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Sample records for hf isotope ratios

  1. Petrogenesis of the Neoproterozoic bimodal volcanic rocks along the western margin of the Yangtze Block: New constraints from Hf isotopes and Fe/Mn ratios

    Institute of Scientific and Technical Information of China (English)

    LI Xianhua; QI Changshi; LIU Ying; LIANG Xirong; TU Xianglin; XIE Liewen; YANG Yueheng

    2005-01-01

    High-precision major element and Hf isotope data are reported for the Neoproterozoic Suxiong volcanic rocks along the western margin of the Yangtze Block. These volcanic rocks have variable εHf(T) values and Fe/Mn ratios. The relatively primitive basalts have high Fe/Mn ratios and high Hf-Nd isotopic compositions, indicating that they were generated by partial melting of garnet clinopyroxene in mantle plume at high pressure. Thus, the Suxiong basalts are genetically related to the proposed Neoproterozoic superplume. On the contrary, a few differentiated basalts have low Fe/Mn ratios and low Hf-Nd isotopic compositions. They are likely to experience assimilation-fractional crystallization process. The Suxiong rhyolites have consistent Hf and Nd model ages of 1.3-1.4 Ga. They are likely generated by shallow dehydration melting of pre-existing young arc igneous rocks associated with the basaltic underplating/intrusion in a continental rift.

  2. Distribution Coefficients of Elements on TODGA Resin in HNO3, HCl and HF: Application to Determination of Lu/Hf Ratio and Hf Isotopic Composition in Meteorites

    Science.gov (United States)

    Pourmand, A.; Dauphas, N.

    2008-03-01

    Distribution coefficients for 60 elements on TODGA resin are presented along with a robust single-column protocol for separation of HSFE, lanthanides and actinides in meteorites and terrestrial rocks for high-precision isotope analysis.

  3. Comprehensive analysis for major, minor and trace element contents and Sr-Nd-Pb-Hf isotope ratios in sediment reference materials, JSd-1 and MAG-1

    Digital Repository Service at National Institute of Oceanography (India)

    Nath, B.N.; Makishima, A.; Noordmann, J.; Tanaka, R.; Nakamura, E.

    In view of the requirement of a well-characterized and easily available aquatic sediment reference material, a comprehensive analysis comprising of fifty major, minor and trace elements as well as Sr–Nd–Pb–Hf isotopes were carried out...

  4. Serpentinization Changes Nd, but not Hf Isotopes of Abyssal Peridotites

    Science.gov (United States)

    Bizimis, M.; Frisby, C. P.; Mallick, S.

    2015-12-01

    Serpentinization of the oceanic lithosphere is a known sink for fluid mobile elements (B, Cl, Li, Sr, etc.), while high field strength elements (HFSE: e.g., Hf, Zr, Ti, Nb) are thought to be unaffected by it. In contrast, the fate of REE during serpentinization is equivocal. Correlations between REE and HFSE concentrations in abyssal peridotites suggest control by magmatic processes (Niu, 2004, J. Pet), while some LREE enrichments in serpentinized peridotites compared to their clinopyroxene (cpx) and Nd, Sr isotope data (Delacour et al., 2008, Chem. Geol.) imply seawater-derived REE addition to the mantle protolith (Paulick et al., 2006, Chem. Geol). To further constrain peridotite-seawater interaction during serpentinization we compare bulk rock and cpx Hf and Nd isotope data in partially (up to ~70%) serpentinized abyssal peridotites (9-16°E South West Indian Ridge). We also present a new method that improves yields in Hf, Nd and Pb separations from depleted (90% of Hf, Zr, Ti are retained in the residue. LA-ICPMS data shows that serpentine after olivine typically has higher LREE/HREE ratios than cpx, pronounced negative Ce anomalies, high U, Sr concentrations and low HFSE, unlike the coexisting cpx. These data are consistent with some seawater-derived LREE addition to peridotite during serpentinization, localized in the serpentine and other secondary phases, while cpx retains the magmatic value. This process will lower the Sm/Nd relative to Lu/Hf ratio in the peridotite and can lead to decoupled radiogenic Hf and unradiogenic Nd isotopes upon recycling and aging. Our data further testifies to the fidelity of Hf isotopes in tracing mantle processes, even in serpentinized rocks.

  5. Hf isotopic compositions of the standard zircons for U-Pb dating

    Institute of Scientific and Technical Information of China (English)

    XU Ping; WU Fuyuan; XIE Liewen; YANG Yueheng

    2004-01-01

    Using the newly published Yb isotopic abundances and the mass bias relationship between Yb and Hf, we carried out an analysis of Hf isotopes in the standard zircon 91500 by means of 193 nm laser attached to Neptune multi-collector ICP-MS (LA-MC-ICPMS). The obtained Hf isotopic data, in either in situ or line scan modes, are not only identical for different spot sizes, but also are consistent with previously published results obtained on TIMS or other MC-ICPMS machines within errors. This indicates that it is possible to obtain reliable 176Hf/177Hf isotopic ratios for zircon in either in situ or line scan conditions on LA-MC-ICPMS machine, and the applied procedures in our study for elemental interfering correction are appropriate for the purpose of acquiring satisfactory accuracy for Hf isotope analyses. The Hf isotopic compositions of four zircon standards in high spatial resolution U-Pb dating, 91500, CZ3,CN92-1 and TEMORA, are measured, respectively. The obtained 176Hf/177Hf ratios are 0.282316+4 (n = 34, 2σ) for 91500, 0.281704±6 (n = 16, 2σ) for CZ3, 0.282200±6 (n = 20,2σ-) for CN92-1 and 0.282684±14 (n = 24, 2σ) for TEMORA,respectively, with 176Lu/177Hf ratios of ~0.00031, 0.000036,0.00083 and 0.00127. Zircons 91500 and CZ3 show narrower variations in 176Hf/177Hf and 176Lu/177Hf ratios than those of zircons CN92-1 and TEMORA, and thus are appropriate standards for the Hf isotope analysis.

  6. Systematic Study on Triaxial Superdeformed Bands of Hf Isotopes

    Institute of Scientific and Technical Information of China (English)

    ZHANG Da-Li; DING Bin-Gang

    2009-01-01

    Properties of the triaxial superdeformed (TSD) bands of Hf isotopes are investigated systematically within the supersymmetry scheme including many-body interactions and a perturbation possessing the SO(5) (or SU(5)) symmetry on the rotational symmetry. Quantitatively good results of the γ-ray energies, the dynamical moments of inertia,and the spin of the TSD bands in Hf isotopes are obtained. It shows that this approach is quite powerful in describing the properties of the triaxial superdeformation in Hf isotopes.

  7. Hf-Nd isotope and trace element constraints on subduction inputs at island arcs: Limitations of Hf anomalies as sediment input indicators

    Science.gov (United States)

    Handley, Heather K.; Turner, Simon; Macpherson, Colin G.; Gertisser, Ralf; Davidson, Jon P.

    2011-04-01

    New Nd-Hf isotope and trace element data for Javanese volcanoes are combined with recently published data to place constraints on subduction inputs at the Sunda arc in Indonesia and assess the value of Hf anomalies (expressed as Hf/Hf* and Sm/Hf ratios) as tracers of such inputs. Hf anomaly does not correlate with Hf isotope ratio in Javanese lavas, however, Hf/Hf* and Sm/Hf ratios do correlate with SiO 2. Contrary to previous work, we show that Hf anomaly variation may be controlled by fractionation of clinopyroxene and/or amphibole during magmatic differentiation and does not represent the magnitude or type of subduction input in some arcs. Correlation of Sm/Hf with indices of differentiation for other arcs (e.g., Vanuatu, New Britain, and Mariana) suggests that differentiation control on Sm/Hf ratios in volcanic arc rocks may be a relatively common phenomenon. This study corroborates the use of Nd-Hf isotope co-variations in arc volcanic rocks to ascertain subduction input characteristics. The trajectories of regional volcano groups (East, Central and West Java) in Nd-Hf isotope space reveal heterogeneity in the subducted sediment input along Java, which reflects present-day spatial variations in sediment compositions on the down-going plate in the Java Trench. The high Sm/Hf ratio required in the sediment end-member for some Javanese basalts suggests that partial melting of subducted sediment occurs in the presence of residual zircon, and is inconsistent with residual monazite or allanite.

  8. Garnet effect on Nd-Hf isotope decoupling: Evidence from the Jinfosi batholith, Northern Tibetan Plateau

    Science.gov (United States)

    Huang, Hui; Niu, Yaoling; Mo, Xuanxue

    2017-03-01

    The initial Nd and Hf isotope ratios of a 420 Ma post-collisional dioritic-granitic batholith from the Northern Tibetan plateau define a negative trend above and orthogonal to the ԐHf(t)-ԐNd(t) terrestrial array. This uncommon trend offers an insight into the origin of the puzzling Nd-Hf isotope decoupling in the crustal rocks. On this trend, samples depleted in heavy rare earth elements (HREEs, i.e., [Dy/Yb]N ≫ 1) deviate most from the terrestrial array whereas samples with flat HREEs (i.e., [Dy/Yb]N ≥ 1) deviate less or plot within the terrestrial array, pointing to the controlling effect of garnet in the magma source. Ancient garnet-bearing residues after melt extraction will have elevated Lu/Hf ratios and can evolve with time to produce high ԐHf(t) at a low ԐNd(t) value. Mixing of melts derived from such source lithologies (high Lu/Hf) with melts possessing a within-terrestrial array Nd-Hf isotopic composition (low Lu/Hf) best explains the observed trend orthogonal to the terrestrial array. The samples from the Jinfosi batholith with the most decoupled Nd-Hf isotope compositions require a larger degree (> 40%) and ancient (i.e., ≥ 1.8 Gyr) previous melt extraction from their source. It follows that the ancient melts with depleted HREEs complementary to those garnet-bearing residues should have low ԐHf values and plot below the terrestrial array, which is indeed shown by some Archean/Paleoproterozic TTGs.

  9. Meteorite zircon constraints on the bulk Lu-Hf isotope composition and early differentiation of the Earth.

    Science.gov (United States)

    Iizuka, Tsuyoshi; Yamaguchi, Takao; Hibiya, Yuki; Amelin, Yuri

    2015-04-28

    Knowledge of planetary differentiation is crucial for understanding the chemical and thermal evolution of terrestrial planets. The (176)Lu-(176)Hf radioactive decay system has been widely used to constrain the timescales and mechanisms of silicate differentiation on Earth, but the data interpretation requires accurate estimation of Hf isotope evolution of the bulk Earth. Because both Lu and Hf are refractory lithophile elements, the isotope evolution can be potentially extrapolated from the present-day (176)Hf/(177)Hf and (176)Lu/(177)Hf in undifferentiated chondrite meteorites. However, these ratios in chondrites are highly variable due to the metamorphic redistribution of Lu and Hf, making it difficult to ascertain the correct reference values for the bulk Earth. In addition, it has been proposed that chondrites contain excess (176)Hf due to the accelerated decay of (176)Lu resulting from photoexcitation to a short-lived isomer. If so, the paradigm of a chondritic Earth would be invalid for the Lu-Hf system. Herein we report the first, to our knowledge, high-precision Lu-Hf isotope analysis of meteorite crystalline zircon, a mineral that is resistant to metamorphism and has low Lu/Hf. We use the meteorite zircon data to define the Solar System initial (176)Hf/(177)Hf (0.279781 ± 0.000018) and further to identify pristine chondrites that contain no excess (176)Hf and accurately represent the Lu-Hf system of the bulk Earth ((176)Hf/(177)Hf = 0.282793 ± 0.000011; (176)Lu/(177)Hf = 0.0338 ± 0.0001). Our results provide firm evidence that the most primitive Hf in terrestrial zircon reflects the development of a chemically enriched silicate reservoir on Earth as far back as 4.5 billion years ago.

  10. Fractionation of Oxygen Isotopes by Thermal Ionization Mass Spectrometry Inferred from Simultaneous Measurement of (17)O/(16)O and (18)O/(16)O Ratios and Implications for the (182)Hf-(182)W Systematics.

    Science.gov (United States)

    Trinquier, Anne

    2016-06-07

    Accurate (182)Hf-(182)W chronology of early planetary differentiation relies on highly precise and accurate tungsten isotope measurements. WO3(-) analysis by negative thermal ionization mass spectrometry requires W(17)O(16)O2(-), W(17)O2(16)O(-), W(18)O(16)O2(-), W(17)O3(-), W(17)O(18)O(16)O(-), and W(18)O2(16)O(-) isotopologue interference corrections on W(16)O3(-) species ( Harper et al. Geochim. Cosmochim. Acta 1996 , 60 , 1131 ; Quitté et al. Geostandard. Newslett. 2002 , 26 , 149 ; Trinquier et al. Anal. Chem. 2016 , 88 , 1542 ; Touboul et al. Nature 2015 , 520 , 530 ; Touboul et al. Int. J. Mass Spectrom. 2012 , 309 , 109 ). In addition, low ion beam intensity counting statistics combined with Faraday cup detection noise limit the precision on the determination of (18)O/(16)O and (17)O/(16)O relative abundances. Mass dependent variability of (18)O/(16)O over the course of an analysis and between different analyses calls for oxide interference correction on a per integration basis, based on the in-run monitoring of the (18)O/(16)O ratio ( Harper et al. Geochim. Cosmochim. Acta 1996 , 60 , 1131 ; Quitté et al. Geostandard. Newslett. 2002 , 26 , 149 ; Trinquier et al. Anal. Chem. 2016 , 88 , 1542 ). Yet, the (17)O/(16)O variation is normally not being monitored and, instead, inferred from the measured (18)O/(16)O variation, assuming a δ(17)O-δ(18)O Terrestrial Fractionation Line ( Trinquier et al. Anal. Chem. 2016 , 88 , 1542 ). The purpose of the present study is to verify the validity of this assumption. Using high resistivity amplifiers, (238)U(17)O2 and (238)U(18)O2 ion beams down to 1.6 fA have been monitored simultaneously with (235,238)U(16)O2 species in a uranium certified reference material. This leads to a characterization of O isotope fractionation by thermal ionization mass spectrometry in variable loading and running conditions (additive-to-sample ratio, PO2 pressure, presence of ionized metal and oxide species). Proper determination of O

  11. Probing Archean lithosphere using the Lu-Hf isotope systematics of peridotite xenoliths from Somerset Island kimberlites, Canada

    Science.gov (United States)

    Schmidberger, Stefanie S.; Simonetti, Antonio; Francis, Don; Gariépy, Clément

    2002-04-01

    A knowledge of the Hf isotopic composition of the subcontinental lithosphere beneath Archean cratons is essential to constrain the Hf isotope budget of the Earth's mantle. Hf isotopic measurements were obtained by MC-ICP-MS for a suite of refractory peridotite xenoliths and constituent garnets from the Nikos kimberlite (100 Ma) on Somerset Island in order to constrain the isotopic composition and age of the lithosphere beneath the northern Canadian craton. The low-temperature Nikos peridotites (Somerset lithosphere, are characterized by higher 176Lu/ 177Hf ratios (0.03-0.05) and Hf isotopic values ( 176Hf/ 177Hf (0.1Ga)=0.28296-0.28419) than the deep-seated high-temperature peridotites (>1100°C; 0.004-0.03, 0.28265-0.28333, respectively). These differences in Hf isotope signatures suggest that shallow and deep subcontinental lithosphere beneath Somerset Island represent isotopically distinct domains and do not share a common petrogenetic history. The Lu-Hf isotope systematics of the shallow low-temperature peridotites define a positively sloped line that plot along a 2.8 Ga reference isochron. A number of these peridotites are characterized by highly radiogenic Hf isotopic compositions suggestive of long-term radiogenic ingrowth (billions of years). These findings are consistent with an interpretation that the shallow Somerset lithosphere (to depths of ˜150 km) stabilized in the Archean. The majority of the high-temperature peridotites plot closer to the composition of the host kimberlite. Although the observed isotopic variation may be attributed in part to kimberlite-related Hf addition, it is possible that these deep-seated xenoliths represent younger mantle. The superchondritic 176Lu/ 177Hf ratios observed for a number of the shallow low-temperature peridotites indicate strong fractionation of Lu and Hf, suggesting mantle root formation in the garnet stability field (depths >80 km). The Hf isotope compositions for the Somerset low-temperature peridotites

  12. Archean Lithosphere Beneath Arctic Canada: Lu-Hf Isotope Systematics for Kimberlite-Hosted Garnet-Peridotites From Somerset Island

    Science.gov (United States)

    Schmidberger, S. S.; Simonetti, A.; Francis, D.; Gariepy, C.

    2001-05-01

    Knowledge of the age of lithospheric mantle underlying the continents provides valuable constraints for the timing of formation and stabilization of Archean cratons. This study reports Lu-Hf isotopic data for garnet-peridotites, and their constituent garnets, from the Nikos kimberlite (100 Ma) on Somerset Island in the Canadian Arctic obtained using a Micromass IsoProbe multicollector inductively coupled plasma mass spectrometer (MC-ICP-MS) at GEOTOP-UQAM. The low temperature peridotites (1100 C; 160-190 km) and their 176Hf/177Hf(0.1Ga) isotopic compositions (0.28265-0.28333; \\epsilonHf(0.1Ga)=-2 to +22) are less radiogenic than those of the shallow xenoliths. A Lu-Hf isochron for six peridotites yields a mid Archean age of 3.4\\pm0.3 Ga and an initial 176Hf/177Hf ratio of 0.28101\\pm24. The remaining peridotites (n=9), in contrast, are characterized by extremely high (+35) initial \\epsilonHf(3.4Ga) values, which correlate negatively with their 176Lu/177Hf ratios, suggesting addition of Hf as a result of metasomatic interaction with the host kimberlite. The garnets from the low temperature (3.4 Ga old) peridotites are characterized by high 176Lu/177Hf ratios and define an errorchron age of 1.4\\pm0.2 Ga, which may reflect re-equilibration of Hf during kimberlite magmatism.

  13. Hf isotope evidence for a hidden mantle reservoir

    DEFF Research Database (Denmark)

    Bizzarro, Martin; Simonetti, A.; Stevenson, R.K.

    2002-01-01

    High-precision Hf isotopic analyses and U-Pb ages of carbonatites and kimberlites from Greenland and eastern North America, including Earth's oldest known carbonatite (3 Ga), indicate derivation from an enriched mantle source. This previously unidentified mantle reservoir-marked by an unradiogeni...

  14. U-Pb ages and Hf isotope compositions of zircons in plutonic rocks from the central Famatinian arc, Argentina

    Science.gov (United States)

    Otamendi, Juan E.; Ducea, Mihai N.; Cristofolini, Eber A.; Tibaldi, Alina M.; Camilletti, Giuliano C.; Bergantz, George W.

    2017-07-01

    The Famatinian arc formed around the South Iapetus rim during the Ordovician, when oceanic lithosphere subducted beneath the West Gondwana margin. We present combined in situ U-Th-Pb and Lu-Hf isotope analyses for zircon to gain insights into the origin and evolution of Famatinian magmatism. Zircon crystals sampled from four intermediate and silicic plutonic rocks confirm previous observations showing that voluminous magmatism took place during a relatively short pulse between the Early and Middle Ordovician (472-465 Ma). The entire zircon population for the four plutonic rocks yields coherent εHf negative values and spreads over several ranges of initial εHf(t) units (-0.3 to -8.0). The range of εHf units in detrital zircons of Famatinian metasedimentary rocks reflects a prolonged history of the cratonic sources during the Proterozoic to the earliest Phanerozoic. Typical tonalites and granodiorites that contain zircons with evolved Hf isotopic compositions formed upon incorporating (meta)sedimentary materials into calc-alkaline metaluminous magmas. The evolved Hf isotope ratios of zircons in the subduction related plutonic rocks strongly reflect the Hf isotopic character of the metasedimentary contaminant, even though the linked differentiation and growth of the Famatinian arc crust was driven by ascending and evolving mantle magmas. Geochronology and Hf isotope systematics in plutonic zircons allow us understanding the petrogenesis of igneous series and the provenance of magma sources. However, these data could be inadequate for computing model ages and supporting models of crustal evolution.

  15. The Yellowstone hotspot in space and time: Nd and Hf isotopes insilici magmas

    Energy Technology Data Exchange (ETDEWEB)

    Nash, Barbara P.; Perkins, Michael E.; Christensen, John N.; Lee,Den-Chuen; Halliday, A.N.

    2006-04-19

    Over the course of its 16 m.y. history, the Yellowstonehotspot has produced silicic magmas exhibiting systematic, and oftensympathetic, variations in isotopic and chemical composition, temperatureand frequency of eruption. Nd and Hf isotopic ratios vary systematicallyfrom initial eruptions at ~;16 Ma, contemporaneous with basalticvolcanism in eastern Oregon and Washington, to the present dayYellowstone Volcanic Plateau. Nd and Hf isotopic ratios co-vary and spanthe range of most terrestrial samples, reflecting mixing of mantle andcrustal sources. Earliest erupted silicic magmas were hot (in excess of1050oC), relatively less evolved and have isotopic ratios within therange of contemporaneous Columbia River flood basalts. The transit of thehotspot across the lithospheric boundary between the western accretedoceanic terrain and the Precambrian craton at 15 Ma is marked by shiftsin eNd from +4 to -11 and in ?Hf from +10 to -10. The duration of thetransit yields a crustal magma source diameter of ~;70 km. In theinterval from 14 to 9 Ma, ?Nd systematically increases from -11 to -7,recording a minimum increase in the mantle component from 5 percent to 30percent. The mantle component could be twice as great, depending upon theisotopic composition of crust and mantle reservoirs. In this sameinterval, peak temperatures of ~;1000oC occurred at 9 Ma. The last 8 m.y.are characterized by less frequent eruption of lower temperature(830-900oC) and more compositionally evolved magmas.

  16. Evolution of continental crust and mantle heterogeneity: Evidence from Hf isotopes

    Science.gov (United States)

    Jonathan, Patchett P.; Kouvo, O.; Hedge, C.E.; Tatsumoto, M.

    1982-01-01

    We present initial 176Hf/177 Hf ratios for many samples of continental crust 3.7-0.3 Gy old. Results are based chiefly on zircons (1% Hf) and whole rocks: zircons are shown to be reliable carriers of essentially the initial Hf itself when properly chosen on the basis of U-Pb studies. Pre-3.0 Gy gneisses were apparently derived from an unfractionated mantle, but both depleted and undepleted mantle are evident as magma sources from 2.9 Gy to present. This mantle was sampled mainly from major crustal growth episodes 2.8, 1.8 and 0.7 Gy ago, all of which show gross heterogeneity of 176Hf/177Hf in magma sources from ??Hf=0 to +14, or about 60% of the variability of the present mantle. The approximate ??Hf=2??Nd relationship in ancient and modern igneous rocks shows that 176Lu/177Hf fractionates in general twice as much as 147Sm/144Nd in mantle melting processes. This allows an estimation of the relative value of the unknown bulk solid/liquid distribution coefficient for Hf. DLu/DHf=??? 2.3 holds for most mantle source regions. For garnet to be an important residual mantle phase, it must hold Hf strongly in order to preserve Hf-Nd isotopic relationships. The ancient Hf initials are consistent with only a small proportion of recycled older cratons in new continental crust, and with quasi-continuous, episodic growth of the continental crust with time. However, recycling of crust less than 150 My old cannot realistically be detected using Hf initials. The mantle shows clearly the general positive ??Hf resulting from a residual geochemical state at least back to 2.9 Gy ago, and seems to have repeatedly possessed a similar degree of heterogeneity, rather than a continuously-developing depletion. This is consistent with a complex dynamic disequilibrium model for the creation, maintenance and destruction of heterogeneity in the mantle. ?? 1981 Springer-Verlag.

  17. Subduction Contributions in the Trans-Mexican Volcanic Belt: Implications from Lava Chemistry and Hf-Nd-Pb Isotopes

    Science.gov (United States)

    Cai, Y.; Goldstein, S. L.; Langmuir, C. H.; Gómez-Tuena, A.; Lagatta, A.; Straub, S. M.; Martín Del Pozzo, A.

    2007-05-01

    Despite thick continental crust, near primitive lavas erupt throughout the Trans-Mexican Volcanic Belt (TMVB). In order to distinguish and better constrain subduction contributions and effects of crustal contamination, we analyzed samples representing subducting sediments from DSDP Site 487, and Quaternary lavas from stratovolcanoes and cinder cones, including alkaline "high-Nb" lavas from the Sierra Chichinautzin Volcanic Field (SCVF) showing negligible subduction signature in its trace element chemistry and representing melts of the mantle wedge. Our primary observations and implications are: (1) The high-Nb SCVF `intraplate' lavas define a linear trend along the "Nd-Hf mantle-crust array", defining the composition of the mantle wedge. (2) Popocatepetl and Nevado de Toluca stratovolcanoes show the highest Nd and Hf isotope ratios, higher than the `intraplate' lavas, indicating their sources are more "depleted mantle-like" than the regional mantle wedge. (3) The Popo and Toluca chemical and isotopic trends sharply contrast with Pico de Orizaba, which shows classic indications of crustal contamination (e.g. high 207Pb/204Pb, low Nd-Hf isotope ratios), consistent with contamination by local Precambrian crust. (4) Higher Nd-Hf isotopes in Popo and Toluca lavas also correlate with lower Pb isotope ratios, and lower Lu/Hf and Zr/Hf. Together, these data indicate contributions from subducted Pacific oceanic crust and hydrothermal sediment. (5) Popo and Toluca are also enriched in Th/LREE compared with `intraplate' lavas, reflecting subducted sediment contributions. (6) Nd-Hf isotope ratios of hydrothermal sediment from DSDP Site 487 lie on the "seawater array", with high Hf isotope ratios compared to the "mantle-crust array". Popo and Toluca Nd-Hf isotopes display a shallower slope than the "intraplate lava Nd-Hf array", reflecting contributions from hydrothermal sediment. Popocatepetl and Toluca lavas therefore avoid substantial crustal contamination of mantle wedge

  18. Early Differentiation of the Crust-Mantle System: a Hf Isotope Perspective

    Science.gov (United States)

    Scherer, E.; Munker, C.; Mezger, K.

    2001-12-01

    The Lu decay constant recently determined by Scherer et al. 2001 (i.e., 1.865 x 10-11 yr-1) agrees with the results of the two latest physical counting experiments (1.86 x 10-11 yr-1; Dalmasso et al 1992, Nir-El and Lavi 1998), but is ca. 4 percent lower than the decay constants that have been used throughout the Hf isotope literature (e.g., 1.94 x 10-11, Tatsumoto et al., 1981; 1.93 x 10-11 Sguigna et al, 1982). In addition to making Lu-Hf ages older by ca. 4 percent, the revised decay constant also shifts the calculated initial epsilon Hf values of early Archean and Hadean rocks and zircons that are used to constrain crust-mantle differentiation in the early Earth. The initial epsilon Hf values for low-Lu/Hf samples such as zircons and evolved felsic rocks shift downward by 2-4 epsilon units, primarily due to the shift in the position of the CHUR evolution curve rather than that of the samples themselves. Mafic rocks, such as komatiites have higher Lu/Hf ratios that are closer to that of CHUR and therefore their initial epsilon Hf values do not shift as much (up to 1.3 epsilon units lower or 0.4 epsilon units higher). Using the old decay constant, some early Archean rocks (e.g., Amitsoq gneisses; Vervoort et al., 1996, Vervoort and Blichert-Toft, 1999) seemed to have very high initial epsilon Hf values (up to +6), implying that the upper mantle was moderately depleted in the early Archean and that a substantial volume of crust was produced in the Hadean. However, when recalculated with the new decay constant, the data suggest that the mantle was only slightly depleted, requiring less early crust extraction, and allowing a later date for the onset of significant crust production. In contrast, the extremely low recalculated epsilon Hf values of Earth's oldest zircons (Amelin et al., 1999, Amelin et al., 2000) indicate that Earth's first crust formed at or before 4.3 Ga, and that this crust remained intact long enough (>200 million years) to evolve to such low

  19. Combined U-Pb and Lu-Hf isotope analyses by laser ablation MC-ICP-MS: methodology and applications

    Energy Technology Data Exchange (ETDEWEB)

    Matteini, Massimo; Dantas, Elton L.; Pimentel, Marcio M.; Bühn, Bernhard, E-mail: massimo@unb.br [Universidade de Brasilia (UnB), DF (Brazil). Instituto de Geociencias

    2010-06-15

    The Lutetium-Hafnium isotopic system represents one of the most innovative and powerful tools for geochronology and isotopic studies. Combined U-Pb and Lu-Hf in situ analyses on zircon by LA-MC-ICP-MS permit to characterize isotopically the host magma from which it crystallized furnishing significant information for sediment provenance and crustal evolution studies. In this paper e describe the Lu-Hf systematic by LA-MC-ICP-MS developed in the laboratory of Geochronology of the University of Brasilia and report the results obtained by repeated analyses of {sup 176}Hf/{sup 177}Hf isotopic ratio of three zircon standards: GJ-1 = 0.282022 ± 11 (n=56), Temora 2 = 0.282693 ± 14 (n=25) and UQZ = 0.282127 ± 33 (n=11). The {sup 176}Hf/{sup 177}Hf ratio (0.282352 ± 22, n=14) of gem quality zircon used as in-house standard have been also characterized. As a geological application, we analyzed two complex zircons selected from a migmatitic rocks from the Borborema Province, NE Brazil. On the basis of U-Pb and Lu-Hf data, two main crystallization events have been identified in both studied zircons. An older event at ca. 2.05 Ga recognized in the inherited cores represents a well-characterized paleoproterozoic magmatic event that affected the whole Borborema Province. A second crystallization event at ∼ 575 Ma, recognized at the rims, represents a Neoproterozoic (Brazilian) high grade metamorphic-magmatic event. (author)

  20. Comprehensive Pb-Sr-Nd-Hf isotopic, trace element, and mineralogical characterization of mafic to ultramafic rock reference materials

    Science.gov (United States)

    Fourny, Anaïs.; Weis, Dominique; Scoates, James S.

    2016-03-01

    Controlling the accuracy and precision of geochemical analyses requires the use of characterized reference materials with matrices similar to those of the unknown samples being analyzed. We report a comprehensive Pb-Sr-Nd-Hf isotopic and trace element concentration data set, combined with quantitative phase analysis by XRD Rietveld refinement, for a wide range of mafic to ultramafic rock reference materials analyzed at the Pacific Centre for Isotopic and Geochemical Research, University of British Columbia. The samples include a pyroxenite (NIM-P), five basalts (BHVO-2, BIR-1a, JB-3, BE-N, GSR-3), a diabase (W-2), a dolerite (DNC-1), a norite (NIM-N), and an anorthosite (AN-G); results from a leucogabbro (Stillwater) are also reported. Individual isotopic ratios determined by MC-ICP-MS and TIMS, and multielement analyses by HR-ICP-MS are reported with 4-12 complete analytical duplicates for each sample. The basaltic reference materials have coherent Sr and Nd isotopic ratios with external precision below 50 ppm (2SD) and below 100 ppm for Hf isotopes (except BIR-1a). For Pb isotopic reproducibility, several of the basalts (JB-3, BHVO-2) require acid leaching prior to dissolution. The plutonic reference materials also have coherent Sr and Nd isotopic ratios (<50 ppm), however, obtaining good reproducibility for Pb and Hf isotopic ratios is more challenging for NIM-P, NIM-N, and AN-G due to a variety of factors, including postcrystallization Pb mobility and the presence of accessory zircon. Collectively, these results form a comprehensive new database that can be used by the geochemical community for evaluating the radiogenic isotope and trace element compositions of volcanic and plutonic mafic-ultramafic rocks.

  1. In situ simultaneous determination of trace elements,U-Pb and Lu-Hf isotopes in zircon and baddeleyite

    Institute of Scientific and Technical Information of China (English)

    XIE LieWen; ZHANG YanBin; ZHANG HuiHuang; SUN JingFeng; WU FuYuan

    2008-01-01

    This paper describes a combined method of simultaneously measuring U-Pb and Lu-Hf isotopes as well as trace elements in Phalaborwa baddeleyite and 91500, GJ-1, TEMORA-1 and SK10-2 zircons by means of Neptune MC-ICPMS and Agilent Q-ICPMS connected to a 193 nm excimer laser ablation system. Material ablated by laser was carried in different proportions into Q-ICPMS for U-Pb isotopic and trace elemental and MC-ICPMS for Lu-Hf isotopic compositions. Experiments indicate that different propor-tions of ablated material for the Q-ICPMS and MC-ICPMS (6∶4, 5∶5 and 4∶6 respectively) do not show any bias for the zircon/baddeleyite U-Pb age, Lu-Hf isotope and trace elemental compositions within ana-lytical errors. Using 40-60 μm spot size, the obtained U-Pb ages of Phalaborwa baddeleyite, 91500, GJ-1, TEMORA and SK10-2 zircons are 2065~15 (2σ, n=20), 1063±6 (2σ, n=19), 613±6 (2σ,=20), 416±5 (2σ, n=20) and 32.6±0.5 (2σ, n=20) Ma, respectively. The 176Hf/177Hf ratios are 0.281231±24 (2SD, n=20), 0.282310±35 (2SD, n=19), 0.282028±34 (2SD, n=20), 0.282687±34 (2SD, n=20) and 0.282752±53 (2SD, n=20), respectively. The obtained trace elemental compositions are identical to the reference values. Therefore, this kind of technique makes it possible to simultaneously obtain the U-Pb age, Lu-Hf iso-topes and trace elemental compositions of zircon and baddeleyite, which could be an important tool in solving problems in earth sciences.

  2. What Hf isotopes in zircon tell us about crust-mantle evolution

    Science.gov (United States)

    Iizuka, Tsuyoshi; Yamaguchi, Takao; Itano, Keita; Hibiya, Yuki; Suzuki, Kazue

    2017-03-01

    The 176Lu-176Hf radioactive decay system has been widely used to study planetary crust-mantle differentiation. Of considerable utility in this regard is zircon, a resistant mineral that can be precisely dated by the U-Pb chronometer and record its initial Hf isotope composition due to having low Lu/Hf. Here we review zircon U-Pb age and Hf isotopic data mainly obtained over the last two decades and discuss their contributions to our current understanding of crust-mantle evolution, with emphasis on the Lu-Hf isotope composition of the bulk silicate Earth (BSE), early differentiation of the silicate Earth, and the evolution of the continental crust over geologic history. Meteorite zircon encapsulates the most primitive Hf isotope composition of our solar system, which was used to identify chondritic meteorites best representative of the BSE (176Hf/177Hf = 0.282793 ± 0.000011; 176Lu/177Hf = 0.0338 ± 0.0001). Hadean-Eoarchean detrital zircons yield highly unradiogenic Hf isotope compositions relative to the BSE, providing evidence for the development of a geochemically enriched silicate reservoir as early as 4.5 Ga. By combining the Hf and O isotope systematics, we propose that the early enriched silicate reservoir has resided at depth within the Earth rather than near the surface and may represent a fractionated residuum of a magma ocean underlying the proto-crust, like urKREEP beneath the anorthositic crust on the Moon. Detrital zircons from world major rivers potentially provide the most robust Hf isotope record of the preserved granitoid crust on a continental scale, whereas mafic rocks with various emplacement ages offer an opportunity to trace the Hf isotope evolution of juvenile continental crust (from εHf[4.5 Ga] = 0 to εHf[present] = + 13). The river zircon data as compared to the juvenile crust composition highlight that the supercontinent cycle has controlled the evolution of the continental crust by regulating the rates of crustal generation and intra

  3. Comparative behavior of Sr, Nd and Hf isotopic systems during fluid-related deformation at middle crust levels

    Science.gov (United States)

    Luais, Béatrice; Le Carlier de Veslud, Christian; Géraud, Yves; Gauthier-Lafaye, François

    2009-05-01

    We have carried out a comparative Rb-Sr, Sm-Nd and Lu-Hf isotopic study of a progressively deformed hercynian leucogranite from the French Massif Central, belonging to the La Marche ductile shear zone, in order to investigate the respective perturbation of these geochronometers with fluid induced deformation. The one-meter wide outcrop presents a strongly deformed and mylonitized zone at the center, and an asymmetric deformation pattern with a higher deformation gradient on the northern side of the zone. Ten samples have been carefully collected every 10 cm North and South away from the strongest deformed mylonitic zone. They have been analyzed for a complete major, trace element data set, oxygen isotopes, Rb-Sr, Sm-Nd and Lu-Hf isotopic systematics. We show that most of major and trace elements except SiO 2, alkaline elements (K 2O, Rb), and some metal transition elements (Cu), are progressively depleted with increasing deformation. This depletion includes REE + Y, but also HFS elements (Ti, Hf, Zr, Nb) which are commonly considered as immobile elements during upper level processes. Variations in elemental ratios with deformation, e.g. decrease in LREE/MREE- HREE, Nd/Hf, Th/Sr, increase in Rb/Sr, U/Th and constant Sr/Nd, lead to propose the following order of element mobility: U ≫ Th > Sr = Nd ≫ Hf + HREE. We conclude in agreement with previous tectonic and metallogenic studies that trace element patterns across the shear zone result from circulation of oxidizing F-rich hydrothermal fluids associated with deformation. A temperature of the fluid of 470-480 °C can be deduced from the δ 18O equilibrium between quartz-muscovite pairs. Elemental fractionation induces perturbation of the Rb-Sr geochronometer. The well-defined 87Rb/ 86Sr- 87Sr/ 86Sr correlation gives an apparent age of 294 ± 19 Ma, slightly younger than the 323 ± 4 Ma age of leucogranites in this area. This apparent age is interpreted as dating event of intense deformation and fluid circulation

  4. Subduction Controls of Hf and Nd Isotopes in Lavas of the Aleutian Island Arc

    Energy Technology Data Exchange (ETDEWEB)

    Yogodzinski, Gene; Vervoort, Jeffery; Brown, Shaun Tyler; Gerseny, Megan

    2010-08-29

    The Hf and Nd isotopic compositions of 71 Quaternary lavas collected from locations along the full length of the Aleutian island arc are used to constrain the sources of Aleutian magmas and to provide insight into the geochemical behavior of Nd and Hf and related elements in the Aleutian subduction-magmatic system. Isotopic compositions of Aleutian lavas fall approximately at the center of, and form a trend parallel to, the terrestrial Hf-Nd isotopic array with {var_epsilon}{sub Hf} of +12.0 to +15.5 and {var_epsilon}{sub Nd} of +6.5 to +10.5. Basalts, andesites, and dacites within volcanic centers or in nearby volcanoes generally all have similar isotopic compositions, indicating that there is little measurable effect of crustal or other lithospheric assimilation within the volcanic plumbing systems of Aleutian volcanoes. Hafnium isotopic compositions have a clear pattern of along-arc increase that is continuous from the eastern-most locations near Cold Bay to Piip Seamount in the western-most part of the arc. This pattern is interpreted to reflect a westward decrease in the subducted sediment component present in Aleutian lavas, reflecting progressively lower rates of subduction westward as well as decreasing availability of trench sediment. Binary bulk mixing models (sediment + peridotite) demonstrate that 1-2% of the Hf in Aleutian lavas is derived from subducted sediment, indicating that Hf is mobilized out of the subducted sediment with an efficiency that is similar to that of Sr, Pb and Nd. Low published solubility for Hf and Nd in aqueous subduction fluids lead us to conclude that these elements are mobilized out of the subducted component and transferred to the mantle wedge as bulk sediment or as a silicate melt. Neodymium isotopes also generally increase from east to west, but the pattern is absent in the eastern third of the arc, where the sediment flux is high and increases from east to west, due to the presence of abundant terrigenous sediment in the

  5. Tracing Proterozoic arc mantle Hf isotope depletion of southern Fennoscandia through coupled zircon U-Pb and Lu-Hf isotopes

    Science.gov (United States)

    Petersson, Andreas; Bjärnborg, Karolina; Scherstén, Anders; Gerdes, Axel; Næraa, Tomas

    2017-07-01

    Constraints on the composition of the depleted mantle Sm-Nd and Lu-Hf crust formation ages have a long history of scientific debate. When calculating mantle extraction ages, and constructing crustal growth models, a linear evolution of incompatible trace elements in a depleted mantle since > 4 Ga is routinely used. Mantle depletion however varies regionally and over time and subduction of sediments and oceanic crust renders a mantle-wedge variously enriched relative to a modelled depleted mantle. Here we show that primitive mantle-derived subduction related gabbroic intrusions from southern Fennoscandia have Hf isotope compositions that are enriched relative to a MORB-like linear depleted mantle evolution curve. Extrapolation of primitive Paleoproterozoic gabbro suites enables the construction of a regional mantle evolution curve, providing improved constraints on model ages, crustal residence times and the fraction of juvenile versus reworked continental crust. Convergent margins are assumed to be one of the main sites of continental crust growth, and using an overly depleted mantle source yield model ages that are too old, and hence cumulative crustal growth models show too much crust generation early in the Earth's history. The approach of using the Hf isotope composition of zircon from primitive subduction related gabbroic intrusions as a proxy for mantle Hf isotope composition, piloted in this study, can be applied to other convergent margins.

  6. Correlated cosmogenic W and Os isotopic variations in Carbo and implications for Hf-W chronology

    Science.gov (United States)

    Qin, Liping; Dauphas, Nicolas; Horan, Mary F.; Leya, Ingo; Carlson, Richard W.

    2015-03-01

    An obstacle for establishing the chronology of iron meteorite formation using 182Hf-182W systematics (t1/2 = 8.9 Myr) is to find proper neutron fluence monitors to correct for cosmic ray modification of W isotopic composition. Recent studies showed that siderophile elements such as Pt and Os could serve such a purpose. To test and calibrate these neutron dosimeters, the isotopic compositions of W and Os were measured in a slab of the IID iron meteorite Carbo. This slab has a well-characterized noble gas depth profile reflecting different degrees of shielding to cosmic rays. The results show that W and Os isotopic ratios correlate with distance from the pre-atmospheric center. Negative correlations, barely resolved within error, were found between ε190Os-ε189Os and ε186Os-ε189Os with slopes of -0.64 ± 0.45 and -1.8(+1.9/-2.1), respectively. These Os isotope correlations broadly agree with model predictions for capture of secondary neutrons produced by cosmic ray irradiation and results reported previously for other groups of iron meteorites. Correlations were also found between ε182W-ε189Os (slope = 1.02 ± 0.37) and ε182W-ε190Os (slope = -1.38 ± 0.58). Intercepts of these two correlations yield pre-exposure ε182W values of -3.32 ± 0.51 and -3.62 ± 0.23, respectively (weighted average ε182W = -3.57 ± 0.21). This value relies on a large extrapolation leading to a large uncertainty but gives a metal-silicate segregation age of -0.5 ± 2.4 Myr after formation of the solar system. Combining the iron meteorite measurements with simulations of cosmogenic effects in iron meteorites, equations are presented to calculate and correct for cosmogenic effects on 182W using Os isotopes.

  7. Measuring Isotope Ratios Across the Solar System

    Science.gov (United States)

    Webster, Chris R.; Mahaffy, Paul R.

    2012-01-01

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

  8. Measuring Isotope Ratios Across the Solar System

    Science.gov (United States)

    Webster, Chris R.; Mahaffy, Paul R.

    2012-01-01

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

  9. Combined U-Pb and Lu-Hf isotope analyses by laser ablation MC-ICP-MS: methodology and applications

    Directory of Open Access Journals (Sweden)

    Massimo Matteini

    2010-06-01

    Full Text Available The Lutetium-Hafnium isotopic system represents one of the most innovative and powerful tools for geochronology and isotopic studies. Combined U-Pb and Lu-Hf in situ analyses on zircon by LA-MC-ICP-MS permit to characterize isotopically the host magma from which it crystallized furnishing significant information for sediment provenance and crustal evolution studies. In this paper e describe the Lu-Hf systematic by LA-MC-ICP-MS developed in the laboratory of Geochronology of the University of Brasilia and report the results obtained by repeated analyses of 176Hf/177Hf isotopic ratio of three zircon standards: GJ-1 = 0.282022 ± 11 (n=56, Temora 2 = 0.282693 ± 14 (n=25 and UQZ = 0.282127 ± 33 (n=11. The 176Hf/177Hf ratio (0.282352 ± 22, n=14 of gem quality zircon used as in-house standard have been also characterized. As a geological application, we analyzed two complex zircons selected from a migmatitic rocks from the Borborema Province, NE Brazil. On the basis of U-Pb and Lu-Hf data, two main crystallization events have been identified in both studied zircons. An older event at ca. 2.05 Ga recognized in the inherited cores represents a well-characterized paleoproterozoic magmatic event that affected the whole Borborema Province. A second crystallization event at ~ 575 Ma, recognized at the rims, represents a Neoproterozoic (Brazilian high grade metamorphic-magmatic event.O sistema isotópico Lutécio-Hafnio representa uma das ferramentas mais recentes e poderosas para estudos isotópicos e geocronológicos. Análises combinadas in situ de U-Pb e Lu-Hf sobre zircão pelo LA-MC-ICP-MS permitem caracterizar iso-topicamente o magma onde ele cristalizou, fornecendo valiosas informações para estudos de proveniência de sedimento e de evolução crustal. Nesse trabalho descrevemos a sistemática de Lu-Hf pelo LA-MC-ICP-MS implantada no laboratório de Geocronologia da Universidade de Brasília e reportamos os resultados obtidos de repetidas an

  10. Hf isotope evidence for variable slab input and crustal addition in basalts and andesites of the Taupo Volcanic Zone, New Zealand

    DEFF Research Database (Denmark)

    Waight, Tod Earle; Troll, Valentin R.; Gamble, J.A.

    2017-01-01

    variations likely represent variability in primary magma compositions as a result of different degrees of sediment addition at the slab-wedge interface. Coupled variations in isotopic composition, LILE/HFSE ratios (e.g. Rb/Zr and Ba/La) and SiO2 also clearly indicate that shallower level crustal interactions......Crustal contamination complicates the identification of primary mantle-derived magma compositions in Continental arcs. However,when crustal processes and components arewell characterised, it is possible to extrapolate through continental arc magma compositional arrays towards the Hf and Nd isotope...... compositions of uncontaminated primary magmas. This is because of the similar behaviour of Hf and Nd during fractional crystallisation and mantle melting, and the subsequent limited variation in Hf/Nd in mantle-derived magmas and in many crustal lithologies, resulting in linear contamination trends for Hf...

  11. Tracking magmatic processes through Zr/Hf ratios in rocks and Hf and Ti zoning in zircons: An example from the Spirit Mountain batholith, Nevada

    Science.gov (United States)

    Lowery, Claiborne L.E.; Miller, C.F.; Walker, B.A.; Wooden, J.L.; Mazdab, F.K.; Bea, F.

    2006-01-01

    Zirconium and Hf are nearly identical geochemically, and therefore most of the crust maintains near-chondritic Zr/Hf ratios of ???35-40. By contrast, many high-silica rhyolites and granites have anomalously low Zr/Hf (15-30). As zircon is the primary reservoir for both Zr and Hf and preferentially incorporates Zr, crystallization of zircon controls Zr/ Hf, imprinting low Zr/Hf on coexisting melt. Thus, low Zr/Hf is a unique fingerprint of effective magmatic fractionation in the crust. Age and compositional zonation in zircons themselves provide a record of the thermal and compositional histories of magmatic systems. High Hf (low Zr/ Hf) in zircon zones demonstrates growth from fractionated melt, and Ti provides an estimate of temperature of crystallization (TTiZ) (Watson and Harrison, 2005). Whole-rock Zr/Hf and zircon zonation in the Spirit Mountain batholith, Nevada, document repeated fractionation and thermal fluctuations. Ratios of Zr/Hf are ???30-40 for cumulates and 18-30 for high-SiO2 granites. In zircons, Hf (and U) are inversely correlated with Ti, and concentrations indicate large fluctuations in melt composition and TTiZ (>100??C) for individual zircons. Such variations are consistent with field relations and ion-probe zircon geochronology that indicate a >1 million year history of repeated replenishment, fractionation, and extraction of melt from crystal mush to form the low Zr/Hf high-SiO2 zone. ?? 2006 The Mineralogical Society.

  12. Refinement of the supercontinent cycle with Hf, Nd and Sr isotopes

    Directory of Open Access Journals (Sweden)

    Kent C. Condie

    2013-11-01

    External and internal orogens show similar patterns in ɛNd and ɛHf with age suggesting that both juvenile and reworked crustal components are produced in both types of orogens with similar proportions. However, both types of orogens clearly produce more juvenile isotopic signatures in retreating mode than in advancing mode. Many secular changes in ɛHf and ɛNd distributions correlate with the supercontinent cycle. Although supercontinent breakup is correlated with short-lived decreasing ɛHf and ɛNd (≤100 Myr for most supercontinents, there is no isotopic evidence for the breakup of the Paleoproterozoic supercontinent Nuna. Assembly of supercontinents by extroversion is recorded by decreasing ɛNd in granitoids and metasediments and decreasing ɛHf in zircons, attesting to the role of crustal reworking in external orogens in advancing mode. As expected, seawater Sr isotopes increase and seawater Nd isotopes decrease during supercontinent assembly by extroversion. Pangea is the only supercontinent that has a clear isotopic record of introversion assembly, during which median ɛNd and ɛHf rise rapidly for ≤100 Myr. Although expected to increase, radiogenic seawater Sr decreases (and seawater Nd increases during assembly of Pangea, a feature that may be caused by juvenile input into the oceans from new ocean ridges and external orogens in retreating mode. The fact that a probable onset of plate tectonics around 3 Ga is not recorded in isotopic distributions may be due the existence of widespread felsic crust formed prior to the onset of plate tectonics in a stagnant lid tectonic regime, as supported by Nd and Hf model ages.

  13. Distribution of p-process 174Hf in early solar system materials and the origin of nucleosynthetic Hf and W isotope anomalies in Ca-Al rich inclusions

    Science.gov (United States)

    Peters, Stefan T. M.; Münker, Carsten; Pfeifer, Markus; Elfers, Bo-Magnus; Sprung, Peter

    2017-02-01

    Some nuclides that were produced in supernovae are heterogeneously distributed between different meteoritic materials. In some cases these heterogeneities have been interpreted as the result of interaction between ejecta from a nearby supernova and the nascent solar system. Particularly in the case of the oldest objects that formed in the solar system - Ca-Al rich inclusions (CAIs) - this view is confirm the hypothesis that a nearby supernova event facilitated or even triggered solar system formation. We present Hf isotope data for bulk meteorites, terrestrial materials and CAIs, for the first time including the low-abundance isotope 174Hf (∼0.16%). This rare isotope was likely produced during explosive O/Ne shell burning in massive stars (i.e., the classical "p-process"), and therefore its abundance potentially provides a sensitive tracer for putative heterogeneities within the solar system that were introduced by supernova ejecta. For CAIs and one LL chondrite, also complementary W isotope data are reported for the same sample cuts. Once corrected for small neutron capture effects, different chondrite groups, eucrites, a silicate inclusion of a IAB iron meteorite, and terrestrial materials display homogeneous Hf isotope compositions including 174Hf. Hafnium-174 was thus uniformly distributed in the inner solar system when planetesimals formed at the system composition, and also variable r-process (or s-process) Hf and W contributions. Based on combined Hf and W isotope compositions, we show that CAIs sampled at least one component in which the proportion of r- and s-process derived Hf and W deviates from that of supernova ejecta. The Hf and W isotope anomalies in CAIs are therefore best explained by selective processing of presolar carrier phases prior to CAI formation, and not by a late injection of supernova materials. Likewise, other isotope anomalies in additional elements in CAIs relative to the bulk solar system may reflect the same process. The isotopic

  14. Source components and magmatic processes in the genesis of Miocene to Quaternary lavas in western Turkey: constraints from HSE distribution and Hf-Pb-Os isotopes

    Science.gov (United States)

    Aldanmaz, Ercan; Pickard, Megan; Meisel, Thomas; Altunkaynak, Şafak; Sayıt, Kaan; Şen, Pınar; Hanan, Barry B.; Furman, Tanya

    2015-08-01

    Hf-Pb-Os isotope compositions and highly siderophile element (HSE) abundance variations are used to evaluate the mantle source characteristics and possible effects of differentiation processes in lavas from western Turkey, where the eruption of Late Miocene to Quaternary OIB-type intraplate mafic alkaline lavas followed pre-Middle Miocene convergent margin-type volcanism. Concentrations of Os, Ir, and Ru (IPGE) in the OIB-type intraplate lavas decrease with fractionation for primitive melts (MgO > 10 wt%), suggesting that these elements reside predominantly in olivine and associated HSE retaining trace phases and behave compatibly during olivine-dominated fractionation. Fractional crystallization trends indicate distinctly lower bulk partition coefficients for IPGE in more evolved lavas, possibly reflecting a change in the fractionating assemblages. Pd and Re in the primitive melts display negative correlations with MgO, demonstrating moderately incompatible behavior of these elements during fractionation, while the significantly scattered variation in Pt against MgO may indicate the effects of micronuggets of a Pt-rich alloy. Os-rich alkaline primary lavas (>50 ppt Os) exhibit a limited range of 187Os/188Os (0.1361-0.1404), with some xenolith-bearing lavas displaying depletions in 187Os/188Os (0.1131-0.1232), suggesting slight compositional modification of primitive melts through contamination with highly depleted, Os-rich mantle lithosphere. More radiogenic Os isotope ratios (187Os/188Os > 0.1954) in the evolved lavas reflect contamination of the magmas by high187Os/188Os crustal material during shallow differentiation. The OIB-type lavas show limited variations in Hf and Pb isotopes with 176Hf/177Hf = 0.282941-0.283051, 206Pb/204Pb = 18.683-19.091, 207Pb/204Pb = 15.579-15.646, 208Pb/204Pb = 38.550-38.993; 176Hf/177Hf ratios correlate negatively with 208Pb*/206Pb*, suggesting the effects of similar mantle processes on the evolution of time-integrated Th/U and Lu/Hf

  15. Final Report on Isotope Ratio Techniques for Light Water Reactors

    Energy Technology Data Exchange (ETDEWEB)

    Gerlach, David C.; Gesh, Christopher J.; Hurley, David E.; Mitchell, Mark R.; Meriwether, George H.; Reid, Bruce D.

    2009-07-01

    The Isotope Ratio Method (IRM) is a technique for estimating the energy or plutonium production in a fission reactor by measuring isotope ratios in non-fuel reactor components. The isotope ratios in these components can then be directly related to the cumulative energy production with standard reactor modeling methods.

  16. Paleoproterozoic basement beneath the southern Jiangxi Province: Evidence from U-Pb ages and Lu-Hf isotopes in zircons from the Doushui Iamprophyre

    Institute of Scientific and Technical Information of China (English)

    YU JinHai; WANG LiJuan; O'REILLY S Y; SHU LiangShu; UN Tao

    2009-01-01

    This paper presents geochemical analyses of a lamprophyre intruding the Caledonian Doushui granite body in Shangyou County, southern Jiangxi Province. U-Pb dating and Hf-isotope analyses are especially carried out for zircons from it. Petrological and geochemical features show that the lamprophyre belongs to a high-K, weakly alkaline pyroxene-biotite iamprophyre. It is characterized by high Mg# (0.74),Ni (253 μg/g) and Cr (893 μg/g) contents, and also enriched in incompatible elements, such as REE, Rb, Sr, Ba and K. It is suggested that its primitive melt probably derived from enriched mantle metasomatized by non-crust-derived agent. Morphology and LAM-ICPMS dating results of zircons in the lam prophyre indicate that they are xenocrysts captured from deep crustal rocks. Most xenocrystic zircons formed at -1.86 Ga, and a few in different Phanerozoic periods. The Paleoproterozoic zircons are of magmatic origin and have similar 176Hf/177Hf and 176Lu/177Hf ratios, indicating that they probably are from the same igneous basement rock. The ages and Hf-isotope compositions of zircons from this basement rock are similar to those of Paleoproterozoic Danzhu granite in the southern Zhejiang Province, but extremely distinguished from the Nanling basement, suggesting that the study area probably is a westward extension part of Paleoproterozoic Wuyishan terrane in the eastern Cathaysia Block. These Paleoproterozoic zircons have low Hf-isotope compositions, characteristic of crustal source. Hf model ages of these zircons and the presence of older inherited cores within them, coupled with available other data reported by previous studies, suggest that the source of Paleoproterozoic magma is Neoarchaean crust, implying the existence of older basement in the Wuyishan terrane. U-Pb ages and Hf isotopes of five Phanerozoic zircons indicate that Paleoproterozoic basement underwent multi-reworking occurring in Caledonian, Indosinian and early Yanshanian, respectively. The Caledonian

  17. Effects of Continental Weathering and Sedimentary Sorting on the Hf, Nd, and Pb Isotopic Composition of Sediments and Implications for Dissolved Input to the Ocean

    Science.gov (United States)

    van de Flierdt, T.; Hemming, S. R.; Goldstein, S. L.

    2005-05-01

    The application of radiogenic isotopes of dissolved trace metals (Hf, Pb, Nd) in the ocean to study climate induced weathering changes on the continents is a relatively new and exciting field of research. Most studies on the radiogenic isotope composition of past seawater are based on chemical sediments such as ferromanganese crusts, and suggest a strong linkage in changes in the style of weathering (chemical vs. physical/glacial) on the continents and the isotopic composition of seawater for elements such as Hf and Pb. This is evidenced by records from the northwest Atlantic, which show significant changes in the Hf and Pb isotopic composition of seawater associated with the onset of Northern Hemisphere Glaciation (NHG) over the past 3 Myr. On the other hand, the impact of glacial weathering on the Nd isotopic composition of seawater is generally thought to be negligible. In order to better understand the systematics and mechanisms of weathering, erosion, and run-off, as well as their bearing on the isotopic composition of the ocean we choose the following strategy: sediments from the Amerilik and Gothabs Fjords near Nuuk (Greenland) have been analyzed for their bulk rock and grain size specific Hf, Nd, and Pb isotopic compositions (sand, silt, mud). Both Fjords are surrounded by early Archean gneisses, among the oldest rocks on Earth, and are filled with glacially floured sediments. Precambrian rocks surround a large fraction of the circum-North Atlantic area that was covered by ice sheets during the NHG, and the source rocks in this region are the most extreme examples. Current knowledge about the impact of weathering processes on isotope systematics implies that the largest changes in the Hf (and Pb) isotopic composition of seawater are expected to arise from glacial weathering of old continental sources. Our data reveal large differences in grain size specific isotope ratios, e.g. between the mud and sand fractions, for sediments with an old provenance

  18. Reconciliation of the excess 176Hf conundrum in meteorites: Recent disturbances of the Lu-Hf and Sm-Nd isotope systematics

    Science.gov (United States)

    Bast, Rebecca; Scherer, Erik E.; Sprung, Peter; Mezger, Klaus; Fischer-Gödde, Mario; Taetz, Stephan; Böhnke, Mischa; Schmid-Beurmann, Hinrich; Münker, Carsten; Kleine, Thorsten; Srinivasan, Gopalan

    2017-09-01

    The long-lived 176Lu-176Hf and 147Sm-143Nd radioisotope systems are commonly used chronometers, but when applied to meteorites, they can reveal disturbances. Specifically, Lu-Hf isochrons commonly yield dates up to ∼300 Myr older than the solar system and varying initial 176Hf/177Hf values. We investigated this problem by attempting to construct mineral and whole rock isochrons for eucrites and angrites. Meteorites from different parent bodies exhibit similar disturbance features suggesting that a common process is responsible. Minerals scatter away from isochron regressions for both meteorite classes, with low-Hf phases such as plagioclase and olivine typically being most displaced above (or left of) reference isochrons. Relatively Hf-rich pyroxene is less disturbed but still to the point of steepening Lu-Hf errorchrons. Using our Lu-Hf and Sm-Nd data, we tested various Hf and Lu redistribution scenarios and found that decoupling of Lu/Hf from 176Hf/177Hf must postdate the accumulation of significant radiogenic 176Hf. Therefore early irradiation or diffusion cannot explain the excess 176Hf. Instead, disturbed meteorite isochrons are more likely caused by terrestrial weathering, contamination, or common laboratory procedures. The partial dissolution of phosphate minerals may predominantly remove rare earth elements including Lu, leaving relatively immobile and radiogenic Hf behind. Robust Lu-Hf (and improved Sm-Nd) meteorite geochronology will require the development of chemical or physical methods for removing unsupported radiogenic Hf and silicate-hosted terrestrial contaminants without disturbing parent-daughter ratios.

  19. Evolution of E2 transition strength in deformed hafnium isotopes from new measurements on $^{172}$Hf, $^{174}$Hf, and $^{176}$Hf

    CERN Document Server

    Rudigier, M; Dannhoff, M; Gerst, R-B; Jolie, J; Saed-Samii, N; Stegemann, S; Régis, J-M; Robledo, L M; Rodríguez-Guzmán, R; Blazhev, A; Fransen, Ch; Warr, N; Zell, K O

    2015-01-01

    The available data for E2 transition strengths in the region between neutron-deficient Hf and Pt isotopes are far from complete. More and precise data are needed to enhance the picture of structure evolution in this region and to test state-of-the-art nuclear models. In a simple model, the maximum collectivity is expected at the middle of the major shell. However, for actual nuclei, this picture may no longer be the case, and one should use a more realistic nuclear-structure model. We address this point by studying the spectroscopy of Hf. We remeasure the 2^+_1 half-lives of 172,174,176Hf, for which there is some disagreement in the literature. The main goal is to measure, for the first time, the half-lives of higher-lying states of the rotational band. The new results are compared to a theoretical calculation for absolute transition strengths. The half-lives were measured using \\gamma-\\gamma and conversion-electron-\\gamma delayed coincidences with the fast timing method. For the determination of half-lives i...

  20. Isotope ratio analysis by Orbitrap mass spectrometry

    Science.gov (United States)

    Eiler, J. M.; Chimiak, L. M.; Dallas, B.; Griep-Raming, J.; Juchelka, D.; Makarov, A.; Schwieters, J. B.

    2016-12-01

    Several technologies are being developed to examine the intramolecular isotopic structures of molecules (i.e., site-specific and multiple substitution), but various limitations in sample size and type or (for IRMS) resolution have so far prevented the creation of a truly general technique. We will discuss the initial findings of a technique based on Fourier transform mass spectrometry, using the Thermo Scientific Q Exactive GC — an instrument that contains an Orbitrap mass analyzer. Fourier transform mass spectrometry is marked by exceptionally high mass resolutions (the Orbitrap reaches M/∆M in the range 250,000-1M in the mass range of greatest interest, 50-200 amu). This allows for resolution of a large range of nearly isobaric interferences for isotopologues of volatile and semi-volatile compounds (i.e., involving isotopes of H, C, N, O and S). It also provides potential to solve very challenging mass resolution problems for isotopic analysis of other, heavier elements. Both internal and external experimental reproducibilities of isotope ratio analyses using the Orbitrap typically conform to shot-noise limits down to levels of 0.2 ‰ (1SE), and routinely in the range 0.5-1.0 ‰, with similar accuracy when standardized to concurrently run reference materials. Such measurements can be made without modifications to the ion optics of the Q Exactive GC, but do require specially designed sample introduction devices to permit sample/standard comparison and long integration times. The sensitivity of the Q Exactive GC permits analysis of sub-nanomolar samples and quantification of multiply-substituted species. The site-specific capability of this instrument arises from the fact that mass spectra of molecular analytes commonly contain diverse fragment ion species, each of which samples a specific sub-set of molecular sites. We will present applications of this technique to the biological and abiological chemistry of amino acids, forensic identification of

  1. Numerical modeling of radioactive neutron capture influence of Hf isotopic composition dynamics rate in the RBMK-1500 reactor

    CERN Document Server

    Jurkevicius, A; Auzelyte, V; Remeikis, V

    2000-01-01

    The nuclide composition of the nuclear fuel and isotopic composition of the hafnium in the radial neutron flux detectors of the RBMK-1500 reactor were numerically modelled. The sequence SAS2 from package SCALE 4.3 was used for calculations. The nuclear fuel nuclide concentrations, the concentration of Hf isotopes, the neutron absorption rate on Hf isotopes and summary absorption rate dependences on the fuel assembly burn up are presented. (author)

  2. Age and genesis of the Myanmar jadeite: Constraints from U-Pb ages and Hf isotopes of zircon inclusions

    Institute of Scientific and Technical Information of China (English)

    QIU ZhiLi; WU FuYuan; YANG ShuFeng; ZHU Min; SUN JinFeng; YANG Ping

    2009-01-01

    Myanmar jadeite (jadeitite) is well known for its economical value and distinctive tectonic locality within the collisional belt between India and Eurasian plates. However, it is less studied for its genesis and geodynamic implications due to precipitous topography, adverse weather and local military conflicts in the area. By means of combined ICP-MS and LA-MC-ICPMS techniques, we have carried out in-situ trace elements, U-Pb and Lu-Hf isotopes for zircon inclusions in a piece of jadeite gem sample. CL imaging suggests that the zircons are metasomatic in origin, and contain mineral inclusions of jadeite and omphacite. Seventy-five analyses on 16 grains of the zircons yield a U-Pb age of 158±2 Ma. The Myanmar zircons differ from other types in that they have no significant Eu anomalies despite high HREE concentrations. Measured 176Hf/177Hf ratios range from 0.282976 to 0.283122, with an average value of 0.283066±7;εHf(t) value of 13.8±0.3 (n=75). These results indicate that the Myanmar jadeite was formed in the Late Jurassic, probably by interaction of fluid released from subducted oceanic slab with mantle wedge. Therefore, its formation has no genetic relationship to the continental collision between Indian and Euroasian plates.

  3. Worldwide lead-isotope ratio in bivalves and sediments

    DEFF Research Database (Denmark)

    Larsen, Martin Mørk; Jacobsen, Gitte; Strand, Jakob

    The lead-isotope ratio have been used to assess and identify impact of leaded gasoline, coal combustion and  mineral activities[ref 1] due to the difference in 206Pb (~52%), 207Pb (~24%) and 208Pb (~23%) isotope ratios. The source of these differences is the decaying of the parent isotopes of 238U...

  4. How the oxygen isotope ratio of rain water influences the isotope ratio of chicken eggshell carbonate

    Science.gov (United States)

    Price, Gregory; Grimes, Stephen

    2015-04-01

    The stable oxygen isotope ratio of chicken eggshell carbonate was analysed from chicken eggs laid under free range, and organic farming regimes from across the UK. The eggshell carbonate oxygen isotope data shows a clear depletion in delta18O distribution from the southwest to the northeast. Although consistently offset by around 1 permil, the same isotopic distribution as that seen in eggshell carbonate is observed in the delta18O ratio of rainfall and groundwater from across the UK. This distribution is related to the Rayleigh distillation of rainfall driven by westerly winds across the UK landmass. The clear relationship observed between eggshell delta18O values and that of rainwater presumably reflects the nature of free range chickens which must be drinking locally derived rainwater and supplementing their diet and water intake with locally derived food. These results suggest that the oxygen isotope value of chicken eggshells can be used as a forensic tool to identify the locality that free range and organic eggs were laid within the UK. Furthermore, if suitable material is preserved in the archaeological and geological record then such a relationship can potentially be used to establish the oxygen isotope value of rainwater from which ancient and / or ancestral birds lived.

  5. Mixing and melt sources in the Miocene Aztec Wash pluton (Nevada, USA) as revealed by zircon Hf and O and whole rock Sr, Nd, and Hf isotopes

    Science.gov (United States)

    Ryan, M.; Miller, J. S.; Miller, C. F.; Bromley, S.; Davies, G. R.; Schmitt, A. K.

    2011-12-01

    The 15.6 Ma Aztec Wash Pluton (AWP) is one of several Miocene intrusions located within the northern Colorado River extensional corridor. Extensive E-W tilting of fault blocks has exposed the pluton from the roof to 5 km structural depth. Earlier field and petrologic studies subdivided the AWP into two distinct zones: (1) a Granite Zone (GZ) comprised of relatively homogeneous granite with subtle differences in textures and mineralogy; (2) a Heterogeneous Zone (HZ), which interfingers the GZ, contains evidence for mafic and felsic magma input with a wide compositional range (42-78 wt% SiO2), and abundant field evidence for hybridization. Previous whole rock geochemistry and zircon trace element analyses indicated that compositional variation was produced by multi-component mixing between mafic and felsic melts within the HZ. New whole rock Sr, Nd, and Hf isotope data from the HZ show that all rocks (including high-silica granites) formed by mixing Precambrian crust and enriched mantle, with mixtures having a large mantle fraction (≥50%). New Hf (n=189) and O (n=241) isotope analyses of zircon from samples in the HZ confirm these melt sources and provide a broader perspective on hybridization processes within the AWP. Zircon grains from all samples show heterogeneous Hf and O isotopic compositions (-5 to -18 ɛHf; 4.5-7.5% δ18O), but despite the clear signature of Precambrian crust in the whole rock data, obvious Precambrian zircons (or cores) were mostly absent; only one zircon was clearly Precambrian (ɛHf = -25). Resolvable intragrain variability is relatively limited (including the Precambrian grain, which is unzoned). Zircons from hand samples and from compositional groups also show heterogeneous ɛHf and δ18O values, although the spreads are more restricted than in the whole data set (6-10 ɛHf in granites, 5-7 ɛHf in intermediate "hybrids", 5-6 ɛHf in gabbro/diorite sheets). Oxygen isotope values for the zircons also show intra-handsample heterogeneity

  6. A linear Hf isotope-age array despite different granitoid sources and complex Archean geodynamics: Example from the Pietersburg block (South Africa)

    Science.gov (United States)

    Laurent, Oscar; Zeh, Armin

    2015-11-01

    Combined U-Pb and Lu-Hf isotope data from zircon populations are widely used to constrain Hadean-Archean crustal evolution. Linear Hf isotope-age arrays are interpreted to reflect the protracted, internal reworking of crust derived from the (depleted) mantle during a short-lived magmatic event, and related 176Lu/177Hf ratios are used to constrain the composition of the reworked crustal reservoir. Results of this study, however, indicate that Hf isotope-age arrays can also result from complex geodynamic processes and crust-mantle interactions, as shown by U-Pb and Lu-Hf isotope analyses of zircons from well characterized granitoids of the Pietersburg Block (PB), northern Kaapvaal Craton (South Africa). Apart from scarce remnants of Paleoarchean crust, most granitoids of the PB with ages between 2.94 and 2.05 Ga (n = 32) define a straight Hf isotope-age array with low 176Lu/177Hf of 0.0022, although they show a wide compositional range, were derived from various sources and emplaced successively in different geodynamic settings. The crustal evolution occurred in five stages: (I) predominately mafic crust formation in an intra-oceanic environment (3.4-3.0 Ga); (II) voluminous TTG crust formation in an early accretionary orogen (3.0-2.92 Ga); (III) internal TTG crust reworking and subduction of TTG-derived sediments in an Andean-type setting (2.89-2.75 Ga); (IV) (post-)collisional high-K magmatism from both mantle and crustal sources (2.71-2.67 Ga); and (V) alkaline magmatism in an intra-cratonic environment (2.05-2.03 Ga). The inferred array results from voluminous TTG crust formation during stage II, and involvement of this crust during all subsequent stages by two different processes: (i) internal crust reworking through both partial melting and assimilation at 2.89-2.75 Ga, leading to the formation of biotite granites coeval with minor TTGs, and (ii) subduction of TTG-derived sediments underneath the PB, causing enrichment of the mantle that subsequently became

  7. Erosion of Archean continents: The Sm-Nd and Lu-Hf isotopic record of Barberton sedimentary rocks

    Science.gov (United States)

    Garçon, M.; Carlson, R. W.; Shirey, S. B.; Arndt, N. T.; Horan, M. F.; Mock, T. D.

    2017-06-01

    Knowing the composition, nature and amount of crust at the surface of the early Earth is crucial to understanding the early geodynamics of our planet. Yet our knowledge of the Hadean-Archean crust is far from complete, limited by the poor preservation of Archean terranes, and the fact that less attention has been paid to the sedimentary record that tracks erosion of these ancient remnants. To address this problem and get a more comprehensive view of what an Archean continent may have looked like, we investigated the trace element and Sm-Nd, Lu-Hf isotopic records of Archean metasedimentary rocks from South Africa. We focused our study on sandstone and mudstone from drill core in the Fig Tree Group (3.23-3.26 Ga) of the Barberton granite-greenstone belt, but also analyzed the 3.4 Ga Buck Reef cherts and still older (3.5-3.6 Ga) meta-igneous rocks from the Ancient Gneiss Complex, Swaziland. Based on principal component analysis of major and trace element data, the Fig Tree metasedimentary rocks can be classified into three groups: crustal detritus-rich sediments, Si-rich sediments and Ca-, Fe-rich sediments. The detritus-rich sediments have preserved the Sm-Nd and Lu-Hf isotopic signatures of their continental sources, and hence can be used to constrain the composition of crust eroded in the Barberton area in the Paleoarchean period. Based on Sm/Nd ratios, we estimate that this crust was more mafic than today, with an average SiO2 content of 60.5 ± 2 wt.%. This composition is further supported by isotopic mixing calculations suggesting that the sedimentary source area contained equal proportions of mafic-ultramafic and felsic rocks. This implies that the Archean crust exposed to weathering was more mafic than today but does not exclude a more felsic composition at depth. Neodymium and Hf crustal residence ages show that the eroded crust was, on average, ∼300-400 Ma older than the deposition age of the sediments, which highlights the importance of intracrustal

  8. Hf isotope evidence for effective impact melt homogenisation at the Sudbury impact crater, Ontario, Canada

    Science.gov (United States)

    Kenny, Gavin G.; Petrus, Joseph A.; Whitehouse, Martin J.; Daly, J. Stephen; Kamber, Balz S.

    2017-10-01

    We report on the first zircon hafnium-oxygen isotope and trace element study of a transect through one of the largest terrestrial impact melt sheets. The differentiated melt sheet at the 1.85 Ga, originally ca. 200 km in diameter Sudbury impact crater, Ontario, Canada, yields a tight range of uniform zircon Hf isotope compositions (εHf(1850) of ca. -9 to -12). This is consistent with its well-established crustal origin and indicates differentiation from a single melt that was initially efficiently homogenised. We propose that the heterogeneity in other isotopic systems, such as Pb, in early-emplaced impact melt at Sudbury is associated with volatility-related depletion during the impact cratering process. This depletion leaves the isotopic systems of more volatile elements more susceptible to contamination during post-impact assimilation of country rock, whereas the systems of more refractory elements preserve initial homogeneities. Zircon oxygen isotope compositions in the melt sheet are also restricted in range relative to those in the impacted target rocks. However, they display a marked offset approximately one-third up the melt sheet stratigraphy that is interpreted to be a result of post-impact assimilation of 18O-enirched rocks into the base of the cooling impact melt. Given that impact cratering was a more dominant process in the early history of the inner Solar System than it is today, and the possibility that impact melt sheets were sources of ex situ Hadean zircon grains, these findings may have significance for the interpretation of the early zircon Hf record. We speculate that apparent εHf-time arrays observed in the oldest terrestrial and lunar zircon datasets may be related to impact melting homogenising previously more diverse crust. We also show that spatially restricted partial melting of rocks buried beneath the superheated impact melt at Sudbury provided a zircon crystallising environment distinct to the impact melt sheet itself.

  9. Uniform Silicon Isotope Ratios Across the Milky Way Galaxy

    Science.gov (United States)

    Monson, Nathaniel N.; Morris, Mark R.; Young, Edward D.

    2017-04-01

    We report the relative abundances of the three stable isotopes of silicon, 28Si, 29Si, and 30Si, across the Galaxy using the v=0,J=1\\to 0 transition of silicon monoxide. The chosen sources represent a range in Galactocentric radii ({R}{GC}) from 0 to 9.8 kpc. The high spectral resolution and sensitivity afforded by the Green Bank Telescope permit isotope ratios to be corrected for optical depths. The optical-depth-corrected data indicate that the secondary-to-primary silicon isotope ratios {}29{Si}{/}28{Si} and {}30{Si}{/}28{Si} vary much less than predicted on the basis of other stable isotope ratio gradients across the Galaxy. Indeed, there is no detectable variation in Si isotope ratios with {R}{GC}. This lack of an isotope ratio gradient stands in stark contrast to the monotonically decreasing trend with {R}{GC} exhibited by published secondary-to-primary oxygen isotope ratios. These results, when considered in the context of the expectations for chemical evolution, suggest that the reported oxygen isotope ratio trends, and perhaps those for carbon as well, require further investigation. The methods developed in this study for SiO isotopologue ratio measurements are equally applicable to Galactic oxygen, carbon, and nitrogen isotope ratio measurements, and should prove useful for future observations of these isotope systems.

  10. A chilling perspective on Greenland's early Cenozoic climate from coupled Hf-Nd isotopes

    Science.gov (United States)

    Scher, H. D.; Bizimis, M.; Buckley, W. P., Jr.; Duggan, B.; Bohaty, S. M.; Wilson, P. A.

    2015-12-01

    The prevailing view of northern hemisphere glaciation has been of ice sheets forming on Greenland after 2.7 Ma, with iceberg rafting as early as 15 Ma. This view is incompatible with recent results from global climate/ice sheet models that predict northern hemisphere glaciation only after CO2 falls below ~280 ppmv (occurring at 25 Ma) and with recent sediment evidence for Arctic iceberg rafting as early as the middle Eocene. However, the amount of northern hemisphere ice represented by these sediments is ambiguous and global ice budget calculations for the early Cenozoic are controversial. Here we use coupled Hf-Nd isotopes of oxyhydroxides in sediments from the upper Eocene to lower Oligocene section in ODP Site U1411 (Newfoundland Ridge) to determine when the circum-North Atlantic came under the influence of a mechanical weathering regime. Leached oxyhydroxide Hf-Nd isotopes are an indicator of weathering intensity because mechanical weathering by ice sheets mobilizes the zircon-bound Hf reservoir in the crust, which has extreme unradiogenic eHf values. Chemical weathering produces a distinct seawater array on Hf-Nd diagrams, while seawater exposed to the products of mechanical weathering plot on divergent arrays closer to the Terrestrial Array. Hf-Nd isotopes of Site U1411 leachates are grouped in a near vertical trend between the seawater and terrestrial global reference arrays. Within this group there are four distinct arrays that can be delineated by age. Samples that are late Eocene in age fall along an array that is slightly divergent from the seawater array. The aspect of the Hf-Nd isotope data changes permanently after the first step of the EOT, falling along arrays that are systematically offset in the direction of the terrestrial arrays. The steepest array, most proximal to the terrestrial array, is comprised of samples deposited between 33.7 and 32.2 Ma. These results indicate a circum-North Atlantic weathering regime appeared in the earliest Oligocene.

  11. Detrital zircon evidence for Hf isotopic evolution of granitoid crust and continental growth

    Science.gov (United States)

    Iizuka, Tsuyoshi; Komiya, Tsuyoshi; Rino, Shuji; Maruyama, Shigenori; Hirata, Takafumi

    2010-04-01

    We have determined U-Pb ages, trace element abundances and Hf isotopic compositions of approximately 1000 detrital zircon grains from the Mississippi, Congo, Yangtze and Amazon Rivers. The U-Pb isotopic data reveal the lack of >3.3 Ga zircons in the river sands, and distinct peaks at 2.7-2.5, 2.2-1.9, 1.7-1.6, 1.2-1.0, 0.9-0.4, and uniformitarian secular change in Hf isotopes of granitoid crusts; Hf isotopic compositions of granitoid crusts deviate from the mantle evolution line from about 3.3 to 2.0 Ga, the deviation declines between 2.0 and 1.3 Ga and again increases afterwards. Consideration of mantle-crust mixing models for granitoid genesis suggests that the noted isotopic trends are best explained if the rate of crust generation globally increased in two stages at around (or before) 3.3 and 1.3 Ga, whereas crustal differentiation was important in the evolution of the continental crust at 2.3-2.2 Ga and after 0.6 Ga. Reconciling the isotopic secular change in granitoid crust with that in sedimentary rocks suggests that sedimentary recycling has essentially taken place in continental settings rather than active margin settings and that the sedimentary mass significantly grew through addition of first-cycle sediments from young igneous basements, until after ˜1.3 Ga when sedimentary recycling became the dominant feature of sedimentary evolution. These findings, coupled with the lack of zircons older than 3.3 Ga in river sands, imply the emergence of large-scale continents at about 3.3 Ga with further rapid growth at around 1.3 Ga. This resulted in the major growth of the sedimentary mass between 3.3 and 1.3 Ga and the predominance of its cannibalistic recycling later.

  12. Application of the Zr/Hf ratio in the determination of hafnium in geochemical samples by high-resolution inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    Liu, Ya Xuan; Li, Qing Xia; Ma, Na; Sun, Xiao Ling; Bai, Jin Feng; Zhang, Qin

    2014-12-02

    Hafnium content and its change are of significance in geochemistry and cosmochemistry; however, the determination of hafnium has always been problematic in analytical chemistry. In this paper, a new idea is proposed for the determination of hafnium in geochemical samples, including rocks, soils, and stream sediments. Through the comparison of two conventional open-type acid digestion methods (HF-HNO3-HClO4 and HF-HNO3-H2SO4), it was found that although neither of these methods could fully digest the zirconium and hafnium in a sample, the zirconium and hafnium digestion behaviors in one sample were consistent in the 60 experimental geochemical reference materials with different properties, so the experimentally determined Zr/Hf ratio in solution could be used to calculate the hafnium content in a sample. In addition, possible mass spectral interferences during the determination of zirconium and hafnium by high resolution inductively coupled plasma mass spectrometry (HR-ICPMS) were studied, and it was found that the mass spectral interferences of the selected isotopes (90)Zr and (178)Hf could be neglected. The mass spectral behaviors of (90)Zr and (178)Hf were also very consistent during the determination by HR-ICPMS. Since the hafnium content was calculated using the ratio value, all of the errors (including the errors in weighing process, the accidental errors during operation and the instrument fluctuation in the determination) of the Zr/Hf ratio could be effectively reduced or even eliminated. The relative standard deviation of the actual samples was lower than 3.2%, and the detection limit of the method (considering the dilution effect and matrix effect during measurement of the Zr/Hf ratio and zirconium content) was 0.04 μg/g. The proposed method could satisfy the requirement for the determination of hafnium in geochemical samples.

  13. Determination of fission gas yields from isotope ratios

    DEFF Research Database (Denmark)

    Mogensen, Mogens Bjerg

    1983-01-01

    This paper describes a method of calculating the actual fission yield of Kr and Xe in nuclear fuel including the effect of neutron capture reactions and decay. The bases for this calculation are the cumulative yields (ref. 1) of Kr and Xe isotopes (or pairs of isotopes) which are unaffected...... by neutron capture reactions, and measured Kr and Xe isotope ratios. Also the burnup contribution from the different fissile heavy isotopes must be known in order to get accurate fission gas yields....

  14. Determination of fission gas yields from isotope ratios

    DEFF Research Database (Denmark)

    Mogensen, Mogens Bjerg

    1983-01-01

    This paper describes a method of calculating the actual fission yield of Kr and Xe in nuclear fuel including the effect of neutron capture reactions and decay. The bases for this calculation are the cumulative yields (ref. 1) of Kr and Xe isotopes (or pairs of isotopes) which are unaffected...... by neutron capture reactions, and measured Kr and Xe isotope ratios. Also the burnup contribution from the different fissile heavy isotopes must be known in order to get accurate fission gas yields....

  15. Tungsten isotopic compositions in stardust SiC grains from the Murchison meteorite: Constraints on the s-process in the Hf-Ta-W-Re-Os region

    CERN Document Server

    Ávila, J N; Ireland, T R; Gyngard, F; Zinner, E; Cristallo, S; Holden, P; Buntain, J; Amari, S; Karakas, A

    2011-01-01

    We report the first tungsten isotopic measurements in stardust silicon carbide (SiC) grains recovered from the Murchison carbonaceous chondrite. The isotopes 182W, 183W, 184W, 186W and 179Hf, 180Hf were measured on both an aggregate (KJB fraction) and single stardust SiC grains (LS+LU fraction) believed to have condensed in the outflows of low-mass carbon-rich asymptotic giant branch (AGB) stars with close-to-solar metallicity. The SiC aggregate shows small deviations from terrestrial (=solar) composition in the 182W/184W and 183W/184W ratios, with deficits in 182W and 183W with respect to 184W. The 186W/184W ratio, however, shows no apparent deviation from the solar value. Tungsten isotopic measurements in single mainstream stardust SiC grains revealed lower than solar 182W/184W, 183W/184W, and 186W/184W ratios. We have compared the SiC data with theoretical predictions of the evolution of W isotopic ratios in the envelopes of AGB stars. These ratios are affected by the slow neutron-capture process and match...

  16. Genesis and open-system evolution of Quaternary magmas beneath southeastern margin of Tibet: Constraints from Sr-Nd-Pb-Hf isotope systematics

    Science.gov (United States)

    Zou, Haibo; Ma, Mingjia; Fan, Qicheng; Xu, Bei; Li, Shuang-Qing; Zhao, Yongwei; King, David T.

    2017-02-01

    Post-collisional volcanic rocks on the Tibetan Plateau and its margins contain valuable information about the geodynamic processes associated with this Cenozoic continent-continent collision. The Quaternary Tengchong volcanic field at the southeastern margin of the Tibetan Plateau formed high-potassium calc-alkaline volcanic rocks. Herein, we present comprehensive Nd-Sr-Pb-Hf isotopic and elemental data for trachybasalts, basaltic trachyandesites, and trachyandesites from four Quaternary Tengchong volcanoes (Maanshan, Dayingshan, Heikongshan, and Laoguipo) in order to understand their magma genesis and evolution as well as tectonic significance. Good correlations between SiO2 content and the ratios 87Sr/86Sr, 143Nd/144Nd, 206Pb/204Pb, and 177Hf/176Hf for these Quaternary volcanics strongly suggest that the combined assimilation and fractional crystallization (AFC) was an important process in the origin of basaltic trachyandesites and trachyandesites. High Y and Yb contents and low Sr/Y ratios of these basaltic trachyandesites and trachyandesites are uncharacteristic of adakites that formed by partial melting of eclogitic lower crust or partial melting of basaltic oceanic crust with eclogite as a restite. A combined assimilation-fractional crystallization model is proposed for these basaltic trachyandesites and trachyandesites. Nd-Sr-Pb-Hf isotopes for the uncontaminated Tengchong magma (trachybasalts with SiO2 5.5% wt.%) reflect a heterogeneous enriched mantle source. High Th/U, Th/Ta, and Rb/Nb ratios and Nd-Sr-Pb-Hf isotope characteristics of the uncontaminated magmas suggest that the enriched mantle beneath Tengchong formed as a result of subduction of clay-rich sediments, which probably came from the Indian continental plate. Partial melting of the enriched mantle was generated by deep continental subduction coupled with recent regional extension in the Tengchong area.

  17. A method for combined Sr-Nd-Hf isotopic analysis of <10 mg dust samples: implication for ice core science

    Science.gov (United States)

    Ujvari, Gabor; Wegner, Wencke; Klötzli, Urs

    2017-04-01

    Aeolian mineral dust particles below the size of 10-20 μm often experience longer distance transport in the atmosphere, and thus Aeolian dust is considered an important tracer of large-scale atmospheric circulation. Since ice core dust is purely Aeolian in origin, discrimination of its potential source region(s) can contribute to a better understanding of past dust activity and climatic/environmental causes. Furthermore, ice core dust source information provides critical experimental constraints for model simulations of past atmospheric circulation patterns [1,2]. However, to identify dust sources in past dust archives such as ice cores, the mineralogy and geochemistry of the wind-blown dust material must be characterized. While the amount of dust in marine cores or common terrestrial archives is sufficient for different types of analyses and even for multiple repeat measurements, dust content in ice cores is usually extremely low even for the peak dusty periods such as the Last Glacial Maximum (LGM) (5-8 mg dust/kg ice; [3]). Since the most powerful dust fingerprinting methods, such as REE composition and Sr-Nd-Pb isotopic analyses are destructive there is a clear need to establish sequential separation techniques of Sr, Nd, Pb and other REEs to get the most information out of small (5-10 mg) dust samples recovered from ice cores. Although Hf isotopes have recently been added as a robust tool of aerosol/dust source discrimination (e.g. [4,5,6,7]), precise Hf isotopic measurements of small (Central Europe (NUS), China (BEI) and the US (JUD) were processed (all acetic acid treated for carbonate removal, i.e. aluminosilicate fractions were analysed). Sr isotopic compositions varied between the aliquots within a range of ˜0.00007 for the three samples. Comparison of these values with previously obtained 87Sr/86Sr isotopic ratios from the same samples (different acid/sample amounts) reveals that these values are very sensitive to the acetic acid treatment (acid

  18. U-Pb isotopic ages and Hf isotope composition of zircons in Variscan gabbros from central Spain: evidence of variable crustal contamination

    Science.gov (United States)

    Villaseca, Carlos; Orejana, David; Belousova, Elena; Armstrong, Richard A.; Pérez-Soba, Cecilia; Jeffries, Teresa E.

    2011-03-01

    Ion microprobe U-Pb analyses of zircons from three gabbroic intrusions from the Spanish Central System (SCS) (Talavera, La Solanilla and Navahermosa) yield Variscan ages (300 to 305 Ma) in agreement with recent studies. Only two zircon crystals from La Solanilla massif gave slightly discordant Paleoproterozoic ages (1,848 and 2,010 Ma). Hf isotope data show a relatively large variation with the juvenile end-members showing ɛHfi values as high as +3.6 to +6.9 and +1.5 to +2.9 in the Navahermosa and Talavera gabbros, respectively. These positive ɛHfi values up to +6.9 might represent the composition of the subcontinental mantle which generates these SCS gabbros. This ɛHfi range is clearly below depleted mantle values suggesting the involvement of enriched mantle components on the origin of these Variscan gabbros, and is consistent with previous whole-rock studies. The presence of zircons with negative ɛHfi values suggest variable, but significant, crustal contamination of the gabbros, mainly by mixing with coeval granite magmas. Inherited Paleoproterozoic zircons of La Solanilla gabbros have similar trace element composition (e.g. Th/U ratios), but more evolved Hf-isotope signatures than associated Variscan zircons. Similar inherited ages have been recorded in zircons from coeval Variscan granitoids from the Central Iberian Zone. Granitic rocks have Nd model ages (TDM) predominantly in the range of 1.4 to 1.6 Ga, suggesting a juvenile addition during the Proterozoic. However, Hf crustal model ages of xenocrystic Proterozoic zircons in La Solanilla gabbro indicate the presence of reworked Archean protoliths (TDM2 model ages of 3.0 to 3.2 Ga) incorporated into the hybridized mafic magma.

  19. Decoupling of whole-rock Nd-Hf and zircon Hf-O isotopic compositions of a 284 Ma mafic-ultramafic intrusion in the Beishan Terrane, NW China

    Science.gov (United States)

    Su, Ben-Xun; Qin, Ke-Zhang; Lu, Ying-Huai; Sun, He; Sakyi, Patrick Asamoah

    2015-10-01

    Abundant Permian mafic-ultramafic intrusions in the Beishan Terrane, NW China, are parts of the Tarim large igneous province. Among these intrusions, Luodong intrusion is composed of dunite, wehrlite and gabbro. These rocks have whole-rock Sr-Nd-Hf and zircon Hf-O isotope compositions that display significant decoupling. The decoupling of these generally well-correlated systems demonstrates contrasting evolving trends. Systematic compositional and mineralogical controls on decoupling have been investigated. Wehrlites and gabbros show MORB-like trace element patterns with negligible crustal contamination. They have high initial 143Nd/144Nd [ɛNd(t) = +6.6 to +11.2] and 176Hf/177HfHf(t) = +12.2 to +16.9] and low initial 87Sr/86Sr [(87Sr/86Sr)i = 0.702949-0.704098] ratios and plot within the MORB field, indicating that their parental magmas were derived from a depleted mantle source. The enrichment features are present in the zircon crystals separated from the gabbro. These homogeneously unzoned zircon crystals have high U concentrations, low Th/U ratios and a U-Pb age of 284.0 ± 2.3 Ma. They are therefore interpreted as having formed rapidly in a highly fractionated/evolved magma. Their ɛHf(t) and δ18O values range from -9.3 to -6.7 and +10.25 ‰ to +11.42 ‰, respectively. The decoupling is linked with crustal contamination by ancient crust (probably Proterozoic schist in the Beishan Terrane) that occurred during zircon crystallization. However, the contamination signature in the whole-rock composition was soon overprinted by magma mixing process. The inference is evidenced by zoning textures preserved in plagioclase, clinopyroxene, spinel and particularly olivine, and the presence of coeval diabase dykes cutting through the intrusion. The isotope decoupling observed in this mantle-plume-related mafic-ultramafic intrusion supports the idea that Nd-Hf decoupling and Lu/Hf and Sm/Nd parent/daughter variations exist only on a small hand-size scale in a

  20. Towards absolute laser spectroscopic CO2 isotope ratio measurements

    Science.gov (United States)

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

    2017-04-01

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

  1. Lead isotopic signatures in Antarctic marine sediment cores: a comparison between 1M HCl partial extraction and HF total digestion pre-treatments for discerning anthropogenic inputs.

    Science.gov (United States)

    Townsend, A T; Snape, I; Palmer, A S; Seen, A J

    2009-12-20

    Sensitive analytical techniques are typically required when dealing with samples from Antarctica as even low concentrations of contaminants can have detrimental environmental effects. Magnetic Sector ICP-MS is an ideal technique for environmental assessment as it offers high sensitivity, multi-element capability and the opportunity to determine isotope ratios. Here we consider the Pb isotope record of five marine sediment cores collected from three sites in the Windmill Islands area of East Antarctica: Brown Bay adjacent to the current Australian station Casey, Wilkes near the abandoned US/Australian Station and McGrady Cove lying midway between the two. Two sediment pre-treatment approaches were considered, namely partial extraction with 1M HCl and total dissolution involving HF. Lead isotope ratio measurements made following sediment partial extraction provided a more sensitive indication of Pb contamination than either Pb concentrations alone (irrespective of sample pre-treatment method) or isotope ratios made after HF digestion, offering greater opportunity for discrimination between impacted and natural/geogenic samples and sites. Over 90% of the easily extractable Pb from sediments near Casey was anthropogenic in origin, consisting of Pb from major Australian deposits. At Wilkes impact from discarded batteries with a unique isotopic signature was found to be a key source of Pb contamination to the marine environment with ~70-80% of Pb being anthropogenic in origin. The country and source of origin of these batteries remain unknown. Little evidence was found suggesting contamination at Wilkes by Pb originating from the major US source, Missouri. No definitive assessment could be made regarding Pb impact at McGrady Cove as the collected sediment core was of insufficient depth. Although Pb isotope ratio signatures may indicate anthropogenic input, spatial concentration gradients at nearby Brown Bay suggest contamination at McGrady Cove is unlikely. We recommend

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

    Energy Technology Data Exchange (ETDEWEB)

    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).

  3. Long-term stability of hydrogen isotope ratios in hydrated volcanic glass

    Science.gov (United States)

    Cassel, Elizabeth J.; Breecker, Daniel O.

    2017-03-01

    The advancement of conceptual and numerical geodynamic models necessitates quantitative, orogen-scale paleoelevation data. Felsic volcanic glasses, which record the hydrogen isotope compositions (δD) of meteoric water shortly after deposition, provide several advantages as a paleoelevation proxy. Questions remain, however, about the reliability of this relatively new proxy, including the effect of hydrofluoric (HF) acid abrasion in the preparation of glass shards for hydrogen isotope analysis and the stability of hydrogen isotope ratios in hydrated glass shards over geologic time (106-107 years). HF acid abrasion of natural ancient glass shards results in systematic shifts in glass δD values away from modern water δD values. To evaluate the effectiveness of HF acid abrasion, we treated 70-150 μm glass shards separated from various natural tephras with deuterium-labeled water (DLW; δD = +18,205‰) for up to 400 days. For all glasses, this treatment resulted in elevated δD values in comparison to untreated samples. HF acid abrasion after DLW exposure, however, removed this effect and restored glass shards to their original untreated δD values in samples older than 104 years. HF acid abrasion removes hydrous alteration precipitates at the glass surface without measurably changing the δD values of the underlying hydrated glass, regardless of abrasion duration or glass composition. Additionally, 45-34 Ma glasses record δD values that directly reflect their depositional environments as determined by stratigraphy: glasses from tuffs deposited in demonstrably evaporative lacustrine environments have relatively high δD values compared to glasses from contemporaneous tuffs deposited in nearby fluvial environments, which have much lower δD values. The preservation of δD values that systematically vary with original depositional environment, despite >30 Myr of post-hydration exposure to the same meteoric water, indicates that these volcanic glasses resisted

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

    OpenAIRE

    Kerstel, E; Gianfrani, L.

    2008-01-01

    Small molecules exhibit characteristic ro-vibrational transitions in the near- and mid-infrared spectral regions, which are strongly influenced by isotopic substitution. This gift of nature has made it possible to use laser spectroscopy for the accurate analysis of the isotopic composition of gaseous samples. Nowadays, laser spectroscopy is clearly recognized as a valid alternative to isotope ratio mass spectrometry. Laser-based instruments are leaving the research laboratory stage and are be...

  5. Magmatic and crustal differentiation history of granitic rocks from Hf-O isotopes in zircon.

    Science.gov (United States)

    Kemp, A I S; Hawkesworth, C J; Foster, G L; Paterson, B A; Woodhead, J D; Hergt, J M; Gray, C M; Whitehouse, M J

    2007-02-16

    Granitic plutonism is the principal agent of crustal differentiation, but linking granite emplacement to crust formation requires knowledge of the magmatic evolution, which is notoriously difficult to reconstruct from bulk rock compositions. We unlocked the plutonic archive through hafnium (Hf) and oxygen (O) isotope analysis of zoned zircon crystals from the classic hornblende-bearing (I-type) granites of eastern Australia. This granite type forms by the reworking of sedimentary materials by mantle-like magmas instead of by remelting ancient metamorphosed igneous rocks as widely believed. I-type magmatism thus drives the coupled growth and differentiation of continental crust.

  6. Plume-Lithosphere Interaction beneath the Snake River Plain, Idaho: Constraints from Pb, Sr, Nd, and Hf Isotopes

    Science.gov (United States)

    Jean, M. M.; Hanan, B. B.; Shervais, J. W.

    2011-12-01

    The Yellowstone-Snake River Plain (YSRP) volcanic province links 17 million years of volcanic activity that extends from the Owyhee Plateau in western Idaho/eastern Oregon to its current terminus underlying the Yellowstone Plateau. This investigation presents new Strontium, Neodymium, Lead, and Hafnium isotopic compositions of 25 basalts that represent four distinct areas of the YSRP (i.e., eastern province, central province, western province, Owyhee Plateau), which transect the ancient cratonic boundary of North America. The purpose of this study is to test and refine models for plume-lithosphere interaction and determines the mantle origin for YSRP basalts. New results shows: (1) low-K tholeiites from the eastern, central, and western SRP have ɛNd (-2 to -5.5), 87Sr/86Sr (0.7060-0.7071) and similar Pb-isotopes [206Pb/204Pb (17.8-18.6), 207Pb/204Pb (15.5-15.66), 208Pb/204Pb (38.4-39.1)]; (2) central SRP tholeiites are enriched in 208Pb/204Pb (~38.5-38.9), relative to eastern SRP basalts and define a 208Pb/204Pb trend, intermediate between the eastern SRP and Craters of the Moon lavas; (3) western SRP high-K basalts are depleted in ɛNd (> -1) and 87Sr/86Sr (0.7050-0.7057), relative to low-K tholeiites, and plot closer to "bulk silicate earth," but are enriched in 206Pb/204Pb (18.66-18.71), and have 207Pb/204Pb (15.62-15.65) and 208Pb/204Pb (39.1-39.2) isotope ratios similar to high-K basalts of Smith Prairie (Boise River Group 2); (4) Silver City basalt (>16.6 Ma) overlaps in Pb-isotope space with Imnaha basalt compositions (Columbia River Basalt Group); (5) new 177Hf/176Hf isotopic data lie above and parallel to the Mantle array in Nd and Hf isotope space and define a linear trend between Leucite Hills lavas and OIB basalts (i.e., Steens and Hawaii); (6) these basalts follow a systematic geographic pattern: eastern and central plain low-K tholeiites have low ɛNd (-3 to -5) and intermediate 206Pb/204Pb (~17.7-18.5), while western plain low-K tholeiites are

  7. Stable carbon isotope ratios of ambient aromatic volatile organic compounds

    Science.gov (United States)

    Kornilova, Anna; Huang, Lin; Saccon, Marina; Rudolph, Jochen

    2016-09-01

    Measurements of mixing ratios and stable carbon isotope ratios of aromatic volatile organic compounds (VOC) in the atmosphere were made in Toronto (Canada) in 2009 and 2010. Consistent with the kinetic isotope effect for reactions of aromatic VOC with the OH radical the observed stable carbon isotope ratios are on average significantly heavier than the isotope ratios of their emissions. The change of carbon isotope ratio between emission and observation is used to determine the extent of photochemical processing (photochemical age, ∫ [OH]dt) of the different VOC. It is found that ∫ [OH]dt of different VOC depends strongly on the VOC reactivity. This demonstrates that for this set of observations the assumption of a uniform ∫ [OH]dt for VOC with different reactivity is not justified and that the observed values for ∫ [OH]dt are the result of mixing of VOC from air masses with different values for ∫ [OH]dt. Based on comparison between carbon isotope ratios and VOC concentration ratios it is also found that the varying influence of sources with different VOC emission ratios has a larger impact on VOC concentration ratios than photochemical processing. It is concluded that for this data set the use of VOC concentration ratios to determine ∫ [OH]dt would result in values for ∫ [OH]dt inconsistent with carbon isotope ratios and that the concept of a uniform ∫ [OH]dt for an air mass has to be replaced by the concept of individual values of an average ∫ [OH]dt for VOC with different reactivity.

  8. Combination of carbon isotope ratio with hydrogen isotope ratio determinations in sports drug testing.

    Science.gov (United States)

    Piper, Thomas; Emery, Caroline; Thomas, Andreas; Saugy, Martial; Thevis, Mario

    2013-06-01

    Carbon isotope ratio (CIR) analysis has been routinely and successfully applied to doping control analysis for many years to uncover the misuse of endogenous steroids such as testosterone. Over the years, several challenges and limitations of this approach became apparent, e.g., the influence of inadequate chromatographic separation on CIR values or the emergence of steroid preparations comprising identical CIRs as endogenous steroids. While the latter has been addressed recently by the implementation of hydrogen isotope ratios (HIR), an improved sample preparation for CIR avoiding co-eluting compounds is presented herein together with newly established reference values of those endogenous steroids being relevant for doping controls. From the fraction of glucuronidated steroids 5β-pregnane-3α,20α-diol, 5α-androst-16-en-3α-ol, 3α-Hydroxy-5β-androstane-11,17-dione, 3α-hydroxy-5α-androstan-17-one (ANDRO), 3α-hydroxy-5β-androstan-17-one (ETIO), 3β-hydroxy-androst-5-en-17-one (DHEA), 5α- and 5β-androstane-3α,17β-diol (5aDIOL and 5bDIOL), 17β-hydroxy-androst-4-en-3-one and 17α-hydroxy-androst-4-en-3-one were included. In addition, sulfate conjugates of ANDRO, ETIO, DHEA, 3β-hydroxy-5α-androstan-17-one plus 17α- and androst-5-ene-3β,17β-diol were considered and analyzed after acidic solvolysis. The results obtained for the reference population encompassing n = 67 males and females confirmed earlier findings regarding factors influencing endogenous CIR. Variations in sample preparation influenced CIR measurements especially for 5aDIOL and 5bDIOL, the most valuable steroidal analytes for the detection of testosterone misuse. Earlier investigations on the HIR of the same reference population enabled the evaluation of combined measurements of CIR and HIR and its usefulness regarding both steroid metabolism studies and doping control analysis. The combination of both stable isotopes would allow for lower reference limits providing the same statistical

  9. Isotopic Ratios of Samarium by TIMS for Nuclear Forensic Application

    Energy Technology Data Exchange (ETDEWEB)

    Louis Jean, James [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Inglis, Jeremy David [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2017-08-08

    The isotopic ratio of Nd, Sm, and Gd can provide important information regarding fissile material (nuclear devices, reactors), neutron environment, and device yield. These studies require precise measurement of Sm isotope ratios, by either TIMS or MC-ICP-MS. There has been an increasing trend to measure smaller and smaller quantities of Sm bearing samples. In nuclear forensics 10-100 ng of Sm are needed for precise measurement. To measure sub-ng Sm samples using TIMS for nuclear forensic analysis.

  10. Evidence for Slab Melt Contributions to the Mexican Volcanic Belt and Other Young Hot Slab Arcs from Lu-Hf Isotopes

    Science.gov (United States)

    Goldstein, S. L.; Cai, Y. M.; Langmuir, C. H.; Lagatta, A.; Straub, S. M.; Gomez-Tuena, A.; Martin Del Pozzo, A.

    2007-12-01

    Despite major advances in delineating the processes that govern magma generation at convergent margins, the problem persists of distinguishing slab, mantle wedge, and crustal contributions. A corrollary question is whether there is significant melting of subducted ocean crust. Especially in thick crust regions, the importance of crustal versus mantle contributions to lavas represents a long-standing fundamental issue in arc magma geochemistry. We show that frontal arc magmas from the Central Mexican Volcanic Belt (CMVB), including the large andesitic stratovolcanoes Popocatepetl and Nevado de Toluca, display negligible crustal contamination, and contain substantial contributions from melting of subducted Pacific ocean crust. Despite ca. 50 km thick continental crust, the CMVB erupts near primitive lavas including "high-Nb" alkaline basalts that show negligible "subduction signatures" in their trace element patterns. These "high-Nb" basalts define the regional mantle wedge composition in isotope-trace element space. The "normal" calcalkaline lavas form a negative correlation between Hf isotopes and Lu/Hf. One endmember is like the high Nb basalts representing the regional mantle wedge. The other endmember has higher Hf isotopes (approaching values of Pacific MORB) and very low Lu/Hf of less than 0.04 (e.g. compared to typical values of ca. 0.2 in Pacific MORB). The low Lu/Hf values require low degree partial melting of a source rich in garnet. The high Hf isotopes require a depleted mantle source with isotopes like Pacific MORB. Together the Lu-Hf data indicate a substantial component derived from melting of eclogitic Pacific ocean crust. A key feature of the data is that the stratovolcano lavas showing the largest slab melt signature also show the highest Hf isotope ratios and thus are more "depleted mantle-like" than the regional mantle wedge. Thus, the integrated data allow us to clearly distinguish between mantle and crustal sources in the CMVB and point to

  11. A Sr-Nd-Hf isotope characterization of dust source areas in Victoria Land and the McMurdo Sound sector of Antarctica

    Science.gov (United States)

    Blakowski, Molly A.; Aciego, Sarah M.; Delmonte, Barbara; Baroni, Carlo; Salvatore, Maria Cristina; Sims, Kenneth W. W.

    2016-06-01

    Determining the geographical provenance of dust provides crucial insight into the global dust cycle. For the East Antarctic Ice Sheet (EAIS), the importance of Southern hemisphere potential dust sources has been thoroughly investigated using radiogenic isotopes, whereas proximal dust source areas located on the periphery of the ice sheet remain poorly documented from a geochemical standpoint. In this work, we expand the existing isotopic (Srsbnd Nd) catalogue of dust and sand-sized sediments from Victoria Land and the McMurdo Sound sector, and incorporate Hf isotopic data to place additional constraints on dust source identification. The isotopic field for materials considered in this study is characterized by 87Sr/86Sr ratios ranging from 0.703 to 0.783, εNd between -12.01 and 6.36, and εHf from -16.77 to 6.89. As reported in previous works, the data reveal close relationships between Antarctic sediments and distinct parent lithologies; in addition, our findings emphasize the background presence of very fine dusts originating from dominant global sources and regional volcanic activity as barriers to direct source-to-sink comparison of isotopic signatures. Thus, geochemical characterizations of dust sources to the Antarctic ice sheet involving multiple size fractions, including coarser-grained particles more susceptible to short-range transport, can help us to rule out global sources of dust when examining local sediment cores and ice cores.

  12. Direct path integral estimators for isotope fractionation ratios

    CERN Document Server

    Cheng, Bingqing

    2014-01-01

    Fractionation of isotopes among distinct molecules or phases is a quantum effect which is often exploited to obtain insights on reaction mechanisms, biochemical, geochemical and atmospheric phenomena. Accurate evaluation of isotope ratios in atomistic simulations is challenging, because one needs to perform a thermodynamic integration with respect to the isotope mass, along with time-consuming path integral calculations. By re-formulating the problem as a particle exchange in the ring polymer partition function, we derive new estimators giving direct access to the differential partitioning of isotopes, which can simplify the calculations by avoiding thermodynamic integration. We demonstrate the efficiency of these estimators by applying them to investigate the isotope fractionation ratios in the gas-phase Zundel cation, and in a few simple hydrocarbons.

  13. Zircon U-Pb geochronology, Sr-Nd-Hf isotopic composition and geological significance of the Late Triassic Baijiazhuang and Lvjing granitic plutons in West Qinling Orogen

    Science.gov (United States)

    Duan, Meng; Niu, Yaoling; Kong, Juanjuan; Sun, Pu; Hu, Yan; Zhang, Yu; Chen, Shuo; Li, Jiyong

    2016-09-01

    The Qinling Orogen was a consequence of continental collision of the South China Craton with the North China Craton in the Triassic and caused widespread granitoid magmatism. However, the petrogenesis of these granitoids remains controversial. In this paper, we choose the Baijiazhuang (BJZ) and Lvjing (LJ) plutons in the West Qinling Orogen for a combined study of the zircon U-Pb geochronology, whole-rock major and trace element compositions and Sr-Nd-Hf isotopic characteristics. We obtained zircon crystallization ages of 216 Ma and 212 Ma for the BJZ and the LJ plutons, respectively. The granitoid samples from both plutons have high K2O metaluminous to peraluminous compositions. They are enriched in large ion lithophile elements (LILEs), light rare earth elements (LREEs) and depleted in high field-strength elements (HFSEs) with significant negative Eu anomalies. The BJZ samples have initial Sr isotopic ratios of 0.7032 to 0.7078, εNd(t) of - 10.99 to - 8.54 and εHf (t) of - 10.22 to - 6.41. The LJ granitoids have initial Sr isotopic ratios of 0.7070 to 0.7080, εNd(t) of - 5.37 to - 4.58 and εHf(t) of - 3.64 to - 1.78. The enriched isotopic characteristics of the two plutons are consistent with their source being dominated by ancient continental crust. However, two BJZ samples show depleted Sr isotope compositions, which may infer possible involvement of mantle materials. Mantle-derived melt, which formed from partial melting of mantle wedge peridotite facilitated by dehydration of the subducted/subducting Mianlue ocean crust, provide the required heat for the crustal melting while also contributing to the compositions of these granitoids. That is, the two granitic plutons are magmatic responses to the closure of the Mianlue ocean basin and the continental collision between the Yangtze and South Qinling crustal terranes.

  14. Sr, Nd, Pb and Hf isotopic constraints on mantle sources and crustal contaminants in the Payenia volcanic province, Argentina

    DEFF Research Database (Denmark)

    Søager, Nina; Holm, Paul Martin; Thirlwall, Matthew F.

    2015-01-01

    The presented Sr, Nd, Hf and double-spike Pb-isotopic analyses of Quaternary basalts from the Payenia volcanic province in southern Mendoza, Argentina, confirm the presence of two distinct mantle types feeding the Payenia volcanism. The southern Payenia mantle source feeding the intraplate-type Río...... is suggested to be caused by step-wise melt extraction due to repeated injections of subduction zone fluids and melts. The lower crustal contamination trends found in the trace element variations of basalt groups from all parts of the Payenia province are also recognized in isotopic space and the dominant...... isotope assimilation trends indicate lower crustal contaminants with more unradiogenic Pb, lower 143Nd/144Nd and 176Hf/177Hf and higher or similar 87Sr/86Sr as the mantle melts. These characteristics are similar to those found in lower crustal xenoliths from the northern Proterozoic Cuyania terrane...

  15. Changes in erosion and ocean circulation recorded in the Hf isotopic compositions of North Atlantic and Indian Ocean ferromanganese crusts

    Science.gov (United States)

    Piotrowski, Alexander M.; Lee, Der-Chuen; Christensen, John N.; Burton, Kevin W.; Halliday, Alex N.; Hein, James R.; Günther, Detlef

    2000-01-01

    High-resolution Hf isotopic records are presented for hydrogenetic Fe–Mn crusts from the North Atlantic and Indian Oceans. BM1969 from the western North Atlantic has previously been shown to record systematically decreasing Nd isotopic compositions from about 60 to ∼4 Ma, at which time both show a rapid decrease to unradiogenic Nd composition, thought to be related to the increasing influence of NADW or glaciation in the northern hemisphere. During the Oligocene, North Atlantic Hf became progressively less radiogenic until in the mid-Miocene (∼15 Ma) it reached +1. It then shifted gradually back to an ϵHf value of +3 at 4 Ma, since when it has decreased rapidly to about −1 at the present day. The observed shifts in the Hf isotopic composition were probably caused by variation in intensity of erosion as glaciation progressed in the northern hemisphere. Ferromanganese crusts SS663 and 109D are from about 5500 m depth in the Indian Ocean and are now separated by ∼2300 km across the Mid-Indian Ridge. They display similar trends in Hf isotopic composition from 20 to 5 Ma, with the more northern crust having a composition that is consistently more radiogenic (by ∼2 ϵHf units). Paradoxically, during the last 20 Ma the Hf isotopic compositions of the two crusts have converged despite increased separation and subsidence relative to the ridge. A correlatable negative excursion at ∼5 Ma in the two records may reflect a short-term increase in erosion caused by the activation of the Himalayan main central thrust. Changes to unradiogenic Hf in the central Indian Ocean after 5 Ma may alternatively have been caused by the expanding influence of NADW into the Mid-Indian Basin via circum-Antarctic deep water or a reduction of Pacific flow through the Indonesian gateway. In either case, these results illustrate the utility of the Hf isotope system as a tracer of paleoceanographic changes, capable of responding to subtle changes in erosional regime not readily resolved

  16. Assessing the isotopic evolution of S-type granites of the Carlos Chagas Batholith, SE Brazil: Clues from U-Pb, Hf isotopes, Ti geothermometry and trace element composition of zircon

    Science.gov (United States)

    Melo, Marilane G.; Lana, Cristiano; Stevens, Gary; Pedrosa-Soares, Antônio C.; Gerdes, Axel; Alkmin, Leonardo A.; Nalini, Hermínio A.; Alkmim, Fernando F.

    2017-07-01

    The Carlos Chagas batholith (CCB) is a very large ( 14,000 km2) S-type granitic body formed during the syn-collisional stage of the Araçuaí orogen (southeastern Brazil). Zircons extracted from the CCB record a wide range of U-Pb ages (from 825 to 490 Ma), indicating a complex history of inheritance, magmatic crystallization and partial melting during the evolution of the orogeny. Magmatic zircons (ca. 578-588 Ma) are marked by similar Hf isotope compositions and REE patterns to those of inherited cores (ca. 825-600 Ma), indicating that these aspects of the chemical signature of the magmatic zircons have likely been inherited from the source. The U-Pb ages and initial 176Hf/177Hf ratios from anatectic and metamorphic zircon domains are consistent with a two-stage metamorphic evolution marked by contrasting mechanisms of zircon growth and recrystallization during the orogeny. Ti-in-zircon thermometry is consistent with the findings of previous metamorphic work and indicates that the two metamorphic events in the batholith reached granulite facies conditions (> 800 °C) producing two generations of garnet via fluid-absent partial melting reactions. The oldest metamorphic episode (ca. 570-550 Ma) is recorded by development of thin anatectic overgrowths on older cores and by growth of new anatectic zircon crystals. Both domains have higher initial 176Hf/177Hf values compared to relict cores and display REE patterns typical of zircon that grew contemporaneously with peritectic garnet through biotite-absent fluid partial melting reactions. Hf isotopic and chemical evidences indicate that a second anatectic episode (ca. 535-500 Ma) is only recorded in parts from the CCB. In these rocks, the growth of new anatectic zircon and/or overgrowths is marked by high initial 176Hf/177Hf values and also by formation of second generation of garnet, as indicated by petrographic observations and REE patterns. In addition, some rocks contain zircon crystals formed by solid

  17. Plutonium isotope ratio variations in North America

    Energy Technology Data Exchange (ETDEWEB)

    Steiner, Robert E [Los Alamos National Laboratory; La Mont, Stephen P [Los Alamos National Laboratory; Eisele, William F [Los Alamos National Laboratory; Fresquez, Philip R [Los Alamos National Laboratory; Mc Naughton, Michael [Los Alamos National Laboratory; Whicker, Jeffrey J [Los Alamos National Laboratory

    2010-12-14

    Historically, approximately 12,000 TBq of plutonium was distributed throughout the global biosphere by thermo nuclear weapons testing. The resultant global plutonium fallout is a complex mixture whose {sup 240}Pu/{sup 239}Pu atom ratio is a function of the design and yield of the devices tested. The average {sup 240}Pu/{sup 239}Pu atom ratio in global fallout is 0.176 + 014. However, the {sup 240}Pu/{sup 239}Pu atom ratio at any location may differ significantly from 0.176. Plutonium has also been released by discharges and accidents associated with the commercial and weapons related nuclear industries. At many locations contributions from this plutonium significantly alters the {sup 240}Pu/{sup 239}Pu atom ratios from those observed in global fallout. We have measured the {sup 240}Pu/{sup 239}Pu atom ratios in environmental samples collected from many locations in North America. This presentation will summarize the analytical results from these measurements. Special emphasis will be placed on interpretation of the significance of the {sup 240}Pu/{sup 239}Pu atom ratios measured in environmental samples collected in the Arctic and in the western portions of the United States.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  19. Zircon U-Pb Age, Trace Element, and Hf Isotope Evidence for Paleoproterozoic Granulite-Facies Metamorphism and Archean Crustal Remnant in the Dabie Orogen

    Institute of Scientific and Technical Information of China (English)

    Lei Nengzhong; Wu Yuanbao

    2008-01-01

    Zircon U-Pb age, trace elements, and Hf isotopes were determined for granulite and gneiss at Huaugtuling (黄土岭), which is hosted by ultrahigh-pressure metamorphic rocks in the Dabie(大别) orogen, east-central China. Cathodolumineseence (CL) images reveal core-rim structure for most zircons in the granulite. The cores show oscillatory zoning, relatively high Th/U and 176 Lu/177 Hf ratios, and high rare earth element (HREE)-enriched pattern, consistent with magmatic origin. They gave a weighted mean 207 Pb/206 Pb age of (2 766±9) Ma, dating magma emplacement of protolith. The rims are characterized by sector ur planar zoning, low Th/U and 176 Lu/177 Hf ratios, negative Euanomalies and flat HREE patterns, consistent with their formation under granulite-facies metamorphicconditions. Zircon U-Pb dating yields an age of (2 029±13) Ma, which is interpreted as a record ofmetamorphic event during the assembly of the supercontinent Columbia. The gneiss has a protolith ageof (1982±14) Ma, which is similar to the zircon U-Pb age for the granulite-facies metamorphism,suggesting complementary processes to granulite-facies metamorphism and partial melting. A fewinherited cores with igneous characteristics have 207 pb/206 Pb ages of approximately 3.53, 3.24, and 2.90Ga, respectively, suggesting the presence of Mesoarchean to Paleoarchean crustal remnants. A fewTriassic and Cretaceous metamorphic ages were obtained, suggesting the influences by the Triassiccontinental collision and postcollisional collapse in response to the Cretaceous extension. Comparingwith abundant occurrence of Triassic metamorphic zircons in ultrahigh-pressure eclogite and granitehydrous melt is evident for zircon growth in theHuangtuling granulite and gneiss during thecontinental collision. The magmatic protolithzircons from the granulite show a large variationin 176 Hf/177 Hf ratios from 0.280 809 to 0.281 289,corresponding to era(t) values of-7.3 to 6.3 andHf model ages of 2.74 to 3.34 Ga. The 2

  20. Comparison of gas chromatography/isotope ratio mass spectrometry and liquid chromatography/isotope ratio mass spectrometry for carbon stable-isotope analysis of carbohydrates

    NARCIS (Netherlands)

    Moerdijk-Poortvliet, T.C.W.; Schierbeek, H.; Houtekamer, M.; van Engeland, T.; Derrien, D.; Stal, L.J.; Boschker, H.T.S.

    2015-01-01

    We compared gas chromatography/isotope ratio mass spectrometry (GC/IRMS) and liquid chromatography/isotope ratio mass spectrometry (LC/IRMS) for the measurement of d13C values in carbohydrates. Contrary to GC/IRMS, no derivatisation is needed for LC/IRMS analysis of carbohydrates. Hence, although

  1. Implications for the evolution of continental crust from Hf isotope systematics of Archean detrital zircons

    Science.gov (United States)

    Stevenson, Ross K.; Patchett, P. Jonathan

    1990-01-01

    Results from the fractionation of zircon by sedimentary processes into continental margin sandstone yield information on the preservation of preexisting continental crust in the form of zircon, making it possible to distinguish between the contrasting theories of gradual growth versus constant volume of continental crust over geologic time. In this work, Hf-176/Hf-177 ratios were determined for detrital zircon fractions from 2.0-2.5, 2.6-3.0, and pre-3.0 Gyr old sandstones from the Canadian-Shield, the North-Atlantic, the Wyoming, and the Kaapvaal Cratons. Results pointed to small amounts of continental crust prior to 3.0 Gyr ago and a rapid addition of continental crust between 2.5 and 3.0 Gyr ago, consistent with the gradual growth of continental crust, and giving evidence against no-growth histories.

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

    Science.gov (United States)

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

    1989-01-01

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

  3. Zircon U-Pb age and Hf isotope of Quanyishang A-type granite in Yichang: Signification for the Yangtze continental cratonization in Paleoproterozoic

    Institute of Scientific and Technical Information of China (English)

    XIONG Qing; ZHENG JianPing; YU ChunMei; SU YuPing; TANG HuaYun; ZHANG ZhiHai

    2009-01-01

    Zircon U-Pb age and Hf isotope, and major and trace element compositions were reported for granite at Quanyishang, which intruded into the Kongling complex in Yichang, Hubei Province. The results show that the Quanyishang granite is rich in silicon and alkalis but poor in calcium and magnesium, and displays enrichment in Ga, Y, Zr, Nb but depletion in Sr and Ba, exhibiting the post-orogenic A-type affinity. 90% zircons from the granite are concordant, and give a middle Paleoproterozoic magmatic crystallization age (mean 1854 Ma). Initial Hf isotope ratios (176Hf/177Hf)1 of the middle Paleoproterozoic zircons range from 0.280863 to 0.281134 and they have negative εHf(t) values with a minimum of -26.3. These zircons give the depleted mantle model ages (TDM) of 2.9-3.3 Ga (mean 3.0 Ga), and the average crustal model ages (Tcrust) of 3.6-4.2 Ga (mean 3.8 Ga)., A Mesoarchean grain with 207pb/206Pb age of 2859 Ma has a slightly high TDM (3.4 Ga) but similar Tcrust (3.8 Ga) to the Paleoproterozoic zircons. All these data suggest that the source materials of the Quanyishang A-type granite are unusually old, at least ≥2.9 Ga (even Eoarchean). The event of crustal remelting, which resulted in the formation of the Quanyishang granite in the middle Paleoproterozoic, recorded the cratonization of the Yangtze conti-nent. The process may have relation to the extension and collapse of the deep crust with Archean ages, in response to the transition stage of the assembly and breakup of the Columbia supercontinent.

  4. Oxygen isotopic ratios in intermediate-mass red giants

    CERN Document Server

    Lebzelter, Thomas; Hinkle, Kenneth; Nowotny, Walter; Aringer, Bernhard

    2015-01-01

    Context. The abundances of the three main isotopes of oxygen are altered in the course of the CNO-cycle. When the first dredge-up mixes the burning products to the surface, the nucleosynthesis processes can be probed by measuring oxygen isotopic ratios. Aims. By measuring 16O/17O and 16O/18O in red giants of known mass we compare the isotope ratios with predictions from stellar and galactic evolution modelling. Methods. Oxygen isotopic ratios were derived from the K-band spectra of six red giants. The sample red giants are open cluster members with known masses of between 1.8 and 4.5 Msun . The abundance determination employs synthetic spectra calculated with the COMARCS code. The effect of uncertainties in the nuclear reaction rates, the mixing length, and of a change in the initial abundance of the oxygen isotopes was determined by a set of nucleosynthesis and mixing models using the FUNS code. Results. The observed 16O/17O ratios are in good agreement with the model results, even if the measured values do ...

  5. Calcium isotope ratios in animal and human bone

    Science.gov (United States)

    Reynard, L. M.; Henderson, G. M.; Hedges, R. E. M.

    2010-07-01

    Calcium isotopes in tissues are thought to be influenced by an individual's diet, reflecting parameters such as trophic level and dairy consumption, but this has not been carefully assessed. We report the calcium isotope ratios (δ 44/42Ca) of modern and archaeological animal and human bone ( n = 216). Modern sheep raised at the same location show 0.14 ± 0.08‰ higher δ 44/42Ca in females than in males, which we attribute to lactation by the ewes. In the archaeological bone samples the calcium isotope ratios of the herbivorous fauna vary by location. At a single site, the archaeological fauna do not show a trophic level effect. Humans have lower δ 44/42Ca than the mean site fauna by 0.22 ± 0.22‰, and the humans have a greater δ 44/42Ca range than the animals. No effect of sex or age on the calcium isotope ratios was found, and intra-individual skeletal δ 44/42Ca variability is negligible. We rule out dairy consumption as the main cause of the lower human δ 44/42Ca, based on results from sites pre-dating animal domestication and dairy availability, and suggest instead that individual physiology and calcium intake may be important in determining bone calcium isotope ratios.

  6. Worldwide lead-isotope ratio in bivalves and sediments

    DEFF Research Database (Denmark)

    Larsen, Martin Mørk; Jacobsen, Gitte; Strand, Jakob

    The lead-isotope ratio have been used to assess and identify impact of leaded gasoline, coal combustion and  mineral activities[ref 1] due to the difference in 206Pb (~52%), 207Pb (~24%) and 208Pb (~23%) isotope ratios. The source of these differences is the decaying of the parent isotopes of 238U...... to 206Pb, 235U to 207Pb and 232Th to 208Pb. 204Pb is the only stable Pb isotope usually contributing 1% of the total Pb. Differences in 206Pb/207Pb ratio ranges from 1.06 to 1.10 in old Pb ores (e.g. the time of the roman empire), whereas recent mining from radiogenic (high U and Th contents) ores can.......35% with recoveries of  98.50 to 100.03%. Geographical differences and comparison with literature values for the different regions will be presented, together with a discussion on the suitability of ICP-quadropole-MS for isotope ratio determinations. ...

  7. TUNGSTEN ISOTOPIC COMPOSITIONS IN STARDUST SiC GRAINS FROM THE MURCHISON METEORITE: CONSTRAINTS ON THE s-PROCESS IN THE Hf-Ta-W-Re-Os REGION

    Energy Technology Data Exchange (ETDEWEB)

    Avila, Janaina N.; Ireland, Trevor R.; Holden, Peter [Research School of Earth Sciences, Australian National University, Canberra, ACT 0200 (Australia); Lugaro, Maria; Buntain, Joelene [Centre for Stellar and Planetary Astrophysics, Monash University, Clayton, VIC 3800 (Australia); Gyngard, Frank; Zinner, Ernst; Amari, Sachiko [Laboratory for Space Sciences and the Department of Physics, Washington University, One Brookings Drive, St. Louis, MO 63130 (United States); Cristallo, Sergio [Departamento de Fisica Teorica y del Cosmos, Universidad de Granada, Granada 18071 (Spain); Karakas, Amanda, E-mail: janaina.avila@anu.edu.au [Mount Stromlo Observatory, Australian National University, Weston Creek, ACT 2611 (Australia)

    2012-01-01

    We report the first tungsten isotopic measurements in stardust silicon carbide (SiC) grains recovered from the Murchison carbonaceous chondrite. The isotopes {sup 182,183,184,186}W and {sup 179,180}Hf were measured on both an aggregate (KJB fraction) and single stardust SiC grains (LS+LU fraction) believed to have condensed in the outflows of low-mass carbon-rich asymptotic giant branch (AGB) stars with close-to-solar metallicity. The SiC aggregate shows small deviations from terrestrial (= solar) composition in the {sup 182}W/{sup 184}W and {sup 183}W/{sup 184}W ratios, with deficits in {sup 182}W and {sup 183}W with respect to {sup 184}W. The {sup 186}W/{sup 184}W ratio, however, shows no apparent deviation from the solar value. Tungsten isotopic measurements in single mainstream stardust SiC grains revealed lower than solar {sup 182}W/{sup 184}W, {sup 183}W/{sup 184}W, and {sup 186}W/{sup 184}W ratios. We have compared the SiC data with theoretical predictions of the evolution of W isotopic ratios in the envelopes of AGB stars. These ratios are affected by the slow neutron-capture process and match the SiC data regarding their {sup 182}W/{sup 184}W, {sup 183}W/{sup 184}W, and {sup 179}Hf/{sup 180}Hf isotopic compositions, although a small adjustment in the s-process production of {sup 183}W is needed in order to have a better agreement between the SiC data and model predictions. The models cannot explain the {sup 186}W/{sup 184}W ratios observed in the SiC grains, even when the current {sup 185}W neutron-capture cross section is increased by a factor of two. Further study is required to better assess how model uncertainties (e.g., the formation of the {sup 13}C neutron source, the mass-loss law, the modeling of the third dredge-up, and the efficiency of the {sup 22}Ne neutron source) may affect current s-process predictions.

  8. Heavy element stable isotope ratios: analytical approaches and applications.

    Science.gov (United States)

    Tanimizu, Masaharu; Sohrin, Yoshiki; Hirata, Takafumi

    2013-03-01

    Continuous developments in inorganic mass spectrometry techniques, including a combination of an inductively coupled plasma ion source and a magnetic sector-based mass spectrometer equipped with a multiple-collector array, have revolutionized the precision of isotope ratio measurements, and applications of inorganic mass spectrometry for biochemistry, geochemistry, and marine chemistry are beginning to appear on the horizon. Series of pioneering studies have revealed that natural stable isotope fractionations of many elements heavier than S (e.g., Fe, Cu, Zn, Sr, Ce, Nd, Mo, Cd, W, Tl, and U) are common on Earth, and it had been widely recognized that most physicochemical reactions or biochemical processes induce mass-dependent isotope fractionation. The variations in isotope ratios of the heavy elements can provide new insights into past and present biochemical and geochemical processes. To achieve this, the analytical community is actively solving problems such as spectral interference, mass discrimination drift, chemical separation and purification, and reduction of the contamination of analytes. This article describes data calibration and standardization protocols to allow interlaboratory comparisons or to maintain traceability of data, and basic principles of isotope fractionation in nature, together with high-selectivity and high-yield chemical separation and purification techniques for stable isotope studies.

  9. The use of carbon stable isotope ratios in drugs characterization

    Energy Technology Data Exchange (ETDEWEB)

    Magdas, D. A., E-mail: gabriela.cristea@itim-cj.ro; Cristea, G., E-mail: gabriela.cristea@itim-cj.ro; Bot, A., E-mail: gabriela.cristea@itim-cj.ro; Mirel, V., E-mail: gabriela.cristea@itim-cj.ro [National Institute for Research and Development of Isotopic and Molecular Technologies, 65-103 Donath Str., 400293 Cluj-Napoca (Romania)

    2013-11-13

    Isotopic Ratio Mass Spectrometry (IRMS) is an effective toll to be used for drug product authentication. The isotopic composition could be used to assist in the differentiation between batches of drugs and assist in the identification of counterfeit materials on the market. Only two factors affect the isotopic ratios in pharmaceutical components: the isotopic composition of the raw materials and the synthetic processes performed upon them. Counterfeiting of pharmaceutical drugs threatens consumer confidence in drug products companies' economical well-being. In this preliminary study, the analyzed samples consist in two types of commercially available analgesics, which were purchases from Romanian pharmacies. Differences in δ{sup 13}C between batches from −29.7 to −31.6% were observed, demonstrating that this method can be used to differentiate among individual drug batches and subsequently identify counterfeits on the market. On the other hand, carbon isotopic ratios differences among producers were recorded, the variations being between −31.3 to −34.9% for the same type of analgesic, but from different manufactures.

  10. Tracking the influence of a continental margin on growth of a magmatic arc, Fiordland, New Zealand, using thermobarometry, thermochronology, and zircon U-Pb and Hf isotopes

    Science.gov (United States)

    Scott, J. M.; Cooper, A. F.; Palin, J. M.; Tulloch, A. J.; Kula, J.; Jongens, R.; Spell, T. L.; Pearson, N. J.

    2009-12-01

    Geothermobarometric, radiogenic isotopic and thermochronologic data are used to track the influence of an ancient continental margin (Western Province) on development of an adjacent Carboniferous-Cretaceous magmatic arc (Outboard Median Batholith) in Fiordland, New Zealand. The data show a record of complicated Mesozoic Gondwana margin growth. Paragneiss within the Outboard Median Batholith is of Carboniferous to Jurassic age and records burial to middle crustal depths in Late Jurassic-Early Cretaceous during subduction-related plutonism and arc thickening. In contrast, Western Province metasedimentary rocks in the area of study immediately west of the Outboard Median Batholith are Late Cambrian-Early Ordovician in age, recrystallized at the amphibolite facies in the Late Devonian-Early Carboniferous and exhibit no evidence for Mesozoic textural or isotopic reequilibration. A phase of deformation, between 128 and 116 Ma deformed, exhumed, and cooled the Outboard Median Batholith to greenschist facies temperatures, while large parts of the Western Province underwent ≥9 kbar metamorphic conditions. Zircon grains from Mesozoic inboard plutons are isotopically more evolved (ɛHf(t) = +2.3 to +4.0) than those in the Outboard Median Batholith (ɛHf(t) = +9.4 to +11.1). The contrasting zircon Hf isotope ratios, absence of S-type plutons or Proterozoic-Early Paleozoic inherited zircon, and the apparent absence of Early Paleozoic metasedimentary rocks indicates that the Outboard Median Batholith is unlikely to be underlain by the Western Province continental lithosphere. The new data are consistent with the Outboard Median Batholith representing an allochthonous (although not necessarily exotic) arc that was juxtaposed onto the Gondwana continental margin along the intervening Grebe Mylonite Zone.

  11. Collective structural evolution in neutron-rich Yb, Hf, W, Os and Pt isotopes

    CERN Document Server

    Nomura, K; Rodriguez-Guzman, R; Robledo, L M; Sarriguren, P

    2011-01-01

    The low-lying quadrupole collective states in neutron-rich even-even Yb, Hf, W, Os, and Pt isotopes are studied in a systematic way. Spectroscopic calculations are performed in terms of the Interacting Boson Model Hamiltonian, which is determined from the Hartree-Fock-Bogoliubov (HFB) approach with Gogny Energy Density Functionals (EDFs). The multi-fermion dynamics of the surface deformation is simulated by the bosonic degrees of freedom so that the potential energy surface (PES) with quadrupole degrees of freedom, obtained from the constrained HFB calculations, is mapped onto the corresponding PES of the IBM system. The interaction strengths of the proton-neutron IBM (IBM-2) Hamiltonian are determined through this procedure, which enables one to access the spectroscopic properties. We demonstrate the occurrence of a prolate-to-oblate shape/phase transition as a function of neutron number in the considered isotope chains in both HFB (with D1S and D1M EDFs) and the corresponding mapped IBM PESs. The shape tran...

  12. A convergent continent marginal volcanism source of ash beds near the Permian-Triassic boundary, South China: Constraints from trace elements and Hf-isotopes

    Science.gov (United States)

    Wang, X.; Zhao, L.; Chen, Z. Q.; Ma, D.; Yan, P.; Guo, F.; Wang, F.; Wan, Q.; Han, X.

    2015-12-01

    Growing evidence shows that volcanism near the Permian-Triassic boundary (PTB) may have been crucial in triggering the PTB biocrisis. However, whether this trigger is the Siberian traps or arc island volcanisms has long been debating. Meanwhile, multiple claystone beds are prominent near the PTB, South China. The nature and origin of the volcanic ashes therefore provide clue to find out the trigger of the PTB mass extinction. Following previous studies (Gao et al., 2013), 21 PTB ash beds from three additional PTB sections, namely the Shangsi, Jianshi and Meishan, all from South China have been systematically sampled. The U-Pb ages, trace elements, and Hf-isotope compositions of zircon grains from these ash beds were analyzed using LA-ICPMS and LA-MC-ICPMS. Volcanic ash geochemistry shows presence of Rhyolite or Dacite and reveal a collision-tectonic setting. Zircons from these ash layers yield comparatively low Nb/Hf and high Th/Nb ratios, dropping into the range of arc/orogenic-related settings. Zircon Hf-isotope compositions show that ɛHf(t) values vary from -11.7 to 1.8, indicating that at least two kinds of crustal component have been involved: juvenile lower crust and ancient middle-upper crust. The ash beds (Ss27a, Js129, Js130, Ms25, Ms26) near biotic extinction horizon have significant larger variation range of ɛHf(t) and relatively positive averages, implying that more juvenile lower crustal material had contributed to the volcanisms. This means that these volcanisms may have originated deeper depth or the volcanisms erupted so rapidly that there was no enough time for the mixing of different components. The volcanisms associated with biotic extinction should be the most intense and have greatest heat put. Spatial and temporal distributions of ash beds from thirty PTB sections worldwide reveal that the PTB volcanic ashes occurred only in the Paleo-Tethys region, suggesting that the volcanisms may be likely limited to the Paleo-Tethys continental

  13. Cross contamination in dual inlet isotope ratio mass spectrometers

    NARCIS (Netherlands)

    Meijer, H.A.J.; Neubert, R.E.M.; Visser, G.H.

    2000-01-01

    Since the early days of geochemical isotope ratio mass spectrometry there has always been the problem of cross contamination, i.e. the contamination of the sample gas with traces of reference gas land vice versa) in a dual inlet system and the analyzer itself. This was attributable to valve leakages

  14. Stable isotope ratios in hair and teeth reflect biologic rhythms.

    Directory of Open Access Journals (Sweden)

    Otto Appenzeller

    Full Text Available Biologic rhythms give insight into normal physiology and disease. They can be used as biomarkers for neuronal degenerations. We present a diverse data set to show that hair and teeth contain an extended record of biologic rhythms, and that analysis of these tissues could yield signals of neurodegenerations. We examined hair from mummified humans from South America, extinct mammals and modern animals and people, both healthy and diseased, and teeth of hominins. We also monitored heart-rate variability, a measure of a biologic rhythm, in some living subjects and analyzed it using power spectra. The samples were examined to determine variations in stable isotope ratios along the length of the hair and across growth-lines of the enamel in teeth. We found recurring circa-annual periods of slow and fast rhythms in hydrogen isotope ratios in hair and carbon and oxygen isotope ratios in teeth. The power spectra contained slow and fast frequency power, matching, in terms of normalized frequency, the spectra of heart rate variability found in our living subjects. Analysis of the power spectra of hydrogen isotope ratios in hair from a patient with neurodegeneration revealed the same spectral features seen in the patient's heart-rate variability. Our study shows that spectral analysis of stable isotope ratios in readily available tissues such as hair could become a powerful diagnostic tool when effective treatments and neuroprotective drugs for neurodegenerative diseases become available. It also suggests that similar analyses of archaeological specimens could give insight into the physiology of ancient people and animals.

  15. Distribution coefficients of 60 elements on TODGA resin: application to Ca, Lu, Hf, U and Th isotope geochemistry.

    Science.gov (United States)

    Pourmand, Ali; Dauphas, Nicolas

    2010-05-15

    Batch equilibration experiments are conducted to measure the distribution coefficients (K(d)) of a large number of elements in nitric, nitric plus hydrofluoric, and hydrochloric acids on Eichrom TODGA extraction chromatography resin. The K(d)s are used to devise a multi-element extraction scheme for high-precision elemental and isotopic analyses of Ca, Hf, Lu, Th and U in geological materials, using high-purity lithium metaborate (LiBO(2)) flux fusion that allows rapid digestion of even the most refractory materials. The fusion melt, dissolved in nitric acid, is directly loaded to a TODGA cartridge on a vacuum chamber for elemental separation. An Ln-Spec cartridge is used in tandem with TODGA for Lu purification. The entire procedure, from flux digestion to preparation for isotopic analysis, can be completed in a day. The accuracy of the proposed technique is tested by measuring the concentrations of Ca (standard bracketing), Hf, Lu, Th and U (isotope dilution), and the isotopic composition of Hf in geostandards (USNM3529, BCR-2, BHVO-1, AGV-1 and AGV-2). All measurements are in excellent agreement with recommended literature values, demonstrating the effectiveness of the proposed analytical procedure and the versatility of TODGA resin.

  16. A continuous flow isotope ratio mass spectrometry method for high precision determination of dissolved gas ratios and isotopic composition

    DEFF Research Database (Denmark)

    Charoenpong, C. N.; Bristow, L. A.; Altabet, M. A.

    2014-01-01

    Dissolved gas ratios and isotopic compositions provide essential information about the biological and physical mechanisms influencing N-2, O-2, and Ar in aquatic systems. Current methods available are either limited by overall cost, labor-intensive sample collection and analysis, or insufficient ...

  17. Finite mixture models for the computation of isotope ratios in mixed isotopic samples

    Science.gov (United States)

    Koffler, Daniel; Laaha, Gregor; Leisch, Friedrich; Kappel, Stefanie; Prohaska, Thomas

    2013-04-01

    Finite mixture models have been used for more than 100 years, but have seen a real boost in popularity over the last two decades due to the tremendous increase in available computing power. The areas of application of mixture models range from biology and medicine to physics, economics and marketing. These models can be applied to data where observations originate from various groups and where group affiliations are not known, as is the case for multiple isotope ratios present in mixed isotopic samples. Recently, the potential of finite mixture models for the computation of 235U/238U isotope ratios from transient signals measured in individual (sub-)µm-sized particles by laser ablation - multi-collector - inductively coupled plasma mass spectrometry (LA-MC-ICPMS) was demonstrated by Kappel et al. [1]. The particles, which were deposited on the same substrate, were certified with respect to their isotopic compositions. Here, we focus on the statistical model and its application to isotope data in ecogeochemistry. Commonly applied evaluation approaches for mixed isotopic samples are time-consuming and are dependent on the judgement of the analyst. Thus, isotopic compositions may be overlooked due to the presence of more dominant constituents. Evaluation using finite mixture models can be accomplished unsupervised and automatically. The models try to fit several linear models (regression lines) to subgroups of data taking the respective slope as estimation for the isotope ratio. The finite mixture models are parameterised by: • The number of different ratios. • Number of points belonging to each ratio-group. • The ratios (i.e. slopes) of each group. Fitting of the parameters is done by maximising the log-likelihood function using an iterative expectation-maximisation (EM) algorithm. In each iteration step, groups of size smaller than a control parameter are dropped; thereby the number of different ratios is determined. The analyst only influences some control

  18. Cretaceous seamounts along the continent ocean transition of the Iberian margin: U Pb ages and Pb Sr Hf isotopes

    Science.gov (United States)

    Merle, Renaud; Schärer, Urs; Girardeau, Jacques; Cornen, Guy

    2006-10-01

    To elucidate the age and origin of seamounts in the eastern North Atlantic, 54 titanite and 10 zircon fractions were dated by the U-Pb chronometer, and initial Pb, Sr, and Hf isotope ratios were measured in feldspars and zircon, respectively. Rocks analyzed are essentially trachy-andesites and trachytes dredged during the "Tore Madeira" cruise of the Atalante in 2001. The ages reveal different pulses of alkaline magmatism occurring at 104.4 ± 1.4 (2 σ) Ma and 102.8 ± 0.7 Ma on the Sponge Bob seamount, at 96.3 ± 1.0 Ma on Ashton seamount, at 92.3 ± 3.8 Ma on the Gago Coutinho seamount, at 89.3 ± 2.3 Ma and 86.5 ± 3.4 Ma on the Jo Sister volcanic complex, and at 88.3 ± 3.3 Ma, 88.2 ± 3.9, and 80.5 ± 0.9 Ma on the Tore locality. No space-time correlation is observed for alkaline volcanism in the northern section of the Tore-Madeira Rise, which occurred 20-30 m.y. after opening of the eastern North Atlantic. Initial isotope signatures are: 19.139-19.620 for 206Pb/ 204Pb, 15.544-15.828 for 207Pb/ 204Pb, 38.750-39.936 for 208Pb/ 204Pb, 0.70231-0.70340 for 87Sr/ 86Sr, and +6.9 to +12.9 for initial epsilon Hf. These signatures are different from Atlantic MORB, the Madeira Archipelago and the Azores, but they lie in the field of worldwide OIB. The Cretaceous seamounts therefore seem to be generated by melts from a OIB-type source that interact with continental lithospheric mantle lying formerly beneath Iberia and presently within the ocean-continent transition zone. Inheritance in zircon and high 207Pb of initial Pb substantiate the presence of very minor amounts of continental material in the lithospheric mantle. A long-lived thermal anomaly is the most plausible explanation for alkaline magmatism since 104 Ma and it could well be that the same anomaly is still the driving force for tertiary and quaternary alkaline magmatism in the eastern North Atlantic region. This hypothesis is agreement with the plate-tectonic position of the region since Cretaceous time

  19. Geochronology, geochemistry, and Sr-Nd-Hf isotopes of the early Paleozoic igneous rocks in the Duobaoshan area, NE China, and their geological significance

    Science.gov (United States)

    Wu, Guang; Chen, Yuchuan; Sun, Fengyue; Liu, Jun; Wang, Guorui; Xu, Bei

    2015-01-01

    The Duobaoshan area of northwestern Heilongjiang Province is the most important copper resource concentration region in NE China. To date, the Duobaoshan superlarge Cu-Mo deposit and the Tongshan large Cu-Mo deposit have been discovered in the Duobaoshan area. Both the deposits are hosted by granodiorites and volcanic rocks. Zircon LA-ICP-MS U-Pb dating indicates that these granodiorites emplaced approximately 479 Ma ago and that those volcanic rocks erupted between 447 and 450 Ma. The early Ordovicain granodiorites belong to the high-K to medium-K calc-alkaline series and are characterized by high Al2O3 and Sr contents, low Yb and Y contents, and relatively low Mg# values and Na2O/K2O ratios, with positive Eu or slight negative Eu anomalies (averaging 1.18). All of these geochemical characters are similar to those of the adakites generated by partial melting of a thickened lower crust in the world. Moreover, the granodiorites have low initial 87Sr/86Sr ratios (varying from 0.703474 to 0.704436), very high zircon εHf(t) and whole-rock εNd(t) values (varying from 13.0 to 16.8 and 5.27 to 5.46, respectively), and young zircon Hf and whole-rock Nd single-stage and two-stage model ages. Taking these geochemical characteristics and Sr-Nd-Hf isotope compositions together, we suggest that the early Ordovician granodiorites in the Duobaoshan area occurred in a post-collision environment and were formed by partial melting of a juvenile thickened lower crust dominated by depleted mantle-derived material. These late Ordovician volcanic rocks, which are composed of basalt, basaltic andesite, and andesite, belong to the tholeiitic or calc-alkaline series. They are generally enriched in large ion lithophile elements (LILEs) and depleted in high field strength elements (HFSEs; e.g., Nb, Ta, Zr, Hf, P, and Ti), consistent with the geochemistry of igneous rocks from island arcs or active continental margins. Compared with the early Ordovician granodiorites, these volcanic rocks

  20. Complexity of In-situ zircon U-Pb-Hf isotope systematics during arc magma genesis at the roots of a Cretaceous arc, Fiordland, New Zealand

    Science.gov (United States)

    Milan, L. A.; Daczko, N. R.; Clarke, G. L.; Allibone, A. H.

    2016-11-01

    Zircons from seventeen samples of Western Fiordland Orthogneiss (WFO) diorites and three samples of country rock (two schists and one Darran Suite diorite) from the lowermost exposed sections of the Median Batholith, Fiordland, New Zealand, were analysed for in-situ U-Pb and Hf-isotopes. The WFO represents the deeper levels of Early Cretaceous continental arc magmatism on the Pacific margin of Gondwana, marking the final stage of long-lived arc magmatism on the margin spanning the Palaeozoic. The WFO plutons were emplaced at high-P (mid to deep crust at c. 8-12 kbar) between 124 and 114 Ma. Minor very high-P (c. 18 kbar) WFO eclogite and omphacite granulite facies orthogneiss (Breaksea Orthogneiss) are inferred to have crystallised in the base of thickened crust at c. 124 Ma. Zircons from the Breaksea Orthogneiss are considered to be variably affected by Pb-loss due to emplacement of the adjacent (Malaspina) Pluton at c. 114 Ma. By identifying Pb-loss, magmatic ages were able to be inferred in respect to apparent Pb-loss ages. Hf isotope data for the WFO define an excursion to less radiogenic Hf isotope ratios with time, reflecting increased recycling of an old source component. Peaks at c. 555, 770 and 2480 Ma, determine the age spectra of inherited populations of zircons within the WFO. This contrasts with detrital zircon patterns in country rocks of the Takaka terrane, which include peaks at c. 465 Ma, and 1250-900 Ma that are absent in the WFO inheritance pattern. These results indicate a previously unrecognised Precambrian lower crustal component of New Zealand. Recycling of this lower crust became increasingly important as a source for the final stage or Mesozoic arc magmatism along this segment of the palaeo-Pacific margin of Gondwana.

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

    Science.gov (United States)

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

    2008-12-15

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

  2. Enhanced spin Hall ratios by Al and Hf impurities in Pt thin films

    Science.gov (United States)

    Nguyen, Minh-Hai; Zhao, Mengnan; Ralph, Daniel C.; Buhrman, Robert A.

    The spin Hall effect (SHE) in Pt has been reported to be strong and hence promising for spintronic applications. In the intrinsic SHE mechanism, which has been shown to be dominant in Pt, the spin Hall conductivity σSH is constant, dependent only on the band structure of the spin Hall material. The spin Hall ratio θSH =σSH . ρ , on the other hand, should be proportional to the electrical resistivity ρ of the spin Hall layer. This suggests the possibility of enhancing the spin Hall ratio by introducing additional diffusive scattering to increase the electrical resistivity of the spin Hall layer. Our previous work has shown that this could be done by increasing the surface scattering by growing thinner Pt films in contact with higher resistivity materials such as Ta. In this talk, we discuss another approach: to introduce impurities of metals with negligible spin orbit torque into the Pt film. Our PtAl and PtHf alloy samples exhibit strong enhancement of the spin Hall torque efficiency with impurity concentration due to increased electrical resistivity. Supported in part by Samsung Electronics.

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

    Energy Technology Data Exchange (ETDEWEB)

    Thompson, Cyril V. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Whitten, William B. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

    2015-11-01

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

  4. Carbon and Oxygen Isotope Ratios in Rona Limestone, Romania

    Directory of Open Access Journals (Sweden)

    Stela Cuna

    2001-04-01

    Full Text Available The carbon and oxygen isotopic compositions of limestones provide criteria for the evaluation of the depositional environment. For Jurassic and younger samples, the best discrimination between marine and fresh-water limestones is given by Z parameter, calculated as a linear correlation between δ13C and δ18O (‰ PDB. Rona Limestone (Upper Paleocene - Lower Eocene, outcropping on a small area in NW Transylvania (Meseş area is a local lacustrine facies. There, it divides Jibou Formation into the Lower Red Member and the Upper Variegated Member, respectively. Recently, a sequence containing a marine nannoplankton assemblage was identified in the base of Rona deposits. The main goal of our study was to characterize, based on the isotopic record, the primary environment of formation of the deposit, as well as that in which some diagenetic processes (the formation of dolomite and of green clay around the siliceous chert nodules took place. Ten samples representing limestones, dolomitic limestone, marls and the green carbonate-rich clay were studied from petrographical and mineralogical points of view, and the carbon and oxygen isotopic ratios from the carbonate (calcite component were measured. In conclusion, it was found that the procedure of extraction of CO2 we used enabled the discrimination between the isotopic prints of calcite vs. dolomite. This pleads for considering our results as a primary isotopic pattern in the bulk rock. The oxygen and carbon isotope data indicate a fresh-water depositional environment with Z<120. The δ13C mean value (-4.96 ‰ PDB is, generally, representative for fresh-water carbonates of the Tertiary period. The same environment characterized also the formation of carbonates within the green clay.

  5. Isotopic ratio of nitrogen on Titan: Photochemical interpretation

    Science.gov (United States)

    Krasnopolsky, Vladimir A.

    2016-12-01

    Nitrogen isotope fractionation in predissociation of N2 (Liang et al., 2007) is combined with production of N(4S), N(2D), and N+ in dissociation and dissociative ionization by the solar EUV photons, photoelectrons, magnetospheric electrons and protons, and cosmic rays from the photochemical model. The calculated 14N/15N ratio in nitriles is 57, in excellent agreement with the observed ratio in HCN. Loss of nitrogen in condensation and polymerization of nitriles is 392 g cm-2 Byr-1 with nitrogen isotope fractionation factor of 2.8. Loss of nitrogen by sputtering is 57 g cm-2 Byr-1 (De La Haye et al., 2007) with fractionation factor of 0.73 (Mandt et al., 2014). If the current loss was constant throughout the age of the Solar System, then the initial 14N/15N ratio on Titan is 129, similar to 127±32 for ammonia in comets (Rousselot et al., 2014). However, the solar EUV and wind were stronger from the young Sun, and this tends to further reduce the initial 14N/15N ratio. Nevertheless uncertainties of the problem and of the ratio in comets support the idea that nitrogen on Titan appeared as ammonia ice with 14N/15N similar to that in comets.

  6. Sr-Nd-Pb-Hf isotope systematics of the Hugo Dummett Cu-Au porphyry deposit (Oyu Tolgoi, Mongolia)

    Science.gov (United States)

    Dolgopolova, A.; Seltmann, R.; Armstrong, R.; Belousova, E.; Pankhurst, R. J.; Kavalieris, I.

    2013-04-01

    Major and trace element geochemistry including Sr-Nd-Pb-Hf isotopic data are presented for a representative sample suite of Late Devonian to Early Carboniferous plutonic and volcanic rocks from the Hugo Dummett deposit of the giant Oyu Tolgoi porphyry Cu-Au district in South Gobi, Mongolia. Sr and Nd isotopes (whole-rock) show restricted ranges of initial compositions, with positive ɛNdt mainly between + 3.4 and + 7.4 and (87Sr/86Sr)t predominantly between 0.7037 and 0.7045 reflecting magma generation from a relatively uniform juvenile lithophile-element depleted source. Previously dated zircons from the plutonic rocks exhibit a sample-averaged range of ɛHft values of + 11.6 to + 14.5. Depleted-mantle model ages of 420-830 (Nd) and 320-730 Ma (zircon Hf) limit the involvement of pre-Neoproterozoic crust in the petrogenesis of the intermediate to felsic calc-alkaline magmas to, at most, a minor role. Pb isotopes (whole-rock) show a narrow range of unradiogenic initial compositions: 206Pb/204Pb 17.40-17.94, 207Pb/204Pb 15.43-15.49 and 208Pb/204Pb 37.25-37.64, in agreement with Sr-Nd-Hf isotopes indicating the dominance of a mantle component. All four isotopic systems suggest that the magmas from which the large Oyu Tolgoi porphyry system was generated originated predominantly from juvenile material within the subduction-related setting of the Gurvansayhan terrane.

  7. TOWARD A UNIQUE NITROGEN ISOTOPIC RATIO IN COMETARY ICES

    Energy Technology Data Exchange (ETDEWEB)

    Rousselot, Philippe; Cordier, Daniel; Mousis, Olivier [Institut UTINAM-UMR CNRS 6213, Observatoire des Sciences de l' Univers THETA, University of Franche-Comté, BP 1615, F-25010 Besançon Cedex (France); Pirali, Olivier; Vervloet, Michel; Martin-Drumel, Marie-Aline; Gruet, Sébastien [Synchrotron SOLEIL, ligne AILES, UMR 8214 CNRS, L' orme des Merisiers, Saint-Aubin, F-91192 Gif-Sur-Yvette (France); Jehin, Emmanuël; Hutsemékers, Damien; Manfroid, Jean; Arpigny, Claude; Decock, Alice, E-mail: rousselot@obs-besancon.fr [Département d' Astrophysique, de Géophysique et d' Océanographie, Université de Liège, Allée du Six Août, B-4000 Liège (Belgium)

    2014-01-10

    Determination of the nitrogen isotopic ratios in different bodies of the solar system provides important information regarding the solar system's origin. We unambiguously identified emission lines in comets due to the {sup 15}NH{sub 2} radical produced by the photodissociation of {sup 15}NH{sub 3}. Analysis of our data has permitted us to measure the {sup 14}N/{sup 15}N isotopic ratio in comets for a molecule carrying the amine (-NH) functional group. This ratio, within the error, appears similar to that measured in comets in the HCN molecule and the CN radical, and lower than the protosolar value, suggesting that N{sub 2} and NH{sub 3} result from the separation of nitrogen into two distinct reservoirs in the solar nebula. This ratio also appears similar to that measured in Titan's atmospheric N{sub 2}, supporting the hypothesis that, if the latter is representative of its primordial value in NH{sub 3}, these bodies were assembled from building blocks sharing a common formation location.

  8. Geochemical proxies of ocean circulation and weathering inputs: Radiogenic isotopes of Nd, Pb, Sr, Hf, and Os

    Energy Technology Data Exchange (ETDEWEB)

    Frank, Martin, E-mail: mfrank@ifm-geomar.de [IFM-GEOMAR, Leibniz Institute of Marine Sciences at the University of Kiel, Wischhofstrasse 1-3, 24148 Kiel (Germany)

    2011-05-15

    Marine records of the radiogenic isotope composition of the elements neodymium (Nd), lead (Pb), hafnium (Hf), strontium (Sr), and osmium (Os) allow the reconstruction of past continental weathering inputs on different time scales as a function of their respective oceanic residence times. Sr and Os have oceanic residence times significantly longer than the global mixing time of the ocean and are efficiently mixed on a global scale. Their isotope composition changes on long time scales as a function of plate tectonics and major orogenies, which allows their use as precise stratigraphic tools for the entire Phanerozoic. In contrast, Hf, Pb, and in particular Nd, have residence times on the order of or shorter than the global mixing time of the ocean, which results in distinct isotopic signatures of water masses and allows the reconstruction of past water mass mixing and weathering inputs on both long and short time scales. Here applications of these isotopes systems with a focus on the shorter residence time tracers are reviewed (without claiming to be comprehensive) and problems and potential solutions are discussed.

  9. Carbon isotope ratios and isotopic correlations between components in fruit juices

    Science.gov (United States)

    Wierzchnicki, Ryszard

    2013-04-01

    Nowadays food products are defined by geographical origin, method of production and by some regulations concerning terms of their authenticity. Important data for confirm the authenticity of product are providing by isotopic methods of food control. The method checks crucial criteria which characterize the authenticity of inspected product. The European Union Regulations clearly show the tendency for application of the isotopic methods for food authenticity control (wine, honey, juice). The aim of the legislation steps is the protection of European market from possibility of the commercial frauds. Method of isotope ratio mass spectrometry is very effective tool for the use distinguishably the food products of various geographical origin. The basic problem for identification of the sample origin is the lack of databases of isotopic composition of components and information about the correlations of the data. The subject of the work was study the isotopic correlations existing between components of fruits. The chemical and instrumental methods of separation: water, sugars, organic acids and pulp from fruit were implemented. IRMS technique was used to measure isotopic composition of samples. The final results for original samples of fruits (apple, strawberry etc.) will be presented and discussed. Acknowledgement: This work was supported by the Polish Ministry of Science and Higher Education under grant NR12-0043-10/2010.

  10. Stable strontium isotopic ratios from archaeological organic remains from the Thorsberg peat bog

    DEFF Research Database (Denmark)

    Nosch, Marie-Louise Bech; von Carnap-Bornheim, Claus; Grupe, Gisela;

    2007-01-01

    Pilot study analysing stable strontium isotopic ratios from Iron Age textile and leather finds from the Thorsberg peat bog.......Pilot study analysing stable strontium isotopic ratios from Iron Age textile and leather finds from the Thorsberg peat bog....

  11. Petrogenesis of Jurassic fractionated I-type granites in Southeast China: Constraints from whole-rock geochemical and zircon U-Pb and Hf-O isotopes

    Science.gov (United States)

    Zhang, Yang; Yang, Jin-Hui; Sun, Jin-Feng; Zhang, Ji-Heng; Chen, Jing-Yuan; Li, Xian-Hua

    2015-11-01

    Whole-rock geochemical and Sr-Nd-Hf isotopic data and zircon in situ U-Pb ages and Hf-O isotopes are reported for twelve granitic intrusions from inland to coastal areas of the Cathaysia Block, Southeast (SE) China, in order to constrain their magma sources and petrogenesis. They are mainly composed of biotite granites with minor granodiorites. Zircon U-Pb dating by LA-ICPMS and SIMS methods gave emplacement ages of 165-154 Ma for these rocks, which are metaluminous to weakly peraluminous (A/CNK = 0.95-1.10), with variable SiO2 contents and high K2O contents. They are all depleted in high field strength elements (HFSEs) and enriched in light rare earth elements (LREEs) and large ion lithophile elements (LILEs), and show negative Sr, Ba and Eu anomalies in the spidergrams. Petrographic and geochemical features suggest the granodiorites that contain hornblende to be typical of I-type, while the biotite granites without hornblende are fractionated I-type granites. Their variable major and trace element concentrations are due to fractional crystallization of feldspar, biotite, hornblende, and accessory minerals, including apatite, allanite and monazite. Moreover, our data indicate significant variations in isotopic compositions of these granitoids from inland to coastal areas. The inland granites, from the Lapu, Fogang, Xinfengjiang and Baishigang plutons, have relatively high initial 87Sr/86Sr ratios (0.7105-0.7155) and low εNd(t) (-11.2 to -7.3) and εHf(t) (-10.9 to -6.3) values for whole rocks, and variable δ18O values of 7.69-9.25‰ and εHf(t) values of -13.5 to -6.7 for zircons. In contrast, the coastal granites, from the Longwo, Wushikeng, Lianhuashan, Shigushan, Chiliao, Hulutian, Mantoushan and Fenghuang plutons, show relatively low initial 87Sr/86Sr ratios (0.7056-0.7110) and high εNd(t) (-7.6 to -6.2) and εHf(t) (-6.5 to -2.8) values for whole-rocks, together with εHf(t) values of -7.2 to 3.9 and δ18O values of 6.69-8.38‰ for zircons. The spatial

  12. In situ isotopic analyses of U and Pb in zircon by remotely operated SHRIMP II, and Hf by LA-ICP-MS: an example of dating and genetic evolution of zircon by {sup 176}Hf/{sup 177}Hf from the Ita Quarry in the Atuba Complex, SE, Brazil; Analises in situ de U e Pb em zircao por SRIMP II por controle remoto e de Hf por LA-ICP-MS: um exemplo de datacao e da evolucao genetica de zircao atraves da razao {sup 176}Hf/{sup 177} em amostra da Pedreira Ita no Complexo Atuba, SE, Brasil

    Energy Technology Data Exchange (ETDEWEB)

    Sato, K.; Siga Junior, Oswaldo; McReath, Ian; Sproesser, Walter; Basei, Miguel Angelo Stipp [Universidade de Sao Paulo (USP), SP (Brazil). Inst. de Geociencias. Centro de Pesquisas Geocronologicas], e-mail: keisato@usp.br, e-mail: osigajr@usp.br, e-mail: ianmcr@usp.br, e-mail: wmspres@usp.br, e-mail: baseimas@usp.br; Silva, Josiane Aline da [Universidade de Sao Paulo (USP), SP (Brazil). Programa de Pos-graduacao em Geoquimica e Geotectonica; Dunyi, Liu [Institute of Geology, Beijing (China); Iizuka, Takafumi; Rino, Shuji; Hirata, Takafumi [Tokyo Institute of Technology, Tokyo (Japan)

    2009-10-15

    Remotely-operated SHRIMP dating of zircon is an interesting alternative for dating of zircon crystals. Although it does not represent any technical progress of the geochronological method using the U-Pb system in zircon it is a very useful and cheap facility. The procedure was first used for mass spectrometric analyses involving two international laboratories in Sao Paulo, Brazil and Beijing, China. It was applied to samples of three gneiss-migmatitic rocks from the Ita quarry in the Atuba Complex (located between the Luis Alves and the Apiai Domain) to test previous controversial hypotheses about its evolution. The presence of important archaean and paleo proterozoic components in the complex is confirmed by analyses of zircon found in probably neo proterozoic leucosomes. Diorite intrusion also occurred during the neo proterozoic, associated with the 0.6Ga continental collisions involved in the assembly of Gondwana. The determination of Hf isotope ratios by LA-ICP/MS represents a new option for checking the relative importance of mantle ({epsilon}{sub Hf} > 0) and crustal contributions (({epsilon}{sub Hf} < 0) during the growth of the zircon crystals. While the archaean component in the complex was derived from the mantle ({epsilon}{sub Hf} + 1.5 to + 8.7) the paleo proterozoic component had a crustal contribution ({epsilon}{sub Hf} - 9.1 to -10.1). (author)

  13. Geodynamic investigation of the processes that control Lu-Hf isotopic differences between different mantle domains and the crust

    Science.gov (United States)

    Jones, Rosie; van Keken, Peter; Hauri, Erik; Vervoort, Jeff; Ballentine, Chris J.

    2016-04-01

    The chemical and isotopic composition of both the Earth's mantle and the continental crust are greatly influenced by subduction zone processes, such as the formation of continental crust through arc volcanism and the recycling of surface material into the deep mantle. Here we use a combined geodynamical-geochemical approach to investigate the long term role of subduction on the Lu-Hf isotopic evolution of the mantle and the continental crust. We apply the geodynamic model developed by Brandenburg et al., 2008. This model satisfies the geophysical constraints of oceanic heat flow and average plate velocities, as well as geochemical observations such as 40Ar in the atmosphere, and reproduces the geochemical distributions observed in multiple isotope systems which define the HIMU, MORB and EM1 mantle endmembers. We extend this application to investigate the detail of terrestrial Lu-Hf isotope distribution and evolution, and specifically to investigate the role of sediment recycling in the generation of EM2 mantle compositions. The model has been updated to produce higher resolution results and to include a self-consistent reorganisation of the plates with regions of up-/down-wellings. The model assumes that subduction is initiated at 4.5 Ga and that a transition from 'dry' to 'wet' subduction occurred at 2.5 Ga. The modelling suggests that the epsilon Hf evolution of the upper mantle can be generated through the extraction and recycling of the oceanic crust, and that the formation of continental crust plays a lesser role. Our future intention is to utilise the model presented here to investigate the differences observed in the noble gas compositions (e.g., 40Ar/36Ar, 3He/4He) of MORB and OIB. Brandenburg, J.P., Hauri, E.H., van Keken, P.E., Ballentine, C.J., 2008. Earth and Planetary Science Letters 276, 1-13.

  14. Hybrid genesis of Jurassic fayalite-bearing felsic subvolcanic rocks in South China: Inspired by petrography, geochronology, and Sr-Nd-O-Hf isotopes

    Science.gov (United States)

    Guo, Chunli; Zeng, Lingsen; Li, Qiuli; Fu, Jianming; Ding, Tiping

    2016-11-01

    Fayalite-bearing felsic (FBF) magmatic rocks are a special type of granitic rocks with controversial origins. A suite of fayalite- and ferrosilite-bearing subvolcanic rocks, namely, the Xishan FBF rocks in South China, is investigated in this study. The Xishan FBF rocks have high SiO2 contents of 69-70 wt.%, high K2O/Na2O ratios of 1.71-1.95, and high FeOt/(FeOt + MgO) ratios of 0.88-0.89. Fayalite (Fo = 7.3-9.6) and ferrosilite (Fs = 74.1-76.5) minerals are found in the Xishan FBF rocks. According to the Unmix function of Isoplot, the zircon U-Pb ages and initial Hf isotope compositions are categorized into two groups with ages of 156.6 Ma and 151.5 Ma and εHf(t) values of - 7.1 and - 5.2, respectively. The minerals show δ18O values of 8.8-9.8‰ for zircon, 6.0-8.1‰ for fayalite, and 7.0-8.2‰ for ferrosilite. The oxygen isotope fractionations between ferrosilite and fayalite (ΔOpx-Ol) vary from - 0.8‰ to + 1.5‰, which indicates disequilibrium crystallization. Whole-rock analyses show high initial 87Sr/86Sr ratios of 0.7169 to 0.7180 and negative εNd(t) values of - 7.3 to - 6.8; zircon analyses show εHf(t) values of - 9.1 to - 3.8 and δ18O values of 8.8-9.8‰. So whole rock and zircon isotopes indicate a crustal signature. Based on these mineralogical and geochemical data, the Xishan FBF rocks were attributed to A-type granites and derived from the mixing of two batches of crustal magmas, which were all derived from the partial melting of ancient igneous protolith under the conditions of high temperature (683-893 °C), moderate water (3-5 wt.%), and low oxygen fugacity (lg fO2 = - 1.21). Such rigorous physical conditions may be common for the FBF igneous rocks all over the world, which may be the primary factors controlling occurrence of the FBF rocks in limited volume and quantity.

  15. Estimating the Isotope Ratio of Ecosystem Respiration Using the Keeling Plot and the Flux Ratio Method

    Science.gov (United States)

    Zhang, J.; Griffis, T. J.; Baker, J. M.

    2004-12-01

    Stable carbon isotope analyses have been used in identifying global carbon sources and sinks and in partitioning ecosystem CO2 exchange into component fluxes. The isotope ratio of ecosystem respiration (δ 13Cr) is a critical parameter in applying stable isotope techniques to carbon cycle problems. The commonly used Keeling plot method in estimating δ 13Cr has limitations related to: 1) insufficient range of CO2 mixing ratio; 2) high sensitivity to curve-fitting techniques; and 3) extrapolation of CO2 mixing ratio beyond observations. In this study, the Keeling plot method was examined and compared with the flux ratio approach using continuous measurements of the mixing ratios of 12CO2 and 13CO2 over an extensive corn canopy during the 2003 growing season. The seasonal variation of δ 13Cr estimated from both methods harmonized with the ecosystem phenology. The δ 13Cr started to increase (became more positive) from mid June and peaked in early August, followed by a decrease into October. The Keeling plot method agreed well with the flux ratio method in the seasonal pattern of δ 13Cr, but tended to give lower values (more negative). The discrepancy between the two approaches was significant in July and August (about 5 per mil) and relatively small in June and September (about 1 to 2 per mil). We examined this discrepancy with respect to wind direction/advection and measurement footprints. In addition, our analysis of high-frequency data (every two minutes) using the flux ratio method indicates that δ 13Cr may vary significantly at short time-scales (e.g., hourly), which could have significant implications for flux partitioning studies.

  16. The lithium isotopic ratio in very metal-poor stars

    CERN Document Server

    Lind, Karin; Asplund, Martin; Collet, Remo; Magic, Zazralt

    2013-01-01

    Un-evolved, very metal-poor stars are the most important tracers of the cosmic abundance of lithium in the early universe. Combining the standard Big Bang nucleosynthesis model with Galactic production through cosmic ray spallation, these stars at [Fe/H]<-2 are expected to show an undetectably small 6Li/7Li isotopic signature. Evidence to the contrary may necessitate an additional pre-galactic production source or a revision of the standard model of Big Bang nucleosynthesis. We revisit the isotopic analysis of four halo stars, two with claimed 6Li-detections in the literature, to investigate the influence of improved model atmospheres and line formation treatment. For the first time, a combined 3D, NLTE (non-local thermodynamic equilibrium) modelling technique for Li, Na, and Ca lines is utilised to constrain the intrinsic line-broadening and to determine the Li isotopic ratio. We discuss the influence of 3D NLTE effects on line profile shapes and assess the realism of our modelling using the Ca excitation...

  17. Measurement system analysis (MSA) of the isotopic ratio for uranium isotope enrichment process control

    Energy Technology Data Exchange (ETDEWEB)

    Medeiros, Josue C. de; Barbosa, Rodrigo A.; Carnaval, Joao Paulo R., E-mail: josue@inb.gov.br, E-mail: rodrigobarbosa@inb.gov.br, E-mail: joaocarnaval@inb.gov.br [Industrias Nucleares do Brasil (INB), Rezende, RJ (Brazil)

    2013-07-01

    Currently, one of the stages in nuclear fuel cycle development is the process of uranium isotope enrichment, which will provide the amount of low enriched uranium for the nuclear fuel production to supply 100% Angra 1 and 20% Angra 2 demands. Determination of isotopic ration n({sup 235}U)/n({sup 238}U) in uranium hexafluoride (UF{sub 6} - used as process gas) is essential in order to control of enrichment process of isotopic separation by gaseous centrifugation cascades. The uranium hexafluoride process is performed by gas continuous feeding in separation unit which uses the centrifuge force principle, establishing a density gradient in a gas containing components of different molecular weights. The elemental separation effect occurs in a single ultracentrifuge that results in a partial separation of the feed in two fractions: an enriched on (product) and another depleted (waste) in the desired isotope ({sup 235}UF{sub 6}). Industrias Nucleares do Brasil (INB) has used quadrupole mass spectrometry (QMS) by electron impact (EI) to perform isotopic ratio n({sup 235}U)/n({sup 238}U) analysis in the process. The decision of adjustments and change te input variables are based on the results presented in these analysis. A study of stability, bias and linearity determination has been performed in order to evaluate the applied method, variations and systematic errors in the measurement system. The software used to analyze the techniques above was the Minitab 15. (author)

  18. Carbon and oxygen isotopic ratios for nearby miras

    CERN Document Server

    Hinkle, K H; Straniero, O

    2016-01-01

    C and O isotopic ratios are reported for a sample of 46 Mira and SRa-type variable AGB stars. Vibration-rotation 1st and 2nd overtone CO lines in 1.5 to 2.5 $\\mu$m spectra were measured to derive isotopic ratios for 12C/13C, 16O/17O, and 16O/18O. Comparisons with previous measurements for individual stars and with various samples of evolved stars are discussed. Models for solar composition AGB stars of different initial masses are used to interpret our results. We find that the majority of the M stars had main sequence masses < 2 Msun and have not experienced sizable third dredge-up episodes. The progenitors of the four S-type stars in our sample are slightly more massive. Of the 6 C stars in the sample three have clear evidence relating their origin to the occurrence of the third dredge-up. Comparisons with O-rich presolar grains from AGB stars that lived before the formation of the solar system reveal variations in the interstellar medium chemical composition. The present generation of low-mass AGB stars...

  19. Understanding radioxenon isotopical ratios originating from radiopharmaceutical facilities

    Science.gov (United States)

    Saey, P. R. J.; Ringbom, A.; Bowyer, T. W.; Becker, A.; de Geer, L.-E.; Nikkinen, M.; Payne, R. F.

    2009-04-01

    It was recently shown that radiopharmaceutical facilities (RPF) are major contributors to the general background of 133Xe and other xenon isotopes both in the northern and southern hemisphere. To distinguish a nuclear explosion signal from releases from civil nuclear facilities, not only the activity concentrations but also the ratios of the four different CTBT relevant radioxenon isotopes (131mXe, 133mXe, 133Xe and 135Xe) have to be well understood. First measurements taken recently in and around two of the world's largest RPF's: NTP at Pelindaba, South Africa and IRE at Fleurus, Belgium have been presented. At both sites, also stack samples were taken in close cooperation with the facility operators. The radioxenon in Belgium could be classified in four classes: the normal European background (133Xe activity between 0 - 5 mBq/m3) on one hand and then the samples where all four isotopes were detected with 133mXe/131mXe > 1. In northern South Africa the Pelindaba RPF is in practice the sole source of radioxenon. It generated a background of 133Xe at the measurement site some 230 km to the west of the RPF of 0 - 5 mBq/m3. In the cases where the air from the Pelindaba facility reached the measurement site directly and in a short time period, the 133Xe was higher, also 135Xe was present and in some samples 133mXe as well. The ratios of the activity concentrations of 135Xe/133Xe vs. 133mXe/131mXe (Multiple Isotope Ratio Plot - MIRC) have been analysed. For both facilities, the possible theoretical ratio's for different scenarios were calculated with the information available and compared with the measurements. It was found that there is an excess of 131mXe present in the European samples compared to theoretical calculations. A similar excess has also been seen in samples measured in northern America. In South Africa, neither the environmental samples nor the stack ones contained 131mXe at measurable levels. This can probably be explained by different processes and

  20. Environmental controls on stable isotope ratios in New Zealand Podocarpaceae : implications for palaeoclimate reconstruction.

    OpenAIRE

    Brett, M.J.; Baldini, J. U. L.; Gröcke, D. R.

    2014-01-01

    Stable isotope ratios of various proxies are widely used for palaeoclimate reconstruction, and it is often assumed that isotope ratios reflect vegetation abundance or type. However, very little research exists on the isotopic equilibration of extant biomes under variable environmental conditions. In this study, carbon and oxygen isotope ratios from leaves of various Podocarpaceae genera, endemic to New Zealand, are linked to environmental parameters from the Land Environments New Zealand mode...

  1. Forensic applications of light-element stable isotope ratios of Ricinus communis seeds and ricin preparations.

    Science.gov (United States)

    Kreuzer, Helen W; West, Jason B; Ehleringer, James R

    2013-01-01

    Seeds of the castor plant Ricinus communis are of forensic interest because they are the source of the poison ricin. We tested whether stable isotope ratios of castor seeds and ricin preparations can be used as a forensic signature. We collected over 300 castor seed samples worldwide and measured the C, N, O, and H isotope ratios of the whole seeds and oil. We prepared ricin by three different procedures, acetone extraction, salt precipitation, and affinity chromatography, and compared their isotope ratios to those of the source seeds. The N isotope ratios of the ricin samples and source seeds were virtually identical. Therefore, N isotope ratios can be used to correlate ricin prepared by any of these methods to source seeds. Further, stable isotope ratios distinguished >99% of crude and purified ricin protein samples in pairwise comparison tests. Stable isotope ratios therefore constitute a valuable forensic signature for ricin preparations. © 2012 American Academy of Forensic Sciences.

  2. The thermal history of char as disclosed by carbon isotope ratios

    DEFF Research Database (Denmark)

    Egsgaard, Helge; Ambus, Per; Ahrenfeldt, Jesper

    pyrolysis and isotope ratio mass spectrometry. The results demonstrate that the temperature history of the char is reflected in the fine variation of carbon isotopes. The compound classes responsible for the variation were identified. Key words: Isotope ratio, flash pyrolysis, hot gas cleaning...

  3. Examining Changes in Radioxenon Isotope Activity Ratios during Subsurface Transport

    Science.gov (United States)

    Annewandter, Robert

    2014-05-01

    The Non-Proliferation Experiment (NPE) has demonstrated and modelled the usefulness of barometric pumping induced gas transport and subsequent soil gas sampling during On-Site inspections. Generally, gas transport has been widely studied with different numerical codes. However, gas transport of radioxenons and radioiodines in the post-detonation regime and their possible fractionation is still neglected in the open peer-reviewed literature. Atmospheric concentrations of the radioxenons Xe-135, Xe-133m, Xe-133 and Xe-131m can be used to discriminate between civilian releases (nuclear power plants or medical isotope facilities), and nuclear explosion sources. It is based on the multiple isotopic activity ratio method. Yet it is not clear whether subsurface migration of the radionuclides, with eventual release into the atmosphere, can affect the activity ratios due to fractionation. Fractionation can be caused by different mass diffusivities due to mass differences between the radionuclides. Cyclical changes in atmospheric pressure can drive subsurface gas transport. This barometric pumping phenomenon causes an oscillatoric flow in upward trending fractures or highly conductive faults which, combined with diffusion into the porous matrix, leads to a net transport of gaseous components - a so-called ratcheting effect. We use a general purpose reservoir simulator (Complex System Modelling Platform, CSMP++) which is recognized by the oil industry as leading in Discrete Fracture-Matrix (DFM) simulations. It has been applied in a range of fields such as deep geothermal systems, three-phase black oil simulations, fracture propagation in fractured, porous media, and Navier-Stokes pore-scale modelling among others. It is specifically designed to account for structurally complex geologic situation of fractured, porous media. Parabolic differential equations are solved by a continuous Galerkin finite-element method, hyperbolic differential equations by a complementary finite

  4. Carbon and Oxygen Isotopic Ratios for Nearby Miras

    Science.gov (United States)

    Hinkle, Kenneth H.; Lebzelter, Thomas; Straniero, Oscar

    2016-07-01

    Carbon and oxygen isotopic ratios are reported for a sample of 46 Mira and SRa-type variable asymptotic giant branch (AGB) stars. Vibration-rotation first and second-overtone CO lines in 1.5-2.5 μm spectra were measured to derive isotopic ratios for 12C/13C, 16O/17O, and 16O/18O. Comparisons with previous measurements for individual stars and with various samples of evolved stars, as available in the extant literature, are discussed. Models for solar composition AGB stars of different initial masses are used to interpret our results. We find that the majority of M-stars have main sequence masses ≤2 M ⊙ and have not experienced sizable third dredge-up (TDU) episodes. The progenitors of the four S-type stars in our sample are slightly more massive. Of the six C-stars in the sample three have clear evidence relating their origin to the occurrence of TDU. Comparisons with O-rich presolar grains from AGB stars that lived before the formation of the solar system reveal variations in the interstellar medium chemical composition. The present generation of low-mass AGB stars, as represented by our sample of long period variables (LPVs), shows a large spread of 16O/17O ratios, similar to that of group 1 presolar grains and in agreement with theoretical expectations for the composition of mass 1.2-2 M ⊙ stars after the first dredge-up. In contrast, the 16O/18O ratios of present-day LPVs are definitely smaller than those of group 1 grains. This is most probably a consequence of the the decrease with time of the 16O/18O ratio in the interstellar medium due to the chemical evolution of the Milky Way. One star in our sample has an O composition similar to that of group 2 presolar grains originating in an AGB star undergoing extra-mixing. This may indicate that the extra-mixing process is hampered at high metallicity, or, equivalently, favored at low metallicity. Similarly to O-rich grains, no star in our sample shows evidence of hot bottom burning, which is expected for

  5. Water isotopic ratios from a continuously melted ice core sample

    Directory of Open Access Journals (Sweden)

    V. Gkinis

    2011-06-01

    Full Text Available A new technique for on-line high resolution isotopic analysis of liquid water, tailored for ice core studies is presented. We build an interface between an Infra Red Cavity Ring Down Spectrometer (IR-CRDS and a Continuous Flow Analysis (CFA system. The system offers the possibility to perform simultaneuous water isotopic analysis of δ18O and δD on a continuous stream of liquid water as generated from a continuously melted ice rod. Injection of sub μl amounts of liquid water is achieved by pumping sample through a fused silica capillary and instantaneously vaporizing it with 100 % efficiency in a home made oven at a temperature of 170 °C. A calibration procedure allows for proper reporting of the data on the VSMOW scale. We apply the necessary corrections based on the assessed performance of the system regarding instrumental drifts and dependance on humidity levels. The melt rates are monitored in order to assign a depth scale to the measured isotopic profiles. Application of spectral methods yields the combined uncertainty of the system at below 0.1 ‰ and 0.5 ‰ for δ18O and δD, respectively. This performance is comparable to that achieved with mass spectrometry. Dispersion of the sample in the transfer lines limits the resolution of the technique. In this work we investigate and assess these dispersion effects. By using an optimal filtering method we show how the measured profiles can be corrected for the smoothing effects resulting from the sample dispersion. Considering the significant advantages the technique offers, i.e. simultaneuous measurement of δ18O and δD, potentially in combination with chemical components that are traditionally measured on CFA systems, notable reduction on analysis time and power consumption, we consider it as an alternative to traditional isotope ratio mass spectrometry with the possibility to be deployed for field ice core studies. We present data acquired in the

  6. Water isotopic ratios from a continuously melted ice core sample

    Directory of Open Access Journals (Sweden)

    V. Gkinis

    2011-11-01

    Full Text Available A new technique for on-line high resolution isotopic analysis of liquid water, tailored for ice core studies is presented. We built an interface between a Wavelength Scanned Cavity Ring Down Spectrometer (WS-CRDS purchased from Picarro Inc. and a Continuous Flow Analysis (CFA system. The system offers the possibility to perform simultaneuous water isotopic analysis of δ18O and δD on a continuous stream of liquid water as generated from a continuously melted ice rod. Injection of sub μl amounts of liquid water is achieved by pumping sample through a fused silica capillary and instantaneously vaporizing it with 100% efficiency in a~home made oven at a temperature of 170 °C. A calibration procedure allows for proper reporting of the data on the VSMOW–SLAP scale. We apply the necessary corrections based on the assessed performance of the system regarding instrumental drifts and dependance on the water concentration in the optical cavity. The melt rates are monitored in order to assign a depth scale to the measured isotopic profiles. Application of spectral methods yields the combined uncertainty of the system at below 0.1‰ and 0.5‰ for δ18O and δD, respectively. This performance is comparable to that achieved with mass spectrometry. Dispersion of the sample in the transfer lines limits the temporal resolution of the technique. In this work we investigate and assess these dispersion effects. By using an optimal filtering method we show how the measured profiles can be corrected for the smoothing effects resulting from the sample dispersion. Considering the significant advantages the technique offers, i.e. simultaneuous measurement of δ18O and δD, potentially in combination with chemical components that are traditionally measured on CFA systems, notable reduction on analysis time and power consumption, we consider it as an alternative to traditional isotope ratio mass spectrometry with the possibility to

  7. Petrogenesis of keratophyes in the Pingshui Group,Zhejiang: Constraints from zircon U-Pb ages and Hf isotopes

    Institute of Scientific and Technical Information of China (English)

    CHEN ZhiHong; XING GuangFu; GUO KungaYi; DONG YongGuan; CHEN Rong; ZENG Yong; LI LongMing; HE ZhengYu; ZHAO Ling

    2009-01-01

    Zircon LA-ICP-MS U-Pb ages and Hf isotopic as well as whole-rock geochemical data are reported for keratophyes in the Pingshui Group, Zhejiang. The results are used to discuss their petrogenesis and geological significance. The keratophyes were dated at 904±8 to 906±10 Ma. These intermediate-felsic rocks are characterized by high LREE contents end depletion of HREE and HFSE (e.g., Nb, Ta, Ti, P), resembling arc-derived rocks. The keratophyes exhibit positive εHf(t) values of 8.6 to 15.4, consistent with their εNd(t) values of 6.4 to 7.9 but far away from those of crust-derived rocks. Such features indicate that they were likely originated from prompt reworking of juvenile crust by arc-continent collision during the early-Neoproterozoic assembly between the Cathaysia and Yangtze Blocks. Combining with their Hf model ages, we suggest that there may exist not only remarkable growth of juvenile crust at ca.1.3-1.1 Ga but also production of juvenile arc-derived crust along the southeastern margin of the Yangtze Block (e.g., the Pingshui area) at ca.1.0-0.9 Ga.

  8. Geochronological, geochemical and Sr-Nd-Hf isotopic constraints on the petrogenesis of Late Cretaceous A-type granites from the Sibumasu Block, Southern Myanmar, SE Asia

    Science.gov (United States)

    Jiang, Hai; Li, Wen-Qian; Jiang, Shao-Yong; Wang, He; Wei, Xiao-Peng

    2017-01-01

    The Late Cretaceous to Paleogene granitoids occur widespread in the Sibumasu block within Myanmar (SE Asia), which show a close association with tin-tungsten mineralization. However, the precise timing, petrogenesis and tectonic significance of these granitoids are poorly constrained so far. In this study, we present a detailed study on geochronology, elemental and Sr-Nd-Hf isotopic geochemistry for the Hermyingyi and Taungphila granites in southern Myanmar, with the aim of determining their petrogenesis and tectonic implications. LA-ICP-MS U-Pb dating of zircon grains from the two granites yield ages of 69-70 Ma, indicating a Late Cretaceous magmatic event. These granitic rocks are weakly peraluminous and belong to the high-K calc-alkaline series. They are both characterized by high SiO2, K2O + Na2O, FeOT/(FeOT + MgO) and Ga/Al ratios and low Al2O3, CaO, MgO, P2O5 and TiO2 contents, enriched in Rb, Th, U and Y, but depleted in Ba, Sr, P, and Eu, suggesting an A-type granite affinity. Moreover, they display prominent tetrad REE patterns and non-CHARAC trace element behavior, which are common in late magmatic differentiates with strong hydrothermal interaction or deuteric alteration. The granites belong to A2-type and probably formed at a high temperature and anhydrous condition. They have zircon εHf(t) values from - 12.4 to - 10.0 and whole-rock εNd(t) values from - 11.3 to - 10.6, with Paleoproterozoic TDM2 ages (1741-1922 Ma) for both Hf and Nd isotopes. Geochemical and isotopic data suggest that these A-type granites were derived from partial melting of the Paleoproterozoic continental crust dominated by metaigneous rocks with tonalitic to granodioritic compositions, without significant input of mantle-derived magma and followed by subsequent fractional crystallization. By integrating all available data for the regional tectonic evolution in SE Asia and adjacent regions, we attribute the formation of the Late Cretaceous A-type granites to a back-arc extension

  9. Expanding the isotopic toolbox: Applications of hydrogen and oxygen stable isotope ratios to food web studies

    Directory of Open Access Journals (Sweden)

    Hannah B Vander Zanden

    2016-03-01

    Full Text Available The measurement of stable carbon (δ13C and nitrogen (δ15N isotopes in tissues of organisms has formed the foundation of isotopic food web reconstructions, as these values directly reflect assimilated diet. In contrast, stable hydrogen (δ2H and oxygen (δ18O isotope measurements have typically been reserved for studies of migratory origin and paleoclimate reconstruction based on systematic relationships between organismal tissue and local environmental water. Recently, innovative applications using δ2H and, to a lesser extent, δ18O values have demonstrated potential for these elements to provide novel insights in modern food web studies. We explore the advantages and challenges associated with three applications of δ2H and δ18O values in food web studies. First, large δ2H differences between aquatic and terrestrial ecosystem end members can permit the quantification of energy inputs and nutrient fluxes between these two sources, with potential applications for determining allochthonous vs. autochthonous nutrient sources in freshwater systems and relative aquatic habitat utilization by terrestrial organisms. Next, some studies have identified a relationship between δ2H values and trophic position, which suggests that this marker may serve as a trophic indicator, in addition to the more commonly used δ15N values. Finally, coupled measurements of δ2H and δ18O values are increasing as a result of reduced analytical challenges to measure both simultaneously and may provide additional ecological information over single element measurements. In some organisms, the isotopic ratios of these two elements are tightly coupled, whereas the isotopic disequilibrium in other organisms may offer insight into the diet and physiology of individuals. Although a coherent framework for interpreting δ2H and δ18O data in the context of food web studies is emerging, many fundamental uncertainties remain. We highlight directions for targeted research that

  10. An experimental study of HF photodissociation: Spin{endash}orbit branching ratio and infrared alignment

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, J.; Riehn, C.W.; Dulligan, M.; Wittig, C. [Department of Chemistry, University of Southern California, Los Angeles, California 90089-0482 (United States)

    1996-05-01

    Single rotational levels of HF ({ital v}=3) were prepared by using overtone excitation and these molecules were then photodissociated by ultraviolet (UV) radiation at 193.3 nm. Time-of-flight spectra of the hydrogen atom fragment provided the spin{endash}orbit state distribution of the fluorine fragment. Changing the UV photolysis laser polarization confirmed an {ital A}{sup 1}{Pi}{l_arrow}{ital X}{sup 1}{Sigma}{sup +} electronic transition in the photodissociation step. Photodissociation of HF at 121.6 nm is also reported. Infrared (IR) induced alignment of the diatom was studied by monitoring the IR laser polarization dependence of the H-atom product angular distribution. Depolarization due to hyperfine interaction was studied by using the {ital R}(0) transition. Agreement with theory is excellent. {copyright} {ital 1996 American Institute of Physics.}

  11. An experimental study of HF photodissociation: Spin-orbit branching ratio and infrared alignment

    Science.gov (United States)

    Zhang, J.; Riehn, C. W.; Dulligan, M.; Wittig, C.

    1996-05-01

    Single rotational levels of HF (v=3) were prepared by using overtone excitation and these molecules were then photodissociated by ultraviolet (UV) radiation at 193.3 nm. Time-of-flight spectra of the hydrogen atom fragment provided the spin-orbit state distribution of the fluorine fragment. Changing the UV photolysis laser polarization confirmed an A 1Π←X 1Σ+ electronic transition in the photodissociation step. Photodissociation of HF at 121.6 nm is also reported. Infrared (IR) induced alignment of the diatom was studied by monitoring the IR laser polarization dependence of the H-atom product angular distribution. Depolarization due to hyperfine interaction was studied by using the R(0) transition. Agreement with theory is excellent.

  12. Hf isotopes of the 3.8 Ga zircons in eastern Hebei Province, China: Implications for early crustal evolution of the North China Craton

    Institute of Scientific and Technical Information of China (English)

    WU Fuyuan; YANG Jinhui; LIU Xiaoming; LI Tiesheng; XIE Liewen; YANG Yueheng

    2005-01-01

    Zircon U-Pb dating indicates that the fuchsite quartzite in eastern Hebei Province was derived from weathering and erosion of the 3.6-3.8 Ga granitic rocks. In-situ zircon Hf analyses show that the Lu-Hf isotopic system remained closed during later thermal disturbances. Zircons with concordant ages have Hf isotopic model ages of about 3.8 Ga, suggesting a recycling of this ancient crust. The ~3.8 Ga zircons have similar Hf isotopic compositions to those of chondrite, indicating that their source rocks (granitic rocks) were derived from partial melting of the juvenile crust which originated from a mantle without significant crust-mantle differentiation. Therefore, it is proposed that there was no large-scale crustal growth before ~3.8 Ga in eastern Hebei Province. Considering zircon Hf isotopic data from other areas, it is concluded that the most ancient crust in the North China Craton probably formed at about 4.0 Ga, and the possibility to find crust older than 4.0 Ga is very limited.

  13. Magnetic dipole moments of High-K isomeric states in Hf isotopes

    CERN Multimedia

    Walters, W; Nishimura, K; Bingham, C R

    2007-01-01

    It is proposed to make precision measurements of the magnetic moments of 5 multi-quasi-particle K-isomers in Hf nuclei by the Nuclear Magnetic Resonance of Oriented Nuclei (NMR/ON) technique using the NICOLE on-line nuclear orientation facility and exploiting the unique HfF$_{3}$ beams recently available at ISOLDE. Results will be used to extract single-particle and collective g-factors of the isomeric states and their excitations and to shed new light on their structure.

  14. Multiple S isotopes, zircon Hf isotopes, whole-rock Sr-Nd isotopes, and spatial variations of PGE tenors in the Jinchuan Ni-Cu-PGE deposit, NW China

    Science.gov (United States)

    Duan, Jun; Li, Chusi; Qian, Zhuangzhi; Jiao, Jiangang; Ripley, Edward M.; Feng, Yanqing

    2016-04-01

    Previous geochemical data for the Jinchuan Ni-Cu-(platinum-group elements, PGE) deposit, the single largest magmatic sulfide deposit in the world, are derived primarily from the upper parts of the deposit. This paper reports new PGE and S-Hf-Sr-Nd isotope data for the lower parts of the deposit that have become accessible for sampling by ongoing underground mining activity. New PGE data from this study, together with previous results, indicate that PGE tenors in the bulk sulfide ores of the deposit increase eastward, except for two fault-offset ore zones which occur together within the western part of the deposit. Generally, these two ore zones show depletions in IPGE (Ir, Ru, Rh) but not in PPGE (Pt, Pd) and Cu, and more fractionated olivine and Cr-spinel compositions than the rest of the deposit. These differences can be explained by a more evolved parental magma for the IPGE-depleted ore zones. The eastward increase of PGE tenors in the rest of the deposit can be explained by upgrading of preexisting sulfide liquid in a subhorizontal conduit by a new surge of magma moving through the conduit from west to east, which took place before the formation of the IPGE-depleted ore zones. The Jinchuan ultramafic rocks are characterized by elevated initial 87Sr/86Sr ratios from 0.7077 to 0.7093, negative ɛ Nd values from -9.2 to -10.5, and zircon ɛ Hf values from -4 to -7. These data indicate up to 20 % of crustal contamination in the Jinchuan magma. Four of nine multiple sulfur isotope analyses for the Jinchuan deposit show anomalous ∆33S values varying from 0.12 to 2.67 ‰. These results, together with elevated δ34S values (>2 ‰) for some of the samples analyzed previously by other researchers, indicate the involvement of external sulfur from Archean and Proterozoic sedimentary rocks. Modeling results based on our olivine data and magma compositions estimated previously by other researchers indicate that fractional crystallization did not play a major role in

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

    Science.gov (United States)

    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.

  16. Stable carbon isotopic composition of gasolines determined by isotope ratio monitoring gas chromatography mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Smallwood, B.J.; Philp, R.P.; Allen, J.D. [University of Oklahoma, Norman, OK (United States). School of Geology and Geophysics

    2002-07-01

    A large number of underground gasoline storage facilities in the United States continuously leak gasoline into the subsurface, which makes gasoline a major groundwater contaminant. Gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS) are used currently to characterize contaminated groundwater and soils. Correlations of contaminants with suspected source(s) are extremely difficult by these techniques because many gasolines have similar hydrocarbon distributions. The present study applied the technique of isotope ratio monitoring gas chromatography-mass spectrometry (irmGC-MS) to 19 gasoline samples from different areas of the USA. This allows a much better correlation of gasoline contaminants to source. Data obtained indicate a wide range of {sup {delta}}{sup 13}C values for 16 ubiquitous compounds in the gasolines. The majority of samples could be distinguished from each other on the basis of {sup {delta}}{sup 13}C hydrocarbon composition. The oxygenated additive methyl tertiary butyl ether (MTBE) was present in ten of the gasolines analyzed, and had a relatively narrow range of {sup {delta}}{sup 13}C values (-30.4 to -28.3 per mille). Preliminary investigations were also made to determine the extent of carbon isotopic fractionation after simple water washing and evaporation experiments. Results indicate that the majority of compounds did not undergo significant carbon isotopic fractionation as a result of these processes. (author)

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

    Science.gov (United States)

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

    2012-01-01

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

  18. Development, optimisation, and application of ICP-SFMS methods for the measurement of isotope ratios

    Energy Technology Data Exchange (ETDEWEB)

    Stuerup, S

    2000-07-01

    The measurement of isotopic composition and isotope ratios in biological and environmental samples requires sensitive, precise, and accurate analytical techniques. The analytical techniques used are traditionally based on mass spectrometry, among these techniques is the ICP-SFMS technique, which became commercially available in the mid 1990s. This technique is characterised by high sensitivity, low background, and the ability to separate analyte signals from spectral interferences. These features are beneficial for the measurement of isotope ratios and enable the measurement of isotope ratios of elements, which it has not previously been possible to measure due to either spectral interferences or poor sensitivity. The overall purpose of the project was to investigate the potential of the single detector ICP-SFMS technique for the measurement of isotope ratios in biological and environmental samples. One part of the work has focused on the fundamental aspects of the ICP-SFMS technique with special emphasize on the features important to the measurement of isotope ratios, while another part has focused on the development, optimisation and application of specific methods for the measurement of isotope ratios of elements of nutritional interest and radionuclides. The fundamental aspects of the ICP-SFMS technique were investigated theoretically and experimentally by the measurement of isotope ratios applying different experimental conditions. It was demonstrated that isotope ratios could be measured reliably using ICP-SFMS by educated choice of acquisition parameters, scanning mode, mass discrimination correction, and by eliminating the influence of detector dead time. Applying the knowledge gained through the fundamental study, ICP-SFMS methods for the measurement of isotope ratios of calcium, zinc, molybdenum and iron in human samples and a method for the measurement of plutonium isotope ratios and ultratrace levels of plutonium and neptunium in environmental samples

  19. Magma mixing and the generation of isotopically juvenile silicic magma at Yellowstone caldera inferred from coupling 238U–230Th ages with trace elements and Hf and O isotopes in zircon and Pb isotopes in sanidine

    Science.gov (United States)

    Stelten, Mark E.; Cooper, Kari M.; Vazquez, Jorge A.; Reid, Mary R.; Barfod, Gry H.; Wimpenny, Josh; Yin, Qing-Zhu

    2013-01-01

    The nature of compositional heterogeneity within large silicic magma bodies has important implications for how silicic reservoirs are assembled and evolve through time. We examine compositional heterogeneity in the youngest (~170 to 70 ka) post-caldera volcanism at Yellowstone caldera, the Central Plateau Member (CPM) rhyolites, as a case study. We compare 238U–230Th age, trace-element, and Hf isotopic data from zircons, and major-element, Ba, and Pb isotopic data from sanidines hosted in two CPM rhyolites (Hayden Valley and Solfatara Plateau flows) and one extracaldera rhyolite (Gibbon River flow), all of which erupted near the caldera margin ca. 100 ka. The Hayden Valley flow hosts two zircon populations and one sanidine population that are consistent with residence in the CPM reservoir. The Gibbon River flow hosts one zircon population that is compositionally distinct from Hayden Valley flow zircons. The Solfatara Plateau flow contains multiple sanidine populations and all three zircon populations found in the Hayden Valley and Gibbon River flows, demonstrating that the Solfatara Plateau flow formed by mixing extracaldera magma with the margin of the CPM reservoir. This process highlights the dynamic nature of magmatic interactions at the margins of large silicic reservoirs. More generally, Hf isotopic data from the CPM zircons provide the first direct evidence for isotopically juvenile magmas contributing mass to the youngest post-caldera magmatic system and demonstrate that the sources contributing magma to the CPM reservoir were heterogeneous in 176Hf/177Hf at ca. 100 ka. Thus, the limited compositional variability of CPM glasses reflects homogenization occurring within the CPM reservoir, not a homogeneous source.

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

    NARCIS (Netherlands)

    Pathirana, S. L.; Van Der Veen, C.; Popa, M. E.; Röckmann, T.

    2015-01-01

    A fully automated system for the determination of δ13C and δ18O in atmospheric CO has been developed. CO is extracted from an air sample and converted into carbon dioxide (CO2) using the Schütze reagent. The isotopic composition is determined with an isotope-ratio mass spectrometer (IRMS) technique.

  1. Big Bang Nucleosynthesis and the Helium Isotope Ratio

    CERN Document Server

    Cooke, Ryan

    2015-01-01

    The conventional approach to search for departures from the standard model of physics during Big Bang Nucleosynthesis involves a careful, and subtle measurement of the mass fraction of baryons consisting of helium. Recent measurements of this quantity tentatively support new physics beyond the standard model but, historically, this method has suffered from hidden systematic uncertainties. In this letter, I show that a combined measurement of the primordial deuterium abundance and the primordial helium isotope ratio has the potential to provide a complementary and reliable probe of new physics beyond the standard model. Using the recent determination of the primordial deuterium abundance and assuming that the measured pre-solar 3He/4He meteoritic abundance reflects the primordial value, a bound can be placed on the effective number of neutrino species, Neff(BBN) = 3.01 (+0.95 -0.76, with 95 per cent confidence). Although this value of Neff supports the standard model, it is presently unclear if the pre-solar 3...

  2. Effects of carbonate leaching on foraminifer stable isotopes ratios

    Science.gov (United States)

    Obrochta, S.; Yokoyama, Y.; Sakai, S.; Ishimura, T.

    2011-12-01

    Stable carbon and oxygen isotope ratios were measured on 125 individual epifaunal and infaunal benthic foraminifers from two discrete Holocene intervals in a shallow-water sediment core (~ 450 m) from the Timor Sea. Methane seeps are common in the area, resulting in significant precipitation of secondary calcite that is confirmed by SEM photomicrographs and has likely resulted in inconsistent downcore results. To assess the degree of removal of contaminants, individual Uvigerina peregrina were subjected to varying degrees of pretreatment prior to analysis. All foraminifers received standard cleaning with ethanol and brief sonication. A subset were further cleaned and sonicated in a dilute HCl solution (~ 0.003 M). Foraminifer tests were photographed using both reflected light and scanning electron microscopes during the course of treatment to monitor the changing degree of contaminant removal as increasingly aggressive cleaning methods were employed. Visible contamination remained on individuals not subjected to HCl treatment. The leached individuals exhibit a lower overall relative standard deviation and consistent results within morphotype groups. Based on these results, a 2% value is expected to be typical of the Holocene, though further downcore analyses are pending restoration of equipment adversely effected by the Eastern Japan 3/11 earthquake.

  3. Role of mantle-derived magma in genesis of early Yanshanian granites in the Nanling Range, South China: in situ zircon Hf-O isotopic constraints

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    Although a number of petrographic observations and isotopic data suggest that magma mixing is common in genesis of many granite plutons, it is still controversial whether the mantle-derived magmas were involved in granites. We carried out in this study a systematic analysis of in situ zircon Hf-O isotopes for three early Yanshanian intrusions dated at ca. 160 Ma from the Nanling Range of Southeast China. The Qinghu monzonite has very homogeneous zircon Hf-O isotopic compositions, εHf(t) =11.6±0.3 and δ18O=5.4‰±0.3‰. In combination with whole-rock geochemical and Sr-Nd isotopic data, the parental magma of the Qinghu monzonite were likely derived from the partial melting of recently-metasomatized, phlogopite-bearing lithospheric mantle without appreciable crustal contamination. The Lisong and Fogang granites and the mafic microgranular enclaves (MME) within the Lisong granites have a wide range of zircon Hf-O isotopic compositions, with Hf and O isotopes being negatively correlated within each pluton. The Lisong MMEs were crystallized from a mantle-derived magma, similar to the parental magma of the Qinghu monzonite, with small amount of crustal assimilation. The Lisong and Fogang granites were formed by reworking of meta-sedimentary materials by mantle-derived magmas and mixing of the mantle-and sediment-derived melts to varying degrees. It is thus concluded that these two Yanshanian granites in the Nanling Range were formed associated with growth and differentiation of continental crust.

  4. Zircon U-Pb dating, geochemical and Sr-Nd-Hf isotopic characteristics of the Jintonghu monzonitic rocks in western Fujian Province, South China: Implication for Cretaceous crust-mantle interactions and lithospheric extension

    Science.gov (United States)

    Li, Bin; Jiang, Shao-Yong; Lu, An-Huai; Zhao, Hai-Xiang; Yang, Tang-Li; Hou, Ming-Lan

    2016-09-01

    Comprehensive petrological, in situ zircon U-Pb dating, Ti-in-zircon temperature and Hf isotopic compositions, whole rock geochemical and Sr-Nd isotopic data are reported for the Jintonghu monzonitic intrusions in the western Fujian Province (Interior Cathaysia Block), South China. The Jintonghu monzonitic intrusions were intruded at 95-96 Ma. Their Sr-Nd-Hf isotopic compositions are similar to the coeval and nearby enriched lithospheric mantle-derived mafic and syenitic rocks, indicating that the Jintonghu monzonitic rocks were likely derived from partial melting of the enriched mantle sources. Their high Nb/Ta ratios (average 21.6) suggest that the metasomatically enriched mantle components were involved, which was attributed to the modification of slab-derived fluid and melt by the subduction of the paleo-Pacific Plate. The presence of mafic xenoliths, together with geochemical and isotopic features indicates a mafic-felsic magma mixing. Furthermore, the Jintonghu intrusions may have experienced orthopyroxene-, biotite- and plagioclase-dominated crystallization. Crust-mantle interaction can be identified as two stages, including that the Early Cretaceous mantle metasomatism and lithospheric extension resulted from the paleo-Pacific slab subduction coupled with slab rollback, and the Late Cretaceous crustal activation and enhanced extension induced by dip-angle subduction and the underplating of mantle-derived mafic magma.

  5. Environmental controls on stable isotope ratios in New Zealand Podocarpaceae: Implications for palaeoclimate reconstruction

    Science.gov (United States)

    Brett, Marianne J.; Baldini, James U. L.; Gröcke, Darren R.

    2014-09-01

    Stable isotope ratios of various proxies are widely used for palaeoclimate reconstruction, and it is often assumed that isotope ratios reflect vegetation abundance or type. However, very little research exists on the isotopic equilibration of extant biomes under variable environmental conditions. In this study, carbon and oxygen isotope ratios from leaves of various Podocarpaceae genera, endemic to New Zealand, are linked to environmental parameters from the Land Environments New Zealand model. The dominant influence on stable isotope ratios within the majority of Podocarpaceae studied here is vapour pressure deficit (VPD). A simple latitudinal trend does not exist, and neither temperature nor rainfall (decoupled from VPD) controls the stable isotope ratios. The results suggest that modern spatial heterogeneity in VPD affects the stable isotope values of vegetation, and that historic VPD variability would change the stable isotope ratios of Podocarpaceae without necessitating a change in vegetation type, density, or productivity. This represents an alternative model for temporal isotope change within geochemical proxies and reinforces the need for increased stable isotopic research in modern plant ecosystems to better understand modern, and eventually palaeoclimatic processes affecting the terrestrial biosphere.

  6. Re-Os and Lu-Hf isotopic constraints on the formation and age of mantle pyroxenites from the Bohemian Massif

    Science.gov (United States)

    Ackerman, Lukáš; Bizimis, Michael; Haluzová, Eva; Sláma, Jiří; Svojtka, Martin; Hirajima, Takao; Erban, Vojtěch

    2016-07-01

    We report on the Lu-Hf and Re-Os isotope systematics of a well-characterized suite of spinel and garnet pyroxenites from the Gföhl Unit of the Bohemian Massif (Czech Republic, Austria). Lu-Hf mineral isochrons of three pyroxenites yield undistinguishable values in the range of 336-338 Ma. Similarly, the slope of Re-Os regression for most samples yields an age of 327 ± 31 Ma. These values overlap previously reported Sm-Nd ages on pyroxenites, eclogites and associated peridotites from the Gföhl Unit, suggesting contemporaneous evolution of all these HT-HP rocks. The whole-rock Hf isotopic compositions are highly variable with initial εHf values ranging from - 6.4 to + 66. Most samples show a negative correlation between bulk rock Sm/Hf and εHf and, when taking into account other characteristics (e.g., high 87Sr/86Sr), this may be explained by the presence of recycled oceanic sediments in the source of the pyroxenite parental melts. A pyroxenite from Horní Kounice has decoupled Hf-Nd systematics with highly radiogenic initial εHf of + 66 for a given εNd of + 7.8. This decoupling is consistent with the presence of a melt derived from a depleted mantle component with high Lu/Hf. Finally, one sample from Bečváry plots close to the MORB field in Hf-Nd isotope space consistent with its previously proposed origin as metamorphosed oceanic gabbro. Some of the websterites and thin-layered pyroxenites have variable, but high Os concentrations paralleled by low initial γOs. This reflects the interaction of the parental pyroxenitic melts with a depleted peridotite wall rock. In turn, the radiogenic Os isotope compositions observed in most pyroxenite samples is best explained by mixing between unradiogenic Os derived from peridotites and a low-Os sedimentary precursor with highly radiogenic 187Os/188Os. Steep increase of 187Os/188Os at nearly uniform 187Re/188Os found in a few pyroxenites may be connected with the absence of primary sulfides, but the presence of minor

  7. A sorghum (Sorghum bicolor) mutant with altered carbon isotope ratio.

    Science.gov (United States)

    Rizal, Govinda; Karki, Shanta; Thakur, Vivek; Wanchana, Samart; Alonso-Cantabrana, Hugo; Dionora, Jacque; Sheehy, John E; Furbank, Robert; von Caemmerer, Susanne; Quick, William Paul

    2017-01-01

    Recent efforts to engineer C4 photosynthetic traits into C3 plants such as rice demand an understanding of the genetic elements that enable C4 plants to outperform C3 plants. As a part of the C4 Rice Consortium's efforts to identify genes needed to support C4 photosynthesis, EMS mutagenized sorghum populations were generated and screened to identify genes that cause a loss of C4 function. Stable carbon isotope ratio (δ13C) of leaf dry matter has been used to distinguishspecies with C3 and C4 photosynthetic pathways. Here, we report the identification of a sorghum (Sorghum bicolor) mutant with a low δ13C characteristic. A mutant (named Mut33) with a pale phenotype and stunted growth was identified from an EMS treated sorghum M2 population. The stable carbon isotope analysis of the mutants showed a decrease of 13C uptake capacity. The noise of random mutation was reduced by crossing the mutant and its wildtype (WT). The back-cross (BC1F1) progenies were like the WT parent in terms of 13C values and plant phenotypes. All the BC1F2 plants with low δ13C died before they produced their 6th leaf. Gas exchange measurements of the low δ13C sorghum mutants showed a higher CO2 compensation point (25.24 μmol CO2.mol-1air) and the maximum rate of photosynthesis was less than 5μmol.m-2.s-1. To identify the genetic determinant of this trait, four DNA pools were isolated; two each from normal and low δ13C BC1F2 mutant plants. These were sequenced using an Illumina platform. Comparison of allele frequency of the single nucleotide polymorphisms (SNPs) between the pools with contrasting phenotype showed that a locus in Chromosome 10 between 57,941,104 and 59,985,708 bps had an allele frequency of 1. There were 211 mutations and 37 genes in the locus, out of which mutations in 9 genes showed non-synonymous changes. This finding is expected to contribute to future research on the identification of the causal factor differentiating C4 from C3 species that can be used in the

  8. Angular momentum limit of Hf isotopes produced in three fusion-evaporation reactions

    CERN Document Server

    Domscheit, J; Ernst, J; Fallon, P; Herskind, B; Hübel, H; Korten, W; Lee, I Y; Macchiavelli, A O; Nenoff, N; Siem, S; Ward, D; Wilson, J N

    2001-01-01

    The compound nucleus sup 1 sup 6 sup 8 Hf was populated in three fusion-evaporation reactions with different beam-target mass asymmetries: sup 5 sup 0 Ti+ sup 1 sup 1 sup 8 Sn, sup 6 sup 4 Ni+ sup 1 sup 0 sup 4 Ru and sup 7 sup 4 Ge+ sup 9 sup 4 Zr. Due to the large negative Q values of these reactions the compound nucleus is formed at low excitation energy. At three or four excitation energies for each reaction gamma-ray spectra of the evaporation residues sup 1 sup 6 sup 6 Hf to sup 1 sup 6 sup 3 Hf, corresponding to the 2n to 5n exit channels, respectively, were recorded with the Ge detectors of the 8 pi-spectrometer array. The gamma-ray multiplicity and total energy were measured using the inner ball of BGO detectors. This data was used to determine the maximum angular momentum transferred to each evaporation channel, the gamma-ray decay entry region and the relative cross sections. No differences are observed between the three reactions. This is explained by the very similar dependence of the excitation ...

  9. Dopant occupancy and exposure energy in Hf:Nd:LiNbO3 crystal as a function of [Li]/[Nb] ratios

    Science.gov (United States)

    Dai, Li; Liu, Chunrui; Han, Xianbo; Yan, Zhehua; Tan, Chao; Wang, Luping; Xu, Yuheng

    2017-09-01

    A series of Hf: Nd: LiNbO3 crystals with various [Li]/[Nb] ratios ([Li]/[Nb] = 0.94, 1.05, 1.20, 1.38) in the melt were grown by conventional Czochralski technique. The distribution coefficients of Hf4+ and Nd3+ ions were recorded by an inductively coupled plasma-atomic emission spectrometer (ICP-AES). The effective distribution coefficient of Hf4+ is reduced and that of Nd3+ is increased with the increase of [Li]/[Nb] ratio in the melts. In all cases, the effective distribution coefficients is less than 1. The IR transmission spectroscopy of the Hf: Nd: LiNbO3 crystals were measured, getting the results that Hf: Yb: Ho: LiNbO3 crystals with 1.05 [Li]/[Nb] ratios was the stoichiometric. The optical damage resistance ability of Hf:Nd:LiNbO3 crystals were studied by light-induced scattering exposure energy flux threshold method and it increases with the increasing of [Li]/[Nb] ratios. When the [Li]/[Nb] ratio is 1.38 in the melt (the sample 4#), the exposure energy achieves 687.35 J/cm2, approximately 441 folds than that of the sample 1# ([Li]/[Nb] = 0.94) in magnitude.

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

    NARCIS (Netherlands)

    Kerstel, E.; Gianfrani, L.

    2008-01-01

    Small molecules exhibit characteristic ro-vibrational transitions in the near- and mid-infrared spectral regions, which are strongly influenced by isotopic substitution. This gift of nature has made it possible to use laser spectroscopy for the accurate analysis of the isotopic composition of gaseou

  11. Formation history and protolith characteristics of granulite facies metamorphic rock in Central Cathaysia deduced from U-Pb and Lu-Hf isotopic studies of single zircon grains

    Institute of Scientific and Technical Information of China (English)

    YU Jinhai; ZHOU Xinmin; Y. S. O'Reilly; ZHAO Lei; W. L. Griffin; WANG Rucheng; WANG Lijuan; CHEN Xiaomin

    2005-01-01

    The petrochemical as well as zircon U-Pb and Lu-Hf isotopic studies of granulite facies metamorphic rock from the Taoxi Group in eastern Nanling Range, Central Cathaysia indicate that its protolith is the sedimentary rock with low maturation index. The clastic materials are mostly from middle Neoproterozoic (~736 Ma) granitoid rocks with minor Neoarchaean and Paleoproterozoic rocks. The timing of this Neoproterozoic magmatism is in agreement with the second period of magmatism widespread surrounding the Yangtze Block. Hf isotopic data indicate that the Neoproterozoic granitoids resulted from the recycled Paleoproterozoic mantle-derived crustal materials. The sedimentary rock was deposited in Late Neoproterozoic Era, and carried into low crust in Early Paleozoic. The partial melting of the meta-sedimentary rock took place at about 480 Ma and subsequently granulite facies metamorphism occurred at ca. 443 Ma. The zircons forming during this time interval (Early Paleozoic) show large Hf isotope variations, and their -Hf(t) values increase from -13.2 to +2.36 with decreasing age, suggesting the injection of mantle-derived materials during partial melting and metamorphism processes in the Early Paleozoic. Calculation results show that this metamorphic rock, if evolved to Mesozoic, has similar isotopic composition to the nearby Mesozoic high Si peraluminous granites, implying that this kind of granulite facies metamorphic rock is probably the source material of some Mesozoic peraluminous granitoids in eastern Nanling Range.

  12. Isotopic ratios at z=0.68 from molecular absorption lines toward B 0218+357

    CERN Document Server

    Wallstrom, S H J; Guelin, M

    2016-01-01

    Isotopic ratios of heavy elements are a key signature of the nucleosynthesis processes in stellar interiors. The contribution of successive generations of stars to the metal enrichment of the Universe is imprinted on the evolution of isotopic ratios over time. We investigate the isotopic ratios of carbon, nitrogen, oxygen, and sulfur through millimeter molecular absorption lines arising in the z=0.68 absorber toward the blazar B 0218+357. We find that these ratios differ from those observed in the Galactic interstellar medium, but are remarkably close to those in the only other source at intermediate redshift for which isotopic ratios have been measured to date, the z=0.89 absorber in front of PKS1830-211. The isotopic ratios in these two absorbers should reflect enrichment mostly from massive stars, and they are indeed close to the values observed toward local starburst galaxies. Our measurements set constraints on nucleosynthesis and chemical evolution models.

  13. Early Paleozoic ridge subduction in the Chinese Altai: Insight from the abrupt change in zircon Hf isotopic compositions

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    Zircons were separated from granitoids, gneisses, and sedimentary rocks of the Chinese Altai. Those with igneous characteristics yielded U-Pb ages of 280-2800 Ma, recording a long history of magmatic activity in the region. Zircon Hf isotopic compositions show an abrupt change at ~420 Ma, indicating that prior to that time the magmas came from both ancient and juvenile sources, whereas younger magmas were derived mainly from juvenile material. This may imply that the lithosphere was signifi- cantly modified in composition by a rapid addition of melt from the mantle. We suggest that this dramatic change was due to the onset of ridge subduction, which can account not only for the formation of voluminous granitoids, mafic rocks with complex compositions, and the association of adakite + high-Mg andesite + boninite + Nb-enriched basalt, but also for the coeval high-T, low-P metamorphism.

  14. Early Paleozoic ridge subduction in the Chinese Altai:Insight from the abrupt change in zircon Hf isotopic compositions

    Institute of Scientific and Technical Information of China (English)

    SUN Min; LONG XiaoPing; CAI KeDa; JIANG YingDe; WANG BuYun; YUAN Chao; ZHAO GuoChun; XIAO WenJiao; WU FuYuan

    2009-01-01

    Zircons were separated from granitoids,gneisses,and sedimentary rocks of the Chinese Altai.Those with igneous characteristics yielded U-Pb ages of 280-2800 Ma,recording a long history of magmatic activity in the region.Zircon Hf isotopic compositions show an abrupt change at ~420 Ma,indicating that prior to that time the magmas came from both ancient and juvenile sources,whereas younger magmas were derived mainly from juvenile material.This may imply that the lithosphere was significantly modified in composition by a rapid addition of melt from the mantle.We suggest that this dramatic change was due to the onset of ridge subduction,which can account not only for the formation of voluminous granitoids,mafic rocks with complex compositions,and the association of adakite + high-Mg andesite+boninite + Nb-enriched basalt,but also for the coeval high-T,Iow-P metamorphism.

  15. Age and origin of post collision Baltoro granites, south Karakoram, North Pakistan: Insights from in-situ U-Pb, Hf and oxygen isotopic record of zircons

    Science.gov (United States)

    Mahar, Munazzam Ali; Mahéo, Gweltaz; Goodell, Philip C.; Pavlis, Terry L.

    2014-09-01

    Origin of post collision plutonism is critical to understand the tectonothermal evolution of the over thickened continental crust in collision zones. This has proven difficult to reconcile with the conventional whole rock geochemical and field based studies alone. We report in-situ study of zircon U-Pb, Hf and O isotopes from five samples of the Baltoro Plutonic Unit (BPU) in south Karakoram. The plutonic unit is the western part of the southern Asian margin of the India-Asia convergent zone. Baltoro granites and a biotite-rich enclave yielded similar and overlapping U-Pb ages ranging from 26 to 15 Ma. Hafnium isotopic composition (εHf (0)) is very heterogeneous ranging from - 17.1 to + 4.4 while the oxygen isotopic composition of the granites is homogeneous with mean δ18O ranging from 7.2 to 9.4‰. Based on U-Pb geochronology and Hf-O isotopic composition, the involvement of two main sources is suggested (1) Cretaceous calc-alkaline Karakoram crust and (2) Karakoram gneisses. Moreover, possible involvement of metasomatized Asian lithospheric mantle is supported by elevated oxygen composition of granites and identical Hf composition of biotite-rich enclave to the mantle derived Baltoro lamprophyre. However, direct contribution from juvenile pristine mantle is unlikely as no juvenile mantle type Hf and oxygen values were obtained. This also precludes the involvement of southward juvenile arc related component of Kohistan-Ladakh batholith. Our new U-Pb and Hf data are comparable to the Mesozoic Karakoram batholith, Miocene two-mica leucogranites in the Pangong Range and magmatism from the Lhasa terrane in south Tibet, suggesting a genetic link between the Karakoram and the rocks to the east. This magmatic event is best explained by lower crust partial melting promoted by both thermal equilibration following crustal thickening and heat advection by ultrapotassic magmas associated with the breakoff of the Indian continental margin.

  16. Oxygen and hydrogen isotope ratios in tree rings: how well do models predict observed values?

    CSIR Research Space (South Africa)

    Waterhouse, JS

    2002-07-30

    Full Text Available the trunk, it is proficient to model the observed annual values of oxygen isotope ratios of alpha-cellulose to a significant level (r = 0.77, P < 0.01). When the same model is applied to hydrogen isotope ratios, results are found, and predictions can be made...

  17. Application of neodymium isotope ratio measurements for the origin assessment of uranium ore concentrates

    NARCIS (Netherlands)

    Krajko, J.; Varga, Z.; Yalcintas, E.; Wallenius, M.; Mayer, K.

    2014-01-01

    A novel procedure has been developed for the measurement of 143Nd/144Nd isotope ratio in various uranium-bearing materials, such as uranium ores and ore concentrates (UOC) in order to evaluate the usefulness and applicability of variations of 143Nd/144Nd isotope ratio for provenance assessment in nu

  18. Quantification and isotope ratio determination of uranium in particles of environmental samples using isotope dilution thermal ionization mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Park, Jong-Ho [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of); Choi, Eun-Ju [Chungnam National University, Daejeon (Korea, Republic of)

    2015-10-15

    Highly accurate and precise quantitative and qualitative analysis of nuclear materials in environmental samples plays essential roles in monitoring undeclared nuclear activities of corresponding facilities. The former focuses on the quantification of uranium (U) and plutonium (Pu) contained in a whole sample, while the latter enables us to acquire the isotopic ratios, which serve as the crucial basis to trace the nuclear histories of a facility. However, the quantity of nuclear materials in a single-particle has not been acquired from the particle analysis, but has been estimated by the size of the particles. This report is to describe the method developed to determine the quantity and the isotopic ratios of uranium in a micro-particle simultaneously. Complete dissolution of particle-spike mixture by repeated addition of nitric acid on a rhenium filament was performed to ensure the homogeneity of the mixture. Thermal ionization mass spectrometry (TIMS) was utilized to measure the U isotope ratios of the mixture with high accuracy. The isotopic ratios of the uranium in the particle sample were determined by mathematical deconvolution of U isotopic ratios of the mixture. Verification using particles of a certified reference material showed that the newly developed method can be used to quantify and to determine the isotopic ratios of U in a particle simultaneously. The development of a method for simultaneous determination of the quantity and the isotope ratios of uranium contained in particles by isotope dilution thermal ionization mass spectrometry (ID-TIMS) was described. For homogeneity of the mixture of particles and spike, repeated dissolution using nitric acid for five times was performed.

  19. Forensic Applications of Light-Element Stable Isotope Ratios of Ricinus communis Seeds and Ricin Preparations

    Energy Technology Data Exchange (ETDEWEB)

    Kreuzer, Helen W.; West, Jason B.; Ehleringer, James

    2013-01-01

    Seeds of the castor plant Ricinus communis, also known as castor beans, are of forensic interest because they are the source of the poison ricin. We have tested whether stable isotope ratios of castor seeds and ricin prepared by various methods can be used as a forensic signature. We collected over 300 castor seed samples from locations around the world and measured the C, N, O, and H stable isotope ratios of the whole seeds, oil, and three types of ricin preparations. Our results demonstrate that N isotope ratios can be used to correlate ricin prepared by any of these methods to source seeds. Further, stable isotope ratios distinguished >99% of crude and purified ricin protein samples in pair-wise comparison tests. Stable isotope ratios therefore constitute a valuable forensic signature for ricin preparations.

  20. Stable carbon isotope ratios from archaeological charcoal as palaeoenvironmental indicators

    CSIR Research Space (South Africa)

    Hall, G

    2008-01-01

    Full Text Available The potential to provide environmental proxies using stable carbon isotopes from modern and archaeological charcoal is explored. Experiments on modern Podocarpus (Yellowwoods) show that δ13C values of stems, branches and charcoal preserve proxy...

  1. Uranium Isotope Ratios in Modern and Precambrian Soils

    Science.gov (United States)

    DeCorte, B.; Planavsky, N.; Wang, X.; Auerbach, D. J.; Knudsen, A. C.

    2015-12-01

    Uranium isotopes (δ238U values) are an emerging paleoredox proxy that can help to better understand the redox evolution of Earth's surface environment. Recently, uranium isotopes have been used to reconstruct ocean and atmospheric redox conditions (Montoya-Pino et al., 2010; Brennecka et al., 2011; Kendall et al., 2013; Dahl et al., 2014). However, to date, there have not been studies on paleosols, despite that paleosols are, arguably better suited to directly tracking the redox conditions of the atmosphere. Sedimentary δ238U variability requires the formation of the soluble, oxidized form of U, U(VI). The formation of U(VI) is generally thought to require oxygen levels orders of magnitude higher than prebiotic levels. Without significant U mobility, it would have been impossible to develop isotopically distinct pools of uranium in ancient Earth environments. Conversely, an active U redox cycle leads to significant variability in δ238U values. Here we present a temporally and geographically expansive uranium isotope record from paleosols and modern soils to better constrain atmospheric oxygen levels during the Precambrian. Preliminary U isotope measurements of paleosols are unfractionated (relative to igneous rocks), possibly because of limited fractionation during oxidation (e.g., {Wang, 2015 #478}) or insufficient atmospheric oxygen levels to oxidize U(IV)-bearing minerals in the bedrock. Further U isotope measurements of paleosols with comparison to modern soils will resolve this issue.

  2. MS fragment isotope ratio analysis for evaluation of citrus essential oils by HRGC-MS.

    Science.gov (United States)

    Satake, Atsushi; Furukawa, Kiyoshi; Ueno, Takao; Ukeda, Hiroyuki; Sawamura, Masayoshi

    2004-02-01

    To evaluate the origin of citrus essential oils, the isotope ratio of fragment peaks on HRGC-MS of the volatile compounds from various citrus oils was measured. The MS fragment ratio was found by the ratio of fragment peak intensity, m+1/m (m/z). This ratio reflects the isotope effect of volatile compounds, that is, it provides information about locality, quality, and species for essential oils. Multivariate analysis based on the MS fragment ratio of monoterpene hydrocarbons clearly distinguished three citrus species, yuzu, lemon, and lime. The carbonyl fractions were also extracted from citrus essential oils by the sodium hydrogensulfite method. The isotope ratio of MS fragments of octanal, nonanal, and decanal was also examined. The results suggest that there was no significant difference in the individual fragment isotope ratios of the three aldehydes.

  3. Equations for lipid normalization of carbon stable isotope ratios in aquatic bird eggs.

    Directory of Open Access Journals (Sweden)

    Kyle H Elliott

    Full Text Available Stable isotope ratios are biogeochemical tracers that can be used to determine the source of nutrients and contaminants in avian eggs. However, the interpretation of stable carbon ratios in lipid-rich eggs is complicated because (13C is depleted in lipids. Variation in (13C abundance can therefore be obscured by variation in percent lipids. Past attempts to establish an algebraic equation to correct carbon isotope ratios for lipid content in eggs have been unsuccessful, possibly because they relied partly on data from coastal or migratory species that may obtain egg lipids from different habitats than egg protein. We measured carbon, nitrogen and sulphur stable isotope ratios in 175 eggs from eight species of aquatic birds. Carbon, nitrogen and sulphur isotopes were enriched in lipid-extracted egg samples compared with non extracted egg samples. A logarithmic equation using the C∶N ratio and carbon isotope ratio from the non extracted egg tissue calculated 90% of the lipid-extracted carbon isotope ratios within ±0.5‰. Calculating separate equations for eggs laid by species in different habitats (pelagic, offshore and terrestrial-influenced improved the fit. A logarithmic equation, rather than a linear equation as often used for muscle, was necessary to accurately correct for lipid content because the relatively high lipid content of eggs compared with muscle meant that a linear relationship did not accurately approximate the relationship between percent lipids and the C∶N ratio. Because lipid extraction alters sulphur and nitrogen isotope ratios (and cannot be corrected algebraically, we suggest that isotopic measurement on bulk tissue followed by algebraic lipid normalization of carbon stable isotope ratio is often a good solution for homogenated eggs, at least when it is not possible to complete separate chemical analyses for each isotope.

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

    Science.gov (United States)

    Coplen, Tyler B.

    2011-01-01

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

  5. Comparison of gas chromatography/isotope ratio mass spectrometry and liquid chromatography/isotope ratio mass spectrometry for carbon stable-isotope analysis of carbohydrates.

    Science.gov (United States)

    Moerdijk-Poortvliet, Tanja C W; Schierbeek, Henk; Houtekamer, Marco; van Engeland, Tom; Derrien, Delphine; Stal, Lucas J; Boschker, Henricus T S

    2015-07-15

    We compared gas chromatography/isotope ratio mass spectrometry (GC/IRMS) and liquid chromatography/isotope ratio mass spectrometry (LC/IRMS) for the measurement of δ(13)C values in carbohydrates. Contrary to GC/IRMS, no derivatisation is needed for LC/IRMS analysis of carbohydrates. Hence, although LC/IRMS is expected to be more accurate and precise, no direct comparison has been reported. GC/IRMS with the aldonitrile penta-acetate (ANPA) derivatisation method was compared with LC/IRMS without derivatisation. A large number of glucose standards and a variety of natural samples were analysed for five neutral carbohydrates at natural abundance as well as at (13)C-enriched levels. Gas chromatography/chemical ionisation mass spectrometry (GC/CIMS) was applied to check for incomplete derivatisation of the carbohydrate, which would impair the accuracy of the GC/IRMS method. The LC/IRMS technique provided excellent precision (±0.08‰ and ±3.1‰ at natural abundance and enrichment levels, respectively) for the glucose standards and this technique proved to be superior to GC/IRMS (±0.62‰ and ±19.8‰ at natural abundance and enrichment levels, respectively). For GC/IRMS measurements the derivatisation correction and the conversion of carbohydrates into CO2 had a considerable effect on the measured δ(13)C values. However, we did not find any significant differences in the accuracy of the two techniques over the full range of natural δ(13)C abundances and (13)C-labelled glucose. The difference in the performance of GC/IRMS and LC/IRMS diminished when the δ(13)C values were measured in natural samples, because the chromatographic performance and background correction became critical factors, particularly for LC/IRMS. The derivatisation of carbohydrates for the GC/IRMS method was complete. Although both LC/IRMS and GC/IRMS are reliable techniques for compound-specific stable carbon isotope analysis of carbohydrates (provided that derivatisation is complete and the

  6. Coupled Hf-Nd-Pb isotope co-variations of HIMU oceanic island basalts from Mangaia, Cook-Austral islands, suggest an Archean source component in the mantle transition zone

    Science.gov (United States)

    Nebel, Oliver; Arculus, Richard J.; van Westrenen, Wim; Woodhead, Jon D.; Jenner, Frances E.; Nebel-Jacobsen, Yona J.; Wille, Martin; Eggins, Stephen M.

    2013-07-01

    Although it is widely accepted that oceanic island basalts (OIB) sample geochemically distinct mantle reservoirs including recycled oceanic crust, the composition, age, and locus of these reservoirs remain uncertain. OIB with highly radiogenic Pb isotope signatures are grouped as HIMU (high-μ, with μ = 238U/204Pb), and exhibit unique Hf-Nd isotopic characteristics, defined as ΔɛHf, deviant from a terrestrial igneous rock array that includes all other OIB types. Here we combine new Hf isotope data with previous Nd-Pb isotope measurements to assess the coupled, time-integrated Hf-Nd-Pb isotope evolution of the most extreme HIMU location (Mangaia, French Polynesia). In comparison with global MORB and other OIB types, Mangaia samples define a unique trend in coupled Hf-Nd-Pb isotope co-variations (expressed in 207Pb/206Pb vs. ΔɛHf). In a model employing subducted, dehydrated oceanic crust, mixing between present-day depleted MORB mantle (DMM) and small proportions (˜5%) of a HIMU mantle endmember can re-produce the Hf-Nd-Pb isotope systematics of global HIMU basalts (sensu stricto; i.e., without EM-1/EM-2/FOZO components). An age range of 3.5 to affected by other enriched mantle endmembers (sensu lato). If correct, this requires isolation of parts of the mantle transition zone for >3 Gyr and implies that OIB chemistry can be used to test geodynamic models.

  7. HFSE (High Field Strength Elements)-transport and U-Pb-Hf isotope homogenization mediated by Ca-bearing aqueous fluids at 2.04 Ga: Constraints from zircon, monazite, and garnet of the Venetia Klippe, Limpopo Belt, South Africa

    Science.gov (United States)

    Zeh, A.; Gerdes, A.

    2014-08-01

    Results from laser-ablation inductively-coupled-plasma mass spectrometry (LA-ICP-MS) and isotope dilution (ID) analyses of minerals and rocks from a single outcrop of the Venetia Klippe of the Limpopo Belt indicate that the U-Pb and Hf isotope system homogenized on the decimetre scale under amphibolite-facies conditions of ⩽645 ± 25 °C and ⩽7.0 ± 1.1 kbar, i.e. in the presence of an aqueous fluid phase. For a metabasite sample, homogenization is supported by isotope analyses of metamorphic zircon, garnet, and whole rock, which yield a six-point Lu-Hf isochron age of 2039.7 ± 3.4 Ma, with initial 176Hf/177Hf of 0.28126 ± 0.00001, and a U-Pb zircon age of 2042 ± 10 Ma. The occurrence of a few inherited magmatic zircon cores with ages up to 2705 Ma, and with significantly lower initial 176Hf/177Hf of 0.28112, however, indicate that homogenization was incomplete. For a chlorite-biotite-garnet schist isotope homogenization is reflected by within error identical zircon and monazite U-Pb ages of 2045 ± 10 Ma and 2041 ± 8 Ma, respectively, and by a zircon-garnet-whole rock Lu-Hf isochron age of 2083 ± 63 Ma, with an initial 176Hf/177Hf of 0.28140 ± 0.00003. Contemporaneous formation of metamorphic zircon, monazite and garnet in the chlorite schist is not only supported by the isotope data, but also by chlorite inclusions in all three minerals, and by inclusions of metamorphic zircon in garnet. The inclusion textures and the identical initial 176Hf/177Hf support the conclusion that metamorphic zircon grains precipitated from an aqueous fluid phase, after dissolution of zirconium-bearing phases elsewhere, followed by a major HFSE transport, and Hf isotope homogenization. This fluid perhaps was Ca-bearing, as is suggested by the fact that garnet in the schist sample is the only Ca-bearing phase, and that metamorphic monazite, dating the metamorphic peak, is partially replacement by apatite. The fact that the metamorphic zircon rims in the metabasite sample have

  8. A Test of Carbon and Oxygen Stable Isotope Ratio Process Models in Tree Rings.

    Science.gov (United States)

    Roden, J. S.; Farquhar, G. D.

    2008-12-01

    Stable isotopes ratios of carbon and oxygen in tree ring cellulose have been used to infer environmental change. Process-based models have been developed to clarify the potential of historic tree ring records for meaningful paleoclimatic reconstructions. However, isotopic variation can be influenced by multiple environmental factors making simplistic interpretations problematic. Recently, the dual isotope approach, where the variation in one stable isotope ratio (e.g. oxygen) is used to constrain the interpretation of variation in another (e.g. carbon), has been shown to have the potential to de-convolute isotopic analysis. However, this approach requires further testing to determine its applicability for paleo-reconstructions using tree-ring time series. We present a study where the information needed to parameterize mechanistic models for both carbon and oxygen stable isotope ratios were collected in controlled environment chambers for two species (Pinus radiata and Eucalyptus globulus). The seedlings were exposed to treatments designed to modify leaf temperature, transpiration rates, stomatal conductance and photosynthetic capacity. Both species were grown for over 100 days under two humidity regimes that differed by 20%. Stomatal conductance was significantly different between species and for seedlings under drought conditions but not between other treatments or humidity regimes. The treatments produced large differences in transpiration rate and photosynthesis. Treatments that effected photosynthetic rates but not stomatal conductance influenced carbon isotope discrimination more than those that influenced primarily conductance. The various treatments produced a range in oxygen isotope ratios of 7 ‰. Process models predicted greater oxygen isotope enrichment in tree ring cellulose than observed. The oxygen isotope ratios of bulk leaf water were reasonably well predicted by current steady-state models. However, the fractional difference between models that

  9. Stable hydrogen and oxygen isotope ratios of bottled waters of the world.

    Science.gov (United States)

    Bowen, Gabriel J; Winter, David A; Spero, Howard J; Zierenberg, Robert A; Reeder, Mathew D; Cerling, Thure E; Ehleringer, James R

    2005-01-01

    Bottled and packaged waters are an increasingly significant component of the human diet. These products are regulated at the regional, national, and international levels, and determining the authenticity of marketing and labeling claims represents a challenge to regulatory agencies. Here, we present a dataset of stable isotope ratios for bottled waters sampled worldwide, and consider potential applications of such data for regulatory, forensic and geochemical standardization applications. The hydrogen and oxygen isotope ratios of 234 samples of bottled water range from -147 per thousand to +15 per thousand and from -19.1 per thousand to +3.0 per thousand, respectively. These values fall within and span most of the normal range for meteoric waters, indicating that these commercially available products represent a source of waters for use as laboratory working standards in applications requiring standardization over a large range of isotope ratios. The measured values of bottled water samples cluster along the global meteoric water line, suggesting that bottled water isotope ratios preserve information about the water sources from which they were derived. Using the dataset, we demonstrate how bottled water isotope ratios provide evidence for substantial evaporative enrichment of water sources prior to bottling and for the marketing of waters derived from mountain and lowland sources under the same name. Comparison of bottled water isotope ratios with natural environmental water isotope ratios demonstrates that on average the isotopic composition of bottled water tends to be similar to the composition of naturally available local water sources, suggesting that in many cases bottled water need not be considered as an isotopically distinct component of the human diet. Our findings suggest that stable isotope ratios of bottled water have the power to distinguish ultimate (e.g., recharge) and proximal (e.g., reservoir) sources of bottled water and constitute a potential

  10. Non-chondritic iron isotope ratios in planetary mantles as a result of core formation

    Science.gov (United States)

    Elardo, Stephen M.; Shahar, Anat

    2017-02-01

    Information about the materials and conditions involved in planetary formation and differentiation in the early Solar System is recorded in iron isotope ratios. Samples from Earth, the Moon, Mars and the asteroid Vesta reveal significant variations in iron isotope ratios, but the sources of these variations remain uncertain. Here we present experiments that demonstrate that under the conditions of planetary core formation expected for the Moon, Mars and Vesta, iron isotopes fractionate between metal and silicate due to the presence of nickel, and enrich the bodies' mantles in isotopically light iron. However, the effect of nickel diminishes at higher temperatures: under conditions expected for Earth's core formation, we infer little fractionation of iron isotopes. From our experimental results and existing conceptual models of magma ocean crystallization and mantle partial melting, we find that nickel-induced fractionation can explain iron isotope variability found in planetary samples without invoking nebular or accretionary processes. We suggest that near-chondritic iron isotope ratios of basalts from Mars and Vesta, as well as the most primitive lunar basalts, were achieved by melting of isotopically light mantles, whereas the heavy iron isotope ratios of terrestrial ocean floor basalts are the result of melting of near-chondritic Earth mantle.

  11. Utility of 5A molecular sieves to measure carbon isotope ratios in lipid biomarkers.

    Science.gov (United States)

    Tolosa, Imma; Ogrinc, Nives

    2007-09-21

    A procedure using 5A zeolite sorption to separate cyclic/branched organic compounds from the linear ones was developed and carbon isotopic fractionation effects were investigated in different families of compounds, e.g. within the hydrocarbon and alcohol compounds. The 5A sieve has a pore size such that only linear components can be incorporated into the pores whereas the cyclic/branched compounds are remaining free in the organic solution. The sorbed compounds were released from the molecular sieve with HF and solvent extracted with hexane. The method enables the isolation of linear saturated classes, such as n-alkanes and n-fatty alcohols from branched/cyclic compounds without isotopic fractionation for compound-specific isotope analysis (CSIA) of delta(13)C. However, alkene hydrocarbons, sterols and some aromatics were completely or partly degraded with the molecular sieve.

  12. BOREAS TE-5 Tree Ring and Carbon Isotope Ratio Data

    Science.gov (United States)

    Hall, Forrest G. (Editor); Curd, Shelaine (Editor); Ehleriinger, Jim; Brooks, J. Renee; Flanagan, Larry

    2000-01-01

    The BOREAS TE-5 team collected several data sets to investigate the vegetation-atmosphere CO2 and H2O exchange processes. These data include tree ring widths and cellulose carbon isotope data from coniferous trees collected at the BOREAS NSA and SSA in 1993 and 1994 by the BOREAS TE-5 team. Ring width data are provided for both Picea mariana and Pinus banksiana. The carbon isotope data are provided only for Pinus banksiana. The data are provided in tabular ASCII files. The data files are available on a CD-ROM (see document number 20010000884), or from the Oak Ridge National Laboratory (ORNL) Distributed Active Archive Center (DAAC).

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

    Science.gov (United States)

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

    2014-05-20

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

  14. Chlorine Isotope Effects from Isotope Ratio Mass Spectrometry Suggest Intramolecular C-Cl Bond Competition in Trichloroethene (TCE Reductive Dehalogenation

    Directory of Open Access Journals (Sweden)

    Stefan Cretnik

    2014-05-01

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

  15. Online stable carbon isotope ratio measurement in formic acid, acetic acid, methanol and ethanol in water by high performance liquid chromatography-isotope ratio mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Tagami, Keiko [National Institute of Radiological Sciences, 4-9-1, Anagawa, Inage-ku, Chiba 263-8555 (Japan)], E-mail: k_tagami@nirs.go.jp; Uchida, Shigeo [National Institute of Radiological Sciences, 4-9-1, Anagawa, Inage-ku, Chiba 263-8555 (Japan)

    2008-05-05

    A suitable analysis condition was determined for high performance liquid chromatography-isotope ratio mass spectrometry (HPLC-IRMS) while making sequential measurements of stable carbon isotope ratios of {delta}{sup 13}C in formic acid, acetic acid, methanol and ethanol dissolved in water. For this online column separation method, organic reagents are not applicable due to carbon contamination; thus, water and KH{sub 2}PO{sub 4} at low concentrations were tested as mobile phase in combination with a HyPURITY AQUASTAR{sup TM} column. Formic acid, acetic acid, methanol and ethanol were separated when 2 mM KH{sub 2}PO{sub 4} aqueous solution was used. Under the determined analysis condition for HPLC-IRMS, carbon concentrations could be measured quantitatively as well as carbon isotope ratio when carbon concentration was higher than 0.4 mM L for each chemical.

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

    Science.gov (United States)

    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.

  17. Water mass circulation and weathering inputs in the Labrador Sea based on coupled Hf-Nd isotope compositions and rare earth element distributions

    Science.gov (United States)

    Filippova, Alexandra; Frank, Martin; Kienast, Markus; Rickli, Jörg; Hathorne, Ed; Yashayaev, Igor M.; Pahnke, Katharina

    2017-02-01

    The Labrador Sea is one of the key areas for deep water formation driving the Atlantic thermohaline circulation and thus plays an important role in Northern Hemisphere climatic fluctuations. In order to better constrain the overturning processes and the origins of the distinct water masses, combined dissolved Hf-Nd isotopic compositions and rare earth element (REE) distribution patterns were obtained from four water depth profiles along a section across the Labrador Sea. These were complemented by one surface sample off the southern tip of Greenland, three shallow water samples off the coast of Newfoundland, and two deep water samples off Nova Scotia. Although light REEs are markedly enriched in the surface waters off the coast of Newfoundland compared to north Atlantic waters, the REE concentration profiles are essentially invariant throughout the water column across the Labrador Sea. The hafnium concentrations of surface waters exhibit a narrow range between 0.6 and 1 pmol/kg but are not significantly higher than at depth. Neodymium isotope signatures (ɛNd) vary from unradiogenic values between -16.8 and -14.9 at the surface to more radiogenic values near -11.0 at the bottom of the Labrador Sea mainly reflecting the advection of the Denmark Strait Overflow Water and North East Atlantic Deep Water, the signatures of which are influenced by weathering contributions from Icelandic basalts. Unlike Nd, water column radiogenic Hf isotope signatures (ɛHf) are more variable representing diverse weathering inputs from the surrounding landmasses. The least radiogenic seawater ɛHf signatures (up to -11.7) are found in surface waters close to Greenland and near the Canadian margin. This reflects the influence of recirculating Irminger Current Waters, which are affected by highly unradiogenic inputs from Greenland. A three to four ɛHf unit difference is observed between Denmark Strait Overflow Water (ɛHf ∼ -4) and North East Atlantic Deep Water (ɛHf ∼ -0

  18. Influence of isotopic re-equilibration on speleothem and fluid inclusion isotope ratios after primary calcite precipitation

    Science.gov (United States)

    Kluge, Tobias; Haderlein, Astrid; Weißbach, Therese

    2016-04-01

    Oxygen isotope ratios in speleothems (notably stalagmites) have been used since decades to successfully infer paleotemperatures and deduce paleo-environmental information. In addition, recent technical developments allow to increasingly use fluid inclusions as an archive for drip-water and together with the surrounding calcite as paleothermometer. A basic requirement for isotope data interpretation is the complete knowledge of the fractionation between calcite and fluid. Most laboratory and in-situ cave experiments focus on calcite growth and the isotope fractionation between calcite and feed solution. Potential isotope exchange and re-equilibration processes after the initial deposition have mostly been neglected. However, experiments of Oelkers et al. (2015) showed that the isotope exchange between minerals and fluid can proceed rapidly (within days), even at chemical equilibrium. In hydrous Mg carbonates a similar process of continuous isotope exchange between carbonate and fluid was observed after the carbonate precipitation was completed (Mavromatis et al., 2015). These observations suggest that the isotope ratios of speleothem calcite may be affected by this continuous exchange, likely driving the isotope composition continuously towards equilibrium at the respective cave conditions. In addition, fluid inclusions are suspected to be sensitive to an isotope exchange with the surrounding carbonate highlighting the need to precisely understand and quantify this effect. We assessed the oxygen isotope exchange between calcite and solution at chemical equilibrium conditions with theoretical estimates and laboratory experiments over an intermediate time scale (hours-weeks). A large isotope gradient (~20 ‰)) between solution and calcite was prepared in the experiment to investigate the dynamics of this re-equilibration process. We used a theoretical model based on a Rayleigh fractionation approach and the direct comparison with the experiment to determine

  19. Geochronological, elemental and Sr-Nd-Hf-O isotopic constraints on the petrogenesis of the Triassic post-collisional granitic rocks in NW Thailand and its Paleotethyan implications

    Science.gov (United States)

    Wang, Yuejun; He, Huiying; Cawood, Peter A.; Srithai, Boontarika; Feng, Qinglai; Fan, Weiming; Zhang, Yuzhi; Qian, Xin

    2016-12-01

    New U-Pb geochronological, petrologic, elemental and Sr-Nd-Hf-O isotopic data for the granites from the Inthanon and Sukhothai zones in NW Thailand in conjunction with correlations with SW China are presented to constrain the age and position of the Paleotethys Ocean in this region and the associated assembly of Southeast Asia. The geochronological data show that the granitic rocks in the Inthanon and Sukhothai zones, herein named Group 1 and Group 2 granites, respectively, yield similar crystallization ages of 230-200 Ma. Group 1 samples are characterized by monzogranite and granite with I- and S-type geochemical affinity and Group 2 samples by I-type monzogranite and granodiorite. They have generally similar chondrite-normalized REE and PM-normalized multi-element patterns but distinct Sr-Nd-Hf-O isotopic compositions. Group 1 samples have slightly higher initial 87Sr/86Sr ratios (0.7111-0.7293) but lower εNd(t) values (- 11.1 to - 14.1) than those of Group 2 samples (87Sr/86Sr(i) = 0.7073-0.7278 and εNd(t) = - 8.3 to - 11.0). Group 1 samples show the lower εHf(t) values (- 5.4 to - 18.2), older TDM (1.62-2.40 Ga) and higher δ18O values (+ 7.95 to + 9.94) than those of Group 2 samples (εHf(t) of - 11.1 to + 4.80, TDM of 0.96-1.95 Ga and δ18O of + 4.95 to + 7.98) for the Triassic crystallization zircons. These geochemical signatures are similar to the Kwangsian and Indosinian granites in the South China and Indochina blocks but distinct from those of the Gangdese I-type granite and Sibumasu Paleozoic granite. Our data suggest that Group 1 samples mainly originated from the early Paleozoic supracrustal rocks containing metapelite and metavolcanic components, which had previously experienced the surface weathering. Group 2 samples were derived from a hybridized source of an old metamorphic and a newly underplated mafic component. Synthesis of our data with available regional observations indicates that the Inthanon zone represents the main suture zone of the

  20. Changes in isotope ratios during domestic wastewater production

    NARCIS (Netherlands)

    Schilperoort, R. P. S.; Meijer, H. A. J.; Flamink, C. M. L.; Clemens, F. H. L. R.

    2007-01-01

    This paper presents considerations for the application of the natural water isotope method on catchment areas. For the estimation of the amount of infiltration and inflow in sewer systems the paper shows two applications in the Netherlands: one successful application on a relatively small catchment

  1. Zircon-apatite U-Pb geochronology, zircon Hf isotope composition and geochemistry of granite batholith in the northern Mexico: Implications for Tectonomagmatic evolution of southern Cordillera.

    Science.gov (United States)

    Mahar, M. A.; Goodell, P.

    2015-12-01

    We present the zircon-apatite U-Pb ages and zircon Hf isotope composition of the granite batholith exposed at the western boundary of Chihuahua. Granidiorite samples were analyzed from both, north and south of the Rio El Fuerte and Sinforosa Lineament. Based on previous studies, the WWN-EES trending Sinforosa Lineament is proposed as the manifestation of a terrane boundary between Seri in the north and Tahue terrane in the south. Zircon U-Pb data indicate that the magmatism spans a time period of 36 Ma from 89 to 53 Ma to the north of the Sinforosa Lineament while granodiorites in the south of the Sinforosa Lineament are dated at 59 Ma. The U-Pb apatite ages are variable in the north of the Sinforosa Lineament and range from 86-51 Ma. These apatite dates are 1-28 Ma younger than the corresponding zircon U-Pb crystallization ages. This indicates variable cooling rates and moderate to shallow emplacement. In contrast, in the south of the Sinforosa Lineament, the U-Pb apatite ages (64-59 Ma) are indistinguishable from the zircon U-Pb age (59 Ma), indicating rapid cooling and shallow emplacement. Zircon morphology and U-Pb dating revealed the absence of inherited component in the zircon ages, as no inheritance of any age has been observed. Most of the northwestern Mexico is underlain by Precambrian-Paleozoic-Jurassic basement. However, in the study area, U-Pb dating does not support the involvement of the older basement in generating the granite magmas. The weighted mean initial ɛHf (t) isotope composition of granodiorites on both sides of the Sinforosa Lineament varies from +2 to +5. However, Hf isotope composition in the south of the Sinforosa Lineament is more heterogeneous and relatively evolved with weighted Mean ɛHf (t) = +1.45. The Hf isotope composition is consistent with the previously reported near bulk silicate Sr-Nd isotope values. We suggest that the magmatic rocks in this region are not derived from melting of a felsic older crust beneath the batholith

  2. Geological, geochronological, geochemical, and Sr-Nd-O-Hf isotopic constraints on origins of intrusions associated with the Baishan porphyry Mo deposit in eastern Tianshan, NW China

    Science.gov (United States)

    Wang, Yinhong; Xue, Chunji; Liu, Jiajun; Zhang, Fangfang

    2016-10-01

    The Baishan porphyry Mo deposit (0.72 Mt; 0.06 % Mo) is located in the interior of the eastern Tianshan orogenic belt in Xinjiang, NW China. The deposit comprises 15 orebodies that are associated with monzogranite and granite porphyry stocks and are structurally controlled by roughly EW-trending faults. Secondary ion mass spectrometry (SIMS) zircon U-Pb dating of the monzogranite and granite porphyry yielded the Middle Triassic age (228 ± 2 to 227 ± 2 Ma), which coincide with the molybdenite Re-Os model ages ranging from 226 ± 3 to 228 ± 3 Ma. The Triassic monzogranite and granite porphyry belong to high-K calc-alkaline series and are characterized by high SiO2 and Al2O3 and low MgO, TiO2, and P2O5 concentrations, with negative Eu anomalies (δEu = 0.55-0.91). The least-altered monzogranite and granite porphyry yield uniform ɛ Nd( t) values from +1.6 to +3.6, and wide (87Sr/86Sr) i ratios ranging between 0.7035 and 0.7071, indicating that they were derived from the lower crust. In situ O-Hf isotopic analyses on zircon using SIMS and laser ablation multi-collector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) indicate that the δ18O and ɛ Hf( t) values of zircon from a monzogranite sample vary from 6.1 to 7.3 ‰ and +8.0 to +11.7, respectively, whereas zircon from a granite porphyry sample vary from 6.2 to 6.9 ‰ and +7.3 to +11.2, respectively. The geochemical and isotopic data imply that the primary magmas of the Baishan granite were likely derived from partial melts from the lower crust involving some mantle components. The Baishan Mo deposit and granitic emplacement were proposed to be most likely related to post-orogenic lithospheric extension and magmatic underplating. An extensional event coupled with the rising of hot mantle-derived melts triggered partial melting of the lower crust, as well as provided metals (Mo).

  3. Hafnium isotope variations in oceanic basalts

    Science.gov (United States)

    Patchett, P. J.; Tatsumoto, M.

    1980-01-01

    Hafnium isotope ratios generated by the beta(-) decay of Lu-176 are investigated in volcanic rocks derived from the suboceanic mantle. Hf-176/Hf-177 and Lu/Hf ratios were determined to precisions of 0.01-0.04% and 0.5%, respectively, by routine, low-blank chemistry. The Hf-176/Hf-177 ratio is found to be positively correlated with the Nd-143/Nd-144 ratio and negatively correlated with the Sr-87/Sr-86 and Pb-206/Pb-204 ratios, and to increase southwards along the Iceland-Reykjanes ridge traverse. An approximate bulk earth Hf-176/Hf-177 ratio of 0.28295 is inferred from the bulk earth Nd-143/Nd-144 ratio, which requires a bulk earth Lu/Hf ratio of 0.25, similar to the Juvinas eucrite. Midocean ridge basalts are shown to account for 60% of the range of Hf isotope ratios, and it is suggested that Lu-Hf fractionation is decoupled from Sm-Nd and Rb-Sr fractionation in very trace-element-depleted source regions as a result of partial melting.

  4. Tracing lead pollution sources in abandoned mine areas using stable Pb isotope ratios.

    Science.gov (United States)

    Yoo, Eun-Jin; Lee, Jung-A; Park, Jae-Seon; Lee, Khanghyun; Lee, Won-Seok; Han, Jin-Seok; Choi, Jong-Woo

    2014-02-01

    This study focused on Pb isotope ratios of sediments in areas around an abandoned mine to determine if the ratios can be used as a source tracer. For pretreatment, sediment samples were dissolved with mixed acids, and a multi-collector inductively coupled plasma mass spectrometer (MC-ICP-MS, Nu plasma II) was used to investigate the Pb isotopic composition of the samples. The measured isotope ratios were then corrected for instrumental mass fractionation by measuring the (203)Tl/(205)Tl ratio. Repeated measurements with the NIST SRM 981 reference material showed that the precision of all ratios was below 104 ppm (±2σ) for 50 ng/g. The isotope ratios ((207)Pb/(206)Pb) found were 0.85073 ± 0.0004~0.85373 ± 0.0003 for the main stream, while they were 0.83736 ± 0.0010 for the tributary and 0.84393 ± 0.0002 for the confluence. A binary mixing equation for isotope ratios showed that the contributions of mine lead to neighboring areas were up to 60%. Therefore, Pb isotope ratios can be a good source tracer for areas around abandoned mines.

  5. Methods and limitations of 'clumped' CO2 isotope (Delta47) analysis by gas-source isotope ratio mass spectrometry.

    Science.gov (United States)

    Huntington, K W; Eiler, J M; Affek, H P; Guo, W; Bonifacie, M; Yeung, L Y; Thiagarajan, N; Passey, B; Tripati, A; Daëron, M; Came, R

    2009-09-01

    The geochemistry of multiply substituted isotopologues ('clumped-isotope' geochemistry) examines the abundances in natural materials of molecules, formula units or moieties that contain more than one rare isotope (e.g. (13)C(18)O(16)O, (18)O(18)O, (15)N(2), (13)C(18)O(16)O(2) (2-)). Such species form the basis of carbonate clumped-isotope thermometry and undergo distinctive fractionations during a variety of natural processes, but initial reports have provided few details of their analysis. In this study, we present detailed data and arguments regarding the theoretical and practical limits of precision, methods of standardization, instrument linearity and related issues for clumped-isotope analysis by dual-inlet gas-source isotope ratio mass spectrometry (IRMS). We demonstrate long-term stability and subtenth per mil precision in 47/44 ratios for counting systems consisting of a Faraday cup registered through a 10(12) ohm resistor on three Thermo-Finnigan 253 IRMS systems. Based on the analyses of heated CO(2) gases, which have a stochastic distribution of isotopes among possible isotopologues, we document and correct for (1) isotopic exchange among analyte CO(2) molecules and (2) subtle nonlinearity in the relationship between actual and measured 47/44 ratios. External precisions of approximately 0.01 per thousand are routinely achieved for measurements of the mass-47 anomaly (a measure mostly of the abundance anomaly of (13)C-(18)O bonds) and follow counting statistics. The present technical limit to precision intrinsic to our methods and instrumentation is approximately 5 parts per million (ppm), whereas precisions of measurements of heterogeneous natural materials are more typically approximately 10 ppm (both 1 s.e.). These correspond to errors in carbonate clumped-isotope thermometry of +/-1.2 degrees C and +/-2.4 degrees C, respectively.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2010-12-01

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

  7. Effect of various nitrogen flow ratios on the optical properties of (Hf:N-DLC films prepared by reactive magnetron sputtering

    Directory of Open Access Journals (Sweden)

    Meng Qi

    2017-08-01

    Full Text Available Hf and N co-doped diamond-like carbon [(Hf:N-DLC] films were deposited on 316L stainless steel and glass substrates through reactive magnetron sputtering of hafnium and carbon targets at various nitrogen flow ratios (R=N2/[N2+CH4+Ar]. The effects of chemical composition and crystal structure on the optical properties of the (Hf:N-DLC films were studied. The obtained films consist of uniform HfN nanocrystallines embedded into the DLC matrix. The size of the graphite clusters with sp2 bonds (La and the ID/IG ratio increase to 2.47 nm and 3.37, respectively, with increasing R. The optical band gap of the films decreases from 2.01 eV to 1.84 eV with increasing R. This finding is consistent with the trends of structural transformations and could be related to the increase in the density of π-bonds due to nitrogen incorporation. This paper reports the influence of nitrogen flow ratio on the correlation among the chemical composition, crystal structure, and optical properties of (Hf:N-DLC films.

  8. Stable carbon isotope ratios of ambient secondary organic aerosols in Toronto

    Science.gov (United States)

    Saccon, M.; Kornilova, A.; Huang, L.; Moukhtar, S.; Rudolph, J.

    2015-09-01

    A method to quantify concentrations and stable carbon isotope ratios of secondary organic aerosols has been applied to study atmospheric nitrophenols in Toronto, Canada. The sampling of five nitrophenols, all with substantial secondary formation from the photooxidation of aromatic volatile organic compounds (VOCs), was conducted in the gas phase and particulate matter (PM) together and in PM alone. Their concentrations in the atmosphere are in the low ng m-3 range and, consequently, a large volume of air (> 1000 m3) is needed to analyze samples for stable carbon isotope ratios, resulting in sampling periods of typically 24 h. While this extended sampling period increases the representativeness of average values, it at the same time reduces possibilities to identify meteorological conditions or atmospheric pollution levels determining nitrophenol concentrations and isotope ratios. Average measured carbon isotope ratios of the different nitrophenols are between -34 and -33 ‰, which is well within the range predicted by mass balance. However, the observed carbon isotope ratios cover a range of nearly 9 ‰ and approximately 20 % of the isotope ratios of the products have isotope ratios lower than predicted from the kinetic isotope effect of the first step of the reaction mechanism and the isotope ratio of the precursor. This can be explained by isotope fractionation during reaction steps following the initial reaction of the precursor VOCs with the OH radical. Limited evidence for local production of nitrophenols is observed since sampling was done in the Toronto area, an urban center with significant anthropogenic emission sources. Strong evidence for significant local formation of nitrophenols is only found for samples collected in summer. On average, the difference in carbon isotope ratios between nitrophenols in the particle phase and in the gas phase is insignificant, but for a limited number of observations in summer, a substantial difference is observed. This

  9. Lead isotope ratios as a tracer for lead contamination sources: A lake Andong case study

    Directory of Open Access Journals (Sweden)

    Kim Y. H

    2013-04-01

    Full Text Available The objective of this study was to evaluate stable Pb isotope signatures as a tracer for Pb contamination in Lake Andong. For Pb isotope analysis, we collected water and sediment from Lake Andong, particles in the air, soils, and stream water, mine tailings, sludge and wastewater from zinc smelting around lake Andong watershed. The results showed that Pb isotope ratios (206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb for zinc concentrate were 18.809 ± 0.322, 15.650 ± 0.062, and 38.728 ± 0.421, respectively. In wastewater, isotopic ratio values (206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb were 17.363 ± 0.133, 15.550 ± 0.025, and 37.217 ± 0.092, respectively. Additionally, isotopic ratio values (206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb for sludge were 17.515 ± 0.155, 15.537 ± 0.018, and 37.357 ± 0.173, respectively. These values were similar to those in zinc and lead concentrate originated from Canada and South America. In contrast, Pb isotope ratios of soil, tailings and sediment from Lake Andong were similar to those of Korean ore. Atmospheric particles showed different patterns of Pb isotope ratios from sediments, soils, and zinc smelting and this needs further investigation in order to identify atmospheric Pb sources.

  10. Paleoproterozoic tectonic transition from collision to extension in the eastern Cathaysia Block, South China: Evidence from geochemistry, zircon U-Pb geochronology and Nd-Hf isotopes of a granite-charnockite suite in southwestern Zhejiang

    Science.gov (United States)

    Zhao, Lei; Zhou, Xiwen; Zhai, Mingguo; Santosh, M.; Ma, Xudong; Shan, Houxiang; Cui, Xiahong

    2014-01-01

    The Badu complex and associated Paleoproterozoic granitoids are among the oldest known rocks in the Cathaysia Block in South China. The Paleoproterozoic units of the Badu complex are dominantly composed of metapelitic rocks and meta-greywackes. Here we report LA-SS-ICP-MS (laser ablation-split-stream inductively coupled plasma-mass spectrometry) zircon U-Pb data from a newly discovered garnet-bearing granite which show an emplacement age of 1929 ± 15 Ma and metamorphism at 1872 ± 34 Ma. We also report U-Pb ages of 1886 ± 16 Ma, 1858 ± 7 Ma, 1848 ± 11 Ma from a gneissic granodiorite, and two charnockites respectively. The garnet-bearing granite is peraluminous with A/CNK range from 1.1 to 1.3. The rock shows relatively high SiO2, K2O and Rb contents, and low total REE, Sr, CaO and ferromagnesian components, typical of leucogranites. The whole rock Nd two-stage model age(TDM2(Nd)) of this rock is ca. 2.7 Ga, zircon Hf crustal model ages(TDMC(Hf)) peak at about 2.7 Ga, and abundant inherited zircons occur with U-Pb ages in the range of 2044 to 2803 Ma. Evidences from zircon U-Pb age and Hf isotope compositions, whole rock Nd isotopes and whole rock major and trace elements suggest a metasedimentary protolith, and that the garnet-bearing granite (leucogranite) was derived by partial melting in a thickened crust at about 1.93 Ga. The gneissic granodiorite and charnockites show indistinguishable major and trace element features, as well as zircon Hf and whole rock Nd isotope compositions, indicating that they were generated from the same source rocks. The gneissic granodiorite and charnockites are ferroan, calc-alkalic and metaluminous with A/CNK range from 0.80 to 0.98. They display relatively low SiO2 contents and Ga/Al ratios, suggesting their A-type affinity. Their zircon TDMC(Hf) age-peak is 2.9 Ga and whole rock TDM2(Nd) ages range from 2.8 to 2.9 Ga. These high temperature rocks were generated possibly through the partial melting of ancient amphibolites (2

  11. Hf isotope study of Palaeozoic metaigneous rocks of La pampa province and implications for the occurrence of juvenile early Neoproterozoic (Tonian) magmatism in south-central Argentina

    Science.gov (United States)

    Chernicoff, C. J.; Zappettini, E. O.; Santos, J. O. S.; Belousova, E.; McNaughton, N. J.

    2011-12-01

    On a global scale, juvenile Tonian (Early Neoproterozoic) magmatic rocks are associated with the extensional events that lead to the breakup of the Rodinia supercontinent. In Argentina, no geological record is available for this time interval, lasting from 1000 to 850 Ma. We present indirect evidence for the existence of Tonian extension in Argentina, as supported by Hf and Nd isotope determinations on Phanerozoic magmatic and sedimentary rocks. We mainly focus on our own Hf isotope determinations carried out on U-Pb SHRIMP dated zircons from Palaeozoic metaigneous rocks of La Pampa province, south-central Argentina, i.e. metagabbros of Valle Daza, dioritic orthogneiss of Estancia Lote 8, and metadiorite of Estancia El Carancho, having found that these rocks were derived from sources of ca. 920 to ca 880 Ma, with ɛHf values between +6.83 and + 9.59. Inherited zircons of this age and character identified in these rocks also point to the same source. We also compile additional Hf and Nd studies from previous work on Phanerozoic magmatic and sedimentary rocks. We preliminarily compare the age of the juvenile Tonian sources referred to in our work with that of two extensional events identified in the São Francisco craton, Brazil.

  12. Stable Carbon Isotope Ratios of Phenolic Compounds in Secondary Particulate Organic Matter Formed by Photooxidation of Toluene

    CERN Document Server

    Irei, Satoshi; Huang, Lin; Auld, Janeen; Collin, Fabrice; Hastie, Donald

    2014-01-01

    Compound-specific stable carbon isotope ratios for phenolic compounds in secondary particulate organic matter (POM) formed by photooxidation of toluene were studied. Secondary POM generated by photooxidation of toluene using a continuous-flow reactor and an 8 cubic meter indoor smog chamber was collected, and then extracted with acetonitrile. Eight phenolic compounds were identified in the extracts by a gas chromatograph coupled with a mass spectrometer, and their compound-specific stable carbon isotope ratios were determined by a gas chromatograph coupled with a combustion furnace followed by an isotope ratio mass spectrometer. The majority of the products, including methylnitrophenols and methylnitrocatechols, were isotopically depleted by 5 to 6 permil compared to the initial isotope ratio for toluene, whereas the isotope ratio for 4_nitrophenol remained the same as the initial isotope ratio for toluene. Based on the reaction mechanisms postulated in literature, stable carbon isotope ratios of these produc...

  13. Accuracy of delta 18O isotope ratio measurements on the same sample by continuous-flow isotope-ratio mass spectrometry

    Science.gov (United States)

    The doubly labeled water method is considered the reference method to measure energy expenditure. Conventional mass spectrometry requires a separate aliquot of the same sample to be prepared and analyzed separately. With continuous-flow isotope-ratio mass spectrometry, the same sample could be analy...

  14. Coupled zircon Lu-Hf and U-Pb isotopic analyses of the oldest terrestrial crust, the >4.03 Ga Acasta Gneiss Complex

    Science.gov (United States)

    Bauer, Ann M.; Fisher, Christopher M.; Vervoort, Jeffrey D.; Bowring, Samuel A.

    2017-01-01

    The Acasta Gneiss Complex of the Northwest Territories, Canada, contains some of the earliest terrestrial continental crust and thus provides a critical sample set for characterization of crust-forming processes on the early Earth. Here we report the results of a combined Lu-Hf and U-Pb isotopic study of zircons from predominantly felsic orthogneisses from the Acasta Gneiss Complex that crystallized between ∼4.0 and 2.9 Ga, many of which contain complex zoning and therefore require an analytical treatment suited to distinguish amongst compositionally distinct age and Hf isotopic domains. To ensure the reliability of the analyses and of subsequent geologic interpretations, we employed the laser ablation split-stream (LASS) technique to concurrently measure the Lu-Hf and U-Pb isotopic systems in zircon. Our results confirm prior findings of precursor Hadean crust (>4.0 Ga) in the source of these rocks and the continued involvement of this reservoir until ∼3.6 Ga. We present evidence for the input of relatively more juvenile material at ∼3.6 Ga, which we suggest corresponds to a fundamental change in the source of the magmas. This study extends the lower bound of the published Acasta Hf isotopic record from 3.6 Ga to 2.9 Ga and demonstrates that the ∼3.6 Ga-2.9 Ga interval is largely represented by reworking of relatively juvenile ∼3.6 Ga crust and the diminution of the >4.0 Ga crustal signal. Significantly, there is no evidence that rocks within the Acasta Gneiss Complex were derived from a strongly depleted mantle.

  15. Observations and sources of carbon and nitrogen isotope ratio variation of pentaerythritol tetranitrate (PETN).

    Science.gov (United States)

    Howa, John D; Lott, Michael J; Ehleringer, James R

    2014-11-01

    Isotope ratio analysis allows forensic investigators to discriminate materials that are chemically identical but differ in their isotope ratios. Here we focused on the discrimination of pentaerythritol tetranitrate (PETN), an explosive with military and civilian applications, using carbon (δ(13)C) and nitrogen (δ(15)N) isotope ratios. Our goal was to understand some of the factors influencing the isotope ratios of commercially manufactured PETN. PETN was isolated from bulk explosives using preparative HPLC, which reduced chemical and isotopic within-sample variability. We observed isotope ratio variation in a survey of 175 PETN samples from 22 manufacturing facilities, with δ(13)C values ranging from -49.7‰ to -28.0‰ and δ(15)N values ranging from -48.6‰ to +6.2‰. Both within-sample variability and variation of PETN within an explosive block were much smaller than between-sample variations. Isotopic ratios of PETN were shown to discriminate explosive blocks from the same manufacturer, whereas explosive component composition measurements by HPLC were not able to do so. Using samples collected from three industrial PETN manufacturers, we investigated the isotopic relationship between PETN and its reactants, pentaerythritol (PE) and nitric acid. Our observations showed that δ(13)C values of PETN were indistinguishable from that of the reactant pentaerythritol. Isotopic separation between nitric acid and PETN was consistent within each sampled manufacturer but differed among manufacturers, and was likely dependent upon reaction conditions. These data indicate that δ(13)C variation in PETN is dependent on δ(13)C variation of PE supplies, while δ(15)N variation in PETN is due to both nitric acid δ(15)N and reaction conditions. Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.

  16. Hf and Nd Isotope Evidence for Production of an Incompatible Trace Element Enriched Crustal Reservoir in Early Earth (Invited)

    Science.gov (United States)

    Brandon, A. D.; Debaille, V.; Lapen, T. J.

    2010-12-01

    The final significant stage of accretion of the Earth was likely a collision between proto-Earth and a Mars sized impactor that formed the Moon. This event is thought to have produced enough thermal energy to melt all or most of the Earth, with a consequent magma ocean (MO). During subsequent cooling, the Earth would have formed its protocrust and corresponding mantle lithosphere, consisting of solidified basalt-komatiitic melt, in combination with buoyant cumulates and late stage residual melts from the MO. Relative to the convecting mantle, portions of this protolithosphere are likely to have been enriched in incompatible trace elements (ITE) in sufficient quantities to contain a significant amount of the bulk Earth’s budget for rare earth elements, U, Th, and Hf. If the protolithosphere was negatively buoyant, it may have overturned at or near the final stages of MO crystallization and a significant portion of that material may have been transported into the deep mantle where it resided and remixed into the convecting mantle over Earth history [1,2]. If the protolithosphere remained positively buoyant, its crust would have likely begun to erode from surface processes, and subsequently recycled back into the mantle over time as sediment and altered crust, once a subduction mechanism arose. The Nd and Hf isotopic compositions of Earth’s earliest rocks support the idea that an early-formed ITE-enriched reservoir was produced. The maxima in 142Nd/144Nd for 3.85 to 3.64 Ga rocks from Isua, Greenland decreases from +20 ppm to +12 ppm relative to the present day mantle value, respectively [3]. This indicates mixing of an early-formed ITE enriched reservoir back into the convecting mantle. In addition, zircons from the 3.1 Ga Jack Hills conglomerate indicate that material with an enriched 176Lu/177Hf of ~0.02 and an age of 4.4 Ga or greater was present at the Earth’s surface over the first 2 Ga of Earth history, supporting the scenario of a positively buoyant

  17. Stable isotope ratio method for the characterisation of the poultry house environment.

    Science.gov (United States)

    Skipitytė, Raminta; Mašalaitė, Agnė; Garbaras, Andrius; Mickienė, Rūta; Ragažinskienė, Ona; Baliukonienė, Violeta; Bakutis, Bronius; Šiugždaitė, Jūratė; Petkevičius, Saulius; Maruška, Audrius Sigitas; Remeikis, Vidmantas

    2017-06-01

    Stable isotope analysis was applied to describe the poultry house environment. The poultry house indoor environment was selected for this study due to the relevant health problems in animals and their caretakers. Air quality parameters including temperature, relative humidity, airflow rate, NH3, CO2 and total suspended particles, as well as mean levels of total airborne bacteria and fungi count, were measured. Carbon isotope ratios ((13)C/(12)C) were obtained in size-segregated aerosol particles. The carbon ((13)C/(12)C) and nitrogen ((15)N/(14)N) isotope ratios were measured in feed, litter, scrapings from the ventilation system, feathers and eggs. Additionally, the distribution of δ(13)C and δ(15)N values in different tissues of the chicken was examined. The airborne bacteria and fungi extracted from the air filters collected from poultry farms were grown in the laboratory in media with known isotope values and measured for stable isotope ratios. Analysis of isotope fractionation between microorganisms and their media indicated the applicability of stable isotope analysis in bulk samples for the identification of source material. The analysed examples imply that stable isotope analysis can be used to examine the indoor environment along with its biology and ecology, and serve as an informative bioanalytical tool.

  18. Zinc Isotope Ratios as Indicators of Diet and Trophic Level in Arctic Marine Mammals.

    Science.gov (United States)

    Jaouen, Klervia; Szpak, Paul; Richards, Michael P

    2016-01-01

    Carbon and nitrogen stable isotope ratios of bone collagen are an established method for dietary reconstruction, but this method is limited by the protein preservation. Zinc (Zn) is found in bioapatite and the isotopic compositions of this element constitute a very promising dietary indicator. The extent of fractionation of Zn isotopes in marine environments, however, remains unknown. We report here on the measurement of zinc, carbon and nitrogen isotopes in 47 marine mammals from the archaeological site of Arvik in the Canadian Arctic. We undertook this study to test and demonstrate the utility of Zn isotopes in recent mammal bone minerals as a dietary indicator by comparing them to other isotopic dietary tracers. We found a correlation between δ66Zn values and trophic level for most species, with the exception of walruses, which may be caused by their large seasonal movements. δ6Zn values can therefore be used as a dietary indicator in marine ecosystems for both modern and recent mammals.

  19. Mare basalt genesis - Modeling trace elements and isotopic ratios

    Science.gov (United States)

    Binder, A. B.

    1985-11-01

    Various types of mare basalt data have been synthesized, leading to the production of an internally consistent model of the mare basalt source region and mare basalt genesis. The model accounts for the mineralogical, major oxide, compatible siderophile trace element, incompatible trace element, and isotopic characteristics of most of the mare basalt units and of all the pyroclastic glass units for which reliable data are available. Initial tests of the model show that it also reproduces the mineralogy and incompatible trace element characteristics of the complementary highland anorthosite suite of rocks and, in a general way, those of the lunar granite suite of rocks.

  20. Implications of the Nitrogen Isotope Ratio in Titan's Atmosphere for the Nitrogen Ratio in Ammonia in Comets

    Science.gov (United States)

    Mandt, K.; Mousis, O.

    2013-12-01

    The D/H ratio of water measured in solar system bodies has been established as a tool for determining the conditions under which bodies such as comets or icy moons formed. This ratio varies significantly and indicates complex thermal and chemical evolution of the solar nebula during solar system and planetary formation. Nitrogen isotope ratios also vary significantly, and in some but not all cases correlate to D/H ratios, but are poorly understood. Nitrogen in the solar nebula was primarily in the form of atomic and molecular nitrogen. The isotope ratio (14N/15N) of this reservoir is expected to be ~435 based on the ratio measured in Jupiter's atmosphere, because the atmosphere of Jupiter is made up of gas captured from the solar nebula (Owen et al., 2001). The terrestrial atmospheric ratio is 272, which is close to the ratio measured in the Earth's mantle. This may be the primordial ratio for nitrogen delivered to Earth depending on the amount of exchange between the atmosphere and the mantle and any atmospheric fractionation processes that may have influenced the ratio over time. Comets are a possible source of nitrogen in the Earth's atmosphere (Hutsmekers et al., 2009), although chondrites have also been suggested as a source (Marty, 2012). In the case of comets, nitrogen would have been essentially retained in the form of ammonia (Mousis et al., 2012), which is the most abundant form of nitrogen in comets. The nitrogen in Titan's atmosphere is expected to have originated as ammonia hydrates and converted to N2 early in Titan's history (Atreya et al., 1978). The nitrogen ratio in Titan's atmosphere is ~170, which is significantly enriched in the heavy isotope compared to the terrestrial value. We will discuss the evolution of the nitrogen ratio in Titan's atmosphere (Mandt et al., 2009), the limits of the primordial ratio in ammonia, and the implications for this ratio for the isotope ratio in ammonia in comets that should be measured by the ROSINA instrument

  1. The thermal history of char as disclosed by carbon isotope ratios

    DEFF Research Database (Denmark)

    Egsgaard, Helge; Ambus, Per; Ahrenfeldt, Jesper

    In laboratory experiments, biomass char was produced under controlled conditions using wood chips from French pinewood. Different char qualities were obtained by pyrolysing the biomass at similar heating rates with end-temperatures ranging from 250 to 1000 o C. The char was analysed by flash...... pyrolysis and isotope ratio mass spectrometry. The results demonstrate that the temperature history of the char is reflected in the fine variation of carbon isotopes. The compound classes responsible for the variation were identified. Key words: Isotope ratio, flash pyrolysis, hot gas cleaning...

  2. Effects of the ratio of O{sub 2}/Ar pressure on wettability and optical properties of HfO{sub 2} films before and after doping with Al

    Energy Technology Data Exchange (ETDEWEB)

    Lin, Su-Shia, E-mail: sushia@ncnu.edu.tw [Department of Applied Materials and Optoelectronic Engineering, National Chi Nan University, Puli, Nantou Hsien 54561, Taiwan, ROC (China); Liao, Chung-Sheng [Department of Electrical Engineering, National Chi Nan University, Puli, Nantou Hsien 54561, Taiwan, ROC (China)

    2016-09-01

    Highlights: • Al-doped HfO{sub 2} (HfO{sub 2}:Al) films had similar structure to HfO{sub 2} films. • Al compounds and HfO{sub 2} coexisted in HfO{sub 2}:Al films by XPS analysis. • Al dopant could change the hydrophobicity of HfO{sub 2} film into hydrophilicity. • HfO{sub 2}:Al films show a large transparent range from NIR to UV at high O{sub 2} pressure. - Abstract: HfO{sub 2} films were doped with Al (HfO{sub 2}:Al) by simultaneous RF magnetron sputtering of HfO{sub 2} and DC magnetron sputtering of Al. This method is characterized by its ability to independently control the Al content. According to XRD and XPS analyses, the HfO{sub 2}:Al film had a structure similar to that of HfO{sub 2} film, and most of the Al atoms were not in the HfO{sub 2} crystalline. A small amount of Al{sup 3+} dopant could transform the hydrophobicity of HfO{sub 2} films into hydrophilicity. Moreover, the hydrophilicity of the HfO{sub 2}:Al films improved as the ratio of O{sub 2}/Ar pressure increased. The nonlinear refractive indices of HfO{sub 2} and HfO{sub 2}:Al films deposited in a pure Ar or a mixed Ar–O{sub 2} atmosphere were measured by Moiré deflectometry, and were of the order of 10{sup –8} cm{sup 2} W{sup –1}. A lower surface roughness, higher optical transmission in the UV–vis–NIR region, and higher linear refractive index were obtained at a higher ratio of O{sub 2}/Ar pressure.

  3. Water isotopic ratios from a continuously melted ice core sample

    CERN Document Server

    Gkinis, V; Blunier, T; Bigler, M; Schüpbach, S; Kettner, E; Johnsen, S J

    2014-01-01

    A new technique for on-line high resolution isotopic analysis of liquid water, tailored for ice core studies is presented. We built an interface between a Wavelength Scanned Cavity Ring Down Spectrometer (WS-CRDS) purchased from Picarro Inc. and a Continuous Flow Analysis (CFA) system. The system offers the possibility to perform simultaneous water isotopic analysis of $\\delta^{18}$O and $\\delta$D on a continuous stream of liquid water as generated from a continuously melted ice rod. Injection of sub ${\\mu}$l amounts of liquid water is achieved by pumping sample through a fused silica capillary and instantaneously vaporizing it with 100% efficiency in a home made oven. A calibration procedure allows for proper reporting of the data on the VSMOW--SLAP scale. Application of spectral methods yields the combined uncertainty of the system at below 0.1 permil and 0.5 permil for $\\delta^{18}$O and $\\delta$D, respectively. This performance is comparable to that achieved with mass spectrometry. Dispersion of the sampl...

  4. Continuous-flow isotope ratio mass spectrometry method for carbon and hydrogen isotope measurements on atmospheric methane

    NARCIS (Netherlands)

    Brass, M.; Roeckmann, T.

    2010-01-01

    We describe a continuous-flow isotope ratio mass spectrometry (CF-IRMS) technique for high-precision δD and δ13C measurements of atmospheric methane on 40 mL air samples. CH4 is separated from other air components by utilizing purely physical processes based on temperature, time and mechanical valve

  5. Bayesian Integration of Isotope Ratios for Geographic Sourcing of Castor Beans

    Energy Technology Data Exchange (ETDEWEB)

    Webb-Robertson, Bobbie-Jo M.; Kreuzer, Helen W.; Hart, Garret L.; Ehleringer, James; West, Jason B.; Gill, Gary A.; Duckworth, Douglas C.

    2012-08-15

    Recent years have seen an increase in the forensic interest associated with the poison ricin, which is extracted from the seeds of the Ricinus communis plant. Both light element (C, N, O, and H) and strontium (Sr) isotope ratios have previously been used to associate organic material with geographic regions of origin. We present a Bayesian integration methodology that can more accurately predict the region of origin for a castor bean than individual models developed independently for light element stable isotopes or Sr isotope ratios. Our results demonstrate a clear improvement in the ability to correctly classify regions based on the integrated model with a class accuracy of 6 0 . 9 {+-} 2 . 1 % versus 5 5 . 9 {+-} 2 . 1 % and 4 0 . 2 {+-} 1 . 8 % for the light element and strontium (Sr) isotope ratios, respectively. In addition, we show graphically the strengths and weaknesses of each dataset in respect to class prediction and how the integration of these datasets strengthens the overall model.

  6. Isotope ratio analysis by HRGC-MS of monoterpene hydrocarbons from citrus essential oils.

    Science.gov (United States)

    Satake, Atsushi; Une, Akitoshi; Ueno, Takao; Ukeda, Hiroyuki; Sawamura, Masayoshi

    2003-03-01

    The isotope ratio of monoterpene hydrocarbons in citrus essential oils of different origins was measured by ordinary high-resolution gas chromatography-mass spectrometry (HRGC-MS). The isotope ratio (Ir) was determined by the ratio of the isotope peak intensity (m/z 137) to the molecular mass peak intensity (m/z 136) of the monoterpene hydrocarbons. The accuracy of Ir was examined by measuring monoterpene hydrocarbon standards and 13C-labeled compounds. The isotope fingerprints based on the values of monoterpene hydrocarbons from lemon, lime and yuzu essential oils were determined. These citrus essential oils were also discriminated by a principal component analysis of their Ir data. The characteristic vectors showed that alpha-terpinene, beta-pinene and beta-phellandrene were important components for distinguishing between the citrus species. It is suggested that this technique will be applicable to evaluate the quality, genuineness and origin of citrus fruits and their products.

  7. Investigating controls on boron isotope ratios in shallow marine carbonates

    Science.gov (United States)

    Zhang, Shuang; Henehan, Michael J.; Hull, Pincelli M.; Reid, R. Pamela; Hardisty, Dalton S.; Hood, Ashleigh v. S.; Planavsky, Noah J.

    2017-01-01

    The boron isotope-pH proxy has been widely used to reconstruct past ocean pH values. In both planktic foraminifera and corals, species-specific calibrations are required in order to reconstruct absolute values of pH, due to the prevalence of so-called vital effects - physiological modification of the primary environmental signals by the calcifying organisms. Shallow marine abiotic carbonate (e.g. ooids and cements) could conceivably avoid any such calibration requirement, and therefore provide a potentially useful archive for reconstructions in deep (pre-Cenozoic) time. However, shallow marine abiotic carbonates could also be affected by local shifts in pH caused by microbial photosynthesis and respiration, something that has up to now not been fully tested. In this study, we present boron isotope measurements from shallow modern marine carbonates, from the Bahama Bank and Belize to investigate the potential of using shallow water carbonates as pH archives, and to explore the role of microbial processes in driving nominally 'abiogenic' carbonate deposition. For Bahama bank samples, our boron-based pH estimates derived from a range of carbonate types (i.e. ooids, peloids, hardground cements, carbonate mud, stromatolitic micrite and calcified filament micrite) are higher than the estimated modern mean-annual seawater pH values for this region. Furthermore, the majority (73%) of our marine carbonate-based pH estimates fall out of the range of the estimated pre-industrial seawater pH values for this region. In shallow sediment cores, we did not observe a correlation between measured pore water pH and boron-derived pH estimates, suggesting boron isotope variability is a depositional rather than early diagenetic signal. For Belize reef cements, conversely, the pH estimates are lower than likely in situ seawater pH at the time of cement formation. This study indicates the potential for complications when using shallow marine non-skeletal carbonates as marine pH archives

  8. Nonlinear Conte-Zbilut-Federici (CZF Method of Computing LF/HF Ratio: A More Reliable Index of Changes in Heart Rate Variability

    Directory of Open Access Journals (Sweden)

    Vernon Bond Jr

    2016-09-01

    Full Text Available Objectives: Acupuncture treatments are safe and effective for a wide variety of diseases involving autonomic dysregulation. Heart rate variability (HRV is a noninvasive method for assessing sympathovagal balance. The low frequency/high frequency (LF/HF spectral power ratio is an index of sympathovagal influence on heart rate and of cardi

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

    Science.gov (United States)

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

    2009-10-15

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

  10. Sulphur isotope ratios in the Canyon Diablo metallic spheroids

    Science.gov (United States)

    McEwing, C. E.; Rees, C. E.; Thode, H. G.

    1983-09-01

    Nininger (1956) has discovered metallic spheroids in the soil surrounding Meteor Crater in Arizona. Nininger suggested that the spheroids condensed from the center of a homogeneous explosion-produced metallic vapor cloud. The present investigation is concerned with measurements of sulfur contents and delta S-34 values of metallic spheroids from the vicinity of Meteor Crater. It is found that the small metallic spheroids have lower sulfur contents and higher delta S-34 values than do the large spheroids. It is concluded that the observed isotopic patterns are unlikely to have arisen during desulfurization of the metallic liquid from which the spheroids were formed or during high temperature oxidation or the spheroids. The most likely process for the production of the observed delta S-34 values and sulfur contents is low temperature oxidation reactions experienced by the spheroids during their surface exposure following formation.

  11. D/H Isotope Ratio Measurements of Atmospheric Volatile Organic Compounds

    Science.gov (United States)

    Meisehen, Thomas; Bühler, Fred; Koppmann, Ralf; Krebsbach, Marc

    2015-04-01

    Analysis of isotope ratios in atmospheric volatile organic compounds (VOC) is a reliable method to allocate their sources, to estimate atmospheric residence times and investigate physical and chemical processes on various temporal and spatial scales. Most investigations yet focus on carbon isotope ratios. Certainly more detailed information can be gained by the ratio of deuterium (D) to hydrogen (H) in VOC, especially due to the high mass ratio. Combining measurements of carbon and hydrogen isotopes could lead to considerable improvement in our understanding of atmospheric processes. For this purpose we set up and thoroughly characterised a gas chromatograph pyrolysis isotope ratio mass spectrometer to measure the D/H ratio in atmospheric VOC. From a custom-made gas standard mixture VOC were adsorbed on Tenax®TA which has the advantage that CO2 is not preconcentrated when measuring ambient air samples. Our results show that the pyrolysis method has significant impact on the D/H ratios. A pyrolysis temperature of at least 1723 K and conditioning of the ceramic tube on a regular basis is essential to obtain reproducible D/H isotope ratios. For an independent comparison D/H ratios of the pure VOC used in the gas standard were determined using elemental analysis by Agroisolab (Jülich, Germany). Comparisons of 10 VOC show perfect agreement within the standard deviations of our measurements and the errors given by Agroisolab, e.g. for n-pentane, toluene, 4-methyl-2-pentanone and n-octane. A slight mean difference of 5.1 o was obtained for n-heptane while significant mean differences of 15.5 o and 20.3 o arose for 1,2,4-trimethylbenzene and isoprene, respectively. We further demonstrate the stability of our system and show that the sample preparation does not affect the isotope ratios. Moreover the applicability of our system to ambient air samples is demonstrated.

  12. Electron-ion temperature ratio estimations in the summer polar mesosphere when subject to HF radio wave heating

    Science.gov (United States)

    Pinedo, H.; La Hoz, C.; Havnes, O.; Rietveld, M.

    2014-10-01

    We have inferred the electron temperature enhancements above mesospheric altitudes under Polar Mesospheric Summer Echoes (PMSE) conditions when the ionosphere is exposed to artificial HF radio wave heating. The proposed method uses the dependence of the radar cross section on the electron-to-ion temperature ratio to infer the heating factor from incoherent scatter radar (ISR) power measurements above 90 km. Model heating temperatures match our ISR estimations between 90 and 130 km with 0.94 Pearson correlation index. The PMSE strength measured by the MORRO MST radar is about 50% weaker during the heater-on period when the modeled electron-to-ion mesospheric temperature is approximately 10 times greater than the unperturbed value. No PMSE weakening is found when the mesospheric temperature enhancement is by a factor of three or less. The PMSE weakening and its absence are consistent with the modeled mesospheric electron temperatures. This consistency supports to the proposed method for estimating mesospheric electron temperatures achieved by independent MST and ISR radar measurements.

  13. CCQM-K140: carbon stable isotope ratio delta values in honey

    Science.gov (United States)

    Dunn, P. J. H.; Goenaga-Infante, H.; Goren, A. C.; Şimşek, A.; Bilsel, M.; Ogrinc, N.; Armishaw, P.; Hai, L.

    2017-01-01

    As there can be small but measureable differences in isotope ratios between different sources of the same element/compound/material, isotope ratio measurements are applied in a number of different fields including archaeology, environmental science, geochemistry, forensic science and ecology. Isotope ratios for the light elements (H, C, N, O and S) are typically reported as δ-values which are isotope ratios expressed relative to an internationally agreed standard (this standard is the zero-point on the scale), although absolute isotope ratios which are traceable to the SI have also been reported. The IAWG has been granted a traceability exception for the use of arbitrary delta scales until SI traceability can be established at the required level of uncertainty but this goal is some years away. While the CCQM IAWG has previously organised several pilot studies on isotope ratio determination (CCQM-P75: Stable isotope delta values in methionine, 2006; CCQM-P105: Sr isotope ratios in wine, 2008; CCQM-K98: Pb isotope ratios in bronze with additional delta values in CCQM-P134, 2011), it has been a number of years since delta values of light elements have been considered and there has been no key comparison (KC). Therefore, the IAWG has included the need for a KC (CCQM-K140) based on an arbitrary delta scale in its program to support ongoing requirements to demonstrate core capabilities as well as specific claims of measurement capability (CMCs) in this area. The performance of all five of the CCQM-K140 participants was very good, illustrating their ability to obtain accurate results for carbon isotope ratios, within the calibration range afforded by internationally agreed reference materials (δ13CVPDB-LSVEC between ‑47.32 % and +535.3 %) with measurement uncertainties of between 0.08 and 0.28 %. This was despite the fact that no two participants used exactly the same approach in terms of instrumentation or data treatment. Main text To reach the main text of this

  14. Final report of the key comparison CCQM-K98: Pb isotope amount ratios in bronze

    Science.gov (United States)

    Vogl, Jochen; Yim, Yong-Hyeon; Lee, Kyoung-Seok; Goenaga-Infante, Heidi; Malinowskiy, Dmitriy; Ren, Tongxiang; Wang, Jun; Vocke, Robert D., Jr.; Murphy, Karen; Nonose, Naoko; Rienitz, Olaf; Noordmann, Janine; Näykki, Teemu; Sara-Aho, Timo; Ari, Betül; Cankur, Oktay

    2014-01-01

    Isotope amount ratios are proving useful in an ever increasing array of applications that range from studies unravelling transport processes, to pinpointing the provenance of specific samples as well as trace element quantification by using isotope dilution mass spectrometry (IDMS). These expanding applications encompass fields as diverse as archaeology, food chemistry, forensic science, geochemistry, medicine and metrology. However, to be effective tools, the isotope ratio data must be reliable and traceable to enable the comparability of measurement results. The importance of traceability and comparability in isotope ratio analysis has already been recognized by the Inorganic Analysis Working Group (IAWG) within the CCQM. While the requirements for isotope ratio accuracy and precision in the case of IDMS are generally quite modest, 'absolute' Pb isotope ratio measurements for geochemical applications as well as forensic provenance studies require Pb isotope ratio measurements of the highest quality. To support present and future CMCs on isotope ratio determinations, a key comparison was urgently needed and therefore initiated at the IAWG meeting in Paris in April 2011. The analytical task within such a comparison was decided to be the measurement of Pb isotope amount ratios in water and bronze. Measuring Pb isotope amount ratios in an aqueous Pb solution tested the ability of analysts to correct for any instrumental effects on the measured ratios, while the measurement of Pb isotope amount ratios in a metal matrix sample provided a real world test of the whole chemical and instrumental procedure. A suitable bronze material with a Pb mass fraction between 10 and 100 mg•kg-1 and a high purity solution of Pb with a mass fraction of approximately 100 mg•kg-1 was available at the pilot laboratory (BAM), both offering a natural-like Pb isotopic composition. The mandatory measurands, the isotope amount ratios n(206Pb)/n(204Pb), n(207Pb)/n(204Pb) and n(208Pb)/n(204Pb

  15. Recent developments in the use of isotope ratio mass spectrometry in sports drug testing.

    Science.gov (United States)

    Piper, Thomas; Emery, Caroline; Saugy, Martial

    2011-08-01

    According to the annual report of the World Anti-Doping Agency, steroids are the most frequently detected class of doping agents. Detecting the misuse of endogenously occurring steroids, i.e. steroids such as testosterone that are produced naturally by humans, is one of the most challenging issues in doping control analysis. The established thresholds for urinary concentrations or concentration ratios such as the testosterone/epitestosterone quotient are sometimes inconclusive owing to the large biological variation in these parameters.For more than 15 years, doping control laboratories focused on the carbon isotope ratios of endogenous steroids to distinguish between naturally elevated steroid profile parameters and illicit administration of steroids. A variety of different methods has been developed throughout the last decade and the number of different steroids under investigation by isotope ratio mass spectrometry has recently grown considerably. Besides norandrosterone, boldenone was found to occur endogenously in rare cases and the misuse of corticosteroids or epitestosterone can now be detected with the aid of carbon isotope ratios as well. In addition, steroids excreted as sulfoconjugates were investigated, and the first results regarding hydrogen isotope ratios recently became available.All of these will be presented in detail within this review together with some considerations on validation issues and on identification of parameters influencing steroidal isotope ratios in urine.

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

    Science.gov (United States)

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

    2012-11-01

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

  17. Isotopic ratios at z = 0.68 from molecular absorption lines toward B 0218+357

    Science.gov (United States)

    Wallström, S. H. J.; Muller, S.; Guélin, M.

    2016-11-01

    Isotopic ratios of heavy elements are a key signature of the nucleosynthesis processes in stellar interiors. The contribution of successive generations of stars to the metal enrichment of the Universe is imprinted on the evolution of isotopic ratios over time. We investigate the isotopic ratios of carbon, nitrogen, oxygen, and sulfur through millimeter molecular absorption lines arising in the z = 0.68 absorber toward the blazar B 0218+357. We find that these ratios differ from those observed in the Galactic interstellar medium, but are remarkably close to those in the only other source at intermediate redshift for which isotopic ratios have been measured to date, the z = 0.89 absorber in front of PKS 1830-211. The isotopic ratios in these two absorbers should reflect enrichment mostly from massive stars, and they are indeed close to the values observed toward local starburst galaxies. Our measurements set constraints on nucleosynthesis and chemical evolution models. The reduced spectra are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/595/A96

  18. A Plant-Based Proxy for the Oxygen Isotope Ratio of Atmospheric Water Vapor

    Science.gov (United States)

    Helliker, B.

    2007-12-01

    Atmospheric water vapor is a major component of the global hydrological cycle, but the isotopic balance of vapor is largely unknown. It is shown here that the oxygen isotope ratio of leaf water in the epiphytic Crassulacean acid metabolism (CAM) plant Tillandsia usneoides (Spanish Moss) is controlled by the oxygen isotope ratio of atmospheric water vapor in both field and lab studies. Assuming that the leaf-water isotopic signature (and hence the atmospheric water vapor signature) is recorded in plant organic material, the atmospheric water vapor oxygen isotope ratios for Miami, Florida (USA) were reconstructed for several years from 1878 to 2005 using contemporary and herbarium specimens. T. usneoides ranges from Virginia, USA southwards through the tropics to Argentina, and the CAM epiphytic lifeform is widespread in other species. Therefore, epiphytes may be used to reconstruct the isotope ratio of atmospheric water for spatial scales that span over 60° of latitude and temporal scales that cover the last century of global temperature increase.

  19. Carbon isotopic ratio analysis by gas chromatography/combustion/isotope ratio mass spectrometry for the detection of gamma-hydroxybutyric acid (GHB) administration to humans.

    Science.gov (United States)

    Saudan, Christophe; Augsburger, Marc; Mangin, Patrice; Saugy, Martial

    2007-01-01

    Since GHB (gamma-hydroxybutyric acid) is naturally produced in the human body, clinical and forensic toxicologists must be able to discriminate between endogenous levels and a concentration resulting from exposure. To suggest an alternative to the use of interpretative concentration cut-offs, the detection of exogenous GHB in urine specimens was investigated by means of gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). GHB was isolated from urinary matrix by successive purification on Oasis MCX and Bond Elute SAX solid-phase extraction (SPE) cartridges prior to high-performance liquid chromatography (HPLC) fractioning using an Atlantis dC18 column eluted with a mixture of formic acid and methanol. Subsequent intramolecular esterification of GHB leading to the formation of gamma-butyrolactone (GBL) was carried out to avoid introduction of additional carbon atoms for carbon isotopic ratio analysis. A precision of 0.3 per thousand was determined using this IRMS method for samples at GHB concentrations of 10 mg/L. The (13)C/(12)C ratios of GHB in samples of subjects exposed to the drug ranged from -32.1 to -42.1 per thousand, whereas the results obtained for samples containing GHB of endogenous origin at concentration levels less than 10 mg/L were in the range -23.5 to -27.0 per thousand. Therefore, these preliminary results show that a possible discrimination between endogenous and exogenous GHB can be made using carbon isotopic ratio analyses.

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

    Science.gov (United States)

    Coplen, Tyler B

    2011-09-15

    To minimize confusion in the expression of measurement results of stable isotope and gas-ratio measurements, recommendations based on publications of the Commission on Isotopic Abundances and Atomic Weights of the International Union of Pure and Applied Chemistry (IUPAC) are presented. Whenever feasible, entries are consistent with the Système International d'Unités, the SI (known in English as the International System of Units), and the third edition of the International Vocabulary of Basic and General Terms in Metrology (VIM, 3rd edition). The recommendations presented herein are approved by the Commission on Isotopic Abundances and Atomic Weights and are designed to clarify expression of quantities related to measurement of isotope and gas ratios to ensure that quantity equations instead of numerical value equations are used for quantity definitions. Examples of column headings consistent with quantity calculus (also called the algebra of quantities) and examples of various deprecated usages connected with the terms recommended are presented. Published in 2011 by John Wiley & Sons, Ltd.

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

    Science.gov (United States)

    Hatzinger, Paul B.; Böhlke, John Karl; Sturchio, Neil C.

    2013-01-01

    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.

  2. Development and application of liquid chromatography coupled to isotope ratio mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Lijun

    2014-02-19

    Stable isotope analysis has found widespread applications in various disciplines such as archaeology, geochemistry, biology, food authenticity, and forensic science. Coupling chromatography to isotope ratio mass spectrometry for compound-specific isotope analysis (CSIA) is a trend, as it provides several advantages over bulk isotope analysis, e.g., relatively simple sample preparation, the ability to measure individual compounds in a complex mixture in one run, and the reduced sample size required for precise isotope analysis. Gas chromatography coupled to isotope ratio mass spectrometry (GC/IRMS) has been well-established for compound-specific isotope analysis of volatile organic compounds within the last two decades. However, an interface combining liquid chromatography with isotope ratio mass spectrometry (LC/IRMS) was not commercially available until 2004. The current design of the interface requires using a carbon-free eluent in chromatographic separation. This requirement limits the application of the most frequently used reversed-phase liquid chromatography in CSIA, because the elution strength of water at room temperature is too low to serve as mobile phase in reversed-phase separations. In order to increase the elution strength of water, we propose using high temperature water for chromatographic elution. The polarity of water decreases with an increase of temperature, yielding increased elution strength in reversed-phase columns. Therefore, high temperature water can be used as eluent instead of organic solvent for combining reversed-phase liquid chromatography with isotope ratio mass spectrometry (RPLC/IRMS). Additionally, temperature gradients can replace organic solvent gradients to increase chromatographic resolution. This is very important for LC/IRMS analysis, as precise isotope analysis requires baseline separation of analytes. In this thesis, high-temperature reversed-phase liquid chromatography was coupled to, and for the first time carefully

  3. Invited review article: Recent developments in isotope-ratio mass spectrometry for geochemistry and cosmochemistry.

    Science.gov (United States)

    Ireland, Trevor R

    2013-01-01

    Mass spectrometry is fundamental to measurements of isotope ratios for applications in isotope geochemistry, geochronology, and cosmochemistry. Magnetic-sector mass spectrometers are most common because these provide the best precision in isotope ratio measurements. Where the highest precision is desired, chemical separation followed by mass spectrometric analysis is carried out with gas (noble gas and stable isotope mass spectrometry), liquid (inductively coupled plasma mass spectrometry), or solid (thermal ionization mass spectrometry) samples. Developments in in situ analysis, including ion microprobes and laser ablation inductively coupled plasma mass spectrometry, have opened up issues concerning homogeneity according to domain size, and allow ever smaller amounts of material to be analyzed. While mass spectrometry is built solidly on developments in the 20th century, there are new technologies that will push the limits in terms of precision, accuracy, and sample efficiency. Developments of new instruments based on time-of-flight mass spectrometers could open up the ultimate levels of sensitivity per sample atom.

  4. Timing and origin of migmatitic gneisses in south Karakoram: Insights from U-Pb, Hf and O isotopic record of zircons

    Science.gov (United States)

    Mahar, Munazzam Ali; Mahéo, Gweltaz; Goodell, Philip C.; Pavlis, Terry L.

    2016-04-01

    The timing and origin of partial melting in collision belts is crucial to understand the thermotectonic evolution and the relationship between HT metamorphism and magmatism in over-thickened crust. In the present study, we used the in-situ isotopic (Hf, O and U-Pb) record of zircons to investigate the timing and origin of migmatitic gneisses exposed in the core of the Dassu dome in south Karakoram. The new U-Pb zircon dating identified the Proterozoic inherited cores (1.8-1.9 Ga and 2.3-2.5 Ga) surrounded by a Neogene overgrowth with ages ranging from ∼6 to ∼20 Ma. These ages imply that the partial melting in the Karakoram Metamorphic Complex lasted from >20 Ma to ∼6 Ma and can be correlated with the Miocene magmatism in the adjacent Baltoro region. Oxygen isotopic data from Proterozoic inherited cores (1.8-1.9 Ga) and Neogene overgrowths are indistinguishable and generally vary from 8‰ to 9.5‰. These values are slightly higher than the most igneous zircons (6.5-8‰, Valley et al., 2005) indicating an igneous precursor with heavy initial O composition that later might have equilibrated with low temperature environment or some involvement of supracrustal material is likely. However, a few low U/Th, relatively old inherited cores (2.3-2.5 Ga) showed mantle-like (δ18O = 5.3 ± 0.6‰, Valley et al., 2005) values of δ18O = 5.5 ± 2.7‰. The present-day weighted mean εHf (0) of the Proterozoic inherited cores ranges from -50 ± 1.0 to -44.3 ± 1.2. In contrast, the Neogene rims are 15-20 ε-units higher than the inherited core with present-day εHf (0) = -30.6 ± 0.9. This implies that the Hf composition of the Neogene overgrowth is not controlled exclusively by the dissolution of the inherited cores and that contamination by external melts is likely. We suggest a contribution from the Neogene, less-evolved magmatism in the Baltoro region (εHf (0) = ∼-4 to -10). The elevated oxygen composition is not consistent with the contribution from pristine

  5. Atmospheric circulation controls on the inter-annual variability in precipitation isotope ratio in Japan

    Directory of Open Access Journals (Sweden)

    N. Kurita

    2014-10-01

    Full Text Available This study explored the primary driver of variations of precipitation isotopes at multiple temporal scales (event, seasonal and inter-annual scales to provide a greater depth of interpretation for isotope proxy records in Japan. A one-year record of the isotopic composition of event-based precipitation at Nagoya in central Japan showed less seasonal variation, but there is large isotopic variability on a storm-to-storm basis. In the summer, southerly flows transport isotopically enriched moisture from subtropical marine regions with the result that the rainfall produced by the subtropical air, or warm rainfall, was relatively enriched in heavy isotopes in comparison with the other rainfall events. In the winter, storm tracks are the dominant driver of storm-to-storm isotopic variation, and relatively lower isotopic values occurred when northerly winds in association with extratropical cyclones passing off the south coast of Japan (Nangan cyclone brings cold precipitation. Using the historical 17 year record of monthly isotopes in precipitation at Tokyo station, we explored if the factors controlling event-scale isotopic variability can account for inter-annual isotopic variability. The relatively higher isotopes in summer precipitation were attributed to the higher contribution of the warm rainfall to the total summer precipitation. On the other hand, year-to-year variation of isotopic values in winter precipitation was negatively correlated with the relative ratio of the Nangan cyclone rainfall to the total winter precipitation. The 17 year precipitation history demonstrates that event-scale isotopic variability related to changes in meridional moisture transport is the primary driver of inter-annual isotopic variability in winter and summer precipitation. The meridional moisture transport to central Japan is likely linked to the activity of the western North Pacific subtropical high in summer and the intensity of the East Asian winter monsoon

  6. Isotope ratio analysis of individual sub-micrometer plutonium particles with inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    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.

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

    NARCIS (Netherlands)

    Stellaard, F; Elzinga, H

    2005-01-01

    An overview is presented of biomedical applications of stable isotopes in general, but mainly focused on the activities of the Center for Liver, Digestive and Metabolic Diseases of the University Medical Center Groningen. The aims of metabolic studies in the areas of glucose, fat, cholesterol and

  8. Research Progress of Series of Uranium Isotope Ratios Measured by AMS

    Institute of Scientific and Technical Information of China (English)

    LIN; De-yu; WANG; Chen; HUANG; Guo-rui; DONG; Ke-jun; HE; Ming; RUAN; Xiang-dong; WU; Shao-yong; ZHAO; Yong-gang; LI; Li-li; DOU; Liang; XIE; Lin-bo; WANG; Xiao-bo; YANG; Xu-ran; WANG; Xiao-ming; LAN; Xiao-xi; JIANG; Shan

    2012-01-01

    <正>The nuclear safeguards system which is used to monitor compliance with the Nuclear Non-proliferation Treaty relies to a significant degree on the analysis of environmental samples. Undeclared nuclear activities can be detected through determination of the isotopic ratios of uranium and plutonium in such samples. It is necessary to be able to measure the full suite of uranium isotopes (234U,

  9. U-Pb ases and Hf isotopes for detrital zircons from quartzite in the Paleoproterozoic Songshan Group on the southwestern margin of the North China Craton

    Institute of Scientific and Technical Information of China (English)

    DIWU ChunRong; SUN Yong; YUAN HongLin; WANG HongLiang; ZHONG XingPing; LIU XiaoMing

    2008-01-01

    In situ U-Pb dating and Lu-Hf isotopic analysis were carried out for detrital zircons from quartzite in the Paleoproterozoic Songshan Group on the southern margin of the North China Craton (NCC). The re-sults provide further constraints on the crustal formation and evolution history of NCC. Four 207Pb/206Pb age populations were obtained from 99 analyses, with clusters at ~3.40 Ga, 2.77-2.80 Ga, ~2.50 Ga and 2.34 Ga, respectively. The 3.40 Ga old zircons have similar Hf isotopic compositions to those from Ar-chean rocks in the Jidong and Anshan areas of NCC. However, crustal remnants older than 3.6 Ga have been identified in the southern margin of NCC, the South China Craton, the northwestern part of the Qinling Orogen and its adjacent area. Thus, it is not easy to trace the source rock from which the 3.40 Ga detrital zircons were derived. It can be inferred that the crustal remnants older than 3.40 Ga might have been widely distributed in the North China Craton. The 2.77-2.80 Ga zircons make up a relatively small proportion and have the highest ε (t) values (up to 6.1±1.6), consistent with the Hf isotopic composition of the depleted mantle at 2.83 Ga. Their single-stage Hf model age of 2.83 Ga is close to their crystallized age, suggesting that their source rocks were extracted from the contemporaneous depleted mantle. The ~2.50 Ga zircon grains constitute about 85% of the total grain population and their Hf isotopic compositions indicate major growth of juvenile crust at ~2.50 Ga but minor reworking of ancient crust. The youngest zircon dated in this study gave an U-Pb age of 2337±23 Ma, which can be considered the maximum depositional age of the formation of the Songshan Group.

  10. Magmatism as a response to exhumation of the Priest River complex, northern Idaho: Constraints from zircon U-Pb geochronology and Hf isotopes

    Science.gov (United States)

    Stevens, L. M.; Baldwin, J. A.; Crowley, J. L.; Fisher, C. M.; Vervoort, J. D.

    2016-10-01

    Zircon and monazite U-Pb geochronology and zircon Hf isotopes place constraints on the temporal and source relationships between crustal anatexis, magmatism, and exhumation of the Priest River metamorphic core complex, northern Idaho. Granitoids that intruded the migmatitic, pelitic Hauser Lake gneiss include the pluton emplacement in the Priest River complex indicates that it was primarily a response to decompression rather than a cause. The mylonitized Silver Point and undeformed Wrencoe plutons bracket the end of a rapid phase of exhumation to c. 50-48 Ma. Zircon εHf(i) values and Lu-Hf isotope evolution indicate that the Silver Point and Wrencoe plutons crystallized from homogeneous magmas sourced from Archean-Proterozoic basement orthogneisses, whereas the Spokane granite and two leucocratic units appear to have been produced by partial melting of the Hauser Lake gneiss. Comparison of the Priest River complex with other deeply exhumed northern Cordilleran complexes indicates variability in the timing and, therefore, relative influences of partial melting and magmatism on the initiation of exhumation, which must be accounted for in numerical models of metamorphic core complex formation and evolution.

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

    Science.gov (United States)

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

    2011-01-01

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

  12. Stable isotope ratios and reforestation potential in Acacia koa populations on Hawai’i

    Directory of Open Access Journals (Sweden)

    Shaneka Lawson

    2014-01-01

    Full Text Available Stable carbon and nitrogen isotopes can be influenced by a multitude of factors including elevation, precipitation rate, season, and temperature. This work examined the variability in foliar stable carbon (δ13C and nitrogen (δ15N isotope ratios of koa (Acacia koa for 17 sites on Hawai’i Island delineated by elevation and precipitation gradients. Sites were identified and grouped with respect to mean annual precipitation (MAP, mean annual temperature (MAT and position along three elevation ranges. Analysis of the resultant δ13C and δ15N isotope ratios from multiple individuals at these sites indicated that certain sites showed a demonstrated correlation between carbon and/or nitrogen content, isotope ratios, precipitation, and elevation however many sites showed no correlation. We used publicly available temperature and moisture data to help eliminate confounding effects by climatic drivers and capture possible points of contention. At sites where the temperature, precipitation, and elevation data were not significantly different we compared stable isotope information to determine if additional variables could have contributed to the lack of more correlative data. Our results note several areas within the Waiakea Forest Reserve and Volcanoes National Park where, based on isotope results, reforestation efforts could be most successfully initiated.

  13. Platinum stable isotope ratio measurements by double-spike multiple collector ICPMS

    DEFF Research Database (Denmark)

    Creech, J.; Baker, J.; Handler, M.

    2013-01-01

    external element (Pb) doping to correct for instrumental mass bias and have identified relative Pt isotope differences of up to 10% from the reference values for this standard. The new isotopic composition of the IRMM-010 standard (Pt = 0.01289%, Pt = 0.7938%, Pt = 32.81%, Pt = 33.79%, Pt = 25.29% and Pt......We present a new technique for the precise determination of platinum (Pt) stable isotope ratios by multiple-collector inductively coupled plasma mass spectrometry (MC-ICPMS) using two different Pt double-spikes ( Pt-Pt and Pt-Pt). Results are expressed relative to the IRMM-010 Pt isotope standard......) can be obtained on Pt stable isotope ratios with either double-spike. Elemental doping tests reveal that double-spike corrected Pt stable isotope ratios are insensitive to the presence of relatively high (up to 10%) levels of matrix elements, although the Pt-Pt double-spike is affected by an isobaric...

  14. Isothermal gas chromatography of short-lived Hf isotopes and element 104 in chlorinating, oxygen containing carrier gas

    Energy Technology Data Exchange (ETDEWEB)

    Jost, D.T.; Dressler, R.; Eichler, B.; Piguet, D.; Tuerler, A.; Gaeggeler, H.W.; Gaertner, M. [Paul Scherrer Inst. (PSI), Villigen (Switzerland); Grantz, M.; Huebener, S. [FZR (Germany); Buklanov, G.; Lebedev, V.; Timkhin, S.; Vedeneev, M.V.; Yakushev, A.; Zvara, I. [Joint Inst. for Nuclear Research, Dubna (Russian Federation)

    1997-09-01

    Based on thermodynamic state functions retention times of Hf and element 104 were calculated in the case of the simple adsorption of the tetrachlorides and the case of a complex adsorption involving a substitution process with oxygen in the chlorinating gas. Preliminary results for {sup 261}104 and Hf are shown. (author) 1 fig., 1 tab., 3 refs.

  15. Helium Isotopic Ratios of Core Samples from IODP Exp. 319 (NanTroSEIZE Stage 2)

    Science.gov (United States)

    Horiguchi, K.; Matsuda, J.; Wiersberg, T.; Shimo, Y.; Tamura, H.; Kumagai, H.; Suzuki, K.; Saito, S.; Kinoshita, M.; Araki, E.; Byrne, T.; McNeill, L. C.; Saffer, D.; Takahashi, K.; Eguchi, N. O.; Toczko, S.

    2009-12-01

    IODP Exp.319 of Nankai Trough Seismogenic Zone Drilling Program Stage 2 started at May 2009. Various advanced technologies including first riser-based scientific ocean drilling were carried out at this cruise. The Hole C0009A (Site C0009/ Hole A) recovered cutting and partly core samples from 703.9-1604 mbsf by riser-drilling. The core samples were collected between the depth of 1510.5 and 1593.9 mbsf. Here we report preliminary helium isotopic ratios of these cores. We collected three types of samples for our study: (1) gas of cores, (2) whole round cores (100 cc) and (3) small whole round cores (10 cc). The gas samples were taken immediately after the core recovery. The gas samples were collected from each core section by using a syringe, and it was transferred to the glass bottle using the water displacement method. The glass bottle was made by Pyrex glass with vacuum valve at each end. We collected two sizes of whole round core samples (100 cc and 10 cc) The 100 cc cores were collected from the bottom and top sections of coring. The 10 cc cores were taken from the other sections. The outer parts of these samples were carefully removed to avoid contaminations from drilling fluid. After the removal of contamination, we immediately stored the 100 cc samples into vacuum container and 10 cc samples into plastic bag under a dry condition, respectively. The gas samples were measured for helium isotopic ratios. The noble gas measurement was carried out at Osaka University by using VG5400 mass spectrometer. We measured helium isotopic ratio and 4He/20Ne ratio. The latter is useful for making correction of the air contamination. The obtained result of helium isotopic ratios shows that the radiogenic helium is prominent in all samples. In addition, the helium isotope ratios show a trend that the ratio at shallower part is slightly higher than that at deeper part. It is conceivable that this trend is due to the larger radiogenic ingrowths at the deeper part. However, the

  16. Zircon and baddeleyite from the economic ultramafic-mafic Noril'sk-1 intrusion (Russia): Hf-isotope constraints on source composition

    Science.gov (United States)

    Malitch, K. N.; Belousova, E. A.; Badanina, I. Yu.; Griffin, W. L.

    2012-04-01

    of the Noril'sk-1 intrusion, which served as the favorable factor for accumulation of ores of unique scales and concentrations, To test this hypothesis, in situ Hf-isotope data were collected on the dated spots within single zircon grains. The analysis used a New Wave LUV213 laser-ablation microprobe attached to a Nu plasma MC-ICP-MS at GEMOC (Griffin et al. 2002). Hf-isotope results grouped on the basis of lithology show notable differences. Zircons from the unmineralized 'layered rock sequence' (e.g., olivine-free gabbro, olivine-bearing gabbro and olivine gabbro) are characterized by the most 'radiogenic' initial 176Hf/177Hf and some of ɛHf values close to those of the Depleted Mantle. Irrespective of zircon population most radiogenic Hf-isotope compositions are typical for olivine-free gabbro (mean ɛHf 7.3 ± 1.1 for sample N1-4), olivine-bearing gabbro (9.2 ± 3.8, sample N1-5) and olivine gabbro (8.3 ± 2.0, sample N1-6). In contrast, zircons from the leucogabbro that encloses the low-sulphide horizon (N1-3), and plagiowehrlite (N1-7) and taxitic-textured rocks (N1-8 and N1-9) with disseminated sulphide ores have less radiogenic Hf-isotope values (e.g., mean ɛHf6.2 ± 1.4, 5.9 ± 2.3, 6.4 ± 1.2 and 4.9±1.4, respectively). The least radiogenic values (ɛHffrom -2.9 to +2.3, mean ɛHf = 0.1 ± 1.9) are recorded in gabbro-diorite from the upper part of intrusion. The baddeleyite from olivine-free gabbro has the narrowest range of ɛHf values (e.g. 6.8-8.4), with a mean of ɛHfof 7.6 ± 0.8, closely matching that of zircon (mean ɛHf= 7.3 ± 1.1). Zircons from the leucogabbro that hosts the low-sulphide horizon (N1-3), and ultramafic and taxitic-textured lithologies with disseminated sulphide ores (N1-7, N1-8 and N1-9) have less radiogenic ɛHf values than those in barren lithologies. The Hf-isotope data for zircons from ore-bearing rocks thus suggest that the Noril'sk magmas represent mixing between a juvenile source equivalent to the Depleted Mantle and a

  17. Determination of the geographical origin of Chinese teas based on stable carbon and nitrogen isotope ratios

    Institute of Scientific and Technical Information of China (English)

    Long ZHANG; Jia-rong PAN; Cheng ZHU

    2012-01-01

    The objective of this study was to investigate the geographical origin of Chinese teas using carbon and nitrogen stable isotope ratio technology.The results showed that inter-provincial dispersion of teas in Guangdong (GD),Guangxi (GX),Hainan (HA),Fujian (F J),Shandong (SD),Sichuan (SC),Chongqing (CQ),and Henan (HN) provinces was high,while in Zhejiang (ZJ),Hubei (HB),Yunnan (YN),and Anhui (AH) provinces,it was low.Tea samples from GD,GX,HA,and FJ provinces were clustered in one group and separated from those from AH and HB provinces.Thus,carbon and nitrogen stable isotope ratio technology could discriminate teas from among some provinces of China,but not from among others.Better separation might be obtained with a combination of isotopic ratios and other indexes,such as elemental data and organic components.

  18. The puzzle of the CNO isotope ratios in asymptotic giant branch carbon stars

    Science.gov (United States)

    Abia, C.; Hedrosa, R. P.; Domínguez, I.; Straniero, O.

    2017-02-01

    Context. The abundance ratios of the main isotopes of carbon, nitrogen and oxygen are modified by the CNO-cycle in the stellar interiors. When the different dredge-up events mix the burning material with the envelope, valuable information on the nucleosynthesis and mixing processes can be extracted by measuring these isotope ratios. Aims: Previous determinations of the oxygen isotopic ratios in asymptotic giant branch (AGB) carbon stars were at odds with the existing theoretical predictions. We aim to redetermine the oxygen ratios in these stars using new spectral analysis tools and further develop discussions on the carbon and nitrogen isotopic ratios in order to elucidate this problem. Methods: Oxygen isotopic ratios were derived from spectra in the K-band in a sample of galactic AGB carbon stars of different spectral types and near solar metallicity. Synthetic spectra calculated in local thermodynamic equillibrium (LTE) with spherical carbon-rich atmosphere models and updated molecular line lists were used. The CNO isotope ratios derived in a homogeneous way, were compared with theoretical predictions for low-mass (1.5-3 M⊙) AGB stars computed with the FUNS code assuming extra mixing both during the RGB and AGB phases. Results: For most of the stars the 16O/17O/18O ratios derived are in good agreement with theoretical predictions confirming that, for AGB stars, are established using the values reached after the first dredge-up (FDU) according to the initial stellar mass. This fact, as far as the oxygen isotopic ratios are concerned, leaves little space for the operation of any extra mixing mechanism during the AGB phase. Nevertheless, for a few stars with large 16O/17O/18O, the operation of such a mechanism might be required, although their observed 12C/13C and 14N/15N ratios would be difficult to reconcile within this scenario. Furthermore, J-type stars tend to have lower 16O/17O ratios than the normal carbon stars, as already indicated in previous studies

  19. Application of neodymium isotope ratio measurements for the origin assessment of uranium ore concentrates.

    Science.gov (United States)

    Krajkó, Judit; Varga, Zsolt; Yalcintas, Ezgi; Wallenius, Maria; Mayer, Klaus

    2014-11-01

    A novel procedure has been developed for the measurement of (143)Nd/(144)Nd isotope ratio in various uranium-bearing materials, such as uranium ores and ore concentrates (UOC) in order to evaluate the usefulness and applicability of variations of (143)Nd/(144)Nd isotope ratio for provenance assessment in nuclear forensics. Neodymium was separated and pre-concentrated by extraction chromatography and then the isotope ratios were measured by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). The method was validated by the measurement of standard reference materials (La Jolla, JB-2 and BCR-2) and the applicability of the procedure was demonstrated by the analysis of uranium samples of world-wide origin. The investigated samples show distinct (143)Nd/(144)Nd ratio depending on the ore type, deposit age and Sm/Nd ratio. Together with other characteristics of the material in question, the Nd isotope ratio is a promising signature for nuclear forensics and suggests being indicative of the source material, the uranium ore.

  20. The puzzle of the CNO isotope ratios in AGB carbon stars

    CERN Document Server

    Abia, Carlos; Domínguez, Inma; Straniero, Oscar

    2016-01-01

    Previous determinations of the oxygen isotopic ratios in AGB carbon stars were at odds with the existing theoretical predictions. We aim to redetermine the oxygen ratios in these stars using new spectral analysis tools and further develop discussions on the carbon and nitrogen isotopic ratios in order to elucidate this problem. Oxygen isotopic ratios were derived from spectra in the K-band in a sample of galactic AGB carbon stars of different spectral types and near solar metallicity. Synthetic spectra calculated in LTE with spherical carbon-rich atmosphere models and updated molecular line lists were used. The CNO isotope ratios derived in a homogeneous way, were compared with theoretical predictions for low-mass (1.5-3 M_o) AGB stars computed with the FUNS code assuming extra mixing both during the RGB and AGB phases. For most of the stars the 16O/17O/18O ratios derived are in good agreement with theoretical predictions confirming that, for AGB stars, are established using the values reached after the FDU a...

  1. On the cross-sensitivity between water vapor mixing ratio and stable isotope measurements of in-situ analyzers

    KAUST Repository

    Parkes, Stephen

    2015-04-01

    In recent years there has been an increasing amount of water vapor stable isotope data collected using in-situ instrumentation. A number of papers have characterized the performance of these in-situ analyzers and suggested methods for calibrating raw measurements. The cross-sensitivity of the isotopic measurements on the mixing ratio has been shown to be a major uncertainty and a variety of techniques have been suggested to characterize this inaccuracy. However, most of these are based on relating isotopic ratios to water vapor mixing ratios from in-situ analyzers when the mixing ratio is varied and the isotopic composition kept constant. An additional correction for the span of the isotopic ratio scale is then applied by measuring different isotopic standards. Here we argue that the water vapor cross-sensitivity arises from different instrument responses (span and offset) of the parent H2O isotope and the heavier isotopes, rather than spectral overlap that could cause a true variation in the isotopic ratio with mixing ratio. This is especially relevant for commercial laser optical instruments where absorption lines are well resolved. Thus, the cross-sensitivity determined using more conventional techniques is dependent on the isotopic ratio of the standard used for the characterization, although errors are expected to be small. Consequently, the cross-sensitivity should be determined by characterizing the span and zero offset of each isotope mixing ratio. In fact, this technique makes the span correction for the isotopic ratio redundant. In this work we model the impact of changes in the span and offset of the heavy and light isotopes and illustrate the impact on the cross-sensitivity of the isotopic ratios on water vapor. This clearly shows the importance of determining the zero offset for the two isotopes. The cross-sensitivity of the isotopic ratios on water vapor is then characterized by determining the instrument response for the individual isotopes for a

  2. Isotope analytics for the evaluation of the feeding influence on the isotope ratio in beef samples; Isotopenanalytik zur Bestimmung des Einflusses der Ernaehrung auf die Isotopenzusammensetzung in Rinderproben

    Energy Technology Data Exchange (ETDEWEB)

    Herwig, Nadine

    2010-11-17

    Information about the origin of food and associated production systems has a high significance for food control. An extremely promising approach to obtain such information is the determination of isotope ratios of different elements. In this study the correlation of the isotope ratios C-13/C-12, N-15/N-14, Mg-25/Mg-24, and Sr-87/Sr-86 in bovine samples (milk and urine) and the corresponding isotope ratios in feed was investigated. It was shown that in the bovine samples all four isotope ratios correlate with the isotope composition of the feed. The isotope ratios of strontium and magnesium have the advantage that they directly reflect the isotope ratios of the ingested feed since there is no isotope fractionation in the bovine organism which is in contrast to the case of carbon and nitrogen isotope ratios. From the present feeding study it is evident, that a feed change leads to a significant change in the delta C-13 values in milk and urine within 10 days already. For the deltaN-15 values the feed change was only visible in the bovine urine after 49 days. Investigations of cows from two different regions (Berlin/Germany and Goestling/Austria) kept at different feeding regimes revealed no differences in the N-15/N-14 and Mg-26/Mg-24 isotope ratios. The strongest correlation between the isotope ratio of the bovine samples and the kind of ingested feed was observed for the carbon isotope ratio. With this ratio even smallest differences in the feed composition were traceable in the bovine samples. Since different regions usually coincide with different feeding regimes, carbon isotope ratios can be used to distinguish bovine samples from different regions if the delta C-13 values of the ingested feed are different. Furthermore, the determination of strontium isotope ratios revealed significant differences between bovine and feed samples of Berlin and Goestling due to the different geologic realities. Hence the carbon and strontium isotope ratios allow the best

  3. U-Pb zircon geochronology and Nd-Hf-O isotopic systematics of the Neoproterozoic Hadb adh Dayheen ring complex, Central Arabian Shield, Saudi Arabia

    Science.gov (United States)

    Ali, Kamal A.; Jeon, Heejin; Andresen, Arild; Li, Shuang-Qing; Harbi, Hesham M.; Hegner, Ernst

    2014-10-01

    A combined study of single zircon U-Pb dating, Hf-O zircon isotopic analyses and whole-rock Nd isotopic compositions was carried out to infer the magma sources of Neoproterozoic post-collisional A-type granitoids in Saudi Arabia. U-Pb zircon dating of magmatic zircons of two samples from the Hadb adh Dayheen ring complex yielded ages of 625 ± 11 Ma for a hornblende-biotite granite sample, and 613 ± 4 Ma for a monzogranite sample. The granitic rocks show initial εNd values of + 4.1 to + 5.3 and εHf of + 4.5 to + 8.4 that are lower than those of a model depleted mantle (εHf ~+ 14 and εNd ~+ 6.5) and consistent with melting of subduction-related crustal protoliths that were formed during the Neoproterozoic assembly of the Arabian-Nubian Shield (ANS). Crustal-model ages (Hf-tNC) of 0.81 to 1.1 Ga are inconsistent with depleted-mantle Nd model ages of 0.71 to 0.81 Ga and indicate that the post-collisional Hadb adh Dayheen granites were derived mostly from juvenile crust formed in Neoproterozoic time. Single zircons data show a wide range in δ18O values from + 3.2‰ to + 6.4‰, possibly indicating crystallization of zircon from magma derived from magmatic rocks altered by meteoric water in a magma chamber-caldera system.

  4. Evaluation strategies for isotope ratio measurements of single particles by LA-MC-ICPMS.

    Science.gov (United States)

    Kappel, S; Boulyga, S F; Dorta, L; Günther, D; Hattendorf, B; Koffler, D; Laaha, G; Leisch, F; Prohaska, T

    2013-03-01

    Data evaluation is a crucial step when it comes to the determination of accurate and precise isotope ratios computed from transient signals measured by multi-collector-inductively coupled plasma mass spectrometry (MC-ICPMS) coupled to, for example, laser ablation (LA). In the present study, the applicability of different data evaluation strategies (i.e. 'point-by-point', 'integration' and 'linear regression slope' method) for the computation of (235)U/(238)U isotope ratios measured in single particles by LA-MC-ICPMS was investigated. The analyzed uranium oxide particles (i.e. 9073-01-B, CRM U010 and NUSIMEP-7 test samples), having sizes down to the sub-micrometre range, are certified with respect to their (235)U/(238)U isotopic signature, which enabled evaluation of the applied strategies with respect to precision and accuracy. The different strategies were also compared with respect to their expanded uncertainties. Even though the 'point-by-point' method proved to be superior, the other methods are advantageous, as they take weighted signal intensities into account. For the first time, the use of a 'finite mixture model' is presented for the determination of an unknown number of different U isotopic compositions of single particles present on the same planchet. The model uses an algorithm that determines the number of isotopic signatures by attributing individual data points to computed clusters. The (235)U/(238)U isotope ratios are then determined by means of the slopes of linear regressions estimated for each cluster. The model was successfully applied for the accurate determination of different (235)U/(238)U isotope ratios of particles deposited on the NUSIMEP-7 test samples.

  5. SHRIMP U-Pb dating and Hf isotopic analyses of Middle Ordovician meta-cumulate gabbro in central Qiangtang, northern Tibetan Plateau

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    Metabasites consisting of metamorphic ultra-mafic rocks, cumulate gabbro, gabbro (diabase), basalt, and plagiogranite are exposed at the Taoxinghu area in central Qiangtang, northern Tibetan Plateau. Zircon SHRIMP U-Pb dating for the cumulate gabbro yields a weighted mean age of 467±4 Ma, which is the oldest and most reliable magmatic age in this area. Zircon 176Hf/177Hf ratios range from 0.282615 to 0.282657, with εHf(t) values of 5.02±0.28, indicating that the cumulate gabbro was mainly derived from the depleted mantle. In addition, geochemical data of metabasites suggest that they have similar characteristics to those in the mid-ocean ridge basalts (MORB). The Taoxinghu metabasites may represent the fragment of Early Paleozoic ophiolite in the "Central Uplift" of the Qiangtang, northern Tibetan Plateau.

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

    Science.gov (United States)

    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

  7. Mechanistic studies of sesquiterpene cyclases based on their carbon isotope ratios at natural abundance.

    Science.gov (United States)

    Tan, Wenhua; Bartram, Stefan; Boland, Wilhelm

    2017-01-03

    During the process of terpene biosynthesis, C-C bond breaking and forming steps are subjected to kinetic carbon isotope effects, leading to distinct carbon isotopic signatures of the products. Accordingly, carbon isotopic signatures could be used to reveal the 'biosynthetic history' of the produced terpenoids. Five known sesquiterpene cyclases, regulating three different pathways, representing simple to complex biosynthetic sequences, were heterologously expressed and used for in vitro assays with farnesyl diphosphate as substrate. Compound specific isotope ratio mass spectrometry measurements of the enzyme substrate farnesyl diphosphate (FDP) and the products of all the five cyclases were performed. The calculated δ(13) C value for FDP, based on δ(13) C values and relative amounts of the products, was identical with its measured δ(13) C value, confirming the reliability of the approach and the precision of measurements. The different carbon isotope ratios of the products reflect the complexity of their structure and are correlated with the frequency of carbon-carbon bond forming and breaking steps on their individual biosynthetic pathways. Thus, the analysis of carbon isotopic signatures of terpenes at natural abundance can be used as a powerful tool in elucidation of associated biosynthetic mechanisms of terpene synthases and in future in vivo studies even without 'touching' the plant. © 2017 John Wiley & Sons Ltd.

  8. Important role of magma mixing in generating the Mesozoic monzodioritic-granodioritic intrusions related to Cu mineralization, Tongling, East China: Evidence from petrological and in situ Sr-Hf isotopic data

    Science.gov (United States)

    Chen, C. J.; Chen, B.; Li, Z.; Wang, Z. Q.

    2016-04-01

    The Mesozoic ore-bearing high-Mg monzodioritic-granodioritic rocks in the Tongling mining district (East China) have been described as having adakitic affinities, and their origin has been attributed to partial melting of delaminated eclogite at depth in the mantle, followed by interaction of the resultant granitic magma with mantle peridotite. Here we present petrological data and in situ Sr isotopic data for zoned plagioclase that are inconsistent with the eclogite-derived model and instead propose a model that involves magma mixing of siliceous crustal melts and basaltic magma that was derived from metasomatized mantle in a back-arc extensional regime. The principal geochemical signatures of these Mesozoic rocks include a high-K calc-alkaline affinity, high values of Mg#, high Sr-Ba abundances, high Sr/Y and La/Yb ratios, εNd(t) = - 13.1 to - 9.0, and ISr = 0.70707-0.70824. The magma mixing model is supported by (1) the common existence of mafic microgranular enclaves (MMEs) and the disequilibrium textures of plagioclase and amphibole, (2) the 87Sr/86Sr ratios of embayed high-Ca cores of plagioclase that are distinctly lower than in the euhedral low-Ca overgrowth rims, (3) the negative correlations between whole-rock Nd and Sr isotopic ratios, and (4) the significant differences in the values of εHf(t) (- 9.5 to - 26) within different zircons from the same intrusion.

  9. Absolute Isotopic Abundance Ratios and the Accuracy of Δ47 Measurements

    Science.gov (United States)

    Daeron, M.; Blamart, D.; Peral, M.; Affek, H. P.

    2016-12-01

    Conversion from raw IRMS data to clumped isotope anomalies in CO2 (Δ47) relies on four external parameters: the (13C/12C) ratio of VPDB, the (17O/16O) and (18O/16O) ratios of VSMOW (or VPDB-CO2), and the slope of the triple oxygen isotope line (λ). Here we investigate the influence that these isotopic parameters exert on measured Δ47 values, using real-world data corresponding to 7 months of measurements; simulations based on randomly generated data; precise comparisons between water-equilibrated CO2 samples and between carbonate standards believed to share quasi-identical Δ47 values; reprocessing of two carbonate calibration data sets with different slopes of Δ47 versus T. Using different sets of isotopic parameters generally produces systematic offsets as large as 0.04 ‰ in final Δ47 values. What's more, even using a single set of isotopic parameters can produce intra- and inter-laboratory discrepancies in final Δ47 values, if some of these parameters are inaccurate. Depending on the isotopic compositions of the standards used for conversion to "absolute" values, these errors should correlate strongly with either δ13C or δ18O, or more weakly with both. Based on measurements of samples expected to display identical Δ47 values, such as 25°C water-equilibrated CO2 with different carbon and oxygen isotope compositions, or high-temperature standards ETH-1 and ETH-2, we conclude that the isotopic parameters used so far in most clumped isotope studies produces large, systematic errors controlled by the relative bulk isotopic compositions of samples and standards, which should be one of the key factors responsible for current inter-laboratory discrepancies. By contrast, the isotopic parameters of Brand et al. [2010] appear to yield accurate Δ47 values regardless of bulk isotopic composition. References:Brand, Assonov and Coplen [2010] http://dx.doi.org/10.1351/PAC-REP-09-01-05

  10. Laser Ablation Split Stream (LASS) U-Pb & Lu-Hf Isotope Analysis of Detrital Zircons from the Old Red Sandstone, NW Svalbard: Implications for Northern Caledonian Paleogeography

    Science.gov (United States)

    Beranek, L. P.; Gee, D. G.; Fisher, C. M.

    2015-12-01

    The Svalbard archipelago consists of three Caledonian provinces that were assembled by thrusting and transcurrent faulting during the Silurian and Devonian in a location directly northeast of the Greenland Caledonides. Syn- to post-orogenic alluvial strata, referred to as the Old Red Sandstones, filled pull-apart basins adjacent to the transcurrent faults and comprise cover assemblages that help constrain the timing of the Caledonian orogeny. To further investigate the tectonic history and paleogeography of the Raudfjorden-Liefdefjorden-Woodfjorden area of Spitsbergen, NW Svalbard, we analyzed rock samples of the Old Red Sandstones and underlying Precambrian basement complexes for detrital zircon analysis. Laboratory studies of the Old Red Sandstones include the novel Laser Ablation Split Stream (LASS) technique, which allows for simultaneous U-Pb & Lu-Hf isotope analysis of zircon crystals. Lower Devonian Red Bay Group strata contain a range of early Neoproterozoic to Neoarchean detrital zircons with prominent age peaks c. 960, 1050, 1370, 1450, 1650, and 2700 Ma; subordinate Ordovician (c. 460-490 Ma) and Cryogenian (c. 650 Ma) detrital zircons occur in a subset of the samples. Underlying Precambrian metasedimentary rocks are composed of similar earliest Neoproterozoic to Neoarchean age populations, which argues for much of the Red Bay Group to be derived from local basement rocks during thrusting and other faulting. The U-Pb ages and Hf isotope compositions of Paleozoic to Neoarchean detrital zircons are consistent with Arctic crustal evolution, and support the hypothesis that northwestern and northeastern provinces of the Svalbard Caledonides are extruded fragments of the northeast Greenland allochthons. The new Hf isotope results further allow paleogeographic and stratigraphic comparisons with rock assemblages proximal to the North Atlantic Caledonides during the Silurian-Devonian, including the Pearya terrane of Ellesmere Island, Alexander terrane of NW

  11. Novel Apparatus for the Real-Time Quantification of Dissolved Gas Concentrations and Isotope Ratios

    Science.gov (United States)

    Gupta, M.; Leen, J.; Baer, D. S.; Owano, T. G.; Liem, J.

    2013-12-01

    Measurements of dissolved gases and their isotopic composition are critical in studying a variety of phenomena, including underwater greenhouse gas generation, air-surface exchange, and pollution migration. These studies typically involve obtaining water samples from streams, lakes, or ocean water and transporting them to a laboratory, where they are degased. The gases obtained are then generally measured using gas chromatography and isotope ratio mass spectrometry for concentrations and isotope ratios, respectively. This conventional, off-line methodology is time consuming, significantly limits the number of the samples that can be measured and thus severely inhibits detailed spatial and temporal mapping of gas concentrations and isotope ratios. In this work, we describe the development of a new membrane-based degassing device that interfaces directly to Los Gatos Research (cavity enhanced laser absorption or Off-Axis ICOS) gas analyzers (cavity enhanced laser absorption or Off-Axis ICOS analyzers) to create an autonomous system that can continuously and quickly measure concentrations and isotope ratios of dissolved gases in real time in the field. By accurately controlling the water flow rate through the membrane degasser, gas pressure on the outside of the membrane, and water pressure on the inside of the membrane, the system is able to generate precise and highly reproducible results. Moreover, by accurately measuring the gas flow rates in and out of the degasser, the gas-phase concentrations (ppm) could be converted into dissolved gas concentrations (nM). We will present detailed laboratory test data that quantifies the linearity, precision, and dynamic range of the system for the concentrations and isotope ratios of dissolved methane, carbon dioxide, and nitrous oxide. By interfacing the degassing device to a novel cavity-enhanced spectrometer (developed by LGR), preliminary data will also be presented for dissolved volatile organics (VOC) and other

  12. Method for determination of stable carbon isotope ratio of methylnitrophenols in atmospheric PM

    Directory of Open Access Journals (Sweden)

    S. Moukhtar

    2011-05-01

    Full Text Available A technique for the measurement of the stable isotope ratio of methylnitrophenols in atmospheric particulate matter (PM is presented. It has been found in numerous laboratory studies that these compounds are photooxidation products of toluene in PM. Atmospheric samples from rural and suburban areas were collected for evaluation of the procedure. PM was collected on quartz fibre filters using dichotomous high volume air samplers for PM 2.5. Methylnitrophenols were extracted from the filters using acetonitrile. The sample was then purified using a combination of high-performance liquid chromatography (HPLC and solid phase extraction (SPE. The final solution was then divided into two aliquots. To one aliquot, a derivatising agent, Bis(trimethylsilyltrifluoroacetamide (BSTFA, was added to the solution for Gas Chromatography/Mass Spectroscopy (GC/MS analysis. The second half of the sample was stored at low temperature. When GC/MS analysis showed high enough concentrations the remaining sample was derivatized with BSTFA and analysed for stable isotope ratio using a Gas Chromatography/Isotope Ratio Mass Spectrometry (GC-IRMS.

    In all atmospheric PM samples analysed, 2-methyl-4-nitrophenol was found to be the most abundant methylnitrophenol. Nevertheless, due to low pollution levels occurring in the rural area, no samples had concentrations high enough to perform stable carbon isotope composition measurements of the methylnitrophenols. Samples collected in the suburban area could be analysed for carbon stable isotope ratio using GC-IRMS.

    The procedure described in this paper provides a very sensitive and selective method for the analysis of methylnitrophenols in atmospheric PM at concentrations as low as 1 pg m−3. For accurate (within ±0.5‰ stable isotope ratio analysis significantly higher concentrations in the range of 100 pg m−3 or more are required.

  13. Irradiated Xenon Isotopic Ratio Measurement for Failed Fuel Detection and Location in Fast Reactor

    Science.gov (United States)

    Ito, Chikara; Iguchi, Tetsuo; Harano, Hideki

    2009-08-01

    The accuracy of xenon isotopic ratio burn-up calculations used for failed fuel identification was evaluated by an irradiation test of xenon tag gas samples in the Joyo test reactor. The experiment was carried out using pressurized steel capsules containing unique blend ratios of stable xenon tag gases in an on-line creep rupture experiment in Joyo. The tag gas samples were irradiated to total neutron fluences of 1.6 to 4.8 × 1026 n/m2. Laser resonance ionization mass spectrometry was used to analyze the cover gas containing released tag gas diluted to isotopic ratios of 100 to 102 ppb. The isotopic ratios of xenon tag gases after irradiation were calculated using the ORIGEN2 code. The neutron cross sections of xenon nuclides were based on the JENDL-3.3 library. These cross sections were collapsed into one group using the neutron spectra of Joyo. The comparison of measured and calculated xenon isotopic ratios provided C/E values that ranged from 0.92 to 1.10. The differences between calculation and measurement were considered to be mainly due to the measurement errors and the xenon nuclide cross section uncertainties.

  14. Proportions of convective and stratiform precipitation revealed in water isotope ratios

    Science.gov (United States)

    Aggarwal, Pradeep K.; Romatschke, Ulrike; Araguas-Araguas, Luis; Belachew, Dagnachew; Longstaffe, Frederick J.; Berg, Peter; Schumacher, Courtney; Funk, Aaron

    2016-08-01

    Tropical and midlatitude precipitation is fundamentally of two types, spatially limited and high-intensity convective or widespread and lower-intensity stratiform, owing to differences in vertical air motions and microphysical processes governing rain formation. These processes are difficult to observe or model and precipitation partitioning into rain types is critical for understanding how the water cycle responds to changes in climate. Here, we combine two independent data sets--convective and stratiform precipitation fractions, derived from the Tropical Rainfall Measuring Mission satellite or synoptic cloud observations, and stable isotope and tritium compositions of surface precipitation, derived from a global network--to show that isotope ratios reflect rain type proportions and are negatively correlated with stratiform fractions. Condensation and riming associated with boundary layer moisture produces higher isotope ratios in convective rain, along with higher tritium when riming in deep convection occurs with entrained air at higher altitudes. On the basis of our data, stable isotope ratios can be used to monitor changes in the character of precipitation in response to periodic variability or changes in climate. Our results also provide observational constraints for an improved simulation of convection in climate models and a better understanding of isotope variations in proxy archives, such as speleothems and tropical ice.

  15. Tracing contamination sources in soils with Cu and Zn isotopic ratios.

    Science.gov (United States)

    Fekiacova, Z; Cornu, S; Pichat, S

    2015-06-01

    Copper (Cu) and zinc (Zn) are naturally present and ubiquitous in soils and are important micronutrients. Human activities contribute to the input of these metals to soils in different chemical forms, which can sometimes reach a toxic level for soil organisms and plants. Isotopic signatures could be used to trace sources of anthropogenic Cu and Zn pollution. The aim of this paper is to determine whether it is possible to identify (i) Cu and Zn contamination in soils and their sources, on the basis of their isotopic signatures, and (ii) situations that are a priori favorable or not for tracing Cu and Zn pollution using the isotopic approach. Therefore, we compiled data from the literature on Cu and Zn isotopes in soils, rocks and pollutants and added to this database the results of our own research. As only a few studies have dealt with agricultural contamination, we also studied a soil toposequence from Brittany, France, that experienced spreading of pig slurry for tens of years. In the surface horizons of the natural soils, the δ(65)Cu values vary from -0.15 to 0.44‰ and the δ(66)Zn from -0.03 to 0.43‰. Furthermore, vertical variations along soil profiles range from -0.95 to 0.44‰ for δ(65)Cu and from -0.53 to 0.64‰ for δ(66)Zn values. We concluded that pedogenetic processes can produce isotopic fractionation, yet, it is not always discernible and can be overprinted by an exogenous isotopic signature. Furthermore, some contaminants are enriched in heavy Cu or in light Zn compared to the rock or soil, but no generalization can be made. The anthropogenic inputs can be identified based on stable Cu and Zn isotope ratios if the isotope ratios of the sources are different from those of the soil, which needs to be tested for each individual case.

  16. A versatile method for stable carbon isotope analysis of carbohydrates by high-performance liquid chromatography/isotope ratio mass spectrometry

    NARCIS (Netherlands)

    Boschker, H.T.S.; Moerdijk-Poortvliet, T.C.W.; Van Breugel, P.; Houtekamer, M.J.; Middelburg, J.J.

    2008-01-01

    We have developed a method to analyze stable carbon isotope (13C/12C) ratios in a variety of carbohydrates using high-performance liquid chromatography/isotope ratio mass spectrometry (HPLC/IRMS). The chromatography is based on strong anion-exchange columns with low strength NaOH eluents. An eluent

  17. A versatile method for simultaneous stable carbon isotope analysis of DNA and RNA nucleotides by liquid chromatography/isotope ratio mass spectrometry

    NARCIS (Netherlands)

    Moerdijk-Poortvliet, T.C.W.; Brasser, J.; de Ruiter, G.; Houtekamer, M.; Bolhuis, H.; Stal, L.J.; Boschker, H.T.S.

    2014-01-01

    RATIONALE Liquid chromatography/isotope ratio mass spectrometry (LC/IRMS) is currently the most accurate and precise technique for the measurement of compound-specific stable carbon isotope ratios (13C/12C) in biological metabolites, at their natural abundance. However, until now this technique coul

  18. A versatile method for simultaneous stable carbon isotope analysis of DNA and RNA nucleotides by liquid chromatography/isotope ratio mass spectrometry

    NARCIS (Netherlands)

    Moerdijk-Poortvliet, T.C.W.; Brasser, J.; de Ruiter, G.; Houtekamer, M.; Bolhuis, H.; Stal, L.J.; Boschker, H.T.S.

    2014-01-01

    RATIONALELiquid chromatography/isotope ratio mass spectrometry (LC/IRMS) is currently the most accurate and precise technique for the measurement of compound-specific stable carbon isotope ratios (C-13/C-12) in biological metabolites, at their natural abundance. However, until now this technique cou

  19. Towards a better understanding of magnesium-isotope ratios from marine skeletal carbonates

    Science.gov (United States)

    Hippler, Dorothee; Buhl, Dieter; Witbaard, Rob; Richter, Detlev K.; Immenhauser, Adrian

    2009-10-01

    This study presents magnesium stable-isotope compositions of various biogenic carbonates of several marine calcifying organisms and an algae species, seawater samples collected from the western Dutch Wadden Sea, and reference materials. The aim of this study is to explore the influence of mineralogy, taxonomy and environmental factors (e.g., seawater isotopic composition, temperature, salinity) on magnesium-isotopic (δ 26Mg) ratios of skeletal carbonates. Using high-precision multi-collector inductively coupled plasma mass spectrometry, we observed that the magnesium-isotopic composition of seawater from the semi-enclosed Dutch Wadden Sea is identical to that of open marine seawater. We further found that a considerable component of the observed variability in δ 26Mg values of marine skeletal carbonates can be attributed to differences in mineralogy. Furthermore, magnesium-isotope fractionation is species-dependent, with all skeletal carbonates being isotopically lighter than seawater. While δ 26Mg values of skeletal aragonite and high-magnesium calcite of coralline red algae indicate the absence or negligibility of metabolic influences, the δ 26Mg values of echinoids, brachiopods and bivalves likely result from a taxon-specific level of control on Mg-isotope incorporation during biocalcification. Moreover, no resolvable salinity and temperature effect were observed for coralline red algae and echinoids. In contrast, Mg-isotope data of bivalves yield ambiguous results, which require further validation. The data presented here, point to a limited use of Mg isotopes as temperature proxy, but highlight the method's potential as tracer of seawater chemistry through Earth's history.

  20. Assessing connectivity of estuarine fishes based on stable isotope ratio analysis

    Science.gov (United States)

    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.

  1. Variation in strontium isotope ratios of archaeological fauna in the Midwestern United States: a preliminary study

    Science.gov (United States)

    Hedman, Kristin M.; Curry, B. Brandon; Johnson, Thomas M.; Fullagar, Paul D.; Emerson, Thomas E.

    2009-01-01

    Strontium isotope values (87Sr/86Sr) in bone and tooth enamel have been used increasingly to identify non-local individuals within prehistoric human populations worldwide. Archaeological research in the Midwestern United States has increasingly highlighted the role of population movement in affecting interregional cultural change. However, the comparatively low level of geologic variation in the Midwestern United States might suggest a corresponding low level of strontium variation, and calls into question the sensitivity of strontium isotopes to identify non-local individuals in this region. Using strontium isotopes of archaeological fauna, we explore the degree of variability in strontium ratios across this region. Our results demonstrate measurable variation in strontium ratios and indicate the potential of strontium analysis for addressing questions of origin and population movement in the Midwestern United States.

  2. Isotope ratio mass spectrometry as a tool for source inference in forensic science: A critical review.

    Science.gov (United States)

    Gentile, Natacha; Siegwolf, Rolf T W; Esseiva, Pierre; Doyle, Sean; Zollinger, Kurt; Delémont, Olivier

    2015-06-01

    Isotope ratio mass spectrometry (IRMS) has been used in numerous fields of forensic science in a source inference perspective. This review compiles the studies published on the application of isotope ratio mass spectrometry (IRMS) to the traditional fields of forensic science so far. It completes the review of Benson et al. [1] and synthesises the extent of knowledge already gathered in the following fields: illicit drugs, flammable liquids, human provenancing, microtraces, explosives and other specific materials (packaging tapes, safety matches, plastics, etc.). For each field, a discussion assesses the state of science and highlights the relevance of the information in a forensic context. Through the different discussions which mark out the review, the potential and limitations of IRMS, as well as the needs and challenges of future studies are emphasized. The paper elicits the various dimensions of the source which can be obtained from the isotope information and demonstrates the transversal nature of IRMS as a tool for source inference.

  3. Locally Grown, Natural Ingredients? The Isotope Ratio Can Reveal a Lot!

    Science.gov (United States)

    Rossier, Joël S; Maury, Valérie; Pfammatter, Elmar

    2016-01-01

    This communication gives an overview of selected isotope analyses applied to food authenticity assessment. Different isotope ratio detection technologies such as isotope ratio mass spectrometry (IRMS) and cavity ring down spectroscopy (CRDS) are briefly described. It will be explained how δ(18)O of water contained in fruits and vegetables can be used to assess their country of production. It will be explained why asparagus grown in Valais, in the centre of the Alps carries much less heavy water than asparagus grown closer to the sea coast. On the other hand, the use of δ(13)C can reveal whether a product is natural or adulterated. Applications including honey or sparkling wine adulteration detection will be briefly presented.

  4. Petrogenesis of Late Mesozoic granitoids and coeval mafic rocks from the Jiurui district in the Middle-Lower Yangtze metallogenic belt of Eastern China: Geochemical and Sr-Nd-Pb-Hf isotopic evidence

    Science.gov (United States)

    Xu, Yao-Ming; Jiang, Shao-Yong; Zhu, Zhi-Yong; Yang, Shui-Yuan; Zhou, Wei

    2014-03-01

    Large-scale Cu-Au mineralization is associated with the Late Mesozoic granitoids in the Jiurui district of the Middle-Lower Yangtze Mineralization Belt in Eastern China. To constrain the petrogenesis of these granitoids and coeval mafic rocks, a detailed geochemical and Sr-Nd-Pb-Hf isotopic study was performed. The Jiurui granitoids are made up primarily of granodiorite porphyry and quartz diorite porphyry. These granitoids are characterized by SiO2 and K2O contents of 58.8 wt.% to 68.6 wt.% and 1.9 wt.% to 5.7 wt.%, respectively. These granitoids show relatively high MgO contents (1.0 wt.% to 3.1 wt.%, average 2.1 wt.%) and high Mg# values (39 to 70, average 54). The Jiurui granitoids are enriched in light rare earth elements (LREE), large ion lithophile elements (LILE), and compatible trace elements (Cr, Ni and V) but are relatively depleted in Nb, Ta, Y and Yb. These rocks show a negligible negative Eu anomaly (Eu/Eu* = 0.76-1.13, average 0.91) and nearly no negative Sr anomaly. The whole-rock initial 87Sr/86Sr ratios range from 0.7060 to 0.7092, and the ɛNd(t) values vary from - 5.4 to - 2.0. The granitoids show radiogenic Pb isotopic ratios with values of 206Pb/204Pb (17.93-18.21), 207Pb/204Pb (15.55-15.58), and 208Pb/204Pb (38.16-38.56) for the plagioclases. The zircon Hf isotopic compositions show ɛHf(t) values from - 11.8 to 2.4. The coeval mafic rocks consist of lamprophyre, diabase and fine-grained mafic dyke. These rocks are characterized by SiO2 contents ranging from 47.6 wt.% to 54.8 wt.%, with a negative Eu anomaly and a positive to negative Sr anomaly. The whole-rock initial 87Sr/86Sr ratios range from 0.7059 to 0.7071, and the ɛNd(t) values vary from - 3.8 to - 1.4. By comparing the geochemical and isotopic compositions of the Jiurui granitoids and the coeval mafic rocks, we conclude that the granitoids are similar to adakites that were likely related to the delamination processes, and the coeval mafic rocks may have originated directly from

  5. Tracing contamination sources in soils with Cu and Zn isotopic ratios

    Energy Technology Data Exchange (ETDEWEB)

    Fekiacova, Z.; Cornu, S. [INRA, UR 1119 Géochimie des Sols et des Eaux, F-13100 Aix en Provence (France); Pichat, S. [Laboratoire de Géologie de Lyon (LGL-TPE), Ecole Normale Supérieure de Lyon, CNRS, UMR 5276, 69007 Lyon (France)

    2015-06-01

    Copper (Cu) and zinc (Zn) are naturally present and ubiquitous in soils and are important micronutrients. Human activities contribute to the input of these metals to soils in different chemical forms, which can sometimes reach a toxic level for soil organisms and plants. Isotopic signatures could be used to trace sources of anthropogenic Cu and Zn pollution. The aim of this paper is to determine whether it is possible to identify (i) Cu and Zn contamination in soils and their sources, on the basis of their isotopic signatures, and (ii) situations that are a priori favorable or not for tracing Cu and Zn pollution using the isotopic approach. Therefore, we compiled data from the literature on Cu and Zn isotopes in soils, rocks and pollutants and added to this database the results of our own research. As only a few studies have dealt with agricultural contamination, we also studied a soil toposequence from Brittany, France, that experienced spreading of pig slurry for tens of years. In the surface horizons of the natural soils, the δ{sup 65}Cu values vary from − 0.15 to 0.44‰ and the δ{sup 66}Zn from − 0.03 to 0.43‰. Furthermore, vertical variations along soil profiles range from − 0.95 to 0.44‰ for δ{sup 65}Cu and from − 0.53 to 0.64‰ for δ{sup 66}Zn values. We concluded that pedogenetic processes can produce isotopic fractionation, yet, it is not always discernible and can be overprinted by an exogenous isotopic signature. Furthermore, some contaminants are enriched in heavy Cu or in light Zn compared to the rock or soil, but no generalization can be made. The anthropogenic inputs can be identified based on stable Cu and Zn isotope ratios if the isotope ratios of the sources are different from those of the soil, which needs to be tested for each individual case. - Highlights: • Pedogenetic processes produce some Cu and Zn isotope fractionation. • Pollution with distinct isotopic signatures can be traced using Cu and Zn isotopes. • Tracing

  6. Detecting shifts in tropical moisture imbalances with satellite-derived isotope ratios in water vapor

    Science.gov (United States)

    Bailey, A.; Blossey, P. N.; Noone, D.; Nusbaumer, J.; Wood, R.

    2017-06-01

    As global temperatures rise, regional differences in evaporation (E) and precipitation (P) are likely to become more disparate, causing the drier E-dominated regions of the tropics to become drier and the wetter P-dominated regions to become wetter. Models suggest that such intensification of the water cycle should already be taking place; however, quantitatively verifying these changes is complicated by inherent difficulties in measuring E and P with sufficient spatial coverage and resolution. This paper presents a new metric for tracking changes in regional moisture imbalances (e.g., E-P) by defining δDq—the isotope ratio normalized to a reference water vapor concentration of 4 mmol mol-1—and evaluates its efficacy using both remote sensing retrievals and climate model simulations in the tropics. By normalizing the isotope ratio with respect to water vapor concentration, δDq isolates the portion of isotopic variability most closely associated with shifts between E- and P-dominated regimes. Composite differences in δDq between cold and warm phases of El Niño-Southern Oscillation (ENSO) verify that δDq effectively tracks changes in the hydrological cycle when large-scale convective reorganization takes place. Simulated δDq also demonstrates sensitivity to shorter-term variability in E-P at most tropical locations. Since the isotopic signal of E-P in free tropospheric water vapor transfers to the isotope ratios of precipitation, multidecadal observations of both water vapor and precipitation isotope ratios should provide key evidence of changes in regional moisture imbalances now and in the future.

  7. The magnetic properties of $^{\\rm 177}$Hf and $^{\\rm 180}$Hf in the strong coupling deformed model

    OpenAIRE

    Muto, S.; Stone, N. J.; Bingham, C. R.; STONE, J.R; Walker, P. M.; Audi, G.; Gaulard, C.; Köster, U.(Institut Laue-Langevin (ILL), Grenoble, France); Nikolov, J.; Nishimura,K; Ohtsubo, T.; Podolyak, Z.; Risegari, L.; Simpson, G.S.; Veskovic, M.

    2014-01-01

    This paper reports NMR measurements of the magnetic dipole moments of two high-K isomers, the 37/2$^-$, 51.4 m, 2740 keV state in $^{\\rm 177}$Hf and the 8$^-$, 5.5 h, 1142 keV state in $^{\\rm 180}$Hf by the method of on-line nuclear orientation. Also included are results on the angular distributions of gamma transitions in the decay of the $^{\\rm 177}$Hf isotope. These yield high precision E2/M1 multipole mixing ratios for transitions in bands built on the 23/2$^+$, 1.1 s, isomer at 1315 keV ...

  8. A supercritical oxidation system for the determination of carbon isotope ratios in marine dissolved organic carbon

    NARCIS (Netherlands)

    Le Clercq, Martijn; Van der Plicht, Johannes; Meijer, Harro A.J.

    1998-01-01

    An analytical oxidation system employing supercritical oxidation has been developed. It is designed to measure concentration and the natural carbon isotope ratios (C-13, C-14) Of dissolved organic carbon (DOC) and is especially suited for marine samples. The oxidation takes place in a ceramic tube a

  9. Lithologically inherited variation in Pb isotope ratios in sedimentary soils in The Netherlands

    NARCIS (Netherlands)

    Walraven, N.; Gaans, P.F.M. van; Veer, G. van der; Os, B.J.H. van; Klaver, G.T.; Vriend, S.P.; Middelburg, J.J.; Davies, G.R.

    2013-01-01

    Knowledge on the lithologically inherited variation in present day Pb isotope ratios in soils is remarkably limited. Such information is essential to determine the anthropogenic Pb fraction and anthropogenic Pb sources in Pb-polluted soils. This study presents results of a survey of subsoil samples

  10. Homogeneous diet of contemporary Japanese inferred from stable isotope ratios of hair

    Science.gov (United States)

    Kusaka, Soichiro; Ishimaru, Eriko; Hyodo, Fujio; Gakuhari, Takashi; Yoneda, Minoru; Yumoto, Takakazu; Tayasu, Ichiro

    2016-09-01

    The globalization of food production and distribution has homogenized human dietary patterns irrespective of geography, but it is uncertain how far this homogenization has progressed. This study investigated the carbon and nitrogen isotope ratios in the scalp hair of 1305 contemporary Japanese and found values of ‑19.4 ± 0.6‰ and 9.4 ± 0.6‰ (mean ± SD), respectively. Within Japan, the inter-regional differences for both isotope ratios was less than 1‰, which indicates low dietary heterogeneity among prefectural divisions. The carbon and nitrogen isotope ratios of the hair showed a significant correlation with the results of questionnaires on self-reported dietary habits. The carbon isotope ratios from Japan were lower than those in samples from the USA but higher than those in samples from Europe. These differences stem from the varying dietary proportions of food products originally derived from C3 and C4 plants. The dietary variation of Japan is as small as those of Europe and USA and smaller than those of some Asian countries. These results indicate that dietary homogeneity has progressed in Japan, which may indicate the influence from the spread of the Western-style diet and food globalization, although dietary heterogeneity among countries is still preserved.

  11. Stages of late Paleozoic to early Mesozoic magmatism in the Song Ma belt, NW Vietnam: evidence from zircon U-Pb geochronology and Hf isotope composition

    Science.gov (United States)

    Hieu, Pham Trung; Li, Shuang-Qing; Yu, Yang; Thanh, Ngo Xuan; Dung, Le Tien; Tu, Vu Le; Siebel, Wolfgang; Chen, Fukun

    2016-05-01

    The Song Ma zone in NW Vietnam bears important tectonic implications as a potential subduction corridor between the Indochina and South China blocks. On the basis of U-Pb ages, the Hf isotopic characteristics of zircons and the geochemical composition of granitoids, a two-stage magmatic evolution process of the Song Ma zone at ~290-260 and ~245-230 Ma can be proposed. Isotopic analyses indicate magmatic contributions from Neoproterozoic oceanic island basalt, Proterozoic continental crust, and depleted mantle or juvenile lithosphere. By combining geochronological and geochemical data from the granitoid rocks, we suggest that the staged magmatic processes of Song Ma zone may be related to a long-lasting period of ocean subduction (ca. 290-260 Ma) and subsequent syn-/post-collisional evolution (ca. 245-230 Ma).

  12. Stable carbon isotope ratios and intrinsic water-use efficiency of Miocene fossil leaves compared to modern congeners

    Energy Technology Data Exchange (ETDEWEB)

    Marshall, J.D.; Zhang, J.; Rember, W.C.; Jennings, D.; Larson, P. (Univ. of Idaho, Moscow, ID (United States))

    1994-06-01

    Miocene fossil leaves of forest trees were extracted from the Clarkia, Idaho fossil beds and their stable carbon isotope ratios were analyzed. Fossils had higher lignin concentrations and lower cellulose concentrations that modern leaves due to diagenesis and the HF used to extract the fossils. Therefore, [delta][sup 13]C of extracted fossil lignin was compared to that of modern lignin. Fossil lignin [delta][sup 13]C was significantly different from that of congeneric modern leaves (paired t-test, P<0.0001), but was 1.9% less negative. Gymnosperms (Metasequoia, Taxodium) were less negative than angiosperms (e.g., Magnolia, Quercus, Acer, Persea), but no difference between evergreen and deciduous species was detected. Using published estimates of the concentration and [delta][sup 13]C of atmospheric CO[sub 2] during the Miocene was estimated the CO[sub 2] partial pressure gradient across the stomata (intrinsic water-use efficiency). Intrinsic water-use efficiency was at least 70% higher during this past [open quotes]greenhouse[close quotes] period than at present.

  13. Petrogenesis of the igneous Mucajaí AMG complex, northern Amazonian craton — Geochemical, U-Pb geochronological, and Nd-Hf-O isotopic constraints

    Science.gov (United States)

    Heinonen, A. P.; Fraga, L. M.; Rämö, O. T.; Dall'Agnol, R.; Mänttäri, I.; Andersen, T.

    2012-10-01

    The ca. 1525 Ma igneous Mucajaí anorthosite-monzonite-granite (AMG) complex in northern Brazil is a rare manifestation of Mesoproterozoic intraplate magmatism in the northern Amazonian Craton. The complex comprises a two-phase rapakivi granite batholith with subordinate quartz-fayalite monzonites and syenites and the closely associated Repartimento anorthosite. Zircon U-Pb (ID-TIMS) geochronology reveals that the anorthosite (1526 ± 2 Ma), monzonite (1526 ± 2 Ma), and the main-phase biotite-hornblende granite (1527 ± 2 Ma) of the complex intruded the Paleoproterozoic (~ 1.94 Ga) country rocks simultaneously at ~ 1526 Ma and that the more evolved biotite granite is marginally younger at 1519 ± 2 Ma. Intraplate magmatism in the Mucajaí region was relatively short-lived and lasted 12 million years (1529-1517 Ma) at maximum. The Nd (whole-rock, ID-TIMS; ɛNd from - 1.9 to - 2.8), Hf (zircon, LAM-ICP-MS; ɛHf from - 2.0 to - 3.1), and O (zircon, SIMS; δ18O from 6.1 to 7.0‰) isotopic compositions of the studied rocks are fairly uniform but still reveal a small degree of isotopic heterogeneity in the Paleoproterozoic crust enclosing the complex. The small isotopic differences observed in the two types of rapakivi granites (biotite-hornblende granite and biotite granite) may result either from an isotopically heterogeneous lower crustal source or, more likely, from contamination of the granitic magma derived from a lower crustal source during prolonged residence at upper crustal levels.

  14. Archean crustal evolution in the Southern São Francisco craton, Brazil: Constraints from U-Pb, Lu-Hf and O isotope analyses

    Science.gov (United States)

    Albert, Capucine; Farina, Federico; Lana, Cristiano; Stevens, Gary; Storey, Craig; Gerdes, Axel; Dopico, Carmen Martínez

    2016-12-01

    In this study we present U-Pb and Hf isotope data combined with O isotopes in zircon from Neoarchean granitoids and gneisses of the southern São Francisco craton in Brazil. The basement rocks record three distinct magmatic events: Rio das Velhas I (2920-2850 Ma), Rio das Velhas II (2800-2760 Ma) and Mamona (2750-2680 Ma). The three sampled metamorphic complexes (Bação, Bonfim and Belo Horizonte) have distinct εHf vs. time arrays, indicating that they grew as separate terranes. Paleoarchean crust is identified as a source which has been incorporated into younger magmatic rocks via melting and mixing with younger juvenile material, assimilation and/or source contamination processes. The continental crust in the southern São Francisco craton underwent a change in magmatic composition from medium- to high-K granitoids in the latest stages, indicating a progressive HFSE enrichment of the sources that underwent anatexis in the different stages and possibly shallowing of the melting depth. Oxygen isotope data shows a secular trend towards high δ18O (up to 7.79‰) indicating the involvement of metasediments in the petrogenesis of the high potassium granitoids during the Mamona event. In addition, low δ18O values (down to 2.50‰) throughout the Meso- and Neoarchean emphasize the importance of meteoritic fluids in intra-crustal magmatism. We used hafnium isotope modelling from a compilation of detrital zircon compositions to constrain crustal growth rates and geodynamics from 3.50 to 2.65 Ga. The modelling points to a change in geodynamic process in the southern São Francisco craton at 2.9 Ga, from a regime dominated by net crustal growth in the Paleoarchean to a Neoarchean regime marked by crustal reworking. The reworking processes account for the wide variety of granitoid magmatism and are attributed to the onset of continental collision.

  15. Simulating stable carbon and chlorine isotope ratios in dissolved chlorinated groundwater pollutants with BIOCHLOR-ISO

    Science.gov (United States)

    Höhener, Patrick

    2016-12-01

    BIOCHLOR is a well-known simple tool for evaluating the transport of dissolved chlorinated solvents in groundwater, ideal for rapid screening and teaching. This work extends the BIOCHLOR model for the calculation of stable isotope ratios of carbon and chlorine isotopes in chloroethenes. An exact solution for the three-dimensional reactive transport of a chain of degrading compounds including sorption is provided in a spreadsheet and applied for modeling the transport of individual isotopes 12C, 13C, 35Cl, 37Cl from a constant source. The model can consider secondary isotope effects that can occur in the breaking of Csbnd Cl bonds. The model is correctly reproducing results for δ13C and δ37Cl modeled by a previously published 1-D numerical model without secondary isotope effects, and is also reproducing results from a microcosm experiment with secondary chlorine isotope effects. Two applications of the model using field data from literature are further given and discussed. The new BIOCHLOR-ISO model is distributed as a spreadsheet (MS EXCEL) along with this publication.

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

    Science.gov (United States)

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

    2008-06-01

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

  17. On-line determination of oxygen isotope ratios of water or ice by mass spectrometry.

    Science.gov (United States)

    Leuenberger, M; Huber, C

    2002-09-15

    Oxygen isotope ratio determination on any of the water phases (water vapor, water, ice) is of great relevance in different research fields such as climate and paleoclimate studies, geological surveys, and hydrological studies. The conventional technique for oxygen isotope measurement involves equilibration with carbon dioxide gas for a given time with a subsequent isotope determination. The equilibration technique is available in different layouts, but all of them are rather time-consuming. Here we report a new on-line technique that processes water samples as well as ice samples. The same principal, CO2 hydration, is used but speeded up by (i) a direct injection and full dissolution of CO2 in the water, (ii) an increased isotope exchange temperature at 50 degrees C, and (iii) a rapid gas extraction by means of an air-permeable membrane into a continuous helium flux supplying the isotope ratio mass spectrometer with the sample gas. The precision is better than 0.1/1000 which is only slightly larger than with the conventional equilibration technique. This on-line technique allows analysis of 1 m of ice with a resolution of 1-3 cm, depending on the meltwater flux, within 1 h. Similarly, continuous and fast analysis can be performed for aqueous samples for hydrological, geological, and perhaps medical applications.

  18. Forensic utility of the carbon isotope ratio of PVC tape backings

    Science.gov (United States)

    Stern, L. A.; Thompson, A. H.; Mehltretter, A. H.; McLaskey, V.; Parish, A.; Aranda, R.

    2008-12-01

    Forensic interest in adhesive tapes with PVC-backings (polyvinyl chloride, electrical tapes) derives from their use in construction of improvised explosive devices, drug packaging and in a variety of other illicit activities. Due to the range of physical characteristics and chemical compositions of such tapes, traditional microscopic and chemical analysis of the tape backings and adhesives offer a high degree of discrimination between tapes from different manufacturers and products. To evaluate whether carbon isotope ratios may be able to increase discrimination of electrical tapes, particularly with regards to different tapes of the same product, we assessed the PVC-backings of 87 rolls of black electrical tape for their δ13C values. The adhesive on these tapes was physically removed with hexane, and plasticizers within the PVC tape backings were removed by three-20 minute extractions with chloroform. The δ13C values of the PVC tape backings ranged between -23.8 and -41.5 (‰ V-PDB). The carbon isotopic variation within a product (identical brand and product identification) is significant, based on five products with at least 3 rolls (ranges of 7.4‰ (n=3), 10.0‰ (n=6), 4.2‰ (n=16), 3.8‰ (n=6), and 11.5‰ (n=8), respectively). There was no measurable carbon isotope variation in regards to the following: a) along the length of a roll (4 samples from 1 roll); b) between the center and edge of a strip of tape (1 pair); c) between rolls assumed to be from the same lot of tape (2 pairs); d) between different rolls from the same batch of tape (same product purchased at the same time and place; 5 pairs); and e) between samples of a tape at room temperature, heated to 50° C and 80° C for 1 week. For each sample within the population of 87 tapes, carbon isotopes alone exclude 80 to 100% of the tapes as a potential match, with an average exclusion power of 92.5%, using a window of ± 0.4‰. Carbon isotope variations originate from variations in starting

  19. Dietary heterogeneity among Western industrialized countries reflected in the stable isotope ratios of human hair.

    Directory of Open Access Journals (Sweden)

    Luciano O Valenzuela

    Full Text Available Although the globalization of food production is often assumed to result in a homogenization of consumption patterns with a convergence towards a Western style diet, the resources used to make global food products may still be locally produced (glocalization. Stable isotope ratios of human hair can quantify the extent to which residents of industrialized nations have converged on a standardized diet or whether there is persistent heterogeneity and glocalization among countries as a result of different dietary patterns and the use of local food products. Here we report isotopic differences among carbon, nitrogen and sulfur isotope ratios of human hair collected in thirteen Western European countries and in the USA. European hair samples had significantly lower δ(13C values (-22.7 to -18.3‰, and significantly higher δ(15N (7.8 to 10.3‰ and δ(34S (4.8 to 8.3‰ values than samples from the USA (δ(13C: -21.9 to -15.0‰, δ(15N: 6.7 to 9.9‰, δ(34S: -1.2 to 9.9‰. Within Europe, we detected differences in hair δ(13C and δ(34S values among countries and covariation of isotope ratios with latitude and longitude. This geographic structuring of isotopic data suggests heterogeneity in the food resources used by citizens of industrialized nations and supports the presence of different dietary patterns within Western Europe despite globalization trends. Here we showed the potential of stable isotope analysis as a population-wide tool for dietary screening, particularly as a complement of dietary surveys, that can provide additional information on assimilated macronutrients and independent verification of data obtained by those self-reporting instruments.

  20. Source and mode of the Permian Panjal Trap magmatism: Evidence from zircon U-Pb and Hf isotopes and trace element data from the Himalayan ultrahigh-pressure rocks

    Science.gov (United States)

    Rehman, Hafiz Ur; Lee, Hao-Yang; Chung, Sun-Lin; Khan, Tahseenullah; O'Brien, Patrick J.; Yamamoto, Hiroshi

    2016-09-01

    We present an integrated study of LA-ICP-MS U-Pb age, Hf isotopes, and trace element geochemistry of zircons from the Himalayan eclogites (mafic rocks) and their host gneisses (felsic rocks) from the Kaghan Valley in Pakistan in order to understand the source and mode of their magmatic protoliths and the effect of metamorphism. Zircons from the so-called Group I (high-pressure) eclogites yielded U-Pb mean ages of 259 ± 10 Ma (MSWD = 0.74), whereas those of Group II (ultrahigh-pressure) eclogites yielded 48 ± 3 Ma (MSWD = 0.71). In felsic gneisses the central or core domains of zircons yielded ages similar to those from Group I eclogites but zircon overgrowth domains yielded 47 ± 1 Ma (MSWD = 1.9). Trace element data suggest a magmatic origin for Group I-derived (having Th/U ratios: > 0.5) and metamorphic origin for Group II-derived (Th/U rocks (Panjal Traps) with almost no contribution from the ancient crustal material. The similar ƐHf(t) values, identical protolith ages and trace element compositions of zircons in felsic (granites or rhyolites) and mafic (basalt and dolerite) rocks attest to a bimodal magmatism accounting for the Panjal Traps during the Permian. Later, during India-Asia collision in Eocene times, both the felsic and mafic lithologies were subducted to mantle-depths (> 90 km: coesite-stable) and experienced ultrahigh-pressure metamorphism before their final exhumation.

  1. Early Earth differentiation processes investigated through the short-lived 146Sm-142Nd and 182Hf-182W isotope systems

    Science.gov (United States)

    Rizo Garza, H. L.; Walker, R. J.; Carlson, R.; Touboul, M.; Horan, M. F.; Puchtel, I. S.; Boyet, M.; Rosing, M. T.

    2016-12-01

    The earliest history of Earth is difficult to capture due to the scarcity and high degrees of alteration of ancient terrains. Nevertheless, short-lived isotope systems can provide important constraints on early geological processes. The 182Hf-182W (t1/2 = 8.9 Ma) and 146Sm-142Nd (t1/2=103 Ma) systems are variably sensitive to differentiation processes that occurred during the first 50 Ma and 500 Ma of Earth's history, respectively. Eoarchean mantle-derived rocks from the Isua supracrustal belt (southwest Greenland) show well-resolved anomalies in both 182W (+5 to +21 ppm) and 142Nd (-10 to +15 ppm) compared to terrestrial standards. While there is evidence that W was mobilized in the crust accessed by the Isua suite, W and Nd isotopic anomalies are interpreted to primarily reflect Hadean processes that affected the mantle precursors of these rocks. Variations in 142Nd do not correlate with those of 182W, however, suggesting different mechanisms for the origin and retention of the isotopic anomalies present in these two systems. The 142Nd data, combined with 143Nd data for the long-lived 147Sm-143Nd system, are interpreted to reflect silicate crystal-liquid fractionation 4.3 Ga ago. Variations of 182W in the Isua lavas mantle source could also have been produced as a result of Hf/W fractionation caused by silicate differentiation during the lifetime of 182Hf, but these processes would have to somehow be decoupled from the processes that affected Sm/Nd. Alternatively, 182W variability could be the result of combined early Hf/W fractionations caused by metal-silicate segregation within discrete mantle domains and late accretion processes. Variations in 182W and 142Nd observed in the Isua supracrustal rocks are similar to those observed in the ancient rocks from Nuvvuagittuq Greenstone Belt, the Acasta Gneiss Complex, and the Saglek Block, suggesting that similar processes affected diverse early Earth rocks.

  2. Bayesian integration of isotope ratio for geographic sourcing of castor beans.

    Science.gov (United States)

    Webb-Robertson, Bobbie-Jo; Kreuzer, Helen; Hart, Garret; Ehleringer, James; West, Jason; Gill, Gary; Duckworth, Douglas

    2012-01-01

    Recent years have seen an increase in the forensic interest associated with the poison ricin, which is extracted from the seeds of the Ricinus communis plant. Both light element (C, N, O, and H) and strontium (Sr) isotope ratios have previously been used to associate organic material with geographic regions of origin. We present a Bayesian integration methodology that can more accurately predict the region of origin for a castor bean than individual models developed independently for light element stable isotopes or Sr isotope ratios. Our results demonstrate a clear improvement in the ability to correctly classify regions based on the integrated model with a class accuracy of 60.9 ± 2.1% versus 55.9 ± 2.1% and 40.2 ± 1.8% for the light element and strontium (Sr) isotope ratios, respectively. In addition, we show graphically the strengths and weaknesses of each dataset in respect to class prediction and how the integration of these datasets strengthens the overall model.

  3. Bayesian Integration of Isotope Ratio for Geographic Sourcing of Castor Beans

    Directory of Open Access Journals (Sweden)

    Bobbie-Jo Webb-Robertson

    2012-01-01

    Full Text Available Recent years have seen an increase in the forensic interest associated with the poison ricin, which is extracted from the seeds of the Ricinus communis plant. Both light element (C, N, O, and H and strontium (Sr isotope ratios have previously been used to associate organic material with geographic regions of origin. We present a Bayesian integration methodology that can more accurately predict the region of origin for a castor bean than individual models developed independently for light element stable isotopes or Sr isotope ratios. Our results demonstrate a clear improvement in the ability to correctly classify regions based on the integrated model with a class accuracy of 60.9±2.1% versus 55.9±2.1% and 40.2±1.8% for the light element and strontium (Sr isotope ratios, respectively. In addition, we show graphically the strengths and weaknesses of each dataset in respect to class prediction and how the integration of these datasets strengthens the overall model.

  4. Tectono-magmatic evolution of the Chihuahua-Sinaloa border region in northern Mexico: Insights from zircon-apatite U-Pb geochronology, zircon Hf isotope composition and geochemistry of granodiorite intrusions

    Science.gov (United States)

    Mahar, Munazzam Ali; Goodell, Philip C.; Feinstein, Michael Nicholas

    2016-11-01

    We present the whole-rock geochemistry, LA-ICP-MS zircon-apatite U-Pb ages and zircon Hf isotope composition of the granodioritic plutons at the southwestern boundary of Chihuahua with the states of Sinaloa and Sonora. These granodiorites are exposed in the north and south of the Rio El Fuerte in southwest Chihuahua and northern Sinaloa. The magmatism spans over a time period of 37 Ma from 90 to 53 Ma. Zircons are exclusively magmatic with strong oscillatory zoning. No inheritance of any age has been observed. Our new U-Pb dating ( 250 analyses) does not support the involvement of older basement lithologies in the generation of the granitic magmas. The U-Pb apatite ages from granodiorites in southwest Chihuahua vary from 52 to 70 Ma. These apatite ages are 1 to 20 Ma younger than the corresponding zircon U-Pb crystallization ages, suggesting variable cooling rates from very fast to 15 °C/Ma ( 800 °C to 500 °C) and shallow to moderate emplacement depths. In contrast, U-Pb apatite ages from the Sinaloa batholith are restricted from 64 to 61 Ma and are indistinguishable from the zircon U-Pb ages range from 67 to 60 Ma within the error, indicating rapid cooling and very shallow emplacement. However, one sample from El Realito showed a larger difference of 20 Ma in zircon-apatite age pair: zircon 80 ± 0.8 Ma and apatite 60.6 ± 4 Ma, suggesting a slower cooling rate of 15 °C/Ma. The weighted mean initial εHf (t) isotope composition (2σ) of granodiorites varies from + 1.8 to + 5.2. The radiogenic Hf isotope composition coupled with previous Sr-Nd isotope data demonstrates a significant shift from multiple crustal sources in the Sonoran batholithic belt to the predominant contribution of the mantle-derived magmas in the southwest Chihuahua and northern Sinaloa. Based on U-Pb ages, the absence of inheritance, typical high Th/U ratio and radiogenic Hf isotope composition, we suggest that the Late Cretaceous-Paleogene magmatic rocks in this region are not derived from

  5. Stable isotope ratios and uric acid preservation in termites belonging to three feeding habits in Thailand.

    Science.gov (United States)

    Tayasu, I; Hyodo, F; Takematsu, Y; Sugimoto, A; Inoue, T; Kirtibutr, N; Abe, T

    2000-01-01

    Nitrogen and carbon stable isotope ratios and uric acid concentrations in termites sampled from a dry evergreen forest in Thailand, were determined across three kinds of feeding habits. Feeding habits of Microcerotermes crassus, which is an abundant wood-feeder, and Dicuspiditermes makhamensis, a common soil-feeding termite, were confirmed by isotopic signatures. Lichen feeding termites (Hospitalitermes birmanicus, H. bicolor and H. ataramensis) were characterized by low delta15N values, suggesting that they assimilated nitrogen deposited from the atmosphere. There was also a significant difference in uric acid concentrations between termites representing different feeding habits. No significant relationships were found between uric acid concentrations and delta15N or delta13C in Hospitalitermes. However, delta15N values were correlated with C/N ratios in H. birmanicus, except in one colony of H. ataramensis. delta13C values in both species were negatively correlated with C/N ratios.

  6. Determination of the Galaxy age by the method of uranium-thorium-plutonium isotopic ratios

    Science.gov (United States)

    Panov, I. V.; Lutostansky, Yu. S.; Eichler, M.; Thielemann, F.-K.

    2017-07-01

    The dependence of the Galaxy age ( T G), as determined by the method of uranium-thorium isotopic ratios, on the parameters of the nucleosynthesis model is studied within the theory of galactic nucleosynthesis. It is shown that TG depends strongly both on the scenario of the production of nuclei in the r-process and those features of neutron-rich nuclei that are used in the respective analysis and on galactic-nucleosynthesis parameters. The effect of a sudden nucleosynthesis spike before the formation of a solar system on the Galaxy age is evaluated. The region of admissible values of the parameters of galacticnucleosynthesis theory is discussed. The method of uranium-thorium isotopic ratios is supplemented with the 244Pu/238U ratio for yet another cosmochronometer pair, and the Galaxy age is estimated on the basis of the model modified in this way.

  7. Similar crustal evolution in the western units of the Adrar Souttouf Massif (Moroccan Sahara) and the Avalonian terranes: Insights from Hf isotope data

    Science.gov (United States)

    Gärtner, Andreas; Villeneuve, Michel; Linnemann, Ulf; Gerdes, Axel; Youbi, Nasrrddine; Hofmann, Mandy

    2016-06-01

    The Adrar Souttouf Massif is located at the western margin of the West African Craton and consists of several NNE-SSW trending units. Of them, the two westernmost have been interpreted to be linked with the Avalonian terrane assemblage and Meguma, respectively. New Hf isotopic data corroborates the Avalon correlation but has no impact one way or another on the possible Meguma connection, as there is no Hf data available from the latter. The obtained pattern of εHf(t) values vs. zircon age of the likely Avalonia related Oued Togba unit is similar to published data from Avalonia. Zircons of this unit show characteristic patterns of crustal mixing at 0.7 to 1.3 Ga and 1.75 to 2.25 Ga, while juvenile crust was likely formed around 0.6 to 0.75 Ga, from 1.2 to 2.2 Ga, and between 2.5 and 3.2 Ga. The zircons of the Sebkha Gezmayet unit reveal crustal mixing for the entire Palaeozoic and Neoproterozoic, from 2.05 to 2.11 Ga, and 2.8 to 2.9 Ga. Juvenile crust formation is interpreted to have occurred from 0.5 to 0.7 Ga, at around 2.1 Ga, and at ca. 2.9 Ga. As Mesoproterozoic zircons are abundant in the likely Avalonia-like Oued Togba unit, but uncommon at the West African Craton, their origin has to be found elsewhere. A comparison of available Hf data from Amazonia and Baltica, the two potential source cratons of Avalonia, shows similarities but is hampered by the lack of available data from Amazonia. Finally, a few grains from both units have Eoarchaean model ages. Among similar grains from other peri-Gondwanan terranes, they give indication of partial recycling of Eoarchaean crust in the vicinity of the northwestern West African Craton.

  8. Geospatial modeling of plant stable isotope ratios - the development of isoscapes

    Science.gov (United States)

    West, J. B.; Ehleringer, J. R.; Hurley, J. M.; Cerling, T. E.

    2007-12-01

    Large-scale spatial variation in stable isotope ratios can yield critical insights into the spatio-temporal dynamics of biogeochemical cycles, animal movements, and shifts in climate, as well as anthropogenic activities such as commerce, resource utilization, and forensic investigation. Interpreting these signals requires that we understand and model the variation. We report progress in our development of plant stable isotope ratio landscapes (isoscapes). Our approach utilizes a GIS, gridded datasets, a range of modeling approaches, and spatially distributed observations. We synthesize findings from four studies to illustrate the general utility of the approach, its ability to represent observed spatio-temporal variability in plant stable isotope ratios, and also outline some specific areas of uncertainty. We also address two basic, but critical questions central to our ability to model plant stable isotope ratios using this approach: 1. Do the continuous precipitation isotope ratio grids represent reasonable proxies for plant source water?, and 2. Do continuous climate grids (as is or modified) represent a reasonable proxy for the climate experienced by plants? Plant components modeled include leaf water, grape water (extracted from wine), bulk leaf material ( Cannabis sativa; marijuana), and seed oil ( Ricinus communis; castor bean). Our approaches to modeling the isotope ratios of these components varied from highly sophisticated process models to simple one-step fractionation models to regression approaches. The leaf water isosocapes were produced using steady-state models of enrichment and continuous grids of annual average precipitation isotope ratios and climate. These were compared to other modeling efforts, as well as a relatively sparse, but geographically distributed dataset from the literature. The latitudinal distributions and global averages compared favorably to other modeling efforts and the observational data compared well to model predictions

  9. Development of On-Line Direct Current Glow Discharge Source for Analysis of Isotope Ratio of Hydrogen

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    <正>The present research is focused on the analysis of isotope ratio of the hydrogen by measuring an intensity ratio of hydrogen/deuterium/tritium fluxes. The direct current glow discharge tube may provide a

  10. Crustal basement controls granitoid magmatism, and implications for generation of continental crust in subduction zones: A Sr-Nd-Hf-O isotopic study from the Paleozoic Tongbai orogen, central China

    Science.gov (United States)

    Wang, Hao; Wu, Yuan-Bao; Yang, Jin-Hui; Qin, Zheng-Wei; Duan, Rui-Chun; Zhou, Lian; Yang, Sai-Hong

    2017-06-01

    Ascertaining the petrogenesis of granitoid rocks in subduction zones holds the key for understanding the processes of how continental crust is produced. The synchronous Taoyuan and Huanggang plutons occur in two different geological units of the Paleozoic Tongbai orogen of central China. They provide an optimal opportunity for a study to address the role of the crustal basement in generating voluminous granitoid magmatism in subduction zones. The Taoyuan and Huanggang plutons have identical U-Pb zircon crystallization ages of 440-444 Ma, which are temporally related to northward subduction of the Paleotethyan Ocean. The Taoyuan samples show high SiO2 (73.36-79.16%) and low Al2O3 (12.00-13.45%) contents, Mg numbers (20.6-38.2), and Sr/Y (2.04-10.1) and (La/Yb)N (2.34-7.32) ratios with negative Eu anomalies (Eu/Eu* = 0.33-0.93). They yielded positive εNd(t) (+ 3.0 to + 6.7) and εHf(t) (+ 11.8 to + 13.2) values, elevated initial Sr isotopic ratios (0.7040-0.7057) and relatively low zircon δ18O values of 4.62-5.39‰. These suggest that they were produced through partial melting of hydrothermally altered lower crust of the accreted Erlangping oceanic arc. In contrast, the Huanggang samples exhibit variable whole-rock geochemical and isotopic compositions with SiO2 contents of 57.01-64.42 wt.%, initial Sr isotopic ratios of 0.7065-0.7078, and εNd(t) values of - 5.7 to - 9.4. Additionally, they have high zircon δ18O values of 7.57-8.45‰ and strongly negative zircon εHf(t) values of - 14.4 to - 10.5. They were suggested to have been mainly derived from ancient continental crust of the Kuanping crustal unit with the addition of 20-40% juvenile, mantle-derived material. Accordingly, the granitoids in both oceanic and continental arcs are likely to be mainly derived from intracrustal melting of their crustal basement. It is revealed by the Huanggang pluton that little net continental crust growth occurs in continental arcs, and addition of new volume of continental

  11. Emerging Techniques in Vegetable Oil Analysis Using Stable Isotope Ratio Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Kelly, S. D.; Rhodes, C.

    2002-07-01

    As the practice of vegetable oil adulteration becomes more sophisticated, the possibility to subvert detection using established techniques such as capillary gas chromatography is increasing. One of the most powerful techniques to be used in food authenticity studies is stable isotope ratio mass spectrometry (SIRMS) which utilises differences in the natural abundance of the stable isotopes of the light bio elements hydrogen, nitrogen, carbon, oxygen and sulfur to detect food fraud. SIRMS has found application in the authentication of a wide range of foodstuffs, including fruit juices, wines, spirits, honey and to detect the adulteration of flavour compounds with synthetic analogues. This papers reviews the current state-of-the-art for the authentication of vegetable oils using SIRMS and highlights emergent techniques such as compound-an position specific-isotope mass spectrometry. These latter developments offer the potential to provide more rapid and improved detection of the economic adulteration of vegetable oils. (Author) 38 refs.

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

    Science.gov (United States)

    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. Paleozoic magmatism and metamorphism in the Central Tianshan block revealed by U-Pb and Lu-Hf isotope studies of detrital zircons from the South Tianshan belt, NW China

    Science.gov (United States)

    Zhang, Xiaoran; Zhao, Guochun; Eizenhöfer, Paul R.; Sun, Min; Han, Yigui; Hou, Wenzhu; Liu, Dongxing; Wang, Bo; Liu, Qian; Xu, Bing

    2015-09-01

    As a major Precambrian microcontinent in the southernmost Central Asian Orogenic Belt (CAOB), the Central Tianshan block (CTS) in the Chinese Tianshan is essential for understanding the final assembly of the southern CAOB. It experienced multistage Paleozoic magmatism and metamorphism, but the detailed processes are still controversial and far from being completely understood. This paper reports coupled U-Pb and Lu-Hf isotopic data of detrital zircons from late Paleozoic (meta-)sedimentary strata in the South Tianshan belt, which can provide new insight into deciphering the Paleozoic evolution of the eastern segment of the CTS block. Characterized by typical oscillatory zoning and high Th/U ratios (> 0.2), detrital zircons in the Permian sedimentary samples yield dominant age populations at ca. 505-490 Ma, 475-440 Ma, 430-400 Ma and 340-250 Ma, pinpointing the development of four episodes of magmatism in the eastern CTS block. Particularly, Ordovician-Silurian (475-440 Ma) zircons, possessing low negative εHf(t) values, predominate in sedimentary strata in and surrounding the CTS block, indicating that the 475-440 Ma magmatic rocks probably constitute the main body of the CTS block. The origin of this (early Paleozoic) episode of magmatism was most likely related to the southward subduction of the Junggar Ocean beneath the CTS block. Carboniferous-Triassic (340-250 Ma) zircons have dominantly positive εHf(t) values, probably derived from the post-collisional juvenile rocks in the CTS block. Combined with previous studies, our data suggest that the single source terrane for the sampled strata was the CTS block, which had been a topographic high providing substantial detritus to the surrounding areas at least since the Early Permian. In the metasedimentary sample, detrital zircons mostly show partially/fully recrystallized internal textures and low Th/U ratios (isotopes and Ti-in-zircon thermometer of metamorphic zircons in this study, as well as previous

  14. The Effect of Aerosol Formation on Stable Isotopes Ratio in Titan's Atmosphere

    Science.gov (United States)

    Gautier, Thomas; Trainer, Melissa G.; Sebree, Joshua; Wold, Allison; Stern, Jennifer

    2016-10-01

    The formation of large amounts of aerosol in Titan atmosphere induces a significant sink for carbon and nitrogen in the atmosphere. Due to the high complexity of the chemistry leading to aerosol formation, there may be isotopic fractionation along the formation pathways of the aerosol. So far several stable isotopes have been measured in Titan atmosphere including the 13C/12C, 15N/14N and D/H ratios for different gaseous species. However, the fractionation effect of the aerosol formation and its impact on atmospheric stable isotope ratios has yet to be fully understood. Two experimental studies were recently published on the stable carbon [1] and nitrogen [1,2] isotope fractionation during aerosol formation in N2-CH4 reactant mixture. To better constrain the fractionation effect of aerosol formation on the Titan atmosphere we have measured the isotopic fractionation induced in laboratory aerosol analogues produced exploring the space of parameters that are expected to have an effect on fractionation processes. Parameters studied include pressure and temperature of aerosol formation and the reactant gas phase composition, including the standard "Titan" mixture of CH4/N2 as well as other trace species such as benzene (C6H6).[1] Sebree, J.A., Stern, J.C., Mandt, K.E., Domagal-Goldman, S.D., and Trainer, M.G.: C and N Fractionation of CH /N Mixtures during Photochemical Aerosol Formation: Relevance to Titan, (2016) Icarus 270:421-428[2] Kuga, M., Carrasco, N., Marty, B., Marrochi, Y., Bernard, S., Rigaudier, T., Fleury, B., Tissandier, L.: Nitrogen isotopic fractionation during abiotic synthesis of organic solid particles, (2014) EPSL 393:2-13

  15. Standardization and optimization of core sampling procedure for carbon isotope analysis in eucalyptus and variation in carbon isotope ratios across species and growth conditions

    CSIR Research Space (South Africa)

    Raju, M

    2011-11-01

    Full Text Available and optimization of core sampling procedure for carbon isotope analysis in eucalyptus and variation in carbon isotope ratios across species and growth conditions Mohan Raju, B#; Nuveshen Naidoo*; Sheshshaayee, M. S; Verryn, S. D*; Kamalkannan, R^; Bindumadhava... isotope analysis in Eucalyptus. Methods Expt 1: * Cores were taken from periphery to pith in 5 year old trees of Eucalyptus * Five half sib families of Eucalyptus grandis & E. urophylla were used ? Cores were further subdivided into 5 fragments...

  16. S Isotope Ratios of Central Italy Waters to Assess Their Origin

    Science.gov (United States)

    Castorina, Francesca; Masi, Umberto

    2010-05-01

    Sr isotopes have so far applied only occasionally to the study of the waters from central Italy. Therefore, we have analyzed more than 30 water samples from thermal and cold springs, and from the lakes located in the Quaternary K-alkaline volcanic districts of Latium, aimed at providing significant information on the sources of Sr and the hydrologic circulation. The 87Sr/86Sr composition of the waters shows a general correlation with the aquifer rocks, resulting in the waters from older carbonatic rocks having a less radiogenic signature than those from younger K-alkaline volcanic rocks. The Sr-isotope ratios of most thermal waters range narrowly by 0.708, indicating a common source of Sr, likely represented by the Upper Triassic Burano Anhydrites, i.e. the lowermost permeable formation in the study area. Moreover, the positive correlation between Sr and Ca suggests that bulk Ca was also supplied from that source. A minor number of thermal waters as well as all the waters from the lakes and cold springs display a larger Sr isotopic range (0.7085-0.7115), suggesting a relative large spectrum of sources for Sr. In particular, some waters derive their Sr from a singular source, but the most show isotopic signatures suggestive of mixed contributions from different aquifers. As a whole, the results from this study confirm that Sr isotopes are a useful tool contributing to explain the geochemical characteristics of surficial and groundwaters.

  17. Forensic utility of carbon isotope ratio variations in PVC tape backings.

    Science.gov (United States)

    Dietz, Marianne E; Stern, Libby A; Mehltretter, Andria Hobbs; Parish, Ashley; McLasky, Velvet; Aranda, Roman

    2012-03-01

    Forensic interest in adhesive tapes with polyvinyl chloride (PVC) backings (electrical tape) derives from their use in a variety of illicit activities. Due to the range of physical characteristics, chemical compositions, and homogeneity within a single roll of tape, traditional microscopic and chemical analyses can offer a high degree of discrimination between tapes, permitting the assessment of potential associations between evidentiary tape samples. The carbon isotope ratios of tapes could provide additional discrimination among tape samples. To evaluate whether carbon isotope ratios may be able to increase discrimination of electrical tapes, particularly with regards to different rolls of tape of the same product, we assessed the δ(13)C values of backings from 87 rolls of PVC-based black electrical tape (~20 brands, >60 products) Prior to analysis, adhesives were removed to prevent contamination by adhering debris, and plasticizers were extracted because of concern over their potential mobility. This result is consistent with each of these tapes having approximately the same plasticizer δ(13)C value and proportion of carbon in these plasticizers. The δ(13)C values of the 87 PVC tape backings ranged between -23.5 and -41.3 (‰, V-PDB), with negligible carbon isotopic variation within single rolls of tape, yet large variations among tape brands and tape products. Within this tape population, carbon isotope ratios permitted an average exclusion power of 93.7%, using a window of +/-0.3‰; the combination of carbon isotope ratio measurement with additional chemical and physical analyses raises the discrimination power to over 98.9%, with only 41 out of a possible 3741 pairs of tape samples being indistinguishable. There was a linear relationship between the δ(13)C value of tape backings and the change in δ(13)C value with the extraction of plasticizers. Analyses of pre- and post-blast tape sample pairs show that carbon isotope signatures are within 0.3‰ of

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

    Science.gov (United States)

    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.

  19. Distinct 238U/235U ratios and REE patterns in plutonic and volcanic angrites: Geochronologic implications and evidence for U isotope fractionation during magmatic processes

    Science.gov (United States)

    Tissot, François L. H.; Dauphas, Nicolas; Grove, Timothy L.

    2017-09-01

    Angrites are differentiated meteorites that formed between 4 and 11 Myr after Solar System formation, when several short-lived nuclides (e.g., 26Al-26Mg, 53Mn-53Cr, 182Hf-182W) were still alive. As such, angrites are prime anchors to tie the relative chronology inferred from these short-lived radionuclides to the absolute Pb-Pb clock. The discovery of variable U isotopic composition (at the sub-permil level) calls for a revision of Pb-Pb ages calculated using an ;assumed; constant 238U/235U ratio (i.e., Pb-Pb ages published before 2009-2010). In this paper, we report high-precision U isotope measurement for six angrite samples (NWA 4590, NWA 4801, NWA 6291, Angra dos Reis, D'Orbigny, and Sahara 99555) using multi-collector inductively coupled plasma mass-spectrometry and the IRMM-3636 U double-spike. The age corrections range from -0.17 to -1.20 Myr depending on the samples. After correction, concordance between the revised Pb-Pb and Hf-W and Mn-Cr ages of plutonic and quenched angrites is good, and the initial (53Mn/55Mn)0 ratio in the Early Solar System (ESS) is recalculated as being (7 ± 1) × 10-6 at the formation of the Solar System (the error bar incorporates uncertainty in the absolute age of Calcium, Aluminum-rich inclusions - CAIs). An uncertainty remains as to whether the Al-Mg and Pb-Pb systems agree in large part due to uncertainties in the Pb-Pb age of CAIs. A systematic difference is found in the U isotopic compositions of quenched and plutonic angrites of +0.17‰. A difference is also found between the rare earth element (REE) patterns of these two angrite subgroups. The δ238U values are consistent with fractionation during magmatic evolution of the angrite parent melt. Stable U isotope fractionation due to a change in the coordination environment of U during incorporation into pyroxene could be responsible for such a fractionation. In this context, Pb-Pb ages derived from pyroxenes fraction should be corrected using the U isotope composition

  20. Analysis of hydrogen isotope ratios by SIMS, and application to determining mineral-fluid isotope fractionation factors

    Energy Technology Data Exchange (ETDEWEB)

    Riciputi, L.R.; Chacko, T.; Cole, D.R.; Horita, J.

    1997-09-01

    Due to the large mass difference between the two isotopes, D/H ratios can be strongly affected by chemical processes. Thus, they can be sensitive monitors of fluid source, temperature, and fluid-rock interactions in geologic settings. The lack of confidence in fractionation factors has significantly hindered realization of the potential of D/H ratios in geochemical studies. The authors describe a new experimental method, relying on SIMS analysis, that allows the precise determination of mineral-water D/H fractionation factors, and the analytical considerations that are required to make both precise and accurate measurements. The development of this method is based on the fact that diffusion rates are markedly anisotropic in many hydrous minerals, varying by over five orders of magnitude depending on the crystallographic orientation. The diffusion rates can be determined by conducting controlled exchange experiments of fixed duration using isotopically labeled waters that are enriched (strongly) with D, and then measuring the depth profile by SIMS.

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

    Science.gov (United States)

    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.

  2. Identification of Marchfeld asparagus using Sr isotope ratio measurements by MC-ICP-MS.

    Science.gov (United States)

    Swoboda, S; Brunner, M; Boulyga, S F; Galler, P; Horacek, M; Prohaska, T

    2008-01-01

    This work focuses on testing and application of Sr isotope signatures for the fast and reliable authentication and traceability of Asparagus officinalis originating from Marchfeld, Austria, using multicollector inductively coupled plasma mass spectrometry after optimised Rb/Sr separation. The major sample pool comprises freeze-dried and microwave-digested asparagus samples from Hungary and Slovakia which are compared with Austrian asparagus originating from the Marchfeld region, which is a protected geographical indication. Additional samples from Peru, The Netherlands and Germany were limited in number and allowed therefore only restricted statistical evaluation. Asparagus samples from Marchfeld were harvested within two subsequent years in order to investigate the annual variation. The results show that the Sr isotope ratio is consistent within these 2 years of investigation. Moreover, the Sr isotope ratio of total Sr in soil was found to be significantly higher than in an NH4NO3 extract, reflecting the mobile (bioavailable) phase. The isotope composition in the latter extract corresponds well to the range found in the asparagus samples in Marchfeld, even though the concentration of Sr in asparagus shows no direct correlation to the concentration of Sr in the mobile phase of the soil. The major question was whether the 'Marchfelder Spargel' can be distinguished from samples from the neighbouring countries of Hungary and Slovakia. According to our findings, they can be clearly (100%) singled out from the Hungarian samples and can be distinguished from the Slovakian asparagus samples with a probability of more than 80%.

  3. Technical Note: Calcium and carbon stable isotope ratios as paleodietary indicators.

    Science.gov (United States)

    Melin, Amanda D; Crowley, Brooke E; Brown, Shaun T; Wheatley, Patrick V; Moritz, Gillian L; Yit Yu, Fred Tuh; Bernard, Henry; DePaolo, Donald J; Jacobson, Andrew D; Dominy, Nathaniel J

    2014-08-01

    Calcium stable isotope ratios are hypothesized to vary as a function of trophic level. This premise raises the possibility of using calcium stable isotope ratios to study the dietary behaviors of fossil taxa and to test competing hypotheses on the adaptive origins of euprimates. To explore this concept, we measured the stable isotope composition of contemporary mammals in northern Borneo and northwestern Costa Rica, two communities with functional or phylogenetic relevance to primate origins. We found that bone collagen δ(13) C and δ(15) N values could differentiate trophic levels in each assemblage, a result that justifies the use of these systems to test the predicted inverse relationship between bioapatite δ(13) C and δ(44) Ca values. As expected, taxonomic carnivores (felids) showed a combination of high δ(13) C and low δ(44) Ca values; however, the δ(44) Ca values of other faunivores were indistinguishable from those of primary consumers. We suggest that the trophic insensitivity of most bioapatite δ(44) Ca values is attributable to the negligible calcium content of arthropod prey. Although the present results are inconclusive, the tandem analysis of δ(44) Ca and δ(13) C values in fossils continues to hold promise for informing paleodietary studies and we highlight this potential by drawing attention to the stable isotope composition of the Early Eocene primate Cantius.

  4. Maintaining high precision of isotope ratio analysis over extended periods of time.

    Science.gov (United States)

    Brand, Willi A

    2009-06-01

    Stable isotope ratios are reliable and long lasting process tracers. In order to compare data from different locations or different sampling times at a high level of precision, a measurement strategy must include reliable traceability to an international stable isotope scale via a reference material (RM). Since these international RMs are available in low quantities only, we have developed our own analysis schemes involving laboratory working RM. In addition, quality assurance RMs are used to control the long-term performance of the delta-value assignments. The analysis schemes allow the construction of quality assurance performance charts over years of operation. In this contribution, the performance of three typical techniques established in IsoLab at the MPI-BGC in Jena is discussed. The techniques are (1) isotope ratio mass spectrometry with an elemental analyser for delta(15)N and delta(13)C analysis of bulk (organic) material, (2) high precision delta(13)C and delta(18)O analysis of CO(2) in clean-air samples, and (3) stable isotope analysis of water samples using a high-temperature reaction with carbon. In addition, reference strategies on a laser ablation system for high spatial resolution delta(13)C analysis in tree rings is exemplified briefly.

  5. In-situ zircon U-Pb age and Hf-O isotopic constraints on the origin of the Hasan-Robat A-type granite from Sanandaj-Sirjan zone, Iran: implications for reworking of Cadomian arc igneous rocks

    Science.gov (United States)

    Honarmand, Maryam; Li, Xian-Hua; Nabatian, Ghasem; Neubauer, Franz

    2017-01-01

    The Lower Permian Hasan-Robat syenogranite occurs as a single pluton and intruded the Upper Carboniferous-Lower Permian sandstones and dolomitic limestones in the central part of the Sanandaj-Sirjan zone. This syenogranitic intrusion shows A-type granitic affinity and is a good representative of Early Permian igneous activity in Iran. SIMS U-Pb zircon analyses indicate a crystallization age of 294.2 ± 2.5 Ma for the Hasan-Robat A-type granite. In-situ Lu-Hf and oxygen isotope analyses of magmatic zircons were carried out to infer the magma sources and evolution of the Hasan-Robat A-type syenogranite. The Hf-O zircon isotopic compositions are relatively homogeneous, with nearly chondritic ɛHf(t) values of -0.8 to +2.4 corresponding to two-stage zircon Hf model ages of 1.15-1.36 Ga. The δ18O values of zircon range from +7.6 to +8.6‰. The Hf model ages of the Hasan-Robat zircons is within the range of those reported from the Cadomian granitoids in Iran. The isotopic features of the Hasan-Robat syenogranite are in good agreement with Hf isotopic values and Hf and Nd model ages reported from the Cadomian arc magmatic suites in Iran. Thus, partial melting of these Cadomian igneous rocks would be the favorite source for the Hasan-Robat syenogranitic magma during the opening of the Neotethys Ocean and separation of Iranian terranes from the northern margin of Gondwana.

  6. Hafnium isotope results from mid-ocean ridges and Kerguelen.

    Science.gov (United States)

    Patchett, P.J.

    1983-01-01

    176Hf/177Hf ratios are presented for oceanic volcanic rocks representing both extremes of the range of mantle Hf-Nd-Sr isotopic variation. Hf from critical mid-ocean ridge basalts shows that 176Hf/177Hf does indeed have a greater variability than 143Nd/144Nd and 87Sr/86Sr in the depleted mantle. This extra variation is essentially of a random nature, and can perhaps be understood in terms of known Rb/Sr-Sm/Nd-Lu/Hf fractionation relationships. At the other extreme of mantle isotopic compositions, 176Hf/177Hf ratios for igneous rocks from the Indian Ocean island of Kerguelen show a closely similar variation to published 143Nd/144Nd ratios for the same samples. Comparison of Hf-Nd-Sr isotopic relatonships for Tristan da Cunha, Kerguelen and Samoa reveals divergences in the mantle array for ocean-island magma sources, and perhaps suggests that these irregularities are largely the result of an extra component of 87Sr/86Sr variation.-G.R.

  7. Emplacement ages, geochemical and Sr-Nd-Hf isotopic characterization of Mesozoic to early Cenozoic granitoids of the Sikhote-Alin Orogenic Belt, Russian Far East: Crustal growth and regional tectonic evolution

    Science.gov (United States)

    Jahn, Bor-ming; Valui, Galina; Kruk, Nikolai; Gonevchuk, V.; Usuki, Masako; Wu, Jeremy T. J.

    2015-11-01

    The Sikhote-Alin Range of the Russian Far East is an important accretionary orogen of the Western Pacific Orogenic Belt. In order to study the formation and tectonic evolution of the orogen, we performed zircon U-Pb dating, as well as geochemical and Sr-Nd-Hf isotopic analyses on 24 granitoid samples from various massifs in the Primorye and Khabarovsk regions. The zircon dating revealed that the granitoids were emplaced from 131 to 56 Ma (Cretaceous to Paleogene). In the Primorye Region, granitoids in the coastal Sikhote-Alin intruded the Cretaceous Taukha Accretionary Terrane from ca. 90 to 56 Ma, whereas those along the Central Sikhote-Alin Fault zone intruded the Jurassic Samarka Accretionary Terrane during ca. 110-75 Ma. The "oldest" monzogranite (131 Ma) was emplaced in the Lermontovka area of the NW Primorye Region. Granitoid massifs along the Central Sikhote-Alin Fault zone in the Khabarovsk Region formed from 109 to 58 Ma. Thus, the most important tectonothermal events in the Sikhote-Alin orogen took place in the Cretaceous. Geochemical analysis indicates that most samples are I-type granitoids. They have initial 87Sr/86Sr ratios ranging from 0.7040 to 0.7083, and initial Nd isotopic ratios, expressed as εNd(t) values, from +3.0 to -5.0 (mostly 0 to -5). The data suggest that the granitoid magmas were generated by partial melting of sources with mixed lithologies, including the subducted accretionary complex ± hidden Paleozoic-Proterozoic basement rocks. Based on whole-rock Nd isotopic data, we estimated variable proportions (36-77%) of juvenile component (=mantle-derived basaltic rocks) in the generation of the granitic magmas. Furthermore, zircon Hf isotopic data (εHf(t) = 0 to +15) indicate that the zircon grains crystallized from melts of mixed sources and that crustal assimilation occurred during magmatic differentiation. The quasi-continuous magmatism in the Sikhote-Alin orogen suggests that the Paleo-Pacific plate subduction was very active in the

  8. On the interference of Kr during carbon isotope analysis of methane using continuous-flow combustion–isotope ratio mass spectrometry

    NARCIS (Netherlands)

    Schmitt, J.; Seth, B.; Bock, M; van der Veen, C.; Möller, L.; Sapart, C.J.; Prokopiou, M.; Sowers, T.; Röckmann, T.; Fischer, H

    2013-01-01

    Stable carbon isotope analysis of methane ( 13C of CH4) on atmospheric samples is one key method to constrain the current and past atmospheric CH4 budget. A frequently applied measurement technique is gas chromatography (GC) isotope ratio mass spectrometry (IRMS) coupled to a combustion-preconcentra

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

    Science.gov (United States)

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

    2017-04-01

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

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

    Science.gov (United States)

    Giebel, Brian M.

    2011-12-01

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

  11. Determination of the Geographical Origin of All Commercial Hake Species by Stable Isotope Ratio (SIR) Analysis.

    Science.gov (United States)

    Carrera, Mónica; Gallardo, José M

    2017-02-08

    The determination of the geographical origin of food products is relevant to comply with the legal regulations of traceability, to avoid food fraud, and to guarantee food quality and safety to the consumers. For these reasons, stable isotope ratio (SIR) analysis using an isotope ratio mass spectrometry (IRMS) instrument is one of the most useful techniques for evaluating food traceability and authenticity. The present study was aimed to determine, for the first time, the geographical origin for all commercial fish species belonging to the Merlucciidae family using SIR analysis of carbon (δ(13)C) and nitrogen (δ(15)N). The specific results enabled their clear classification according to the FAO (Food and Agriculture Organization of the United Nations) fishing areas, latitude, and geographical origin in the following six different clusters: European, North African, South African, North American, South American, and Australian hake species.

  12. Late Miocene evolution of the Black Sea: insights from palynology and strontium isotope ratios

    Science.gov (United States)

    Grothe, Arjen; van Baak, Christiaan; Vasiliev, Iuliana; Sangiorgi, Francesca; Reichart, Gert-Jan; Stoica, Marius; Krijgsman, Wout

    2016-04-01

    During the late Miocene, the connection(s) between the Mediterranean Basin and the Atlantic Ocean deteriorated, which ultimately culminated in thick evaporite deposits and a water level drop in the Mediterranean Basin during the so-called Messinian Salinity Crisis (MSC, 5.97 - 5.33 Ma). It has been claimed that Black Sea, in response to the MSC, also desiccated but these claims have been proven incorrectly. Here we present palynological (dinoflagellate cysts and pollen) and strontium isotope ratios from two Black Sea records: the Zheleznyi Rog outcrop section and Deep Sea Drilling Project Hole 380A. Organic walled cyst-producing dinoflagellates are highly sensitive to even small changes in surface waters and strontium isotope ratios are excellent recorders of changing connectivity. Our records provide therefore more insights in the sensitivity of the Black Sea to Messinian Salinity Crisis and the general evolution of the late Miocene Black Sea.

  13. Ultratrace and isotope ratios analyses of some radionuclides by ICP-MS

    Energy Technology Data Exchange (ETDEWEB)

    Helal, A.I.; Zahran, N.F.; Abd El-Lateef, A.M.; Mohsen, H.T. [Central Lab. for Elemental and Isotopic Analysis, N.R.C. Atomic Energy Authority, Cairo (Egypt); Amr, M.A. [Central Lab. for Elemental and Isotopic Analysis, N.R.C. Atomic Energy Authority, Cairo (Egypt); Nuclear Physics Dept., N.R.C., Atomic Energy Authority, Cairo (Egypt); Bashter, I.I. [Physics Dept., Faculty of Science, Zagazig Univ. (Egypt); Abbas, Y. [Physics Dept., Faculty of Science, Suez Canal Univ., Ismailia (Egypt)

    2004-07-01

    Extensive work is under way using high resolution-ICP-MS for {sup 90}Sr, {sup 234}U, {sup 235}U, {sup 238}U, {sup 239}Pu, {sup 240}Pu, and {sup 241}Am detection. Sample preparation procedures based on liquid-liquid extraction and ion exchange chromatography were developed. Sr, U, Pu, and Am were separated from their matrix and concentrated to improve the power of detection in the mass spectrometer. A microconcentric nebulizer with a desolvation introduction system (Ardius) is used. Instrumental limits of detection using Sr and U standard solutions are 0.01 ppt and 0.006 ppt for Sr and U, respectively. A study is presented on the mass interferences for the specified radionuclides. In the environmental samples investigated the {sup 90}Sr/{sup 86}Sr isotope ratio is 6.02 x 10{sup -9} and for {sup 240}Pu/{sup 239}Pu the isotope ratio is 0.17. (orig.)

  14. A Widely Tunable Infrared Laser Spectrometer for Measurements of Isotopic Ratios of Carbon Cycle Gases

    Energy Technology Data Exchange (ETDEWEB)

    Joanne H. Shorter; J. Barry McManus; David D. Nelson; Charles E. Kolb; Mark S. Zahniser; Ray Bambha; Uwe Lehmann; Tomas Kulp; Stanley C. Tyler

    2005-01-31

    The atmospheric abundances of carbon dioxide and methane have increased dramatically during the industrial era. Measurements of the isotopic composition of these gases can provide a powerful tool for quantifying their sources and sinks. This report describes the development of a portable instrument for isotopic analysis CO{sub 2} and CH{sub 4} using tunable infrared laser absorption spectroscopy. This instrument combines novel optical design and signal processing methods with a widely tunable mid-infrared laser source based on difference frequency generation (DFG) which will can access spectral regions for all the isotopes of CO{sub 2} and CH{sub 4} with a single instrument. The instrument design compensates for the large difference in concentration between major and minor isotopes by measuring them with path lengths which differ by a factor of 100 within the same multipass cell. During Phase I we demonstrated the basic optical design and signal processing by determining {sup 13}CO{sub 2} isotopic ratios with precisions as small as 0.2{per_thousand} using a conventional lead salt diode laser. During Phase II, the DFG laser source was coupled with the optical instrument and was demonstrated to detect {sup 13}CH{sub 4}/{sup 12}CH{sub 4} ratios with a precision of 0.5{per_thousand} and an averaging time of 20 s using concentrated methane in air with a mixing ratio of 2700 ppm. Methods for concentrating ambient air for isotopic analysis using this technique have been evaluated. Extensions of this instrument to other species such as {sup 13}CO{sub 2}, C{sup 18}OO, and CH{sub 3}D are possible by substituting lasers at other wavelengths in the DFG source module. The immediate commercial application of this instrument will be to compete with existing mass spectrometric isotope instruments which are expensive, large and relatively slow. The novel infrared source developed in this project can be applied to the measurement of many other gas species and will have wide

  15. Traceability of synthetic drugs by position-specific deuterium isotope ratio analysis

    Energy Technology Data Exchange (ETDEWEB)

    Brenna, Elisabetta [Dipartimento di Chimica, Materiali e di Ingegneria Chimica del Politecnico di Milano and Istituto CNR per la Chimica del Riconoscimento Molecolare, Via Mancinelli 7, Milan I-20131 (Italy)], E-mail: elisabetta.brenna@polimi.it; Fronza, Giovanni [Dipartimento di Chimica, Materiali e di Ingegneria Chimica del Politecnico di Milano (Italy) and Instituto CNR per la Chimica del Riconoscimento Molecolare, Via Mancinelli 7, Milan I-20131 (Italy)], E-mail: giovanni.fronza@polimi.it; Fuganti, Claudio [Dipartimento di Chimica, Materiali e di Ingegneria Chimica del Politecnico di Milano (Italy) and Istituto CNR per la Chimica del Riconoscimento Molecolare, Via Mancinelli 7, Milan I-20131 (Italy)

    2007-10-10

    Samples of fluoxetine of different origin were submitted to natural abundance {sup 2}H NMR spectroscopy. The deuterium content at the various sites of the molecule was found to depend on its synthetic history. Hints on the synthetic procedure can be obtained by comparison with standard compounds, whose synthesis is known. These preliminary results give an idea of the potential of site-specific isotope ratio analysis in the fight against patent infringement and drug counterfeiting.

  16. Assessment of Non-Traditional Isotopic Ratios by Mass Spectrometry for Analysis of Nuclear Activities

    Science.gov (United States)

    2016-03-01

    Assessment of Non-traditional Isotopic Ratios by Mass Spectrometry for Analysis of Nuclear Activities Distribution Statement A. Approved for pubic...12. DISTRIBUTION / AVAILABILITY STATEMENT 13. SUPPLEMENTARY NOTES 14. ABSTRACT 15. SUBJECT TERMS 16. SECURITY CLASSIFICATION OF...Fahrenheit ( o F) [T( o F) + 459.67]/1.8 kelvin (K) Radiation curie (Ci) [ activity of radionuclides] 3.7 × 10 10 per second (s –1 ) [becquerel (Bq

  17. Method for determination of stable carbon isotope ratio of methylnitrophenols in atmospheric particulate matter

    Directory of Open Access Journals (Sweden)

    S. Moukhtar

    2011-11-01

    Full Text Available A technique for the measurement of the stable isotope ratio of methylnitrophenols in atmospheric particulate matter is presented. Atmospheric samples from rural and suburban areas were collected for evaluation of the procedure. Particulate matter was collected on quartz fibre filters using dichotomous high volume air samplers. Methylnitrophenols were extracted from the filters using acetonitrile. The sample was then purified using a combination of high-performance liquid chromatography and solid phase extraction. The final solution was then divided into two aliquots. To one aliquot, a derivatising agent, Bis(trimethylsilyltrifluoroacetamide, was added for Gas Chromatography-Mass Spectrometry analysis. The second half of the sample was stored in a refrigerator. For samples with concentrations exceeding 1 ng μl−1, the second half of the sample was used for measurement of stable carbon isotope ratios by Gas Chromatography-Isotope Ratio Mass Spectrometry.

    The procedure described in this paper provides a method for the analysis of methylnitrophenols in atmospheric particulate matter at concentrations as low as 0.3 pg m−3 and for stable isotope ratios with an accuracy of better than ±0.5‰ for concentrations exceeding 100 pg m−3.

    In all atmospheric particulate matter samples analysed, 2-methyl-4-nitrophenol was found to be the most abundant methylnitrophenol, with concentrations ranging from the low pg m−3 range in rural areas to more than 200 pg m−3 in some samples from a suburban location.

  18. Methodological Study on AMS Measurement of Ultra-trace Pu Isotope Ratios at CIAE

    Institute of Scientific and Technical Information of China (English)

    DONG; Ke-jun; ZHAO; Qing-zhang; WANG; Chen; HE; Ming; JIANG; Shan; ZHANG; Hui; PANG; Yi-jun; SHEN; Hong-tao; WANG; Xiao-ming; XU; Yong-ning; WU; Shao-yong; YANG; Xu-ran; WANG; Xiang-gao

    2015-01-01

    The determination of ultra-trace plutonium is very important in different fields.A new measurement method of plutonium isotopic ratios with accelerator mass spectrometry(AMS)was developed at China Institute of Atomic Energy(CIAE).Two laboratory reference standards of 239Pu/240 Pu(ST1)and 239Pu/242 Pu(ST2)are17.241and 10.059,a flow blank,a commercial blank and three real samples were respectively

  19. In-situ U-Pb, Hf and Re-Os isotopic analyses of the Xiangshan Ni-Cu-Co deposit in Eastern Tianshan (Xinjiang), Central Asia Orogenic Belt: Constraints on the timing and genesis of the mineralization

    Science.gov (United States)

    Han, Chunming; Xiao, Wenjiao; Zhao, Guochun; Ao, Songjian; Zhang, Jien; Qu, Wenjun; Du, Andao

    2010-12-01

    The timing and genesis of the major Ni-Cu-Co sulfide deposit in the Xiangshan intrusion have been studied based on newly obtained in-situ U-Pb, Hf and Re-Os isotopic analyses. The SIMS U-Pb zircon ages of the gabbro hosting the Ni-Cu-Co sulfide deposit indicate that the Xiangshan intrusion was emplaced at 279.6 ± 1.1 Ma (95% confidence level, MSWD = 1.30, n = 15). On the basis of combined geological and geochronological evidence, we suggest that the Xiangshan and other adjacent Ni-Cu deposits were formed in the same period. Sulphides have low common Os concentrations and high Re/Os ratios, similar to sulphide ores from the Duluth, Sally Malay and Voisey Bay complexes. The Re-Os isotopic data from the disseminated and massive ores from the Xiangshan intrusion do not form a single isochron, as they have different initial Os ratios. The Hf and Os isotopic data suggest that the Xiangshan intrusion and associated Ni-Cu-Co mineralization were derived from crustally contaminated mantle melts. The geochemical data show a tholeiitic affinity and a strong suprasubduction zone signature with negative Nb, Sr, and Ti anomalies similar to N-MORB and E-MORB. We suggest that the mafic-ultramafic rocks and associated Ni-Cu mineralization of the Eastern Tianshan orogen formed in an Alaska-type subduction zone-arc setting. Some diagnostic features of ridge-trench interaction are present in the Chinese East Tianshan orogen (e.g. granites, adakites, high-Mg andesites, near-trench magmatism, Alaskan-type mafic-ultramafic complexes, high-temperature metamorphic belts that prograde rapidly from low-grade belts, and orogenic gold deposits). The above distinctive rock groups are probably related to the same thermal event, ridge subduction, as in the Cenozoic orogen of Alaska. We suggest that ridge subduction is the most plausible mechanism to provide the necessary heat. Ridge subduction provides an important promising model for understanding many aspects of the evolution of the Chinese

  20. Crustal-scale recycling in caldera complexes and rift zones along the Yellowstone hotspot track: O and Hf isotopic evidence in diverse zircons from voluminous rhyolites of the Picabo volcanic field, Idaho

    Science.gov (United States)

    Drew, Dana L.; Bindeman, Ilya N.; Watts, Kathryn E.; Schmitt, Axel K.; Fu, Bin; McCurry, Michael

    2013-01-01

    Rhyolites of the Picabo volcanic field (10.4–6.6 Ma) in eastern Idaho are preserved as thick ignimbrites and lavas along the margins of the Snake River Plain (SRP), and within a deep (>3 km) borehole near the central axis of the Yellowstone hotspot track. In this study we present new O and Hf isotope data and U–Pb geochronology for individual zircons, O isotope data for major phenocrysts (quartz, plagioclase, and pyroxene), whole rock Sr and Nd isotope ratios, and whole rock geochemistry for a suite of Picabo rhyolites. We synthesize our new datasets with published Ar–Ar geochronology to establish the eruptive framework of the Picabo volcanic field, and interpret its petrogenetic history in the context of other well-studied caldera complexes in the SRP. Caldera complex evolution at Picabo began with eruption of the 10.44±0.27 Ma (U–Pb) Tuff of Arbon Valley (TAV), a chemically zoned and normal-δ18O (δ18O magma=7.9‰) unit with high, zoned 87Sr/86Sri (0.71488–0.72520), and low-εNd(0) (−18) and εHf(0) (−28). The TAV and an associated post caldera lava flow possess the lowest εNd(0) (−23), indicating ∼40–60% derivation from the Archean upper crust. Normal-δ18O rhyolites were followed by a series of lower-δ18O eruptions with more typical (lower crustal) Sr–Nd–Hf isotope ratios and whole rock chemistry. The voluminous 8.25±0.26 Ma West Pocatello rhyolite has the lowest δ18O value (δ18Omelt=3.3‰), and we correlate it to a 1,000 m thick intracaldera tuff present in the INEL-1 borehole (with published zircon ages 8.04–8.35 Ma, and similarly low-δ18O zircon values). The significant (4–5‰) decrease in magmatic-δ18O values in Picabo rhyolites is accompanied by an increase in zircon δ18O heterogeneity from ∼1‰ variation in the TAV to >5‰ variation in the late-stage low-δ18O rhyolites, a trend similar to what is characteristic of Heise and Yellowstone, and which indicates remelting of variably hydrothermally altered tuffs

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

    Science.gov (United States)

    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 (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., Henne, S. & Emmenegger, L. Tracking isotopic signatures of CO2 at the high altitude site Jungfraujoch with laser spectroscopy: Analytical improvements and representative re-sults. Atmospheric Measurement Techniques 6, 1659-1671 (2013). 2 Tuzson, B. et al. Continuous isotopic composition measurements of tropospheric CO2 at Jungfraujoch (3580 m a.s.l.), Switzerland: real-time observation of regional pollution events. Atmospheric Chemistry and Physics

  2. Carbon isotope ratio (delta13C) values of urinary steroids for doping control in sport.

    Science.gov (United States)

    Cawley, Adam T; Trout, Graham J; Kazlauskas, Rymantas; Howe, Christopher J; George, Adrian V

    2009-03-01

    The detection of steroids originating from synthetic precursors in relation to their chemically identical natural analogues has proven to be a significant challenge for doping control laboratories accredited by the World Anti-Doping Agency (WADA). Endogenous steroid abuse may be confirmed by utilising the atomic specificity of gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS) that enables the precise measurement of differences in stable isotope ratios that arise as a result of fractionation patterns inherent in the source of steroids. A comprehensive carbon isotope ratio (delta(13)C) profiling study (n=1262) of urinary ketosteroids is reported that demonstrates the inter-individual variation that can be expected from factors such as diet, ethnicity, gender and age within and between different populations (13 countries). This delta(13)C distribution is shown by principal component analysis (PCA) to provide a statistical comparison to delta(13)C values observed following administration of testosterone enanthate. A limited collection of steroid diol data (n=100; consisting of three countries) is also presented with comparison to delta(13)C values of excreted testosterone to validate criteria for WADA accredited laboratories to prove doping offences.

  3. Can amino acid carbon isotope ratios distinguish primary producers in a mangrove ecosystem?

    Science.gov (United States)

    Larsen, Thomas; Wooller, Matthew J; Fogel, Marilyn L; O'Brien, Diane M

    2012-07-15

    The relative contribution of carbon from terrestrial vs. marine primary producers to mangrove-based food webs can be challenging to resolve with bulk carbon isotope ratios (δ(13)C). In this study we explore whether patterns of δ(13)C values among amino acids (AAs) can provide an additional tool for resolving terrestrial and marine origins of carbon. Amino acid carbon isotope ratios (δ(13)C(AA)) were measured for several terrestrial and marine primary producers in a mangrove ecosystem at Spanish Lookout Caye (SLC), Belize, using gas chromatography-combustion-isotope ratio mass spectrometry. The δ(13)C values of essential amino acids (δ(13)C(EAA)) were measured to determine whether they could be used to differentiate terrestrial and marine producers using linear discriminant analysis. Marine and terrestrial producers had distinct patterns of δ(13)C(EAA) values in addition to their differences in bulk δ(13)C values. Microbial mat samples and consumers (Crassostrea rhizophorae, Aratus pisonii, Littoraria sp., Lutjanus griseus) were most similar to marine producers. Patterns of δ(13)C(EAA) values for terrestrial producers were very similar to those described for other terrestrial plants. The findings suggest that δ(13)C(EAA) values may provide another tool for estimating the contribution of terrestrial and marine sources to detrital foodwebs. Preliminary analyses of consumers indicate significant use of aquatic resources, consistent with other studies of mangrove foodwebs. Copyright © 2012 John Wiley & Sons, Ltd.

  4. DoE optimization of a mercury isotope ratio determination method for environmental studies.

    Science.gov (United States)

    Berni, Alex; Baschieri, Carlo; Covelli, Stefano; Emili, Andrea; Marchetti, Andrea; Manzini, Daniela; Berto, Daniela; Rampazzo, Federico

    2016-05-15

    By using the experimental design (DoE) technique, we optimized an analytical method for the determination of mercury isotope ratios by means of cold-vapor multicollector ICP-MS (CV-MC-ICP-MS) to provide absolute Hg isotopic ratio measurements with a suitable internal precision. By running 32 experiments, the influence of mercury and thallium internal standard concentrations, total measuring time and sample flow rate was evaluated. Method was optimized varying Hg concentration between 2 and 20 ng g(-1). The model finds out some correlations within the parameters affect the measurements precision and predicts suitable sample measurement precisions for Hg concentrations from 5 ng g(-1) Hg upwards. The method was successfully applied to samples of Manila clams (Ruditapes philippinarum) coming from the Marano and Grado lagoon (NE Italy), a coastal environment affected by long term mercury contamination mainly due to mining activity. Results show different extents of both mass dependent fractionation (MDF) and mass independent fractionation (MIF) phenomena in clams according to their size and sampling sites in the lagoon. The method is fit for determinations on real samples, allowing for the use of Hg isotopic ratios to study mercury biogeochemical cycles in complex ecosystems.

  5. Strontium isotopic ratios of the volcanic rocks from Dogo of the Oki Islands, Japan

    Energy Technology Data Exchange (ETDEWEB)

    Kurasawa, Hajime

    1984-12-01

    The isotopic composition of strontium and the abundances of rubidium and strontium in volcanic rocks from Dogo of the Oki Islands and Takashima in the northwest Kyushu, West Japan, and Ulrungdo of Korea, have been determined. The rubidium and strontium contents for alkakine basalts range from 27.6 to 51.2 ppm and 444 to 723 ppm, and 148 to 208 ppm and 3.7 to 205 ppm for intermediate to felsic suites, respectively. The alkaline basalts are divided into two groups with /sup 87/Sr//sup 86/Sr ratios of the restricted ranges of 0.70481 - 0.70496 and 0.70540 - 0.70575, respectively. However, the /sup 87/Sr//sup 86/Sr ratios of intermediate to felsic rocks of Dogo are relatively high and variable ranging from 0.70706 to 0.71019, which probably reflect the contamination and/or produced by body or partial melting of the basement rocks in this area without crustal assimilation of basaltic magma. In addition, the lead isotopic results indicate that the melting of Precambrian basement rocks possibly yields less radiogenic lead. In the southwest Japan, the /sup 87/Sr//sup 86/Sr ratios of Cenozoic basaltic rocks are clearly different between the San-in and the northwest Kyushu regions, which includes Jeju island. The higher /sup 87/Sr//sup 86/Sr ratios of basalts from the San-in region than that of basalts from the northwest Kyushu region also reflect the different properties of the upper mantle, which means there is regional heterogeneity of Sr isotopic ratios under the southwest Japan arcs. Furthermore, the relatively high and variable /sup 87/Sr//sup 86/Sr ratios of volcanic rocks are particularly concentrated in the southwestern Japan arcs which has probably more continental properties than northeastern Japan arcs.

  6. Detection of adulteration in Australian orange juices by stable carbon isotope ratio analysis (SCIRA).

    Science.gov (United States)

    Antolovich, M; Li, X; Robards, K

    2001-05-01

    Stable carbon isotope ratio analysis (SCIRA) was used to determine the authenticity of commercial Australian orange juices. Thirty-five samples of Valencia (delta(13)C values from -23.8 to -24.7 ppt) and eight samples of Navel juices (delta(13)C values from -24.1 to -24.5 ppt) of known origin were used to establish a decision level before analysis. No significant seasonal variations in (13)C/(12)C ratio were observed. Variations in combustion temperature in the method were also found to be insignificant.

  7. U-Pb zircon, geochemical and Sr-Nd-Hf-O isotopic constraints on age and origin of the ore-bearing intrusions from the Nurkazgan porphyry Cu-Au deposit in Kazakhstan

    Science.gov (United States)

    Shen, Ping; Pan, Hongdi; Seitmuratova, Eleonora; Jakupova, Sholpan

    2016-02-01

    Nurkazgan, located in northeastern Kazakhstan, is a super-large porphyry Cu-Au deposit with 3.9 Mt metal copper and 229 tonnage gold. We report in situ zircon U-Pb age and Hf-O isotope data, whole rock geochemical and Sr-Nd isotopic data for the ore-bearing intrusions from the Nurkazgan deposit. The ore-bearing intrusions include the granodiorite porphyry, quartz diorite porphyry, quartz diorite, and diorite. Secondary ion mass spectrometry (SIMS) zircon U-Pb dating indicates that the granodiorite porphyry and quartz diorite porphyry emplaced at 440 ± 3 Ma and 437 ± 3 Ma, respectively. All host rocks have low initial 87Sr/86Sr ratios (0.70338-0.70439), high whole-rock εNd(t) values (+5.9 to +6.3) and very high zircon εHf(t) values (+13.4 to +16.5), young whole-rock Nd and zircon Hf model ages, and consistent and slightly high zircon O values (+5.7 to +6.7), indicating that the ore-bearing magmas derived from the mantle without old continental crust involvement and without marked sediment contamination during magma emplacement. The granodiorite porphyry and quartz diorite porphyry are enriched in large ion lithophile elements (LILE) and light rare earth elements (LREE) and depleted in high-field strength elements (HFSE), Eu, Ba, Nb, Sr, P and Ti. The diorite and quartz diorite have also LILE and LREE enrichment and HFSE, Nb and Ti depletion, but have not negative Eu, Ba, Sr, and P anomalies. These features suggest that the parental magma of the granodiorite porphyry and quartz diorite porphyry originated from melting of a lithospheric mantle and experienced fractional crystallization, whereas the diorite and quartz diorite has a relatively deeper lithospheric mantle source region and has not experienced strong fractional crystallization. Based on these, together with the coeval ophiolites in the area, we propose that a subduction of the Balkhash-Junggar oceanic plate took place during the Early Silurian and the ore-bearing intrusions and associated Nurkazgan

  8. Tunable Diode Laser Measurements of Leaf-scale Carbon Isotope Discrimination and Ecosystem Respired Carbon and Oxygen Isotope Ratios in a Semi-arid Woodland

    Science.gov (United States)

    McDowell, N.; Chris, B.; Hanson, D.; Kern, S.; Meyer, C.; Pockman, W.; Powers, H.

    2005-12-01

    We present results and speculative interpretation of leaf-level carbon isotope discrimination and ecosystem respired carbon and oxygen isotope ratios from a semi-arid, C3/C4 woodland located in northern New Mexico, USA. Overstory leaf area index (LAI) is dominated by live juniper (Juniperus monosperma) trees with an LAI value of approximately 1.0 m2 per m2 ground area, and has a seasonally dynamic understory of mixed C3 forbs and C4 grasses and cacti, with a maximum LAI of 0.30 m2 per m2 ground area. Ecosystem respired carbon isotope ratios showed values characteristic of C3 dominated photosynthesis (Keeling plot intercepts of -35 to -22 per mil). Seasonal variation was typical of that found in wetter, C3 dominated forests, as was the dependence on climate (e.g. relationships with vapor pressure deficit, soil water content, and canopy conductance). Leaf-level carbon isotope discrimination of the junipers, measured by coupling a Li-Cor 6400 photosynthesis system to the TDL, provided discrimination-Ci and discrimination-vpd relationships consistent with measured ecosystem respired carbon isotope ratios. The oxygen isotope ratio of ecosystem respiration was dependent on rain water isotope composition, but was correlated with soil water content during rain-free periods. The cumulative effect of vapor pressure deficit after a rain event was tightly correlated with the oxygen isotope ratio of ecosystem respiration, suggesting the primary drivers are evaporative enrichment of soil water and perhaps nocturnal leaf enrichment. Instrument precision for carbon and oxygen isotope ratios of carbon dioxide is 0.06 to 0.18 per mil; however, overall precision is somewhat lower due to pressure and sampling effects.

  9. Mg isotope ratios in giant stars of the globular clusters M 13 and M 71

    CERN Document Server

    Yong, D; Lambert, D L; Yong, David; Aoki, Wako; Lambert, David L.

    2006-01-01

    We present Mg isotope ratios in 4 red giants of the globular cluster M 13 and 1 red giant of the globular cluster M 71 based on spectra obtained with HDS on the Subaru Telescope. We confirm earlier results by Shetrone that for M 13, the ratio varies from (25+26)Mg/24Mg = 1 in stars with the highest Al abundance to (25+26)Mg/24Mg = 0.2 in stars with the lowest Al abundance. However, we separate the contributions of all three isotopes and find a spread in the ratio 24Mg:25Mg:26Mg with values ranging from 48:13:39 to 78:11:11. As in NGC 6752, we find a positive correlation between 26Mg and Al, an anticorrelation between 24Mg and Al, and no correlation between 25Mg and Al. In M 71, our one star has a ratio 70:13:17. For both clusters, the lowest ratios of 25Mg/24Mg and 26Mg/24Mg exceed those observed in field stars at the same metallicity, a result also found in NGC 6752. The contribution of 25Mg to the total Mg abundance is constant within a given cluster and between clusters with 25Mg/(24+25+26)Mg = 0.13. For M...

  10. Environmental and biosynthetic influences on carbon and hydrogen isotope ratios of leaf wax n-alkanes

    Science.gov (United States)

    McInerney, F. A.; Freeman, K. H.; Polissar, P. J.; Feakins, S. J.

    2013-12-01

    Both carbon and hydrogen isotope ratios of leaf-wax n-alkanes are influenced by the availability of water in a plant's growth environment. Carbon isotope ratios of bulk tissues in C3 plants demonstrate a strong inverse relationship with measures of available moisture (e.g. mean annual precipitation and precipitation/evaporation). Similarly, hydrogen isotope ratios of leaf wax n-alkanes (δDl) can be enriched relative to precipitation (δDw) by transpiration, which is related to relative humidity and the leaf-to-air vapor pressure deficit. Thus, D-enrichment of leaf-wax n-alkanes relative to precipitation, termed the apparent fractionation (2ɛl/w), becomes more positive with increasing aridity. In theory, more positive values of leaf-wax δ13C (δ13Cl) and 2ɛl/w of leaf-wax n-alkanes should both correspond to more arid conditions in C3 plants. Here we review published and unpublished data on over 100 plants to examine this relationship. Contrary to expectations, C3 dicots show no clear relationship between δ13Cl and 2ɛl/w. This global lack of correlation is surprising given our understanding of aridity related isotopic effects in C3 plants. One possibility is that the implicit assumption of constant fractionation between lipid and bulk tissue is flawed due to the effects of different biosynthetic carriers and reaction pathways. We explore this possibility by examining the offset of leaf-wax carbon isotopes from the bulk leaf tissue (13ɛl/bulk). Different offsets would indicate additional biosynthetic processes are affecting δ13Cl in addition to any direct effects from aridity. We find that 13ɛl/bulk is highly variable, ranging from -1 to -16‰, which could explain the lack of correlation between δ13Cl and 2ɛl/w. In addition, 13ɛl/bulk values for C3 and C4 monocots (averages of -10.6 and -11.4‰ respectively) represent significantly greater offset between leaf wax and bulk tissue than in C3 dicots (average of -4.3‰), which is consistent with previous

  11. Tap water isotope ratios reflect urban water system structure and dynamics across a semiarid metropolitan area

    Science.gov (United States)

    Jameel, Yusuf; Brewer, Simon; Good, Stephen P.; Tipple, Brett J.; Ehleringer, James R.; Bowen, Gabriel J.

    2016-08-01

    Water extraction for anthropogenic use has become a major flux in the hydrological cycle. With increasing demand for water and challenges supplying it in the face of climate change, there is a pressing need to better understand connections between human populations, climate, water extraction, water use, and its impacts. To understand these connections, we collected and analyzed stable isotopic ratios of more than 800 urban tap water samples in a series of semiannual water surveys (spring and fall, 2013-2015) across the Salt Lake Valley (SLV) of northern Utah. Consistent with previous work, we found that mean tap water had a lower 2H and 18O concentration than local precipitation, highlighting the importance of nearby montane winter precipitation as source water for the region. However, we observed strong and structured spatiotemporal variation in tap water isotopic compositions across the region which we attribute to complex distribution systems, varying water management practices and multiple sources used across the valley. Water from different sources was not used uniformly throughout the area and we identified significant correlation between water source and demographic parameters including population and income. Isotopic mass balance indicated significant interannual and intra-annual variability in water losses within the distribution network due to evaporation from surface water resources supplying the SLV. Our results demonstrate the effectiveness of isotopes as an indicator of water management strategies and climate impacts within regional urban water systems, with potential utility for monitoring, regulation, forensic, and a range of water resource research.

  12. Zn/Cd ratios and cadmium isotope evidence for the classification of lead-zinc deposits.

    Science.gov (United States)

    Wen, Hanjie; Zhu, Chuanwei; Zhang, Yuxu; Cloquet, Christophe; Fan, Haifeng; Fu, Shaohong

    2016-04-28

    Lead-zinc deposits are often difficult to classify because clear criteria are lacking. In recent years, new tools, such as Cd and Zn isotopes, have been used to better understand the ore-formation processes and to classify Pb-Zn deposits. Herein, we investigate Cd concentrations, Cd isotope systematics and Zn/Cd ratios in sphalerite from nine Pb-Zn deposits divided into high-temperature systems (e.g., porphyry), low-temperature systems (e.g., Mississippi Valley type [MVT]) and exhalative systems (e.g., sedimentary exhalative [SEDEX]). Our results showed little evidence of fractionation in the high-temperature systems. In the low-temperature systems, Cd concentrations were the highest, but were also highly variable, a result consistent with the higher fractionation of Cd at low temperatures. The δ(114/110)Cd values in low-temperature systems were enriched in heavier isotopes (mean of 0.32 ± 0.31‰). Exhalative systems had the lowest Cd concentrations, with a mean δ(114/110)Cd value of 0.12 ± 0.50‰. We thus conclude that different ore-formation systems result in different characteristic Cd concentrations and fraction levels and that low-temperature processes lead to the most significant fractionation of Cd. Therefore, Cd distribution and isotopic studies can support better understanding of the geochemistry of ore-formation processes and the classification of Pb-Zn deposits.

  13. An analytical approach to Sr isotope ratio determination in Lambrusco wines for geographical traceability purposes.

    Science.gov (United States)

    Durante, Caterina; Baschieri, Carlo; Bertacchini, Lucia; Bertelli, Davide; Cocchi, Marina; Marchetti, Andrea; Manzini, Daniela; Papotti, Giulia; Sighinolfi, Simona

    2015-04-15

    Geographical origin and authenticity of food are topics of interest for both consumers and producers. Among the different indicators used for traceability studies, (87)Sr/(86)Sr isotopic ratio has provided excellent results. In this study, two analytical approaches for wine sample pre-treatment, microwave and low temperature mineralisation, were investigated to develop accurate and precise analytical method for (87)Sr/(86)Sr determination. The two procedures led to comparable results (paired t-test, with twine sample), processed during each sample batch (calculated Relative Standard Deviation, RSD%, equal to 0.002%. Lambrusco PDO (Protected Designation of Origin) wines coming from four different vintages (2009, 2010, 2011 and 2012) were pre-treated according to the best procedure and their isotopic values were compared with isotopic data coming from (i) soils of their territory of origin and (ii) wines obtained by same grape varieties cultivated in different districts. The obtained results have shown no significant variability among the different vintages of wines and a perfect agreement between the isotopic range of the soils and wines has been observed. Nevertheless, the investigated indicator was not enough powerful to discriminate between similar products. To this regard, it is worth to note that more soil samples as well as wines coming from different districts will be considered to obtain more trustworthy results.

  14. Variation in oxygen isotope ratio of dissolved orthophosphate induced by uptake process in natural coral holobionts

    Science.gov (United States)

    Ferrera, Charissa M.; Miyajima, Toshihiro; Watanabe, Atsushi; Umezawa, Yu; Morimoto, Naoko; San Diego-McGlone, Maria Lourdes; Nadaoka, Kazuo

    2016-06-01

    A model incubation experiment using natural zooxanthellate corals was conducted to evaluate the influence of phosphate uptake by coral holobionts on oxygen isotope ratio of dissolved PO4 3- (δ18Op). Live coral samples of Acropora digitifera, Porites cylindrica, and Heliopora coerulea were collected from coral reefs around Ishigaki Island (Okinawa, Japan) and Bolinao (northern Luzon, Philippines) and incubated for 3-5 d after acclimatization under natural light conditions with elevated concentrations of PO4 3-. Phosphate uptake by corals behaved linearly with incubation time, with uptake rate depending on temperature. δ18Op usually increased with time toward the equilibrium value with respect to oxygen isotope exchange with ambient seawater, but sometimes became higher than equilibrium value at the end of incubation. The magnitude of the isotope effect associated with uptake depended on coral species; the greatest effect was in A. digitifera and the smallest in H. coerulea. However, it varied even within samples of a single coral species, which suggests multiple uptake processes with different isotope effects operating simultaneously with varying relative contributions in the coral holobionts used. In natural environments where concentrations of PO4 3- are much lower than those used during incubation, PO4 3- is presumably turned over much faster and the δ18Op easily altered by corals and other major primary producers. This should be taken into consideration when using δ18Op as an indicator of external PO4 3- sources in coastal ecosystems.

  15. Source Attribution of Cyanides Using Anionic Impurity Profiling, Stable Isotope Ratios, Trace Elemental Analysis and Chemometrics.

    Science.gov (United States)

    Mirjankar, Nikhil S; Fraga, Carlos G; Carman, April J; Moran, James J

    2016-02-02

    Chemical attribution signatures (CAS) for chemical threat agents (CTAs), such as cyanides, are being investigated to provide an evidentiary link between CTAs and specific sources to support criminal investigations and prosecutions. Herein, stocks of KCN and NaCN were analyzed for trace anions by high performance ion chromatography (HPIC), carbon stable isotope ratio (δ(13)C) by isotope ratio mass spectrometry (IRMS), and trace elements by inductively coupled plasma optical emission spectroscopy (ICP-OES). The collected analytical data were evaluated using hierarchical cluster analysis (HCA), Fisher-ratio (F-ratio), interval partial least-squares (iPLS), genetic algorithm-based partial least-squares (GAPLS), partial least-squares discriminant analysis (PLSDA), K nearest neighbors (KNN), and support vector machines discriminant analysis (SVMDA). HCA of anion impurity profiles from multiple cyanide stocks from six reported countries of origin resulted in cyanide samples clustering into three groups, independent of the associated alkali metal (K or Na). The three groups were independently corroborated by HCA of cyanide elemental profiles and corresponded to countries each having one known solid cyanide factory: Czech Republic, Germany, and United States. Carbon stable isotope measurements resulted in two clusters: Germany and United States (the single Czech stock grouped with United States stocks). Classification errors for two validation studies using anion impurity profiles collected over five years on different instruments were as low as zero for KNN and SVMDA, demonstrating the excellent reliability associated with using anion impurities for matching a cyanide sample to its factory using our current cyanide stocks. Variable selection methods reduced errors for those classification methods having errors greater than zero; iPLS-forward selection and F-ratio typically provided the lowest errors. Finally, using anion profiles to classify cyanides to a specific stock

  16. Geochronology and Hf Isotope Study of Pegmatite in the Xiaoqinling Area of NW China:Implication for Petrogenesis and Regional Metamorphism

    Institute of Scientific and Technical Information of China (English)

    Haixiang Zhao; Shaoyong Jiang; Baozhang Dai; Liang Ma; Jianwei Li

    2015-01-01

    In this study, we carried out petrography, zircon U-Pb geochronology and Hf isotopic analyses on a granitic pegmatite dyke in the Xiaoqinling area in southern margin of the North China Craton (NCC). Our study suggests that the pegmatite dyke likely crystallized from a volatile-rich peg-matitic magma. Different from most other pegmatite elsewhere, zircon from this pegmatite dyke does not contain unusually high U and Th concentrations and suffered no evident radioactive damage, therefore we successfully obtained a zircon U-Pb dating using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS), which yields an average 207Pb/206Pb age of 1 814±6 Ma, representing the intrusive age of the granitic pegmatite dyke. ZirconεHf(t) values are between-8.3 and-3.0, corresponding to Hf depleted mantle model ages from 2 649 to 2 991 Ma with an average of 2 881 Ma. These data indicate that this granitic pegmatite dyke may have been derived from partial melting of Meso-Neoarchean metamorphic rocks from the Xiaoqinling basement. Granitic pegmatite magma may have emplaced within the Taihua Group wall rocks during the last stage of the middle to high grade metamorphism. Furthermore, according to the petrographic observation, the 1.81 Ga pegmatite dyke and the 1 800–1 750 Ma Xiong’er Group rocks were not undergone middle to high grade meta-morphism, indicating 1.81 Ga as the termination of the latest regional metamorphism in the southern margin of the NCC.

  17. Timing and tectonic implications of the Pan-African Bangangte syenomonzonite, West Cameroon: Constraints from in-situ zircon U-Pb age and Hf-O isotopes

    Science.gov (United States)

    Tchouankoue, Jean Pierre; Li, Xian-Hua; Belnoun, Rose Noel Ngo; Mouafo, Lucas; Ferreira, Valderez Pinto

    2016-12-01

    The Bangangte pluton is a SW-NE elongated (5 × 20 km) massif located in the southeastern part of the Pan-African North Equatorial Fold Belt in Cameroon, consisting of two units with dominant monzonites in the south and syenites in the north. SIMS U-Pb zircon dating yields consistent emplacement ages of 585 ± 4 Ma and 583 ± 4 Ma for the southern unit and the northern unit, respectively. The Bangangte rocks display typical shoshonitic compositions characterized by Na2O + K2O > 5 wt%, K2O/Na2O ∼2, enrichment in LILE and LREE, but depletion in HFSE. Rocks from both units have similar O-Hf isotopes, with the monzonite zircons from the southern unit showing slightly higher δ18O (7.0 ± 0.4‰) but lower εHf(t) (-15.3 ± 1.4) value than the syenite zircons from southern unit (δ18O = 6.0 ± 0.4‰; εHf(t) = -14.0 ± 2.0). They were generated by partial melting of an enriched mantle source metasomatized by previous subduction processes, accompanied by crystal fractionation of pyroxene, Ti-Fe oxides and apatite, as well as crustal contamination to varying degrees. These rocks display a transitional geochemical feature of the subduction-related and within-plate shoshonites, suggesting that they were most likely emplaced in a post-collisional setting at the waning stage of the Pan-African orogeny.

  18. Neoproterozoic granitic magmatism along the Ailao Shan-Red River belt: U-Pb zircon geochronology, Lu-Hf isotopes and tectonic implications

    Science.gov (United States)

    Chen, Xiaoyu; Liu, Junlai; Qi, Yinchuan; Fan, Wenkui; Burg, Jean-Pierre

    2017-04-01

    The Neoproterozoic tectonic characteristics of the high grade metamorphic massifs along the Ailao Shan-Red River belt are debated. Controversies are on 1) whether the massifs were parts of the Yangtze block to the northeast or 2) parts of the Indochina block to the southwest and 3) the magmatic rocks represent arc magmatism or rifting linked to break-up of the Rodinia supercontinent. This study presents new and precise LA-ICP-MS U-Pb age dating and geochemical and Hf isotopic analyses of granitic intrusions along the Ailao Shan-Red River belt in an attempt to elucidate the Neoproterozoic magmatic evolution of this belt. In general, zircon U-Pb ages of the studied granitic rocks are between 804 and 724Ma, with a weighted mean of ca. 770 Ma, thus confirming Neoproterozoic magmatism. All samples plot into the peraluminous domain, indicating a major crustal resource. In consistency with these conclusions, most of the Neoproterozoic granitoids show negative ɛHf (t) values near the chondrite line. A few samples possess low positiveɛ Hf (t) values, being signatures of mantle sources. It is therefore concluded that the Neoproterozoic magmatism along the ASRR belt originated from mantle sources with important contributions through anatexis of ancient lower crust. Discrimination diagrams of tectonic settings suggest continental arc magmatism. Neoproterozoic magmatism is widely reported along the margins of the Yangtze block, especially in the northern margin. However, there are fewer reports about Neoproterozoic magmatic activity along the southern and southwestern margins. The geochronology spectrum and geochemisty of the studied Neoproterozoic granitic rocks are similar to those along the western margin of the Yangtze block. The present study, combined with previous results, suggests that oceanic subduction contributed to the generation of the arc magmatisms along the western and southwestern margin of the Yangtze plate and along the ASRR belt (as part of the

  19. Neoarchean (2.5–2.8 Ga crustal growth of the North China Craton revealed by zircon Hf isotope: A synthesis

    Directory of Open Access Journals (Sweden)

    Andong Wang

    2012-03-01

    Full Text Available The crustal growth of the North China Craton (NCC during the Neoarchean time (2.5–2.8 Ga is a hotly controversial topic, with some proposing that the main crustal growth occurred in the late Neoarchean (2.5–2.6 Ga, in agreement with the time of the magmatism, whereas others suggest that the main crustal accretion took place during early Neoarchean time (2.7–2.8 Ga, consistent with the time of crustal-formation of other cratons in the world. Zircon U-Pb ages and Hf isotope compositions can provide rigorous constraints on the time of crustal growth and the evolution and tectonic division of the NCC. In this contribution, we make a comprehensive review of zircon Hf isotope data in combination with zircon U-Pb geochronology and some geochemistry data from various divisions of the NCC with an aim to constrain the Neoarchean crustal growth of the NCC. The results suggest that both 2.7–2.8 Ga and 2.5–2.6 Ga crustal growth are distributed over the NCC and the former is much wider than previously suggested. The Eastern block is characterized by the main 2.7–2.8 Ga crustal growth with local new crustal-formation at 2.5–2.6 Ga, and the Yinshan block is characterized by ∼2.7 Ga crustal accretion as revealed by Hf-isotope data of detrital zircons from the Zhaertai Group. Detrital zircon data of the Khondalite Belt indicate that the main crustal growth period of the Western block is Paleoproterozoic involving some ∼2.6 Ga and minor Early- to Middle-Archean crustal components, and the crustal accretion in the Trans-North China Orogen (TNCO has a wide age range from 2.5 Ga to 2.9 Ga with a notable regional discrepancy. Zircon Hf isotope compositions, coupled with zircon ages and other geochemical data suggest that the southern margin may not be an extension of the TNCO, and the evolution and tectonic division of the NCC is more complex than previously proposed, probably involving multi-stage crustal growth and subduction processes

  20. Devonian alkaline magmatism in the northern North China Craton: Geochemistry, SHRIMP zircon U-Pb geochronology and Sr-Nd-Hf isotopes

    Directory of Open Access Journals (Sweden)

    Dingling Huang

    2017-01-01

    Full Text Available The Wulanhada pluton is among the rare suite of Devonian alkaline plutons occurring along the northern margin of the North China Craton (NCC. The intrusion is mainly composed of quartz-monzonite. Here we report zircon SHRIMP U-Pb data from this intrusion which shows emplacement age of ca. 381.5 Ma. The rock is metaluminous with high (Na2O + K2O values ranging from 8.46 to 9.66 wt.%. The REE patterns of the rocks do not show any Eu anomaly whereas the primitive-mantle-normalized spider diagram shows strong positive Sr and Ba anomalies. The Wulanhada rocks exhibit high initial values of (87Sr/86Srt = 0.70762–0.70809, low ɛNd(t = −12.76 to −12.15 values and negative values of ɛHf(t = −23.49 to −17.02 with small variations in (176Hf/177Hft (0.281873–0.282049. These geochemical features and quantitative isotopic modeling results suggest that the rocks might have been formed through the partial melting of Neoarchean basic rocks in the lower crust of the NCC. The Wulanhada rocks, together with the Devonian alkaline rocks and mafic-ultramafic complex from neighboring regions, constitute a post-collisional magmatic belt along the northern NCC.

  1. Zircon U-Pb age, Hf isotope and geochemistry of Carboniferous intrusions from the Langshan area, Inner Mongolia: Petrogenesis and tectonic implications

    Science.gov (United States)

    Liu, Min; Zhang, Da; Xiong, Guangqiang; Zhao, Hongtao; Di, Yongjun; Wang, Zhong; Zhou, Zhiguang

    2016-04-01

    Late Paleozoic was a critical period for the tectonic evolution of the northern margin of the Alxa-North China craton, but the evolutionary history is not well constrained. The Carboniferous intrusions in the Langshan area in the western part of the northern margin of the Alxa-North China craton are mainly composed of tonalite, quartz diorite, olivine gabbro and pyroxene peridotite. Zircon LA-ICP-MS U-Pb dating indicates that the Langshan Carboniferous intrusions were emplaced at ca. 338-324 Ma. The quartz diorites are characterized by high amounts of compatible trace elements (Cr, Ni and V) and high Mg# values, which may suggest a significant mantle source. The positive Pb and negative Nb-Ta-Ti anomalies, the variable εHf(t) (-6.9 to 2.0) values and the old Hf model ages (1218-1783 Ma) imply some involvement of ancient continental materials in its petrogenesis. The tonalite has relatively high Sr/Y ratios, low Mg#, Yb and Y contents, features of adakite-like rocks, negative εHf(t) values (-9.8 to -0.1) and older Hf model ages (1344-1953 Ma), which suggest significant involvement of ancient crust materials and mantle-derived basaltic component in its petrogenesis. The high Mg# values, high Cr and Ni contents, and low Zr and Hf contents of the mafic-ultramafic rocks show evidence of a mantle source, and the relatively low zircon εHf(t) values (-5.9 to 3.2) might point to an enriched mantle. The trace element characteristics indicate the influence of subducted sediments and slab-derived fluids. In the tectonic discrimination diagrams, all the rocks plot in subduction-related environment, such as volcanic arc and continental arc. Considering the regional geology, we suggest that the Carboniferous intrusions in the Langshan area were likely emplaced during the late stage of the southward subduction of the Paleo-Asian Ocean plate, which formed a continental arc along the northern margin of the Alxa-North China craton.

  2. Identifying the Presence of AMD-Derived Soil CO2 in Field Investigations Using Isotope Ratios

    Directory of Open Access Journals (Sweden)

    Kwame Awuah-Offei

    2016-03-01

    Full Text Available Recent incidents of hazardous accumulations of CO2 in homes on or adjacent to reclaimed mine land have been shown to be linked to neutralization reactions between acidic mine drainage and carbonate material. An efficient and economic method is necessary to identify the presence of acid mine drainage- (AMD- derived CO2 on reclaimed mine land, prior to construction. One approach to identify the presence of AMD-derived CO2 is to characterize stable carbon isotope ratios of soil CO2. To do so, a viable method is necessary to acquire soil gas samples for isotope ratio analysis. This paper presents preliminary investigations of the effectiveness of two methods of acquiring gas samples (sampling during soil flux measurements and using slam bar for isotope analysis. The results indicate that direct soil gas sampling is cheaper and provides better results. Neither method is adequate without accounting for temporal effects due to changing gas transport mechanisms. These results have significant implications for safe post-mining land uses and future investigations of leakages from geologic carbon sequestration sites.

  3. Development and Airborne Operation of a Compact Water Isotope Ratio Infrared Spectrometer

    Science.gov (United States)

    Iannone, Rosario Q.; Kassi, Samir; Jost, Hans-Juerg; Chenevier, Marc; Romanini, Daniele; Meijer, Harro A. J.; Dhaniyala, Suresh; Snels, Marcel; Kerstel, Erik R. T.

    2009-01-01

    A sensitive laser spectrometer, named IRIS (water isotope ratio infrared spectrometer), was developed for the in situ detection of the isotopic composition of water vapour in the upper troposphere and the lower stratosphere. Isotope ratio measurements can be used to quantify troposphere stratosphere exchange, and to study the water chemistry in the stratosphere. IRIS is based on the technique of optical feedback cavity-enhanced absorption spectroscopy. It uses a room temperature near-infrared laser, and does not require cryogenic cooling of laser or detectors. The instrument weighs 51 kg including its support structure. Airborne operation was demonstrated during three flights aboard the European M55-Geophysica stratospheric research aircraft, as part of the AMMA/SCOUT-03 (African Monsoon Multidisciplinary Analysis/Stratospheric Climate links with emphasis on the Upper Troposphere and lower stratosphere) campaign in Burkina Faso in August 2006. The data are discussed with reference to a Rayleigh distillation model. As expected, there is no indication of non-mass-dependent fractionation (also known as mass-independent fractionation) in the troposphere. Furthermore, improvements to the thermal management system and a move to a (cryogen-free) longer-wavelength laser source are discussed, which together should result in approximately two orders of magnitude improvement of the sensitivity

  4. The high-spin {sup 178m2}Hf isomer: production, chemical and isotopic separations, gamma spectrometry and internal conversion electrons spectrometry; L`isomere de haut spin {sup 178m2}Hf: production, separations chimiques et isotopiques, spectrometrie gamma et spectrometrie d`electrons de conversion interne

    Energy Technology Data Exchange (ETDEWEB)

    Kim, J.B.

    1993-10-13

    The high-spin isometric state of the nucleus 178Hf is a challenge for new and exotic nuclear physics studies. With its long half-life of 31 years, the production of a reasonable micro-weight quantity, with an isometric to ground state ratio as high as 5 per cent, is now regularly performed by intensive irradiations of ytterbium targets with helium ions of 36 MeV. Using sur-enriched, at 99,998 per cent, ytterbium 176 that we have prepared at the PARIS mass separator, the isomer purity has been improved. Targets of such material but also of enriched stable isotopes of hafnium have been prepared by electro-spraying of methanolic and acetic solutions. By inelastic diffusion of protons and deuton on these targets, the energy of the first state of the rotation band built on the isomer has been measured. Isotopic separations of the isomer have been performed, with a yield greater than 20 per cent, by the use of isotopically pure hafnium 176 as carrier. The separated beam of the mass 178 allowed to record the complete hyperfine spectrum of the isomer and to measure, for the first time, the magnetic dipole moment and the electric quadrupole moment. Isomer targets, implanted in various materials like copper, iron and hafnium monocrystal, provide the opportunity to accurately measure gamma and internal conversion decay of this nuclei and so to precise the multipolarity mixing of all transitions from K=16{sup +} to K=8{sup -}. (author). 49 refs., 47 figs., 11 tabs.

  5. 87Sr/86Sr isotope ratio measurements by laser ablation multicollector inductively coupled plasma mass spectrometry: Reconsidering matrix interferences in bioapatites and biogenic carbonates

    Science.gov (United States)

    Irrgeher, Johanna; Galler, Patrick; Prohaska, Thomas

    2016-11-01

    This study is dedicated to the systematic investigation of the effect of interferences on Sr isotopic analyses in biological apatite and carbonate matrices using laser ablation multicollector inductively coupled plasma mass spectrometry (LA-MC ICP-MS). Trends towards higher 87Sr/86Sr ratios for LA-MC ICP-MS compared to solution-nebulization based MC ICP-MS when analysing bioapatite matrices (e.g. human teeth) and lower ratios in case of calcium carbonates (e.g. fish ear stones) were observed. This effect can be related to the presence of significant matrix-related interferences such as molecular ions (e.g. (40Ca-31P-16O)+, (40Ar-31P-16O)+, (42Ca-44Ca)+, (46Ca40Ar)+) as well as in many cases concomitant atomic ions (e.g. 87Rb+, 174Hf2 +). Direct 87Sr/86Sr ratio measurements in Ca-rich samples are conducted without the possibility of prior sample separation, which can be accomplished routinely for solution-based analysis. The presence of Ca-Ar and Ca-Ca molecular ion interferences in the mass range of Sr isotopes is shown using the mass resolving capabilities of a single collector inductively coupled plasma sector field mass spectrometer operated in medium mass resolution when analysing bioapatites and calcium carbonate samples. The major focus was set on analysing human tooth samples, fish hard parts and geological carbonates. Potential sources of interferences were identified and corrected for. The combined corrections of interferences and adequate instrumental isotopic fractionation correction procedures lead to accurate data even though increased uncertainties have to be taken into account. The results are discussed along with approaches presented in literature for data correction in laser ablation analysis.

  6. Microbial activities and phosphorus cycling: An application of oxygen isotope ratios in phosphate

    Science.gov (United States)

    Stout, Lisa M.; Joshi, Sunendra R.; Kana, Todd M.; Jaisi, Deb P.

    2014-08-01

    Microorganisms carry out biochemical transformations of nutrients that make up their cells. Therefore, understanding how these nutrients are transformed or cycled in natural environments requires knowledge of microbial activity. Commonly used indicators for microbial activity typically include determining microbial respiration by O2/CO2 measurements, cell counts, and measurement of enzyme activities. However, coupled studies on nutrient cycling and microbial activity are not given enough emphasis. Here we apply phosphate oxygen isotope ratios (δ18OP) as a tool for measurement of microbial activity and compare the rate of isotope exchange with methods of measuring microbial activities that are more commonly applied in environmental studies including respiration, dehydrogenase activity, alkaline phosphatase activity, and cell counts. Our results show that different bacteria may have different strategies for P uptake, storage and release, their respiration and consequently expression of DHA and APase activities, but in general the trend of their enzyme activities are comparable. Phosphate δ18OP values correlated well with these other parameters used to measure microbial activity with the strongest linear relationships between δ18OP and CO2 evolution (r = -0.99). Even though the rate of isotope exchange for each microorganism used in this study is different, the rate per unit CO2 respiration showed one general trend, where δ18OP values move towards equilibrium while CO2 is generated. While this suggests that P cycling among microorganisms used in this study can be generalized, further research is needed to determine whether the microorganism-specific isotope exchange trend may occur in natural environments. In summary, phosphate oxygen isotope measurements may offer an alternative for use as a tracer to measure microbial activity in soils, sediments, and many other natural environments.

  7. Isotopic 32S/33S ratio as a diagnostic of presolar grains from novae

    Directory of Open Access Journals (Sweden)

    A. Parikh

    2014-10-01

    Full Text Available Measurements of sulphur isotopes in presolar grains can help to identify the astrophysical sites in which these grains were formed. A more precise thermonuclear rate of the 33S(p,γ34Cl reaction is required, however, to assess the diagnostic ability of sulphur isotopic ratios. We have studied the 33S(3He,d34Cl proton-transfer reaction at 25 MeV using a high-resolution quadrupole–dipole–dipole–dipole magnetic spectrograph. Deuteron spectra were measured at ten scattering angles between 10° and 55°. Twenty-four levels in 34Cl over Ex=4.6–5.9 MeV were observed, including three levels for the first time. Proton spectroscopic factors were extracted for the first time for levels above the 33S + p threshold, spanning the energy range required for calculations of the thermonuclear 33S(p,γ34Cl rate in classical nova explosions. We have determined a new 33S(p,γ34Cl rate using a Monte Carlo method and have performed new hydrodynamic nova simulations to determine the impact on nova nucleosynthesis of remaining nuclear physics uncertainties in the reaction rate. We find that these uncertainties lead to a factor of ≤5 variation in the 33S(p,γ34Cl rate over typical nova peak temperatures, and variation in the ejected nova yields of SCa isotopes by ≤20%. In particular, the predicted 32S/33S ratio is 110–130 for the nova model considered, compared to 110–440 with previous rate uncertainties. As recent type II supernova models predict ratios of 130–200, the 32S/33S ratio may be used to distinguish between grains of nova and supernova origin.

  8. Hydrogen-Isotopic Ratios of Lipids From Hydrogen-Consuming Bacteria

    Science.gov (United States)

    Campbell, B. J.; Fox, D. N.; Sessions, A. L.; Valentine, D. L.

    2005-12-01

    Molecular hydrogen (H2) plays several key roles in aquatic sediments. Metabolized by a wide variety of prokaryotes, it both serves a vehicle for interspecies electron transfer and exerts thermodynamic control over microbial metabolic processes. H2 is typically depleted in deuterium (D) by up to 600‰ relative to water, providing a potential isotopic marker for H2-consuming organisms. Preservation of that isotopic signal in sediments requires that molecular H2 can be an indirect source of carbon-bound hydrogen in microbial lipids, a question that is the target of our ongoing laboratory-based investigations. Here we report compound-specific H-isotopic analyses of lipids extracted from H2-consuming bacteria grown under defined isotopic conditions (δD-H2 and δD-H2O). Cupriavidus necator, an aerobe, is a facultatively lithoautotrophic "knallgas" bacterium. C. necator was grown on H2 + O2 + CO2 in liquid media with differing δD-H2O values. The results of compound-specific isotopic analysis show a strong correlation between the H-isotopic ratio of lipids and that of H2O in the growth medium. Cultures grown in media of δD-H2O = -24‰ produced lipids in which δD values were from -258‰ to -197‰. In media of δD-H2O = +527‰, δD-lipid values were from +117‰ to +228‰. In media of δD-H2O = +1115‰, δD-lipid values were from +514‰ to +675‰. Linear regression was performed on the data from each lipid compound (R2 > 0.9994 in all cases). Regression lines intercepted the δD-lipid axis between -966‰ ([D]/[H] = 5.23×10-6) and -827‰ ([D]/[H] = 1.60×10-5); slopes were between and 0.670 and 0.764. These results indicate that the isotopic composition of lipids is entirely controlled by that of water, i.e. that the isotopic depletion of H2 is not recorded in the lipids - in sharp contrast to previous results from another hydrogenotroph, Sporomusa sp., where part of lipid H is derived indirectly from H2. The results are consistent with two possibilities: 1

  9. Petrogenesis of highly fractionated I-type granites in the Zayu area of eastern Gangdese, Tibet: Constraints from zircon U-Pb geochronology, geochemistry and Sr-Nd-Hf isotopes

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    The Cretaceous granitoids in the middle and northern Gangdese, Tibet are generally interpreted as the products of anatexis of thickened deep crust genetically associated with the Lhasa-Qiangtang collision. This paper reports bulk-rock major element, trace element and Sr-Nd isotopic data, zircon U-Pb age data, and zircon Hf isotopic data on the Zayu pluton in eastern Gangdese, Tibet. These data shed new light on the petrogenesis of the pluton. Our SHRIMP zircon U-Pb age dates, along with LA-ICPMS zircon U-Pb age dates recently reported in the literature, indicate that the Zayu pluton was emplaced at about 130 Ma, coeval with Early Cretaceous magmatic rocks in other areas of eastern Gangdese (e.g., Rawu, Baxoi areas) and the Middle Gangdese. The Zayu pluton samples lack amphibole and muscovite, and are compositionally characterized by high SiO2 (69.9%―76.8%), K2O (4.4%―5.7%), and low P2O5 (0.05%―0.12%). These samples also have A/CNK values of 1.00-1.05, and are enriched in Rb, Th, U, and Pb, and depleted in Ba, Nb, Ta, Sr, P, Ti, and Eu. These geochemical features suggest that the Zayu pluton samples are metaluminous to slightly peraluminous and are of highly fractionated I-type granite. The Zayu pluton samples have high εNd(t) values (-10.9--7.6) and low initial 87Sr/86Sr ratios (0.7120- 0.7179) relative to melts derived from mature continental crust in the Gangdese (e.g., Ningzhong Early Jurassic strongly peraluminous granite). The Zayu pluton samples are heterogeneous in zircon εHf(t) values (-12.8--2.9), yielding ancient zircon Hf crustal model ages of 1.4―2.0 Ga. The data obtained in this study together with the data in the recent literature suggest that the Early Cretaceous granitoids in eastern Gangdese represent the eastward extension of the Early Cretaceous magmatism in the middle Gangdese, and that the Lhasa micro-continent block with ancient basement may extend for ~2000 km from east to west. Zircon Hf isotopic data and bulk-rock zircon

  10. Petrogenesis of highly fractionated Ⅰ-type granites in the Zayu area of eastern Gangdese,Tibet:Constraints from zircon U-Pb geochronology,geochemistry and Sr-Nd-Hf isotopes

    Institute of Scientific and Technical Information of China (English)

    ZHU DiCheng; MO XuanXue; WANG LiQuan; ZHAO ZhiDan; NIU Yaoling; ZHOU ChangYong; YANG YueHeng

    2009-01-01

    The Cretaceous granitoids in the middle and northern Gangdese,Tibet are generally interpreted as the products of anatexis of thickened deep crust genetically associated with the Lhasa-Qiangtang collision.This paper reports bulk-rock major element,trace element and Sr-Nd isotopic data,zircon U-Pb age data,and zircon Hf isotopic data on the Zayu pluton in eastern Gangdese,Tibet.These data shed new light on the petrogenesis of the pluton.Our SHRIMP zircon U-Pb age dates,along with LA-ICPMS zircon U-Pb age dates recently reported in the literature,indicate that the Zayu pluton was emplaced at about 130 Ma,coeval with Early Cretaceous magmatic rocks in other areas of eastern Gangdese (e.g.,Rawu,Baxoi areas) and the Middle Gangdese.The Zayu pluton samples lack amphibole and muscovite,and are compositionally characterized by high SiO2 (69.9%-76.8%),K20 (4.4%-5.7%),and low P2O5 (0.05%-0.12%).These samples also have A/CNK values of 1.00-1.05,and are enriched in Rb,Th,U,and Pb,and depleted in Ba,Nb,Ta,Sr,P,Ti,and Eu.These geochemical features suggest that the Zayu pluton samples ere metaluminous to slightly peraluminous and are of highly fractionated Ⅰ-type granite.The Zayu pluton samples have high εNd(t) values (-10.9-7.6) and low initial 87Sr/86Sr ratios (0.7120-0.7179) relative to melts derived from mature continental crust in the Gangdese (e.g.,Ningzhong Early Jurassic strongly peraluminous granite).The Zayu pluton samples are heterogeneous in zircon εHf(t) values (-12.8-2.9),yielding ancient zircon Hf crustal model ages of 1.4-2.0 Ga.The data obtained in this study together with the data in the recent literature suggest that the Early Cretaceous granitoids in eastern Gangdese represent the eastward extension of the Early Cretaceous magmatism in the middle Gangdese,and that the Lhasa micro-continent block with ancient basement may extend for ~2000 km from east to west.Zircon Hf isotopic data and bulk-rock zircon saturation temperature (789-821℃) indicate that

  11. Ion/Ioff ratio enhancement and scalability of gate-all-around nanowire negative-capacitance FET with ferroelectric HfO2

    Science.gov (United States)

    Jang, Kyungmin; Saraya, Takuya; Kobayashi, Masaharu; Hiramoto, Toshiro

    2017-10-01

    We have investigated the energy efficiency and scalability of ferroelectric HfO2 (FE:HfO2)-based negative-capacitance field-effect-transistor (NCFET) with gate-all-around (GAA) nanowire (NW) channel structure. Analytic simulation is conducted to characterize NW-NCFET by varying NW diameter and/or thickness of gate insulator as device structural parameters. Due to the negative-capacitance effect and GAA NW channel structure, NW-NCFET is found to have 5× higher Ion/Ioff ratio than classical NW-MOSFET and 2× higher than double-gate (DG) NCFET, which results in wider design window for high Ion/Ioff ratio. To analyze these obtained results from the viewpoint of the device scalability, we have considered constraints regarding very limited device structural spaces to fit by the gate insulator and NW channel for aggresively scaled gate length (Lg) and/or very tight NW pitch. NW-NCFET still has design point with very thinned gate insulator and/or narrowed NW. Therefore, FE:HfO2-based NW-NCFET is applicable to the aggressively scaled technology node of sub-10 nm Lg and to the very tight NW integration of sub-30 nm NW pitch for beyond 7 nm technology. From 2011 to 2014, he engaged in developing high-speed optical transceiver module as an alternative military service in Republic of Korea. His research interest includes the development of steep slope MOSFETs for high energy-efficient operation and ferroelectric HfO2-based semiconductor devices, and fabrication of nanostructured devices. He joined the IBM T.J. Watson Research Center, Yorktown Heights, NY, in 2010, where he worked on advanced CMOS technologies such as FinFET, nanowire FET, SiGe channel and III-V channel. He was also engaged in launching 14 nm SOI FinFET and RMG technology development. Since 2014, he has been an Associate Professor in Institute of Industrial Science, University of Tokyo, Tokyo, Japan, where he has been working on ultralow power transistor and memory technology. Dr. Kobayashi is a member of IEEE

  12. Palaeoproterozoic continental arc magmatism, and Neoproterozoic metamorphism in the Aravalli-Delhi orogenic belt, NW India: New constraints from in situ zircon U-Pb-Hf isotope systematics, monazite dating and whole-rock geochemistry

    Science.gov (United States)

    Kaur, Parampreet; Zeh, Armin; Chaudhri, Naveen

    2017-04-01

    Presently, the extent, origin and petrogenesis of late Palaeoproterozoic (ca. 1.85 Ga) magmatism in the north-central Aravalli-Delhi orogenic belt, NW India and subsequent metamorphic overprints are poorly constrained. Results of new in situ zircon U-Pb-Hf isotope analyses in combination with whole-rock elemental and isotopic data provide the first hard evidence that granitoid magmatism occurred in a continental magmatic arc setting between 1.86 and 1.81 Ga. The Hf-Nd model ages of 3.0-2.6 Ga and inherited zircon grains of 3.3-2.5 Ga indicate abundant reworking of Archaean crust. Flat HREE patterns with negative Eu anomalies furthermore reveal that the granitoids were generated from garnet-free and plagioclase-rich sources at shallow depths. Significant isotope variation among granitoid samples (εHft = -3.7 to -9.0; εNdt = -4.8 to -7.9) indicate that the reworked Archaean crust was not completely homogenised during the Palaeoproterozoic. This is best reflected by zircon Hf-isotope variation of ca. 9.5 epsilon units within the oldest granitoid sample. Zircon grains from this sample define three discrete Hf-isotope groups at εHf1.86Ga = -8.9, -4.8 and -1.6. These are interpreted to result from mixing of zircon-saturated magmas derived from three distinct sources within the crust prior to solidification. A monazite U-Pb isochron age of 868 ± 4 Ma from one of the granitoid samples furthermore indicates that the Aravalli fold belt was affected by an important post-magmatic overprint, perhaps related to the widespread metasomatic, granulite metamorphic and/or magmatic events during the same time span.

  13. Identification of Marchfeld asparagus using Sr isotope ratio measurements by MC-ICP-MS

    Energy Technology Data Exchange (ETDEWEB)

    Swoboda, S.; Brunner, M.; Boulyga, S.F.; Galler, P.; Prohaska, T. [University of Natural Resources and Applied Life Sciences, Department of Chemistry-VIRIS Project, Vienna (Austria); Horacek, M. [Austrian Research Centers GmbH, Seibersdorf (Austria)

    2008-01-15

    This work focuses on testing and application of Sr isotope signatures for the fast and reliable authentication and traceability of Asparagus officinalis originating from Marchfeld, Austria, using multicollector inductively coupled plasma mass spectrometry after optimised Rb/Sr separation. The major sample pool comprises freeze-dried and microwave-digested asparagus samples from Hungary and Slovakia which are compared with Austrian asparagus originating from the Marchfeld region, which is a protected geographical indication. Additional samples from Peru, the Netherlands and Germany were limited in number and allowed therefore only restricted statistical evaluation. Asparagus samples from Marchfeld were harvested within two subsequent years in order to investigate the annual variation. The results show that the Sr isotope ratio is consistent within these 2 years of investigation. Moreover, the Sr isotope ratio of total Sr in soil was found to be significantly higher than in an NH{sub 4}NO{sub 3} extract, reflecting the mobile (bioavailable) phase. The isotope composition in the latter extract corresponds well to the range found in the asparagus samples in Marchfeld, even though the concentration of Sr in asparagus shows no direct correlation to the concentration of Sr in the mobile phase of the soil. The major question was whether the 'Marchfelder Spargel' can be distinguished from samples from the neighbouring countries of Hungary and Slovakia. According to our findings, they can be clearly (100%) singled out from the Hungarian samples and can be distinguished from the Slovakian asparagus samples with a probability of more than 80%. (orig.)

  14. Performance evaluation of nitrogen isotope ratio determination in marine and lacustrine sediments: An inter-laboratory comparison

    NARCIS (Netherlands)

    Bahlmann, E.; Bernasconi, S.M.; Bouillon, S.; Houtekamer, M.; Korntheuer, M.; Langenberg, F.; Mayr, C.; Metzke, M.; Middelburg, J.J.; Nagel, B.; Struck, U.; Voß, M.; Emeis, K.C.

    2010-01-01

    Nitrogen isotopes of organic matter are increasingly studied in marine biogeochemistry and geology, plant and animal ecology, and paleoceanography. Here, we present results of an inter-laboratory test on determination of nitrogen isotope ratios in marine and lacustrine sediments. Six different

  15. Performance evaluation of nitrogen isotope ratio determination in marine and lacustrine sediments: An inter-laboratory comparison

    NARCIS (Netherlands)

    Bahlmann, E.; Bernasconi, S.M.; Bouillon, S.; Houtekamer, M.; Korntheuer, M.; Langenberg, F.; Mayr, C.; Metzke, M.; Middelburg, J.J.; Nagel, B.; Struck, U.; Voß, M.; Emeis, K.C.

    2010-01-01

    Nitrogen isotopes of organic matter are increasingly studied in marine biogeochemistry and geology, plant and animal ecology, and paleoceanography. Here, we present results of an inter-laboratory test on determination of nitrogen isotope ratios in marine and lacustrine sediments. Six different sampl

  16. Isotope ratios of H, C, and O in CO2 and H2O of the martian atmosphere

    NARCIS (Netherlands)

    Webster, C.R.; Mahaffy, P.R.; Flesch, G.J.; Niles, P.B.; Jones, J.H.; Leshin, L.A.; Atreya, S.K.; Stern, J.C.; Christensen, L.E.; Owen, T.; Franz, H.; Pepin, R.O.; Steele, A.; MSL Science Team, the

    2013-01-01

    Stable isotope ratios of H, C, and O are powerful indicators of a wide variety of planetary geophysical processes, and for Mars they reveal the record of loss of its atmosphere and subsequent interactions with its surface such as carbonate formation. We report in situ measurements of the isotopic ra

  17. Stable carbon isotope ratios of intact GDGTs indicate heterogeneous sources to marine sediments

    Science.gov (United States)

    Pearson, Ann; Hurley, Sarah J.; Walter, Sunita R. Shah; Kusch, Stephanie; Lichtin, Samantha; Zhang, Yi Ge

    2016-05-01

    Thaumarchaeota, the major sources of marine glycerol dibiphytanyl glycerol tetraether lipids (GDGTs), are believed to fix the majority of their carbon directly from dissolved inorganic carbon (DIC). The δ13C values of GDGTs (δ13CGDGT) may be powerful tools for reconstructing variations in the ocean carbon cycle, including paleoproductivity and water mass circulation, if they can be related to values of δ13CDIC. To date, isotope measurements primarily are made on the C40 biphytane skeletons of GDGTs, rather than on complete tetraether structures. This approach erases information revealed by the isotopic heterogeneity of GDGTs within a sample and may impart an isotopic fractionation associated with the ether cleavage. To circumvent these issues, we present δ13C values for GDGTs from twelve recent sediments representing ten continental margin locations. Samples are purified by orthogonal dimensions of HPLC, followed by measurement of δ13C values by Spooling Wire Microcombustion (SWiM)-isotope ratio mass spectrometry (IRMS) with 1σ precision and accuracy of ±0.25‰. Using this approach, we confirm that GDGTs, generally around -19‰, are isotopically "heavy" compared to other marine lipids. However, measured δ13CGDGT values are inconsistent with predicted values based on the 13C content of DIC in the overlying water column and the previously-published biosynthetic isotope fractionation for a pure culture of an autotrophic marine thaumarchaeon. In some sediments, the isotopic composition of individual GDGTs differs, indicating multiple source inputs. The data appear to confirm that crenarchaeol primarily is a biomarker for Thaumarchaeota, but its δ13C values still cannot be explained solely by autotrophic carbon fixation. Overall the complexity of the results suggests that both organic carbon assimilation (ca. 25% of total carbon) and multiple source(s) of exogenous GDGTs (contributing generally <30% of input to sediments) are necessary to explain the observed

  18. Origin of Meso-Proterozoic post-collisional leucogranite suites (Kaokoveld, Namibia): constraints from geochronology and Nd, Sr, Hf, and Pb isotopes

    Science.gov (United States)

    Jung, S.; Mezger, K.; Nebel, O.; Kooijman, E.; Berndt, J.; Hauff, F.; Münker, C.

    2012-01-01

    Leucocratic granites of the Proterozoic Kaoko Belt, northern Namibia, now preserved as meta-granites, define a rock suite that is distinct from the surrounding granitoids based on their chemical and isotopic characteristics. Least evolved members of this ~1.5-1.6-Ga-old leucogranite suite can be distinguished from ordinary calc-alkaline granites that occur elsewhere in the Kaoko Belt by higher abundances of Zr, Y, and REE, more radiogenic initial ɛNd values and unradiogenic initial 87Sr/86Sr. The leucogranites have high calculated zircon saturation temperatures (mostly > 920°C for least fractionated samples), suggesting that they represent high-temperature melts originating from deep crustal levels. Isotope data (i.e., ɛNdi: +2.3 to -4.2) demonstrate that the granites formed from different sources and differentiated by a variety of processes including partial melting of mantle-derived meta-igneous rocks followed by crystal fractionation and interaction with older crustal material. Most fractionation-corrected Nd model ages (TDM) are between 1.7 and 1.8 Ga and only slightly older than the inferred intrusion age of ca. 1.6 Ga, indicating that the precursor rocks must have been dominated by juvenile material. Epsilon Hf values of zircon separated from two granite samples are positive (+11 and +13), and Hf model ages (1.5 and 1.6 Ga) are similar to the U-Pb zircon ages, again supporting the dominance of juvenile material. In contrast, the Hf model ages of the respective whole rock samples are 2.3 and 2.4 Ga, demonstrating the involvement of older material in the generation of the granites. The last major tectonothermal event in the Kaoko Belt in the Proterozoic occurred at ca. 2.0 Ga and led to reworking of mostly 2.6-Ga-old rocks. However, the presence of 1.6 Ga "post-collisional" granites reflects addition of some juvenile mantle-derived material after the last major tectonic event. The results suggest that similar A-type leucogranites are potentially more

  19. Zircon U-Pb geochronology, geochemistry, and Sr-Nd-Hf isotopes of granitoids in the Yulekenhalasu copper ore district, northern Junggar, China: Petrogenesis and tectonic implications

    Science.gov (United States)

    Yang, Fuquan; Chai, Fengmei; Zhang, Zhixin; Geng, Xinxia; Li, Qiang

    2014-03-01

    The Yulekenhalasu porphyry copper deposit is located in the Kalaxiange'er metallogenic belt in northern Junggar, China. We present the results from zircon U-Pb geochronology, and geochemical and Sr-Nd-Hf isotope analyses of the granitoids associated with the ore deposits with a view to constrain their petrogenesis and tectonic setting. The granitoids consist of quartz diorite, diorite porphyry, porphyritic monzonite, and quartz porphyry, emplaced at 382, 379, 375-374, and 348 Ma, respectively, which span Late Devonian to early Carboniferous ages. The ore-bearing intrusion is mainly diorite porphyry, with subordinate porphyritic monzonite. The Late Devonian intrusions are characterized by SiO2 contents of 54.5-64.79 wt.%, Na2O contents of 3.82-8.24 wt.%, enrichment in Na, light rare-earth elements (LREEs), and large ion lithophile elements. They also display relative depletion in Y, Ba, P, Nb, Ta, and Ti, and weak negative Eu anomalies (δEu = 0.6-0.87). The early Carboniferous quartz porphyry is characterized by high SiO2 content (72.26-73.35 wt.%), enrichment in LREEs, K, and Sr, and relative depletion in Y (10.82-12.52 ppm) and Yb (1.06-1.15 ppm). The Late Devonian and early Carboniferous granitoids are characterized by positive ɛNd(t) values (5.2-10.1, one sample at - 1.9), positive ɛHf(t) values (7.46-18.45), low (87Sr/86Sr)i values (0.70363-0.70476), and young crustal residence ages. These data indicate that the sources of the granitoids were mainly mantle-derived juvenile rocks. Geochemical and Nd-Sr-Hf isotopic data demonstrate that the Late Devonian granitoids formed in an oceanic island arc, and they were formed from different sources, among which the mineralized diorite porphyry might have originated from a mixed slab-derived and mantle wedge melt source. The early Carboniferous quartz porphyry was likely emplaced in a mature island arc environment, and was probably derived from juvenile crust.

  20. Origin of the granites and related Sn and Pb-Zn polymetallic ore deposits in the Pengshan district, Jiangxi Province, South China: constraints from geochronology, geochemistry, mineral chemistry, and Sr-Nd-Hf-Pb-S isotopes

    Science.gov (United States)

    Xu, Bin; Jiang, Shao-Yong; Luo, Lan; Zhao, Kui-Dong; Ma, Liang

    2016-05-01

    The Pengshan Sn and Pb-Zn polymetallic deposits are located in the south margin of the Jiujiang-Ruichang (Jiurui) district of the Middle-Lower Yangtze River Metallogenic Belt in South China. Four large deposits include Huangjinwa, Zengjialong, Jianfengpo, and Zhangshiba, the former three are Sn-dominant deposits which occur as stratiform orebodies in the contact zones of the Pengshan granites and within the country rock strata, whereas Zhangshiba consists of stratiform Pb-Zn orebodies within the Precambrian metasedimentary strata. In this study, we present results on zircon U-Pb ages, major and trace elements, and mineral chemistry as well as Sr-Nd-Hf isotope data of the granites, Pb and S isotopes of both the Sn-dominant and Pb-Zn dominant deposits, and U-Pb dating of cassiterite from the Pengshan district. SHRIMP and LA-ICP-MS zircon U-Pb dating shows that the Pengshan granites were emplaced in the Early Cretaceous (129-128 Ma), which is in good agreement with the U-Pb dating (130-128 Ma) of cassiterite from the Jianfengpo Sn deposit. The Pengshan granites consist mainly of weakly peraluminous highly fractionated I-type affinity granitic rocks. Detailed elemental and isotopic data suggest that the granites formed by partial melting of Mesoproterozoic metamorphic basement materials with minor input of mantle-derived melts. The mineral chemistry of biotite demonstrates that the Pengshan granitic magma had a low oxygen fugacity, thereby precluding the tin dominantly partitioning into the rock-forming silicate minerals and favoring accumulation in the exsolved residual liquid during magma crystallization stages. Sulfur isotopes show a relatively heavy sulfur isotopic composition from 5.8 to 17.6 ‰, and no difference for sulfur isotopes between the Sn deposits (5.8-13.4 ‰, Huangjinwa, Zengjialong, Jianfengpo) and the Pb-Zn deposit (mostly 7.1-13.0 ‰, except for one 17.6 ‰, Zhangshiba). The sulfur isotope data of pyrite from the host sedimentary rocks show

  1. Origin of the granites and related Sn and Pb-Zn polymetallic ore deposits in the Pengshan district, Jiangxi Province, South China: constraints from geochronology, geochemistry, mineral chemistry, and Sr-Nd-Hf-Pb-S isotopes

    Science.gov (United States)

    Xu, Bin; Jiang, Shao-Yong; Luo, Lan; Zhao, Kui-Dong; Ma, Liang

    2017-03-01

    The Pengshan Sn and Pb-Zn polymetallic deposits are located in the south margin of the Jiujiang-Ruichang (Jiurui) district of the Middle-Lower Yangtze River Metallogenic Belt in South China. Four large deposits include Huangjinwa, Zengjialong, Jianfengpo, and Zhangshiba, the former three are Sn-dominant deposits which occur as stratiform orebodies in the contact zones of the Pengshan granites and within the country rock strata, whereas Zhangshiba consists of stratiform Pb-Zn orebodies within the Precambrian metasedimentary strata. In this study, we present results on zircon U-Pb ages, major and trace elements, and mineral chemistry as well as Sr-Nd-Hf isotope data of the granites, Pb and S isotopes of both the Sn-dominant and Pb-Zn dominant deposits, and U-Pb dating of cassiterite from the Pengshan district. SHRIMP and LA-ICP-MS zircon U-Pb dating shows that the Pengshan granites were emplaced in the Early Cretaceous (129-128 Ma), which is in good agreement with the U-Pb dating (130-128 Ma) of cassiterite from the Jianfengpo Sn deposit. The Pengshan granites consist mainly of weakly peraluminous highly fractionated I-type affinity granitic rocks. Detailed elemental and isotopic data suggest that the granites formed by partial melting of Mesoproterozoic metamorphic basement materials with minor input of mantle-derived melts. The mineral chemistry of biotite demonstrates that the Pengshan granitic magma had a low oxygen fugacity, thereby precluding the tin dominantly partitioning into the rock-forming silicate minerals and favoring accumulation in the exsolved residual liquid during magma crystallization stages. Sulfur isotopes show a relatively heavy sulfur isotopic composition from 5.8 to 17.6 ‰, and no difference for sulfur isotopes between the Sn deposits (5.8-13.4 ‰, Huangjinwa, Zengjialong, Jianfengpo) and the Pb-Zn deposit (mostly 7.1-13.0 ‰, except for one 17.6 ‰, Zhangshiba). The sulfur isotope data of pyrite from the host sedimentary rocks show

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

    Science.gov (United States)

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

    2011-12-01

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

  3. Compact diode-laser spectrometer ISOWAT for highly sensitive airborne measurements of water-isotope ratios

    Science.gov (United States)

    Dyroff, C.; Fütterer, D.; Zahn, A.

    2010-02-01

    The tunable diode-laser absorption spectrometer ISOWAT for airborne measurements of the water-isotope ratios 18O/16O and D/H is described. The spectrometer uses a distributed feedback (DFB) diode laser to probe fundamental rovibrational water-absorption lines at around 2.66 μm. Very-low-noise system components along with signal averaging allow for a detection limit of 1.2 and 4.5 ‰ for measurements of 18O/16O and D/H, respectively, for a water-vapour mixing ratio of 100 ppmv and an averaging time of 60 s. This corresponds to a minimum detectable absorbance of ˜5×10-6 or ˜6.6×10-10 cm-1 when normalized to pathlength. In addition to its high sensitivity, the spectrometer is highly compact (19-inch rack at a height of 35 cm, excluding pump and calibration unit) and light weight (automated. ISOWAT will be calibrated during flight with known water-isotope ratios using a compact calibration-gas source.

  4. New manuscript guidelines for the reporting of stable hydrogen, carbon, and oxygen isotope-ratio data

    Energy Technology Data Exchange (ETDEWEB)

    Anon.

    1995-10-01

    To eliminate possible confusion in the reporting of isotopic abundances on non-corresponding scales, the Commission on Atomic Weights and Isotopic Abundances recommended at the 37{sup th} General Assembly at Lisbon, Portugal that (i) {sup 2}H/{sup 1}H relative ratios of all substances be expressed relative to VSMOW (Vienna Standard Mean Ocean Water) on a scale such that {sup 2}H/{sup 1}H of SLAP (Standard Light Antartic Precipitation) is 0.572 times that of VSMOW, (ii) {sup 13}C/{sup 12}C relative ratios of all substances be expressed relative to VPDB (Vienna Peedee belemnite) on a scale such that {sup 13}C/{sup 12}C of NBS 19 carbonate is 1.00195 times that of VPDB, and (iii) {sup 18}O/{sup 16}O ratios of all substances be expressed relative to either VSMOW or VPDB on scales such that {sup 18}O/{sup 16}O of SLAP is 0.9445 times that of VSMOW. (Author)

  5. Investigation of two technical toxaphene products by using isotope ratio mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Vetter, W.; Armbruster, W. [Hohenheim Univ., Stuttgart (Germany). Inst. fuer Lebensmittelchemie; Gleixner, G. [Max-Planck-Institut fuer Biogeochemie, Jena (Germany)

    2004-09-15

    Organochlorine compounds have been used in high quantities throughout the past 60 years. Being long-lived in the environment and toxic to humans and wildlife, some of them were classified as persistent organic pollutants (POPs). One of the POPs of special concern is toxaphene which is produced by the chlorination of the natural product camphene (or {alpha}-pinene). The technical products consist of several hundred compounds, mainly of chlorobornanes with an average number of eight chlorine substituents. Toxaphene has been produced in high quantities in different parts of the world. Even though the use has been discontinued during the last two decades, there are still several ecosystems which are heavily contaminated with this chloropesticide. Due to the huge variety of the technical products accompanied with a severe change of composition in the environment, analytical tracing back of toxaphene residues to a specific product has not yet been achieved. One of the potential analytical tools for distinguishing substances that differ only in their way of production is the determination of ratios of stable isotopes ({sup 13}C/{sup 12}C; {sup 2}H/{sup 1}H; {sup 15}N/{sup 14}N). Since the synthesis of toxaphene is starting from natural compounds obtained from different continents, the technical products could have different ratios of stable isotopes. In this study, we investigated the {sup 13}C/{sup 12}C ratio of two former major toxaphene products.

  6. He and Ne isotopic ratios along the Terceira Rift: implications for the Azores mantle source

    Science.gov (United States)

    Madureira, P.; Moreira, M. A.; Nunes, J.; Lourenco, N.; Carvalho, M.; Mata, J.; Pinto de Abreu, M.

    2010-12-01

    Noble gas data (He and Ne) on olivine phenocrysts obtained from Azores’ lavas sampled along the Terceira Rift will be presented in this work. The Terceira Rift is considered as one of the slowest spreading system in the world (Vogt & Jung, 2004). Lava samples were collected inland at S. Miguel, Terceira, Graciosa, Pico and Faial Islands as well at sea at D. João de Castro Bank and south Hirondelle basin, the latter being sampled by the ROV cruises in 2008 and 2009. Noble gas data were analyzed in the Noblesse mass spectrometer housed at the IPGP. The most primitive He isotopic ratios were obtained from Pico, Terceira and Hirondelle olivines. Most Ne isotopic ratios are similar to the present-day atmosphere, but distinct 20Ne/22Ne ratios were found for the majority of submarine samples and also Pico and Faial Islands, defining mixing lines with the atmospheric end-member with slopes greater than that defined from MORB lavas. The He-Ne systematics shows that most of the new noble gas data fit in a mixing model between a dominant MORB-type mantle source and a relatively primitive mantle source related with the regional Azores component. However, data from the D. João de Castro Bank argue for the presence of a radiogenic He end-member distinct from MORB. References: Vogt, P. & Jung W. (2004). Earth Planet. Sci. Lett., 218: 77 90.

  7. ICP-MS with hexapole collision cell for isotope ratio measurements of Ca, Fe, and Se.

    Science.gov (United States)

    Boulyga, S F; Becker, J S

    2001-07-01

    To avoid mass interferences on analyte ions caused by argon ions and argon molecular ions via reactions with collision gases, an rf hexapole filled with helium and hydrogen has been used in inductively coupled plasma mass spectrometry (ICP-MS), and its performance has been studied. Up to tenfold improvement in sensitivity was observed for heavy elements (m > 100 u), because of better ion transmission through the hexapole ion guide. A reduction of argon ions Ar+ and the molecular ions of argon ArX+ (X = O, Ar) by up to three orders of magnitude was achieved in a hexapole collision cell of an ICP-MS ("Platform ICP", Micromass, Manchester, UK) as a result of gas-phase reactions with hydrogen when the hexapole bias (HB) was set to 0 V; at an HB of 1.6 V argon, and argon-based ions of masses 40 u, 56 u, and 80 u, were reduced by approximately four, two, and five orders of magnitude, respectively. The signal-to-noise ratio 80Se/ 40Ar2+ was improved by more than five orders of magnitude under optimized experimental conditions. Dependence of mass discrimination on collision-cell properties was studied in the mass range 10 u (boron) to 238 u (uranium). Isotopic analysis of the elements affected by mass-spectrometric interference, Ca, Fe, and Se, was performed using a Meinhard nebulizer and an ultrasonic nebulizer (USN). The measured isotope ratios were comparable with tabulated values from IUPAC. Precision of 0.26%, 0.19%, and 0.12%, respectively, and accuracy of 0.13% 0.25%, and 0.92%, respectively, was achieved for isotope ratios 44Ca/ 40Ca and 56Fe/57Fe in 10 microg L(-1) solution nebulized by means of a USN and for 78Se/80Se in 100 microg L(-1) solution nebulized by means of a Meinhard nebulizer.

  8. Analytical Validation of Accelerator Mass Spectrometry for Pharmaceutical Development: the Measurement of Carbon-14 Isotope Ratio.

    Energy Technology Data Exchange (ETDEWEB)

    Keck, B D; Ognibene, T; Vogel, J S

    2010-02-05

    Accelerator mass spectrometry (AMS) is an isotope based measurement technology that utilizes carbon-14 labeled compounds in the pharmaceutical development process to measure compounds at very low concentrations, empowers microdosing as an investigational tool, and extends the utility of {sup 14}C labeled compounds to dramatically lower levels. It is a form of isotope ratio mass spectrometry that can provide either measurements of total compound equivalents or, when coupled to separation technology such as chromatography, quantitation of specific compounds. The properties of AMS as a measurement technique are investigated here, and the parameters of method validation are shown. AMS, independent of any separation technique to which it may be coupled, is shown to be accurate, linear, precise, and robust. As the sensitivity and universality of AMS is constantly being explored and expanded, this work underpins many areas of pharmaceutical development including drug metabolism as well as absorption, distribution and excretion of pharmaceutical compounds as a fundamental step in drug development. The validation parameters for pharmaceutical analyses were examined for the accelerator mass spectrometry measurement of {sup 14}C/C ratio, independent of chemical separation procedures. The isotope ratio measurement was specific (owing to the {sup 14}C label), stable across samples storage conditions for at least one year, linear over 4 orders of magnitude with an analytical range from one tenth Modern to at least 2000 Modern (instrument specific). Further, accuracy was excellent between 1 and 3 percent while precision expressed as coefficient of variation is between 1 and 6% determined primarily by radiocarbon content and the time spent analyzing a sample. Sensitivity, expressed as LOD and LLOQ was 1 and 10 attomoles of carbon-14 (which can be expressed as compound equivalents) and for a typical small molecule labeled at 10% incorporated with {sup 14}C corresponds to 30 fg

  9. Carbon isotopic characterization of cider CO2 by isotope ratio mass spectrometry: a tool for quality and authenticity assessment.

    Science.gov (United States)

    Cabañero, Ana I; Rupérez, Mercedes

    2012-08-30

    The cider market is an important sector of the food industry in certain regions. Adulteration of cider can happen in several ways: for example, by the addition of sugar, or of exogenous CO(2) to certain types of cider. Because such practices are not allowed by either Spanish legislation or the legislation of other countries, it is essential to study possible methods to detect these unauthorized practices. For this purpose a procedure was required to study the stable carbon isotopic composition of CO(2) in cider. A liquid sample of cider was transferred to a vial and CO(2) from the headspace of the vial was analyzed using a peripheral device interfaced to an isotope ratio mass spectrometer. Separation of the CO(2) from water and ethanol was achieved using a gas chromatography column located in the peripheral device. The values for repeatability and reproducibility obtained indicated the robustness of the method, which is required for routine analysis. Ninety cider samples from various origins were analyzed, most of which showed a (13)C content consistent with the declared origin. The δ(13)C ranged from -24.80‰ to -20.89‰ for ciders with endogenous carbon dioxide (-22.74 ± 0.79‰) and -37.13‰ to -26.00‰ if industrial CO(2) was added. Several samples were also suspected of C4 sugar addition prior to the fermentation. A fast, accurate and simple method for cider adulteration detection was developed. The addition of exogenous CO(2) as well as C4 sugar addition prior to fermentation could be detected. The method showed advantages over existing methods in term of simplicity (no sample preparation and very long-term stability of the sample), speed (less than 10 min/sample) and precision ((r ≤0.32 and R ≤0.42). Copyright © 2012 John Wiley & Sons, Ltd.

  10. Discrimination of geographical origin of lentils (Lens culinaris Medik.) using isotope ratio mass spectrometry combined with chemometrics.

    Science.gov (United States)

    Longobardi, F; Casiello, G; Cortese, M; Perini, M; Camin, F; Catucci, L; Agostiano, A

    2015-12-01

    The aim of this study was to predict the geographic origin of lentils by using isotope ratio mass spectrometry (IRMS) in combination with chemometrics. Lentil samples from two origins, i.e. Italy and Canada, were analysed obtaining the stable isotope ratios of δ(13)C, δ(15)N, δ(2)H, δ(18)O, and δ(34)S. A comparison between median values (U-test) highlighted statistically significant differences (pprotein and starch fractions and the relevant results are reported.

  11. Carbon isotope ratios of C4 plants in loess areas of North China

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    Carbon isotope ratios (δ13C) of 89 C4 plant samples were determined from the loess area in North China. δ13C values vary between -10.5‰ and -14.6‰ with a mean of -12.6‰. Along a precipitation gradient from the semi-moist area to the semiarid area, then to the arid area, the δ13C values of C4 plants show a slight decreasing trend. The δ13C values of C4 plants in the dry season are found lower than those in the wet season. These trends are opposite to those observed for C3 species.

  12. Unusual stable isotope ratios in amino acid and carboxylic acid extracts from the Murchison meteorite

    Science.gov (United States)

    Epstein, S.; Krishnamurthy, R. V.; Cronin, J. R.; Pizzarello, S.; Yuen, G. U.

    1987-01-01

    The isotopic composition of hydrogen, nitrogen, and carbon in amino acid and monocarboxylic acid extracts from the Murchison meteorite has been determined. The unusually high D/H and N-15/N-14 ratios in the amino acid fraction are uniquely characteristic of known interstellar organic materials. The delta D value of the monocarboxylic acid fraction is lower but still consistent with an interstellar origin. These results confirm the extraterrestrial origin of both classes of compound and provide the first evidence suggesting a direct relationship between the massive organosynthesis occurring in interstellar clouds and the presence of prebiotic compounds in primitive planetary bodies.

  13. Isotopic Abundances and Ratios in Arsenic Irradiated by High-Energy Neutrons

    Energy Technology Data Exchange (ETDEWEB)

    Parker, W. E. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Hall, J. M. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

    2010-06-07

    This document provides derivations of the 73As, 74As and 75As isotopic abundances and ratios in an arsenic sample irradiated by high-energy (14 MeV) neutrons for 0 ≤ t ≤ T, where T is short compared to the natural decay times of the reaction products (t1/2 (73As) ~ 80.3 d, t1/2 (74As) ~ 17.8 d). The document also outlines the historic approach used to analyze arsenic data from experiments.

  14. Source Attribution of Cyanides using Anionic Impurity Profiling, Stable Isotope Ratios, Trace Elemental Analysis and Chemometrics

    Energy Technology Data Exchange (ETDEWEB)

    Mirjankar, Nikhil S.; Fraga, Carlos G.; Carman, April J.; Moran, James J.

    2016-01-08

    Chemical attribution signatures (CAS) for chemical threat agents (CTAs) are being investigated to provide an evidentiary link between CTAs and specific sources to support criminal investigations and prosecutions. In a previous study, anionic impurity profiles developed using high performance ion chromatography (HPIC) were demonstrated as CAS for matching samples from eight potassium cyanide (KCN) stocks to their reported countries of origin. Herein, a larger number of solid KCN stocks (n = 13) and, for the first time, solid sodium cyanide (NaCN) stocks (n = 15) were examined to determine what additional sourcing information can be obtained through anion, carbon stable isotope, and elemental analyses of cyanide stocks by HPIC, isotope ratio mass spectrometry (IRMS), and inductively coupled plasma optical emission spectroscopy (ICP-OES), respectively. The HPIC anion data was evaluated using the variable selection methods of Fisher-ratio (F-ratio), interval partial least squares (iPLS), and genetic algorithm-based partial least squares (GAPLS) and the classification methods of partial least squares discriminate analysis (PLSDA), K nearest neighbors (KNN), and support vector machines discriminate analysis (SVMDA). In summary, hierarchical cluster analysis (HCA) of anion impurity profiles from multiple cyanide stocks from six reported country of origins resulted in cyanide samples clustering into three groups: Czech Republic, Germany, and United States, independent of the associated alkali metal (K or Na). The three country groups were independently corroborated by HCA of cyanide elemental profiles and corresponded to countries with known solid cyanide factories. Both the anion and elemental CAS are believed to originate from the aqueous alkali hydroxides used in cyanide manufacture. Carbon stable isotope measurements resulted in two clusters: Germany and United States (the single Czech stock grouped with United States stocks). The carbon isotope CAS is believed to

  15. High-Sensitivity Measurement of 3He-4He Isotopic Ratios for Ultracold Neutron Experiments

    CERN Document Server

    Mumm, H P; Bauder, W; Abrams, N; Deibel, C M; Huffer, C R; Huffman, P R; Schelhammer, K W; Swank, C M; Janssens, R; Jiang, C L; Scott, R H; Pardo, R C; Rehm, K E; Vondrasek, R; O'Shaughnessy, C M; Paul, M; Yang, L

    2016-01-01

    Research efforts ranging from studies of solid helium to searches for a neutron electric dipole moment require isotopically purified helium with a ratio of 3He to 4He at levels below that which can be measured using traditional mass spectroscopy techniques. We demonstrate an approach to such a measurement using accelerator mass spectroscopy, reaching the 10e-14 level of sensitivity, several orders of magnitude more sensitive than other techniques. Measurements of 3He/4He in samples relevant to the measurement of the neutron lifetime indicate the need for substantial corrections. We also argue that there is a clear path forward to sensitivity increases of at least another order of magnitude.

  16. Effects of several variable factors on the isotope ratio by HRGC-MS.

    Science.gov (United States)

    Sawamura, Masayoshi; Satake, Atsushi; Ueno, Takao; Une, Akitoshi; Ukeda, Hiroyuki

    2004-01-01

    In the isotope ratio (Ir) analysis using GC-MS, several variable factors in sampling incidental to any food analysis were investigated for yuzu fruit. The Irs of ten monoterpene hydrocarbons in yuzu essential oils from each of six fruiting positions of three trees were measured. The sign test following t-test of all the Ir values demonstrated that there was no significant difference between both sampling years of 2001 and 2002. There was also no significant variation in the Ir values among the three trees and six fruiting positions in the individual two years.

  17. Direct isotope ratio analysis of individual uranium-plutonium mixed particles with various U/Pu ratios by thermal ionization mass spectrometry.

    Science.gov (United States)

    Suzuki, Daisuke; Esaka, Fumitaka; Miyamoto, Yutaka; Magara, Masaaki

    2015-02-01

    Uranium and plutonium isotope ratios in individual uranium-plutonium (U-Pu) mixed particles with various U/Pu atomic ratios were analyzed without prior chemical separation by thermal ionization mass spectrometry (TIMS). Prior to measurement, micron-sized particles with U/Pu ratios of 1, 5, 10, 18, and 70 were produced from uranium and plutonium certified reference materials. In the TIMS analysis, the peaks of americium, plutonium, and uranium ion signals were successfully separated by continuously increasing the evaporation filament current. Consequently, the uranium and plutonium isotope ratios, except the (238)Pu/(239)Pu ratio, were successfully determined for the particles at all U/Pu ratios. This indicates that TIMS direct analysis allows for the measurement of individual U-Pu mixed particles without prior chemical separation.

  18. Mapping and defining sources of variability in bioavailable strontium isotope ratios in the Eastern Mediterranean

    Science.gov (United States)

    Hartman, Gideon; Richards, Mike

    2014-02-01

    The relative contributions of bedrock and atmospheric sources to bioavailable strontium (Sr) pools in local soils was studied in Northern Israel and the Golan regions through intensive systematic sampling of modern plants and invertebrates, to produce a map of modern bioavailable strontium isotope ratios (87Sr/86Sr) for regional reconstructions of human and animal mobility patterns. The study investigates sources of variability in bioavailable 87Sr/86Sr ratios, in particular the intra-and inter-site range of variation in plant 87Sr/86Sr ratios, the range of 87Sr/86Sr ratios of plants growing on marine sedimentary versus volcanic geologies, the differences between ligneous and non-ligneous plants with varying growth and water utilization strategies, and the relative contribution of atmospheric Sr sources from different soil and vegetation types and climatic zones. Results indicate predictable variation in 87Sr/86Sr ratios. Inter- and intra-site differences in bioavailable 87Sr/86Sr ratios average of 0.00025, while the range of 87Sr/86Sr ratios measured regionally in plants and invertebrates is 0.7090 in Pleistocene calcareous sandstone and 0.7074 in mid-Pleistocene volcanic pyroclast. The 87Sr/86Sr ratios measured in plants growing on volcanic bedrock show time dependent increases in atmospheric deposition relative to bedrock weathering. The 87Sr/86Sr ratios measured in plants growing on renzina soils depends on precipitation. The spacing between bedrock 87Sr/86Sr ratios and plants is highest in wet conditions and decreases in dry conditions. The 87Sr/86Sr ratios measured in plants growing on terra rossa soils is relatively constant (0.7085) regardless of precipitation. Ligneous plants are typically closer to bedrock 87Sr/86Sr ratios than non-ligneous plants. Since the bioavailable 87Sr/86Sr ratios currently measured in the region reflect a mix of both exogenous and endogenous sources, changes in the relative contribution of exogenous sources can cause variation

  19. Drought and flood signals in subtropical estuaries recorded by stable isotope ratios in bivalve shells

    Science.gov (United States)

    Walther, B. D.; Rowley, J. L.

    2013-11-01

    Isotope ratios of carbon and oxygen recorded in biogenic carbonates can be effective proxies for ambient conditions in estuaries including salinity and temperature. Together, they have the potential to allow periods of drought and flooding to be identified in subtropical estuaries that receive stochastic and aperiodic delivery of freshwater inflow. We investigated the ability of δ13C and δ18O values in shell increments from the eastern oyster Crassostrea virginica sampled from subtropical estuaries in the western Gulf of Mexico to indicate differences in temperature and salinity dynamics at fine spatial scales. Oyster shells at locations that experienced both hypersalinity during droughts and dramatic decreases in salinity during floods showed distinct variations in shell δ13C and δ18O values that reflected local salinity conditions. In contrast, oysters at sites where no major salinity fluctuation occurred showed only seasonal fluctuations in isotopes reflecting temperature and possibly feeding patterns. Further, similar isotopic patterns were observed across multiple individuals from each site. Our results show that δ13C and δ18O values in shells measured together provide a powerful method to identify droughts and floods in subtropical estuaries and therefore extend records of dynamic inflow to these stressed ecosystems.

  20. Gas chromatographic separation for the H and C stable isotope ratio determination of coal compounds

    Energy Technology Data Exchange (ETDEWEB)

    Antenucci, D.; Jacquemin, C. [Institut Scientifique de Service Public, Liege (Belgium); Bouquegneau, J.M.; Brasseur, A.; Dauby, P.; Pirard, J.P. [Universite de Liege (Belgium); Letolle, R. [Universite Pierre et Marie Curie, Paris (France)

    1997-06-01

    A new, completely automated gas chromatography technique has been developed to separate the different gaseous compounds produced during underground coal gasification for their {sup 13}C/{sup 12}C and D/H isotope ratio measurements. The technique was designed for separation and collection of H{sub 2}, CO, CO{sub 2}, H{sub 2}O, H{sub 2}S, CH{sub 4}, and heavier hydrocarbons. These gaseous compounds are perfectly separated by the gas-phase chromatograph and quantitatively sent to seven combustion and collection lines. H{sub 2}, CO, CH{sub 4}, and heavier hydrocarbons are quantitatively oxidized to CO{sub 2} and/or H{sub 2}O. The isotopic analyses are performed by the sealed-tube method. The zinc method is used for reduction of both water and H{sub 2}S to hydrogen for D/H analysis. Including all preparation steps, the reproducibility of isotope abundance values, for a quantity higher than or equal to 0.1 mL of individual components in a mixture (5 mL of gases being initially injected in the gas chromatograph), is {+-}0.1 per mil for {delta}{sup 13}C{sub PDB} and {+-}6 per mil for {delta}D{sub SMOW}. 20 refs., 3 figs., 4 tabs.

  1. A fast switching electrostatic deflector system for actinide isotopic ratio measurements

    Science.gov (United States)

    Zorko, Benjamin; Child, D. P.; Hotchkis, M. A. C.

    2010-04-01

    We have implemented a fast switching electrostatic system on the actinides beamline on the ANTARES accelerator at ANSTO, to improve the precision of analyses by accelerator mass spectrometry. This high-energy bouncing system is based on a pair of deflector plates, deflecting in the orbit plane, set at the entrance and exit of the analysing magnet. The design of deflector plates is unique, and it was modelled by SIMION in order to minimize field inhomogenity and fringe field effects. The pair of deflector plates are supplied by a high-voltage amplifier driven by an EPICS-enabled control unit, with two 4 W power supplies providing up to ±10 kV modulation. The high-energy bouncing system is synchronized with the existing low-energy bouncing system. To measure the isotopic ratio with the new system, the magnetic fields of the injector and analysing magnets are set to transmit selected isotopes along the beam line with zero voltage applied. The other isotopes of interest are transmitted by keeping the magnetic fields constant and modulating the voltages on the injector magnet chamber and on the high-energy deflector plates.

  2. Historical variations of mercury stable isotope ratios in Arctic glacier firn and ice cores

    Science.gov (United States)

    Zdanowicz, C. M.; Krümmel, E. M.; Poulain, A. J.; Yumvihoze, E.; Chen, J.; Å trok, M.; Scheer, M.; Hintelmann, H.

    2016-09-01

    The concentration and isotopic composition of mercury (Hg) were determined in glacier core samples from Canadian Arctic ice caps dating from preindustrial to recent time (early 21st century). Mean Hg levels increased from ≤ 0.2 ng L-1 in preindustrial time to ~0.8-1.2 ng L-1 in the modern industrial era (last ~200 years). Hg accumulated on Arctic ice caps has Δ199Hg and Δ201Hg that are higher (~ -1 to 2.9‰) than previously reported for Arctic snow impacted by atmospheric Hg depletion events (mostly < -1‰), suggesting that these events contribute little to Hg accumulation on ice caps. The range of δ202Hg, Δ199Hg, and Δ201Hg in glacier cores overlaps with that of Arctic Hg0(g) and of seawater in Baffin Bay and also with that of midlatitude precipitation and industrial Hg sources, including coal and Hg ores. A core from Agassiz ice cap (80.7°N) shows a ~ +1‰ shift in δ202Hg over the nineteenth to twentieth centuries that could reflect changes in the isotopic composition of the atmospheric Hg pool in the High Arctic in response to growing industrial emissions at lower latitudes. This study is the first ever to report on historical variations of Hg stable isotope ratios in Arctic ice cores. Results could help constrain future modeling efforts of the global Hg biogeochemical cycle and the atmosphere's response to changing Hg emissions, past and future.

  3. Intra-Shell boron isotope ratios in benthic foraminifera: Implications for paleo-pH reconstructions

    Science.gov (United States)

    Rollion-Bard, C.; Erez, J.

    2009-12-01

    The boron isotope composition of marine carbonates is considered to be a seawater pH proxy. Nevertheless, the use of δ11B has some limitations: 1) the knowledge of fractionation factor (α4-3) between the two boron dissolved species (boric acid and borate ion), 2) the δ11B of seawater may have varied with time and 3) the amplitude of the "vital effects" of this proxy. Using secondary ion mass spectrometry (SIMS), we looked at the internal variability in the boron isotope ratio of the shallow water, symbionts bearing foraminiferan Amphistegina lobifera. Specimens were cultured at constant temperature (24±0.1 °C) in seawater with pH ranging between 7.90 and 8.45. We performed 6 to 8 measurements of δ11B in each foraminifera. Intra-shell boron isotopes show large variability with an upper threshold value of pH ~ 9. The ranges of the skeletal calculated pH values in different cultured foraminifera, show strong correlation with the culture pH values and may thus serve as proxy for pH in the past ocean.

  4. Recent measurements of 234U/238U isotope ratio in spring waters from the Hadzici area.

    Science.gov (United States)

    Vidic, Alfred; Ilić, Zorana; Benedik, Ljudmila

    2013-06-01

    The Hadzici area has become interesting for investigation since depleted uranium ammunition had been employed in 1995 during the NATO air strike campaign in Bosnia and Herzegovina. The purpose of this study is to determine uranium concentration and (234)U/(238)U activity ratio in the spring waters of this area and to investigate their relationship, as well as spatial variations. The spring water samples were taken at 18 sites in total. For the determination of uranium radioisotopes, radiochemical separation procedure followed by alpha-particle spectrometry was applied. Uranium concentration in analyzed waters range from 0.15 to 1.12 μg/L. Spring waters from carbonate based sediments have a lower uranium concentration of between 0.15 and 0.43 μg/L, in comparison to waters sampled within sandstone-based sediments ranging from 0.53 to 1.12 μg/L. Dissolved uranium shows significant spatial variability and correlation with bedrock type confirmed by Principal Component Analysis and Hierarchical Cluster Analysis. The majority of the analyzed waters have a (234)U/(238)U activity ratio ranging from 1.02 to 1.90, of which half of the results range between 1.02 and 1.16. No apparent depleted uranium (DU) contamination was observed, as (234)U/(238)U activity ratio is dependent on geochemical conditions in the environment. Even though the tested spring waters demonstrate significant variability in uranium concentration, (234)U/(238)U activity ratio and (234)U excess, waters with similar uranium isotopic signatures are observable within the region. The guidelines on the spatial redistribution of dissolved uranium (corresponding to (238)U mass concentration), along with (234)U/(238)U activity ratios were provided by the Inverse Distance Weighting (IDW) method. Waters having similar isotopic signature have been delineated.

  5. Gas Compositions and He-C Isotopic Ratios of Fumarolic Samples from Negros Island, Central Philippines

    Science.gov (United States)

    Lee, Hsiao-Fen; Yang, Tsanyao Frank; Faith Lan, Tefang; Chen, Yue-Gau; Sincioco, Jaime S.; Solidum, Renato U., Jr.

    2010-05-01

    Four volcanoes that are distributed in the Negros Island, Central Philippines, include Kanlaon Volcano which is considered as one of the most active volcanoes in Philippines. All of these volcanoes are related to subduction system of Negros trench and form the Negros volcanic arc. Besides Kanlaon, from north to south, the volcanoes in Negros Island are Silay Volcano, Mandalagan Volcano and Cuernos de Negros Volcano. Although there is no eruption record of these three volcanoes in last 10,000 years, due to the ongoing solfataric/fumarolic activities, the Philippine Institute of Volcanology and Seismology (PHIVOLCS) classifies these as 'potentially active' volcanoes. It means that there is still a considerable threat and risk of eruption. Fumarolic gas samples and bubbling gas samples of hot spring were collected in February 2007 and April 2008 to compare the compositions with others in the world. We analyzed the gas composition, carbon isotopes of CO2, and helium isotopes of these samples. The results of these samples show a similar composition as those of low-temperature fumaroles in other parts of the world, i.e., temperature 1. H2O is the major species of these gas samples, and CO2 is the dominant component after de-watering. Minor components include H2S, N2 and CH4. The gas composition of most of these samples falls in the range of affinity with convergent plate gases associated with groundwater based on the plot of N2-He-Ar diagram. The high 3He/4He ratios indicate a mantle-derived degassing source in origin, i.e., magma chambers could still exist beneath these volcanoes. Helium isotopes ratios show a decreasing trend from north to south, such distribution could be due to more crustal contamination caused by the collision event which happened in the northern part of the island. The carbon isotopic values of CO2 are far less negative than the values from a magma source. There are other carbon sources of CO2, most likely a thick sequence of limestone formation in

  6. Zircon U-Pb ages, Hf-O isotopes and trace elements of Mesozoic high Sr/Y porphyries from Ningzhen, eastern China: Constraints on their petrogenesis, tectonic implications and Cu mineralization

    Science.gov (United States)

    Wang, Fangyue; Liu, Sheng-Ao; Li, Shuguang; Akhtar, Shamim; He, Yongsheng

    2014-07-01

    The relationship between high Sr/Y (adakitic) rocks and Cu mineralization has been long recognized but the mechanism remains unclear. The Cretaceous high Sr/Y porphyries in the Ningzhen area host major Cu polymetallic deposits in the Lower Yangtze River Belt (LYRB) of eastern China. These rocks exhibit some geochemical characteristics (e.g., non-radiogenic Pb isotope ratios) that differ from adakitic rocks from adjacent locations in the LYRB. In this study, we present a study of the zircon U-Pb-Hf-O isotope and trace element compositions for five porphyries from Ningzhen to reveal their petrogenesis and how that correlates with Cu-Fe-Mo mineralization. Zircon U-Pb ages of Anjishan (Cu deposit), Tongshan (Cu-Mo deposit) and Xiangshan (Fe deposit) plutons in the Ningzhen area are 108.8 ± 1.5 Ma, 105-107 Ma and 100-105 Ma, respectively, which are significantly younger than the ore-bearing adakites (140 ± 5 Ma) in the western part of the LYRB. Zircon εHf(t) and δ18O values range from - 23.4 to - 10.6 and from 5.7 to 7.0‰, respectively, falling between subduction-related adakites from the other regions in the LYRB and delamination-related adakitic rocks from the adjacent South Tan-Lu Fault Zone. The similarities of Ce4 +/Ce3 + and Eu/Eu* ratios in zircons from Ningzhen and those from the western LYRB indicate higher oxygen fugacity in their magma sources. Ti-in-zircon thermometer yields magma temperatures of 550 to 700 °C (with an average of ~ 650 °C) for the Ningzhen porphyries, which are significantly lower than those of the South Tan-Lu Fault adakites (> 750 °C), but similar to those for the LYRB adakites ( 50), non-radiogenic Pb, enriched Sr-Nd isotopic compositions, negative zircon εHf(t), mantle-like δ18O values, high oxygen fugacities and low magma temperatures. Mafic rocks that co-exist with ore-bearing porphyries or occur as xenoliths in porphyries are widespread. We proposed that the Ningzhen high Sr/Y porphyries originated from mixing of magmas

  7. Stable isotope ratios of atmospheric CO_{2} and CH_{4} over Siberia measured at ZOTTO

    Science.gov (United States)

    Timokhina, Anastasiya; Prokushkin, Anatily; Lavric, Jost; Heimann, Martin

    2016-04-01

    The boreal and arctic zones of Siberia housing the large amounts of carbon stored in the living biomass of forests and wetlands, as well as in soils and specifically permafrost, play a crucial role in earth's global carbon cycle. The long-term studies of greenhouse gases (GHG) concentrations are important instruments to analyze the response of these systems to climate warming. In parallel to GHG observations, the measurements of their stable isotopic composition can provide useful information for distinguishing contribution of individual GHG source to their atmospheric variations, since each source has its own isotopic signature. In this study we report first results of laboratory analyses of the CO2 and CH4 concentrations, the stable isotope ratio of δ13C-CO2, δ18O-CO2, δ13C-CH4, δD-CH4 measured in one-liter glass flasks which were obtained from 301 height of ZOTTO (Zotino Tall Tower Observatory, near 60° N, 90° E, about 20 km west of the Yenisei River) during 2008 - 2013 and 2010 - 2013 for stable isotope composition of CO2 and CH4. The magnitudes of δ13C-CO2 and δ18O-CO2 in a seasonal cycle are -1.4±0.1‰ (-7.6 - -9.0‰) and -2.2±0.2‰ (-0.1 - -2.3‰), respectively. The δ13C-CO2 seasonal pattern opposes the CO2 concentrations, with a gradual enrichment in heavy isotope occurring during May - July, reflecting its discrimination in photosynthesis, and further depletion in August - September as photosynthetic activity decreases comparatively to ecosystem respiration. Relationship between the CO2 concentrations and respective δ13C-CO2 (Keeling plot) reveals isotopic source signature for growing season (May - September) -27.3±1.4‰ and -30.4±2.5‰ for winter (January - March). The behavior of δ18O-CO2 associated with both high photosynthetic rate in the June (enrichment of atmospheric CO2 by 18O as consequence of CO2 equilibrium with "heavy" leaf water) and respiratory activity of forest floor in June - October (depletion of respired CO2 by 18O

  8. Fractionation in position-specific isotope composition during vaporization of environmental pollutants measured with isotope ratio monitoring by ¹³C nuclear magnetic resonance spectrometry.

    Science.gov (United States)

    Julien, Maxime; Parinet, Julien; Nun, Pierrick; Bayle, Kevin; Höhener, Patrick; Robins, Richard J; Remaud, Gérald S

    2015-10-01

    Isotopic fractionation of pollutants in terrestrial or aqueous environments is a well-recognized means by which to track different processes during remediation. As a complement to the common practice of measuring the change in isotope ratio for the whole molecule using isotope ratio monitoring by mass spectrometry (irm-MS), position-specific isotope analysis (PSIA) can provide further information that can be exploited to investigate source and remediation of soil and water pollutants. Position-specific fractionation originates from either degradative or partitioning processes. We show that isotope ratio monitoring by (13)C NMR (irm-(13)C NMR) spectrometry can be effectively applied to methyl tert-butylether, toluene, ethanol and trichloroethene to obtain this position-specific data for partitioning. It is found that each compound exhibits characteristic position-specific isotope fractionation patterns, and that these are modulated by the type of evaporative process occurring. Such data should help refine models of how remediation is taking place, hence back-tracking to identify pollutant sources.

  9. Evaluation of Affinity-Tagged Protein Expression Strategies using Local and Global Isotope Ratio Measurements

    Energy Technology Data Exchange (ETDEWEB)

    Hervey, IV, William Judson [ORNL; Khalsa-Moyers, Gurusahai K [ORNL; Lankford, Patricia K [ORNL; Owens, Elizabeth T [ORNL; McKeown, Catherine K [ORNL; Lu, Tse-Yuan S [ORNL; Foote, Linda J [ORNL; Morrell-Falvey, Jennifer L [ORNL; McDonald, W Hayes [ORNL; Pelletier, Dale A [ORNL; Hurst, Gregory {Greg} B [ORNL

    2009-01-01

    Protein enrichments of engineered, affinity-tagged (or bait ) fusion proteins with interaction partners are often laden with background, non-specific proteins, due to interactions that occur in vitro as an artifact of the technique. Furthermore, the in vivo expression of the bait protein may itself affect physiology or metabolism. In this study, intrinsic affinity purification challenges were investigated in a model protein complex, DNA-dependent RNA polymerase (RNAP), encompassing chromosome- and plasmid-encoding strategies for bait proteins in two different microbial species: Escherichia coli and Rhodopseudomonas palustris. Isotope ratio measurements of bait protein expression strains relative to native, wild-type strains were performed by liquid chromatography tandem mass spectrometry (LC-MS-MS) to assess bait protein expression strategies in each species. Authentic interacting proteins of RNAP were successfully discerned from artifactual co-isolating proteins by the isotopic differentiation of interactions as random or targeted (I-DIRT) method (A. J. Tackett et al. J. Proteome Res. 2005, 4 (5), 1752-1756). To investigate broader effects of bait protein production in the bacteria, we compared proteomes from strains harboring a plasmid that encodes an affinity-tagged subunit (RpoA) of the RNAP complex with the corresponding wild-type strains using stable isotope metabolic labeling. The ratio of RpoA abundance in plasmid strains versus wild type was 0.8 for R. palustris and 1.7 for E. coli. While most other proteins showed no appreciable difference, proteins significantly increased in abundance in plasmid-encoded bait-expressing strains of both species included the plasmid encoded antibiotic resistance protein, GenR and proteins involved in amino acid biosynthesis. Together, these local, complex-specific and more global, whole proteome isotopic abundance ratio measurements provided a tool for evaluating both in vivo and in vitro effects of plasmid

  10. Authenticity of carbon dioxide bubbles in French ciders through multiflow-isotope ratio mass spectrometry measurements.

    Science.gov (United States)

    Gaillard, Laetitia; Guyon, Francois; Salagoïty, Marie-Hélène; Médina, Bernard

    2013-12-01

    A procedure to detect whether carbon dioxide was added to French ciders has been developed. For this purpose, an optimised and simplified method is proposed to determine (13)C/(12)C isotope ratio of carbon dioxide (δ(13)C) in ciders. Three critical steps were checked: (1) influence of atmospheric CO2 remaining in the loaded vial, (2) impact of helium flush, (3) sampling speed. This study showed that atmospheric CO2 does not impact the measurement, that helium flush can lead to isotopic fractionation and finally, that a fractionation occurs only 5h after bottle opening. The method, without any other preparation, consists in sampling 0.2 mL of cold (4 °C) cider in a vial that is passed in an ultrasonic bath for 10 min at room temperature to enhance cider de-carbonation. The headspace CO2 is then analysed using the link Multiflow®-isotope ratio mass spectrometer. Each year, a data bank is developed by fermenting authentic apples juices in order to control cider authenticity. Over a four year span (2008-2011), the CO2 produced during the fermentation step was studied. This set of 61 authentic ciders, from various French production areas, was used to determine a δ(13)C value range of -22.59±0.92‰ for authentic ciders CO2 bubbles. 75 commercial ciders were analysed with this method. Most of the samples analysed present a gas δ(13)C value in the expected range. Nevertheless, some ciders have δ(13)C values outside the 3σ limit, revealing carbonation by technical CO2. This practice is not allowed for organic, "Controlled Appellation of Origin" ciders and ciders specifying natural carbonation on the label. Copyright © 2013 Elsevier Ltd. All rights reserved.

  11. Chemometrical exploration of an isotopic ratio data set of acetylsalicylic acid

    Energy Technology Data Exchange (ETDEWEB)

    Stanimirova, I. [ChemoAC, FABI, Analytical Chemistry and Pharmaceutical Technology, Vrije Universiteit Brussel-VUB, Laarbeeklaan 103, B-1090 Brussels (Belgium); Daszykowski, M. [ChemoAC, FABI, Analytical Chemistry and Pharmaceutical Technology, Vrije Universiteit Brussel-VUB, Laarbeeklaan 103, B-1090 Brussels (Belgium); Van Gyseghem, E. [Eurofins Scientific Analytics, Rue Pierre Adolphe Bobierre, 44323 Nantes Cedex 3 (France); Bensaid, F.F. [Eurofins Scientific Analytics, Rue Pierre Adolphe Bobierre, 44323 Nantes Cedex 3 (France); Lees, M. [Eurofins Scientific Analytics, Rue Pierre Adolphe Bobierre, 44323 Nantes Cedex 3 (France); Smeyers-Verbeke, J. [ChemoAC, FABI, Analytical Chemistry and Pharmaceutical Technology, Vrije Universiteit Brussel-VUB, Laarbeeklaan 103, B-1090 Brussels (Belgium); Massart, D.L. [ChemoAC, FABI, Analytical Chemistry and Pharmaceutical Technology, Vrije Universiteit Brussel-VUB, Laarbeeklaan 103, B-1090 Brussels (Belgium); Vander Heyden, Y. [ChemoAC, FABI, Analytical Chemistry and Pharmaceutical Technology, Vrije Universiteit Brussel-VUB, Laarbeeklaan 103, B-1090 Brussels (Belgium)]. E-mail: yvanvdh@vub.ac.be

    2005-11-03

    A data set consisting of fourteen isotopic ratios or quantities derived from such ratios for samples of acetylsalicylic acid (aspirin), commercialized by various pharmaceutical companies from different countries, was analyzed. The goal of the data analysis was to explore whether results can be linked to geographical origin or other features such as different manufacturing processes, of the samples. The methods of data analysis used were principal component analysis (PCA), robust principal component analysis (RPCA), projection pursuit (PP) and multiple factor analysis (MFA). The results do not seem to depend on geographic origin, except for some samples from India. They do depend on the pharmaceutical companies. Moreover, it seems that the samples from certain pharmaceutical companies form clusters of similar samples, suggesting that there is some common feature between those pharmaceutical companies. Variable selection performed by means of MFA showed that the number of variables can be reduced to five without loss of information.

  12. Hf Isotope Composition and REE Pattern of Zircons from Early Precambrian Metamorphic Rocks in the Daqing Mountains, Inner Mongolia%内蒙古大青山地区早前寒武纪变质岩的锆石Hf同位素组成和稀土模式

    Institute of Scientific and Technical Information of China (English)

    董春艳; 刘敦一; 万渝生; 徐仲元; 王伟; 颉颃强

    2009-01-01

    This paper reports Hf isotope and REE composition of zircons from metamorphic rocks in the Daqing Mountains, Inner Mongolia. Detrital zircons from two meta - sedimentary rock samples have [n(176Hf)/n(177Hf)]c, tDM1(Hf) and tDM2(Hf) ranging from 0. 281079~0. 281502, 2548~3000 Ma and 2612 ~ 3153 Ma and from 0. 280916 ~0. 281451, 2533 ~ 2717 Ma and 2600 ~ 3404 Ma, respectively. The eHf (t) and tym (Hf) of magmatic zircon from one meta-gabbro sample range from-5. 45 -6.68 and 2319-2647 Ma, respectively. These indicate that late Neoarhcaean - early Palaeoproterozoic tectono-magmatic events occurred in the Daqing Mountains and adjacent areas, with both mantle addition and crustal recycling. Metamorphic zircon rims commonly show young tDM2 (Hf) when comparing with detrital and magmatic zircon cores, suggesting that Lu-Hf compositions of the rocks and minerals were changed during metamorphic processes. Metamorphic zircon rims are similar in REE pattern to adjacent detrital and magmatic cores, but commonly being lower in total REE content. Most of the metamorphic rims are smaller than 0. 1 in Th/U ratio, being quite different from the cores which Th/U ratios are generally higher than 0. 5. It is speculated that metamorphic fluid was high in w(176Hf)/w(177Hf) ratio and U and low in Th and REE and played an important role in metamorphic zircon formation.%本文报道了内蒙古大青山地区早前寒武纪变质岩石的锆石Hf同位素和稀土组成.两个古元古代晚期(1.9~2.1 Ga)变质碎屑沉积岩样品中碎屑锆石的[n(176Hf)/n(177Hf)]c、tDM1(Hf)和tDM2(Hf)分别为0.281079~0.281502、2548~3000 Ma、2612~3153 Ma和0.280g16~0.281451、2533~2717 Ma、2600~3404 Ma;一个古元古代早期(2.37 Ga)变质辉长岩样品中岩浆锆石的εHf(t)和tDM1(Hf)分别为1.50~6.68和2449~2647 Ma,表明大青山及邻区在新太古代晚期-古元古代早期存在强烈的构造岩浆热事件,既有地幔添加又有壳内再循环作用.三个样

  13. High Precision 142Nd/144Nd and 143Nd/144Nd Isotope Ratio Measurements in Rock Samples

    Science.gov (United States)

    Ali, A.; Srinivasan, G.

    2009-05-01

    The long-lived 147Sm-143Nd system with a half-life (T1/2) of 106 Gyr is generally used for geochronology. The short-lived 146Sm-142Nd system (T1/2= 103 Myr) is used as a geological tracer to track early (˜500 Ma) silicate differentiation [1] events in different planetary bodies. The isotope composition measurements by thermal ionization mass spectrometry (TIMS) require purification of Nd using chemical separation methods. This is important as an impure sample will give both a very poor ion yield and cause beam instability in the mass spectrometer, potentially resulting in a poor analysis [2]. The separation of Nd for 143Nd isotope measurement is, fairly straightforward because there is no isobaric interference of any other REE. While 142Nd isotope analysis needs chemically separated Nd fraction to be ˜100% Ce-free as latter is composed of a substantial amount of 142Ce isotope. A 4-steps technique, modified from Caro et al., [3], for the separation of Nd is established at the Cosmochemistry Laboratory of University of Toronto, Canada and applied to the measurement of Nd isotope ratios in geological reference sample BCR-2 (USGS, Columbia River basalt) using TIMS. Results of the isotopic ratios obtained for BCR-2 are in good agreement with published values [e.g., 4]. Analytical work on the samples discovered as the oldest rocks on Earth [5] from Nuvvuagittuq greenstone belt in Québec, Canada and various meteorites is in progress. An account of the procedures involved is briefly described here. All working solutions and acids were prepared using >18.2 MΩ.cm-1 H2O from a Milli-Q water system. Experiments were performed under Class 100 clean work bench with acid-cleaned apparatus and plastic-ware. The whole rock powders were weighed (20-30 mg) and dissolved in a mixture of HF and HNO3 using PFA vials and heated at 110°C. Further decomposition was done in Teflon bomb in the oven at 205°C. Later on contents of the Teflon bomb were transferred to vials and fluorides

  14. Determining the geographical origin of Chinese cabbages using multielement composition and strontium isotope ratio analyses.

    Science.gov (United States)

    Bong, Yeon-Sik; Shin, Woo-Jin; Gautam, Mukesh Kumar; Jeong, Youn-Joong; Lee, A-Reum; Jang, Chang-Soon; Lim, Yong-Pyo; Chung, Gong-Soo; Lee, Kwang-Sik

    2012-12-15

    Recently, the Korean market has seen many cases of Chinese cabbage (Brassica rapa ssp. pekinensis) that have been imported from China, yet are sold as a Korean product to illegally benefit from the price difference between the two products. This study aims to establish a method of distinguishing the geographical origin of Chinese cabbage. One hundred Chinese cabbage heads from Korea and 60 cabbage heads from China were subjected to multielement composition and strontium isotope ratio ((87)Sr/(86)Sr) analyses. The (87)Sr/(86)Sr ratio differed, based on the geological characteristics of their district of production. In addition, the content of many elements differed between cabbages from Korea and China. In particular, the difference in the content of Sr and Ti alone and the combination of Sr, Ca, and Mg allowed us to distinguish relatively well between Korea and China as the country of origin. The present study demonstrates that the chemical and Sr isotopic analyses exactly reflect the geology of the production areas of Chinese cabbage.

  15. Determining the geographical origin of Chinese cabbages using multielement composition and strontium isotope ratio analyses

    Science.gov (United States)

    BONG, Y.; Shin, W.; Gautam, M. K.; Jeong, Y.; Lee, A.; Jang, C.; Lim, Y.; Chung, G.; Lee, K.

    2012-12-01

    Recently, the Korean market has seen many cases of Chinese cabbage (Brassica rapa ssp. pekinensis) that have been imported from China, yet are sold as a Korean product to illegally benefit from the price difference between the two products. This study aims to establish a method of distinguishing the geographical origin of Chinese cabbage. One hundred Chinese cabbage heads from Korea and 60 cabbage heads from China were subjected to multielement composition and strontium isotope ratio (87Sr/86Sr) analyses. The 87Sr/86Sr ratio differed, based on the geological characteristics of their district of production. In addition, the content of many elements differed between cabbages from Korea and China. In particular, the difference in the content of Sr and Ti alone and the combination of Sr, Ca, and Mg allowed us to distinguish relatively well between Korea and China as the country of origin. The present study demonstrates that the chemical and Sr isotopic analyses exactly reflect the geology of the production areas of Chinese cabbage. Also, multivariate statistical analyses of multiple elements were found to be very effective in distinguishing the geographical origin of Chinese cabbages.

  16. Line shift, line asymmetry, and the 6Li/7Li isotopic ratio determination

    CERN Document Server

    Cayrel, Roger; Chand, Hum; Bonifacio, Piercarlo; Spite, Monique; Spite, François; Petitjean, Patrick; Ludwig, Hans-Günter; Caffau, Elisabetta

    2007-01-01

    Context: Line asymmetries are generated by convective Doppler shifts in stellar atmospheres, especially in metal-poor stars, where convective motions penetrate to higher atmospheric levels. Such asymmetries are usually neglected in abundance analyses. The determination of the 6Li/7Li isotopic ratio is prone to suffering from such asymmetries, as the contribution of 6Li is a slight blending reinforcement of the red wing of each component of the corresponding 7Li line, with respect to its blue wing. Aims: The present paper studies the halo star HD 74000 and estimates the impact of convection-related asymmetries on the Li isotopic ratio determination. Method: Two methods are used to meet this aim. The first, which is purely empirical, consists in deriving a template profile from another element that can be assumed to originate in the same stellar atmospheric layers as Li I, producing absorption lines of approximately the same equivalent width as individual components of the 7Li I resonance line. The second metho...

  17. Effects of shock and Martian alteration on Tissint hydrogen isotope ratios and water content

    Science.gov (United States)

    Hallis, L. J.; Huss, G. R.; Nagashima, K.; Taylor, G. J.; Stöffler, D.; Smith, C. L.; Lee, M. R.

    2017-03-01

    The Tissint meteorite, a picritic shergottite, fell to Earth in Morocco on the 18th of July 2011, and is only the fifth Martian meteorite witnessed to fall. Hydrogen isotope ratios and water contents are variable within different minerals in Tissint. Ringwoodite and shock melt pockets contain elevated D/H ratios relative to terrestrial values (δD = 761-4224‰). These high ratios in recrystallized phases indicate significant implantation of hydrogen from the D-rich Martian atmosphere during shock. In contrast, although olivine has detectable water abundances (230-485 ppm), it exhibits much lower D/H ratios (δD = +88 to -150‰), suggesting this water was not implanted from the Martian atmosphere. The minimal terrestrial weathering experienced by Tissint gives confidence that the olivine-hosted water has a Martian origin, but its high concentration indicates direct inheritance from the parental melt is improbable, especially given the low pressure of olivine crystallisation. Incorporation of a low δD crustal fluid, or deuteric alteration during crystallisation, could explain the relatively high water contents and low D/H ratios in Tissint olivine.

  18. Light-noble-gas isotopic ratios in gases from Mt. Etna (Southern Italy). Implications for mantle contamination and volcanic activity

    Energy Technology Data Exchange (ETDEWEB)

    Italiano, F. [Consiglio Nazionale delle Ricerche, Palermo (Italy). Ist. di Geochimica dei Fluidi; Nuccio, P.M. [Palermo Univ., Palermo (Italy). Ist. di Mineralogia, Petrografia e Geochimica; Nakai, S. [Tokyo Univ., Tokyo (Japan). Lab. for Earthquake Chemistry; Wakita, H. [Tokyo Univ., Tokyo (Japan). Earthquake Research Inst.

    1999-08-01

    Taking into account the light-noble-isotopic ratios signature of gas samples coming from the Etnean area (Southern Italy), it seems that in this area the crustal contamination played a minor role. Instead, processes that enriched the original MORB-type mantle in incompatible elements, have to be considered. The {sup 3}He/{sup 4}He ratios are, thus, lowered because of {sup 1}He produced by radioactive decay of U and Th. On the other hand, helium isotopic ratios have shown wide temporal variations sometimes reaching values as high as 7.6 Ra, out pf typical Etnean range. As these unusually high ratios have been measured during phases of unrest of the volcanic activity at Mt. Etna, this apparent discrepancy in the helium isotopic ratios is considered, as the effect of fractionation processes occurred during the magma uprising.

  19. What climate information is recorded in stable isotope ratios of wood lignin methoxyl groups?

    Science.gov (United States)

    Greule, Markus; Keppler, Frank

    2010-05-01

    The stable isotope composition of the bioelements C, O, H and N in plant organic matter is known to be a very powerful for various environmental impacts. Particularly tree rings are suitable for this analysis because they exhibit a "climate archive" with a yearly or even biannual resolution. One of the most determined wood compounds is cellulose which amongst others is used to reconstruct the temperature due to measurement of stable hydrogen and oxygen isotopes. Therefore cellulose is converted into cellulose nitrate to eliminate the exchangeable hydroxyl hydrogen or equilibration methods are used. However, a general problem associated with the determination of the stable hydrogen values of marker compounds for the study of climate and environmental conditions is the isolation of the pure compound for analysis by isotope ratio mass spectrometry. Exploitation of components of wood as markers, in particular, has been restricted by the very labour intensive and time consuming preparation of samples (e.g. cellulose nitrate). An alternative way to record climate information from tree rings was recently proposed by Keppler et al. (2007) who measured the stable hydrogen values of methoxyl groups in wood. Lignin methoxyl groups are considered to be stable, i.e. the hydrogen atoms of the methoxyl moiety do not exchange with those of plant water during ongoing metabolic reactions in the plant. Thus the initial deuterium content of the methoxyl groups of lignin in woody tissue at formation is retained throughout the lifetime of the tree and in preserved tissue. The methoxyl content of lignin in wood is usually determined by the Zeisel method (Zeisel, 1885) - the reaction between methyl ethers and hydroiodic acid to form methyl iodide. Exploiting this reaction for the measurement of stable hydrogen values of lignin methoxyl groups ensures that during the entire analytical procedure the isotope signal is preserved since no isotopic exchange occurs between the methyl groups and

  20. An autochthonous Avalonian basement source for the latest Ordovician Brenton Pluton in the Meguma terrane of Nova Scotia: U-Pb-Hf isotopic constraints and paleogeographic implications

    Science.gov (United States)

    Duncan Keppie, J.; Gregory Shellnutt, J.; Dostal, Jaroslav; Fraser Keppie, D.

    2017-06-01

    The Ediacaran-Ordovician Meguma Supergroup was thrust over Avalonia basement prior to the intrusion of post-Acadian, ca. 370 Ma, S-type granitic batholiths. This has led to two main hypotheses regarding the original location of the Meguma terrane, a continental rise prism bordering either NW Africa or Avalonia. On the other hand, the pre-Acadian, ca. 440 Ma Brenton pluton has yielded the following U/Pb LA-ICP-MS zircon data: (1) 448 ± 3 Ma population peak inferred to be the intrusive age and (2) ca. 550 and 700 Ma inherited ages common to both Avalonia and NW Africa. In contrast, Hf isotopic analyses of zircon yielded model ages ranging from 814 to 1127 Ma with most between 940 and 1040 Ma: such ages are typical of Avalonia and not NW Africa. The ages of the inherited zircons found within the Brenton pluton suggest that it was probably derived by partial melting of sub-Meguma, mid-crustal Avalonian rocks, upon which the Meguma Supergroup was deposited. Although Avalonia is commonly included in the peri-Gondwanan terranes off NW Africa or Amazonia, paleomagnetic data, faunal provinciality, and Hf data suggest that, during the Ediacaran-Early Cambrian, it was an island chain lying near the tropics (ca. 20-30 °S) and was possibly a continuation of the Bolshezemel volcanic arc accreted to northern Baltica during the Ediacaran Timanide orogenesis. This is consistent with the similar derital zircon population in the Ediacaran-Cambrian Meguma Supergroup and the Dividal Group in northeastern Baltica.

  1. Zircon U-Pb ages, Hf isotope data, and tectonic implications of Early-Middle Triassic granitoids in the Ailaoshan high-grade metamorphic belt of Southeast Tibet

    Science.gov (United States)

    Wu, Wenbin; Liu, Junlai; Chen, Xiaoyu; Zhang, Lisheng

    2017-04-01

    The Ailaoshan tectonic belt, where the effects of the Paleo-Tethyan ocean evolution and Indian-Eurasian plate collision are superimposed, is one of the most significant geological discontinuities in western Yunnan province of southeast Tibet. An Ailaoshan micro-block within the belt is bounded by the Ailaoshan suture zone to the west and the Red River Fault to the east, and consists of low- and high-grade metamorphic belts. Late Permian-Middle Triassic granitoids that are widely distributed to the west of the Ailaoshan suture zone and within the Ailaoshan micro-block may yield significant information on the Tethyan tectonic evolution of the Ailaoshan tectonic belt. This study reports new LA-ICP-MS zircon U-Pb geochronology and Hf isotope data of four granitoids from the Ailaoshan high-grade metamorphic belt. Zircon grains from the Yinjie granitoid do not have inherited cores and yield a weighted mean U-Pb age of 247.1 ± 2.0 Ma. The zircon ɛ Hf( t) values range from 7.8 to 12.1, and Hf model ages from 775 to 546 Ma, indicating that the granitoid was derived from juvenile crust. The rims of zircons from the Majie and Yuanjiang granitoids yield weighted mean U-Pb ages of 239.5 ± 1.8 and 237.9 ± 2.6 Ma, respectively, whereas the cores yield ages of 1608-352 Ma. The ɛ Hf( t) values of zircon rims range from -20.4 to -5.3, yielding Hf model ages from 2557 to 1606 Ma and suggesting that the source magma of the Majie and Yuanjiang granitoids was derived from ancient crust. An additional granitoid located near the Majie Village yields a zircon U-Pb age of 241.2 ± 1.0 Ma. Based on our geochronological and geochemical data, combined with geological observations, we propose that the Ailaoshan micro-block was derived from the western margin of the Yangtze block, and is comparable to the Zhongzan and Nam Co micro-blocks. The presence of late Permian mafic rocks with rift-related geochemical characteristics within the Ailaoshan micro-block, together with granitoids derived

  2. Zircon U-Pb ages, Hf isotope data, and tectonic implications of Early-Middle Triassic granitoids in the Ailaoshan high-grade metamorphic belt of Southeast Tibet

    Science.gov (United States)

    Wu, Wenbin; Liu, Junlai; Chen, Xiaoyu; Zhang, Lisheng

    2016-05-01

    The Ailaoshan tectonic belt, where the effects of the Paleo-Tethyan ocean evolution and Indian-Eurasian plate collision are superimposed, is one of the most significant geological discontinuities in western Yunnan province of southeast Tibet. An Ailaoshan micro-block within the belt is bounded by the Ailaoshan suture zone to the west and the Red River Fault to the east, and consists of low- and high-grade metamorphic belts. Late Permian-Middle Triassic granitoids that are widely distributed to the west of the Ailaoshan suture zone and within the Ailaoshan micro-block may yield significant information on the Tethyan tectonic evolution of the Ailaoshan tectonic belt. This study reports new LA-ICP-MS zircon U-Pb geochronology and Hf isotope data of four granitoids from the Ailaoshan high-grade metamorphic belt. Zircon grains from the Yinjie granitoid do not have inherited cores and yield a weighted mean U-Pb age of 247.1 ± 2.0 Ma. The zircon ɛ Hf(t) values range from 7.8 to 12.1, and Hf model ages from 775 to 546 Ma, indicating that the granitoid was derived from juvenile crust. The rims of zircons from the Majie and Yuanjiang granitoids yield weighted mean U-Pb ages of 239.5 ± 1.8 and 237.9 ± 2.6 Ma, respectively, whereas the cores yield ages of 1608-352 Ma. The ɛ Hf(t) values of zircon rims range from -20.4 to -5.3, yielding Hf model ages from 2557 to 1606 Ma and suggesting that the source magma of the Majie and Yuanjiang granitoids was derived from ancient crust. An additional granitoid located near the Majie Village yields a zircon U-Pb age of 241.2 ± 1.0 Ma. Based on our geochronological and geochemical data, combined with geological observations, we propose that the Ailaoshan micro-block was derived from the western margin of the Yangtze block, and is comparable to the Zhongzan and Nam Co micro-blocks. The presence of late Permian mafic rocks with rift-related geochemical characteristics within the Ailaoshan micro-block, together with granitoids derived

  3. Recycling and Mantle Stirring Determined by 142Nd/144Nd Isotopic Ratios

    Science.gov (United States)

    Jacobsen, S. B.; Ranen, M. C.

    2004-12-01

    It is now well established that 146Sm was live in the early solar system with an initial uniform 146Sm/144Sm ratio of ~0.008. Harper and Jacobsen (1992) discovered that a sample from Isua (~3.8 Ga old) had a positive 142Nd/144Nd anomaly of 33 ppm when compared to normal terrestrial and chondritic Nd. Furthermore, Jacobsen and Harper (1996) reported results from other Isua as well as Acasta (~4 Ga old) samples. Three other Isua samples had a possible small range (about -15 to +15), while two Acasta samples had no anomalies (normal to within 5 ppm). The presence of 142Nd anomalies at Isua has recently been confirmed by two other groups (Boyet et al. 2003; Caro et al. 2003). The available data demonstrate both the existence of early depleted mantle and that the early mantle was isotopically heterogeneous. As discussed by Jacobsen and Harper (1996), the recycling rate can be determined by tracing the decay of the average 142Nd/144Nd value of the depleted mantle. In addition, by using the 142Nd/144Nd heterogeneity in the depleted mantle through time we can determine the stirring rate of the mantle (Kellogg, Jacobsen and O'Connell, 2002) as a function of time. For this project our goal is to obtain a resolution in 142Nd/144Nd measurements of ~1 ppm. We have thus compared results obtained for the Nd isotope composition and 142Nd enriched standards for three different TIMS instruments: The Finnigan MAT 262 at Harvard, the Isoprobe-T and Finnigan TRITON mass spectrometers in GV Instrument's and Thermo Electron's demo laboratories in Manchester and Bremen, respectively. The Finnigan TRITON was designed in response to a request from the senior author for such an instrument. The results obtained so far demonstrate that all three instruments yield the same 142Nd/144Nd, 143Nd/144Nd and 145Nd/144Nd isotopic ratios to within a few ppm, while 148Nd/144Nd and 150Nd/144Nd ratios agree to within 10-20 ppm, when all ratios are normalized to 146Nd/144Nd using the exponential law. Due to

  4. Zircon U-Pb and Lu-Hf isotope study of the Neoproterozoic Haizhou Group in the Sulu orogen: Provenance and tectonic implications

    Science.gov (United States)

    Zhou, Jian-Bo; Wilde, Simon A.; Liu, Fu-Lai; Han, Jie

    2012-04-01

    The Neoproterozoic Haizhou Group crops out sporadically in the Sulu orogen in east-central China. It is divided into the Jinping and Yuntai formations and consists of quartzite, quartz schist, marble and graphite- and apatite-bearing sequences. Major and trace element data for quartz schist from the two formations indicate that these rocks have a greywacke protolith and have been deposited during strong tectonic activity. LA-ICPMS U-Pb dating of detrital zircon yields ages of 635 to 1074 Ma for three samples from the Jinping Formation and 611 to 943 Ma for two samples from the Yuntai Formation. More than 78% of the detrital zircons from the two formations have U-Pb ages grouped between 700 and 890 Ma, with two clusters peaking at 758 Ma and 828 Ma, respectively. This indicates that their provenance is magmatic rocks of Neoproterozoic age that have a tectonic affinity to the South China Block (SCB). A few older zircon populations with peak U-Pb ages at 943 and 1074 Ma are also present. A younger population shows peaks at 661 and 611 Ma. This suggests that deposition of the Haizhou Group was later than ~ 611 Ma rather than during the Mesoproterozoic as previously thought. Zircon Lu-Hf isotope data collected from the same U-Pb sites show negative ɛHf(t) values of - 22.8 to - 7.4 and Hf model ages of 2341 to 3100 Ma. This indicates that the Neoproterozoic magmatic rocks were derived from reworking of ancient Paleoproterozoic to Archean crust. The results support the contention that the Haizhou Group is similar to the Wulian Group at the northwestern edge of the Sulu orogen, both having a SCB affinity, but that the Penglai Group does not belong to the SCB because of the absence of Neoproterozoic ages. This lends support to the conclusion that the Triassic suture between the North China and South China blocks is located along the Baichihe-Yantai Fault, which lies north of the Wulian Complex and south of the Jiaobei Terrane; thus the Wulian-Yantai Fault is not the suture

  5. Oxygen and carbon isotope ratios of hydrothermal minerals from Yellowstone drill cores

    Science.gov (United States)

    Sturchio, N. C.; Keith, T. E. C.; Muehlenbachs, K.

    1990-01-01

    Oxygen and carbon isotope ratios were measured for hydrothermal minerals (silica, clay and calcite) from fractures and vugs in altered rhyolite, located between 28 and 129 m below surface ( in situ temperatures ranging from 81 to 199°C) in Yellowstone drill holes. The purpose of this study was to investigate the mechanism of formation of these minerals. The δ 18O values of the thirty-two analyzed silica samples (quartz, chalcedony, α-cristobalite, and β-cristobalite) range from -7.5 to +2.8‰ . About one third of the silica 7samples have δ 18O values that are consistent with isotopic equilibrium with present thermal waters; most of the other silica samples appear to have precipitated from water enriched in 18O (up to 4.7‰) relative to present thermal water, assuming precipitation at present in situ temperatures. Available data on fluid-inclusion homogenization temperatures in hydrothermal quartz indicate that silica precipitation occurred mostly at temperatures above those measured during drilling and imply that 15O enrichments in water during silica precipitation were generally larger than those estimated from present conditions. Similarly, clay minerals (celadonite and smectite) have δ 18O values higher (by 3.5 to 7.9‰) than equilibrium values under present conditions. In contrast, all eight analyzed calcite samples are close to isotopic equilibrium with present thermal waters. The frequent incidence of apparent 18O enrichment in thermal water from which the hydrothermal minerals precipitated may indicate that a higher proportion of strongly 18O-enriched deep hydrothermal fluid once circulated through shallow portions of the Yellowstone system, or that a recurring transient 18O-enrichment effect occurs at shallow depths and is caused either by sudden decompressional boiling or by isotopic exchange at low water/rock ratios in new fractures. The mineralogy and apparent 18O enrichments of hydrothermal fracture-filling minerals are consistent with

  6. U-Pb Zircon Ages,Geochemical and Sr-Nd-Hf Isotopic Compositions of Granitoids in Western Songpan-Garze Fold Belt: Petrogenesis and Implication for Tectonic Evolution

    Institute of Scientific and Technical Information of China (English)

    Cai Hongming; Zhang Hongfei; Xu Wangchun

    2009-01-01

    Granitoids are widespread in the Songpan-Garze (松潘-甘孜) fold belt,western China.These granitoids provide insight into regional tectono-magmatic events,basement nature and tectonic evolution.However,previous studies mainly focused on the eastern Songpan-Garze fold belt In this article,five granitoid intrusions from the western Songpan-Garze fold belt have been studied.These intrusions are composed of quartz-diorite and granodiorite.Using LA-ICP-MS zircon dating method,the obtained magma crystallization ages are 219±2 Ma for the quartz-diorite and 216±5 Ma for the granodiorite.The ages,combined with regional geological analyses,show that they formed in a post-collisional tectonic setting.The quartz-diorite and granodiorite display co-linear variation in their chemical compositions.REE compositions for both the quartz-diorite and granodiorite show strongly fractionated patterns with (La/Yb)N=5.02-18.34 and Eu/Eu*=0.44-0.89.The quartz-diorites have initial 87Sr/86Sr ratios (7Sr) of 0.709 29-0.711 97 and εNd(t) values of -8.6 to -6.1 and the granodiorites have Isr values of 0.705 49-0.709 97 and εNd(t) values of -8.3 to -4.3.Zircon Hf isotopic data show εHr(t) values of -3.8 to +1.6 for the quartz-diorites and -1.2 to +3.0 for the granodiorites.Geochemical and Sr-Nd-Hf isotopic compositions indicate that the quartz-diorites and granodiorites have similar petrogenesis.We suggest that the magmas for the quartz-diorites and granodiorites were derived from partial melting of lower crustal mafic source,resulting from amphibole dehydration melting reaction.The probing of the magma source reveals that the western Songpan-Garze fold belt contains an unexposed continental basement,which is similar to the eastern Songpan-Garze fold belt.Geodynamically,it is proposed that a lithospheric delamination model can account for the magma generation for the quartz-diorites and granodiorites in the western Songpan-Garze fold belt.

  7. Zircon U-Pb and molybdenite Re-Os geochronology and Sr-Nd-Pb-Hf isotopic constraints on the genesis of the Xuejiping porphyry copper deposit in Zhongdian, Northwest Yunnan, China

    Science.gov (United States)

    Leng, Cheng-Biao; Zhang, Xing-Chun; Hu, Rui-Zhong; Wang, Shou-Xu; Zhong, Hong; Wang, Wai-Quan; Bi, Xian-Wu

    2012-10-01

    The Xuejiping porphyry copper deposit is located in northwestern Yunnan Province, China. Tectonically, it lies in the southern part of the Triassic Yidun island arc. The copper mineralization is mainly hosted in quartz-dioritic and quartz-monzonitic porphyries which intruded into clastic-volcanic rocks of the Late Triassic Tumugou Formation. There are several alteration zones including potassic, strong silicific and phyllic, argillic, and propylitic alteration zones from inner to outer of the mineralized porphyry bodies. The ages of ore-bearing quartz-monzonitic porphyry and its host andesite are obtained by using the zircon SIMS U-Pb dating method, with results of 218.3 ± 1.6 Ma (MSWD = 0.31, N = 15) and 218.5 ± 1.6 Ma (MSWD = 0.91, N = 16), respectively. Meanwhile, the molybdenite Re-Os dating yields a Re-Os isochronal age of 221.4 ± 2.3 Ma (MSWD = 0.54, N = 5) and a weighted mean age of 219.9 ± 0.7 Ma (MSWD = 0.88). They are quite in accordance with the zircon U-Pb ages within errors. Furthermore, all of them are contemporary with the timing of the Garzê-Litang oceanic crust subduction in the Yidun arc. Therefore, the Xuejiping deposit could be formed in a continental margin setting. There are negative ɛNd(t) values ranging from -3.8 to -2.1 and relatively high initial 87Sr/86Sr ratios from 0.7051 to 0.7059 for the Xuejiping porphyries and host andesites. The (206Pb/204Pb)t, (207Pb/204Pb)t and (208Pb/204Pb)t values of the Xuejiping porphyries and host andesites vary from 17.899 to 18.654, from 15.529 to 15.626, and from 37.864 to 38.52, respectively, indicative of high radiogenic Pb isotopic features. In situ Hf isotopic analyses on zircons by using LA-MC-ICP-MS exhibit that there are quite uniform and slightly positive ɛHf(t) values ranging from -0.2 to +3.2 (mostly between 0 and +2), corresponding to relatively young single-stage Hf model ages from 735 Ma to 871 Ma. These isotopic features suggest that the primary magmas of the Xuejiping porphyries and

  8. Juvenile crust formation in the Zimbabwe Craton deduced from the O-Hf isotopic record of 3.8-3.1 Ga detrital zircons

    Science.gov (United States)

    Bolhar, Robert; Hofmann, Axel; Kemp, Anthony I. S.; Whitehouse, Martin J.; Wind, Sandra; Kamber, Balz S.

    2017-10-01

    Hafnium and oxygen isotopic compositions measured in-situ on U-Pb dated zircon from Archaean sedimentary successions belonging to the 2.9-2.8 Ga Belingwean/Bulawayan groups and previously undated Sebakwian Group are used to characterize the crustal evolution of the Zimbabwe Craton prior to 3.0 Ga. Microstructural and compositional criteria were used to minimize effects arising from Pb loss due to metamorphic overprinting and interaction with low-temperature fluids. 207Pb/206Pb age spectra (concordance >90%) reveal prominent peaks at 3.8, 3.6, 3.5, and 3.35 Ga, corresponding to documented geological events, both globally and within the Zimbabwe Craton. Zircon δ18O values from +4 to +10‰ point to both derivation from magmas in equilibrium with mantle oxygen and the incorporation of material that had previously interacted with water in near-surface environments. In εHf-time space, 3.8-3.6 Ga grains define an array consistent with reworking of a mafic reservoir (176Lu/177Hf ∼0.015) that separated from chondritic mantle at ∼3.9 Ga. Crustal domains formed after 3.6 Ga depict a more complex evolution, involving contribution from chondritic mantle sources and, to a lesser extent, reworking of pre-existing crust. Protracted remelting was not accompanied by significant mantle depletion prior to 3.35 Ga. This implies that early crust production in the Zimbabwe Craton did not cause complementary enriched and depleted reservoirs that were tapped by later magmas, possibly because the volume of crust extracted and stabilised was too small to influence (asthenospheric) mantle isotopic evolution. Growth of continental crust through pulsed emplacement of juvenile (chondritic mantle-derived) melts, into and onto the existing cratonic nucleus, however, involved formation of complementary depleted subcontinental lithospheric mantle since the early Archaean, indicative of strongly coupled evolutionary histories of both reservoirs, with limited evidence for recycling and lateral

  9. Zircon U-Pb Geochronology, Hf Isotopic Composition and Geological Implications of the Neoproterozoic Huashan Group in the Jingshan Area, Northern Yangtze Block, China

    Science.gov (United States)

    Yang, Z.; Yang, K.

    2015-12-01

    In the northern Yangtze Block, a clear angular unconformity between the Mesoproterozoic sequences (e.g. Dagushi Group) and the overlying Neoproterozoic strata (e.g. Huashan Group) marks the the Jinning orogeny. A combined study of Lu-Hf isotopes and U-Pb ages for detrital zircons from Huashan Group can provide information on the crustal evolution of sedimentary provenances and the timing of the Jinning orogeny. Detrital zircons from Huashan Group have two major U-Pb age populations of about 2.0Ga, 2.65Ga, and three subordinate age groups of about 0.82Ga, 2.5Ga, 2.9Ga with minor >3.0Ga ages. The youngest five analyses yield a weighted average age of 816±9Ma, which is consistent with that of interlayered basalt (824±9Ma, Deng et al., 2013) and roughly defines the minimum depositional age of Huashan Group. Detrital zircons of Huashan Group mostly have two stage Hf isotope model ages (TDM2) between 3.0 to 3.3Ga, indicating that the northern Yangtze Block experienced significant continental crustal growth during the Paleo- to Meso-archean. Similar U-Pb ages of detrital zircons have been obtained from Precambrian sedimentary rocks in the northern Yangtze Block from previous studies (Liu et al., 2008; Guo et al., 2014 and references therein). Recently, ca. 2.65Ga A-type granites had been reported from the Kongling and Huji area, which likely record the thermally stable lithosphere (Chen et al., 2013; Zhou et al., 2015). In combination with this study, it documents the widespread 2.6-2.7Ga magmatic rocks in the northern Yangtze Block. Zhao et al. (2013) demonstrated both the ca. 850Ma tonalite and trondhjemite of the Huangling igneous complex were formed in a continental arc setting. This suggests the Miaowan-Huashan oceanic basin proposed by Bader et al. (2013) has not been closed at ca. 850Ma. This evidence, together with the depositional age of the Huashan Group, indicates the Jinning orogeny took place at 850-820 Ma. [1] Bader et al., 2013 Tectonics [2] Deng et al

  10. Isotope systematics of a juvenile intraplate volcano: Pb, Nd, and srisotope ratios of basalts from Loihi Seamount, Hawaii

    Energy Technology Data Exchange (ETDEWEB)

    Staudigel, H. (Columbia Univ., Palisades, NY (USA). Lamont-Doherty Geological Observatory; Scripps Institution of Oceanography, La Jolla, CA (USA)); Zindler, A.; Leslie, T. (Columbia Univ., Palisades, NY (USA). Lamont-Doherty Geological Observatory); Hart, S.R.; Chen, C.Y. (Massachusetts Inst. of Tech., Cambridge (USA). Dept. of Earth and Planetary Sciences); Clague, D. (Geological Survey, Menlo Park, CA (USA))

    1984-07-01

    Sr, Nd, and Pb isotope ratios for a representative suite of 15 basanites, alkali basalts, transitional basalts and tholeiites from Loihi Seamount, Hawaii, display unusually large variations for a single volcano, but lie within known ranges for Hawaiian basalts. Nd isotope ratios in alkali basalts show the largest relative variation (0.51291 - 0.51305), and include the nearly constant tholeiite value (approx.= 0.51297). Pb isotope ratios show similarly large ranges for tholeiites and alkali basalts and continue Tatsumoto's (31) 'Loa' trend towards higher /sup 206/Pb//sup 204/Pb, ratios, resulting in a substantial overlap with the 'Kea' trend. /sup 206/Pb//sup 204/Pb ratios for Loihi and other volcanoes along the Loa and Kea trends (31) are observed to correlate with the age of the underlying lithosphere suggesting lithosphere involvement in the formation of Hawaiian tholeiites. Loihi lavas display no correlation of Nd, Sr, or Pb isotope ratios with major element compositions or eruptive age, in contrast with observations of some other Hawaiian volcanoes. Isotope data for Loihi, as well as average values for Hawaiian volcanoes, are not adequately explained by previously proposed two-end-member models; new models for the origin and the development of Hawaiian volcanoes must include mixing of at least three geochemically distinct source regions and allow for the involvement of heterogeneous oceanic lithosphere.

  11. Estimating the distribution of strontium isotope ratios (87Sr/86Sr in the Precambrian of Finland

    Directory of Open Access Journals (Sweden)

    Lars Kaislaniemi

    2011-12-01

    Full Text Available A method to estimate the 87Sr/86Sr ratio of a rock based on its age and Rb/Sr ratio is presented. This method, together with data from the Rock Geochemical Database of Finland (n=6544 is used to estimate the 87Sr/86Sr ratios in the Precambrian of Finland and in its different major units. A generalization to cover the whole area of Finland is achieved by smoothing of estimation points. The estimation method is evaluated by comparing its results to published Rb-Sr isotope analyses (n=138 obtained on the Finnish Precambrian. The results show correspondence to different geological units of Finland,but no systematic difference between Archaean and younger areas is evident. Evaluation of the method shows that most of the estimates are reliable and accurate to be used as background material for provenance studies in archaeology, paleontology and sedimentology. However, some granitic rocks may have large (>1.0 % relative errors.Strontium concentration weighted average of the estimates differs only by 0.001 from the average 87Sr/86Sr ratio (0.730 of the rivers on the Fennoscandian shield.

  12. Optimization of on-line hydrogen stable isotope ratio measurements of halogen- and sulfur-bearing organic compounds using elemental analyzer–chromium/high-temperature conversion isotope ratio mass spectrometry (EA-Cr/HTC-IRMS)

    Science.gov (United States)

    Gehre, Matthias; Renpenning, Julian; Geilmann, Heike; Qi, Haiping; Coplen, Tyler B.; Kümmel, Steffen; Ivdra, Natalija; Brand, Willi A.; Schimmelmann, Arndt

    2017-01-01

    Rationale: Accurate hydrogen isotopic analysis of halogen- and sulfur-bearing organics has not been possible with traditional high-temperature conversion (HTC) because the formation of hydrogen-bearing reaction products other than molecular hydrogen (H2) is responsible for non-quantitative H2 yields and possible hydrogen isotopic fractionation. Our previously introduced, new chromium-based EA-Cr/HTC-IRMS (Elemental Analyzer–Chromium/High-Temperature Conversion Isotope Ratio Mass Spectrometry) technique focused primarily on nitrogen-bearing compounds. Several technical and analytical issues concerning halogen- and sulfur-bearing samples, however, remained unresolved and required further refinement of the reactor systems.

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

    Energy Technology Data Exchange (ETDEWEB)

    Isselhardt, Brett H. [Univ. of California, Berkeley, CA (United States)

    2011-09-01

    Resonance Ionization Mass Spectrometry (RIMS) has been developed as a method to measure relative uranium isotope abundances. In this approach, RIMS is used as an element-selective ionization process to provide a distinction between uranium atoms and potential isobars without the aid of chemical purification and separation. We explore the laser parameters critical to the ionization process and their effects on the measured isotope ratio. Specifically, the use of broad bandwidth lasers with automated feedback control of wavelength was applied to the measurement of 235U/238U ratios to decrease laser-induced isotopic fractionation. By broadening the bandwidth of the first laser in a 3-color, 3-photon ionization process from a bandwidth of 1.8 GHz to about 10 GHz, the variation in sequential relative isotope abundance measurements decreased from >10% to less than 0.5%. This procedure was demonstrated for the direct interrogation of uranium oxide targets with essentially no sample preparation. A rate equation model for predicting the relative ionization probability has been developed to study the effect of variation in laser parameters on the measured isotope ratio. This work demonstrates that RIMS can be used for the robust measurement of uranium isotope ratios.

  14. Activation cross sections and isomeric ratios in reactions induced by 14. 5 MeV neutrons on [sup 152]Sm, [sup 154]Sm and [sup 178]Hf

    Energy Technology Data Exchange (ETDEWEB)

    Kirov, A. (Washington Univ., St. Louis, MO (United States). Dept. of Chemistry); Nenoff, N.; Georgieva, E.; Necheva, C. (Sofia Univ. (Bulgaria). Atomic Physics Dept.); Ephtimov, I. (IZR, Kostinbrod (Bulgaria))

    1993-05-01

    Cross sections for the reactions [sup 152]Sm(n, p)[sup 152g,m1,m2P]m, [sup 154]Sm(n, p)[sup 154g,m]Pm, [sup 178]Hf(n, p)[sup 178m,g]Lu, [sup 154]Sm(n, d)[sup 153]Pm and [sup 152]Sm(n, [alpha])[sup 149]Nd were measured at 14.5 meV neutron energy by the activation method. On the basis of these cross sections, the associated isomeric ratios in [sup 154]Pm, [sup 152]Pm, [sup 178]Lu and the comparison with the predictions of different compound and precompound models, conclusions are drawn about the role of the preequilibrium processes in 14.5 MeV neutron induced reactions. Calculations for equal angular momentum removal by equilibrium and preequilibrium emitted particles better reproduced the experimental isomeric ratios, than for higher angular momentum removal in the preequilibrium phase. The isomeric ratios may be used as a source of additional information about the spin of the isomeric states in [sup 152]Pm and [sup 154]Pm for which the spectroscopic information is uncertain. (orig.).

  15. Activation cross sections and isomeric ratios in reactions induced by 14.5 MeV neutrons on152Sm,154Sm and178Hf

    Science.gov (United States)

    Kirov, A.; Nenoff, N.; Georgieva, E.; Necheva, C.; Ephtimov, I.

    1993-09-01

    Cross sections for the reactions152Sm( n, p)152 g,m1, m2 Pm,154Sm( n, p)154 g,m Pm,178Hf( n, p)178 m,g Lu,154Sm( n, d)153Pm and152Sm( n, α)149Nd were measured at 14.5 MeV neutron energy by the activation method. On the basis of these cross sections, the associated isomeric ratios in154Pm,152Pm,178Lu and the comparison with the predictions of different compound and precompound models, conclusions are drawn about the role of the preequilibrium processes in 14.5 MeV neutron induced reactions. Calculations for equal angular momentum removal by equilibrium and preequilibrium emitted particles better reproduced the experimental isomeric ratios, than for higher angular momentum removal in the preequilibrium phase. The isomeric ratios may be used as a source of additional information about the spin of the isomeric states in152Pm and154Pm for which the spectroscopic information is uncertain.

  16. Fidelity of Stable Oxygen Isotope Ratios as Environmental Recorders Using Multiple Coral Cores From Coastal Kenya

    Science.gov (United States)

    Naish, T.; Carter, B.; Abbott, S.; Field, B.; Zhu, H.; Wilson, G.; Alloway, B.; Edwards, S.; Pillans, B.; Barker, A.; Niessen, F.; Maslen, G.; Beu, A.; Fleitmann, D.; Dunbar, R. B.; Mucciarone, D. A.

    2004-12-01

    Climate variability in the western equatorial Indian Ocean reflects the combined influence of seasonally changing sea surface temperature (SST), ocean currents, and monsoon circulation, as well as inter-annual to -decadal variability associated with ENSO in the Pacific. However, the Indian Ocean also exhibits variability that appears unrelated to ENSO in the Pacific. The nature of interactions between air-sea variability in the Indian and Pacific oceans is not yet fully resolved, in part because of the lack of long-term, high-resolution SST records from key localities in the Indian Ocean. Such records are now being obtained using oxygen isotope profiles measured on corals from East Africa, Indonesia, Australia, and Indian Oceania (Maldives, Seychelles), with the longest coral-based time series from Malindi, Kenya, covering the last 300 years at near-monthly resolution. The value of these developing coral records depends on the fidelity with which they record regional climate variability. In order to assess the fidelity of oxygen isotope ratios (\\delta18O) in Indian Ocean corals as a proxy for sea surface temperature, we have generated stable isotopic time series from multiple Porites lutea coral heads collected along the coast of Kenya. Coral-based isotopic paleoclimatology is labor and time-intensive so detailed analyses using multiple coral heads from different sites within a region are extremely rare. Most published records are produced from a single coral head, yet questions have been raised about the accuracy of such records. To address such concerns, near-monthly resolution isotopic profiles, spanning 10 to 50 years prior to 1997, were measured on a total of 8 cores from five sites along a north-south transect between 2° and 4° S (Kiwayu: 2° 2'S, 41° 2'E, Malindi: 3° 14'S, 40° 8'E, Watamu: 3° 23'S, 39° 52'E, Mombasa: 3° 59'S, 39° 5'E, and Kisite: 4° 43'S, 39° 23'E. Correlations among individual \\delta18O time series (r values range from 0.65 to

  17. Carbon and nitrogen isotope ratios of factory-produced RDX and HMX.

    Science.gov (United States)

    Howa, John D; Lott, Michael J; Chesson, Lesley A; Ehleringer, James R

    2014-07-01

    RDX and HMX are explosive compounds commonly used by the military and also occasionally associated with acts of terrorism. The isotopic characterization of an explosive can be a powerful approach to link evidence to an event or an explosives cache. We sampled explosive products and their reactants from commercial RDX manufacturers that used the direct nitration and/or the Bachmann synthesis process, and then analyzed these materials for carbon and nitrogen isotope ratios. For manufacturers using the Bachmann process, RDX (13)C enrichment relative to the hexamine substrate was small (+0.9‰) compared to RDX produced using the direct nitration process (+8.2‰ to +12.0‰). RDX (15)N depletion relative to the nitrogen-containing substrates (-3.6‰) was smaller in the Bachmann process than in the direct nitration process (-12.6‰ to -10.6‰). The sign and scale of these differences agree with theorized mechanisms of mass-dependent fractionation. We also examined the isotopic relationship between RDX and HMX isolated from explosive samples. The δ(13)C and δ(15)N values of RDX generally matched those of the HMX with few exceptions, most notably from a manufacturer known to make RDX using two different synthesis processes. The range in δ(13)C values of RDX in a survey of 100 samples from 12 manufacturers spanned 33‰ while the range spanned by δ(15)N values was 26‰; these ranges were much greater than any previously published observations. Understanding the relationship between products and reactants further explains the observed variation in industrially manufactured RDX and can be used as a diagnostic tool to analyze explosives found at a crime scene. Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.

  18. Heavy with child? Pregnancy status and stable isotope ratios as determined from biopsies of humpback whales

    Science.gov (United States)

    Clark, Casey T.; Fleming, Alyson H.; Calambokidis, John; Kellar, Nicholas M.; Allen, Camryn D.; Catelani, Krista N.; Robbins, Michelle; Beaulieu, Nicole E.; Steel, Debbie; Harvey, James T.

    2016-01-01

    Understanding reproductive rates of wild animal populations is crucially important for management and conservation. Assessing pregnancy status of free-ranging cetaceans has historically been difficult; however, recent advances in analytical techniques have allowed the diagnosis of pregnancy from small samples of blubber tissue. The primary objectives of this study were as follows: (i) to test the efficacy of blubber progesterone assays as a tool for diagnosing pregnancy in humpback whales (Megaptera novaeangliae); (ii) to estimate the pregnancy rate of humpback whales in Monterey Bay, California; and (iii) to investigate the relationship between stable isotopes and reproductive status of these whales. Progesterone concentrations of female whales fell into two distinct groups, allowing for diagnostic separation of pregnant and non-pregnant individuals. Pregnancy rate varied between years of the study (48.4%% in 2011 and 18.5% in 2012), but fell within the range of other estimates of reproductive success for this population. Stable carbon and nitrogen isotope ratios were examined to investigate the impacts of pregnancy on these values. Neither δ15N nor δ13C varied in a consistent way among animals of different sex or reproductive status. The relationship between δ15N and δ13C was strongly positive for male and non-pregnant female humpbacks; however, no relationship existed for pregnant whales. This difference may be indicative of the effects of pregnancy on δ15N, resulting from tissue synthesis and reduced excretion of nitrogenous waste, as well as on δ13C through increased mobilization of lipid stores to meet the energetic demands of pregnancy. Ultimately, our results support the use of blubber progesterone assays for diagnosing pregnancy in humpback whales and indicate that, when paired with other approaches (e.g. stable isotope analysis), pregnancy status can be an informative tool for addressing questions about animal physiology, ecology and population

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2009-12-01

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

  20. ICP-MS with hexapole collision cell for isotope ratio measurements of Ca, Fe, and Se

    Energy Technology Data Exchange (ETDEWEB)

    Boulyga, S.F. [Radiation Physics and Chemistry Problems Inst., Minsk (Belarus); Becker, J.S. [Central Department for Analytical Chemistry, Research Centre Juelich (Germany)

    2001-07-01

    To avoid mass interferences on analyte ions caused by argon ions and argon molecular ions via reactions with collision gases, an rf hexapole filled with helium and hydrogen has been used in inductively coupled plasma mass spectrometry (ICP-MS), and its performance has been studied. Up to tenfold improvement in sensitivity was observed for heavy elements (m > 100 u), because of better ion transmission through the hexapole ion guide. A reduction of argon ions Ar{sup +} and the molecular ions of argon ArX{sup +} (X = O, Ar) by up to three orders of magnitude was achieved in a hexapole collision cell of an ICP-MS (''Platform ICP'', Micromass, Manchester, UK) as a result of gas-phase reactions with hydrogen when the hexapole bias (HB) was set to 0 V; at an HB of 1.6 V argon, and argon-based ions of masses 40 u, 56 u, and 80 u, were reduced by approximately four, two, and five orders of magnitude, respectively. The signal-to-noise ratio {sup 80}Se/ {sup 40}Ar{sub 2}{sup +} was improved by more than five orders of magnitude under optimized experimental conditions. Dependence of mass discrimination on collision-cell properties was studied in the mass range 10 u (boron) to 238 u (uranium). Isotopic analysis of the elements affected by mass-spectrometric interference, Ca, Fe, and Se, was performed using a Meinhard nebulizer and an ultrasonic nebulizer (USN). The measured isotope ratios were comparable with tabulated values from IUPAC. Precision of 0.26%, 0.19%, and 0.12%, respectively, and accuracy of 0.13% 0.25%, and 0.92%, respectively, was achieved for isotope ratios {sup 44}Ca/ {sup 40}Ca and {sup 56}Fe/{sup 57}Fe in 10 {mu}g L{sup -1} solution nebulized by means of a USN and for {sup 78}Se/{sup 80}Se in 100 {mu}g L{sup -1} solution nebulized by means of a Meinhard nebulizer. (orig.)

  1. The pre-Atlantic Hf isotope evolution of the east Laurentian continental margin: Insights from zircon in basement rocks and glacial tillites from northern New Jersey and southeastern New York

    Science.gov (United States)

    Zirakparvar, N. Alex; Setera, Jacob; Mathez, Edmond; Vantongeren, Jill; Fossum, Ryanna

    2017-02-01

    This paper presents laser ablation U-Pb age and Hf isotope data for zircons from basement rocks and glacial deposits in northern New Jersey and southeastern New York. The purpose is to understand the eastern Laurentian continental margin's Hf isotope record in relation to its geologic evolution prior to the opening of the Atlantic Ocean. The basement samples encompass a Meso- to Neoproterozoic continental margin arc, an anatectic magmatic suite, as well as a Late Ordovician alkaline igneous suite emplaced during post-orogenic melting of the lithospheric mantle. Additional samples were collected from terminal moraines of two Quaternary continental ice sheets. Across the entire dataset, zircons with ages corresponding to the timing of continental margin arc magmatism ( 1.4 Ga to 1.2 Ga) have positive εHf(initial) values that define the more radiogenic end of a crustal evolution array. This array progresses towards more unradiogenic εHf(initial) values along a series of low 176Lu/177Hf (0.022 to 0.005) trajectories during subsequent anatectic magmatism ( 1.2 Ga to 1.0 Ga) and later metamorphic and metasomatic re-working ( 1.0 Ga to 0.8 Ga) of the continental margin arc crust. In contrast, nearly chondritic εHf(initial) values from the Late Ordovician alkaline magmas indicate that the Laurentian margin was underlain by a re-fertilized mantle source. Such a source may have developed by subduction enrichment of the mantle wedge beneath the continental margin during the Mesoproterozoic. Additionally, preliminary data from a metasedimentary unit of unknown provenance hints at the possibility that some of the sediments occupying this portion of the Laurentian margin prior to the Ordovician were sourced from crust older than 1.9 Ga.

  2. Use of isotope ratios to identify sources contributing to pediatric lead poisoning in Peru.

    Science.gov (United States)

    Naeher, Luke P; Rubin, Carol S; Hernandez-Avila, Mauricio; Noonan, Gary P; Paschal, Dan; Narciso, Juan; Lain, Rocio Espinoza; Gastanaga, Carmen; Almeyda, Rosa; Jarrett, Jeff; Caldwell, Kathleen L; McGeehin, Michael

    2003-09-01

    In 1998, a school-based blood lead level (BLL) survey of 2,510 children, conducted in Lima and Callao, Peru, revealed elevated BLLs in children from 2 Callao schools (mean BLL = 25.6 microg/dl; n = 314) and in children from Callao overall (mean BLL = 15.2 microg/dl; n = 898), compared with children from Lima (mean BLL = 7.1 microg/dl; n = 1,612). Public health officials at Peru's Direccion General de Salud Ambiental (DIGESA) hypothesized that a possible source of the elevated pediatric BLLs observed in Callao was a large depository near the port where mineral concentrates are stored prior to shipment. The U.S. Centers for Disease Control and Prevention worked with DIGESA to identify source(s) that contributed to the pediatric lead poisonings by comparing isotopic profiles of lead in blood, mineral, gasoline, and air filter samples. The lead isotope ratio (IR) observed in mineral samples from the depository in Callao differed from those in gasoline samples from Lima and Callao. The blood lead IRs of children living near the depository were similar to the IRs of the mineral samples and different from the IRs of the gasoline samples, suggesting that lead from the depository-and not gasoline-was the primary source of lead in these children. Lead IR analysis of regional air filter samples supported these findings.

  3. Stable isotope ratio analysis for verifying the authenticity of balsamic and wine vinegar.

    Science.gov (United States)

    Perini, M; Paolini, M; Simoni, M; Bontempo, L; Vrhovsek, U; Sacco, M; Thomas, F; Jamin, E; Hermann, A; Camin, F

    2014-08-13

    In this paper, we investigate whether the analysis of stable isotope ratios D/H and ¹³C/¹²C in ethanol and acetic acid and of ¹⁸O/¹⁶O in water can be applied to the ingredients of "aceto balsamico di Modena IGP" (ABM) to evaluate their authenticity. We found that impurities in the extraction solution do not affect the ¹³C/¹²C of acetic acid and the D/H values of acetic acid are not affected under a composite NMR experiment. The standard deviation of repeatability and standard deviation of reproducibility are comparable in wine vinegar and ABM and generally lower than those quoted in the official methods. This means that the validation parameters quoted in the official methods can also be applied to the ingredients of ABM. In addition, we found no changes in the isotopic values from wine to vinegar and to ABM, and from the original must to the ABM must, providing experimental evidence that reference data from wine databanks can also be used to evaluate the authenticity of vinegar and ABM.

  4. 锡林浩特杂岩中斜长角闪岩锆石U-Pb年代学及Hf同位素研究%U-Pb Dating and Hf Isotopic Composition of Zircons in Amphibolite from the Xilinhot Complex

    Institute of Scientific and Technical Information of China (English)

    王善辉; 陈岳龙; 李大鹏

    2012-01-01

    206Pb/238U-Pb ages is (316 ±4) Ma, which indicates the Xilinhot complex should not be Precambrian. According to the field observations and petrography, the complex may be a suite of Late Paleozoic volcanic-sedimentary formation which had been subjected to strong deformation and metamorphism. According to the zircon Hf isotopic compositions of plagioclase amphibolite in the Xilinhot complex, εHι(t) value is positive ( + 4. 1 to + 17. 0) , it should have originated from the depleted mantle or crust-mantle mixing source. A mixing calculating of depleted mantle and ancient crustal end-members based on zircon Hf isotopic compositions shows that depleted mantle-derived accretion component was dominant in the plagioclase amphibolite ( after calculation, the crust to mantle mixing <