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Sample records for isotope abundance analysis

  1. Isotopic abundance in atom trap trace analysis

    DOEpatents

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

    2014-03-18

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

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

    PubMed

    Chew, Gina; Walczyk, Thomas

    2013-04-01

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

  3. 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

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

    SciTech Connect

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

    2009-12-01

    This report describes method development and preliminary evaluation for analyzing castor samples for signatures of purifying ricin. Ricin purification from the source castor seeds is essentially a problem of protein purification using common biochemical methods. Indications of protein purification will likely manifest themselves as removal of the non-protein fractions of the seed. Two major, non-protein, types of biochemical constituents in the seed are the castor oil and various carbohydrates. The oil comprises roughly half the seed weight while the carbohydrate component comprises roughly half of the remaining “mash” left after oil and hull removal. Different castor oil and carbohydrate components can serve as indicators of specific toxin processing steps. Ricinoleic acid is a relatively unique fatty acid in nature and is the most abundant component of castor oil. The loss of ricinoleic acid indicates a step to remove oil from the seeds. The relative amounts of carbohydrates and carbohydrate-like compounds, including arabinose, xylose, myo-inositol fucose, rhamnose, glucosamine and mannose detected in the sample can also indicate specific processing steps. For instance, the differential loss of arabinose relative to mannose and N-acetyl glucosamine indicates enrichment for the protein fraction of the seed using protein precipitation. The methods developed in this project center on fatty acid and carbohydrate extraction from castor samples followed by derivatization to permit analysis by gas chromatography-mass spectrometry (GC-MS). Method descriptions herein include: the source and preparation of castor materials used for method evaluation, the equipment and description of procedure required for chemical derivatization, and the instrument parameters used in the analysis. Two types of derivatization methods describe analysis of carbohydrates and one procedure for analysis of fatty acids. Two types of GC-MS analysis is included in the method development, one

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

    SciTech Connect

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

    2011-03-11

    Atom trap trace analysis, a laser-based atom counting method, has been applied to analyze atmospheric {sup 39}Ar (half-life=269 yr), a cosmogenic isotope with an isotopic abundance of 8x10{sup -16}. In addition to the superior selectivity demonstrated in this work, the counting rate and efficiency of atom trap trace analysis have been improved by 2 orders of magnitude over prior results. The significant applications of this new analytical capability lie in radioisotope dating of ice and water samples and in the development of dark matter detectors.

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

    NASA Technical Reports Server (NTRS)

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

    2015-01-01

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

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

    SciTech Connect

    Gunnink, R

    1991-09-01

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

  8. Evaluation of strontium isotope abundance ratios in combination with multi-elemental analysis as a possible tool to study the geographical origin of ciders.

    PubMed

    García-Ruiz, Silvia; Moldovan, Mariella; Fortunato, Giuseppino; Wunderli, Samuel; García Alonso, J Ignacio

    2007-05-01

    In order to evaluate alternative analytical methodologies to study the geographical origin of ciders, both multi-elemental analysis and Sr isotope abundance ratios in combination with multivariate statistical analysis were estimated in 67 samples from England, Switzerland, France and two Spanish regions (Asturias and the Basque Country). A methodology for the precise and accurate determination of the (87)Sr/(86)Sr isotope abundance ratio in ciders by multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) was developed. Major elements (Na, K, Ca and Mg) were measured by ICP-AES and minor and trace elements (Li, Be, B, Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Se, Rb, Sr, Y, Mo, Cd, Sn, Sb, Cs, Ba, La, Ce, W, Tl, Pb, Bi, Th and U) were measured by ICP-MS using a collision cell instrument operated in multitune mode. An analysis of variance (ANOVA test) indicated that group means for B, Cr, Fe, Ni, Cu, Se, Cd, Cs, Ce, W, Pb, Bi and U did not show any significant differences at the 95% confidence level, so these elements were rejected for further statistical analysis. Another group of elements (Li, Be, Sc, Co, Ga, Y, Sn, Sb, La, Tl, Th) was removed from the data set because concentrations were close to the limits of detection for many samples. Therefore, the remaining elements (Na, Mg, Al, K, Ca, Ti, V, Mn, Zn, As, Rb, Sr, Mo, Ba) together with (87)Sr/(86)Sr isotope abundance ratio were considered for principal component analysis (PCA) and linear discriminant analysis (LDA). Finally, LDA was able to classify correctly 100% of cider samples coming from different Spanish regions, France, England and Switzerland when considering Na, Mg, Al, K, Ca, Ti, V, Mn, Zn, As, Rb, Sr, Mo, Ba and (87)Sr/(86)Sr isotope abundance ratio as original variables. PMID:17416223

  9. Helium isotopic abundance variation in nature

    SciTech Connect

    Holden, N.E.

    1993-08-01

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

  10. Carbonate abundances and isotopic compositions in chondrites

    NASA Astrophysics Data System (ADS)

    Alexander, C. M. O'd.; Bowden, R.; Fogel, M. L.; Howard, K. T.

    2015-04-01

    We report the bulk C abundances, and C and O isotopic compositions of carbonates in 64 CM chondrites, 14 CR chondrites, 2 CI chondrites, LEW 85332 (C2), Kaba (CV3), and Semarkona (LL3.0). For the unheated CMs, the total ranges of carbonate isotopic compositions are δ13C ≈ 25-75‰ and δ18O ≈ 15-35‰, and bulk carbonate C contents range from 0.03 to 0.60 wt%. There is no simple correlation between carbonate abundance and isotopic composition, or between either of these parameters and the extent of alteration. Unless accretion was very heterogeneous, the uncorrelated variations in extent of alteration and carbonate abundance suggests that there was a period of open system behavior in the CM parent body, probably prior to or at the start of aqueous alteration. Most of the ranges in CM carbonate isotopic compositions can be explained by their formation at different temperatures (0-130 °C) from a single fluid in which the carbonate O isotopes were controlled by equilibrium with water (δ18O ≈ 5‰) and the C isotopes were controlled by equilibrium with CO and/or CH4 (δ13C ≈ -33‰ or -20‰ for CO- or CH4-dominated systems, respectively). However, carbonate formation would have to have been inefficient, otherwise carbonate compositions would have resembled those of the starting fluid. A quite similar fluid composition (δ18O ≈ -5.5‰, and δ13C ≈ -31‰ or -17‰ for CO- or CH4-dominated systems, respectively) can explain the carbonate compositions of the CIs, although the formation temperatures would have been lower (~10-40 °C) and the relative abundances of calcite and dolomite may play a more important role in determining bulk carbonate compositions than in the CMs. The CR carbonates exhibit a similar range of O isotopes, but an almost bimodal distribution of C isotopes between more (δ13C ≈ 65-80‰) and less altered samples (δ13C ≈ 30-40‰). This bimodality can still be explained by precipitation from fluids with the same isotopic

  11. Carbon isotope analysis in urea at high 13C-abundances using the 13/12CO2-breath test device FANci2.

    PubMed

    Schmidt, G

    2002-09-01

    The increasing application of 13C-labelled urea in medicine requires simple and reasonable methods for measuring highly enriched C in urea. The combination: ultimate organic analysis--mass spectrometry so far prescribed is complicated and expensive. For medical diagnosis, however, isotope selective nondispersive infrared spectrometers (NDIRS) have been available for many years. One of these tools is FANci2 which is very reasonable and easily to be operated. By means of such devices also urea highly enriched in 13C can be analysed, provided that the samples are first diluted with a defined amount of urea of natural isotopic composition and then transformed into carbon dioxide by means of urease. The relative abundance of 13C in this carbon dioxide, measured by nondispersive infrared spectrometry, is then a measure of the 13C abundance in the initial urea sample. Comparison of results of such measurements with those attained by mass spectrometry proves that this procedure is feasible and yields precis results.

  12. Secondary ion mass spectrometry combined with alpha track detection for isotope abundance ratio analysis of individual uranium-bearing particles.

    PubMed

    Esaka, Fumitaka; Magara, Masaaki

    2014-03-01

    Secondary ion mass spectrometry (SIMS) was used in combination with alpha track detection for the efficient analysis of uranium-bearing particles with higher (235)U abundances in environmental samples. A polycarbonate film containing particles was prepared and placed in contact with a CR-39 plastic detector. After exposure for 28 days, the detector was etched in a NaOH solution and each uranium-bearing particle was identified through observation of the alpha tracks recorded in the detector. A portion of the film containing each uranium-bearing particle was cut out and put onto a glassy carbon planchet. The films on the planchet were decomposed through plasma ashing for subsequent uranium abundance ratio analysis with SIMS. The alpha track-SIMS analysis of 10 uranium-bearing particles in a sample taken from a nuclear facility enabled n((235)U)/n((238)U) abundance ratios in the range 0.0072-0.25 to be detected, which were significantly higher than those obtained by SIMS without alpha track detection. The duration of the whole analytical process for analysis of 10 particles was about 32 days. The detection efficiency was calculated to be 27.1±6.5%, based on the analysis of the particles in uranium reference materials. The detection limits, defined as the diameter of the particle which produces alpha tracks more than one for a 28-days exposure, were estimated to be 0.8, 0.9, 1.1, 2.1 and 3.0 μm for the particles having the same uranium abundance ratios with NBL CRM U850, U500, U350, U050 and U010 reference materials, respectively. The use of alpha track detection for subsequent SIMS analysis is an inexpensive and an efficient way to measure uranium-bearing particles with higher (235)U abundances. PMID:24468381

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

    DOEpatents

    Harney, Robert C.; Bloom, Stewart D.

    1978-01-01

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

  14. Position-Specific Isotope Analysis of Xanthines: A (13)C Nuclear Magnetic Resonance Method to Determine the (13)C Intramolecular Composition at Natural Abundance.

    PubMed

    Diomande, Didier G; Martineau, Estelle; Gilbert, Alexis; Nun, Pierrick; Murata, Ariaki; Yamada, Keita; Watanabe, Naoharu; Tea, Illa; Robins, Richard J; Yoshida, Naohiro; Remaud, Gérald S

    2015-07-01

    The natural xanthines caffeine, theobromine, and theophylline are of major commercial importance as flavor constituents in coffee, cocoa, tea, and a number of other beverages. However, their exploitation for authenticity, a requirement in these commodities that have a large origin-based price-range, by the standard method of isotope ratio monitoring by mass spectrometry (irm-MS) is limited. We have now developed a methodology that overcomes this deficit that exploits the power of isotopic quantitative (13)C nuclear magnetic resonance (NMR) spectrometry combined with chemical modification of the xanthines to enable the determination of positional intramolecular (13)C/(12)C ratios (δ(13)Ci) with high precision. However, only caffeine is amenable to analysis: theobromine and theophylline present substantial difficulties due to their poor solubility. However, their N-methylation to caffeine makes spectral acquisition feasible. The method is confirmed as robust, with good repeatability of the δ(13)Ci values in caffeine appropriate for isotope fractionation measurements at natural abundance. It is shown that there is negligible isotope fractionation during the chemical N-methylation procedure. Thus, the method preserves the original positional δ(13)Ci values. The method has been applied to measure the position-specific variation of the (13)C/(12)C distribution in caffeine. Not only is a clear difference between caffeine isolated from different sources observed, but theobromine from cocoa is found to show a (13)C pattern distinct from that of caffeine. PMID:26067163

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

    SciTech Connect

    HOLDEN, N.E.

    2005-08-07

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

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

    NASA Technical Reports Server (NTRS)

    Lauretta, D. S.

    2004-01-01

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

  17. 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.

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

    NASA Technical Reports Server (NTRS)

    Blum, J. D.; Klaue, Bjorn

    2005-01-01

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

  19. Elemental and isotopic abundances in the solar wind

    NASA Technical Reports Server (NTRS)

    Geiss, J.

    1972-01-01

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

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

    SciTech Connect

    HOLDEN, N.E.

    2005-08-13

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

  1. Some isotopic abundances in the cosmic radiation

    NASA Technical Reports Server (NTRS)

    Young, J. S.; Freier, P. S.; Waddington, C. J.

    1980-01-01

    Cosmic ray nuclei with Z not less than 10 have been observed in a detector which measures charge with a double scintillator-Cherenkov array and mass by combining the Cherenkov signal with residual range measured in nuclear emulsions. Results are presented for the isotopic analyses of Al, Ca, Sc, Mn, Fe, Co, Ni and Cu in the energy range 300-800 MeV/amu.

  2. Variations in lead isotopic abundances in Sprague-Dawley rat tissues: possible reason of formation.

    PubMed

    Liu, Duojian; Wu, Jing; Ouyang, Li; Wang, Jingyu

    2014-01-01

    It has been reported in previous research that the lead isotopic composition of blood, urine and feces samples statistically differed from the given lead sources in Sprague-Dawley (SD) rats. However, the reason for this phenomenon is still unclear. An animal experiment was performed to investigate the lead isotope fractionation in diverse biological samples (i.e., lungs, liver, kidneys, bone) and to explore the possible reasons. SD rats were intratracheally instilled with lead acetate at the concentrations of 0, 0.02, 0.2, and 2 mg/kg body weight. Biological samples were collected for lead isotope analysis using an inductively coupled plasma mass spectrometry (ICP-MS). Significant differences are observed in lead isotope abundances among the diverse biological samples. The lead isotope abundances ((206)Pb, (207)Pb and (208)Pb) in diverse biological samples show different degrees and directions of departure from the given lead source. The results suggest that differences in enrichment or depletion capacity for each lead isotope in the various tissues might lead to the variation in lead isotopic abundances in tissues. Moreover, a nonlinear relationship between the blood lead level and the lead isotope abundances in liver and bone is observed. When the whole-blood level is higher than 50 ng/mL, the lead isotopic compositions of biological samples tend to be the same. Thus, the data support the speculation of a fractionation functional threshold.

  3. Variations in Lead Isotopic Abundances in Sprague-Dawley Rat Tissues: Possible Reason of Formation

    PubMed Central

    Liu, Duojian; Wu, Jing; Ouyang, Li; Wang, Jingyu

    2014-01-01

    It has been reported in previous research that the lead isotopic composition of blood, urine and feces samples statistically differed from the given lead sources in Sprague-Dawley (SD) rats. However, the reason for this phenomenon is still unclear. An animal experiment was performed to investigate the lead isotope fractionation in diverse biological samples (i.e., lungs, liver, kidneys, bone) and to explore the possible reasons. SD rats were intratracheally instilled with lead acetate at the concentrations of 0, 0.02, 0.2, and 2 mg/kg body weight. Biological samples were collected for lead isotope analysis using an inductively coupled plasma mass spectrometry (ICP-MS). Significant differences are observed in lead isotope abundances among the diverse biological samples. The lead isotope abundances (206Pb, 207Pb and 208Pb) in diverse biological samples show different degrees and directions of departure from the given lead source. The results suggest that differences in enrichment or depletion capacity for each lead isotope in the various tissues might lead to the variation in lead isotopic abundances in tissues. Moreover, a nonlinear relationship between the blood lead level and the lead isotope abundances in liver and bone is observed. When the whole-blood level is higher than 50 ng/mL, the lead isotopic compositions of biological samples tend to be the same. Thus, the data support the speculation of a fractionation functional threshold. PMID:24587048

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

    SciTech Connect

    Holden, N.E. )

    1989-08-09

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

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

    USGS Publications Warehouse

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

    2002-01-01

    Documented variations in the isotopic compositions of some chemical elements are responsible for expanded uncertainties in the standard atomic weights published by the Commission on Atomic Weights and Isotopic Abundances of the International Union of Pure and Applied Chemistry. This report summarizes reported variations in the isotopic compositions of 20 elements that are due to physical and chemical fractionation processes (not due to radioactive decay) and their effects on the standard atomic-weight uncertainties. For 11 of those elements (hydrogen, lithium, boron, carbon, nitrogen, oxygen, silicon, sulfur, chlorine, copper, and selenium), standard atomic-weight uncertainties have been assigned values that are substantially larger than analytical uncertainties because of common isotope-abundance variations in materials of natural terrestrial origin. For 2 elements (chromium and thallium), recently reported isotope-abundance variations potentially are large enough to result in future expansion of their atomic-weight uncertainties. For 7 elements (magnesium, calcium, iron, zinc, molybdenum, palladium, and tellurium), documented isotope variations in materials of natural terrestrial origin are too small to have a significant effect on their standard atomic-weight uncertainties. This compilation indicates the extent to which the atomic weight of an element in a given material may differ from the standard atomic weight of the element. For most elements given above, data are graphically illustrated by a diagram in which the materials are specified in the ordinate and the compositional ranges are plotted along the abscissa in scales of (1) atomic weight, (2) mole fraction of a selected isotope, and (3) delta value of a selected isotope ratio.

  6. The abundance and isotopic composition of water in eucrites

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

  7. The abundances of isotopes in the cosmic radiation

    NASA Technical Reports Server (NTRS)

    Mewaldt, R. A.

    1989-01-01

    Studies of the isotopic composition of nuclei in the cosmic radiation are reviewed, including abundances of the isotopes of elements from H to Ni, together with their implications for cosmic ray origin, acceleration, and transport in the Galaxy. The review focuses on determinations of the composition of cosmic ray source material, and the extent to which the isotopic composition of this material is different from, or similar to, typical solar system material and other samples of Galactic matter. Theoretical models that have been advanced to explain the observed overabundance of neutron-rich isotopes in cosmic rays are described. Also discussed are studies of various radioactive clocks that record the time-scales associated with the nucleosynthesis, acceleration, and transport of cosmic ray nuclei, and studies of the so-called anomalous cosmic ray component, thought to represent a sample of the neutral interstellar medium.

  8. Simultaneous analysis of abundance and isotopic composition of nitrogen, carbon, and noble gases in lunar basalts: Insights into interior and surface processes on the Moon

    NASA Astrophysics Data System (ADS)

    Mortimer, J.; Verchovsky, A. B.; Anand, M.; Gilmour, I.; Pillinger, C. T.

    2015-07-01

    Simultaneous static-mode mass spectrometric measurements of nitrogen, carbon, helium, neon, and argon extracted from the same aliquot of sample by high-resolution stepped combustion have been made for a suite of six lunar basalts. Collecting abundance and isotopic data for several elements simultaneously from the same sample aliquot enables more detailed identification of different volatile components present in the basalts by comparing release patterns for volatiles across a range of temperature steps. This approach has yielded new data, from which new insights can be gained regarding the indigenous volatile inventory of the Moon. By taking into account N and C data for mid-temperature steps, unaffected by terrestrial contamination or cosmogenic additions, it is possible to determine the indigenous N and C signatures of the lunar basalts. With an average δ15N value of around +0.35‰, the indigenous N component seen in these samples is similar within error to other (albeit limited in number) isotopic measurements of indigenous lunar N. Average C/N ratios for indigenous volatiles in these six basalt samples are much lower than those of the terrestrial depleted mantle, or bulk silicate Earth, possibly suggesting much less C in the lunar interior, relative to N, than on Earth. Cosmogenic isotopes in these samples are well-correlated with published sample exposure ages, and record the rate of in situ production of spallogenic volatiles within material on the lunar surface.

  9. 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.

  10. Calcium isotope analysis by mass spectrometry.

    PubMed

    Boulyga, Sergei F

    2010-01-01

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

  11. Meteoritic Sulfur Isotopic Analysis

    NASA Technical Reports Server (NTRS)

    Thiemens, Mark H.

    1996-01-01

    Funds were requested to continue our program in meteoritic sulfur isotopic analysis. We have recently detected a potential nucleosynthetic sulfur isotopic anomaly. We will search for potential carriers. The documentation of bulk systematics and the possible relation to nebular chemistry and oxygen isotopes will be explored. Analytical techniques for delta(sup 33), delta(sup 34)S, delta(sup 36)S isotopic analysis were improved. Analysis of sub milligram samples is now possible. A possible relation between sulfur isotopes and oxygen was detected, with similar group systematics noted, particularly in the case of aubrites, ureilites and entstatite chondrites. A possible nucleosynthetic excess S-33 has been noted in bulk ureilites and an oldhamite separate from Norton County. High energy proton (approximately 1 GeV) bombardments of iron foils were done to experimentally determine S-33, S-36 spallogenic yields for quantitation of isotopic measurements in iron meteorites. Techniques for measurement of mineral separates were perfected and an analysis program initiated. The systematic behavior of bulk sulfur isotopes will continue to be explored.

  12. Nitrogen isotope abundances in the recent solar wind.

    PubMed

    Kim, J S; Kim, Y; Marti, K; Kerridge, J F

    1995-06-01

    Although lunar crystalline rocks are essentially devoid of nitrogen, the same is not true of the lunar regolith. The nitrogen contents of individual regolith samples (which can be as high as 0.012% by mass) correlate strongly with abundances of noble gases known to be implanted in the lunar surface by solar radiation, indicating that lunar regolith nitrogen is also predominantly of solar origin. The large variability in 15N/14N ratios measured in different regolith samples may thus reflect long-term changes in the isotopic composition of the solar radiation. But attempts to explain these variations have been hampered by the lack of any firm constraint on 15N/14N in the present solar wind. Here we report measurements of nitrogen isotopes from two lunar samples that have had simple (and relatively recent) exposure histories. We find that nitrogen implanted in the lunar surface during the past 10(5) to 5 x 10(7) years has a 15N/14N ratio approximately 40% higher than that in the terrestrial atmosphere, which is substantially lower than most previous estimates. This isotopic signature probably represents the best measure of 15N/14N in the present-day solar wind.

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

    NASA Technical Reports Server (NTRS)

    Wiedenbeck, M. E.

    1977-01-01

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

  14. The Measurement of Iron-Group Isotopic Abundances in the Cosmic Rays Using the Magpie Detector

    NASA Astrophysics Data System (ADS)

    Yanasak, Nathan Eugene

    This thesis details the analysis of data from the MAGPIE detector, a balloon-borne detector designed to measure cosmic ray isotope abundances between 300 and 900 MeV/a μ in the Fe group. MAGPIE consists of a magnetic spectrometer for measuring particle rigidity, and nine stacks of CR-39 plastic nuclear track detectors for measuring charge and velocity. After an Antarctic flight in December of 1991 during which ~2000 Fe nuclei were collected, damage occurred to the spectrometer during the landing of the balloon payload, limiting the analysis to cosmic ray particles that stop in the plastic stack. This limited the energy range of data to between 100 MeV/a μ and 400 MeV/a μ for Fe group elements. The measurement of Fe group isotopes is an important one. Because nuclei from this group have the highest binding energy of all the elements, they represent the primary products during late stellar nucleosynthesis. This characteristic makes Fe group isotopes unique in their ability to probe the interior environment during the final stages of stellar evolution. In addition, the primary decay channel by e- capture for some of the Ni and Co isotopes makes these isotopes ideal for probing the time delay between production of cosmic rays and their acceleration. Finally, the radioactive isotope 54Mn has a mean lifetime that is comparable to residence time of lighter elements in the galaxy, which has been measured using the 10Be isotopic abundance. Both of these abundances are produced primarily through spallation during propagation, and Mn can measure the average density of the propagation medium and residence time for Fe group elements with isotopic abundance measurements of stable spallation products. After etching, the MAGPIE CR-39 plastic was scanned for tracks using an automated microscope and image processing system. This system offers a data acquisition method that is as efficient and much quicker than techniques using a microscope and reticle. Cosmic ray data were

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

    NASA Technical Reports Server (NTRS)

    Webster, Christopher R.; Mahaffy, Paul R.

    2011-01-01

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

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

    NASA Technical Reports Server (NTRS)

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

    1978-01-01

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

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

    NASA Technical Reports Server (NTRS)

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

    2001-01-01

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

  18. Quantitative and In-Depth Survey of the Isotopic Abundance Distribution Errors in Shotgun Proteomics.

    PubMed

    Chang, Cheng; Zhang, Jiyang; Xu, Changming; Zhao, Yan; Ma, Jie; Chen, Tao; He, Fuchu; Xie, Hongwei; Zhu, Yunping

    2016-07-01

    Accuracy is an important metric when mass spectrometry (MS) is used in large-scale quantitative proteomics research. For MS-based quantification by extracting ion chromatogram (XIC), both the mass and intensity dimensions must be accurate. Although much research has focused on mass accuracy in recent years, less attention has been paid to intensity errors. Here, we investigated signal intensity measurement errors systematically and quantitatively using the natural properties of isotopic distributions. First, we defined a normalized isotopic abundance error model and presented its merits and demerits. Second, a comprehensive survey of the isotopic abundance errors using data sets with increasing sample complexities and concentrations was performed. We examined parameters such as error distribution, relationships between signal intensities within one isotopic cluster, and correlations between different peak errors in isotopic profiles. Our data demonstrated that the high resolution MS platforms might also generate large isotopic intensity measurement errors (approximately 20%). Meanwhile, this error can be reduced to less than 5% using a novel correction algorithm, which is based on the theoretical isotopic abundance distribution. Finally, a nonlinear relationship was observed as the abundance error decreased in isotopic profiles with higher intensity. Our findings are expected to provide insight into isotopic abundance recalibration in quantitative proteomics.

  19. Nitrogen abundances and isotopic compositions in lunar samples

    NASA Technical Reports Server (NTRS)

    Becker, R. H.; Clayton, R. N.

    1975-01-01

    Isotopic analyses were carried out on soil separates as well as on bulk samples. Analyses of nitrogen fractions obtained by step-wise heating of the separates were also conducted. It was also attempted to obtain a value for the isotopic composition of indigenous lunar nitrogen from analyses of igneous rock samples. Several breccias were also analyzed for their nitrogen isotope ratios. The significance of the obtained results is discussed. Several lines of evidence point to the conclusion that the isotope ratio of the nitrogen being implanted into the lunar regolith has increased by some 15% over a period of at least 450 million years and possibly as long as 3,700 million years or more. This may be the result of changes in the nitrogen isotope ratio of the solar wind with time, or it may be due to outgassing and subsequent reimplantation of an isotopically light indigenous lunar nitrogen from the lunar interior in the early history of the moon.

  20. Preliminary report on isotope abundance measurements in groundwater samples from the Talbert Injection Barrier Area, Orange County Water District

    SciTech Connect

    Hudson, G.B.; Davisson, M.L.; Velsko, C.; Niemeyer, S.; Esser, B.; Beiriger, J.

    1995-02-01

    This report discusses isotope abundance measurements made on a collection of groundwater samples from the Orange County Water District. The water samples were collected in May, 1994 as part of a preliminary study conducted by LLNL to assess the feasibility of tracing and dating reclaimed water used in the Talbert Injection Barrier. A set of samples were collected both near to and far from the barrier and also at different depths in available monitoring wells. A variety of elements were selected for isotopic analysis; hydrogen (tritium), helium, neon, carbon, chlorine and strontium. The tritium abundance combined with the {sup 3}He and {sup 20}Ne abundance provides a method for age dating young (< 40 yr.) groundwater. The abundance of {sup 14}C provides an age dating technique for older (1,000--50,000 yr.) groundwater. The concentrations of {sup 36}Cl and {sup 87}Sr/{sup 86}Sr give information on sea water mixing and water-rock chemical interactions.

  1. 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

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

    NASA Technical Reports Server (NTRS)

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

    1994-01-01

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

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

    USGS Publications Warehouse

    Meier, A.L.

    1982-01-01

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

  4. Code System to Determine Pu Isotope Abundances from Multichannel Analyzer Gamma Spectra.

    2008-09-26

    Version 00 The MGA (Multiple Group Analysis) program determines the relative abundances of plutonium and other actinide isotopes in different materials. The program analyzes spectra taken of such samples using a 4096-channel germanium (Ge) gamma-ray spectrometer. The code can be run in a one or two detector mode. The first spectrum, which is required and must be taken at a gain of 0.075 Kev/channel with a high resolution planar detector, contains the 0-300Kev energy region.more » The second spectrum, which is optional, must be taken at a gain of 0.25 Kev/channel; it becomes important when analyzing high burnup samples (concentration of Pu241 greater than one percent). Isotopic analysis precisions of one percent or better can be obtained, and no calibrations are required. The system also measures the abundances of U235, U238, Np237, and Am241. A special calibration option is available to perform a one-time peak-shape characterization when first using a new detector system.« less

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

    NASA Technical Reports Server (NTRS)

    Wiedenbeck, M. E.

    1983-01-01

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

  6. System and method for high precision isotope ratio destructive analysis

    SciTech Connect

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

    2013-07-02

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

  7. Conditional flux analysis and stable isotopes

    NASA Astrophysics Data System (ADS)

    Zeeman, M. J.; Knohl, A.; Sturm, P.; Buchmann, N. C.; Thomas, C. K.

    2009-12-01

    We propose to investigate to what extend conditional flux analysis can benefit from the addition of stable isotope information. Stable isotopes have been recognized for their potential as process tracer, and could add an extra dimension to the conditional flux concept, which aims at directly quantifying component fluxes and identifying their sources. Differences in 13C abundance in carbon dioxide can be used to distinguish assimilation or respiration sources, whereas the 18O abundance expresses differences in water exchange, for instance between canopy and soil. Lending to recent advances in measurement technology, stable isotopes can now be measured at high temporal resolutions (10Hz) required for commonly applied micrometeorological methods such as the eddy-covariance technique, or related conditional flux methods. We will present current ideas on how the conditional flux method, as recently proposed and evaluated by Thomas et al. (2008), Scanlon & Sahu (2008), to perform daytime flux partitioning at the ecosystem level, can be refined by stable isotope analysis (13C and 18O) of carbon dioxide as additional dimension for identification of fluxes.

  8. Stable isotope and elemental analysis in ants.

    PubMed

    Smith, Chris R; Tillberg, Chadwick V

    2009-07-01

    Over the past 20 yr, the use of stable isotopes to infer feeding ecology and the examination of how energetic and elemental exchanges are affected by and affect life (ecological stoichiometry) have gained momentum. The ecological diversity of ants makes them interesting models to explore dietary ecology and their role in food webs. Moreover, their ecological dominance in most habitats facilitates sampling. The protocol described here will produce samples adequate for submission to most labs that specialize in high-throughput analysis of stable isotopes; one should check with any particular lab for specific submission instructions. Note, however, that this protocol is designed specifically for the quantification of the natural abundance of stable isotopes; it does not cover the preparation of trace samples. PMID:20147207

  9. Chemical Abundance Analysis of the Symbiotic Red Giants

    NASA Astrophysics Data System (ADS)

    Galan, Cezary; Mikolajewska, Joanna; Hinkle, Kenneth H.

    2015-01-01

    The study of symbiotic stars - the long period, interacting binary systems - composed of red giant donor and a hot, compact companion is important for our understanding of binary stellar evolution in systems where mass loss or transfer take place involving RGB/AGB stars. The elemental abundances of symbiotic giants can track the mass exchange history and can determine their parent stellar population. However, the number of these objects with fairly well determined photospheric composition is insufficient for statistical considerations. Here we present the detailed chemical abundance analysis obtained for the first time for 14 M-type symbiotic giants. The analysis is based on the high resolution (R ˜ 50000), high S/N ˜ 100, near-IR spectra (at H- and K-band regions) obtained with Phoenix/Gemini South spectrometer. Spectrum synthesis employing standard LTE analysis and atmosphere models was used to obtain photospheric abundances of CNO and elements around the iron peak (Sc, Ti, Fe, and Ni). Our analysis reveals mostly slightly sub-solar or near-solar metallicities. We obtained significantly subsolar metallicities for RW Hya, RT Ser, and Hen 3-1213 and slightly super-solar metallicity in V455 Sco. The very low ^{12}C/^{13}C isotopic ratios, ˜6-11, and significant enrichment in nitrogen ^{14}N isotope in almost all giants in our sample indicate that they have experienced the first dredge-up.

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

    SciTech Connect

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

    2008-11-11

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

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

    NASA Technical Reports Server (NTRS)

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

    1986-01-01

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

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

    NASA Technical Reports Server (NTRS)

    Marti, K.

    1980-01-01

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

  13. The isotopic and elemental abundances of neon nuclei accelerated in solar flares

    NASA Technical Reports Server (NTRS)

    Dietrich, W. F.; Simpson, J. A.

    1979-01-01

    The relative isotopic abundances of Ne-20 and Ne-22 in seven solar flares were determined from measurements of the satellite IMP 8, yielding the ratio Ne-20/Ne-22 = 7.7 (+2.3, -1.5) for solar chromospheric matter. This value is in agreement with the ratio for the component neon-A (the 'primordial' component) found in carbonaceous chondrites. An elemental abundance ratio Ne/O = 0.14 + or - 0.01 also has been obtained which agrees closely with earlier reported measurements. It is shown that the effects of preferential acceleration relative to solar-system abundances with increasing charge number observed for some solar flares - though biasing the elemental ratio - does not appear to influence the neon isotopic abundances.

  14. Chemical abundance analysis of symbiotic giants - III. Metallicity and CNO abundance patterns in 24 southern systems

    NASA Astrophysics Data System (ADS)

    Gałan, Cezary; Mikołajewska, Joanna; Hinkle, Kenneth H.; Joyce, Richard R.

    2016-01-01

    The elemental abundances of symbiotic giants are essential to address the role of chemical composition in the evolution of symbiotic binaries, to map their parent population, and to trace their mass transfer history. However, the number of symbiotic giants with fairly well determined photospheric composition is still insufficient for statistical analyses. This is the third in a series of papers on the chemical composition of symbiotic giants determined from high-resolution (R ˜ 50 000), near-infrared spectra. Here we present results for 24 S-type systems. Spectrum synthesis methods employing standard local thermal equilibrium analysis and atmosphere models were used to obtain photospheric abundances of CNO and elements around the iron peak (Fe, Ti, Ni, and Sc). Our analysis reveals metallicities distributed in a wide range from slightly supersolar ([Fe/H] ˜ +0.35 dex) to significantly subsolar ([Fe/H] ˜ -0.8 dex) but principally with near-solar and slightly subsolar metallicity ([Fe/H] ˜ -0.4 to -0.3 dex). The enrichment in 14N isotope, found in all these objects, indicates that the giants have experienced the first dredge-up. This was confirmed in a number of objects by the low 12C/13C ratio (5-23). We found that the relative abundance of [Ti/Fe] is generally large in red symbiotic systems.

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

    NASA Technical Reports Server (NTRS)

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

    1987-01-01

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

  16. Isotopic Analysis and Evolved Gases

    NASA Technical Reports Server (NTRS)

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

    1996-01-01

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

  17. Abundance Analysis of 10 Kepler Planetary Hosts

    NASA Astrophysics Data System (ADS)

    Vaz, Zachary A.; Schuler, Simon C.; Williams, Drake; Cunha, Katia M. L.; Smith, Verne V.; Ghezzi, Luan; Teske, Johanna

    2016-01-01

    This study aims to identify possible connections between the detailed chemical abundances of stars and the existence of small planets discovered by NASA's Kepler spacecraft. We have analyzed high quality Keck/HIRES spectra of the planetary hosts Kepler-65, Kepler-93, Kepler-97, Kepler-98, Kepler-102, Kepler 128, Kepler-406, Kepler-408, Kepler-409, and Kepler-411 and derived the abundances of up to 17 elements for these stars. Results from previous studies have suggested that stellar abundance patterns or "signatures" may indicate the presence of planets, possibly terrestrial planets in particular. Should such patterns exist, they could be used to identify stars with small planets. Here we present the results of our abundance analysis of 10 stars with a variety of exoplanet systems discovered by Kepler and address the hypothesis that chemical abundance signatures can indicate the presence of small planets.This work is generously supported by NASA through a Kepler Participating Scientist grant to SCS (Grant #NNX13AH78G).

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

    NASA Technical Reports Server (NTRS)

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

    2012-01-01

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

  19. Plutonium Isotopic Gamma-Ray Analysis

    1992-01-08

    The MGA8 (Multiple Group Analysis) program determines the relative abundances of plutonium and other actinide isotopes in different materials. The program analyzes spectra taken of such samples using a 4096-channel germanium (Ge) gamma-ray spectrometer. The code can be run in a one or two detector mode. The first spectrum, which is required and must be taken at a gain of 0.075 Kev/channel with a high resolution planar detector, contains the 0-300 Kev energy region. Themore » second spectrum, which is optional, must be taken at a gain of 0.25 Kev/channel; it becomes important when analyzing high burnup samples (concentration of Pu241 greater than one percent). Isotopic analysis precisions of one percent or better can be obtained, and no calibrations are required. The system also measures the abundances of U235, U238, Np237, and Am241. A special calibration option is available to perform a one-time peak-shape characterization when first using a new detector system.« less

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

    NASA Astrophysics Data System (ADS)

    Fujiya, Wataru; Hoppe, Peter; Ott, Ulrich

    2016-07-01

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

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

    NASA Astrophysics Data System (ADS)

    Fujiya, Wataru; Hoppe, Peter; Ott, Ulrich

    2016-09-01

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

  2. Chemical abundance analysis of 19 barium stars

    NASA Astrophysics Data System (ADS)

    Yang, Guo-Chao; Liang, Yan-Chun; Spite, Monique; Chen, Yu-Qin; Zhao, Gang; Zhang, Bo; Liu, Guo-Qing; Liu, Yu-Juan; Liu, Nian; Deng, Li-Cai; Spite, Francois; Hill, Vanessa; Zhang, Cai-Xia

    2016-01-01

    We aim at deriving accurate atmospheric parameters and chemical abundances of 19 barium (Ba) stars, including both strong and mild Ba stars, based on the high signal-to-noise ratio and high resolution Echelle spectra obtained from the 2.16 m telescope at Xinglong station of National Astronomical Observatories, Chinese Academy of Sciences. The chemical abundances of the sample stars were obtained from an LTE, plane-parallel and line-blanketed atmospheric model by inputting the atmospheric parameters (effective temperatures Teff, surface gravities log g, metallicity [Fe/H] and microturbulence velocity ξt) and equivalent widths of stellar absorption lines. These samples of Ba stars are giants as indicated by atmospheric parameters, metallicities and kinematic analysis about UVW velocity. Chemical abundances of 17 elements were obtained for these Ba stars. Their Na, Al, α- and iron-peak elements (O, Na, Mg, Al, Si, Ca, Sc, Ti, V, Cr, Mn, Ni) are similar to the solar abundances. Our samples of Ba stars show obvious overabundances of neutron-capture (n-capture) process elements relative to the Sun. Their median abundances of [Ba/Fe], [La/Fe] and [Eu/Fe] are 0.54, 0.65 and 0.40, respectively. The Y I and Zr I abundances are lower than Ba, La and Eu, but higher than the α- and iron-peak elements for the strong Ba stars and similar to the iron-peak elements for the mild stars. There exists a positive correlation between Ba intensity and [Ba/Fe]. For the n-capture elements (Y, Zr, Ba, La), there is an anti-correlation between their [X/Fe] and [Fe/H]. We identify nine of our sample stars as strong Ba stars with [Ba/Fe] >0.6 where seven of them have Ba intensity Ba=2-5, one has Ba=1.5 and another one has Ba=1.0. The remaining ten stars are classified as mild Ba stars with 0.17<[Ba/Fe] <0.54.

  3. Analysis of hydrogen isotope mixtures

    DOEpatents

    Villa-Aleman, Eliel

    1994-01-01

    An apparatus and method for determining the concentrations of hydrogen isotopes in a sample. Hydrogen in the sample is separated from other elements using a filter selectively permeable to hydrogen. Then the hydrogen is condensed onto a cold finger or cryopump. The cold finger is rotated as pulsed laser energy vaporizes a portion of the condensed hydrogen, forming a packet of molecular hydrogen. The desorbed hydrogen is ionized and admitted into a mass spectrometer for analysis.

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

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

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

  5. 13C and 15N natural isotope abundance reflects breast cancer cell metabolism

    PubMed Central

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

    2016-01-01

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

  6. Modeling stable isotope abundances in atmospheric nitrate using a photochemical box model

    NASA Astrophysics Data System (ADS)

    Mase, D. F.; Michalski, G. M.

    2012-12-01

    NOx is converted into HNO3 in the atmosphere through a complex series of chemical reactions and stable isotopes may be useful for understanding the relative importance of these reactions. Presented here are a series of relatively simple photochemical box model simulations of HNO3 production that utilize stable oxygen and nitrogen isotopes as a tool for understanding the specific chemistry of HNO3 production. These simulations are compared with observations in wet deposition NO3- at 8 National Atmospheric Deposition Program (NADP) sites in the Midwestern US and at several sites in the southwestern US. These comparisons help to address several unanswered questions, including which HNO3-production pathways are the most prevalent and how this prevalence varies in space and time. Additionally, these comparisons lend insights to the role of source and chemistry on nitrogen stable isotope abundances in atmospheric NO3-. The isotope chemical mechanisms can be incorporated into 2D and 3D chemical transport models such as the Community Scale Air Quality model to better understand the chemistry that generates air pollution.

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

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

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

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

    SciTech Connect

    HOLDEN,N.E.

    2007-07-23

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

  9. Relative abundance of the helium isotopes He-3 and He-4 in the cosmic radiation

    NASA Technical Reports Server (NTRS)

    Jordan, S. P.; Meyer, P.

    1984-01-01

    The geomagnetic field near the equator is used to measure the He-3/He-4 abundance ratio near 6 GeV/nucleon. This ratio is found to be 0.24 + or - 0.05, under the assumption that the helium rigidity spectrum has the form dI/dR = about R exp(-2.65). If all He-3 is of secondary origin, this implies an interstellar mean escape-path length of about 15 g/sq cm, a value considerably larger than that determined from observations of heavier elements but compatible with measurements of the helium isotopic ratio at lower energies.

  10. Biological control of calcium isotopic abundances in the global calcium cycle

    SciTech Connect

    Skulan, J.; DePaolo, D.J.; Owens, T.L. |

    1997-06-01

    Measurements of {sup 44}Ca/{sup 40}Ca, expressed as {delta}{sup 44}Ca, were made on igneous rocks and on shell and bone material from modern organisms to investigate the magnitude and origins of calcium isotopic fractionation in nature. The results document a span of 4{per_thousand} in {delta}{sup 44}Ca, measured with the double spike technique to a precision of {+-}0.15{per_thousand}. Volcanic rocks, including basalt and rhyolite, show little variability and cluster near {delta}{sup 44}Ca = 0 {+-}0.2. Systematic analysis of biological samples indicates that biological processing of calcium discriminates against heavy isotopes, and that biological fractionation is the primary generator of calcium isotopic fractionation in nature. Preliminary data suggest that calcium becomes isotopically lighter as it moves through food chains. Calcium carbonate shells of marine microorganisms and deep-sea carbonate ooze have {delta}{sup 44}Ca about 1.0{per_thousand}, lower than seawater; this fractionation causes seawater to be enriched in heavy calcium ({delta}{sup 44}Ca = +0.9) relative to igneous rocks. Marine organisms consequently are isotopically heavier than their terrestrial counterparts at similar trophic level. The calcium isotopic composition of living and fossil organisms may record information on diet and environment. 22 refs., 3 figs., 2 tabs.

  11. The isotopic abundances of neon, magnesium and silicon nuclei accelerated in solar flares

    NASA Technical Reports Server (NTRS)

    Dietrich, W. F.; Simpson, J. A.

    1980-01-01

    Direct measurements of the relative abundance of the isotopes Ne-20 and Ne-22 are reported along with a preliminary value for the Mg-26/Mg-24 ratio and an upper limit to the abundance of Si-30 in solar flare accelerated nuclei. A Ne-20/Ne-22 ratio of 7.7 plus 2.3 or minus 1.7 is in agreement with the ratio for the component Neon-A found in carbonaceous chondrites, while a preliminary value of 0.22 plus or minus 0.07 for Mg-26/Mg-24 is larger by approximately one standard deviation than the expected ratio of 0.14 given by Cameron (1973).

  12. Partitioning Respiration Between Plant and Microbial Sources Using Natural Abundance Stable Carbon Isotopes

    NASA Astrophysics Data System (ADS)

    Dawson, T. E.; Tu, K. P.

    2009-12-01

    Partitioning plant and microbial respiration is important for understanding the mechanistic basis of ecosystem respiration, as each can respond to changes in environmental conditions in different ways and at different timescales. In theory, natural abundance stable C isotopes can allow source partitioning when the isotopic difference between the sources can be resolved. The longstanding notion is that such differences do not exist, yet field measurements to support this conclusion are rare. The question remains as to how much isotopic difference exists between the plant and microbial respiration and whether or not this difference is sufficient for partitioning. We addressed this question by measuring the C isotope ratios (13C/12C) of plant, microbial, and whole ecosystem respiration from three contrasting ecosystems in California. We found significant variation in the 13C/12C ratios between plant and microbial sources. However, isotopic mass balance was not observed in more than half the cases. When isotopic mass balance was observed, the largest isotopic differences were always between CO2 evolved during leaf respiration and SOC decomposition, with leaf respiration more depleted by 1-8 per mil. Within plants, the leaf respiration was more depleted than rhizosphere respiration by 2-6 per mil. Among microbial sources, litter decomposition was more depleted than SOC decomposition by 1-5 per mil. The 13C/12C ratio of bulk C and respired CO2 exhibited similar trends, but bulk C values were clearly not a good surrogate for the 13C/12C ratios of respired CO2. Based on the 13C/12C ratios of respired CO2, belowground respiration accounted for 25% in the redwood forest, 37% in the grassland and 84% in the pine forest. Belowground respiration was further partitioned between rhizosphere, litter and SOC decomposition. Each contributed nearly equal amounts in the redwood forest (30/40/30) whereas litter respiration dominated in the grassland (20/70/10) and pine forest (15

  13. The evolution of the global selenium cycle: Secular trends in Se isotopes and abundances

    NASA Astrophysics Data System (ADS)

    Stüeken, E. E.; Buick, R.; Bekker, A.; Catling, D.; Foriel, J.; Guy, B. M.; Kah, L. C.; Machel, H. G.; Montañez, I. P.; Poulton, S. W.

    2015-08-01

    The Earth's surface has undergone major transitions in its redox state over the past three billion years, which have affected the mobility and distribution of many elements. Here we use Se isotopic and abundance measurements of marine and non-marine mudrocks to reconstruct the evolution of the biogeochemical Se cycle from ∼3.2 Gyr onwards. The six stable isotopes of Se are predominantly fractionated during redox reactions under suboxic conditions, which makes Se a potentially valuable new tool for identifying intermediate stages from an anoxic to a fully oxygenated world. δ82/78Se shows small fractionations of mostly less than 2‰ throughout Earth's history and all are mass-dependent within error. In the Archean, especially after 2.7 Gyr, we find an isotopic enrichment in marine (+0.37 ± 0.27‰) relative to non-marine samples (-0.28 ± 0.67‰), paired with increasing Se abundances. Student t-tests show that these trends are statistically significant. Although we cannot completely rule out the possibility of volcanic Se addition, these trends may indicate the onset of oxidative weathering on land, followed by non-quantitative reduction of Se oxyanions during fluvial transport. The Paleoproterozoic Great Oxidation Event (GOE) is not reflected in the marine δ82/78Se record. However, we find a major inflection in the secular δ82/78Se trend during the Neoproterozoic, from a Precambrian mean of +0.42 ± 0.45‰ to a Phanerozoic mean of -0.19 ± 0.59‰. This drop probably reflects the oxygenation of the deep ocean at this time, stabilizing Se oxyanions throughout the water column. Since then, reduction of Se oxyanions has likely been restricted to anoxic basins and diagenetic environments in sediments. In light of recent Cr isotope data, it is likely that oxidative weathering before the Neoproterozoic produced Se oxyanions in the intermediate redox state SeIV, whereas the fully oxidized species SeVI became more abundant after the Neoproterozoic rise of

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

    NASA Astrophysics Data System (ADS)

    Yang, Weifeng; Guo, Laodong

    2014-11-01

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

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

    NASA Technical Reports Server (NTRS)

    Blake, Geoffrey A.

    2004-01-01

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

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

    NASA Technical Reports Server (NTRS)

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

    1991-01-01

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

  17. Chlorine Isotopes: As a Possible Tracer of Fluid/Bio-Activities on Mars and a Progress Report on Chlorine Isotope Analysis by TIMs

    NASA Technical Reports Server (NTRS)

    Nakamura, N.; Nyquist, L.E.; Reese, Y.; Shih, C-Y.; Numata, M.; Fujitani, T.; Okano, O.

    2009-01-01

    Significantly large mass fractionations between chlorine isotopes (Cl-35, Cl-37) have been reported for terrestrial materials including both geological samples and laboratory materials. Also, the chlorine isotopic composition can be used as a tracer for early solar system processes. Moreover, chlorine is ubiquitous on the Martian surface. Typical chlorine abundances in Gusev soils are approx.0.5 %. The global surface average chlorine abundance also is approx.0.5 %. Striking variations among outcrop rocks at Meridiani were reported with some chlorine abundances as high as approx.2%. Characterizing conditions under which chlorine isotopic fractionation may occur is clearly of interest to planetary science. Thus, we have initiated development of a chlorine isotopic analysis technique using TIMS at NASA-JSC. We present here a progress report on the current status of development at JSC and discuss the possible application of chlorine isotopic analysis to Martian meteorites in a search for fluid- and possibly biological activity on Mars.

  18. Amino acid isotopic analysis in agricultural systems

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A relatively new approach to stable isotopic analysis—referred to as compound-specific isotopic analysis (CSIA)—has emerged, centering on the measurement of 15N:14N ratios in amino acids (glutamic acid and phenylalanine). CSIA has recently been used to generate trophic position estimates among anima...

  19. Helium isotopes and heavier noble gas abundances of water in adjacent sea of Japan

    NASA Astrophysics Data System (ADS)

    Sano, Y.; Takahata, N.; Watanabe, T.; Shirai, K.; Nishizawa, M.

    2003-12-01

    We have measured helium isotopic ratios of water samples collected with various depths in adjacent sea of Japan. The 3He/4He ratios vary significantly from 0.989 Ratm to 1.242 Ratm where Ratm is the atmospheric ratio of 1.39x10-6. It is confirmed that all deep sea water (2000 - 2500 m) of western North Pacific is affected by the mantle helium with a high 3He/4He ratio. More precisely mid-depth (750 - 1500 m) profiles of 3He/4He ratios of northwestern Philippine Sea (Nansei Trench) and east of East China Sea (northeast and southwest of Okinawa Trough) are higher than those of western North Pacific (Off Joban) and comparable to those of northern Philippine Sea (Nankai Trough). Excess 3He of the mid-depth samples may be attributable to the subduction-type mantle helium originated from high-temperature hydrothermal sites in the Okinawa Trough. Noble gas abundances (neon, argon, krypton and xenon) were measured in water samples collected in western North Pacific and northwestern Philippine Sea. Neon abundances show slight excess relative to air saturated sea water at ambient temperature and salinity. This may be due to either air bubble effect or contamination during the sampling. When these effects are corrected using the neon anomaly, heavier noble gas abundances (argon, krypton and xenon) of samples with the temperature higher than 5° C (shallower than 500m) agree well with those of calculated air saturated seawater, while the lower temperature samples (deeper than 500 m) indicate anomaly of -7% to +10%.

  20. Systematic Analysis of Uranium Isotopes

    SciTech Connect

    Young, Phillip G.; Chadwick, Mark B.; MacFarlane, Robert E.; Madland, David G.; Moeller, Peter; Wilson, William B.; Talou, Patrick; Kawano, Toshihiko

    2005-05-24

    We describe recent nuclear model calculations and evaluations of neutron reactions on the uranium isotopes 232-241U in the keV to 30-MeV energy range. This work makes use of extensive sets of measurements for fission, elastic, inelastic (n,xn) and capture, as well as fission probability data. The 235U(n.f) standard cross section was revised, and the fission cross sections of the uranium isotopes, as well as 237Np and 239Pu, were updated using the revised standard. Nuclear reaction model calculations were performed for the whole suite of uranium isotopes to allow us to take advantage of the systematical properties from isotope-to-isotope, which is especially useful for nuclides where few measurements exist. In addition to improving the neutron cross sections and energy-angle distributions, new prompt fission neutron spectra and prompt/delayed neutron multiplicity evaluations are included for several isotopes. These evaluations are among the pre-ENDF/B-VII evaluations that are currently being considered for the new ENDF file. A companion paper in this Conference by MacFarlane describes critical-assembly integral data testing results for U isotopes.

  1. Systematic Analysis of Uranium Isotopes

    NASA Astrophysics Data System (ADS)

    Young, Phillip G.; Chadwick, Mark B.; MacFarlane, Robert E.; Madland, David G.; Möller, Peter; Wilson, William B.; Talou, Patrick; Kawano, Toshihiko

    2005-05-01

    We describe recent nuclear model calculations and evaluations of neutron reactions on the uranium isotopes 232-241U in the keV to 30-MeV energy range. This work makes use of extensive sets of measurements for fission, elastic, inelastic, (n,xn) and capture, as well as fission probability data. The 235U(n.f) standard cross section was revised, and the fission cross sections of the uranium isotopes, as well as 237Np and 239Pu, were updated using the revised standard. Nuclear reaction model calculations were performed for the whole suite of uranium isotopes to allow us to take advantage of the systematical properties from isotope-to-isotope, which is especially useful for nuclides where few measurements exist. In addition to improving the neutron cross sections and energy-angle distributions, new prompt fission neutron spectra and prompt/delayed neutron multiplicity evaluations are included for several isotopes. These evaluations are among the pre-ENDF/B-VII evaluations that are currently being considered for the new ENDF file. A companion paper in this Conference by MacFarlane describes critical-assembly integral data testing results for U isotopes.

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

    PubMed

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

    2013-07-19

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

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

    PubMed

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

    2013-07-19

    Volume mixing and isotope ratios secured with repeated atmospheric measurements taken with the Sample Analysis at Mars instrument suite on the Curiosity rover are: carbon dioxide (CO2), 0.960(±0.007); argon-40 ((40)Ar), 0.0193(±0.0001); nitrogen (N2), 0.0189(±0.0003); oxygen, 1.45(±0.09) × 10(-3); carbon monoxide, < 1.0 × 10(-3); and (40)Ar/(36)Ar, 1.9(±0.3) × 10(3). The (40)Ar/N2 ratio is 1.7 times greater and the (40)Ar/(36)Ar ratio 1.6 times lower than values reported by the Viking Lander mass spectrometer in 1976, whereas other values are generally consistent with Viking and remote sensing observations. The (40)Ar/(36)Ar ratio is consistent with martian meteoritic values, which provides additional strong support for a martian origin of these rocks. The isotopic signature δ(13)C from CO2 of ~45 per mil is independently measured with two instruments. This heavy isotope enrichment in carbon supports the hypothesis of substantial atmospheric loss. PMID:23869014

  4. 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)

  5. Hg stable isotope analysis by the double-spike method.

    PubMed

    Mead, Chris; Johnson, Thomas M

    2010-06-01

    Recent publications suggest great potential for analysis of Hg stable isotope abundances to elucidate sources and/or chemical processes that control the environmental impact of mercury. We have developed a new MC-ICP-MS method for analysis of mercury isotope ratios using the double-spike approach, in which a solution containing enriched (196)Hg and (204)Hg is mixed with samples and provides a means to correct for instrumental mass bias and most isotopic fractionation that may occur during sample preparation and introduction into the instrument. Large amounts of isotopic fractionation induced by sample preparation and introduction into the instrument (e.g., by batch reactors) are corrected for. This may greatly enhance various Hg pre-concentration methods by correcting for minor fractionation that may occur during preparation and removing the need to demonstrate 100% recovery. Current precision, when ratios are normalized to the daily average, is 0.06 per thousand, 0.06 per thousand, 0.05 per thousand, and 0.05 per thousand (2sigma) for (202)Hg/(198)Hg, (201)Hg/(198)Hg, (200)Hg/(198)Hg, and (199)Hg/(198)Hg, respectively. This is slightly better than previously published methods. Additionally, this precision was attained despite the presence of large amounts of other Hg isotopes (e.g., 5.0% atom percent (198)Hg) in the spike solution; substantially better precision could be achieved if purer (196)Hg were used.

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

    NASA Technical Reports Server (NTRS)

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

    1986-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-11-01

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

  8. Natural abundance stable carbon isotope evidence for the routing and de novo synthesis of bone FA and cholesterol.

    PubMed

    Jim, Susan; Ambrose, Stanley H; Evershed, Richard P

    2003-02-01

    This research reported in this paper investigated the relationship between diet and bone FA and cholesterol in rats raised on a variety of isotopically controlled diets comprising 20% C3 or C4 protein (casein) and C3 and/or C4 nonprotein or energy (sucrose, starch, and oil) macronutrients. Compound-specific stable carbon isotope analysis (delta13C) was performed on the FA (16:0, 18:0, 18:1, and 18:2) and cholesterol isolated from the diet (n = 4) and bone (n = 8) of these animals. The dietary signals reflected by the bone lipids were investigated using linear regression analysis. delta13C values of bone cholesterol and stearic (18:0) acid were shown to reflect whole-diet delta13C values, whereas the delta13C values of bone palmitic (16:0), oleic (18:1), and linoleic (18:2) acids reflected dietary FA delta13C values. Dietary signal differences are a result of the balance between direct incorporation (or routing) and de novo synthesis of each of these bone lipids. Estimates of the degree of routing of these bone lipids gleaned from correlations between delta13C(dlipid-wdiet) (= delta13C(diet lipid) - delta13C(whole diet)) spacings and delta13C(blipid-wdiet) (= delta13C(bone lipid) - delta13C(whole diet)) fractionations demonstrated that the extent of routing, where 18:2 > 16:0 > 18:1 > 18:0 > cholesterol, reflected the relative abundances of these lipids in the diet. These findings provide the basis for more accurate insights into diet when the delta13C analysis of bone fatty FA or cholesterol is employed.

  9. Abundance recovery error analysis using simulated AVIRIS data

    NASA Technical Reports Server (NTRS)

    Stoner, William W.; Harsanyi, Joseph C.; Farrand, William H.; Wong, Jennifer A.

    1992-01-01

    Measurement noise and imperfect atmospheric correction translate directly into errors in the determination of the surficial abundance of materials from imaging spectrometer data. The effects of errors on abundance recovery were investigated previously using Monte Carlo simulation methods by Sabol et. al. The drawback of the Monte Carlo approach is that thousands of trials are needed to develop good statistics on the probable error in abundance recovery. This computational burden invariably limits the number of scenarios of interest that can practically be investigated. A more efficient approach is based on covariance analysis. The covariance analysis approach expresses errors in abundance as a function of noise in the spectral measurements and provides a closed form result eliminating the need for multiple trials. Monte Carlo simulation and covariance analysis are used to predict confidence limits for abundance recovery for a scenario which is modeled as being derived from Airborne Visible/Infrared Imaging Spectrometer (AVIRIS).

  10. [Humus composition and stable carbon isotope natural abundance in paddy soil under long-term fertilization].

    PubMed

    Ma, Li; Yang, Lin-Zhang; Ci, En; Wang, Yan; Yin, Shi-Xue; Shen, Ming-Xing

    2008-09-01

    Soil samples were collected from an experimental paddy field with long-term (26 years) fertilization in Taihu Lake region of Jiangsu Province to study the effects of different fertilization on the organic carbon distribution and stable carbon isotope natural abundance (delta 13C) in the soil profile, and on the humus composition. The results showed that long-term fertilization increased the organic carbon content in top soil significantly, and there was a significantly negative exponential correlation between soil organic carbon content and soil depth (P < 0.01). The organic carbon content in 10-30 cm soil layer under chemical fertilizations and in 20-40 cm soil layer under organic fertilizations was relatively stable. Soil delta 13C increased gradually with soil depth, its variation range being from -24% per thousand to -28 per thousand, and had a significantly negative linear correlation with soil organic carbon content (P < 0.05). In 0-20 cm soil layer, the delta 13C in treatments organic manure (M), M + NP, M + NPK, M + straw (R) + N, and R + N decreased significantly; while in 30-50 cm soil layer, the delta 13C in all organic fertilization treatments except R + N increased significantly. Tightly combined humus (humin) was the main humus composition in the soil, occupying 50% or more, and the rest were loosely and stably combined humus. Long-term fertilization increased the content of loosely combined humus and the ratio of humic acid (HA) to fulvic acid (FA).

  11. Zn Isotope Abundances of Lunar Soils 64801, 68841, 69941, and 69961

    NASA Astrophysics Data System (ADS)

    Xue, S.; Herzog, G. F.; Hall, G. S.

    1995-09-01

    Mass fractionation is well established for the isotopes of several elements in lunar soils, notably O, Si, K, Ca (to a lesser extent), and S (see [1,2]). Zinc is nearly as volatile as S and is associated with it in the coatings of pyroclastic deposits (see [3]). It therefore seemed plausible that zinc might also be fractionated and that the degree of fractionation might be correlated with that of sulfur. To test this inference, we have begun to measure Zn isotopic abundances in lunar soils. Here we report results for four Apollo 16 samples from which the magnetic fraction had been previously removed. The samples were ground, weighed, and dissolved in HF, HNO3 and HCl in a Teflon bomb. Zn was separated by anion exchange and analyzed isotopically by using ICP/MS. Only the data for 64Zn, 66Zn, and 68Zn are reported: The molecular ion ^35Cl^16O(sub)2+ interfered with the measurement of 67Zn and counting statistics for 70Zn gave only %-level precision. We used Zn atomic absorption solutions as standards with a known concentration of Ga added to control for instrumental drift. Measured elemental Zn contents are consistent with literature values [4-6]. The isotopic ratios of the samples were expressed as delta-values calculated relative to the corresponding isotopic ratios of the standards. No fractionation (i.e., < 0.2%/AMU) was observed for any of several ordinary chondrites, among them Suizhou and Dhajala. In all four lunar soils, however, we found delta 68Zn~2xdelta 66Zn and delta 66Zn>0 at the one-sigma level. These results indicate mass dependent fractionation. If we make the oversimplified assumption that the Zn isotopic fractionation reflects Rayleigh distillation from a single well-mixed reservoir of material from which Zn evaporated as the atom, then the fraction of Zn retained is given approximately by (1+delta ^YZn/1000)^(-2M(sub)Y/Delta M where Y=66 or 68, M is mass, and Delta M is the mass difference M(sub)Y - M(sub)64. The computations suggest that the

  12. Compound specific isotope analysis of organophosphorus pesticides.

    PubMed

    Wu, Langping; Yao, Jun; Trebse, Polonca; Zhang, Ning; Richnow, Hans H

    2014-09-01

    Compound-specific isotope analysis (CSIA) has been established as a tool to study the environmental fate of a wide range of contaminants. In this study, CSIA was developed to analyse the stable carbon isotope signatures of the widely used organophosphorus pesticides: dichlorvos, omethoate and dimethoate. The linearity of the GC-C-IRMS system was tested for target pesticides and led to an acceptable isotope composition within the uncertainty of the instrument. In order to assess the accuracy of the developed method, the effect of the evaporation procedure on measured carbon isotope composition (δ(13)C) values was studied and showed that concentration by evaporation of solvents had no significant isotope effect. The CSIA was then applied to investigate isotope fractionation of the hydrolysis and photolysis of selected pesticides. The carbon isotope fractionation of tested pesticides was quantified by the Rayleigh model, which revealed a bulk enrichment factor (ε) of -0.2±0.1‰ for hydrolysis of dichlorvos, -1.0±0.1‰ and -3.7±1.1‰ for hydrolysis and photolysis of dimethoate respectively. This study is a first step towards the application of CSIA to trace the transport and degradation of organophosphorus pesticides in the environment.

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

    NASA Astrophysics Data System (ADS)

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

    2001-09-01

    Calibrated values have been obtained for sulfur isotope abundance ratios of sulfur isotope reference materials distributed by the IAEA (Vienna). For the calibration of the measurements, a set of synthetic isotope mixtures were prepared gravimetrically from high purity Ag 2S materials enriched in 32S, 33S, and 34S. All materials were converted into SF 6 gas and subsequently, their sulfur isotope ratios were measured on the SF 5+ species using a special gas source mass spectrometer equipped with a molecular flow inlet system (IRMM's Avogadro II amount comparator). Values for the 32S/ 34S abundance ratios are 22.650 4(20), 22.142 4(20), and 23.393 3(17) for IAEA-S-1, IAEA-S-2, and IAEA-S-3, respectively. The calculated 32S/ 34S abundance ratio for V-CDT is 22.643 6(20), which is very close to the calibrated ratio obtained by Ding et al. (1999). In this way, the zero point of the VCDT scale is anchored firmly to the international system of units SI. The 32S/ 33S abundance ratios are 126.942(47), 125.473(55), 129.072(32), and 126.948(47) for IAEA-S-1, IAEA-S-2, IAEA-S-3, and V-CDT, respectively. In this way, the linearity of the V-CDT scale is improved over this range. The values of the sulfur molar mass for IAEA-S-1 and V-CDT were calculated to be 32.063 877(56) and 32.063 911(56), respectively, the values with the smallest combined uncertainty ever reported for the sulfur molar masses (atomic weights).

  14. The Zn abundance and isotopic composition of diatom frustules, a proxy for Zn availability in ocean surface seawater

    NASA Astrophysics Data System (ADS)

    Andersen, Morten B.; Vance, Derek; Archer, Corey; Anderson, Robert F.; Ellwood, Michael J.; Allen, Claire S.

    2011-01-01

    We have developed cleaning methods for extracting diatomopal from bulk marine sediment samples, for measurement of both zinc (Zn) abundance and isotope composition. This cleaning technique was then applied to a set of Holocene core-top samples from the Southern Ocean. The measured δ66Zn (reported relative to the JMCLyon standard) and Zn/Si ratios from the Southern Ocean diatomopal samples range from 0.7 to 1.5‰, and from 14 to 0.9 μmol/mol, respectively. The Zn abundance and isotope composition data show a clear correlation with opal burial rates and other oceanographic parameters. In common with previous work, we interpret the systematic changes in the Zn/Si ratio to be linked to the variability in the concentrations of bioavailable Zn in the ambient surface seawater where the diatom opal is formed. This variability is likely to be primarily controlled by the degree to which Zn is taken up into phytoplankton biomass. The observed systematic pattern in the δ66Zn compositions of the diatomopal core-top samples is, similarly, likely to reflect changes in the δ66Zn composition of the ambient Zn in the surface waters above the core-top sites, which is progressively driven towards isotopically heavier values by preferential incorporation of the lighter isotopes into phytoplankton organic material. Thus, the systematic relationship between Zn isotopes and abundance observed in the core-top diatomopal samples suggests a potential tool for investigating the biogeochemical cycling of Zn in the past surface ocean for down-core diatomopal material. In this respect, it may be possible to test hypotheses that attribute variations in atmospheric CO2 on glacial-interglacial timescales to the degree to which trace metals limited primary productivity in HNLC zones.

  15. The potential for application of ink stable isotope analysis in questioned document examination.

    PubMed

    Chesson, Lesley A; Tipple, Brett J; Barnette, Janet E; Cerling, Thure E; Ehleringer, James R

    2015-01-01

    We investigated a novel application of stable isotope abundance analysis of nitrogen (15N), carbon (13C), hydrogen (2H), and oxygen (18O) to characterize pen ink. We focused on both ballpoint and gel pen inks. We found that the isotope ratios of ink from pens purchased together in a package were similar and within-package stable isotope ratio variability was not significantly larger than the variability of isotope reference materials used during analysis. In contrast, the isotope ratios of ink from pens of the same brand purchased in three states of the continental USA were significantly different from each other and there was isotope ratio variation among pens of the same brand but different, unknown production periods. The stable isotope ratios of inked paper were statistically distinguishable using measured δ15N values. Paper inked with different gel pens was statistically distinguishable using measured δ2H values. The capacity of stable isotope ratios to differentiate among ballpoint inks as well as gel inks shows that stable isotope analysis may be a useful and quantifiable investigative technique for questioned document examination, although current sample size requirements limit its utility. Application of the technique in casework will require the development of micro-scale sampling and analysis methods.

  16. The potential for application of ink stable isotope analysis in questioned document examination.

    PubMed

    Chesson, Lesley A; Tipple, Brett J; Barnette, Janet E; Cerling, Thure E; Ehleringer, James R

    2015-01-01

    We investigated a novel application of stable isotope abundance analysis of nitrogen (15N), carbon (13C), hydrogen (2H), and oxygen (18O) to characterize pen ink. We focused on both ballpoint and gel pen inks. We found that the isotope ratios of ink from pens purchased together in a package were similar and within-package stable isotope ratio variability was not significantly larger than the variability of isotope reference materials used during analysis. In contrast, the isotope ratios of ink from pens of the same brand purchased in three states of the continental USA were significantly different from each other and there was isotope ratio variation among pens of the same brand but different, unknown production periods. The stable isotope ratios of inked paper were statistically distinguishable using measured δ15N values. Paper inked with different gel pens was statistically distinguishable using measured δ2H values. The capacity of stable isotope ratios to differentiate among ballpoint inks as well as gel inks shows that stable isotope analysis may be a useful and quantifiable investigative technique for questioned document examination, although current sample size requirements limit its utility. Application of the technique in casework will require the development of micro-scale sampling and analysis methods. PMID:25577004

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

    NASA Technical Reports Server (NTRS)

    Clayton, D. D.

    1978-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

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

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

    PubMed

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

    1998-04-17

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

  20. 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.

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

    PubMed

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

    2015-02-01

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

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

    PubMed

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

    2010-12-15

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

  3. Isotopic abundance measurements on solid nuclear-type samples by glow discharge mass spectrometry.

    PubMed

    Betti, M; Rasmussen, G; Koch, L

    1996-07-01

    A double-focusing Glow Discharge Mass Spectrometer (GDMS) installed in a glovebox for nuclear sample screening has been employed for isotopic measurements. Isotopic compositions of zirconium, silicon, lithium, boron, uranium and plutonium which are elements of nuclear concern have been determined. Interferences arising from the matrix sample and the discharge gas (Ar) for each of these elements are discussed. The GDMS results are compared with those from Thermal Ionization Mass Spectrometry (TIMS). For boron and lithium at microg/g-ng/g levels, the two methods gave results in good agreement. In samples containing uranium the isotopic composition obtained by GDMS was in agreement with those from TIMS independently of the enrichment. Attempts for the determination of plutonium isotopic composition were also made. In this case, due to the interferences of uranium at mass 238 and americium at mass 241, the GDMS raw data are complementary with those values obtained from physical non-destructive techniques.

  4. 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.

  5. Abundance of Hepatic Transporters in Caucasians: A Meta-Analysis

    PubMed Central

    Burt, Howard J.; Riedmaier, Arian Emami; Harwood, Matthew D.; Crewe, H. Kim; Gill, Katherine L.

    2016-01-01

    This study aimed to derive quantitative abundance values for key hepatic transporters suitable for in vitro–in vivo extrapolation within a physiologically based pharmacokinetic modeling framework. A meta-analysis was performed whereby data on abundance measurements, sample preparation methods, and donor demography were collated from the literature. To define values for a healthy Caucasian population, a subdatabase was created whereby exclusion criteria were applied to remove samples from non-Caucasian individuals, those with underlying disease, or those with subcellular fractions other than crude membrane. Where a clinically relevant active genotype was known, only samples from individuals with an extensive transporter phenotype were included. Authors were contacted directly when additional information was required. After removing duplicated samples, the weighted mean, geometric mean, standard deviation, coefficient of variation, and between-study homogeneity of transporter abundances were determined. From the complete database containing 24 transporters, suitable abundance data were available for 11 hepatic transporters from nine studies after exclusion criteria were applied. Organic anion transporting polypeptides OATP1B1 and OATP1B3 showed the highest population abundance in healthy adult Caucasians. For several transporters, the variability in abundance was reduced significantly once the exclusion criteria were applied. The highest variability was observed for OATP1B3 > OATP1B1 > multidrug resistance protein 2 > multidrug resistance gene 1. No relationship was found between transporter expression and donor age. To our knowledge, this study provides the first in-depth analysis of current quantitative abundance data for a wide range of hepatic transporters, with the aim of using these data for in vitro–in vivo extrapolation, and highlights the significance of investigating the background of tissue(s) used in quantitative transporter proteomic studies. Similar

  6. Abundance of Hepatic Transporters in Caucasians: A Meta-Analysis.

    PubMed

    Burt, Howard J; Riedmaier, Arian Emami; Harwood, Matthew D; Crewe, H Kim; Gill, Katherine L; Neuhoff, Sibylle

    2016-10-01

    This study aimed to derive quantitative abundance values for key hepatic transporters suitable for in vitro-in vivo extrapolation within a physiologically based pharmacokinetic modeling framework. A meta-analysis was performed whereby data on abundance measurements, sample preparation methods, and donor demography were collated from the literature. To define values for a healthy Caucasian population, a subdatabase was created whereby exclusion criteria were applied to remove samples from non-Caucasian individuals, those with underlying disease, or those with subcellular fractions other than crude membrane. Where a clinically relevant active genotype was known, only samples from individuals with an extensive transporter phenotype were included. Authors were contacted directly when additional information was required. After removing duplicated samples, the weighted mean, geometric mean, standard deviation, coefficient of variation, and between-study homogeneity of transporter abundances were determined. From the complete database containing 24 transporters, suitable abundance data were available for 11 hepatic transporters from nine studies after exclusion criteria were applied. Organic anion transporting polypeptides OATP1B1 and OATP1B3 showed the highest population abundance in healthy adult Caucasians. For several transporters, the variability in abundance was reduced significantly once the exclusion criteria were applied. The highest variability was observed for OATP1B3 > OATP1B1 > multidrug resistance protein 2 > multidrug resistance gene 1. No relationship was found between transporter expression and donor age. To our knowledge, this study provides the first in-depth analysis of current quantitative abundance data for a wide range of hepatic transporters, with the aim of using these data for in vitro-in vivo extrapolation, and highlights the significance of investigating the background of tissue(s) used in quantitative transporter proteomic studies. Similar

  7. Sniffing for Clues to the Dinosaurs Demise: Measurement of Osmium Isotope Compositions and Platinum Group Element Abundances in Volcanic Emissions

    NASA Astrophysics Data System (ADS)

    Sims, K. W.; Peucker-Ehrenbrink, B.; Mather, T.; Pyle, D.; Martin, R.; Gauthier, P.; Aiuppa, A.

    2005-12-01

    Platinum Group Elements (PGE: Os, Ir, Rh, Ru, Pt, Pd) and osmium isotopes measured in marine and terrestrial sediment, snow and ice records are important paleo-tracers of riverine, hydrothermal, extraterrestrial, volcanic and anthropogenic inputs into the global surficial environment. For instance, the marine Os isotope record across the Cretaceous-Tertiary Boundary (KTB) indicates that the onset of the main phase of Deccan volcanism and the transient late Maastrichtian warming preceded the large extraterrestrial impact and the related KTB mass extinction by several hundred thousand years [Ravizza and Peucker-Ehrenbrink, 2003]. Distinguishing extraterrestrial from volcanic PGE sources has been difficult due to the similarity in Os isotopic compositions, complex PGE fractionations, and our lack of knowledge of the Os isotopic composition and PGE abundances in volcanic aerosols. These difficulties have fueled vigorous debate about extraterrestrial vs. volcanic triggers of mass extinctions in the geologic record. To assess the volcanic contribution to the global Re-Os-PGE cycle we have initiated a study of Os isotopic compositions and PGE abundances in volcanic emissions from volcanoes around the globe. Here we report preliminary data on PGE abundances and Os isotopes measured in gas and aerosol filter samples from Vulcan Masaya, Nicaragua and Mt Etna, Italy. Samples were analyzed by ID-ICPMS (ThermoFinnigan ELEMENT 2 and NEPTUNE) at the Woods Hole Oceanographic Institution. Osmium isotope compositions of the filters are unradiogenic (0.1272 to 0.187). Osmium concentrations range from 28 to 97 pg/cubic meter and are 3-4 orders of magnitude lower than those measured by Krahenbuhl et al. [1992] during the spring 1984 eruption of Mauna Loa just after the lava fountaining phase. Normalized PGE abundance patterns are fractionated relative to carbonaceous chondrites and two important features distinguish the pattern from other important PGE sources: 1) Os/Ir is much higher

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

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

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

  9. Silicon isotopic abundance toward evolved stars and its application for presolar grains

    NASA Astrophysics Data System (ADS)

    Peng, T.-C.; Humphreys, E. M. L.; Testi, L.; Baudry, A.; Wittkowski, M.; Rawlings, M. G.; de Gregorio-Monsalvo, I.; Vlemmings, W.; Nyman, L.-A.; Gray, M. D.; de Breuck, C.

    2013-11-01

    Aims: Galactic chemical evolution (GCE) is important for understanding the composition of the present-day interstellar medium (ISM) and of our solar system. In this paper, we aim to track the GCE by using the 29Si/30Si ratios in evolved stars and tentatively relate this to presolar grain composition. Methods: We used the APEX telescope to detect thermal SiO isotopologue emission toward four oxygen-rich M-type stars. Together with the data retrieved from the Herschel science archive and from the literature, we were able to obtain the 29Si/30Si ratios for a total of 15 evolved stars inferred from their optically thin 29SiO and 30SiO emission. These stars cover a range of masses and ages, and because they do not significantly alter 29Si/30Si during their lifetimes, they provide excellent probes of the ISM metallicity (or 29Si/30Si ratio) as a function of time. Results: The 29Si/30Si ratios inferred from the thermal SiO emission tend to be lower toward low-mass oxygen-rich stars (e.g., down to about unity for W Hya), and close to an interstellar or solar value of 1.5 for the higher-mass carbon star IRC+10216 and two red supergiants. There is a tentative correlation between the 29Si/30Si ratios and the mass-loss rates of evolved stars, where we take the mass-loss rate as a proxy for the initial stellar mass or current stellar age. This is consistent with the different abundance ratios found in presolar grains. Before the formation of the Sun, the presolar grains indicate that the bulk of presolar grains already had 29Si/30Si ratios of about 1.5, which is also the ratio we found for the objects younger than the Sun, such as VY CMa and IRC+10216. However, we found that older objects (up to possibly 10 Gyr old) in our sample trace a previous, lower 29Si/30Si value of about 1. Material with this isotopic ratio is present in two subclasses of presolar grains, providing independent evidence of the lower ratio. Therefore, the 29Si/30Si ratio derived from the SiO emission of

  10. Oxygen isotopes in nitrite: Analysis, calibration, and equilibration

    USGS Publications Warehouse

    Casciotti, K.L.; Böhlke, J.K.; McIlvin, M.R.; Mroczkowski, S.J.; Hannon, J.E.

    2007-01-01

    Nitrite is a central intermediate in the nitrogen cycle and can persist in significant concentrations in ocean waters, sediment pore waters, and terrestrial groundwaters. To fully interpret the effect of microbial processes on nitrate (NO3-), nitrite (NO2-), and nitrous oxide (N2O) cycling in these systems, the nitrite pool must be accessible to isotopic analysis. Furthermore, because nitrite interferes with most methods of nitrate isotopic analysis, accurate isotopic analysis of nitrite is essential for correct measurement of nitrate isotopes in a sample that contains nitrite. In this study, nitrite salts with varying oxygen isotopic compositions were prepared and calibrated and then used to test the denitrifier method for nitrite oxygen isotopic analysis. The oxygen isotopic fractionation during nitrite reduction to N2O by Pseudomonas aureofaciens was lower than for nitrate conversion to N2O, while oxygen isotopic exchange between nitrite and water during the reaction was similar. These results enable the extension of the denitrifier method to oxygen isotopic analysis of nitrite (in the absence of nitrate) and correction of nitrate isotopes for the presence of nitrite in "mixed" samples. We tested storage conditions for seawater and freshwater samples that contain nitrite and provide recommendations for accurate oxygen isotopic analysis of nitrite by any method. Finally, we report preliminary results on the equilibrium isotope effect between nitrite and water, which can play an important role in determining the oxygen isotopic value of nitrite where equilibration with water is significant. ?? 2007 American Chemical Society.

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

    USGS Publications Warehouse

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

    2008-01-01

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

  12. Chromium-Isotope and iridium-Abundance Measurements for Late Eocene Impact-Derived Spherule Deposits

    NASA Astrophysics Data System (ADS)

    Kyte, F. T.; Shukolyukov, A.; Hildebrand, A. R.; Lugmair, G. W.; Hanova, J.

    2004-05-01

    The late Eocene (approx. 35 Ma) was a time of multiple large body impacts superimposed within an interval of dust accretion. At least two spherule layers are preserved in deep sea sediments: North American microtektites and the slightly older cpx spherules. The two largest impact structures in the Cenozoic, the 45 km Chesapeake Bay structure and the 100 km Popigai structure, are indicated as the respective spherule sources. Enhanced 3He concentrations extending across a 3 m.y. duration in upper Eocene sediments from the Massignano quarry in Italy indicate accretion of <50 micron dust over this time interval. To characterize one of the impactors we have analyzed splits from the 125-250 micron cpx spherules from ODP 709C, and two fractions from the Massignano layer. Splits of each sample were analyzed for minor and trace elements by instrumental activation analysis (INAA) including Ir, Cr, Fe, Ni, and Co. Additional splits were analyzed for their Cr-isotopic composition, using thermal ionization mass spectrometry. Significant concentrations of Ir were found in all samples, with the highest levels in the Massignano coarse sample and the lowest in the 709C sample. In all cases, element/Ir ratios are much higher than in chondritic meteorites; this may reflect elemental fractionation due to preferential concentration of Cr in spinel growing in the impact fireball. The Cr-isotopic compositions of the 709C and Massignano coarse samples are both non-terrestrial with a positive epsilon 53, indicating a 53Cr/52Cr ratio higher than in terrestrial materials. Microprobe surveys showed that the Massignano samples had significant fine grained oxide grains (mixed with the spherules in the coarse sample) that were not Ni- or Cr-rich, including Ti-rich spinels (likely terrestrial contaminants). In contrast, the ODP 709C sample is a pure extract of generally well-preserved cpx spherules composed of clinopyroxene in a glass matrix. Both the Massignano coarse and the 709C cpx samples

  13. Food Resources of Stream Macronivertebrates Determined by Natural-Abundance stable C and N Isotopes and a 15N Tracer Addition

    SciTech Connect

    Mulholland, P. J.

    2000-01-01

    Trophic relationships were examined using natural-abundance {sup 13}C and {sup 15}N analyses and a {sup 15}N-tracer addition experiment in Walker Branch, a 1st-order forested stream in eastern Tennessee. In the {sup 15}N-tracer addition experiment, we added {sup 15}NH{sub 4} to stream water over a 6-wk period in early spring, and measured {sup 15}N:{sup 14}N ratios in different taxa and biomass compartments over distance and time. Samples collected from a station upstream from the {sup 15}N addition provided data on natural-abundance {sup 13}C:{sup 12}C and {sup 15}N:{sup 14}N ratios. The natural-abundance {sup 15}N analysis proved to be of limited value in identifying food resources of macroinvertebrates because {sup 15}N values were not greatly different among food resources. In general, the natural-abundance stable isotope approach was most useful for determining whether epilithon or detritus were important food resources for organisms that may use both (e.g., the snail Elimia clavaeformis), and to provide corroborative evidence of food resources of taxa for which the {sup 15}N tracer results were not definitive. The {sup 15}N tracer results showed that the mayflies Stenonema spp. and Baetis spp. assimilated primarily epilithon, although Baetis appeared to assimilate a portion of the epilithon (e.g., algal cells) with more rapid N turnover than the bulk pool sampled. Although Elimia did not reach isotopic equilibrium during the tracer experiment, application of a N-turnover model to the field data suggested that it assimilated a combination of epilithon and detritus. The amphipod Gammarus minus appeared to depend mostly on fine benthic organic matter (FBOM), and the coleopteran Anchytarsus bicolor on epixylon. The caddisfly Diplectrona modesta appeared to assimilate primarily a fast N-turnover portion of the FBOM pool, and Simuliidae a fast N-turnover component of the suspended particulate organic matter pool rather than the bulk pool sampled. Together, the

  14. ATTA - A New Method of Ultrasensitive Trace-Isotope Analysis

    NASA Astrophysics Data System (ADS)

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

    2000-10-01

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

  15. Phosphoprotein Isotope-coded Affinity Tags: Application to the Enrichment and Identification of Low-Abundance Phosphoproteins

    SciTech Connect

    Goshe, Michael; Veenstra, Timothy D. ); Panisko, Ellen A.; Conrads, Thomas P. ); Angell, Nicolas H.; Smith, Richard D. )

    2002-02-01

    A novel approach using different isotopic labeling and biotinylation has been developed for the enrichment and quantitation of phosphoseryl and phosphothreonyl-peptides. The phosphoprotein isotope-coded affinity tag (PhIAT) exploits the high affinity biotin-avidin interaction to isolate modified phosphopeptides from a complex mixture of peptides. The PhIAT strategy for quantifying and enriching mixtures for phosphopeptides was demonstrated using a commercially available sample of the phosphoprotein B-casein. A denatured solution of B-casein was labeled using the PhIAT method and after proteolytic digestion, the labeled peptides were isolated using immobilize avidin. The recovered peptides were separated by capillary reversed-phase liquid chromatography and identified by tandem mass spectrometry. PhIAT-labeled peptides corresponding to known O-phosphorylated peptides from B-casein were identified as were phosphorylated peptides from as1-casein and ase-casein, known low-level (< 5%) contaminants of commercially available B-casein. All of the identified phosphopeptides from these caseins have been previously documented to be phosphorylated at the sites elucidated by the PhIAT approach. The results illustrate the efficancy of the PhIAT-labeling strategy to enrich mixtures for phosphopeptides and permit the detection and identification of low abundance phosphopeptides. In addition, experiments using light and heavy isotopic version of the PhIAT reagents demonstrated that a 10% difference in phosphorylation state could be determined between phosphopeptides in comparative samples.

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

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

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

  17. Carbon, nitrogen and sulfur in lunar fines 15012 and 15013 - Abundances, distributions and isotopic compositions

    NASA Technical Reports Server (NTRS)

    Chang, S.; Lawless, J.; Romiez, M.; Kaplan, I. R.; Petrowski, C.; Sakai, H.; Smith, J. W.

    1974-01-01

    Lunar fines 15012,16 and 15013,3 were analyzed by stepwise pyrolysis and acid hydrolysis as well as complete combustion in oxygen to determine carbon, nitrogen and sulfur. In addition, hydrogen was analysed during pyrolysis as well as during hydrolysis. By comparison of the distribution frequencies of C, N, S, H2 and Fe with He-4, considered to have arisen from solar wind contribution, it is concluded that nitrogen and hydrogen have largely a solar origin. Carbon has a significant solar contribution, and metallic iron may have resulted from solar wind interaction with ferrous minerals on the lunar surface. Sulfur probably has a predominantly lunar origin. There is no direct evidence for meteorotic contribution to these samples. Solar wind interaction also has a marked effect on the stable isotope distribution of C-13/C-12, N-15/N-14, and S-34/S-32. In all cases, the heavy isotope was most enriched in the smallest grain-size fraction.

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

    USGS Publications Warehouse

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

    1955-01-01

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

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

    PubMed Central

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

    1979-01-01

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

  20. Abundance analysis of s-process enhanced barium stars

    NASA Astrophysics Data System (ADS)

    Mahanta, Upakul; Karinkuzhi, Drisya; Goswami, Aruna; Duorah, Kalpana

    2016-08-01

    Detailed chemical composition studies of stars with enhanced abundances of neutron-capture elements can provide observational constraints for neutron-capture nucleosynthesis studies and clues for understanding their contribution to the Galactic chemical enrichment. We present abundance results from high-resolution spectral analyses of a sample of four chemically peculiar stars characterized by s-process enhancement. High-Resolution spectra (R ˜42000) of these objects spanning a wavelength range from 4000 to 6800 Å, are taken from the ELODIE archive. We have estimated the stellar atmospheric parameters, the effective temperature Teff, the surface gravity log g, and metallicity [Fe/H] from local thermodynamic equilibrium analysis using model atmospheres. We report estimates of elemental abundances for several neutron-capture elements, Sr, Y, Zr, Ba, La, Ce, Pr, Nd, Sm, Eu and Dy. While HD 49641 and HD 58368 show [Ba/Fe] ≥ 1.16 the other two objects HD 119650 and HD 191010 are found to be mild barium stars with [Ba/Fe] ˜ 0.4. The derived abundances of the elements are interpreted on the basis of existing theories for understanding their origin and evolution.

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

    NASA Technical Reports Server (NTRS)

    Waddington, C. J.

    1975-01-01

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

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

    PubMed

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

    2008-11-01

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

  3. Cyberinfrastructure for isotope analysis and modeling

    NASA Astrophysics Data System (ADS)

    Bowen, Gabriel J.; West, Jason B.; Zhao, Lan; Takahashi, George; Miller, Chris; Zhang, Tonglin

    2012-05-01

    As the quantity and complexity of scientific data expand, accessible interfaces for data manipulation and analysis are needed to support broad and efficient data use. The Isoscapes Modeling, Analysis, and Prediction (IsoMAP; http://isomap.org) Web-based geographical information system (GIS) gateway is an example of such a resource. Recently launched with support from the U.S. National Science Foundation (NSF) Division of Biological Infrastructure, IsoMAP enables analysis and integration of diverse light stable isotope and environmental data by a broad-based user community. It provides an intuitive, spatial interface that streamlines data analysis, modeling, and exploration in research ranging from greenhouse gas biogeochemistry to food science.

  4. Secondary Ionization Mass Spectrometric Analysis of Impurity Element Isotope Ratios in Nuclear Reactor Materials

    SciTech Connect

    Gerlach, David C.; Cliff, John B.; Hurley, David E.; Reid, Bruce D.; Little, Winston W.; Meriwether, George H.; Wickham, Anthony J.; Simmons, Tere A.

    2006-07-30

    Secondary ion mass spectrometry (SIMS) analysis has been used to measure isotope ratios of selected impurity elements in irradiated reactor materials. Samples of reactor materials such as graphite or aluminum alloys are obtained from fuel channels or supporting materials. During reactor operations and fuel burn up, some isotopic abundances change due to nuclear reactions and provide sensitive indicators of neutron fluence. The rate of change is related to cross section for a particular isotope. Different isotopes can be used as indicators of burn up during different stages in the reactor operating history. Isotope ratios of B are useful indicators for low burnup stages early in reactor operations, Ti isotope ratios are useful at later burn up stages, and Cl isotope ratios are useful in both early and later stages. Knowledge of the sample position within the reactor also yields information on the fluence shape or profile. In a sequence of samples from one reactor, 10B/11B ratios decreased from near natural values of 0.25 to < 0.03. Direct SIMS measurements of isotope ratios have been possible in materials, following shaping and surface cleaning trials which have included dry ice micropellet blasting, plasma etching, and vacuum furnace treatment.

  5. The Kaidun chondrite breccia: Petrology, oxygen isotopes, and trace element abundances

    NASA Astrophysics Data System (ADS)

    MacPherson, Glenn J.; Mittlefehldt, David W.; Lipschutz, Michael E.; Clayton, Robert N.; Bullock, Emma S.; Ivanov, Andrei V.; Mayeda, Toshiko K.; Wang, Ming-Sheng

    2009-09-01

    Oxygen isotope and trace element data for 13 samples of the Kaidun chondritic breccia reaffirm the complex polymict nature of this unique meteorite. Bulk Kaidun samples most closely resemble CR chondrites, but the matrix is CI-like. Two separated clasts are CR-like but have some properties that resemble CM, two clasts are enstatite chondrites (one EL and one EH), one clast is an aubrite-like metal-rich impact melt, and one clast is a unique layered olivine-bearing pyroxenite with the isotopic composition of an aubrite. Yet, although each clast resembles a known meteorite group, all deviate in some respect from the norms for those groups. Collectively, Kaidun has sampled materials not yet represented in the world meteorite collections and which greatly extend the definitions of known meteorite groups. Phyllosilicates in Kaidun span a very wide range in composition and vary from clast to clast, suggesting that the aqueous alteration experienced by the clasts predated assembly of the Kaidun parent body.

  6. Applications of stable isotope analysis in mammalian ecology.

    PubMed

    Walter, W David; Kurle, Carolyn M; Hopkins, John B

    2014-01-01

    In this editorial, we provide a brief introduction and summarize the 10 research articles included in this Special Issue on Applications of stable isotope analysis in mammalian ecology. The first three articles report correction and discrimination factors that can be used to more accurately estimate the diets of extinct and extant mammals using stable isotope analysis. The remaining seven applied research articles use stable isotope analysis to address a variety of wildlife conservation and management questions from the oceans to the mountains.

  7. High-resolution abundance analysis of HD 140283

    NASA Astrophysics Data System (ADS)

    Siqueira-Mello, C.; Andrievsky, S. M.; Barbuy, B.; Spite, M.; Spite, F.; Korotin, S. A.

    2015-12-01

    Context. HD 140283 is a reference subgiant that is metal poor and confirmed to be a very old star. The element abundances of this type of old star can constrain the nature and nucleosynthesis processes that occurred in its (even older) progenitors. The present study may shed light on nucleosynthesis processes yielding heavy elements early in the Galaxy. Aims: A detailed analysis of a high-quality spectrum is carried out, with the intent of providing a reference on stellar lines and abundances of a very old, metal-poor subgiant. We aim to derive abundances from most available and measurable spectral lines. Methods: The analysis is carried out using high-resolution (R = 81 000) and high signal-to-noise ratio (800 analysis in non-LTE (NLTE) is based on the MULTI code. We present LTE abundances for 26 elements, and NLTE calculations for the species C i, O i, Na i, Mg i, Al i, K i, Ca i, Sr ii, and Ba ii lines. Results: The abundance analysis provided an extensive line list suitable for metal-poor subgiant stars. The results for Li, CNO, α-, and iron peak elements are in good agreement with literature. The newly NLTE Ba abundance, along with a NLTE Eu correction and a 3D Ba correction from literature, leads to [Eu/Ba] = + 0.59 ± 0.18. This result confirms a dominant r-process contribution, possibly together with a very small contribution from the main s-process, to the neutron-capture elements in HD 140283. Overabundances of the lighter heavy elements and the high abundances derived for Ba, La, and Ce favour the operation of the weak r-process in HD 140283

  8. Accurate experimental determination of the isotope effects on the triple point temperature of water. I. Dependence on the 2H abundance

    NASA Astrophysics Data System (ADS)

    Faghihi, V.; Peruzzi, A.; Aerts-Bijma, A. T.; Jansen, H. G.; Spriensma, J. J.; van Geel, J.; Meijer, H. A. J.

    2015-12-01

    Variation in the isotopic composition of water is one of the major contributors to uncertainty in the realization of the triple point of water (TPW). Although the dependence of the TPW on the isotopic composition of the water has been known for years, there is still a lack of a detailed and accurate experimental determination of the values for the correction constants. This paper is the first of two articles (Part I and Part II) that address quantification of isotope abundance effects on the triple point temperature of water. In this paper, we describe our experimental assessment of the 2H isotope effect. We manufactured five triple point cells with prepared water mixtures with a range of 2H isotopic abundances encompassing widely the natural abundance range, while the 18O and 17O isotopic abundance were kept approximately constant and the 18O  -  17O ratio was close to the Meijer-Li relationship for natural waters. The selected range of 2H isotopic abundances led to cells that realised TPW temperatures between approximately  -140 μK to  +2500 μK with respect to the TPW temperature as realized by VSMOW (Vienna Standard Mean Ocean Water). Our experiment led to determination of the value for the δ2H correction parameter of A2H  =  673 μK / (‰ deviation of δ2H from VSMOW) with a combined uncertainty of 4 μK (k  =  1, or 1σ).

  9. Effectiveness of leaded petrol phase-out in Tianjin, China based on the aerosol lead concentration and isotope abundance ratio.

    PubMed

    Wang, Wan; Liu, Xiande; Zhao, Liwei; Guo, Dongfa; Tian, Xiaodan; Adams, Freddy

    2006-07-01

    The phase-out of leaded petrol has been a measure widely used to reduce atmospheric lead pollution. Since the 1980s, China began to promote unleaded petrol. In order to assess the effectiveness of the measure an isotope fingerprint technique was applied for aerosol samples in the city of Tianjin. After dilute acid leaching, the lead concentration and isotope abundance ratios were determined for 123 samples collected in Tianjin during eight years (1994-2001). The 206Pb/207Pb ratio was lower in summer, when coal combustion emission was low and vehicle exhaust became more important, indicating that the 206Pb/207Pb ratio of leaded petrol in Tianjin is lower than that of aerosol samples. The 206Pb/207Pb ratio gradually increased from 1994 to 2001, a trend that suggests that the contribution from vehicle exhaust was diminishing. Overall, the measurements matched well with national statistical data of leaded and unleaded petrol production. After the nationwide switch to unleaded gasoline, comprehensive control measures are urgently needed to reduce air lead pollution in China, as aerosol lead reduced slightly but remains at a relatively high level.

  10. Comparison of the isotopic abundance of U235 and U238 and the radium activity ratios in Colorado Plateau uranium ores

    USGS Publications Warehouse

    Senftle, F.E.; Stieff, L.; Cuttitta, F.; Kuroda, P.K.

    1957-01-01

    The isotopic abundances of uranium and the radium activity ratios of eleven samples of uranium ore from the Colorado Plateau have been measured. No significant variation in the isotopic abundance of the uranium was noted; with'in the experimental error, the average U235/U238 ratio is 137.7. There is a significant variation in the Ra226/Ra223 activity ratios (0.048-0.143), which indicates a relatively recent alteration of the ore samples. The variations do not, however, explain the lead-uranium and lead-lead age discrepancies. ?? 1957.

  11. Estimating Culicoides sonorensis biting midge abundance using digital image analysis.

    PubMed

    Osborne, C J; Mayo, C E; Mullens, B A; Maclachlan, N J

    2014-12-01

    ImageJ is an open-source software tool used for a variety of scientific objectives including cell counting, shape analysis and image correction. This technology has previously been used to estimate mosquito abundance in surveillance efforts. However, the utility of this application for estimating abundance or parity in the surveillance of Culicoides spp. (Diptera: Ceratopogonidae) has not yet been tested. Culicoides sonorensis (Wirth and Jones), a biting midge often measuring 2.0-2.5 mm in length, is an economically important vector of ruminant arboviruses in California. Current surveillance methods use visual sorting for the characteristics of midges and are very time-intensive for large studies. This project tested the utility of ImageJ as a tool to assist in gross trap enumeration as well as in parity analysis of C. sonorensis in comparison with traditional visual methods of enumeration using a dissecting microscope. Results confirmed that automated counting of midges is a reliable means of approximating midge numbers under certain conditions. Further evaluation confirmed accurate and time-efficient parity analysis in comparison with hand sorting. The ImageJ software shows promise as a tool that can assist and expedite C. sonorensis surveillance. Further, these methods may be useful in other insect surveillance activities.

  12. Carbon-isotopic analysis of dissolved acetate

    NASA Technical Reports Server (NTRS)

    Gelwicks, J. T.; Hayes, J. M.

    1990-01-01

    Heating of dried, acetate-containing solids together with oxalic acid dihydrate conveniently releases acetic acid for purification by gas chromatography. For determination of the carbon-isotopic composition of total acetate, the acetate-containing zone of the chromatographic effluent can be routed directly to a combustion furnace coupled to a vacuum system allowing recovery, purification, and packaging of CO2 for mass-spectrometric analysis. For analysis of methyl carbon, acetic acid can be cryogenically trapped from the chromatographic effluent, then transferred to a tube containing excess NaOH. The tube is evacuated, sealed, and heated to 500 degrees C to produce methane by pyrolysis of sodium acetate. Subsequent combustion of the methane allows determination of the 13C content at the methyl position in the parent acetate. With typical blanks, the standard deviation of single analyses is less than 0.4% for acetate samples larger than 5 micromoles. A full treatment of uncertainties is outlined.

  13. Using natural isotopic abundances to determine the source of nitrous oxide (N2O) emissions

    NASA Astrophysics Data System (ADS)

    Mothet, A.; Sebilo, M.; Laverman, A. M.; Vaury, V.; Mariotti, A.

    2012-04-01

    Numerous greenhouse gas studies have focused on carbon dioxide (CO2), whereas nitrous oxide (N2O) also plays a major role in global warming. Indeed, while nitrous oxide is 1000 times less concentrated than CO2 in the atmosphere, it is 300 times more efficient in terms of global warming potential. In addition, its atmospheric concentration increases with 0,3 % per year. According to the literature, nitrous oxide is produced, in soils and sediments, by two major processes: (1) Nitrification, mediated by autotrophic nitrifying bacteria under oxic conditions; (2) Denitrification, mediated by heterotrophic denitrifying bacteria under anoxic conditions. Denitrification induces intensive, localized and instantaneous fluxes. N2O emissions can be easily measured and modeled. In contrast, nitrification induces weak emissions, but spatially and temporally extended. Therefore, this process could represent a large potential of N2O emissions from soils and sediments. The study of isotopomer's isotopic composition of N2O, i.e. the intramolecular distribution or site preference (SP) determined by 15N measurement allows the determination of the origin of N2O emissions (nitrification vs. denitrification). Recent studies on pure cultures have showed that SP associated with nitrification is 35 ‰ while SP associated with denitrification is 0 ‰. The aim of this study was to determine SP associated with denitrification in soils and sediments, taking into account the environmental denitrifying bacterial communities, and under different environmental variables. To this end, flow-through reactors were used to determine denitrification rates at different temperatures and varying substrate (nitrate) concentrations. Site preference was measured for the different experiments. Different experiments of denitrification were realized in sediment flow through reactors under denitrifying conditions (anoxia, presence of organic matter and nitrate). We used acetylene (25°C) to block the enzyme

  14. Compound specific stable isotope analysis vs. bulk stable isotope analysis of agricultural food products

    NASA Astrophysics Data System (ADS)

    Psomiadis, David; Horváth, Balázs; Nehlich, Olaf; Bodiselitsch, Bernd

    2015-04-01

    The bulk analysis of stable isotopes (carbon, nitrogen, sulphur, oxygen and hydrogen) from food staples is a common tool for inferring origin and/or fraud of food products. Many studies have shown that bulk isotope analyses of agricultural products are able to separate large geographical areas of food origin. However, in micro-localities (regions, districts, and small ranges) these general applications fail in precision and discriminative power. The application of compound specific analysis of specific components of food products helps to increase the precision of established models. Compound groups like fatty acids (FAMEs), vitamins or amino acids can help to add further detailed information on physiological pathways and local conditions (micro-climate, soil, water availability) and therefore might add further information for the separation of micro-localities. In this study we are aiming to demonstrate the power and surplus of information of compound specific isotope analysis in comparison to bulk analysis of agricultural products (e.g. olive oil, cereal crops or similar products) and discuss the advantages and disadvantages of such (labor intense) analysis methods. Here we want to identify tools for further detailed analysis of specific compounds with high powers of region separation for better prediction models.

  15. Petrology, trace element abundances and oxygen isotopic compositions of a compound CAI-chondrule object from Allende

    NASA Astrophysics Data System (ADS)

    Wakaki, S.; Itoh, S.; Tanaka, T.; Yurimoto, H.

    2013-02-01

    We report the petrology, trace element abundances and oxygen isotopic characteristics of a compound CAI-chondrule object, WI-025, found in the Allende CV3 chondrite. The WI-025 is an irregularly shaped inclusion consisting of three texturally and chemically distinct portions: the interior portion, the igneous rim and the intermediate zone located between these two portions. The interior portion consists of anorthite, spinel, olivine and Al-bearing low-Ca pyroxene. The major element chemistry of the interior portion corresponds to that of Al-rich chondrules and is of intermediate character between fine-grained spinel-rich CAIs and ferromagnesian chondrules. The interior portion has abundant 16O-rich spinel (Δ17O = -14.2 to -24.7) and displays a group II CAI-like REE composition. These observations indicate that the interior portion contains a CAI component formed by fractional condensation. The major and trace element chemistry of the interior portion indicate that the CAI had subsequently assimilated chondrule materials through partial melting. The maximum heating temperature of the partial melting is estimated at approximately 1400 °C, similar to the maximum heating temperature of Type-B CAIs. The oxygen isotopic compositions of the olivine and low-Ca pyroxene (Δ17O = -6.3) in the interior portion indicate that the partial melting and chondrule assimilation took place under a moderately 16O-poor nebular gas. The igneous rim is texturally and chemically similar to ferromagnesian chondrules and entirely surrounds the interior portion. The oxygen isotopic compositions of the olivine and low-Ca pyroxene in the igneous rim are indistinguishable from those of the interior olivine and Al-bearing low-Ca pyroxenes. These observations indicate that a chondrule material, which was melted in the same nebular gas as the interior portion, was accreted to the interior portion. The intermediate zone represents a reaction zone accompanying the igneous rim formation. The

  16. Characterizing the Spatial and Temporal Variations in Organic Carbon Abundance and Stable Isotope Ratios in Lake Sediments Containing Evidence of Prehistoric Agriculture

    NASA Astrophysics Data System (ADS)

    Taylor, Z. P.; Finkelstein, D. B.; Horn, S. P.

    2009-12-01

    Intra-basin spatial variability in lake sediments has the potential to limit the utility of interpretations based on the analysis of a single sediment core. We analyzed a network of five sediment cores to assess geochemical and isotopic spatial variability across a lake in southern Costa Rica. Laguna Zoncho (8.813°N, 82.963°W) provides an excellent opportunity to detect spatial variability because it is a small lake (0.75 ha) with a known history of prehistoric maize agriculture in its watershed. During the agricultural period (1770-570 cal BP) at Zoncho, stable carbon isotope values in the five cores average -23 ‰ V-PDB; these values increase to -27 ‰ V-PDB during the subsequent period of forest recovery. In prior work at the lake, this forest recovery was assumed to have been initiated by the Spanish Conquest about AD 1500, but our new findings suggest it may have occurred earlier and have been driven by a different set of circumstances. We attribute the more positive values during the agricultural period to a greater abundance of C4 vegetation in the watershed as the result of agricultural activity that removed native C3 forest vegetation and created fields and disturbed environments that favor C4 plants. Organic carbon contents during the agricultural period average 5 % and increase to an average of 16 % post-Conquest. Molar C/N ratios range from 13 during the agricultural period to 16 after the cessation of agriculture in the watershed. The cores may indicate a non-simultaneous end to agriculture in the watershed. Stable carbon isotope values and organic carbon contents in three of the four cores collected closer to shore contain evidence of an abrupt end of agriculture around 1000 cal. BP. In these cores, stable carbon isotope values indicate a dramatic shift from C4 to C3 inputs and a rapid increase in organic contents. The fourth core shows this shift around 700 cal. BP. The core recovered from the center of the lake records a gradual end to

  17. Chemical preparation of an isotopically enriched superoxide dismutase and its characterization as a standard for species-specific isotope dilution analysis.

    PubMed

    Deitrich, Christian L; Raab, Andrea; Pioselli, Barbara; Thomas-Oates, Jane E; Feldmann, Jörg

    2007-11-01

    The development of methods to analyze accurately and precisely individual metalloproteins is of increasing importance. Here we describe for the first time the chemical preparation and characterization of an isotopically enriched metalloenzyme containing two different metal isotopes. Its evaluation as a standard in species-specific isotope dilution analysis by HPLC coupled to inductively coupled plasma mass spectrometry is carefully evaluated. Our model enzyme bovine superoxide dismutase (SOD) contains both Cu and Zn and is remarkably stable at high temperatures and even under denaturing conditions. The enzyme's metal cofactors were removed under a range of different conditions and replaced with isotopically enriched 65Cu and 68Zn. Depending on the conditions, various isotopic ratios differing from the natural Cu and Zn abundances were obtained for the reconstituted enzyme. Both the wild type and isotopically enriched enzyme had the same migration pattern on native 1D-PAGE. Using an enzyme activity test, we showed that the incorporated 65Cu was bound to the right SOD-binding site, since the measured activity correlated directly with the amount of Cu incorporated. Mixing the native and the isotopically enriched enzyme standard with free enriched 65Cu and 68Zn or a metal chelator did not result in any exchange or loss of the metals from the enzyme at neutral pH. This verifies the stability of the enzyme metal center under the chosen conditions. The isotopically enriched enzyme standard was spiked into a wild type SOD solution to evaluate its use for species-specific isotope dilution experiments. To our knowledge, this is the first report of the chemical preparation of a metalloenzyme containing two different isotopically enriched metals. We provide evidence that the incorporated isotopically enriched metals are bound to the right binding site of SOD using an specific enzymatic activity assay.

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

    PubMed

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

    2014-07-15

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

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

    NASA Technical Reports Server (NTRS)

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

    2013-01-01

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

  20. Radionuclide Data Analysis and Evaluation: More Information From Fewer Isotopes

    NASA Astrophysics Data System (ADS)

    Prinke, A.; McIntyre, J.; Cooper, M.; Haas, D.; Lowrey, J.; Miley, H.; Schrom, B.; Suckow, T.

    2013-12-01

    The analysis of the International Monitoring System radionuclide data sets provides daily concentrations for both particulate and radioxenon isotopes. These isotopes can come from many potential sources such as nuclear reactors, nuclear physics experiments, and medical isotope production. These interesting but irrelevant sources have several of the same radio-isotopic signatures from above or underground nuclear explosions and must be ruled out as part of the determination that an event originated as a nuclear explosion. There are several methods under development that aid in this determination and this poster will briefly cover each: radio-isotopic ratios and parent daughter relationships, co-detection of radioxenon and isotopes found on particulates, and past detection history.

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

    PubMed

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

    1985-01-01

    Several diamond drill cores from formations within the Hamersley Group of Western Australia have been studied for evidence of short-range variations in the isotopic compositions of the carbonates. For a set of 32 adjacent microbands analyzed in a specimen from the Marra Mamba Iron Formation, carbon isotope compositions of individual microbands ranged from -2.8 to -19.8 per mil compared to PDB and oxygen isotope compositions ranged from 10.2 to 20.8 per mil compared to SMOW. A pattern of alternating abundances was present, with the average isotopic contrasts between adjacent microbands being 3.0 per mil for carbon and 3.1 per mil for oxygen. Similar results were obtained for a suite of 34 microbands (in four groups) from the Bruno's Band unit of the Mount Sylvia Formation. Difficulties were experienced in preparing samples of single microbands from the Dales Gorge Member of the Brockman Iron Formation, but overall isotopic compositions were in good agreement with values reported by previous authors. Chemical analyses showed that isotopically light carbon and oxygen were correlated with increased concentrations of iron. The preservation of these millimeter-scale variations in isotopic abundances is interpreted as inconsistent with a metamorphic origin for the isotopically light carbon in the BIF carbonates. A biological origin is favored for the correlated variations in 13C and Fe, and it is suggested that the 13C-depleted carbonates may derive either from fermentative metabolism or from anaerobic respiration. A model is presented in which these processes occur near the sediment-water interface and are coupled with an initial oxidative precipitation of the iron. PMID:11539027

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

    NASA Technical Reports Server (NTRS)

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

    1985-01-01

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

  3. Use of stable isotope analysis in determining aquatic food webs

    EPA Science Inventory

    Stable isotope analysis is a useful tool for describing resource-consumer dynamics in ecosystems. In general, organisms of a given trophic level or functional feeding group will have a stable isotope ratio identifiable different than their prey because of preferential use of one ...

  4. Trophic hierarchies revealed via amino acid isotopic analysis

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Despite the potential of isotopic methods to illuminate trophic function, accurate estimates of lifetime feeding tendencies have remained elusive. A relatively new approach—referred to as compound-specific isotopic analysis (CSIA)—has emerged, centering on the measurement of 15N:14N ratios in amino ...

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

    NASA Astrophysics Data System (ADS)

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

    2010-12-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2001-08-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

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

  8. Potential for using isotopically altered metalloproteins in species-specific isotope dilution analysis of proteins by HPLC coupled to inductively coupled plasma mass spectrometry.

    PubMed

    Harrington, Chris F; Vidler, Daniel S; Watts, Michael J; Hall, John F

    2005-07-01

    The production and evaluation of an isotopically enriched metalloprotein standard for use as a calibrant in species-specific isotope dilution analysis by HPLC coupled to inductively coupled plasma mass spectrometry is described. Using a model system involving the copper-containing protein rusticyanin (Rc) from the bacterium Acido-thiobacillus ferrooxidans, it was possible to demonstrate the analytical conditions that could be used for the measurement of metalloproteins by on-line IDMS analysis. Rc was chosen because it is a well-characterized protein with an established amino acid sequence and can be produced in suitable quantities using a bacterial recombinant system. Three different forms of the protein were studied by organic and inorganic mass spectrometry: the native form of the protein containing a natural isotopic profile for copper, an isotopically enriched species containing virtually all of its copper as the 65Cu isotope, and the nonmetalated apo form. Incorporation of the copper isotopes into the apo form of the protein was determined using a UV-vis spectrophotometric assay and shown to be complete for each of the copper-containing species. The experimental conditions required to maintain the conformational form of the protein with a nonexchangeable copper center were established using +ve electrospray mass spectrometry. A pH 7.0 buffer was found to afford the most appropriate conditions, and this was then used with HPLC-ICP-MS to verify the stability of the copper center by analysis of mixtures of different isotopic solutions. No exchange of the enriched copper isotope from Rc with an added naturally abundant inorganic copper cation was observed under a neutral pH environment, indicating that species-specific ID-MS analysis of metalloproteins is possible.

  9. Changes in biomarker abundances and sulfur isotopes of pyrite across the Permian Triassic (P/Tr) Schuchert Dal section (East Greenland)

    NASA Astrophysics Data System (ADS)

    Fenton, Stephen; Grice, Kliti; Twitchett, Richard J.; Böttcher, Michael E.; Looy, Cindy V.; Nabbefeld, Birgit

    2007-10-01

    In this study, we report on biomarker abundances through parts of the Permian/Triassic boundary (PTB) of Schuchert Dal (East Greenland) that contains rich marine faunal records and excellent terrestrial palynological records. Biomarker abundances and sulfur isotopes are used to correlate the series of events (including changes in element cycling and associated redox conditions of the ocean) surrounding the collapse of the marine and terrestrial ecosystems through this record of a major crisis of life on Earth during a mass extinction episode. The Upper Schuchert Dal Formation contains a low diversity palynological assemblage, ascribed to arborescent cordiaite-conifer-pteridosperm vegetation. Samples from this pre-collapse interval are characterised by high abundances of dibenzofuran (DBF), dibenzothiophene (DBT) and biphenyl. Since these compounds have similar base structures, and show comparable abundance curves, it is plausible that they probably derive from a common source. We propose that phenolic compounds of lignin of the woody plants present during this period could be the source for DBF, DBT and biphenyl. The redox conditions during this period of time also support the formation of DBF and DBT. Just above the extinction interval, there is a dramatic decrease in the abundances of DBF and DBT which occurs at the same time as a sudden change in the stable sulfur isotopic composition ( δ34S) of pyrite, indicating a change in redox conditions from oxic to anoxic/euxinic conditions. δ34S values leading up to the extinction are highly depleted in the heavy sulfur isotope (about - 40‰ vs. VCDT), whilst shortly after the extinction interval much more positive isotope values are observed (about - 25‰). An inferred change in the biogeochemical sulfur cycle is supported by facies evidence from similar neighbouring sections. It is suggested that two processes are operating closely here; 1) Changes in redox conditions and 2) extinction and/or transgression

  10. Isotope ratio determination in boron analysis.

    PubMed

    Sah, R N; Brown, P H

    1998-01-01

    Traditionally, boron (B) isotope ratios have been determined using thermal ionization mass spectrometry (TIMS) and, to some extent, secondary ion mass spectrometry (SIMS). Both TIMS and SIMS use a high-resolution mass analyzer, but differ in analyte ionization methods. TIMS uses electrons from a hot filament, whereas SIMS employs an energetic primary ion beam of Ga+, Cs+, or O- for analyte ionization. TIMS can be used in negative or positive ion modes with high sensitivity and precision of B isotope ratio determination. However, isobaric interferences may be a problem, if the sample is not well purified and/or memory of the previous sample is not removed. Time-consuming sample preparation, analyte (B) purification, and sample determination processes limit the applications of TIMS for routine analyses. SIMS can determine B and its isotope ratio in intact solid samples without destroying them, but has poorer resolution and sensitivity than TIMS, and is difficult to standardize for biological samples. Development of plasma-source mass spectrometry (MS) enabled the determination of B concentration and isotope ratio without requiring sample purification. Commonly used plasma-source MS uses an Ar inductively coupled plasma (ICP) as an ionization device interfaced to a low-resolution quadrupole mass analyzer. The quadrupole ICP-MS is less precise than TIMS and SIMS, but is a popular method for B isotope ratio determination because of its speed and convenience. B determination by ICP-MS suffers no spectroscopic interferences. However, sample matrices, memory effects, and some instrument parameters may affect the accuracy and precision of B isotope ratio determination if adequate precautions are not taken. New generations of plasma-source MS instruments using high-resolution mass analyzers provide better sensitivity and precision than the currently used quadrupole ICP-MS. Because of the convenience and high sample throughput, the high-resolution ICP-MS is expected to be the

  11. Use of Stable Isotopes in Forensic Analysis of Microorganisms

    SciTech Connect

    Kreuzer-Martin, Helen W.; Hegg, Eric L.

    2012-01-18

    The use of isotopic signatures for forensic analysis of biological materials is well-established, and the same general principles that apply to interpretation of stable isotope content of C, N, O, and H apply to the analysis of microorganisms. Heterotrophic microorganisms derive their isotopic content from their growth substrates, which are largely plant and animal products, and the water in their culture medium. Thus the isotope signatures of microbes are tied to their growth environment. The C, N, O, and H isotope ratios of spores have been demonstrated to constitute highly discriminating signatures for sample matching. They can rule out specific samples of media and/or water as possible production media, and can predict isotope ratio ranges of the culture media and water used to produce a given sample. These applications have been developed and tested through analyses of approximately 250 samples of Bacillus subtilis spores and over 500 samples of culture media, providing a strong statistical basis for data interpretation. A Bayesian statistical framework for integrating stable isotope data with other types of signatures derived from microorganisms has been able to characterize the culture medium used to produce spores of various Bacillus species, leveraging isotopic differences in different medium types and demonstrating the power of data integration for forensic investigations.

  12. Multivariate Stable Isotope Analysis to Determine Linkages between Benzocaine Seizures

    NASA Astrophysics Data System (ADS)

    Kemp, H. F.; Meier-Augenstein, W.; Collins, M.; Salouros, H.; Cunningham, A.; Harrison, M.

    2012-04-01

    In July 2010, a woman was jailed for nine years in the UK after the prosecution successfully argued that attempting to import a cutting agent was proof of involvement in a conspiracy to supply Cocaine. That landmark ruling provided law enforcement agencies with much greater scope to tackle those involved in this aspect of the drug trade, specifically targeting those importing the likes of benzocaine or lidocaine. Huge quantities of these compounds are imported into the UK and between May and August 2010, four shipments of Benzocaine amounting to more then 4 tons had been seized as part of Operation Kitley, a joint initiative between the UK Border Agency and the Serious Organised Crime Agency (SOCA). By diluting cocaine, traffickers can make it go a lot further for very little cost, leading to huge profits. In recent years, dealers have moved away from inert substances, like sugar and baby milk powder, in favour of active pharmaceutical ingredients (APIs), including anaesthetics like Benzocaine and Lidocaine. Both these mimic the numbing effect of cocaine, and resemble it closely in colour, texture and some chemical behaviours, making it easier to conceal the fact that the drug has been diluted. API cutting agents have helped traffickers to maintain steady supplies in the face of successful interdiction and even expand the market in the UK, particularly to young people aged from their mid teens to early twenties. From importation to street-level, the purity of the drug can be reduced up to a factor of 80 and street level cocaine can have a cocaine content as low as 1%. In view of the increasing use of Benzocaine as cutting agent for Cocaine, a study was carried out to investigate if 2H, 13C, 15N and 18O stable isotope signatures could be used in conjunction with multivariate chemometric data analysis to determine potential linkage between benzocaine exhibits seized from different locations or individuals to assist with investigation and prosecution of drug

  13. Basalt Pb isotope analysis and the prehistoric settlement of Polynesia.

    PubMed

    Weisler, M I; Woodhead, J D

    1995-03-14

    The prehistoric settlement of the Pacific Ocean has intrigued scholars and stimulated anthropological debate for the past two centuries. Colonized over a few millennia during the mid to late Holocene, the islands of the Pacific--displaying a wide diversity of geological and biotic variability--provided the stage for endless "natural experiments" in human adaptation. Crucial to understanding the evolution and transformation of island societies is documenting the relative degree of interisland contacts after island colonization. In the western Pacific, ideal materials for archaeologically documenting interisland contact--obsidian, pottery, and shell ornaments--are absent or of limited geographic distribution in Polynesia. Consequently, archaeologists have relied increasingly on fine-grained basalt artifacts as a means for documenting colonization routes and subsequent interisland contacts. Routinely used x-ray fluorescence characterization of oceanic island basalt has some problems for discriminating source rocks and artifacts in provenance studies. The variation in trace and major element abundances is largely controlled by near-surface magma-chamber processes and is broadly similar between most oceanic islands. We demonstrate that Pb isotope analysis accurately discriminates rock source and is an excellent technique for charting the scale, frequency, and temporal span of imported fine-grained basalt artifacts found throughout Polynesia. The technique adds another tool for addressing evolutionary models of interaction, isolation, and cultural divergence in the eastern Pacific. PMID:7892194

  14. Basalt Pb isotope analysis and the prehistoric settlement of Polynesia.

    PubMed

    Weisler, M I; Woodhead, J D

    1995-03-14

    The prehistoric settlement of the Pacific Ocean has intrigued scholars and stimulated anthropological debate for the past two centuries. Colonized over a few millennia during the mid to late Holocene, the islands of the Pacific--displaying a wide diversity of geological and biotic variability--provided the stage for endless "natural experiments" in human adaptation. Crucial to understanding the evolution and transformation of island societies is documenting the relative degree of interisland contacts after island colonization. In the western Pacific, ideal materials for archaeologically documenting interisland contact--obsidian, pottery, and shell ornaments--are absent or of limited geographic distribution in Polynesia. Consequently, archaeologists have relied increasingly on fine-grained basalt artifacts as a means for documenting colonization routes and subsequent interisland contacts. Routinely used x-ray fluorescence characterization of oceanic island basalt has some problems for discriminating source rocks and artifacts in provenance studies. The variation in trace and major element abundances is largely controlled by near-surface magma-chamber processes and is broadly similar between most oceanic islands. We demonstrate that Pb isotope analysis accurately discriminates rock source and is an excellent technique for charting the scale, frequency, and temporal span of imported fine-grained basalt artifacts found throughout Polynesia. The technique adds another tool for addressing evolutionary models of interaction, isolation, and cultural divergence in the eastern Pacific.

  15. Basalt Pb isotope analysis and the prehistoric settlement of Polynesia.

    PubMed Central

    Weisler, M I; Woodhead, J D

    1995-01-01

    The prehistoric settlement of the Pacific Ocean has intrigued scholars and stimulated anthropological debate for the past two centuries. Colonized over a few millennia during the mid to late Holocene, the islands of the Pacific--displaying a wide diversity of geological and biotic variability--provided the stage for endless "natural experiments" in human adaptation. Crucial to understanding the evolution and transformation of island societies is documenting the relative degree of interisland contacts after island colonization. In the western Pacific, ideal materials for archaeologically documenting interisland contact--obsidian, pottery, and shell ornaments--are absent or of limited geographic distribution in Polynesia. Consequently, archaeologists have relied increasingly on fine-grained basalt artifacts as a means for documenting colonization routes and subsequent interisland contacts. Routinely used x-ray fluorescence characterization of oceanic island basalt has some problems for discriminating source rocks and artifacts in provenance studies. The variation in trace and major element abundances is largely controlled by near-surface magma-chamber processes and is broadly similar between most oceanic islands. We demonstrate that Pb isotope analysis accurately discriminates rock source and is an excellent technique for charting the scale, frequency, and temporal span of imported fine-grained basalt artifacts found throughout Polynesia. The technique adds another tool for addressing evolutionary models of interaction, isolation, and cultural divergence in the eastern Pacific. PMID:7892194

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

    SciTech Connect

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

    2015-04-09

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

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

    NASA Technical Reports Server (NTRS)

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

    1976-01-01

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

  18. Isotope analysis in the transmission electron microscope

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

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

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

    NASA Astrophysics Data System (ADS)

    Erba, E.

    2005-12-01

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

  20. Optimizing sample pretreatment for compound-specific stable carbon isotopic analysis of amino sugars in marine sediment

    NASA Astrophysics Data System (ADS)

    Zhu, R.; Lin, Y.-S.; Lipp, J. S.; Meador, T. B.; Hinrichs, K.-U.

    2014-09-01

    Amino sugars are quantitatively significant constituents of soil and marine sediment, but their sources and turnover in environmental samples remain poorly understood. The stable carbon isotopic composition of amino sugars can provide information on the lifestyles of their source organisms and can be monitored during incubations with labeled substrates to estimate the turnover rates of microbial populations. However, until now, such investigation has been carried out only with soil samples, partly because of the much lower abundance of amino sugars in marine environments. We therefore optimized a procedure for compound-specific isotopic analysis of amino sugars in marine sediment, employing gas chromatography-isotope ratio mass spectrometry. The whole procedure consisted of hydrolysis, neutralization, enrichment, and derivatization of amino sugars. Except for the derivatization step, the protocol introduced negligible isotopic fractionation, and the minimum requirement of amino sugar for isotopic analysis was 20 ng, i.e., equivalent to ~8 ng of amino sugar carbon. Compound-specific stable carbon isotopic analysis of amino sugars obtained from marine sediment extracts indicated that glucosamine and galactosamine were mainly derived from organic detritus, whereas muramic acid showed isotopic imprints from indigenous bacterial activities. The δ13C analysis of amino sugars provides a valuable addition to the biomarker-based characterization of microbial metabolism in the deep marine biosphere, which so far has been lipid oriented and biased towards the detection of archaeal signals.

  1. Isotopic ratio correlation for the isotopic composition analysis of plutonium in Am-Pu mixed samples having high americium content.

    PubMed

    Patra, Sabyasachi; Agarwal, Chhavi; Chaudhury, Sanhita; Newton Nathaniel, T; Gathibandhe, M; Goswami, A

    2013-08-01

    Interference of high amount of americium in the plutonium isotopic composition analysis has been studied by simulating gamma-ray spectra for Am-Pu samples over a wide composition range (5-97% (241)Am) for both power and research reactor grade plutonium. An alternate way for isotopic composition analysis has been proposed by correlating the isotopic ratios available in our old database with the experimentally obtained (241)Pu/(239)Pu isotopic ratio. The proposed method has been validated using simulated spectra of known isotopic compositions.

  2. In Situ Analysis of Organics and Isotopes at Mars

    NASA Astrophysics Data System (ADS)

    Mahaffy, P. R.; Atreya, S. K.; Brinckerhoff, W. B.; Cabane, M.; Coll, P.; Demick, J.; Harpold, D. N.; Ming, D.; Niemann, H.; Owen, T.; Raulin, F.; Scott, J.; Webster, C.

    2003-05-01

    The recent success of the "follow the water" imperative for Mars exploration is tempered by the fact that more than 2 decades after Viking, much remains unknown about the state of carbon at the planet's surface. Therefore, a key objective for lander missions that follow MER will be a search for the location and nature of organic molecules and other carbon containing species. Reduced or partially oxidized compounds may reveal the nature of ancient or even present biotic or prebiotic processes. Ongoing definition and development of advanced techniques and protocols to "follow the carbon" will be described. For example, an instrument suite presently under development to be proposed for inclusion on the 2009 Mars Science Laboratory consists of an advanced gas chromatograph mass spectrometer (GCMS) with derivatization capability coupled with a laser desorption time-of-flight mass spectrometer (LDMS) and a tunable laser spectrometer (TLS). The suite is designated SAM (for Sample Analysis at Mars) and is designed to carry out analysis of both atmospheric gases and volatiles released from solid phase soils, rock samples, and ices. Volatile organic molecules and their pyrolysis products are analyzed by the GCMS and TLS, and refractory organics and elements by the LDMS. Additional objectives include higher precision measurements than have been obtained, to date, of the abundances and isotope ratios of the noble gases and a range of light elements including H, C, O, and N in both the atmosphere and soil. SAM can also contribute to geochemical objectives with the identification of various minerals through evolved gas analysis (EGA) of stable thermal decomposition products such as H2O, CO2, and oxides of nitrogen and sulfur using the MS and TLS as the detector. Recent EGA studies on Mars analogue materials that illustrate this capability are described. This work is supported by funding from NASA and CNES

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

    PubMed Central

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

    2012-01-01

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

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

    PubMed

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

    2012-11-01

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

  5. Method for isotopic analysis of chlorinated organic compounds

    DOEpatents

    Holt, Ben D.; Sturchio, Neil C.

    1999-01-01

    The present invention provides a method for preparing a VOC sample for carbon and chlorine isotope ratio analysis by mass spectrometer. A VOC sample is placed in a combustion tube and reacted with CuO to form CO.sub.2 and CuCl. The CO.sub.2 is then extracted and analyzed for the carbon isotope ratio. The CuCl is separated from the excess CuO and reacted with CH.sub.3 I to form CH.sub.3 Cl, extracted and analyzed for chlorine isotope ratio.

  6. Method for isotopic analysis of chlorinated organic compounds

    DOEpatents

    Holt, B.D.; Sturchio, N.C.

    1999-08-24

    The present invention provides a method for preparing a VOC sample for carbon and chlorine isotope ratio analysis by mass spectrometer. A VOC sample is placed in a combustion tube and reacted with CuO to form CO{sub 2} and CuCl. The CO{sub 2} is then extracted and analyzed for the carbon isotope ratio. The CuCl is separated from the excess CuO and reacted with CH{sub 3}I to form CH{sub 3}Cl, extracted and analyzed for chlorine isotope ratio. 9 figs.

  7. Identification of gasoline lead in children's blood using isotopic analysis.

    PubMed

    Tera, O; Schwartzman, D W; Watkins, T R

    1985-01-01

    The isotopic composition and concentrations of lead were measured, using mass spectrometric analysis, in blood drawn from 14 young children who lived in Washington, D.C. The isotopic composition of lead in ambient air, which reflects the changing sources of gasoline lead, was also determined for the period of sampling. Blood lead concentrations ranged from 4.38 to 24.7 micrograms/100 g blood. Based on linear patterns that involved ratios of all four isotopes consistent with two component mixing, we estimate a minimum contribution of recent gasoline lead ranging from 0 to 57% of the blood lead burden.

  8. Old Masters' lead white pigments: investigations of paintings from the 16th to the 17th century using high precision lead isotope abundance ratios.

    PubMed

    Fortunato, G; Ritter, A; Fabian, D

    2005-06-01

    White lead (2PbCO(3).Pb(OH)(2)), a common component in 17c. artists' painting materials, was singled out to investigate the potential of lead isotope abundance ratios in the field of authentication and origin assignment. Paintings by Peter Paul Rubens, Anthony van Dyck and other Old Masters of the Northern and Southern schools were chosen for this study. An interdisciplinary approach was chosen using both analytical instrumental methods, art technological and art historical knowledge. Minute samples taken from paintings from selected art collections worldwide were investigated using mass spectrometry, scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX). The high precision lead isotope abundance ratios were measured by multiple collector inductively coupled plasma mass spectrometry (MC-ICP-MS). The determination of the calcium matrix influence with respect to possible bias effects to the isotope ratios gave clear decision support, to whether a result lies within the stated combined measurement uncertainty of the result, to eliminate time-consuming matrix separations. The scatter plots of the measured isotope abundance ratios for the painting pigments from P. P. Rubens, A. van Dyck and other Flemish painters exhibit a very narrow distribution forming a cluster. The range of the measured ratio (206)Pb/(204)Pb amounts to 0.55% and for the ratio (207)Pb/(204)Pb to 0.2%. The comparison of the data to cis-alpine (Italian) sample pigments from paintings from the same time period reveals a clear distinction between the two fields. With respect to the lead isotope data originating from the ores it is assumed that the pigment isotope ratio distribution can be explained by very distinct origin of raw materials. Presumably, no mixing of different lead ores from Europe took place. The comparison of the measured white lead isotope ratio values (Flemish paintings) and the data from ore samples led to the unexpected conclusion that local ores were not

  9. Determination of geographic provenance of cotton fibres using multi-isotope profiles and multivariate statistical analysis

    NASA Astrophysics Data System (ADS)

    Daeid, N. Nic; Meier-Augenstein, W.; Kemp, H. F.

    2012-04-01

    The analysis of cotton fibres can be particularly challenging within a forensic science context where discrimination of one fibre from another is of importance. Normally cotton fibre analysis examines the morphological structure of the recovered material and compares this with that of a known fibre from a particular source of interest. However, the conventional microscopic and chemical analysis of fibres and any associated dyes is generally unsuccessful because of the similar morphology of the fibres. Analysis of the dyes which may have been applied to the cotton fibre can also be undertaken though this can be difficult and unproductive in terms of discriminating one fibre from another. In the study presented here we have explored the potential for Isotope Ratio Mass Spectrometry (IRMS) to be utilised as an additional tool for cotton fibre analysis in an attempt to reveal further discriminatory information. This work has concentrated on un-dyed cotton fibres of known origin in order to expose the potential of the analytical technique. We report the results of a pilot study aimed at testing the hypothesis that multi-element stable isotope analysis of cotton fibres in conjunction with multivariate statistical analysis of the resulting isotopic abundance data using well established chemometric techniques permits sample provenancing based on the determination of where the cotton was grown and as such will facilitate sample discrimination. To date there is no recorded literature of this type of application of IRMS to cotton samples, which may be of forensic science relevance.

  10. Light stable isotope analysis of meteorites by ion microprobe

    NASA Technical Reports Server (NTRS)

    Mcsween, Harry Y., Jr.

    1994-01-01

    The main goal was to develop the necessary secondary ion mass spectrometer (SIMS) techniques to use a Cameca ims-4f ion microprobe to measure light stable isotope ratios (H, C, O and S) in situ and in non-conducting mineral phases. The intended application of these techniques was the analysis of meteorite samples, although the techniques that have been developed are equally applicable to the investigation of terrestrial samples. The first year established techniques for the analysis of O isotope ratios (delta O-18 and delta O-17) in conducting mineral phases and the measurement of S isotope ratios (delta S-34) in a variety of sulphide phases. In addition, a technique was developed to measure delta S-34 values in sulphates, which are insulators. Other research undertaken in the first year resulted in SIMS techniques for the measurement of wide variety of trace elements in carbonate minerals, with the aim of understanding the nature of alteration fluids in carbonaceous chondrites. In the second year we developed techniques for analyzing O isotope ratios in nonconducting mineral phases. These methods are potentially applicable to the measurement of other light stable isotopes such as H, C and S in insulators. Also, we have further explored the analytical techniques used for the analysis of S isotopes in sulphides by analyzing troilite in a number of L and H ordinary chondrites. This was done to see if there was any systematic differences with petrological type.

  11. 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.

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

    NASA Astrophysics Data System (ADS)

    Ahad, J. M.; Pakdel, H.

    2013-12-01

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

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

    USGS Publications Warehouse

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

    2009-01-01

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

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

    PubMed

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

    2009-11-01

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

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

    PubMed

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

    2013-10-01

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

  16. Isotopic analysis of cometary organic matter

    NASA Astrophysics Data System (ADS)

    Kerridge, J. F.

    1991-04-01

    Carbon isotope ratios have been measured for CN in the coma of Comet Halley and for several CHON particles emitted by Halley. Of these, only the CHON-particle data may be reasonably related to organic matter in the cometary nucleus, but the true range of (C-13)/(C-12) values in those particles is quite uncertain. The D/H ratio in H2O in the Halley coma resembles that in Titan/Uranus.

  17. Isotopic analysis of cometary organic matter

    NASA Technical Reports Server (NTRS)

    Kerridge, John F.

    1991-01-01

    Carbon isotope ratios have been measured for CN in the coma of Comet Halley and for several CHON particles emitted by Halley. Of these, only the CHON-particle data may be reasonably related to organic matter in the cometary nucleus, but the true range of (C-13)/(C-12) values in those particles is quite uncertain. The D/H ratio in H2O in the Halley coma resembles that in Titan/Uranus.

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

    PubMed Central

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

    2014-01-01

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

  19. High-resolution analysis of Quaternary calcretes: a coupled stable isotope and micromorphological approach

    NASA Astrophysics Data System (ADS)

    Adamson, Kathryn; Candy, Ian; Whitfield, Liz

    2015-04-01

    Pedogenic calcretes are abundant in arid and semi-arid regions, and they are widely used as proxy records of palaeoclimatic change. Calcrete oxygen (δ18O) and carbon (δ13C) isotopic signatures are indicative of temperature, aridity, or vegetation at the time of calcrete formation. Their microfabrics also reflect carbonate formation mechanisms in response to the prevailing environmental conditions. Many studies have explored calcrete micromorphology or stable isotope composition, but these techniques have not yet been applied simultaneously. This co-analysis is important as it allows us to establish whether calcrete morphology directly reflects environmental change. This study tests the potential of combining these analyses to examine the relationships between calcrete microfabrics, their isotopic signals, and Quaternary climate change. Calcretes from four river terraces of the Rio Alias in southeast Spain have been analysed in detail. On the basis of morphostratigraphic correlation (Maher et al., 2007) and Uranium-series ages (Candy et al., 2005), these span the period from 304 ± 26 ka (MIS 9) to the Holocene. The oldest profiles have therefore been exposed to multiple glacial-interglacial cycles. A total of 37 micromorphological profiles have been used to extract stable oxygen and carbon isotopic indicators from 77 microfacies. The morphological and isotopic complexity of the calcrete profiles increases with progressive age. The oldest samples display multiple calcretisation phases, and their microfabrics have a larger isotopic range than the younger samples. Alpha (non-biogenic) fabrics have higher δ13C and δ18O values than beta (biogenic) fabrics. Strong positive covariance between δ13C and δ18O within all profiles suggests that both isotopes are responding to the same environmental parameter. We suggest that this is relative aridity. The study demonstrates that the detailed co-analysis of calcrete micromorphology and stable isotope signatures allows

  20. Stable-Isotopic Analysis of Porcine, Bovine, and Ovine Heparins

    PubMed Central

    Jasper, John P.; Zhang, Fuming; Poe, Russell B.; Linhardt, Robert J.

    2014-01-01

    The assessment of provenance of heparin is becoming a major concern for the pharmaceutical industry and its regulatory bodies. Batch-specific [carbon (δ13C), nitrogen (δ15N), oxygen (δ18O), sulfur (δ34S), and hydrogen (δD)] stable-isotopic compositions of five different animal-derived heparins were performed. Measurements readily allowed their differentiation into groups and/or subgroups based on their isotopic provenance. Principle component analysis showed that a bivariate plot of δ13C and δ18O is the best single, bivariate plot that results in the maximum discrimination ability when only two stable isotopes are used to describe the variation in the data set. Stable-isotopic analyses revealed that (i) stable-isotope measurements on these highly-sulfated polysaccharide (MW ~15 kDa) natural products (“biologics”) were feasible; (ii) in bivariate plots, the δ13C versus δ18O plot reveals a well-defined relationship for source differentiation of hogs raised in the US from hogs raised in Europe and China; (iii) the δD versus δ18O plot revealed the most well-defined relationship for source differentiation based on the hydrologic-environmental isotopes of water (D/H and 18O/16O), and (iv) the δ15N versus δ18O and δ34S versus δ18O relationships are both very similar, possibly reflecting the food sources used by the different heparin producers. PMID:25186630

  1. Stable isotopic analysis of porcine, bovine, and ovine heparins.

    PubMed

    Jasper, John P; Zhang, Fuming; Poe, Russell B; Linhardt, Robert J

    2015-02-01

    The assessment of provenance of heparin is becoming a major concern for the pharmaceutical industry and its regulatory bodies. Batch-specific [carbon (δ(13) C), nitrogen (δ(15) N), oxygen (δ(18) O), sulfur (δ(34) S), and hydrogen (δD)] stable isotopic compositions of five different animal-derived heparins were performed. Measurements readily allowed their differentiation into groups and/or subgroups based on their isotopic provenance. Principle component analysis showed that a bivariate plot of δ(13) C and δ(18) O is the best single, bivariate plot that results in the maximum discrimination ability when only two stable isotopes are used to describe the variation in the data set. Stable isotopic analyses revealed that (1) stable isotope measurements on these highly sulfated polysaccharide (molecular weight ∼15 kDa) natural products ("biologics") were feasible; (2) in bivariate plots, the δ(13) C versus δ(18) O plot reveals a well-defined relationship for source differentiation of hogs raised in the United States from hogs raised in Europe and China; (3) the δD versus δ(18) O plot revealed the most well-defined relationship for source differentiation based on the hydrologic environmental isotopes of water (D/H and (18) O/(16) O); and (4) the δ(15) N versus δ(18) O and δ(34) S versus δ(18) O relationships are both very similar, possibly reflecting the food sources used by the different heparin producers. PMID:25186630

  2. Stable isotopic analysis of porcine, bovine, and ovine heparins.

    PubMed

    Jasper, John P; Zhang, Fuming; Poe, Russell B; Linhardt, Robert J

    2015-02-01

    The assessment of provenance of heparin is becoming a major concern for the pharmaceutical industry and its regulatory bodies. Batch-specific [carbon (δ(13) C), nitrogen (δ(15) N), oxygen (δ(18) O), sulfur (δ(34) S), and hydrogen (δD)] stable isotopic compositions of five different animal-derived heparins were performed. Measurements readily allowed their differentiation into groups and/or subgroups based on their isotopic provenance. Principle component analysis showed that a bivariate plot of δ(13) C and δ(18) O is the best single, bivariate plot that results in the maximum discrimination ability when only two stable isotopes are used to describe the variation in the data set. Stable isotopic analyses revealed that (1) stable isotope measurements on these highly sulfated polysaccharide (molecular weight ∼15 kDa) natural products ("biologics") were feasible; (2) in bivariate plots, the δ(13) C versus δ(18) O plot reveals a well-defined relationship for source differentiation of hogs raised in the United States from hogs raised in Europe and China; (3) the δD versus δ(18) O plot revealed the most well-defined relationship for source differentiation based on the hydrologic environmental isotopes of water (D/H and (18) O/(16) O); and (4) the δ(15) N versus δ(18) O and δ(34) S versus δ(18) O relationships are both very similar, possibly reflecting the food sources used by the different heparin producers.

  3. Pitfalls in compound-specific isotope analysis of environmental samples.

    PubMed

    Blessing, Michaela; Jochmann, Maik A; Schmidt, Torsten C

    2008-01-01

    In the last decade compound-specific stable isotope analysis (CSIA) has evolved as a valuable technique in the field of environmental science, especially in contaminated site assessment. Instrumentation and methods exist for highly precise measurements of the isotopic composition of organic contaminants even in a very low concentration range. Nevertheless, the determination of precise and accurate isotope data of environmental samples can be a challenge. Since CSIA is gaining more and more popularity in the assessment of in situ biodegradation of organic contaminants, an increasing number of authorities and environmental consulting offices are interested in the application of the method for contaminated site remediation. Because of this, it is important to demonstrate the problems and limitations associated with compound-specific isotope measurements of environmental samples. In this review, potential pitfalls of the analytical procedure are critically discussed and strategies to avoid possible sources of error are provided. In order to maintain the analytical quality and to ensure the basis for reliable stable isotope data, recommendations on groundwater sampling, and sample preservation and storage are given. Important aspects of sample preparation and preconcentration techniques to improve sensitivity are highlighted. Problems related to chromatographic resolution and matrix interference are discussed that have to be considered in order to achieve accurate gas chromatography/isotope ratio mass spectrometry measurements. As a result, the need for a thorough investigation of compound-specific isotope fractionation effects introduced by any step of the overall analytical method by standards with known isotopic composition is emphasized. Finally, we address some important points that have to be considered when interpreting data from field investigations.

  4. Technical Note: A simple method for vaterite precipitation in isotopic equilibrium: implications for bulk and clumped isotope analysis

    NASA Astrophysics Data System (ADS)

    Kluge, T.; John, C. M.

    2014-12-01

    Calcium carbonate (CaCO3) plays an important role in the natural environment as a major constituent of the skeleton and supporting structure of marine life and has high economic importance as additive in food, chemicals and medical products. Pure CaCO3 occurs in the three different polymorphs calcite, aragonite and vaterite, whereof calcite is the most abundant and best characterized mineral. In contrast, little is known about the rare polymorph vaterite, in particular with regard to the oxygen isotope fractionation between H2O and the mineral. Synthetic precipitation of vaterite in the laboratory typically involves rapid processes and isotopic non-equilibrium, which excludes isotope studies focused on characterization of vaterite at equilibrium conditions. Here, we used a new experimental approach that enables vaterite mineral formation from an isotopically equilibrated solution. The solution consists of a ~ 0.007 mol L-1 CaCO3 solution that is saturated with NaCl at room temperature (up to 6.5 mol L-1). Vaterite precipitated as single phase or major phase (≥ 94%) in experiments performed between 23 and 91 °C. Only at 80 °C was vaterite a minor phase with a relative abundance of 27%. The high mineral yield of up to 235 mg relative to a total dissolved CaCO3 amount of 370 mg enables an investigation of the oxygen isotope fractionation between mineral and water, and the determination of clumped isotope values in vaterite.

  5. Enantioselective stable isotope analysis (ESIA) of polar Herbicides

    NASA Astrophysics Data System (ADS)

    Maier, Michael; Qiu, Shiran; Elsner, Martin

    2013-04-01

    The complexity of aquatic systems makes it challenging to assess the environmental fate of chiral micropolutants. As an example, chiral herbicides are frequently detected in the environment (Buser and Muller, 1998); however, hydrological data is needed to determine their degradability from concentration measurements. Otherwise declining concentrations cannot unequivocally be attributed to degradation, but could also be caused by dilution effects. In contrast, isotope ratios or enantiomeric ratios are elegant alternatives that are independent of dilution and can even deliver insights into reaction mechanisms. To combine the advantages of both approaches we developed an enatioselective stable isotope analysis (ESIA) method to investigate the fate of the chiral herbicides 4-CPP ((RS)-2-(4-chlorophenoxy)-propionic acid), mecoprop (2-(4-Chloro-2-methylphenoxy)-propionic acid) and dichlorprop (2-(2,4-Dichlorophenoxy)-propionic acid). After testing the applicable concentration range of the method, enantioselective isotope fractionation was investigated by microbial degradation using dichlorprop as a model compound. The method uses enantioselective gas-chromatography (GC) to separate enantiomers. Subsequently samples are combusted online to CO2 and carbon isotope ratios are determined for each enantiomer by isotope-ratio-mass-spectrometry (IRMS). Because the analytes contain a polar carboxyl-group, samples were derivatised prior to GC-IRMS analysis with methanolic BF3 solution. Precise carbon isotope analysis (2σ ≤0.5‰) was achieved with a high sensitivity of ≥ 7 ng C that is needed on column for one analysis. Microbial degradation of the model compound dichlorprop was conducted with Delftia acidovorans MC1 and pronounced enantiomer fractionation, but no isotope fractionation was detected. The absence of isotope fractionation can be explained by two scenarios: either the degrading enzyme has no isotopic preference, or another step in the reaction without an isotopic

  6. Potential of isotope analysis (C, Cl) to identify dechlorination mechanisms

    NASA Astrophysics Data System (ADS)

    Cretnik, Stefan; Thoreson, Kristen; Bernstein, Anat; Ebert, Karin; Buchner, Daniel; Laskov, Christine; Haderlein, Stefan; Shouakar-Stash, Orfan; Kliegman, Sarah; McNeill, Kristopher; Elsner, Martin

    2013-04-01

    Chloroethenes are commonly used in industrial applications, and detected as carcinogenic contaminants in the environment. Their dehalogenation is of environmental importance in remediation processes. However, a detailed understanding frequently accounted problem is the accumulation of toxic degradation products such as cis-dichloroethylene (cis-DCE) at contaminated sites. Several studies have addressed the reductive dehalogenation reactions using biotic and abiotic model systems, but a crucial question in this context has remained open: Do environmental transformations occur by the same mechanism as in their corresponding in vitro model systems? The presented study shows the potential to close this research gap using the latest developments in compound specific chlorine isotope analysis, which make it possible to routinely measure chlorine isotope fractionation of chloroethenes in environmental samples and complex reaction mixtures.1,2 In particular, such chlorine isotope analysis enables the measurement of isotope fractionation for two elements (i.e., C and Cl) in chloroethenes. When isotope values of both elements are plotted against each other, different slopes reflect different underlying mechanisms and are remarkably insensitive towards masking. Our results suggest that different microbial strains (G. lovleyi strain SZ, D. hafniense Y51) and the isolated cofactor cobalamin employ similar mechanisms of reductive dechlorination of TCE. In contrast, evidence for a different mechanism was obtained with cobaloxime cautioning its use as a model for biodegradation. The study shows the potential of the dual isotope approach as a tool to directly compare transformation mechanisms of environmental scenarios, biotic transformations, and their putative chemical lab scale systems. Furthermore, it serves as an essential reference when using the dual isotope approach to assess the fate of chlorinated compounds in the environment.

  7. Analysis of proteome dynamics in mice by isotopic labeling.

    PubMed

    Price, John C; Ghaemmaghami, Sina

    2014-01-01

    Recent advances in mass spectrometry and in vivo isotopic labeling have enabled proteome-wide analyses of protein turnover in complex organisms. Here, we describe a protocol for analyzing protein turnover rates in mouse tissues by comprehensive (15)N labeling. The procedure involves the complete isotopic labeling of blue green algae (Spirulina platensis) with (15)N and utilizing it as a source of dietary nitrogen for mice. We outline a detailed protocol for in-house production of (15)N-labeled algae, labeling of mice, and analysis of isotope incorporation kinetics by mass spectrometry. The methodology can be adapted to analyze proteome dynamics in most murine tissues and may be particularly useful in the analysis of proteostatic disruptions in mouse models of disease. PMID:24791984

  8. Enantiomeric and Isotopic Analysis of Organic Compounds in Carbonaceous Meteorites

    NASA Technical Reports Server (NTRS)

    Cooper, George

    2004-01-01

    Carbonaceous meteorites are relatively enriched in soluble organic compounds. The Murchison and Murray meteorites contain numerous compounds of interest in the study of early solar system organic chemistry and organic compounds of potential importance for the origin of life. These include: amino acids, amides, carboxylic acids, and polyols. This talk will focus on the enantiomeric and isotopic analysis of individual meteoritic compounds - primarily polyol acids. The analyses will determine if, in addition to certain amino acids from Murchison, another potentially important class of prebiotic compounds also contains enantiomeric excesses, i.e., excesses that could have contributed to the current homochirality of life. Preliminary enantiomeric and isotopic (C- 13) measurements of Murchison glyceric acid show that it is indeed extraterrestrial. C-13 and D isotope analysis of meteoritic sugar alcohols (glycerol, threitol, ribitol, etc.) has shown that they are also indigenous to the meteorite.

  9. Selection of Isotopes and Elements for Fuel Cycle Analysis

    SciTech Connect

    Steven J. Piet

    2009-04-01

    Fuel cycle system analysis simulations examine how the selection among fuel cycle options for reactors, fuel, separation, and waste management impact uranium ore utilization, waste masses and volumes, radiotoxicity, heat to geologic repositories, isotope-dependent proliferation resistance measures, and so forth. Previously, such simulations have tended to track only a few actinide and fission product isotopes, those that have been identified as important to a few criteria from the standpoint of recycled material or waste, taken as a whole. After accounting for such isotopes, the residual mass is often characterized as “fission product other” or “actinide other”. However, detailed assessment of separation and waste management options now require identification of key isotopes and residual mass for Group 1A/2A elements (Rb, Cs, Sr, Ba), inert gases (Kr, Xe), halogens (Br, I), lanthanides, transition metals, transuranic (TRU), uranium, actinide decay products. The paper explains the rationale for a list of 81 isotopes and chemical elements to better support separation and waste management assessment in dynamic system analysis models such as Verifiable Fuel Cycle Simulation (VISION)

  10. Examination of the kinetic isotopic effect to the acetylation derivatization for the gas chromatographic-combustion-isotope ratio mass spectrometric doping control analysis of endogenous steroids.

    PubMed

    Angelis, Yiannis S; Kioussi, Maroula K; Kiousi, Polyxeni; Brenna, J Thomas; Georgakopoulos, Costas G

    2012-12-01

    In gas chromatographic-combustion-isotope ratio mass spectrometry (GC-C-IRMS) doping control analysis, endogenous androgenic anabolic steroids and their metabolites are commonly acetylated using acetic anhydride reagent, thus incorporating exogenous carbon that contributes to the measured isotope ratio. Comparison of the endogenous δ(13)C of free, mono-, and di-acetylated steroids requires application of corrections, typically through straightforward use of the mass balance equation. Variability in kinetic isotope effects (KIE) due to steroid structures could cause fractionation of endogenous steroid carbon, resulting in inaccurate results. To test for possible KIE influence on δ(13)C, acetic anhydride of graded isotope ratio within the natural abundance range was used under normal derivatization conditions to test for linearity. In all cases, plots of measured steroid acetate δ(13)C versus acetic anhydride δ(13)C were linear and slopes were not significantly different. Regression analysis of the Δδ(13)C of enriched acetic anhydrides versus Δδ(13)C of derivatized steroids shows that KIE are similar in all cases. We conclude that δ(13)C calculated from the mass balance equation is independent of the δ(13)C of the acetic anhydride reagent, and that net KIE under normal derivatization conditions do not bias the final reported steroid δ(13)C.

  11. Copper and tin isotopic analysis of ancient bronzes for archaeological investigation: development and validation of a suitable analytical methodology.

    PubMed

    Balliana, Eleonora; Aramendía, Maite; Resano, Martin; Barbante, Carlo; Vanhaecke, Frank

    2013-03-01

    Although in many cases Pb isotopic analysis can be relied on for provenance determination of ancient bronzes, sometimes the use of "non-traditional" isotopic systems, such as those of Cu and Sn, is required. The work reported on in this paper aimed at revising the methodology for Cu and Sn isotope ratio measurements in archaeological bronzes via optimization of the analytical procedures in terms of sample pre-treatment, measurement protocol, precision, and analytical uncertainty. For Cu isotopic analysis, both Zn and Ni were investigated for their merit as internal standard (IS) relied on for mass bias correction. The use of Ni as IS seems to be the most robust approach as Ni is less prone to contamination, has a lower abundance in bronzes and an ionization potential similar to that of Cu, and provides slightly better reproducibility values when applied to NIST SRM 976 Cu isotopic reference material. The possibility of carrying out direct isotopic analysis without prior Cu isolation (with AG-MP-1 anion exchange resin) was investigated by analysis of CRM IARM 91D bronze reference material, synthetic solutions, and archaeological bronzes. Both procedures (Cu isolation/no Cu isolation) provide similar δ (65)Cu results with similar uncertainty budgets in all cases (±0.02-0.04 per mil in delta units, k = 2, n = 4). Direct isotopic analysis of Cu therefore seems feasible, without evidence of spectral interference or matrix-induced effect on the extent of mass bias. For Sn, a separation protocol relying on TRU-Spec anion exchange resin was optimized, providing a recovery close to 100 % without on-column fractionation. Cu was recovered quantitatively together with the bronze matrix with this isolation protocol. Isotopic analysis of this Cu fraction provides δ (65)Cu results similar to those obtained upon isolation using AG-MP-1 resin. This means that Cu and Sn isotopic analysis of bronze alloys can therefore be carried out after a single chromatographic

  12. Trophic Hierarchies Illuminated via Amino Acid Isotopic Analysis

    PubMed Central

    Steffan, Shawn A.; Chikaraishi, Yoshito; Horton, David R.; Ohkouchi, Naohiko; Singleton, Merritt E.; Miliczky, Eugene; Hogg, David B.; Jones, Vincent P.

    2013-01-01

    Food web ecologists have long sought to characterize the trophic niches of animals using stable isotopic analysis. However, distilling trophic position from isotopic composition has been difficult, largely because of the variability associated with trophic discrimination factors (inter-trophic isotopic fractionation and routing). We circumvented much of this variability using compound-specific isotopic analysis (CSIA). We examined the 15N signatures of amino acids extracted from organisms reared in pure culture at four discrete trophic levels, across two model communities. We calculated the degree of enrichment at each trophic level and found there was a consistent trophic discrimination factor (~7.6‰). The constancy of the CSIA-derived discrimination factor permitted unprecedented accuracy in the measurement of animal trophic position. Conversely, trophic position estimates generated via bulk-15N analysis significantly underestimated trophic position, particularly among higher-order consumers. We then examined the trophic hierarchy of a free-roaming arthropod community, revealing the highest trophic position (5.07) and longest food chain ever reported using CSIA. High accuracy in trophic position estimation brings trophic function into sharper focus, providing greater resolution to the analysis of food webs. PMID:24086703

  13. Connecting laboratory behavior to field function through stable isotope analysis.

    PubMed

    Glon, Mael G; Larson, Eric R; Pangle, Kevin L

    2016-01-01

    Inherent difficulties of tracking and observing organisms in the field often leave researchers with no choice but to conduct behavioral experiments under laboratory settings. However, results of laboratory experiments do not always translate accurately to natural conditions. A fundamental challenge in ecology is therefore to scale up from small area and short-duration laboratory experiments to large areas and long durations over which ecological processes generally operate. In this study, we propose that stable isotope analysis may be a tool that can link laboratory behavioral observations to past field interactions or function of individual organisms. We conducted laboratory behavioral assays to measure dominance of invasive rusty crayfish, Orconectes rusticus, and used stable isotope analysis to hindcast trophic positions of these crayfish under preceding natural conditions. We hypothesized that more dominant crayfish in our assays would have higher trophic positions if dominance were related to competitive ability or willingness to pursue high-risk, high-reward prey. We did not find a relationship between crayfish dominance and trophic position, and therefore infer that laboratory dominance of crayfish may not necessarily relate to their ecology in the field. However, this is to our knowledge the first attempt to directly relate laboratory behavior to field performance via stable isotope analysis. We encourage future studies to continue to explore a possible link between laboratory and field behavior via stable isotope analysis, and propose several avenues to do so. PMID:27077010

  14. Trophic spectra under the lens of amino acid isotopic analysis

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Recent advances in compound specific isotopic ratio analysis (CSIRA) have allowed researchers to measure trophic fractionation of 15N in specific amino acids, namely glutamic acid and phenylalanine. These amino acids have proven useful in food web studies because of the wide and consistent disparity...

  15. Connecting laboratory behavior to field function through stable isotope analysis

    PubMed Central

    Larson, Eric R.; Pangle, Kevin L.

    2016-01-01

    Inherent difficulties of tracking and observing organisms in the field often leave researchers with no choice but to conduct behavioral experiments under laboratory settings. However, results of laboratory experiments do not always translate accurately to natural conditions. A fundamental challenge in ecology is therefore to scale up from small area and short-duration laboratory experiments to large areas and long durations over which ecological processes generally operate. In this study, we propose that stable isotope analysis may be a tool that can link laboratory behavioral observations to past field interactions or function of individual organisms. We conducted laboratory behavioral assays to measure dominance of invasive rusty crayfish, Orconectes rusticus, and used stable isotope analysis to hindcast trophic positions of these crayfish under preceding natural conditions. We hypothesized that more dominant crayfish in our assays would have higher trophic positions if dominance were related to competitive ability or willingness to pursue high-risk, high-reward prey. We did not find a relationship between crayfish dominance and trophic position, and therefore infer that laboratory dominance of crayfish may not necessarily relate to their ecology in the field. However, this is to our knowledge the first attempt to directly relate laboratory behavior to field performance via stable isotope analysis. We encourage future studies to continue to explore a possible link between laboratory and field behavior via stable isotope analysis, and propose several avenues to do so. PMID:27077010

  16. Automated CO2 extraction from air for clumped isotope analysis in the atmo- and biosphere

    NASA Astrophysics Data System (ADS)

    Hofmann, Magdalena; Ziegler, Martin; Pons, Thijs; Lourens, Lucas; Röckmann, Thomas

    2015-04-01

    The conventional stable isotope ratios 13C/12C and 18O/16O in atmospheric CO2 are a powerful tool for unraveling the global carbon cycle. In recent years, it has been suggested that the abundance of the very rare isotopologue 13C18O16O on m/z 47 might be a promising tracer to complement conventional stable isotope analysis of atmospheric CO2 [Affek and Eiler, 2006; Affek et al. 2007; Eiler and Schauble, 2004; Yeung et al., 2009]. Here we present an automated analytical system that is designed for clumped isotope analysis of atmo- and biospheric CO2. The carbon dioxide gas is quantitatively extracted from about 1.5L of air (ATP). The automated stainless steel extraction and purification line consists of three main components: (i) a drying unit (a magnesium perchlorate unit and a cryogenic water trap), (ii) two CO2 traps cooled with liquid nitrogen [Werner et al., 2001] and (iii) a GC column packed with Porapak Q that can be cooled with liquid nitrogen to -30°C during purification and heated up to 230°C in-between two extraction runs. After CO2 extraction and purification, the CO2 is automatically transferred to the mass spectrometer. Mass spectrometric analysis of the 13C18O16O abundance is carried out in dual inlet mode on a MAT 253 mass spectrometer. Each analysis generally consists of 80 change-over-cycles. Three additional Faraday cups were added to the mass spectrometer for simultaneous analysis of the mass-to-charge ratios 44, 45, 46, 47, 48 and 49. The reproducibility for δ13C, δ18O and Δ47 for repeated CO2 extractions from air is in the range of 0.11o (SD), 0.18o (SD) and 0.02 (SD)o respectively. This automated CO2 extraction and purification system will be used to analyse the clumped isotopic signature in atmospheric CO2 (tall tower, Cabauw, Netherlands) and to study the clumped isotopic fractionation during photosynthesis (leaf chamber experiments) and soil respiration. References Affek, H. P., Xu, X. & Eiler, J. M., Geochim. Cosmochim. Acta 71, 5033

  17. Discrimination of ginseng cultivation regions using light stable isotope analysis.

    PubMed

    Kim, Kiwook; Song, Joo-Hyun; Heo, Sang-Cheol; Lee, Jin-Hee; Jung, In-Woo; Min, Ji-Sook

    2015-10-01

    Korean ginseng is considered to be a precious health food in Asia. Today, thieves frequently compromise ginseng farms by pervasive theft. Thus, studies regarding the characteristics of ginseng according to growth region are required in order to deter ginseng thieves and prevent theft. In this study, 6 regions were selected on the basis of Korea regional criteria (si, gun, gu), and two ginseng-farms were randomly selected from each of the 6 regions. Then 4-6 samples of ginseng were acquired from each ginseng farm. The stable isotopic compositions of H, O, C, and N of the collected ginseng samples were analyzed. As a result, differences in the hydrogen isotope ratios could be used to distinguish regional differences, and differences in the nitrogen isotope ratios yielded characteristic information regarding the farms from which the samples were obtained. Thus, stable isotope values could be used to differentiate samples according to regional differences. Therefore, stable isotope analysis serves as a powerful tool to discriminate the regional origin of Korean ginseng samples from across Korea.

  18. Stable Isotope Ratios and the Forensic Analysis of Microorganisms

    SciTech Connect

    Kreuzer-Martin, Helen W.; Jarman, Kristin H.

    2007-06-01

    In the aftermath of the anthrax letters of 2001, researchers have been exploring various analytical signatures for the purpose of characterizing the production environment of microorganisms. One such signature is stable isotope ratios, which in heterotrophs are a function of nutrient and water sources. Here we discuss the use of stable isotope ratios in microbe forensics, using as a database the carbon, nitrogen, oxygen and hydrogen stable isotope ratios of 247 separate cultures of B. subtilis 6051 spores produced on a total of 32 different culture media. In the context of using stable isotope ratios as a signature for sample matching, we present an analysis of variation between individual samples, between cultures produced in tandem, and between cultures produced in the same medium but at different times. Additionally, we correlate the stable isotope ratios of carbon, nitrogen, oxygen, and hydrogen for growth medium nutrients or water with those of spores and show examples of how these relationships can be used to exclude nutrient or water samples as possible growth substrates for specific cultures.

  19. Stable isotope analysis of breath using the optogalvanic effect

    NASA Astrophysics Data System (ADS)

    Murnick, Daniel E.; Colgan, M. J.; Lie, H. P.; Stoneback, D.

    1996-05-01

    A new technique based on the optogalvanic effect has been developed for the measurement of stable isotope ratios in the carbon dioxide of exhaled breath. Data obtained before and after ingestion of harmless stable isotope labeled compounds, metabolized to carbon dioxide, can be used for sensitive noninvasive diagnostics of various disease conditions. The technique uses the specificity of laser resonance spectroscopy and achieves sensitivity and accuracy typical of sophisticated isotope ratio mass spectrometers. Using fixed frequency carbon dioxide lasers, 13C/12C ratios can be determined with a precision of 2 ppm with 100 second averaging times. Multiple samples can be analyzed simultaneously providing real time continuous calibration. In a first application, analysis of 13C/12C ratios in exhaled human breath after ingestion of 13C labeled urea is being developed as a diagnostic for the bacterium H-pylori, known to be the causative agent for most peptic and duodenal ulcers.

  20. STABLE CARBON ISOTOPE ANALYSIS OF SUBFOSSIL WOOD FROM AUSTRIAN ALPS

    PubMed Central

    KŁUSEK, MARZENA; PAWEŁCZYK, SŁAWOMIRA

    2015-01-01

    The presented studies were carried out in order to check the usefulness of subfossil wood for stable isotope analysis. The aim of research was also to define the optimal method of subfossil samples preparation. Subfossil samples used during the presented studies are a part of the multi-century dendrochronological scale. This chronology originates in an area situated around a small mountain lake — Schwarzersee, in Austria. The obtained results of stable carbon isotope measurements confirmed that the method of α-cellulose extraction by the application of acidic sodium chlorite and sodium hydroxide solutions removes resins and other mobile compounds from wood. Therefore, in the case of the analysed samples, the additional chemical process of extractives removing was found to be unnecessary. Studied wood samples contained an adequate proportion of α-cellulose similar to the values characteristic for the contemporary trees. This proved an adequate wood preservation which is essential for the conduction of isotopic research. PMID:26346297

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

    NASA Astrophysics Data System (ADS)

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

    2009-12-01

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

  2. Frontiers of QC Laser spectroscopy for high precision isotope ratio analysis of greenhouse gases

    NASA Astrophysics Data System (ADS)

    Emmenegger, Lukas; Mohn, Joachim; Harris, Eliza; Eyer, Simon; Ibraim, Erkan; Tuzson, Béla

    2016-04-01

    An important milestone for laser spectroscopy was achieved when isotope ratios of greenhouse gases were reported at precision levels that allow addressing research questions in environmental sciences. Real-time data with high temporal resolution at moderate cost and instrument size make the optical approach highly attractive, complementary to the well-established isotope-ratio mass-spectrometry (IRMS) method. Especially appealing, in comparison to IRMS, is the inherent specificity to structural isomers having the same molecular mass. Direct absorption in the MIR in single or dual QCL configuration has proven highly reliable for the sta-ble isotopes of CO2, N2O and CH4. The longest time series of real-time measurements is currently available for δ13C and δ18O in CO2 at the high-alpine station Jung-fraujoch. At this well-equipped site, QCL based direct absorption spectroscopy (QCLAS) measurements are ongoing since 2008 1,2. Applications of QCLAS for N2O and CH4 stable isotopes are considerably more challenging because of the lower atmospheric mixing ratios, especially for the less abundant species, such as N218O and CH3D. For high precision (< 0.1 ‰) measurements in ambient air, QCLAS may be combined with a fully automated preconcentration unit yielding an up to 500 times concentration increase and the capability to separate the target gas from spectral interferants by se-quential desorption 3. Here, we review our recent developments on high precision isotope ratio analysis of greenhouse gases, with special focus on the isotopic species of N2O and CH4. Furthermore, we show environ-mental applications illustrating the highly valuable information that isotope ratios of atmospheric trace gases can carry. For example, the intramolecular distribution of 15N in N2O gives important information on the geochemical cycle of N2O4-6, while the analysis of δ13C and δ D in CH4 may be applied to disentangle microbial, fossil and landfill sources 7. 1 Sturm, P., Tuzson, B

  3. Hf sbnd Nd sbnd Sr isotopes and incompatible element abundances in island arcs: implications for magma origins and crust-mantle evolution

    NASA Astrophysics Data System (ADS)

    White, William M.; Patchett, Jonathan

    1984-02-01

    We present Hf, Nd and Sr isotopic data and abundances of K, Rb, Cs, Ba, Sr, Hf and REE for 32 samples from seven intra-oceanic island arcs. Samples from the Marianas, Izu, Aleutian and New Britain arcs have tightly grouped 176Hf/ 177Hf˜ 0.28320, 143Nd/ 144Nd˜ 0.51303 and 87Sr/ 86Sr˜ 0.7035 close to, but distinct from, mid-ocean ridge basalts (MORB) for 143Nd/ 144Nd and 87Sr/ 86Sr . In contrast, samples from the Sunda, Banda and Lesser Antilles arcs are much more variable towards lower 176Hf/ 177Hf and 143Nd/ 144Nd , and higher 87Sr/ 86Sr . Isotopically, island arcs on the whole are closely similar to ocean islands. Some commonly-occurring features of the trace element geochemistry of island arcs are apparent in our data: alkali and alkaline-earth elements, particularly Cs, have high abundance relative to LREE compared to oceanic basalts; negative Ce anomalies occur in six out of seven arcs. However, Hf does not appear underabundant relative to REE. The isotopic data require a continental component in all island arcs, in addition to probable mantle and oceanic crust contributions, even for the arcs with isotope ratios close to MORB. In the absence of continental crust, we can best explain this component by subducted pelagic sediment in the arc magma source region. The involvement of sediments in all arcs implies that there is an inherent recycling of older continent to island arcs, and potentially to new continent, of at least 1%. Conservative calculations show that the upper subducted slab (basalt + sediment) passes beyond the arc magma genesis zone and enters the deep mantle with a minimum of 500-1000 ppm K, and corresponding amounts of other incompatible elements. If this material is not completely homogenized with the mantle and later becomes part of the source of ocean island magmas, then the ocean island—island arc isotopic similarity is a result of their similar mix of source materials—mantle peridotite with trace element signatures from oceanic crust

  4. Stable isotopic analysis of pyrogenic organic matter in soils by liquid chromatography-isotope-ratio mass spectrometry of benzene polycarboxylic acids.

    PubMed

    Yarnes, Christopher; Santos, Fernanda; Singh, Nimisha; Abiven, Samuel; Schmidt, Michael W I; Bird, Jeffrey A

    2011-12-30

    Pyrogenic organic matter (PyOM), the incomplete combustion product of organic materials, is considered stable in soils and represents a potentially important terrestrial sink for atmospheric carbon dioxide. One well-established method of measuring PyOM in the environment is as benzene polycarboxylic acids (BPCAs), a compound-specific method, which allows both qualitative and quantitative estimation of PyOM. Until now, stable isotope measurement of PyOM carbon involved measurement of the trimethylsilyl (TMS) or methyl (Me) polycarboxylic acid derivatives by gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS). However, BPCA derivatives can contain as much as 150% derivative carbon, necessitating post-analysis correction for the accurate measurement of δ¹³C values, leading to increased measurement error. Here, we describe a method for δ¹³C isotope ratio measurement and quantification of BPCAs from soil-derived PyOM, based on ion-exchange chromatography (IEC-IRMS). The reproducibility of the δ¹³C measurement of individual BPCAs by IEC-IRMS was better than 0.35‰ (1σ). The δ¹³C-BPCA analysis of PyOM in soils, including at natural and artificially enriched ¹³C-abundance, produced accurate and precise δ¹³C measurements. Analysis of samples that differed in δ¹³C by as much as 900‰ revealed carryover of <1‰ between samples. The weighted sum of individual δ¹³C-BPCA measurements was correlated with previous isotopic measurements of whole PyOM, providing complementary information for bulk isotopic measurements. We discuss potential applications of δ¹³C-BPCA measurements, including the study of turnover rates of PyOM in soils and the partitioning of PyOM sources based on photosynthetic pathways. PMID:22468329

  5. Isotopic disproportionation during hydrogen isotopic analysis of nitrogen-bearing organic compounds

    USGS Publications Warehouse

    Nair, Sreejesh; Geilmann, Heike; Coplen, Tyler B.; Qi, Haiping; Gehre, Matthias; Schimmelmann, Arndt; Brand, Willi A.

    2015-01-01

    Rationale High-precision hydrogen isotope ratio analysis of nitrogen-bearing organic materials using high-temperature conversion (HTC) techniques has proven troublesome in the past. Formation of reaction products other than molecular hydrogen (H2) has been suspected as a possible cause of incomplete H2 yield and hydrogen isotopic fractionation. Methods The classical HTC reactor setup and a modified version including elemental chromium, both operated at temperatures in excess of 1400 °C, have been compared using a selection of nitrogen-bearing organic compounds, including caffeine. A focus of the experiments was to avoid or suppress hydrogen cyanide (HCN) formation and to reach quantitative H2 yields. The technique also was optimized to provide acceptable sample throughput. Results The classical HTC reaction of a number of selected compounds exhibited H2 yields from 60 to 90 %. Yields close to 100 % were measured for the experiments with the chromium-enhanced reactor. The δ2H values also were substantially different between the two types of experiments. For the majority of the compounds studied, a highly significant relationship was observed between the amount of missing H2and the number of nitrogen atoms in the molecules, suggesting the pyrolytic formation of HCN as a byproduct. A similar linear relationship was found between the amount of missing H2 and the observed hydrogen isotopic result, reflecting isotopic fractionation. Conclusions The classical HTC technique to produce H2 from organic materials using high temperatures in the presence of glassy carbon is not suitable for nitrogen-bearing compounds. Adding chromium to the reaction zone improves the yield to 100 % in most cases. The initial formation of HCN is accompanied by a strong hydrogen isotope effect, with the observed hydrogen isotope results on H2 being substantially shifted to more negative δ2H values. The reaction can be understood as an initial disproportionation leading to H2 and HCN

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

    NASA Astrophysics Data System (ADS)

    Amiri, N.; Norman, A. L.

    2015-12-01

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

  7. Documenting the diet in ancient human populations through stable isotope analysis of hair.

    PubMed

    Macko, S A; Engel, M H; Andrusevich, V; Lubec, G; O'Connell, T C; Hedges, R E

    1999-01-29

    Fundamental to the understanding of human history is the ability to make interpretations based on artefacts and other remains which are used to gather information about an ancient population. Sequestered in the organic matrices of these remains can be information, for example, concerning incidence of disease, genetic defects and diet. Stable isotopic compositions, especially those made on isolates of collagen from bones, have been used to help suggest principal dietary components. A significant problem in the use of collagen is its long-term stability, and the possibility of isotopic alteration during early diagenesis, or through contaminating condensation reactions. In this study, we suggest that a commonly overlooked material, human hair, may represent an ideal material to be used in addressing human diets of ancient civilizations. Through the analysis of the amino-acid composition of modern hair, as well as samples that were subjected to radiation (thus simulating ageing of the hair) and hair from humans that is up to 5200 years old, we have observed little in the way of chemical change. The principal amino acids observed in all of these samples are essentially identical in relative abundances and content. Dominating the compositions are serine, glutamic acid, threonine, glycine and leucine, respectively accounting for approximately 15%, 17%, 10%, 8% and 8% of the total hydrolysable amino acids. Even minor components (for example, alanine, valine, isoleucine) show similar constancy between the samples of different ages. This constancy clearly indicates minimal alteration of the amino-acid composition of the hair. Further, it would indicate that hair is well preserved and is amenable to isotopic analysis as a tool for distinguishing sources of nutrition. Based on this observation, we have isotopically characterized modern individuals for whom the diet has been documented. Both stable nitrogen and carbon isotope compositions were assessed, and together provide an

  8. Documenting the diet in ancient human populations through stable isotope analysis of hair.

    PubMed Central

    Macko, S A; Engel, M H; Andrusevich, V; Lubec, G; O'Connell, T C; Hedges, R E

    1999-01-01

    Fundamental to the understanding of human history is the ability to make interpretations based on artefacts and other remains which are used to gather information about an ancient population. Sequestered in the organic matrices of these remains can be information, for example, concerning incidence of disease, genetic defects and diet. Stable isotopic compositions, especially those made on isolates of collagen from bones, have been used to help suggest principal dietary components. A significant problem in the use of collagen is its long-term stability, and the possibility of isotopic alteration during early diagenesis, or through contaminating condensation reactions. In this study, we suggest that a commonly overlooked material, human hair, may represent an ideal material to be used in addressing human diets of ancient civilizations. Through the analysis of the amino-acid composition of modern hair, as well as samples that were subjected to radiation (thus simulating ageing of the hair) and hair from humans that is up to 5200 years old, we have observed little in the way of chemical change. The principal amino acids observed in all of these samples are essentially identical in relative abundances and content. Dominating the compositions are serine, glutamic acid, threonine, glycine and leucine, respectively accounting for approximately 15%, 17%, 10%, 8% and 8% of the total hydrolysable amino acids. Even minor components (for example, alanine, valine, isoleucine) show similar constancy between the samples of different ages. This constancy clearly indicates minimal alteration of the amino-acid composition of the hair. Further, it would indicate that hair is well preserved and is amenable to isotopic analysis as a tool for distinguishing sources of nutrition. Based on this observation, we have isotopically characterized modern individuals for whom the diet has been documented. Both stable nitrogen and carbon isotope compositions were assessed, and together provide an

  9. High-Precision Selenium Isotope Analysis by Hydride Generation MC-ICP-MS: Environmental Applications

    NASA Astrophysics Data System (ADS)

    Schmidberger, S.; Simonetti, A.; Gariépy, C.

    2003-04-01

    The global cycle and the natural isotopic variation of Se in the lithosphere, biosphere, hydrosphere and atmosphere are currently little constrained. The study of Se isotope systematics by negative thermal ionization mass spectrometry (NTIMS) has documented large Se isotope variations up to 15 ppm in various natural samples (δ80Se/76Se; Johnson et al., 1999), indicating its important potential as a tracer in geological and biological processes. Recently, Se isotope measurements on sulfide deposits from hydrothermal systems were obtained using a Micromass IsoProbe multicollector inductively coupled plasma mass spectrometer coupled to a hydride generator (Rouxel et al. 2002). This technique allows for high-precision Se isotope analysis on small sample sizes (<= 100 ng), and thus is a prerequisite for precise Se isotope measurements in low abundance samples such as precipitations, freshwaters and atmospheric aerosols (1 ppb or less). We have developed a 74-82Se double spike technique, which corrects for instrumental mass fractionation during both isotopic analysis and chemical processing. During double spike calibration, mass discrimination was monitored using a Germanium Specpuretextregistered standard (25 ppb). The isotopic composition of the Ge standard was accurately determined using a 10 ppb solution of the isotopic Gallium standard SRM 994. Repeated measurements (n=8) of the Ge standard yielded an external reproducibility of 0.13 ppm and a 74Ge/72Ge ratio of 1.32987. Instrumental mass bias evaluated with the Ge standard was essentially invariant over a three-month period. Our results yield an external reproducibility of 0.4 ppm (80Se/76Se) for a 100 ppb solution of the Se standard SRM 3149 (˜100 ng of total Se consumed). This ongoing study focuses on determining the Se isotopic compositions of precipitations and aerosol samples from remote and urban areas in northeastern North America. The preliminary results for precipitation samples (˜100 to 300 ml of rain

  10. Demonstration of compound-specific isotope analysis of hydrogen isotope ratios in chlorinated ethenes.

    PubMed

    Kuder, Tomasz; Philp, Paul

    2013-02-01

    High-temperature pyrolysis conversion of organic analytes to H(2) in hydrogen isotope ratio compound-specific isotope analysis (CSIA) is unsuitable for chlorinated compounds such as trichloroethene (TCE) and cis-1,2-dichloroethene (DCE), due to competition from HCl formation. For this reason, the information potential of hydrogen isotope ratios of chlorinated ethenes remains untapped. We present a demonstration of an alternative approach where chlorinated analytes reacted with chromium metal to form H(2) and minor amounts of HCl. The values of δ(2)H were obtained at satisfactory precision (± 10 to 15 per thousand), however the raw data required daily calibration by TCE and/or DCE standards to correct for analytical bias that varies over time. The chromium reactor has been incorporated into a purge and trap-CSIA method that is suitable for CSIA of aqueous environmental samples. A sample data set was obtained for six specimens of commercial product TCE. The resulting values of δ(2)H were between -184 and +682 ‰, which significantly widened the range of manufactured TCE δ(2)H signatures identified by past work. The implications of this finding to the assessment of TCE contamination are discussed.

  11. Isotope Analysis Reveals Foraging Area Dichotomy for Atlantic Leatherback Turtles

    PubMed Central

    Angulo, Elena; Das, Krishna; Girondot, Marc

    2008-01-01

    Background The leatherback turtle (Dermochelys coriacea) has undergone a dramatic decline over the last 25 years, and this is believed to be primarily the result of mortality associated with fisheries bycatch followed by egg and nesting female harvest. Atlantic leatherback turtles undertake long migrations across ocean basins from subtropical and tropical nesting beaches to productive frontal areas. Migration between two nesting seasons can last 2 or 3 years, a time period termed the remigration interval (RI). Recent satellite transmitter data revealed that Atlantic leatherbacks follow two major dispersion patterns after nesting season, through the North Gulf Stream area or more eastward across the North Equatorial Current. However, information on the whole RI is lacking, precluding the accurate identification of feeding areas where conservation measures may need to be applied. Methodology/Principal Findings Using stable isotopes as dietary tracers we determined the characteristics of feeding grounds of leatherback females nesting in French Guiana. During migration, 3-year RI females differed from 2-year RI females in their isotope values, implying differences in their choice of feeding habitats (offshore vs. more coastal) and foraging latitude (North Atlantic vs. West African coasts, respectively). Egg-yolk and blood isotope values are correlated in nesting females, indicating that egg analysis is a useful tool for assessing isotope values in these turtles, including adults when not available. Conclusions/Significance Our results complement previous data on turtle movements during the first year following the nesting season, integrating the diet consumed during the year before nesting. We suggest that the French Guiana leatherback population segregates into two distinct isotopic groupings, and highlight the urgent need to determine the feeding habitats of the turtle in the Atlantic in order to protect this species from incidental take by commercial fisheries. Our

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

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

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

  13. Statistical analysis from recent abundance determinations in HgMn stars

    NASA Astrophysics Data System (ADS)

    Ghazaryan, S.; Alecian, G.

    2016-08-01

    To better understand the hot chemically peculiar group of HgMn stars, we have considered a compilation of a large number of recently published data obtained for these stars from spectroscopy. We compare these data to the previous compilation by Smith. We confirm the main trends of the abundance peculiarities, namely the increasing overabundances with increasing atomic number of heavy elements, and their large spread from star to star. For all the measured elements, we have looked for correlations between abundances and effective temperature (Teff). In addition to the known correlation for Mn, some other elements are found to show some connection between their abundances and Teff. We have also checked if multiplicity is a determinant parameter for abundance peculiarities determined for these stars. A statistical analysis using a Kolmogorov-Smirnov test shows that the abundances anomalies in the atmosphere of HgMn stars do not present significant dependence on the multiplicity.

  14. Application Of Stable Isotope Analysis To Study Temporal Changes In Foraging Ecology In A Highly Endangered Amphibian

    PubMed Central

    Gillespie, J. Hayley

    2013-01-01

    Background Understanding dietary trends for endangered species may be essential to assessing the effects of ecological disturbances such as habitat modification, species introductions or global climate change. Documenting temporal variation in prey selection may also be crucial for understanding population dynamics. However, the rarity, secretive behaviours and obscure microhabitats of some endangered species can make direct foraging observations difficult or impossible. Furthermore, the lethality or invasiveness of some traditional methods of dietary analysis (e.g. gut contents analysis, gastric lavage) makes them inappropriate for such species. Stable isotope analysis facilitates non-lethal, indirect analysis of animal diet that has unrealized potential in the conservation of endangered organisms, particularly amphibians. Methodology/findings I determined proportional contributions of aquatic macroinvertebrate prey to the diet of an endangered aquatic salamander Eurycea sosorum over a two-year period using stable isotope analysis of 13/12C and 15/14N and the Bayesian stable isotope mixing model SIAR. I calculated Strauss’ dietary electivity indices by comparing these proportions with changing relative abundance of potential prey species through time. Stable isotope analyses revealed that a previously unknown prey item (soft-bodied planarian flatworms in the genus Dugesia) made up the majority of E. sosorum diet. Results also demonstrate that E. sosorum is an opportunistic forager capable of diet switching to include a greater proportion of alternative prey when Dugesia populations decline. There is also evidence of intra-population dietary variation. Conclusions/significance Effective application of stable isotope analysis can help circumvent two key limitations commonly experienced by researchers of endangered species: the inability to directly observe these species in nature and the invasiveness or lethality of traditional methods of dietary analysis. This

  15. Mars Molecular and Isotopic Analysis Research Study

    NASA Technical Reports Server (NTRS)

    Manning, Heidi L. K.

    1998-01-01

    Recently, the Martian atmosphere and surface constituents have become of great interest. The Viking in situ gas chromatograph mass spectrometer experiment contributed greatly to our knowledge of the composition of the Martian atmosphere. However, important questions remain such as the abundance of water on Mars. The Viking experiment employed solid reagents to enhance their carbon measurements. Techniques of chemical conversion using simple solid reagents have advanced considerably in the past 20 years. In this investigation we researched the advancements in techniques to reversibly adsorb and desorb water and focused on the techniques potentially useful for the temperatures and pressures on the Martian surface. During the granting period from June 15, 1998 to August 14, 1998, a literature study of the material appropriate for use in a chemical conversion device and the availability of these materials were undertaken. The focus of this investigation was searching for methods and materials potentially useful in enhancing the measurements of water. Three different methods were considered for the means to extract water from a given gas sample. These methods included adsorption in a desiccant, adsorption on a clean metal surface, and adsorption in a carbon molecular sieve or zeolite. Each method was evaluated with feasibility and reversibility in mind. By far the simplest and perhaps cheapest way to remove water from a gaseous sample is by means of a bulk desiccant. Desiccants are commercially available from many companies including those that supply chemicals. The main feature of a desiccant is its ability to rapidly bind or absorb water from the atmosphere. Calcium chloride, for example, is frequently incorporated into drying tubes by organic chemists when reactions require the absence of water. Other desiccants include sodium hydroxide, calcium hydride, and commercial products such as Drierite, available from Aldrich Chemical. The disadvantage to most desiccants is

  16. A landscape analysis of cougar distribution and abundance in Montana, USA.

    PubMed

    Riley, S J; Malecki, R A

    2001-09-01

    Recent growth in the distribution and abundance of cougars (Puma concolor) throughout western North America has created opportunities, challenges, and problems for wildlife managers and raises questions about what factors affect cougar populations. We present an analysis of factors thought to affect cougar distribution and abundance across the broad geographical scales on which most population management decisions are made. Our objectives were to: (1) identify and evaluate landscape parameters that can be used to predict the capability of habitats to support cougars, and (2) evaluate factors that may account for the recent expansion in cougar numbers. Habitat values based on terrain ruggedness and forested cover explained 73% of the variation in a cougar abundance index. Indices of cougar abundance also were spatially and temporally correlated with ungulate abundance. An increase in the number and total biomass of ungulate prey species is hypothesized to account for recent increases in cougars. Cougar populations in Montana are coping with land development by humans when other components of habitat and prey populations are sufficient. Our analysis provides a better understanding of what may have influenced recent growth in cougar distribution and abundance in Montana and, when combined with insights about stakeholder acceptance capacity, offers a basis for cougar management at broad scales. Long-term conservation of cougars necessitates a better understanding of ecosystem functions that affect prey distribution and abundance, more accurate estimates of cougar populations, and management abilities to integrate these components with human values.

  17. 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

  18. Technical Note: A simple method for vaterite precipitation for isotopic studies: implications for bulk and clumped isotope analysis

    NASA Astrophysics Data System (ADS)

    Kluge, T.; John, C. M.

    2015-06-01

    Calcium carbonate (CaCO3) plays an important role in the natural environment as a major constituent of the skeleton and supporting structure of marine life and has high economic importance as an additive in food, chemicals and medical products. Anhydrous CaCO3 occurs in the three different polymorphs calcite, aragonite and vaterite, whereof calcite is the most abundant and best characterized mineral. In contrast, little is known about the rare polymorph vaterite, in particular with regard to the oxygen isotope fractionation between H2O and the mineral. Synthetic precipitation of vaterite in the laboratory typically involves rapid processes and isotopic non-equilibrium, which excludes isotope studies focused on the characterization of vaterite under equilibrium conditions. Here, we used a new experimental approach that enables vaterite mineral formation from an isotopically equilibrated solution. The solution consists of a ~0.007 mol L-1 CaCO3 solution that is saturated with NaCl at room temperature (up to 6.4 mol L-1). Vaterite precipitated as single phase or major phase (≥94%) in experiments performed between 23 and 91 °C. Only at 80 °C was vaterite a minor phase with a relative abundance of 27%. The high mineral yield per experiment of up to 235 mg relative to the initially dissolved CaCO3 amount of on average 360 mg enables an investigation of the oxygen isotope fractionation between the mineral and water, and the determination of clumped isotope values in vaterite.

  19. On-site isotopic analysis of dissolved inorganic carbon using an isotope ratio infrared spectrometer

    NASA Astrophysics Data System (ADS)

    Stoltmann, Tim; Mandic, Magda; Stöbener, Nils; Wapelhorst, Eric; Aepfler, Rebecca; Hinrichs, Kai-Uwe; Taubner, Heidi; Jost, Hj; Elvert, Marcus

    2016-04-01

    An Isotope Ratio Infrared Spectrometer (IRIS) has been adapted to perform measurements of δ13C of dissolved inorganic carbon (DIC) in marine pore waters. The resulting prototype allowed highly automated analysis of δ13C isotopic ratios and CO2 concentration. We achieved a throughput of up to 70 samples per day with DIC contents as low as 1.7 μmol C. We achieved an internal precision of 0.066 ‰ and an external precision of 0.16 ‰, which is comparable to values given for Isotope Ratio Mass Spectrometers (IRMS). The prototype instrument is field deployable, suitable for shipboard analysis of deep sea core pore waters. However, the validation of the prototype was centered around a field campaign in Eckernförde Bay, NW- Baltic Sea. As a proof of concept, a shallow site within an area of submarine groundwater discharge (SGD) and a site outside this area was investigated. We present profiles of δ13C of DIC over 50 cm exhibiting well understood methane turnover processes (anaerobic oxidation of methane). At the lowest point below the seafloor, microbial reduction of CO2 to CH4 dominates. 12CO2 is reduced preferentially over 13CO2, leading to more positive δ13C values in the remaining DIC pool; in layers closer to the surface, the oxidation of CH4 to CO2 becomes more prominent. Since the CH4 pool is enriched in 12C a shift to more negative δ13C can be observed in the DIC pool. In the upper 15 cm, the pore water DIC mixes with the sea water DIC, increasing δ13C again. Finally, we will present recent developments to further improve performance and future plans for deployments on research cruises.

  20. On-site isotopic analysis of dissolved inorganic carbon using an isotope ratio infrared spectrometer

    NASA Astrophysics Data System (ADS)

    Jost, H. J. H.; Stoltmann, T.; Stöbener, N.; Wapelhorst, E.; Mandic, M.; Aepfler, R.; Hinrichs, K. U.; Taubner, H.; Elvert, M.

    2015-12-01

    An Isotope Ratio Infrared Spectrometer (IRIS) has been adapted to perform measurements of δ13C of dissolved inorganic carbon (DIC) in marine pore waters. The resulting prototype allowed highly automated analysis of δ13C isotopic ratios and CO2 concentration. We achieved a throughput of up to 70 samples per day with DIC contents as low as 1.7 μmol C. We achieved an internal precision of 0.066 ‰ and an external precision of 0.16 ‰, which is comparable to values given for Isotope Ratio Mass Spectrometers (IRMS). The prototype instrument is field deployable, suitable for shipboard analysis of deep sea core pore waters. However, the validation of the prototype was centered around a field campaign in Eckernförde Bay, NW- Baltic Sea. As a proof of concept, a shallow site within an area of submarine groundwater discharge (SGD) and a site outside this area was investigated. We present profiles of δ13C of DIC over 50 cm exhibiting well understood methane turnover processes (anaerobic oxidation of methane). At the lowest point below the seafloor, microbial reduction of CO2 to CH4 dominates. 12CO2 is reduced preferentially over 13CO2, leading to more positive δ13C values in the remaining DIC pool; in layers closer to the surface, the oxidation of CH4 to CO2 becomes more prominent. Since the CH4 pool is enriched in 12C a shift to more negative δ13C can be observed in the DIC pool. In the upper 15 cm, the pore water DIC mixes with the sea water DIC, increasing δ13C again. Finally, we will present recent developments to further improve performance and future plans for deployments on research cruises.

  1. Compound-specific isotope analysis of benzotriazole and its derivatives.

    PubMed

    Spahr, Stephanie; Huntscha, Sebastian; Bolotin, Jakov; Maier, Michael P; Elsner, Martin; Hollender, Juliane; Hofstetter, Thomas B

    2013-03-01

    Compound-specific isotope analysis (CSIA) is an important tool for the identification of contaminant sources and transformation pathways, but it is rarely applied to emerging aquatic micropollutants owing to a series of instrumental challenges. Using four different benzotriazole corrosion inhibitors and its derivatives as examples, we obtained evidence that formation of organometallic complexes of benzotriazoles with parts of the instrumentation impedes isotope analysis. Therefore, we propose two strategies for accurate [Formula: see text]C and [Formula: see text]N measurements of polar organic micropollutants by gas chromatography isotope ratio mass spectrometry (GC/IRMS). Our first approach avoids metallic components and uses a Ni/Pt reactor for benzotriazole combustion while the second is based on the coupling of online methylation to the established GC/IRMS setup. Method detection limits for on-column injection of benzotriazole, as well as its 1-CH[Formula: see text]-, 4-CH[Formula: see text]-, and 5-CH[Formula: see text]-substituted species were 0.1-0.3 mM and 0.1-1.0 mM for δ(13)C and δ(15)N analysis respectively, corresponding to injected masses of 0.7-1.8 nmol C and 0.4-3.0 nmol N, respectively. The Ni/Pt reactor showed good precision and was very long-lived ([Formula: see text]1000 successful measurements). Coupling isotopic analysis to offline solid-phase extraction enabled benzotriazole-CSIA in tap water, wastewater treatment effluent, activated sludge, and in commercial dishwashing products. A comparison of [Formula: see text]C and [Formula: see text]N values from different benzotriazoles and benzotriazole derivatives, both from commercial standards and in dishwashing detergents, reveals the potential application of the proposed method for source apportionment. PMID:23224662

  2. Automated SIMS Isotopic Analysis Of Small Dust Particles

    NASA Astrophysics Data System (ADS)

    Nittler, L.; Alexander, C.; Gyngard, F.; Morgand, A.; Zinner, E. K.

    2009-12-01

    The isotopic compositions of sub-μm to μm sized dust grains are of increasing interest in cosmochemistry, nuclear forensics and terrestrial aerosol research. Because of its high sensitivity and spatial resolution, Secondary Ion Mass Spectrometry (SIMS) is the tool of choice for measuring isotopes in such small samples. Indeed, SIMS has enabled an entirely new sub-field of astronomy: presolar grains in meteorites. In recent years, the development of the Cameca NanoSIMS ion probe has extended the reach of isotopic measurements to particles as small as 100 nm in diameter, a regime where isotopic precision is strongly limited by the total number of atoms in the sample. Many applications require obtaining isotopic data on large numbers of particles, necessitating the development of automated techniques. One such method is isotopic imaging, wherein images of multiple isotopes are acquired, each containing multiple dispersed particles, and image processing is used to determine isotopic ratios for individual particles. This method is powerful, but relatively inefficient for raster-based imaging on the NanoSIMS. Modern computerized control of instrumentation has allowed for another approach, analogous to commercial automated SEM-EDS particle analysis systems, in which images are used solely to locate particles followed by fully automated grain-by-grain analysis. The first such system was developed on the Carnegie Institution’s Cameca ims-6f, and was used to generate large databases of presolar grains. We have recently developed a similar system for the NanoSIMS, whose high sensitivity allows for smaller grains to be analyzed with less sample consumption than is possible with the 6f system. The 6f and NanoSIMS systems are functionally identical: an image of dispersed grains is obtained with sufficient statistical precision for an algorithm to identify the positions of individual particles, the primary ion beam is deflected to each particle in turn and rastered in a small

  3. Isotopic Ratio Outlier Analysis Global Metabolomics of Caenorhabditis elegans

    PubMed Central

    Szewc, Mark A.; Garrett, Timothy; Menger, Robert F.; Yost, Richard A.; Beecher, Chris; Edison, Arthur S.

    2014-01-01

    We demonstrate the global metabolic analysis of Caenorhabditis elegans stress responses using a mass spectrometry-based technique called Isotopic Ratio Outlier Analysis (IROA). In an IROA protocol, control and experimental samples are isotopically labeled with 95% and 5% 13C, and the two sample populations are mixed together for uniform extraction, sample preparation, and LC-MS analysis. This labeling strategy provides several advantages over conventional approaches: 1) compounds arising from biosynthesis are easily distinguished from artifacts, 2) errors from sample extraction and preparation are minimized because the control and experiment are combined into a single sample, 3) measurement of both the molecular weight and the exact number of carbon atoms in each molecule provides extremely accurate molecular formulae, and 4) relative concentrations of all metabolites are easily determined. A heat shock perturbation was conducted on C. elegans to demonstrate this approach. We identified many compounds that significantly changed upon heat shock, including several from the purine metabolism pathway, which we use to demonstrate the approach. The metabolomic response information by IROA may be interpreted in the context of a wealth of genetic and proteomic information available for C. elegans. Furthermore, the IROA protocol can be applied to any organism that can be isotopically labeled, making it a powerful new tool in a global metabolomics pipeline. PMID:24274725

  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. Assessment of marine-derived nutrients in the Copper River Delta, Alaska, using natural abundance of the stable isotopes of nitrogen, sulfur, and carbon

    USGS Publications Warehouse

    Kline, Thomas C.; Woody, Carol Ann; Bishop, Mary Anne; Powers, Sean P.; Knudsen, E. Eric

    2007-01-01

    We performed nitrogen, sulfur, and carbon stable isotope analysis (SIA) on maturing and juvenile anadromous sockeye and coho salmon, and periphyton in two Copper River delta watersheds of Alaska to trace salmonderived nutrients during 2003–2004. Maturing salmon were isotopically enriched relative to alternate freshwater N, S, and C sources as expected, with differences consistent with species trophic level differences, and minor system, sex, and year-to-year differences, enabling use of SIA to trace these salmon-derived nutrients. Periphyton naturally colonized, incubated, and collected using Wildco Periphtyon Samplers in and near spawning sites was 34S- and 15N-enriched, as expected, and at all freshwater sites was 13C-depleted. At nonspawning and coho-only sites, periphyton 34S and 15N was generally low. However, 34S was low enough at some sites to be suggestive of sulfate reduction, complicating the use of S isotopes. Juvenile salmon SIA ranged in values consistent with using production derived from re-mineralization as well as direct utilization, but only by a minority fraction of coho salmon. Dependency on salmon-derived nutrients ranged from relatively high to relatively low, suggesting a space-limited system. No one particular isotope was found to be superior for determining the relative importance of salmon-derived nutrients.

  6. Carbon kinetic isotope effects at natural abundances during iron-catalyzed photolytic cleavage of Csbnd C bonds in aqueous phase α,ω-dicarboxylic acids

    NASA Astrophysics Data System (ADS)

    Irei, Satoshi

    2016-09-01

    Carbon kinetic isotope effects (KIEs) at natural abundances during photolysis of Fe3+-oxalato, malonato, and succinato complexes in aqueous solution were studied to identify the Csbnd C bond cleaving mechanism of Fe3+-oxalato complexes under sunlight irradiation. Observed overall KIEs were 5.9‰, 11.5‰, and 8.4‰, respectively. This variation is inconsistent with secondary carbon KIEs for the Fesbnd O bond cleavage, but consistent with primary carbon KIEs for sequential cleavage of Fesbnd O and Csbnd C bonds. Position-specific probability of 13C content estimated KIEs of 5.9‰, 17.2‰, and 17‰ for 12Csbnd 13C bond cleavage, respectively, indicating the different KIEs for carboxyl-carboxyl and methyl-carboxyl cleavage.

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

    NASA Technical Reports Server (NTRS)

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

    1983-01-01

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

  8. The Advanced Spectral Library (ASTRAL): Abundance Analysis of the CP Star HR 465

    NASA Astrophysics Data System (ADS)

    Carpenter, Kenneth G.; Nielsen, Krister E.; Kober, Gladys V.

    2016-01-01

    We present the results of a spectrum analysis of the prototypical A-type magnetic CP star HR465. Synthetic spectra, using an non-LTE atmosphere model, were generated to fit high-resolution ultraviolet spectra (1200-3100 A) obtained as a part of the "Advanced Spectral Library (ASTRAL) Project: Hot Stars" program (GO-13346: Ayres PI). The ultraviolet data were supplemented by high resolution optical data recorded at the Nordic Optical Telescope with the SOFIN spectrograph. The optical data was used as a complement to the high line density ultraviolet spectrum and primarily used to derive accurate iron-group element abundances.HR 465 has previously been analyzed using IUE spectra. We revisit the object with this high quality data. Large parts of the spectrum have been synthesized with an ATLAS model (Teff=10750K, logg=4.0) and we present abundance results for more than 50 elements. We can confirm some of the abundance characteristics previously derived from IUE data, where elements heavier than Z=30 show significant abundance enhancements compared to solar values, while some of the lighter elements show abundance deficiencies. We will place these results in context of other AP stars, and the large number of element abundances will also help us to put some constraint on stellar abundance and evolution theories.

  9. Combustion influences on natural abundance nitrogen isotope ratio in soil and plants following a wildfire in a sub-alpine ecosystem.

    PubMed

    Huber, Edith; Bell, Tina L; Adams, Mark A

    2013-11-01

    This before-and-after-impact study uses the natural abundance N isotope ratio (δ(15)N) to investigate the effects of a wildfire on sub-alpine ecosystem properties and processes. We measured the (15)N signatures of soil, charred organic material, ash and foliage in three sub-alpine plant communities (grassland, heathland and woodland) in south-eastern Australia. Surface bulk soil was temporarily enriched in (15)N immediately after wildfire compared to charred organic material and ash in all plant communities. We associated the enrichment of bulk soil with fractionation of N during combustion and volatilization of N, a process that also explains the sequential enrichment of (15)N of unburnt leaves > ash > charred organic material in relation to duration and intensity of heating. The rapid decline in (15)N of bulk soil to pre-fire values indicates that depleted ash, containing considerable amounts of total N, was readily incorporated into the soil. Foliar δ(15)N also increased with values peaking 1 year post-fire. Foliar enrichment was foremost coupled with the release of enriched NH4(+) into the soil owing to isotopic discrimination during volatilization of soluble N and combustion of organic material. The mode of post-fire regeneration influenced foliar (15)N enrichment in two species indicating use of different sources of N following fire. The use of natural abundance of (15)N in soil, ash and foliage as a means of tracing transformation of N during wildfire has established the importance of combustion products as an important, albeit temporary source of inorganic N for plants regenerating after wildfire. PMID:23649752

  10. Combustion influences on natural abundance nitrogen isotope ratio in soil and plants following a wildfire in a sub-alpine ecosystem.

    PubMed

    Huber, Edith; Bell, Tina L; Adams, Mark A

    2013-11-01

    This before-and-after-impact study uses the natural abundance N isotope ratio (δ(15)N) to investigate the effects of a wildfire on sub-alpine ecosystem properties and processes. We measured the (15)N signatures of soil, charred organic material, ash and foliage in three sub-alpine plant communities (grassland, heathland and woodland) in south-eastern Australia. Surface bulk soil was temporarily enriched in (15)N immediately after wildfire compared to charred organic material and ash in all plant communities. We associated the enrichment of bulk soil with fractionation of N during combustion and volatilization of N, a process that also explains the sequential enrichment of (15)N of unburnt leaves > ash > charred organic material in relation to duration and intensity of heating. The rapid decline in (15)N of bulk soil to pre-fire values indicates that depleted ash, containing considerable amounts of total N, was readily incorporated into the soil. Foliar δ(15)N also increased with values peaking 1 year post-fire. Foliar enrichment was foremost coupled with the release of enriched NH4(+) into the soil owing to isotopic discrimination during volatilization of soluble N and combustion of organic material. The mode of post-fire regeneration influenced foliar (15)N enrichment in two species indicating use of different sources of N following fire. The use of natural abundance of (15)N in soil, ash and foliage as a means of tracing transformation of N during wildfire has established the importance of combustion products as an important, albeit temporary source of inorganic N for plants regenerating after wildfire.

  11. Contrasting behavior of oxygen and iron isotopes in banded iron formation revealed by in situ analysis

    NASA Astrophysics Data System (ADS)

    Beard, B.; Li, W.; Kita, N.; Valley, J. W.; Johnson, C.

    2012-12-01

    Banded iron formations (BIFs) record a period of dramatic secular change in Earth's geologic history, when abundant aqueous Fe(II) was removed from Archean and Proterozoic oceans by oxidation. BIFs are characterized by co-existing of quartz and iron minerals, including oxides and carbonates, and alternating iron-rich and iron-poor layers range from m to isotope ratios in minerals in BIFs provide valuable information about the origin of BIFs, as well as diagenetic and metamorphic effects that were superimposed on primary layering. We analyzed O and Fe isotope compositions of magnetite and hematite in BIFs from the 2.5 Ga Dales Gorge Member of the Brockman Iron Formation, Hamersley Group, Western Australia. Oxygen isotope ratios were measured by Secondary Ion Mass Spectrometry (SIMS), and Fe isotope ratios were measured by femtosecond Laser ablation Multi-Collector ICP-MS (fs-LA-MC-ICP-MS), with spatial resolutions of 15 mm (O) and 30-50 mm (Fe), and external precisions (2s) of +0.7 ‰ for δ18O and +0.2 ‰ for δ56Fe, respectively. Analysis of δ18O in iron oxides by SIMS employed special tuning with a 3kV primary beam to minimize orientation effects (Huberty et al. 2010 ). For hematite, δ18O values range from -7.1 ‰ to -0.6 ‰, with the majority of data clustering around -4.5 ‰, and δ56Fe values range from -0.50 ‰ to +1.53‰. Magnetite has a δ18O range of -5.6 ‰ to +5.6 ‰ and a δ56Fe range of -0.76 ‰ to +1.33 ‰. Notably, magnetite shows significant O isotope heterogeneity at a mineral grain scale, and the highest δ18O values were commonly measured from Si-rich (1-3 wt% SiO2) magnetite overgrowths or magnetite grains that have a recrystallization texture. In contrast, lowest δ18O values were measured from magnetite that contains less than 1 wt% SiO2. Individual magnetite grains can have up to 6 ‰ variation in δ18O values between low-Si core and Si-rich overgrowth. Iron

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

    USGS Publications Warehouse

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

    2011-01-01

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

  13. History of the paired lunar meteorites MAC88104 and MAC88105 derived from noble gas isotopes, radionuclides, and some chemical abundances

    SciTech Connect

    Eugster, O.; Burger, M.; Kraehenbuehl, U.; Michel, T. ); Beer, J. ); Finkel, R.C. ); Hofmann, H.J.; Synal, H.A.; Woelfli, W. )

    1991-11-01

    Noble gas isotopes, radionuclides, and chemical abundances were studied in the lunar meteorites MAC88104 and MAC88105 collected in the MacAlpine Hills area of Antarctica. The concentrations of the noble gas isotopes and the radionuclide activities in the two meteorites are essentially identical, proving that the two meteorites are paired. From {sup 40}K-{sup 40}Ar dating the authors obtain a gas retention age of 3,550 {plus minus} 400 Ma, typical for lunar surface material. Probably before breccia compaction the MAC88104/5 material resided for 630 {plus minus} 200 Ma at an average shielding depth of 85 g/cm{sup 2}, that is, about 50 cm below the lunar surface in the lunar regolith, as judged from the concentration of cosmic-ray produced Kr and Xe isotopes. Although this duration of lunar regolith residence is relatively long, MAC88104/5 represent immature regolith material: the concentration of solar wind implanted noble gases are two orders of magnitude lower than those in mature lunar soil. The {sup 40}Ar/{sup 36}Ar ratio of the trapped component is 5.7 {plus minus} 1.0, indicating an intermediate antiquity of the material; the authors estimate that the solar wind and lunar atmospheric particles were implanted about 2,000 Ma ago. The radionuclide activities allow a determination of the exposure history of the MAC88104/5 material. The duration of the Moon-Earth transfer was {much lt} 0.24 Ma. The exposure histories of the lunar meteorites discussed in this work indicate that at least two impact events are required for their ejection from the Moon. The authors first noble gas results for lunar meteorite Yamato-793274 show that it represents mature lunar regolith material with relatively high concentrations of solar wind implanted noble gas and a duration of several hundred million years of exposure to cosmic rays.

  14. Hanford Isotope Project strategic business analysis Cesium-137 (Cs-137)

    SciTech Connect

    1995-10-01

    The purpose of this business analysis is to address the beneficial reuse of Cesium 137 (Cs-137) in order to utilize a valuable national asset and possibly save millions of tax dollars. Food irradiation is the front runner application along with other uses. This business analysis supports the objectives of the Department of Energy National Isotope Strategy distributed in August 1994 which describes the DOE plans for the production and distribution of isotope products and services. As part of the Department`s mission as stated in that document. ``The Department of Energy will also continue to produce and distribute other radioisotopes and enriched stable isotopes for medical diagnostics and therapeutics, industrial, agricultural, and other useful applications on a businesslike basis. This is consistent with the goals and objectives of the National Performance Review. The Department will endeavor to look at opportunities for private sector to co-fund or invest in new ventures. Also, the Department will seek to divest from ventures that can more profitably or reliably be operated by the private sector.``

  15. Stable isotope analysis of energy dynamics in aquatic ecosystems suggests trophic shifts following severe wildfire

    NASA Astrophysics Data System (ADS)

    Martens, A. M.; Silins, U.; Bladon, K. D.; Williams, C.; Wagner, M. J.; Luchkow, E.

    2015-12-01

    Wildfire alters landscapes and can have significant impacts on stream ecosystems. The 2003 Lost Creek wildfire was one of the most severe on Alberta's eastern rocky mountain slopes, resulting in elevated sediment production and nutrient (phosphorus, nitrogen, and carbon) export in impacted streams. These resulted in increased algal productivity and macroinvertebrate abundance and diversity, and as a result, fish in watersheds draining wildfire affected catchments were larger than those in the same age class from reference (unburned) watersheds. In the present investigation, stable isotope analysis of C and N was utilized to evaluate ecosystem energy dynamics and describe trophic relationships in those watersheds. Aquatic invertebrates from burned catchments showed enrichment in δ13C and δ15N relative to algae suggesting a reliance on algae (autochthony) as a primary source of energy. Invertebrates from unburned systems were depleted in δ13C relative to algae indicating reliance on allochthonous or terrestrial primary energy sources. Preliminary analysis of δ15N in macroinvertebrates showed slight enrichment in burned catchments suggesting a trophic shift. More comprehensive macroinvertebrate sampling and identification has been conducted; isotopic analysis will provide greater resolution of how specific families within feeding guilds have been affected by wildfire. This will provide more robust insights into how wildfires may impact stream ecology in mountain environments.

  16. Full Range MGA Plutonium Isotopic Analysis using Single Ge Detector

    SciTech Connect

    Buckley, W.M.; Wang, T.F.; Friensehner, A.; Kreek, S.A.; Lanier, R.G.; Parker, W.E.; Ruhter, W.; Twomey, T.; Martinez, D.; Keyser, R.; Sangsingkeow, P.

    2000-06-26

    The Gamma-Ray multi-group analysis code MGA developed at Lawrence Livermore National Laboratory has been widely used in the area of gamma-ray non-destructive plutonium assay. This plutonium isotopic analysis code de-convolutes the complicated, 100-keV x-ray and gamma-ray region to obtain the ratio of Pu isotopes. Calibration of the detector efficiency is not required, but is determined intrinsically from the measured spectra. The code can either analyze low-energy gamma-ray spectrum taken using a high-resolution HPGe detector for energies below 300 keV, or analyze the low-energy spectrum combined with a high-energy spectrum (up to 1 MeV) in the two-detector analysis mode. In the latter case, the use of two detectors has been mandated by the conflicting requirements: excellent resolution at low energies (characteristic of small planar detectors) with good high-energy efficiency (characteristic of coaxial detectors). Usually, a high-energy spectrum taken using a coaxial Ge detector will not provide sufficient energy resolution for 100-keV plutonium isotopic analysis, while the small planar used at low energies has inadequate high-energy efficiency. An optimized-geometry ORTEC HPGe detector has been developed which combines good energy resolution at 100 keV combined with acceptable high-energy ({approx} 1 MeV) efficiency in a single detector. It has been used to gather spectra of both low- and high-energy regions of plutonium spectra simultaneously, for analysis by MGA in the two-detector mode. Five Pu gamma-ray calibration standard sources were used in this study of this special detector.

  17. Application of Natural Isotopic Abundance ¹H-¹³C- and ¹H-¹⁵N-Correlated Two-Dimensional NMR for Evaluation of the Structure of Protein Therapeutics.

    PubMed

    Arbogast, Luke W; Brinson, Robert G; Marino, John P

    2016-01-01

    Methods for characterizing the higher-order structure of protein therapeutics are in great demand for establishing consistency in drug manufacturing, for detecting drug product variations resulting from modifications in the manufacturing process, and for comparing a biosimilar to an innovator reference product. In principle, solution NMR can provide a robust approach for characterization of the conformation(s) of protein therapeutics in formulation at atomic resolution. However, molecular weight limitations and the perceived need for stable isotope labeling have to date limited its practical applications in the biopharmaceutical industry. Advances in NMR magnet and console technologies, cryogenically cooled probes, and new rapid acquisition methodologies, particularly selective optimized flip-angle short transient pulse schemes and nonuniform sampling, have greatly ameliorated these limitations. Here, we describe experimental methods for the collection and analysis of 2D (1)H(N)-(15)N-amide- and (1)H-(13)C-methyl-correlated spectra applied to protein drug products at natural isotopic abundance, including representatives from the rapidly growing class of monoclonal antibody (mAb) therapeutics. Practical aspects of experimental setup and data acquisition for both standard and rapid acquisition NMR techniques are described. Furthermore, strategies for the statistical comparison of 2D (1)H(N)-(15)N-amide- and (1)H-(13)C-methyl-correlated spectra are detailed.

  18. Characterization of phenols biodegradation by compound specific stable isotope analysis

    NASA Astrophysics Data System (ADS)

    Wei, Xi; Gilevska, Tetyana; Wenzig, Felix; Hans, Richnow; Vogt, Carsten

    2015-04-01

    -cresol degradation and 2.2±0.3‰ for m-cresol degradation, respectively. The carbon isotope fractionation patterns of phenol degradation differed more profoundly. Oxygen-dependent monooxygenation of phenol by A.calcoaceticus as the initial reaction yielded ƐC values of -1.5±0.02‰. In contrast, the anaerobic degradation initiated by ATP-dependent carboxylation performed by Thauera aromatia DSM 6984, produced no detectable fractionation (ƐC 0±0.1‰). D. cetonica showed a slight inverse carbon isotope fractionation (ƐC 0.4±0.1‰). In conclusion, a validated method for compound specific stable isotope analysis was developed for phenolic compounds, and the first data set of carbon enrichment factors upon the biodegradation of phenol and cresols with different activation mechanisms has been obtained in the present study. Carbon isotope fractionation analysis is a potentially powerful tool to monitor phenolic compounds degradation in the environment.

  19. Isotopic analysis for degradation diagnosis of calcite matrix in mortar.

    PubMed

    Dotsika, E; Psomiadis, D; Poutoukis, D; Raco, B; Gamaletsos, P

    2009-12-01

    Mortar that was used in building as well as in conservation and restoration works of wall paintings have been analysed isotopically (delta(13)C and delta(18)O) in order to evaluate the setting environments and secondary processes, to distinguish the structural components used and to determine the exact causes that incurred the degradation phenomena. The material undergoes weathering and decay on a large proportion of its surface and in depth, due to the infiltration of water through the structural blocks. Mineralogical analysis indicated signs of sulphation and dissolution/recrystallisation processes taking place on the material, whereas stable isotopes provided information relative to the origin of the CO(2) and water during calcite formation and degradation processes. Isotopic change of the initial delta(13)C and delta(18)O in carbonate matrix was caused by alteration of the primary source of CO(2) and H(2)O in mortar over time, particularly by recrystallisation of calcite with porewater, evaporated or re-condensed water, and CO(2) from various sources of atmospheric and biogenic origin. Human influence (surface treatment) and biological growth (e.g. fungus) are major exogenic processes which may alter delta(18)O and delta(13)C in lime mortar.

  20. The Separation and Isotopic Analysis Seawater Cu and Zn

    NASA Astrophysics Data System (ADS)

    Bermin, J.; Vance, D.; Archer, C.; Statham, P. J.

    2004-12-01

    Many transition metals are key micronutrients and their concentration profiles in the oceans often show nutrient-like patterns, with strong surface depletions and deep enrichments1. In addition, their biological usage has been shown to induce isotopic fractionations2 so that the precise and accurate analysis of their isotope systems in seawater has potential applications in tracing metal micronutrient usage in the past ocean. The analytical challenges involved in realising this goal are, however, considerable, given the low concentrations of transition metals in seawater and the requirement to extract small amounts from large samples at low blank and with no artificial isotopic fractionation. Here we present a method for the separation an analysis of Cu and Zn isotopes that is applicable to 0.1-5 L samples of seawater. Trace metals were concentrated from seawater using a Chelex-100 ion-exchange column3 and further purified and separated from each other using a small anion column4,5. All isotopic analyses were performed on a ThermoFinnigan Neptune instrument at the University of Bristol. The main requirements for precise and accurate isotopic analyses are a low contribution from analytical blank and the robust correction for analytical mass discrimination. Our blanks allow the analysis of seawater samples of 50-250 mL for Cu, samples of about 100 mL for Zn in the deep oceans and for Zn-depleted open ocean surface water samples of around 5L. The correction for mass discrimination is most readily considered as two components - that occurring during the chemical separation procedure in response to non-100% yields and that occurring in the mass spectrometer. Correction of all mass discrimination throughout the procedure is most robustly done for Zn and Fe using a double-spike that is added prior to any chemical treatment. This approach has been tested using standard-doped seawater samples that had previously been stripped of their metal contents using the Chelex column

  1. Quantitative determination of mineral types and abundances from reflectance spectra using principal components analysis

    NASA Technical Reports Server (NTRS)

    Smith, M. O.; Adams, J. B.; Johnson, P. E.

    1985-01-01

    A procedure was developed for analyzing remote reflectance spectra, including multispectral images, that quantifies parameters such as types of mineral mixtures, the abundances of mixed minerals, and particle sizes. Principal components analysis reduced the spectral dimensionality and allowed testing the uniqueness and validity of spectral mixing models. By analyzing variations in the overall spectral reflectance curves, the type of spectral mixture was identified, mineral abundances quantified and the effects of particle size identified. The results demonstrate an advantage in classification accuracy over classical forms of analysis that ignore effects of particle-size or mineral-mixture systematics on spectra. The approach is applicable to remote sensing data of planetary surfaces for quantitative determinations of mineral abundances.

  2. 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.

  3. Enantiomeric and Isotopic Analysis of Sugar Derivatives in Carbonaceous Meteorites

    NASA Technical Reports Server (NTRS)

    Cooper, George; Asiyo, Cynthia; Turk, Kendra; DeVincenzi, Donald (Technical Monitor)

    2002-01-01

    Several classes of organic compounds are found in carbonaceous meteorites including amino acids, carboxylic acids, hydroxy acids, purines, and pyrimidines. Such compounds are thought to have been delivered to the early Earth in asteroids and comets and may have played a role in the origin of life. Likewise, sugar derivatives are critical to all known lifeforms. Recent analyses of the Murchison and Murray carbonaceous meteorites revealed a diverse suite of such derivatives, i.e., sugar alcohols, and sugar acids. This presentation will focus primarily on the analysis of individual sugar acids - their enantiomeric and isotopic composition. Analysis of these compounds may reveal the nature of past (or present) meteoritic sugars themselves. For example, if parent sugars decomposed (by well-known mechanisms) to give the present acids, were their enantiomeric ratios preserved? Combined with other evidence, the enantiomeric composition of such compounds as glyceric acid and (especially) rare acids may help to answer such questions. C-13 and D isotope analysis of meteoritic sugar alcohols (glycerol, threitol, ribitol, etc.) as a group revealed that they were indigenous to the meteorite. Preliminary C-13 analysis of glyceric acid shows that it is also extraterrestrial.

  4. Monte Carlo isotopic inventory analysis for complex nuclear systems

    NASA Astrophysics Data System (ADS)

    Phruksarojanakun, Phiphat

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

  5. The isotopes of hydrogen and helium in the Galactic cosmic radiation - Their source abundances and interstellar propagation

    NASA Technical Reports Server (NTRS)

    Beatty, James J.

    1986-01-01

    A self-consistent model describing the interstellar propagation of Galactic cosmic radiation is developed using low-energy measurements and calculations of the effects of interstellar propagation and solar modulation. The source ratio H-1/He-4 at constant energy per nucleon is determined to be 12.2 + or - 1.5, and the mean path length for an exponential path length weighting function required to account for the data is 7.2 + or - 1.0 g/sq cm. The measured H-2/He-4 and He-3/He-4 ratios do not vary by more than about 30 percent over the solar cycle. The behavior of the ratios during the solar cycle reflects the energy dependence of the local interstellar ratios, and leads to an energy dependence of the mean path length below 1 GeV per nucleon weaker than that inferred from boron/carbon. The source ratio H-1/He-4 inferred from the low-energy data is consistent both with the value inferred from high-energy cosmic ray data using a model of rigidity-dependent confinement and with the solar system abundance ratio.

  6. Volatile, isotope, and organic analysis of martian fines with the Mars Curiosity rover.

    PubMed

    Leshin, L A; Mahaffy, P R; Webster, C R; Cabane, M; Coll, P; Conrad, P G; Archer, P D; Atreya, S K; Brunner, A E; Buch, A; Eigenbrode, J L; Flesch, G J; Franz, H B; Freissinet, C; Glavin, D P; McAdam, A C; Miller, K E; Ming, D W; Morris, R V; Navarro-González, R; Niles, P B; Owen, T; Pepin, R O; Squyres, S; Steele, A; Stern, J C; Summons, R E; Sumner, D Y; Sutter, B; Szopa, C; Teinturier, S; Trainer, M G; Wray, J J; Grotzinger, J P

    2013-09-27

    Samples from the Rocknest aeolian deposit were heated to ~835°C under helium flow and evolved gases analyzed by Curiosity's Sample Analysis at Mars instrument suite. H2O, SO2, CO2, and O2 were the major gases released. Water abundance (1.5 to 3 weight percent) and release temperature suggest that H2O is bound within an amorphous component of the sample. Decomposition of fine-grained Fe or Mg carbonate is the likely source of much of the evolved CO2. Evolved O2 is coincident with the release of Cl, suggesting that oxygen is produced from thermal decomposition of an oxychloride compound. Elevated δD values are consistent with recent atmospheric exchange. Carbon isotopes indicate multiple carbon sources in the fines. Several simple organic compounds were detected, but they are not definitively martian in origin.

  7. Volatile, isotope, and organic analysis of martian fines with the Mars Curiosity rover.

    PubMed

    Leshin, L A; Mahaffy, P R; Webster, C R; Cabane, M; Coll, P; Conrad, P G; Archer, P D; Atreya, S K; Brunner, A E; Buch, A; Eigenbrode, J L; Flesch, G J; Franz, H B; Freissinet, C; Glavin, D P; McAdam, A C; Miller, K E; Ming, D W; Morris, R V; Navarro-González, R; Niles, P B; Owen, T; Pepin, R O; Squyres, S; Steele, A; Stern, J C; Summons, R E; Sumner, D Y; Sutter, B; Szopa, C; Teinturier, S; Trainer, M G; Wray, J J; Grotzinger, J P

    2013-09-27

    Samples from the Rocknest aeolian deposit were heated to ~835°C under helium flow and evolved gases analyzed by Curiosity's Sample Analysis at Mars instrument suite. H2O, SO2, CO2, and O2 were the major gases released. Water abundance (1.5 to 3 weight percent) and release temperature suggest that H2O is bound within an amorphous component of the sample. Decomposition of fine-grained Fe or Mg carbonate is the likely source of much of the evolved CO2. Evolved O2 is coincident with the release of Cl, suggesting that oxygen is produced from thermal decomposition of an oxychloride compound. Elevated δD values are consistent with recent atmospheric exchange. Carbon isotopes indicate multiple carbon sources in the fines. Several simple organic compounds were detected, but they are not definitively martian in origin. PMID:24072926

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

    USGS Publications Warehouse

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

    1983-01-01

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

  9. Purification, characterization and structural analysis of an abundant beta-1,3-glucanase from banana fruit.

    PubMed

    Peumans, W J; Barre, A; Derycke, V; Rougé, P; Zhang, W; May, G D; Delcour, J A; Van Leuven, F; Van Damme, E J

    2000-02-01

    An abundant, catalytically active beta-1,3-endoglucanase (EC 3.2.1. 39) has been isolated from the pulp of ripe bananas. Biochemical analysis of the purified protein, molecular modelling, and molecular cloning of the corresponding gene indicate that this banana enzyme closely resembles previously characterized plant beta-glucanases with respect to its amino-acid sequence, structure and biological activity. The results described in this paper demonstrate both the occurrence of an abundant active beta-1,3-endoglucanases in fruits and also readdress the question of the possible involvement of these enzymes in the ripening and/or softening process.

  10. An elemental abundance analysis of the superficially normal A star Vega

    NASA Technical Reports Server (NTRS)

    Adelman, Saul J.; Gulliver, Austin F.

    1990-01-01

    An elemental abundance analysis of Vega has been performed using high-signal-to-noise 2.4 A/mm Reticon observations of the region 4313-4809 A. Vega is found to be a metal-poor star with a mean underabundance of 0.60 dex. The He/H ratio of 0.03 as derived from He I 4472 A suggests that the superficial helium convection zone has disappeared and that radiative diffusion is producing the photospheric abundance anomalies.

  11. An elemental abundance analysis of the superficially normal A star Vega

    SciTech Connect

    Adelman, S.J.; Gulliver, A.F. Brandon Univ. )

    1990-01-01

    An elemental abundance analysis of Vega has been performed using high-signal-to-noise 2.4 A/mm Reticon observations of the region 4313-4809 A. Vega is found to be a metal-poor star with a mean underabundance of 0.60 dex. The He/H ratio of 0.03 as derived from He I 4472 A suggests that the superficial helium convection zone has disappeared and that radiative diffusion is producing the photospheric abundance anomalies. 45 refs.

  12. Subterranean Sympatry: An Investigation into Diet Using Stable Isotope Analysis

    PubMed Central

    Robb, Gillian N.; Woodborne, Stephan; Bennett, Nigel C.

    2012-01-01

    In the Western Cape three species of mole-rat occur in sympatry, however, little is known about differences in their dietary preferences. Dietary composition of the three species; the common mole-rat (Cryptomys hottentotus hottentotus), the Cape mole-rat (Georychus capensis) and the Cape dune mole-rat (Bathyergus suillus) were examined using stable isotope analysis. Blood, fur and claw samples were collected from 70 mole-rats, in addition to several potential food items, to assess food selection of the three species under natural conditions. Overall there was a significant difference in the isotopic composition (δ13C and δ15N) between all three species and significant differences in their diet composition. There were also significant differences between tissues in all three species suggesting temporal variation in diet. The small size and colonial lifestyle of C. h. hottentotus allows it to feed almost 100% on bulbs, while the solitary and larger species G. capensis and B. suillus fed to a greater extent on other resources such as grasses and clover. B. suillus, the largest of the species, had the most generalized diet. However, overall all species relied most heavily upon geophytes and consumed the same species suggesting competition for resources could exist. We also showed a high level of individual variation in diet choices. This was most pronounced in B. suillus and G. capensis and less so in C. h. hottentotus. We demonstrate that stable isotope analysis can successfully be applied to examine dietary patterns in subterranean mammals and provide insights into foraging patterns and dietary variation at both the inter and intra population level. PMID:23139795

  13. Stable isotope analysis indicates a lack of inter- and intra-specific dietary redundancy among ecologically important coral reef fishes

    NASA Astrophysics Data System (ADS)

    Plass-Johnson, J. G.; McQuaid, C. D.; Hill, J. M.

    2013-06-01

    Parrotfish are critical consumers on coral reefs, mediating the balance between algae and corals, and are often categorised into three functional groups based on adult morphology and feeding behaviour. We used stable isotope analysis (δ13C, δ15N) to investigate size-related ontogenetic dietary changes in multiple species of parrotfish on coral reefs around Zanzibar. We compared signatures among species and functional groups (scrapers, excavators and browsers) as well as ontogenetic stages (immature, initial and terminal phase) within species. Stable isotope analysis suggests that ontogenetic dietary shifts occurred in seven of the nine species examined; larger individuals had enriched δ13C values, with no relationship between size and δ15N. The relationship between fish length and δ13C signature was maintained when species were categorised as scrapers and excavators, but was more pronounced for scrapers than excavators, indicating stronger ontogenetic changes. Isotopic mixing models classified the initial phase of both the most abundant excavator ( Chlorurus sordidus) as a scraper and the immature stage of the scraper Scarus ghobban (the largest species) as an excavator, indicating that diet relates to size rather than taxonomy. The results indicate that parrotfish may show similar intra-group changes in diet with length, but that their trophic ecology is more complex than suggested by morphology alone. Stable isotope analyses indicate that feeding ecology may differ among species within functional groups, and according to ontogenetic stage within a species.

  14. Assessment of international reference materials for isotope-ratio analysis (IUPAC Technical Report)

    USGS Publications Warehouse

    Brand, Willi A.; Coplen, Tyler B.; Vogl, Jochen; Rosner, Martin; Prohaska, Thomas

    2014-01-01

    Since the early 1950s, the number of international measurement standards for anchoring stable isotope delta scales has mushroomed from 3 to more than 30, expanding to more than 25 chemical elements. With the development of new instrumentation, along with new and improved measurement procedures for studying naturally occurring isotopic abundance variations in natural and technical samples, the number of internationally distributed, secondary isotopic reference materials with a specified delta value has blossomed in the last six decades to more than 150 materials. More than half of these isotopic reference materials were produced for isotope-delta measurements of seven elements: H, Li, B, C, N, O, and S. The number of isotopic reference materials for other, heavier elements has grown considerably over the last decade. Nevertheless, even primary international measurement standards for isotope-delta measurements are still needed for some elements, including Mg, Fe, Te, Sb, Mo, and Ge. It is recommended that authors publish the delta values of internationally distributed, secondary isotopic reference materials that were used for anchoring their measurement results to the respective primary stable isotope scale.

  15. NEON AND CNO ABUNDANCES FOR EXTREME HELIUM STARS-A NON-LTE ANALYSIS

    SciTech Connect

    Pandey, Gajendra; Lambert, David L. E-mail: dll@astro.as.utexas.edu

    2011-02-01

    A non-LTE (NLTE) abundance analysis was carried out for three extreme helium stars (EHes): BD+10{sup 0} 2179, BD-9{sup 0} 4395, and LS IV+6{sup 0} 002, from their optical spectra with NLTE model atmospheres. NLTE TLUSTY model atmospheres were computed with H, He, C, N, O, and Ne treated in NLTE. Model atmosphere parameters were chosen from consideration of fits to observed He I line profiles and ionization equilibria of C and N ions. The program SYNSPEC was then used to determine the NLTE abundances for Ne as well as H, He, C, N, and O. LTE neon abundances from Ne I lines in the EHes: LSE 78, V1920 Cyg, HD 124448, and PV Tel, are derived from published models and an estimate of the NLTE correction applied to obtain the NLTE Ne abundance. We show that the derived abundances of these key elements, including Ne, are well matched with semi-quantitative predictions for the EHe resulting from a cold merger (i.e., no nucleosynthesis during the merger) of an He white dwarf with a C-O white dwarf.

  16. Neon and CNO Abundances for Extreme Helium Stars—A Non-LTE Analysis

    NASA Astrophysics Data System (ADS)

    Pandey, Gajendra; Lambert, David L.

    2011-02-01

    A non-LTE (NLTE) abundance analysis was carried out for three extreme helium stars (EHes): BD+10° 2179, BD-9° 4395, and LS IV+6° 002, from their optical spectra with NLTE model atmospheres. NLTE TLUSTY model atmospheres were computed with H, He, C, N, O, and Ne treated in NLTE. Model atmosphere parameters were chosen from consideration of fits to observed He I line profiles and ionization equilibria of C and N ions. The program SYNSPEC was then used to determine the NLTE abundances for Ne as well as H, He, C, N, and O. LTE neon abundances from Ne I lines in the EHes: LSE 78, V1920 Cyg, HD 124448, and PV Tel, are derived from published models and an estimate of the NLTE correction applied to obtain the NLTE Ne abundance. We show that the derived abundances of these key elements, including Ne, are well matched with semi-quantitative predictions for the EHe resulting from a cold merger (i.e., no nucleosynthesis during the merger) of an He white dwarf with a C-O white dwarf.

  17. 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

  18. Using PLFA Biomarkers and Natural Abundance Stable and Radiocarbon Isotopes to Characterize the Microbial Ecology and Metabolism of Methane Cycling

    NASA Astrophysics Data System (ADS)

    Mills, C. T.; Mandernack, K. W.; Slater, G. F.; Dias, R. F.

    2008-12-01

    Methane generated in the subsurface is a major source of atmospheric CH4, but its release is mitigated by CH4-oxidizing bacteria (methanotrophs). Therefore, it is important to understand the ecology of methanotroph communities in various environments. Phospholipid fatty acid (PLFA) analyses are a particularly useful method for characterizing these communities for two reasons: (1) Many type I and II methanotrophs produce specific PLFA biomarkers that can be used to estimate their populations, and (2) because CH4 is often very depleted in 13C and sometimes 14C, natural abundance δ13CPLFA and Δ14CPLFA values can be used to trace the flow of CH4- derived carbon through microbial ecosystems. We used these tools to evaluate the role of methanotrophs in carbon flow in three different environments: (1) a soil column overlying a coal bed methane (CBM) seep in southwest CO, and pristine, oligotrophic groundwaters within (2) sedimentary and (3) granitic host rocks in Japan. In the soil column impacted by CBM seepage, concentrations of the biomarker PLFAs for type I (16:1ω8cis) and type II (18:1ω8cis) methanotrophs were as high as 13 and 18 nmoles (g dry soil)-1, respectively. Depth profiles of methanotroph PLFA concentrations varied over different sampling dates indicating dynamic populations. δ13CPLFA values of the CBM soils (-25.1 to - 66.9‰) were substantially more negative than those for the control soil (-14.5 to -32.5‰) indicating that CBM is an important carbon source for the CBM-impacted soil microbial community. Δ14CPLFA values (-351 to -936‰) indicate the importance of 14C-dead CBM as a carbon source to the microbial communities, contributing 32 to 66% of total carbon in PLFA structures isolated from shallow soils and 67 to 97% for those isolated from deeper soils. The biomarker for type II methanotrophs, comprised 3 and 18% of total PLFAs in sedimentary and granitic groundwaters, respectively. The Δ14C values determined for type II methanotroph PLFAs

  19. Existing and emerging technologies for measuring stable isotope labelled retinol in biological samples: isotope dilution analysis of body retinol stores.

    PubMed

    Preston, Tom

    2014-01-01

    This paper discusses some of the recent improvements in instrumentation used for stable isotope tracer measurements in the context of measuring retinol stores, in vivo. Tracer costs, together with concerns that larger tracer doses may perturb the parameter under study, demand that ever more sensitive mass spectrometric techniques are developed. GCMS is the most widely used technique. It has high sensitivity in terms of sample amount and uses high resolution GC, yet its ability to detect low isotope ratios is limited by background noise. LCMSMS may become more accessible for tracer studies. Its ability to measure low level stable isotope tracers may prove superior to GCMS, but it is isotope ratio MS (IRMS) that has been designed specifically for low level stable isotope analysis through accurate analysis of tracer:tracee ratios (the tracee being the unlabelled species). Compound-specific isotope analysis, where GC is interfaced to IRMS, is gaining popularity. Here, individual 13C-labelled compounds are separated by GC, combusted to CO2 and transferred on-line for ratiometric analysis by IRMS at the ppm level. However, commercially-available 13C-labelled retinol tracers are 2 - 4 times more expensive than deuterated tracers. For 2H-labelled compounds, GC-pyrolysis-IRMS has now become more generally available as an operating mode on the same IRMS instrument. Here, individual compounds are separated by GC and pyrolysed to H2 at high temperature for analysis by IRMS. It is predicted that GC-pyrolysis-IRMS will facilitate low level tracer procedures to measure body retinol stores, as has been accomplished in the case of fatty acids and amino acids. Sample size requirements for GC-P-IRMS may exceed those of GCMS, but this paper discusses sample preparation procedures and predicts improvements, particularly in the efficiency of sample introduction.

  20. Evaluation of Stable Isotope Analysis as a Tool to Determine Nitrate Sources in Irish Groundwaters

    NASA Astrophysics Data System (ADS)

    Minet, E.; Coxon, C.; Kalin, R.

    2004-12-01

    Natural abundance of stable isotope ratios of nitrogen (\\delta15N) and oxygen (\\delta18O) in NO3 were measured in a nitrate-vulnerable aquifer in eastern Ireland underlying an intensive agricultural area. The aim was to determine whether the dual stable isotope approach (\\delta15N and \\delta18O) could provide a more power tool than \\delta15N measurements alone for determining the source of groundwater nitrate. Forty-five private wells and boreholes representing a range of potential N sources (diffuse sources such as synthetic fertiliser spreading and/or farmyard effluents and/or septic tank effluents) were sampled on seven occasions between 2002 and 2004. Additionally, nitrate leachate samples were collected from the unsaturated zone under small-scale experiments simulating different agricultural practices. Nitrate was extracted from each water sample using an anion exchange resin technique (Silva et al., 2000), and \\delta15N and \\delta18O values were both measured by Continuous-Flow Isotopic Ratio Mass Spectrometry. The initial hypothesis was that, in a shallow gravel aquifer where nitrate leaching is important and fast, groundwater nitrates are likely to display the isotopic characteristics of their source (low \\delta15N and high \\delta18O for diffuse sources, compared to high \\delta15N and low \\delta18O for point sources). The first set of results indicates that the \\delta15N values only follow this trend, although the \\delta18O values suggest the occurrence of denitrification. The levelling of \\delta18O values may in fact be caused by the Mineralisation-Immobilisation Turnover processes (MIT) that have previously been found to occur in the unsaturated zone, incorporating new oxygen atoms during the remineralisation of the nitrate (Mengis et al., 2001). References Mengis, M.; Walther, U.; Bernasconi, S.M.; Wehrli, B. (2001) Limitations of using \\delta18O for the source identification of nitrate in agricultural soils. Environmental Science

  1. Isotopic Biogeochemistry

    NASA Technical Reports Server (NTRS)

    Hayes, J. M.

    1985-01-01

    An overview is provided of the biogeochemical research. The funding, productivity, personnel and facilities are reviewed. Some of the technical areas covered are: carbon isotopic records; isotopic studies of banded iron formations; isotope effects in microbial systems; studies of organic compounds in ancient sediments; and development in isotopic geochemistry and analysis.

  2. Forensic isotope analysis to refine a hydrologic conceptual model.

    PubMed

    Bassett, R L; Steinwand, Aaron; Jorat, Saeed; Petersen, Christian; Jackson, Randy

    2008-01-01

    Water resources in the arid southwestern United States are frequently the subject of conflict from competing private and public interests. Legal remedies may remove impasses, but the technical analysis of the problem often determines the future success of legal solutions. In Owens Valley, California, the source of water for the Los Angeles Aqueduct (LAA) is flow diverted from the Owens River and its tributaries and ground water from valley aquifers. Future management of ground water delivered to the LAA needs technical support regarding quantity available, interconnection of shallow and confined aquifers, impact on local springs, and rate of recharge. Ground water flow models and ground water composition are tools already in use, but these have large uncertainty for local interpretations. This study conducted targeted sampling of springs and wells to evaluate the hydrologic system to corroborate conceptual and numerical models. The effort included measurement of intrinsic isotopic composition at key locations in the aquifers. The stable isotopic data of boron (delta(11)B), sulfur (delta(34)S), oxygen (delta(18)O), hydrogen (delta D), and tritium ((3)H) supported by basic chemical data provided rules for characterizing the upper and the lower aquifer system, confirmed the interpretation of ground water flow near faults and flow barriers, and detected hydraulic connections between the LAA and the perennial springs at key locations along the unlined reach of the LAA. This study exemplifies the use of forensic isotopic approaches as independent checks on the consistency of interpretations of conceptual models of a ground water system and the numerical hydrologic simulations.

  3. CD −24°17504 REVISITED: A NEW COMPREHENSIVE ELEMENT ABUNDANCE ANALYSIS

    SciTech Connect

    Jacobson, Heather R.; Frebel, Anna

    2015-07-20

    With [Fe/H] ∼ −3.3, CD −24°17504 is a canonical metal-poor main-sequence turn-off star. Though it has appeared in numerous literature studies, the most comprehensive abundance analysis for the star based on high-resolution, high signal-to-noise ratio (S/N) spectra is nearly 15 years old. We present a new detailed abundance analysis for 21 elements based on combined archival Keck-HIRES and Very Large Telescope-UVES spectra of the star that is higher in both spectral resolution and S/N than previous data. Our results are very similar to those of an earlier comprehensive study of the star, but we present for the first time a carbon abundance from the CH G-band feature as well as improved upper limits for neutron-capture species such as Y, Ba, and Eu. In particular, we find that CD −24°17504 has [Fe/H] = −3.41, [C/Fe] = +1.10, [Sr/H] = −4.68, and [Ba/H] ≤ −4.46, making it a carbon-enhanced metal-poor star with neutron-capture element abundances among the lowest measured in Milky Way halo stars.

  4. Evaluation of relative isotopic abundance measurements in a quadrupole time-of-flight mass spectrometer for elemental composition determination of natural products in traditional Chinese medicine.

    PubMed

    Wu, Zhi-Jun; Huo, Jia-Li; Chen, Jian-Zhong; Li, Na; Fang, Dong-Mei; Chen, Xiao-Zhen; Zhang, Guo-Lin; Wang, Jian-Hua; Xu, Xiao-Ying

    2013-01-01

    The relative isotopic abundance (RIA) measurement errors of a quadrupole time-of-flight (Q-ToF) instrument incorporating analog-to-digital converter detectors were systemically evaluated by stochastically collecting about 200 data in positive ion mass spectrometry (MS) mode. Errors varied with peak intensities at definite spectral acquisition rates but were very close, even if peak intensities changed sharply at different spectral acquisition rates with the same concentration. Intensity thresholds were systematically defined at 1 Hz of spectral acquisition rates. RIA measurement errors were also evaluated using peak area. It seemed that peak area was better adapted for the high-intensity ions while peak intensity was suited for very low-intensity ions. Several known compounds were selected for RIA measurements for product ions in tandem mass spectropmetry (MS/MS) mode. An extract of a representative traditional Chinese medicinal, Paederia scandens was analyzed with high-performance liquid chromatography-electrospray ionization-QToF-MS/MS. The unique elemental compositions of some compounds could not be identified even with exact masses and MS/MS spectra of measured and reference compounds. RIA errors, especially of (M+2)M(-1), provided vital information for determining the elemental composition. PMID:24261081

  5. Evaluation of relative isotopic abundance measurements in a quadrupole time-of-flight mass spectrometer for elemental composition determination of natural products in traditional Chinese medicine.

    PubMed

    Wu, Zhi-Jun; Huo, Jia-Li; Chen, Jian-Zhong; Li, Na; Fang, Dong-Mei; Chen, Xiao-Zhen; Zhang, Guo-Lin; Wang, Jian-Hua; Xu, Xiao-Ying

    2013-01-01

    The relative isotopic abundance (RIA) measurement errors of a quadrupole time-of-flight (Q-ToF) instrument incorporating analog-to-digital converter detectors were systemically evaluated by stochastically collecting about 200 data in positive ion mass spectrometry (MS) mode. Errors varied with peak intensities at definite spectral acquisition rates but were very close, even if peak intensities changed sharply at different spectral acquisition rates with the same concentration. Intensity thresholds were systematically defined at 1 Hz of spectral acquisition rates. RIA measurement errors were also evaluated using peak area. It seemed that peak area was better adapted for the high-intensity ions while peak intensity was suited for very low-intensity ions. Several known compounds were selected for RIA measurements for product ions in tandem mass spectropmetry (MS/MS) mode. An extract of a representative traditional Chinese medicinal, Paederia scandens was analyzed with high-performance liquid chromatography-electrospray ionization-QToF-MS/MS. The unique elemental compositions of some compounds could not be identified even with exact masses and MS/MS spectra of measured and reference compounds. RIA errors, especially of (M+2)M(-1), provided vital information for determining the elemental composition.

  6. Source apportionment of atmospheric PAHs in the Western Balkans by natural abundance radiocarbon analysis

    SciTech Connect

    Zdenek Zencak; Jana Klanova; Ivan Holoubek; Oerjan Gustafsson

    2007-06-01

    Progress in source apportionment of priority combustion-derived atmospheric pollutants can be made by an inverse approach to inventory emissions, namely, receptor-based compound class-specific radiocarbon analysis (CCSRA) of target pollutants. In the present study, CCSRA of the combustion-derived polycyclic aromatic hydrocarbons (PAHs) present in the atmosphere of the countries of the former republic of Yugoslavia was performed. The carbon stable isotope composition ({delta}{sup 13}C) of PAHs varied between -27.68 and -27.19{per_thousand}, whereas {Delta}{sup 14}C values ranged from -568{per_thousand} for PAHs sampled in Kosovo to -288{per_thousand} for PAHs sampled in the Sarajevo area. The application of an isotopic mass balance model to these {Delta}{sup 14}C data revealed a significant contribution (35-65%) from the combustion of non-fossil material to the atmospheric PAH pollution, even in urban and industrialized areas. Furthermore, consistency was observed between the isotopic composition of PAHs obtained by high-volume sampling and those collected by passive sampling. This encourages the use of passive samplers for CCSRA applications. This marks the first time that a CCSRA investigation could be executed on a geographically wide scale, providing a quantitative field-based source apportionment, which points out that also non-fossil combustion processes should be targeted for remedial action. 36 refs., 1 fig., 3 tabs.

  7. Coenzyme F430, quantification and isotope analysis from the Eel River Basin California

    NASA Astrophysics Data System (ADS)

    Bird, L. R.; Fulton, J. M.; Dawson, K.; Orphan, V. J.; Freeman, K. H.

    2012-12-01

    Large amounts of methane are oxidized by communities of methanotrophic archaea and sulphate-reducing bacteria, preventing this greenhouse gas from reaching the atmosphere (Orphan et al., 2001; Scheller et al., 2010). Methyl-coenzyme M reductase, an enzyme traditionally associated with methanogenesis, has recently been linked to the anaerobic oxidation of methane suggesting methane oxidation follows a pathway similar to reverse methanogenesis. Coenzyme F430, a tetrapyrrole-nickel complex within the active site of methyl-coenzyme M, is used in methanogenesis and is hypothesized to play a key role in archaeal methanotrophy (Scheller et al., 2010). We recently developed a method to extract and isolate F430 from natural sediments so it can be purified for carbon and nitrogen stable isotope analysis. Sediments are extracted using an ultrasonic homogenizer, first in water (pH 7), then twice in dilute formic acid (pH 3). The combined extract is neutralized and the F430-containing fraction is isolated using Sephadex and Amberlite column chromatography. Further purification is performed using two dimensional high performance liquid chromatography, first with a reverse phase C-18 column followed by separation on a ThermoFisher Hypercarb column. F430 is then quantified using photo diode array detection with fractions collected for isotope analysis using a nano-scale elemental analyzer isotope ratio mass spectrometer (nano-EA-IRMS; Polissar et al., 2009). Compound identity and purity are confirmed using molar C:N ratios, UV absorbance and MSn detection of the parent ion (m/z 905). Here, we report F430 concentrations and isotopic data determined from active seep sediment cores from the Eel River Basin (California), a site where the anoxic oxidation of methane occurs. A spike in the concentration of F430 is observed at the 3-6 cm depth horizon corresponding with peak abundance in ANME-2/Desulfosarcina/Desulfococcus aggregate counts. Carbon isotope values of F430 are significantly

  8. Abundance analysis of an extended sample of open clusters: A search for chemical inhomogeneities

    NASA Astrophysics Data System (ADS)

    Reddy, Arumalla B. S.; Giridhar, Sunetra; Lambert, David L.

    We have initiated a program to explore the presence of chemical inhomogeneities in the Galactic disk using the open clusters as ideal probes. We have analyzed high-dispersion echelle spectra (R ≥ 55,000) of red giant members for eleven open clusters to derive abundances for many elements. The membership to the cluster has been confirmed through their radial velocities and proper motions. The spread in temperatures and gravities being very small among the red giants, nearly the same stellar lines were employed thereby reducing the random errors. The errors of average abundance for the cluster were generally in 0.02 to 0.07 dex range. Our present sample covers galactocentric distances of 8.3 to 11.3 kpc and an age range of 0.2 to 4.3 Gyrs. Our earlier analysis of four open clusters (Reddy A.B.S. et al., 2012, MNRAS, 419,1350) indicate that abundances relative to Fe for elements from Na to Eu are equal within measurement uncertainties to published abundances for thin disk giants in the field. This supports the view that field stars come from disrupted open clusters. In the enlarged sample of eleven open clusters we find cluster to cluster abundance variations for some s- and r- process elements, with certain elements such as Zr and Ba showing large variation. These differences mark the signatures that these clusters had formed under different environmental conditions (Type II SN, Type Ia SN, AGB stars or a mixture of any of these) unique to the time and site of formation. These eleven clusters support the widely held impression that there is an abundance gradient such that the metallicity [Fe/H] at the solar galactocentric distance decreases outwards at about -0.1 dex per kpc.

  9. Isotope fractionation studies of molybdenum

    NASA Astrophysics Data System (ADS)

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

    2007-08-01

    Mass spectrometric studies of the isotopic composition of molybdenum have become an active area of research in stable isotope geochemistry, biogeochemistry and cosmochemistry. The redox chemistry of Mo, together with its proclivity for covalent bonding, indicates its importance in isotope fractionation studies such as palaeoceanography. The measurement of the magnitude of isotope fractionation of Mo in natural systems is a challenging task, in that natural fractionation has to be carefully distinguished from chemical and instrumental isotope fractionation. An ion exchange chemical separation procedure has been developed with high efficiency and low blank, to ensure that the isobaric elements Zr and Ru are removed from the samples before mass spectrometric analysis. The isotope fractionation resulting from this procedure is 0.14[per mille sign] per u. The isotopic composition of Mo of a Laboratory Standard has been measured by positive and negative thermal ionization mass spectrometry (P-TIMS and N-TIMS, respectively), to give an isotope fractionation of 6.4[per mille sign] and 0.5[per mille sign] per u, respectively, with respect to the absolute isotope abundances of Mo. In both cases the lighter isotopes are enhanced with respect to the heavier isotopes. An ascorbic acid activator has enabled the sensitivity of P-TIMS to be improved as compared to traditional methods. The same experiment was repeated using a multiple collector-inductively coupled plasma-mass spectrometer (MC-ICP-MS) to give an isotope fractionation of approximately 17.0[per mille sign] per u. In this case the heavier isotopes are enhanced with respect to the lighter isotopes. The strengths and weaknesses of these three mass spectrometric techniques are evaluated. We conclude that MC-ICP-MS is the optimum mass spectrometric method for accurately measuring the isotope fractionation of Mo in natural materials, provided chemical and instrumental isotope fractionation can be resolved from naturally

  10. Spectral analysis software improves confidence in plant and soil water stable isotope analyses performed by isotope ratio infrared spectroscopy (IRIS).

    PubMed

    West, A G; Goldsmith, G R; Matimati, I; Dawson, T E

    2011-08-30

    Previous studies have demonstrated the potential for large errors to occur when analyzing waters containing organic contaminants using isotope ratio infrared spectroscopy (IRIS). In an attempt to address this problem, IRIS manufacturers now provide post-processing spectral analysis software capable of identifying samples with the types of spectral interference that compromises their stable isotope analysis. Here we report two independent tests of this post-processing spectral analysis software on two IRIS systems, OA-ICOS (Los Gatos Research Inc.) and WS-CRDS (Picarro Inc.). Following a similar methodology to a previous study, we cryogenically extracted plant leaf water and soil water and measured the δ(2)H and δ(18)O values of identical samples by isotope ratio mass spectrometry (IRMS) and IRIS. As an additional test, we analyzed plant stem waters and tap waters by IRMS and IRIS in an independent laboratory. For all tests we assumed that the IRMS value represented the "true" value against which we could compare the stable isotope results from the IRIS methods. Samples showing significant deviations from the IRMS value (>2σ) were considered to be contaminated and representative of spectral interference in the IRIS measurement. Over the two studies, 83% of plant species were considered contaminated on OA-ICOS and 58% on WS-CRDS. Post-analysis, spectra were analyzed using the manufacturer's spectral analysis software, in order to see if the software correctly identified contaminated samples. In our tests the software performed well, identifying all the samples with major errors. However, some false negatives indicate that user evaluation and testing of the software are necessary. Repeat sampling of plants showed considerable variation in the discrepancies between IRIS and IRMS. As such, we recommend that spectral analysis of IRIS data must be incorporated into standard post-processing routines. Furthermore, we suggest that the results from spectral analysis be

  11. Performance testing of the upgraded uranium isotopics multi-group analysis code MGAU

    NASA Astrophysics Data System (ADS)

    Berlizov, A. N.; Gunnink, R.; Zsigrai, J.; Nguyen, C. T.; Tryshyn, V. V.

    2007-06-01

    The paper describes recent developments of the MGAU (Multi-Group Analysis for Uranium) method, which resulted in the creation of an upgraded version 4.0 of the MGAU code. The major improvements concerned the procedure of the intrinsic efficiency calibration, particularly in the 120-205 keV region. The results of the tests carried out with the use of certified reference uranium isotopic materials SRM 969 and CRM 146 showed a significantly improved performance of the upgraded MGAU code for the accurate characterization of 235U and 234U abundances. The relative systematic biases of the abundances measured were evaluated not to exceed 1% and 3% over the concentration intervals 0.32-93.2 and 0.002-0.98 mass% for 235U and 234U, respectively. The influence of an up to 4-5 mm steel equivalent absorber and sample thickness on the measurement results was found to be much smaller than in previous versions of the code.

  12. Long-term Records of Pacific Salmon Abundance From Sediment Core Analysis: Relationships to Past Climatic Change, and Implications for the Future

    NASA Astrophysics Data System (ADS)

    Finney, B.

    2002-12-01

    The response of Pacific salmon to future climatic change is uncertain, but will have large impacts on the economy, culture and ecology of the North Pacific Rim. Relationships between sockeye salmon populations and climatic change can be determined by analyzing sediment cores from lakes where sockeye return to spawn. Sockeye salmon return to their natal lake system to spawn and subsequently die following 2 - 3 years of feeding in the North Pacific Ocean. Sockeye salmon abundance can be reconstructed from stable nitrogen isotope analysis of lake sediment cores as returning sockeye transport significant quantities of N, relatively enriched in N-15, from the ocean to freshwater systems. Temporal changes in the input of salmon-derived N, and hence salmon abundance, can be quantified through downcore analysis of N isotopes. Reconstructions of sockeye salmon abundance from lakes in several regions of Alaska show similar temporal patterns, with variability occurring on decadal to millennial timescales. Over the past 2000 years, shifts in sockeye salmon abundance far exceed the historical decadal-scale variability. A decline occurred from about 100 BC - 800 AD, but salmon were consistently more abundant 1200 - 1900 AD. Declines since 1900 AD coincide with the period of extensive commercial fishing. Correspondence between these records and paleoclimatic data suggest that changes in salmon abundance are related to large scale climatic changes over the North Pacific. For example, the increase in salmon abundance c.a. 1200 AD corresponds to a period of glacial advance in southern Alaska, and a shift to drier conditions in western North America. Although the regionally coherent patterns in reconstructed salmon abundance are consistent with the hypothesis that climate is an important driver, the relationships do not always follow patterns observed in the 20th century. A main feature of recorded climate variability in this region is the alternation between multi-decade periods of

  13. Oxygen isotope corrections for online δ34S analysis

    USGS Publications Warehouse

    Fry, B.; Silva, S.R.; Kendall, C.; Anderson, R.K.

    2002-01-01

    Elemental analyzers have been successfully coupled to stable-isotope-ratio mass spectrometers for online measurements of the δ34S isotopic composition of plants, animals and soils. We found that the online technology for automated δ34S isotopic determinations did not yield reproducible oxygen isotopic compositions in the SO2 produced, and as a result calculated δ34S values were often 1–3‰ too high versus their correct values, particularly for plant and animal samples with high C/S ratio. Here we provide empirical and analytical methods for correcting the S isotope values for oxygen isotope variations, and further detail a new SO2-SiO2 buffering method that minimizes detrimental oxygen isotope variations in SO2.

  14. Using compound-specific stable carbon isotope analysis to trace metabolism and trophic transfer of PCBs and PBDEs in fish from an e-waste site, South China.

    PubMed

    Zeng, Yan-Hong; Luo, Xiao-Jun; Yu, Le-Huan; Chen, Hua-Shan; Wu, Jiang-Ping; Chen, She-Jun; Mai, Bi-Xian

    2013-05-01

    Two fish species (mud carp and northern snakehead) forming a predator/prey relationship and sediment samples were collected from a pond contaminated by e-waste. The concentrations and stable carbon isotope ratios (δ(13)C) of individual polychlorinated biphenyl (PCB) and polybrominated diphenyl ether (PBDE) congeners were measured to determine if compound-specific carbon isotope analysis (CSIA) could be used to provide insight into the metabolism and trophic dynamics of PCBs and PBDEs. Significant correlations were found in the isotopic data of PCB congeners between the sediment and the fish species and between the two fish indicating identical origin of PCBs in sediment and fish. Most PCB congeners in the fish species were enriched in (13)C compared with the PCB congeners in the sediments as a result of isotopic fractionation during the metabolism of PCBs in fish. The isotopic data of several PCB congeners showing isotopic agreement or isotopic depletion could be used for source apportionment or to trace the reductive dechlorination process of PCBs in the environment. The PCB isotopic data covaried more in the northern snakehead than in the mud carp when compared to the sediment, implying that a similar isotopic fractionation occurs from the prey to the predator fish for a PCB congener possibly due to similar metabolic pathways. The PBDE congener patterns differed in the three sample types with a high abundance of BDE209, 183, 99, and 47 in the sediment, BDE47, 153, and 49 in the mud carp and BDE47, 100, and 154 in the northern snakehead. The isotopic change of BDE congeners, such as BDE47 and BDE49, in two fish species, provides evidence for biotransformation of PBDEs in biota. The results of this study suggest that CSIA is a promising tool for deciphering the fate of PCBs and PBDEs in the environment. PMID:23560888

  15. In-depth analysis of low abundant proteins in bovine colostrum using different fractionation techniques.

    PubMed

    Nissen, Asger; Bendixen, Emøke; Ingvartsen, Klaus Lønne; Røntved, Christine Maria

    2012-09-01

    Bovine colostrum is well known for its large content of bioactive components and its importance for neonatal survival. Unfortunately, the colostrum proteome is complicated by a wide dynamic range, because of a few dominating proteins that hamper sensitivity and proteome coverage achieved on low abundant proteins. Moreover, the composition of colostrum is complex and the proteins are located within different physical fractions that make up the colostrum. To gain a more exhaustive picture of the bovine colostrum proteome and gather information on protein location, we performed an extensive pre-analysis fractionation of colostrum prior to 2D-LC-MS/MS analysis. Physical and chemical properties of the proteins and colostrum were used alone or in combination for the separation of proteins. ELISA was used to quantify and verify the presence of proteins in colostrum. In total, 403 proteins were identified in the nonfractionated colostrum (NF) and seven fractions (F1-F7) using six different fractionation techniques. Fractionation contributed with 69 additional proteins in the fluid phase compared with NF. Different fractionation techniques each resulted in detection of unique subsets of proteins. Whey production by high-speed centrifugation contributed most to detection of low abundant proteins. Hence, prefractionation of colostrum prior to 2D-LC-MS/MS analysis expanded our knowledge on the presence and location of low abundant proteins in bovine colostrum. PMID:22848049

  16. Isotopic gas analysis through Purcell cavity enhanced Raman scattering

    NASA Astrophysics Data System (ADS)

    Petrak, B.; Cooper, J.; Konthasinghe, K.; Peiris, M.; Djeu, N.; Hopkins, A. J.; Muller, A.

    2016-02-01

    Purcell enhanced Raman scattering (PERS) by means of a doubly resonant Fabry-Perot microcavity (mode volume ≈ 100 μm3 and finesse ≈ 30 000) has been investigated as a technique for isotopic ratio gas analysis. At the pump frequency, the resonant cavity supports a buildup of circulating power while simultaneously enabling Purcell spontaneous emission rate enhancement at the resonant Stokes frequency. The three most common isotopologues of CO2 gas were quantified, and a signal was obtained from 13C16O2 down to a partial pressure of 2 Torr. Due to its small size and low pump power needed (˜10 mW) PERS lends itself to miniaturization. Furthermore, since the cavity is resonant with the emission frequency, future improvements could allow it to serve as its own spectral analyzer and no separate spectroscopic device would be needed.

  17. Carbon isotope analysis of carbonaceous compounds in Puget Sound and Lake Washington

    SciTech Connect

    Swanson, J.R.

    1980-01-01

    A new method has been developed and tested for determining chronological profiles of organic pollutants. This method, Carbon Isotope Analysis (CIA), involves measurements of /sup 12/C, /sup 13/C and /sup 14/C in carbonaceous compounds found in layers of sediment. Lipids, total aliphatic hydrocarbons (TAHs) and polycyclic aromatic hydrocarbons (PAHs) are separated from kg quantities of sediment. Large Soxhlet extractors are used to remove the extractable organics, using ultra-pure benzene-methanol solution and having an extraction efficiency of about 86% for compounds with boiling points higher than n-tetradecane (n-C/sub 14/). The basic steps in compound separation include freeze-drying, extraction, fractionation, column chromatography and evaporation. Isolating the TAH and PAH fractions is accomplished by eluting samples from Sephadex and alumina/silica-gel columns. The amount of each fraction recovered is determined by converting the hydrocarbons to carbon dioxide and measuring this gas manometrically. Variations in /sup 12/C and /sup 13/C abundances for carbonaceous compounds are primarily due to thermodynamic, photosynthetic and metabolic fractionation processes. Thus, the source of a particular organic compound can often be determined by measuring its /sup 13/C//sup 12/C ratio. Combining the information from both the /sup 13/C analysis and /sup 14/C analysis makes source identification more certain. In addition, this investigation reviews carbon isotopic data and carbon cycling and analyzes organic pollution in two limited ecosystems (Puget Sound and Lake Washington). Specifically, distinct carbonaceous species are analyzed for pollution in sediments of Lake Washington, Elliott Bay, Commencement Bay, central Puget Sound and northern Puget Sound near the Cherry Point oil refineries.

  18. A non-LTE spectral analysis of the 3He and 4He isotopes in the HgMn star κ Cancri

    NASA Astrophysics Data System (ADS)

    Maza, Natalia L.; Nieva, María-Fernanda; Przybilla, Norbert

    2014-12-01

    Aims: We present a pilot study on non-local thermodynamic equilibrium (NLTE) line-formation computations for the isotopes 3He and 4He in the mercury-manganese star κ Cancri. The impact of NLTE effects on the determination of isotopic abundances and the vertical stratification of helium in the atmosphere is investigated. Methods: Modern NLTE line-formation computations were employed to analyse a high-resolution and high signal-to-noise ratio ESO-VLT/UVES spectrum of κ Cnc. The atmospheric parameters were determined from fitting the hydrogen Balmer lines and the spectral energy distribution. Multiple He i lines were investigated, including He i λ4921 Å and λ6678 Å, which show the widest isotopic splits. Results: Half of the observed He i lines in the spectrum of κ Cnc show significant NLTE strengthening, the effects are strongest in the red lines He iλ5875 Å and He iλ6678 Å. NLTE abundances from individual He i lines are up to a factor of ~3 lower than LTE values. Helium is found to be stratified in the atmosphere of κ Cnc. While the LTE analysis indicates a step-like profile of the helium abundance, a gradual decrease with height is indicated by the NLTE analysis. A 3He/4He ratio of ~0.25-0.30 is found. With the available data it cannot be decided whether the two isotopes follow the same stratification profile, or not. Conclusions: This work implies that NLTE effects may be ubiquitous in the atmospheres of HgMn stars and may have a significant impact on abundance determinations and the interpretation of the vertical abundance stratification of elements. Based on data products from observations made with ESO Telescopes at the La Silla Paranal Observatory under programme ID 076.B-0055(A).Figures 3 and 4 are available in electronic form at http://www.aanda.org

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

    SciTech Connect

    Anheier, Norman C.; Bushaw, Bruce A.

    2010-01-01

    signals on a shot-to-shot basis. The media is translated by a micron resolution scanning system, allowing the isotope analysis to cover the entire sample surface. We also report, to the best of our knowledge, the first demonstration of laser-based isotopic measurements on individual micron-sized particles that are minor target components in a much larger heterogeneous mix of ‘background’ particles. This composition is consistent with swipe and environmental aerosol samples typically collected for safeguards ES purposes. Single-shot detection sensitivity approaching the femtogram range and relative isotope abundance uncertainty better than 10% has been demonstrated using gadolinium isotopes as surrogate materials.

  20. Proteomic analysis of an unculturable bacterial endosymbiont (Blochmannia) reveals high abundance of chaperonins and biosynthetic enzymes

    PubMed Central

    Fan, Yongliang; Thompson, J. Will; Dubois, Laura G.; Moseley, M. Arthur; Wernegreen, Jennifer J.

    2013-01-01

    Many insect groups have coevolved with bacterial endosymbionts that live within specialized host cells. As a salient example, ants in the tribe Camponotini rely on Blochmannia, an intracellular bacterial mutualist that synthesizes amino acids and recycles nitrogen for the host. We performed a shotgun, label-free, LC/MS/MS quantitative proteomic analysis to investigate the proteome of Blochmannia associated with Camponotus chromaiodes. We identified more than 330 Blochmannia proteins, or 54% coverage of the predicted proteome, as well as 244 Camponotus proteins. Using the average intensity of the top 3 “best flier” peptides along with spiking of a surrogate standard at a known concentration, we estimated the concentration (fmol/μg) of those proteins with confident identification. The estimated dynamic range of Blochmannia protein abundance spanned three orders of magnitude and covered diverse functional categories, with particularly high representation of metabolism, information transfer, and chaperones. GroEL, the most abundant protein, totaled 6% of Blochmannia protein abundance. Biosynthesis of essential amino acids, fatty acids, and nucleotides, and sulfate assimilation had disproportionately high coverage in the proteome, further supporting a nutritional role of the symbiosis. This first quantitative proteomic analysis of an ant endosymbiont illustrates a promising approach to study the functional basis of intimate symbioses. PMID:23205679

  1. Quantitative Analysis of Age Specific Variation in the Abundance of Human Female Parotid Salivary Proteins

    PubMed Central

    Ambatipudi, Kiran S.; Lu, Bingwen; Hagen, Fred K; Melvin, James E.; Yates, John R.

    2010-01-01

    Summary Human saliva is a protein-rich, easily accessible source of potential local and systemic biomarkers to monitor changes that occur under pathological conditions; however little is known about the changes in abundance associated with normal aging. In this study, we performed a comprehensive proteomic profiling of pooled saliva collected from the parotid glands of healthy female subjects, divided into two age groups 1 and 2 (20–30 and 55–65 years old, respectively). Hydrophobic charge interaction chromatography was used to separate high from low abundant proteins prior to characterization of the parotid saliva using multidimensional protein identification technology (MudPIT). Collectively, 532 proteins were identified in the two age groups. Of these proteins, 266 were identified exclusively in one age group, while 266 proteins were common to both groups. The majority of the proteins identified in the two age groups belonged to the defense and immune response category. Of note, several defense related proteins (e.g. lysozyme, lactoferrin and histatin-1) were significantly more abundant in group 2 as determined by G-test. Selected representative mass spectrometric findings were validated by western blot analysis. Our study reports the first quantitative analysis of differentially regulated proteins in ductal saliva collected from young and older female subjects. This study supports the use of high-throughput proteomics as a robust discovery tool. Such results provide a foundation for future studies to identify specific salivary proteins which may be linked to age-related diseases specific to women. PMID:19764810

  2. Quantitative Determination of Isotope Ratios from Experimental Isotopic Distributions

    PubMed Central

    Kaur, Parminder; O’Connor, Peter B.

    2008-01-01

    Isotope variability due to natural processes provides important information for studying a variety of complex natural phenomena from the origins of a particular sample to the traces of biochemical reaction mechanisms. These measurements require high-precision determination of isotope ratios of a particular element involved. Isotope Ratio Mass Spectrometers (IRMS) are widely employed tools for such a high-precision analysis, which have some limitations. This work aims at overcoming the limitations inherent to IRMS by estimating the elemental isotopic abundance from the experimental isotopic distribution. In particular, a computational method has been derived which allows the calculation of 13C/12C ratios from the whole isotopic distributions, given certain caveats, and these calculations are applied to several cases to demonstrate their utility. The limitations of the method in terms of the required number of ions and S/N ratio are discussed. For high-precision estimates of the isotope ratios, this method requires very precise measurement of the experimental isotopic distribution abundances, free from any artifacts introduced by noise, sample heterogeneity, or other experimental sources. PMID:17263354

  3. 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)

  4. A new method for carbon isotopic analysis of protein

    SciTech Connect

    Nelson, D.E. )

    1991-02-01

    The reaction of ninhydrin with amino acids can be used in carbon isotopic studies of protein. The reaction can be applied to extract as carbon dioxide only peptide-bonded carbon in proteinaceous material, thus avoiding most, if not all, contaminants. Test radiocarbon dates on ancient bone indicate that the method provides reliable ages, and stable carbon isotopic data suggest that our understanding of isotopic dietary reconstruction needs detailed examination. The technique should also be useful in biochemical tracing experiments and in global carbon budget studies, and the underlying principle may be applicable to other isotopes and molecules. 28 refs., 1 fig., 1 tab.

  5. Stable isotope analysis of precipitation samples obtained via crowdsourcing reveals the spatiotemporal evolution of Superstorm Sandy.

    PubMed

    Good, Stephen P; Mallia, Derek V; Lin, John C; Bowen, Gabriel J

    2014-01-01

    Extra-tropical cyclones, such as 2012 Superstorm Sandy, pose a significant climatic threat to the northeastern United Sates, yet prediction of hydrologic and thermodynamic processes within such systems is complicated by their interaction with mid-latitude water patterns as they move poleward. Fortunately, the evolution of these systems is also recorded in the stable isotope ratios of storm-associated precipitation and water vapor, and isotopic analysis provides constraints on difficult-to-observe cyclone dynamics. During Superstorm Sandy, a unique crowdsourced approach enabled 685 precipitation samples to be obtained for oxygen and hydrogen isotopic analysis, constituting the largest isotopic sampling of a synoptic-scale system to date. Isotopically, these waters span an enormous range of values (> 21‰ for δ(18)O, > 160‰ for δ(2)H) and exhibit strong spatiotemporal structure. Low isotope ratios occurred predominantly in the west and south quadrants of the storm, indicating robust isotopic distillation that tracked the intensity of the storm's warm core. Elevated values of deuterium-excess (> 25‰) were found primarily in the New England region after Sandy made landfall. Isotope mass balance calculations and Lagrangian back-trajectory analysis suggest that these samples reflect the moistening of dry continental air entrained from a mid-latitude trough. These results demonstrate the power of rapid-response isotope monitoring to elucidate the structure and dynamics of water cycling within synoptic-scale systems and improve our understanding of storm evolution, hydroclimatological impacts, and paleo-storm proxies.

  6. Stable Isotope Analysis of Precipitation Samples Obtained via Crowdsourcing Reveals the Spatiotemporal Evolution of Superstorm Sandy

    PubMed Central

    Good, Stephen P.; Mallia, Derek V.; Lin, John C.; Bowen, Gabriel J.

    2014-01-01

    Extra-tropical cyclones, such as 2012 Superstorm Sandy, pose a significant climatic threat to the northeastern United Sates, yet prediction of hydrologic and thermodynamic processes within such systems is complicated by their interaction with mid-latitude water patterns as they move poleward. Fortunately, the evolution of these systems is also recorded in the stable isotope ratios of storm-associated precipitation and water vapor, and isotopic analysis provides constraints on difficult-to-observe cyclone dynamics. During Superstorm Sandy, a unique crowdsourced approach enabled 685 precipitation samples to be obtained for oxygen and hydrogen isotopic analysis, constituting the largest isotopic sampling of a synoptic-scale system to date. Isotopically, these waters span an enormous range of values (21‰ for O, 160‰ for H) and exhibit strong spatiotemporal structure. Low isotope ratios occurred predominantly in the west and south quadrants of the storm, indicating robust isotopic distillation that tracked the intensity of the storm's warm core. Elevated values of deuterium-excess (25‰) were found primarily in the New England region after Sandy made landfall. Isotope mass balance calculations and Lagrangian back-trajectory analysis suggest that these samples reflect the moistening of dry continental air entrained from a mid-latitude trough. These results demonstrate the power of rapid-response isotope monitoring to elucidate the structure and dynamics of water cycling within synoptic-scale systems and improve our understanding of storm evolution, hydroclimatological impacts, and paleo-storm proxies. PMID:24618882

  7. [Distribution characteristics of soil humus fractions stable carbon isotope natural abundance (delta 13C) in paddy field under long-term ridge culture].

    PubMed

    Tang, Xiao-hong; Luo, You-jin; Ren, Zhen-jiang; Lü, Jia-ke; Wei, Chao-fu

    2011-04-01

    A 16-year field experiment was conducted in a ridge culture paddy field in the hilly region of Sichuan Basin, aimed to investigate the distribution characteristics of stable carbon isotope natural abundance (delta 13C) in soil humus fractions. The soil organic carbon (SOC) content in the paddy field under different cultivation modes ranked in the order of wide ridge culture > ridge culture > paddy and upland rotation. In soil humus substances (HS), humin (HU) was the main composition, occupying 21% - 30% of the total SOC. In the extracted soil carbon, humic acid (HA) dominated, occupying 17% - 21% of SOC and 38% - 65% of HS. The delta 13C value of SOC ranged from -27.9 per thousand to -25.6 per thousand, and the difference of the delta 13C value between 0-5 cm and 20-40 cm soil layers was about 1.9 per thousand. The delta 13C value of HA under different cultivation modes was 1 per thousand - 2 per thousand lower than that of SOC, and more approached to the delta 13C value of rapeseed and rice residues. As for fulvic acid (FA), its delta 13C value was about 2 per thousand and 4 per thousand higher than that of SOC and HA, respectively. The delta 13C value of HU in plough layer (0-20 cm) and plow layer (20-40 cm) ranged from -23.7 per thousand - -24.9 per thousand and -22.6 per thousand - -24.2 per thousand, respectively, reflecting the admixture of young and old HS. The delta 13C value in various organic carbon fractions was HU>FA>SOC>rapeseed and rice residues>HA. Long-term rice planting benefited the increase of SOC content, and cultivation mode played an important role in affecting the distribution patterns of soil humus delta 13C in plough layer and plow layer. PMID:21774322

  8. [Distribution characteristics of soil humus fractions stable carbon isotope natural abundance (delta 13C) in paddy field under long-term ridge culture].

    PubMed

    Tang, Xiao-hong; Luo, You-jin; Ren, Zhen-jiang; Lü, Jia-ke; Wei, Chao-fu

    2011-04-01

    A 16-year field experiment was conducted in a ridge culture paddy field in the hilly region of Sichuan Basin, aimed to investigate the distribution characteristics of stable carbon isotope natural abundance (delta 13C) in soil humus fractions. The soil organic carbon (SOC) content in the paddy field under different cultivation modes ranked in the order of wide ridge culture > ridge culture > paddy and upland rotation. In soil humus substances (HS), humin (HU) was the main composition, occupying 21% - 30% of the total SOC. In the extracted soil carbon, humic acid (HA) dominated, occupying 17% - 21% of SOC and 38% - 65% of HS. The delta 13C value of SOC ranged from -27.9 per thousand to -25.6 per thousand, and the difference of the delta 13C value between 0-5 cm and 20-40 cm soil layers was about 1.9 per thousand. The delta 13C value of HA under different cultivation modes was 1 per thousand - 2 per thousand lower than that of SOC, and more approached to the delta 13C value of rapeseed and rice residues. As for fulvic acid (FA), its delta 13C value was about 2 per thousand and 4 per thousand higher than that of SOC and HA, respectively. The delta 13C value of HU in plough layer (0-20 cm) and plow layer (20-40 cm) ranged from -23.7 per thousand - -24.9 per thousand and -22.6 per thousand - -24.2 per thousand, respectively, reflecting the admixture of young and old HS. The delta 13C value in various organic carbon fractions was HU>FA>SOC>rapeseed and rice residues>HA. Long-term rice planting benefited the increase of SOC content, and cultivation mode played an important role in affecting the distribution patterns of soil humus delta 13C in plough layer and plow layer.

  9. Hanford isotope project strategic business analysis yttrium-90 (Y-90)

    SciTech Connect

    1995-10-01

    The purpose of this analysis is to address the short-term direction for the Hanford yttrium-90 (Y-90) project. Hanford is the sole DOE producer of Y-90, and is the largest repository for its source in this country. The production of Y-90 is part of the DOE Isotope Production and Distribution (IP and D) mission. The Y-90 is ``milked`` from strontium-90 (Sr-90), a byproduct of the previous Hanford missions. The use of Sr-90 to produce Y-90 could help reduce the amount of waste material processed and the related costs incurred by the clean-up mission, while providing medical and economic benefits. The cost of producing Y-90 is being subsidized by DOE-IP and D due to its use for research, and resultant low production level. It is possible that the sales of Y-90 could produce full cost recovery within two to three years, at two curies per week. Preliminary projections place the demand at between 20,000 and 50,000 curies per year within the next ten years, assuming FDA approval of one or more of the current therapies now in clinical trials. This level of production would incentivize private firms to commercialize the operation, and allow the government to recover some of its sunk costs. There are a number of potential barriers to the success of the Y-90 project, outside the control of the Hanford Site. The key issues include: efficacy, Food and Drug Administration (FDA) approval and medical community acceptance. There are at least three other sources for Y-90 available to the US users, but they appear to have limited resources to produce the isotope. Several companies have communicated interest in entering into agreements with Hanford for the processing and distribution of Y-90, including some of the major pharmaceutical firms in this country.

  10. Biometrics from the carbon isotope ratio analysis of amino acids in human hair.

    PubMed

    Jackson, Glen P; An, Yan; Konstantynova, Kateryna I; Rashaid, Ayat H B

    2015-01-01

    This study compares and contrasts the ability to classify individuals into different grouping factors through either bulk isotope ratio analysis or amino-acid-specific isotope ratio analysis of human hair. Using LC-IRMS, we measured the isotope ratios of 14 amino acids in hair proteins independently, and leucine/isoleucine as a co-eluting pair, to provide 15 variables for classification. Multivariate analysis confirmed that the essential amino acids and non-essential amino acids were mostly independent variables in the classification rules, thereby enabling the separation of dietary factors of isotope intake from intrinsic or phenotypic factors of isotope fractionation. Multivariate analysis revealed at least two potential sources of non-dietary factors influencing the carbon isotope ratio values of the amino acids in human hair: body mass index (BMI) and age. These results provide evidence that compound-specific isotope ratio analysis has the potential to go beyond region-of-origin or geospatial movements of individuals-obtainable through bulk isotope measurements-to the provision of physical and characteristic traits about the individuals, such as age and BMI. Further development and refinement, for example to genetic, metabolic, disease and hormonal factors could ultimately be of great assistance in forensic and clinical casework.

  11. Isotope coded protein labeling coupled immunoprecipitation (ICPL-IP): a novel approach for quantitative protein complex analysis from native tissue.

    PubMed

    Vogt, Andreas; Fuerholzner, Bettina; Kinkl, Norbert; Boldt, Karsten; Ueffing, Marius

    2013-05-01

    High confidence definition of protein interactions is an important objective toward the understanding of biological systems. Isotope labeling in combination with affinity-based isolation of protein complexes has increased in accuracy and reproducibility, yet, larger organisms--including humans--are hardly accessible to metabolic labeling and thus, a major limitation has been its restriction to small animals, cell lines, and yeast. As composition as well as the stoichiometry of protein complexes can significantly differ in primary tissues, there is a great demand for methods capable to combine the selectivity of affinity-based isolation as well as the accuracy and reproducibility of isotope-based labeling with its application toward analysis of protein interactions from intact tissue. Toward this goal, we combined isotope coded protein labeling (ICPL)(1) with immunoprecipitation (IP) and quantitative mass spectrometry (MS). ICPL-IP allows sensitive and accurate analysis of protein interactions from primary tissue. We applied ICPL-IP to immuno-isolate protein complexes from bovine retinal tissue. Protein complexes of immunoprecipitated β-tubulin, a highly abundant protein with known interactors as well as the lowly expressed small GTPase RhoA were analyzed. The results of both analyses demonstrate sensitive and selective identification of known as well as new protein interactions by our method.

  12. Multi element (C, H, O) stable isotope analysis for the authentication of balsamic vinegars.

    PubMed

    Werner, Roland A; Roßmann, Andreas

    2015-01-01

    Balsamic vinegars are important and well-acknowledged products and have become more important all over Europe during the recent past. For their analytical control, stable isotope methods play an important role to check the authenticity of the raw materials applied. For vinegar, but not yet for balsamic vinegar analysis, stable isotope methods using hydrogen, carbon, and oxygen isotope analyses by isotope ratio mass spectrometry and (2)H-NMR have already been introduced as official methods. Nevertheless, the official procedure can be also applied for balsamic vinegars. The evaluation of the stable isotope parameters obtained for the ingredients of balsamic vinegars requires a knowledge and understanding of the natural and industrial processes on which the production of balsamic vinegars is based. Ranges and 'cut-off' values for the multi element stable isotope parameters of balsamic vinegars are described, and a suitable analytical strategy is suggested.

  13. Detailed abundance analysis of the brightest star in Segue 2, the least massive galaxy

    NASA Astrophysics Data System (ADS)

    Roederer, Ian U.; Kirby, Evan N.

    2014-05-01

    We present the first high-resolution spectroscopic observations of one red giant star in the ultra-faint dwarf galaxy Segue 2, which has the lowest total mass (including dark matter) estimated for any known galaxy. These observations were made using the Magellan Inamori Kyocera Echelle (MIKE) spectrograph on the Magellan II Telescope at Las Campanas Observatory. We perform a standard abundance analysis of this star, SDSS J021933.13+200830.2, and present abundances of 21 species of 18 elements as well as upper limits for 25 additional species. We derive [Fe/H] = -2.9, in excellent agreement with previous estimates from medium-resolution spectroscopy. Our main result is that this star bears the chemical signatures commonly found in field stars of similar metallicity. The heavy elements produced by neutron-capture reactions are present, but they are deficient at levels characteristic of stars in other ultra-faint dwarf galaxies and a few luminous dwarf galaxies. The otherwise normal abundance patterns suggest that the gas from which this star formed was enriched by metals from multiple Type II supernovae reflecting a relatively well-sampled IMF. This adds to the growing body of evidence indicating that Segue 2 may have been substantially more massive in the past.

  14. Lipid Correction for Carbon Stable Isotope Analysis of Deep-sea Fishes

    EPA Science Inventory

    Lipid extraction is used prior to stable isotope analysis of fish tissues to remove variability in the carbon stable isotope ratio (d13C) caused by varying lipid content among samples. Our objective was to evaluate an application of a mass balance correction for the effect of lip...

  15. Spectral Properties of Cool Stars: Extended Abundance Analysis of 1,617 Planet-search Stars

    NASA Astrophysics Data System (ADS)

    Brewer, John M.; Fischer, Debra A.; Valenti, Jeff A.; Piskunov, Nikolai

    2016-08-01

    We present a catalog of uniformly determined stellar properties and abundances for 1,617 F, G, and K stars using an automated spectral synthesis modeling procedure. All stars were observed using the HIRES spectrograph at Keck Observatory. Our procedure used a single line list to fit model spectra to observations of all stars to determine effective temperature, surface gravity, metallicity, projected rotational velocity, and the abundances of 15 elements (C, N, O, Na, Mg, Al, Si, Ca, Ti, V, Cr, Mn, Fe, Ni, and Y). Sixty percent of the sample had Hipparcos parallaxes and V-band photometry, which we combined with the spectroscopic results to obtain mass, radius, and luminosity. Additionally, we used the luminosity, effective temperature, metallicity and α-element enhancement to interpolate in the Yonsei-Yale isochrones to derive mass, radius, gravity, and age ranges for those stars. Finally, we determined new relations between effective temperature and macroturbulence for dwarfs and subgiants. Our analysis achieved precisions of 25 K in {T}{eff}, 0.01 dex in [M/H], 0.028 dex for {log}g, and 0.5 km s-1 in v\\sin i based on multiple observations of the same stars. The abundance results were similarly precise, between ˜0.01 and ˜0.04 dex, though trends with respect to {T}{eff} remained for which we derived empirical corrections. The trends, though small, were much larger than our uncertainties and are shared with published abundances. We show that changing our model atmosphere grid accounts for most of the trend in [M/H] between 5000 and 5500 K, indicating a possible problem with the atmosphere models or opacities.

  16. Spectral Properties of Cool Stars: Extended Abundance Analysis of 1,617 Planet-search Stars

    NASA Astrophysics Data System (ADS)

    Brewer, John M.; Fischer, Debra A.; Valenti, Jeff A.; Piskunov, Nikolai

    2016-08-01

    We present a catalog of uniformly determined stellar properties and abundances for 1,617 F, G, and K stars using an automated spectral synthesis modeling procedure. All stars were observed using the HIRES spectrograph at Keck Observatory. Our procedure used a single line list to fit model spectra to observations of all stars to determine effective temperature, surface gravity, metallicity, projected rotational velocity, and the abundances of 15 elements (C, N, O, Na, Mg, Al, Si, Ca, Ti, V, Cr, Mn, Fe, Ni, and Y). Sixty percent of the sample had Hipparcos parallaxes and V-band photometry, which we combined with the spectroscopic results to obtain mass, radius, and luminosity. Additionally, we used the luminosity, effective temperature, metallicity and α-element enhancement to interpolate in the Yonsei–Yale isochrones to derive mass, radius, gravity, and age ranges for those stars. Finally, we determined new relations between effective temperature and macroturbulence for dwarfs and subgiants. Our analysis achieved precisions of 25 K in {T}{eff}, 0.01 dex in [M/H], 0.028 dex for {log}g, and 0.5 km s‑1 in v\\sin i based on multiple observations of the same stars. The abundance results were similarly precise, between ˜0.01 and ˜0.04 dex, though trends with respect to {T}{eff} remained for which we derived empirical corrections. The trends, though small, were much larger than our uncertainties and are shared with published abundances. We show that changing our model atmosphere grid accounts for most of the trend in [M/H] between 5000 and 5500 K, indicating a possible problem with the atmosphere models or opacities.

  17. Detailed abundance analysis of five field blue horizontal-branch stars

    NASA Astrophysics Data System (ADS)

    Kafando, I.; LeBlanc, F.; Robert, C.

    2016-06-01

    Previous studies have shown that hot blue horizontal-branch (BHB) stars in globular clusters present abundance anomalies of certain chemical elements in their atmosphere; some metals are overabundant while helium is underabundant. Vertical stratification of chemical species, including iron, is also found in the atmosphere of a number of these objects. The aim of our work is to do a detailed abundance analysis of BHB stars found in the field. We studied the stars HD 128801, HD 143459, HD 213781, and HZ 27, using our high-resolution spectra in the visible region obtained with ESPaDOnS at the Canada-France-Hawaii Telescope, and also Feige 86, using existing Ultraviolet and Visual Echelle Spectrograph visible spectra from the ESO archives. We searched for vertical stratification of the elements identified in our five stars, with the ZEEMAN2 code and stellar model atmospheres of PHOENIX. We confirm here the star rotational and radial velocities previously found, along with their average abundances. For the three cooler stars in our sample (HD 128801, HD 143459, and HZ 27), most elements detected are underabundant. For the two hotter stars (Feige 86 and HD 213781), the abundances of most elements are near or above their solar value. Of all the elements studied, only phosphorus is clearly found to be vertically stratified in the atmosphere of HD 213781. Marginal indications of vertical stratification of iron is observed for Feige 86. The chemical properties of the five field BHB stars are consistent with those of their globular-cluster counterparts.

  18. Environmental controls on microbial abundance and activity on the greenland ice sheet: a multivariate analysis approach.

    PubMed

    Stibal, Marek; Telling, Jon; Cook, Joe; Mak, Ka Man; Hodson, Andy; Anesio, Alexandre M

    2012-01-01

    Microbes in supraglacial ecosystems have been proposed to be significant contributors to regional and possibly global carbon cycling, and quantifying the biogeochemical cycling of carbon in glacial ecosystems is of great significance for global carbon flow estimations. Here we present data on microbial abundance and productivity, collected along a transect across the ablation zone of the Greenland ice sheet (GrIS) in summer 2010. We analyse the relationships between the physical, chemical and biological variables using multivariate statistical analysis. Concentrations of debris-bound nutrients increased with distance from the ice sheet margin, as did both cell numbers and activity rates before reaching a peak (photosynthesis) or a plateau (respiration, abundance) between 10 and 20 km from the margin. The results of productivity measurements suggest an overall net autotrophy on the GrIS and support the proposed role of ice sheet ecosystems in carbon cycling as regional sinks of CO(2) and places of production of organic matter that can be a potential source of nutrients for downstream ecosystems. Principal component analysis based on chemical and biological data revealed three clusters of sites, corresponding to three 'glacier ecological zones', confirmed by a redundancy analysis (RDA) using physical data as predictors. RDA using data from the largest 'bare ice zone' showed that glacier surface slope, a proxy for melt water flow, accounted for most of the variation in the data. Variation in the chemical data was fully explainable by the determined physical variables. Abundance of phototrophic microbes and their proportion in the community were identified as significant controls of the carbon cycling-related microbial processes.

  19. A spectroscopic study of southern (candidate) γ Doradus stars. II. Detailed abundance analysis and fundamental parameters

    NASA Astrophysics Data System (ADS)

    Bruntt, H.; De Cat, P.; Aerts, C.

    2008-02-01

    Context: The γ Doradus stars are a recent class of variable main sequence F-type stars located on the red edge of the Cepheid instability strip. They pulsate in gravity modes, and this makes them particularly interesting for detailed asteroseismic analysis, which can provide fundamental knowledge of properties near the convective cores of intermediate-mass main sequence stars. Aims: To improve current understanding of γ Dor stars through theoretical modelling, additional constraints are needed. Our aim is to estimate the fundamental atmospheric parameters and determine the chemical composition of these stars. Detailed analyses of single stars have previously suggested links to Am and λ Boo stars, so we wish to explore this interesting connection between chemical peculiarity and pulsation. Methods: We analysed a sample of γ Dor stars for the first time, including nine bona fide and three candidate members of the class. We determined the fundamental atmospheric parameters and compared the abundance pattern with other A-type stars. We used the semi-automatic software package VWA for the analysis. This code relies on the calculation of synthetic spectra and thus takes line-blending into account. This is important because of the fast rotation in some of the sample stars, and we made a thorough analysis of how VWA performs when increasing v sin i. We obtained good results in agreement with previously derived fundamental parameters and abundances in a few selected reference stars with properties similar to the γ Dor stars. Results: We find that the abundance pattern in the γ Dor stars is not distinct from the constant A- and F-type stars we analysed. Appendices A and B are only available in electronic form at http://www.aanda.org

  20. Internal correction of hafnium oxide spectral interferences and mass bias in the determination of platinum in environmental samples using isotope dilution analysis.

    PubMed

    Rodríguez-Castrillón, José Angel; Moldovan, Mariella; García Alonso, J Ignacio

    2009-05-01

    A method has been developed for the accurate determination of platinum by isotope dilution analysis, using enriched (194)Pt, in environmental samples containing comparatively high levels of hafnium without any chemical separation. The method is based on the computation of the contribution of hafnium oxide as an independent factor in the observed isotope pattern of platinum in the spiked sample. Under these conditions, the ratio of molar fractions between natural abundance and isotopically enriched platinum was independent of the amount of hafnium present in the sample. Additionally, mass bias was corrected by an internal procedure in which the regression variance was minimised. This was possible as the mass bias factor for hafnium oxide was very close to that of platinum. The final procedure required the measurement of three platinum isotope ratios (192/194, 195/194 and 196/194) to calculate the concentration of platinum in the sample. The methodology has been validated using the reference material "BCR-723 road dust" and has been applied to different environmental matrices (road dust, air particles, bulk wet deposition and epiphytic lichens) collected in the Aspe Valley (Pyrenees Mountains). A full uncertainty budget, using Kragten's spreadsheet method, showed that the total uncertainty was limited only by the uncertainty in the measured isotope ratios and not by the uncertainties of the isotopic composition of platinum and hafnium.

  1. Analysis of sequential reactive transformations using stable isotope analysis: a theoretical assessment

    NASA Astrophysics Data System (ADS)

    Thullner, Martin; Jin, Shuang; Stadler, Susanne

    2016-04-01

    Stable isotope methods have been establish as powerful tools for the analysis of reactive transformation in the subsurface with applications ranging from the field of contaminant hydrology to biogeochemical cycling. While the link between single transformations based on stable isotope signatures and their changes is commonly well understood and allows for qualitative and - in case certain requirements are met - also quantitative analysis, the interpretation of sequential reactive transformations, e.g. decay chains, is more complicated. In the latter case isotope signature changes of individual reactive compounds are affected by more than one transformation which challenges the interpretation of these changes. In recent years, some methods have been proposed (e.g. isotope mass balance approaches) which allow at least for a qualitative or semi-quantitative estimation of sequential reactive transformation processes. However, a systematic assessment of the validity of these estimation methods is missing so far and the accuracy of these methods - in general and for specific conditions encountered in the field - is not fully validated. In this presentation we use a combination of mathematical analyses and numerical modeling to test the validity of the proposed estimation methods and to determine the limits of their applicability. Results recommend modifications of existing theoretical estimation approaches and identify sorption processes as potential limitation of their applicability.

  2. Nitrogen isotopes in the recent solar wind from the analysis of genesis targets: evidence for large scale isotope heterogeneity in the nascent solar system

    SciTech Connect

    Wiens, Roger C; Marty, Bernard; Zimmermann, Laurent; Burnard, Peter G; Burnett, Donald L; Heber, Veronika S; Wieler, Rainer; Bochsler, Peter

    2009-01-01

    Nitrogen, the fifth most abundant element in the universe, displays the largest stable isotope variations in the solar system reservoirs after hydrogen. Yet the value of isotopic composition of solar nitrogen, presumably the best proxy of the protosolar nebula composition, is not known. Nitrogen isotopes trapped in Genesis spacecraft target material indicate a 40 % depletion of {sup 15}N in solar wind N relative to inner planets and meteorites, and define a composition for the present-day Sun undistinguishable from that of Jupiter's atmosphere. These results indicate that the isotopic composition of of nitrogen in the outer convective zone of the Sun (OCZ) has not changed through time, and is representative of the protosolar nebula. Large {sup 15}N enrichments during e.g., irradiation, or contributions from {sup 15}N-rich presolar components, are required to account for planetary values.

  3. Dissolution of barite for the analysis of strontium isotopes and other chemical and isotopic variations using aqueous sodium carbonate

    USGS Publications Warehouse

    Breit, G.N.; Simmons, E.C.; Goldhaber, M.B.

    1985-01-01

    A simple procedure for preparing barite samples for chemical and isotopic analysis is described. Sulfate ion, in barite, in the presence of high concentrations of aqueous sodium carbonate, is replaced by carbonate. This replacement forms insoluble carbonates with the cations commonly in barite: Ba, Sr, Ca and Pb. Sulfate is released into the solution by the carbonate replacement and is separated by filtration. The aqueous sulfate can then be reprecipitated for analysis of the sulfur and oxygen isotopes. The cations in the carbonate phase can be dissolved by acidifying the solid residue. Sr can be separated from the solution for Sr isotope analysis by ion-exchange chromatography. The sodium carbonate used contains amounts of Sr which will affect almost all barite 87Sr 86Sr ratios by less than 0.00001 at 1.95?? of the mean. The procedure is preferred over other techniques used for preparing barite samples for the determination of 87Sr 86Sr ratios because it is simple, rapid and enables simultaneous determination of many compositional parameters on the same material. ?? 1985.

  4. Direct analysis of air filter samples for alpha emitting isotopes

    SciTech Connect

    Mohagheghi, A.H.; Ghanbari, F.; Ebara, S.B.; Enghauser, M.E.; Bakhtiar, S.N.

    1997-04-01

    The traditional method for determination of alpha emitting isotopes on air filters has been to process the samples by radiochemical methods. However, this method is too slow for cases of incidents involving radioactive materials where the determination of personnel received dose is urgent. A method is developed to directly analyze the air filters taken from personal and area air monitors. The site knowledge is used in combination with alpha spectral information to identify isotopes. A mathematical function is developed to estimate the activity for each isotope. The strengths and weaknesses of the method are discussed.

  5. Carbon isotope and abundance systematics of Icelandic geothermal gases, fluids and subglacial basalts with implications for mantle plume-related CO2 fluxes

    NASA Astrophysics Data System (ADS)

    Barry, P. H.; Hilton, D. R.; Füri, E.; Halldórsson, S. A.; Grönvold, K.

    2014-06-01

    We report new carbon dioxide (CO2) abundance and isotope data for 71 geothermal gases and fluids from both high-temperature (HT > 150 °C at 1 km depth) and low-temperature (LT < 150 °C at 1 km depth) geothermal systems located within neovolcanic zones and older segments of the Icelandic crust, respectively. These data are supplemented by CO2 data obtained by stepped heating of 47 subglacial basaltic glasses collected from the neovolcanic zones. The sample suite has been characterized previously for He-Ne (geothermal) and He-Ne-Ar (basalt) systematics (Füri et al., 2010), allowing elemental ratios to be calculated for individual samples. Geothermal fluids are characterized by a wide range in carbon isotope ratios (δ13C), from -18.8‰ to +4.6‰ (vs. VPDB), and CO2/3He values that span eight orders of magnitude, from 1 × 104 to 2 × 1012. Extreme geothermal values suggest that original source compositions have been extensively modified by hydrothermal processes such as degassing and/or calcite precipitation. Basaltic glasses are also characterized by a wide range in δ13C values, from -27.2‰ to -3.6‰, whereas CO2/3He values span a narrower range, from 1 × 108 to 1 × 1012. The combination of both low δ13C values and low CO2 contents in basalts indicates that magmas are extensively and variably degassed. Using an equilibrium degassing model, we estimate that pre-eruptive basaltic melts beneath Iceland contain ∼531 ± 64 ppm CO2 with δ13C values of -2.5 ± 1.1‰, in good agreement with estimates from olivine-hosted melt inclusions (Metrich et al., 1991) and depleted MORB mantle (DMM) CO2 source estimates (Marty, 2012). In addition, pre-eruptive CO2 compositions are estimated for individual segments of the Icelandic axial rift zones, and show a marked decrease from north to south (Northern Rift Zone = 550 ± 66 ppm; Eastern Rift Zone = 371 ± 45 ppm; Western Rift Zone = 206 ± 24 ppm). Notably, these results are model dependent, and selection of a lower

  6. Laboratory and field methods for stable isotope analysis in human biology.

    PubMed

    Reitsema, Laurie J

    2015-01-01

    Stable isotope analysis (SIA; carbon, hydrogen, nitrogen, sulfur, and oxygen) of human tissues offers a means for assessing diet among living humans. Stable isotope ratios of broad categories of food and drink food vary systematically, and stable isotope ratios in consumer tissues represent a composite of the isotopic ratios of food and drink consumed during an individual's life. Isotopic evidence for diet is independent of errors in informant recall, and accrues during time periods when researchers are absent. Beyond diet reconstruction, tissue stable isotope ratios are sensitive to excursions from homeostasis, such as starvation and rapid growth. Because of their relationship to diet, geographic location, hydration, and nutritional status, stable isotope signatures in human tissues offer a window into human biocultural adaptations, past and present. This article describes methods for SIA that may be usefully applied in studies of living humans, with emphasis placed on carbon and nitrogen. Some of the ecological, physiological, and evolutionary applications of stable isotope data among living humans are discussed. By incorporating SIA in research, human biologists facilitate a productive dialog with bioarchaeologists, who routinely use stable isotope evidence, mingling different perspectives on human biology and behavior.

  7. Non-lethal sampling of walleye for stable isotope analysis: a comparison of three tissues

    USGS Publications Warehouse

    Chipps, Steven R.; VanDeHey, J.A.; Fincel, M.J.

    2012-01-01

    Stable isotope analysis of fishes is often performed using muscle or organ tissues that require sacrificing animals. Non-lethal sampling provides an alternative for evaluating isotopic composition for species of concern or individuals of exceptional value. Stable isotope values of white muscle (lethal) were compared with those from fins and scales (non-lethal) in walleye, Sander vitreus (Mitchill), from multiple systems, size classes and across a range of isotopic values. Isotopic variability was also compared among populations to determine the potential of non-lethal tissues for diet-variability analyses. Muscle-derived isotope values were enriched compared with fins and depleted relative to scales. A split-sample validation technique and linear regression found that isotopic composition of walleye fins and scales was significantly related to that in muscle tissue for both δ13C and δ15N (r2 = 0.79–0.93). However, isotopic variability was significantly different between tissue types in two of six populations for δ15N and three of six populations for δ13C. Although species and population specific, these findings indicate that isotopic measures obtained from non-lethal tissues are indicative of those obtained from muscle.

  8. Applications, considerations, and sources of uncertainty when using stable isotope analysis in ecotoxicology.

    PubMed

    Jardine, Timothy D; Kidd, Karen A; Fisk, Aaron T

    2006-12-15

    Stable isotope analysis (SIA) has become a powerful tool for ecotoxicologists to study dietary exposure and biomagnification of contaminants in wild animal populations. The use of SIA in ecotoxicology continues to expand and, while much more is known about the mechanisms driving patterns of isotopic ratios in consumers, there remain several considerations or sources of uncertainty that can influence interpretation of data from field studies. We outline current uses of SIA in ecotoxicology, including estimating the importance of dietary sources of carbon and their application in biomagnification studies, and we present six main considerations or sources of uncertainty associated with the approach: (1) unequal diet-tissue stable isotope fractionation among species, (2) variable diet-tissue stable isotope fractionation within a given species, (3) different stable isotope ratios in different tissues of the animal, (4) fluctuating baseline stable isotope ratios across systems, (5) the presence of true omnivores, and (6) movement of animals and nutrients between food webs. Since these considerations or sources of uncertainty are difficult to assess in field studies, we advocate that researchers consider the following in designing ecotoxicological research and interpreting results: assess and utilize variation in stable isotope diet-tissue fractionation among animal groups available in the literature; determine stable isotope ratios in multiple tissues to provide a temporal assessment of feeding; adequately characterize baseline isotope ratios; utilize stomach contents when possible; and assess and integrate life history of study animals in a system.

  9. Sensitivity analysis and quantification of uncertainty for isotopic mixing relationships in carbon cycle research

    NASA Astrophysics Data System (ADS)

    Zobitz, J. M.; Keener, J. P.; Bowling, D. R.

    2004-12-01

    Quantifying and understanding the uncertainty in isotopic mixing relationships is critical to isotopic applications in carbon cycle studies at all spatial and temporal scales. Studies associated with the North American Carbon Program will depend on stable isotope approaches and quantification of isotopic uncertainty. An important application of isotopic mixing relationships is determination of the isotopic content of large-scale respiration (δ 13CR) via an inverse relationship (a Keeling plot) between atmospheric CO2 concentrations ([CO2]) and carbon isotope ratios of CO2 (δ 13C). Alternatively, a linear relationship between [CO2] and the product of [CO2] and δ 13C (a Miller/Tans plot) can also be applied. We used an extensive dataset from the Niwot Ridge Ameriflux Site of [CO2] and δ 13C in forest air to examine contrasting approaches to determine δ 13CR and its uncertainty. These included Keeling plots, Miller/Tans plots, Model I, and Model II regressions Our analysis confirms previous observations that increasing the range of measurements ([CO2] range) reduces the uncertainty associated with δ 13CR. For carbon isotope studies, uncertainty in the isotopic measurements has a greater effect on the uncertainty of δ 13CR than the uncertainty in [CO2]. Reducing the uncertainty of isotopic measurements reduces the uncertainty of δ 13CR even when the [CO2] range of samples is small (< 20 ppm). As a result, improvement in isotope (rather than CO2) measuring capability is needed to substantially reduce uncertainty in δ 13CR. We also find for carbon isotope studies no inherent advantage to using either a Keeling or a Miller/Tans approach to determine δ 13CR.

  10. Mammoth tooth enamel growth rates inferred from stable isotope analysis and histology

    NASA Astrophysics Data System (ADS)

    Metcalfe, Jessica Z.; Longstaffe, Fred J.

    2012-05-01

    Mammoth (Mammuthus sp.) teeth are relatively abundant in Quaternary deposits from Eurasia and North America, and their isotopic compositions can be used to reconstruct past seasonal patterns in precipitation, diet, and migration. Strategies for collecting and interpreting such data, however, are strongly dependent on growth rates, which can vary among species, individuals, and within teeth. In this study, we use histological and isotopic measurements to determine enamel growth rates for a Columbian mammoth (Mammuthus columbi) tooth in two directions. Using histology, the growth rate through the enamel thickness (ET; perpendicular to the height of the tooth) is estimated at 0.8 to 1.5 mm/yr. Isotopic sampling through the innermost 0.36 mm of the ET recovered less than half a period of variation (i.e., half an inferred year of growth), which is consistent with the histological estimate for ET growth rate. A combination of histological and isotopic measurements suggests that the enamel extension rate (growth in the height of the tooth) is 13-14 mm/yr. Knowledge of enamel growth rates should improve the design and interpretation of future isotopic studies of mammoth teeth. The combination of histological and isotopic measurements may also prove useful in determining growth rates for other extinct taxa.

  11. Mapping of replication initiation sites in human ribosomal DNA by nascent-strand abundance analysis.

    PubMed Central

    Yoon, Y; Sanchez, J A; Brun, C; Huberman, J A

    1995-01-01

    New techniques for mapping mammalian DNA replication origins are needed. We have modified the existing nascent-strand size analysis technique (L. Vassilev and E.M. Johnson, Nucleic Acids Res. 17:7693-7705, 1989) to provide an independent means of studying replication initiation sites. We call the new method nascent-strand abundance analysis. We confirmed the validity of this method with replicating simian virus 40 DNA as a model. We then applied nascent-strand abundance and nascent-strand size analyses to mapping of initiation sites in human (HeLa) ribosomal DNA (rDNA), a region previously examined exclusively by two-dimensional gel electrophoresis methods (R.D. Little, T.H.K. Platt, and C.L. Schildkraut, Mol. Cell. Biol. 13:6600-6613, 1993). Our results partly confirm those obtained by two-dimensional gel electrophoresis techniques. Both studies suggest that replication initiates at relatively high frequency a few kilobase pairs upstream of the transcribed region and that many additional low-frequency initiation sites are distributed through most of the remainder of the ribosomal DNA repeat unit. PMID:7739533

  12. 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‰).

  13. 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

  14. Cu isotope fractionation during bornite dissolution: An in situ X-ray diffraction analysis

    SciTech Connect

    Wall, Andrew J.; Mathur, Ryan; Post, Jeffrey E.; Heaney, Peter J.

    2012-10-24

    Low-temperature ore deposits exhibit a large variation in {delta}{sup 65}Cu ({approx}12{per_thousand}), and this range has been attributed, in part, to isotope fractionation during weathering reactions of primary minerals such as chalcocite and chalcopyrite. Here, we examine the fractionation of Cu isotopes during dissolution of another important Cu ore mineral, bornite, using a novel approach that combines time-resolved X-ray diffraction (XRD) and isotope analysis of reaction products. During the initial stages of bornite oxidative dissolution by ferric sulfate (< 5 mol% of total Cu leached), dissolved Cu was enriched in isotopically heavy Cu ({sup 65}Cu) relative to the solid, with an average apparent isotope fractionation ({Delta}{sub aq - min} = {delta}{sup 65}Cu{sub aq} - {delta}{sup 65}Cu{sub min}{sup 0}) of 2.20 {+-} 0.25{per_thousand}. When > 20 mol% Cu was leached from the solid, the difference between the Cu isotope composition of the aqueous and mineral phases approached zero, with {Delta}{sub aq - min}{sup 0} values ranging from - 0.21 {+-} 0.61{per_thousand} to 0.92 {+-} 0.25{per_thousand}. XRD analysis allowed us to correlate changes in the atomic structure of bornite with the apparent isotope fractionation as the dissolution reaction progressed. These data revealed that the greatest degree of apparent fractionation is accompanied by a steep contraction in the unit-cell volume, which we identified as a transition from stoichiometric to non-stoichiometric bornite. We propose that the initially high {Delta}{sub aq - min} values result from isotopically heavy Cu ({sup 65}Cu) concentrating within Cu{sup 2+} during dissolution. The decrease in the apparent isotope fractionation as the reaction progresses occurs from the distillation of isotopically heavy Cu ({sup 65}Cu) during dissolution or kinetic isotope effects associated with the depletion of Cu from the surfaces of bornite particles.

  15. 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)

  16. GUM Analysis for TIMS and SIMS Isotopic Ratios in Graphite

    SciTech Connect

    Heasler, Patrick G.; Gerlach, David C.; Cliff, John B.; Petersen, Steven L.

    2007-04-01

    This report describes GUM calculations for TIMS and SIMS isotopic ratio measurements of reactor graphite samples. These isotopic ratios are used to estimate reactor burn-up, and currently consist of various ratios of U, Pu, and Boron impurities in the graphite samples. The GUM calculation is a propagation of error methodology that assigns uncertainties (in the form of standard error and confidence bound) to the final estimates.

  17. Stable isotope analysis of Pacific salmon: insight into trophic status and oceanographic conditions over the last 30 years

    NASA Astrophysics Data System (ADS)

    Satterfield, Franklin R.; Finney, Bruce P.

    Food web interactions and the response of Pacific salmon to physical processes in the North Pacific Ocean over interannual and interdecadal timescales are explored using naturally occurring stable isotope ratios of carbon ( 13C/ 12C) and nitrogen ( 15N/ 14N). Stable isotope analyses of five species of sexually mature North Pacific salmon from Alaska ( Oncorhynchus spp.) cluster into three groups: chinook salmon ( O. tshawytscha) have the highest values, followed by coho ( O. kisutch), with chum ( O. keta), sockeye ( O. nerka), and pink ( O. gorbuscha) together having the lowest values. Although detailed isotopic data on salmon prey are lacking, there are limited data on relevant prey items from areas in which they are found in high abundance. These data suggest that the characteristics of the sockeye, pink and chum we have analyzed are compatible with their diets including open ocean squid and zooplankton, which are in general agreement with stomach content analyses. Isotope relationships between muscle and scale show consistent relationships for both δ13C ( R2=0.98) and δ 15N ( R2=0.90). Thus, scales, which have been routinely archived for many systems, can be used for retrospective analyses. Archived sockeye salmon scales spanning 1966-1999 from Red Lake, Kodiak Island, Alaska were analyzed for their stable isotope ratios of carbon and nitrogen. The δ15N record displays a decreasing trend of ~3‰ from 1969-1982 and an increasing trend of ~3‰ from 1982-1992, while the variations in δ13C are relatively minor. These trends may result from factors such as shifts in trophic level of feeding and/or feeding location, or may originate at the base of the food web via changes in processes such as nutrient cycling or primary productivity. Detailed studies on prey isotopic variability and its controls are needed to distinguish between these factors, and thus to improve the use of stable isotope analysis as a tool to learn more about present and past ecosystem change

  18. Accurate abundance analysis of late-type stars: advances in atomic physics

    NASA Astrophysics Data System (ADS)

    Barklem, Paul S.

    2016-05-01

    The measurement of stellar properties such as chemical compositions, masses and ages, through stellar spectra, is a fundamental problem in astrophysics. Progress in the understanding, calculation and measurement of atomic properties and processes relevant to the high-accuracy analysis of F-, G-, and K-type stellar spectra is reviewed, with particular emphasis on abundance analysis. This includes fundamental atomic data such as energy levels, wavelengths, and transition probabilities, as well as processes of photoionisation, collisional broadening and inelastic collisions. A recurring theme throughout the review is the interplay between theoretical atomic physics, laboratory measurements, and astrophysical modelling, all of which contribute to our understanding of atoms and atomic processes, as well as to modelling stellar spectra.

  19. Oceanic and Climate phasing analysis across Marine Isotope Stage 3

    NASA Astrophysics Data System (ADS)

    Henry, G., III; McManus, J. F.; Curry, W. B.; Roberts, N. L.; Piotrowski, A. M.; Keigwin, L. D.

    2015-12-01

    Glacial climate oscillated between cold stadial periods similar to the Last Glacial Maximum and warmer periods more similar to today from 25,000 to 60,000 years BP, an envelop of time referred to as marine isotope stage three (MIS3). The sudden warmings (Dansgaard-Oeschger events) and ice sheet surges (Heinrich events) have long captured researchers' attention as a means of exploring significant perturbations to the climate system. The climate dynamics associated with these events have been recently elucidated throughhigh-resolution analysis of ice and sediment core archives. In particular, it has been recently demonstrated through synchronization of Greenlandic and Antarctic ice cores that abrupt climate events propagated from the Northern to Southern hemisphere. Likewise, during Heinrich events ice rafted detritus appeared in the Northern North Atlantic generally after cold stadial conditions had already been established. These results indict the ocean's conveyor as the vehicle hemispheric partitioning heat across these events. Here we test the phased response of multiple paleoproxies sensitive to circulation across these abrupt climate events through all of MIS3. Through correlation analysis of multiple paleoproxy records generated from a high accumulation sediment core taken from the Bermuda Rise, we examine the phase relationship of high latitude climate records with the kinematic circulation proxy Pa/Th, benthic d13C and d18O, SST, d18Osw, CaCO3 content, 230Th-normalized bulk and component fluxes in order to infer the sequence of change across these abrupt millennial events. We find that shifts in water mass composition precede increases in temperatures across the identified time interval, while the export of Pa relative to Th increases in tandem with changes in with Bermuda Rise SST estimates during warmings, but lags during cooling. Rapid shifts in thorium normalized carbonate flux supply secondary evidence for changes in preservation accompanying changes

  20. Analysis of Hydrogen Isotopic Exchange: Lava Creek Tuff Ash and Isotopically Labeled Water

    NASA Astrophysics Data System (ADS)

    Ross, A. M.; Seligman, A. N.; Bindeman, I. N.; Nolan, G. S.

    2015-12-01

    Nolan and Bindeman (2013) placed secondarily hydrated ash from the 7.7 ka eruption of Mt. Mazama (δD=-149‰, 2.3wt% H2Ot) in isotopically labeled water (+650 ‰ δD, +56 ‰ δ18O) and observed that the H2Ot and δ18O values remained constant, but the δD values of ash increased with the surrounding water at 20, 40 and 70 °C. We expand on this work by conducting a similar experiment with ash from the 640 ka Lava Creek Tuff (LCT, δD of -128 ‰; 2.1 wt.% H2Ot) eruption of Yellowstone to see if significantly older glass (with a hypothesized gel layer on the surface shielding the interior from alteration) produces the same results. We have experiments running at 70, 24, and 5 °C, and periodically remove ~1.5 mg of glass to measure the δD (‰) and H2Ot (wt.%) of water extracted from the glass on a TC/EA MAT 253 continuous flow system. After 600 hours, the δD of the samples left at 5 and 24 °C remains at -128 ‰, but increased 8‰ for the 70 °C run series. However, there is no measurable change in wt.% of H2Ot, indicating that hydrogen exchange is not dictated by the addition of water. We are measuring and will report further progress of isotope exchange. We also plan to analyze the water in the LCT glass for δ18O (‰) to see if, as is the case for the Mt. Mazama glass, the δ18O (‰) remains constant. We also analyzed Mt. Mazama glass from the Nolan and Bindeman (2013) experiments that have now been sitting in isotopically labeled water at room temperature for ~5 years. The water concentration is still unchanged (2.3 wt.% H2Ot), and the δD of the water in the glass is now -111 ‰, causing an increase of 38 ‰. Our preliminary results show that exchange of hydrogen isotopes of hydrated glass is not limited by the age of the glass, and that the testing of hydrogen isotopes of secondarily hydrated glass, regardless of age, may not be a reliable paleoclimate indicator.

  1. The Ontogenetically Variable Trophic Niche of a Praying Mantid Revealed by Stable Isotope Analysis.

    PubMed

    Hurd, Lawrence E; Dehart, Pieter A P; Taylor, Joseph M; Campbell, Meredith C; Shearer, Megan M

    2015-04-01

    Praying mantids have been shown to exert strong influences on arthropod community composition. However, they may not occupy the same trophic level throughout their lives. Trophic shifting over a life cycle could explain the documented variation in results from field studies, but specific interactions of predators within food webs have been difficult to determine simply by comparing control and treatment assemblages in field experiments. We examined the trophic position of the Chinese praying mantid, Tenodera aridifolia sinensis (Saussure), using stable isotope analysis (SIA). We measured the δ(13)C and δ(15)N of field-collected arthropods, and of laboratory groups of mantids fed known diets of these arthropods chosen from the most abundant trophic guilds: herbivores (sap feeders and plant chewers), and carnivores. We also collected mantids from the field over a growing season and compared their SIA values to those of the laboratory groups. Both δ(13)C and δ(15)N of mantids fed carnivorous prey (spiders or other mantids) were higher than those fed herbivores (grasshoppers). SIA values from field-collected mantids were highly variable, and indicated that they did not take prey from trophic guilds in proportion to their abundances, i.e., were not frequency-dependent predators. Further, δ(15)N decreased from a high at egg hatch to a low at the third instar as early nymphs fed mainly on lower trophic levels, and increased steadily thereafter as they shifted to feeding on higher levels. We suggest that the community impact of generalist predators can be strongly influenced by ontogenetic shifts in diet. PMID:26313177

  2. Meta-analysis: abundance, behavior, and hydraulic energy shape biotic effects on sediment transport in streams.

    PubMed

    Albertson, L K; Allen, D C

    2015-05-01

    An increasing number of studies have emphasized the need to bridge the disciplines of ecology and geomorphology. A large number of case studies show that organisms can affect erosion, but a comprehensive understanding of biological impacts on sediment transport conditions is still lacking. We use meta-analysis to synthesize published data to quantify the effects of the abundance, body size, and behavior of organisms on erosion in streams. We also explore the influence of current velocity, discharge, and sediment grain size on the strength of biotic effects on erosion. We found that species that both increase erosion (destabilizers) and decrease erosion (stabilizers) can alter incipient sediment motion, sediment suspension, and sediment deposition above control conditions in which the organisms were not present. When abundance was directly manipulated, these biotic effects were consistently stronger in the higher abundance treatment, increasing effect sizes by 66%. Per capita effect size and per capita biomass were also consistently positively correlated. Fish and crustaceans were the most studied organisms, but aquatic insects increased the effect size by 550 x compared to other types of organisms after accounting for biomass. In streams with lower discharge and smaller grain sizes, we consistently found stronger biotic effects. Taken collectively, these findings provide synthetic evidence that biology can affect physical processes in streams, and these effects can be mediated by hydraulic energy. We suggest that future studies focus on understudied organisms, such as biofilms, conducting experiments under realistic field conditions, and developing hypotheses for the effect of biology on erosion and velocity currents in the context of restoration to better understand the forces that mediate physical disturbances in stream ecosystems. PMID:26236846

  3. Meta-analysis: abundance, behavior, and hydraulic energy shape biotic effects on sediment transport in streams.

    PubMed

    Albertson, L K; Allen, D C

    2015-05-01

    An increasing number of studies have emphasized the need to bridge the disciplines of ecology and geomorphology. A large number of case studies show that organisms can affect erosion, but a comprehensive understanding of biological impacts on sediment transport conditions is still lacking. We use meta-analysis to synthesize published data to quantify the effects of the abundance, body size, and behavior of organisms on erosion in streams. We also explore the influence of current velocity, discharge, and sediment grain size on the strength of biotic effects on erosion. We found that species that both increase erosion (destabilizers) and decrease erosion (stabilizers) can alter incipient sediment motion, sediment suspension, and sediment deposition above control conditions in which the organisms were not present. When abundance was directly manipulated, these biotic effects were consistently stronger in the higher abundance treatment, increasing effect sizes by 66%. Per capita effect size and per capita biomass were also consistently positively correlated. Fish and crustaceans were the most studied organisms, but aquatic insects increased the effect size by 550 x compared to other types of organisms after accounting for biomass. In streams with lower discharge and smaller grain sizes, we consistently found stronger biotic effects. Taken collectively, these findings provide synthetic evidence that biology can affect physical processes in streams, and these effects can be mediated by hydraulic energy. We suggest that future studies focus on understudied organisms, such as biofilms, conducting experiments under realistic field conditions, and developing hypotheses for the effect of biology on erosion and velocity currents in the context of restoration to better understand the forces that mediate physical disturbances in stream ecosystems.

  4. A retro-biosynthetic approach to the prediction of biosynthetic pathways from position-specific isotope analysis as shown for tramadol.

    PubMed

    Romek, Katarzyna M; Nun, Pierrick; Remaud, Gérald S; Silvestre, Virginie; Taïwe, Germain Sotoing; Lecerf-Schmidt, Florine; Boumendjel, Ahcène; De Waard, Michel; Robins, Richard J

    2015-07-01

    Tramadol, previously only known as a synthetic analgesic, has now been found in the bark and wood of roots of the African medicinal tree Nauclea latifolia. At present, no direct evidence is available as to the biosynthetic pathway of its unusual skeleton. To provide guidance as to possible biosynthetic precursors, we have adopted a novel approach of retro-biosynthesis based on the position-specific distribution of isotopes in the extracted compound. Relatively recent developments in isotope ratio monitoring by (13)C NMR spectrometry make possible the measurement of the nonstatistical position-specific natural abundance distribution of (13)C (δ(13)Ci) within the molecule with better than 1‰ precision. Very substantial variation in the (13)C positional distribution is found: between δ(13)Ci = -11 and -53‰. Distribution is not random and it is argued that the pattern observed can substantially be interpreted in relation to known causes of isotope fractionation in natural products. Thus, a plausible biosynthetic scheme based on sound biosynthetic principals of precursor-substrate relationships can be proposed. In addition, data obtained from the (18)O/(16)O ratios in the oxygen atoms of the compound add support to the deductions made from the carbon isotope analysis. This paper shows how the use of (13)C NMR at natural abundance can help with proposing a biosynthetic route to compounds newly found in nature or those difficult to tackle by conventional means.

  5. A retro-biosynthetic approach to the prediction of biosynthetic pathways from position-specific isotope analysis as shown for tramadol

    PubMed Central

    Romek, Katarzyna M.; Nun, Pierrick; Remaud, Gérald S.; Silvestre, Virginie; Taïwe, Germain Sotoing; Lecerf-Schmidt, Florine; Boumendjel, Ahcène; De Waard, Michel; Robins, Richard J.

    2015-01-01

    Tramadol, previously only known as a synthetic analgesic, has now been found in the bark and wood of roots of the African medicinal tree Nauclea latifolia. At present, no direct evidence is available as to the biosynthetic pathway of its unusual skeleton. To provide guidance as to possible biosynthetic precursors, we have adopted a novel approach of retro-biosynthesis based on the position-specific distribution of isotopes in the extracted compound. Relatively recent developments in isotope ratio monitoring by 13C NMR spectrometry make possible the measurement of the nonstatistical position-specific natural abundance distribution of 13C (δ13Ci) within the molecule with better than 1‰ precision. Very substantial variation in the 13C positional distribution is found: between δ13Ci = −11 and −53‰. Distribution is not random and it is argued that the pattern observed can substantially be interpreted in relation to known causes of isotope fractionation in natural products. Thus, a plausible biosynthetic scheme based on sound biosynthetic principals of precursor–substrate relationships can be proposed. In addition, data obtained from the 18O/16O ratios in the oxygen atoms of the compound add support to the deductions made from the carbon isotope analysis. This paper shows how the use of 13C NMR at natural abundance can help with proposing a biosynthetic route to compounds newly found in nature or those difficult to tackle by conventional means. PMID:26106160

  6. Quantitative Analysis of rRNA Modifications Using Stable Isotope Labeling and Mass Spectrometry

    PubMed Central

    2015-01-01

    Post-transcriptional RNA modifications that are introduced during the multistep ribosome biogenesis process are essential for protein synthesis. The current lack of a comprehensive method for a fast quantitative analysis of rRNA modifications significantly limits our understanding of how individual modification steps are coordinated during biogenesis inside the cell. Here, an LC-MS approach has been developed and successfully applied for quantitative monitoring of 29 out of 36 modified residues in the 16S and 23S rRNA from Escherichia coli. An isotope labeling strategy is described for efficient identification of ribose and base methylations, and a novel metabolic labeling approach is presented to allow identification of MS-silent pseudouridine modifications. The method was used to measure relative abundances of modified residues in incomplete ribosomal subunits compared to a mature 15N-labeled rRNA standard, and a number of modifications in both 16S and 23S rRNA were present in substoichiometric amounts in the preribosomal particles. The RNA modification levels correlate well with previously obtained profiles for the ribosomal proteins, suggesting that RNA is modified in a schedule comparable to the association of the ribosomal proteins. Importantly, this study establishes an efficient workflow for a global monitoring of ribosomal modifications that will contribute to a better understanding of mechanisms of RNA modifications and their impact on intracellular processes in the future. PMID:24422502

  7. Characterization of phenol and cresol biodegradation by compound-specific stable isotope analysis.

    PubMed

    Wei, Xi; Gilevska, Tetyana; Wetzig, Felix; Dorer, Conrad; Richnow, Hans-Hermann; Vogt, Carsten

    2016-03-01

    Microbial degradation of phenol and cresols can occur under oxic and anoxic conditions by different degradation pathways. One recent technique to take insight into reaction mechanisms is compound-specific isotope analysis (CSIA). While enzymes and reaction mechanisms of several degradation pathways have been characterized in (bio)chemical studies, associated isotope fractionation patterns have been rarely reported, possibly due to constraints in current analytical methods. In this study, carbon enrichment factors and apparent kinetic isotope effects (AKIEc) of the initial steps of different aerobic and anaerobic phenol and cresols degradation pathways were analyzed by isotope ratio mass spectrometry connected with liquid chromatography (LC-IRMS). Significant isotope fractionation was detected for aerobic ring hydroxylation, anoxic side chain hydroxylation, and anoxic fumarate addition, while anoxic carboxylation reactions produced small and inconsistent fractionation. The results suggest that several microbial degradation pathways of phenol and cresols are detectable in the environment by CSIA.

  8. Development of isotope dilution gamma-ray spectrometry for plutonium analysis

    SciTech Connect

    Li, T.K.; Parker, J.L. ); Kuno, Y.; Sato, S.; Kurosawa, A.; Akiyama, T. )

    1991-01-01

    We are studying the feasibility of determining the plutonium concentration and isotopic distribution of highly radioactive, spent-fuel dissolver solutions by employing high-resolution gamma-ray spectrometry. The study involves gamma-ray plutonium isotopic analysis for both dissolver and spiked dissolver solution samples, after plutonium is eluted through an ion-exchange column and absorbed in a small resin bead bag. The spike is well characterized, dry plutonium containing {approximately}98% of {sup 239}Pu. By using measured isotopic information, the concentration of elemental plutonium in the dissolver solution can be determined. Both the plutonium concentration and the isotopic composition of the dissolver solution obtained from this study agree well with values obtained by traditional isotope dilution mass spectrometry (IDMS). Because it is rapid, easy to operate and maintain, and costs less, this new technique could be an alternative method to IDMS for input accountability and verification measurements in reprocessing plants. 7 refs., 4 figs., 4 tabs.

  9. Application of stable isotope ratio analysis for biodegradation monitoring in groundwater.

    PubMed

    Hatzinger, Paul B; Böhlke, J K; Sturchio, Neil C

    2013-06-01

    Stable isotope ratio analysis is increasingly being applied as a tool to detect, understand, and quantify biodegradation of organic and inorganic contaminants in groundwater. An important feature of this approach is that it allows degradative losses of contaminants to be distinguished from those caused by non-destructive processes such as dilution, dispersion, and sorption. Recent advances in analytical techniques, and new approaches for interpreting stable isotope data, have expanded the utility of this method while also exposing complications and ambiguities that must be considered in data interpretations. Isotopic analyses of multiple elements in a compound, and multiple compounds in the environment, are being used to distinguish biodegradative pathways by their characteristic isotope effects. Numerical models of contaminant transport, degradation pathways, and isotopic composition are improving quantitative estimates of in situ contaminant degradation rates under realistic environmental conditions. PMID:23279929

  10. Abundance quantification by independent component analysis of hyperspectral imagery for oil spill coverage calculation

    NASA Astrophysics Data System (ADS)

    Han, Zhongzhi; Wan, Jianhua; Zhang, Jie; Zhang, Hande

    2016-08-01

    The estimation of oil spill coverage is an important part of monitoring of oil spills at sea. The spatial resolution of images collected by airborne hyper-spectral remote sensing limits both the detection of oil spills and the accuracy of estimates of their size. We consider at-sea oil spills with zonal distribution in this paper and improve the traditional independent component analysis algorithm. For each independent component we added two constraint conditions: non-negativity and constant sum. We use priority weighting by higher-order statistics, and then the spectral angle match method to overcome the order nondeterminacy. By these steps, endmembers can be extracted and abundance quantified simultaneously. To examine the coverage of a real oil spill and correct our estimate, a simulation experiment and a real experiment were designed using the algorithm described above. The result indicated that, for the simulation data, the abundance estimation error is 2.52% and minimum root mean square error of the reconstructed image is 0.030 6. We estimated the oil spill rate and area based on eight hyper-spectral remote sensing images collected by an airborne survey of Shandong Changdao in 2011. The total oil spill area was 0.224 km2, and the oil spill rate was 22.89%. The method we demonstrate in this paper can be used for the automatic monitoring of oil spill coverage rates. It also allows the accurate estimation of the oil spill area.

  11. Analysis of Carbohydrate and Fatty Acid Marker Abundance in Ricin Toxin Preparations for Forensic Information

    SciTech Connect

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

    2010-07-15

    One challenge in the forensic analysis of ricin samples is determining the method and extent of sample preparation. Ricin purification from the source castor seeds is essentially a protein purification through removal of the non-protein fractions of the seed. Two major, non-protein constituents in the seed are the castor oil and carbohydrates. Ricinoleic acid is a relatively unique fatty acid in nature and is the most abundant component of castor oil, which comprises roughly half the seed weight. The carbohydrate component comprises roughly half of the remaining “mash” left after oil and hull removal. We used derivatization of carbohydrate and fatty acid markers followed by identification and quantification using gas chromatography/mass spectrometry (GC/MS) to assess compositional changes in ricin samples purified by different methods. The loss of ricinoleic acid indicated steps for oil removal had occurred. Changes to the carbohydrate content of the sample were also observed following protein precipitation. The differential loss of arabinose relative to mannose indicated removal of the major carbohydrate fraction of the seed and enrichment of the protein content. Taken together, these changes in fatty acid and carbohydrate abundance are indicative of the preparation method used for each sample.

  12. Direct mutation analysis by high-throughput sequencing: from germline to low-abundant, somatic variants

    PubMed Central

    Gundry, Michael; Vijg, Jan

    2011-01-01

    DNA mutations are the source of genetic variation within populations. The majority of mutations with observable effects are deleterious. In humans mutations in the germ line can cause genetic disease. In somatic cells multiple rounds of mutations and selection lead to cancer. The study of genetic variation has progressed rapidly since the completion of the draft sequence of the human genome. Recent advances in sequencing technology, most importantly the introduction of massively parallel sequencing (MPS), have resulted in more than a hundred-fold reduction in the time and cost required for sequencing nucleic acids. These improvements have greatly expanded the use of sequencing as a practical tool for mutation analysis. While in the past the high cost of sequencing limited mutation analysis to selectable markers or small forward mutation targets assumed to be representative for the genome overall, current platforms allow whole genome sequencing for less than $5,000. This has already given rise to direct estimates of germline mutation rates in multiple organisms including humans by comparing whole genome sequences between parents and offspring. Here we present a brief history of the field of mutation research, with a focus on classical tools for the measurement of mutation rates. We then review MPS, how it is currently applied and the new insight into human and animal mutation frequencies and spectra that has been obtained from whole genome sequencing. While great progress has been made, we note that the single most important limitation of current MPS approaches for mutation analysis is the inability to address low-abundance mutations that turn somatic tissues into mosaics of cells. Such mutations are at the basis of intra-tumor heterogeneity, with important implications for clinical diagnosis, and could also contribute to somatic diseases other than cancer, including aging. Some possible approaches to gain access to low-abundance mutations are discussed, with a

  13. An Abundance Analysis of R-Coronae Stars in the Galaxy and the Large Magellanic Cloud

    NASA Astrophysics Data System (ADS)

    Pollard, K. R.; Cottrell, P. L.; Lawson, W. A.

    1994-05-01

    High-resolution echelle spectra have been obtained of one galactic and two Large Magellanic Cloud (LMC) R Coronae Borealis (RCB) stars with the Anglo-Australian Telescope. An analysis of these data using He- and C- rich models and the WIDTH6 model atmosphere code of Kurucz indicates that the galactic RCB star SU Tau and the two LMC stars, HV 12842 and W Men (HV 966), have similar atmospheric parameters to the warmer galactic RCB and hydrogen-deficient carbon (HdC) stars such as R CrB and XX Cam. The newly analysed RCB stars have T_eff_ ~ 7000 K, log g = 0.5 to 1.0, microturbulent velocities between 7 and 8 km s^-1^ and C/He ratios ranging from 0.0034 to 0.011. An abundance analysis has been performed on these stars for a wide range of species. Special emphasis has been placed on H, He, Li, C, N, O, Fe and the s-process elements. Specific values for [H/He], [Li/Fe] and [Fe/total] (expressed relative to the total abundance of all species) in SU Tau, HV 12842 and W Men are -5,4, -6.2 and -6.5; +2.6, +2.4 and +2.1; and -0.4, -0.7 and -0.7 respectively. The analysis of RCB stars in the LMC provides us with the opportunity to study the metallicity dependence of RCB star evolution.

  14. High-resolution abundance analysis of very metal-poor r-I stars

    NASA Astrophysics Data System (ADS)

    Siqueira Mello, C.; Hill, V.; Barbuy, B.; Spite, M.; Spite, F.; Beers, T. C.; Caffau, E.; Bonifacio, P.; Cayrel, R.; François, P.; Schatz, H.; Wanajo, S.

    2014-05-01

    Context. Moderately r-process-enriched stars (r-I; +0.3 ≤ [Eu/Fe] ≤ +1.0) are at least four times as common as those that are greatly enriched in r-process elements (r-II; [Eu/Fe] > +1.0), and the abundances in their atmospheres are important tools for obtaining a better understanding of the nucleosynthesis processes responsible for the origin of the elements beyond the iron peak. Aims: The main aim of this work is to derive abundances for a sample of seven metal-poor stars with -3.4 ≤ [Fe/H] ≤ -2.4 classified as r-I stars, to understand the role of these stars for constraining the astrophysical nucleosynthesis event(s) that is (are) responsible for the production of the r-process, and to investigate whether they differ, in any significant way, from the r-II stars. Methods: We carried out a detailed abundance analysis based on high-resolution spectra obtained with the VLT/UVES spectrograph, using spectra in the wavelength ranges 3400-4500 Å, 6800-8200 Å, and 8700-10 000 Å, with resolving power R ~ 40 000 (blue arm) and R ~ 55 000 (red arm). The OSMARCS LTE 1D model atmosphere grid was employed, along with the spectrum synthesis code Turbospectrum. Results: We have derived abundances of the light elements Li, C, and N, the α-elements Mg, Si, S, Ca, and Ti, the odd-Z elements Al, K, and Sc, the iron-peak elements V, Cr, Mn, Fe, Co, and Ni, and the trans-iron elements from the first peak (Sr, Y, Zr, Mo, Ru, and Pd), the second peak (Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Yb), the third peak (Os and Ir, as upper limits), and the actinides (Th) regions. The results are compared with values for these elements for r-II and "normal" very and extremely metal-poor stars reported in the literature, ages based on radioactive chronometry are explored using different models, and a number of conclusions about the r-process and the r-I stars are presented. Hydrodynamical models were used for some elements, and general behaviors for the 3D corrections

  15. Correction of MS data for naturally occurring isotopes in isotope labelling experiments.

    PubMed

    Millard, Pierre; Letisse, Fabien; Sokol, Serguei; Portais, Jean-Charles

    2014-01-01

    Mass spectrometry (MS) in combination with isotope labelling experiments is widely used for investigations of metabolism and other biological processes. Quantitative applications-e.g., (13)C metabolic flux analysis-require correction of raw MS data (isotopic clusters) for the contribution of all naturally abundant isotopes. This chapter describes how to perform such correction using the software IsoCor. This flexible, user-friendly software can be used to exploit any isotopic tracer, from well-known ((13)C, (15)N, (18)O, etc.) to unusual ((57)Fe, (77)Se, etc.) isotopes. It also provides options-e.g., correction for the isotopic purity of the tracer-to improve the accuracy of quantitative isotopic studies, and allows automated correction of large datasets that can be collected with modern MS methods.

  16. Compound Specific Stable Isotope Analysis of Southern African Aerosols

    NASA Astrophysics Data System (ADS)

    Billmark, K. A.; Swap, R. J.; Macko, S. A.

    2001-12-01

    Southern Africa has recently been the focus of intensive subcontinental level study, particularly with regard to atmospheric aerosols and regional atmospheric transport. Results from these analyses have shown that emissions from extensive, often anthropogenic, biomass burning in southern Africa affects biogeochemical cycling in the region, and that emitted trace gases and aerosols as well as industrial emissions, marine aerosols and mineral dust tend to accumulate and recirculate in the well defined anticyclonic atmospheric gyre that persists for long time periods over southern Africa. The long-range transport of these materials is an important component of biogeochemical dynamics in this nutrient limited region. A recent field campaign, the Southern African Regional Science Initiative (SAFARI 2000), was conducted in part to investigate the impacts of this large-scale transport and deposition of aerosols on southern African biogeochemical cycling. As a part of the SAFARI 2000 initiative, we present data illustrating that compound specific stable isotope analysis of individual molecular components is a useful tool for the evaluation of the origins of aerosols and their generating processes. This study specifically examines fatty acids extracted from aerosols to more precisely characterize emissions produced in the high intensity biomass burning region of western Zambia, the slightly less intense biomass burning region of northeastern South Africa and a site downwind of these two regions within the gyre circulation at Sua Pan, Botswana. This discrete characterization of fatty acids contained within the organic fraction of collected aerosols establishes a means to trace biomass burning products as they are transported within the gyre and subsequently deposited on the subcontinent.

  17. High Resolution Gamma Ray Analysis of Medical Isotopes

    NASA Astrophysics Data System (ADS)

    Chillery, Thomas

    2015-10-01

    Compton-suppressed high-purity Germanium detectors at the University of Massachusetts Lowell have been used to study medical radioisotopes produced at Brookhaven Linac Isotope Producer (BLIP), in particular isotopes such as Pt-191 used for cancer therapy in patients. The ability to precisely analyze the concentrations of such radio-isotopes is essential for both production facilities such as Brookhaven and consumer hospitals across the U.S. Without accurate knowledge of the quantities and strengths of these isotopes, it is possible for doctors to administer incorrect dosages to patients, thus leading to undesired results. Samples have been produced at Brookhaven and shipped to UML, and the advanced electronics and data acquisition capabilities at UML have been used to extract peak areas in the gamma decay spectra. Levels of Pt isotopes in diluted samples have been quantified, and reaction cross-sections deduced from the irradiation parameters. These provide both cross checks with published work, as well as a rigorous quantitative framework with high quality state-of-the-art detection apparatus in use in the experimental nuclear physics community.

  18. Study of medical isotope production facility stack emissions and noble gas isotopic signature using automatic gamma-spectra analysis platform

    NASA Astrophysics Data System (ADS)

    Zhang, Weihua; Hoffmann, Emmy; Ungar, Kurt; Dolinar, George; Miley, Harry; Mekarski, Pawel; Schrom, Brian; Hoffman, Ian; Lawrie, Ryan; Loosz, Tom

    2013-04-01

    The nuclear industry emissions of the four CTBT (Comprehensive Nuclear-Test-Ban Treaty) relevant radioxenon isotopes are unavoidably detected by the IMS along with possible treaty violations. Another civil source of radioxenon emissions which contributes to the global background is radiopharmaceutical production companies. To better understand the source terms of these background emissions, a joint project between HC, ANSTO, PNNL and CRL was formed to install real-time detection systems to support 135Xe, 133Xe, 131mXe and 133mXe measurements at the ANSTO and CRL 99Mo production facility stacks as well as the CANDU (CANada Deuterium Uranium) primary coolant monitoring system at CRL. At each site, high resolution gamma spectra were collected every 15 minutes using a HPGe detector to continuously monitor a bypass feed from the stack or CANDU primary coolant system as it passed through a sampling cell. HC also conducted atmospheric monitoring for radioxenon at approximately 200 km distant from CRL. A program was written to transfer each spectrum into a text file format suitable for the automatic gamma-spectra analysis platform and then email the file to a server. Once the email was received by the server, it was automatically analysed with the gamma-spectrum software UniSampo/Shaman to perform radionuclide identification and activity calculation for a large number of gamma-spectra in a short period of time (less than 10 seconds per spectrum). The results of nuclide activity together with other spectrum parameters were saved into the Linssi database. This database contains a large amount of radionuclide information which is a valuable resource for the analysis of radionuclide distribution within the noble gas fission product emissions. The results could be useful to identify the specific mechanisms of the activity release. The isotopic signatures of the various radioxenon species can be determined as a function of release time. Comparison of 133mXe and 133Xe activity

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

    PubMed

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

    2013-12-01

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

  20. High resolution and high precision on line isotopic analysis of Holocene and glacial ice performed in the field

    NASA Astrophysics Data System (ADS)

    Gkinis, V.; Popp, T. J.; Johnsen, S. J.; Blunier, T.; Bigler, M.; Stowasser, C.; Schüpbach, S.; Leuenberger, D.

    2010-12-01

    Ice core records as obtained from polar ice caps provide a wealth of paleoclimatic information. One of the main features of ice cores is their potential for high temporal resolution. The isotopic signature of the ice, expressed through the relative abundances of the two heavy isotopologues H218O and HD16O, is a widely used proxy for the reconstruction of past temperature and accumulation. One step further the combined information obtained from these two isotopologues, commonly referred to as the deuterium excess, can be utilized to infer additional information about the source of the precipitated moisture. Until very recently isotopic analysis of polar ice was performed with isotope Ratio Mass Spectrometry (IRMS) in a discrete fashion resulting in a high workload related to the preparation of samples. Most important though the available temporal resolution of the ice core was in many cases not fully exploited. In order to overcome these limitations we have developed a system that interfaces a commercially available IR laser cavity ring-down spectrometer tailored for water isotope analysis to a stream of liquid water as extracted from a continuously melted ice rod. The system offers the possibility for simultaneous δ18O and δD analysis with a sample requirement of approximately 0.1 ml/min. The system has been deployed in the field during the NEEM ice core drilling project on 2009 and 2010. In this study we present actual on line measurements of Holocene and glacial ice. We also discuss how parameters as the melt rate, acquisition rate and integration time affect the obtained precision and resolution and we describe data analysis techniques that can improve these last two parameters. By applying spectral methods we are able to quantify the smoothing effects imposed by diffusion of the sample in the sample transfer lines and the optical cavity of the instrument. We demonstrate that with an acquisition rate of 0.2 Hz we are able to obtain a precision of 0.5‰ and 0

  1. Neutron Activation Analysis and Product Isotope Inventory Code System.

    1990-10-31

    Version 00 NAC was designed to predict the neutron-induced gamma-ray radioactivity for a wide variety of composite materials. The NAC output includes the input data, a list of all reactions for each constituent element, and the end-of-irradiation disintegration rates for each reaction. NAC also compiles a product isotope inventory containing the isotope name, the disintegration rate, the gamma-ray source strength, and the absorbed dose rate at 1 meter from an unshielded point source. The inducedmore » activity is calculated as a function of irradiation and decay times; the effect of cyclic irradiation can also be calculated.« less

  2. Application of dual carbon-bromine isotope analysis for investigating abiotic transformations of tribromoneopentyl alcohol (TBNPA).

    PubMed

    Kozell, Anna; Yecheskel, Yinon; Balaban, Noa; Dror, Ishai; Halicz, Ludwik; Ronen, Zeev; Gelman, Faina

    2015-04-01

    Many of polybrominated organic compounds, used as flame retardant additives, belong to the group of persistent organic pollutants. Compound-specific isotope analysis is one of the potential analytical tools for investigating their fate in the environment. However, the isotope effects associated with transformations of brominated organic compounds are still poorly explored. In the present study, we investigated carbon and bromine isotope fractionation during degradation of tribromoneopentyl alcohol (TBNPA), one of the widely used flame retardant additives, in three different chemical processes: transformation in aqueous alkaline solution (pH 8); reductive dehalogenation by zero-valent iron nanoparticles (nZVI) in anoxic conditions; oxidative degradation by H2O2 in the presence of CuO nanoparticles (nCuO). Two-dimensional carbon-bromine isotope plots (δ(13)C/Δ(81)Br) for each reaction gave different process-dependent isotope slopes (Λ(C/Br)): 25.2 ± 2.5 for alkaline hydrolysis (pH 8); 3.8 ± 0.5 for debromination in the presence of nZVI in anoxic conditions; ∞ in the case of catalytic oxidation by H2O2 with nCuO. The obtained isotope effects for both elements were generally in agreement with the values expected for the suggested reaction mechanisms. The results of the present study support further applications of dual carbon-bromine isotope analysis as a tool for identification of reaction pathway during transformations of brominated organic compounds in the environment.

  3. Comprehensive study of carbon and oxygen isotopic compositions, trace element abundances, and cathodoluminescence intensities of calcite in the Murchison CM chondrite

    NASA Astrophysics Data System (ADS)

    Fujiya, Wataru; Sugiura, Naoji; Marrocchi, Yves; Takahata, Naoto; Hoppe, Peter; Shirai, Kotaro; Sano, Yuji; Hiyagon, Hajime

    2015-07-01

    We have performed in situ analyses of C and O isotopic compositions, trace element concentrations, and cathodoluminescence (CL) intensities on calcite in Murchison, a weakly altered CM chondrite. We found that the trace element (Mg, Mn, and Fe) concentrations are heterogeneous within single calcite grains. Grain to grain heterogeneity is even more pronounced. The analyzed calcite grains can be separated into two distinct types with respect to their C isotopic ratios, trace element concentrations, and CL characteristics: Calcite grains with higher δ13CPDB values (∼75‰) have low trace element concentrations and uniformly dark CL, while grains with lower δ13C values (∼35‰) have higher trace element concentrations and CL zoning. In contrast to the C isotopic ratios, O isotopic ratios are similar for both types of calcites (δ18OSMOW ∼ 34‰). The O isotopic ratios, trace element concentrations, and CL characteristics provide no evidence for C-isotope evolution in fluids from a single C reservoir by Rayleigh-type isotope fractionation (i.e., removal of C-bearing gaseous species). Also, it seems difficult to explain the O and C isotopic compositions of the two types of calcites by their formation at different temperatures from a single fluid. Instead, the δ13C variation suggests the presence of at least two C reservoirs with different isotopic ratios in the aqueous fluids from which the calcites precipitated. The C reservoirs with lower δ13C values are likely to be organic matter. The same holds for the C reservoirs with higher δ13C values which might have significant contributions from the 13C-enriched grains identified in meteoritic insoluble organic matter. Thermodynamic calculations show that calcite with lower Fe concentrations formed under more reduced conditions than calcite with higher Fe concentrations. If this is the case, the 13C-rich organic grains may have been destroyed and dissolved in the fluids under more reduced conditions than other

  4. Compound-specific isotope analysis of diesel fuels in a forensic investigation

    PubMed Central

    Muhammad, Syahidah A.; Frew, Russell D.; Hayman, Alan R.

    2015-01-01

    Compound-specific isotope analysis (CSIA) offers great potential as a tool to provide chemical evidence in a forensic investigation. Many attempts to trace environmental oil spills were successful where isotopic values were particularly distinct. However, difficulties arise when a large data set is analyzed and the isotopic differences between samples are subtle. In the present study, discrimination of diesel oils involved in a diesel theft case was carried out to infer the relatedness of the samples to potential source samples. This discriminatory analysis used a suite of hydrocarbon diagnostic indices, alkanes, to generate carbon and hydrogen isotopic data of the compositions of the compounds which were then processed using multivariate statistical analyses to infer the relatedness of the data set. The results from this analysis were put into context by comparing the data with the δ13C and δ2H of alkanes in commercial diesel samples obtained from various locations in the South Island of New Zealand. Based on the isotopic character of the alkanes, it is suggested that diesel fuels involved in the diesel theft case were distinguishable. This manuscript shows that CSIA when used in tandem with multivariate statistical analysis provide a defensible means to differentiate and source-apportion qualitatively similar oils at the molecular level. This approach was able to overcome confounding challenges posed by the near single-point source of origin, i.e., the very subtle differences in isotopic values between the samples. PMID:25774366

  5. Compound-Specific Isotope Analysis of Diesel Fuels in a Forensic Investigation

    NASA Astrophysics Data System (ADS)

    Muhammad, Syahidah; Frew, Russell; Hayman, Alan

    2015-02-01

    Compound-specific isotope analysis (CSIA) offers great potential as a tool to provide chemical evidence in a forensic investigation. Many attempts to trace environmental oil spills were successful where isotopic values were particularly distinct. However, difficulties arise when a large data set is analyzed and the isotopic differences between samples are subtle. In the present study, discrimination of diesel oils involved in a diesel theft case was carried out to infer the relatedness of the samples to potential source samples. This discriminatory analysis used a suite of hydrocarbon diagnostic indices, alkanes, to generate carbon and hydrogen isotopic data of the compositions of the compounds which were then processed using multivariate statistical analyses to infer the relatedness of the data set. The results from this analysis were put into context by comparing the data with the δ13C and δ2H of alkanes in commercial diesel samples obtained from various locations in the South Island of New Zealand. Based on the isotopic character of the alkanes, it is suggested that diesel fuels involved in the diesel theft case were distinguishable. This manuscript shows that CSIA when used in tandem with multivariate statistical analysis provide a defensible means to differentiate and source-apportion qualitatively similar oils at the molecular level. This approach was able to overcome confounding challenges posed by the near single-point source of origin i.e. the very subtle differences in isotopic values between the samples.

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

    SciTech Connect

    Piper, Stephen C; Keeling, Ralph F

    2012-01-03

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

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

    SciTech Connect

    Duffin, Andrew M.; Springer, Kellen WE; Ward, Jesse D.; Jarman, Kenneth D.; Robinson, John W.; Endres, Mackenzie C.; Hart, Garret L.; Gonzalez, Jhanis J.; Oropeza, Dayana; Russo, Richard; Willingham, David G.; Naes, Benjamin E.; Fahey, Albert J.; Eiden, Gregory C.

    2015-02-06

    We have utilized femtosecond laser ablation coupled to multi-collector inductively couple plasma mass spectrometry to measure the uranium isotopic content of NIST 61x (x=0,2,4,6) glasses. The uranium content of these glasses is a linear two-component mixing between isotopically natural uranium and the isotopically depleted spike used in preparing the glasses. Laser ablation results match extremely well, generally within a few ppm, with solution analysis following sample dissolution and chemical separation. In addition to isotopic data, sample utilization efficiency measurements indicate that over 1% of ablated uranium atoms reach a mass spectrometer detector, making this technique extremely efficient. Laser sampling also allows for spatial analysis and our data indicate that rare uranium concentration inhomogeneities exist in NIST 616 glass.

  8. Quantifying plant phenotypes with isotopic labeling and metabolic flux analysis

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Analyses of metabolic flux using stable isotopes in plants have traditionally been restricted to tissues with presumed homogeneous cell populations such as developing seeds, cell suspensions, or cultured roots and root tips. It is now possible to describe these and other more complex tissues such a...

  9. STABLE CHLORINE ISOTOPE ANALYSIS OF CHLORINATED ORGANIC CONTAMINANTS

    EPA Science Inventory

    The biogeochemical cycling of chlorinated organic contaminants in the environment is often difficult to understand because of the complex distributions of these compounds and variability of sources. To address these issues from an isotopic perspective, we have measured the, 37Cl...

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

    SciTech Connect

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

    2014-06-20

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

  11. 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.

  12. Carbon and Sulfur Isotopic Composition of Yellowknife Bay Sediments: Measurements by the Sample Analysis at Mars (SAM) Quadrupole Mass Spectrometer

    NASA Technical Reports Server (NTRS)

    Franz, H. B.; Mahaffy, P. R.; Stern, J. C.; Eigenbrode, J. L.; Steele, A.; Ming, D. W.; McAdam, A. C.; Freissinet, C.; Glavin, D. P.; Archer, P. D.; Brunner, A. E.; Grotzinger,J. P.; Jones, J. H.; Leshin, L. A.; Miller, K.; Morris, R. V.; Navarro-Gonzalez, R.; Niles, P. B.; Owen, T. C.; Summons, R. E.; Sutter, B.; Webster, C. R.

    2014-01-01

    Since landing at Gale Crater in Au-gust 2012, the Sample Analysis at Mars (SAM) instru-ment suite on the Mars Science Laboratory (MSL) “Curiosity” rover has analyzed solid samples from the martian regolith in three locations, beginning with a scoop of aeolian deposits from the Rocknest (RN) sand shadow. Curiosity subsequently traveled to Yellowknife Bay, where SAM analyzed samples from two separate holes drilled into the Sheepbed Mudstone, designated John Klein (JK) and Cumberland (CB). Evolved gas analysis (EGA) of all samples revealed the presence of H2O as well as O-, C- and S-bearing phas-es, in most cases at abundances below the detection limit of the CheMin instrument. In the absence of definitive mineralogical identification by CheMin, SAM EGA data can help provide clues to the mineralogy of volatile-bearing phases through examination of tem-peratures at which gases are evolved from solid sam-ples. In addition, the isotopic composition of these gas-es may be used to identify possible formation scenarios and relationships between phases. Here we report C and S isotope ratios for CO2 and SO2 evolved from the JK and CB mudstone samples as measured with SAM’s quadrupole mass spectrometer (QMS) and draw com-parisons to RN.

  13. Rapid Determination of Bacterial Abundance, Biovolume, Morphology, and Growth by Neural Network-Based Image Analysis

    PubMed Central

    Blackburn, Nicholas; Hagström, Åke; Wikner, Johan; Cuadros-Hansson, Rocio; Bjørnsen, Peter Koefoed

    1998-01-01

    Annual bacterial plankton dynamics at several depths and locations in the Baltic Sea were studied by image analysis. Individual bacteria were classified by using an artificial neural network which also effectively identified nonbacterial objects. Cell counts and frequencies of dividing cells were determined, and the data obtained agreed well with visual observations and previously published values. Cell volumes were measured accurately by comparison with bead standards. The survey included 690 images from a total of 138 samples. Each image contained approximately 200 bacteria. The images were analyzed automatically at a rate of 100 images per h. Bacterial abundance exhibited coherent patterns with time and depth, and there were distinct subsurface peaks in the summer months. Four distinct morphological classes were resolved by the image analyzer, and the dynamics of each could be visualized. The bacterial growth rates estimated from frequencies of dividing cells were different from the bacterial growth rates estimated by the thymidine incorporation method. With minor modifications, the image analysis technique described here can be used to analyze other planktonic classes. PMID:9726867

  14. Stable isotope analysis of dissolved carbon species of Hot Lake, WA

    NASA Astrophysics Data System (ADS)

    Courtney, S.; Moran, J.; Cory, A. B.; Lindemann, S. R.; Fredrickson, J.

    2013-12-01

    Hot Lake is a hypersaline, meromictic lake in north-central Washington. The lake is epsomitic, with seasonably-variable salinity (.2 to 2 M magnesium sulfate) and produces carbonates and salt precipitates. The maximum depth of the lake is around 2.5 m, and below a thermocline there is intense solar heat retention in the monolimnion, often exceeding 50°C. Despite these extreme and variable conditions, a microbial mat of up to 1.5 cm thick thrives annually in Hot Lake. The mat is widespread throughout the lake at water depths (during our experiments) ranging from 60cm-140cm. It is comprised of a variety of cyanobacteria along with other autotrophic and heterotrophic bacteria. These populations are visibly stratified with four consistent laminae displaying differences in bacterial pigmentation. Many of the layers contain carbonate species, but the full relationship between the mat and the carbonate crystallization is not known. We are studying the microbial interactions and carbon cycling of the mat communities, using stable isotope analysis of the mat and the lake water, both in situ and ex situ. We are exploring the incorporation and movement of carbon in the mat, spatially and temporally, to understand the fixation mechanisms and metabolic processes at play in this environment. This was done primarily using stable isotope ratio mass spectrometry. The focus of this work is on the study and measurement of dissolved organic and inorganic carbon using a GasBench and IRMS setup, following methods adapted from Lang et al. (2012). To account for the unique chemistry of Hot Lake, trials on the effects of oxidation conditions and salinity were done on lab-synthesized samples to compare to Hot Lake results. The majority of lake water analyses were done in conjunction with a stable isotope probing (SIP) experiment, completed during two 24-hour periods at Hot Lake in June and July of 2013. The SIP experiments included ex situ incubations (in separate glass containers on the

  15. Sources of organic matter in Ria Formosa revealed by stable isotope analysis

    NASA Astrophysics Data System (ADS)

    Machás, Raquel; Santos, Rui

    1999-07-01

    The aim of this study is to assess the major sources of organic matter for macroconsumers in the Ria Formosa tidal lagoon. The C, S and N isotopic natural abundances of abundant primary producers of particulate organic matter (POM) and Mytilus galloprovincialis muscle and digestive gland were analysed. The chlorophyll a (Chl a), the suspended particulate matter (SPM) and the POM were measured along the Faro-Olhão channel. The range of variation of stable isotope values among primary producers in Ria Formosa was low suggesting difficulties in the assessment of their relative contribution to higher levels of the food web. Chl a values decreased from outer station to inner station, while SPM and POM values increased. The multiple isotope approach illustrates that POM values along the Faro-Olhão channel, may result from a mixture of upland plants, benthic plants and phytoplankton. Mussel values indicate a selective diet of benthic macrophytes and phytoplankton, with the relative proportions of each determined by the location in the channel. During winters, the upland plants may be an important source of organic matter in the inner lagoon while phytoplankton was an important source of organic matter in the outer lagoon.

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

    SciTech Connect

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

    1995-03-01

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

  17. Quantifying plant phenotypes with isotopic labeling & metabolic flux analysis.

    PubMed

    Allen, Doug K

    2016-02-01

    Analyses of metabolic flux using stable isotopes in plants have traditionally been restricted to tissues with presumed homogeneous cell populations and long metabolic steady states such as developing seeds, cell suspensions, or cultured roots and root tips. It is now possible to describe these and other metabolically more dynamic tissues such as leaves in greater detail using novel methods in mass spectrometry, isotope labeling strategies, and transient labeling-based flux analyses. Such studies are necessary for a systems level description of plant function that more closely represents biological reality, and provides insights into the genes that will need to be modified as natural resources become ever more limited and environments change. PMID:26613198

  18. The conflict between cheetahs and humans on Namibian farmland elucidated by stable isotope diet analysis.

    PubMed

    Voigt, Christian C; Thalwitzer, Susanne; Melzheimer, Jörg; Blanc, Anne-Sophie; Jago, Mark; Wachter, Bettina

    2014-01-01

    Large areas of Namibia are covered by farmland, which is also used by game and predator species. Because it can cause conflicts with farmers when predators, such as cheetahs (Acinonyx jubatus), hunt livestock, we assessed whether livestock constitutes a significant part of the cheetah diet by analysing the stable isotope composition of blood and tissue samples of cheetahs and their potential prey species. According to isotopic similarities, we defined three isotopic categories of potential prey: members of a C4 food web with high δ15N values (gemsbok, cattle, springhare and guinea fowl) and those with low δ15N values (hartebeest, warthog), and members of a C3 food web, namely browsers (eland, kudu, springbok, steenbok and scrub hare). We quantified the trophic discrimination of heavy isotopes in cheetah muscle in 9 captive individuals and measured an enrichment for 15N (3.2‰) but not for 13C in relation to food. We captured 53 free-ranging cheetahs of which 23 were members of groups. Cheetahs of the same group were isotopically distinct from members of other groups, indicating that group members shared their prey. Solitary males (n = 21) and males in a bachelor groups (n = 11) fed mostly on hartebeest and warthogs, followed by browsers in case of solitary males, and by grazers with high δ15N values in case of bachelor groups. Female cheetahs (n = 9) predominantly fed on browsers and used also hartebeest and warthogs. Mixing models suggested that the isotopic prey category that included cattle was only important, if at all, for males living in bachelor groups. Stable isotope analysis of fur, muscle, red blood cells and blood plasma in 9 free-ranging cheetahs identified most individuals as isotopic specialists, focussing on isotopically distinct prey categories as their food. PMID:25162403

  19. Carbon and chlorine isotope analysis to identify abiotic degradation pathways of 1,1,1-trichloroethane.

    PubMed

    Palau, Jordi; Shouakar-Stash, Orfan; Hunkeler, Daniel

    2014-12-16

    This study investigates dual C-Cl isotope fractionation during 1,1,1-TCA transformation by heat-activated persulfate (PS), hydrolysis/dehydrohalogenation (HY/DH) and Fe(0). Compound-specific chlorine isotope analysis of 1,1,1-TCA was performed for the first time, and transformation-associated isotope fractionation ε bulk C and ε bulk Cl values were -4.0 ± 0.2‰ and no chlorine isotope fractionation with PS, -1.6 ± 0.2‰ and -4.7 ± 0.1‰ for HY/DH, -7.8 ± 0.4‰ and -5.2 ± 0.2‰ with Fe(0). Distinctly different dual isotope slopes (Δδ13C/Δδ37Cl): ∞ with PS, 0.33 ± 0.04 for HY/DH and 1.5 ± 0.1 with Fe(0) highlight the potential of this approach to identify abiotic degradation pathways of 1,1,1-TCA in the field. The trend observed with PS agreed with a C-H bond oxidation mechanism in the first reaction step. For HY/DH and Fe(0) pathways, different slopes were obtained although both pathways involve cleavage of a C-Cl bond in their initial reaction step. In contrast to the expected larger primary carbon isotope effects relative to chlorine for C-Cl bond cleavage, ε bulk C < ε bulk Cl was observed for HY/DH and in a similar range for reduction by Fe(0), suggesting the contribution of secondary chlorine isotope effects. Therefore, different magnitude of secondary chlorine isotope effects could at least be partly responsible for the distinct slopes between HY/DH and Fe(0) pathways. Following this dual isotope approach, abiotic transformation processes can unambiguously be identified and quantified.

  20. Degradation and Volatilization of Chlorofluorocarbons in Contaminated Groundwater Explored by Stable Carbon Isotope Analysis

    NASA Astrophysics Data System (ADS)

    Horst, A.; Lacrampe-Couloume, G.; Sherwood Lollar, B.

    2015-12-01

    Chlorofluorocarbons (CFCs) are ozone depleting compounds whose production was phased out by the regulations of the Montreal Protocol (1987). Accidental release and disposal also led to contamination of groundwater at many locations, however, and this legacy persists. Although very stable, CFCs may degrade via abiotic and biotic pathways. Quantification of the degree of transformation of CFCs has been challenging due to other processes such as dilution, sorption and volatilization. Compound specific stable carbon isotope analysis (CSIA) has been successfully applied for a variety of priority pollutants to distinguish degradation from other processes and to quantify transformation rates. A Purge & Trap - CSIA method developed in our lab was applied to determine the stable carbon isotopic signature of CFCs and HCFCs (hydrochlorofluorocarbons) in groundwater samples from a contaminated site. Preliminary results suggest that degradation of CFCs and HCFCs may result in enriched δ13C values, consistent with fractionation during bond breakage as has been reported for many other hydrocarbon pollutants. The effect of volatile loss during sampling on the isotopic signatures of CFCs was examined in laboratory experiments. Volatilization from pure phase CFCs showed a small inverse isotope effect during open system volatilization, opposite to the normal isotope effect generally observed during biodegradation. For volatilization of CFCs dissolved in water a much smaller isotope effect was observed. An important result from this work is that any volatile loss may introduce only a small change in CFC isotopic signatures in groundwater, and importantly, due to the opposite direction of isotope effects associated with volatilization versus degradation, any effects of volatile loss on the isotopic signatures cannot be confused with transformation of CFCs. At most, volatilization might contribute to a conservative estimate of the extent of degradation.

  1. Degradation and Volatilization of Chlorofluorocarbons in Contaminated Groundwater Explored by Stable Carbon Isotope Analysis

    NASA Astrophysics Data System (ADS)

    Hangx, S.; Pijnenburg, R. P.; Niemeijer, A. R.; Bakker, E.; Samuelson, J. E.; Spiers, C. J.

    2014-12-01

    Chlorofluorocarbons (CFCs) are ozone depleting compounds whose production was phased out by the regulations of the Montreal Protocol (1987). Accidental release and disposal also led to contamination of groundwater at many locations, however, and this legacy persists. Although very stable, CFCs may degrade via abiotic and biotic pathways. Quantification of the degree of transformation of CFCs has been challenging due to other processes such as dilution, sorption and volatilization. Compound specific stable carbon isotope analysis (CSIA) has been successfully applied for a variety of priority pollutants to distinguish degradation from other processes and to quantify transformation rates. A Purge & Trap - CSIA method developed in our lab was applied to determine the stable carbon isotopic signature of CFCs and HCFCs (hydrochlorofluorocarbons) in groundwater samples from a contaminated site. Preliminary results suggest that degradation of CFCs and HCFCs may result in enriched δ13C values, consistent with fractionation during bond breakage as has been reported for many other hydrocarbon pollutants. The effect of volatile loss during sampling on the isotopic signatures of CFCs was examined in laboratory experiments. Volatilization from pure phase CFCs showed a small inverse isotope effect during open system volatilization, opposite to the normal isotope effect generally observed during biodegradation. For volatilization of CFCs dissolved in water a much smaller isotope effect was observed. An important result from this work is that any volatile loss may introduce only a small change in CFC isotopic signatures in groundwater, and importantly, due to the opposite direction of isotope effects associated with volatilization versus degradation, any effects of volatile loss on the isotopic signatures cannot be confused with transformation of CFCs. At most, volatilization might contribute to a conservative estimate of the extent of degradation.

  2. The conflict between cheetahs and humans on Namibian farmland elucidated by stable isotope diet analysis.

    PubMed

    Voigt, Christian C; Thalwitzer, Susanne; Melzheimer, Jörg; Blanc, Anne-Sophie; Jago, Mark; Wachter, Bettina

    2014-01-01

    Large areas of Namibia are covered by farmland, which is also used by game and predator species. Because it can cause conflicts with farmers when predators, such as cheetahs (Acinonyx jubatus), hunt livestock, we assessed whether livestock constitutes a significant part of the cheetah diet by analysing the stable isotope composition of blood and tissue samples of cheetahs and their potential prey species. According to isotopic similarities, we defined three isotopic categories of potential prey: members of a C4 food web with high δ15N values (gemsbok, cattle, springhare and guinea fowl) and those with low δ15N values (hartebeest, warthog), and members of a C3 food web, namely browsers (eland, kudu, springbok, steenbok and scrub hare). We quantified the trophic discrimination of heavy isotopes in cheetah muscle in 9 captive individuals and measured an enrichment for 15N (3.2‰) but not for 13C in relation to food. We captured 53 free-ranging cheetahs of which 23 were members of groups. Cheetahs of the same group were isotopically distinct from members of other groups, indicating that group members shared their prey. Solitary males (n = 21) and males in a bachelor groups (n = 11) fed mostly on hartebeest and warthogs, followed by browsers in case of solitary males, and by grazers with high δ15N values in case of bachelor groups. Female cheetahs (n = 9) predominantly fed on browsers and used also hartebeest and warthogs. Mixing models suggested that the isotopic prey category that included cattle was only important, if at all, for males living in bachelor groups. Stable isotope analysis of fur, muscle, red blood cells and blood plasma in 9 free-ranging cheetahs identified most individuals as isotopic specialists, focussing on isotopically distinct prey categories as their food.

  3. The Conflict between Cheetahs and Humans on Namibian Farmland Elucidated by Stable Isotope Diet Analysis

    PubMed Central

    Voigt, Christian C.; Thalwitzer, Susanne; Melzheimer, Jörg; Blanc, Anne-Sophie; Jago, Mark; Wachter, Bettina

    2014-01-01

    Large areas of Namibia are covered by farmland, which is also used by game and predator species. Because it can cause conflicts with farmers when predators, such as cheetahs (Acinonyx jubatus), hunt livestock, we assessed whether livestock constitutes a significant part of the cheetah diet by analysing the stable isotope composition of blood and tissue samples of cheetahs and their potential prey species. According to isotopic similarities, we defined three isotopic categories of potential prey: members of a C4 food web with high δ15N values (gemsbok, cattle, springhare and guinea fowl) and those with low δ15N values (hartebeest, warthog), and members of a C3 food web, namely browsers (eland, kudu, springbok, steenbok and scrub hare). We quantified the trophic discrimination of heavy isotopes in cheetah muscle in 9 captive individuals and measured an enrichment for 15N (3.2‰) but not for 13C in relation to food. We captured 53 free-ranging cheetahs of which 23 were members of groups. Cheetahs of the same group were isotopically distinct from members of other groups, indicating that group members shared their prey. Solitary males (n = 21) and males in a bachelor groups (n = 11) fed mostly on hartebeest and warthogs, followed by browsers in case of solitary males, and by grazers with high δ15N values in case of bachelor groups. Female cheetahs (n = 9) predominantly fed on browsers and used also hartebeest and warthogs. Mixing models suggested that the isotopic prey category that included cattle was only important, if at all, for males living in bachelor groups. Stable isotope analysis of fur, muscle, red blood cells and blood plasma in 9 free-ranging cheetahs identified most individuals as isotopic specialists, focussing on isotopically distinct prey categories as their food. PMID:25162403

  4. Assessing connectivity of estuarine fishes based on stable isotope ratio analysis

    NASA Astrophysics Data System (ADS)

    Herzka, Sharon Z.

    2005-07-01

    Assessing connectivity is fundamental to understanding the population dynamics of fishes. I propose that isotopic analyses can greatly contribute to studies of connectivity in estuarine fishes due to the high diversity of isotopic signatures found among estuarine habitats and the fact that variations in isotopic composition at the base of a food web are reflected in the tissues of consumers. Isotopic analysis can be used for identifying nursery habitats and estimating their contribution to adult populations. If movement to a new habitat is accompanied by a shift to foods of distinct isotopic composition, recent immigrants and residents can be distinguished based on their isotopic ratios. Movement patterns thus can be reconstructed based on information obtained from individuals. A key consideration is the rate of isotopic turnover, which determines the length of time that an immigrant to a given habitat will be distinguishable from a longtime resident. A literature survey indicated that few studies have measured turnover rates in fishes and that these have focused on larvae and juveniles. These studies reveal that biomass gain is the primary process driving turnover rates, while metabolic turnover is either minimal or undetectable. Using a simple dilution model and biomass-specific growth rates, I estimated that young fishes with fast growth rates will reflect the isotopic composition of a new diet within days or weeks. Older or slower-growing individuals may take years or never fully equilibrate. Future studies should evaluate the factors that influence turnover rates in fishes during various stages of the life cycle and in different tissues, as well as explore the potential for combining stable isotope and otolith microstructure analyses to examine the relationship between demographic parameters, movement and connectivity.

  5. Compound-Specific Isotope Analysis of Amino Acids for Stardust-Returned Samples

    NASA Technical Reports Server (NTRS)

    Cook, Jamie; Elsila, Jamie E.; Stern J. C.; Glavin, D. P.; Dworkin, J. P.

    2008-01-01

    Significant portions of the early Earth's prebiotic organic inventory , including amino acids, could have been delivered to the Earth's sur face by comets and their fragments. Analysis of comets via spectrosc opic observations has identified many organic molecules, including me thane, ethane, arnmonia, cyanic acid, formaldehyde, formamide, acetal ehyde, acetonitrile, and methanol. Reactions between these identifie d molecules could allow the formation of more complex organics such a s amino acids. Isotopic analysis could reveal whether an extraterrest rial signature is present in the Stardust-exposed amines and amino ac ids. Although bulk isotopic analysis would be dominated by the EACA contaminant's terrestrial signature, compoundspecific isotope analysi s (CSIA) could determine the signature of each of the other individua l amines. Here, we report on progress made towards CSIA of the amino acids glycine and EACA in Stardustreturned samples.

  6. Exoproteome analysis reveals higher abundance of proteins linked to alkaline stress in persistent Listeria monocytogenes strains.

    PubMed

    Rychli, Kathrin; Grunert, Tom; Ciolacu, Luminita; Zaiser, Andreas; Razzazi-Fazeli, Ebrahim; Schmitz-Esser, Stephan; Ehling-Schulz, Monika; Wagner, Martin

    2016-02-01

    The foodborne pathogen Listeria monocytogenes, responsible for listeriosis a rare but severe infection disease, can survive in the food processing environment for month or even years. So-called persistent L. monocytogenes strains greatly increase the risk of (re)contamination of food products, and are therefore a great challenge for food safety. However, our understanding of the mechanism underlying persistence is still fragmented. In this study we compared the exoproteome of three persistent strains with the reference strain EGDe under mild stress conditions using 2D differential gel electrophoresis. Principal component analysis including all differentially abundant protein spots showed that the exoproteome of strain EGDe (sequence type (ST) 35) is distinct from that of the persistent strain R479a (ST8) and the two closely related ST121 strains 4423 and 6179. Phylogenetic analyses based on multilocus ST genes showed similar grouping of the strains. Comparing the exoproteome of strain EGDe and the three persistent strains resulted in identification of 22 differentially expressed protein spots corresponding to 16 proteins. Six proteins were significantly increased in the persistent L. monocytogenes exoproteomes, among them proteins involved in alkaline stress response (e.g. the membrane anchored lipoprotein Lmo2637 and the NADPH dehydrogenase NamA). In parallel the persistent strains showed increased survival under alkaline stress, which is often provided during cleaning and disinfection in the food processing environments. In addition, gene expression of the proteins linked to stress response (Lmo2637, NamA, Fhs and QoxA) was higher in the persistent strain not only at 37 °C but also at 10 °C. Invasion efficiency of EGDe was higher in intestinal epithelial Caco2 and macrophage-like THP1 cells compared to the persistent strains. Concurrently we found higher expression of proteins involved in virulence in EGDe e.g. the actin-assembly-inducing protein ActA and the

  7. Isotopic analysis of Bothrops atrox in Amazonian forest

    NASA Astrophysics Data System (ADS)

    Martinez, M. G.; Silva, A. M.; Chalkidis, H.; de Oliveira Júnior, R. C.; Camargo, P. B.

    2012-12-01

    The poisoning of snakes is considered a public health problem, especially in populations from rural areas of tropical and subtropical countries. In Brazil, the 26,000 snakebites, 90% are of the genus Bothrops, and Bothrops atrox species predominant in the Amazon region including all the Brazilian Amazon. Research shows that using stable isotopes, we can verify the isotopic composition of tissues of animals that depend mainly on food, water ingested and inhaled gases. For this study, samples taken from Bothrops atrox (B. atrox), in forest using pitfall traps and fall ("Pitt-fall traps with drift fence"). The analyzes were performed by mass spectrometry, where the analytical error is 0.3‰ for carbon and 0.5‰ to nitrogen. The results of the forest animals are significantly different from results of animal vivarium. The average values of the tissues and venoms of snakes of the forest for carbon-13 and nitrogen-15 are: δ13C = -24.68‰ and δ15N = 14.22‰ and mean values of tissue and poisons snakes vivarium (Instituto Butantan) to carbon-13 and nitrogen-15 are δ13C = -20.47‰ and δ15N = 8.36‰, with a significantly different due to different sources of food animals. Based on all results isotopic δ13C and δ15N, we can suggest that changes as the power of the serpent, (nature and captivity), changes occur in relation to diet and environment as the means of the isotopic data are quite distinct, showing that these changes can also cause metabolic changes in the body of the animal itself and the different periods of turnover of each tissue analyzed.

  8. VARIATION IN JUVENILE COHO SALMON SUMMER ABUNDANCE: HIERARCHICAL ANALYSIS OF HABITAT EFFECTS

    EPA Science Inventory

    Varying habitat conditions found across a stream network during the summer months may limit the abundance of salmonids such as coho (Oncorhynchus kisutch). We examined the abundance of juvenile coho salmon across a stream network in an Oregon coast range basin from 2002 through ...

  9. Is it really organic?--multi-isotopic analysis as a tool to discriminate between organic and conventional plants.

    PubMed

    Laursen, K H; Mihailova, A; Kelly, S D; Epov, V N; Bérail, S; Schjoerring, J K; Donard, O F X; Larsen, E H; Pedentchouk, N; Marca-Bell, A D; Halekoh, U; Olesen, J E; Husted, S

    2013-12-01

    Novel procedures for analytical authentication of organic plant products are urgently needed. Here we present the first study encompassing stable isotopes of hydrogen, carbon, nitrogen, oxygen, magnesium and sulphur as well as compound-specific nitrogen and oxygen isotope analysis of nitrate for discrimination of organically and conventionally grown plants. The study was based on wheat, barley, faba bean and potato produced in rigorously controlled long-term field trials comprising 144 experimental plots. Nitrogen isotope analysis revealed the use of animal manure, but was unable to discriminate between plants that were fertilised with synthetic nitrogen fertilisers or green manures from atmospheric nitrogen fixing legumes. This limitation was bypassed using oxygen isotope analysis of nitrate in potato tubers, while hydrogen isotope analysis allowed complete discrimination of organic and conventional wheat and barley grains. It is concluded, that multi-isotopic analysis has the potential to disclose fraudulent substitutions of organic with conventionally cultivated plants.

  10. Stable isotopic analysis of human diet in the Marianas Archipelago, western Pacific.

    PubMed

    Ambrose, S H; Butler, B M; Hanson, D B; Hunter-Anderson, R L; Krueger, H W

    1997-11-01

    Proportions of marine vs. terrestrial resources in prehistoric human diets in the southern Mariana Islands (Guam, Rota, Saipan), Micronesia, have been estimated by analysis of stable isotope ratios of carbon and nitrogen in bone collagen and of carbon in apatite. The isotopic composition of marine and terrestrial food resources from the Marianas have also been determined. Experimental evidence shows that collagen carbon isotopes mainly reflect those of dietary protein sources and thus overestimate the contribution of marine animal foods. Marine protein consumption apparently ranges from approximately 20% to approximately 50% on these islands. Experiments also demonstrate the carbon isotope ratio of bone apatite carbonate accurately reflects that of the whole diet. Carbonate carbon isotope data suggest some individuals consumed significant amounts of 13C-enriched (C4) plants or seaweeds. Sugar cane is an indigenous C4 crop and seaweeds are eaten throughout the Pacific, but they have not been considered by archaeologists to have been prehistoric dietary staples. Apatite carbon isotope analysis has apparently identified previously unrecognized prehistoric dietary adaptations in the Mariana Islands, but this must be confirmed by archaeobotanical evidence.

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

    PubMed

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

    2011-03-01

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

  12. Re-Os Abundance and Isotope Systematics of Al-undepleted Komatiites in the Kidd-Munro Assemblage: Results From Dundonald Beach, Abitibi Greenstone Belt, Canada

    NASA Astrophysics Data System (ADS)

    Gangopadhyay, A.; Sproule, R. A.; Walker, R. J.; Lesher, C. M.

    2004-05-01

    Petrographic and geochemical studies suggest that all Precambrian komatiites have undergone variable degrees of weathering, hydrothermal alteration and metamorphism. The effects of these secondary processes in some suites have manifested into large-scale open-system behavior of Re-Os elemental and isotope systematics of whole rocks, which, in some cases, yield inaccurate age and large uncertainties in calculated initial Os isotopic compositions of the emplaced lavas. Thus, some of the previous Os isotopic studies of Precambrian komatiites for which the crystallization ages were known from other radiogenic isotope systematics (e.g., Sm-Nd, Pb-Pb) have relied on Os-rich, relatively well-preserved primary igneous minerals (e.g., olivine and chromite) in order to calculate the initial Os isotopic compositions of the host lavas. Consequently, the whole-rock concentrations of Re and Os in these altered komatiites can neither be used to infer their concentrations in the parental liquids nor their partitioning behaviors during generation and subsequent differentiation of komatiitic magmas. Here we report the Re-Os concentrations of whole rocks from a suite of ca. 2.7-Ga komatiitic rocks from the Dundonald Beach area, part of the Kidd-Munro volcanic assemblage in the Abitibi greenstone belt, Canada. We show that it is possible to calculate the original Re concentrations in the emplaced lavas, and to estimate the gain or loss of Re through comparison of their measured concentrations and those recalculated from their correlations with other incompatible, yet relatively immobile major oxide and trace elements (e.g., Al2O3, Zr, Hf, Yb). We also demonstrate the statistical significance of this scheme of correction with the reduced values of MSWD (by an order of magnitude) and respective uncertainties in slope (by 2-3 orders of magnitude) of regressions involving Re and the immobile elements. Based on the absence of a correlation between loss of Re and the Os isotopic

  13. Assessment of degradation pathways in an aquifer with mixed chlorinated hydrocarbon contamination using stable isotope analysis.

    PubMed

    Hunkeler, Daniel; Aravena, Ramon; Berry-Spark, Karen; Cox, Evan

    2005-08-15

    The demonstration of monitored natural attenuation (MNA) of chlorinated hydrocarbons in groundwater is typically conducted through the evaluation of concentration trends and parent-daughter product relationships along prevailing groundwater flow paths. Unfortunately, at sites contaminated by mixtures of chlorinated ethenes, ethanes, and methanes, the evaluation of MNA by using solely concentration data and parent-daughter relationships can result in erroneous conclusions regarding the degradation mechanisms that are truly active at the site, since many of the daughter products can be derived from multiple parent compounds. Stable carbon isotope analysis was used, in conjunction with concentration data, to clarify and confirm the active degradation pathways at a former waste solvent disposal site where at least 14 different chlorinated hydrocarbons have been detected in the groundwater. The isotope data indicate that TCE, initially believed to be present as a disposed product and/or a PCE dechlorination intermediate, is attributable to dehydrochlorination of 1,1,2,2-PCA. The isotope data further support that vinyl chloride and ethene in the site groundwater result from dichloroelimination of 1,1,2-trichlorethane and 1,2-dichloroethane, respectively, rather than from reductive dechlorination of the chlorinated ethenes PCE, TCE, or 1,2-DCE. The isotope data confirm that the chlorinated ethanes and chlorinated methanes are undergoing significant intrinsic degradation, whereas degradation of the chlorinated ethenes may be limited. In addition to the classical trend of enriched isotope values of the parent compounds with increasing distance associated to biodegradation, shifts of isotope ratios of degradation byproduct in the opposite direction due to mixing of isotopically light byproducts of biodegradation with compounds from the source are shown to be of high diagnostic value. These data underline the value of stable isotope analysis in confirming transformation

  14. Linking cases of illegal shootings of the endangered California condor using stable lead isotope analysis

    SciTech Connect

    Finkelstein, Myra E.; Kuspa, Zeka E.; Welch, Alacia; Eng, Curtis; Clark, Michael; Burnett, Joseph; Smith, Donald R.

    2014-10-15

    Lead poisoning is preventing the recovery of the critically endangered California condor (Gymnogyps californianus) and lead isotope analyses have demonstrated that ingestion of spent lead ammunition is the principal source of lead poisoning in condors. Over an 8 month period in 2009, three lead-poisoned condors were independently presented with birdshot embedded in their tissues, evidencing they had been shot. No information connecting these illegal shooting events existed and the timing of the shooting(s) was unknown. Using lead concentration and stable lead isotope analyses of feathers, blood, and recovered birdshot, we observed that: i) lead isotope ratios of embedded shot from all three birds were measurably indistinguishable from each other, suggesting a common source; ii) lead exposure histories re-constructed from feather analysis suggested that the shooting(s) occurred within the same timeframe; and iii) two of the three condors were lead poisoned from a lead source isotopically indistinguishable from the embedded birdshot, implicating ingestion of this type of birdshot as the source of poisoning. One of the condors was subsequently lead poisoned the following year from ingestion of a lead buckshot (blood lead 556 µg/dL), illustrating that ingested shot possess a substantially greater lead poisoning risk compared to embedded shot retained in tissue (blood lead ∼20 µg/dL). To our knowledge, this is the first study to use lead isotopes as a tool to retrospectively link wildlife shooting events. - Highlights: • We conducted a case-based analysis of illegal shootings of California condors. • Blood and feather Pb isotopes were used to reconstruct the illegal shooting events. • Embedded birdshot from the three condors had the same Pb isotope ratios. • Feather and blood Pb isotopes indicated that the condors were shot in a common event. • Ingested shot causes substantially greater lead exposure compared to embedded shot.

  15. The applicability of MGA method for depleted and natural uranium isotopic analysis in the presence of actinides (232Th, 237Np, 233Pa and 241Am).

    PubMed

    Yücel, Haluk

    2007-11-01

    The multi-group analysis (MGA) method for the determination of uranium isotopic abundances in depleted uranium (DU) and natural uranium (NU) samples is applied in this study. A set of non-destructive gamma-ray measurements of DU and NU samples were performed using a planar Ge detector. The relative abundances of 235U and 238U isotopes were compared with the declared values of the standards. The relative abundance for 235U obtained by MGA for a "clean" DU or NU sample with a content of uranium>1wt% is determined with an accuracy of about +/-5%. However, when several actinides such as 232Th, 237Np, 233Pa and 241Am are present along with uranium isotopes simulating "dirty" DU or NU, it has been observed that MGA method gives erroneous results. The 235U abundance results for the samples were 6-25 times higher than the declared values in the presence of above-mentioned actinides, since MGA is utilized the X-ray and gamma-ray peaks in the 80-130 keV energy region, covering XKalpha and XKbeta regions. After the least-squares fitting of the spectra, it is found that the increases in the intensities of the X-ray and gamma-ray peaks of uranium are remarkably larger in the complex 80-130 keV region. On the other hand, it is observed that the interferences of the actinide peaks are relatively less dominant in the higher gamma-ray region of 130-300 keV. The results imply the need for dirty DU and NU samples that the MGA method should utilize the higher energy gamma-rays (up to 1001 keV of (234m)Pa) combined with lower energies of the spectra, which may be collected in a two detector mode (a planar Ge and a high efficient coaxial Ge).

  16. The applicability of MGA method for depleted and natural uranium isotopic analysis in the presence of actinides (232Th, 237Np, 233Pa and 241Am).

    PubMed

    Yücel, Haluk

    2007-11-01

    The multi-group analysis (MGA) method for the determination of uranium isotopic abundances in depleted uranium (DU) and natural uranium (NU) samples is applied in this study. A set of non-destructive gamma-ray measurements of DU and NU samples were performed using a planar Ge detector. The relative abundances of 235U and 238U isotopes were compared with the declared values of the standards. The relative abundance for 235U obtained by MGA for a "clean" DU or NU sample with a content of uranium>1wt% is determined with an accuracy of about +/-5%. However, when several actinides such as 232Th, 237Np, 233Pa and 241Am are present along with uranium isotopes simulating "dirty" DU or NU, it has been observed that MGA method gives erroneous results. The 235U abundance results for the samples were 6-25 times higher than the declared values in the presence of above-mentioned actinides, since MGA is utilized the X-ray and gamma-ray peaks in the 80-130 keV energy region, covering XKalpha and XKbeta regions. After the least-squares fitting of the spectra, it is found that the increases in the intensities of the X-ray and gamma-ray peaks of uranium are remarkably larger in the complex 80-130 keV region. On the other hand, it is observed that the interferences of the actinide peaks are relatively less dominant in the higher gamma-ray region of 130-300 keV. The results imply the need for dirty DU and NU samples that the MGA method should utilize the higher energy gamma-rays (up to 1001 keV of (234m)Pa) combined with lower energies of the spectra, which may be collected in a two detector mode (a planar Ge and a high efficient coaxial Ge). PMID:17606378

  17. Human baby hair amino acid natural abundance 15N-isotope values are not related to the 15N-isotope values of amino acids in mother's breast milk protein.

    PubMed

    Romek, Katarzyna M; Julien, Maxime; Frasquet-Darrieux, Marine; Tea, Illa; Antheaume, Ingrid; Hankard, Régis; Robins, Richard J

    2013-12-01

    Since exclusively breast-suckled infants obtain their nutrient only from their mother's milk, it might be anticipated that a correlation will exist between the (15)N/(14)N isotope ratios of amino acids of protein of young infants and those supplied by their mother. The work presented here aimed to determine whether amino nitrogen transfer from human milk to infant hair protein synthesized within the first month of life conserves the maternal isotopic signature or whether post-ingestion fractionation dominates the nitrogen isotope spectrum. The study was conducted at 1 month post-birth on 100 mother-infant pairs. Isotope ratios (15)N/(14)N and (13)C/(12)C were measured using isotope ratio measurement by Mass Spectrometry (irm-MS) for whole maternal milk, and infant hair and (15)N/(14)N ratios were also measured by GC-irm-MS for the N-pivaloyl-O-isopropyl esters of amino acids obtained from the hydrolysis of milk and hair proteins. The δ(15)N and δ(13)C (‰) were found to be significantly higher in infant hair than in breast milk (δ(15)N, P < 0.001; δ(13)C, P < 0.001). Furthermore, the δ(15)N (‰) of individual amino acids in infant hair was also significantly higher than that in maternal milk (P < 0.001). By calculation, the observed shift in isotope ratio was shown not to be accounted for by the amino acid composition of hair and milk proteins, indicating that it is not simply due to differences in the composition in the proteins present. Rather, it would appear that each pool-mother and infant-turns over independently, and that fractionation in infant N-metabolism even in the first month of life dominates over the nutrient N-content.

  18. Diet of spotted bats (Euderma maculatum) in Arizona as indicated by fecal analysis and stable isotopes

    EPA Science Inventory

    We assessed diet of spotted bats (Euderma maculatum (J.A. Allen, 1891)) by visual analysis of bat feces and stable carbon (δ13C) and nitrogen (δ15N) isotope analysis of bat feces, wing, hair, and insect prey. We collected 33 fecal samples from spotted bats and trapped 3755 insect...

  19. Bayesian change point analysis of abundance trends for pelagic fishes in the upper San Francisco Estuary.

    PubMed

    Thomson, James R; Kimmerer, Wim J; Brown, Larry R; Newman, Ken B; Mac Nally, Ralph; Bennett, William A; Feyrer, Frederick; Fleishman, Erica

    2010-07-01

    We examined trends in abundance of four pelagic fish species (delta smelt, longfin smelt, striped bass, and threadfin shad) in the upper San Francisco Estuary, California, USA, over 40 years using Bayesian change point models. Change point models identify times of abrupt or unusual changes in absolute abundance (step changes) or in rates of change in abundance (trend changes). We coupled Bayesian model selection with linear regression splines to identify biotic or abiotic covariates with the strongest associations with abundances of each species. We then refitted change point models conditional on the selected covariates to explore whether those covariates could explain statistical trends or change points in species abundances. We also fitted a multispecies change point model that identified change points common to all species. All models included hierarchical structures to model data uncertainties, including observation errors and missing covariate values. There were step declines in abundances of all four species in the early 2000s, with a likely common decline in 2002. Abiotic variables, including water clarity, position of the 2 per thousand isohaline (X2), and the volume of freshwater exported from the estuary, explained some variation in species' abundances over the time series, but no selected covariates could explain statistically the post-2000 change points for any species. PMID:20666259

  20. Bayesian change point analysis of abundance trends for pelagic fishes in the upper San Francisco Estuary

    USGS Publications Warehouse

    Thompson, James R.; Kimmerer, Wim J.; Brown, Larry R.; Newman, Ken B.; Mac Nally, Ralph; Bennett, William A.; Feyrer, Frederick; Fleishman, Erica

    2010-01-01

    We examined trends in abundance of four pelagic fish species (delta smelt, longfin smelt, striped bass, and threadfin shad) in the upper San Francisco Estuary, California, USA, over 40 years using Bayesian change point models. Change point models identify times of abrupt or unusual changes in absolute abundance (step changes) or in rates of change in abundance (trend changes). We coupled Bayesian model selection with linear regression splines to identify biotic or abiotic covariates with the strongest associations with abundances of each species. We then refitted change point models conditional on the selected covariates to explore whether those covariates could explain statistical trends or change points in species abundances. We also fitted a multispecies change point model that identified change points common to all species. All models included hierarchical structures to model data uncertainties, including observation errors and missing covariate values. There were step declines in abundances of all four species in the early 2000s, with a likely common decline in 2002. Abiotic variables, including water clarity, position of the 2‰ isohaline (X2), and the volume of freshwater exported from the estuary, explained some variation in species' abundances over the time series, but no selected covariates could explain statistically the post-2000 change points for any species.

  1. Isotope ratio analysis of actinides, fission products, and geolocators by high-efficiency multi-collector thermal ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Bürger, S.; Riciputi, L. R.; Bostick, D. A.; Turgeon, S.; McBay, E. H.; Lavelle, M.

    2009-09-01

    A ThermoFisher "Triton" multi-collector thermal ionization mass spectrometer (MC-TIMS) was evaluated for trace and ultra-trace level isotope ratio analysis of actinides (uranium, plutonium, and americium), fission products and geolocators (strontium, cesium, and neodymium). Total efficiencies (atoms loaded to ions detected) of up to 0.5-2% for U, Pu, and Am, and 1-30% for Sr, Cs, and Nd can be reported employing resin bead load techniques onto flat ribbon Re filaments or resin beads loaded into a millimeter-sized cavity drilled into a Re rod. This results in detection limits of <0.1 fg (104 atoms to 105 atoms) for 239-242+244Pu, 233+236U, 241-243Am, 89,90Sr, and 134,135,137Cs, and <=1 pg for natural Nd isotopes (limited by the chemical processing blank) using a secondary electron multiplier (SEM) or multiple-ion counters (MICs). Relative standard deviations (RSD) as small as 0.1% and abundance sensitivities of 1 × 106 or better using a SEM are reported here. Precisions of RSD [approximate]0.01-0.001% using a multi-collector Faraday cup array can be achieved at sub-nanogram concentrations for strontium and neodymium and are suitable to gain crucial geolocation information. The analytical protocols reported herein are of particular value for nuclear forensic and nuclear safeguard applications.

  2. Carbon and nitrogen stable isotopic inventory of the most abundant demersal fish captured by benthic gears in southwestern Iceland (North Atlantic)

    NASA Astrophysics Data System (ADS)

    Sarà, Gianluca; de Pirro, Maurizio; Sprovieri, Mario; Rumolo, Paola; Halldórsson, Halldór Pálmar; Svavarsson, Jörundur

    2009-12-01

    Stable isotopes (δ13C and δ15N) were used to examine the origin of organic matter for the most representative demersal species of the SW Icelandic fishery, accounting for over 70% of landings of those species in the North Atlantic. Samples were collected during a 2-week period in early September 2004 from landings and directly during fishing cruises. Stable isotopes showed that particulate organic matter and sedimentary organic matter were at the base of the food web and appeared to fill two different compartments: the pelagic and the benthic. The pelagic realm was composed of only capelin and sandeel; krill and redfish occupied an intermediate position between pelagic and benthic realms; while anglerfish, haddock, cod and ling resulted as the true demersal species while tusk, rays and plaice were strongly linked to the benthic habitat.

  3. 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.

  4. Approaching the Final Frontier in Lateral Resolution for Isotopic and Chemical Analysis with CHILI

    NASA Astrophysics Data System (ADS)

    Davis, A. M.; Stephan, T.; Pellin, M.; Savina, M.; Yokochi, R.; Trappitsch, R.; Liu, N.; King, A.

    2011-12-01

    The small sizes of samples returned by recent (Stardust, Hayabusa) and future (OSIRIS-REx) sample return missions to comets and asteroids, as well as the small sizes of presolar grains in and interplanetary dust particles (IDPs) are driving improvements in lateral resolution and sensitivity beyond what is available with current state-of-the-art secondary ion mass spectrometry (SIMS) instruments. SIMS lateral resolution has reached ~50 nm and useful yields are at most a few percent. We are completing construction of CHILI (the CHicago Instrument for Laser Ionization), a resonant ionization mass spectrometry (RIMS) nanobeam instrument designed for isotopic and chemical analysis at the few-nm scale with a useful yield of ≥35% [1]. CHILI is equipped with a COBRA-FIB high resolution liquid metal ion gun (LMIG) and an e-CLIPSE Plus field emission electron gun from Orsay Physics, each of which can be focused to <4 nm. The electron gun will be used for secondary electron imaging, as the built-in optical microscope is diffraction-limited to ~0.5 μm. A piezoelectric stage capable of reproducible nm-scale motions and equipped with a sample holder that will accept a wide variety of sample mounts is operational. The flight tube for the time-of-flight mass spectrometer mounted vertically above the sample chamber; this assembly is mounted in the center of an H-shaped laser table equipped with active vibration cancellation devices. The table has been demonstrated to have a vertical vibrational amplitude of less than 0.2 nm. Resonant ionization will be done with six Ti:sapphire tunable solid state lasers pumped with three 40W Nd:YLF lasers, which will allow two to three elements to be analyzed simultaneously. Ion detection in existing RIMS instruments [2,3] is done with a microchannel plate with a single anode. Isotope ratio precision is limited by counting statistics, as no more than one ion of the most abundant isotope of an element can be counted for each pulse. CHILI will

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

    SciTech Connect

    Keeling, Ralph

    2014-12-12

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

  6. Detailed Abundance Analysis of a Metal-poor Giant in the Galactic Center

    NASA Astrophysics Data System (ADS)

    Ryde, N.; Fritz, T. K.; Rich, R. M.; Thorsbro, B.; Schultheis, M.; Origlia, L.; Chatzopoulos, S.

    2016-11-01

    We report the first results from our program to examine the metallicity distribution of the Milky Way nuclear star cluster connected to Sgr A*, with the goal of inferring the star formation and enrichment history of this system, as well as its connection and relationship with the central 100 pc of the bulge/bar system. We present the first high-resolution (R ∼ 24,000), detailed abundance analysis of a K = 10.2 metal-poor, alpha-enhanced red giant projected at 1.5 pc from the Galactic center, using NIRSPEC on Keck II. A careful analysis of the dynamics and color of the star locates it at about {26}-16+54 pc line-of-sight distance in front of the nuclear cluster. It probably belongs to one of the nuclear components (cluster or disk), not to the bar/bulge or classical disk. A detailed spectroscopic synthesis, using a new line list in the K band, finds [Fe/H] ∼ ‑1.0 and [α/Fe] ∼ +0.4, consistent with stars of similar metallicity in the bulge. As known giants with comparable [Fe/H] and alpha enhancement are old, we conclude that this star is most likely to be a representative of the ∼10 Gyr old population. This is also the most metal-poor-confirmed red giant yet discovered in the vicinity of the nuclear cluster of the Galactic center. We consider recent reports in the literature of a surprisingly large number of metal-poor giants in the Galactic center, but the reported gravity of {log}g∼ 4 for these stars calls into question their reported metallicities.

  7. Estimating pathway-specific contributions to biodegradation in aquifers based on dual isotope analysis: theoretical analysis and reactive transport simulations.

    PubMed

    Centler, Florian; Heße, Falk; Thullner, Martin

    2013-09-01

    At field sites with varying redox conditions, different redox-specific microbial degradation pathways contribute to total contaminant degradation. The identification of pathway-specific contributions to total contaminant removal is of high practical relevance, yet difficult to achieve with current methods. Current stable-isotope-fractionation-based techniques focus on the identification of dominant biodegradation pathways under constant environmental conditions. We present an approach based on dual stable isotope data to estimate the individual contributions of two redox-specific pathways. We apply this approach to carbon and hydrogen isotope data obtained from reactive transport simulations of an organic contaminant plume in a two-dimensional aquifer cross section to test the applicability of the method. To take aspects typically encountered at field sites into account, additional simulations addressed the effects of transverse mixing, diffusion-induced stable-isotope fractionation, heterogeneities in the flow field, and mixing in sampling wells on isotope-based estimates for aerobic and anaerobic pathway contributions to total contaminant biodegradation. Results confirm the general applicability of the presented estimation method which is most accurate along the plume core and less accurate towards the fringe where flow paths receive contaminant mass and associated isotope signatures from the core by transverse dispersion. The presented method complements the stable-isotope-fractionation-based analysis toolbox. At field sites with varying redox conditions, it provides a means to identify the relative importance of individual, redox-specific degradation pathways.

  8. Microbial degradation of alpha-cypermethrin in soil by compound-specific stable isotope analysis.

    PubMed

    Xu, Zemin; Shen, Xiaoli; Zhang, Xi-Chang; Liu, Weiping; Yang, Fangxing

    2015-09-15

    To assess microbial degradation of alpha-cypermethrin in soil, attenuation of alpha-cypermethrin was investigated by compound-specific stable isotope analysis. The variations of the residual concentrations and stable carbon isotope ratios of alpha-cypermethrin were detected in unsterilized and sterilized soils spiked with alpha-cypermethrin. After an 80 days' incubation, the concentrations of alpha-cypermethrin decreased to 0.47 and 3.41 mg/kg in the unsterilized soils spiked with 2 and 10 mg/kg, while those decreased to 1.43 and 6.61 mg/kg in the sterilized soils. Meanwhile, the carbon isotope ratios shifted to -29.14 ± 0.22‰ and -29.86 ± 0.33‰ in the unsterilized soils spiked with 2 and 10 mg/kg, respectively. The results revealed that microbial degradation contributed to the attenuation of alpha-cypermethrin and induced the carbon isotope fractionation. In order to quantitatively assess microbial degradation, a relationship between carbon isotope ratios and residual concentrations of alpha-cypermethrin was established according to Rayleigh equation. An enrichment factor, ϵ = -1.87‰ was obtained, which can be employed to assess microbial degradation of alpha-cypermethrin. The significant carbon isotope fractionation during microbial degradation suggests that CSIA is a proper approach to qualitatively detect and quantitatively assess the biodegradation during attenuation process of alpha-cypermethrin in the field.

  9. Metal Oxide-Based Selective Enrichment Combined with Stable Isotope Labeling-Mass Spectrometry Analysis for Profiling of Ribose Conjugates.

    PubMed

    Chu, Jie-Mei; Qi, Chu-Bo; Huang, Yun-Qing; Jiang, Han-Peng; Hao, Yan-Hong; Yuan, Bi-Feng; Feng, Yu-Qi

    2015-07-21

    Some modified ribonucleosides in biological fluids have been evaluated as cancer-related metabolites. Detection of endogenous modified ribonucleosides in biological fluids may serve as a noninvasive cancers diagnostic method. However, determination of modified ribonucleosides is still challenging because of their low abundance and serious matrix interferences in biological fluids. Here, we developed a novel strategy for comprehensive profiling of ribose conjugates from biological fluids using metal oxide-based dispersive solid-phase extraction (DSPE) followed with in vitro stable isotope labeling and double neutral loss scan-mass spectrometry analysis (DSPE-SIL-LC-DNLS-MS). Cerium dioxide (CeO2) was used to selectively recognize and capture ribose conjugates from complex biological samples under basic environment. The enriched ribose conjugates were subsequently labeled with a pair of isotope labeling reagents (acetone and acetone-d6). The glucosidic bond of acetone labeled ribose conjugates is readily ruptured, and the generated ribose that carries an isotope tag can be lost as a neutral fragment under collision induced dissociation (CID). Since the light (acetone) and heavy (acetone-d6) labeled compounds have the same chemical structures and can generate different neutral loss fragments (NL 172 and 178 Da), it is therefore highly convenient to profile ribose conjugates by double neutral loss scan mode in mass spectrometry analysis. In this respect, the light and heavy labeled compounds were ionized at the same condition but recorded separately on MS spectra, which can significantly improve the detection specificity and facilitate the identification of ribose conjugates. Using the developed DSPE-SIL-LC-DNLS-MS strategy, we profiled the ribose conjugates in human urine, and 49 ribose conjugates were readily identified, among which 7 ribose conjugates exhibited significant contents change between healthy controls and lymphoma patients. The DSPE

  10. Recent developments in application of stable isotope analysis on agro-product authenticity and traceability.

    PubMed

    Zhao, Yan; Zhang, Bin; Chen, Gang; Chen, Ailiang; Yang, Shuming; Ye, Zhihua

    2014-02-15

    With the globalisation of agro-product markets and convenient transportation of food across countries and continents, the potential for distribution of mis-labelled products increases accordingly, highlighting the need for measures to identify the origin of food. High quality food with identified geographic origin is a concern not only for consumers, but also for agriculture farmers, retailers and administrative authorities. Currently, stable isotope ratio analysis in combination with other chemical methods gradually becomes a promising approach for agro-product authenticity and traceability. In the last five years, a growing number of research papers have been published on tracing agro-products by stable isotope ratio analysis and techniques combining with other instruments. In these reports, the global variety of stable isotope compositions has been investigated, including light elements such as C, N, H, O and S, and heavy isotopes variation such as Sr and B. Several factors also have been considered, including the latitude, altitude, evaporation and climate conditions. In the present paper, an overview is provided on the authenticity and traceability of the agro-products from both animal and plant sources by stable isotope ratio analysis.

  11. Isotope ratio analysis of individual sub-micrometer plutonium particles with inductively coupled plasma mass spectrometry.

    PubMed

    Esaka, Fumitaka; Magara, Masaaki; Suzuki, Daisuke; Miyamoto, Yutaka; Lee, Chi-Gyu; Kimura, Takaumi

    2010-12-15

    Information on plutonium isotope ratios in individual particles is of great importance for nuclear safeguards, nuclear forensics and so on. Although secondary ion mass spectrometry (SIMS) is successfully utilized for the analysis of individual uranium particles, the isobaric interference of americium-241 to plutonium-241 makes difficult to obtain accurate isotope ratios in individual plutonium particles. In the present work, an analytical technique by a combination of chemical separation and inductively coupled plasma mass spectrometry (ICP-MS) is developed and applied to isotope ratio analysis of individual sub-micrometer plutonium particles. The ICP-MS results for individual plutonium particles prepared from a standard reference material (NBL SRM-947) indicate that the use of a desolvation system for sample introduction improves the precision of isotope ratios. In addition, the accuracy of the (241)Pu/(239)Pu isotope ratio is much improved, owing to the chemical separation of plutonium and americium. In conclusion, the performance of the proposed ICP-MS technique is sufficient for the analysis of individual plutonium particles. PMID:21111176

  12. Isotope ratio analysis of individual sub-micrometer plutonium particles with inductively coupled plasma mass spectrometry.

    PubMed

    Esaka, Fumitaka; Magara, Masaaki; Suzuki, Daisuke; Miyamoto, Yutaka; Lee, Chi-Gyu; Kimura, Takaumi

    2010-12-15

    Information on plutonium isotope ratios in individual particles is of great importance for nuclear safeguards, nuclear forensics and so on. Although secondary ion mass spectrometry (SIMS) is successfully utilized for the analysis of individual uranium particles, the isobaric interference of americium-241 to plutonium-241 makes difficult to obtain accurate isotope ratios in individual plutonium particles. In the present work, an analytical technique by a combination of chemical separation and inductively coupled plasma mass spectrometry (ICP-MS) is developed and applied to isotope ratio analysis of individual sub-micrometer plutonium particles. The ICP-MS results for individual plutonium particles prepared from a standard reference material (NBL SRM-947) indicate that the use of a desolvation system for sample introduction improves the precision of isotope ratios. In addition, the accuracy of the (241)Pu/(239)Pu isotope ratio is much improved, owing to the chemical separation of plutonium and americium. In conclusion, the performance of the proposed ICP-MS technique is sufficient for the analysis of individual plutonium particles.

  13. Sr Isotope Analysis of Lacustrine Fossils Reveals Paleohydrological Reorganisation in the Turkana Basin Through the Holocene.

    NASA Astrophysics Data System (ADS)

    Vonhof, H.; Lubbe, J. V. D.; Joordens, J. J.; Feibel, C. S.; Junginger, A.; Garcin, Y.; Krause-Nehring, J.; Beck, C.; Johnson, T. C.

    2015-12-01

    Lake Turkana in northern Kenya is one of the largest lakes in the East African Rift System (EARS) that experienced significant climate-driven lake level variation over the Holocene. Arguably the most important feature of Holocene climate change in the EARS is the termination of the African Humid Period (AHP), that caused a ~70 meter lake level drop in Lake Turkana. The precise hydrological response to the termination of the AHP is potentially complex, because Lake Turkana lies at the cross roads of two large atmospheric convection systems; the Intertropical Convergence Zone (ITCZ) and the Congo Air Boundary (CAB). Shifting of these atmospheric systems around the end of the AHP dramatically rearranged spatial rainfall patterns in the Turkana Basin catchment, causing changes in relative runoff contributions from the different sub-catchments in the Turkana Basin. We here present a Holocene Turkana lake water Sr-isotope reconstruction, based on the analysis of well-dated lacustrine ostracods and shells. This reconstruction reveals consistently high Sr isotope values for the early Holocene, followed by a remarkable drop of Sr isotope ratios around the AHP termination. We interpret this pattern to represent a westward shift in the location of the CAB, leading to the reduction and eventual shutdown of runoff contribution from the Chew Bahir Basin to the Turkana Basin at the end of the AHP. The record demonstrates the exceptional suitability of Sr isotope data for this type of paleohydrological reconstructions. This is mainly due to the chemically conservative Sr-isotope mass balance in EARS lake systems, which is insensitive to environmental change at seasonal timescales that so often overprints the longer term climate signal in stable (oxygen and carbon) isotope records of these lakes. Furthermore, when Sr-isotope signatures of the contributing sub-catchments are known, the observed Sr isotope trends can be interpreted in terms of spatial shifts in climate driven runoff

  14. Micro-scale (1.5 microm) sulphur isotope analysis of contemporary and early Archean pyrite.

    PubMed

    Nishizawa, Manabu; Maruyama, Shigenori; Urabe, Tetsuro; Takahata, Naoto; Sano, Yuji

    2010-05-30

    We present a method for in situ sulphur (S) isotopic analysis of significantly small areas (1.5 microm in diameter) in pyrite using secondary ion mass spectrometry (NanoSIMS) to interpret microbial sulphur metabolism in the early earth. We evaluated the precision and accuracy of S isotopic ratios obtained by this method using hydrothermal pyrite samples with homogeneous S isotopic ratios. The internal precision of the delta(34)S value was 1.5 per thousand at the level of 1 sigma of standard error (named 1SE) for a single spot, while the external reproducibility was estimated to be 1.6 per thousand at the level of 1 sigma of standard deviation (named 1SD, n = 25). For each separate sample, the average delta(34)S value was comparable with that measured by a conventional method, and the accuracy was better than 2.3 per thousand. Consequently, the in situ method is sufficiently accurate and precise to detect the S isotopic variations of small sample of the pyrite (less than 20 microm) that occurs ubiquitously in ancient sedimentary rocks. This method was applied to measure the S isotopic distribution of pyrite within black chert fragments in early Archean sandstone. The pyrite had isotopic zoning with a (34)S-depleted core and (34)S-enriched rim, suggesting isotopic evolution of the source H(2)S from -15 to -5 per thousand. Production of H(2)S by microbial sulphate reduction (MSR) in a closed system provides a possible explanation for both the (34)S-depleted initial H(2)S and the progressive increase in the delta(34)S(H2S) value. Although more extensive data are necessary to strengthen the explanation for the origin of the MSR, the results show that the S isotopic distribution within pyrite crystals may be a key tracer for MSR activity in the early earth.

  15. Micro-scale (1.5 microm) sulphur isotope analysis of contemporary and early Archean pyrite.

    PubMed

    Nishizawa, Manabu; Maruyama, Shigenori; Urabe, Tetsuro; Takahata, Naoto; Sano, Yuji

    2010-05-30

    We present a method for in situ sulphur (S) isotopic analysis of significantly small areas (1.5 microm in diameter) in pyrite using secondary ion mass spectrometry (NanoSIMS) to interpret microbial sulphur metabolism in the early earth. We evaluated the precision and accuracy of S isotopic ratios obtained by this method using hydrothermal pyrite samples with homogeneous S isotopic ratios. The internal precision of the delta(34)S value was 1.5 per thousand at the level of 1 sigma of standard error (named 1SE) for a single spot, while the external reproducibility was estimated to be 1.6 per thousand at the level of 1 sigma of standard deviation (named 1SD, n = 25). For each separate sample, the average delta(34)S value was comparable with that measured by a conventional method, and the accuracy was better than 2.3 per thousand. Consequently, the in situ method is sufficiently accurate and precise to detect the S isotopic variations of small sample of the pyrite (less than 20 microm) that occurs ubiquitously in ancient sedimentary rocks. This method was applied to measure the S isotopic distribution of pyrite within black chert fragments in early Archean sandstone. The pyrite had isotopic zoning with a (34)S-depleted core and (34)S-enriched rim, suggesting isotopic evolution of the source H(2)S from -15 to -5 per thousand. Production of H(2)S by microbial sulphate reduction (MSR) in a closed system provides a possible explanation for both the (34)S-depleted initial H(2)S and the progressive increase in the delta(34)S(H2S) value. Although more extensive data are necessary to strengthen the explanation for the origin of the MSR, the results show that the S isotopic distribution within pyrite crystals may be a key tracer for MSR activity in the early earth. PMID:20411578

  16. Compound specific isotope analysis to investigate pesticide degradation in lysimeter experiments at field conditions

    NASA Astrophysics Data System (ADS)

    Ryabenko, Evgenia; Elsner, Martin; Bakkour, Rani; Hofstetter, Thomas; Torrento, Clara; Hunkeler, Daniel

    2015-04-01

    The frequent detection of organic micropollutants such as pesticides, consumer care products or pharmaceuticals in water is an increasing concern for human and ecosystem health. Degradation analysis of these compounds can be challenging in complex systems due to the fact that metabolites are not always found and mass balances frequently cannot be closed. Many abiotic and biotic degradation pathways cause, however, distinct isotope fractionation, where light isotopes are transferred preferentially from the reactant to the product pool (normal isotope fractionation). Compound-specific isotope analysis (CSIA) of multiple elements is a particularly powerful method to evaluate organic micropollutant transformation, because it can even give pathway-specific isotope fractionation (1,2). Available CSIA field studies, however, have focused almost exclusively on volatile petroleum and chlorinated hydrocarbons, which are present in high concentrations in the environment and can be extracted easily from water for GC-IRMS analysis. In the case of micropollutants, such as pesticides, CSIA in more challenging since it needs to be conducted at lower concentrations and requires pre-concentration, purification and high chromatographic performance (3). In this study we used lysimeters experiments to analyze transformation of atrazine, acetochlor, metolachlor and chloridazone by studying associated isotope fractionation. The project combines a) analytical method development for CSIA, b) identification of pathways of micropollutant degradation and c) quantification of transformation processes under field condition. The pesticides were applied both, at the soil surface and below the top soil under field-relevant concentrations in May 2014. After typical irrigation of the lysimeters, seepage water was collected in 50L bottles and stored for further SPE and CSIA. Here we present the very first result of a) analytical method development, b) improvement of SPE methods for complex pesticide

  17. Microcalorimeter Q-spectroscopy for rapid isotopic analysis of trace actinide samples

    NASA Astrophysics Data System (ADS)

    Croce, M. P.; Bond, E. M.; Hoover, A. S.; Kunde, G. J.; Mocko, V.; Rabin, M. W.; Weisse-Bernstein, N. R.; Wolfsberg, L. E.; Bennett, D. A.; Hays-Wehle, J.; Schmidt, D. R.; Ullom, J. N.

    2015-06-01

    We are developing superconducting transition-edge sensor (TES) microcalorimeters that are optimized for rapid isotopic analysis of trace actinide samples by Q-spectroscopy. By designing mechanically robust TESs and simplified detector assembly methods, we have developed a detector for Q-spectroscopy of actinides that can be assembled in minutes. We have characterized the effects of each simplification and present the results. Finally, we show results of isotopic analysis of plutonium samples with Q-spectroscopy detectors and compare the results to mass spectrometry.

  18. Stable isotope analysis of the karst hydrological systems in the Bay of Kvarner (Croatia).

    PubMed

    Mance, D; Hunjak, T; Lenac, D; Rubinić, J; Roller-Lutz, Z

    2014-08-01

    Here we present the results of the first systematic analysis of the stable isotope composition of the karst hydrological systems in the Bay of Kvarner. Gaussian mixture modelling, time series analysis and autoregressive integrated moving average (ARIMA) modelling were applied using the stable isotope compositions of the karst groundwater. This study revealed that the recharge is dominated by winter precipitation, the dual-porosity system is dominated by baseflow, the hinterlands of the individual springs have different degrees of karstification and the springs within the Rječina River catchment have higher recharge elevations than the springs in the Bakar Bay catchment.

  19. Compound specific 13C- and 18O-isotope analysis of organic aerosols

    NASA Astrophysics Data System (ADS)

    Blees, Jan; Saurer, Matthias; Siegwolf, Rolf T. W.; Dommen, Josef; Baltensperger, Urs

    2014-05-01

    The wide ranging environmental and health effects of aerosols are increasingly coming to light. Various studies have further highlighted the complex nature of organic aerosols, particularly oxidised organics with multiple functional groups. Source apportionment studies on aerosols are crucial to successful implementation of mitigation strategies, but this is complicated by their complex nature. Ideally, individual components of aerosols can be tracked from their source to their atmospheric sink. However, chemical alteration and the formation of secondary aerosols in the atmosphere often preclude this direct tracking on a compound specific basis. Compound specific isotope analysis could overcome these problems, as certain processes and sources impose characteristic isotope ratios on products, which may be retained even after chemical alteration in the atmosphere. Progress has been made over the past decades in the separation and identification of individual compounds that contribute to aerosol formation. Compound separation by gas chromatography (GC), coupled to mass spectrometry (MS), has enabled identification of organic compounds of various sources. On the other hand, only few studies have addressed the isotopic composition of these compounds. For successful isotopic analysis of specific compounds, using GC coupled to isotope ratio MS (GC-irMS), several challenges must be faced that go beyond the requirements for GC-MS-based compound identification. Sample extraction and handling techniques must avoid isotope fractionation. This is especially important in the light of sample extraction by e.g. thermal desorption, which may impose a temperature-induced fractionation on complex organics. Furthermore, derivatisation techniques, necessary for adequate GC compound separation, must not lead to exchange reactions of the element of interest, which would alter the measured isotope ratio. So far most studies have dealt with carbon, and other elements have been neglected

  20. 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

  1. The influence of trophic level and feeding location of the levels of organochlorine contaminants in seabird eggs as revealed by stable carbon and nitrogen isotope analysis

    SciTech Connect

    Hobson, K.; Jarman, W.M.; Bott, J.A.; Bacon, C.E.; Sydeman, W.

    1994-12-31

    Seabird eggs have been used extensively to assay contaminants in marine food webs, but links to trophic level or feeding location have remained poorly understood due to limitations inherent in conventional dietary studies. Stable-isotope analysis of bird eggs may be used to infer trophic position and feeding location of adult seabirds and can be readily correlated with measurements of egg contaminant levels. The authors measured stable-carbon ({delta}{sup 13}C) and nitrogen ({delta}{sup 15}N) isotope abundance, and organochlorine contaminants (DDTs, PCBs, chlordanes, etc.) in eggs from Cassin`s Auklet (Ptychoramphus aleutica), Common Murre (Uria aalge), Pigeon Guillemot (Cepphus columba). Rhinoceros Auklet (Cerorhinca monocerata), Pelagic Cormorant (Phalacrocorax pelagicus), Brandt`s Cormorant (Phalacrocorax penicillatus), and Western Gull (Larus) from Southeast Farallon Island together with rockfish (Sebastes spp.), anchovy (Engraulis spp.), and euphausiid prey from the Gulf of the Farallones. Consistent with its planktivorous diet and pelagic feeding habits, Cassin`s Auklet showed the lowest mean {delta}{sup 15}N value and the least enriched {delta}{sup 13}C values. Measures of trophic level and foraging location were constructed for all other seabirds relative to these isotopic endpoints. Contaminant levels in the eggs and fish will be interpreted in light of the stable-isotope results.

  2. [Meta-analysis of stable carbon and nitrogen isotopic enrichment factors for aquatic animals].

    PubMed

    Guo, Liang; Sun, Cui-ping; Ren, Wei-zheng; Zhang, Jian; Tang, Jian-iun; Hu, Liana-liang; Chen, Xin

    2016-02-01

    Isotopic enrichment factor (Δ, the difference between the δ value of food and a consumer tissue) is an important parameter in using stable isotope analysis (SIA) to reconstruct diets, characterize trophic relationships, elucidate patterns of resource allocation, and construct food webs. Isotopic enrichment factor has been considered as a constancy value across a broad range of animals. However, recent studies showed that the isotopic enrichment factor differed among various types of animals although the magnitude of variation was not clear. Here, we conducted a meta-analysis to synthesize and compare Δ13C and Δ15N among four types of aquatic animals (teleosts, crustaceans, reptiles and molluscs). We searched for papers published before 2014 on Web of Science and CNKI using the key words "stable isotope or isotopic fractionation or fractionation factor or isotopic enrichment or trophic enrichment". Forty-two publications that contain 140 studies on Δ13C and 159 studies on Δ15N were obtained. We conducted three parallel meta-analyses by using three types of weights (the reciprocal of variance as weights, the sample size as weights, and equal weights). The results showed that no significant difference in Δ13C among different animal types (teleosts 1.0 per thousand, crustaceans 1.3 per thousand, reptiles 0.5 per thousand, and molluscs 1.5 per thousand), while Δ15N values were significantly different (teleosts 2.4 per thousand, crustaceans 3.6 per thousand, reptiles 1.0 per thousand and molluscs 2.5 per thousand). Our results suggested that the overall mean of Δ13C could be used as a general enrichment factor, but Δ15N should be chosen according to the type of aquatic animals in using SIA to analyze trophic relationships, patterns of resource allocation and food webs. PMID:27396136

  3. [Meta-analysis of stable carbon and nitrogen isotopic enrichment factors for aquatic animals].

    PubMed

    Guo, Liang; Sun, Cui-ping; Ren, Wei-zheng; Zhang, Jian; Tang, Jian-iun; Hu, Liana-liang; Chen, Xin

    2016-02-01

    Isotopic enrichment factor (Δ, the difference between the δ value of food and a consumer tissue) is an important parameter in using stable isotope analysis (SIA) to reconstruct diets, characterize trophic relationships, elucidate patterns of resource allocation, and construct food webs. Isotopic enrichment factor has been considered as a constancy value across a broad range of animals. However, recent studies showed that the isotopic enrichment factor differed among various types of animals although the magnitude of variation was not clear. Here, we conducted a meta-analysis to synthesize and compare Δ13C and Δ15N among four types of aquatic animals (teleosts, crustaceans, reptiles and molluscs). We searched for papers published before 2014 on Web of Science and CNKI using the key words "stable isotope or isotopic fractionation or fractionation factor or isotopic enrichment or trophic enrichment". Forty-two publications that contain 140 studies on Δ13C and 159 studies on Δ15N were obtained. We conducted three parallel meta-analyses by using three types of weights (the reciprocal of variance as weights, the sample size as weights, and equal weights). The results showed that no significant difference in Δ13C among different animal types (teleosts 1.0 per thousand, crustaceans 1.3 per thousand, reptiles 0.5 per thousand, and molluscs 1.5 per thousand), while Δ15N values were significantly different (teleosts 2.4 per thousand, crustaceans 3.6 per thousand, reptiles 1.0 per thousand and molluscs 2.5 per thousand). Our results suggested that the overall mean of Δ13C could be used as a general enrichment factor, but Δ15N should be chosen according to the type of aquatic animals in using SIA to analyze trophic relationships, patterns of resource allocation and food webs.

  4. Isotopic composition analysis and age dating of uranium samples by high resolution gamma ray spectrometry

    NASA Astrophysics Data System (ADS)

    Apostol, A. I.; Pantelica, A.; Sima, O.; Fugaru, V.

    2016-09-01

    Non-destructive methods were applied to determine the isotopic composition and the time elapsed since last chemical purification of nine uranium samples. The applied methods are based on measuring gamma and X radiations of uranium samples by high resolution low energy gamma spectrometric system with planar high purity germanium detector and low background gamma spectrometric system with coaxial high purity germanium detector. The "Multigroup γ-ray Analysis Method for Uranium" (MGAU) code was used for the precise determination of samples' isotopic composition. The age of the samples was determined from the isotopic ratio 214Bi/234U. This ratio was calculated from the analyzed spectra of each uranium sample, using relative detection efficiency. Special attention is paid to the coincidence summing corrections that have to be taken into account when performing this type of analysis. In addition, an alternative approach for the age determination using full energy peak efficiencies obtained by Monte Carlo simulations with the GESPECOR code is described.

  5. First stable isotope analysis of Asiatic wild ass tail hair from the Mongolian Gobi

    PubMed Central

    Horacek, Micha; Sturm, Martina Burnik; Kaczensky, Petra

    2015-01-01

    Stable isotope analysis has become a powerful tool to study feeding ecology, water use or movement pattern in contemporary, historic and ancient species. Certain hair and teeth grow continuously, and when sampled longitudinally can provide temporally explicit information on dietary regime and movement pattern. In an initial trial, we analysed a tail sample of an Asiatic wild ass (Equus hemionus) from the Mongolian Gobi. We found seasonal variations in H, C and N isotope patterns, likely being the result of temporal variations in available feeds, water supply and possibly physiological status. Thus stable isotope analysis shows promise to study the comparative ecology of the three autochthonous equid species in the Mongolian Gobi. PMID:26339116

  6. RVC-CAL library for endmember and abundance estimation in hyperspectral image analysis

    NASA Astrophysics Data System (ADS)

    Lazcano López, R.; Madroñal Quintín, D.; Juárez Martínez, E.; Sanz Álvaro, C.

    2015-10-01

    Hyperspectral imaging (HI) collects information from across the electromagnetic spectrum, covering a wide range of wavelengths. Although this technology was initially developed for remote sensing and earth observation, its multiple advantages - such as high spectral resolution - led to its application in other fields, as cancer detection. However, this new field has shown specific requirements; for instance, it needs to accomplish strong time specifications, since all the potential applications - like surgical guidance or in vivo tumor detection - imply real-time requisites. Achieving this time requirements is a great challenge, as hyperspectral images generate extremely high volumes of data to process. Thus, some new research lines are studying new processing techniques, and the most relevant ones are related to system parallelization. In that line, this paper describes the construction of a new hyperspectral processing library for RVC-CAL language, which is specifically designed for multimedia applications and allows multithreading compilation and system parallelization. This paper presents the development of the required library functions to implement two of the four stages of the hyperspectral imaging processing chain--endmember and abundances estimation. The results obtained show that the library achieves speedups of 30%, approximately, comparing to an existing software of hyperspectral images analysis; concretely, the endmember estimation step reaches an average speedup of 27.6%, which saves almost 8 seconds in the execution time. It also shows the existence of some bottlenecks, as the communication interfaces among the different actors due to the volume of data to transfer. Finally, it is shown that the library considerably simplifies the implementation process. Thus, experimental results show the potential of a RVC-CAL library for analyzing hyperspectral images in real-time, as it provides enough resources to study the system performance.

  7. Temporal variation of isotope and rare earth element abundances in volcanic rocks from Guam: implications for the evolution of the Mariana Arc

    NASA Astrophysics Data System (ADS)

    Hickey-Vargas, Rosemary; Reagan, Mark K.

    1987-12-01

    Volcanic rocks exposed on Guam were erupted during the Late Middle Eocene (Facpi Fm.), Late Eocene-Oligocene (Alutom Fm.) and Miocene (Umatac Fm.). Four magma series are recognized: the boninite series (44 m.y.b.p.), the tholeiite and calc-alkaline series, which were erupted along with boninite series lavas at 32 36 m.y.b.p. and high-K lavas of the Umatac Fm. (14 m.y.b.p.). Isotope and and rare earth element (REE) characteristics of the four magma series are distinct. Boninite series lavas have U-shaped REE patterns, relatively low 143Nd/144Nd (0.51294 0.51298), and high 206Pb/204Pb (19.0 19.2). Tholeiite series lavas are LREE (light REE) depleted, and have high 143Nd/144Nd (0.51304 0.51306) and low 206Pb/204Pb (18.4 18.5). Calc-alkaline series lavas have Sr, Nd and Pb isotope ratios similar to tholeiite series lavas, but flat to U-shaped REE patterns. Umatac Fm. lavas are strongly LREE-enriched, and have higher 87Sr/ 86Sr (0.70375 0.70380) and 207Pb/204Pb relative to 206Pb/ 204Pb than Facpi and Alutom Fm. lavas. Boninite and tholeiite series magmas, erupted in the position of the Palau-Kyushu Ridge, were probably derived from distinct mantle sources having OIB and N-MORB-like isotopic characteristics, together with fluids derived from subducted Pacific plate basalt. Calc-alkaline series lavas were most likely derived from the tholeiite series by extensive crystal fractionation, wallrock contamination and magma mixing. Lavas of the Umatac Fm., erupted in the position of the West Mariana Ridge, may include up to 2 3% subducted sediment, similar to some active Mariana arc lavas.

  8. Humidity affects relative ion abundance in direct analysis in real time mass spectrometry of hexamethylene triperoxide diamine.

    PubMed

    Newsome, G Asher; Ackerman, Luke K; Johnson, Kevin J

    2014-12-16

    Unstable explosive hexamethylene triperoxide diamine (HMTD) is dangerous in quantity and benefits from the minimal sampling handling associated with atmospheric pressure chemical ionization for mass spectral analysis. Seasonal variation observed in HMTD mass spectra suggested a humidity dependence. Therefore, direct analysis in real time (DART) ionization mass spectra were acquired at a range of humidity values. An enclosure was designed to fit around the ion source and mass spectrometer inlet at atmospheric pressure. The enclosure was supplied with controlled amounts of humidified air from a test atmosphere generator to create programmable conditions for ambient analysis. The relative abundance and fragmentation of analyte ions were observed to change reliably with changing humidity values and, to a lesser degree, temperature. Humidity at such plasma-based ion sources should be regulated to avoid ∼90% shifts in relative ion abundance and provide stability and reproducibility of HMTD analysis.

  9. Atomic Weights and Isotopic Compositions

    National Institute of Standards and Technology Data Gateway

    SRD 144 Atomic Weights and Isotopic Compositions (Web, free access)   The atomic weights are available for elements 1 through 111, and isotopic compositions or abundances are given when appropriate.

  10. Monitoring of the aerobe biodegradation of chlorinated organic solvents by stable isotope analysis

    NASA Astrophysics Data System (ADS)

    Horváth, Anikó; Futó, István; Palcsu, László

    2014-05-01

    Our chemical-biological basic research aims to eliminate chlorinated environmental contaminants from aquifers around industrial areas in the frame of research program supported by the European Social Fund (TÁMOP-4.2.2.A-11/1/KONV-2012-0043). The most careful and simplest way includes the in situ biodegradation with the help of cultured and compound specific strains. Numerous members of Pseudomonas bacteria are famous about function of bioremediation. They can metabolism the environmental hazardous chemicals like gas oils, dyes, and organic solvents. Our research based on the Pseudomonas putida F1 strain, because its ability to degrade halogenated hydrocarbons such as trichloroethylene. Several methods were investigated to estimate the rate of biodegradation, such as the measurement of the concentration of the pollutant along the contamination pathway, the microcosm's studies or the compound specific stable isotope analysis. In this area in the Transcarpathian basin we are pioneers in the stable isotope monitoring of biodegradation. The main goal is to find stable isotope fractionation factors by stable isotope analysis, which can help us to estimate the rate and effectiveness of the biodegradation. The subsequent research period includes the investigation of the method, testing its feasibility and adaptation in the environment. Last but not least, the research gives an opportunity to identify the producer of the contaminant based on the stable isotope composition of the contaminant.

  11. Tracing combustion-derived atmospheric pollutants using compound-specific isotope analysis

    NASA Astrophysics Data System (ADS)

    Ballentine, Donna Christine

    1997-04-01

    The use of compound specific carbon isotopic analysis (CSIA) has been investigated as a means to trace the origin and fate of organic pollutants in the atmosphere. Polycyclic aromatic hydrocarbons (PAH) and fatty acids have been suggested as two chemical classes which may serve as suitable molecular markers for anthropogenic combustion processes, such as fossil fuel combustion and biomass burning, that introduce significant quantities of organic pollutants into the atmospheric environment. First, analytical procedures for the extraction and isolation of these compounds from particulate aerosols, as well as a description of the isotopic measurement techniques, have been presented. Second, the precision and accuracy of these methods and measurements have been demonstrated. Third, the isotopic variability of PAH and fatty acids produced from different combustion processes has been investigated. In addition, in order to demonstrate the applicability of this technique as a means to monitor the fate of atmospheric pollutants, isotopic measurements of PAH, fatty acids, and alkanes isolated from a series of ambient aerosol samples have been made in a preliminary attempt to determine if compound specific isotope analysis of molecular markers in aerosols can be used in conjunction with other chemical and atmospheric data in order to reflect the transport of pollution episodes.

  12. Compound-specific stable isotope analysis of herbicides in stream water: a combined monitoring and modeling approach to assess pollutant degradation at catchment scale

    NASA Astrophysics Data System (ADS)

    Lutz, Stefanie; Van der Velde, Ype; Elsayed, Omniea; Imfeld, Gwenael; Lefrancq, Marie; Payraudeau, Sylvain; Van Breukelen, Boris

    2014-05-01

    Compound-specific stable isotope analysis (CSIA) measures the isotopic composition of a compound, i.e. the relative abundance of light and heavy stable isotopes of an element contained in the compound (e.g. 12C and 13C). As degradation processes may induce a change in isotopic composition (i.e. isotope fractionation), CSIA allows distinguishing degradation from non-destructive processes such as dilution or sorption. CSIA can be combined with model-assisted interpretation to evaluate degradation of contaminants in the environment. Although CSIA methods have also been developed for diffuse pollutants such as pesticides and nitrate, they have not yet been continuously applied in monitoring of diffuse pollution in surface water. Results of a virtual experiment of isotope fractionation at hillslope scale have suggested that CSIA qualifies as a feasible and useful complement to concentration measurements of diffuse pollutants (Lutz et al., 2013). We now present the first continuously measured concentration and carbon CSIA data of herbicides from a 49-ha agricultural catchment (Alsace, France). Stream concentrations of two chloroacetanilide herbicides, i.e. S-metolachlor and acetochlor, were highest (65 μg/L) following an extreme rainfall event in the first month after herbicide application, and subsequently decreased to background concentration level (0.1 μg/L). This decrease was accompanied by an increase of more than 2 ‰ in carbon isotope ratios, which was also observed in surface runoff samples from a plot experiment in the study catchment. The increase of carbon isotope ratios over time indicates the occurrence of herbicide degradation during transport to the stream, and thus demonstrates the advantage of CSIA over pesticide concentration measurements only. Despite providing evidence of herbicide degradation, the field CSIA data do not allow for a comprehensive characterization of herbicide sources, fate and transport in the study catchment. Therefore, we

  13. Origin of the eclogitic clasts with graphite-bearing and graphite-free lithologies in the Northwest Africa 801 (CR2) chondrite: Possible origin from a Moon-sized planetary body inferred from chemistry, oxygen isotopes and REE abundances

    NASA Astrophysics Data System (ADS)

    Hiyagon, H.; Sugiura, N.; Kita, N. T.; Kimura, M.; Morishita, Y.; Takehana, Y.

    2016-08-01

    In order to clarify the origin of the eclogitic clasts found in the NWA801 (CR2) chondrite (Kimura et al., 2013), especially, that of the high pressure and temperature (P-T) condition (∼3 GPa and ∼1000 °C), we conducted ion microprobe analyses of oxygen isotopes and rare earth element (REE) abundances in the clasts. Oxygen isotopic compositions of the graphite-bearing lithology (GBL) and graphite-free lithology (GFL) show a slope ∼0.6 correlation slightly below the CR-CH-CB chondrites field in the O three-isotope-diagram, with a large variation for the former and almost homogeneous composition for the latter. The average REE abundances of the two lithologies show almost unfractionated patterns. Based on these newly obtained data, as well as mineralogical observations, bulk chemistry, and considerations about diffusion timescales for various elements, we discuss in detail the formation history of the clasts. Consistency of the geothermobarometers used by Kimura et al. (2013), suggesting equilibration of various elements among different mineral pairs, provides a strong constraint for the duration of the high P-T condition. We suggest that the high P-T condition lasted 102-103 years. This clearly precludes a shock high pressure (HP) model, and hence, strongly supports a static HP model. A static HP model requires a Moon-sized planetary body of ∼1500 km in radius. Furthermore, it implies two successive violent collisions, first at the formation of the large planetary body, when the clasts were placed its deep interior, and second, at the disruption of the large planetary body, when the clasts were expelled out of the parent body and later on transported to the accretion region of the CR chondrites. We also discuss possible origin of O isotopic variations in GBL, and presence/absence of graphite in GBL/GFL, respectively, in relation to smelting possibly occurred during the igneous process(es) which formed the two lithologies. Finally we present a possible

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

    PubMed

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

    2012-12-01

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

  15. Exploring the Potential of Stable Isotope (Resonance) Raman Microspectroscopy and Surface-Enhanced Raman Scattering for the Analysis of Microorganisms at Single Cell Level.

    PubMed

    Kubryk, Patrick; Kölschbach, Janina S; Marozava, Sviatlana; Lueders, Tillmann; Meckenstock, Rainer U; Niessner, Reinhard; Ivleva, Natalia P

    2015-07-01

    Raman microspectroscopy is a prime tool to characterize the molecular and isotopic composition of microbial cells. However, low sensitivity and long acquisition times limit a broad applicability of the method in environmental analysis. In this study, we explore the potential, the applicability, and the limitations of stable isotope Raman microspectroscopy (SIRM), resonance SIRM, and SIRM in combination with surface-enhanced Raman scattering (SERS) for the characterization of single bacterial cells. The latter two techniques have the potential to significantly increase sensitivity and decrease measurement times in SIRM, but to date, there are no (SERS-SIRM) or only a limited number (resonance SIRM) of studies in environmental microbiology. The analyzed microorganisms were grown with substrates fully labeled with the stable isotopes (13)C or (2)H and compounds with natural abundance of atomic isotopes ((12)C 98.89% or (1)H 99.9844%, designated as (12)C or (1)H, respectively). Raman bands of bacterial cell compounds in stable isotope-labeled microorganisms exhibited a characteristic red-shift in the spectra. In particular, the sharp phenylalanine band was found to be an applicable marker band for SIRM analysis of the Deltaproteobacterium strain N47 growing anaerobically on (13)C-naphthalene. The study of G. metallireducens grown with (13)C- and (2)H-acetate showed that the information on the chromophore cytochrome c obtained by resonance SIRM at 532 nm excitation wavelength can be successfully complemented by whole-organism fingerprints of bacteria cells achieved by regular SIRM after photobleaching. Furthermore, we present here for the first time the reproducible SERS analysis of microbial cells labeled with stable isotopes. Escherichia coli strain DSM 1116 cultivated with (12)C- or (13)C-glucose was used as a model organism. Silver nanoparticles synthesized in situ were applied as SERS media. We observed a reproducible red-shift of an adenine-related marker band

  16. Evaluating abundance and trends in a Hawaiian avian community using state-space analysis

    USGS Publications Warehouse

    Camp, Richard J.; Brinck, Kevin W.; Gorresen, P.M.; Paxton, Eben

    2015-01-01

    Estimating population abundances and patterns of change over time are important in both ecology and conservation. Trend assessment typically entails fitting a regression to a time series of abundances to estimate population trajectory. However, changes in abundance estimates from year-to-year across time are due to both true variation in population size (process variation) and variation due to imperfect sampling and model fit. State-space models are a relatively new method that can be used to partition the error components and quantify trends based only on process variation. We compare a state-space modelling approach with a more traditional linear regression approach to assess trends in uncorrected raw counts and detection-corrected abundance estimates of forest birds at Hakalau Forest National Wildlife Refuge, Hawai‘i. Most species demonstrated similar trends using either method. In general, evidence for trends using state-space models was less strong than for linear regression, as measured by estimates of precision. However, while the state-space models may sacrifice precision, the expectation is that these estimates provide a better representation of the real world biological processes of interest because they are partitioning process variation (environmental and demographic variation) and observation variation (sampling and model variation). The state-space approach also provides annual estimates of abundance which can be used by managers to set conservation strategies, and can be linked to factors that vary by year, such as climate, to better understand processes that drive population trends.

  17. Isotopic analysis of uranium in natural waters by alpha spectrometry

    USGS Publications Warehouse

    Edwards, K.W.

    1968-01-01

    A method is described for the determination of U234/U238 activity ratios for uranium present in natural waters. The uranium is coprecipitated from solution with aluminum phosphate, extracted into ethyl acetate, further purified by ion exchange, and finally electroplated on a titanium disc for counting. The individual isotopes are determined by measurement of the alpha-particle energy spectrum using a high resolution low-background alpha spectrometer. Overall chemical recovery of about 90 percent and a counting efficiency of 25 percent allow analyses of water samples containing as little as 0.10 ?g/l of uranium. The accuracy of the method is limited, on most samples, primarily by counting statistics.

  18. Project VeSElkA: results of abundance analysis I - HD 71030, HD 95608, HD 116235 and HD 186568

    NASA Astrophysics Data System (ADS)

    LeBlanc, F.; Khalack, V.; Yameogo, B.; Thibeault, C.; Gallant, I.

    2015-11-01

    A portion of main-sequence stars, called chemically peculiar (CP) stars, show important abundance anomalies mainly due to atomic diffusion of the species within these stars. Certain CP stars have hydrodynamically stable atmospheres where atomic diffusion may dominate and lead to vertical abundance stratification there. Recently, Project VeSElkA (a word meaning rainbow in Ukrainian and standing for `Vertical Stratification of Element Abundances') was initiated with the goal to detect vertical stratification of chemical abundances in selected CP stars using high-resolution spectra with large signal-to-noise ratios. The first extensive and detailed series of results from atomic-line analysis is presented here for four stars of Project VeSElkA: HD 71030, HD 95608, HD 116235 and HD 186568. These stars were recently observed with ESPaDOnS at Canada-France-Hawaii Telescope. Strong evidence of iron stratification in the atmospheres of HD 95608 and HD 116235 was found. Chromium also shows a steep abundance gradient in the upper atmospheres of these two stars. No evidence of stratification is found for HD 71030 and HD 186568.

  19. Climatic/Hydrologic Oscillations since 155,000 yr B.P. at Owens Lake, California, Reflected in Abundance and Stable Isotope Composition of Sediment Carbonate

    USGS Publications Warehouse

    Menking, K.M.; Bischoff, J.L.; Fitzpatrick, J.A.; Burdette, J.W.; Rye, R.O.

    1997-01-01

    Sediment grain size, carbonate content, and stable isotopes in 70-cm-long (???1500-yr) channel samples from Owens Lake core OL-92 record many oscillations representing climate change in the eastern Sierra Nevada region since 155,000 yr B.P. To first order, the records match well the marine ??18O record. At Owens Lake, however, the last interglaciation appears to span the entire period from 120,000 to 50,000 yr B.P., according to our chronology, and was punctuated by numerous short periods of wetter conditions during an otherwise dry climate. Sediment proxies reveal that the apparent timing of glacial-interglacial transitions, notably the penultimate one, is proxy-dependent. In the grain-size and carbonate-content records this transition is abrupt and occurs at ??? 120,000 yr B.P. In contrast, in the isotopic records the transition is gradual and occurs between 145,000 and 120,000 yr B. P. Differences in timing of the transition are attributed to variable responses by proxies to climate change. ?? 1997 University of Washington.

  20. Sulfur isotopic analysis of carbonyl sulfide and its application for biogeochemical cycles

    NASA Astrophysics Data System (ADS)

    Hattori, Shohei; Kamezaki, Kazuki; Ogawa, Takahiro; Toyoda, Sakae; Katayama, Yoko; Yoshida, Naohiro

    2016-04-01

    Carbonyl sulfide (OCS or COS) is the most abundant gas containing sulfur in the atmosphere, with an average mixing ratio of 500 p.p.t.v. in the troposphere. OCS is suggested as a sulfur source of the stratospheric sulfate aerosols (SSA) which plays an important role in Earth's radiation budget and ozone depletion. Therefore, OCS budget should be validated for prediction of climate change, but the global OCS budget is imbalance. Recently we developed a promising new analytical method for measuring the stable sulfur isotopic compositions of OCS using nanomole level samples: the direct isotopic analytical technique of on-line gas chromatography-isotope ratio mass spectrometry (GC-IRMS) using fragmentation ions S+ (Hattori et al., 2015). The first measurement of the δ34S value for atmospheric OCS coupled with isotopic fractionation for OCS sink reactions in the stratosphere (Hattori et al., 2011; Schmidt et al., 2012; Hattori et al., 2012) explains the reported δ34S value for background stratospheric sulfate, suggesting that OCS is a potentially important source for background (nonepisodic or nonvolcanic) stratospheric sulfate aerosols. This new method measuring δ34S values of OCS can be used to investigate OCS sources and sinks in the troposphere to better understand its cycle. It is known that some microorganisms in soil can degrade OCS, but the mechanism and the contribution to the OCS in the air are still uncertain. In order to determine sulfur isotopic enrichment factor of OCS during degradation via microorganisms, incubation experiments were conducted using strains belonging to the genera Mycobacterium, Williamsia and Cupriavidus, isolated from natural soil environments (Kato et al., 2008). As a result, sulfur isotope ratios of OCS were increased during degradation of OCS, indicating that reaction for OC32S is faster than that for OC33S and OC34S. OCS degradation via microorganisms is not mass-independent fractionation (MIF) process, suggesting that this

  1. When other separation techniques fail: compound-specific carbon isotope ratio analysis of sulfonamide containing pharmaceuticals by high-temperature-liquid chromatography-isotope ratio mass spectrometry.

    PubMed

    Kujawinski, Dorothea M; Zhang, Lijun; Schmidt, Torsten C; Jochmann, Maik A

    2012-09-18

    Compound-specific isotope analysis (CISA) of nonvolatile analytes has been enabled by the introduction of the first commercial interface to hyphenate liquid chromatography with an isotope ratio mass spectrometer (LC-IRMS) in 2004, yet carbon isotope analysis of unpolar and moderately polar compounds is still a challenging task since only water as the eluent and no organic modifiers can be used to drive the separation in LC. The only way to increase the elution strength of aqueous eluents in reversed phase LC is the application of high temperatures to the mobile and stationary phases (HT-LC-IRMS). In this context we present the first method to determine carbon isotope ratios of pharmaceuticals that cannot be separated by already existing separation techniques for LC-IRMS, such as reversed phase chromatography at normal temperatures, ion-chromatography, and mixed mode chomatography. The pharmaceutical group of sulfonamides, which is generally mixed with trimethoprim in pharmaceutical products, has been chosen as probe compounds. Substance amounts as low as 0.3 μg are sufficient to perform a precise analysis. The successful applicability and reproducibility of this method is shown by the analysis of real pharmaceutical samples. The method provides the first tool to study the pharmaceutical authenticity as well as degradation and mobility of such substances in the environment by using the stable isotopic signature of these compounds.

  2. Compound-Specific Isotope Analysis of Nitroaromatic Contaminant Transformations by Nitroarene Dioxygenases

    NASA Astrophysics Data System (ADS)

    Pati, Sarah G.; Kohler, Hans-Peter E.; Hofstetter, Thomas B.

    2014-05-01

    Dioxygenation is an important biochemical reaction that often initiates the mineralization of recalcitrant organic contaminants such as nitroaromatic explosives, chlorinated benzenes, and polycyclic aromatic hydrocarbons. However, to assess the extent of dioxygenation in contaminated environments is difficult because of competing transformation processes and further reactions of the dioxygenation products. Compound-specific isotope analysis (CSIA) offers a new approach to reliably quantify biodegradation initiated by dioxygenation based on changes in stable isotope ratios of the pollutant. For CSIA it is essential to know the kinetic isotope effects (KIEs) pertinent to the dioxygenation mechanism of organic contaminants. Unfortunately, the range of KIEs of such reactions is poorly constrained although many dioxygenase enzymes with a broad substrate specificity have been reported. Dioxygenase enzymes usually exhibit complex reaction kinetics involving multiple substrates and substrate-specific binding modes which makes the determination of KIEs challenging. The goal of this study was to explore the magnitude and variability of 13C-, 2H-, and 15N-KIEs for the dioxygenation of one contaminant class, that is nitroaromatic contaminants (NACs). To this end, we investigated the C, H, and N isotope fractionation during the dioxygenation of nitrobenzene (NB), 2-nitrotoluene (2-NT), and 3-nitrotoluene (3-NT) by pure cultures, E. coli clones, cell extracts, and purified enzymes. From isotope fractionations measured in the substrates and reaction products, we determined dioxygenation KIEs for different combinations of the three substrates with nitrobenzene dioxygenase (NBDO) and 2-nitrotoluene dioxygenase (2NTDO). The 13C-, 2H-, and 15N-KIEs for the dioxygenation of NB by NBDO were consistent for all experimental systems considered (i.e., Comamonas sp. Strain JS765, E. coli clones, cell extracts of E. coli clones, and purified NBDO). This observation suggests that the isotope

  3. Food webs in Mongolian grasslands: the analysis of 13C and 15N natural abundances.

    PubMed

    Kohzu, Ayato; Iwata, T; Kato, M; Nishikawa, J; Wada, Eitaro; Amartuvshin, N; Namkhaidorj, B; Fujita, N

    2009-09-01

    Overgrazing often lowers species richness and productivity of grassland communities. For Mongolian grassland ecosystems, a lack of detailed information about food-web structures makes it difficult to predict the effects of overgrazing on species diversity and community composition. We analysed the delta13C and delta15N signatures of herbaceous plants, arthropods (grouped by feeding habit), wild and domestic mammals, and humans in central Mongolia to understand the predominant food-web pathways in this grassland ecosystem. The delta13C and delta15N values of mammals showed little variation within species, but varied considerably with slope position for arthropods. The apparent isotopic discrimination between body tissue and hair of mammals was estimated as 2.0 per thousand for delta13C and 2.1 per thousand for delta15N, which was large enough to cause overestimation of the trophic level of mammals if not taken into account when using hair samples to measure isotopic enrichment.

  4. CHEMICAL ABUNDANCE ANALYSIS OF A NEUTRON-CAPTURE ENHANCED RED GIANT IN THE BULGE PLAUT FIELD

    SciTech Connect

    Johnson, Christian I.; Rich, R. Michael; McWilliam, Andrew E-mail: rmr@astro.ucla.edu E-mail: andy@obs.carnegiescience.edu

    2013-09-20

    We present chemical abundances for 27 elements ranging from oxygen to erbium in the metal-poor ([Fe/H] = –1.67) bulge red giant branch star 2MASS 18174532-3353235. The results are based on equivalent width and spectrum synthesis analyses of a high-resolution (R ∼ 30, 000) spectrum obtained with the Magellan-MIKE spectrograph. While the light (Z ∼< 30) element abundance patterns match those of similar metallicity bulge and halo stars, the strongly enhanced heavy element abundances are more similar to 'r-II' halo stars (e.g., CS 22892-052) typically found at [Fe/H] ∼< – 2.5. We find that the heaviest elements (Z ≥ 56) closely follow the scaled-solar r-process abundance pattern. We do not find evidence supporting significant s-process contributions; however, the intermediate mass elements (e.g., Y and Zr) appear to have been produced through a different process than the heaviest elements. The light and heavy element abundance patterns of 2MASS 18174532-3353235 are in good agreement with the more metal-poor r-process enhanced stars CS 22892-052 and BD +17{sup o}3248. 2MASS 18174532-3353235 also shares many chemical characteristics with the similar metallicity but comparatively α-poor Ursa Minor dwarf galaxy giant COS 82. Interestingly, the Mo and Ru abundances of 2MASS 18174532-3353235 are also strongly enhanced and follow a similar trend recently found to be common in moderately metal-poor main-sequence turn-off halo stars.

  5. Enhanced understanding of ectoparasite: host trophic linkages on coral reefs through stable isotope analysis

    USGS Publications Warehouse

    Demopoulos, Amanda W. J.; Sikkel, Paul C.

    2015-01-01

    Parasitism, although the most common type of ecological interaction, is usually ignored in food web models and studies of trophic connectivity. Stable isotope analysis is widely used in assessing the flow of energy in ecological communities and thus is a potentially valuable tool in understanding the cryptic trophic relationships mediated by parasites. In an effort to assess the utility of stable isotope analysis in understanding the role of parasites in complex coral-reef trophic systems, we performed stable isotope analysis on three common Caribbean reef fish hosts and two kinds of ectoparasitic isopods: temporarily parasitic gnathiids (Gnathia marleyi) and permanently parasitic cymothoids (Anilocra). To further track the transfer of fish-derived carbon (energy) from parasites to parasite consumers, gnathiids from host fish were also fed to captive Pederson shrimp (Ancylomenes pedersoni) for at least 1 month. Parasitic isopods had δ13C and δ15N values similar to their host, comparable with results from the small number of other host–parasite studies that have employed stable isotopes. Adult gnathiids were enriched in 15N and depleted in13C relative to juvenile gnathiids, providing insights into the potential isotopic fractionation associated with blood-meal assimilation and subsequent metamorphosis. Gnathiid-fed Pedersen shrimp also had δ13C values consistent with their food source and enriched in 15N as predicted due to trophic fractionation. These results further indicate that stable isotopes can be an effective tool in deciphering cryptic feeding relationships involving parasites and their consumers, and the role of parasites and cleaners in carbon transfer in coral-reef ecosystems specifically.

  6. Enhanced understanding of ectoparasite–host trophic linkages on coral reefs through stable isotope analysis

    PubMed Central

    Demopoulos, Amanda W.J.; Sikkel, Paul C.

    2015-01-01

    Parasitism, although the most common type of ecological interaction, is usually ignored in food web models and studies of trophic connectivity. Stable isotope analysis is widely used in assessing the flow of energy in ecological communities and thus is a potentially valuable tool in understanding the cryptic trophic relationships mediated by parasites. In an effort to assess the utility of stable isotope analysis in understanding the role of parasites in complex coral-reef trophic systems, we performed stable isotope analysis on three common Caribbean reef fish hosts and two kinds of ectoparasitic isopods: temporarily parasitic gnathiids (Gnathia marleyi) and permanently parasitic cymothoids (Anilocra). To further track the transfer of fish-derived carbon (energy) from parasites to parasite consumers, gnathiids from host fish were also fed to captive Pederson shrimp (Ancylomenes pedersoni) for at least 1 month. Parasitic isopods had δ13C and δ15N values similar to their host, comparable with results from the small number of other host–parasite studies that have employed stable isotopes. Adult gnathiids were enriched in 15N and depleted in 13C relative to juvenile gnathiids, providing insights into the potential isotopic fractionation associated with blood-meal assimilation and subsequent metamorphosis. Gnathiid-fed Pedersen shrimp also had δ13C values consistent with their food source and enriched in 15N as predicted due to trophic fractionation. These results further indicate that stable isotopes can be an effective tool in deciphering cryptic feeding relationships involving parasites and their consumers, and the role of parasites and cleaners in carbon transfer in coral-reef ecosystems specifically. PMID:25830112

  7. Enhanced understanding of ectoparasite-host trophic linkages on coral reefs through stable isotope analysis.

    PubMed

    Demopoulos, Amanda W J; Sikkel, Paul C

    2015-04-01

    Parasitism, although the most common type of ecological interaction, is usually ignored in food web models and studies of trophic connectivity. Stable isotope analysis is widely used in assessing the flow of energy in ecological communities and thus is a potentially valuable tool in understanding the cryptic trophic relationships mediated by parasites. In an effort to assess the utility of stable isotope analysis in understanding the role of parasites in complex coral-reef trophic systems, we performed stable isotope analysis on three common Caribbean reef fish hosts and two kinds of ectoparasitic isopods: temporarily parasitic gnathiids (Gnathia marleyi) and permanently parasitic cymothoids (Anilocra). To further track the transfer of fish-derived carbon (energy) from parasites to parasite consumers, gnathiids from host fish were also fed to captive Pederson shrimp (Ancylomenes pedersoni) for at least 1 month. Parasitic isopods had δ(13)C and δ(15)N values similar to their host, comparable with results from the small number of other host-parasite studies that have employed stable isotopes. Adult gnathiids were enriched in (15)N and depleted in (13)C relative to juvenile gnathiids, providing insights into the potential isotopic fractionation associated with blood-meal assimilation and subsequent metamorphosis. Gnathiid-fed Pedersen shrimp also had δ(13)C values consistent with their food source and enriched in (15)N as predicted due to trophic fractionation. These results further indicate that stable isotopes can be an effective tool in deciphering cryptic feeding relationships involving parasites and their consumers, and the role of parasites and cleaners in carbon transfer in coral-reef ecosystems specifically. PMID:25830112

  8. Effects of nitrate and water on the oxygen isotopic analysis of barium sulfate precipitated from solution

    USGS Publications Warehouse

    Hannon, Janet E.; Bohlke, Johnkarl F.; Mroczkowski, Stanley J.

    2008-01-01

    BaSO4 precipitated from mixed salt solutions by common techniques for SO isotopic analysis may contain quantities of H2O and NOthat introduce errors in O isotope measurements. Experiments with synthetic solutions indicate that δ18O values of CO produced by decomposition of precipitated BaSO4 in a carbon reactor may be either too low or too high, depending on the relative concentrations of SO and NO and the δ18O values of the H2O, NO, and SO. Typical δ18O errors are of the order of 0.5 to 1‰ in many sample types, and can be larger in samples containing atmospheric NO, which can cause similar errors in δ17O and Δ17O. These errors can be reduced by (1) ion chromatographic separation of SO from NO, (2) increasing the salinity of the solutions before precipitating BaSO4 to minimize incorporation of H2O, (3) heating BaSO4 under vacuum to remove H2O, (4) preparing isotopic reference materials as aqueous samples to mimic the conditions of the samples, and (5) adjusting measured δ18O values based on amounts and isotopic compositions of coexisting H2O and NO. These procedures are demonstrated for SO isotopic reference materials, synthetic solutions with isotopically known reagents, atmospheric deposition from Shenandoah National Park, Virginia, USA, and sulfate salt deposits from the Atacama Desert, Chile, and Mojave Desert, California, USA. These results have implications for the calibration and use of O isotope data in studies of SOsources and reaction mechanisms.

  9. Isotopic Dilution Analysis and Secular Equilibrium Study: Two Complementary Radiochemistry Experiments.

    ERIC Educational Resources Information Center

    Williams, Kathryn R.; Lipford, Levin C.

    1985-01-01

    Describes a complementary pair of radiochemistry experiments for instruction of isotopic dilution analysis and secular equilibrium. Both experiments use the readily available cesium-137 nuclide and the simple precipitation technique for cesium with the tetraphenylborate anion. Procedures used and typical results obtained are provided and…

  10. Analysis of tarnished plant bug movement using carbon and nitrogen isotopes

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Tarnished plant bug, Lygus lineolaris (Palisot de Beauvois), is the primary pest of cotton across the Midsouth of the United States. Movement into cotton fields occurs during the summer from other host plants, both cultivated and wild. Stable isotope analysis (SIA) has been used in other studies to ...

  11. Mucus: A new tissue fraction for rapid determination of fish diet switching using stable isotope analysis

    EPA Science Inventory

    Stable isotope analysis of diet switching by fishes often is hampered by slow turnover rates of the tissues analyzed (usually muscle or fins). We examined epidermal mucus as a potentially faster turnover “tissue” that might provide a more rapid assessment of diet switching. In a ...

  12. Mucus: a new tissue fraction for rapid determination of fish diet switching using stable isotope analysis.

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Stable isotope analysis of diet switching by fishes is often hampered by slow turnover rates of the tissues analyzed (usually muscle or fins). We examined epidermal mucus as a potentially faster turnover “tissue” that might provide a more rapid assessment of diet switching. In a controlled hatchery...

  13. Grazing food web view from compound-specific stable isotope analysis of amino acids

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Knowledge of the trophic position (TP) of organisms in food webs allows ecologists to track energy flow and trophic linkages among organisms in complex networks of ecosystems. Compound-specific stable isotope analysis (CSIA) of amino acids has been employed as a relatively new method with the high p...

  14. Linking ramped pyrolysis isotope data to oil content through PAH analysis

    NASA Astrophysics Data System (ADS)

    Pendergraft, Matthew A.; Dincer, Zeynep; Sericano, José L.; Wade, Terry L.; Kolasinski, Joanna; Rosenheim, Brad E.

    2013-12-01

    Ramped pyrolysis isotope (13C and 14C) analysis coupled with polycyclic aromatic hydrocarbon (PAH) analysis demonstrates the utility of ramped pyrolysis in screening for oil content in sediments. Here, sediments from Barataria Bay, Louisiana, USA that were contaminated by oil from the 2010 BP Deepwater Horizon spill display relationships between oil contamination, pyrolysis profiles, and isotopic composition. Sediment samples with low PAH concentrations are thermochemically stable until higher temperatures, while samples containing high concentrations of PAHs pyrolyze at low temperatures. High PAH samples are also depleted in radiocarbon (14C), especially in the fractions that pyrolyze at low temperatures. This lack of radiocarbon in low temperature pyrolyzates is indicative of thermochemically unstable, 14C-free oil content. This study presents a proof of concept that oil contamination can be identified by changes in thermochemical stability in organic material and corroborated by isotope analysis of individual pyrolyzates, thereby providing a basis for application of ramped pyrolysis isotope analysis to samples deposited in different environments for different lengths of time.

  15. Chemical Imaging and Stable Isotope Analysis of Atmospheric Particles by NanoSIMS (Invited)

    NASA Astrophysics Data System (ADS)

    Sinha, B.; Harris, E. J.; Pöhlker, C.; Wiedemann, K. T.; van Pinxteren, D.; Tilgner, A.; Fomba, K. W.; Schneider, J.; Roth, A.; Gnauk, T.; Fahlbusch, B.; Mertes, S.; Lee, T.; Collett, J. L.; Shiraiwa, M.; Gunthe, S. S.; Smith, M.; Artaxo, P. P.; Gilles, M.; Kilcoyne, A. L.; Moffet, R.; Weigand, M.; Martin, S. T.; Poeschl, U.; Andreae, M. O.; Hoppe, P.; Herrmann, H.; Borrmann, S.

    2013-12-01

    Chemical imaging analysis of the internal distribution of chemical compounds by a combination of SEM-EDX, and NanoSIMS allows investigating the physico-chemical properties and isotopic composition of individual aerosol particles. Stable sulphur isotope analysis provides insight into the sources, sinks and oxidation pathways of SO2 in the environment. Oxidation by OH radicals, O3 and H2O2 enriches the heavier isotope in the product sulphate, whereas oxidation by transition metal ions (TMI), hypohalites and hypohalous acids depletes the heavier isotope in the product sulphate. The isotope fractionation during SO2 oxidation by stabilized Criegee Intermediate radicals is unknown. We studied the relationship between aerosol chemical composition and predominant sulphate formation pathways in continental clouds in Central Europe and during the wet season in the Amazon rain forest. Sulphate formation in continental clouds in Central Europe was studied during HCCT-2010, a lagrangian-type field experiment, during which an orographic cloud was used as a natural flow-through reactor to study in-cloud aerosol processing (Harris et al. 2013). Sulphur isotopic compositions in SO2 and H2SO4 gas and particulate sulphate were measured and changes in the sulphur isotope composition of SO2 between the upwind and downwind measurement sites were used to determine the dominant SO2 chemical removal process occurring in the cloud. Changes in the isotopic composition of particulate sulphate revealed that transition metal catalysis pathway was the dominant SO2 oxidation pathway. This reaction occurred primarily on coarse mineral dust particles. Thus, sulphate produced due to in-cloud SO2 oxidation is removed relatively quickly from the atmosphere and has a minor climatic effect. The aerosol samples from the Amazonian rainforest, a pristine tropical environment, were collected during the rainy season. The samples were found to be dominated by SOA particles in the fine mode and primary

  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. INCA: a computational platform for isotopically non-stationary metabolic flux analysis

    PubMed Central

    2014-01-01

    Summary: 13C flux analysis studies have become an essential component of metabolic engineering research. The scope of these studies has gradually expanded to include both isotopically steady-state and transient labeling experiments, the latter of which are uniquely applicable to photosynthetic organisms and slow-to-label mammalian cell cultures. Isotopomer network compartmental analysis (INCA) is the first publicly available software package that can perform both steady-state metabolic flux analysis and isotopically non-stationary metabolic flux analysis. The software provides a framework for comprehensive analysis of metabolic networks using mass balances and elementary metabolite unit balances. The generation of balance equations and their computational solution is completely automated and can be performed on networks of arbitrary complexity. Availability and implementation: MATLAB p-code files are freely available for non-commercial use and can be downloaded at http://mfa.vueinnovations.com. Commercial licenses are also available. Contact: j.d.young@vanderbilt.edu PMID:24413674

  18. 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

  19. Analysis of gas centrifuge cascade for separation of multicomponent isotopes and optimal feed position

    SciTech Connect

    Chuntong Ying; Hongjiang Wu; Mingsheng Zhou; Yuguang Nie; Guangjun Liu

    1997-10-01

    Analysis of the concentration distribution in a gas centrifuge cascade for separation of multicomponent isotope mixtures is different from that in a cascade for separation of two-component mixtures. This paper presents the governing equations for a multicomponent isotope separation cascade. Numerically predicted separation factors for the gas centrifuge cascade agree well with the experimental data. A theoretical optimal feed position is derived for a short square cascade for a two-component mixture in a close-separation case. The optimal feed position for a gas centrifuge cascade for separation of multicomponent mixture is discussed.

  20. Relativistic astrophysics. [design analysis and performance tests of Cerenkov counters for detection of iron isotopes

    NASA Technical Reports Server (NTRS)

    Price, P. B.

    1976-01-01

    The design, experimental testing, and calibration (error analysis) of a high resolution Cerenkov-scintillation detector is presented. The detector is capable of detecting iron isotopes and heavy ions of cosmic rays, and of performing direct measurements of individual neighboring isotopes at charge resolution 26. It utilizes Lexan (trademark) sheets, and has been used in flight packages of balloons and on the Skylab. The detector will be able to provide more information on violet astrophysical processes, such as thermonuclear reactions on neutron stars. Ground support and display equipment which are to be used in conjunction with the detector are also discussed.

  1. Uranium Isotopic and Quantitative Analysis Using a Mechanically-Cooled HPGe Detector

    SciTech Connect

    Solodov, Alexander A

    2008-01-01

    A new, portable high-resolution spectroscopy system based on a high-purity germanium detector cooled with a miniature Stirling-cycle cooler, ORTEC trans-SPEC, has recently become commercially available. The use of a long-life mechanical cooling system eliminates the need for liquid nitrogen. The purpose of this study was to determine the applicability of this new instrument for isotopic and quantitative analyses of uranium samples. The results of the performance of the trans-SPEC with the combination of PC-FRAM and ISOTOPIC software packages are described in this paper. An optimal set of analysis parameters for uranium measurements is proposed.

  2. The Impact of Land Abandonment on Species Richness and Abundance in the Mediterranean Basin: A Meta-Analysis

    PubMed Central

    Plieninger, Tobias; Hui, Cang; Gaertner, Mirijam; Huntsinger, Lynn

    2014-01-01

    Land abandonment is common in the Mediterranean Basin, a global biodiversity hotspot, but little is known about its impacts on biodiversity. To upscale existing case-study insights to the Pan-Mediterranean level, we conducted a meta-analysis of the effects of land abandonment on plant and animal species richness and abundance in agroforestry, arable land, pastures, and permanent crops of the Mediterranean Basin. In particular, we investigated (1) which taxonomic groups (arthropods, birds, lichen, vascular plants) are more affected by land abandonment; (2) at which spatial and temporal scales the effect of land abandonment on species richness and abundance is pronounced; (3) whether previous land use and current protected area status affect the magnitude of changes in the number and abundance of species; and (4) how prevailing landforms and climate modify the impacts of land abandonment. After identifying 1240 potential studies, 154 cases from 51 studies that offered comparisons of species richness and abundance and had results relevant to our four areas of investigation were selected for meta-analysis. Results are that land abandonment showed slightly increased (effect size  = 0.2109, P<0.0001) plant and animal species richness and abundance overall, though results were heterogeneous, with differences in effect size between taxa, spatial-temporal scales, land uses, landforms, and climate. In conclusion, there is no “one-size-fits-all” conservation approach that applies to the diverse contexts of land abandonment in the Mediterranean Basin. Instead, conservation policies should strive to increase awareness of this heterogeneity and the potential trade-offs after abandonment. The strong role of factors at the farm and landscape scales that was revealed by the analysis indicates that purposeful management at these scales can have a powerful impact on biodiversity. PMID:24865979

  3. MyGIsFOS: an automated code for parameter determination and detailed abundance analysis in cool stars

    NASA Astrophysics Data System (ADS)

    Sbordone, L.; Caffau, E.; Bonifacio, P.; Duffau, S.

    2014-04-01

    Context. The current and planned high-resolution, high-multiplexity stellar spectroscopic surveys, as well as the swelling amount of underutilized data present in public archives, have led to an increasing number of efforts to automate the crucial but slow process of retrieving stellar parameters and chemical abundances from spectra. Aims: We present MyGIsFOS1, a code designed to derive atmospheric parameters and detailed stellar abundances from medium- to high-resolution spectra of cool (FGK) stars. We describe the general structure and workings of the code, present analyses of a number of well-studied stars representative of the parameter space MyGIsFOS is designed to cover, and give examples of the exploitation of MyGIsFOS very fast analysis to assess uncertainties through Monte Carlo tests. Methods: MyGIsFOS aims to reproduce a "traditional" manual analysis by fitting spectral features for different elements against a precomputed grid of synthetic spectra. The lines of Fe i and Fe ii can be employed to determine temperature, gravity, microturbulence, and metallicity by iteratively minimizing the dependence of Fe i abundance from line lower energy and equivalent width, and imposing Fe i-Fe ii ionization equilibrium. Once parameters are retrieved, detailed chemical abundances are measured from lines of other elements. Results: MyGIsFOS replicates closely the results obtained in similar analyses on a set of well-known stars. It is also quite fast, performing a full parameter determination and detailed abundance analysis in about two minutes per star on a mainstream desktop computer. Currently, its preferred field of application are high-resolution and/or large spectral coverage data (e.g., UVES, X-shooter, HARPS, Sophie). My God It's Full Of Stars, http://mygisfos.obspm.fr

  4. The impact of land abandonment on species richness and abundance in the Mediterranean Basin: a meta-analysis.

    PubMed

    Plieninger, Tobias; Hui, Cang; Gaertner, Mirijam; Huntsinger, Lynn

    2014-01-01

    Land abandonment is common in the Mediterranean Basin, a global biodiversity hotspot, but little is known about its impacts on biodiversity. To upscale existing case-study insights to the Pan-Mediterranean level, we conducted a meta-analysis of the effects of land abandonment on plant and animal species richness and abundance in agroforestry, arable land, pastures, and permanent crops of the Mediterranean Basin. In particular, we investigated (1) which taxonomic groups (arthropods, birds, lichen, vascular plants) are more affected by land abandonment; (2) at which spatial and temporal scales the effect of land abandonment on species richness and abundance is pronounced; (3) whether previous land use and current protected area status affect the magnitude of changes in the number and abundance of species; and (4) how prevailing landforms and climate modify the impacts of land abandonment. After identifying 1240 potential studies, 154 cases from 51 studies that offered comparisons of species richness and abundance and had results relevant to our four areas of investigation were selected for meta-analysis. Results are that land abandonment showed slightly increased (effect size  = 0.2109, P<0.0001) plant and animal species richness and abundance overall, though results were heterogeneous, with differences in effect size between taxa, spatial-temporal scales, land uses, landforms, and climate. In conclusion, there is no "one-size-fits-all" conservation approach that applies to the diverse contexts of land abandonment in the Mediterranean Basin. Instead, conservation policies should strive to increase awareness of this heterogeneity and the potential trade-offs after abandonment. The strong role of factors at the farm and landscape scales that was revealed by the analysis indicates that purposeful management at these scales can have a powerful impact on biodiversity.

  5. The impact of land abandonment on species richness and abundance in the Mediterranean Basin: a meta-analysis.

    PubMed

    Plieninger, Tobias; Hui, Cang; Gaertner, Mirijam; Huntsinger, Lynn

    2014-01-01

    Land abandonment is common in the Mediterranean Basin, a global biodiversity hotspot, but little is known about its impacts on biodiversity. To upscale existing case-study insights to the Pan-Mediterranean level, we conducted a meta-analysis of the effects of land abandonment on plant and animal species richness and abundance in agroforestry, arable land, pastures, and permanent crops of the Mediterranean Basin. In particular, we investigated (1) which taxonomic groups (arthropods, birds, lichen, vascular plants) are more affected by land abandonment; (2) at which spatial and temporal scales the effect of land abandonment on species richness and abundance is pronounced; (3) whether previous land use and current protected area status affect the magnitude of changes in the number and abundance of species; and (4) how prevailing landforms and climate modify the impacts of land abandonment. After identifying 1240 potential studies, 154 cases from 51 studies that offered comparisons of species richness and abundance and had results relevant to our four areas of investigation were selected for meta-analysis. Results are that land abandonment showed slightly increased (effect size  = 0.2109, P<0.0001) plant and animal species richness and abundance overall, though results were heterogeneous, with differences in effect size between taxa, spatial-temporal scales, land uses, landforms, and climate. In conclusion, there is no "one-size-fits-all" conservation approach that applies to the diverse contexts of land abandonment in the Mediterranean Basin. Instead, conservation policies should strive to increase awareness of this heterogeneity and the potential trade-offs after abandonment. The strong role of factors at the farm and landscape scales that was revealed by the analysis indicates that purposeful management at these scales can have a powerful impact on biodiversity. PMID:24865979

  6. Abundance analysis of the supergiant stars HD 80057 and HD 80404 based on their UVES Spectra

    NASA Astrophysics Data System (ADS)

    Tanrıverdi, T.; Baştürk, Ö.

    2016-08-01

    This study presents elemental abundances of the early A-type supergiant HD 80057 and the late A-type supergiant HD 80404. High resolution and high signal-to-noise ratio spectra published by the UVES Paranal Observatory Project (Bagnulo et al., 2003)1

  7. Evidence for a possible dietary effect on the isotopic composition of Zn in blood via isotopic analysis of food products by multi-collector ICP-mass spectrometry.

    PubMed

    Costas-Rodríguez, Marta; Van Heghe, Lana; Vanhaecke, Frank

    2014-01-01

    In this work, the hypothesis of a possible dietary effect on the isotopic composition of Zn in blood from populations with different feeding habits, i.e. lacto-ovo vegetarians and omnivores, was investigated through isotopic analysis of Zn in common food products by multi-collector ICP - mass spectrometry (MC-ICP-MS). Several certified reference materials (CRMs) were also included in the sample set for comparison purposes. For these CRMs, the isotopic composition of Zn is expressed as δ-values, calculated with respect to both IRMM-3702 and JMC-ZnLyon, as isotopic standards. The range of δ(66)Zn values observed in food products was approximately 1.9‰. In general, vegetables, cereals and derived products showed an enrichment of the heavier Zn isotopes, whereas a depletion was observed in products of animal origin (meat, fish, egg and semi-skimmed milk), relative to human blood samples. Mussel, however, showed a significant enrichment of the heavier isotopes, which is hypothetically attributed to its accumulation behaviour. Thus, the lower δ(66)Zn values found in food products of animal origin appear to be reflected in the lower δ(66)Zn value observed in blood from an omnivorous population compared to that for a vegetarian population.

  8. Compound Specific Isotope Analysis of Fatty Acids in Southern African Aerosols

    NASA Astrophysics Data System (ADS)

    Billmark, K. A.; Macko, S. A.; Swap, R. J.

    2003-12-01

    This study, conducted as a part of the Southern African Regional Science Initiative (SAFARI 2000), applied compound specific isotope analysis to describe aerosols at source regions and rural locations. Stable carbon isotopic compositions of individual fatty acids were determined for aerosol samples collected at four sites throughout southern Africa. Mongu, Zambia and Skukuza, South Africa were chosen for their location within intense seasonal Miombo woodland savanna and bushveld savanna biomass burning source regions, respectively. Urban aerosols were collected at Johannesburg, South Africa and rural samples were collected at Sua Pan, Botswana. Fatty acid isotopic compositions varied temporally. Urban aerosols showed significant isotopic enrichment of selected short chain fatty acids (C < 20) compared to aerosols produced during biomass combustion. Sua Pan short chain fatty acid signatures were significantly different from the other non-urban sites, which suggests that sources other than biomass combustion products, such as organic eolian material, impact the Sua Pan aerosol profile. However, a high degree of correlation between Sua Pan and Skukuza long chain fatty acid δ 13C values confirm atmospheric linkages between the two areas and that isotopic signatures of combusted fatty acids are unaltered during atmospheric transport highlighting their potential for use as a conservative tracer.

  9. Collection of NO and NO2 for isotopic analysis of NO(x) emissions.

    PubMed

    Fibiger, Dorothy L; Hastings, Meredith G; Lew, Audrey F; Peltier, Richard E

    2014-12-16

    There have been several measurements made of the nitrogen isotopic composition of gaseous NOx (NOx = NO + NO2) from various emission sources, utilizing a wide variety of methods to collect the NOx in solution as nitrate or nitrite. However, previous collection techniques have not been verified for complete or efficient capture of NOx such that the isotopic composition of NOx remains unaltered during collection. Here, we present a method of collecting NOx (NO + NO2) in solution as nitrate to evaluate the nitrogen isotopic composition of the NOx (δ(15)N-NOx). Using a 0.25 M KMnO4 and 0.5 M NaOH solution, quantitative NOx collection was achieved under a variety of conditions in laboratory and field settings, allowing for isotopic analysis without correcting for fractionations. The uncertainty across the entire analytic procedure is ±1.5‰ (1σ). With this method, a more robust inventory of NOx source isotopic composition is possible, which has implications for studies of air quality and acid deposition. PMID:25415365

  10. Linking cases of illegal shootings of the endangered California condor using stable lead isotope analysis.

    PubMed

    Finkelstein, Myra E; Kuspa, Zeka E; Welch, Alacia; Eng, Curtis; Clark, Michael; Burnett, Joseph; Smith, Donald R

    2014-10-01

    Lead poisoning is preventing the recovery of the critically endangered California condor (Gymnogyps californianus) and lead isotope analyses have demonstrated that ingestion of spent lead ammunition is the principal source of lead poisoning in condors. Over an 8 month period in 2009, three lead-poisoned condors were independently presented with birdshot embedded in their tissues, evidencing they had been shot. No information connecting these illegal shooting events existed and the timing of the shooting(s) was unknown. Using lead concentration and stable lead isotope analyses of feathers, blood, and recovered birdshot, we observed that: i) lead isotope ratios of embedded shot from all three birds were measurably indistinguishable from each other, suggesting a common source; ii) lead exposure histories re-constructed from feather analysis suggested that the shooting(s) occurred within the same timeframe; and iii) two of the three condors were lead poisoned from a lead source isotopically indistinguishable from the embedded birdshot, implicating ingestion of this type of birdshot as the source of poisoning. One of the condors was subsequently lead poisoned the following year from ingestion of a lead buckshot (blood lead 556 µg/dL), illustrating that ingested shot possess a substantially greater lead poisoning risk compared to embedded shot retained in tissue (blood lead ~20 µg/dL). To our knowledge, this is the first study to use lead isotopes as a tool to retrospectively link wildlife shooting events.

  11. Stable Isotope Analysis Reveals Detrital Resource Base Sources of the Tree Hole Mosquito, Aedes triseriatus

    PubMed Central

    Kaufman, Michael G.; Pelz-Stelinski, Kirsten S.; Yee, Donald A.; Juliano, Steven A.; Ostrom, Peggy H.; Walker, Edward D.

    2010-01-01

    1. Detritus that forms the basis for mosquito production in tree hole ecosystems can vary in type and timing of input. We investigated the contributions of plant- and animal-derived detritus to the biomass of Aedes triseriatus (Say) pupae and adults by using stable isotope (15N and 13C) techniques in lab experiments and field collections. 2. Lab-reared mosquito isotope values reflected their detrital resource base, providing a clear distinction between mosquitoes reared on plant or animal detritus. 3. Isotope values from field-collected pupae were intermediate between what would be expected if a single (either plant or animal) detrital source dominated the resource base. However, mosquito isotope values clustered most closely with plant-derived values, and a mixed feeding model analysis indicated tree floral parts contributed approximately 80% of mosquito biomass. The mixed model also indicated that animal detritus contributed approximately 30% of mosquito tissue nitrogen. 4. Pupae collected later in the season generally had isotope values that were consistent with an increased contribution from animal detritus, suggesting this resource became more nutritionally important for mosquitoes as plant inputs declined over the summer. PMID:21132121

  12. Linking cases of illegal shootings of the endangered California condor using stable lead isotope analysis.

    PubMed

    Finkelstein, Myra E; Kuspa, Zeka E; Welch, Alacia; Eng, Curtis; Clark, Michael; Burnett, Joseph; Smith, Donald R

    2014-10-01

    Lead poisoning is preventing the recovery of the critically endangered California condor (Gymnogyps californianus) and lead isotope analyses have demonstrated that ingestion of spent lead ammunition is the principal source of lead poisoning in condors. Over an 8 month period in 2009, three lead-poisoned condors were independently presented with birdshot embedded in their tissues, evidencing they had been shot. No information connecting these illegal shooting events existed and the timing of the shooting(s) was unknown. Using lead concentration and stable lead isotope analyses of feathers, blood, and recovered birdshot, we observed that: i) lead isotope ratios of embedded shot from all three birds were measurably indistinguishable from each other, suggesting a common source; ii) lead exposure histories re-constructed from feather analysis suggested that the shooting(s) occurred within the same timeframe; and iii) two of the three condors were lead poisoned from a lead source isotopically indistinguishable from the embedded birdshot, implicating ingestion of this type of birdshot as the source of poisoning. One of the condors was subsequently lead poisoned the following year from ingestion of a lead buckshot (blood lead 556 µg/dL), illustrating that ingested shot possess a substantially greater lead poisoning risk compared to embedded shot retained in tissue (blood lead ~20 µg/dL). To our knowledge, this is the first study to use lead isotopes as a tool to retrospectively link wildlife shooting events. PMID:25173094

  13. First high-precision differential abundance analysis of extremely metal-poor stars

    NASA Astrophysics Data System (ADS)

    Reggiani, Henrique; Meléndez, Jorge; Yong, David; Ramírez, Ivan; Asplund, Martin

    2016-02-01

    Context. Studies of extremely metal-poor stars indicate that chemical abundance ratios [X/Fe] have a root mean square scatter as low as 0.05 dex (12%). It remains unclear whether this reflects observational uncertainties or intrinsic astrophysical scatter arising from physical conditions in the interstellar medium at early times. Aims: We measure differential chemical abundance ratios in extremely metal-poor stars to investigate the limits of precision and to understand whether cosmic scatter or observational errors are dominant. Methods: We used high-resolution (R ~ 95 000) and high signal-to-noise (S/N = 700 at 5000 Å) HIRES/Keck spectra to determine high-precision differential abundances between two extremely metal-poor stars through a line-by-line differential approach. We determined stellar parameters for the star G64-37 with respect to the standard star G64-12. We performed EW measurements for the two stars for the lines recognized in both stars and performed spectral synthesis to study the carbon abundances. Results: The differential approach allowed us to obtain errors of σ(Teff) = 27 K, σ(log g) = 0.06 dex, σ( [Fe/H] ) = 0.02 dex and σ(vt) = 0.06 km s-1. We estimated relative chemical abundances with a precision as low as σ([X/Fe]) ≈ 0.01 dex. The small uncertainties demonstrate that there are genuine abundance differences larger than the measurement errors. The observed Li difference cannot be explained by the difference in mass because the less massive star has more Li. Conclusions: It is possible to achieve an abundance precision around ≈ 0.01-0.05 dex for extremely metal-poor stars, which opens new windows on the study of the early chemical evolution of the Galaxy. Table A.1 is also available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (ftp://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/586/A67

  14. Geostatistical Analysis of Spatial Variability of Mineral Abundance and Kd in Frenchman Flat, NTS, Alluvium

    SciTech Connect

    Carle, S F; Zavarin, M; Pawloski, G A

    2002-11-01

    LLNL hydrologic source term modeling at the Cambric site (Pawloski et al., 2000) showed that retardation of radionuclide transport is sensitive to the distribution and amount of radionuclide sorbing minerals. While all mineralogic information available near the Cambric site was used in these early simulations (11 mineral abundance analyses from UE-5n and 9 from RNM-l), these older data sets were qualitative in nature, with detection limits too high to accurately measure many of the important radionuclide sorbing minerals (e.g. iron oxide). Also, the sparse nature of the mineral abundance data permitted only a hypothetical description of the spatial distribution of radionuclide sorbing minerals. Yet, the modeling results predicted that the spatial distribution of sorbing minerals would strongly affect radionuclide transport. Clearly, additional data are needed to improve understanding of mineral abundances and their spatial distributions if model predictions in Frenchman Flat are to be defensible. This report evaluates new high-resolution quantitative X-Ray Diffraction (XRD) data on mineral distributions and their abundances from core samples recently collected from drill hole ER-5-4. The total of 94 samples from ER-5-4 were collected at various spacings to enable evaluation of spatial variability at a variety of spatial scales as small as 0.3 meters and up to hundreds of meters. Additional XRD analyses obtained from drillholes UE-Sn, ER-5-3, and U-11g-1 are used to augment evaluation of vertical spatial variability and permit some evaluation of lateral spatial variability. A total of 163 samples are evaluated. The overall goal of this study is to understand and characterize the spatial variation of sorbing minerals in Frenchman Flat alluvium using geostatistical techniques, with consideration for the potential impact on reactive transport of radionuclides. To achieve this goal requires an effort to ensure that plausible geostatistical models are used to

  15. Stable isotope analysis of plant-derived nitrate - novel method for discrimination between organically and conventionally grown vegetables.

    PubMed

    Mihailova, A; Pedentchouk, N; Kelly, S D

    2014-07-01

    The lack of reliable markers for the discrimination between organic and conventional products makes the organic food market susceptible to attempted fraud. Robust analytical methodologies for organic food authentication are urgently needed. In this study a new approach, compound-specific nitrogen and oxygen isotope analysis of plant-derived nitrate, has been applied alongside bulk nitrogen isotope analysis for discrimination between organically and conventionally greenhouse-grown lettuce and retail potatoes and tomatoes. The method revealed significant differences between conventional and organic fertilisation. An intra-plant isotopic variation as well as significant impact of the fertiliser application rate on the nitrogen and oxygen isotope values of plant-derived nitrate has been observed. Nitrogen and oxygen isotope analysis of nitrate has a potential for differentiation between organic and conventional crops. Further analysis is needed to improve our understanding of the scope of application and robustness of this compound-specific approach. PMID:24518338

  16. Stable isotope analysis of plant-derived nitrate - novel method for discrimination between organically and conventionally grown vegetables.

    PubMed

    Mihailova, A; Pedentchouk, N; Kelly, S D

    2014-07-01

    The lack of reliable markers for the discrimination between organic and conventional products makes the organic food market susceptible to attempted fraud. Robust analytical methodologies for organic food authentication are urgently needed. In this study a new approach, compound-specific nitrogen and oxygen isotope analysis of plant-derived nitrate, has been applied alongside bulk nitrogen isotope analysis for discrimination between organically and conventionally greenhouse-grown lettuce and retail potatoes and tomatoes. The method revealed significant differences between conventional and organic fertilisation. An intra-plant isotopic variation as well as significant impact of the fertiliser application rate on the nitrogen and oxygen isotope values of plant-derived nitrate has been observed. Nitrogen and oxygen isotope analysis of nitrate has a potential for differentiation between organic and conventional crops. Further analysis is needed to improve our understanding of the scope of application and robustness of this compound-specific approach.

  17. Actinide abundances in ordinary chondrites

    NASA Technical Reports Server (NTRS)

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

    1990-01-01

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

  18. Understanding N2O sources and sinks with laser based isotopic analysis

    NASA Astrophysics Data System (ADS)

    Mohn, J.

    2015-12-01

    Nitrous oxide (N2O) is a potent greenhouse gas and the strongest stratospheric ozone-destroying substance released in the 21st century. Main N2O emissions are linked to different microbial pathways, therefore sources are disperse and highly variable, complicating their interpretation. Isotopic measurements have great potential to distinguish between individual source and sink processes. Developments in laser spectroscopy allow both the intramolecular distribution of 15N substitutions (15N14N16O versus 14N15N16O) and the oxygen isotopic composition of N2O to be measured in real-time, at high precision and in excellent compatibility to IRMS [1]. In a number of laboratory and pilot plant studies we investigated the isotopic signature of distinct microbial and abiotic N2O production and consumption pathways in soil and aqueous solution [e.g. 2-4]. Specific pathways were favoured by selection of the nitrogen substrates and process conditions and their isotopic signatures identified by real-time laser spectroscopic analysis. Results from our laboratory studies are in accordance with pure culture experiments and can therefore be applied to other ecosystems. High precision isotopic analysis at ambient N2O concentration is feasible by combining laser spectroscopy with automated preconcentration. Field deployment was demonstrated by real-time monitoring of the isotopic composition of N2O emissions above an intensively managed grassland in central Switzerland. The responses of the N2O isotopic signatures were analysed with respect to management events and climatic conditions [5]. In a follow-up project we combine real-time N2O isotopic analysis at a tall tower in central Switzerland with atmospheric transport simulations and a biogeochemical model of surface fluxes of N2O isotopomers. The working hypothesis is that this approach will allow us to quantify regional N2O sources, identify emission hot spots, and constrain source processes, which will significantly advance our

  19. In-situ chemical and isotopic analysis of a comet by Ptolemy

    NASA Astrophysics Data System (ADS)

    Morse, A. D.; Barber, S. J.; Leese, M. R.; Morgan, G. H.; Sheridan, S.; Wright, I. P.; Zarnecki, J. C.; Pillinger, C. T.

    2003-04-01

    Ptolemy is a Gas Chromatograph - Mass Spectrometer, one of the instruments on board the Rosetta Lander, intended to land on comet Wirtanen. Ptolemy is designed to measure the composition and isotope ratios of gases released from comet samples during pyrolysis or combustion. The total mass of the instrument is 4.6 kg and it fits into a space of 33 x 25 x 11 cm. Following touchdown on the comet nucleus, comet samples are obtained by the SD2 instrument, which drills a core sample and loads it into one of 26 ovens on a carousel. One of the ovens already contains a molecular sieve absorbent so that the comet "atmosphere" can also be sampled. The sample is then heated by the oven and the gases released are transferred to the Ptolemy instrument. Within Ptolemy, the raw sample gases can be chemically processed to convert them into molecules suitable for isotopic analysis. The processed sample mixture gas is injected into one of three GC columns to separate it into its constituent components before anal