysis of solid material

    NASA Astrophysics Data System (ADS)

    Ganeev, A. A.; Gubal, A. R.; Potapov, S. V.; Agafonova, N. N.; Nemets, V. M.

    2016-04-01

    Methods for the direct analysis of solids have a number of undeniable advantages over the methods that require preliminary dissolution of samples. High sensitivity and selectivity make the direct mass spectrometric techniques the most in-demand. The review concerns spark source mass spectrometry, laser ionization mass spectrometry, laser ablation inductively coupled plasma mass spectrometry, secondary ion mass spectrometry, secondary neutral mass spectrometry and glow discharge mass spectrometry. Basic principles, analytical characteristics and trends in the development of these techniques are discussed. Particular attention is given to applications of the techniques as well as to their competitive advantages and drawbacks. The bibliography includes 123 references.

  9. Alternative method for gas chromatography-mass spectrometry analysis of short-chain fatty acids in faecal samples.

    PubMed

    García-Villalba, Rocio; Giménez-Bastida, Juan A; García-Conesa, Maria T; Tomás-Barberán, Francisco A; Carlos Espín, Juan; Larrosa, Mar

    2012-08-01

    Short-chain fatty acids are the major end products of bacterial metabolism in the large bowel. They derive mostly from the bacterial breakdown of carbohydrates and are known to have positive health benefits. Due to the biological relevance of these compounds it is important to develop efficient, cheap, fast, and sensitive analytical methods that enable the identification and quantification of the short-chain fatty acids in a large number of biological samples. In this study, a gas chromatography-mass spectrometry method was developed and validated for the analysis of short-chain fatty acids in faecal samples. These volatile compounds were extracted with ethyl acetate and 4-methyl valeric acid was used as an internal standard. No further cleanup, concentration, and derivatization steps were needed and the extract was directly injected onto the column. Recoveries ranged between 65 and 105%, and no matrix effects were observed. The proposed method has wide linear ranges, good inter- and intraday variability values (below 2.6 and 5.6%, respectively) and limits of detection between 0.49 μM (0.29 μg/g) and 4.31 μM (3.8 μg/g). The applicability of this analytical method was successfully tested in faecal samples from rats and humans. PMID:22865755

  10. Alternative method for gas chromatography-mass spectrometry analysis of short-chain fatty acids in faecal samples.

    PubMed

    García-Villalba, Rocio; Giménez-Bastida, Juan A; García-Conesa, Maria T; Tomás-Barberán, Francisco A; Espín, Juan Carlos; Larrosa, Mar

    2012-06-01

    Short-chain fatty acids are the major end products of bacterial metabolism in the large bowel. They derive mostly from the bacterial breakdown of carbohydrates and are known to have positive health benefits. Due to the biological relevance of these compounds it is important to develop efficient, cheap, fast, and sensitive analytical methods that enable the identification and quantification of the short-chain fatty acids in a large number of biological samples. In this study, a gas chromatography-mass spectrometry method was developed and validated for the analysis of short-chain fatty acids in faecal samples. These volatile compounds were extracted with ethyl acetate and 4-methyl valeric acid was used as an internal standard. No further cleanup, concentration, and derivatization steps were needed and the extract was directly injected onto the column. Recoveries ranged between 65 and 105%, and no matrix effects were observed. The proposed method has wide linear ranges, good inter- and intraday variability values (below 2.6 and 5.6%, respectively) and limits of detection between 0.49 μM (0.29 μg/g) and 4.31 μM (3.8 μg/g). The applicability of this analytical method was successfully tested in faecal samples from rats and humans. PMID:22674825

  11. High-Precision Tungsten Isotopic Analysis by Multicollection Negative Thermal Ionization Mass Spectrometry Based on Simultaneous Measurement of W and (18)O/(16)O Isotope Ratios for Accurate Fractionation Correction.

    PubMed

    Trinquier, Anne; Touboul, Mathieu; Walker, Richard J

    2016-02-01

    Determination of the (182)W/(184)W ratio to a precision of ± 5 ppm (2σ) is desirable for constraining the timing of core formation and other early planetary differentiation processes. However, WO3(-) analysis by negative thermal ionization mass spectrometry normally results in a residual correlation between the instrumental-mass-fractionation-corrected (182)W/(184)W and (183)W/(184)W ratios that is attributed to mass-dependent variability of O isotopes over the course of an analysis and between different analyses. A second-order correction using the (183)W/(184)W ratio relies on the assumption that this ratio is constant in nature. This may prove invalid, as has already been realized for other isotope systems. The present study utilizes simultaneous monitoring of the (18)O/(16)O and W isotope ratios to correct oxide interferences on a per-integration basis and thus avoid the need for a double normalization of W isotopes. After normalization of W isotope ratios to a pair of W isotopes, following the exponential law, no residual W-O isotope correlation is observed. However, there is a nonideal mass bias residual correlation between (182)W/(i)W and (183)W/(i)W with time. Without double normalization of W isotopes and on the basis of three or four duplicate analyses, the external reproducibility per session of (182)W/(184)W and (183)W/(184)W normalized to (186)W/(183)W is 5-6 ppm (2σ, 1-3 μg loads). The combined uncertainty per session is less than 4 ppm for (183)W/(184)W and less than 6 ppm for (182)W/(184)W (2σm) for loads between 3000 and 50 ng. PMID:26751903

  12. Accuracy and Reproducibility in Quantification of Plasma Protein Concentrations by Mass Spectrometry without the Use of Isotopic Standards

    PubMed Central

    Kramer, Gertjan; Woolerton, Yvonne; van Straalen, Jan P.; Vissers, Johannes P. C.; Dekker, Nick; Langridge, James I.; Beynon, Robert J.; Speijer, Dave; Sturk, Auguste; Aerts, Johannes M. F. G.

    2015-01-01

    Ba