Sample records for neodymium isotopic composition

  1. Do foraminifera accurately record seawater neodymium isotope composition? (United States)

    Scrivner, Adam; Skinner, Luke; Vance, Derek


    Palaeoclimate studies involving the reconstruction of past Atlantic meridional overturning circulation increasingly employ isotopes of neodymium (Nd), measured on a variety of sample media (Frank, 2002). In the open ocean, Nd isotopes are a conservative tracer of water mass mixing and are unaffected by biological and low-temperature fractionation processes (Piepgras and Wasserburg, 1987; Lacan and Jeandel, 2005). For decades, benthic foraminifera have been widely utilised in stable isotope and geochemical studies, but have only recently begun to be exploited as a widely distributed, high-resolution Nd isotope archive (Klevenz et al., 2008), potentially circumventing the difficulties associated with other methods used to recover past deep-water Nd isotopes (Klevenz et al., 2008; Rutberg et al., 2000; Tachikawa et al., 2004). Thus far, a single pilot study (Klevenz et al., 2008) has indicated that core-top sedimentary benthic foraminifera record a Nd isotope composition in agreement with the nearest available bottom seawater data, and has suggested that this archive is potentially useful on both millennial and million-year timescales. Here we present seawater and proximal core-top foraminifer Nd isotope data for samples recovered during the 2008 "RETRO" cruise of the Marion Dufresne. The foraminifer samples comprise a depth-transect spanning 3000m of the water column in the Angola Basin and permit a direct comparison between high-resolution water column and core-top foraminiferal Nd isotope data. We use these data to assess the reliability of both planktonic and benthic foraminifera as recorders of water column neodymium isotope composition. Frank, M., 2002. Radiogenic isotopes: Tracers of past ocean circulation and erosional input, Rev. Geophys., 40 (1), 1001, doi:10.1029/2000RG000094. Klevenz, V., Vance, D., Schmidt, D.N., and Mezger, K., 2008. Neodymium isotopes in benthic foraminifera: Core-top systematics and a down-core record from the Neogene south Atlantic

  2. Absolute isotopic composition and atomic weight of neodymium using thermal ionization mass spectrometry. (United States)

    Zhao, Motian; Zhou, Tao; Wang, Jun; Lu, Hai; Fang, Xiang; Guo, Chunhua; Li, Qiuli; Li, Chaofeng


    Synthetic mixtures prepared gravimetrically from highly enriched isotopes of neodymium in the form of oxides of well-defined purity were used to calibrate a thermal ionization mass spectrometer. A new error analysis was applied to calculate the final uncertainty of the atomic weight value. Measurements on natural neodymium samples yielded an absolute isotopic composition of 27.153(19) atomic percent (at.%) 142Nd, 12.173(18) at.% 143Nd, 23.798(12) at.% 144Nd, 8.293(7) at.% 145Nd, 17.189(17) at.% 146Nd, 5.756(8) at.% 148Nd, and 5.638(9) at.% 150Nd, and the atomic weight of neodymium as 144.2415(13), with uncertainties given on the basis of 95% confidence limits. No isotopic fractionation was found in terrestrial neodymium materials.

  3. Accurate measurement of neodymium isotopic composition using Neptune MC-ICP-MS

    Institute of Scientific and Technical Information of China (English)

    Yueheng YANG; Hongfu ZHANG; Liewen XIE; Fuyuan WU


    This paper reports the measurement of the Neodymium isotopic composition by Neptune Multiple Collector Inductively Coupled Plasma Mass Spectrometry (MC-ICP-MS) over the last two years. Although there is concomitant Cerium in the chemical separation process, this has no significant influence on the Neodymium analysis. As for the sample containing small amounts of Samarium (Sm/Nd<0.04), direct calibration for isobaric interference and mass discrimina-tion by the exponential law can be obtained by assuming that Samarium mass discrimination is the same as that of Neodymium. Geological samples after traditional chemi-cal separation were measured by Neptune MC-ICP-MS and Thermal Ionization Mass Spectrometry (TIMS) respectively. The results show that Neptune MC-ICP-MS can measure Neodymium isotopic composition as precisely the TIMS does and is even more effective and less time-consuming than the TIMS Method.

  4. Mineralogy of the mid-ocean-ridge basalt source from neodymium isotopic composition of abyssal peridotites. (United States)

    Salters, Vincent J M; Dick, Henry J B


    Inferring the melting process at mid-ocean ridges, and the physical conditions under which melting takes place, usually relies on the assumption of compositional similarity between all mid-ocean-ridge basalt sources. Models of mantle melting therefore tend to be restricted to those that consider the presence of only one lithology in the mantle, peridotite. Evidence from xenoliths and peridotite massifs show that after peridotite, pyroxenite and eclogite are the most abundant rock types in the mantle. But at mid-ocean ridges, where most of the melting takes place, and in ophiolites, pyroxenite is rarely found. Here we present neodymium isotopic compositions of abyssal peridotites to investigate whether peridotite can indeed be the sole source for mid-ocean-ridge basalts. By comparing the isotopic compositions of basalts and peridotites at two segments of the southwest Indian ridge, we show that a component other than peridotite is required to explain the low end of the (143)Nd/(144)Nd variations of the basalts. This component is likely to have a lower melting temperature than peridotite, such as pyroxenite or eclogite, which could explain why it is not observed at mid-ocean ridges.

  5. Neodymium and strontium isotope evidence for crustal contamination of continental volcanics. (United States)

    Carter, S R; Evensen, N M; Hamilton, P J; O'nions, R K


    Combined neodymium and strontium isotope studies on Tertiary volcanics from northwest Scotland indicate that their parental mantle isotopic compositions have been substantially modified in many instances by contamination with the Precambrian continental crust through which they were erupted. The occurrence of samarium-neodymium and rubidium-strontium "pseudoisochrons" of different ages in these contaminated continental volcanics indicates that they are artifacts of the contamination processes and have no temporal significance with respect to mantle fractionation events.

  6. Boundary processes traced by neodymium isotopes (United States)

    Jeandel, C.; Lacan, F.


    Continental margins have been identified as preferential sites for removing of reactive elements from the ocean, on the base of U-series measurements (more specifically 231Pa/230Th). This process is called boundary scavenging (Bacon, 1988). Five years of neodymium isotopes data in water masses along the ocean margins (Indonesia, Papua New Guinea, Greenland-Scotland ridge and Labrador Sea) suggests that Nd is transferred from the sediments to the ocean but the reverse also occurs via the so-called boundary scavenging. These processes are only detectable by isotopic ratio measurements because they affect the isotopic signature of the water mass coming in contact with the margin, without changing its concentration. They can involve much higher fluxes than net input processes: for example, the modification of the AAIW signature along the Papua New Guinea slope involves exchange processes only (Lacan and Jeandel, 2001). Since we suspect that such processes not only affect the Nd oceanic chemistry but also the chemical fate of other reactive elements in the ocean, we suggest that the concept of boundary scavenging should be extended to "boundary exchange".

  7. Groundtruthing the Neodymium Isotope Proxy in Deep-Sea Corals (United States)

    van de Flierdt, T.; Robinson, L. F.; Adkins, J. F.


    The Nd isotopic composition of marine precipitates is increasingly recognized as a powerful tool in paleoceanography. Unlike nutrient proxies such as δ13C or Cd/Ca, Nd isotopes are not thought to be altered by biological processes, and thus may serve as a quasi-conservative water mass mixing tracer. However, any archive, which is used to extract authigenic Nd isotopes, needs careful examination, to test the integrity of the inferred seawater signal. Here we present first data on cleaning experiments and modern calibration experiments on different species of deep-sea corals. Seven different coral samples ranging in age from modern to ~220ka were selected for experiments designed to remove ferromanganese crusts and / or organic residues that may contain high concentrations of Nd and Th. The aim was to determine whether the rigorous chemical procedure we use to remove Th associated with these crusts is effective at removing Nd, and whether it causes any fractionation in the Nd isotopic composition of the coral aragonite. Crusts were found to contain Th-232 concentrations of up to ~160ppm, with 232Th/230Th ratios dependent on the oceanic location of the coral. Un-cleaned corals had Th-232 concentrations of up to 8ppb and the cleaning procedure reduced these values to less than 0.2ppb in both modern and fossil specimens. Neodymium isotopic compositions reveal that for modern corals, with no visible coating, a pre-cleaning step is sufficient to yield the isotopic composition of ambient seawater. The ferromanganese coating around fossil corals however may have a very different isotopic composition than the coral aragonite since it may be a time-integrated signal biased towards modern values. This bias is observed for intermediate water depth D. dianthus corals from stage 3 in the northwest Atlantic. Modern D. dianthus skeletons from the northwest Atlantic and the Drake Passage reflect the seawater Nd isotopic composition, and we are extending this modern calibration to


    NARCIS (Netherlands)



    Low-lying hexadecapole states in stable even-even neodymium isotopes have been investigated by means of inelastic electron scattering. Transition charge densities were extracted in a Fourier-Bessel analysis of the form factors. The analysis of the experimental results within the interacting sdg-boso

  9. Dissolved Neodymium Isotopes and Concentrations in the South Pacific (United States)

    Basak, C.; Pahnke, K.


    The isotopic composition of dissolved Neodymium (expressed as ɛNd) in seawater is becoming increasingly established as a tracer for present and past water mass structure and flow paths. The South Pacific represents the largest sector of the Southern Ocean and harbors major areas of bottom and intermediate water mass formation and is therefore a key area for understanding present and past deep ocean circulation. While more dissolved Nd data are becoming available from different ocean basins, the South Pacific is still understudied with respect to the distribution of Nd isotopes and concentrations. In this study we have analyzed dissolved Nd isotopes and concentrations from 11 water column profiles across the South Pacific between 46°S and 69°S that sample all water masses. Our data show that the bottom water in the vicinity of the Ross Sea (Ross Sea Bottom water, RSBW) is represented by an ɛNd value of ~ -7, while the overlying Circumpolar Deep Water (CDW) carries a signature of ɛNd = -8 to -9. The characteristic Nd isotopic signal of RSBW can be tracked along its flow path into the southeast Pacific where it progressively looses its signal through interaction with ambient CDW. The easternmost stations, closer to South America, exhibit an excursion towards radiogenic ɛNd at ≤2000 m water depth. This change towards more positive ɛNd coincides with low oxygen and high phosphate concentrations representing Pacific Deep Water (PDW) and possibly indicates water mass mixing of CDW with more radiogenic PDW. While the Nd isotopic composition shows apparent variations between stations and different water masses, the concentration profiles show a rather uniform and gradual increase with depth, a pattern typical for open ocean settings. Spatial and vertical contrasts in Nd isotopic values throughout the South Pacific indicate that Nd isotopes can be used as a water mass tracer in this region. It is reasonable to infer that local lithology in the Ross Sea influenced

  10. Neodymium isotope heterogeneity of ordinary and carbonaceous chondrites and the origin of non-chondritic 142Nd compositions in the Earth (United States)

    Fukai, Ryota; Yokoyama, Tetsuya


    We present high-precision Nd isotope compositions for ordinary and carbonaceous chondrites determined using thermal ionization mass spectrometry with dynamic and multistatic methods. The ordinary chondrites had uniform and non-terrestrial μ142 Nd , μ148 Nd , and μ150 Nd values, with data that plot along the mixing line between s-process and terrestrial components in μ150 Nd versus μ148 Nd and μ142 Nd versus μ148,150Nd diagrams. In contrast, the carbonaceous chondrites were characterized by larger anomalies in their μ142 Nd , μ148 Nd , and μ150 Nd values compared to ordinary chondrites. Importantly, the data for carbonaceous chondrites plot along the s-process and terrestrial mixing line in a μ150 Nd versus μ148 Nd diagram, whereas they have systematically lower μ142 Nd values than the s-process and terrestrial mixing line in μ142 Nd versus μ148,150Nd diagrams. This shift likely results from the incorporation of calcium- and aluminum-rich inclusions (CAIs), indicating that the Nd isotopic variability in the ordinary chondrites and CAI-free carbonaceous chondrites was caused solely by the heterogeneous distribution of s-process nuclides. The isotopic variation most likely results from nebular thermal processing that caused selective destruction of s-process-depleted (or r-process-enriched) dust grains in the inner Solar System where the parent bodies of ordinary chondrites formed, whereas such grains were preserved in the region of carbonaceous chondrite parent body formation. The Nd isotope dichotomy between ordinary and bulk aliquots of carbonaceous chondrites can be related to the presence of Jupiter, which may have separated two isotopically distinct reservoirs that were present in the solar nebula. After correcting for s-process anomalies and CAI contributions to the Nd isotopes observed in the chondrites, we obtained a μ142 Nd value (- 2.4 ± 4.8 ppm) that was indistinguishable from the terrestrial value. Our results corroborate the

  11. Origin of the Sudbury Complex by meteoritic impact: Neodymium isotopic evidence (United States)

    Faggart, B.E.; Basu, A.R.; Tatsumoto, M.


    Samarium-neodymium isotopic data on whole rocks and minerals of the Sudbury Complex in Canada gave an igneous crystallization age of 1840 ?? 21 ?? 106 years. The initial epsilon neodymium values for 15 whole rocks are similar to those for average upper continental crust, falling on the crustal trend of neodymium isotopic evolution as defined by shales. The rare earth element concentration patterns of Sudbury rocks are also similar to upper crustal averages. These data suggest that the Sudbury Complex formed from melts generated in the upper crust and are consistent with a meteoritic impact.

  12. A modeling sensitivity study of the influence of the Atlantic meridional overturning circulation on neodymium isotopic composition at the Last Glacial Maximum

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    T. Arsouze


    Full Text Available Using a simple parameterisation that resolves the first order global Nd isotopic composition (hereafter expressed as εNd in an Ocean Global Circulation Model, we have tested the impact of different circulation scenarios on the εNd in the Atlantic for the Last Glacial Maximum (LGM, relative to a modern control run. Three different LGM freshwater forcing experiments are performed to test for variability in the εNd oceanic distribution as a function of ocean circulation. Highly distinct representations of the ocean circulation are generated in the three simulations, which drive significant differences in εNd, particularly in deep waters of the western part of the basin. However, at the LGM, the Atlantic is more radiogenic than in the modern control run, particularly in the Labrador basin and in the Southern Ocean. A fourth experiment shows that changes in Nd sources and bathymetry drive a shift in the εNd signature of the basin that is sufficient to explain the changes in the εNd signature of the northern end-member (NADW or GNAIW glacial equivalent in our LGM simulations. All three of our LGM circulation scenarios show good agreement with the existing intermediate depth εNd paleo-data. This study cannot indicate the likelihood of a given LGM oceanic circulation scenario, even if simulations with a prominent water mass of southern origin provide the most conclusive results. Instead, our modeling results highlight the need for more data from deep and bottom waters from western Atlantic, where the εNd change in the three LGM scenarios is the most important (up to 3 εNd. This would also aid more precise conclusions concerning the evolution of the northern end-member εNd signature, and thus the potential use of εNd as a tracer of past oceanic circulation.

  13. Robustness of fossil fish teeth for seawater neodymium isotope reconstructions under variable redox conditions in an ancient shallow marine setting (United States)

    Huck, Claire E.; van de Flierdt, Tina; Jiménez-Espejo, Francisco J.; Bohaty, Steven M.; Röhl, Ursula; Hammond, Samantha J.


    Fossil fish teeth from pelagic open ocean settings are considered a robust archive for preserving the neodymium (Nd) isotopic composition of ancient seawater. However, using fossil fish teeth as an archive to reconstruct seawater Nd isotopic compositions in different sedimentary redox environments and in terrigenous-dominated, shallow marine settings is less proven. To address these uncertainties, fish tooth and sediment samples from a middle Eocene section deposited proximal to the East Antarctic margin at Integrated Ocean Drilling Program Site U1356 were analyzed for major and trace element geochemistry, and Nd isotopes. Major and trace element analyses of the sediments reveal changing redox conditions throughout deposition in a shallow marine environment. However, variations in the Nd isotopic composition and rare earth element (REE) patterns of the associated fish teeth do not correspond to redox changes in the sediments. REE patterns in fish teeth at Site U1356 carry a typical mid-REE-enriched signature. However, a consistently positive Ce anomaly marks a deviation from a pure authigenic origin of REEs to the fish tooth. Neodymium isotopic compositions of cleaned and uncleaned fish teeth fall between modern seawater and local sediments and hence could be authigenic in nature, but could also be influenced by sedimentary fluxes. We conclude that the fossil fish tooth Nd isotope proxy is not sensitive to moderate changes in pore water oxygenation. However, combined studies on sediments, pore waters, fish teeth, and seawater are needed to fully understand processes driving the reconstructed signature from shallow marine sections in proximity to continental sources.

  14. Analysis of high burnup pressurized water reactor fuel using uranium, plutonium, neodymium, and cesium isotope correlations with burnup

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Jung Suk; Jeon, Young Shin; Park, Soon Dal; Ha, Yeong Keong; Song, Kyu Seok [Nuclear Chemistry Research Division, Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)


    The correlation of the isotopic composition of uranium, plutonium, neodymium, and cesium with the burnup for high burnup pressurized water reactor fuels irradiated in nuclear power reactors has been experimentally investigated. The total burnup was determined by Nd-148 and the fractional {sup 235}U burnup was determined by U and Pu mass spectrometric methods. The isotopic compositions of U, Pu, Nd, and Cs after their separation from the irradiated fuel samples were measured using thermal ionization mass spectrometry. The contents of these elements in the irradiated fuel were determined through an isotope dilution mass spectrometric method using {sup 233}U, {sup 242}Pu, {sup 150}Nd, and {sup 133}Cs as spikes. The activity ratios of Cs isotopes in the fuel samples were determined using gamma-ray spectrometry. The content of each element and its isotopic compositions in the irradiated fuel were expressed by their correlation with the total and fractional burnup, burnup parameters, and the isotopic compositions of different elements. The results obtained from the experimental methods were compared with those calculated using the ORIGEN-S code.

  15. The geochemistry of seawater neodymium isotopes in the TAG hydrothermal plume at the Mid Atlantic Ridge (United States)

    Stichel, T.; Pahnke, K.; Goldstein, S. L.; Hartman, A. E.; Scher, H.


    Neodymium (Nd) isotopes are useful tracers for ocean circulation and trace metal cycling. However, there are many unknowns regarding the input mechanisms and removal processes, which need to be understood in order to utilize this tracer optimally. For example, there is only one published study of Nd isotopes in ocean ridge hydrothermal vent fluids and nearby seawater [1]. Rare earth elements (REE) patterns hydrothermal particles in earlier studies indicate a net removal of these elements [2]. However, the degree that this process impacts the dissolved REE budget, and whether there is isotopic exchange between the Nd in particulates and in seawater, is still largely unconstrained. We present new results on the distribution of Nd isotopes and Nd concentrations ([Nd]) from the Trans-Atlantic Geotraverse (TAG) hydrothermal vent field located at 26.14°N, 44.83°W and 3800 m water depth. The plume was detected by elevated particle density between 400 m and 600 m above the seafloor. The dominant water mass around TAG is North Atlantic Deep Water (NADW). First results show that Nd isotopes and [Nd] at about 200 m below the plume do not significantly deviate from overlying NADW. The Nd isotope composition of seawater here is ɛNd = -12.3 (±0.8). This value is identical to the lower NADW in this part of the Atlantic, and to the ɛNd value measured above the plume at 2100 m water depth with ɛNd = -12.2 (±0.3). We observe a higher [Nd] of 21.7 pmol/kg below the plume at 3600 m compared to 17.1 pmol/kg above the plume at 2100 m. At other open Atlantic sites, [Nd] are between 21 and 22 pmol/kg at this depth and thus reflecting typical values. We therefore conclude that the pronounced hydrothermal activity at the TAG field does not significantly influence Nd isotope ratios nor Nd concentrations in seawater directly over- and underlying the plume. More detailed analyses from within the actual plume will be carried out and presented to further address processes involved here

  16. Rb-Sr whole-rock and mineral ages, K-Ar, 40Ar/39Ar, and U-Pb mineral ages, and strontium, lead, neodymium, and oxygen isotopic compositions for granitic rocks from the Salinian Composite Terrane, California: (United States)

    Kistler, R.W.; Champion, D.E.


    This report summarizes new and published age and isotopic data for whole-rocks and minerals from granitic rocks in the Salinian composite terrane, California. Rubidium-strontium whole-rock ages of plutons are in two groups, Early Cretaceous (122 to 100 Ma) and Late Cretaceous (95 to 82 Ma). Early Cretaceous plutons occur in all granitic rock exposures from Bodega Head in the north to those from the Santa Lucia and Gabilan Ranges in the central part of the terrane. Late Cretaceous plutons have been identified in the Point Reyes Peninsula, the Santa Lucia and the Gabilan Ranges, and in the La Panza Range in the southern part of the terrane. Ranges of initial values of isotopic compositions are 87Sr/86Sr, 0.7046-0.7147, δ18O, +8.5 to +12.5 per mil, 206Pb/204Pb, 18.901-19.860, 207Pb/204Pb, 15.618-15.814, 208Pb/204Pb, 38.569- 39.493, and εNd, +0.9 to -8.6. The initial 87Sr/86Sr=0.706 isopleth is identified in the northern Gabilan Range and in the Ben Lomond area of the Santa Cruz Mountains, in Montara Mountain, in Bodega Head, and to the west of the Farallon Islands on the Cordell Bank. This isotopic boundary is offset about 95 miles (160km) by right-lateral displacements along the San Gregorio-Hosgri and San Andreas fault systems.

  17. Neodymium isotopes in biogenic carbonates: reliable archives of ɛNd (United States)

    Montagna, P.; Goldstein, S. L.; Taviani, M.; Frank, N.; McCulloch, M. T.


    Neodymium isotope (143Nd/144Nd) compositions from dispersed authigenic ferromanganese oxide fraction in marine sediments, ferromanganese crusts, foraminiferal shells and fossil fish teeth are employed to trace provenance and water mass mixing in the past, having the advantage of not being fractionated by biological processes in the water column. In the modern ocean the different water masses ultimately derive their ɛNd values through continental weathering, erosion and particle-seawater interactions. This geochemical tracer has been only recently applied to scleractinian deep-water coral skeletons sourced from various sites and depths in the Atlantic ocean. Aragonitic corals can be precisely dated by U-series, potentially providing century-long records of intermediate and bathyal zone variability at sub-decadal resolution. Motivated by these recent findings we have investigated the Nd isotopic compositions of living specimens of various calcifying organisms collected in two key locations of the Mediterranean Sea and in the Southern Ocean. In particular, we analyzed several specimens of the aragonitic deep-water corals Desmophyllum dianthus, Lophelia pertusa, Madrepora oculata, Flabellum impensum, the temperate coral Cladocora caespitosa, the calcitic gorgonian coral Corallium rubrum, the bivalves Glans aculeata and Karnekampia bruei and the polychate Serpula vermicularis. Most of the samples were retrieved from the Strait of Sicily and the Southern Adriatic Sea at different water depths. Ten seawater samples from three new profiles in the Mediterranean were also collected at the same locations and depths, offering a unique opportunity to compare the Nd isotopic composition of biogenic carbonates directly with the surrounding ambient seawater. The Mediterranean Sea is particularly suited for this comparison exercise since it is characterized by water masses displaying a large range of ɛNd values, from -10.5 in the Western Mediterranean to -4.8 in the Eastern

  18. Chondrite barium, neodymium, and samarium isotopic heterogeneity and early Earth differentiation. (United States)

    Carlson, Richard W; Boyet, Maud; Horan, Mary


    Isotopic variability in barium, neodymium, and samarium in carbonaceous chondrites reflects the distinct stellar nucleosynthetic contributions to the early solar system. We used 148Nd/144Nd to correct for the observed s-process deficiency, which produced a chondrite 146Sm-142Nd isochron consistent with previous estimates of the initial solar system abundance of 146Sm and a 142Nd/144Nd at average chondrite Sm/Nd ratio that is lower than that measured in terrestrial rocks by 21 +/- 3 parts per million. This result strengthens the conclusion that the deficiency in 142Nd in chondrites relative to terrestrial rocks reflects 146Sm decayand earlyplanetary differentiation processes.

  19. Neodymium isotope constraints on the tectonic evolution of East Gondwana (United States)

    Harris, N. B. W.; Bartlett, J. M.; Santosh, M.

    East Gondwana incorporates a collage of polymetamorphic terrains with long-lived tectonic histories from the Early Archaean to the Neoproterozoic. The oldest cratonic areas have been identified in South India (north of the Palghat-Cauvery shear zone) and East Antarctica (the Napier Complex). These terrains are remnants of an East Gondwana craton that underwent initial crustal growth during the Early Archaean and granulite-facies metamorphism at ˜2.5 Ga. Both were virtually unaffected by the Pan-African orogeny (1.1-0.5 Ga). In contrast, Proterozoic terrains were subject to high-grade metamorphism during the Pan-African event. On the basis of published Nd model ages, a direct correlation can be made between southern Madagascar (south of the Ranotsara shear zone), southern India (the Madurai Block and Kerala Khondalite Belt) and the Highland/Southwestern Complex of Sri Lanka, which comprise a Later Archaean-Palaeoproterozoic (3.2-2.0 Ga) mobile belt that may extend eastwards into East Antarctica. The youngest period of crustal growth in East Gondwana has been recognised at 1.5-0.8 Ga from isotopic studies of the Mozambique Belt of East Africa, the Vijayan Complex of Sri Lanka and the Yamato-Belgica Complex/Sør Rondane Mountains of East Antarctica. Small slivers of terrain of intermediate age (1.9-1.2 Ga) have been recognised in South India (Achankovil metasediments) and Sri Lanka (Wanni Complex) that may represent mixed-age contributions to clastic sedimentary basins.

  20. Strontium and neodymium isotopic evidence for the heterogeneous nature and development of the mantle beneath Afar (Ethiopia)

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    Betton, P.J. (Leeds Univ. (UK). Dept. of Earth Sciences); Civetta, L. (Naples Univ. (Italy). Dipartimento di Geofisica e Vulcanologia)


    Neodymium isotope and REE analyses of recent volcanic rocks and spinel lherzolite nodules from the Afar area are reported. The /sup 143/Nd//sup 144/Nd ratios of the volcanic rocks range from 0.51286 to 0.51304, similar to the range recorded from Iceland. However, the /sup 87/Sr//sup 86/Sr ratios display a distinctly greater range (0.70328-0.70410) than those reported from the primitive rocks of Iceland. Whole rock samples and mineral separates from the spinel lherzolite nodules exhibit uniform /sup 143/Nd//sup 144/Nd ratios (ca. 0.5129) but varied /sup 87/Sr//sup 86/Sr ratios in the range 0.70427-0.70528. The Sr-Nd isotope variations suggest that the volcanic rocks may have been produced by mixing between two reservoirs with distinct isotopic compositions. Two possible magma reservoirs in this area are the source which produced the 'MORB-type' volcanics in the Red Sea and Gulf of Aden and the anomalous source represented by the nodule suite. The isotopic composition of the volcanics is compatible with mixing between these two reservoirs. It is shown that the anomalous source with a high /sup 87/Sr//sup 86/Sr ratio cannot have been produced by simple processes of partial melting and mixing within normal mantle. Instead the high /sup 87/Sr//sup 86/Sr is equated with a fluid phase. A primitive cognate fluid, subducted seawater or altered oceanic lithosphere may have been responsible for the generation of the source with a high /sup 87/Sr//sup 86/Sr ratio.

  1. Constraints on ocean circulation at the Paleocene–Eocene Thermal Maximum from neodymium isotopes

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    A. N. Abbott


    Full Text Available Global warming during the Paleocene Eocene Thermal Maximum (PETM ~55 million years ago (Ma coincided with a massive release of carbon to the ocean–atmosphere system, as indicated by carbon isotopic data. Previous studies have argued for a role for changing ocean circulation, possibly as a trigger or response to climatic changes. We use neodymium (Nd isotopic data to reconstruct short high-resolution records of deep-water circulation across the PETM. These records are derived by reductively leaching sediments from seven globally distributed sites and comparing data with published data from fossil fish debris to reconstruct past deep ocean circulation across the PETM. The Nd data for the leachates are interpreted to be consistent with previous studies that have used fish teeth and benthic foraminiferal δ13C to constrain regions of convection. There is some evidence from combining Nd isotope and δ13C records that the three major ocean basins may not have had substantial exchanges of deep waters. If the isotopic data are interpreted within this framework, then the observed pattern may be explained if the strength of overturning in each basin varied distinctly over the PETM, resulting in differences in deep-water aging gradients between basins. Results are consistent with published interpretations from proxy data and model simulations that suggest modulation of overturning circulation had an important role for global recovery of the ocean–atmosphere system after the PETM.

  2. Application of neodymium isotope ratio measurements for the origin assessment of uranium ore concentrates. (United States)

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


    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.

  3. Atomic Weights and Isotopic Compositions (United States)

    SRD 144 Atomic Weights and Isotopic Compositions (Web, free access)   The atomic weights are available for elements 1 through 111, and isotopic compositions or abundances are given when appropriate.

  4. Synthesis and characterization of composites of mixed oxides of iron and neodymium in polymer matrix of aniline–formaldehyde

    Indian Academy of Sciences (India)

    Sajdha; H N Sheikh; B L Kalsotra; N Kumar; S Kumar


    Nanocomposites of mixed oxides of iron and neodymium in polymer matrix of anilineformaldehyde are reported. The composites have been obtained by treating the aqueous solution of aniline, hydrochloric acid and formaldehyde with halide of iron and neodymium oxide. The infra-red spectra show broad peaks at ∼ 590 cm-1 and at ∼ 610 cm-1 due to the presence of oxides of both iron and neodymium. In heated samples, the absorption peaks due to metal oxides are better resolved. A broad and strong peak in XRD spectra at 2 value of 35.69920 corresponds to spinel -Fe2O3. 57Fe Mössbauer spectrum for unheated sample gives Mössbauer parameters, i.e. isomer shift (), quadrupole splitting ( ) and effective magnetic field (Heff). Transmission electron microscopy (TEM) micrographs reveal well dispersed particles at different magnifications. Vibrating sample magnetometry (VSM) studies indicate that the ferrite nanoparticles exhibit characteristics of ferromagnetism.

  5. 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.


    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

  6. Zinc isotopic compositions of breast cancer tissue. (United States)

    Larner, Fiona; Woodley, Laura N; Shousha, Sami; Moyes, Ashley; Humphreys-Williams, Emma; Strekopytov, Stanislav; Halliday, Alex N; Rehkämper, Mark; Coombes, R Charles


    An early diagnostic biomarker for breast cancer is essential to improve outcome. High precision isotopic analysis, originating in Earth sciences, can detect very small shifts in metal pathways. For the first time, the natural intrinsic Zn isotopic compositions of various tissues in breast cancer patients and controls were determined. Breast cancer tumours were found to have a significantly lighter Zn isotopic composition than the blood, serum and healthy breast tissue in both groups. The Zn isotopic lightness in tumours suggests that sulphur rich metallothionein dominates the isotopic selectivity of a breast tissue cell, rather than Zn-specific proteins. This reveals a possible mechanism of Zn delivery to Zn-sequestering vesicles by metallothionein, and is supported by a similar signature observed in the copper isotopic compositions of one breast cancer patient. This change in intrinsic isotopic compositions due to cancer has the potential to provide a novel early biomarker for breast cancer.

  7. Lead and neodymium isotopic results from metabasalts of the Haveri Formation, southern Finland: evidence for Palaeoproterozoic enriched mantle

    Directory of Open Access Journals (Sweden)

    Vaasjoki, M.


    Full Text Available Tholeiitic metabasalts and coexisting sulphides have been analysed for their Pb and Nd isotopic compositions from the Proterozoic Haveri Formation, which forms the basal unit of the Tampere Schist Belt in southern Finland. Ten whole rock samples analysed for Pb isotopes form a sublinear array which yields rather uncertain age estimates in the 1900-2000 Ma range and lies on the 207Pb/204Pb vs. 206Pb/204Pb diagram well below the average global lead evolution curve. The initial lead isotopic composition inferred from the whole rock data and measured on chalcopyrite is the least radiogenic obtained from the Svecofennian domain, and precludes involvement of old upper crustal material in basalt genesis. This together with the geochemical composition and initial eNd (1900 of +0.5±0.6 suggest that the Haveri mafic metavolcanic rocks were not derived from convective MORB-type mantle. The source was rather a mantle, which had been enriched in LREE for a considerable time period. Some chalcopyrite trace leads plot close to the whole rock array while others lie above it. This is interpreted as indicating two distinct mineralisation processes. The primary and major process involved lead which was cogenetic with the basalts, while the second mineralising fluid introduced radiogenic (high 207Pb upper crustal lead scavenged from the adjacent sedimentary rocks. The least radiogenic leads at Haveri and in the Outokumpu ophiolite complex some 300 km NE are similar and the two occurrences can be coeval. The preservation of original mantle material at Haveri may be interpreted as suggesting that continental crust had formed in the Tampere area 1900-2000 Ma ago.

  8. Rare earth element and neodymium isotope tracing of element input and past ocean circulation. Study from north and south pacific seawater and sediments

    Energy Technology Data Exchange (ETDEWEB)

    Froellje, Henning


    Ocean circulation and cycling of trace elements within the oceanic water column is of great significance for modern and past climates. The global overturning circulation is responsible for the distribution of water masses, heat and particulate and dissolved compounds, while biological and chemical processes, such as primary productivity or particle scavenging, control the cycling of nutrients and trace elements in the ocean, and ultimately influence the ocean-atmosphere exchange of carbon. Rare earth elements (REE) and neodymium (Nd) isotopes are widely used as tracers for lithogenic element fluxes and modern and past ocean circulation and water mass mixing. The use of Nd isotopes in paleoceanographic investigations is based on the precise knowledge of processes involved in REE cycling and of the modern oceanic Nd isotope distribution. The Pacific is the largest of the world oceans, but it is highly underrepresented in present-day and past seawater Nd isotope and REE investigations compared to the Atlantic Ocean. In this study, Nd isotopes and REEs are analysed in North Pacific seawater (chapter 2) and sediment samples from the South Pacific (chapters 3-5) to contribute to a better understanding of sources and cycling of REEs and Nd isotopes in present-day seawater and to investigate past water mass mixing and circulation changes during the last glacial termination and throughout the last glacial-interglacial cycle. Neodymium isotopes in seawater and sedimentary archives (fossil fish teeth and debris, foraminifera, ferromanganese oxides, lithogenic particles) were analysed using multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS), and REE concentrations were analysed using isotope dilution ICP-MS. Results from combined analysis of REEs, and Nd and radium isotopes from North Pacific seawater (coastal seawaters of the Hawaiian Island of Oahu and seawater from the offshore Hawaii Ocean Time-series Station ALOHA) show a clear influence of the

  9. A Nd Isotopic Composition Modeling Approach of the Oceanic Thermohaline Circulation Change During LGM (United States)

    Arsouze, T.; Dutay, J.; Lacan, F.; Jeandel, C.; Alkama, R.; Kageyama, M.; Piotrowski, A.


    The role of thermohaline circulation in climate change has been a matter of debate for a long time. Proxies of past ocean circulation such as δ13C or 231Pa/230Th suggest a relationship between North Atlantic Deep Water (NADW) strength and rapid climate change. Neodymium isotopic composition (Nd IC) is a quasi conservative geochemical tracer of water masses in the ocean interior and thus can be used as a proxy for NADW. Seawater Nd IC being recorded in marine sediments, this proxy is used to infer paleo-circulations on various time scales. Recent studies of Nd IC records, in the ferromanganese oxide components of a South Atlantic core, confirm the close relation between thermohaline circulation and North Atlantic climate changes through the last deglaciation (Piotrowski et al., 2004). Our purpose here is to model the Nd IC during the LGM and the Holocene with the Ocean Global Circulation Model NEMO, in the ORCA2 (2°) configuration. The explicit simulation of this proxy in the model allows to investigate and quantify the circulation change that corresponds to the Nd isotopic composition variation recorded in the sediments. We consider that the main source of Nd into the ocean is the interaction between water masses and continental margins (Boundary Exchange process; (Lacan and Jeandel, 2005). Boundary exchange is parameterized using a relaxing term (Arsouze et al., 2006). Simulated Nd IC distributions are evaluated by comparison with available records for the LGM and Holocene. References: Arsouze, T., Dutay, J.-C., Lacan, F. and Jeandel, C., 2006. Modeling the neodymium isotopic composition with a global ocean circulation model Chemical Geology, in press. Lacan, F. and Jeandel, C., 2005. Neodymium isotopes as a new tool for quantifying exchange fluxes at the continent - ocean interface. Earth and Planetary Science Letters, 232(3-4): 245-257. Piotrowski, A.M., Goldstein, S.L., Hemming, S.R. and Fairbanks, R.G., 2004. Intensification and variability of ocean

  10. Nickel isotopic composition of the mantle (United States)

    Gall, Louise; Williams, Helen M.; Halliday, Alex N.; Kerr, Andrew C.


    This paper presents a detailed high-precision study of Ni isotope variations in mantle peridotites and their minerals, komatiites as well as chondritic and iron meteorites. Ultramafic rocks display a relatively large range in δ60 Ni (permil deviation in 60 Ni /58 Ni relative to the NIST SRM 986 Ni isotope standard) for this environment, from 0.15 ± 0.07‰ to 0.36 ± 0.08‰, with olivine-rich rocks such as dunite and olivine cumulates showing lighter isotope compositions than komatiite, lherzolite and pyroxenite samples. The data for the mineral separates shed light on the origin of these variations. Olivine and orthopyroxene display light δ60 Ni whereas clinopyroxene and garnet are isotopically heavy. This indicates that peridotite whole-rock δ60 Ni may be controlled by variations in modal mineralogy, with the prediction that mantle melts will display variable δ60 Ni values due to variations in residual mantle and cumulate mineralogy. Based on fertile peridotite xenoliths and Phanerozoic komatiite samples it is concluded that the upper mantle has a relatively homogeneous Ni isotope composition, with the best estimate of δ60Nimantle being 0.23 ± 0.06‰ (2 s.d.). Given that >99% of the Ni in the silicate Earth is located in the mantle, this also defines the Ni isotope composition of the Bulk Silicate Earth (BSE). This value is nearly identical to the results obtained for a suite of chondrites and iron meteorites (mean δ60 Ni 0.26 ± 0.12‰ and 0.29 ± 0.10‰, respectively) showing that the BSE is chondritic with respect to its Ni isotope composition, with little to no Ni mass-dependent isotope fractionation resulting from core formation.

  11. Determination of mass-dependent isotopic fractionation of cerium and neodymium in geochemical samples by MC-ICPMS. (United States)

    Ohno, Takeshi; Hirata, Takafumi


    We have developed a new analytical method to determine the mass-dependent isotopic fractionations on Ce and Nd in geochemical samples. Mass discrimination effects on Ce and Nd were externally corrected by normalizing (149)Sm/(147)Sm and (153)Eu/(151)Eu, being 0.92124 and 1.0916, respectively based on an exponential law. The reproducibility of the isotopic ratio measurements on (142)Ce/(140)Ce, (146)Nd/(144)Nd and (148)Nd/(144)Nd were 0.08‰ (2SD, n = 25), 0.06‰ (2SD, n = 39) and 0.12‰ (2SD, n = 39), respectively. The present technique was applied to determine the variations of the Ce and Nd isotopic ratios for five geochemical reference materials (igneous rocks, JB-1a and JA-2; sedimentary rocks, JMn-1, JCh-1 and JDo-1). The resulting ratios for two igneous rocks (JB-1a and JA-2) and two sedimentary rocks (JMn-1 and JCh-1) did not vary significantly among the samples, whereas the Ce and Nd isotope ratios for the carbonate samples (JDo-1) were significantly higher than those for igneous and sedimentary rock samples. The 1:1 simple correlation between δ(142)Ce and δ(146)Nd indicates that there were no significant difference in the degree of isotopic fractionation between the Ce and Nd. This suggests that the isotopic fractionation for Ce found in the JDo-1 could be induced by geochemical or physicochemical processes without changing the oxidation status of Ce, since the redox-reaction can produce larger isotopic fractionation than the reactions without changing the oxidation state. The variations in the Ce and Nd isotope ratios for geochemical samples could provide new information concerning the physico-chemical processes of the sample formation.

  12. Hafnium and neodymium isotopes and REY distribution in the truly dissolved, nanoparticulate/colloidal and suspended loads of rivers in the Amazon Basin, Brazil (United States)

    Merschel, Gila; Bau, Michael; Schmidt, Katja; Münker, Carsten; Dantas, Elton L.


    Radiogenic isotopes in river sediments and river waters have been widely used in provenance studies, as these samples naturally integrate the geology/chemistry of the entire catchment. While the Hf and Nd isotope systems are coupled during igneous processes, they are decoupled during supergene processes at the Earth's surface, which is reflected by the isotope composition of riverine sediments. We present the first data for both Hf and Nd isotope compositions of the dissolved (0.2 μm-filtrates rich in nanoparticles and colloids, NPCs) and the truly dissolved (1 kDa-ultrafiltrates) load of rivers. Hafnium and Nd isotope compositions and concentrations of the Rare Earths and Yttrium (REY) and Hf were determined for suspended particles (>0.2 μm) as well as for the dissolved and the truly dissolved load of the Rio Solimões, the Amazon's largest tributary draining the Andes, and of the Rio Negro, an organic NPC- and particle-rich river draining the rainforest of northern Amazonia. We also analyzed the Nd isotope compositions of suspended sediments and 0.2 μm-filtered water samples from the Amazon River and its tributaries Rio Tapajos, Rio Xingu and Rio Jari. Our novel results clearly show that the decoupling of the Hf and Nd isotope systems is related to incongruent weathering processes on the continent, as this decoupling can already be observed in the different Hf and Nd pools, i.e. in the particulate, the NPC-dominated dissolved and the truly dissolved load of rivers. In the Rio Negro and Rio Solimões, a strong particle size-dependent difference in Hf isotope composition is observed. Values of εHf become more radiogenic as filter poresize decreases, which can be related to the density- and size-dependent distribution of Hf-rich minerals, e.g. zircons, and their absence from the truly dissolved pool. In contrast, the Nd isotope composition of Amazonian river waters reflects that of their catchment geology. Tributaries draining the Precambrian Brazilian and


    Energy Technology Data Exchange (ETDEWEB)

    Pizzarello, Sandra, E-mail: [Department of Chemistry and Biochemistry, Arizona State University, Tempe, AZ 85018-1604 (United States)


    HCN is ubiquitous in extraterrestrial environments and is central to current theories on the origin of early solar system organic compounds such as amino acids. These compounds, observed in carbonaceous meteorites, were likely important in the origin and/or evolution of early life. As part of our attempts to understand the origin(s) of meteoritic CN{sup –}, we have analyzed the {sup 15}N/{sup 14}N isotopic composition of HCN gas released from water extracts of the Murchison meteorite and found its value to be near those of the terrestrial atmosphere. The findings, when evaluated viz-a-viz molecular abundances and isotopic data of meteoritic organic compounds, suggest that HCN formation could have occurred during the protracted water alteration processes known to have affected the mineralogy of many asteroidal bodies during their solar residence. This was an active synthetic stage, which likely involved simple gasses, organic molecules, their presolar precursors, as well as mineral catalysts and would have lead to the formation of molecules of differing isotopic composition, including some with solar values.

  14. Strontium and neodymium isotope systematics of target rocks and impactites from the El'gygytgyn impact structure: Linking impactites and target rocks (United States)

    Wegner, Wencke; Koeberl, Christian


    The 3.6 Ma El'gygytgyn structure, located in northeastern Russia on the Chukotka Peninsula, is an 18 km diameter complex impact structure. The bedrock is formed by mostly high-silica volcanic rocks of the 87 Ma old Okhotsk-Chukotka Volcanic Belt (OCVB). Volcanic target rocks and impact glasses collected on the surface, as well as drill core samples of bedrock and impact breccias have been investigated by thermal ionization mass spectrometry (TIMS) to obtain new insights into the relationships between these lithologies in terms of Nd and Sr isotope systematics. Major and trace element data for impact glasses are added to compare with the composition of target rocks and drill core samples. Sr isotope data are useful tracers of alteration processes and Nd isotopes reveal characteristics of the magmatic sources of the target rocks, impact breccias, and impact glasses. There are three types of target rocks mapped on the surface: mafic volcanics, dacitic tuff and lava of the Koekvun' Formation, and dacitic to rhyolitic ignimbrite of the Pykarvaam Formation. The latter represents the main contributor to the impact rocks. The drill core is divided into a suevite and a bedrock section by the Sr isotope data, for which different postimpact alteration regimes have been detected. Impact glasses from the present-day surface did not suffer postimpact hydrothermal alteration and their data indicate a coherent alteration trend in terms of Sr isotopes with the target rocks from the surface. Surprisingly, the target rocks do not show isotopic coherence with the Central Chukotka segment of the OCVB or with the Berlozhya magmatic assemblage (BMA), a late Jurassic felsic volcanic suite that crops out in the eastern part of the central Chukotka segment of the OCVB. However, concordance for these rocks exists with the Okhotsk segment of the OCVB. This finding argues for variable source magmas having contributed to the build-up of the OCVB.

  15. The isotopic composition of CO in vehicle exhaust (United States)

    Naus, Stijn; Röckmann, Thomas; Popa, Elena


    The isotopic composition of atmospheric carbon monoxide (CO) and its sources can be a powerful tool to help constrain the CO budget, but data on the isotopic composition of CO sources is sparse. We investigated the isotopic composition (13C16O and 12C18O) of one of the main sources of CO in urban areas: traffic emissions. Samples from individual passenger cars and atmospheric samples from polluted areas were measured. The results show strong indications that CO emissions from traffic are dominated by a small subset of cars or driving conditions, which, in this study, were cold petrol cars. The spread in isotopic composition of the full dataset was large, but this dominant subset showed a relatively stable isotopic composition. Therefore, the individual car samples result in a well-defined overall traffic signature, which was in agreement with the atmospheric isotopic signature derived from the atmospheric samples.

  16. Modeling the Nd isotopic composition in the North Atlantic basin using an eddy-permitting model (United States)

    Arsouze, T.; Treguier, A. M.; Peronne, S.; Dutay, J.-C.; Lacan, F.; Jeandel, C.


    Boundary Exchange (BE - exchange of elements between continental margins and the open ocean) has been emphasized as a key process in the oceanic cycle of neodymium (Nd) (Lacan and Jeandel, 2005a). Here, we use a regional eddy-permitting resolution Ocean General Circulation Model (1/4°) of the North Atlantic basin to simulate the distribution of the Nd isotopic composition, considering BE as the only source. Results show good agreement with the data, confirming previous results obtained using the same parameterization of the source in a coarse resolution global model (Arsouze et al., 2007), and therefore the major control played by the BE processes in the Nd cycle on the regional scale. We quantified the exchange rate of the BE, and found that the time needed for the continental margins to significantly imprint the chemical composition of the surrounding seawater (further referred as characteristic exchange time) is of the order of 0.2 years. However, the timescale of the BE may be subject to large variations as a very short exchange time (a few days) is needed to reproduce the highly negative values of surface waters in the Labrador Sea, whereas a longer one (up to 0.5 years) is required to simulate the radiogenic influence of basaltic margins and distinguish the negative isotopic signatures of North Atlantic Deep Water from the more radiogenic southern origin water masses. This likely represents geographical variations in erosion fluxes and the subsequent particle load onto the continental margins. Although the parameterization of the BE is the same in both configurations of the model, the characteristic exchange time in the eddy-permitting configuration is significantly lower than the previous evaluations using a low resolution configuration (6 months to 10 years), but however in agreement with the available seawater Nd isotope data. This results highlights the importance of the model dynamics in simulating the BE process.

  17. Magnesium Isotopic Composition of Subducting Marine Sediments (United States)

    Hu, Y.; Teng, F. Z.; Plank, T. A.; Huang, K. J.


    Subducted marine sediments have recently been called upon to explain the heterogeneous Mg isotopic composition (δ26Mg, ‰) found in mantle wehrlites (-0.39 to +0.09 [1]) in the context of a homogeneous mantle (-0.25 ± 0.07 [2]). However, no systematic measurements of δ26Mg on marine sediments are currently available to provide direct support to this model. To characterize the Mg inputs to global subduction zones, we measured δ26Mg data for a total of 90 marine sediments collected from 12 drill sites outboard of the world's major subduction zones. These sediments span a 1.73‰ range in δ26Mg. The detritus-dominated sediments have δ26Mg (-0.59 to +0.53) comparable to those of weathered materials on continents (e.g. -0.52 to +0.92 [3]), while the calcareous oozes yield δ26Mg (as light as -1.20) more similar to the seawater value (-0.83 [4]). The negative correlation between δ26Mg and CaO/Al2O3 in these sediments indicates the primary control of mineralogy over the Mg isotopic distribution among different sediment types, as carbonates are enriched in light Mg isotopes (-5.10 to -0.40 [5]) whereas clay-rich weathering residues generally have heavier δ26Mg (e.g. up to +0.65 in saprolite [6]). In addition, chemical weathering and grain-size sorting drive sediments to a heavier δ26Mg, as indicated by the broad positive trends between δ26Mg with CIA (Chemical Index of Alteration [7]) and Al2O3/SiO2, respectively. Collectively, the arc systems sampled in this study represent ~30% of global arc length and the extrapolated global Mg flux of subducting marine sediments accounts for ~9% of the yearly Mg riverine input with a flux-weighted average δ26Mg at -0.26. Subduction of these heterogeneous sediments may not cause significant mantle heterogeneity on a global scale, but the highly variable Mg fluxes and δ26Mg of sediments delivered to different trenches are capable of producing local mantle variations. Volcanic rocks sourced from these mantle domains are thus

  18. Isotopic compositional Characteristics of Terrigenous Natural Gases in China

    Institute of Scientific and Technical Information of China (English)

    沈平; 徐永昌


    The C and H isotopic compositions of the methane in more than 160 gas samples from 10 basins in China are presented in this paper.The natural gases are classified as four types: biogenic gas ,bio-thermocatalytic transitional gas, gas associated with condensate oil ,and coal-type gas. The isotopic compositions of these gases closely related to the depositional basins, the types of organic matter,the stages of thermal evolution and the genetic characteristics of different gas reservoirs.Studies of the C and H isotopic compositions of terrigenous natural gases will provide valua-ble information on the prospecting and development of natural gases of different genetic types.

  19. Modelling the Oceanic Nd Isotopic Composition With a North Atlantic Eddy Permitting Model (United States)

    Peronne, S.; Treguier, A.; Arsouze, T.; Dutay, J.; Lacan, F.; Jeandel, C.


    the margins of the Iceland-Scotland Ridge and south of Iceland. The model does not account for all the complexity of the Nd profiles observed downstream of Denmark Strait and in the Labrador Sea. This is partly due to the representation of the deep western boundary currents, still marginally resolved in this eddy-permitting model. However, these promising results with an eddy permitting model pointed out the deficiencies of the parameterization of the input function, and confirm the potential of epsilon-Nd as a powerful dynamic tracer, already presumed with the low resolution model. Reference: Arsouze, T., Dutay, J.-C., Lacan, F. and Jeandel, C., 2006. Modeling the neodymium isotopic composition with a global ocean circulation model Chemical Geology, in press.

  20. Isotope composition and volume of Earth’s early oceans


    Pope, Emily C.; Bird, Dennis K.; Rosing, Minik T.


    Oxygen and hydrogen isotope compositions of Earth’s seawater are controlled by volatile fluxes among mantle, lithospheric (oceanic and continental crust), and atmospheric reservoirs. Throughout geologic time the oxygen mass budget was likely conserved within these Earth system reservoirs, but hydrogen’s was not, as it can escape to space. Isotopic properties of serpentine from the approximately 3.8 Ga Isua Supracrustal Belt in West Greenland are used to characterize hydrogen and oxygen isotop...

  1. The Late Quaternary Oxygen Isotope Composition of Lake Michigan (United States)

    MacDonald, R. A.; Longstaffe, F. J.; Crowe, A. S.


    We present stable isotope records for porewater (oxygen, hydrogen) and biogenic carbonates (oxygen, carbon; ostracode and clam shells) in sediment cores from the Chippewa, Milwaukee and South Chippewa Basins of Lake Michigan. The oxygen and hydrogen isotope compositions of porewater from the South Chippewa Basin core showed very little variation with depth. At the maximum depth of 16.6m, δ18O values were within 2‰ and δD values were within 12‰ of modern Lake Michigan water (average δ18O = -5.9‰; average δD = -45‰); original porewater compositions have not been preserved. The oxygen isotope results for the biogenic carbonates, by comparison, provide a record of the isotopic composition of Lake Michigan over the last ~11,000 years, including significant incursions of very low-18O water, as first reported by Colman et al. (1990) and Forester et al. (1994). The low-18O waters originated from the retreating Laurentide ice sheet and may have been routed through Lakes Agassiz and Superior and discharged as large volumes over very short intervals of time. Periods characterized by much higher oxygen isotope compositions likely record the isotopic composition of regional precipitation over the catchment area. In summary, the large variations in the oxygen isotope composition of early Lake Michigan water arose from regional climate change and changing water sources during the times of ice-sheet retreat.

  2. Isotopic composition of precipitation in Ljubljana (Slovenia

    Directory of Open Access Journals (Sweden)

    Polona Vreča


    Full Text Available The stable isotopic composition of hydrogen and oxygen (δ2H and δ18O and tritium activity (3H are monitored in monthly precipitation at Ljubljana since 1981. Here we present complete set of numerical data and the statistical analysis for period 1981–2006. Seasonal variations of δ2H and δ18O are observed and are typical for continental stations of the Northern Hemisphere. The weighted mean δ2H and δ18O values are –59 ‰ and –8.6 ‰, respectively.The orthogonal Local Meteoric Water Line is δ2H = (8.06 ± 0.08δ18O + (9.84 ± 0.71, and the temperature coefficient of δ18O is 0.29 ‰/°C. Deuterium excess weighted mean value is 9.5 ‰ and indicates the prevailing influence of the Atlantic air masses. Tritium activity in monthly precipitation shows also seasonal variations which are superposed to the decreasing trend of mean annual activity.

  3. Isotopic compositions of boron in sediments and their implications

    Digital Repository Service at National Institute of Oceanography (India)

    Shirodkar, P.V.; Yingkai, X.

    of sediments are mostly closer to the boron isotopic composition of minerals. Such low delta sup(11)B values are attributed to the presence of borates, ulexite and other carbonate minerals in sediments of the salt lakes of Qaidam Basin....

  4. Synthesis and characterisation of nanostructured neodymium titanium oxides by sol-gel process: Controlling the phase composition, crystal structure and grain size

    Energy Technology Data Exchange (ETDEWEB)

    Mohammadi, M.R., E-mail: [Department of Materials Science and Engineering, Sharif University of Technology, Azadi Street, Tehran (Iran, Islamic Republic of); Department of Materials Science and Metallurgy, University of Cambridge, Pembroke Street, Cambridge CB2 3QZ (United Kingdom); Fray, D.J., E-mail: [Department of Materials Science and Metallurgy, University of Cambridge, Pembroke Street, Cambridge CB2 3QZ (United Kingdom)


    Nanocrystalline neodymium titanium oxide thin films and powders with different phase compositions with mesoporous structure were produced by a straightforward particulate sol-gel route. The sols were prepared in various Nd:Ti molar ratios and they showed a narrow particle size distribution in the range 20-26 nm. X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) revealed that the powders contained mixtures of Nd{sub 4}Ti{sub 9}O{sub 24}, Nd{sub 2}Ti{sub 4}O{sub 11}, Nd{sub 3}Ti{sub 4}O{sub 12} for titanium dominant powders (Nd:Ti {<=} 45:60), mixtures of Nd{sub 2}TiO{sub 5} and Nd{sub 2}O{sub 3} for neodymium dominant powders (Nd:Ti {>=} 75:25) and pure Nd{sub 3}Ti{sub 4}O{sub 12} phase for equal molar ratio of Nd:Ti, depending on the annealing temperature and Nd:Ti molar ratio. Moreover, it was found that Nd:Ti molar ratio influences the preferable orientation growth of the neodymium titanium oxide compounds. Transmission electron microscope (TEM) images confirmed that the average crystallite size of the powders annealed at 400 {sup o}C was in the range 1.0-2.8 nm and a gradual increase was occurred up to 6.7 nm by heat treatment at 1000 {sup o}C. The activation energy of crystal growth reduced with a decrease of Nd:Ti molar ratio, calculated in the range 6.90-18.12 kJ mol{sup -1}. Low activation energies indicating that the grain size will not change much with increase in temperature. Field emission scanning electron microscope (FE-SEM) analysis revealed that the deposited thin films had uniform, mesoporous and nanocrystalline structure. Moreover, atomic force microscope (AFM) images presented that the thin films had a columnar like morphology with average grain size in the range 17-30 nm at 600 {sup o}C and 47-60 nm at 800 {sup o}C, depending upon the Nd:Ti molar ratio. Based on Brunauer-Emmett-Taylor (BET) analysis, the synthesized powders showed mesoporous structure containing pores with sphere like shapes. The surface area of the

  5. Isotopic compositions of the elements 2013 (IUPAC Technical Report) (United States)

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


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

  6. Oxygen isotopic composition of carbon dioxide in the middle atmosphere


    Liang, Mao-Chang; Blake, Geoffrey A.; Lewis, Brenton R.; Yung, Yuk L.


    The isotopic composition of long-lived trace molecules provides a window into atmospheric transport and chemistry. Carbon dioxide is a particularly powerful tracer, because its abundance remains >100 parts per million by volume (ppmv) in the mesosphere. Here, we successfully reproduce the isotopic composition of CO2 in the middle atmosphere, which has not been previously reported. The mass-independent fractionation of oxygen in CO2 can be satisfactorily explained by the exchange reaction with...

  7. A first roadmap for kryptology. [isotopic composition from supernovae (United States)

    Heymann, D.; Dziczkaniec, M.


    Studies of the complex variations of the isotopic composition of xenon in the solar system have been christened 'xenology'. In the title of the present investigation, the word 'kryptology' is employed to indicate the primary objective of the reported studies. This objective is related to the prediction of the isotopic composition of krypton which comes from a number of specific locations of a supernova in association with the isotopic compositions of xenon from these locations. Krypton is a logical candidate for testing the stellar theory on geochemical grounds, taking into account also the point of view of nucleosynthesis, because the isotopes of xenon and krypton are formed by the same thermonuclear processes in stars. The data and arguments presented in the investigation show that the treatment by Heymann and Dziczkaniec (1979), although not wrong, is too simplistic, because it has ignored the possibility of holdup and arrest in Xe network.

  8. Neodymium in the oceans: a global database, a regional comparison and implications for palaeoceanographic research (United States)

    van de Flierdt, Tina; Griffiths, Alexander M.; Lambelet, Myriam; Little, Susan H.; Stichel, Torben; Wilson, David J.


    The neodymium (Nd) isotopic composition of seawater has been used extensively to reconstruct ocean circulation on a variety of time scales. However, dissolved neodymium concentrations and isotopes do not always behave conservatively, and quantitative deconvolution of this non-conservative component can be used to detect trace metal inputs and isotopic exchange at ocean-sediment interfaces. In order to facilitate such comparisons for historical datasets, we here provide an extended global database for Nd isotopes and concentrations in the context of hydrography and nutrients. Since 2010, combined datasets for a large range of trace elements and isotopes are collected on international GEOTRACES section cruises, alongside classical nutrient and hydrography measurements. Here, we take a first step towards exploiting these datasets by comparing high-resolution Nd sections for the western and eastern North Atlantic in the context of hydrography, nutrients and aluminium (Al) concentrations. Evaluating those data in tracer-tracer space reveals that North Atlantic seawater Nd isotopes and concentrations generally follow the patterns of advection, as do Al concentrations. Deviations from water mass mixing are observed locally, associated with the addition or removal of trace metals in benthic nepheloid layers, exchange with ocean margins (i.e. boundary exchange) and/or exchange with particulate phases (i.e. reversible scavenging). We emphasize that the complexity of some of the new datasets cautions against a quantitative interpretation of individual palaeo Nd isotope records, and indicates the importance of spatial reconstructions for a more balanced approach to deciphering past ocean changes. This article is part of the themed issue 'Biological and climatic impacts of ocean trace element chemistry'.

  9. The ruthenium isotopic composition of the oceanic mantle (United States)

    Bermingham, K. R.; Walker, R. J.


    The approximately chondritic relative, and comparatively high absolute mantle abundances of the highly siderophile elements (HSE), suggest that their concentrations in the bulk silicate Earth were primarily established during a final ∼0.5 to 1% of ;late accretion; to the mantle, following the cessation of core segregation. Consequently, the isotopic composition of the HSE Ru in the mantle reflects an amalgamation of the isotopic compositions of late accretionary contributions to the silicate portion of the Earth. Among cosmochemical materials, Ru is characterized by considerable mass-independent isotopic variability, making it a powerful genetic tracer of Earth's late accretionary building blocks. To define the Ru isotopic composition of the oceanic mantle, the largest portion of the accessible mantle, we report Ru isotopic data for materials from one Archean and seven Phanerozoic oceanic mantle domains. A sample from a continental lithospheric mantle domain is also examined. All samples have identical Ru isotopic compositions, within analytical uncertainties, indicating that Ru isotopes are well mixed in the oceanic mantle, defining a μ100Ru value of 1.2 ± 7.2 (2SD). The only known meteorites with the same Ru isotopic composition are enstatite chondrites and, when corrected for the effects of cosmic ray exposure, members of the Main Group and sLL subgroup of the IAB iron meteorite complex which have a collective CRE corrected μ100Ru value of 0.9 ± 3.0. This suggests that materials from the region(s) of the solar nebula sampled by these meteorites likely contributed the dominant portion of late accreted materials to Earth's mantle.

  10. Calcium isotopic compositions of mid-ocean ridge basalts (United States)

    Zhu, H.; Zhang, Z.; Sun, W.; Wang, G. Q.


    Previous studies have demonstrated that Earth's mantle has heterogeneous calcium isotopic compositions. But the reason why mantle has its heterogeneity remains uncertain. In general, δ44/40Ca values of mantle xenolith samples have a variation of >0.45‰. While ultramafic rocks, especially dunites, have higher δ44/40Ca values than volcanic rocks, and there is a positive correlation between δ44/40Ca and Ca/Mg. These phenomena imply that the heterogeneity of Ca isotopic compositions of mantle xenolith samples might result from different degrees of melt extraction, as indicated by large Ca isotopic fractionation between co-existing clinopyroxene and orthopyroxene. However, because ancient marine carbonate has its own unique calcium isotopic characteristics, recycling of even a small amount of ancient marine carbonates into the mantle could also cause the heterogeneity of Ca isotopes in Earth's mantle. This could be the reason why oceanic island basalts (OIB) have lighter Ca isotopic compositions than the mantle xenolith. Thus, the lighter Ca isotopic compositions in the mantle source cannot only be ascribed to magmatic processes. Therefore, it is more important to know calcium isotopic characteristics during partial melting and oceanic crust contamination.Mid-ocean ridge basalts (MORB) are formed from the partial melts of the upper mantle and are rarely affected by crustal contamination. Different types of MORB, including D-MORB, N-MORB and E-MORB, have experienced different degrees of partial melting and contamination of enriched end-members. Here we report calcium isotopic characteristic of different types of MORB, we believe it will be very helpful to understand the behaviors of Ca isotopes during partial melting and it is possible to provide further information to discover the reason why calcium isotopic compositions is heterogeneous in Earth's mantle. This work was supported by Natural Science Foundation of China (No. 41373007, No. 41490632 and No. 91328204

  11. Discovery and cross-section measurement of neutron-rich isotopes in the element range from neodymium to platinum with the FRS

    Energy Technology Data Exchange (ETDEWEB)

    Kurcewicz, J., E-mail: [GSI Helmholtzzentrum fuer Schwerionenforschung, 64291 Darmstadt (Germany); Farinon, F.; Geissel, H. [GSI Helmholtzzentrum fuer Schwerionenforschung, 64291 Darmstadt (Germany); Justus-Liebig-Universitaet Giessen, 35392 Giessen (Germany); Pietri, S.; Nociforo, C. [GSI Helmholtzzentrum fuer Schwerionenforschung, 64291 Darmstadt (Germany); Prochazka, A. [GSI Helmholtzzentrum fuer Schwerionenforschung, 64291 Darmstadt (Germany); Justus-Liebig-Universitaet Giessen, 35392 Giessen (Germany); Weick, H.; Winfield, J.S. [GSI Helmholtzzentrum fuer Schwerionenforschung, 64291 Darmstadt (Germany); Estrade, A. [GSI Helmholtzzentrum fuer Schwerionenforschung, 64291 Darmstadt (Germany); Astronomy and Physics Department, Saint Mary' s University, Halifax, Nova Scotia B3H 3C3 (Canada); Allegro, P.R.P. [Institute of Physics, Universidade de Sao Paulo, CEP 05508-090 Cidade Universitaria, Sao Paulo (Brazil); Bail, A.; Belier, G. [CEA DAM DiF, 91290 Arpajon Cedex (France); Benlliure, J. [Universidad de Santiago de Compostela, E-15706 Santiago de Compostella (Spain); Benzoni, G. [INFN sezione di Milano, I-20133 Milano (Italy); Bunce, M.; Bowry, M. [Department of Physics, University of Surrey, Guildford, Surrey, GU2 7XH (United Kingdom); Caballero-Folch, R. [Universitat Politecnica de Catalunya, 08034 Barcelona (Spain); and others


    Using the high-resolution performance of the fragment separator FRS at GSI we have discovered 60 new neutron-rich isotopes in the atomic number range of 60 Less-Than-Or-Slanted-Equal-To Z Less-Than-Or-Slanted-Equal-To 78. The new isotopes were unambiguously identified in reactions with a {sup 238}U beam impinging on a Be target at 1 GeV/nucleon. The production cross-section for the new isotopes have been measured down to the pico-barn level and compared with predictions of different model calculations. For elements above hafnium fragmentation is the dominant reaction mechanism which creates the new isotopes, whereas fission plays a dominant role for the production of the new isotopes up to thulium.

  12. Isotopic compositions of cometary matter returned by Stardust. (United States)

    McKeegan, Kevin D; Aléon, Jerome; Bradley, John; Brownlee, Donald; Busemann, Henner; Butterworth, Anna; Chaussidon, Marc; Fallon, Stewart; Floss, Christine; Gilmour, Jamie; Gounelle, Matthieu; Graham, Giles; Guan, Yunbin; Heck, Philipp R; Hoppe, Peter; Hutcheon, Ian D; Huth, Joachim; Ishii, Hope; Ito, Motoo; Jacobsen, Stein B; Kearsley, Anton; Leshin, Laurie A; Liu, Ming-Chang; Lyon, Ian; Marhas, Kuljeet; Marty, Bernard; Matrajt, Graciela; Meibom, Anders; Messenger, Scott; Mostefaoui, Smail; Mukhopadhyay, Sujoy; Nakamura-Messenger, Keiko; Nittler, Larry; Palma, Russ; Pepin, Robert O; Papanastassiou, Dimitri A; Robert, François; Schlutter, Dennis; Snead, Christopher J; Stadermann, Frank J; Stroud, Rhonda; Tsou, Peter; Westphal, Andrew; Young, Edward D; Ziegler, Karen; Zimmermann, Laurent; Zinner, Ernst


    Hydrogen, carbon, nitrogen, and oxygen isotopic compositions are heterogeneous among comet 81P/Wild 2 particle fragments; however, extreme isotopic anomalies are rare, indicating that the comet is not a pristine aggregate of presolar materials. Nonterrestrial nitrogen and neon isotope ratios suggest that indigenous organic matter and highly volatile materials were successfully collected. Except for a single (17)O-enriched circumstellar stardust grain, silicate and oxide minerals have oxygen isotopic compositions consistent with solar system origin. One refractory grain is (16)O-enriched, like refractory inclusions in meteorites, suggesting that Wild 2 contains material formed at high temperature in the inner solar system and transported to the Kuiper belt before comet accretion.

  13. Zinc isotope fractionation during magmatic differentiation and the isotopic composition of the bulk Earth (United States)

    Chen, Heng; Savage, Paul S.; Teng, Fang-Zehn; Helz, Rosalind T.; Moynier, Frédéric


    he zinc stable isotope system has been successfully applied to many and varied fields in geochemistry, but to date it is still not completely clear how this isotope system is affected by igneous processes. In order to evaluate the potential application of Zn isotopes as a proxy for planetary differentiation and volatile history, it is important to constrain the magnitude of Zn isotopic fractionation induced by magmatic differentiation. In this study we present high-precision Zn isotope analyses of two sets of chemically diverse, cogenetic samples from Kilauea Iki lava lake, Hawaii, and Hekla volcano, Iceland, which both show clear evidence of having undergone variable and significant degrees of magmatic differentiation. The Kilauea Iki samples display small but resolvable variations in Zn isotope composition (0.26‰66Zn66Zn defined as the per mille deviation of a sample's 66Zn/64Zn compositional ratio from the JMC-Lyon standard), with the most differentiated lithologies exhibiting more positive δ66Zn values. This fractionation is likely a result of the crystallization of olivine and/or Fe–Ti oxides, which can both host Zn in their crystal structures. Samples from Hekla have a similar range of isotopic variation (0.22‰66Zn66Zn=0.28±0.05‰ (2s.d.).

  14. Iron isotope composition of some Archean and Proterozoic iron formations (United States)

    Planavsky, Noah; Rouxel, Olivier J.; Bekker, Andrey; Hofmann, Axel; Little, Crispin T. S.; Lyons, Timothy W.


    Fe isotopes can provide new insight into redox-dependent biogeochemical processes. Precambrian iron formations (IF) are deserving targets for Fe isotope studies because they are composed predominantly of authigenic Fe phases and record a period of unprecedented iron deposition in Earth's history. We present Fe isotope data for bulk samples from 24 Archean and Proterozoic IF and eight Phanerozoic Fe oxide-rich deposits. These data reveal that many Archean and early Paleoproterozoic iron formations were a sink for isotopically heavy Fe, in contrast to later Proterozoic and Phanerozoic Fe oxide-rich rocks. The positive δ56Fe values in IF are best explained by delivery of particulate ferric oxides formed in the water column to the sediment-water interface. Because IF are a net sink for isotopically heavy Fe, there must be a corresponding pool of isotopically light Fe in the sedimentary record. Earlier work suggested that Archean pyritic black shales were an important part of this light sink before 2.35 billion years ago (Ga). It is therefore likely that the persistently and anomalously low δ56Fe values in shales are linked with the deposition of isotopically heavy Fe in IF in the deeper parts of basins. IF deposition produced a residual isotopically light dissolved Fe pool that was captured by pyritic Fe in shales. Local dissimilatory Fe reduction in porewater and associated diagenetic reactions resulting in pyrite and carbonate precipitation may have further enhanced Fe isotope heterogeneity in marine sediments, and an 'iron shuttle' may have transported isotopically light Fe from shelf sediments to the basin. Nevertheless, water-column processing of hydrothermally delivered Fe likely had the strongest influence on the bulk iron isotope composition of Archean and Paleoproterozoic iron formations and other marine sediments.

  15. Soil Carbon: Compositional and Isotopic Analysis

    Energy Technology Data Exchange (ETDEWEB)

    Moran, James J.; Alexander, M. L.; Laskin, Alexander


    This is a short chapter to be included in the next edition of the Encyclopedia of Soil Science. The work here describes techniques being developed at PNNL for investigating organic carbon in soils. Techniques discussed include: laser ablation isotope ratio mass spectrometry, laser ablation aerosol mass spectrometry, and nanospray desorption electrospray ionization mass spectrometry.

  16. Stable isotope composition of human fingernails from Slovakia

    Energy Technology Data Exchange (ETDEWEB)

    Grolmusová, Zuzana, E-mail: [Comenius University in Bratislava, Faculty of Mathematics, Physics and Informatics, Department of Experimental Physics, Mlynská dolina F2, 842 48 Bratislava (Slovakia); State Geological Institute of Dionýz Štúr, Laboratory of Isotope Geology, Mlynská dolina 1, 817 04 Bratislava (Slovakia); Rapčanová, Anna [Comenius University in Bratislava, Faculty of Mathematics, Physics and Informatics, Department of Experimental Physics, Mlynská dolina F2, 842 48 Bratislava (Slovakia); Michalko, Juraj; Čech, Peter [State Geological Institute of Dionýz Štúr, Laboratory of Isotope Geology, Mlynská dolina 1, 817 04 Bratislava (Slovakia); Veis, Pavel [Comenius University in Bratislava, Faculty of Mathematics, Physics and Informatics, Department of Experimental Physics, Mlynská dolina F2, 842 48 Bratislava (Slovakia); State Geological Institute of Dionýz Štúr, Laboratory of Isotope Geology, Mlynská dolina 1, 817 04 Bratislava (Slovakia)


    Stable isotope composition of human fingernails has proven to be useful for documenting human dietary information and geographical patterns in archeological, forensic, anthropological and biological studies. Therefore, it is of interest to detect all factors influencing the stable isotopic composition in the certain regions in the world. Carbon and nitrogen isotope data of human fingernail keratin from 52 individuals from Slovakia were reported in this study. The online combustion and continuous flow isotope-ratio mass spectrometer Delta V Advantage was used for δ{sup 13}C and δ{sup 15}N analysis of fingernail keratin samples from 24 vegetarian and 28 omnivorous individuals. A group of people with frequent meat consumption showed enrichment in {sup 13}C and {sup 15}N isotopes in fingernails. A similar trend was observed with increasing seafood in an individual's diet. Moreover a significant difference was revealed between smokers and nonsmokers for both δ{sup 13}C and δ{sup 15}N values. These data were compared to previously published δ{sup 13}C and δ{sup 15}N fingernail values from across the globe. This study brings new information on the stable isotope signature of individuals from Slovakia and characterizes the Central European region for the first time. The stable isotope composition of fingernails is influenced by the frequency of meat and seafood consumption as well as smoking. - Highlights: • This study deals with stable isotope analyses of fingernails from Slovak volunteers. • δ{sup 13}C and δ{sup 15}N values of vegetarian and omnivore fingernails were compared. • Influence of sex, diet and smoking was studied.

  17. Aerosol carbon isotope composition over Baltic Sea (United States)

    Garbaras, Andrius; Pabedinskas, Algirdas; Masalaite, Agne; Petelski, Tomasz; Gorokhova, Elena; Sapolaite, Justina; Ezerinskis, Zilvinas; Remeikis, Vidmantas


    Particulate carbonaceous matter is significant contributor to ambient particulate matter originating from intervening sources which contribution is difficult to quantify due to source diversity, chemical complexity and processes during atmospheric transport. Carbon isotope analysis can be extremely useful in source apportionment of organic matter due to the unique isotopic signatures associated with anthropocentric (fossil fuel), continental (terrestrial plants) and marine sources, and is particularly effective when these sources are mixed (Ceburnis et al., 2011;Ceburnis et al., 2016). We will present the isotope ratio measurement results of aerosol collected during the cruise in the Baltic Sea. Sampling campaign of PM10 and size segregated aerosol particles was performed on the R/V "Oceania" in October 2015. Air mass back trajectories were prevailing both from the continental and marine areas during the sampling period. The total carbon concentration varied from 1 µg/m3 to 8 µg/m3. Two end members (δ13C = -25‰ and δ13C = -28 ‰ ) were established from the total stable carbon isotope analysis in PM10 fraction. δ13C analysis in size segregated aerosol particles revealed δ13C values being highest in the 1 - 2.5 µm range (δ13C = -24.9 ‰ ) during continental transport, while lowest TC δ13C values (δ13C ≈ -27 ‰ ) were detected in the size range D50 dual carbon pools contributing to organic matter enrichment in marine aerosol, Scientific Reports, 6, 2016. Masalaite, A., Remeikis, V., Garbaras, A., Dudoitis, V., Ulevicius, V., and Ceburnis, D.: Elucidating carbonaceous aerosol sources by the stable carbon δ13C TC ratio in size-segregated particles, Atmospheric Research, 158, 1-12, 2015.

  18. Carbon isotopic composition of individual Precambrian microfossils. (United States)

    House, C H; Schopf, J W; McKeegan, K D; Coath, C D; Harrison, T M; Stetter, K O


    Ion microprobe measurements of carbon isotope ratios were made in 30 specimens representing six fossil genera of microorganisms petrified in stromatolitic chert from the approximately 850 Ma Bitter Springs Formation, Australia, and the approximately 2100 Ma Gunflint Formation, Canada. The delta 13C(PDB) values from individual microfossils of the Bitter Springs Formation ranged from -21.3 +/- 1.7% to -31.9 +/- 1.2% and the delta 13C(PDB) values from microfossils of the Gunflint Formation ranged from -32.4 +/- 0.7% to -45.4 +/- 1.2%. With the exception of two highly 13C-depleted Gunflint microfossils, the results generally yield values consistent with carbon fixation via either the Calvin cycle or the acetyl-CoA pathway. However, the isotopic results are not consistent with the degree of fractionation expected from either the 3-hydroxypropionate cycle or the reductive tricarboxylic acid cycle, suggesting that the microfossils studied did not use either of these pathways for carbon fixation. The morphologies of the microfossils suggest an affinity to the cyanobacteria, and our carbon isotopic data are consistent with this assignment.

  19. Strontium and neodymium isotopic variations in early Archean gneisses affected by middle to late Archean high-grade metamorphic processes: West Greenland and Labrador (United States)

    Collerson, K. D.; Mcculloch, M. T.; Bridgwater, D.; Mcgregor, V. R.; Nutman, A. P.


    Relicts of continental crust formed more than 3400 Ma ago are preserved fortuitously in most cratons. The cratons provide the most direct information about crust and mantle evolutionary processes during the first billion years of Earth history. In view of their polymetamorphic character, these terrains are commonly affected by subsequent tectonothermal events. Hence, their isotope systematics may be severely disturbed as a result of bulk chemical change or local isotopic homogenization. This leads to equivocal age and source information for different components within these terrains. The Sr and Nd isotopic data are presented for early Archean gneisses from the North Atlantic Craton in west Greenland and northern Labrador which were affected by younger metamorphic events.

  20. What controls the isotopic composition of Greenland surface snow?

    Directory of Open Access Journals (Sweden)

    H. C. Steen-Larsen


    Full Text Available Water stable isotopes in Greenland ice core data provide key paleoclimatic information, and have been compared with precipitation isotopic composition simulated by isotopically-enabled atmospheric models. However, post-deposition processes linked with snow metamorphism remain poorly documented. For this purpose, a monitoring of the isotopic composition (δ18O, δD of surface water vapor, precipitation and samples of top (0.5 cm snow surface has been conducted during two summers (2011–2012 at NEEM, NW Greenland. The measurements also include a subset of 17O-excess measurements over 4 days, and the measurements span the 2012 Greenland heat wave. Our observations are consistent with calculations assuming isotopic equilibrium between surface snow and water vapor. We observe a strong correlation between surface vapor δ18O and air temperature (0.85 ± 0.11 ‰ °C−1 (R = 0.76 for 2012. The correlation with air temperature is not observed in precipitation data or surface snow data. Deuterium excess (d-excess is strongly anti-correlated with δ18O with a stronger slope for vapor than for precipitation and snow surface data. During nine 1–5 days periods between precipitation events, our data demonstrate parallel changes of δ18O and d-excess in surface snow and surface vapor. The changes in δ18O of the vapor are similar or larger than those of the snow δ18O. It is estimated that 6 to 20% of the surface snow mass is exchanged with the atmosphere using the CROCUS snow model. In our data, the sign of surface snow isotopic changes is not related to the sign or magnitude of sublimation or condensation. Comparisons with atmospheric models show that day-to-day variations in surface vapor isotopic composition are driven by synoptic weather and changes in air mass trajectories and distillation histories. We suggest that, in-between precipitation events, changes in the surface snow isotopic composition are driven by these changes in surface vapor isotopic

  1. What controls the isotopic composition of Greenland surface snow?

    Directory of Open Access Journals (Sweden)

    H. C. Steen-Larsen


    Full Text Available Water stable isotopes in Greenland ice core data provide key paleoclimatic information, and have been compared with precipitation isotopic composition simulated by isotopically enabled atmospheric models. However, post-depositional processes linked with snow metamorphism remain poorly documented. For this purpose, monitoring of the isotopic composition (δ18O, δD of near-surface water vapor, precipitation and samples of the top (0.5 cm snow surface has been conducted during two summers (2011–2012 at NEEM, NW Greenland. The samples also include a subset of 17O-excess measurements over 4 days, and the measurements span the 2012 Greenland heat wave. Our observations are consistent with calculations assuming isotopic equilibrium between surface snow and water vapor. We observe a strong correlation between near-surface vapor δ18O and air temperature (0.85 ± 0.11‰ °C−1 (R = 0.76 for 2012. The correlation with air temperature is not observed in precipitation data or surface snow data. Deuterium excess (d-excess is strongly anti-correlated with δ18O with a stronger slope for vapor than for precipitation and snow surface data. During nine 1–5-day periods between precipitation events, our data demonstrate parallel changes of δ18O and d-excess in surface snow and near-surface vapor. The changes in δ18O of the vapor are similar or larger than those of the snow δ18O. It is estimated using the CROCUS snow model that 6 to 20% of the surface snow mass is exchanged with the atmosphere. In our data, the sign of surface snow isotopic changes is not related to the sign or magnitude of sublimation or deposition. Comparisons with atmospheric models show that day-to-day variations in near-surface vapor isotopic composition are driven by synoptic variations and changes in air mass trajectories and distillation histories. We suggest that, in between precipitation events, changes in the surface snow isotopic composition are driven by these changes in near

  2. What controls the isotopic composition of Greenland surface snow? (United States)

    Steen-Larsen, H. C.; Masson-Delmotte, V.; Hirabayashi, M.; Winkler, R.; Satow, K.; Prié, F.; Bayou, N.; Brun, E.; Cuffey, K. M.; Dahl-Jensen, D.; Dumont, M.; Guillevic, M.; Kipfstuhl, S.; Landais, A.; Popp, T.; Risi, C.; Steffen, K.; Stenni, B.; Sveinbjörnsdottír, A. E.


    Water stable isotopes in Greenland ice core data provide key paleoclimatic information, and have been compared with precipitation isotopic composition simulated by isotopically enabled atmospheric models. However, post-depositional processes linked with snow metamorphism remain poorly documented. For this purpose, monitoring of the isotopic composition (δ18O, δD) of near-surface water vapor, precipitation and samples of the top (0.5 cm) snow surface has been conducted during two summers (2011-2012) at NEEM, NW Greenland. The samples also include a subset of 17O-excess measurements over 4 days, and the measurements span the 2012 Greenland heat wave. Our observations are consistent with calculations assuming isotopic equilibrium between surface snow and water vapor. We observe a strong correlation between near-surface vapor δ18O and air temperature (0.85 ± 0.11‰ °C-1 (R = 0.76) for 2012). The correlation with air temperature is not observed in precipitation data or surface snow data. Deuterium excess (d-excess) is strongly anti-correlated with δ18O with a stronger slope for vapor than for precipitation and snow surface data. During nine 1-5-day periods between precipitation events, our data demonstrate parallel changes of δ18O and d-excess in surface snow and near-surface vapor. The changes in δ18O of the vapor are similar or larger than those of the snow δ18O. It is estimated using the CROCUS snow model that 6 to 20% of the surface snow mass is exchanged with the atmosphere. In our data, the sign of surface snow isotopic changes is not related to the sign or magnitude of sublimation or deposition. Comparisons with atmospheric models show that day-to-day variations in near-surface vapor isotopic composition are driven by synoptic variations and changes in air mass trajectories and distillation histories. We suggest that, in between precipitation events, changes in the surface snow isotopic composition are driven by these changes in near-surface vapor

  3. Oxygen Isotope Composition of Nitrate Produced by Freshwater Nitrification (United States)

    Boshers, D.; Granger, J.; Bohlke, J. K.


    Measurements of the naturally occurring nitrogen and oxygen stable isotope ratios of nitrate (NO3-), δ15N and δ18O, can be used to determine the source, dispersal, and fate of natural and contaminant NO3- in aquatic environments. To this end, it is necessary to know the extent to which NO3- isotopologues are modified by biological reactions, as heavy and light isotopes have different reaction rates. The purpose of this study was to determine the influence of the δ18O of ambient water on the isotope composition of NO3- produced during nitrification, the biological oxidation of ammonium (NH4+) to nitrite (NO2-) and then NO3-, which is poorly constrained in freshwater systems. To determine the δ18O of NO3- produced by nitrification in freshwater, we collected water from a stream in New England, which we amended with NH4+ and with increments of 18O-enriched water, to monitor the isotope composition of NO3- produced by a natural consortium of nitrifiers. Added NH4+ was completely oxidized to NO3- over 26 days. The final δ18O of nitrified NO3- revealed sensitivity to the δ18O of water mediated by (a) isotopic equilibration between water and NO2- and (b) kinetic isotope fractionation during O-atom incorporation from water into NO2- and NO3-. Our results concur with nitrifying culture experiments that have demonstrated analogous sensitivity of the δ18O of nitrified NO3- to equilibrium and kinetic O isotope effects (Buchwald et al. 2012), as well as show that these dynamics need to be considered to interpret NO3- isotope distribution in freshwater environments.

  4. Measurement of Plutonium Isotopic Composition - MGA

    Energy Technology Data Exchange (ETDEWEB)

    Vo, Duc Ta [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)


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

  5. Authentication of bell peppers using boron and strontium isotope compositions (United States)

    Rosner, Martin; Pritzkow, Wolfgang; Vogl, Jochen; Voerkelius, Susanne


    The wrong declaration of food in terms of geographical origin and production method is a major problem for the individual consumer and public regulatory authorities. The authentication of food matrices using H-C-N-O-S isotopic compositions is already well established. However, specific questions require additional isotopic systems, which are more diagonstic for the source reservoires involved or production methods used. Here we present B and Sr isotopic compositions of bell peppers from Europe (Germany, Austria, Netherlands, Spain) and Israel to verfiy their origin. The bell peppers' B isotopic compositions between different locations are highly variable (d11BNISTSRM951 -8 to +35 ‰), whereas the 87Sr/86Sr ratios are all close to modern seawater Sr isotopic composition of about 0.7092 (0.7078 to 0.7107), but still can reliably be distinguished. Distinct isotopically heavy and light B isotopic fingerprints are obtained for bell peppers from Israel and the Netherlands. Samples from Germany, Austria, and Spain display overlapping d11B values between 0 and +12 ‰. Bell peppers from Israel show high d11B values (+28 to +35 ‰) combined with 87Sr/86Sr ratios slightly more unradiogenic than modern seawater (ca 0.7079). Bell peppers from the Netherlands, however, show low d11B values (-8 ‰) combinded with 87Sr/86Sr ratios of modern seawater (approx. 0.7085). Mainly based on diagnostic B isotopic compositions bell peppers from Israel and the Netherlands can be related to a specific geographical growing environment (Israel) or production method (Netherlands). The isotope fingerprints of bell peppers from the Netherlands are consistent with growing conditions in greenhouses typical for the Netherlands vegetable farming. Using optimized production methods crops in greenhouses were supplied with nutritients by liquid fertilizers on artificial substrates. As most fertilizers derive from non-marine salt deposits, fertilization typically imprints invariant d11B values close

  6. Isotope composition and volume of Earth's early oceans. (United States)

    Pope, Emily C; Bird, Dennis K; Rosing, Minik T


    Oxygen and hydrogen isotope compositions of Earth's seawater are controlled by volatile fluxes among mantle, lithospheric (oceanic and continental crust), and atmospheric reservoirs. Throughout geologic time the oxygen mass budget was likely conserved within these Earth system reservoirs, but hydrogen's was not, as it can escape to space. Isotopic properties of serpentine from the approximately 3.8 Ga Isua Supracrustal Belt in West Greenland are used to characterize hydrogen and oxygen isotope compositions of ancient seawater. Archaean oceans were depleted in deuterium [expressed as δD relative to Vienna standard mean ocean water (VSMOW)] by at most 25 ± 5‰, but oxygen isotope ratios were comparable to modern oceans. Mass balance of the global hydrogen budget constrains the contribution of continental growth and planetary hydrogen loss to the secular evolution of hydrogen isotope ratios in Earth's oceans. Our calculations predict that the oceans of early Earth were up to 26% more voluminous, and atmospheric CH(4) and CO(2) concentrations determined from limits on hydrogen escape to space are consistent with clement conditions on Archaean Earth.

  7. Tracing anthropogenic thallium in soil using stable isotope compositions. (United States)

    Kersten, Michael; Xiao, Tangfu; Kreissig, Katharina; Brett, Alex; Coles, Barry J; Rehkämper, Mark


    Thallium stable isotope data are used in this study, for the first time, to apportion Tl contamination in soils. In the late 1970s, a cement plant near Lengerich, Germany, emitted cement kiln dust (CKD) with high Tl contents, due to cocombustion of Tl-enriched pyrite roasting waste. Locally contaminated soil profiles were obtained down to 1 m depth and the samples are in accord with a binary mixing relationship in a diagram of Tl isotope compositions (expressed as ε(205)Tl, the deviation of the (205)Tl/(203)Tl ratio of a sample from the NIST SRM 997 Tl isotope standard in parts per 10(4)) versus 1/[Tl]. The inferred mixing endmembers are the geogenic background, as defined by isotopically light soils at depth (ε(205)Tl ≈ -4), and the Tl emissions, which produce Tl-enriched topsoils with ε(205)Tl as high as ±0. The latter interpretation is supported by analyses of the CKD, which is also characterized by ε(205)Tl ≈ ± 0, and the same ε(205)Tl value was found for a pyrite from the deposit that produced the cocombusted pyrite roasting waste. Additional measurements for samples from a locality in China, with outcrops of Tl sulfide mineralization and associated high natural Tl backgrounds, reveal significant isotope fractionation between soils (ε(205)Tl ≈ +0.4) and locally grown green cabbage (ε(205)Tl between -2.5 and -5.4). This demonstrates that biological isotope fractionation cannot explain the isotopically heavy Tl in the Lengerich topsoils and the latter are therefore clearly due to anthropogenic Tl emissions from cement processing. Our results thus establish that isotopic data can reinforce receptor modeling for the toxic trace metal Tl.

  8. Characteristics of carbon and hydrogen isotopic compositions of light hydrocarbons

    Institute of Scientific and Technical Information of China (English)



    Light hydrocarbons named in the present paper refer to the natural gas-associated light oil and condensate 46 light oil and condensate samples from 11 oil-bearing basins of China were collected and their carbon and hydrogen isotopic compositions were analysed in terms of their total hydrocarbons, saturated hydrocarbons and a part of aromatic fractions, and gas-source materials and their sedimentary environments were discussed based on the above-mentioned data and the geological background of each area. From the view of carbon and hydrogen isotopic composition of total hydrocarbons and saturated hydrocarbons, it is revealed that the condensate related to coal-bearing strata is enriched in 13C and D while that related to the source material of type I-II is enriched in 12C. In general, the isotopic composition of carbon is mainly attributed to the inheriting effect of their source materials, whereas that of hydrogen principally reflects the correlationship between hydrogen isotopes and the sedimentary envi

  9. The isotopic composition of solar flare accelerated neon (United States)

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


    The individual isotopes of neon in energetic solar-flare particles have been clearly resolved with a rms mass resolution of 0.20 amu. The ratios found are Ne-20/Ne-22 = 7.6 (+2.0, -1.8) and Ne-21/Ne-22 of no more than about 0.11 in the 11-26 MeV per nucleon interval. This isotopic composition is essentially the same as that of meteoritic planetary neon-A and is significantly different from that of the solar wind.

  10. Stable isotope composition and volume of Early Archaean oceans

    DEFF Research Database (Denmark)

    Pope, Emily Catherine; Rosing, Minik Thorleif; Bird, Dennis K.

    Oxygen and hydrogen isotope compositions of seawater are controlled by volatile fluxes between mantle, lithospheric (oceanic and continental crust) and atmospheric reservoirs. Throughout geologic time oxygen was likely conserved within these Earth system reservoirs, but hydrogen was not, as it can...... escape to space [1]. Hydrogen isotope ratios of serpentinites from the ~3.8Ga Isua Supracrustal Belt in West Greenland are between -53 and -99‰; the highest values are in antigorite ± lizardite serpentinites from a low-strain lithologic domain where hydrothermal reaction of Archaean seawater with oceanic...

  11. C-isotope composition of fossil sedges and grasses (United States)

    Kurschner, Wolfram M.


    C4 plants differ from C3 plants regarding their anatomy and their C-isotope composition. Both features can be used in the geological record to determine the presence of C4 plants. Yet, the evolution of the C4 pathway in the fossil record is enigmatic as palaeobotanical and geological evidence for C4 plants is sparse. The oldest structural evidence for Kranz anatomy has been found in Late Miocene permineralized grass leaf remains. But studies on the C-isotope composition of sedimentary organic matter indicate that abundant C4 biomass was present in N-America and Asia throughout the Miocene in expanding savannahs and grasslands. The success of C4 plants appears to be related also to an increasing seasonal aridity in the tropical climate belts and the co-evolution of grazers. However, C- isotope composition of palaeosols or vertebrate teeth only allows to estimate the abundance of C4 plant biomass in the vegetation or in the diet without further taxonomical specification which plant groups would have had C4 metabolism. In this contribution the first extensive C-isotope analysis of fossil seeds of sedges and a few grasses are presented. The age of the carpological material ranges from Late Eocene to Pliocene and was collected from several central European brown coal deposits. The 52 different taxa studied include several species of Carex, Cladiocarya, Eriopherum, Eleocharis, Scirpus, Sparganium. Most of them representing herbaceous elements of a (sub)tropical vegetation growing near the edge of a lake. The C-isotope composition of the fossil seeds varies between -30 and -23 o/oo indicating C3 photosynthesis. This first systematic inventory shows that C4 plants were absent in the European (sub)tropical brown coal forming wetland vegetation during the Tertiary. These preliminary data are in agreement with phylogenetic studies which predict the origin of C4 plants outside the European realm.

  12. Boron isotopic compositions of some boron minerals

    Energy Technology Data Exchange (ETDEWEB)

    Oi, Takao; Musashi, Masaaki; Ossaka, Tomoko; Kakihana, Hidetake (Sophia Univ., Tokyo (Japan)); Nomura, Masao; Okamoto, Makoto (Tokyo Institute of Technology (Japan))


    Boron minerals that have different structural formulae but are supposed to have the same geologic origin have been collected and analyzed for the {sup 11}B/{sup 10}B isotopic ratio. It has been reconfirmed that minerals of marine origin have higher {sup 11}B/{sup 10}B ratios than those of nonmarine origin. It has been found that the sequence of decreasing {sup 11}B/{sup 10}B values among the minerals with the same geologic origin is; borax, tincal, kernite (Na borates) > ulexite (Na/Ca borate) > colemanite, iyoite, meyerhofferite (Ca borates). This sequence is explainable on the basis of the difference in crystal structure among the minerals. That is, minerals with high BO{sub 3}/BO{sub 4} ratios, (the ratio of the number of the BO{sub 3} triangle units to the number of the BO{sub 4} tetrahedron units in the structural formula of a mineral) have higher {sup 11}B/{sup 10}B ratios.

  13. Stable isotope composition and volume of Early Archaean oceans

    DEFF Research Database (Denmark)

    Pope, Emily Catherine; Rosing, Minik Thorleif; Bird, Dennis K.

    Oxygen and hydrogen isotope compositions of seawater are controlled by volatile fluxes between mantle, lithospheric (oceanic and continental crust) and atmospheric reservoirs. Throughout geologic time oxygen was likely conserved within these Earth system reservoirs, but hydrogen was not, as it can...... escape to space [1]. Hydrogen isotope ratios of serpentinites from the ~3.8Ga Isua Supracrustal Belt in West Greenland are between -53 and -99‰; the highest values are in antigorite ± lizardite serpentinites from a low-strain lithologic domain where hydrothermal reaction of Archaean seawater with oceanic...... of continents present at that time), and the mass of Early Archaean oceans to ~109 to 126% of present day oceans. Oxygen isotope analyses from these Isua serpentinites (δ18O = +0.1 to 5.6‰ relative to VSMOW) indicate that early Archaean δ18OSEAWATER similar to modern oceans. Our observations suggest...

  14. Triple oxygen isotope composition of the Campi Flegrei magma systems (United States)

    Iovine, Raffaella Silvia; Wörner, Gerhard; Pack, Andreas; Sengupta, Sukanya; Carmine Mazzeo, Fabio; Arienzo, Ilenia; D'Antonio, Massimo


    Sr-O isotope relationships in igneous rocks are a powerful tool to distinguish magma sources and quantify assimilation processes in magmatic rocks. Isotopic (87Sr/86Sr and 18O/16O-17O/16O) data have been acquired on whole rocks and separated minerals (feldspar, Fe-cpx, Mg-cpx, olivine phenocrysts) from pyroclastic products of the Campi Flegrei volcanic complex (Gulf of Naples, Southern Italy). Oxygen isotope ratios were measured by infrared laser fluorination using a Thermo MAT253 gas source isotope ratio mass spectrometer in dual inlet mode, on ˜2 mg of hand-picked phenocrysts. Variations in triple oxygen isotope ratios (17O/16O, 18O/16O) are expressed as the δ notation relative to VSMOW. Sr isotopic compositions were determined by thermal ionization mass spectrometry after standard cation-exchange methods on separated hand-picked phenocrysts (˜300 mg), and on whole rocks, in case of insufficient sample size to separate crystals. Sr-isotopes in Campi Flegrei minerals range from 0.707305 to 0.707605 and δ18O varies from 6.5 to 8.3‰ . Recalculated δ18Omelt values accordingly show a large range between 7.2 and 8.6‰ . Our data, compared with published δ18O-isotope data from other Italian volcanic centers (Alban Hills, Mts. Ernici, Ischia, Mt. Vesuvius, Aeolian Islands, Tuscany and Sardinia) and from subduction zones worldwide (Kamchatka, Lesser Antilles, Indonesia and Central Andean ignimbrites), show compositions that are very different from typical mantle values. Distinct trends and sources are recognized in our compilation from global data: (1) serpentinized mantle (Kamchatka), (2) sediment-enrichment in the mantle source (Indonesia, Lesser Antilles, Eolian arc), (3) assimilation of old radiogenic continental crust affecting magmas derived from sediment-modified mantle sources (Tuscany, Sardinia), (4) assimilation of lower crustal lithologies (Central Andes, Alban Hills, Mts. Ernici, Ischia). Sr-O-isotope values of Campi Flegrei and Vesuvius magmas

  15. Stable isotopic composition of bottled mineral waters from Romania (United States)

    Bădăluţă, Carmen; Nagavciuc, Viorica; Perșoiu, Aurel


    Romania has a high potential of mineral waters resources, featuring one of the largest mineral resources at European and global level. In the last decade, due to increased in consumption of bottled water, numerous brands have appeared on the market, with equally numerous and variable sources of provenance. In this study we have analyzed the isotopic composition of bottled mineral waters from Romania in order to determine their source and authenticity. We have analysed 32 carbonated and 24 non-carbonated mineral waters from Romania. and the results were analysed in comparison with stable isotope data from precipitation and river waters. Generally, the isotopic values of the mineral waters follow those in precipitation; however, differences occur in former volcanic regions (due to deep circulation of meteoric waters and increased exchange with host rock and volcanic CO2), as well as in mountainous regions, where high-altitude recharge occurs.

  16. The chromium isotope composition of reducing and oxic marine sediments (United States)

    Gueguen, Bleuenn; Reinhard, Christopher T.; Algeo, Thomas J.; Peterson, Larry C.; Nielsen, Sune G.; Wang, Xiangli; Rowe, Harry; Planavsky, Noah J.


    The chromium (Cr) isotope composition of marine sediments has the potential to provide new insights into the evolution of Earth-surface redox conditions. There are significant but poorly constrained isotope fractionations associated with oxidative subaerial weathering and riverine transport, the major source of seawater Cr, and with partial Cr reduction during burial in marine sediments, the major sink for seawater Cr. A more comprehensive understanding of these processes is needed to establish global Cr isotope mass balance and to gauge the utility of Cr isotopes as a paleoredox proxy. For these purposes, we investigated the Cr isotope composition of reducing sediments from the upwelling zone of the Peru Margin and the deep Cariaco Basin. Chromium is present in marine sediments in both detrital and authigenic phases, and to estimate the isotopic composition of the authigenic fraction, we measured δ53Cr on a weakly acid-leached fraction in addition to the bulk sediment. In an effort to examine potential variability in the Cr isotope composition of the detrital fraction, we also measured δ53Cr on a variety of oxic marine sediments that contain minimal authigenic Cr. The average δ53Cr value of the oxic sediments examined here is -0.05 ± 0.10‰ (2σ, n = 25), which is within the range of δ53Cr values characteristic of the bulk silicate Earth. This implies that uncertainty in estimates of authigenic δ53Cr values based on bulk sediment analyses is mainly linked to estimation of the ratio of Cr in detrital versus authigenic phases, rather than to the Cr-isotopic composition of the detrital pool. Leaches of Cariaco Basin sediments have an average δ53Cr value of +0.38 ± 0.10‰ (2σ, n = 7), which shows no dependency on sample location within the basin and is close to that of Atlantic deepwater Cr (∼+0.5‰). This suggests that authigenic Cr in anoxic sediments may reliably reflect the first-order Cr isotope composition of deepwaters. For Peru Margin samples

  17. Modeling the carbon isotope composition of bivalve shells (Invited) (United States)

    Romanek, C.


    The stable carbon isotope composition of bivalve shells is a valuable archive of paleobiological and paleoenvironmental information. Previous work has shown that the carbon isotope composition of the shell is related to the carbon isotope composition of dissolved inorganic carbon (DIC) in the ambient water in which a bivalve lives, as well as metabolic carbon derived from bivalve respiration. The contribution of metabolic carbon varies among organisms, but it is generally thought to be relatively low (e.g., organism and high (>90%) in the shells from terrestrial organisms. Because metabolic carbon contains significantly more C-12 than DIC, negative excursions from the expected environmental (DIC) signal are interpreted to reflect an increased contribution of metabolic carbon in the shell. This observation contrasts sharply with modeled carbon isotope compositions for shell layers deposited from the inner extrapallial fluid (EPF). Previous studies have shown that growth lines within the inner shell layer of bivalves are produced during periods of anaerobiosis when acidic metabolic byproducts (e.g., succinic acid) are neutralized (or buffered) by shell dissolution. This requires the pH of EPF to decrease below ambient levels (~7.5) until a state of undersaturation is achieved that promotes shell dissolution. This condition may occur when aquatic bivalves are subjected to external stressors originating from ecological (predation) or environmental (exposure to atm; low dissolved oxygen; contaminant release) pressures; normal physiological processes will restore the pH of EPF when the pressure is removed. As a consequence of this process, a temporal window should also exist in EPF at relatively low pH where shell carbonate is deposited at a reduced saturation state and precipitation rate. For example, EPF chemistry should remain slightly supersaturated with respect to aragonite given a drop of one pH unit (6.5), but under closed conditions, equilibrium carbon isotope

  18. Alkali elemental and potassium isotopic compositions of Semarkona chondrules (United States)

    Alexander, C.M. O'D.; Grossman, J.N.


    We report measurements of K isotope ratios in 28 Semarkona chondrules with a wide range of petrologic types and bulk compositions as well as the compositions of CPX-mesostasis pairs in 17 type I Semarkona chondrules, including two chondrules with radial alkali zonation and 19 type II chondrules. Despite the wide range in K/Al ratios, no systematic variations in K isotopic compositions were found. Semarkona chondrules do not record a simple history of Rayleigh-type loss of K. Experimentally determined evaporation rates suggest that considerable alkali evaporation would have occurred during chondrule formation. Nevertheless, based on Na CPX-mesostasis distribution coefficients, the alkali contents of the cores of most chondrules in Semarkona were probably established at the time of final crystallization. However, Na CPX-mesostasis distribution coefficients also show that alkali zonation in type I Semarkona chondrules was produced by entry of alkalis after solidification, probably during parent body alteration. This alkali metasomatism may have gone to completion in some chondrules. Our preferred explanation for the lack of systematic isotopic enrichments, even in alkali depleted type I chondrule cores, is that they exchanged with the ambient gas as they cooled. ?? The Meteoritical Society, 2005.

  19. Light and heavy element isotopic compositions of mainstream SiC grains.

    Energy Technology Data Exchange (ETDEWEB)

    Amari, S.; Clayton, R. N.; Davis, A. M.; Lewis, R. S.; Pellin, M. J.


    Although a variety of types of pre-solar SiC grains have been classified by their C, N, and Si isotopic composition, the majority of such grains are so-called mainstream grains and are believed to have come from asymptotic giant branch stars [1]. We have previously reported the Mo isotopic compositions of presolar SiC grains whose C, N, and Si isotopic compositions were not known [2]. Since most presolar SiC grains fall in the mainstream group, we assumed that these grains were mainstream. The excellent match of the Mo isotopic data with expectations for nucleosynthesis in AGB stars was consistent with this identification. In order to better understand the distribution of isotopic compositions in presolar grains, we have begun to measure heavy element isotopic compositions of presolar SiC grains of known C, N and Si isotopic composition.

  20. Clumped-isotope geochemistry of carbonates: A new tool for the reconstruction of temperature and oxygen isotope composition of seawater

    Energy Technology Data Exchange (ETDEWEB)

    Bernasconi, Stefano M., E-mail: [Geological Institute, ETH Zuerich, Sonneggstrasse 5, 8092 Zuerich (Switzerland); Schmid, Thomas W.; Grauel, Anna-Lena [Geological Institute, ETH Zuerich, Sonneggstrasse 5, 8092 Zuerich (Switzerland); Mutterlose, Joerg [Institut fuer Geologie, Mineralogie und Geophysik, Ruhr Universitaet Bochum, Universitaetsstr. 150, 44801 Bochum (Germany)


    Highlights: > Clumped-isotope thermometry of carbonates is discussed. > Clumped isotopes of Belemnites show higher sea surface temperatures than commonly assumed for the lower Cretaceous. > The potential of clumped-isotope measurement on foraminifera is discussed. - Abstract: Clumped-isotope geochemistry deals with State of ordering of rare isotopes in molecules, in particular with their tendency to form bonds with other rare isotopes rather than with the most abundant ones. Among its possible applications, carbonate clumped-isotope thermometry is the one that has gained most attention because of the wide potential of applications in many disciplines of the earth sciences. In particular, it allows reconstructing the temperature of formation of carbonate minerals without knowledge of the isotopic composition of the water from which they were formed. In addition, the O isotope composition of the waters from which they were formed can be calculated using the {delta}{sup 18}O of the same carbonate sample. This feature offers new approaches in paleoclimatology for reconstructing past global geochemical cycles. In this contribution two applications of this method are presented. First the potential of a new analytical method of measurement of clumped isotopes on small samples of foraminifera, for high-resolution SST and seawater {delta}{sup 18}O reconstructions from marine sediments is shown. Furthermore the potential of clumped isotope analysis of belemnites, for reconstructing seawater {delta}{sup 18}O and temperatures in the Cretaceous is shown.

  1. Magnesium stable isotope composition of Earth's upper mantle (United States)

    Handler, Monica R.; Baker, Joel A.; Schiller, Martin; Bennett, Vickie C.; Yaxley, Gregory M.


    The mantle is Earth's largest reservoir of Mg containing > 99% of Earth's Mg inventory. However, no consensus exists on the stable Mg isotope composition of the Earth's mantle or how variable it is and, in particular, whether the mantle has the same stable Mg isotope composition as chondrite meteorites. We have determined the Mg isotope composition of olivine from 22 mantle peridotites from eastern Australia, west Antarctica, Jordan, Yemen and southwest Greenland by pseudo-high-resolution MC-ICP-MS on Mg purified to > 99%. The samples include fertile lherzolites, depleted harzburgites and dunites, cryptically metasomatised ('dry') peridotites and modally metasomatised apatite ± amphibole-bearing harzburgites and wehrlites. Olivine from these samples of early Archaean through to Permian lithospheric mantle have δ25Mg DSM-3 = - 0.22 to - 0.08‰. These data indicate the bulk upper mantle as represented by peridotite olivine is homogeneous within current analytical uncertainties (external reproducibility ≤ ± 0.07‰ [2 sd]). We find no systematic δ25Mg variations with location, lithospheric age, peridotite fertility, or degree or nature of mantle metasomatism. Although pyroxene may have slightly heavier δ25Mg than coexisting olivine, any fractionation between mantle pyroxene and olivine is also within current analytical uncertainties with a mean Δ25Mg pyr-ol = +0.06 ± 0.10‰ (2 sd; n = 5). Our average mantle olivine δ25Mg DSM-3 = - 0.14 ± 0.07‰ and δ26Mg DSM-3 = - 0.27 ± 0.14‰ (2 sd) are indistinguishable from the average of data previously reported for terrestrial basalts, confirming that basalts have stable Mg isotope compositions representative of the mantle. Olivine from five pallasite meteorites have δ25Mg DSM-3 = - 0.16 to - 0.11‰ that are identical to terrestrial olivine and indistinguishable from the average δ25Mg previously reported for chondrites. These data provide no evidence for measurable heterogeneity in the stable Mg isotope

  2. The triple isotopic composition of oxygen in leaf water (United States)

    Landais, A.; Barkan, E.; Yakir, D.; Luz, B.


    The isotopic composition of atmospheric O 2 depends on the rates of oxygen cycling in photosynthesis, respiration, photochemical reactions in the stratosphere and on δ17O and δ18O of ocean and leaf water. While most of the factors affecting δ17O and δ18O of air O 2 have been studied extensively in recent years, δ17O of leaf water—the substrate for all terrestrial photosynthesis—remained unknown. In order to understand the isotopic composition of atmospheric O 2 at present and in fossil air in ice cores, we studied leaf water in field experiments in Israel and in a European survey. We measured the difference in δ17O and δ18O between stem and leaf water, which is the result of isotope enrichment during transpiration. We calculated the slopes of the lines linking the isotopic compositions of stem and leaf water. The obtained slopes in ln( δ17O + 1) vs. ln( δ18O + 1) plots are characterized by very high precision (˜0.001) despite of relatively large differences between duplicates in both δ17O and δ18O (0.02-0.05‰). This is so because the errors in δ18O and δ17O are mass-dependent. The slope of the leaf transpiration process varied between 0.5111 ± 0.0013 and 0.5204 ± 0.0005, which is considerably smaller than the slope linking liquid water and vapor at equilibrium (0.529). We further found that the slope of the transpiration process decreases with atmospheric relative humidity ( h) as 0.522-0.008 × h, for h in the range 0.3-1. This slope is neither influenced by the plant species, nor by the environmental conditions where plants grow nor does it show strong variations along long leaves.

  3. A method for determining the nitrogen isotopic composition of porphyrins. (United States)

    Higgins, Meytal B; Robinson, Rebecca S; Casciotti, Karen L; McIlvin, Matthew R; Pearson, Ann


    We describe a new method for analysis of the nitrogen isotopic composition of sedimentary porphyrins. This method involves separation and purification of geoporphyrins from sediment samples using liquid chromatography and HPLC, oxidation of the nitrogen within porphyrin-enriched fractions using a two-step process, and isotopic analysis of the resulting nitrate using the denitrifier method. By analysis of these degradation products of chlorophylls, we are able to measure an isotopic signature that reflects the nitrogen utilized by primary producers. The high sensitivity of the denitrifier method allows measurement of small samples that contain low concentrations of porphyrins. Extraction of only 50 nmol of nitrogen (nmol N) allows the following five analyses to be made (each on approximately 10 nmol N): nitrogen concentration, an assessment of potential contamination by nonporphyrin N, and three replicate isotopic measurements. The measured values of delta15N have an average analytical precision of +/-0.5 per thousand (1sigma) and an average contribution from Rayleigh fractionation of 0.7 per thousand from incomplete oxidation of porphyrin N to nitrate. The overall method will enable high-resolution records of delta15N values to be obtained for geological and ecological applications.

  4. Tellurium isotope compositions of calcium-aluminum-rich inclusions (United States)

    Fehr, M. A.; Rehkämper, M.; Halliday, A. N.; Hattendorf, B.; Günther, D.


    A method for the precise and accurate determination of the tellurium (Te) isotope compositions of calcium-aluminum-rich inclusions (CAIs) has been developed. The technique utilizes multiple-collector inductively coupled plasma-mass spectrometry (MC-ICPMS) with either Faraday detectors or a dual ion-counting system. The external reproducibility (2σ) for 126Te/125Te was ~15‰ and ~2‰ when 3 pg and 65 pg of Te were analyzed with the electron multipliers. Measurements performed on 200 pg of Te using Faraday detectors and time-resolved software displayed an external reproducibility of ~8‰ for 126Te/124Te, whereas 3 ng Te could be measured to a precision of about 0.6‰. Analyses of five CAIs from the Allende chondrite yielded Te concentrations that range from 12 to 537 ppb and the inclusions are therefore depleted in Te relative to bulk Allende by factors of about 2 to 86. The Sn/Te ratios of the CAIs are also fractionated compared to bulk Allende (which displays 124Sn/128Te ≍ 0.1) with 124Sn/128Te ratios of about 0.1 to 2.5. The Te isotope measurements for these refractory inclusions yielded no 126Te excesses from the decay of the short-lived radionuclide 126Sn (τ½ = 234,500 years) and the most precise analysis provided a ɛ126Te value of 1 ± 6 (ɛ126Te = 126Te/ 124Te normalized to 122Te/124Te = 0.53594 and reported relative to the JMC Te standard). Minor differences in the Te isotope composition of the CAIs relative to the terrestrial standard and bulk Allende hint at the presence of small deficits in r-process Te isotopes or excess of s-process Te, but these nucleosynthetic anomalies are barely resolvable given the analytical uncertainties. Hence, it is also conceivable that these effects reflect small unresolved analytical artifacts.

  5. Oxygen isotope composition of mafic magmas at Vesuvius (United States)

    Dallai, L.; Cioni, R.; Boschi, C.; D'Oriano, C.


    The oxygen isotope composition of olivine and clinopyroxene from four plinian (AD 79 Pompeii, 3960 BP Avellino), subplinian (AD 472 Pollena) and violent strombolian (Middle Age activity) eruptions were measured to constrain the nature and evolution of the primary magmas of the last 4000 years of Mt. Vesuvius activity. A large set of mm-sized crystals was accurately separated from selected juvenile material of the four eruptions. Crystals were analyzed for their major and trace element compositions (EPMA, Laser Ablation ICP-MS), and for 18O/16O ratios. As oxygen isotope composition of uncontaminated mantle rocks on world-wide scale is well constrained (δ18Oolivine = 5.2 ± 0.3; δ18Ocpx = 5.6 ± 0.3 ‰), the measured values can be conveniently used to monitor the effects of assimilation/contamination of crustal rocks in the evolution of the primary magmas. Instead, typically uncontaminated mantle values are hardly recovered in Italian Quaternary magmas, mostly due to the widespread occurrence of crustal contamination of the primary magmas during their ascent to the surface (e.g. Alban Hills, Ernici Mts., and Aeolian Islands). Low δ18O values have been measured in olivine from Pompeii eruption (δ18Oolivine = 5.54 ± 0.03‰), whereas higher O-compositions are recorded in mafic minerals from pumices or scoria of the other three eruptions. Measured olivine and clinopyroxene share quite homogeneous chemical compositions (Olivine Fo 85-90 ; Diopside En 45-48, respectively), and represent phases crystallized in near primary mafic magmas, as also constrained by their trace element compositions. Data on melt inclusions hosted in crystals of these compositions have been largely collected in the past demonstrating that they crystallized from mafic melt, basaltic to tephritic in composition. Published data on volatile content of these melt inclusions reveal the coexistence of dissolved water and carbon dioxide, and a minimum trapping pressure around 200-300 MPa, suggesting

  6. Purification of cerium, neodymium and gadolinium for low background experiments

    Directory of Open Access Journals (Sweden)

    Boiko R.S.


    Full Text Available Cerium, neodymium and gadolinium contain double beta active isotopes. The most interesting are 150Nd and 160Gd (promising for 0ν2β search, 136Ce (2β+ candidate with one of the highest Q2β. The main problem of compounds containing lanthanide elements is their high radioactive contamination by uranium, radium, actinium and thorium. The new generation 2β experiments require development of methods for a deep purification of lanthanides from the radioactive elements. A combination of physical and chemical methods was applied to purify cerium, neodymium and gadolinium. Liquid-liquid extraction technique was used to remove traces of Th and U from neodymium, gadolinium and for purification of cerium from Th, U, Ra and K. Co-precipitation and recrystallization methods were utilized for further reduction of the impurities. The radioactive contamination of the samples before and after the purification was tested by using ultra-low-background HPGe gamma spectrometry. As a result of the purification procedure the radioactive contamination of gadolinium oxide (a similar purification efficiency was reached also with cerium and neodymium oxides was decreased from 0.12 Bq/kg to 0.007 Bq/kg in 228Th, from 0.04 Bq/kg to <0.006 Bq/kg in 226Ra, and from 0.9 Bq/kg to 0.04 Bq/kg in 40K. The purification methods are much less efficient for chemically very similar radioactive elements like actinium, lanthanum and lutetium.

  7. Isotopic Composition of Cosmic Rays:. Results from the Cosmic Ray Isotope Spectrometer on the Ace Spacecraft (United States)

    Israel, M. H.

    Over the past seven years the Cosmic Ray Isotope Spectrometer (CRIS) on the ACE spacecraft has returned data with an unprecedented combination of excellent mass resolution and high statistics, describing the isotopic composition of elements from lithium through nickel in the energy interval ~ 50 to 500 MeV/nucleon. These data have demonstrated: * The time between nucleosynthesis and acceleration of the cosmic-ray nuclei is at least 105 years. The supernova in which nucleosynthesis takes place is thus not the same supernova that accelerates a heavy nucleus to cosmic-ray energy. * The mean confinement time of cosmic rays in the Galaxy is 15 Myr. * The isotopic composition of the cosmic-ray source is remarkably similar to that of solar system. The deviations that are observed, particularly at 22Ne and 58Fe, are consistent with a model in which the cosmic-ray source is OB associations in which the interstellar medium has solar-system composition enriched by roughly 20% admixture of ejecta from Wolf-Rayet stars and supernovae. * Cosmic-ray secondaries that decay only by electron capture provide direct evidence for energy loss of cosmic rays as they penetrate the solar system. This invited overview paper at ECRS 19 was largely the same as an invited paper presented a month earlier at the 8th Nuclei in the Cosmos Conference in Vancouver. The proceedings of that conference will be published shortly by Elsevier as a special edition of Nuclear Physics A. For further summary of results from CRIS, the reader is referred to URL and links on that page to CRIS and to Science News.

  8. Isotopic composition and origin of the precipitation in Northern Chile

    Energy Technology Data Exchange (ETDEWEB)

    Aravena, R. [Department of Earth Sciences, University of Waterloo, Waterloo (Canada); Suzuki, O. [Exploracion y Desarrollo de Recursos Hidricos, Santiago (Chile); Pena, H. [Direccion General de Aguas, Ministerio de Obras Publicas, Santiago (Chile); Pollastri, A. [Comision Chilena de Energia Nuclear, Santiago (Chile); Fuenzalida, H. [Departamento de Geofisica, Universidad of Chile, Santiago (Chile); Grilli, A. [Empresa Metropolitana de Obras Sanitarias, Santiago (Chile)


    A 3 a data set of isotopes in precipitation from northern Chile show a very distinct pattern, with {delta}{sup 18}O values ranging between -18 and -15per thousand at high altitude stations, compared to {delta}{sup 18}O values between -10 and -6per thousand at the lower altitude areas. The {sup 18}O-depleted values observed in the high altitude area, the Altiplano, are related to processes that affect the air masses that originated over the Atlantic, cross the Amazon Basin (continental effect), ascend the Andes (altitude effect) and precipitated (convective effect) in the Altiplano. It is postulated that a second source of moisture, associated with air masses from the Pacific, may contribute to the {sup 18}O-enriched values observed in the lower altitude areas. Similar isotopic patterns are documented in springs and groundwater indicating that the data presented in this paper are an accurate representation of the long term behavior isotopic composition of rain in northern Chile. (Copyright (c) 1999 Elsevier Science B.V., Amsterdam. All rights reserved.)

  9. On the isotopic composition of magmatic carbon in SNC meteorites (United States)

    Wright, I. P.; Grady, M. M.; Pillinger, C. T.


    SNC meteorites are thought, from many lines of evidence, to come from Mars. A line of investigation which has been pursued in our laboratory over the years involves measurement of the stable isotopic composition of carbon, in its various forms, in SNC meteorites. In order to establish a firm basis for studying the isotopic systematics of carbon in the martian surface environment, it is first necessary to try and constrain the delta C-13 of bulk Mars. Taking all of the available information, it would seem that the delta C-13 of the Earth's mantle lies somewhere in the range of -5 to -7 percent. Preliminary assessment of magnetic carbon in SNC meteorites, would tend to suggest a delta C-13 of 20 to 30 percent, which is conspicuously different from that of the terrestrial mantle. It is not obvious why there should be such a difference between the two planets, although many explanations are possible. One of these possibilities, that previous delta C-13 measurements for magnetic carbon in SNC meteorites are in error to some degree, is being actively investigated. The most recent results seem to constrain the theta C-13 of the magnetic carbon in SNC meteorites to about -20 percent, which is not at odds with previous estimates. As such, it is considered that a detailed investigation of the carbon isotopic systematics of martian surface materials does have the necessary information with which to proceed.

  10. 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


    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)

  11. Recent insights into intramolecular 13C isotope composition of biomolecules (United States)

    Gilbert, A.; Yamada, K.; Julien, M.; Yoshida, N.; Remaud, G.; Robins, R.


    In 1961 Abelson & Hoering shown that the intramolecular 13C distribution in amino acids was not homogeneous, namely the carboxylic acid positions were 13C-enriched compared with the mean of the remaining C-atoms in the molecule [1]. Nearly 20 years later, Monson & Hayes were able to demonstrate that even and odd positions in acetogenic fatty acids also showed non-statistical 13C isotope distributions, and that the pattern varied depending on the organism [2]. It took a further decade for the intramolecular 13C distribution in the key metabolite, glucose, to be defined [3]. Although informative, much of this work was incomplete, a number of positions having to be deduced by difference. This limitation arose mainly due to the lack of techniques enabling the separation and quantification of 13C isotopomers of the target molecule. In the past decade, quantitative 13C NMR has been developed for the determination of the intramolecular isotope composition of a given molecule with a precision of 1‰ or better [4]. This breakthrough has made possible a comprehensive view of the determinants governing intramolecular isotope composition of biological molecules. In particular, it can be shown that intramolecular pattern in sugars is influenced by the C-assimilation pathway and by post-photosynthetic fractionation associated with carbohydrate metabolism [5]. In addition, analysis by NMR of the alkyl chain of acetogenic lipids (fatty acids, n-alkanes) shows an alternation between odd and even C-atom positions, as observed by Monson& Hayes [2], throughout the molecule [6]. Overall, it is becoming apparent that this pattern is influenced by two principal metabolic factors: (i) the 13C pattern extant in the starting compounds; (ii) isotope fractionation associated with the enzymes involved in the biosynthetic pathway. On the whole, the determination of intramolecular isotope patterns in biomolecules allows better insights into the conditions and pathways by which they are formed

  12. Isotope composition of bicarbonate carbon in bed waters of oil and gas deposits

    Energy Technology Data Exchange (ETDEWEB)

    Golyshev, S.I.; Cherepnin, A.V.; Ivanov, V.G.; Manylova, L.S.


    A study is made of the isotope composition of bicarbonate carbon in bed waters of the Jurassic water complex in southeast West Siberia. It has been established that waters of empty and transcontour structures have isotope composition of carbon 5/sup 0//oo, while in waters which contact the hydrocarbon formations, the isotope composition of carbon is lighter on the average by 5-8/sup 0//oo. The isotope composition of bicarbonate carbon in bed waters reflects both the conditions for primary sedimentation, and secondary processes associated with organic matter transformation.

  13. The chlorine isotopic composition of Martian meteorites 1: Chlorine isotope composition of Martian mantle and crustal reservoirs and their interactions (United States)

    Williams, J. T.; Shearer, C. K.; Sharp, Z. D.; Burger, P. V.; McCubbin, F. M.; Santos, A. R.; Agee, C. B.; McKeegan, K. D.


    The Martian meteorites record a wide diversity of environments, processes, and ages. Much work has been done to decipher potential mantle sources for Martian magmas and their interactions with crustal and surface environments. Chlorine isotopes provide a unique opportunity to assess interactions between Martian mantle-derived magmas and the crust. We have measured the Cl-isotopic composition of 17 samples that span the range of known ages, Martian environments, and mantle reservoirs. The 37Cl of the Martian mantle, as represented by the olivine-phyric shergottites, NWA 2737 (chassignite), and Shergotty (basaltic shergottite), has a low value of approximately -3.8‰. This value is lower than that of all other planetary bodies measured thus far. The Martian crust, as represented by regolith breccia NWA 7034, is variably enriched in the heavy isotope of Cl. This enrichment is reflective of preferential loss of 35Cl to space. Most basaltic shergottites (less Shergotty), nakhlites, Chassigny, and Allan Hills 84001 lie on a continuum between the Martian mantle and crust. This intermediate range is explained by mechanical mixing through impact, fluid interaction, and assimilation-fractional crystallization.

  14. Continuous measurements of isotopic composition of water vapour on the East Antarctic Plateau (United States)

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


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

  15. Perchlorate in The Great Lakes: Distribution, Isotopic Composition and Origin (United States)

    Poghosyan, A.; Sturchio, N. C.; Jackson, W. A.; Guan, Y.; Eiler, J. M.; Hatzinger, P. B.


    Concentrations, stable chlorine and oxygen isotopic compositions, and 36Cl abundances of perchlorate were investigated in the five Laurentian Great Lakes. Samples were collected during monitoring cruises in 2007 and 2008 of the U.S. EPA's RV Lake Guardian and in 2010 at the water supply intake of Marquette, MI on the southern shore of Lake Superior. Concentrations of perchlorate were measured by IC/MS/MS at 24 locations, including one or two depth profiles in each lake. Mean concentrations (μg/L) are: Superior, 0.06 × 0.01; Michigan, 0.10 × 0.01; Huron, 0.11 × 0.01; Erie, 0.08 × 0.01, and Ontario, 0.09 × 0.01. Concentration vs. depth is nearly constant in each lake, indicating well-mixed conditions. Perchlorate was extracted from near-surface water by passing 15,000 to 80,000 L of water through 1-L cartridges containing Purolite A530E bifunctional anion-exchange resin. In the laboratory, perchlorate was eluted from the resin, purified, and precipitated as a >99% pure crystalline phase. Milligram amounts were recovered from each lake. Chlorine and oxygen isotopic analyses were performed at Caltech using the Cameca 7f-GEO SIMS instrument, following validation of the SIMS method with analyses of USGS-37 and USGS-38 isotopic reference materials. Results indicate a relatively narrow range in δ37Cl values (+2.9 to +3.9 ‰) and a wider range in δ18O values (-4.0 to +4.1 ‰), with a general geographic trend of increasing δ18O from west to east. Oxygen-17 was measured at UIC using dual-inlet IRMS of O2 produced by decomposition of KClO4. Great Lakes perchlorate has mass-independent oxygen isotopic variations with positive Δ17O values (+1.6 ‰ to +2.7 ‰) divided into two distinct groups: Lake Superior (+2.7 ‰) and the other four lakes (~ +1.7 ‰). The isotopic data indicate that perchlorate is dominantly of natural origin, having stable isotopic compositions resembling those of perchlorate from pre-industrial groundwaters in the western USA. The 36Cl

  16. Spectroscopic metrology for isotope composition measurements and transfer standards (United States)

    Anyangwe Nwaboh, Javis; Balslev-Harder, David; Kääriäinen, Teemu; Richmond, Craig; Manninen, Albert; Mohn, Joachim; Kiseleva, Maria; Petersen, Jan C.; Werhahn, Olav; Ebert, Volker


    The World Meteorological Organization (WMO) has identified greenhouse gases such as CO2, CH4 and N2O as critical for global climate monitoring. Other molecules such as CO that has an indirect effect of enhancing global warming are also monitored. WMO has stated compatibility goals for atmospheric concentration and isotope ratio measurements of these gases, e.g. 0.1 ppm for CO2 concentration measurements in the northern hemisphere and 0.01 ‰ for δ13C-CO2. For measurements of the concentration of greenhouse gases, gas analysers are typically calibrated with static gas standards e.g. traceable to the WMO scale or to the International System of Units (SI) through a national metrology institute. However, concentrations of target components, e.g. CO, in static gas standards have been observed to drift, and typically the gas matrix as well as the isotopic composition of the target component does not always reflect field gas composition, leading to deviations of the analyser response, even after calibration. The deviations are dependent on the measurement technique. To address this issue, part of the HIGHGAS (Metrology for high-impact greenhouse gases) project [1] focused on the development of optical transfer standards (OTSs) for greenhouse gases, e.g. CO2 and CO, potentially complementing gas standards. Isotope ratio mass spectrometry (IRMS) [2] is currently used to provide state-of-the-art high precision (in the 0.01 ‰ range) measurements for the isotopic composition of greenhouse gases. However, there is a need for field-deployable techniques such as optical isotope ratio spectroscopy (OIRS) that can be combined with metrological measurement methods. Within the HIGHGAS project, OIRS methods and procedures based on e.g. cavity enhanced spectroscopy (CES) and tunable diode laser absorption spectroscopy (TDLAS), matched to metrological principles have been established for the measurement of 13C/12C and 18O/16O ratios in CO2, 15N/14N ratios in N2O, and 13C/12C and 2H

  17. Evaluating Foraminifera as an Archive for Seawater Chromium Isotopic Composition (United States)

    Wang, X.; Planavsky, N.; Hull, P. M.; Tripati, A.; Reinhard, C.; Zou, H.; Elder, L. E.; Henehan, M. J.


    In recent years there has been growing interest in using chromium isotopes (δ53Cr) as a proxy to investigate the redox evolution of Earth's ocean-atmosphere system throughout geological history. Potential archives for seawater δ53Cr that have been identified to date include iron formations and organic-rich siliciclastic sediments. However, these types of sediments are not common and they are discontinuous over geologic time. As a result, alternative types of archives are needed. Here we evaluate the utility of foraminifera tests as a recorder of seawater δ53Cr. Core-tops used were from different ocean basins. Mono-specific samples of Globigerinoides sacculifer, Orbulina universa, Pulleniatina obliquiloculata, Globoratalia crassula-crassaformis, Globoratalia truncatulinoides, and Globigerinella siphonifera were isolated to investigate inter-species isotope fractionation. Chromium concentrations were measured by isotope dilution method to be 0.1-0.3 μg/g. The δ53Cr values of these species range from 0.2‰ to 2.4‰, with an analytical uncertainty of 0.3‰ (95% confidence). Despite the high analytical uncertainty due to the extremely low levels of Cr present, there is still large detectable variation in foraminiferal δ53Cr values, which overlap presently available seawater values (Bonnand et al., 2013; Scheiderich et al., 2015). Possible explanations for such variations in foraminiferal δ53Cr values include heterogeneity of seawater δ53Cr in the modern oceans, and/or photobiochemical redox cycling of Cr in the surface oceans. Therefore, care should be taken when using foraminifera to reconstruct past seawater δ53Cr values. ReferencesBonnand, P., James, R., Parkinson, I., Connelly, D., Fairchild, I., 2013. The chromium isotopic composition of seawater and marine carbonates. Earth and Planetary Science Letters, 382: 10-20. Scheiderich, K., Amini, M., Holmden, C., Francois, R., 2015. Global variability of chromium isotopes in seawater demonstrated by Pacific

  18. Isotopic composition of the ice cores obtained on the Western Plateau of the Mt Elbrus

    Directory of Open Access Journals (Sweden)

    A. V. Kozachek


    Full Text Available The results of the isotopic investigations of several ice cores obtained at the Western Plateau of Mt. Elbrus (the Caucasus are presented. There is a distinct seasonal cycle in the isotopic composition record in these cores. Mean annual and seasonal values of the isotopic composition and accumulation rate were reconstructed for 89 years (1924–2012. These values were compared with the available regional meteorological data and the atmospheric circulation characteristics. It was shown that in the summer season the isotopic composition reflects the local temperature while in winter it depends on the atmospheric circulation.

  19. Osmium Isotopic Composition of the Sumbar Cretaceous- Tertiary Boundary, Turkmenia (United States)

    Meisel, T.; Krahenbuhl, U.; Nazarov, M. A.


    Turekian (1982) propagated the use of the osmium isotopic composition as a cosmic indicator for the origin of the high osmium (and iridium) layers at the K/T boundaries. He did not consider the osmium isotopic signature of the terrestrial mantle, which also has a chondritic evolution of the Re-Os system. Osmium cannot serve alone as an infallible indicator of the impact theory, but interesting results can be obtained from their investigation. Different K/T boundary section have been analyzed so far for ^187Os/^186Os. An overview of the values is presented in the table. Boundary Clay layer Os ratio Reference Stevns Klint fish clay 1.66 Luck and Turekian, 1983 Woodside Creek 1.12 Lichte et al., 1986 Raton Basin 1.23 Kraehenbuehl et al., 1988 Raton Basin (several) 1.15-1.23 Esser and Turekian, 1989 Sumbar (0-1 cm) 1.16 This work We obtained a complete marine section of the K/T boundary in southern Turkmenia (decribed by Alekseyev, 1988). It shows a very high Ir concentration (66 ppb) at the boundary layer and a remarkable Ir enrichment over crustal rocks continuing up to 30 cm above the boundary. Our aim of this investigation is to analyze several samples from above and below the boundary for the ^187Os/^186Os ratio to obtain a complete picture of the isotopic evolution of the section. We want to evaluate mixing of Os with chondritic ratios with Os from upper crustal rocks. Another goal is to investigate a mobilization of Os. So far only one sample has been analyzed with NTI-MS after fire assay digestion of the sample. The sample 0 to 1 cm has an ^187Os/^186Os ratio of 1.162 +- 13, which is quite low. We expect an even lower value for the boundary clay (0 cm) itself not taking into account a contribution of radiogenic osmium from the decay of terrestrial rhenium. This might put this K/T boundary section closest of all to the present day chondritic value (approx. 1.05). Further analysis will be presented at the meeting. References Alekseyev A. S., Nazarov M. A

  20. Triple sulfur isotope composition of Late Archean seawater sulfate (United States)

    Paris, G.; Fischer, W. W.; Sessions, A. L.; Adkins, J. F.


    Multiple sulfur isotope ratios in Archean sedimentary rocks have provided powerful insights into the behavior of the ancient sulfur cycle, the redox state of fluid Earth, and the timing of the rise of atmospheric oxygen [1]. Most processes fractionate sulfur isotopes in proportion to their mass differences, but the Archean sulfur isotope record is marked by pronounced mass-independent fractionation (MIF, Δ33S≠0). The origin of these signatures has been traditionally interpreted as the result of photolysis of SO2 from short wavelength UV light, with positive Δ33S values recorded in pyrite and negative Δ33S values in sulfate-bearing phases [2]. This long-held hypothesis rests on observations of negative Δ33S from enigmatic barite occurrences from mixed volcanic sedimentary strata in Mesoarchean greenstone terrains. Despite forming the framework for understanding Archean sulfur cycle processes [3], it is largely untested [3]. It is largely untested. Consequently, the biggest challenge to our current understanding of the early sulfur cycle is a poor understanding of the isotopic composition of seawater sulfate. Sulfate evaporite minerals are absent from Archean strata and the sulfur isotope record is written entirely by measurements of pyrite. Carbonate associated sulfate (CAS) provides an important archive for assaying the isotopic composition of ancient seawater sulfate It has been exploited in many studies of Phanerozoic and Proterozoic sulfate but have been only marginally used thus far for Archean samples because of the extremely low concentration of CAS in limestones and dolomites from this era. We have developed a novel MC-ICP-MS approach to solve this problem [4]. This new method lowers the detection limit by up to three orders of magnitude for δ34S and Δ33S measurements, enabling to work on a few nmols of sulfate which represent only tens of mg of sample powders micromilled from specific carbonate textures. Two stratigraphic sections from the 2

  1. Isotopic composition of sulfate accumulations, Northern Calcareous Alps, Austria (United States)

    Bojar, Ana-Voica; Halas, Stanislaw; Bojar, Hans-Peter; Trembaczowski, Andrzej


    The Eastern Alps are characterised by the presence of three main tectonic units, such as the Lower, Middle and Upper Austroalpine, which overlie the Penninicum (Tollmann, 1977). The Upper Austroalpine unit consists of the Northern Calcareous Alps (NCA) overlying the Greywacke zone and corresponding to the Graz Paleozoic, Murau Paleozoic and the Gurktal Nappe. Evaporitic rocks are lacking in the later ones. The Northern Calcareous Alps are a detached fold and thrust belt. The sedimentation started in the Late Carboniferous or Early Permian, the age of the youngest sediments being Eocene. The NCA are divided into the Bajuvaric, Tirolic and Juvavic nappe complexes. The evaporitic Haselgebirge Formation occurs in connection with the Juvavic nappe complex at the base of the Tirolic units (Leitner et al., 2013). The Haselgebirge Formation consists mainly of salt, shales, gypsum and anhydrite and includes the oldest sediments of the NCA. The age of the Haselgebirge Formation, established by using spors and geochronological data, is Permian to Lower Triassic. For the Northern Calcareous Alps, the mineralogy of sulphate accumulations consists mainly of gypsum and anhydrite and subordonates of carbonates. The carbonates as magnesite, dolomite and calcite can be found either as singular crystals or as small accumulations within the hosting gypsum. Sulfides (sphalerite, galena, pyrite), sulfarsenides (enargite, baumhauerite) and native sulphur enrichments are known from several deposits (Kirchner, 1987; Postl, 1990). The investigated samples were selected from various gypsum and halite rich deposits of the Northern Calcareous Alps. A total of over 20 samples were investigated, and both oxygen and sulfur isotopic composition were determined for anhydrite, gyps, polyhalite, blödite and langbeinite. The sulfur isotopic values vary between 10.1 to 14 ‰ (CDT), with three values higher than 14 ‰. The Oxygen isotopic values show a range from 9 to 23 ‰ (SMOW). The sulfur

  2. Oxygen Isotopic Composition of Carbon Dioxide in the Middle Atmosphere (United States)

    Liang, M.; Blake, G. A.; Lewis, B. R.; Yung, Y. L.


    The isotopic composition of long-lived trace gases provides a window into atmospheric transport and chemistry. Carbon dioxide is a particularly powerful tracer, because its abundance remains >100 ppmv in the mesosphere. Current models consider O3 as the main source of O(1D) in the mesosphere, but we note that the photolysis of 16O17O and 16O18O by solar Lyman-α radiation yields O(1D) 10-100 times more enriched in 17O and 18O than that from ozone photodissociation. We therefore incorporate both photochemical sources into stratospheric and mesospheric chemical transport models that quantitatively predict the unusual enhancement of 17O in CO2 from the middle atmosphere. New laboratory and atmospheric measurements are proposed to test our model and validate the use of CO2 isotopic fractionation as a tracer of atmospheric chemical and dynamical processes. Once fully understood the `anomalous' oxygen signature in CO2 can be used in turn to study biogeochemical cycles, in particular to constrain the gross carbon fluxes between the atmosphere and terrestrial biosphere.

  3. Volatile Concentrations and H-Isotope Composition of Unequilibrated Eucrites (United States)

    Sarafian, Adam R.; Nielsen, Sune G.; Marschall, Horst R.; Gaetani, Glenn A.; Hauri, Erik H.; Righter, Kevin; Berger, Eve L.


    Eucrites are among the oldest and best studied asteroidal basalts (1). They represent magmatism that occurred on their parent asteroid, likely 4-Vesta, starting at 4563 Ma and continuing for approx. 30 Myr. Two hypotheses are debated for the genesis of eucrites, a magma ocean model (2), and a mantle partial melting model. In general, volatiles (H, C, F, Cl) have been ignored for eucrites and 4-Vesta, but solubility of wt% levels of H2O are possible at Vestan interior PT conditions. Targeted measurements on samples could aid our understanding considerably. Recent studies have found evidence of volatile elements in eucrites, but quantifying the abundance of volatiles remains problematic (6). Volatile elements have a disproportionately large effect on melt properties and phase stability, relative to their low abundance. The source of volatile elements can be elucidated by examining the hydrogen isotope ratio (D/H), as different H reservoirs have drastically different H isotope compositions. Recent studies of apatite in eucrites have shown that the D/H of 4-Vesta matches that of Earth and carbonaceous chondrites, however, the D/H of apatites may not represent the D/H of a primitive 4-Vesta melt due to the possibility of degassing prior to the crystallization of apatite. Therefore, the D/H of early crystallizing phases must be measured to determine if the D/H of 4-Vesta is equal to that of the Earth and carbonaceous chondrites.

  4. Nitrate isotopic composition and ancillary variables (land use, redox, excess N2, age, water isotopics) in California groundwater (United States)

    Veale, Nathan; Moran, Jean; Visser, Ate; Singleton, Michael; Esser, Bradley


    Nitrate is a critical water quality issue in California, the United States and the world. Lawrence Livermore National Laboratory (LLNL) has compiled a large, unique database of California groundwater nitrate isotopic compositions (δ15N-NO3 and δ18O-NO3), acquired largely through more than a decade of coordination with the State of California Groundwater Ambient Monitoring and Assessment (GAMA) program. The water samples are predominantly from shallow aquifers accessed by domestic and monitoring wells. The database of >1,300 nitrate isotopic compositions includes a number of important ancillary parameters: DO, ORP and DOC (measured for 18% of samples); excess air and dissolved N2 (24%); water isotopic composition (δ18O-H2O and δD-H2O) (43%); and tritium/3He groundwater age (27%). Methods used at LLNL include sample preparation by the denitrifier method (for δ15N-NO3 and δ18O-NO3) and Isotope Ratio Mass Spectrometry with (δ15N-NO3 and δ18O-NO3 and δ18O-H2O and δD-H2O), Noble Gas Mass Spectrometry (NGMS; for excess air and groundwater age), and Membrane Inlet Mass Spectrometry (MIMS; for major dissolved gases and excess N2). Redox indicators (DO, ORP and DOC) in conjunction with excess N2, groundwater age, and nitrate isotopic composition are used to assess the presence or absence, and potentially the rate of, saturated-zone denitrification. Comparison of δ18O-NO3 to δ18O-H2O isotopic composition is used to distinguish synthetic nitrate from nitrification of reduced forms of nitrogen as a source of groundwater nitrate. Groundwater age is used to discern timing and temporal trends in groundwater nitrate isotopic composition. The relationship of nitrate isotopic composition to ancillary parameters (redox, excess N2, water isotopic composition and groundwater age) is explored, along with its relationship to well location, screened interval, and land use, with a focus on the extent of saturated-zone denitrification and the significance of synthetic nitrate as

  5. Rapid neodymium release to marine waters from lithogenic sediments in the Amazon estuary (United States)

    Rousseau, Tristan C. C.; Sonke, Jeroen E.; Chmeleff, Jérôme; van Beek, Pieter; Souhaut, Marc; Boaventura, Geraldo; Seyler, Patrick; Jeandel, Catherine


    Rare earth element (REE) concentrations and neodymium isotopic composition (ɛNd) are tracers for ocean circulation and biogeochemistry. Although models suggest that REE release from lithogenic sediment in river discharge may dominate all other REE inputs to the oceans, the occurrence, mechanisms and magnitude of such a source are still debated. Here we present the first simultaneous observations of dissolved (<0.45 μm), colloidal and particulate REE and ɛNd in the Amazon estuary. A sharp drop in dissolved REE in the low-salinity zone is driven by coagulation of colloidal matter. At mid-salinities, total dissolved REE levels slightly increase, while ɛNd values are shifted from the dissolved Nd river endmember (−8.9) to values typical of river suspended matter (−10.6). Combining a Nd isotope mass balance with apparent radium isotope ages of estuarine waters suggests a rapid (3 weeks) and globally significant Nd release by dissolution of lithogenic suspended sediments. PMID:26158849

  6. Stable isotope composition of atmospheric carbon monoxide. A modelling study

    Energy Technology Data Exchange (ETDEWEB)

    Gromov, Sergey S.


    This study aims at an improved understanding of the stable carbon and oxygen isotope composition of the carbon monoxide (CO) in the global atmosphere by means of numerical simulations. At first, a new kinetic chemistry tagging technique for the most complete parameterisation of isotope effects has been introduced into the Modular Earth Submodel System (MESSy) framework. Incorporated into the ECHAM/MESSy Atmospheric Chemistry (EMAC) general circulation model, an explicit treatment of the isotope effects on the global scale is now possible. The expanded model system has been applied to simulate the chemical system containing up to five isotopologues of all carbon- and oxygen-bearing species, which ultimately determine the δ{sup 13}C, δ{sup 18}O and Δ{sup 17}O isotopic signatures of atmospheric CO. As model input, a new stable isotope-inclusive emission inventory for the relevant trace gases has been compiled. The uncertainties of the emission estimates and of the resulting simulated mixing and isotope ratios have been analysed. The simulated CO mixing and stable isotope ratios have been compared to in-situ measurements from ground-based observatories and from the civil-aircraft-mounted CARIBIC-1 measurement platform. The systematically underestimated {sup 13}CO/{sup 12}CO ratios of earlier, simplified modelling studies can now be partly explained. The EMAC simulations do not support the inferences of those studies, which suggest for CO a reduced input of the highly depleted in {sup 13}C methane oxidation source. In particular, a high average yield of 0.94 CO per reacted methane (CH{sub 4}) molecule is simulated in the troposphere, to a large extent due to the competition between the deposition and convective transport processes affecting the CH{sub 4} to CO reaction chain intermediates. None of the other factors, assumed or disregarded in previous studies, however hypothesised to have the potential in enriching tropospheric CO in {sup 13}C, were found significant

  7. Tooth enamel maturation reequilibrates oxygen isotope compositions and supports simple sampling methods (United States)

    Trayler, Robin B.; Kohn, Matthew J.


    Oxygen isotope and major element zoning patterns of several disparate ungulate teeth were collected to evaluate the timing and geometry of enamel formation, records of isotope zoning, and tooth enamel sampling strategies. Isotopic zoning in mammalian tooth enamel encodes a sub-annual time series of isotopic variation of an animal's body water composition, with a damping factor that depends on the specifics of how enamel mineralizes. Enamel formation comprises two stages: precipitation of appositional enamel with a high CO3:PO4 ratio, followed by precipitation of maturational enamel with a lower CO3:PO4. If appositional and maturational enamel both contribute to isotope compositions (but with different CO3:PO4), and if isotope compositions vary seasonally, paired δ18O values from CO3 and PO4 profiles should show a spatial separation. CO3 isotope patterns should be shifted earlier seasonally than PO4 isotope patterns. Such paired profiles for new and published data show no resolvable shifts, i.e. CO3 and PO4 δ18O profiles show coincident maxima and minima. This coincidence suggests that enamel maturation reequilibrates appositional isotope compositions. If enamel maturation establishes enamel isotope compositions, the geometry of maturation, not apposition, should be considered when devising sampling protocols. X-ray maps of Ca zoning show that the majority of enamel (inner and middle layers) mineralizes heavily at a high angle to the external tooth surface and the enamel-dentine junction over length scales of 2-4 mm, while the outer enamel surface mineralizes more slowly. These data suggest that isotopic sampling strategies should parallel maturational geometry and focus on interior enamel to improve data fidelity. The magnitude of isotopic damping is also smaller than implied in previous studies, so tooth enamel zoning more closely reflects original body water isotopic variations than previously assumed.

  8. Isotopic and Elemental Composition of Roasted Coffee as a Guide to Authenticity and Origin. (United States)

    Carter, James F; Yates, Hans S A; Tinggi, Ujang


    This study presents the stable isotopic and elemental compositions of single-origin, roasted coffees available to retail consumers. The δ(13)C, δ(15)N, and δ(18)O compositions were in agreement with those previously reported for green coffee beans. The δ(15)N composition was seen to be related to organic cultivation, reflected in both δ(2)H and δ(18)O compositions. The δ(13)C composition of extracted caffeine differed little from that of the bulk coffee. Stepwise discriminant analysis with jackknife tests, using isotopic and elemental data, provided up to 77% correct classification of regions of production. Samples from Africa and India were readily classified. The wide range in both isotopic and elemental compositions of samples from other regions, specifically Central/South America, resulted in poor discrimination between or within these regions. Simpler X-Y and geo-spatial plots of the isotopic data provided effective visual means to distinguish between coffees from different regions.

  9. Light element isotopic compositions of cometary matter returned by the STARDUST mission

    Energy Technology Data Exchange (ETDEWEB)

    McKeegan, K D; Aleon, J; Bradley, J; Brownlee, D; Busemann, H; Butterworth, A; Chaussidon, M; Fallon, S; Floss, C; Gilmour, J; Gounelle, M; Graham, G; Guan, Y; Heck, P R; Hoppe, P; Hutcheon, I D; Huth, J; Ishii, H; Ito, M; Jacobsen, S B; Kearsley, A; Leshin, L A; Liu, M; Lyon, I; Marhas, K; Marty, B; Matrajt, G; Meibom, A; Messenger, S; Mostefaoui, S; Nakamura-Messenger, K; Nittler, L; Palma, R; Pepin, R O; Papanastassiou, D A; Robert, F; Schlutter, D; Snead, C J; Stadermann, F J; Stroud, R; Tsou, P; Westphal, A; Young, E D; Ziegler, K; Zimmermann, L; Zinner, E


    Hydrogen, carbon, nitrogen, and oxygen isotopic compositions are heterogeneous among comet 81P/Wild2 particle fragments, however extreme isotopic anomalies are rare, indicating that the comet is not a pristine aggregate of presolar materials. Non-terrestrial nitrogen and neon isotope ratios suggest that indigenous organic matter and highly volatile materials were successfully collected. Except for a single circumstellar stardust grain, silicate and oxide minerals have oxygen isotopic compositions consistent with solar system origin. One refractory grain is {sup 16}O-enriched like refractory inclusions in meteorites, suggesting formation in the hot inner solar nebula and large-scale radial transport prior to comet accretion in the outer solar system.

  10. Constraints on the neodymium (Nd) oceanic cycle in the Mediterranean Sea using a high resolution coupled model (United States)

    Ayache, Mohamed; Jeandel, Catherine; Dutay, Jean-claude; Arsouze, Thomas


    Neodymium isotopic composition (Nd IC) is a tracer of oceanic circulation and lithogenic inputs to the ocean. An extensive compilation of published Nd isotopic values was realized in order to establish a database and a map of ɛNd and Nd concentrations characterizing all the Mediterranean margins. This was built based on different kinds of samples: riverine solid discharge deposited on the shelf, sedimentary material collected along the margins and geological material above or close to an oceanic margin (following Jeandel et al., 2007). The margin Nd isotopic signatures vary from non-radiogenic values around the Gulf of Lions (Nd IC values between -11.5 and -10), to radiogenic values around the Aegean and the Levantine sub-basins (Nd IC up to +6). Such West-East variation was also observed in the seawater data, which are becoming more radiogenic along the eastward circulation in the Mediterranean Sea (Tachikawa et al., 2004). The Nd budget proposed by these authors raised the hypothesis that the exchange of Nd along the margins could play a significant role in driving the oceanic distribution of this tracer. On a more global scale, it was further demonstrated and modelled that dissolved/particulate exchanges between continental margin sediments and open ocean (termed boundary exchange, BE), could be the dominant source-sink terms that determine the distribution of neodymium isotopes in the global ocean (Lacan and Jeandel, 2005a, Arsouze et al 2009). But this global scale study with it low-resolution configuration ORCA2 (2° of horizontal resolution) could not resolve many local and regional-scale features Our purpose is to test this hypothesis for the first time in the Mediterranean Sea by using a high resolution regional coupled model (1/12° of horizontal resolution). In a first approach we considered that boundary exchange is the only term governing Nd distribution in the Mediterranean Sea (other sources have been neglected). This aimed to validate the "Boundary

  11. Modelling and interpreting the isotopic composition of water vapour in convective updrafts

    Directory of Open Access Journals (Sweden)

    M. Bolot


    Full Text Available The isotopic compositions of water vapour and its condensates have long been used as tracers of the global hydrological cycle, but may also be useful for understanding processes within individual convective clouds. We review here the representation of processes that alter water isotopic compositions during processing of air in convective updrafts and present a unified model for water vapour isotopic evolution within undiluted deep convective cores, with a special focus on the out-of-equilibrium conditions of mixed-phase zones where metastable liquid water and ice coexist. We use our model to show that a combination of water isotopologue measurements can constrain critical convective parameters, including degree of supersaturation, supercooled water content and glaciation temperature. Important isotopic processes in updrafts include kinetic effects that are a consequence of diffusive growth or decay of cloud particles within a supersaturated or subsaturated environment; isotopic re-equilibration between vapour and supercooled droplets, which buffers isotopic distillation; and differing mechanisms of glaciation (droplet freezing vs. the Wegener–Bergeron–Findeisen process. As all of these processes are related to updraft strength, particle size distribution and the retention of supercooled water, isotopic measurements can serve as a probe of in-cloud conditions of importance to convective processes. We study the sensitivity of the profile of water vapour isotopic composition to differing model assumptions and show how measurements of isotopic composition at cloud base and cloud top alone may be sufficient to retrieve key cloud parameters.

  12. Controls on the stable isotope compositions of travertine from hyperalkaline springs in Oman: Insights from clumped isotope measurements (United States)

    Falk, E. S.; Guo, W.; Paukert, A. N.; Matter, J. M.; Mervine, E. M.; Kelemen, P. B.


    Carbonate formation at hyperalkaline springs is typical of serpentinization in peridotite massifs worldwide. These travertines have long been known to exhibit large variations in their carbon and oxygen isotope compositions, extending from apparent equilibrium values to highly depleted values. However, the exact causes of these variations are not well constrained. We analyzed a suite of well-characterized fresh carbonate precipitates and travertines associated with hyperalkaline springs in the peridotite section of the Samail ophiolite, Sultanate of Oman, and found their clumped isotope compositions vary systematically with formation environments. Based on these findings, we identified four main processes controlling the stable isotope compositions of these carbonates. These include hydroxylation of CO2, partial isotope equilibration of dissolved inorganic carbon, mixing between isotopically distinct carbonate end-members, and post-depositional recrystallization. Most notably, in fresh crystalline films on the surface of hyperalkaline springs and in some fresh carbonate precipitates from the bottom of hyperalkaline pools, we observed large enrichments in Δ47 (up to ∼0.2‰ above expected equilibrium values) which accompany depletions in δ18O and δ13C, yielding about 0.01‰ increase in Δ47 and 1.1‰ decrease in δ13C for every 1‰ decrease in δ18O, relative to expected equilibrium values. This disequilibrium trend, also reflected in preserved travertines ranging in age from modern to ∼40,000 years old, is interpreted to arise mainly from the isotope effects associated with the hydroxylation of CO2 in high-pH fluids and agrees with our first-order theoretical estimation. In addition, in some fresh carbonate precipitates from the bottom of hyperalkaline pools and in subsamples of one preserved travertine terrace, we observed additional enrichments in Δ47 at intermediate δ13C and δ18O, consistent with mixing between isotopically distinct carbonate end

  13. Seasonality of Oxygen isotope composition in cow (Bos taurus) hair and its model interpretation (United States)

    Chen, Guo; Schnyder, Hans; Auerswald, Karl


    Oxygen isotopes in animal and human tissues are expected to be good recorders of geographical origin and migration histories based on the isotopic relationship between hair oxygen and annual precipitation and the well-known spatial pattern of oxygen isotope composition in meteoric water. However, seasonal variation of oxygen isotope composition may diminish the origin information in the tissues. Here the seasonality of oxygen isotope composition in tail hair was investigated in a domestic suckler cow (Bos taurus) that underwent different ambient conditions, physiological states, and keeping and feeding strategies during five years. A detailed mechanistic model involving in ambient conditions, soil properties and animal physiology was built to explain this variation. The measured oxygen isotope composition in hair was significantly related (pwater in a regression analysis. Modelling suggested that this relation was only partly derived from the direct influence of feed moisture. Ambient conditions (temperature, moisture) did not only influence the isotopic signal of precipitation but also affected the animal itself (drinking water demand, transcutaneous vapor etc.). The clear temporal variation thus resulted from complex interactions with multiple influences. The twofold influence of ambient conditions via the feed and via the animal itself is advantageous for tracing the geographic origin because the oxygen isotope composition is then less influenced by variations in moisture uptake; however, it is unfavorable for indicating the production system, e.g. to distinguish between milk produced from fresh grass or from silage.

  14. Clumped Isotope Composition of Cold-Water Corals: A Role for Vital Effects? (United States)

    Spooner, P.; Guo, W.; Robinson, L. F.


    Measurements on a set of cold-water corals (mainly Desmophyllum dianthus) have suggested that their clumped isotope composition could serve as a promising proxy for reconstructing paleocean temperatures. Such measurements have also offered support for certain isotope models of coral calcification. However, there are differences in the clumped isotope compositions between warm-water and cold-water corals, suggesting that different kinds of corals could have differences in their biocalcification processes. In order to understand the systematics of clumped isotope variations in cold-water corals more fully, we present clumped isotope data from a range of cold-water coral species from the tropical Atlantic and the Southern Ocean.Our samples were either collected live or recently dead (14C ages biocalcification may not apply equally well to all corals. Clumped isotope vital effects may be present in certain cold-water corals as they are in warm-water corals, complicating the use of this paleoclimate proxy.

  15. Sources and input mechanisms of hafnium and neodymium in surface waters of the Atlantic sector of the Southern Ocean (United States)

    Stichel, Torben; Frank, Martin; Rickli, Jörg; Hathorne, Ed C.; Haley, Brian A.; Jeandel, Catherine; Pradoux, Catherine


    Radiogenic isotopes of hafnium (Hf) and neodymium (Nd) are powerful tracers for water mass transport and trace metal cycling in the present and past oceans. However, due to the scarcity of available data the processes governing their distribution are not well understood. Here we present the first combined dissolved Hf and Nd isotope and concentration data from surface waters of the Atlantic sector of the Southern Ocean. The samples were collected along the Zero Meridian, in the Weddell Sea and in the Drake Passage during RV Polarstern expeditions ANTXXIV/3 and ANTXXIII/3 in the frame of the International Polar Year (IPY) and the GEOTRACES program. The general distribution of Hf and Nd concentrations in the region is similar. However, at the northernmost station located 200 km southwest of Cape Town a pronounced increase of the Nd concentration is observed, whereas the Hf concentration is minimal, suggesting much less Hf than Nd is released by the weathering of the South African Archean cratonic rocks. From the southern part of the Subtropical Front (STF) to the Polar Front (PF) Hf and Nd show the lowest concentrations (data show significant increases to ɛHf = 6.1 and ɛNd = -4.0 documenting exchange of seawater Nd and Hf with the Antarctic Peninsula. In the open Southern Ocean the Nd isotope compositions are relatively homogeneous (ɛNd ˜ -8 to -8.5) towards the STF, within the Antarctic Circumpolar Current, in the Weddell Gyre, and the Drake Passage. The Hf isotope compositions in the entire study area only show a small range between ɛHf = + 6.1 and +2.8 support Hf to be more readily released from young mafic rocks compared to old continental ones. The Nd isotope composition ranges from ɛNd = -18.9 to -4.0 showing Nd isotopes to be a sensitive tracer for the provenance of weathering inputs into surface waters of the Southern Ocean.

  16. Hydrogen and oxygen in brine shrimp chitin reflect environmental water and dietary isotopic composition (United States)

    Nielson, Kristine E.; Bowen, Gabriel J.


    Hydrogen and oxygen isotope ratios of the common structural biopolymer chitin are a potential recorder of ecological and environmental information, but our understanding of the mechanisms of incorporation of H and O from environmental substrates into chitin is limited. We report the results of a set of experiments in which the isotopic compositions of environmental water and diet were varied independently in order to assess the contribution of these variables to the H and O isotopic composition of Artemia franciscana chitin. Hydrogen isotope ratios of chitin were strongly linearly correlated with both food and water, with approximately 26% of the hydrogen signal reflecting food and approximately 38% reflecting water. Oxygen isotopes were also strongly correlated with the isotopic composition of water and food, but whereas 69% of oxygen in chitin exchanged with environmental water, only 10% was derived from food. We propose that these observations reflect the position-specific, partial exchange of H and O atoms with brine shrimp body water during the processes of digestion and chitin biosynthesis. Comparison of culture experiments with a set of natural samples collected from the Great Salt Lake, UT in 2006 shows that, with some exceptions, oxygen isotope compositions of chitin track those of water, whereas hydrogen isotopes vary inversely with those of lake water. The different behavior of the two isotopic systems can be explained in terms of a dietary shift from allochthonous particulate matter with relatively higher δ 2H values in the early spring to autochthonous particulate matter with significantly lower δ 2H values in the late summer to autumn. These results suggest oxygen in chitin may be a valuable proxy for the oxygen isotopic composition of environmental water, whereas hydrogen isotope values from the same molecule may reveal ecological and biogeochemical changes within lakes.

  17. The iron isotope composition of enstatite meteorites: Implications for their origin and the metal/sulfide Fe isotopic fractionation factor (United States)

    Wang, Kun; Savage, Paul S.; Moynier, Frédéric


    Despite their unusual chemical composition, it is often proposed that the enstatite chondrites represent a significant component of Earth’s building materials, based on their terrestrial similarity for numerous isotope systems. In order to investigate a possible genetic relationship between the Fe isotope composition of enstatite chondrites and the Earth, we have analyzed 22 samples from different subgroups of the enstatite meteorites, including EH and EL chondrites, aubrites (main group and Shallowater) and the Happy Canyon impact melt. We have also analyzed the Fe isotopic compositions of separated (magnetic and non-magnetic) phases from both enstatite chondrites and achondrites. On average, EH3-5 chondrites (δ56Fe = 0.003 ± 0.042‰; 2 standard deviation; n = 9; including previous literature data) as well as EL3 chondrites (δ56Fe = 0.030 ± 0.038‰; 2 SD; n = 2) have identical and homogeneous Fe isotopic compositions, indistinguishable from those of the carbonaceous chondrites and average terrestrial peridotite. In contrast, EL6 chondrites display a larger range of isotopic compositions (-0.180‰ < δ56Fe < 0.181‰; n = 11), a result of mixing between isotopically distinct mineral phases (metal, sulfide and silicate). The large Fe isotopic heterogeneity of EL6 is best explained by chemical/mineralogical fragmentation and brecciation during the complex impact history of the EL parent body. Enstatite achondrites (aubrites) also exhibit a relatively large range of Fe isotope compositions: all main group aubrites are enriched in the light Fe isotopes (δ56Fe = -0.170 ± 0.189‰; 2 SD; n = 6), while Shallowater is, isotopically, relatively heavy (δ56Fe = 0.045 ± 0.101‰; 2 SD; n = 4; number of chips). We take this variation to suggest that the main group aubrite parent body formed a discreet heavy Fe isotope-enriched core, whilst the Shallowater meteorite is most likely from a different parent body where core and silicate material remixed. This could be

  18. 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.


    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 ...

  19. Near Surface CO2 Triple Oxygen Isotope Composition

    Directory of Open Access Journals (Sweden)

    Sasadhar Mahata


    Full Text Available The isotopic composition of carbon dioxide in the atmosphere is a powerful tool for constraining its sources and sinks. In particular, the 17O oxygen anomaly [Δ17O = 1000 × ln(1 + δ17O/1000 - 0.516 × 1000 × ln(1 + δ18O/1000], with a value > 0.5‰ produced in the middle atmosphere, provides an ideal tool for probing the exchange of carbon dioxide between the biosphere/hydrosphere and atmosphere. The biosphere/hydrosphere and anthropogenic emissions give values ≤ 0.3‰. Therefore, any anomaly in near surface CO2 would reflect the balance between stratospheric input and exchange with the aforementioned surface sources. We have analyzed Δ17O values of CO2 separated from air samples collected in Taipei, Taiwan, located in the western Pacific region. The obtained mean anomaly is 0.42 ± 0.14‰ (1-σ standard deviation, in good agreement with model prediction and a published decadal record. Apart from typically used δ13C and δ18O values, the Δ17O value could provide an additional tracer for constraining the carbon cycle.

  20. Q-Switching in a Neodymium Laser (United States)

    Holgado, Warein; Sola, Inigo J.; Jarque, Enrique Conejero; Jarabo, Sebastian; Roso, Luis


    We present a laboratory experiment for advanced undergraduate or graduate laser-related classes to study the performance of a neodymium laser. In the experiment, the student has to build the neodymium laser using an open cavity. After that, the cavity losses are modulated with an optical chopper located inside, so the Q-switching regime is…

  1. Monitoring the water vapor isotopic composition in the temperate North Atlantic (United States)

    Sveinbjörnsdottir, Arny E.; Steen-Larsen, Hans Christian; Jonsson, Thorsteinn; Johnsen, Sigfus J.


    Water stable isotopes have during many decades been used as climate proxies and indicators for variations in the hydrological cycle. However we are to a great extent still using simple empirical relationships without any deeper theoretical understanding. In order to properly relate changes in the climate and hydrological cycle to changes in the observed stable water isotopic signal we must understand the underlying physical processes. Furthermore it is a challenge for General Climate Models to adequately represent the isotopes in the hydrological cycle because of lack of in-situ measurements of the atmospheric water-vapor composition in the source regions. During the fall of 2010 we installed an autonomous water vapor spectroscopy laser (from Los Gatos Research) in a lighthouse on the South Coast of Iceland (63.83 N 21.47W) with the plan to be operational for several years. The purpose of this installation was through monitoring of the water vapor isotopic composition to understand the physical processes governing the isotopic composition of the water vapor evaporated from the ocean as well as the processes of mixing between the free troposphere and marine boundary layer. Because of the remoteness of the monitoring site and simple topography we are able to isolate the 'fingerprint' on the isotopic signal in the water vapor from respectively the ocean and the interior highland leading to a near perfect case-study area. Using back-trajectories we find a strong influence of the origin of the air masses on the measured isotopic composition. The mixing of the marine-boundary layer is found to strongly influence the measured isotopic composition. The second order isotopic parameter, d-excess, is contrary to theory and previous observations found not to depend on the relative humidity. However we do find a good correlation between the d-excess and the measured isotopic composition. We speculate that the lack of correlation between d-excess and relative humidity can be

  2. Isotopic composition of Pb and Th in interplinian volcanics from Somma-Vesuvius volcano, Italy (United States)

    Cortini, M.; Ayuso, R.A.; de Vivo, B.; Holden, P.; Somma, R.


    We present a detailed isotopic study of volcanic rocks emitted from Somma-Vesuvius volcano during three periods of interplinian activity: "Protohistoric" (3550 y B.P. to 79 A.D.), "Ancient Historic" (79 to 472 A.D.) and "Medieval" (472 to 1631 A.D.). Pb isotopic compositions of two acid leached fractions and whole rock residues of 37 whole rock samples (determined by Somma et al., 2001) show that each of the three interplinian periods is distinguished by small, systematic, and unique uranogenic and thorogenic Pb isotopic trends. This key and novel feature is compatible with the notion that the Pb isotopic data reflect small-scale source heterogeneity operating over relatively short periods of time. From this representative group of samples, a selected set of nine whole rocks were analysed for Th isotopes. 232Th/238U ratios in the source can be obtained independently from Pb and from Th isotopes. Those obtained from Pb isotopes represent source ratios, time-integrated over the whole age of the Earth; they range from 3.9 to 4.1. 232Th/238U obtained from Th isotopes are those of the present source. They are lower, and cluster around 3.5; this difference probably indicates recent U enrichment of the present source. The behaviour of Pb, as inferred by its isotopic ratios, is quite distinct from that of Sr and Nd isotopes: Pb isotope variations are not correlated to Sr or Nd isotope variations. The isotopic contrast is compatible with the idea that the isotopes were decoupled during magmatic production, evolution, and ascent through the crust. Thus, the Pb isotopes do not reflect the effects of the same processes as in the case of the Sr and Nd isotopes, or, as we also favor, they do not necessarily reflect the same source contributions into the magmas. Moreover, the Pb isotopic evolution of the interplinian rocks chiefly reflects mixing, driven by processes that are superimposed on, and independent of, other source contributions that determine the isotopic compositions

  3. Natural isotopic composition of nitrogen in suspended particulate matter in the Bay of Bengal

    Digital Repository Service at National Institute of Oceanography (India)

    Kumar, S.; Ramesh, R.; Bhosle, N.B.; Sardessai, S.; Sheshshayee, M.S.

    The first measurements of nitrogen isotopic composition (delta sup(15) N) in suspended particulate matter (SPM) of the surface Bay of Bengal (BOB) at 24 different locations during pre- (April-May 2003) and post- (September-October 2002) monsoon...

  4. Evolution of Organic Molecules in Space: Characterization and Isotope Composition of Experimental Analogues (United States)

    Piani, L.; Tachibana, S.; Hama, T.; Endo, Y.; Fujita, K.; Nakatsubo, S.; Fukushi, H.; Mori, S.; Chigai, T.; Yurimoto, H.; Kouchi, A.


    Laboratory experiments are conducted to investigate the organic compound formation in molecular cloud conditions and its evolution through UV irradiation and heating. A particular attention is given to the isotope composition of the organic residue.

  5. Usage of burnt fuel isotopic compositions from engineering codes in Monte-Carlo code calculations

    Energy Technology Data Exchange (ETDEWEB)

    Aleshin, Sergey S.; Gorodkov, Sergey S.; Shcherenko, Anna I. [Nuclear Research Centre ' ' Kurchatov Institute' ' , Moscow (Russian Federation)


    A burn-up calculation of VVER's cores by Monte-Carlo code is complex process and requires large computational costs. This fact makes Monte-Carlo codes usage complicated for project and operating calculations. Previously prepared isotopic compositions are proposed to use for the Monte-Carlo code (MCU) calculations of different states of VVER's core with burnt fuel. Isotopic compositions are proposed to calculate by an approximation method. The approximation method is based on usage of a spectral functionality and reference isotopic compositions, that are calculated by engineering codes (TVS-M, PERMAK-A). The multiplication factors and power distributions of FA and VVER with infinite height are calculated in this work by the Monte-Carlo code MCU using earlier prepared isotopic compositions. The MCU calculation data were compared with the data which were obtained by engineering codes.

  6. Carbon and hydrogen isotopic composition and generation pathway of biogenic gas in China

    Institute of Scientific and Technical Information of China (English)

    SHEN Ping; WANG Xiaofeng; XU Yin; SHI Baoguang; XU Yongchang


    The carbon and hydrogen isotopic composition of biogenic gas is of great importance for the study of its generation pathway and reservoiring characteristics. In this paper, the formation pathways and reservoiring characteristics of biogenic gas reservoirs in China are described in terms of the carbon and hydrogen isotopic compositions of 31 gas samples from 10 biogenic gas reservoirs. The study shows that the hydrogen isotopic compositions of these biogenic gas reservoirs can be divided into three intervals:δDCH4>-200‰,-250‰<δDCH4<-200‰ and δDCH4<-250‰. The forerunners believed that the main generation pathway of biogenic gas under the condition of continental fresh water is acetic fermentation. Our research results showed that the generation pathway of biogenic gas under the condition of marine facies is typical CO2- reduction, the biogenic gas has heavy hydrogen isotopic composition: its δDCH4 values are higher than -200‰; that the biogenic gas under the condition of continental facies also was generated by the same way, but its hydrogen isotopic composition is lighter than that of biogenetic gas generated under typical marine facies condition: -250‰<δDCH4<-200‰, the δDCH4 values may be related to the salinity of the water medium in ancient lakes. From the relevant data of the Qaidam Basin, it can be seen that the hydrogen isotopic composition of biogenic methane has the same variation trend with increasing salinity of water medium. There are biogenic gas reservoirs formed in transitional regions under the condition of continental facies. These gas reservoirs resulted from both CO2- reduction and acetic fermentation, the formation of which may be related to the non-variant salinity of ancient water medium and the relatively high geothermal gradient, as is the case encountered in the Baoshan Basin. The biogenic gas generating in these regions has light hydrogen isotopic composition: δDCH4<-250‰, and relatively heavy carbon isotopic

  7. Non-destructive measurement of carbonic anhydrase activity and the oxygen isotope composition of soil water (United States)

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


    Carbonic anhydrases are a group of metalloenzymes that catalyse the hydration of aqueous carbon dioxide (CO2). The expression of carbonic anhydrase by bacteria, archaea and eukarya has been linked to a variety of important biological processes including pH regulation, substrate supply and biomineralisation. As oxygen isotopes are exchanged between CO2 and water during hydration, the presence of carbonic anhydrase in plants and soil organisms also influences the oxygen isotope budget of atmospheric CO2. Leaf and soil water pools have distinct oxygen isotope compositions, owing to differences in pool sizes and evaporation rates, which are imparted on CO2during hydration. These differences in the isotopic signature of CO2 interacting with leaves and soil can be used to partition the contribution of photosynthesis and soil respiration to net terrestrial CO2 exchange. However, this relies on our knowledge of soil carbonic anhydrase activity and currently, the prevalence and function of these enzymes in soils is poorly understood. Isotopic approaches used to estimate soil carbonic anhydrase activity typically involve the inversion of models describing the oxygen isotope composition of CO2 fluxes to solve for the apparent, potentially catalysed, rate of oxygen exchange during hydration. This requires information about the composition of CO2 in isotopic equilibrium with soil water obtained from destructive, depth-resolved soil water sampling. This can represent a significant challenge in data collection given the considerable potential for spatial and temporal variability in the isotopic composition of soil water and limited a priori information with respect to the appropriate sampling resolution and depth. We investigated whether we could circumvent this requirement by constraining carbonic anhydrase activity and the composition of soil water in isotopic equilibrium with CO2 by solving simultaneously the mass balance for two soil CO2 steady states differing only in the

  8. Spatiotemporal variation of stable isotopic composition in precipitation

    DEFF Research Database (Denmark)

    Müller, Sascha; Stumpp, Christine; Sørensen, Jens Havskov


    gradient and predominant westerly winds. Data showed the local meteoric water line for this region is expressed by the equation δ2H = 7.4δ18O + 5.4‰. A significant trend correlating enriched isotopic values to humidities around 70% during dry season and more depleted isotopic values to humidities around 90...

  9. Spatial gradients in the isotopic composition of paleoprecipitation for terrestrial climate and altimetry studies (United States)

    Chamberlain, C. P.; Winnick, M.; Ibarra, D. E.; Caves, J. K.; Ritch, A. J.


    The oxygen and hydrogen isotopic composition of authigenic minerals in terrestrial sediments provides one of the critical measures of past climate change. Frequently, these measurements are made at single sites to determine how climate and/or topography have changed over specific time intervals of interest. We argue here that spatial gradients in the oxygen and hydrogen isotope of precipitation along specific storm tracks provide a more powerful method to determine changes in paleoclimate and paleotopography. We use a nondimensional isotopic vapor transport model coupled with a soil water isotope model to evaluate how moisture recycling and the relative role of eddy diffusion and advective transport of water vapor affect horizontal isotopic gradients on continents. Relatively large changes in the isotopic composition of precipitation can occur by changes in water balance and the transport mechanism of water vapor - certainly as high as can be induced by the uplift of major mountain belts and large changes in global/regional temperature. As an example, we point to Miocene to Recent oxygen isotopic records of paleo-mid latitude sediments that tend to increase with time, globally. We suggest that this increase in the oxygen isotope of precipitation is the result of increased aridity and the expansion of grasslands during the Miocene. Further, we suggest that many of the Miocene to Recent isotopic records collected in the mountainous regions of Central Asia, Western North America, and South America reflect changes in water balance that are, in part, independent of changes in surface topography.

  10. Long-term data set analysis of stable isotopic composition in German rivers (United States)

    Reckerth, Anne; Stichler, Willibald; Schmidt, Axel; Stumpp, Christine


    Stable isotopes oxygen-18 (18O) and deuterium (2H) are commonly used to investigate hydrological processes in catchments. However, only a few isotope studies have been conducted on a large scale and rarely over long time periods. The objective of this study was to identify the spatial and seasonal variability of isotopic composition in river water and how it is affected by geographical and hydrological factors. The stable isotopic composition of river water has been measured in nine large river catchments in Germany for a time period of 12 years or 26 years. We conducted time series and correlation analyses to identify spatial and temporal patterns of the isotopic composition in the rivers. Further, we compared it to isotopic composition in local precipitation and catchments characteristics. In the majority of the rivers, the spatial and temporal patterns of precipitation were directly reflected in river water. The isotopic signals of the river water were time shifted and show attenuated amplitudes. Further deviations from isotopic compositions in local precipitation were observed in catchments with complex flow systems. These deviations were attributed to catchment processes and influences like evaporation, damming and storage. The seasonality of the isotopic composition was mainly determined by the discharge regimes of the rivers. We found correlations between isotopic long-term averages and catchment altitude as well as latitude and longitude, resulting in a northwest-southeast gradient. Furthermore, it was shown that long-term averages of d-excess were inversely related to flow length and catchment size, which indicates that evaporation enrichment has an impact on the isotopic composition even in catchments of humid climates. This study showed that isotopic composition in rivers can serve as a proxy for the local precipitation and can be utilized as an indicator for hydrological processes even in large river basins. In future, such long time series will help to

  11. Investigation of the Effect of Yttrium Oxide Nanoparticles Doped with Cerium and Neodymium on Electro-Optics of Liquid Crystal Polymer Composites (United States)

    Zharkova, G. M.; Osipov, V. V.; Platonov, V. V.; Podkin, A. V.; Strel'tsov, S. A.


    Morphology and properties of liquid crystal polymer composites doped with inorganic nanoparticles are described. These composites comprised nematic liquid crystal 5CB, polyvinyl acetate, and nanoparticles of oxides (Y2O3, CeO2:Y2O3, and Nd2O3:Y2O3). Nanopowders were synthesized by the laser method of vaporization of a solid target under CO2-laser or fiber ytterbium laser irradiation. The effect of oxides on the electro-optical properties of the composites and times of response to an electrical pulse is investigated. It is shown that incorporation of CeO2:Y2O3 nanopowder in liquid crystal polymer composites affects the decrease of the control field and the increase of light transmission in an electric field stronger than incorporation of Nd2O3:Y2O3 nanoparticles.

  12. Elemental and iron isotopic composition of aerosols collected in a parking structure. (United States)

    Majestic, Brian J; Anbar, Ariel D; Herckes, Pierre


    The trace metal contents and iron isotope composition of size-resolved aerosols were determined in a parking structure in Tempe, AZ, USA. Particulate matter (PM)2.5 microm were collected. Several air toxics (e.g., arsenic, cadmium, and antimony) were enriched above the crustal average, implicating automobiles as an important source. Extremely high levels of fine copper (up to 1000 ng m(-3)) were also observed in the parking garage, likely from brake wear. The iron isotope composition of the aerosols were found to be +0.15+/-0.03 per thousand and +0.18+/-0.03 per thousand for the PM2.5 microm fractions, respectively. The similarity of isotope composition indicates a common source for each size fraction. To better understand the source of iron in the parking garage, the elemental composition in four brake pads (two semi-metallic and two ceramic), two tire tread samples, and two waste oil samples were determined. Striking differences in the metallic and ceramic brake pads were observed. The ceramic brake pads contained 10-20% copper by mass, while the metallic brake pads contained about 70% iron, with very little copper. Both waste oil samples contained significant amounts of calcium, phosphorous, and zinc, consistent with the composition of some engine oil additives. Differences in iron isotope composition were observed between the source materials; most notably between the tire tread (average=+0.02 per thousand) and the ceramic brake linings (average=+0.65 per thousand). Differences in isotopic composition were also observed between the metallic (average=+0.18 per thousand) and ceramic brake pads, implying that iron isotope composition may be used to resolve these sources. The iron isotope composition of the metallic brake pads was found to be identical to the aerosols, implying that brake dust is the dominant source of iron in a parking garage.

  13. The oxygen isotope composition of dissolved anthropogenic phosphates: a new tool for eutrophication research? (United States)

    Gruau, Gérard; Legeas, Michèle; Riou, Christine; Gallacier, Eve; Martineau, François; Hénin, O


    High-precision oxygen isotope analyses were carried out on dissolved phosphate extracted from discharge waters from three wastewater treatment plants (WTP) located in western France, as well as on the different phosphate-based fertilizers applied by farmers in the same region. Measured delta(18)O values of phosphate from chemical fertilizers range from 19.6 to 23.1 per thousand, while those of phosphate from WTP discharge waters are more tightly grouped between 17.7 and 18.1 per thousand. The variability in delta(18)O values of phosphate fertilizers is attributed to oxygen isotope variations of the phosphorite deposits from which France's fertilizers are manufactured. The significance of the delta(18)O values of phosphate from WTP discharge waters is less straightforward. At present, it is not clear whether these values are primary isotopic compositions corresponding, e.g., to the oxygen isotope composition of phosphate builders included in detergents (delta(18)O(P)=17.9 per thousand), or represent secondary values reflecting biological recycling of the phosphate in equilibrium with ambient WTP water The restricted difference in isotopic composition obtained between phosphate from fertilizers and phosphate from WTP discharge waters (isotopic variability observed in both end-members (>/=1.5 per thousand), cast doubt about the possibility that the oxygen isotope composition could serve as a tracer for the source of anthropogenic phosphates in waters.

  14. Carbon and oxygen isotope compositions of the carbonate facies in the Vindhyan Supergroup, central India

    Indian Academy of Sciences (India)

    S Banerjee; S K Bhattacharya; S Sarkar


    The Vindhyan sedimentary succession in central India spans a wide time bracket from the Paleopro- terozoic to the Neoproterozoic period.Chronostratigraphic significance of stable carbon and oxygen isotope ratios of the carbonate phase in Vindhyan sediments has been discussed in some recent studies.However,the subtle controls of facies variation,depositional setting and post-depositional diagenesis on stable isotope compositions are not yet clearly understood.The Vindhyan Super- group hosts four carbonate units,exhibiting a wide variability in depositional processes and paleogeography.A detailed facies-specific carbon and oxygen isotope study of the carbonate units was undertaken by us to investigate the effect of these processes and to identify the least altered isotope values.It is seen that both carbon and oxygen isotope compositions have been affected by early meteoric water diagenesis.The effect of diagenetic alteration is,however,more pronounced in case of oxygen isotopes than carbon isotopes.Stable isotope compositions remained insensitive to facies only when sediments accumulated in a shallow shelf setting without being exposed.Major alteration of original isotope ratios was observed in case of shallow marine carbonates,which became exposed to meteoric fluids during early diagenetic stage.Duration of exposure possibly determined the magnitude of alteration and shift from the original values.Moreover,dolomitization is found to be accompanied by appreciable alteration of isotope compositions in some of the carbonates.The present study suggests that variations in sediment depositional settings,in particular the possibility of subaerial exposure,need to be considered while extracting chronostratigraphic signi ficance from 13C data.

  15. Variations in isotopic compositions of chlorine in evaporation-controlled salt lake brines of Qaidam Basin, China

    Digital Repository Service at National Institute of Oceanography (India)

    Xiao, Ying-kai; Liu, Wei-guo; Zhou, Y.M.; Wang, Yun-hui; Shirodkar, P.V.

    The variations in the isotopic compositions of chlorine in evaporation-controlled saline lake brines were determined by using an improved procedure for precise measurement of chlorine isotopes based on Cs sub(2) Cl sup(+) ion by thermal ionization...

  16. Oxygen isotopic composition of low-temperature authigenic clinoptilolite (United States)

    Nähr, T.; Botz, R.; Bohrmann, G.; Schmidt, M.


    Oxygen isotope ratios were obtained from authigenic clinoptilolites from Barbados Accretionary Complex, Yamato Basin, and Exmouth Plateau sediments (ODP Sites 672, 797, and 762) in order to investigate the isotopic fractionation between clinoptilolite and pore water at early diagenetic stages and low temperatures. Dehydrated clinoptilolites display isotopic ratios for the zeolite framework ( δ18O f) that extend from +18.7‰ to +32.8‰ (vs. SMOW). In combination with associated pore water isotope data, the oxygen isotopic fractionation between clinoptilolite and pore fluids could be assessed in the temperature range from 25°C to 40°C. The resulting fractionation factors of 1.032 at 25°C and 1.027 at 40°C are in good agreement with the theoretically determined oxygen isotope fractionation between clinoptilolite and water. Calculations of isotopic temperatures illustrate that clinoptilolite formation occurred at relatively low temperatures of 17°C to 29°C in Barbados Ridge sediments and at 33°C to 62°C in the Yamato Basin. These data support a low-temperature origin of clinoptilolite and contradict the assumption that elevated temperatures are the main controlling factor for authigenic clinoptilolite formation. Increasing clinoptilolite δ18O f values with depth indicate that clinoptilolites which are now in the deeper parts of the zeolite-bearing intervals had either formed at lower temperatures (17-20°C) or under closed system conditions.

  17. Magnesium isotopic composition of the oceanic mantle and oceanic Mg cycling (United States)

    Liu, Ping-Ping; Teng, Fang-Zhen; Dick, Henry J. B.; Zhou, Mei-Fu; Chung, Sun-Lin


    To constrain the Mg isotopic composition of the oceanic mantle, investigate Mg isotope fractionation of abyssal peridotites during seafloor alteration, and assess Mg budget in the oceans, a suite of 32 abyssal peridotite samples from the Gakkel Ridge and Southwest Indian Ridge (SWIR) was, for the first time, selected for high-precision Mg isotope analyses. Although most of these samples are extensively altered, largely by serpentinization and weathering, primary olivine, diopside and enstatite grains are preserved in some samples. Olivine grains from the least altered samples have δ26Mg varying from -0.30 to -0.12‰ (n = 7), whereas enstatite and diopside have δ26Mg varying from -0.27 to -0.16‰ (n = 7), and from -0.23 to -0.09‰ (n = 6), respectively. Whole-rock δ26Mg values range from -0.24 to 0.03‰ with an average of -0.12 ± 0.13‰ (2SD, n = 32). Strongly serpentinized peridotites have lower average δ26Mg values (δ26Mg = -0.19 ± 0.07‰, 2SD, n = 7) than weathering-dominated ones (δ26Mg = -0.10 ± 0.12‰, 2SD, n = 25). Calculated Mg isotopic compositions of fresh mantle peridotites vary from -0.29 to -0.13‰, beyond the previously reported range of the subcontinental lithospheric mantle (-0.25 ± 0.04‰) and the analytical uncertainty (±0.07‰, 2SD). Our study therefore indicates that the oceanic mantle may have similar but slightly heterogeneous Mg isotopic compositions to that of subcontinental lithospheric mantle. Secondary serpentinization does not fractionate Mg isotopes of abyssal peridotites, whereas low-T weathering and formation of clay can result in the enrichment of heavy Mg isotopes in abyssal peridotites. This study also demonstrates that fluid-rock interaction does not necessarily produce rocks with intermediate Mg isotopic compositions. Magnesium isotopes of the rocks thereafter are dependent on the secondary minerals formed. We also conclude that the release of light Mg isotopes into the ocean during alteration of abyssal

  18. Abyssal peridotites reveal the near-chondritic Fe isotopic composition of the Earth (United States)

    Craddock, Paul R.; Warren, Jessica M.; Dauphas, Nicolas


    Terrestrial oceanic and continental basalts are enriched by approximately +0.1‰ in 56Fe/54Fe ratio relative to primitive, undifferentiated meteorites (chondrites). The δ56Fe values of terrestrial basalts are also distinct from those of basalts from Mars and asteroid Vesta, which have chondritic Fe isotopic compositions. The processes responsible for the isotopic enrichment of terrestrial basalts are debated, in part because the Fe isotopic composition of the mantle source of terrestrial basalts is unknown. Here we report Fe isotopic measurements of abyssal peridotites, which are the residues of limited melting at oceanic ridges and are thus the best proxies for the composition of the convective portion of the mantle. Our data show that abyssal peridotites have a mean δ56Fe value of +0.010±0.007‰ (relative to IRMM-014), which is indistinguishable from chondrites. After correcting this data for seafloor weathering and mantle melting, we estimate the average Fe isotopic composition of the terrestrial mantle to be δ56Fe=+0.025±0.025‰, which is also indistinguishable from chondrites, within current analytical precision. We determine that the maximum shift in δ56Fe for peridotite residues during partial mantle melting is 0.01‰. Our results argue against isotopic fractionation during core-mantle differentiation or iron vaporization during the Moon-forming giant impact, because both processes would yield a bulk mantle δ56Fe value that is non-chondritic. In addition, our results suggest that disproportionation of mantle Fe2+-Fe3+ in perovskite and Fe0 metal and segregation of metal to the core could not have been a driver for Fe isotopic fractionation in the silicate mantle. Instead, the different iron isotopic compositions of abyssal peridotites and MORBs support mounting evidence for iron isotopic fractionation of melts but not residues during the formation of oceanic and continental crust.

  19. Isotopic composition of Lake Agassiz-Ojibway water just prior to final drainage (United States)

    Hillaire-Marcel, C.; Helie, J.; McKay, J.; Lalonde, A.


    Controversies persist with respect to the impact of the final drainage of Lake Agassiz-Ojibway on the thermohaline circulation of the North Atlantic, some 8.4 ka ago. The lack of response of planktic foraminifer isotope records, off Hudson Strait (i.e., at the outlet of the drainage channel) constitutes one of the most puzzling elements in this debate. However, data on the isotopic composition of drainage waters are needed to estimate the response of the 18-O-salinity relationship in NW Atlantic surface waters. In the literature, a large array of isotopic compositions have been suggested, notably for modeling experiment purposes. Scattered information about the isotopic composition of Lake Agassiz water does exist. It includes isotopic measurements of pore waters of lacustrine sediments [1], analyses of oxygen isotopes in cellulose from algal or plant remains [2], and stable isotope compositions of concretions from varves [3]. Whereas, relatively low oxygen isotope values (apx. -25 per mil vs. VSMOW) are inferred for Lake Agassiz waters during cold pulses of the deglaciation, most data suggest much higher values during the final stages of Lake Agassiz-Ojiway, just prior to its drainage. Calcareous concretions from Lake Ojibway varves (not necessarily contemporaneous to the lacustrine stage) yielded oxygen isotope compositions of about -10 per mil (vs. VPDB), suggesting values as high as -14 per mil (vs. VSMOW) for pore waters (assuming a 0-4 degrees C temperature range). Similar high values (as high as -8 per mil vs. VSMOW [1]) were also estimated from pore water analyses of contemporaneous Lake Agassiz sediments. Here, we used a core raised from Eastern Hudson Bay, off Great Whale River, to further document isotopic compositions of the lake waters prior to their drainage into the North Atlantic. The 7.40 m long core has an apx. 1.3 m-thick lacustrine layer at its base, including the drainage sub- layer. It is overlain by Tyrrell Sea clays. Scarce valves of Candona

  20. Stable isotopic composition of perchlorate and nitrate accumulated in plants: Hydroponic experiments and field data (United States)

    Estrada, Nubia Luz; Böhlke, John Karl; Sturchio, Neil C.; Gu, Baohua; Harvey, Greg; Burkey, Kent O.; Grantz, David A.; McGrath, Margaret T.; Anderson, Todd A.; Rao, Balaji; Sevanthi, Ritesh; Hatzinger, Paul B.; Jackson, W. Andrew


    Natural perchlorate (ClO4−) in soil and groundwater exhibits a wide range in stable isotopic compositions (δ37Cl, δ18O, and Δ17O), indicating that ClO4− may be formed through more than one pathway and/or undergoes post-depositional isotopic alteration. Plants are known to accumulate ClO4−, but little is known about their ability to alter its isotopic composition. We examined the potential for plants to alter the isotopic composition of ClO4− in hydroponic and field experiments conducted with snap beans (Phaseolus vulgaris L.). In hydroponic studies, anion ratios indicated that ClO4− was transported from solutions into plants similarly to NO3− but preferentially to Cl− (4-fold). The ClO4− isotopic compositions of initial ClO4− reagents, final growth solutions, and aqueous extracts from plant tissues were essentially indistinguishable, indicating no significant isotope effects during ClO4− uptake or accumulation. The ClO4− isotopic composition of field-grown snap beans was also consistent with that of ClO4− in varying proportions from irrigation water and precipitation. NO3− uptake had little or no effect on NO3− isotopic compositions in hydroponic solutions. However, a large fractionation effect with an apparent ε (15N/18O) ratio of 1.05 was observed between NO3− in hydroponic solutions and leaf extracts, consistent with partial NO3− reduction during assimilation within plant tissue. We also explored the feasibility of evaluating sources of ClO4− in commercial produce, as illustrated by spinach, for which the ClO4− isotopic composition was similar to that of indigenous natural ClO4−. Our results indicate that some types of plants can accumulate and (presumably) release ClO4− to soil and groundwater without altering its isotopic characteristics. Concentrations and isotopic compositions of ClO4−and NO3− in plants may be useful for determining sources of fertilizers and sources of ClO4− in their growth environments and

  1. Lanthanum and Neodymium Doped Barium Ferrite-TiO₂/MCNTs/poly(3-methyl thiophene) Composites with Nest Structures: Preparation, Characterization and Electromagnetic Microwave Absorption Properties. (United States)

    Zhao, Jie; Yu, Jian; Xie, Yu; Le, Zhanggao; Hong, Xiaowei; Ci, Suqin; Chen, Junhong; Qing, Xiaoyan; Xie, Weijie; Wen, Zhenhai


    We report herein the synthesis of a novel nest structured electromagnetic composite through in-situ chemical polymerization of 3-methyl thiophene (3MT) in the presence of the BaFe11.92(LaNd)0.04O19-TiO2 (BFTO) nanoparticles and MCNTs. As an absorbing material, the BFTO/MCNTs/P3MT/wax composites were prepared at various loadings of BFTO/MCNTs/P3MT (0.2:0.10:1.0 ~ 0.2:0.30:1.0), and they exhibited strong microwave absorption properties in the range of 1.0-18 GHz. When the loading of BFTO/MCNTs/P3MT is 0.2:0.30:1.0, the composite has a strongest absorbing peak at 11.04 GHz, and achieves a maximum absorbing value of -21.56 dB. The absorbing peak position moves to higher frequencies with the increase of MCNTs content. The mechanism for microwave absorption of these composites has been explained in detail.

  2. Normal variations in the isotopic composition of metabolically relevant transition metals in human blood (United States)

    Van Heghe, L.; Cloquet, C.; Vanhaecke, F.


    Cu, Fe and Zn are transition metals with great catalytic, structural and regulating importance in the human body. Hence, an aberrant metabolism of these elements can have serious implications on the health of a person. It is assumed that, due to differences in isotope fractionation, the isotopic composition of these elements in whole blood of patients can be different from that in blood of healthy subjects. Therefore, isotopic analysis of the element affected by the disease can be a promising approach for early diagnosis. A method for isotopic analysis of Cu, Fe and Zn in human whole blood was developed. The simultaneous chromatographic isolation of these elements and the conditions for isotope ratio measurement via multi-collector ICP - mass spectrometry (MC-ICP-MS) were optimized. So far, only whole blood of supposedly healthy volunteers (reference population) was analyzed. Results for Fe confirmed the known differences in isotopic composition between male and female blood. It is also shown that other parameters can have influence as well, e.g., the isotopic composition of Zn seems to be governed by the diet.

  3. The stable Cr isotopic compositions of chondrites and silicate planetary reservoirs (United States)

    Schoenberg, Ronny; Merdian, Alexandra; Holmden, Chris; Kleinhanns, Ilka C.; Haßler, Kathrin; Wille, Martin; Reitter, Elmar


    The depletion of chromium in Earth's mantle (∼2700 ppm) in comparison to chondrites (∼4400 ppm) indicates significant incorporation of chromium into the core during our planet's metal-silicate differentiation, assuming that there was no significant escape of the moderately volatile element chromium during the accretionary phase of Earth. Stable Cr isotope compositions - expressed as the ‰-difference in 53Cr/52Cr from the terrestrial reference material SRM979 (δ53/52CrSRM979 values) - of planetary silicate reservoirs might thus yield information about the conditions of planetary metal segregation processes when compared to chondrites. The stable Cr isotopic compositions of 7 carbonaceous chondrites, 11 ordinary chondrites, 5 HED achondrites and 2 martian meteorites determined by a double spike MC-ICP-MS method are within uncertainties indistinguishable from each other and from the previously determined δ53/52CrSRM979 value of -0.124 ± 0.101‰ for the igneous silicate Earth. Extensive quality tests support the accuracy of the stable Cr isotope determinations of various meteorites and terrestrial silicates reported here. The uniformity in stable Cr isotope compositions of samples from planetary silicate mantles and undifferentiated meteorites indicates that metal-silicate differentiation of Earth, Mars and the HED parent body did not cause measurable stable Cr isotope fractionation between these two reservoirs. Our results also imply that the accretionary disc, at least in the inner solar system, was homogeneous in its stable Cr isotopic composition and that potential volatility loss of chromium during accretion of the terrestrial planets was not accompanied by measurable stable isotopic fractionation. Small but reproducible variations in δ53/52CrSRM979 values of terrestrial magmatic rocks point to natural stable Cr isotope variations within Earth's silicate reservoirs. Further and more detailed studies are required to investigate whether silicate

  4. Hafnium at subduction zones: isotopic budget of input and output fluxes; L'hafnium dans les zones de subduction: bilan isotopique des flux entrant et sortant

    Energy Technology Data Exchange (ETDEWEB)

    Marini, J.Ch


    Subduction zones are the primary regions of mass exchanges between continental crust and mantle of Earth through sediment subduction toward the earth's mantle and by supply of mantellic magmas to volcanic arcs. We analyze these mass exchanges using Hafnium and Neodymium isotopes. At the Izu-Mariana subduction zone, subducting sediments have Hf and Nd isotopes equivalent to Pacific seawater. Altered oceanic crust has Hf and Nd isotopic compositions equivalent to the isotopic budget of unaltered Pacific oceanic crust. At Luzon and Java subduction zones, arc lavas present Hf isotopic ratios highly radiogenic in comparison to their Nd isotopic ratios. Such compositions of the Luzon and Java arc lavas are controlled by a contamination of their sources by the subducted oceanic sediments. (author)

  5. The effect of small scale variablity in isotopic composition of precipitation on hydrograph separation results (United States)

    Fischer, Benjamin; van Meerveld, Ilja; Seibert, Jan


    Understanding runoff processes is important for predictions of streamflow quantity and quality. The two-component isotope hydrograph separation (IHS) method is a valuable tool to study how catchments transform rainfall into runoff. IHS allows the stormflow hydrograph to be separated into rainfall (event water) and water that was stored in the catchment before the event (pre-event water). To be able to perform an IHS, water samples of baseflow (pre-event water) and stormflow are collected at the stream outlet. Rainfall is usually collected at one location by hand as an event total or sampled sequentially during the event. It is usually assumed that the spatial variability in rainfall and the isotopic composition of rainfall are negligible for small (area of 0.15, 0.23, and 0.7 km2). The isotopic composition of rainfall and streamflow were sampled for 10 different rain events (P: 5 mm intervals, Q: 12 to 51 samples per events). This dataset was used to perform a two-component isotope hydrograph separation. The results show that for some events the spatial variability in total rainfall, mean and maximum rainfall intensity and stable isotope composition of rainfall was high. There was no relation between the stable isotope composition of rainfall and the rainfall sum, rainfall intensity or altitude. The spatial variability of the isotopic composition of rainfall was for 4 out of the 10 events as large as the temporal variability in the isotopic composition. Different rainfall weighing methods resulted in different minimum pre-event water fractions in streamflow. For small events with a small mean temporal range in stable isotope composition of rainfall, the different rainfall weighing methods had little effect on the calculated minimum pre-event water fractions. However with increasing temporal variability in stable isotope composition of rainfall, the range in the minimum pre-event water fractions increased and therefore the choice of the rainfall weighing method

  6. Chromium isotope composition of reducing and anoxic sediments from the Peru Margin and Cariaco Basin (United States)

    Gueguen, B.; Planavsky, N.; Wang, X.; Algeo, T. J.; Peterson, L. C.; Reinhard, C. T.


    Chromium isotope systematics in marine sediments are now being used as a new redox proxy of the modern and ancient Earth's surface. Chromium is primarily delivered to the oceans by riverine inputs through weathering of Cr(III)-rich minerals present in the continental crust and oxidation of insoluble Cr(III) to soluble Cr(VI) species. Since oxidation-reduction reactions fractionate Cr isotopes whereby oxidized Cr(VI) species are preferentially enriched in heavy Cr isotopes, the Cr isotope composition of marine sediments may be useful tracers of redox conditions at the Earth's surface through geological time. Chromium is quantitatively removed in organic-rich sediments where reducing conditions prevail and promote reduction of Cr(VI) to Cr(III), and thus, these sediments should capture the ambient seawater Cr isotope composition. However, the isotopic composition of modern organic-rich sediments is poorly documented so far, and this step is essential for further modeling the global oceanic Cr isotope mass balance and assessing the effects of sedimentation and post-depositional processes on the marine Cr isotopes archive. In this study, we have characterized modern marine organic-rich sediments for their Cr isotope composition (δ53/52Cr) from two different settings, the Peru margin upwelling zone and the anoxic Cariaco Basin (Venezuela). Chromium isotopes were measured on a MC-ICP-MS (Nu Plasma) using a double-spike correction method. The authigenic fraction of shallow samples from the Peru margin sedimentary sequence with a high Total Organic Carbon (TOC) content (>10 wt%) yield an average δ53/52Crauthigenic value of +0.67 ±0.05 ‰ (2sd). However, although this value is close to the seawater value (Atlantic Ocean) and to Cariaco basin sediments (~ +0.6 ‰), reducing sediments from the Peru margin are on average isotopically slightly heavier, especially in samples having a low authigenic fraction and a low TOC content (δ53/52Crauthigenic values up to +1.30

  7. Comparative studies of neodymium (III)-selective PVC membrane sensors

    Energy Technology Data Exchange (ETDEWEB)

    Gupta, Vinod K., E-mail: [Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee 247 667 (India); Goyal, Rajendra N.; Sharma, Ram A. [Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee 247 667 (India)


    Sensors based on two neutral ionophores, N,N'-bis((1H-pyrrol-2-yl)methylene)cyclohexane-1,2-diamine (L{sub 1}) and 3,3'-(cyclohexane-1,2-diylbis(azan-1-yl-1-ylidene) bis(methan-1-yl-1-ylidene)bis(5-hydroxymethyl)pyridine-2-ol) (L{sub 2}) are described for quantification of neodymium (III). Effect of various plasticizers; 2-nitrophenyloctylether (o-NPOE), dibutyl butylphosphonate (DBBP), tri-n-butyl phosphates (TBP), dioctylpthalate (DOP) and chloronapthalen (CN) and anion excluder, sodiumtetraphenylborate (NaTPB) has been studied. The membrane composition of PVC:o-NPOE:ionophore (L{sub 1}):NaTPB (w/w; mg) of 150:300:5:5 exhibited best performance. The sensor with ionophore (L{sub 1}) exhibits significantly enhanced selectivity towards neodymium (III) in the concentration range 5.0 x 10{sup -7} to 1.0 x 10{sup -2} M with a detection limit of 1.0 x 10{sup -7} M and a Nernstian compliance (19.8 {+-} 0.3 mV decade{sup -1} of activity) within pH range 4.0-8.0. The response time of sensor was found as 10 s. The influence of the membrane composition and possible interfering ions has also been investigated on the response properties of the electrode. The fast and stable response, good reproducibility and long-term stability of the sensor are observed. The sensor has been found to work satisfactorily in partially non-aqueous media up to 20% (v/v) content of methanol, ethanol or acetonitrile and could be used for a period of 3 months. The selectivity coefficients determined by using fixed interference method (FIM) indicate high selectivity for neodymium. The proposed electrode shows fairly good discrimination of neodymium (III) from other cations. The application of prepared sensor has been demonstrated in the determination of neodymium (III) in spiked water samples.

  8. The isotopic composition of dissolved cadmium in the water column of the West Philippine Sea

    Directory of Open Access Journals (Sweden)

    Shun-Chung eYang


    Full Text Available The dissolved concentration and isotopic compositions of cadmium (Cd in the seawater of the West Philippine Sea were determined. In general, Cd isotopic composition in the water column decreased with depth, with ε114/110Cd (ε114/110Cd = [(114Cd/110Cdsample / (114Cd/110CdNIST 3108 - 1]×10000 ranging from +7.2 to +10.1 in the top 60 m, from +4.8 to +5.1 between 100 and 150 m, peaking at +8.2 at 200 m, decreasing from +4.5 to +3.3 from 400 to 1000 m, and remaining constant at +3.0 from 1000 m and deeper. Different to a Rayleigh fractionation model, the isotopic composition and log scale concentrations of Cd do not exhibit a linear relationship. However, from the deep water to thermocline, the variations in Cd concentration and ε114/110Cd are relevant to the variations of temperature and salinity, indicating that water mixing is the dominant processes determining the concentration and isotopic composition in the interval. At 200 m where North Pacific Tropic Water dominates the water mass, the elevated ε114/110Cd could be linked to the composition in the upper portions of the water mass. In the top 150 m, the ε114/110Cd varies similarly to the phytoplankton community structures, implying that Cd uptake by various phytoplankton species may be associated with the isotopic variation. However, the effects of atmospheric inputs to the ε114/110Cd in the surface water cannot be excluded. A box model calculation is used to constrain the contributions of various processes to the Cd isotopes of surface water, and the results indicate that the Cd concentration and isotopic composition in most of the water body of the region are controlled by physical mixing, while the effects of biological fractionation and atmospheric inputs are limited in the euphotic zone.

  9. The minor sulfur isotope composition of Cretaceous and Cenozoic seawater sulfate (United States)

    Masterson, A. L.; Wing, Boswell A.; Paytan, Adina; Farquhar, James; Johnston, David T.


    The last 125 Myr capture major changes in the chemical composition of the ocean and associated geochemical and biogeochemical cycling. The sulfur isotopic composition of seawater sulfate, as proxied in marine barite, is one of the more perplexing geochemical records through this interval. Numerous analytical and geochemical modeling approaches have targeted this record. In this study we extend the empirical isotope record of seawater sulfate to therefore include the two minor sulfur isotopes, 33S and 36S. These data record a distribution of values around means of Δ33S and Δ36S of 0.043 ± 0.016‰ and -0.39 ± 0.15‰, which regardless of δ34S-based binning strategy is consistent with a signal population of values throughout this interval. We demonstrate with simple box modeling that substantial changes in pyrite burial and evaporite sulfate weathering can be accommodated within the range of our observed isotopic values.

  10. The atomic weight and isotopic composition of nitrogen and their variation in nature

    Energy Technology Data Exchange (ETDEWEB)

    Holden, N.E.


    Two stable isotopes of nitrogen exist in nature, /sup 14/N and /sup 15/N. The less abundant isotope, /sup 15/N, was discovered in 1929 by Naude, who studied the band spectra of nitric oxide, NO. However, the main source of a standard for this element is the air in the atmosphere, which is made up of approximately 78% N/sub 2/. Reviewed in this paper is the measurements of the isotopic composition in air and its variation around the world. Also investigated is the variation of the isotopic composition in the various compounds or sources of nitrogen compared to the value in air. Data on the atomic weight and non-terrestrial data for nitrogen is also reviewed.

  11. On the isotopic composition of precipitation; Sur la composition isotopique des precipitations

    Energy Technology Data Exchange (ETDEWEB)

    Gonfiantini, R. [Paris-11 Univ., 91 - Orsay (France). Laboratoire d`Hydrologie et de Geochimie Isotopique


    The paper discusses some aspects of the isotopic composition (tritium and stable isotopes) of global precipitation which is being monitored since the late fifties through the network established by the International Atomic Energy Agency. Three quarters of the tritium formed during the atmospheric thermonuclear tests were released in the biennium 1961-1962. The successive five years of the test moratorium provide a unique information on the tritium transfer rate from the stratosphere to the troposphere. The tritium concentration decreased steadily, and the decrease rate appears to be greater at high latitude. This fact can possibly be explained by precipitation recycling by evapotranspiration, which is more important at low latitudes, and tritium concentration ratio between two successive years, is close to 0.68 {+-} 0.02, with the exception of the year 1965, when the tritium content dropped to 0.50 {+-} 0.02 with respect to the previous year. At latitudes between 30 and 60 deg C, the correlations between {delta}{sup 2}H and {delta}{sup 18}O show almost identical slopes in winter and summer precipitation, but different intercepts. The correlations are: {delta}{sup 2}H (8.36{+-}0.13) {delta}{sup 18}O+(14.2{+-}4.2) for January and {delta}{sup 2}H 8.33{+-}0.013) {delta}{sup 18}O+(8.2{+-}3.9) for July. This reflects a different seasonal deuterium excess (defined as d {delta}{sup 2}H - 8{delta}{sup 18}O), which has a mean value of 10.7{+-} 0.6 %0 in July, and a higher average value of 10.7 {+-} 0.6%0 in January and 5.8{+-} 0.5%0 in July, and a higher average value in stations with prevailing winter rains. Also, the slope becomes about 8 when summer and winter precipitation are considered all together. The altitude effect on the isotopic composition of precipitation on Mount Cameroon is re-examined. The model which best fits the data is based on the adiabatic condensation of the atmospheric vapour with a liquid/vapor ratio increasing from 0.15 at sea level to 0.45 at 4

  12. Natural variations in the rhenium isotopic composition of meteorites (United States)

    Liu, R.; Hu, L.; Humayun, M.


    Rhenium is an important element with which to test hypotheses of isotope variation. Historically, it has been difficult to precisely correct the instrumental mass bias in thermal ionization mass spectrometry. We used W as an internal standard to correct mass bias on the MC-ICP-MS, and obtained the first precise δ187Re values ( ±0.02‰, 2SE) for iron meteorites and chondritic metal. Relative to metal from H chondrites, IVB irons are systematically higher in δ187Re by 0.14 ‰. δ187Re for other irons are similar to H chondritic metal, although some individual samples show significant isotope fractionation. Since 185Re has a high neutron capture cross section, the effect of galactic cosmic-ray (GCR) irradiation on δ187Re was examined using correlations with Pt isotopes. The pre-GCR irradiation δ187Re for IVB irons is lower, but the difference in δ187Re between IVB irons and other meteoritic metal remains. Nuclear volume-dependent fractionation for Re is about the right magnitude near the melting point of iron, but because of the refractory and compatible character of Re, a compelling explanation in terms of mass-dependent fractionation is elusive. The magnitude of a nucleosynthetic s-process deficit for Re estimated from Mo and Ru isotopes is essentially unresolvable. Since thermal processing reduced nucleosynthetic effects in Pd, it is conceivable that Re isotopic variations larger than those in Mo and Ru may be present in IVBs since Re is more refractory than Mo and Ru. Thus, the Re isotopic difference between IVBs and other irons or chondritic metal remains unexplained.

  13. Magmatic recharge buffers the isotopic compositions against crustal contamination in formation of continental flood basalts (United States)

    Yu, Xun; Chen, Li-Hui; Zeng, Gang


    Isotopic compositions of continental flood basalts are essential to understand their genesis and to constrain the character of their mantle sources. Because of potential crustal contamination, it needs to be evaluated if and to which degree these basalts record original isotopic signals of their mantle sources and/or crustal signatures. This study examines the Sr, Nd, Hf, and Pb isotopic compositions of the late Cenozoic Xinchang-Shengzhou (XS) flood basalts, a small-scale continental flood basalt field in eastern China. The basalts show positive correlations between 87Sr/86Sr and 143Nd/144Nd, and negative correlations between 143Nd/144Nd and 176Hf/177Hf, which deviate from compositional arrays of crustal contamination and instead highlight variations in magmatic recharge intensity and mantle source compositions. The lava samples formed by high-volume magmatic recharge recorded signals of recycled sediments in the mantle source, which are characterized by moderate Ba/Th (91.9-106.5), excess 208Pb/204Pb relative to 206Pb/204Pb, and excess 176Hf/177Hf relative to 143Nd/144Nd. Thus, we propose that magmatic recharge buffers the original isotopic compositions of magmas against crustal contamination. Identifying and utilizing the isotope systematics of continental flood basalts generated by high volumes of magmatic recharge are thus crucial to trace their mantle sources.

  14. Variation in the terrestrial isotopic composition and atomic weight of argon (United States)

    Böhlke, John Karl


    The isotopic composition and atomic weight of argon (Ar) are variable in terrestrial materials. Those variations are a source of uncertainty in the assignment of standard properties for Ar, but they provide useful information in many areas of science. Variations in the stable isotopic composition and atomic weight of Ar are caused by several different processes, including (1) isotope production from other elements by radioactive decay (radiogenic isotopes) or other nuclear transformations (e.g., nucleogenic isotopes), and (2) isotopic fractionation by physical-chemical processes such as diffusion or phase equilibria. Physical-chemical processes cause correlated mass-dependent variations in the Ar isotope-amount ratios (40Ar/36Ar, 38Ar/36Ar), whereas nuclear transformation processes cause non-mass-dependent variations. While atmospheric Ar can serve as an abundant and homogeneous isotopic reference, deviations from the atmospheric isotopic ratios in other Ar occurrences limit the precision with which a standard atomic weight can be given for Ar. Published data indicate variation of Ar atomic weights in normal terrestrial materials between about 39.7931 and 39.9624. The upper bound of this interval is given by the atomic mass of 40Ar, as some samples contain almost pure radiogenic 40Ar. The lower bound is derived from analyses of pitchblende (uranium mineral) containing large amounts of nucleogenic 36Ar and 38Ar. Within this interval, measurements of different isotope ratios (40Ar/36Ar or 38Ar/36Ar) at various levels of precision are widely used for studies in geochronology, water–rock interaction, atmospheric evolution, and other fields.

  15. Molybdenum isotopic composition of single silicon carbides from supernovae.

    Energy Technology Data Exchange (ETDEWEB)

    Amari, S.; Clayton, R. N.; Davis, A. M.; Lewis, R. S.; Pellin, M. J.


    Presolar silicon carbide grains form in a variety of types of stars, including asymptotic giant branch red giant stars and supernovae. The dominant mechanisms of heavy element nucleosynthesis, the s-process and r-process, are thought to occur in AGB stars and supernovae, respectively. We have previously reported that mainstream SiC grains have strong enrichments in the s-process isotopes of Sr, Zr and Mo. We report here the first measurements of Mo isotopes in X-type SiC grains, which have previously been identified as having formed from supernova ejecta.

  16. Is my C isotope excursion global, local, or both? Insights from the Mg and Ca isotopic composition of primary, diagenetic, and authigenic carbonates (United States)

    Higgins, J. A.; Blättler, C. L.; Husson, J. M.


    The C isotopic composition of ancient limestones and dolomites is a widely used proxy for the global geochemical cycles of carbon and oxygen in the ocean-atmosphere system and a critical tool for chemostratigraphy in Precambrian rocks. Although relatively robust to diagenesis, the C isotopic composition of bulk carbonates can be reset when conditions favor high water-to-rock ratios or fluids with high C concentrations and distinct isotopic compositions. Authigenic carbonates and different pools of primary carbonate (e.g. calcite vs. aragonite) may also bias the C isotopic composition of bulk carbonates if they are both abundant and isotopically distinct. New approaches to quantifying contributions from diagenesis, authigenesis, and mixing of primary carbonates to the C isotopic composition of bulk sedimentary carbonates are needed. Here we present preliminary Mg and Ca isotope data sets of primary, diagenetic, and authigenic carbonates, both modern and ancient. We show that recrystallization, dolomitization, and authigenesis produce Mg and Ca isotope fingerprints that may be used to identify and characterize these processes in ancient carbonate sediments.

  17. Potassium Isotopic Compositions of NIST Potassium Standards and 40Ar/39Ar Mineral Standards (United States)

    Morgan, Leah; Tappa, Mike; Ellam, Rob; Mark, Darren; Higgins, John; Simon, Justin I.


    Knowledge of the isotopic ratios of standards, spikes, and reference materials is fundamental to the accuracy of many geochronological methods. For example, the 238U/235U ratio relevant to U-Pb geochronology was recently re-determined [1] and shown to differ significantly from the previously accepted value employed during age determinations. These underlying values are fundamental to accurate age calculations in many isotopic systems, and uncertainty in these values can represent a significant (and often unrecognized) portion of the uncertainty budget for determined ages. The potassium isotopic composition of mineral standards, or neutron flux monitors, is a critical, but often overlooked component in the calculation of K-Ar and 40Ar/39Ar ages. It is currently assumed that all terrestrial materials have abundances indistinguishable from that of NIST SRM 985 [2]; this is apparently a reasonable assumption at the 0.25per mille level (1s) [3]. The 40Ar/39Ar method further relies on the assumption that standards and samples (including primary and secondary standards) have indistinguishable 40K/39K values. We will present data establishing the potassium isotopic compositions of NIST isotopic K SRM 985, elemental K SRM 999b, and 40Ar/39Ar biotite mineral standard GA1550 (sample MD-2). Stable isotopic compositions (41K/39K) were measured by the peak shoulder method with high resolution MC-ICP-MS (Thermo Scientific NEPTUNE Plus), using the accepted value of NIST isotopic SRM 985 [2] for fractionation [4] corrections [5]. 40K abundances were measured by TIMS (Thermo Scientific TRITON), using 41K/39K values from ICP-MS measurements (or, for SRM 985, values from [2]) for internal fractionation corrections. Collectively these data represent an important step towards a metrologically traceable calibration of 40K concentrations in primary 40Ar/39Ar mineral standards and improve uncertainties by ca. an order of magnitude in the potassium isotopic compositions of standards.

  18. About the possibility of creating a continuous range of standards with different isotopic composition of carbon

    Directory of Open Access Journals (Sweden)

    S. A. Sadykov


    Full Text Available It is established that the carbon isotopic composition in the formation of calcium carbonate is changed depending on the magnetic field strength. The formation of calcium carbonate occurred due to the interaction of calcium hydroxide with atmospheric carbon dioxide. The profile of isotopic relations13C/12C of the newly formed calcium carbonate is approximated by the equation of the parabola for certain values of tension solenoidal magnetic field. The possibility of creating standards with a continuous series of values of the content of carbon stable isotopes based on the data suggested.

  19. The isotopic composition of dissolved inorganic nitrogen in hydrothermal vent fluids (United States)

    Lehmann, M. F.; Bourbonnais, A.; Butterfield, D. A.


    Hydrothermal vent systems at mid-ocean ridges are sites with rapid rates of biomass production, sustained by chemolithoautotrophic bacteria at the base of the vent community food chains. The exact metabolic pathways, in particular those that involve nitrogen (N), and the rates at which the metabolic reactions take place are poorly constrained. In previous studies, very low 15N/14N ratios have been attributed to strong N isotope fractionation during chemosynthetic assimilation of ammonium. However, actual data on the N isotopic composition of dissolved inorganic N in vent systems, which could provide coherent information on the sources of N during chemolithoautotrophic biosynthesis, do not exist. Furthermore, the fate of hydrothermally discharged ammonium as well as that of nitrate that is mixed in from the ocean water column have not been the focus of much attention. As a consequence, little is known about N-cycle reactions within hydrothermal vent systems. We will present nitrate isotope (15N/14N and 18O/16O) data from various sites at Axial Volcano on the Juan de Fuca ridge. Their integration with nitrate concentration data suggests non-conservative behavior of nitrate along temperature gradients. Highest N and O isotope ratios (7.6 permil and 21.0 permil, respectively) are found in average diffuse fluids (17°C). Elevated N and O isotope ratios were associated with decreased nitrate concentrations and indicate a nitrate consuming process that fractionates both N and O isotopes. The ratio of 15N versus 18O enrichment in residual nitrate is, however, not consistent with previous reports on nitrate N versus O isotope fractionation during denitrification in the suboxic ocean water column, implying anomalous N and O isotope fractionation during denitrification in hydrothermal vent fluids and/or the presence of additional microbially mediated N transformations that affect the N and O isotope composition of the nitrate pool in the Axial hydrothermal vent system in a

  20. Zirconium isotope constraints on the composition of Theia and current Moon-forming theories (United States)

    Akram, W.; Schönbächler, M.


    The giant impact theory is the most widely recognized formation scenario of the Earth's Moon. Giant impact models based on dynamical simulations predict that the Moon acquired a significant amount of impactor (Theia) material, which is challenging to reconcile with geochemical data for O, Si, Cr, Ti and W isotopes in the Earth and Moon. Three new giant impact scenarios have been proposed to account for this discrepancy - hit-and-run impact, impact with a fast-spinning protoEarth and massive impactors - each one reducing the proportion of the impactor in the Moon compared to the original canonical giant impact model. The validity of each theory and their different dynamical varieties are evaluated here using an integrated approach that considers new high-precision Zr isotope measurements of lunar rocks, and quantitative geochemical modelling of the isotopic composition of the impactor Theia. All analysed lunar samples (whole-rock, ilmenite and pyroxene separates) display identical Zr isotope compositions to that of the Earth within the uncertainty of 13 ppm for 96Zr/90Zr (2σ weighted average). This 13 ppm upper limit is used to infer the most extreme isotopic composition that Theia could have possessed, relative to the Earth, for each of the proposed giant impact theories. The calculated Theian composition is compared with the Zr isotope compositions of different solar system materials in order to constrain the source region of the impactor. As a first order approximation, we show that all considered models (including the canonical) are plausible, alleviating the initial requirement for the new giant impact models. Albeit, the canonical and hit-and-run models are the most restrictive, suggesting that the impactor originated from a region close to the Earth. The fast-spinning protoEarth and massive impactor models are more relaxed and increase the allowed impactor distance from the Earth. Similar calculations carried out for O, Cr, Ti and Si isotope data support

  1. Water transport in protoplanetary disks and the hydrogen isotopic composition of chondrites

    CERN Document Server

    Jacquet, Emmanuel


    The D/H ratios of carbonaceous chondrites, believed to reflect that of water in the inner early solar system, are intermediate between the protosolar value and that of most comets. The isotopic composition of cometary water has been accounted for by several models where the isotopic composition of water vapor evolved by isotopic exchange with hydrogen gas in the protoplanetary disk. However, the position and the wide variations of the distribution of D/H ratios in carbonaceous chondrites have yet to be explained. In this paper, we assume that the D/H composition of cometary ice was achieved in the disk building phase and model the further isotopic evolution of water in the inner disk in the classical T Tauri stage. Reaction kinetics compel isotopic exchange between water and hydrogen gas to stop at $\\sim$500 K, but equilibrated water can be transported to the snow line (and beyond) via turbulent diffusion and consequently mix with isotopically comet-like water. Under certain simplifying assumptions, we calcul...


    Poitrasson, F.; Zambardi, T.; Magna, T.; Neal, C. R.


    It is difficult to estimate the bulk chemical and isotopic properties of planets, especially for the Moon for which our sampling is far more limited than for the Earth. As a result, there is currently a debate on the bulk Fe isotope composition of the Moon: Whereas in a first study we proposed that the bulk lunar Fe isotope composition (δ57Fe ~0.2‰) was twice as heavy as that of the Earth (δ57Fe ~0.1‰) relative to chondrites (δ57Fe ~0‰), normalized to IRMM-14, others proposed that there is no difference between Earth and Moon. This question is of crucial importance because the first case may track the Moon-forming giant interplanetary impact, whereas the alternative situation may also result from a very high pressure metal-silicate fractionation during the Earth’s core formation, assuming that the Moon subsequently inherited the Earth Fe isotope composition. To reassess this question, we analyzed a suite of 18 mare basalts (both high- and low-Ti) by MC-ICP-MS using the nickel doping technique developed at LMTG. Combined with our previous measurements of lunar rocks, we obtained a mean δ57Fe of 0.138±0.035‰ (2SE, n=11) for low-Ti basalts, 0.269±0.026‰ (2SE, n=16) for high-Ti ones and 0.177±0.036‰ (2SE, n=6) for highland rocks. T-tests confirm that averages of low- and high-Ti basalts are significantly different at the 95% confidence level. Similarly, t-tests indicate that highland rocks are significantly different from high-Ti basalts, but not from low-Ti ones. These new data therefore confirm suggestion from previous groups that low- and high-Ti basalts contain distinct Fe isotope signatures. This shows that on the Moon, high temperature processes can significantly change the Fe isotope composition of bulk mafic rocks at the planetary scale. This cannot result from simple equilibrium magmatic fractionation or assimilation of ilmenite given its Fe isotope fractionation factor, however. We conclude that another process, yet to be identified, is

  3. Thallium-isotopic compositions of euxinic sediments as a proxy for global manganese-oxide burial (United States)

    Owens, Jeremy D.; Nielsen, Sune G.; Horner, Tristan J.; Ostrander, Chadlin M.; Peterson, Larry C.


    Thallium (Tl) isotopes are a new and potentially powerful paleoredox proxy that may track bottom water oxygen conditions based on the global burial flux of manganese oxides. Thallium has a residence time of ∼20 thousand years, which is longer than the ocean mixing time, and it has been inferred that modern oxic seawater is conservative with respect to both concentration and isotopes. Marine sources of Tl have nearly identical isotopic values. Therefore, the Tl sinks, adsorption onto manganese oxides and low temperature oceanic crust alteration (the dominant seawater output), are the primary controls of the seawater isotopic composition. For relatively short-term, ∼million years, redox events it is reasonable to assume that the dominant mechanism that alters the Tl isotopic composition of seawater is associated with manganese oxide burial because large variability in low temperature ocean crust alteration is controlled by long-term, multi-million years, average ocean crust production rates. This study presents new Tl isotope data for an open ocean transect in the South Atlantic, and depth transects for two euxinic basins (anoxic and free sulfide in the water column), the Cariaco Basin and Black Sea. The Tl isotopic signature of open ocean seawater in the South Atlantic was found to be homogeneous with ε205Tl = -6.0 ± 0.3 (±2 SD, n = 41) while oxic waters from Cariaco and the Black Sea are -5.6 and -2.2, respectively. Combined with existing data from the Pacific and Arctic Oceans, our Atlantic data establish the conservatism of Tl isotopes in the global ocean. In contrast, partially- and predominantly-restricted basins reveal Tl isotope differences that vary between open-ocean (-6) and continental material (-2) ε205Tl, scaling with the degree of restriction. Regardless of the differences between basins, Tl is quantitatively removed from their euxinic waters below the chemocline. The burial of Tl in euxinic sediments is estimated to be an order of magnitude

  4. The oxygen isotopic composition of the Sun inferred from captured solar wind. (United States)

    McKeegan, K D; Kallio, A P A; Heber, V S; Jarzebinski, G; Mao, P H; Coath, C D; Kunihiro, T; Wiens, R C; Nordholt, J E; Moses, R W; Reisenfeld, D B; Jurewicz, A J G; Burnett, D S


    All planetary materials sampled thus far vary in their relative abundance of the major isotope of oxygen, (16)O, such that it has not been possible to define a primordial solar system composition. We measured the oxygen isotopic composition of solar wind captured and returned to Earth by NASA's Genesis mission. Our results demonstrate that the Sun is highly enriched in (16)O relative to the Earth, Moon, Mars, and bulk meteorites. Because the solar photosphere preserves the average isotopic composition of the solar system for elements heavier than lithium, we conclude that essentially all rocky materials in the inner solar system were enriched in (17)O and (18)O, relative to (16)O, by ~7%, probably via non-mass-dependent chemistry before accretion of the first planetesimals.

  5. Zinc isotope fractionation during mantle melting and constraints on the Zn isotope composition of Earth's upper mantle (United States)

    Wang, Ze-Zhou; Liu, Sheng-Ao; Liu, Jingao; Huang, Jian; Xiao, Yan; Chu, Zhu-Yin; Zhao, Xin-Miao; Tang, Limei


    compositions of MORB. Therefore, preferential melting of spinel in the peridotites may account for the Zn isotopic difference between spinel peridotites and basalts. By contrast, the absence of Zn isotope fractionation between silicate minerals suggests that Zn isotopes are not significantly fractionated during partial melting of spinel-free garnet-facies mantle. If the studied non-metasomatized peridotites represent the refractory upper mantle, mass balance calculation shows that the depleted MORB mantle (DMM) has a δ66Zn value of +0.20 ± 0.05‰ (2SD), which is lighter than the primitive upper mantle (PUM) estimated in previous studies (+0.28 ± 0.05‰, 2SD, Chen et al., 2013b; +0.30 ± 0.07‰, 2SD, Doucet et al., 2016). This indicates that the Earth's upper mantle has a heterogeneous Zn isotopic composition vertically, which is probably due to shallow mantle melting processes.

  6. Variation in the Carbon Isotope Compositions of Phytoliths Across a Climate Gradient (United States)

    Webb, E. A.; Longstaffe, F. J.


    The carbon isotope composition of plant organic matter within a single species may vary in response to changes in temperature, relative humidity, precipitation amount, altitude, nutrient availability, light levels and amount of canopy. All of these factors affect the rate of carbon assimilation during photosynthesis. Silica phytoliths, which form in the cells and intercellular spaces of terrestrial plants, occlude some of the plant's organic matrix. Carbon sequestered in phytoliths is protected from decay and may therefore be preserved in soils after most other plant material has decomposed. The carbon isotope composition of phytoliths may therefore have potential as an archive of climatic conditions during soil accumulation. In this study, the carbon isotope compositions of modern plant tissues and their phytoliths are compared for the C4 grass species Calamovilfa longifolia across the climate gradient of the North American prairies. The carbon isotope compositions of C. longifolia tissues ranged from -15 to -10 permil, with lower values being most typical of leaf tissues and with greater variability occurring in samples from lower latitudes. Carbonaceous compounds occluded in the phytoliths, by comparison, were depleted of carbon-13 by 5 to 15 permil relative to the tissues from the same plant. Understanding the causes of this offset, which is significantly larger and more variable than reported in previous studies, is necessary before the full potential of the carbon-isotope phytolith proxy can be realized.

  7. SIMSISH technique does not alter the apparent isotopic composition of bacterial cells.

    Directory of Open Access Journals (Sweden)

    Olivier Chapleur

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

  8. SIMSISH technique does not alter the apparent isotopic composition of bacterial cells. (United States)

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


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

  9. Spurious and functional correlates of the isotopic composition of a generalist across a tropical rainforest landscape

    Directory of Open Access Journals (Sweden)

    Poirson Evan K


    Full Text Available Abstract Background The isotopic composition of generalist consumers may be expected to vary in space as a consequence of spatial heterogeneity in isotope ratios, the abundance of resources, and competition. We aim to account for the spatial variation in the carbon and nitrogen isotopic composition of a generalized predatory species across a 500 ha. tropical rain forest landscape. We test competing models to account for relative influence of resources and competitors to the carbon and nitrogen isotopic enrichment of gypsy ants (Aphaenogaster araneoides, taking into account site-specific differences in baseline isotope ratios. Results We found that 75% of the variance in the fraction of 15N in the tissue of A. araneoides was accounted by one environmental parameter, the concentration of soil phosphorus. After taking into account landscape-scale variation in baseline resources, the most parsimonious model indicated that colony growth and leaf litter biomass accounted for nearly all of the variance in the δ15N discrimination factor, whereas the δ13C discrimination factor was most parsimoniously associated with colony size and the rate of leaf litter decomposition. There was no indication that competitor density or diversity accounted for spatial differences in the isotopic composition of gypsy ants. Conclusion Across a 500 ha. landscape, soil phosphorus accounted for spatial variation in baseline nitrogen isotope ratios. The δ15N discrimination factor of a higher order consumer in this food web was structured by bottom-up influences - the quantity and decomposition rate of leaf litter. Stable isotope studies on the trophic biology of consumers may benefit from explicit spatial design to account for edaphic properties that alter the baseline at fine spatial grains.

  10. The isotopic composition of methane in the stratosphere: high-altitude balloon sample measurements

    Directory of Open Access Journals (Sweden)

    T. Röckmann


    Full Text Available The isotopic composition of stratospheric methane has been determined on a large suite of air samples from stratospheric balloon flights covering subtropical to polar latitudes and a time period of 16 yr. 154 samples were analyzed for δ13C and 119 samples for δD, increasing the previously published dataset for balloon borne samples by an order of magnitude, and more than doubling the total available stratospheric data (including aircraft samples published to date. The samples also cover a large range in mixing ratio from tropospheric values near 1800 ppb down to only 250 ppb, and the strong isotope fractionation processes accordingly increase the isotopic composition up to δ13C = −14‰ and δD = +190‰, the largest enrichments observed for atmospheric CH4 so far. When analyzing and comparing kinetic isotope effects (KIEs derived from single balloon profiles, it is necessary to take into account the residence time in the stratosphere in combination with the observed mixing ratio and isotope trends in the troposphere, and the range of isotope values covered by the individual profile. The isotopic composition of CH4 in the stratosphere is affected by both chemical and dynamical processes. This severely hampers interpretation of the data in terms of the relative fractions of the three important sink mechanisms (reaction with OH, O(1D and Cl. It is shown that a formal sink partitioning using the measured data severely underestimates the fraction removed by OH, which is likely due to the insensitivity of the measurements to the kinetic fractionation in the lower stratosphere. Full quantitative interpretation of the CH4 isotope data in terms of the three sink reactions requires a global model.

  11. Hydrogen isotope composition of mantle-derived mica megacryst from ion micro probe analysis

    Institute of Scientific and Technical Information of China (English)

    夏群科; 陈道公; 支霞臣


    The hydrogen isotope composition of a mantle-derived mica megacryst from Cenozoic basanite from NUshan, Anhui Province has been determined by ion micro probe. The results demonstrate that δD and water content of the megacryst were heterogeneous on the micro scale, which resulted from reaction with meteoric water after being brought to the surface. The primary δD of mica megacrysts was about-23‰, suggesting the recycled crustal materials in its source. By combining these values with those of other researchers, it is believed that the hydrogen isotope composition of the mantle is heterogeneous at least on the large scale.

  12. Samarium-neodymium systematics in kimberlites and in the minerals of garnet lherzolite inclusions (United States)

    Basu, A.R.; Tatsumoto, M.


    The initial ratios of neodymium-143 to neodymium-144 in kimberlites ranging in age between 90 ?? 106 to 1300 ?? 106 years from South Africa, India, and the United States are different from the corresponding ratios in the minerals of peridotite inclusions in the kimberlites but are identical to the ratios in the basaltic achondrite Juvinas at the times of emplacement of the respective kimberlite pipes. This correlation between the kimberlites and Juvinas, which represents the bulk chondritic earth in rare-earth elements, strongly indicates that the kimberlite's source in the mantle is chondritic in rare-earth elements and relatively primeval in composition. Copyright ?? 1979 AAAS.

  13. Sulfur isotopic composition of modern seafloor hydrothermal sediment and its geological significance

    Institute of Scientific and Technical Information of China (English)

    曾志刚; 李军; 蒋富清; 秦蕴珊; 翟世奎


    A total of 1 264 sulfur isotopic values for modem seafloor hydrothermel sediments from different hydrothermal fidds have been collected. On this basis, combining our sulfur isotpic data for surface hydrothermal sediments from the Jade hydrohtermal field in the Okinawa Trough and the TAG hydrothermal field in the Mid-Atlantic Ridge, respectively, and comparing the sulfur isotopic compositions and analyzing their sources of sulfur in seafloor hydrothermal sediments from different geologic-tectonic setting, the results show that: ( 1 ) sulfur isotopic values of sulfides and sulfates in modern seafloor hydrothermal sediments are concentrated in a narrow range, δ34S values of sulfides vary from l × 10-3 to 9 × 10- 3, with a mean of 4.5 × 10- 3 ( n = 1 042), δ34S values of sulfates vary from 19 × 10- 3 to 24× 10-3, with a mean of 21.3× 10-3 (n =217); (2) comparing the sulfur isotopic compositions of hydrothermal sediments from the sediment-hosted hydrothermal fields, the range of sulfur isotopic values for hydrothermal sediments from the sediment-free hydrothermal fields is narrow relatively; (3) the differences of sulfur isotopic compositions in sulfides from different hydrothermal fields show the differences in the sources of sulfur. The sulfur of hydrothermal sulfides in the sediment-free mid-ocean ridges is mainly from mid-ocean ridge basalt, and partially from the reduced seawater sulfate, and it is the result of partially reduced seawater sulfate mixed with basaltic sulfur. In the sediment-hosted nid-ocean ridges and the back-arc basins, the volcanics, the sediments and the organic matters also can offer their sulfur for forming hydrothermal sulfides; (4) the variations of sulfur isotopic compositions and the different sources of sulfur for hydrothermal sediments may be attributed to the various physical-chemical characteristics of hydrothermal fluids, the magmatic evolution and the different geologic-tectonic settings of seafloor hydrothermal systems.

  14. Plutonium isotopes in the atmosphere of Central Europe: Isotopic composition and time evolution vs. circulation factors. (United States)

    Kierepko, Renata; Mietelski, Jerzy W; Ustrnul, Zbigniew; Anczkiewicz, Robert; Wershofen, Herbert; Holgye, Zoltan; Kapała, Jacek; Isajenko, Krzysztof


    This paper reports evidence of Pu isotopes in the lower part of the troposphere of Central Europe. The data were obtained based on atmospheric aerosol fraction samples collected from four places in three countries (participating in the informal European network known as the Ring of Five (Ro5)) forming a cell with a surface area of about 200,000km(2). We compared our original data sets from Krakow (Poland, 1990-2007) and Bialystok (Poland, 1991-2007) with the results from two other locations, Prague (Czech Republic; 1997-2004) and Braunschweig (Germany; 1990-2003) to find time evolution of the Pu isotopes. The levels of the activity concentration for (238)Pu and for ((239+240))Pu were estimated to be a few and some tens of nBqm(-3), respectively. However, we also noted some results were much higher (even about 70 times higher) than the average concentration of (238)Pu in the atmosphere. The achieved complex data sets were used to test a new approach to the problem of solving mixing isotopic traces from various sources (here up to three) in one sample. Results of our model, supported by mesoscale atmospheric circulation parameters, suggest that Pu from nuclear weapon accidents or tests and nuclear burnt-up fuel are present in the air.

  15. The effect of phosphomonoesterases on the oxygen isotope composition of phosphate (United States)

    von Sperber, Christian; Kries, Hajo; Tamburini, Federica; Bernasconi, Stefano M.; Frossard, Emmanuel


    Plants and microorganisms under phosphorus (P) stress release extracellular phosphatases as a strategy to acquire inorganic phosphate (Pi). These enzymes catalyze the hydrolysis of phosphoesters leading to a release of Pi. During the enzymatic hydrolysis an isotopic fractionation (ε) occurs leaving an imprint on the oxygen isotope composition of the released Pi which might be used to trace phosphorus in the environment. Therefore, enzymatic assays with acid phosphatases from wheat germ and potato tuber and alkaline phosphatase from Escherichia coli were prepared in order to determine the oxygen isotope fractionation caused by these enzymes. Adenosine 5‧ monophosphate and glycerol phosphate were used as substrates. The oxygen isotope fractionation caused by acid phosphatases is 20-30‰ smaller than for alkaline phosphatases, resulting in a difference of 5-7.5‰ in δ18O of Pi depending on the enzyme. We attribute the enzyme dependence of the isotopic fractionation to distinct reaction mechanisms of the two types of phosphatases. The observed difference is large enough to distinguish between the two enzymatic processes in environmental samples. These findings show that the oxygen isotope composition of Pi can be used to trace different enzymatic processes, offering an analytical tool that might contribute to a better understanding of the P-cycle in the environment.

  16. Carbon isotope composition of latex does not reflect temporal variations of photosynthetic carbon isotope discrimination in rubber trees (Hevea brasiliensis). (United States)

    Kanpanon, Nicha; Kasemsap, Poonpipope; Thaler, Philippe; Kositsup, Boonthida; Gay, Frédéric; Lacote, Régis; Epron, Daniel


    Latex, the cytoplasm of laticiferous cells localized in the inner bark of rubber trees (Hevea brasiliensis Müll. Arg.), is collected by tapping the bark. Following tapping, latex flows out of the trunk and is regenerated, whereas in untapped trees, there is no natural exudation. It is still unknown whether the carbohydrates used for latex regeneration in tapped trees is coming from recent photosynthates or from stored carbohydrates, and in the former case, it is expected that latex carbon isotope composition of tapped trees will vary seasonally, whereas latex isotope composition of untapped trees will be more stable. Temporal variations of carbon isotope composition of trunk latex (δ(13)C-L), leaf soluble compounds (δ(13)C-S) and bulk leaf material (δ(13)C-B) collected from tapped and untapped 20-year-old trees were compared. A marked difference in δ(13)C-L was observed between tapped and untapped trees whatever the season. Trunk latex from tapped trees was more depleted (1.6‰ on average) with more variable δ(13)C values than those of untapped trees. δ(13)C-L was higher and more stable across seasons than δ(13)C-S and δ(13)C-B, with a maximum seasonal difference of 0.7‰ for tapped trees and 0.3‰ for untapped trees. δ(13)C-B was lower in tapped than in untapped trees, increasing from August (middle of the rainy season) to April (end of the dry season). Differences in δ(13)C-L and δ(13)C-B between tapped and untapped trees indicated that tapping affects the metabolism of both laticiferous cells and leaves. The lack of correlation between δ(13)C-L and δ(13)C-S suggests that recent photosynthates are mixed in the large pool of stored carbohydrates that are involved in latex regeneration after tapping.

  17. Coupled isotopes of plant wax and hemicellulose markers record information on relative humidity and isotopic composition of precipitation

    Directory of Open Access Journals (Sweden)

    M. Tuthorn


    Full Text Available The δ2H isotopic composition of leaf waxes is used increasingly for paleohydrological and -climate reconstructions. However, it is challenging to disentangle past changes in the isotopic composition of precipitation and changes in evapotranspirative enrichment of leaf water. We analyzed δ2H on n-alkanes and fatty acids in topsoils along a climate transect in Argentina, for which we had previously measured δ18O on plant-derived sugars. Our results indicate that leaf wax biomarker δ2H values (δ2Hlipids primarily reflect δ2Hsource water (precipitation, but are modulated by evapotranspirative enrichment. A mechanistic model is able to produce the main trends in δ2Hlipids along the transect, but seems to slightly underestimate evapotranspirative enrichment in arid regions and overestimate it in grass-dominated ecosystems. Furthermore, the (i coupling of the δ2Hlipid and δ18Osugar biomarker results and (ii application of biosynthetic fractionation factors allows calculating the δ2H-δ18O isotopic composition of leaf water along the transect. This also yields the deuterium excess (d excess of leaf water, which mainly reflects evapotranspirative enrichment, and can be used to model relative air humidity (RH. The high correlation of modeled (reconstructed based on biomarker results and measured RH, as well as the good agreement between modeled and actual δ2H and δ18O of precipitation along the transect lends support to the coupled δ2Hlipid and δ18Osugar biomarker approach for future paleoclimate research.

  18. Molybdenum Isotopic Composition of the Archean Mantle As Inferred from Studies of Komatiites (United States)

    Greber, N. D.; Puchtel, I. S.; Nagler, T. F.; Mezger, K.


    Molybdenum isotopic composition has been shown to be a powerful tool in studies of planetary processes, e.g. estimating core formation temperatures [1,2]. However, Mo isotope compositions of terrestrial reservoirs are not well constrained. In order to better constrain the Mo isotopic composition of the early Earth's mantle, komatiites from four locations were analyzed for their Mo concentrations and isotopic compositions. Komatiites are particularly appropriate for this type of study because they formed by high degrees of partial melting of the mantle leading to a complete base metal sulfide removal from the residual mantle and the production of sulfur-undersaturated melts and thus a quantitative removal of Mo from the source into the melt. All samples, except for two strongly altered specimens specifically chosen to study the effects of secondary alteration, are very fresh having preserved most of their primary mineralogy. The Mo concentrations in komatiites range from 10 to 120 ng/g. Fresh komatiites have lighter δ98Mo (NIST SRM 3134 = 0.25‰, [3]) than altered samples. The estimated primary Mo isotope compositions of the studied komatiite melts range from 0.02 ± 0.16‰ to 0.19 ± 0.14‰ and are therefore indistinguishable within analytical uncertainty (2SD) from published values for chondritic meteorites (0.09 ± 0.04 ‰; 2SD; [2]) and lighter than the proposed average for Earth's continental crust (0.3 to 0.4‰ [4]). All data combined, although overlapping in errors, show a consistent trend of lighter δ98Mo and lower Mo concentrations in more melt-depleted mantle sources, indicating incompatible behaviour of Mo and preferential mobilization of heavy Mo isotopes during mantle melting. [1] Hin et al. (2013) EPSL, 379 [2] Burkhardt et al. (2014) EPSL, 391 [3] Nägler, et al. (2014) GGR, 38. [4] Voegelin et al. (2014) Lithos, 190-191.

  19. Lead isotope studies of the Guerrero composite terrane, west-central Mexico: implications for ore genesis (United States)

    Potra, Adriana; Macfarlane, Andrew W.


    New thermal ionization mass spectrometry and multi-collector inductively coupled plasma mass spectrometry Pb isotope analyses of three Cenozoic ores from the La Verde porphyry copper deposit located in the Zihuatanejo-Huetamo subterrane of the Guerrero composite terrane are presented and the metal sources are evaluated. Lead isotope ratios of 3 Cenozoic ores from the El Malacate and La Esmeralda porphyry copper deposits located in the Zihuatanejo-Huetamo subterrane and of 14 ores from the Zimapan and La Negra skarn deposits from the adjoining Sierra Madre terrane are also presented to look for systematic differences in the lead isotope trends and ore metal sources among the proposed exotic tectonostratigraphic terranes of southern Mexico. Comparison among the isotopic signatures of ores from the Sierra Madre terrane and distinct subterranes of the Guerrero terrane supports the idea that there is no direct correlation between the distinct suspect terranes of Mexico and the isotopic signatures of the associated Cenozoic ores. Rather, these Pb isotope patterns are interpreted to reflect increasing crustal contribution to mantle-derived magmas as the arc advanced eastward onto a progressively thicker continental crust. The lead isotope trend observed in Cenozoic ores is not recognized in the ores from Mesozoic volcanogenic massive sulfide and sedimentary exhalative deposits. The Mesozoic ores formed prior to the amalgamation of the Guerrero composite terrane to the continental margin, which took place during the Late Cretaceous, in intraoceanic island arc and intracontinental marginal basin settings, while the Tertiary deposits formed after this event in a continental arc setting. Lead isotope ratios of the Mesozoic and Cenozoic ores appear to reflect these differences in tectonic setting of ore formation. Most Pb isotope values of ores from the La Verde deposit (206Pb/204Pb = 18.674-18.719) are less radiogenic than those of the host igneous rocks, but plot within the

  20. Unexpected variations in the triple oxygen isotope composition of stratospheric carbon dioxide. (United States)

    Wiegel, Aaron A; Cole, Amanda S; Hoag, Katherine J; Atlas, Elliot L; Schauffler, Sue M; Boering, Kristie A


    We report observations of stratospheric CO2 that reveal surprisingly large anomalous enrichments in (17)O that vary systematically with latitude, altitude, and season. The triple isotope slopes reached 1.95 ± 0.05(1σ) in the middle stratosphere and 2.22 ± 0.07 in the Arctic vortex versus 1.71 ± 0.03 from previous observations and a remarkable factor of 4 larger than the mass-dependent value of 0.52. Kinetics modeling of laboratory measurements of photochemical ozone-CO2 isotope exchange demonstrates that non-mass-dependent isotope effects in ozone formation alone quantitatively account for the (17)O anomaly in CO2 in the laboratory, resolving long-standing discrepancies between models and laboratory measurements. Model sensitivities to hypothetical mass-dependent isotope effects in reactions involving O3, O((1)D), or CO2 and to an empirically derived temperature dependence of the anomalous kinetic isotope effects in ozone formation then provide a conceptual framework for understanding the differences in the isotopic composition and the triple isotope slopes between the laboratory and the stratosphere and between different regions of the stratosphere. This understanding in turn provides a firmer foundation for the diverse biogeochemical and paleoclimate applications of (17)O anomalies in tropospheric CO2, O2, mineral sulfates, and fossil bones and teeth, which all derive from stratospheric CO2.

  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


    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. Isotopic composition of Murchison organic compounds: Intramolecular carbon isotope fractionation of acetic acid. Simulation studies of cosmochemical organic syntheses (United States)

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


    Recently, in our laboratories, samples of Murchison acetic acid were decarboxylated successfully and the carbon isotopic composition was measured for the methane released by this procedure. These analyses showed significant differences in C-13/C-12 ratios for the methyl and carboxyl carbons of the acetic acid molecule, strongly suggesting that more than one carbon source may be involved in the synthesis of the Murchison organic compounds. On the basis of this finding, laboratory model systems simulating cosmochemical synthesis are being studied, especially those processes capable of involving two or more starting carbon sources.

  3. In situ observations of the isotopic composition of methane at the Cabauw tall tower site (United States)

    Röckmann, Thomas; Eyer, Simon; van der Veen, Carina; Popa, Maria E.; Tuzson, Béla; Monteil, Guillaume; Houweling, Sander; Harris, Eliza; Brunner, Dominik; Fischer, Hubertus; Zazzeri, Giulia; Lowry, David; Nisbet, Euan G.; Brand, Willi A.; Necki, Jaroslav M.; Emmenegger, Lukas; Mohn, Joachim


    High-precision analyses of the isotopic composition of methane in ambient air can potentially be used to discriminate between different source categories. Due to the complexity of isotope ratio measurements, such analyses have generally been performed in the laboratory on air samples collected in the field. This poses a limitation on the temporal resolution at which the isotopic composition can be monitored with reasonable logistical effort. Here we present the performance of a dual isotope ratio mass spectrometric system (IRMS) and a quantum cascade laser absorption spectroscopy (QCLAS)-based technique for in situ analysis of the isotopic composition of methane under field conditions. Both systems were deployed at the Cabauw Experimental Site for Atmospheric Research (CESAR) in the Netherlands and performed in situ, high-frequency (approx. hourly) measurements for a period of more than 5 months. The IRMS and QCLAS instruments were in excellent agreement with a slight systematic offset of (+0.25 ± 0.04) ‰ for δ13C and (-4.3 ± 0.4) ‰ for δD. This was corrected for, yielding a combined dataset with more than 2500 measurements of both δ13C and δD. The high-precision and high-temporal-resolution dataset not only reveals the overwhelming contribution of isotopically depleted agricultural CH4 emissions from ruminants at the Cabauw site but also allows the identification of specific events with elevated contributions from more enriched sources such as natural gas and landfills. The final dataset was compared to model calculations using the global model TM5 and the mesoscale model FLEXPART-COSMO. The results of both models agree better with the measurements when the TNO-MACC emission inventory is used in the models than when the EDGAR inventory is used. This suggests that high-resolution isotope measurements have the potential to further constrain the methane budget when they are performed at multiple sites that are representative for the entire European domain.

  4. Multiple sulfur isotope composition of oxidized Samoan melts and the implications of a sulfur isotope 'mantle array' in chemical geodynamics (United States)

    Labidi, J.; Cartigny, P.; Jackson, M. G.


    To better address how subducted protoliths drive the Earth's mantle sulfur isotope heterogeneity, we report new data for sulfur (S) and copper (Cu) abundances, S speciation and multiple S isotopic compositions (32S, 33S, 34S, 36S) in 15 fresh submarine basaltic glasses from the Samoan archipelago, which defines the enriched-mantle-2 (EM2) endmember. Bulk S abundances vary between 835 and 2279 ppm. About 17 ± 11% of sulfur is oxidized (S6+) but displays no consistent trend with bulk S abundance or any other geochemical tracer. The S isotope composition of both dissolved sulfide and sulfate yield homogeneous Δ33S and Δ36S values, within error of Canyon Diablo Troilite (CDT). In contrast, δ34S values are variable, ranging between +0.11 and +2.79‰ (±0.12‰ 1σ) for reduced sulfur, whereas oxidized sulfur values vary between +4.19 and +9.71‰ (±0.80‰, 1σ). Importantly, δ34S of the reduced S pool correlates with the 87Sr/86Sr ratios of the glasses, in a manner similar to that previously reported for South-Atlantic MORB, extending the trend to δ34S values up to + 2.79 ± 0.04 ‰, the highest value reported for undegassed oceanic basalts. As for EM-1 basalts from the South Atlantic ridge, the linear δ34S-87Sr/86Sr trend requires the EM-2 endmember to be relatively S-rich, and only sediments can account for these isotopic characteristics. While many authors argue that both the EM-1 and EM-2 mantle components record subduction of various protoliths (e.g. upper or lower continental crust, lithospheric mantle versus intra-metasomatized mantle, or others), it is proposed here that they primarily reflect sediment recycling. Their distinct Pb isotope variation can be accounted for by varying the proportion of S-poor recycled oceanic crust in the source of mantle plumes.

  5. Isotopic composition analysis and age dating of uranium samples by high resolution gamma ray spectrometry (United States)

    Apostol, A. I.; Pantelica, A.; Sima, O.; Fugaru, V.


    Non-destructive methods were applied to determine the isotopic composition and the time elapsed since last chemical purification of nine uranium samples. The applied methods are based on measuring gamma and X radiations of uranium samples by high resolution low energy gamma spectrometric system with planar high purity germanium detector and low background gamma spectrometric system with coaxial high purity germanium detector. The "Multigroup γ-ray Analysis Method for Uranium" (MGAU) code was used for the precise determination of samples' isotopic composition. The age of the samples was determined from the isotopic ratio 214Bi/234U. This ratio was calculated from the analyzed spectra of each uranium sample, using relative detection efficiency. Special attention is paid to the coincidence summing corrections that have to be taken into account when performing this type of analysis. In addition, an alternative approach for the age determination using full energy peak efficiencies obtained by Monte Carlo simulations with the GESPECOR code is described.

  6. Isotopic Composition of Xenon in Petroleum from the Shell Bullwinkle Field

    Indian Academy of Sciences (India)

    J Nuzzo*; M Hyman; M W Rowe; Mnraoz; R L Palma; J Westrich


    We have measured the abundance and isotopic composition of xenon in petroleum samples from the Shell Bullwinkle Field off the coast of Louisiana. We used an oxidation and purification procedure designed to insure complete extraction and clean up of xenon from the petroleum. The xenon isotopic composition was found to be similar to the atmospheric value for one petroleum sample. While the results of the second sample suggest possible enrichment of the heavier isotopes, the errors associated with these excesses preclude a definitive statement to that effect. No monoisotopic enrichment in 129Xe was detected in either sample, the presence of which might have allowed us to deduce the petroleum age. Our results represent only the second xenon measurement from petroleum, and the concentrations are within the range of values published in the earlier report.

  7. Isotope composition and volume of Earth´s early oceans

    DEFF Research Database (Denmark)

    Pope, Emily Catherine; Bird, Dennis K.; Rosing, Minik Thorleif


    Oxygen and hydrogen isotope compositions of Earth´s seawater are controlled by volatile fluxes among mantle, lithospheric (oceanic and continental crust), and atmospheric reservoirs. Throughout geologic time the oxygen mass budget was likely conserved within these Earth system reservoirs......, but hydrogen´s was not, as it can escape to space. Isotopic properties of serpentine from the approximately 3.8 Ga Isua Supracrustal Belt in West Greenland are used to characterize hydrogen and oxygen isotope compositions of ancient seawater. Archaean oceans were depleted in deuterium [expressed as Î...... in Earth´s oceans. Our calculations predict that the oceans of early Earth were up to 26% more voluminous, and atmospheric CH4 and CO2 concentrations determined from limits on hydrogen escape to space are consistent with clement conditions on Archaean Earth....

  8. Abnormal composition of carbon isotopes in underground alkaline waters of Kuzbass (United States)

    Shvartsev, S. L.; Lepokurova, O. E.; Ponomarchuk, V. A.; Domrocheva, E. V.; Sizikov, D. A.


    The first data on abnormally high δ13C values in hydrocarbonates (HCO 3 - ) dissolved in underground waters of coal deposits of Kuzbass (up to +30.9‰) are reported. It is shown that such an unusual isotope composition of waters results from the long, strictly directed interaction in the water-rock-gas-organic material system occurring under the conditions of hindered water exchange. Extensive fractionation of C isotopes is the result of the evolution of the water-rock-gas-coal system after penetration of infiltration waters into the coal deposits and their long interaction with all these components, rather than metamorphism of organic material upon its transformation into coal. With respect to such an approach, the isotope composition of dissolved C may indicate the duration of the evolution in the water-rock-gas-organic material system.

  9. Isotopic composition of carbon and oxygen of carbonates of oil and gas-bearing deposits of Western Siberia

    Energy Technology Data Exchange (ETDEWEB)

    Golyshev, S.I.; Cherepnin, A.V.; Rozhnev, A.N.


    There is measured the isotopic composition of carbon and oxygen in 129 samples of carbonates and carbonate cements of oil and gas-bearing Paleozoic and Mezozoic deposits of Western Siberia. The isotopic composition of samples of marine deposits varies from -1.2 to +6.1% for carbon and from 19.8 to 29.1% for oxygen and has a mean isotopic composition of 1.9 to 24.8%. Catagenetic processes lead to lightening of the isotopic composition of secondary carbonate on the average by 5% for carbon and 9% for oxygen. The most intense lightening of isotopic composition is observed in samples disposed near oil and gas deposits.

  10. Isotope variations of dissolved Zn in the Rio Grande watershed, USA: The role of adsorption on Zn isotope composition (United States)

    Szynkiewicz, Anna; Borrok, David M.


    In order to better understand the factors influencing zinc (Zn) isotope composition in hydrological systems, we analyzed the δ66Zn of dissolved Zn in the streams and groundwater of the Upper and Middle Rio Grande watershed in Colorado and New Mexico, United States. The stream water samples have a wider variation of δ66Zn (-0.57 to + 0.41 ‰ relative to the JMC 3-0749-Lyon standard) than groundwater samples (-0.13 to + 0.12 ‰) and than samples from streams that are in close proximity to abandoned mining sites (+0.24 to + 0.40 ‰). Regional changes of bedrock geology, from primarily igneous rocks to primarily sedimentary rocks, have no resolvable effect on the δ66Zn of aqueous samples. Instead, an increase in water pH from 7.5 to 8.5 corresponds to a considerable decrease in the δ66Zn of dissolved Zn (R2 = - 0.37, p = 0.003, n = 22). Consequently, we link the observed Zn isotope variations to the process of adsorption of Zn onto suspended sediment and bedrock minerals (average Δ66Znadsorbed-dissolved = + 0.31 ‰). Our results are in good agreement with previous experimental and empirical studies suggesting that Zn adsorption leads to a residual dissolved pool enriched in light Zn isotopes. Given that anthropogenic Zn sources can also be responsible for lowering of δ66Zn, and may overlap with the pH/adsorption effect on δ66Zn, the latter needs to be carefully considered in future studies to differentiate between natural and anthropogenic factors influencing Zn isotopes in this and other aquatic systems.

  11. Calcium isotopic compositions as tracers of vegetation activity in boreal permafrost ecosystems (Kulingdakan watershed, Central Siberia) (United States)

    Bagard, M.; Schmitt, A.; Chabaux, F. J.; Viers, J.; Pokrovsky, O. S.; Prokushkin, A. S.; Stille, P.; Dupré, B.


    In this work, we propose to investigate the geochemical potential of calcium isotopic fractionations in a forested boreal watershed to trace the impact of vegetation activity. This is the first study carried out in a geographical area characterized by deep and continuous permafrost. For this survey, we measured Ca and Sr isotopic compositions in the different compartments (stream waters, soil solutions, precipitations, rock, soils and soil leachates, vegetation) of a 4,100 ha Siberian watershed, the Kulingdakan watershed (Putorana Plateau, Central Siberia). Our results show that the activity of the vegetation is the only process that fractionates significantly calcium isotopes within the watershed. Indeed, Ca uptake by plants and its subsequent storage in larch tree organs favours 40Ca relatively to 44Ca. Vegetation decomposition releases light δ44/40Ca that affects calcium isotopic compositions of soil solution and soil exchangeable fractions. However, this biological impact is significant only for the South-facing slope of the watershed. Indeed, soil pools from the North-facing slope present no imprint of organic matter degradation in their δ44/40Ca signatures. Furthermore, the major difference between South- and North- facing slopes lies in the importance of the vegetation and its decomposition rate. Thus, we propose that in boreal permafrost areas with limited runoff, the available stock of biomass is critical to induce or not a significant vegetation impact on the calcium isotopic compositions in the soil-water system. As a consequence, the study of preserved calcium isotopic compositions in paleosoil exchangeable phases might bring relevant information on the evolution of biological activity at the watershed scale.

  12. Stable water isotopic composition of the Antarctic subglacial Lake Vostok: implications for understanding the lake's hydrology. (United States)

    Ekaykin, Alexey A; Lipenkov, Vladimir Y; Kozachek, Anna V; Vladimirova, Diana O


    We estimated the stable isotopic composition of water from the subglacial Lake Vostok using two different sets of samples: (1) water frozen on the drill bit immediately after the first lake unsealing and (2) water frozen in the borehole after the unsealing and re-drilled one year later. The most reliable values of the water isotopic composition are: -59.0 ± 0.3 ‰ for oxygen-18, -455 ± 1 ‰ for deuterium and 17 ± 1 ‰ for d-excess. This result is also confirmed by the modelling of isotopic transformations in the water which froze in the borehole, and by a laboratory experiment simulating this process. A comparison of the newly obtained water isotopic composition with that of the lake ice (-56.2 ‰ for oxygen-18, -442.4 ‰ for deuterium and 7.2 ‰ for d-excess) leads to the conclusion that the lake ice is very likely formed in isotopic equilibrium with water. In turn, this means that ice is formed by a slow freezing without formation of frazil ice crystals and/or water pockets. This conclusion agrees well with the observed physical and chemical properties of the lake's accreted ice. However, our estimate of the water's isotopic composition is only valid for the upper water layer and may not be representative for the deeper layers of the lake, so further investigations are required.

  13. The carbon isotope composition of atmospheric CO 2 in Paris (United States)

    Widory, David; Javoy, Marc


    One characteristic of air pollution in the urban environment is high CO 2 concentrations resulting from human activities. Determining the relative contributions of the different CO 2 sources can be addressed simply and elegantly by combining isotope and concentration measurements. Using this approach on atmospheric CO 2 samples collected in Paris, its suburbs and the open country provides fairly accurate conclusions. Our results show that air pollution within the first few metres above ground results basically from binary mixtures among which road traffic is the main contributor and, in particular, vehicles using unleaded gasoline (˜90% of the total). Heating sources, which account for 50% of the CO 2 input below the atmospheric inversion level, and vehicles using diesel contribute very little. Human respiration has a recognisable signature at street level under certain circumstances. The combined isotope and concentration analysis provides a sensitive tracer of local variations, even detecting the occasional prevalence of human respiration and the onset of actions in which natural gas is burnt. It also detects surprising inlets of 'clean air' (CO 2-wise) in the very centre of the city.

  14. The isotopic composition of methane in polar ice cores (United States)

    Craig, H.; Chou, C. C.; Welhan, J. A.; Stevens, C. M.; Engelkemeir, A.


    Air bubbles in polar ice cores indicate that about 300 years ago the atmospheric mixing ratio of methane began to increase rapidly. Today the mixing ratio is about 1.7 parts per million by volume, and, having doubled once in the past several hundred years, it will double again in the next 60 years if current rates continue. Carbon isotope ratios in methane up to 350 years in age have been measured with as little as 25 kilograms of polar ice recovered in 4-meter-long ice-core segments. The data show that: (1) in situ microbiology or chemistry has not altered the ice-core methane concentrations, and (2) that the carbon-13 to carbon-12 ratio of atmospheric CH4 in ice from 100 years and 300 years ago was about 2 per mil lower than at present. Atmospheric methane has a rich spectrum of isotopic sources: the ice-core data indicate that anthropogenic burning of the earth's biomass is the principal cause of the recent C-13H4 enrichment, although other factors may also contribute.

  15. Diet control on carbon isotopic composition of land snail shell carbonate

    Institute of Scientific and Technical Information of China (English)

    LIU ZongXiu; GU ZhaoYan; WU NaiQin; XU Bing


    Carbon isotope compositions for both the carbonate shells and soft bodies (organic tissue) of living land snails collected mostly from the Loess Plateau, China have been measured. The result shows that δ13C values range from -13.1‰ to -4.3‰ for the aragonite shell samples and from -26.8‰ to -18.0‰ for the soft body samples. Although the shells are enriched in 13C relative to the bodies averagely by 14.2(±0.8)‰, the shell δ13Ca values are closely correlated to the body δ13Corg values, expressed as δ13Ca = 1.021 δ13Corg + 14.38 (R = 0.965; N = 31). This relationship indicates that δ13Ca is primarily a function of the isotopic composition of the snail diets since previous studies have proved that the snail body is the same as their food in carbon isotope composition. In other words, carbon isotope compo-sition of the carbonate shell can be used as a proxy to estimate the dietary 13C abundance of the land snails. The data also support that the 13C enrichment of the carbonate shells results mainly from the equilibrium fractionations between the metabolic CO2, HCO3- in the hemolymph and shell aragonite, and partially from kinetic fractionations when snail shells form during their activity.

  16. The atomic weight and isotopic composition of boron and their variation in nature

    Energy Technology Data Exchange (ETDEWEB)

    Holden, N.E.


    The boron isotopic composition and atomic weight value and their variation in nature are reviewed. Questions are raised about the previously recommended value and the uncertainty for the atomic weight. The problem of what constitutes an acceptable range for normal material and what should then be considered geologically exceptional is discussed. Recent measurements make some previous decisions in need of re-evaluation.

  17. Impact of metabolism and growth phase on the hydrogen isotopic composition of microbial fatty acids

    NARCIS (Netherlands)

    Heinzelmann, S.M.; Villanueva, L.; Sinke-Schoen, D.; Sinninghe Damsté, J.S.; Schouten, S.; Van der Meer, M.T.J.


    Microorganisms are involved in all elemental cycles and therefore it is important to study their metabolism in the natural environment. A recent technique to investigate this is the hydrogen isotopic composition of microbial fatty acids, i.e., heterotrophic microorganisms produce fatty acids enriche

  18. Interpretation of groundwater origin in the Velenje coal mine on the basis of isotope composition

    Directory of Open Access Journals (Sweden)

    Janko Urbanc


    Full Text Available The aim of the investigation was to determine the isotopic properties of cave waters from the Velenje coal mine and define the recharge areas of individual aquifers. With regard to the oxygen isotope composition, groundwater in the Velenje coal mine can beclassified into three types. Typical d18O values of the first type are around -9 ‰ and are found in surface waters in the vicinity of the mine, therefore it is supposed that these waters are recharged locally. The second type is represented mainly by waters from thelower part of the pliocene aquifer. The average oxygen composition of these waters is about -11 ‰. This isotope composition is considerably different from the isotope composition of recent waters from the mine’s vicinity, which leads to the conclusion that these are older, fossile waters. These waters also have a very high degree of mineralization and consequently conductivity. Waters of the third type have average δ18O values around -10 ‰ and originate mainly from triassic dolomites. These waters could be a mixture of recentand old waters, but it is also possible that they flow into the coal mine from the higher areas of Paški Kozjak.

  19. Soil moisture effects on the carbon isotope composition of soil respiration (United States)

    Claire L. Phillips; Nick Nickerson; David Risk; Zachary E. Kayler; Chris Andersen; Alan Mix; Barbara J. Bond


    The carbon isotopic composition (δ13C) of recently assimilated plant carbon is known to depend on water-stress, caused either by low soil moisture or by low atmospheric humidity. Air humidity has also been shown to correlate with the δ13C of soil respiration, which suggests indirectly that recently fixed photosynthates...

  20. Single-molecule fluorescence autocorrelation experiments on pentacene : The dependence of intersystem crossing on isotopic composition

    NARCIS (Netherlands)

    Brouwer, A.C.J.; Köhler, J.; Oijen, A.M. van; Groenen, E.J.J.; Schmidt, J.


    Single pentacene molecules containing 13C or 1H in a pentacene-d14 doped p-terphenyl crystal have been studied by fluorescence autocorrelation. The triplet dynamics has been analyzed and a systematic dependence of the S1→T1 intersystem crossing rate on isotopic composition was found. This variation

  1. New approach to global barium cycle understanding: barium isotopic composition of marine carbonates and seawater. (United States)

    Pretet, Chloé; Nägler, Thomas F.; Reynaud, Stéphanie; de Lange, Gert J.; Turpin, Mélanie; Immenhauser, Adrian; Böttcher, Michael E.; Samankassou, Elias


    In this communication we present the Ba isotope fractionation (delta137/134Ba) study on marine carbonates and seawater, initiated to gain a first order view of the marine Ba isotope cycle. A special focus is the question whether the nutrient type distribution of Ba in the water column, as well as different Ba sources, are reflected in Ba isotope ratios of carbonate archives. The approach ultimately aims to provide an improved Ba based paleonutrient proxy. The data set is composed of carbonates (micrites and limestone standard), coral skeleton and seawater (IAPSO standard and Mediterranean seawater). Part of the corals were cultured in monitored environments (CSM, Monaco) others originate from natural environments (shallow and warm water corals from the Bahamas/Florida and cold water corals from the Norwegian shelf). The analytical procedure includes the application of a 130Ba/135Ba double spike, a cation exchange column followed by isotope measurements on a Nu Instruments Multicollector ICP-MS. The Ba fractionation of the samples is compared to a Ba nitrate standard solution and a standard natural limestone BSC-CRM 393 (0.05 ± 0.04 ‰, 2SEM). No isotopic fractionation has been observed in the limestone standard and micrites (N=8) (-0.01 ± 0.04 ‰, 2SEM) compared to the Ba nitrate standard. On the contrary, coral skeletons show a significant positive fractionation (mean = 0.4 ± 0.05 ‰, 2 SEM). No significant difference was found between different cultured coral species. Thus no species-specific fractionation is identified within the same environmental conditions. Diagenetic influence on Ba isotopic composition was further tested on 5 natural samples with varying calcite to aragonite ratios (0 to 0.3). No significant effect was observed. Moreover, the Ba isotope composition seems independant from the Ba concentration in the studied coral skeleton, within our measurement resolution. Seawater isotopic composition (-0.05 ± 0.07 ‰, 2SD) is lighter than coral

  2. The Cl Isotope Composition of the Moon as evidence for an Anhydrous Mantle (Invited) (United States)

    Sharp, Z. D.; Shearer, C., Jr.; McKeegan, K. D.; Barnes, J.; Wang, Y.


    The chlorine isotope composition of primitive terrestrial basalts and carbonaceous chondrites cover a narrow range centered around 0‰ with a total variation of ± 0.5‰. In contrast, the chlorine isotope composition of bulk samples and in situ ion microprobe analyses of lunar basalts and glasses cover a range of 25‰. Three possibilities were considered to explain the large spread: 1) initial isotopic heterogeneities, 2) devolatilization from solar wind/micrometeorite bombardment, 3) degassing under anhydrous conditions. The first of these possibilities is rejected because the Moon went through an magma ocean stage which would have homogenized any isotopic heterogeneities. To examine surface effects, we chose samples that have extremely different degrees of surface exposure. We find no correlation between the Cl isotope composition and surface exposure. We also conducted a laboratory experiment in which a thin film of NaCl was bombarded with a proton source for 24 hours with no change in Cl isotope composition. The third possibility is that the fractionation is explained by the anhydrous character of the Moon. On Earth, the volatiling Cl species is HCl. HCl is known to preferentially incorporate 37Cl relative to 35Cl due to the high bond strength of the molecule. This is offset by the higher translational velocity of H35Cl, so that overall, there is very little Cl isotope fractionation during degassing. We propose that lunar basalts were anhydrous and the volatile Cl species were metal chlorides, such as ZnCl2, NaCl, FeCl2, etc. The bond strength of metal chlorides and Cl dissolved in a basalt are similar, so that fractionation is caused mainly by volatilization, with the light isotopologue preferentially lost to the vapor phase. This idea is supported by the consistent lower Cl isotope ratios of water soluble salt fraction (~10 ‰ lower) and the lowest lunar Cl isotope values close to those of bulk Earth. The H content of lunar magmas must have been lower

  3. Isotopic composition and neutronics of the Okelobondo natural reactor (United States)

    Palenik, Christopher Samuel

    The Oklo-Okelobondo and Bangombe uranium deposits, in Gabon, Africa host Earth's only known natural nuclear fission reactors. These 2 billion year old reactors represent a unique opportunity to study used nuclear fuel over geologic periods of time. The reactors in these deposits have been studied as a means by which to constrain the source term of fission product concentrations produced during reactor operation. The source term depends on the neutronic parameters, which include reactor operation duration, neutron flux and the neutron energy spectrum. Reactor operation has been modeled using a point-source computer simulation (Oak Ridge Isotope Generation and Depletion, ORIGEN, code) for a light water reactor. Model results have been constrained using secondary ionization mass spectroscopy (SIMS) isotopic measurements of the fission products Nd and Te, as well as U in uraninite from samples collected in the Okelobondo reactor zone. Based upon the constraints on the operating conditions, the pre-reactor concentrations of Nd (150 ppm +/- 75 ppm) and Te (<1 ppm) in uraninite were estimated. Related to the burnup measured in Okelobondo samples (0.7 to 13.8 GWd/MTU), the final fission product inventories of Nd (90 to 1200 ppm) and Te (10 to 110 ppm) were calculated. By the same means, the ranges of all other fission products and actinides produced during reactor operation were calculated as a function of burnup. These results provide a source term against which the present elemental and decay abundances at the fission reactor can be compared. Furthermore, they provide new insights into the extent to which a "fossil" nuclear reactor can be characterized on the basis of its isotopic signatures. In addition, results from the study of two other natural systems related to the radionuclide and fission product transport are included. A detailed mineralogical characterization of the uranyl mineralogy at the Bangombe uranium deposit in Gabon, Africa was completed to improve

  4. Oxygen and nitrogen isotopic composition of nitrate in commercial fertilizers, nitric acid, and reagent salts. (United States)

    Michalski, Greg; Kolanowski, Michelle; Riha, Krystin M


    Nitrate is a key component of synthetic fertilizers that can be beneficial to crop production in agro-ecosystems, but can also cause damage to natural ecosystems if it is exported in large amounts. Stable isotopes, both oxygen and nitrogen, have been used to trace the sources and fate of nitrate in various ecosystems. However, the oxygen isotope composition of synthetic and organic nitrates is poorly constrained. Here, we present a study on the N and O isotope composition of nitrate-based fertilizers. The δ(15)N values of synthetic and natural nitrates were 0 ± 2 ‰ similar to the air N2 from which they are derived. The δ(18)O values of synthetic nitrates were 23 ± 3 ‰, similar to air O2, and natural nitrate fertilizer δ(18)O values (55 ± 5 ‰) were similar to those observed in atmospheric nitrate. The Δ(17)O values of synthetic fertilizer nitrate were approximately zero following a mass-dependent isotope relationship, while natural nitrate fertilizers had Δ(17)O values of 18 ± 2 ‰ similar to nitrate produced photochemically in the atmosphere. These narrow ranges of values can be used to assess the amount of nitrate arising from fertilizers in mixed systems where more than one nitrate source exists (soil, rivers, and lakes) using simple isotope mixing models.

  5. Impacts of microbial community composition on isotope fractionation during reductive dechlorination of tetrachloroethylene. (United States)

    Dong, Yiran; Butler, Elizabeth C; Philp, R Paul; Krumholz, Lee R


    Isotope fractionation has been used with increasing frequency as a tool to quantify degradation of chlorinated aliphatic pollutants in the environment. The objective of this research was to determine if the electron donor present in enrichment cultures prepared from uncontaminated sediments influenced the extent of isotope fractionation of tetrachloroethylene (PCE), either directly, or through its influence on microbial community composition. Two PCE-degrading enrichment cultures were prepared from Duck Pond (DP) sediment and were incubated with formate (DPF) or H(2) (DPH) as electron donor. DPF and DPH were significantly different in both product distribution and extent of isotope fractionation. Chemical and isotope analyses indicated that electron donors did not directly affect the product distribution or the extent of isotope fractionation for PCE reductive dechlorination. Instead, restriction fragment length polymorphism (RFLP) and sequence analysis of the 16S rRNA clone libraries of DPF and DPH identified distinct microbial communities in each enrichment culture, suggesting that differences in microbial communities were responsible for distinct product distributions and isotope fractionation between the two cultures. A dominant species identified only in DPH was closely related to known dehalogenating species (Sulfurospirillum multivorans and Sulfurospirillum halorespirans) and may be responsible for PCE degradation in DPH. Our study suggests that different dechlorinators exist at the same site and can be preferentially stimulated by different electron donors, especially over the long-term (i.e., years), typical of in-situ ground water remediation.

  6. Sedimentary nitrate reduction and its effect on the N-isotopic composition of oceanic nitrate (United States)

    Lehmann, M. F.; Sigman, D. M.; McCorkle, D. C.


    A prerequisite for assessing denitrification fluxes in a specific environment using water column nitrate N isotope ratios is the knowledge of the expressed N isotope effects of water column and/or benthic denitrification in this environment. Here, we aim at assessing the effects of benthic nitrogen cycling on the N isotopic composition of the oceanic nitrate pool in deep-sea sediments, which are believed to harbour a large portion of the global benthic denitrification. We report 15N/14N ratios of pore water nitrate in pelagic sediments from the deep Bering Sea, where benthic nitrate reduction has previously been identified as a significant sink of fixed nitrogen. Porewater profiles from multicores indicate strong 15N enrichment in porewater nitrate at all stations, as one goes deeper in the sediments and nitrate concentrations decrease (δ15N generally reached 25-35‰). Our data are consistent with variable biological isotope effect (ɛ) for dissimilatory nitrate reduction ranging between 13 to 30 ‰. A one-dimensional diffusion-reaction model including organic matter degradation, nitrification, and denitrification indicates that, although denitrification leads to a pore water nitrate pool that is enriched in 15N, N isotope fractionation is poorly expressed at the scale of sediment-water nitrate exchange, independent of whether sediments are a net sink or a net source of nitrate. The apparent nitrate isotope effect of sedimentary denitrification on nitrate in overlying waters is generally below 2‰, as a result of diffusive transport limitation into, and within, the sediments and/or the production of light nitrate during nitrification. Thus, our data suggest that the low expressed isotope effect of benthic denitrification observed previously in reactive shelf sediments also applies to deep-sea sediments. However, where ammonium fluxes out of the sediments, it is enriched in 15-N, and may ultimately lead to an N-isotopic enrichment of the water-column nitrate

  7. Influence of sea ice cover on evaporation and water vapour isotopic composition in the Arctic (United States)

    Bonne, Jean-Louis; Werner, Martin; Meyer, Hanno; Kipfstuhl, Sepp; Rabe, Benjamin; Behrens, Melanie; Schönicke, Lutz; Steen-Larsen, Hans Christian


    Since July 2015, water stable isotopes (HDO and H218O) have been measured at two Arctic facilities: during the summer on board of the research vessel Polarstern, and year-round at the Siberian coastal site of Samoylov, situated in the Lena delta (N 72°22', E 126°29'), close to the Laptev Sea. In both places, the isotopic composition of water vapour is analysed continuously in surface air. Additional isotopic measurements are performed on a daily basis in ocean surface water samples taken on Polarstern and on an event basis from precipitation sampled in Samoylov. The two Polarstern summer campaigns cover a large region of the western Artic Ocean, including a one-month campaign in the central and eastern Arctic crossing the North Pole in September 2015, with very cold conditions (up to -20°C). Combining ocean and atmospheric observations from Polarstern allows an evaluation of local surface water evaporation and its isotopic fingerprint relative to the oceanic and meteorological conditions as well as the partial sea ice cover. In the central and eastern Arctic, a large area of complete sea ice cover also revealed a strong impact on the advected moisture above the ice cap under very cold conditions. A first year of Siberian observations at Samoylov depicted a large seasonal variability, with extremely dry and isotopically depleted winter values. Contrasted seasonal isotopic regimes might be utilized for identifying moisture sources changes in the region, such as ocean surface closure by sea ice, or freezing of the Lena River. Besides documenting the present meteorology and changes in the Arctic, our measurements will contribute to a better interpretation of regional paleoclimate records based on water isotopes and to the evaluation of climate models in the Arctic. A first model-data comparison of our measurements with simulation results by the isotope-enabled atmospheric general circulation model ECHAM5-wiso have revealed relevant model biases in the Arctic realm.

  8. Regulation of Isotopic Composition of Water - way of Improvement of Cosmonauts Drinking Water Functional Properties (United States)

    Kulikova, Ekaterina; Utina, Dina; Vorozhtsova, Svetlana; Severyuhin, Yuri; Abrosimova, Anna; Sinyak, Yuri; Ivanov, Alexander

    The problem in providing drinking water to cosmonauts is solved - at this moment there is a task to improve the functional properties of the water. One of the perspectives of this trend is the use of light isotopic water. The animal studies have shown that long-term consumption of water with a depletion of deuterium and oxygen heavy isotopes accelerates the rise of mass non-irradiated mice, the phase fluctuations reducing or increasing hematological parameters were having adaptive nature. These fluctuations didn’t overcome values beyond the physiological norm of this type of animal. It is established that the therapeutic use of light isotopic water with 35 - 90 ppm in deuterium increases the survival of irradiated mice by an average of 30%, contributes to the preservation of irradiated animals body weight. Treatment of acute radiation sickness with light isotopic water stimulates hematopoietic recovery. At the same time, keeping mice drinking light isotopic water for 7 - 8 days before the irradiation (from 4 to 8.5 Gr) has no effect on the level of radio resistance. Longer keeping mice on light isotopic water, for 14 -21 days - reduction in life expectancy, animal mass, bone marrow cellularity and the level of white blood cells in irradiated animals is noted. It was established that keeping mice on light isotopic water for 14 days before exposure in experimental animals causes an increase in the mitotic index and the frequency of formation of aberrant mitosis after 24 hours of Co(60) gamma radiation in doses of 1 , 2, and 4 Gr. Thus, it is clear that the regulation of the isotopic composition of drinking water - way to improve its functional properties.

  9. The influence of traffic and wood combustion on the stable isotopic composition of carbon monoxide

    Directory of Open Access Journals (Sweden)

    M. Saurer


    Full Text Available Carbon monoxide in the atmosphere is originating from various combustion and oxidation processes. Recently, the proportion of CO resulting from the combustion of wood for domestic heating may have increased due to political measures promoting this renewable energy source. Here, we used the stable isotope composition of CO (δ13C and δ18O for the characterization of different CO sources in Switzerland, along with other indicators for traffic and wood combustion (NOx-concentration, aerosol light absorption at different wavelengths. We assessed diurnal variations of the isotopic composition of CO at 3 sites during winter: a village site dominated by domestic heating, a site close to a motorway and a rural site. The isotope ratios of wood combustion emissions were studied at a test facility, indicating significantly lower δ18O of CO from wood combustion compared to traffic emissions. At the village and the motorway site, we observed very pronounced diurnal δ18O-variations of CO with an amplitude of up to 8‰. Solving the isotope mass balance equation for three distinct sources (wood combustion, traffic, clean background air resulted in diurnal patterns consistent with other indicators for wood burning and traffic. The average night-time contribution of wood-burning to total CO was 70% at the village site, 49% at the motorway site and 29% at the rural site based on the isotope mass balance. The results, however, depend strongly on the pure source isotope values, which are not very well known. We therefore additionally applied a combined CO/NOx-isotope model for verification. Here, we separated the CO emissions into different sources based on distinct CO/NOx emissions ratios for wood combustion and traffic, and inserted this information in the isotope mass balance equation. Accordingly, a highly significant agreement between measured and calculated δ18

  10. Isotopic Composition of Gaseous Elemental Mercury (Hg0) at Various Sites in Japan (United States)

    Yamakawa, A.; Moriya, K.; Yoshinaga, J.


    Mercury (Hg) is a toxic heavy metal, which exists in various chemical forms in the environmental system. In the atmosphere, Hg exists in three forms (Hg0(g), Hg+2(g), and Hg(p)). Hg0(g) is the dominant species of atmospheric Hg, accounting for >95% of the total Hg in the atmosphere. Because Hg0(g) is highly volatile and has limited solubility in water, it cannot be easily removed by wet or dry deposition processes. Therefore, the residence time of Hg0(g) in the atmosphere is relatively long (1 to 2 years), allowing long-range transport from mercury emission source(s). Conversely, Hg+2(g) and Hg(p) are effectively removed from the atmosphere through wet and dry depositions. The determination of mercury source attribution using quantitative data is challenging because Hg0(g) may be deposited on an area upon oxidation to Hg+2(g) and associated with aerosols and particulates to form Hg(p) while the global cycling of Hg0(g). Over the last decade, the development of analytical methods of highly precise Hg isotopic measurements demonstrated mass-dependent fractionation (MDF) and mass-independent fractionation (MIF) of Hg isotopes in environmental samples. For instance, MDF of Hg isotopes is thought to occur during various natural and industrial Hg transformations. MIF of Hg isotopes is observed during abiotic reduction, photochemical and non-photochemical, and physical and chemical processes. Such processes lead to differences in the Hg isotopic composition of different emission sources, both natural and anthropogenic, and atmospheric processes (i.e., transportation, oxidation/reduction, deposition, and reemission). Therefore, Hg isotopic compositions could be used to trace the sources and processes of atmospheric Hg. For securing the reliability and accuracy of atmospheric Hg isotope data, the methods of collection, pretreatment, and isotopic measurement for Hg0(g) were developed to obtain high recovery yield of samples with no Hg isotopic fractionation during each

  11. Chemical and Oxygen Isotopic Composition of Roman and Late Antique Glass from Northern Greece

    Directory of Open Access Journals (Sweden)

    Alberta Silvestri


    Full Text Available The present paper emphasizes the importance of measuring the oxygen isotopic and chemical compositions of ancient glass, in order to constrain some features such as age, raw materials, and production technologies and to identify the “fingerprint” of local productions. In this context, thirty-nine Roman and late Antique glass samples and eight chert samples from northern Greece were selected and analysed for their oxygen isotopic and chemical compositions. Results show that the majority of glass samples are produced using natron as flux and have δ18O values of about 15.5‰, plus or minus a few tenths of one per mil, suggesting that raw materials probably come from Levantine area. Four samples are heavily enriched in 18O, and their chemical composition clearly shows that they were made with soda plant ash as flux. Isotopic and chemical data of Greek chert samples support the hypothesis of local production of the above samples. About half of the glass samples have chemical compositions, which allow their age to be constrained to the late Antique period. For the remaining glass, similarities with literature compositional groups are reported and discussed.

  12. A non-terrestrial 16O-rich isotopic composition for the protosolar nebula. (United States)

    Hashizume, Ko; Chaussidon, Marc


    The discovery in primitive components of meteorites of large oxygen isotopic variations that could not be attributed to mass-dependent fractionation effects has raised a fundamental question: what is the composition of the protosolar gas from which the host grains formed? This composition is probably preserved in the outer layers of the Sun, but the resolution of astronomical spectroscopic measurements is still too poor to be useful for comparison with planetary material. Here we report a precise determination of the oxygen isotopic composition of the solar wind from particles implanted in the outer hundreds of nanometres of metallic grains in the lunar regolith. These layers of the grains are enriched in 16O by >20 +/- 4 per thousand relative to the Earth, Mars and bulk meteorites, which implies the existence in the solar accretion disk of reactions--as yet unknown--that were able to change the 17O/16O and 18O/16O ratios in a way that was not dependent strictly on the mass of the isotope. Photochemical self-shielding of the CO gas irradiated by ultraviolet light may be one of these key processes, because it depends on the abundance of the isotopes, rather than their masses.

  13. The specific carbon isotopic compositions of branched and cyclic hydrocarbons from Fushun oil shale

    Institute of Scientific and Technical Information of China (English)

    DUAN Yi; WU Baoxiang; ZHENG Guodong; ZHANG Hui; ZHENG Chaoyang


    Various branched and cyclic hydrocarbons are isolated from the Fushun oil shale and their carbon isotopes are determined. The analytical results show that the branched and cyclic hydrocarbons are fully separated from n-alkanes by 5 A Molecular-sieve adduction using long time and cold solvent. The branched and cyclic hydrocarbon fraction obtained by this method is able to satisfy the analytic requests of GC-IRMS. The carbon isotopic compositions of these branched and cyclic hydrocarbons obtained from the sample indicate that they are derived from photoautotrophic algae, chemoautotrophic bacteria (-3.4‰ --39.0‰) and methanotrophic bacteria (-38.4‰--46.3‰). However the long-chain 2-methyl-branched alkanes indicate that their carbon isotopic compositions reflect biological origin from higher plants. The carbon isotopic composition of C30 4-methyl sterane (-22.1‰) is the heaviest in all studied ste- ranes, showing that the carbon source or growth condition for its precursor, dinoflagellate, may be different from that of regular steranes. The variation trend of δ13C values between isomers of hopanes shows that 13C-enriched precursors take precedence in process of their epimerization. Methanotrophic hopanes presented reveal the processes of strong transformation of organic matter and cycling of organic carbon in the water column and early diagenesis of oil shale.

  14. Stable carbon isotope composition of monoterpanes in essential oils and crude oils

    Institute of Scientific and Technical Information of China (English)


    Twenty-five monoterpanes from six types of essential oils and hydrogenated turpentine oil have been identified and their stable carbon isotope composition determined.Monoterpanes in essential oils sourced from terrestrial higher plants display a δ13C value in the range of-34‰-26‰,and mostly between-29‰ and-27‰.The δ13C value of any single monoterpane is very consistent in different essential oils.Acyclic monoterpanes show closer isotope composition between-28.6‰ and-26.2‰,with an average value of-27.7‰.In contrast,the isotope composition of cyclic monoterpanes is more scattered with an average value of-28.6‰.Isotopic fractionation with 13C enrichment has been observed during both artificial and geological hydrogenation of monoterpenoids to monoterpanes,and this is more obvious for the acyclic monoterpenoids.In addition to higher plants,acyclic monoterpane 2,6-dimethylheptane in crude oil can also be originated from other organic inputs.

  15. Preservation of Earth-forming events in the tungsten isotopic composition of modern flood basalts (United States)

    Rizo, Hanika; Walker, Richard J.; Carlson, Richard W.; Horan, Mary F.; Mukhopadhyay, Sujoy; Manthos, Vicky; Francis, Don; Jackson, Matthew G.


    How much of Earth's compositional variation dates to processes that occurred during planet formation remains an unanswered question. High-precision tungsten isotopic data from rocks from two large igneous provinces, the North Atlantic Igneous Province and the Ontong Java Plateau, reveal preservation to the Phanerozoic of tungsten isotopic heterogeneities in the mantle. These heterogeneities, caused by the decay of hafnium-182 in mantle domains with high hafnium/tungsten ratios, were created during the first ~50 million years of solar system history, indicating that portions of the mantle that formed during Earth’s primary accretionary period have survived to the present.

  16. The Oxygen Isotopic Composition of MIL 090001: A CR2 Chondrite with Abundant Refractory Inclusions (United States)

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


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

  17. On the iron isotope composition of Mars and volatile depletion in the terrestrial planets (United States)

    Sossi, Paolo A.; Nebel, Oliver; Anand, Mahesh; Poitrasson, Franck


    Iron is the most abundant multivalent element in planetary reservoirs, meaning its isotope composition (expressed as δ57Fe) may record signatures of processes that occurred during the formation and subsequent differentiation of the terrestrial planets. Chondritic meteorites, putative constituents of the planets and remnants of undifferentiated inner solar system bodies, have δ57Fe ≈ 0 ‰; an isotopic signature shared with the Martian Shergottite-Nakhlite-Chassignite (SNC) suite of meteorites. The silicate Earth and Moon, as represented by basaltic rocks, are distinctly heavier, δ57Fe ≈ + 0.1 ‰. However, some authors have recently argued, on the basis of iron isotope measurements of abyssal peridotites, that the composition of the Earth's mantle is δ57Fe = + 0.04 ± 0.04 ‰, indistinguishable from the mean Martian value. To provide a more robust estimate for Mars, we present new high-precision iron isotope data on 17 SNC meteorites and 5 mineral separates. We find that the iron isotope compositions of Martian meteorites reflect igneous processes, with nakhlites and evolved shergottites displaying heavier δ57Fe (+ 0.05 ± 0.03 ‰), whereas MgO-rich rocks are lighter (δ57Fe ≈ - 0.01 ± 0.02 ‰). These systematics are controlled by the fractionation of olivine and pyroxene, attested to by the lighter isotope composition of pyroxene compared to whole rock nakhlites. Extrapolation of the δ57Fe SNC liquid line of descent to a putative Martian mantle yields a δ57Fe value lighter than its terrestrial counterpart, but indistinguishable from chondrites. Iron isotopes in planetary basalts of the inner solar system correlate positively with Fe/Mn and silicon isotopes. While Mars and IV-Vesta are undepleted in iron and accordingly have chondritic δ57Fe, the Earth experienced volatile depletion at low (1300 K) temperatures, likely at an early stage in the solar nebula, whereas additional post-nebular Fe loss is possible for the Moon and angrites.

  18. A Record of Oceanic Lithium Isotope Composition for the Last 7Ma (United States)

    Marriott, C. S.; Henderson, G. M.


    Continental weathering plays an important role in global climate change but has proved difficult to reconstruct for the past. New geological tools with which to assess the past rate and style of weathering are therefore urgently required. One such tool is Li isotope fractionation. Recent studies [1,2] have shown preferential release of 7Li into the aqueous phase and retention/adsorption of 6Li during weathering processes such as partial dissolution and secondary mineral formation. Lithium behaves conservatively in the oceans, with a residence time of ˜1Ma, so that a history of ocean Li isotope composition provides information about the average rate and style of global continental weathering on long timescales. The incorporation of lithium as a trace element in marine carbonates enables the construction of a record of oceanic Li-isotopic variation and is the focus of this work. Carbonate Li-isotope compositions are lighter than seawater by ˜8 per mil, but this fractionation is not temperature dependent. This has been demonstrated by measurement of Li isotopes in inorganically precipitated calcites (5-30° C) [3], in coralline aragonite (25-30° C) [3] and in benthic foraminifera Uvigerina (7-23° C). This lack of T-dependent fractionation suggests that the variation in the isotope composition of planktonic foraminifera will solely reflect changes in oceanic Li isotope composition, which in turn is strongly influence by changes in continental weathering. ODP site 758, located on the Ninetyeast Ridge in the Indian Ocean (5° N, 90° E; 2925m), was sampled at 2m intervals, over a depth corresponding to the last 7Ma, to produce 55 samples with a temporal resolution of approximately 130Ka. Site 758 is previously well studied with an existing chronology and high resolution Sr, O and Nd isotope data. Individual foram species in the core top were first investigated to assess inter-species fractionation effects. Down core lithium isotope variation was examined by

  19. Temperature and Oxygen Isotope Composition of The Ediacaran Ocean: Constraints From Clumped Isotope Carbonate Thermometry (United States)

    Bonifacie, M.; Eiler, J. M.; Fike, D. A.


    The temperature and chemical variations of the early oceans on Earth are highly debated, particularly for periods associated with significant evolutionary change and/or extinction. The temperature of past oceans has been estimated based on conventional carbonate-water and/or silicate-water stable oxygen isotope thermometry. Precambrian carbonates and silicates both exhibit a long-term secular trend of increasing δ18O values with decreasing age. This trend has been used to support two opposite - though related - interpretations: the Earth's oceans gradually cooled over the course of the Proterozoic eon, from a maximum of ~ 60-90°C at ~ 2.5Ga (and were, on average, relatively warm during much of the Paleozoic era) [1]. This interpretation has been supported by Si-isotope proxies and the thermal tolerances of proteins in various classes of microbial organisms [2-3]. Alternatively, the δ18O value of the oceans has gradually increased through time [4-5], and mean Earth surface temperatures varied over a narrow range similar to modern conditions. In other terms, one either assumes an ocean of constant δ18O and infers that climate varied dramatically, or vise versa. Finally, it is possible that post- depositional processes (e.g., diagenesis, burial metamorphism, weathering) has modified the δ18O values of all or most Precambrian sedimentary carbonates and silicates, overprinting any paleoclimatic variations. Carbonate 'clumped isotope' thermometry provides a new way to independently test these hypotheses because it allows one to determine the apparent growth temperatures of carbonate minerals based on their abundances of 13C-18O bonds, as reflected by the 'Δ47' value of CO2 extracted by phosphoric acid digestion [6]. This method is thermodynamically based and independent of the δ18O of water from which the carbonate grew. We will report the initial results of measurements of 'Δ47 for a suite of carbonates from the Sultanate of Oman. This Ediacaran age (~ 635 to

  20. Change of Sm-Nd isotope composition during weathering of till (United States)

    Öhlander, Björn; Ingri, Johan; Land, Magnus; Schöberg, Hans


    Weathering of till in northern Sweden results in the formation of well-developed spodosols. The till is dominated by 1.9-1.8 Ga granitic material. The REE are among the elements most strongly depleted during weathering, and the loss of REE from the E-horizon decreases as the atomic number increases. To study if weathering leads to a change of the Nd isotope composition, we have analysed the Nd isotopic composition of the various horizons including living plants and humus of two profiles of weathered till (typic haplocryods) in northern Sweden. As much as between 65.6 and 75.3% of the Sm and Nd in the fraction has been lost from the E-horizon, and between 32.5 and 54.7% from the B-horizon. Nd has been lost to a slightly greater extent than Sm. The two C-horizon samples have ɛ Nd(0) values of -22.1 and -23.2. Corresponding E-horizon values are -18.1 and -20.2. The B-horizon values are intermediate between the values of the E and C horizons. It is concluded that the weathering leads to a change in the Sm/Nd ratio resulting in a change of the Sm-Nd isotope composition. The plant and humus samples deviate even more from the unweathered till. For one station the results could be interpreted as if the Sm and Nd taken up by the plants had similar isotope characteristics as the amounts of these elements released by weathering in the E-horizon. For the other station it is probable that the Nd isotope composition of the organic samples is dominated by Nd released by till weathering which, however, is mixed with another Nd-source, possibly an airborne component. The explanation to the change of isotope compostion in the till is that a larger proportion of the Nd released by weathering is released from minerals with a lower Sm/Nd ratio than the bulk soil, compared with the amount released from minerals with a higher Sm/Nd ratio. Although the various REE-carrying minerals had the same initial Nd isotopic composition, 1.8-1.9 Ga of decay of 147Sm to 143Nd has resulted in a

  1. Predicting the Isotopic Composition of Subduction-Filtered Subducted Oceanic Crust and Sediment (United States)

    White, W. M.


    The chemical and isotopic character of mantle plumes, which produce oceanic island volcanoes, are widely thought to reflect the presence of recycled oceanic crust and sediment. Isotopic systematics suggest the “cycle time” for this process is 1 Ga or longer, but it should be possible to use a simple mass balance approach to discern how the presently operating subduction zone filter affects the ratios of radioactive parent to radiogenic daughter isotopes. Simple uniformitarian assumptions can then be used to predict the present isotopic composition of anciently subducted lithosphere. Our underlying assumption in deciphering the subduction zone filter is that the flux of an element into the deep mantle is simply equal to the flux of element into the subduction zone less the flux of that element into subduction zone magmas. The former is readily calculated from published data. The latter can be calculated by estimating parental magma compositions, arc accretion rates, and the assumption that arc magma compositions differ from MORB only because of material derived from subducting crust and sediment. Using this approach for 8 intra-oceanic subduction zones, we find 73% of Th and Pb, 79% of U, 80% of Rb and Sr, 93% of Nd and 98% of Sm survive the subduction zone filter. The subduction zone filter systematically increases Sm/Nd ratios in all subduction zones, but the effect is small, with a weighted mean increase of 1.5%. The effect of subduction is to decrease the Sm/Nd of the mantle, but only slightly. The effect of subduction is to increase the Rb/Sr of the mantle, but the subduction zone filter does not have a systematic effect on Rb/Sr ratios: it significantly increases in Rb/Sr in 3 subduction zones and significantly decreases it in one; the weighted mean shows no significant change. The effect of the subduction zone filter on U/Pb is also not systematic. U/Pb ratios in the mantle fluxes are bimodal, with values equal to or lower than the bulk Earth value in 4

  2. Stable isotope and chemical compositions of European and Australasian ciders as a guide to authenticity. (United States)

    Carter, James F; Yates, Hans S A; Tinggi, Ujang


    This paper presents a data set derived from the analysis of bottled and canned ciders that may be used for comparison with suspected counterfeit or substitute products. Isotopic analysis of the solid residues from ciders (predominantly sugar) provided a means to determine the addition of C4 plant sugars. The added sugars were found to comprise cane sugar, high-fructose corn syrup, glucose, or combinations. The majority of ciders from Australia and New Zealand were found to contain significant amounts of added sugar, which provided a limited means to distinguish these ciders from European ciders. The hydrogen and oxygen isotopic compositions of the whole ciders (predominantly water) were shown to be controlled by two factors, the water available to the parent plant and evaporation. Analysis of data derived from both isotopic and chemical analysis of ciders provided a means to discriminate between regions and countries of manufacture.

  3. Modelling the regional climate and isotopic composition of Svalbard precipitation using REMOiso

    DEFF Research Database (Denmark)

    Divine..[], D.V.; Sjolte, Jesper; Isaksson, E.;


    Simulations of a regional (approx. 50 km resolution) circulation model REMOiso with embedded stable water isotope module covering the period 1958-2001 are compared with the two instrumental climate and four isotope series (d18O) from western Svalbard. We examine the data from ice cores drilled...... on Svalbard ice caps in 1997 (Lomonosovfonna, 1250 m asl) and 2005 (Holtedahlfonna, 1150 m asl) and the GNIP series from Ny-angstrom lesund and Isfjord Radio. The surface air temperature (SAT) and precipitation data from Longyearbyen and Ny-angstrom lesund are used to assess the skill of the model...... in reproducing the local climate. The model successfully captures the climate variations on the daily to multidecadal times scales although it tends to systematically underestimate the winter SAT. Analysis suggests that REMOiso performs better at simulating isotope compositions of precipitation in the winter...

  4. Carbon isotope composition of low molecular weight hydrocarbons and monocarboxylic acids from Murchison meteorite (United States)

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


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

  5. Stable isotope study of a new chondrichthyan fauna (Kimmeridgian, Porrentruy, Swiss Jura): an unusual freshwater-influenced isotopic composition for the hybodont shark Asteracanthus (United States)

    Leuzinger, L.; Kocsis, L.; Billon-Bruyat, J.-P.; Spezzaferri, S.; Vennemann, T.


    Chondrichthyan teeth (sharks, rays, and chimaeras) are mineralized in isotopic equilibrium with the surrounding water, and parameters such as water temperature and salinity can be inferred from the oxygen isotopic composition (δ18Op) of their bioapatite. We analysed a new chondrichthyan assemblage, as well as teeth from bony fish (Pycnodontiformes). All specimens are from Kimmeridgian coastal marine deposits of the Swiss Jura (vicinity of Porrentruy, Ajoie district, NW Switzerland). While the overall faunal composition and the isotopic composition of bony fish are generally consistent with marine conditions, unusually low δ18Op values were measured for the hybodont shark Asteracanthus. These values are also lower compared to previously published data from older European Jurassic localities. Additional analyses on material from Solothurn (Kimmeridgian, NW Switzerland) also have comparable, low-18O isotopic compositions for Asteracanthus. The data are hence interpreted to represent a so far unique, freshwater-influenced isotopic composition for this shark that is classically considered a marine genus. While reproduction in freshwater or brackish realms is established for other hybodonts, a similar behaviour for Asteracanthus is proposed here. Regular excursions into lower salinity waters can be linked to the age of the deposits and correspond to an ecological adaptation, most likely driven by the Kimmeridgian transgression and by the competition of the hybodont shark Asteracanthus with the rapidly diversifying neoselachians (modern sharks).

  6. Stable isotope study of a new chondrichthyan fauna (Kimmeridgian, Porrentruy, Swiss Jura: an unusual freshwater-influenced isotopic composition for the hybodont shark Asteracanthus

    Directory of Open Access Journals (Sweden)

    L. Leuzinger


    Full Text Available Chondrichthyan teeth (sharks, rays and chimaeras are mineralised in isotopic equilibrium with the surrounding water, and parameters such as water temperature and salinity can be inferred from the oxygen isotopic composition (δ18Op of their bioapatite. We analysed a new chondrichthyan assemblage, as well as teeth from bony fish (Pycnodontiformes. All specimens are from Kimmeridgian coastal marine deposits of the Swiss Jura (vicinity of Porrentruy, Ajoie district, NW Switzerland. While the overall faunal composition and the isotopic composition of bony fish are consistent with marine conditions, unusually low δ18Op values were measured for the hybodont shark Asteracanthus. These values are also lower compared to previously published data from older European Jurassic localities. Additional analyses on material from Solothurn (Kimmeridgian, NW Switzerland also have comparable, low-18O isotopic compositions for Asteracanthus. The data are hence interpreted to represent a so far unique, freshwater-influenced isotopic composition for this shark that is classically considered as a marine genus. While reproduction in freshwater or brackish realms is established for other hybodonts, a similar behaviour for Asteracanthus is proposed here. Regular excursions into lower salinity waters can be linked to the age of the deposits and correspond to an ecological adaptation, most likely driven by the Kimmeridgian transgression and by the competition of the primitive shark Asteracanthus with the rapidly diversifying neoselachians (modern sharks.

  7. Experimental assessment of environmental influences on the stable isotopic composition of Daphnia pulicaria and their ephippia (United States)

    Schilder, J.; Tellenbach, C.; Möst, M.; Spaak, P.; van Hardenbroek, M.; Wooller, M. J.; Heiri, O.


    The stable isotopic composition of fossil resting eggs (ephippia) of Daphnia spp. is being used to reconstruct past environmental conditions in lake ecosystems. However, the underlying assumption that the stable isotopic composition of the ephippia reflects the stable isotopic composition of the parent Daphnia, of their diet and of the environmental water have yet to be confirmed in a controlled experimental setting. We performed experiments with Daphnia pulicaria cultures, which included a control treatment conducted at 12 °C in filtered lake water and with a diet of fresh algae, and three treatments in which we manipulated the stable carbon isotopic composition (δ13C value) of the algae, stable oxygen isotopic composition (δ18O value) of the water, and the water temperature, respectively. The stable nitrogen isotopic composition (δ15N value) of the algae was similar for all treatments. At 12 °C, differences in algal δ13C values and in δ18O values of water are reflected in those of Daphnia. The differences between ephippia and Daphnia stable isotope ratios were similar in the different treatments (δ13C: + 0.2 ± 0.4‰ (SD); δ15N: -1.6 ± 0.4‰; δ18O: -0.9 ± 0.4‰) indicating that changes in dietary δ13C and δ18O values of water are passed on to these fossilizing structures. A higher water temperature (20 °C) resulted in lower δ13C values in Daphnia and ephippia than in the other treatments with the same food source and in a minor change in the difference between δ13C values of ephippia and Daphnia (to -1.3 ± 0.3‰). This may have been due to microbial processes or increased algal respiration rates in the experimental containers, which may not affect Daphnia in natural environments. There was no significant difference in the offset between δ18O and δ15N values of ephippia and Daphnia between the 12 °C and 20 °C treatments, but the δ18O values of Daphnia and ephippia were on average 1.2‰ lower at 20 °C compared with 12 °C. We conclude

  8. Lead isotopic compositions of common arsenical pesticides used in New England (United States)

    Ayuso, Robert; Foley, Nora; Robinson, Gilpin; Wandless, Gregory; Dillingham, Jeremy


    The three most important arsenical pesticides and herbicides that were extensively used on apple, blueberry, and potato crops in New England from mid-1800s to recent times are lead arsenate, calcium arsenate, and sodium arsenate. Lead arsenate was probably the most heavily used of the arsenical pesticides until it was banned in 1988. Other metal-arsenic pesticides were also used but in lesser amounts. A recent report identified areas in New England where arsenical pesticides were used extensively (Robinson and Ayuso, 2004). On the basis of factor analysis of metal concentrations in stream sediment samples, a positive correlation with pesticide use was shown in regions having stream sediment sample populations that contained concentrations of high arsenic and lead. Lead isotope compositions of stream sediments from areas with heavy use of the pesticides could not be entirely explained by lead originating from rock sulfides and their weathering products. An industrial lead contribution (mostly from atmospheric deposition of lead) was suggested in general to explain the lead isotopic distributions of the stream sediments that could not be accounted for by the natural lead in the environment. We concluded that when agricultural land previously contaminated with arsenical pesticides is urbanized, pesticide residues in the soils and stream sediments could be released into the groundwater. No lead isotopic data characterizing the compositions of pesticides were available for comparison. We have determined the lead isotopic compositions of commonly used pesticides in New England, such as lead arsenate, sodium metaarsenite, and calcium arsenate, in order to assist in future isotopic comparisons and to better establish anthropogenic sources of Pb and As. New data are also presented for copper acetoarsenite (or Paris green), methyl arsonic acid and methane arsonic acid, as well as for arsanilic acid, all of which are used as feed additives to promote swine and poultry growth

  9. Soil Drying Effects on the Carbon Isotope Composition of Soil Respiration (United States)

    Phillips, C. L.; Nickerson, N.; Risk, D.; Kayler, Z. E.; Rugh, W.; Mix, A. C.; Bond, B. J.


    Stable isotopes are used widely as a tool for determining sources of carbon (C) fluxes in ecosystem C studies. Environmental factors that change over time, such as moisture, can create dynamic changes in the isotopic composition of C assimilated by plants, and offers a unique opportunity to distinguish fast- responding plant C from slower-responding soil C pools, which under steady-state conditions may be too similar isotopically to partition. Monitoring the isotopic composition of soil respiration over a period of changing moisture conditions is potentially a useful approach for characterizing plant contributions to soil respiration. But this partitioning hinges on the assumption that any change in the isotopic signature of soil respiration is solely due to recent photosynthetic discrimination, and that post-photosynthetic processes, such as microbial respiration, do not discriminate as moisture decreases. The purpose of the present study is to test the assumption that δ13CO2 from microbial respiration remains static as soil dries. We conducted a series of greenhouse experiments employing different techniques to isolate microbial respiration from root respiration. The first involves removing roots from soil, and showed that when roots are present, respiration from dry soil is enriched in 13C relative to moist soil, but when roots are absent, respiration is isotopically similar from moist and dry soils. This indicates that rhizospheric respiration changes isotopically with moisture whereas soil microbial respiration does not. In contrast, a second experiment in which soil columns without plants were monitored as they dried, showed respiration from very dry soil to be enriched by 8‰ relative to moist soil. However, simulations with an isotopologue-based soil gas diffusion model demonstrate that at least a portion of the apparent enrichment is due to non-steady state gas transport processes. Careful sampling methodologies which prevent or account for non

  10. REE characteristics and Pb, Sr and Nd isotopic compositions of steel plant emissions. (United States)

    Geagea, M Lahd; Stille, P; Millet, M; Perrone, Th


    A comprehensive Pb-Sr-Nd isotope and REE tracer study of atmospheric trace metal pollution by a steel plant situated to the north of the urban communities of Strasbourg (France) and Kehl (Germany) has been performed using tree barks as biomonitors. The 206Pb/207Pb and 208Pb/207Pb isotopic ratios of the steel plant's filter dust are similar to values found in dust of waste incinerators. The 87Sr/86Sr ratio is similar to present-day ratios of Phanerozoic or Precambrian granitic rocks. The 143Nd/144Nd isotopic composition is very low and corresponds to an (Nd) value of -17.5. Such a low value is characteristic of old Precambrian granitic rocks and banded iron formations. Thus, this low (Nd) value might point to the origin of the iron necessary for the steel production. The fact, that this isotopic composition does not occur in crustal rocks of Western Central Europe makes the Nd isotope ratio a powerful tool to trace steel plants atmospheric emissions. The rare earth element (REE) distribution pattern of the steel plant's filter dust shows very specific fractionations like La and Nd enrichments which are traceable in tree barks over a distance of 4 km. The Pb, Sr and Nd isotope ratios not only enable the steel plant's emissions to be traced in a north-easterly direction, along the principal wind pathway but also enables the interference of this emission at 4 km NE from the steel plant with another atmospheric component originating from the Strasbourg Rhine harbour to be identified.

  11. Detection of phosphohydrolytic enzyme activity through the oxygen isotope composition of dissolved phosphate (United States)

    Colman, A. S.


    Phosphohydrolytic enzymes play an important role in phosphorus remineralization. As they release phosphate (Pi) from various organophosphorus compounds, these enzymes facilitate the transfer of oxygen atoms from water to the phosphoryl moieties. Most such enzymatic reactions impart a significant isotopic fractionation to the oxygen transferred. If this reaction occurs within a cell, then the resultant oxygen isotope signal is overprinted by continued recycling of the Pi. However, if this reaction occurs extracellularly, then the isotopic signal will be preserved until the Pi is transported back into a cell. Thus, the oxygen isotope composition of Pi (δ18Op) in an aquatic ecosystem can serve as a useful indicator of the mechanisms by which P is remineralized. We develop a time-dependent model illustrating the sensitivity of the δ18O of dissolved phosphate to various modes of P remineralization. The model is informed by cell lysis experiments that reveal the relative proportions of P­i that are directly liberated from cytosol vs. regenerated from co-liberated dissolved organic phosphorus compounds via extracellular hydrolysis. By incorporating both cellular uptake and release fluxes of P, we show that the degree of isotopic disequilibrium in an aquatic ecosystem can be a strong indicator of P remineralization mode. Apparent oxygen isotope equilibrium between Pi and water arises in this model as a steady-state scenario in which fractionation upon cellular uptake of Pi counterbalances the hydrolytic source flux of disequilibrated Pi. Low and high rates of extracellular phosphohydrolase activity are shown to produce steady-state δ18Op values that are respectively above or below thermodynamic equilibrium compositions.

  12. Diamond growth history from in situ measurement of Pb and S isotopic compositions of sulfide inclusions (United States)

    Rudnick, Roberta L.; Eldridge, C. Stewart; Bulanova, Galina P.


    In a continuing effort to understand crust-mantle dynamics, we have determined the S and Pb isotopic compositions of mantle sulfides encapsulated within diamonds from under the Siberian craton and compared these results to those of previously investigated African counterparts. Because diamond inclusions are isolated from exchange with surrounding mantle, they may preserve the history of diamond growth and act as direct tracers of the origins of mantle materials. Study of these inclusions may thus offer the best chance of recognizing global-scale interaction between Earth's crust and mantle. Although δ34S values of the Siberian sulfides do not deviate significantly from the mantle value of 0‰ ± 3‰, Pb isotopic compositions are highly variable. Pb isotopic compositions of sulfides from peridotitic suite diamonds generally plot near the terrestrial Pb growth curve, with model ages ranging between 0 and 2 Ga, whereas sulfides from eclogitic suite diamonds have radiogenic compositions, plotting beyond the growth curve. These results, which are similar to those for sulfides in African diamonds, suggest that the sulfides from eclogitic suite diamonds were derived from a source with an unusually high U/Pb ratio and may indicate a common process (such as subduction of crystal materials into the mantle) operating beneath Africa and Siberia. The absence of extremely radiogenic Pb in sulfides from eclogite xenoliths suggests that the radiogenic material from which eclogitic suite diamonds grew was a transient feature of the mantle, associated with diamond growth. The ultimate origin of this high U/Pb signature, however, remains enigmatic. Large variations in Pb isotopic composition of sulfides from different zones in a single peridotitic suite diamond document (1) crystallization of the diamond's core near 2.0 Ga, (2) growth of its outer zone in an environment with a high U/Pb ratio similar to the growth environment of eclogitic suite diamonds, and (3) growth of the

  13. Isotope composition of winter precipitation and snow cover in the foothills of the Altai

    Directory of Open Access Journals (Sweden)

    N. S. Malygina


    Full Text Available Over the past three decades, several general circulation models of the atmosphere and ocean (atmospheric and oceanic general circulation models  – GCMs have been improved by modeling the hydrological cycle with the use of isotopologues (isotopes of water HDO and H2 18O. Input parameters for the GCM models taking into account changes in the isotope composition of atmospheric precipitation were, above all, the results obtained by the network GNIP – Global Network of Isotopes in Precipitation. At different times, on the vast territory of Russia there were only about 40 simultaneously functioning stations where the sampling of atmospheric precipitation was performed. In this study we present the results of the isotope composition of samples taken on the foothills of the Altai during two winter seasons of 2014/15 and 2015/16. Values of the isotope composition of precipitation changed in a wide range and their maximum fluctuations were 25, 202 and 18‰ for δ18О, dexc and δD, respectively. The weighted-mean values of δ18О and δD of the precipitation analyzed for the above two seasons were close to each other (−21.1 and −158.1‰ for the first season and −21.1 and −161.9‰ for the second one, while dexc values differed significantly. The comparison of the results of isotope analysis of the snow cover integral samples with the corresponding in the time interval the weighted-mean values of precipitation showed high consistency. However, despite the similarity of values of δ18О and δD, calculated for precipitation and snow cover, and the results, interpolated in IsoMAP (from data of the GNIP stations for 1960–2010, the dexc values were close to mean annual values of IsoMAP for only the second winter season. According to the trajectory analysis (the HYSPLIT model, the revealed differences between both, the seasons, and the long-term average values of IsoMAP, were associated with a change of main regions where the air masses

  14. 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


    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.

  15. Controlling Factors of the Stable Isotope Composition in the Precipitation of Islamabad, Pakistan

    Directory of Open Access Journals (Sweden)

    Shakir Hussain


    Full Text Available Significant temporal variations in δ18O and deuterium isotopes were found in the rainfall water of Islamabad, Pakistan, over a 15-year period (1992–2006. The data were obtained from the International Atomic Energy Agency/Global Network of Isotopes in Precipitation (IAEA/GNIP database, and statistical correlations were investigated. In particular, this study provides the first detailed analysis of GNIP data for Islamabad. Both dry (1999-2000 and wet years (1994, 1997, and 2000 were chosen to investigate the correlations between precipitation amount, vapor flux, and temperature. We observed obvious differences between the dry and wet years and among seasons as well. Long-term features in the isotope composition agreed with the global meteorological water line, whereas short-term values followed rainfall amounts; that is, a total of 72% of the precipitation’s isotopic signature was dependent on the rainfall amount, and temperature controlled 73% of the isotopic features during October to May. The lower d-excess values were attributed to conditions during the spring season and a secondary evaporation boost during dry years; precipitation originating from the Mediterranean Sea showed high d-excess values. Overall, the results of this study contribute to the understanding of precipitation variations and their association with water vapor transport over Islamabad, Pakistan.

  16. Neoproterozoic variations in the C-isotopic composition of seawater: stratigraphic and biogeochemical implications. (United States)

    Kaufman, A J; Knoll, A H


    The recent proliferation of stratigraphic studies of delta 13C variation in carbonates and organic C in later Neoproterozoic and basal Cambrian successions (approximately 850-530 Ma) indicates a strong oscillating trend in the C-isotopic composition of surface seawater. Alone, this trend does not adequately characterize discrete intervals in Neoproterozoic time. However, integrated with the vectorial signals provided by fossils and Sr-isotopic variations, C isotope chemostratigraphy facilitates the interbasinal correlation of later Neoproterozoic successions. Results of these studies are evaluated in terms of four stratigraphic intervals: (1) the Precambrian/Cambrian boundary, (2) the post-Varanger terminal Proterozoic, (3) the late Cryogenian, and (4) the early Cryogenian. Where biostratigraphic or radiometric data constrain the age of Neoproterozoic sedimentary sequences, secular variations in C and Sr isotopes can provide a level of stratigraphic resolution exceeding that provided by fossils alone. Isotopic data place strong constraints on the chemical evolution of seawater, linking it to major tectonic and paleoclimatic events. They also provide a biogeochemical framework for the understanding of the initial radiation of macroscopic metazoans, which is associated stratigraphically, and perhaps causally, with a global increase in the burial of organic C and a concomitant rise of atmospheric O2.

  17. Anthropogenic Pb input into Bohai Bay, China: Evidence from stable Pb isotopic compositions in sediments (United States)

    Hu, Ningjing; Huang, Peng


    Anthropogenic Pb input into Bohai Bay, China: Evidence from stable Pb isotopic compositions in sediments Hu Ning-jinga, Huang Pengb,, Liu Ji-huaa, a First Institute of Oceanography, State Oceanic Administration, Qingdao 266061, China b Institute of Oceanology, Chinese Academy of Sciences, Qingdao 266071, China To investigate the source of Pb within Bohai Bay, Pb concentrations and Pb isotopic compositions (204Pb, 206Pb, 207Pb, and 208Pb) of surface sediments in this area were determined. The Pb concentration in this bay varied widely from 6.9 to 39.2 μg/g (average: 21.8 ± 7.8 μg/g), and the Pb isotopic compositions ranged from 0.8338 to 0.8864 (average: 2.0997 ± 0.0180) for 208Pb/206Pb and from 2.0797 to 2.1531 (average: 0.8477 ± 0.0135) for 207Pb/206Pb, presenting in three distinct clusters. The Pb isotopic ratios of sediments from the northeastern (NE zone) and northwestern (NW zone) coastal areas were significantly influenced by anthropogenic sources such as coal combustion and automobile emission. In sediments from the central and southern Bohai Bay (C-S zone); however, Pb mainly originated from the Yellow River catchment, as a result of lithogenic sediment (from rock weathering) accumulation. The Pb isotopic ratios further indicate that, apart from riverine inputs, the neighboring large-scale ports and aerosols significantly contributed to the anthropogenic Pb contained in these sediments. Pb contamination in the Haihe and Luanhe river mouths as well as in the regions near ports is also suggested from anthropogenic enrichment factors. As cities and ports continue to develop around Bohai Bay, a long-term extensive sewage monitoring program is highly recommended.

  18. Stable chromium isotopic composition of meteorites and metal-silicate experiments: Implications for fractionation during core formation (United States)

    Bonnand, P.; Williams, H. M.; Parkinson, I. J.; Wood, B. J.; Halliday, A. N.


    We present new mass independent and mass dependent Cr isotope compositions for meteorites measured by double spike thermal ionisation mass spectrometry. Small differences in both mass independent 53Cr and 54Cr relative to the Bulk Silicate Earth are reported and are very similar to previously published values. Carbonaceous chondrites are characterised by an excess in 54Cr compared to ordinary and enstatite chondrites which make mass independent Cr isotopes a useful tool for distinguishing between meteoritic groups. Mass dependent stable Cr isotope compositions for the same samples are also reported. Carbonaceous and ordinary chondrites are identical within uncertainty with average δ53 Cr values of - 0.118 ± 0.040 ‰ and - 0.143 ± 0.074 ‰ respectively. The heaviest isotope compositions are recorded by an enstatite chondrite and a CO carbonaceous chondrite, both of which have relatively reduced chemical compositions implying some stable Cr isotope fractionation related to redox processes in the circumstellar disk. The average δ53 Cr values for chondrites are within error of the estimate for the Bulk Silicate Earth (BSE) also determined by double spiking. The lack of isotopic difference between chondritic material and the BSE provides evidence that Cr isotopes were not fractionated during core formation on Earth. A series of high-pressure experiments was also carried out to investigate stable Cr isotope fractionation between metal and silicate and no demonstrable fractionation was observed, consistent with our meteorites data. Mass dependent Cr isotope data for achondrites suggest that Cr isotopes are fractionated during magmatic differentiation and therefore further work is required to constrain the Cr isotopic compositions of the mantles of Vesta and Mars.

  19. Reconstructing Cambro-Ordovician Seawater Composition using Clumped Isotope Paleothermometry on Calcitic and Phosphatic Brachiopods (United States)

    Bergmann, K.; Robles, M.; Finnegan, S.; Hughes, N. C.; Eiler, J. M.; Fischer, W. W.


    A secular increase in δ18O values of marine fossils through early Phanerozoic time raises questions about the evolution of climate and the water cycle. This pattern suggests two end-member hypotheses 1) surface temperatures during early Paleozoic time were very warm, in excess of 40°C (tropical MAT), or 2) the isotopic composition of seawater increased by up to 7-8‰. It has been difficult to evaluate these hypotheses because the δ18O composition of fossils depends on both temperature and the δ18O of water. Furthermore, primary isotopic signatures can be overprinted by diagenetic processes that modify geological materials. This too could explain the decrease in δ18O values of marine fossils with age. Carbonate clumped isotope thermometry can constrain this problem by providing an independent measure of crystallization temperature and, when paired with classical δ18O paleothermometry, can determine the isotopic composition of the fluid the mineral last equilibrated with. Combined with traditional tools, this method has the potential to untangle primary isotopic signatures from diagenetic signals. We measured the isotopic ordering of CO3 groups (Δ47) substituted into the phosphate lattice of phosphatic brachiopods in Cambrian strata. Phosphatic fossils are generally less soluble than carbonates in surface and diagenetic environments, and so are hypothesized to provide a more robust record of primary growth conditions. They also provide an archive prior to the rise of thick shelled calcitic fossils during the Ordovician Radiation. Additionally, measurements of the δ18O of the CO3 groups can be compared with the δ18O of PO4 groups to test whether their mutual fractionation is consistent with primary growth and the apparent temperature recorded by carbonate clumped isotope measurements. We are constructing a phosphatic brachiopod calibration for carbonate clumped isotope thermometry, and Δ47 values of CO2 extracted from modern phosphatic brachiopods suggest

  20. Pb Isotope Compositions of Shibaqinghao Gold Deposit in Central Inner Mongolia, China

    Institute of Scientific and Technical Information of China (English)

    ZHANG Hongying; LIANG Yibo


    There are two types of gold ore in Shibaqinghao gold deposit, a mylonite ore and a quartz - vein ore. Pb isotope compositions for mylonite ore are characterized by lower Pb isotope ratios ranging from 16.63 to 17.45 (206Pb/204Pb), 15.31 to15.48 (207Pb/204pb), 36.52 to 38.85 (208Pb/204Pb). They are scattered very close to a model curve of the mantle evolution. These ratios suggest that gold in the mylonite ore might be derived from the country rocks, which originated directly in the upper mantle. Pb isotope compositions for quartz - vein ore are characterized by higher Pb isotope ratios ranging from 18.23 to 19.74 (206Pb/204Pb), 15.69 to 15.89 (207Pb/204Pb), 38.64 to 40. 13 (208Pb/204Pb). They are scattered very close to a model curve of the upper crustal evolution. These facts indicate that the gold in the quartz - vein ore might be related to some granitic magma generated in the crust.

  1. Lead isotope and trace element composition of urban soils in Mongolia (United States)

    Tserenpil, Sh.; Sapkota, A.; Liu, C.-Q.; Peng, J.-H.; Liu, B.; Segebade, P. Chr.


    Lead (Pb) pollution in and around Ulaanbaatar is of national concern, given that the Mongolian capital is home to nearly half of the country's entire population. By comparison, Mongolian countryside is a pristine environment because of its sparse population and low industrial activity. The concentration of Pb in urban soils (average of 39.1 mg kg-1) was twice the values found (average 18.6 mg kg-1) in background territories (i.e., Mongolian rural sites). Furthermore, Pb contamination was examined by using Pb stable isotopic composition, and covariance of Pb isotopic ratios showed two groups between rural and urban soils as pristine and disturbed sites. The 206Pb/207Pb ratio, the most prominent fingerprint for Pb pollution, was 1.163-1.185 for the urban whereas values for rural soils (1.186-1.207) were analogue to the regional Pb isotopic signatures. Local coal sources and their combustion products, one of the potential Pb pollution sources in Ulaanbaatar, have significant radiogenic properties in terms of Pb isotopic composition and revealed an average of 1.25 for 206Pb/207Pb and 19.551 for 206Pb/204Pb ratios. Thus, contributions from coal firing activity to Pb pollution lower than it was assumed, and smaller range of these values measured in urban soils may be attributed to the mixing of less radiogenic Pb as a constituent of the leaded gasolines.

  2. Elemental and isotopic fingerprint of Argentinean wheat. Matching soil, water, and crop composition to differentiate provenance. (United States)

    Podio, Natalia S; Baroni, María V; Badini, Raúl G; Inga, Marcela; Ostera, Héctor A; Cagnoni, Mariana; Gautier, Eduardo A; García, Pilar Peral; Hoogewerff, Jurian; Wunderlin, Daniel A


    The aim of this study was to investigate if elemental and isotopic signatures of Argentinean wheat can be used to develop a reliable fingerprint to assess its geographical provenance. For this pilot study we used wheat cultivated at three different regions (Buenos Aires, Córdoba, and Entre Ríos), together with matching soil and water. Elemental composition was determined by ICP-MS. δ(13)C and δ(15)N were measured by isotopic ratio mass spectrometry, while (87)Sr/(86)Sr ratio was determined using thermal ionization mass spectrometry. Wheat samples from three sampling sites were differentiated by the combination of 11 key variables (K/Rb, Ca/Sr, Ba, (87)Sr/(86)Sr, Co, Mo, Zn, Mn, Eu, δ(13)C, and Na), demonstrating differences among the three studied regions. The application of generalized Procrustes analysis showed 99.2% consensus between cultivation soil, irrigation water, and wheat samples, in addition to clear differences between studied areas. Furthermore, canonical correlation analysis showed significant correlation between the elemental and isotopic profiles of wheat and those corresponding to both soil and water (r(2) = 0.97, p wheat samples using different statistical methods, showing that wheat elemental and isotopic compositions are mainly related to soil and irrigation water characteristics of the site of growth.

  3. Spacial and temporal variation of H and O isotopic compositions of the Xijiang Rivers System (United States)

    Han, G.


    Pin Lv1, Fushan Li2, Yang Tang2 School of Water Resources and Environment, China University of Geosciences (Beijing), Beijing 10083, China The State Laboratory of Environmental Geochemistry, Institute of Geochemistry, Chinese Academy of Sciences, Guiyang 550002, China The H and O isotope compositions in the Xijiang River water was investigated on the sample collected from the mainstream and main tributaries in Aug. 2014 and in Jan. 2015. Large variation ranges were observed for δD with (-35.3‰ to -77.1‰ in summer, -31.3‰ to -76.6‰ in winter) andδ18O (-4.8‰ to -10.3‰ in summer, -4.5‰ to -10.3‰ in winter). From the river head to the river mouth, the H and O isotope compositions of the river water collected in the high-discharge and low-discharge period display always a similar variation pattern. On the basis of isotopic composition of river water, the Xijiang River may be separated by three subbasins including the upper basin, the middle basin and the lower basin. The upper reached river water contains relatively low values of δD and δ18O. The values of δD and δ18O in the middle reaches are quite variable because of the middle basin severely disturbed through water impoundments. The lower reaches river water contains high values of δD and δ18O. The differences of δD and δ18O compositions between various tributaries and its effect to the δD and δ18O of the mainstream reflects also the constraint of the meteoric water to the Xijiang River. Evaporation has also important effect to the H and O isotope compositions of the Xijiang River, and it is found that evaporation can also raise the δD and δ18O values of the water during the dry season. Our investigation indicates that the H and O isotope tracing method can play a key role in studying the interaction between river water and other waters, such as the meteoric water, underground water, and lake water. The combination of proper H and O isotope study with conventional meteoric and

  4. Hydrogen isotope composition of leaf wax n-alkanes in Arabidopsis lines with different transpiration rates (United States)

    Pedentchouk, N.; Lawson, T.; Eley, Y.; McAusland, L.


    Stable isotopic compositions of oxygen and hydrogen are used widely to investigate modern and ancient water cycles. The D/H composition of organic compounds derived from terrestrial plants has recently attracted significant attention as a proxy for palaeohydrology. However, the role of various plant physiological and biochemical factors in controlling the D/H signature of leaf wax lipids in extant plants remains unclear. The focus of this study is to investigate the effect of plant transpiration on the D/H composition of n-alkanes in terrestrial plants. This experiment includes 4 varieties of Arabidopsis thaliana that differ with respect to stomatal density and stomatal geometry. All 4 varieties were grown indoors under identical temperature, relative humidity, light and watering regimes and then sampled for leaf wax and leaf water stable isotopic measurements. During growth, stomatal conductance to carbon dioxide and water vapour were also determined. We found that the plants varied significantly in terms of their transpiration rates. Transpiration rates were significantly higher in Arabidopsis ost1 and ost1-1 varieties (2.4 and 3.2 mmol m-2 s-1, respectively) than in Arabidopsis RbohD and Col-0 (1.5 and 1.4). However, hydrogen isotope measurements of n-alkanes extracted from leaf waxes revealed a very different pattern. Varieties ost1, ost1-1, and RbohD have very similar deltaD values of n-C29 alkane (-125, -128, and -127 per mil), whereas the deltaD value of Col-0 is more negative (-137 per mil). The initial results of this work suggest that plant transpiration is decoupled from the D/H composition of n-alkanes. In other words, physical processes that affect water vapour movement between the plant and its environment apparently cannot account for the stable hydrogen isotope composition of organic compounds that comprise leaf waxes. Additional, perhaps biochemical, processes that affect hydrogen isotope fractionation during photosynthesis might need to be invoked

  5. Atmospheric control on isotopic composition and d-excess in water vapor over ocean surface (United States)

    Fan, Naixin

    For decades, stable isotopes of water have been used as proxies to infer the variation of the hydrological cycle. However, it is still not clear how various atmospheric processes quantitatively control kinetic fractionation during evaporation over the ocean. Understanding kinetic fractionation is important in that the interpretation of the isotopic composition record preserved in ice cores and precipitation relies in part on the isotopic information at the moisture source. In addition, the isotopic composition of vapor contains information about variation of atmospheric processes such as turbulence and change in moisture source region which is useful for studying meteorological processes and climate change. In this study the isotopic composition of water vapor in the marine boundary layer (MBL) over the ocean was investigated using a combination of a newly developed marine boundary layer (MBL) model and observational data. The new model has a more realistic MBL structure than previous models and includes new features such as vertical advection of air and diffusion coefficients that vary continuously in the vertical direction. A robust linear relationship between deltaD and delta18O was found in observational oceanic water vapor data and the model can well capture the characteristics of this relationship. The individual role of atmospheric processes or variables on deltaD, delta18O and d-excess was quantitatively investigated and an overview of the combined effect of all the meteorological processes is provided. In particular, we emphasize that the properties of subsiding air (such as its mixing ratio and isotopic values) are crucial to the isotopic composition of surface water vapor. Relative humidity has been used to represent the moisture deficit that drives evaporative isotopic fluxes, however, we argue that it has serious limitations in explaining d-excess variation as latitude varies. We introduce a new quantity Gd=SST-Td, the difference between the sea

  6. Modelling the isotopic composition of snow using backward trajectories : a particular precipitation event in Dronning Maud Land, Antarctica

    NARCIS (Netherlands)

    Helsen, MM; Van de Wal, RSW; Van den Broeke, MR; Kerstel, ERT; Masson-Delmotte, [No Value; Meijer, HAJ; Reijmer, CH; Scheele, MP; Jacka, J


    We consider a specific accumulation event that occurred in January 2002 in western Dronning Maud Land, Antarctica. Snow samples were obtained a few days after accumulation. We combine meteorological analyses and isotopic modelling to describe the isotopic composition of moisture during transport. Ba

  7. The effects of growth phase and salinity on the hydrogen isotopic composition of alkenones produced by coastal haptophyte algae

    NARCIS (Netherlands)

    Chivall, D.; M'Boule, D.; Sinke-Schoen, D.; Sinninghe Damsté, J.S.; Schouten, S.; van der Meer, M.T.J.


    The isotopic fractionation of hydrogen during the biosynthesis of alkenones produced by marine haptophyte algae has been shown to depend on salinity and, as such, the hydrogen isotopic composition of alkenones is emerging as a palaeosalinity proxy. The relationship between fractionation and salinity

  8. Situation of sewage input reflected by nitrogen isotopic composition in a sediment core of Hongfeng Lake

    Institute of Scientific and Technical Information of China (English)


    Nitrogen in Hongfeng South Lake water mainly comes from sewage with high N concentrations from Pingba Chemical Fertilizer Plant (PCFP). Studies on the sediment core HF010427 sampled in the lake showed that the upward increase of nitrogen isotopic composition of sedimentary organic nitrogen (δ15Norg) accorded with the trend of industrial total production (TP) of PCFC. On the contrary, diagenesis will theoretically cause an upward decrease of δ15Norg. Because no treatment of sewage water was carried out, TP corresponds with sewage emission, indicating that sedimentary δ15Norg can reflect well the total trend of sewage input. The very similar profile shape between nitrogen isotopic composition of sedimentary absorbed ammonium (δ15NH4+absorbed) and TP of PCFP suggests that δ15NH4+absorbed can be used to reconstruct more detailed situation of sewage input. The study has a reference to history investigation of sewage input.

  9. A rapid method for determination of the isotopic composition of uranium samples by alpha spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Martin Sanchez, A.; Tome, F.V.; Diaz Bejarano, J.; Jurado Vargas, M. (Dept. de Fisica, Univ. Extremadura, Badajoz (Spain))


    A simple method of analyzing alpha spectra from natural and enriched or depleted uranium samples is developed. The procedure is non-iterative, and takes into consideration low-energy tail and branching-ratio corrections to accurately calculate the area corresponding to each uranium isotope ({sup 234}U, {sup 235}U, {sup 236}U, {sup 238}U) in the spectrum, and then the isotopic composition of the sample. A BASIC computer program, called ENURA, has been developed to perform all the necessary calculations to give the results together with their uncertainties. Several samples were prepared with different uranium concentrations made from standard solutions with known compositions, and the method was checked against the experimental measurements from these samples. Other series of uranium spectra were theoretically constructed using a given line shape in order to cover the required range of enriched or depleted uranium. (orig.).

  10. Isotopic compositions and probable origins of organic molecules in the Eocene Messel shale (United States)

    Hayes, J. M.; Takigiku, Ray; Ocampo, Ruben; Callot, Enry J.; Albrecht, Pierre


    It is shown here that the carbon isotopic compositions of biomarkers from the Eocene Messel shale, accumulated 47 + or - 2 million years ago in anaerobic waters at the bottom of a lake, allow identification of specific sources for some materials and reconstruction of carbon flows within the lake and its sediments. The C-13 content of organic matter synthesized by lacustrine primary producers can be estimated from the observed C-13 content of the geoporphyrins derived from their chlorophylls. Total organic material in the shale is depleted in C-13 by six parts per thousand relative to that input. This difference cannot be explained by selective loss of components enriched in C-13, nor, as shown by isotopic compositions of other biomarkers, by inputs from land plants surrounding the lake or from methanogenic bacteria.

  11. Experimental assessment of environmental influences on the stable isotopic composition of Daphnia pulicaria and their ephippia

    Directory of Open Access Journals (Sweden)

    J. Schilder


    δ15N values of ephippia and Daphnia between the 12 °C and 20 °C treatments, but the δ18O values of Daphnia and ephippia were on average 1.2‰ lower at 20 °C compared with 12 °C. We conclude that the stable isotopic composition of Daphnia ephippia provides information on that of the parent Daphnia and of the food and water they were exposed to, with small offsets between Daphnia and ephippia relative to variations in Daphnia stable isotopic composition reported from downcore studies. However, our experiments also indicate that temperature may have a minor influence on the δ13C, δ15N and δ18O values of Daphnia body tissue and ephippia. This aspect deserves attention in further controlled experiments.

  12. Where Did the Ureilite Parent Body Accrete? Constraints from Chemical and Isotopic Compositions (United States)

    Goodrich, Cyrena; O'Brien, David P.


    Almahata Sitta and other polymict ureilites contain a remarkable diversity of materials, including EH, EL, OC, R- and CB chondrites, in addition to the dominant ureilitic material [1]. These materials represent at least 6 different parent asteroids and a wide range of chemical and isotopic environments in the early Solar System. To understand the origin of this diversity it is critical to know where (heliocentric distance) the ureilite parent body (UPB) accreted. The chemical and isotopic compositions of ureilite precursors (inferred from the compositions of ureilites) can provide clues. Lithophile element ratios such as Si/Mg and Mn/Mg [2,3], and deficits in neutron-rich Cr, Ti and Ni isotopes [3], indicate that ureilite precursors were similar to ordinary or enstatite chondrites (OC or EC), not carbonaceous chondrites (CC). In contrast, high carbon contents, carbon isotopes and oxygen isotopes suggest a genetic link to CC. This poses a conundrum considering the variation of asteroid types, which suggests that EC and OC dominate the inner asteroid belt and CC the outer belt. However, the CC-like oxygen isotopes of ureilites strongly suggest the effects of parent-body aqueous alteration [4,5], which clearly implies that the UPB accreted beyond the ice line. Lithophile element properties of ureilites compared with chondrites may not be a reliable indicator of location of accretion, because lithophile elements in chondrites are sited mainly in chondrules and the UPB accreted before most chondrules formed [6]. Ureilite Cr, Ti and Ni isotopes may indicate late introduction of the neutron rich isotopes of these elements to the CC-formation region [7]. We conclude that the UPB accreted in the outer belt, like CC. The UPB or one of its offspring must have migrated to the inner belt to acquire OC, EC and R-chondrite materials.[1] Horstmann M. & Bischoff A. [2014] Chemie der Erde 74, 149.[2] Goodrich C. [1999] MAPS 34, 109.[3] Warren P. [2011] GCA 46, 53.[4] Young E. [1999

  13. Mineralogy and Oxygen Isotope Compositions of an Unusual Hibonite-Perovskite Refractory Inclusion from Allende (United States)

    Keller, L. P.; Snead, C.; Rahman, Z.; McKeegan, K. D.


    Hibonite-rich Ca- and Al-rich inclusions (CAIs) are among the earliest formed solids that condensed in the early nebula. We discovered an unusual refractory inclusion from the Allende CV3 chondrite (SHAL) containing an approx 500 micron long single crystal of hibonite and co-existing coarse-grained perovskite. The mineralogy and petrography of SHAL show strong similarities to some FUN inclusions, especially HAL. Here we report on the mineralogy, petrography, mineral chemistry and oxygen isotopic compositions in SHAL.

  14. U and Th Concentration and Isotopic Composition of Hydrothermal Fluids at the Lost City Hydrothermal Field (United States)

    Ludwig, K. A.; Shen, C.; Cheng, H.; Edwards, R.; Kelley, D. S.; Butterfield, D. A.


    Uranium and Th concentration and isotopic composition of hydrothermal fluids at the Lost City Hydrothermal Field (LCHF) were determined using multi-collector inductively coupled plasma mass spectrometry (MC-ICP- MS). The LCHF is an off-axis, serpentinite-hosted hydrothermal system located at 30°N near the Mid- Atlantic Ridge. Carbonate chimneys reaching 60 m in height vent alkaline (pH~10), calcium-rich fluids at 40- 91°C and the towers are home to dense microbial communities. Vent fluid and seawater U and Th concentration and isotopic composition data provide critical information for constraining U-Th chimney ages. The increased sensitivity (1-2%) of MC-ICP-MS combined with an Aridus nebulization system allows the precise measurement of small quantities of sample (~150 ml) with low concentrations (ICP-MS techniques to measure the U and Th concentration and isotopic composition (234U, 238U, 230Th, and 232Th) of eight hydrothermal fluid samples. Endmember fluids with ~1mmol/kg Mg have ~0.02 ng/g U, confirming that end-member fluids contain near-zero values of both Mg and U. Thorium concentrations of fluids are close to deep seawater values. U and Th isotopic compositions are reported at the permil level. These data may provide new insights into the role of serpentinite-hosted hydrothermal systems in the budgets of U and Th in the ocean. Techniques presented in this study may be applied to other hydrothermal and seep environments.

  15. An assessment of upper mantle heterogeneity based on abyssal peridotite isotopic compositions (United States)

    Warren, J. M.; Shimizu, N.; Sakaguchi, C.; Dick, H. J. B.; Nakamura, E.


    Abyssal peridotites, the depleted solid residues of ocean ridge melting, are the most direct samples available to assess upper oceanic mantle composition. We present detailed isotope and trace element analyses of pyroxene mineral separates from Southwest Indian Ridge abyssal peridotites and pyroxenites in order to constrain the size and length scale of mantle heterogeneity. Our results demonstrate that the mantle can be highly heterogeneous to account adequately for the complexities of ancient and recent melting processes.

  16. Spatial variability in the isotopic composition of rainfall in a small headwater catchment and its effect on hydrograph separation (United States)

    Fischer, Benjamin M. C.; van Meerveld, H. J. (Ilja); Seibert, Jan


    Isotope hydrograph separation (IHS) is a valuable tool to study runoff generation processes. To perform an IHS, samples of baseflow (pre-event water) and streamflow are taken at the catchment outlet. For rainfall (event water) either a bulk sample is collected or it is sampled sequentially during the event. For small headwater catchment studies, event water samples are usually taken at only one sampling location in or near the catchment because the spatial variability in the isotopic composition of rainfall is assumed to be small. However, few studies have tested this assumption. In this study, we investigated the spatiotemporal variability in the isotopic composition of rainfall and its effects on IHS results using detailed measurements from a small pre-alpine headwater catchment in Switzerland. Rainfall was sampled sequentially at eight locations across the 4.3 km2 Zwäckentobel catchment and stream water was collected in three subcatchments (0.15, 0.23, and 0.70 km2) during ten events. The spatial variability in rainfall amount, average and maximum rainfall intensity and the isotopic composition of rainfall was different for each event. There was no significant relation between the isotopic composition of rainfall and total rainfall amount, rainfall intensity or elevation. For eight of the ten studied events the temporal variability in the isotopic composition of rainfall was larger than the spatial variability in the rainfall isotopic composition. The isotope hydrograph separation results, using only one rain sampler, varied considerably depending on which rain sampler was used to represent the isotopic composition of event water. The calculated minimum pre-event water contributions differed up to 60%. The differences were particularly large for events with a large spatial variability in the isotopic composition of rainfall and a small difference between the event and pre-event water isotopic composition. Our results demonstrate that even in small catchments

  17. Investigating the source, transport, and isotope composition of water vapor in the planetary boundary layer (United States)

    Griffis, Timothy J.; Wood, Jeffrey D.; Baker, John M.; Lee, Xuhui; Xiao, Ke; Chen, Zichong; Welp, Lisa R.; Schultz, Natalie M.; Gorski, Galen; Chen, Ming; Nieber, John


    Increasing atmospheric humidity and convective precipitation over land provide evidence of intensification of the hydrologic cycle - an expected response to surface warming. The extent to which terrestrial ecosystems modulate these hydrologic factors is important to understand feedbacks in the climate system. We measured the oxygen and hydrogen isotope composition of water vapor at a very tall tower (185 m) in the upper Midwest, United States, to diagnose the sources, transport, and fractionation of water vapor in the planetary boundary layer (PBL) over a 3-year period (2010 to 2012). These measurements represent the first set of annual water vapor isotope observations for this region. Several simple isotope models and cross-wavelet analyses were used to assess the importance of the Rayleigh distillation process, evaporation, and PBL entrainment processes on the isotope composition of water vapor. The vapor isotope composition at this tall tower site showed a large seasonal amplitude (mean monthly δ18Ov ranged from -40.2 to -15.9 ‰ and δ2Hv ranged from -278.7 to -113.0 ‰) and followed the familiar Rayleigh distillation relation with water vapor mixing ratio when considering the entire hourly data set. However, this relation was strongly modulated by evaporation and PBL entrainment processes at timescales ranging from hours to several days. The wavelet coherence spectra indicate that the oxygen isotope ratio and the deuterium excess (dv) of water vapor are sensitive to synoptic and PBL processes. According to the phase of the coherence analyses, we show that evaporation often leads changes in dv, confirming that it is a potential tracer of regional evaporation. Isotope mixing models indicate that on average about 31 % of the growing season PBL water vapor is derived from regional evaporation. However, isoforcing calculations and mixing model analyses for high PBL water vapor mixing ratio events ( > 25 mmol mol-1) indicate that regional evaporation can account

  18. Neodymium as the main feature of permanent magnets from hard disk drives (HDDs). (United States)

    München, Daniel Dotto; Veit, Hugo Marcelo


    As a way to manage neodymium-iron-boron (NdFeB) magnets wasted in end-of-life hard disk drives (HDDs), a waste characterization is needed prior to a recycling process. Due to their magnetic properties, NdFeB magnets are essential in technological applications nowadays, thus causing an increase in the industrial demand for rare earth metals. However, these metals have a short supply, since they are difficult to obtain from ores, creating a critical market. In this work, a study of the characterization of sintered neodymium-iron-boron magnets was undertaken by qualitatively and quantitatively uncovering the neodymium recovery potential from this type of electronic waste. From the collection and disassembly of hard disk drives, in which the magnet represents less than 3% of the total weight, an efficient demagnetization process was proceeded at 320°C. Then, the magnet was ground and screened for an X-ray diffraction (XRD) analysis, which showed the Nd2Fe14B tetragonal phase as the dominant constituent of the sample. An analysis was also carried out in a scanning electron microscope (SEM) and an inductively coupled plasma optical emission spectrometer (ICP-OES), where the magnet composition showed 21.5wt% of neodymium and 65.1wt% of iron, among other chemicals. This Nd content is higher than the one found in Nd ores, enhancing the recyclability and the importance of waste management.

  19. Luminescent behavior of CdTe quantum dots: Neodymium(III) complex-capped nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Miranda, Margarida S. [Centro de Geologia do Porto, Faculdade de Ciencias, Universidade do Porto, Rua do Campo Alegre s/n, 4169-007 Porto (Portugal); Algarra, Manuel, E-mail: [Centro de Geologia do Porto, Faculdade de Ciencias, Universidade do Porto, Rua do Campo Alegre s/n, 4169-007 Porto (Portugal); Jimenez-Jimenez, Jose; Rodriguez-Castellon, Enrique [Departamento de Quimica Inorganica, Facultad de Ciencias, Universidad de Malaga, Campus de Teatinos s/n 29071, Malaga (Spain); Campos, Bruno B.; Esteves da Silva, Joaquim C.G. [Centro de Investigacao em Quimica (CIQ-UP), Faculdade de Ciencias, Universidade do Porto, Rua do Campo Alegre s/n, 4169-007 Porto (Portugal)


    A water soluble complex of neodymium(III) with CdTe quantum dots nanoparticles was synthesized. The obtained homogeneous solutions were characterized by fluorescence, X-ray photoelectron and energy dispersive X-ray spectroscopies. The effect of the refluxing time of the reaction on the fluorescence intensity and emission wavelength has been studied. It was found that the emission wavelength of the solutions of neodymium(III) complex capped CdTe QDs nanoparticles shifted from about 540 to 735 nm. For an emission wavelength of 668 nm, the most reproducible nanoparticles obtained, the pH effect over the fluorescence emission and its intensity were studied. The purified and lyophilized solid obtained was morphologically characterized by transmission electron microscopy (TEM). The quantitative composition was determined by fluorescence X-ray spectroscopy (EDAX) and the X-ray photoelectron analysis (XPS) confirmed the presence of neodymium(III) at the surface of the CdTe nanoparticles forming a complex with the carboxylate groups from 3-mercaptopropanoic acid of the CdTe QDs. Due to the optical behavior of this complex, it could be of potential interest as a light source in optical devices. - Highlights: Black-Right-Pointing-Pointer CdTe quantum dots nanoparticles. Black-Right-Pointing-Pointer Neodymium(III) complexed quantum dots. Black-Right-Pointing-Pointer Strong red fluorescent emission nanomaterial soluble in water.

  20. Neodymium-rich precipitate phases in a high-chromium ferritic/martensitic steel (United States)

    Shen, Yinzhong; Zhou, Xiaoling; Shang, Zhongxia


    Neodymium being considered as nitride forming element has been used in a design of advanced ferritic/martensitic (FM) steels for fossil fired power plants at service temperatures of 630 °C to 650 °C to effectively improve the creep strength of the steels. To fully understand the characteristics of neodymium precipitates in high-Cr FM steels, precipitate phases in an 11Cr FM steel with 0.03 wt% addition of Nd have been investigated by transmission electron microscopy. Three neodymium phases with a face-centered cubic crystal structure and different composition were observed in the steel. They consisted of neodymium carbonitride with an average lattice parameter of 1.0836 nm, Nd-rich carbonitride mainly containing Mn, and Nd-rich MN nitride mainly containing Mn and Co. Other three Nd-rich and Nd-containing phases, which appear to be Nd-Co-Cr/Nd-rich intermetallic compounds and Cr-Fe-rich nitride containing Nd, were also detected in the steel. Nd-relevant precipitates were found to be minor phases compared with M23C6 and Nb/V/Ta-rich MX phases in the steel. The content of Nd in other precipitate phases was very low. Most of added Nd is considered to be present as solid solution in the matrix of the steel.

  1. Li Isotopic Composition and Concentration of the Upper Continental Crust: New Insights from Desert Loess (United States)

    Sauzeat, L.; Rudnick, R. L.; Chauvel, C.


    The isotopic composition of lithium (δ7Li) is recognized to be an excellent proxy of near-surface fluid-rock reactions during weathering. Using Li as a tracer of these processes however requires constraints on the average Li composition of terrestrial reservoirs, in particular that of the upper continental crust. To date, only one value for the average δ7Li value of the upper continental crust, derived from periglacial loess, shales, and granites is available in the literature (7δLi = 0 ± 4 (2σ), Teng et al., 2004). Several values exist for the average [Li] of the upper crust, but they differ by more than 30%. We measured the Li isotopic composition of about 30 desert and periglacial loess (unweathered windblown sediments) from several parts of the world (Europe, Argentina, China and Tajikistan). We demonstrate that desert loess, which is more homogeneous and representative of larger portions of the Earth's surface, provides a better proxy for the average composition of the upper continental crust compared to periglacial loess. The Li isotopic compositions and concentrations of desert loess are controlled by eolian sorting, which can be quantified as a binary isotopic mixing between a weathered fine-grained end-member and an unweathered coarse-grained end-member. Using correlations between Li isotopic compositions, Li concentrations and trace element concentrations in desert loess, we estimate new average values for the upper continental crust: 1 ± 2 (2σ); [Li] = 35.3 ± 4.6 (2σ) ppm. This δ7Li value is slightly higher than that previously published in Teng et al. (2004), but overlaps within uncertainty, whereas the [Li] is identical to that of Teng et al. (2004: 35 ± 11, 2σ); both new estimates have lower uncertainty. Our new estimate of [Li], along with that of Teng et al. (2004), are higher than all previous estimates for the upper continental crust, raising the question as to whether the average concentrations of other mobile alkali metals such as

  2. Temporal variations in lead concentrations and isotopic composition in the Southern California Bight

    Energy Technology Data Exchange (ETDEWEB)

    Sanudo-Wilhelmy, S.A.; Flegal, A.R. (Univ. of California, Santa Cruz, CA (United States))


    Lead concentrations in surface waters of the Southern California Bight appear to have decreased threefold (from >170 to <60 pM) since they were initially measured by Clair Patterson and his associates in the 1970s. The decrease parallels a threefold decline in anthropogenic inputs of industrial lead to the bight over the past two decades. Moreover, mass balance calculations indicate that the primary source of lead to the bight now is upwelling. This is evidenced by the isotopic compositions of surface waters in the bight, which are most characteristic of Asian industrial lead aerosols (0.4793 [le] [sup 206]Pb/[sup 208]Pb [le] 0.4833) deposited in oceanic waters of the North Pacific. While the decrease in surface water lead concentrations in the bight reflects the reduction in industrial lead emissions from the United States, the isotopic compositions of surface waters in the southern reach of the bight reflect a concurrent increase in industrial lead emissions from Mexico (0.4852 [le] [sup 206]Pb/[sup 208]Pb [le] 0.4877). The isotopic composition ([sup 208]Pb/[sup 207]Pb [approximately] 2.427) of elevated lead concentrations of surface waters in San Diego Bay indicate that lead is being remobilized from contaminated sediments within that bay.

  3. Stable carbon and radiocarbon isotope compositions of particle size fractions to determine origins of sedimentary organic matter in an estuary

    NARCIS (Netherlands)

    Megens, L; van der Plicht, J; de Leeuw, JW; Smedes, F; Altabet, M.


    Stable and radioactive carbon isotopic compositions of particle size fractions of a surface sediment from the Ems-Dollard estuary vary considerably with particle size. The organic material in the fine fractions (

  4. Stable carbon and radiocarbon isotope compositions of particle size fractions to determine origins of sedimentary organic matter in an estuary

    NARCIS (Netherlands)

    Megens, L; van der Plicht, J; de Leeuw, JW; Smedes, F; Altabet, M.


    Stable and radioactive carbon isotopic compositions of particle size fractions of a surface sediment from the Ems-Dollard estuary vary considerably with particle size. The organic material in the fine fractions (

  5. Limitations of the isotopic composition of nitrates as a tracer of their origin (United States)

    Kloppmann, Wolfram; Mayer, Bernhard; Otero, Neus; Sebilo, Mathieu; Gooddy, Daren; Lapworth, Dan; Surridge, Ben; Petelet Giraud, Emmanuelle; Flehoc, Christine; Baran, Nicole


    Nitrogen and oxygen isotopes are traditionally considered and frequently used as tracers of nitrate sources in watersheds used for drinking water production. The enrichment of synthetic nitrate-containing fertilizers in 18O due to the contribution of atmospheric oxygen in the production process confers a specific isotopic fingerprint to mineral fertilizers. In spite of the still widespread use on nitrate-containing synthetic fertilizers, their characteristic N and O isotope signatures are rarely unambiguously observed in nitrate-contaminated groundwater. We postulate, in line with Mengis et al. (2001), that fertilizer-derived nitrate is not directly and rapidly transferred to groundwater but rather retained in the soil-plant system as organic N and then mineralized and re-oxidized (termed the mineralization-immobilization turnover, MIT) thereby re-setting the oxygen isotope composition of nitrate and also changing its N isotope ratios. We show examples from watersheds on diverse alluvial/clastic and carbonate aquifers in eastern and northern France where, in spite of the use of mineral fertilizers, evidenced also through other isotopic tracers (boron isotopes), both N and O-isotope ratios are very homogeneous and compatible with nitrification of ammonium where 2/3 of oxygen is derived from soil water and 1/3 from atmospheric O2. These field data are corroborated by lysimeter data from Canada. Even if in areas where ammonium is derived from chemical fertilizers, N values still tend to be lower than in areas where ammonium is derived from manure/sewage, this is clearly a limitation to the dual isotope method (N, O) for nitrate source identification, but has important implications for the nitrogen mobility and residence time in soils amended with synthetic fertilizers (Sebilo et al., 2013). Mengis M., Walther U., Bernasconi S. M., Wehrli B. (2001) Limitations of Using δ18O for the Source Identification of Nitrate in Agricultural Soils. Environmental Science

  6. Triple oxygen isotopic composition of the high-3He/4He mantle (United States)

    Starkey, N. A.; Jackson, C. R. M.; Greenwood, R. C.; Parman, S.; Franchi, I. A.; Jackson, M.; Fitton, J. G.; Stuart, F. M.; Kurz, M.; Larsen, L. M.


    Measurements of Xe isotope ratios in ocean island basalts (OIB) suggest that Earth's mantle accreted heterogeneously, and that compositional remnants of accretion are sampled by modern, high-3He/4He OIB associated with the Icelandic and Samoan plumes. If so, the high-3He/4He source may also have a distinct oxygen isotopic composition from the rest of the mantle. Here, we test if the major elements of the high-3He/4He source preserve any evidence of heterogeneous accretion using measurements of three oxygen isotopes on olivine from a variety of high-3He/4He OIB locations. To high precision, the Δ17O value of high-3He/4He olivines from Hawaii, Pitcairn, Baffin Island and Samoa, are indistinguishable from bulk mantle olivine (Δ17OBulk Mantle - Δ17OHigh 3He/4He olivine = -0.002 ± 0.004 (2 × SEM)‰). Thus, there is no resolvable oxygen isotope evidence for heterogeneous accretion in the high-3He/4He source. Modelling of mixing processes indicates that if an early-forming, oxygen-isotope distinct mantle did exist, either the anomaly was extremely small, or the anomaly was homogenised away by later mantle convection. The δ18O values of olivine with the highest 3He/4He ratios from a variety of OIB locations have a relatively uniform composition (∼5‰). This composition is intermediate to values associated with the depleted MORB mantle and the average mantle. Similarly, δ18O values of olivine from high-3He/4He OIB correlate with radiogenic isotope ratios of He, Sr, and Nd. Combined, this suggests that magmatic oxygen is sourced from the same mantle as other, more incompatible elements and that the intermediate δ18O value is a feature of the high-3He/4He mantle source. The processes responsible for the δ18O signature of high-3He/4He mantle are not certain, but δ18O-87Sr/86Sr correlations indicate that it may be connected to a predominance of a HIMU-like (high U/Pb) component or other moderate δ18O components recycled into the high-3He/4He source.

  7. Tracking nitrous oxide emission processes at a suburban site with semicontinuous, in situ measurements of isotopic composition (United States)

    Harris, Eliza; Henne, Stephan; Hüglin, Christoph; Zellweger, Christoph; Tuzson, Béla; Ibraim, Erkan; Emmenegger, Lukas; Mohn, Joachim


    The isotopic composition of atmospheric nitrous oxide (N2O) was measured semicontinuously, at ˜35 min frequency in intermittent periods of 1-6 days over one and a half years, using preconcentration coupled to a quantum cascade laser spectrometer at the suburban site of Dübendorf, Switzerland. The achieved measurement repeatability was 0.08‰, 0.11‰, and 0.10‰ for δ18O, site preference, and δ15Nbulk respectively, which is better than or equal to standard flask sampling-based isotope ratio mass spectrometry performance. The observed mean diurnal cycle reflected the buildup of N2O from isotopically light sources on an isotopically heavy tropospheric background. The measurements were used to determine the source isotopic composition, which varied significantly compared to chemical and meteorological parameters monitored at the site. FLEXPART-COSMO transport modeling in combination with modified Emissions Database for Global Atmospheric Research inventory emissions was used to model N2O mole fractions at the site. Additionally, isotopic signatures were estimated for different source categories using literature data and used to simulate N2O isotopic composition over the measurement period. The model was able to capture variability in N2O mole fraction well, but simulations of isotopic composition showed little agreement with observations. In particular, measured source isotopic composition exhibited one magnitude larger variability than simulated, clearly indicating that the range of isotopic source signatures estimated from literature significantly underestimates true variability of source signatures. Source δ18O signature was found to be the most sensitive tracer for urban/industry versus agricultural N2O. δ15Nbulk and site preference may provide more insight into microbial and chemical emission processes than partitioning of anthropogenic source categories.

  8. Isotopic composition for source identification of mercury in atmospheric fine particles (United States)

    Huang, Qiang; Chen, Jiubin; Huang, Weilin; Fu, Pingqing; Guinot, Benjamin; Feng, Xinbin; Shang, Lihai; Wang, Zhuhong; Wang, Zhongwei; Yuan, Shengliu; Cai, Hongming; Wei, Lianfang; Yu, Ben


    The usefulness of mercury (Hg) isotopes for tracing the sources and pathways of Hg (and its vectors) in atmospheric fine particles (PM2.5) is uncertain. Here, we measured Hg isotopic compositions in 30 potential source materials and 23 PM2.5 samples collected in four seasons from the megacity Beijing (China) and combined the seasonal variation in both mass-dependent fractionation (represented by the ratio 202Hg / 198Hg, δ202Hg) and mass-independent fractionation of isotopes with odd and even mass numbers (represented by Δ199Hg and Δ200Hg, respectively) with geochemical parameters and meteorological data to identify the sources of PM2.5-Hg and possible atmospheric particulate Hg transformation. All PM2.5 samples were highly enriched in Hg and other heavy metals and displayed wide ranges of both δ202Hg (-2.18 to 0.51 ‰) and Δ199Hg (-0.53 to 0.57 ‰), as well as small positive Δ200Hg (0.02 to 0.17 ‰). The results indicated that the seasonal variation in Hg isotopic composition (and elemental concentrations) was likely derived from variable contributions from anthropogenic sources, with continuous input due to industrial activities (e.g., smelting, cement production and coal combustion) in all seasons, whereas coal combustion dominated in winter and biomass burning mainly found in autumn. The more positive Δ199Hg of PM2.5-Hg in spring and early summer was likely derived from long-range-transported Hg that had undergone extensive photochemical reduction. The study demonstrated that Hg isotopes may be potentially used for tracing the sources of particulate Hg and its vectors in the atmosphere.

  9. Probing the homogeneity of the isotopic composition and molar mass of the ‘Avogadro’-crystal (United States)

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


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

  10. The bulk isotopic composition of hydrocarbons in subaerial volcanic-hydrothermal emissions from different tectonic settings (United States)

    Fiebig, J.; Tassi, F.; Vaselli, O.; Viveiros, M. F.; Silva, C.; Lopez, T. M.; D'Alessandro, W.; Stefansson, A.


    Assuming that methane and its higher chain homologues derive from a common source, carbon isotope patterns have been applied as a criterion to identify occurrences of abiogenic hydrocarbons. Based on these, it has been postulated that abiogenic hydrocarbon production occurs within several (ultra)mafic environments. More evolved volcanic-hydrothermal systems may also provide all the prerequisites necessary for abiogenic hydrocarbon production, such as availability of inorganic CO2, hydrogen and heat. We have investigated the chemical and isotopic composition of n-alkanes contained within subaerial hydrothermal discharges emitted from a range of hot spot, subduction and rift-related volcanoes to determine the origin of hydrocarbons in these systems. Amongst these are Nisyros (Greece), Vesuvio, Campi Flegrei, Ischia, Pantelleria and Vulcano (all Italy), Mt. Mageik and Trident (USA), Copahue (Argentina), Teide (Spain), Furnas and Fogo (Portugal). The carbon isotopic composition of methane emitted from these sites varies from -65 to -8‰ , whereas δ13C of ethane and propane exhibit a much narrower variation from -17‰ to -31‰. Methane that occurs most enriched in 13C is also characterized by relatively positive δD values ranging up to -80‰. Carbon isotope reversals between methane and ethane are only observed for locations exhibiting δ13C-CH4 values > -20‰, such as Teide, Pantelleria, Trident and Furnas. At Furnas, δ13C-CH4 varies by 50‰ within a relatively short distance of <50m between two vents, whereas δ13C-C2H6 varies by less than 2‰ only. For some of the investigated locations apparent carbon isotopic temperatures between methane and CO2 are in agreement with those derived from gas concentration geothermometers. At these locations methane, however seems to be in disequilibrium with ethane and propane. These findings imply that methane on the one hand and the C2+ hydrocarbons on the other hand often might derive from distinct sources.

  11. Sulfur isotopic composition and source identification of atmospheric environment in central Zhejiang,China

    Institute of Scientific and Technical Information of China (English)


    Sulfur dioxide and sulfate aerosols in the atmosphere are significant factors leading to acidification of the atmospheric environment and worsening the pollution of acid deposition. Because of the "fingerprint" characteristics of the stable sulfur isotopic composition, sulfur isotope has been widely adopted in environmental researches concerning sulfur cycle and source identification. In this study, the atmospheric environment of Jinhua City, central Zhejiang Province, was continuously monitored, and the sulfur isotopic composition of SO2 and sulfate aerosols in the atmosphere was analyzed. The results indicate that the variation of δ34S values for SO2 ranges from 1.0‰ to 7.5‰, and annual average is 4.7‰±2.3‰, whereas that of sulfate aerosols ranges from 6.4‰ to 9.8‰,and annual average is 8.1‰±1.0‰. The δ 34S values for SO2 have significant seasonal variations, which are 7.0‰ in winter and 3.3‰ in summer. These variations cannot be attributed to a single factor, and we suggest a temperature-dependent isotope equilibrium fractionation and elevated biogenic sulfur emissions of isotopically light S in summer may be the main controlling mechanisms. Furthermore, we also discuss the δ 34S model of atmospheric SO2 oxidation to form sulfate, and suggest that heterogeneous oxidation dominates in the oxidation reactions of atmospheric SO2 in the central Zhejiang Province. We further suggest that the relative humidity in the atmosphere plays an important role in the oxidation mechanism of atmospheric SO2.

  12. Assessing the ability of isotope-enabled General Circulation Models to simulate the variability of Iceland water vapor isotopic composition (United States)

    Erla Sveinbjornsdottir, Arny; Steen-Larsen, Hans Christian; Jonsson, Thorsteinn; Ritter, Francois; Riser, Camilla; Messon-Delmotte, Valerie; Bonne, Jean Louis; Dahl-Jensen, Dorthe


    During the fall of 2010 we installed an autonomous water vapor spectroscopy laser (Los Gatos Research analyzer) in a lighthouse on the Southwest coast of Iceland (63.83°N, 21.47°W). Despite initial significant problems with volcanic ash, high wind, and attack of sea gulls, the system has been continuously operational since the end of 2011 with limited down time. The system automatically performs calibration every 2 hours, which results in high accuracy and precision allowing for analysis of the second order parameter, d-excess, in the water vapor. We find a strong linear relationship between d-excess and local relative humidity (RH) when normalized to SST. The observed slope of approximately -45 o/oo/% is similar to theoretical predictions by Merlivat and Jouzel [1979] for smooth surface, but the calculated intercept is significant lower than predicted. Despite this good linear agreement with theoretical calculations, mismatches arise between the simulated seasonal cycle of water vapour isotopic composition using LMDZiso GCM nudged to large-scale winds from atmospheric analyses, and our data. The GCM is not able to capture seasonal variations in local RH, nor seasonal variations in d-excess. Based on daily data, the performance of LMDZiso to resolve day-to-day variability is measured based on the strength of the correlation coefficient between observations and model outputs. This correlation coefficient reaches ~0.8 for surface absolute humidity, but decreases to ~0.6 for δD and ~0.45 d-excess. Moreover, the magnitude of day-to-day humidity variations is also underestimated by LMDZiso, which can explain the underestimated magnitude of isotopic depletion. Finally, the simulated and observed d-excess vs. RH has similar slopes. We conclude that the under-estimation of d-excess variability may partly arise from the poor performance of the humidity simulations.


    Institute of Scientific and Technical Information of China (English)


    The variations in the isotopic compositions of chlorine in evaporation-controlled saline lake brines were determined by using an improved procedure for precise measurement of chlorine isotopes based on Cs2Cl+ ion by thermal ionization mass spectrometry. The results showed that variation in δ37Cl values in these evaporation-controlled brines are attributable to evaporation of brine accompanied by the deposition of saline minerals. The isotopic fractionation of chlorine between the deposited saline mineral and the co-existing brine caused the variation of δ37Cl values in the brine. In general the isotopic fractionation of chlorine in nature indicates enrichment of 37Cl in the solid phase relative to 35Cl. The reverse isotopic fractionation of chlorine in which 35Cl is enriched in the solid phase, was observed to some extent during quick deposition under laboratory conditions as well as in nature. The mechanism of isotopic fractionation of chlorine during evaporation deposition was studied.

  14. A thirty year record of the isotopic composition of atmospheric methane from North America (United States)

    Rice, A. L.; Teama, D. G.; Roeger, F. H.; Butenhoff, C. L.; Khalil, A. K.


    Methane (CH4) is one of the most important greenhouse gases after water vapor and carbon dioxide. Its atmospheric concentration increased from 650 ppb during the preindustrial era to nearly 1800 ppb in the present day due to human activities such as rice cultivation, animal husbandry, biomass burning, and fossil fuel production and use. Since the 1980s, the long-term growth rate of atmospheric CH4 slowed dramatically consistent with a leveling off of CH4 sources with significant interannual variability over this period. One powerful tool to constrain changes in sources and sinks is the use of stable isotopes of atmospheric CH4 because of the distinct values of carbon isotope (δ13C) and hydrogen isotope (δD) ratios in CH4 sources and characteristic isotopic fractionation effects in sinks. Measurements of the long-term trend of the isotopic composition of CH4 can improve the constraint of changes to the CH4 budget from microbial sources (e.g., wetlands, ruminants, and rice agriculture, δ13C ~-60 ‰, δD ~-300‰), fossil sources (e.g. natural gas and coal mining, δ13C ~-40‰, δD ~-200‰), and biomass burning (δ13C ~-25‰, δD ~-100‰). In this work, we present measurements of δ13C and δD of atmospheric CH4 from a unique archive of more than 200 air samples collected at Cape Meares, Oregon (45.5°N, 124°W) from 1978 to 1998. The measurements from this archive indicate enrichments in both isotope tracers over this period which average 0.017 (±0.002) ‰yr-1 for δ13C and 0.68 (±0.04) ‰yr-1 for δD. Seasonal cycles in δ13C and δD are also evident with amplitudes of ~ 0.3 ‰ and ~ 4 ‰, respectively; maximum values are found May-July and minimum values September-December, consistent with previous results from the mid-latitude northern hemisphere. Combining our results with more recent timeseries since 1988 from Olympic Peninsula (WA, 48°N), Montana de Oro (CA, 35°N), and Niwot Ridge (CO, 40°N) provides a composite record of the isotopic

  15. Measurement of position-specific 13C isotopic composition of propane at the nanomole level (United States)

    Gilbert, Alexis; Yamada, Keita; Suda, Konomi; Ueno, Yuichiro; Yoshida, Naohiro


    We have developed a novel method for analyzing intramolecular carbon isotopic distribution of propane as a potential new tracer of its origin. The method is based on on-line pyrolysis of propane followed by analysis of carbon isotope ratios of the pyrolytic products methane, ethylene and ethane. Using propane samples spiked with 13C at the terminal methyl carbon, we characterize the origin of the pyrolytic fragments. We show that the exchange between C-atoms during the pyrolytic process is negligible, and thus that relative intramolecular isotope composition can be calculated. Preliminary data from 3 samples show that site-preference (SP) values, defined as the difference of δ13C values between terminal and sub-terminal C-atom positions of propane, range from -1.8‰ to -12.9‰. In addition, SP value obtained using our method for a thermogenic natural gas sample is consistent with that expected from theoretical models of thermal cracking, suggesting that the isotope fractionation associated with propane pyrolysis is negligible. The method will provide novel insights into the characterization of the origin of propane and will help better understand the biogeochemistry of natural gas deposits.

  16. Laboratory and Field Measurements of the Nitrogen Isotopic Composition of NOx (United States)

    Fibiger, D. L.; Miller, D. J.; Dahal, B. R.; Lew, A. F.; Peltier, R.; Hastings, M. G.


    The nitrogen isotopic composition of nitrogen oxides (NOx = NO + NO2) has been measured from several NOx emissions sources in prior studies. These measurements have utilized a variety of methods for collecting the NOx as nitrate or nitrite for isotopic analysis, but none of these methods have been verified for complete conversion of NOx. Less than 100% conversion can result in isotopic fractionations. We present a method for accurately measuring the nitrogen isotopic composition of NOx using a .25 M KMnO4 and 0.5 M NaOH solution. Based on laboratory tests, this technique has been found to collect all NOx passed through under a variety of conditions (e.g., air flow rate, NOx concentration, temperature, humidity), allowing for diagnosis of δ15N-NOx without correction for fractionation. The precision across the entire analytic technique is 1.5‰. This active collection method is advantageous for collecting NOx over short time scales in environments with highly variable NOx sources and concentrations. The major drawback of the NaOH/KMnO4 method is a significant nitrate background found in the KMnO4, but this background is consistent and can be easily accounted for. We aim to use this method to provide more robust constraints on the isotopic signatures of NOx emissions from different sources. Initial results will be presented from lab- and field-based collections of NOx emissions. Emissions from a diesel engine were measured in a laboratory smog chamber and yielded δ15N values with a mean of -18.0‰ (n = 5, 1σ = 0.97‰). Measurements of δ15N-NOx were also made on a rooftop between two highways in Providence, RI. The values ranged from -7.7 to -0.63‰ for different time periods sampled, with excellent reproducibility in side-by-side collections. Additionally, the NaOH/KMnO4 was deployed in a laboratory study of biomass burning (FLAME4) to analyze the nitrogen isotopic composition of NOx produced from the burning of variety of materials (e.g. trees, agricultural

  17. Uranium isotope composition of a laterite profile during extreme weathering of basalt in Guangdong, South China (United States)

    Huang, J.; Zhou, Z.; Gong, Y.; Lundstrom, C.; Huang, F.


    Rock weathering and soil formation in the critical zone are important for material cycle from the solid Earth to superficial system. Laterite is a major type of soil in South China forming at hot-humid climate, which has strong effect on the global uranium cycle. Uranium is closely related to the environmental redox condition because U is stable at U(Ⅳ) in anoxic condition and U(Ⅵ) as soluble uranyl ion (UO22+) under oxic circumstance. In order to understand the behavior of U isotopes during crust weathering, here we report uranium isotopic compositions of soil and base rock samples from a laterite profile originated from extreme weathering of basalt in Guangdong, South China. The uranium isotopic data were measured on a Nu Plasma MC-ICP-MS at the University of Illinois at Urbana-Champaign using the double spike method. The δ238U of BCR-1 is -0.29±0.03‰ (relative to the international standard CRM-112A), corresponding to a 238U/235U ratio of 137.911±0.004. Our result of BCR-1 agrees with previous analyses (e.g., -0.28‰ in Weyer et al. 2008) [1]. U contents of the laterite profile decrease from 1.9 ppm to 0.9 ppm with depth, and peak at 160 - 170 cm (2.3 ppm), much higher than the U content of base rocks (~0.5 ppm). In contrary, U/Th of laterites is lower than that of base rock (0.27) except the peak at the depth of 160-170 cm (0.38), indicating significant U loss during weathering. Notably, U isotope compositions of soils show a small variation from -0.38 to -0.28‰, consistent with the base rock within analytical error (0.05‰ to 0.08‰, 2sd). Such small variation can be explained by a "rind effect" (Wang et al., 2015) [2], by which U(Ⅳ) can be completely oxidized to U(VI) layer by layer during basalt weathering by dissolved oxygen. Therefore, our study indicates that U loss during basalt weathering at the hot-humid climate does not change U isotope composition of superficial water system. [1] Weyer S. et al. (2008) Natural fractionation of 238U/235

  18. Stable isotope composition of land snail body water and its relation to environmental waters and shell carbonate (United States)

    Goodfriend, Glenn A.; Magaritz, Mordeckai; Gat, Joel R.


    Day-to-day and within-day (diel) variations in δD and δ18O of the body water of the land snail, Theba pisana, were studied at a site in the southern coastal plain of Israel. Three phases of variation, which relate to isotopic changes in atmospheric water vapor, were distinguished: 1) on rain days, snail water becomes isotopically depleted approximately in the direction of the rain isotope values, but always less depleted in D as is atmospheric water vapor; 2) during the 1-3 days following a rain, the snail water becomes isotopically enriched along a line with slope persists until the next rain event. The isotopic variations can be explained by isotopic equilibration with atmospheric water vapor and/or uptake of dew derived therefrom. During the winter, when the snails are active, there is only very minor enrichment in 18O relative to equilibrium with water vapor or dew, apparently as a result of metabolic activity. But this enrichment becomes pronounced after long periods of inactivity. Within-day variation in body water isotopic composition is minor on non-rain days. Shell carbonate is enriched in 18O by ca. 1-2%. relative to equilibrium with body water. In most regions, the isotopic composition of atmospheric water vapor (or dew) is a direct function of that of rain. Because the isotopic composition of snail body water is related to that of atmospheric water vapor and the isotopic composition of shell carbonate in turn is related to that of body water, land snail shell carbonate 18O should provide a reliable indication of rainfall 18O. However, local environmental conditions and the ecological properties of the snail species must be taken into account.

  19. The isotope composition of inorganic germanium in seawater and deep sea sponges (United States)

    Guillermic, Maxence; Lalonde, Stefan V.; Hendry, Katharine R.; Rouxel, Olivier J.


    Although dissolved concentrations of germanium (Ge) and silicon (Si) in modern seawater are tightly correlated, uncertainties still exist in the modern marine Ge cycle. Germanium stable isotope systematics in marine systems should provide additional constraints on marine Ge sources and sinks, however the low concentration of Ge in seawater presents an analytical challenge for isotopic measurement. Here, we present a new method of pre-concentration of inorganic Ge from seawater which was applied to measure three Ge isotope profiles in the Southern Ocean and deep seawater from the Atlantic and Pacific Oceans. Germanium isotopic measurements were performed on Ge amounts as low as 2.6 ng using a double-spike approach and a hydride generation system coupled to a MC-ICP-MS. Germanium was co-precipitated with iron hydroxide and then purified through anion-exchange chromatography. Results for the deep (i.e. >1000 m depth) Pacific Ocean off Hawaii (nearby Loihi Seamount) and the deep Atlantic off Bermuda (BATS station) showed nearly identical δ74/70Ge values at 3.19 ± 0.31‰ (2SD, n = 9) and 2.93 ± 0.10‰ (2SD, n = 2), respectively. Vertical distributions of Ge concentration and isotope composition in the deep Southern Ocean for water depth > 1300 m yielded an average δ74/70Ge = 3.13 ± 0.25‰ (2SD, n = 14) and Ge/Si = 0.80 ± 0.09 μmol/mol (2SD, n = 12). Significant variations in δ74/70Ge, from 2.62 to 3.71‰, were measured in the first 1000 m in one station of the Southern Ocean near Sars Seamount in the Drake Passage, with the heaviest values measured in surface waters. Isotope fractionation by diatoms during opal biomineralization may explain the enrichment in heavy isotopes for both Ge and Si in surface seawater. However, examination of both oceanographic parameters and δ74/70Ge values suggest also that water mass mixing and potential contribution of shelf-derived Ge also could contribute to the variations. Combining these results with new Ge isotope data

  20. Noble gas abundances and isotopic compositions in mantle-derived xenoliths,NE China

    Institute of Scientific and Technical Information of China (English)


    Following the researches of helium isotopic compositions in mantle-derived xenoliths in eastern China,this study reported noble gas abundances and isotopic compositions of mantle-derived xenoliths from Kuandian of Liaoning Province, Huinan of Jilin Province and Hannuoba of Hebei Province. Compared with the middle ocean ridge basalt (MORB) and other continental areas, mantle-derived xenoliths in NE China are characterized by slightly low noble gas abundances, 3He/4He equivalent to or lower than that of MORB, 40Ar/36Ar lower than that of MORB, 38Ar/36Ar and Ne-Kr-Xe isotopic ratios equivalent to those of atmosphere. These results indicate the heterogeneity of subcontinentai lithospheric mantle beneath northeastern China, that is, a MORB reservoir-like mantle beneath Kuandian and an enriched/metasomatized mantle beneath Huinan. Low 40Ar/36Ar ratios in the three studied areas may imply that a subducted atmospheric component has been preserved in the subcontinental lithospheric mantle.``

  1. The relationship between carbon and oxygen isotopic composition characteristics of carbonates in loess sediments and paleoclimate

    Institute of Scientific and Technical Information of China (English)

    李春园; 王先彬; 文启彬; 邵波


    Based on the carbon and oxygen isotopic compositions of carbonates in loess sediments meas-ured by the methods of stepwise heating and phosphoric acid decomposition from five pieces of samples ofpaleosol,loess and eolian sand,respectively,the distributive characteristics in different temperature steps andthe fractionation mechanisms of carbon and oxygen isotope and their relation to the paleoclirnate are discussed.The preliminary results show that,by means of stepwise heating,different carbon and oxygen isotopiccompositions are obtained in different temperature steps and carbon and oxygen isotopic compositions ofpaleosol,loess and eolian sand are in a different distributive pattern in the range of studied temperaturesteps.The results also show that the δ13C ratios in 700-800℃ are more sensitive tracers of paleoclimatethan those measured by the method of phosphoric acid decomposition.The susceptibility to climatic changesof δ18O ratios analysed by the method of phosphoric acid decomposition is higher than those analysed by themethod of stepwise heating,but the δ18O ratios measured by these two methods do not effectively reflect cli-matic changes.

  2. Tracing the secular evolution of the UCC using the iron isotope composition of ancient glacial diamictites (United States)

    Liu, X. M.; Gaschnig, R. M.; Rudnick, R. L.; Hazen, R. M.; Shahar, A.


    Iron is the fourth most abundant element in the continental crust and influences global climate and biogeochemical cycles in the ocean1. Continental inputs, including river waters, sediments and atmospheric dust are dominant sources (>95%) of iron into the ocean2. Therefore, understanding how continental inputs may have changed through time is important in understanding the secular evolution of the marine Fe cycle. We analysed the Fe isotopic composition of twenty-four glacial diamictite composites, upper continental crust (UCC) proxies, with ages ranging from the Mesoarchean to the Paleozoic eras to characterize the secular evolution of the UCC. The diamictites all have elevated chemical index of alteration (CIA) and other characteristics of weathered regolith (e.g., strong depletion in soluble elements such as Sr), which they inherited from their upper crustal source region3. δ56Fe in the diamictite composites range from -0.59 to +0.23‰, however, most diamictites cluster with an average δ56Fe of 0.11± 0.20 (2s), overlapping juvenile continental material such as island arc basalts (IABs), which show a narrow range in δ56Fe from -0.04 to +0.14 ‰4. There is no obvious correlation between δ56Fe of the glacial diamictites and the CIA, except that the diamictite with the lowest δ56Fe at -0.59 ‰ also has the highest CIA = 89 (the Paleoproterozoic Makganyene Fm.). The data suggest that the Fe isotope compositions in the upper continental crust did not vary throughout Earth history. Interestingly, chemical weathering and sedimentary transport likely play only a minor role in producing Fe isotope variations in the upper continental crust. Anoxic weathering pre-GOE (Great Oxidation Event) does not seem to generate different Fe isotopic signatures from the post-GOE oxidative weathering environment in the upper continental crust. Therefore, large Fe isotopic fractionations observed in various marine sedimentary records are likely due to other processes occurring

  3. Mineral composition control on inter-mineral iron isotopic fractionation in granitoids (United States)

    Wu, Hongjie; He, Yongsheng; Bao, Leier; Zhu, Chuanwei; Li, Shuguang


    This study reports elemental and iron isotopic compositions of feldspar and its coexisting minerals from four Dabie I-type granitoids to evaluate the factors that control inter-mineral Fe isotopic fractionation in granitoids. The order of heavy iron isotope enrichment is feldspar > pyrite > magnetite > biotite ≈ hornblende. Feldspar has heavier iron isotopic compositions than its co-existing magnetite (Δ56Feplagioclase-magnetite = +0.376‰ to +1.084‰, Δ56Fealkali-feldspar-magnetite = +0.516‰ to +0.846‰), which can be attributed to its high Fe3+/Fetot ratio and low coordination number (tetrahedrally-coordinated) of Fe3+. Δ56Femagnetite-biotite of coexisting magnetite and biotite ranges from 0.090‰ to 0.246‰. Based on homogeneous major and iron isotopic compositions of mineral replicates, the inter-mineral fractionation in this study should reflect equilibrium fractionation. The large variations of inter-mineral fractionation among feldspar, magnetite and biotite cannot be simply explained by temperature variation, but strongly depend on mineral compositions. The Δ56Feplagioclase-magnetite and Δ56Fealkali-feldspar-magnetite are positively correlated with albite mode in plagioclase and orthoclase mode in alkali-feldspar, respectively. This could be explained by different Fe-O bond strength in feldspar due to different Fe3+/∑Fe or different crystal parameters. The Δ56Femagnetite-biotite increases with decreasing Fe3+/∑Febiotite and increasing mole (Na + K)/Mgbiotite, indicating a decrease of β factor in low Fe3+/∑Fe and high (Na + K)/Mg biotite. High-silica leucosomes from Dabie migmatites with a feldspar accumulation petrogenesis have higher δ56Fe values (δ56Fe = 0.42-0.567‰) than leucosome that represents pristine partial melt (δ56Fe = 0.117 ± 0.016‰), indicating that accumulation of feldspar could account for high δ56Fe values of these rocks. High δ56Fe values are also predicted for other igneous rocks that are mainly composed of

  4. Hydrogen isotopic composition of the Martian mantle inferred from the newest Martian meteorite fall, Tissint (United States)

    Mane, P.; Hervig, R.; Wadhwa, M.; Garvie, L. A. J.; Balta, J. B.; McSween, H. Y.


    The hydrogen isotopic composition of planetary reservoirs can provide key constraints on the origin and history of water on planets. The sources of water and the hydrological evolution of Mars may be inferred from the hydrogen isotopic compositions of mineral phases in Martian meteorites, which are currently the only samples of Mars available for Earth-based laboratory investigations. Previous studies have shown that δD values in minerals in the Martian meteorites span a large range of -250 to +6000‰. The highest hydrogen isotope ratios likely represent a Martian atmospheric component: either interaction with a reservoir in equilibrium with the Martian atmosphere (such as crustal water), or direct incorporation of the Martian atmosphere due to shock processes. The lowest δD values may represent those of the Martian mantle, but it has also been suggested that these values may represent terrestrial contamination in Martian meteorites. Here we report the hydrogen isotopic compositions and water contents of a variety of phases (merrillites, maskelynites, olivines, and an olivine-hosted melt inclusion) in Tissint, the latest Martian meteorite fall that was minimally exposed to the terrestrial environment. We compared traditional sample preparation techniques with anhydrous sample preparation methods, to evaluate their effects on hydrogen isotopes, and find that for severely shocked meteorites like Tissint, the traditional sample preparation techniques increase water content and alter the D/H ratios toward more terrestrial-like values. In the anhydrously prepared Tissint sample, we see a large range of δD values, most likely resulting from a combination of processes including magmatic degassing, secondary alteration by crustal fluids, shock-related fractionation, and implantation of Martian atmosphere. Based on these data, our best estimate of the δD value for the Martian depleted mantle is -116 ± 94‰, which is the lowest value measured in a phase in the

  5. Gas Compositions and He-C Isotopic Ratios of Fumarolic Samples from Negros Island, Central Philippines (United States)

    Lee, Hsiao-Fen; Yang, Tsanyao Frank; Faith Lan, Tefang; Chen, Yue-Gau; Sincioco, Jaime S.; Solidum, Renato U., Jr.


    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. Chemical and Isotope Compositions of Neogene Hippopotamidae Teeth From Lake Albert (Uganda): Implications for Environmental Change (United States)

    Brugmann, G. E.; Brachert, T. C.; Ssemmanda, I.; Mertz, D. F.


    The Neogene was a period of long-term global cooling and increasing climatic variability on astronomical time scales. Lake systems strongly depend on rainfall patterns and size or geographical distribution of river networks. To unravel environmental change and watershed dynamics in the western branch of the East African Rift (Lake Albert, Uganda) during the Late Neogene, we use proxy data (trace elements, O, C and Sr isotopes) from Hippopotamidae teeth. Laser ablation ICPMS profiles in enamel measured from the outside rim towards the dentin show an asymmetric trace element distribution in that the concentrations continuously decrease by up to 5 orders of magnitude within a distance of about 1 mm until a minimum is reached (migration pathways and palaeoenvironmental changes. On geological time scales δ13C compositions reflect a transition from pure C3 browsers (-11 per mil PDB) at 5 to 6 Ma towards C4 dominated grazers (0 per mil PDB) at 2.0 to 2.5 Ma. The oxygen stable isotope (δ18O) composition of enamel rises from 26 per mil at 5 to 6 Ma to a maximum of 32 per mil SMOW at 2.3 Ma. Increasing δ18O values suggest enhanced evaporation of the lake due to rising aridity. This is in agreement with a synchronous spread of C4 vegetation in the reach of Hippopotamid populations. The Sr isotopic composition of enamel displays a large variation and 87Sr/86Sr is 0.714 about 5 Ma ago, reaches a maximum of 0.717 at about 2.3 Ma and decreases from there on to about 0.708. Thus, Sr and O isotopic compositions correlate with each other on the geological time scale. This is plausible if the Sr isotopic composition of Hippopotamid enamel dominantly reflects the changes of the water chemistry of the lake, and is therefore a powerful tool for tracing ancient hydrological networks. The large variation of the Sr isotope composition can be explained if the lake is fed by different sources: water draining Cenozoic volcanic terrains have low 87Sr/86Sr (~ 0.704), whereas Proterozoic

  7. Chlorine isotopic compositions of deep saline fluids in Ibusuki coastal geothermal region, Japan : using B–Cl isotopes to interpret fluid sources

    NARCIS (Netherlands)

    Musashi, Masaaki; Oi, Takao; Kreulen, Rob


    We report chlorine stable isotopic compositions (δ37Cl, expressed in ‰ relative to the standard mean ocean chloride) as well as δ2H and δ18O values of deep saline fluids taken at eight drill-holes reaching from 73 to 780 m below sea level in the Ibusuki coastal geothermal region, Japan. Analytical r

  8. Molecular and carbon isotopic compositions of gas inclusions of deep carbonate rocks in the Tarim Basin

    Institute of Scientific and Technical Information of China (English)

    ZHOU Shixin; WANG Xianbin; MENG Zifang; LI Yuan; Paul Farrimond; LI Liwu; DUAN Yi


    Gaseous components of gas inclusions in deep carbonate rocks (>5700 m) from the Tacan 1 well were analyzed by online mass spectrometry by means of either the stepwise heating technique or vacuum electromagnetism crushing. The carbon isotopic compositions of gases released by vacuum electromagnetism crushing were also measured. Although the molecular compositions of gas inclusions show differences between the two methods, the overall characteristics are that gas inclusions mainly contain CO2, whilst hydrocarbon gases, such as CH4, C2H6 and C3H8, are less abundant. The content of CO is higher in the stepwise heating experiment than that in the method of vacuum electromagnetism crushing, and there are only minor amounts of N2, H2 and O2 in gas inclusions. Methane δ13C values of gas inclusions in Lower Ordovician and Upper Cambrian rocks (from 5713.7 to 6422 m; -52‰-63‰) are similar to those of bacterial methane, but their chemical compositions do not exhibit the dry character in comparison with biogenic gases. These characteristics of deep gas inclusions may be related to the migration fractionation. Some deep natural gases with light carbon isotopic characteristics in the Tazhong Uplift may have a similar origin. The δ13C1 values of gas inclusions in Lower Cambrian rocks (7117-7124 m) are heavier (-39‰), consistent with highly mature natural gases. Carbon isotopic compositions of CO2 in the gas inclusions of deep carbonate rocks are similar (from -4‰ to -13‰) to those of deep natural gases, indicating predominantly an inorganic origin.

  9. Oxygen isotopic compositions of zircons from pyroxenite of Daoshichong, Dabieshan: Implications for crust-mantle interaction

    Institute of Scientific and Technical Information of China (English)


    Oxygen isotopic compositions of zircons from pyroxenite (~145 Ma) of Daoshichong, Dabieshan have been measured by an ion microprobe. Both within the single grain and among different grains, oxygen isotopic ratios are homogeneous, δ 18O = (7.66‰±0.46)‰ (1 SD, 1 σ = 0.10, n = 22). High δ 18O values indicate that the mantle-derived parent magma of Daoshichong pyroxenite have undergone interaction with crustal materials. Combing with other geochemical constraints, the way of crust-mantle interaction is suggested to be source mixing other than crustal contamination. The time interval between crust-mantle interaction and formation of the parent magma of Daoshichong pyroxenite is less than several million years. The crustal component involving in crust-mantle interaction is mafic lower crust, and the parent magma of pyroxenite possibly contain large proportion (>37%) of such lower crust.

  10. Mass-independent isotopic compositions in terrestrial and extraterrestrial solids and their applications. (United States)

    Thiemens, M H; Savarino, J; Farquhar, J; Bao, H


    In 1983, Thiemens and Heidenreich reported the first chemically produced mass-independent isotope effect. This work has been shown to have a wide range of applications, including atmospheric chemistry, solar system evolution, and chemical physics. This work has recently been reviewed (Weston, R. E. Chem. Rev. 1999, 99, 2115-2136; Thiemens, M. H. Science 1999, 283, 341-345). In this Account, observations of mass-independent isotopic compositions in terrestrial and Martian solids are reviewed. A wide range of applications, including formation and transport of aerosols in the present atmosphere, chemistry of ancient atmospheres and oceans, history and coupling of the atmosphere-surface in the Antarctic dry valleys, origin and evolution of oxygen in the Earth's earliest environment, and the chemistry of the atmosphere and surface of Mars, are discussed.

  11. Assessment of dissolved Pb concentration and isotopic composition in surface waters of the modern global ocean (United States)

    Pinedo-Gonzalez, P.; West, A. J.; Sanudo-Wilhelmy, S. A.


    Lead (Pb) produced by human activities, mainly from leaded gasoline combustion and high-temperature industries, dominates Pb in our present-day oceans. Previous studies have shown that surface ocean Pb concentrations and isotope ratios have varied in time and space, reflecting the changes in the amount of inputs and sources of anthropogenic Pb. However, data on surface ocean Pb is quite limited, especially for some basins like the Indian Ocean. In the present study, Pb concentrations and stable isotopes (208, 207, and 206) have been analyzed in surface water samples (3m depth) collected during the Malaspina Circumnavigation Expedition, 2010. Our results are compared with data from the literature to i) evaluate the changing status of metal contamination in surface waters of the global ocean over the last 30 years, and ii) propose potential sources of modern Pb to the oceans. Our results show that Pb concentrations in surface waters of the North Atlantic Ocean have decreased ~ 40% since 1975, attributable to the phase-out of leaded gasoline in North America. This result is corroborated by stable Pb isotope measurements. Furthermore, the isotopic gradient observed in surface waters of the studied transects in the north tropical and subtropical Atlantic Ocean can be attributed to simple mixing of European and African aerosols and Saharan Holocene loess. Results from an understudied transect in the Southern Indian Ocean give an indication of the source region of Pb delivered to this region. Although comparison with literature data is limited, mixing of Australian ores and African and Australian coals could potentially explain the measured Pb isotope composition. This study provides an opportunity to build on the work of previous oceanographic campaigns, enabling us to assess the impact of anthropogenic Pb inputs to the ocean and the relative importance of various Pb sources, providing new insights into the transport and fate of Pb in the oceans.

  12. Triple oxygen isotope composition of leaf waters in Mpala, central Kenya (United States)

    Li, Shuning; Levin, Naomi E.; Soderberg, Keir; Dennis, Kate J.; Caylor, Kelly K.


    Variations in triple oxygen isotopes have been used in studies of atmospheric photochemistry, global productivity and increasingly in studies of hydroclimate. Understanding the distribution of triple oxygen isotopes in plant waters is critical to studying the fluxes of oxygen isotopes between the atmosphere and hydrosphere, in which plants play an important role. In this paper we report triple oxygen isotope data for stem and leaf waters from Mpala, Kenya and explore how Δ17 O, the deviation from an expected relationship between 17O /16O and 18O /16O ratios, in plant waters vary with respect to relative humidity and deuterium excess (d-excess). We observe significant variation in Δ17 O among waters in leaves and stems from a single plant (up to 0.16‰ range in Δ17 O in leaf water in a plant over the course of a signal day), which correlates to changes in relative humidity. A steady state model for evaporation in leaf water reproduces the majority of variation in Δ17 O and d-excess we observed in leaf waters, except for samples that were collected in the morning, when relative humidity is high and the degree of fractionation in the system is minimal. The data and the steady state model indicate that the slope, λtransp, that links δ17 O and δ18 O values of stem and leaf waters and characterizes the fractionation during transpiration, is strongly influenced by the isotopic composition of ambient vapor when relative humidity is high. We observe a strong, positive relationship between d-excess and Δ17 O, with a slope 2.2 ± 0.2 per meg ‰-1, which is consistent with the observed relationship in tropical rainfall and in water in an evaporating open pan. The strong linear relationship between d-excess and Δ17 O should be typical for any process involving evaporation or any other fractionation that is governed by kinetic effects.

  13. Isotopic composition of dissolved iron in the Equatorial Pacific and the Southern oceans (United States)

    Radic, A.; Lacan, F.; Jeandel, C.; Poitrasson, F.; Sarthou, G.


    Iron is a fundamental element linking ocean biogeochemistry and climate. Iron isotopes are a very promising tool for the study of the iron oceanic cycle, notably for tracing its sources to the ocean and/or for studying its speciation. Several studies reports iron isotopic data in the marine environment: in plankton tows, pore waters, aerosols, seafloor or marginal seas (Bergquist and Boyle, 2006; Severmann et al., 2006; De Jong et al., 2007). To link these isotopic data together and to fully study the iron isotope marine cycle, we need to document the central reservoir in the marine environment : dissolved iron in seawater, espacially in High Nutrient Low Chlorophyll (NHLC) areas. So far there are very few comunicated data of dissolved iron isotopic composition in the open ocean (Rouxel, 2008; Lacan et al., 2008; John and Andkins, 2009;). Here, the first profiles in HNLC areas will be presented : 2 full-depth profiles in the Equatorial Pacific Ocean (EUCFe 2006), 2 full-depth profiles in the Atlantic sector of the Southern Ocean (Bonus-GoodHope 2008) and some data from the Kerguelen area (Southern Ocean, KEOPS 2005). δ56Fe values range from -0.7‰ to more than 1.0‰. All the samples from the Equatorial Pacific Ocean display positive values (heavy iron) whereas samples from the Sourthern Ocean display rather negative values (light iron), especially around 450 m deepth. These results will be discussed in terms of iron sources to ocean. Potential applications of this new tracer for studying internal oceanic processes, such as biological uptake, will be discussed.

  14. Mercury Stable Isotopic Composition of Monomethylmercury in Estuarine Sediments and Pure Cultures of Mercury Methylating Bacteria (United States)

    Janssen, S.; Johnson, M. W.; Barkay, T.; Blum, J. D.; Reinfelder, J. R.


    Tracking monomethylmercury (MeHg) from its source in soils and sediments through various environmental compartments and transformations is critical to understanding its accumulation in aquatic and terrestrial food webs. Advances in the field of mercury (Hg) stable isotopes have allowed for the tracking of discrete Hg sources and the examination of photochemical and bacterial transformations. Despite analytical advances, measuring the Hg stable isotopic signature of MeHg in environmental samples or laboratory experiments remains challenging due to difficulties in the quantitative separation of MeHg from complex matrices with high concentrations of inorganic Hg. To address these challenges, we have developed a MeHg isolation method for sediments and bacterial cultures which involves separation by gas chromatography. The MeHg eluting from the GC is passed through a pyrolysis column and purged onto a gold amalgam trap which is then desorbed into a final oxidizing solution. A MeHg reference standard carried through our separation process retained its isotopic composition within 0.02 ‰ for δ202Hg, and for native estuarine sediments, MeHg recoveries were 80% to 100%. For sediment samples from the Hackensack and Passaic Rivers (New Jersey, USA), δ202Hg values for MeHg varied from -1.2 to +0.58 ‰ (relative to SRM 3133) and for individual samples were significantly different from that of total Hg (-0.38 ± 0.06 ‰). No mass independent fractionation was observed in MeHg or total Hg from these sediments. Pure cultures of Geobacter sulfurreducens, grown under fermentative conditions showed preferential enrichment of lighter isotopes (lower δ202Hg) during Hg methylation. The Hg stable isotope signatures of MeHg in sediments and laboratory methylation experiments will be discussed in the context of the formation and degradation of MeHg in the environment and the bioaccumulation of MeHg in estuarine food webs.

  15. Water mass circulation and weathering inputs in the Labrador Sea based on coupled Hf-Nd isotope compositions and rare earth element distributions (United States)

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


    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

  16. Carbon isotopic composition of fossil leaves from the Early Cretaceous sediments of western India

    Indian Academy of Sciences (India)

    S Chakraborty; B N Jana; S K Bhattacharya; I Robertson


    Stable carbon isotope analysis of fossil leaves from the Bhuj Formation, western India was carried out to infer the prevailing environmental conditions. Compression fossil leaves such as Pachypteris indica, Otozamite kachchhensis, Brachyphyllum royii and Dictyozamites sp. were recovered from three sedimentary successions of the Bhuj Formation, Early Cretaceous in age. A chronology was established based on faunal assemblage and palyno-stratigraphy and further constrained by carbon isotope stratigraphy. The three sampling sites were the Karawadi river bank near Dharesi; the Chawad river bank near Mathal; and the Pur river section near Trambau village in Gujarat. The Dharesi sample was also analyzed to investigate intra-leaf 13C variability. The mean 13C of the leaf was −24.6 ± 0.4‰ which implied negligible systematic change along the leaf axis. The Mathal sample was fragmented in nature and showed considerable variation in carbon isotopic composition. The Trambau sample considered to be the oldest, dating to the middle of Aptian (ca. 116 Ma), shows the most depleted value in 13C among all of them. The overall 13C trend ranging from mid Aptian (ca. 116 Ma) to early Albian (ca. 110 Ma) shows a progressive increase in 13C from −26.8 to −20.5‰. Based on these measurements the carbon isotopic composition of atmospheric carbon dioxide of the Aptian–Albian period is estimated to be between −7.4 and −1.7‰. The ratio of the partial pressure of carbon dioxide in leaf to that of the ambient atmosphere calculated based on a model is estimated to be similar to that of the modern plants. This indicates that the Early-Cretaceous plants adapted to the prevailing high carbon dioxide regime by increasing their photosynthetic uptake.

  17. Altitude effect on leaf wax carbon isotopic composition in humid tropical forests (United States)

    Wu, Mong Sin; Feakins, Sarah J.; Martin, Roberta E.; Shenkin, Alexander; Bentley, Lisa Patrick; Blonder, Benjamin; Salinas, Norma; Asner, Gregory P.; Malhi, Yadvinder


    The carbon isotopic composition of plant leaf wax biomarkers is commonly used to reconstruct paleoenvironmental conditions. Adding to the limited calibration information available for modern tropical forests, we analyzed plant leaf and leaf wax carbon isotopic compositions in forest canopy trees across a highly biodiverse, 3.3 km elevation gradient on the eastern flank of the Andes Mountains. We sampled the dominant tree species and assessed their relative abundance in each tree community. In total, 405 sunlit canopy leaves were sampled across 129 species and nine forest plots along the elevation profile for bulk leaf and leaf wax n-alkane (C27-C33) concentration and carbon isotopic analyses (δ13C); a subset (76 individuals, 29 species, five forest plots) were additionally analyzed for n-alkanoic acid (C22-C32) concentrations and δ13C. δ13C values display trends of +0.87 ± 0.16‰ km-1 (95% CI, r2 = 0.96, p families, suggesting the biochemical response to environment is robust to taxonomic turnover. We calculate fractionations and compare to adiabatic gradients, environmental variables, leaf wax n-alkane concentrations, and sun/shade position to assess factors influencing foliar chemical response. For the 4 km forested elevation range of the Andes, 4-6‰ higher δ13C values are expected for upland versus lowland C3 plant bulk leaves and their n-alkyl lipids, and we expect this pattern to be a systematic feature of very wet tropical montane environments. This elevation dependency of δ13C values should inform interpretations of sedimentary archives, as 13C-enriched values may derive from C4 grasses, petrogenic inputs or upland C3 plants. Finally, we outline the potential for leaf wax carbon isotopes to trace biomarker sourcing within catchments and for paleoaltimetry.

  18. Carbon elemental and isotopic composition in mantle xenoliths from Spain: Insights on sources and petrogenetic processes (United States)

    Bianchini, G.; Natali, C.


    The carbon elemental concentration (C wt%) and isotopic (δ13C ‰) composition of mantle xenoliths from the Tallante and Calatrava volcanic occurrences (in South-East and Central Spain, respectively) have been investigated to identify carbon sources and processes occurring in distinct geodynamic settings of the Iberian Peninsula. The peridotitic mantle xenoliths from Calatrava show elemental C ranging from 0.11 to 2.87 wt% which is coupled with a continuous isotopic variation from very negative values (δ13C - 26.1‰) to typical mantle values (δ13C - 5.9‰). On the other hand, the Tallante mantle xenolith suite displays lower C contents (0.06-0.15 wt%) showing a tighter variation with 13C-depleted values ranging between - 20.1 and - 23.7‰; higher elemental C up to 0.41 wt% displaying distinctly less negative isotopic values (δ13C between - 13.8 and - 11.9‰) have been recorded in veins crosscutting Tallante peridotites, plausibly representing the product of metasomatic reactions. The data from the two investigated xenolith suites invariably display a good correlation between elemental and isotopic composition, suggesting a mantle origin for carbon and Rayleigh-type fractionation as the process responsible for the observed C-δ13C variation. However, the correlation between the carbon isotopic data with other isotopic tracers (e.g. 87Sr/86Sr, 3He/4He) used to identify distinct mantle components and metasomatic reactions, indicates systematic differences between the two xenolith suites suggesting that beneath the Betic Cordillera (where Tallante is located) the deep C-cycle involves recycling, via subduction preceding/accompanying continental collision, of crustal components back in the mantle. Coherently, geochemical trends observed in the Tallante xenoliths seem to be influenced by metasomatic agents generated by melting of crustal lithologies that according to the analysis of a metasedimentary xenolith can contain C up to 1.2 wt% having δ13C of ca. - 18

  19. Preservation of Primary Carbonate Clumped Isotope Compositions: Insights from Fossil Brachiopod Calcite (United States)

    Henkes, G. A.; Perez-Huerta, A.; Grossman, E. L.; Passey, B. H.


    Invertebrate fossils, mainly mollusks and brachiopods, are keystone recorders of primary elemental and isotopic compositions of ancient oceans. Certifying these biominerals as robust archives has been the focus of decades of study, the results of which have established petrographic and geochemical diagenetic screening tests for identifying ostensibly pristine fossils. Despite this fact, the oxygen isotope (δ18O) thermometer `water problem'—the unknown seawater δ18O over most of Earth's history—has restricted shell δ18O paleothermometry. Carbonate clumped isotopes are a promising solution, but the study of preservation of primary compositions is in relative infancy. Analyses of brachiopod shells have confirmed that while petrographic and geochemical tests effectively screen for `open-system' exchange, they do not completely address `closed-system' exchange. Elevated clumped isotope temperatures (T(Δ47)) without signs for recrystallization have been attributed to solid-state C-O bond reordering, which re-equilibrate the 13C-18O bonds that are the basis of the thermometer at elevated burial temperatures. Currently there are no a priori methods for identifying geologic samples that have been affected by bond reordering. An alternative approach is to employ experimentally validated kinetic models to test whether a sample has passed through burial conditions—temperatures >100°C for timescales <108 years—that would've activated reordering. New and existing experimental data on reordering reaction kinetics confirm that the rate constants are virtually identical for an optical spar and brachiopod and crinoid fossils, suggesting uniform behavior across calcite morphologies during heating. Yet questions remain over distinguishing marginal clumped isotope reordering from cryptic recrystallization in natural samples. To this end, we are exploring electron backscatter diffraction as an additional test for confirming isotopic preservation over geologic timescales

  20. Circum-Antarctic Nd isotope variability during the last 30 kyrs (United States)

    Struve, T.; van de Flierdt, T.; Hines, S. K.; Burke, A.; Adkins, J. F.; Robinson, L. F.; Crocket, K. C.; Auro, M. E.


    The modern Southern Ocean is a key area for the global ocean circulation as wind-driven mixing, upwelling and redistribution of water masses in the Antarctic Circumpolar Current (ACC) all have a significant impact on the properties and flow patterns of global water masses. It has been suggested that the Southern Ocean plays a critical role in oceanographic and climatic changes observed on glacial-interglacial timescales, in particular with respect to carbon sequestration between the deep ocean and the atmosphere. For the purpose of unravelling Southern Ocean water mass composition at intermediate depth during the past 30 kyrs, we here utilise the Nd isotopic composition of the aragonitic skeletons of solitary deep-sea corals. These corals were collected from two locations, the Drake Passage and the area south of Tasmania, and from water depths between 300 and 1750 m. Modern coral specimen were calibrated against nearby seawater. Neodymium was collected from the wash fraction of the anion-exchange column, which represents the first step in preparing samples for precise U-series dating. Subsequent Nd separation utilised a two-stage ion chromatography (RE-spec/cation exchange and Ln-spec resins). Isotopic analyses were performed as NdO+ on a Triton TIMS using a TaF5 activator on W filaments yielding 2σ external reproducibilities of ~20 ppm. (Sub-) millenial scale deep-sea coral neodymium isotope results from the Drake Passage suggest that the modern homogenous ACC neodymium isotopic composition of ɛNd≈ -8 is a very recent feature. During the past 30 kyrs Nd isotope variability on the order of two epsilon units are observed at intermediate water depths as well as repeated changes in water column stratification. We will discuss our new results in the context of other Southern Ocean records, as well as preliminary Nd isotope data from glacial to deglacial deep-sea corals from south of Tasmania in order to constrain the last glacial to deglacial circum-Antarctic Nd

  1. Isotopic composition and identification of the origins of individuals buried in a Neolithic collective grave at Bronocice (southern Poland). (United States)

    Szostek, K; Haduch, E; Stepańczak, B; Kruk, J; Szczepanek, A; Pawlyta, J; Głąb, H; Milisauskas, S


    The oxygen present in a human organism comes from numerous sources, but the major factor that causes variation in the isotopic composition of this element in a tissue is available drinking water. The isotopic ratio of oxygen in an organism's tissue, including that found in bones and teeth, reflects the isotopic oxygen composition typical for the area where a given individual developed and lived. Of particular interest with regard to this issue were a series of skeletons from the multiple grave discovered at the Funnel Beaker-Baden settlement at Bronocice (southern Poland). The question therefore arose whether the specimens buried in this grave were part of the local community. The oxygen isotope level was established using apatite isolated from bones or teeth. A femur and root dentine samples taken from permanent teeth were subjected to oxygen isotope analysis. The oxygen isotope level of the site was established on the basis of local water precipitation and measurements taken from the oxygen isotope concentration in apatite samples isolated from the bones of animals co-occurring with the studied human group. It has been found that the oxygen isotope levels in the bones and dentine of almost all the analysed specimens from the excavated site at Bronocice were within the established range for the area's environment, providing evidence for their local origin. Thus, it can be assumed that the analysed group inhabiting the macrosettlement at Bronocice during the Funnel Beaker phase of the Baden culture was most probably of local origin.

  2. The precise measurement of Tl isotopic compositions by MC-ICPMS: Application to the analysis of geological materials and meteorites

    Energy Technology Data Exchange (ETDEWEB)

    Rehkaemper, M. [Univ. of Michigan, Ann Arbor, MI (United States). Dept. of Geological Sciences]|[Univ. Muenster (Germany). Zentrallabor fuer Geochronologie; Halliday, A.N. [Univ. of Michigan, Ann Arbor, MI (United States). Dept. of Geological Sciences]|[ETH Zuerich (Switzerland). Inst. for Isotope Geology and Mineral Resources


    The precision of Tl isotopic measurements by thermal ionization mass spectrometry (TIMS) is severely limited by the fact that Tl possesses only two naturally occurring isotopes, such that there is no invariant isotope ratio that can be used to correct for instrumental mass discrimination. In this paper the authors describe new chemical and mass spectrometric techniques for the determination of Tl isotopic compositions at a level of precision hitherto unattained. Thallium is first separated from the geological matrix using a two-stage anion-exchange procedure. Thallium isotopic compositions are then determined by multiple-collector inductively coupled plasma-mass spectrometry with correction for mass discrimination using the known isotopic composition of Pb that is admixed to the sample solutions. With these procedures they achieve a precision of 0.01--0.02% for Tl isotope ratio measurements in geological samples and this is a factor of {ge}3--4 better than the best published results by TIMS. Results are discussed for five terrestrial samples and for the C3V chondrite Allende.

  3. Sulfur Isotopic Compositions of Submicrometer SiC Grains from the Murchison Meteorite (United States)

    Xu, Yuchen; Zinner, Ernst; Gallino, Roberto; Heger, Alexander; Pignatari, Marco; Lin, Yangting


    We report C, Si, N, S, Mg-Al, and Ca-Ti isotopic compositions of presolar silicon carbide (SiC) grains from the SiC-rich KJE size fraction (0.5-0.8 μm) of the Murchison meteorite. One thousand one hundred thirteen SiC grains were identified based on their C and Si isotopic ratios. Mainstream, AB, C, X, Y, and Z subtypes of SiC, and X-type silicon nitride (Si3N4) account for 81.4%, 5.7%, 0.1%, 1.5%, 5.8%, 4.9%, and 0.4%, respectively. Twenty-five grains with unusual Si isotopic ratios, including one C grain, 16 X grains, 1 Y grain, 5 Z grains, and 2 X-type Si3N4 grains were selected for N, S, Mg-Al, and Ca-Ti isotopic analysis. The C grain is highly enriched in 29Si and 30Si (δ29Si = 1345‰ ± 19‰, δ30Si = 1272‰ ± 19‰). It has a huge 32S excess, larger than any seen before, and larger than that predicted for the Si/S supernova (SN) zone, providing evidence against the elemental fractionation model by Hoppe et al. Two SN models investigated here present a more satisfying explanation in terms of a radiogenic origin of 32S from the decay of short-lived 32Si (τ1/2 = 153 yr). Silicon-32 as well as 29Si and 30Si can be produced in SNe by short neutron bursts; evidence for initial 44Ti (τ1/2 = 60 yr) in the C grain is additional evidence for an SN origin. The X grains have marginal 32S excesses, much smaller than expected from their large 28Si excesses. Similarly, the Y and Z grains do not show the S-isotopic anomalies expected from their large Si isotopic anomalies. Low intrinsic S contents and contamination with isotopically normal S are the most likely explanations.


    Energy Technology Data Exchange (ETDEWEB)

    Xu, Yuchen [Institute of Geochemistry, Chinese Academy of Sciences, Guiyang 550002 (China); Zinner, Ernst [Laboratory for Space Sciences and Physics Department, Washington University, St. Louis, MO 63130 (United States); Gallino, Roberto [Dipartimento di Fisica, Università di Torino, I-10125 Torino (Italy); Heger, Alexander [Monash Centre for Astrophysics, School of Mathematical Sciences, Monash University, Vic 3800 (Australia); Pignatari, Marco [Department of Physics, University of Basel, CH-4056 Basel (Switzerland); Lin, Yangting, E-mail: [Key Laboratory of Earth' s Deep Interior, Institute of Geology and Geophysics, Chinese Academy of Sciences, Beijing 100029 (China)


    We report C, Si, N, S, Mg-Al, and Ca-Ti isotopic compositions of presolar silicon carbide (SiC) grains from the SiC-rich KJE size fraction (0.5-0.8 μm) of the Murchison meteorite. One thousand one hundred thirteen SiC grains were identified based on their C and Si isotopic ratios. Mainstream, AB, C, X, Y, and Z subtypes of SiC, and X-type silicon nitride (Si{sub 3}N{sub 4}) account for 81.4%, 5.7%, 0.1%, 1.5%, 5.8%, 4.9%, and 0.4%, respectively. Twenty-five grains with unusual Si isotopic ratios, including one C grain, 16 X grains, 1 Y grain, 5 Z grains, and 2 X-type Si{sub 3}N{sub 4} grains were selected for N, S, Mg-Al, and Ca-Ti isotopic analysis. The C grain is highly enriched in {sup 29}Si and {sup 30}Si (δ{sup 29}Si = 1345‰ ± 19‰, δ{sup 30}Si = 1272‰ ± 19‰). It has a huge {sup 32}S excess, larger than any seen before, and larger than that predicted for the Si/S supernova (SN) zone, providing evidence against the elemental fractionation model by Hoppe et al. Two SN models investigated here present a more satisfying explanation in terms of a radiogenic origin of {sup 32}S from the decay of short-lived {sup 32}Si (τ{sub 1/2} = 153 yr). Silicon-32 as well as {sup 29}Si and {sup 30}Si can be produced in SNe by short neutron bursts; evidence for initial {sup 44}Ti (τ{sub 1/2} = 60 yr) in the C grain is additional evidence for an SN origin. The X grains have marginal {sup 32}S excesses, much smaller than expected from their large {sup 28}Si excesses. Similarly, the Y and Z grains do not show the S-isotopic anomalies expected from their large Si isotopic anomalies. Low intrinsic S contents and contamination with isotopically normal S are the most likely explanations.

  5. Osmium Isotopic Composition of the K/T Boundary Sediments from Sumbar: A Progress Report (United States)

    Meisel, T.; Krahenbuhl, U.; Nazarov, M. A.


    Osmium isotope measurements have been performed on the boundary clay at different Cretaceous-Tertiary boundary (KTB) sites [1-5] since [6] suggested that Os isotopes are an indicator of an extraterrestrial component. The debate over "impact vs. volcanic" could not be resolved, but an isotope ratio close to chondritic could be demonstrated. The study of the distribution of iridium in the stratigraphy of the KTB cannot distinguish the contribution of chondritic and/or terrestrial Ir respectively, whereas the Os isotopes allow us to better constrain a mixing model. The ^187Os/^186Os ratio of the continental crust and chondritic reservoirs differ by at least 10-30 times. Assuming certain parameters, we should be able to calculate the proportion of the reservoirs making up the sediments of the KTB section. We studied a complete section of the KTB of Sumbar, Turkmenistan [7], for its Os isotopic composition. In the section 0-30 cm above the boundary clay, the ^187Os/^186Os ratio increases from 1.15 to 1.47, whereas the Ir concentration decreases from 66 to 1.4 ng/g or 66 to 4.7 ng/g on a carbonate-free basis respectively. Calculations show that the chondritic component makes up 9% at the boundary layer and decreases down to 0.6% at +30 cm. The data cannot be simply explained by varying admixtures of a chondritic component to a sediment of constant Os concentration and isotopic signature. To explain the Os ratios completely it is necessary to consider a mixture of four components (extraterrestrial, ejecta material, local terrigeneous, and carbonacous sediments) with certain assumptions: (1) The extraterrestrial source is chondritic in its Os and Re content and has an initial Os isotope ratio of 1.12 at 65 Ma (time of impact), which is above the average for normal chondrites but is within the range measured so far (e.g., Murray). (2) The ejecta material has a higher Os concentration (0.2 ng/g) than the sediments and is only present in the first 5 cm of the sequence above

  6. The summer 2012 Greenland heat wave: monitoring water vapour isotopic composition along an atmospheric river event (United States)

    Bonne, Jean-Louis; Steen-Larsen, Hans Christian; Masson-Delmotte, Valérie; Sodemann, Harald; Lacour, Jean-Lionel; Risi, Camille; Werner, Martin; Clerbaux, Cathy; Fettweis, Xavier


    In July 2012, an extreme warm event occurred in Greenland, leading to surface melt over almost all the ice sheet. This event was recorded in the isotopic composition of water vapour measured by the IASI satellite along the transport pathway and at two sites where continuous in situ surface vapour isotopic measurements were conducted, situated at a coastal station of South Greenland (Ivittuut) and further North on top of the ice sheet (NEEM, NW Greenland). These observations allowed us to monitor the isotopic composition of the air mass at different stages of its advection towards Greenland, which can inform on processes along this trajectory, such as cloud properties and moisture sources. In addition, two simulations of this event, using the atmospheric general circulation models LMDZiso and ECHAM5wiso equipped with water stable isotopes and nudged towards large scale wind fields, are investigated. Furthermore, a regional high-resolution model was used to study the moisture transport to Greenland during this event using tagged water tracers of the North Atlantic ocean and coastal land evaporation. Using moisture source diagnostic based on the Lagrangian particle dispersion model Flexpart, we show that this 2012 heat wave event corresponds to moisture sources located over the subtropical Atlantic Ocean, where intense evaporation was caused by dry air masses associated with the US intense summer drought. This moisture was then advected northward along a narrow band, due to a very stationary surface cyclone southwest of Greenland, reached southern Greenland and Ivittuut coastal station on July 9th, travelled along the west coast of Greenland, continued eastwards above the ice sheet and arrived above the NEEM deep drilling camp on July 11th. Surface isotopic observations during the event show larger variations at NEEM than in Ivittuut, strongly reducing the isotopic and deuterium excess latitudinal gradient usually observed between South and North Greenland. This

  7. Tracing changes in atmospheric sources of lead contamination using lead isotopic compositions in Australian red wine. (United States)

    Kristensen, Louise Jane; Taylor, Mark Patrick; Evans, Andrew James


    Air quality data detailing changes to atmospheric composition from Australia's leaded petrol consumption is spatially and temporally limited. In order to address this data gap, wine was investigated as a potential proxy for atmospheric lead conditions. Wine spanning sixty years was collected from two wine regions proximal to the South Australian capital city, Adelaide, and analysed for lead concentration and lead and strontium isotopic composition for source apportionment. Maximum wine lead concentrations (328 μg/L) occur prior to the lead-in-air monitoring in South Australia in the later 1970s. Wine lead concentrations mirror available lead-in-air measurements and show a declining trend reflecting parallel reductions in leaded petrol emissions. Lead from petrol dominated the lead in wine ((206)Pb/(207)Pb: 1.086; (208)Pb/(207)Pb: 2.360) until the introduction of unleaded petrol, which resulted in a shift in the wine lead isotopic composition closer to vineyard soil ((206)Pb/(207)Pb: 1.137; (208)Pb/(207)Pb: 2.421). Current mining activities or vinification processes appear to have no impact with recent wine samples containing less than 4 μg/L of lead. This study demonstrates wine can be used to chronicle changes in environmental lead emissions and is an effective proxy for atmospherically sourced depositions of lead in the absence of air quality data.

  8. Comparison of neutron cross sections for selected fission products and isotopic composition analyses with burnup

    Energy Technology Data Exchange (ETDEWEB)

    Kim, D. H.; Gil, C. S.; Kim, J. D.; Jang, J. H.; Lee, Y. D. [KAERI, Taejon (Korea)


    The neutron absorption cross sections for 18 fission products evaluated within the framework of the KAERI-BNL international collaboration have been compared with the ENDF/B-VI release 7. Also, the influence of the new evaluations on isotopic compositions of the fission products as a function of burnup has been analyzed through the OECD/NEA burnup credit criticality benchmarks (Phase 1B) and the LWR/Pu recycling benchmarks. These calculations were performed by WIMSD-5B with the 69 group libraries prepared from three evaluated nuclear data libraries: ENDF/B-VI.7, ENDF/B-VI.8 including new evaluations in resonance region covering thermal region, and ENDF/B-VII expected including those in upper resonance region up to 20 MeV. For Xe-131, the composition calculated with ENDF/B-VI.8 shows maximum difference of 4.78% compared to ENDF/B-VI.7. However, the isotopic compositions of all fission products calculated with ENDF/B-VII shows no differences compared to ENDF/B-VI.7.

  9. Comparisons of Neutron Cross Sections and Isotopic Composition Calculations for Fission-Product Evaluations (United States)

    Kim, Do Heon; Gil, Choong-Sup; Chang, Jonghwa; Lee, Yong-Deok


    The neutron absorption cross sections for 18 fission products evaluated within the framework of the KAERI (Korea Atomic Energy Research Institute)-BNL (Brookhaven National Laboratory) international collaboration have been compared with ENDF/B-VI.7. Also, the influence of the new evaluations on the isotopic composition calculations of the fission products has been estimated through the OECD/NEA burnup credit criticality benchmarks (Phase 1B) and the LWR/Pu recycling benchmarks. These calculations were performed by WIMSD-5B with the 69-group libraries prepared from three evaluated nuclear data libraries: ENDF/B-VI.7, ENDF/B-VI.8 including the new evaluations in the resonance region covering the thermal region, and the expected ENDF/B-VII including those in the upper resonance region up to 20 MeV. For Xe-131, the composition calculated with ENDF/B-VI.8 shows a maximum difference of 5.02% compared to ENDF/B-VI.7. However, the isotopic compositions of all the fission products calculated with the expected ENDF/B-VII show no differences when compared to ENDF/B-VI.7 for the thermal reactor benchmark cases.

  10. A method for in situ monitoring of the isotope composition of tree xylem water using laser spectroscopy. (United States)

    Volkmann, Till H M; Kühnhammer, Kathrin; Herbstritt, Barbara; Gessler, Arthur; Weiler, Markus


    Field studies analyzing the stable isotope composition of xylem water are providing important information on ecosystem water relations. However, the capacity of stable isotopes to characterize the functioning of plants in their environment has not been fully explored because of methodological constraints on the extent and resolution at which samples could be collected and analysed. Here, we introduce an in situ method offering the potential to continuously monitor the stable isotope composition of tree xylem water via its vapour phase using a commercial laser-based isotope analyser and compact microporous probes installed into the xylem. Our technique enables efficient high-frequency measurement with intervals of only a few minutes per sample while eliminating the need for costly and cumbersome destructive collection of plant material and laboratory-based processing. We present field observations of xylem water hydrogen and oxygen isotope compositions obtained over several days including a labelled irrigation event and compare them against results from concurrent destructive sampling with cryogenic distillation and mass spectrometric analysis. The data demonstrate that temporal changes as well as spatial patterns of integration in xylem water isotope composition can be resolved through direct measurement. The new technique can therefore present a valuable tool to study the hydraulic architecture and water utilization of trees.

  11. Derivation of correction factor to be applied for calculated results of PWR fuel isotopic composition by ORIGEN2 code

    Energy Technology Data Exchange (ETDEWEB)

    Suyama, Kenya; Nomura, Yasushi [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment; Murazaki, Minoru [Tokyo Nuclear Service Inc., Tokyo (Japan); Mochizuki, Hiroki [The Japan Research Institute Ltd., Tokyo (Japan)


    For providing conservative PWR spent fuel compositions from the view point of nuclear criticality safety, correction factors applicable for result of burnup calculation by ORIGEN2 were evaluated. Its conservativeness was verified by criticality calculations using MVP. To calculate these correction factors, analyses of spent fuel isotopic composition data were performed by ORIGEN2. Maximum or minimum value of the ratio of calculation result to experimental data was chosen as correction factor. These factors are given to each set of fuel assembly and ORIGEN2 library. They could be considered as the re-definition of recommended isotopic composition given in Nuclear Criticality Safety Handbook. (author)

  12. Pore-water isotopic compositions and unsaturated-zone flow, Yucca Mountain, Nevada

    Energy Technology Data Exchange (ETDEWEB)

    Yang, In C.


    Isotopic compositions of core-water samples from boreholes USW SD-6 and USW WT-24 indicate that recent water has been introduced at depth. Tritium, carbon, oxygen, and deuterium isotopic compositions all support younger water at depth in the two boreholes. Peaks in tritium concentrations in pore-water samples, indicating younger water than the other samples, observed near the basal vitrophyre of the Topopah Spring Tuff and at the bottom of the CHF and the top of the PP in both boreholes SD-6 and WT-24. Larger {sup 14}C activities in two pore-water samples from WT-24 at the bottom of the CHF and the top of the PP indicate younger water than in other samples from WT-24. More positive {delta}{sup 18}O and {delta}D values indicate younger water in samples of pore water at the bottom of the CHF in boreholes SD-6 and WT-24. The isotopic compositions indicating younger water at depth in boreholes SD-6 and WT-24 occur at the basal vitrophyre zone of the Topopah Spring Tuff and the bottom of the CHF/upper part of the PP, probably from lateral preferential flow through connected fractures (fast-flow paths). The source of the young water at borehole WT-24 probably was recharge from The Prow to the north, which then flowed laterally southward through the highly fractured TSw. The source of the young water at borehole SD-6 probably was water flow from the Solitario Canyon fault to the west, which then flowed laterally through the TSw and CHF.

  13. Isotopic composition of inorganic mercury and methylmercury downstream of a historical gold mining region (United States)

    Donovan, Patrick M.; Blum, Joel D.; Singer, Michael B.; Marvin-DiPasquale, Mark C.; Tsui, Martin T.K.


    We measured total mercury (THg) and monomethyl mercury (MMHg) concentrations and mercury (Hg) isotopic compositions in sediment and aquatic organisms from the Yuba River (California, USA) to identify Hg sources and biogeochemical transformations downstream of a historical gold mining region. Sediment THg concentrations and δ202Hg decreased from the upper Yuba Fan to the lower Yuba Fan and the Feather River. These results are consistent with the release of Hg during gold mining followed by downstream mixing and dilution. The Hg isotopic composition of Yuba Fan sediment (δ202Hg = −0.38 ± 0.17‰ and Δ199Hg = 0.04 ± 0.03‰; mean ± 1 SD, n = 7) provides a fingerprint of inorganic Hg (IHg) that could be methylated locally or after transport downstream. The isotopic composition of MMHg in the Yuba River food web was estimated using biota with a range of %MMHg (the percent of THg present as MMHg) and compared to IHg in sediment, algae, and the food web. The estimated δ202Hg of MMHg prior to photodegradation (−1.29 to −1.07‰) was lower than that of IHg and we suggest this is due to mass-dependent fractionation (MDF) of up to −0.9‰ between IHg and MMHg. This result is in contrast to net positive MDF (+0.4 to +0.8‰) previously observed in lakes, estuaries, coastal oceans, and forests. We hypothesize that this unique relationship could be due to differences in the extent or pathway of biotic MMHg degradation in stream environments.

  14. Measurement of the Carbon Isotopic Composition of Methane Using Helicoidal Laser Eigenstates (United States)

    Jacob, D.; Le Floch, A.; Bretenaker, F.; Guenot, P.


    The spatially generalized Jones matrix formalism is used to design a laser cavity to make intracavity measurements of the carbon isotopic composition of methane. the method is based on a double optical lever effect for helicoidally polarized eigenstates, permitting to measure successively the ^{12}CH_4 and ^{13}CH_4 concentrations. To choose the probed isotope, one simply tunes the frequency of the laser by Zeeman effect. The experiment exhibits a good agreement with the predictions and permits to measure the ^{13}CH4/^{12}CH_4 composition ratio of methane with an uncertainty of the order of ± 0.07% for a sample containing only 6× 10^{-9} mole of methane. On utilise le formalisme des matrices de Jones généralisées spatialement pour concevoir une cavité laser permettant la mesure intra-cavité de la composition isotopique du carbone présent dans le méthane. La méthode est fondée sur une double application de l'effet de levier optique pour les états propres hélicoïdaux, permettant de mesurer successivement les concentrations de ^{12}CH_4 et de ^{13}CH_4. Pour passer d'un isotope à l'autre, on ajuste simplement la fréquence du laser par effet Zeeman. L'expérience est en bon accord avec les prédictions et permet d'effectuer la mesure du rapport isotopique ^{13}CH4/^{12}CH_4 avec une fourchette d'incertitude de ± 0,07% pour des échantillons de gaz ne contenant que 6× 10^{-9} mole de méthane.

  15. Isotopic Composition of Inorganic Mercury and Methylmercury Downstream of a Historical Gold Mining Region. (United States)

    Donovan, Patrick M; Blum, Joel D; Singer, Michael Bliss; Marvin-DiPasquale, Mark; Tsui, Martin T K


    We measured total mercury (THg) and monomethyl mercury (MMHg) concentrations and mercury (Hg) isotopic compositions in sediment and aquatic organisms from the Yuba River (California, USA) to identify Hg sources and biogeochemical transformations downstream of a historical gold mining region. Sediment THg concentrations and δ(202)Hg decreased from the upper Yuba Fan to the lower Yuba Fan and the Feather River. These results are consistent with the release of Hg during gold mining followed by downstream mixing and dilution. The Hg isotopic composition of Yuba Fan sediment (δ(202)Hg = -0.38 ± 0.17‰ and Δ(199)Hg = 0.04 ± 0.03‰; mean ± 1 SD, n = 7) provides a fingerprint of inorganic Hg (IHg) that could be methylated locally or after transport downstream. The isotopic composition of MMHg in the Yuba River food web was estimated using biota with a range of %MMHg (the percent of THg present as MMHg) and compared to IHg in sediment, algae, and the food web. The estimated δ(202)Hg of MMHg prior to photodegradation (-1.29 to -1.07‰) was lower than that of IHg and we suggest this is due to mass-dependent fractionation (MDF) of up to -0.9‰ between IHg and MMHg. This result is in contrast to net positive MDF (+0.4 to +0.8‰) previously observed in lakes, estuaries, coastal oceans, and forests. We hypothesize that this unique relationship could be due to differences in the extent or pathway of biotic MMHg degradation in stream environments.

  16. Box-modeling of bone and tooth phosphate oxygen isotope compositions as a function of environmental and physiological parameters. (United States)

    Langlois, C; Simon, L; Lécuyer, Ch


    A time-dependent box model is developed to calculate oxygen isotope compositions of bone phosphate as a function of environmental and physiological parameters. Input and output oxygen fluxes related to body water and bone reservoirs are scaled to the body mass. The oxygen fluxes are evaluated by stoichiometric scaling to the calcium accretion and resorption rates, assuming a pure hydroxylapatite composition for the bone and tooth mineral. The model shows how the diet composition, body mass, ambient relative humidity and temperature may control the oxygen isotope composition of bone phosphate. The model also computes how bones and teeth record short-term variations in relative humidity, air temperature and delta18O of drinking water, depending on body mass. The documented diversity of oxygen isotope fractionation equations for vertebrates is accounted for by our model when for each specimen the physiological and diet parameters are adjusted in the living range of environmental conditions.

  17. Sulfur isotope composition of metasomatised mantle xenoliths from the Bultfontein kimberlite (Kimberley, South Africa): Contribution from subducted sediments and the effect of sulfide alteration on S isotope systematics (United States)

    Giuliani, Andrea; Fiorentini, Marco L.; Martin, Laure A. J.; Farquhar, James; Phillips, David; Griffin, William L.; LaFlamme, Crystal


    Sulfur isotopes are a powerful geochemical tracer in high-temperature processes, but have rarely been applied to the study of mantle metasomatism. In addition, there are very limited S isotope data on sub-continental lithospheric mantle (SCLM) material. For cratonic regions, these data are restricted to sulfide inclusions in diamonds. To provide new constraints on the S isotope composition of the SCLM and on the source(s) of mantle metasomatic fluids beneath the diamondiferous Kimberley region (South Africa), we investigated the S isotope systematics of five metasomatised mantle xenoliths from the Bultfontein kimberlite. Pentlandite and chalcopyrite in these xenoliths were analysed by in situ secondary-ion mass spectrometry (SIMS), with bulk-rock material measured by gas source isotope ratio mass spectrometry techniques. Based on previous studies, the xenoliths experienced different types of metasomatism to one another at distinct times (∼180 and ∼90-80 Ma). Contained pentlandite grains show variable alteration to heazlewoodite (i.e. Ni sulfide) + magnetite. The in situ S isotope analyses of pentlandite exhibit a relatively restricted range between -5.9 and - 1.4 ‰δ34 S (compared to VCDT), with no statistically meaningful differences between samples. Chalcopyrite only occurs in one sample and shows δ34 S values between -5.4 and - 1.0 ‰. The bulk-rock Ssulfide isotope analyses vary between -3.4 and + 0.8 ‰δ34 S. Importantly, the only sample hosting dominantly fresh sulfides shows a bulk-rock δ34 S value consistent with the mean value for the sulfides, whereas the other samples exhibit higher bulk 34S/32S ratios. The differences between bulk-rock and average in situδ34 S values are directly correlated with the degree of sulfide alteration. This evidence indicates that the elevated 34S/32S ratios in the bulk samples are not due to the introduction of heavy S (commonly as sulfates) and are best explained by isotopic fractionation coupled with the removal

  18. The Oxygen Isotope Composition of Dark Inclusions in HEDs, Ordinary and Carbonaceous Chondrites (United States)

    Greenwood, R. C.; Zolensky, M. E.; Buchanan, P. C.; Franchi, I. A.


    Dark inclusions (DIs) are lithic fragments that form a volumetrically small, but important, component in carbonaceous chondrites. Carbonaceous clasts similar to DIs are also found in some ordinary chondrites and HEDs. DIs are of particular interest because they provide a record of nebular and planetary processes distinct from that of their host meteorite. DIs may be representative of the material that delivered water and other volatiles to early Earth as a late veneer. Here we focus on the oxygen isotopic composition of DIs in a variety of settings with the aim of understanding their formational history and relationship to the enclosing host meteorite.

  19. The Oxygen Isotopic Composition of Water in the Inner Solar System


    Nunn, Morgan


    Where there is water, there can be life. Improving our understanding of how life, as we know it, arose uniquely in our solar system on Earth depends critically on our understanding of the history of water in the solar system. Better characterizing the sources of water to the Earth-Moon system is crucial in constraining this history and motivated the experiments described in this dissertation.The oxygen isotopic composition of water in lunar samples in addition to meteorites from Mars and seve...

  20. Re-Os isotopic composition of the Dongling ⅢCD iron meteorite

    Institute of Scientific and Technical Information of China (English)


    Re,Os concentrations and Os isotopic compositions of the Dongling ⅢCD iron meteorite were determined by N-TIMS technique. The result was compared with that of the other irons and chondrites. The Re and Os concentrations of the Dongling iron meteorite were plotted on the trends of the group ⅢA and ⅣA irons. The Pt-Os relation of the Dongling iron meteorite is similar to that of the group ⅡA irons. That suggests a higher fractionation for the Dongling iron meteorite.

  1. Isotopic composition of ground waters from Kufra (Lybia) as indicator for ground water formation

    Energy Technology Data Exchange (ETDEWEB)

    Swailem, F.M.; Hamza, M.S.; Aly, A.I.M. (Middle Eastern Regional Radioisotope Centre for the Arab Countries, Cairo (Egypt))


    The results of the isotopic composition of shallow and deep ground waters from the Kufra region indicate the fossil origin of these waters and that they are not recharged under the present climatic conditions. The virtual absence of tritium and the radiocarbon ages of these waters show that they were formed mainly in the past pluvial periods. Deuterium and oxygen-18 data indicate that the ground waters were recharged under cooler climatic conditions. These results may explain the origin of the large amounts of ground water which existed in the region.

  2. Validation of the scale system for PWR spent fuel isotopic composition analyses

    Energy Technology Data Exchange (ETDEWEB)

    Hermann, O.W.; Bowman, S.M.; Parks, C.V. [Oak Ridge National Lab., TN (United States); Brady, M.C. [Sandia National Laboratories, Las Vegas, NV (United States)


    The validity of the computation of pressurized-water-reactor (PWR) spent fuel isotopic composition by the SCALE system depletion analysis was assessed using data presented in the report. Radiochemical measurements and SCALE/SAS2H computations of depleted fuel isotopics were compared with 19 benchmark-problem samples from Calvert Cliffs Unit 1, H. B. Robinson Unit 2, and Obrigheim PWRs. Even though not exhaustive in scope, the validation included comparison of predicted and measured concentrations for 14 actinides and 37 fission and activation products. The basic method by which the SAS2H control module applies the neutron transport treatment and point-depletion methods of SCALE functional modules (XSDRNPM-S, NITAWL-II, BONAMI, and ORIGEN-S) is described in the report. Also, the reactor fuel design data, the operating histories, and the isotopic measurements for all cases are included in detail. The underlying radiochemical assays were conducted by the Materials Characterization. Center at Pacific Northwest Laboratory as part of the Approved Testing Material program and by four different laboratories in Europe on samples processed at the Karlsruhe Reprocessing Plant.

  3. Abnormal lithium isotope composition from the ancient lithospheric mantle beneath the North China Craton. (United States)

    Tang, Yan-Jie; Zhang, Hong-Fu; Deloule, Etienne; Su, Ben-Xun; Ying, Ji-Feng; Santosh, M; Xiao, Yan


    Lithium elemental and isotopic compositions of olivines in peridotite xenoliths from Hebi in the North China Craton provide direct evidence for the highly variable δ(7)Li in Archean lithospheric mantle. The δ(7)Li in the cores of olivines from the Hebi high-Mg# peridotites (Fo > 91) show extreme variation from -27 to +21, in marked deviation from the δ(7)Li range of fresh MORB (+1.6 to +5.6) although the Li abundances of the olivines are within the range of normal mantle (1-2 ppm). The Li abundances and δ(7)Li characteristics of the Hebi olivines could not have been produced by recent diffusive-driven isotopic fractionation of Li and therefore the δ(7)Li in the cores of these olivines record the isotopic signature of the subcontinental lithospheric mantle. Our data demonstrate that abnormal δ(7)Li may be preserved in the ancient lithospheric mantle as observed in our study from the central North China Craton, which suggest that the subcontinental lithospheric mantle has experienced modification of fluid/melt derived from recycled oceanic crust.

  4. Isotopic compositions of strontium in river water of Guizhou karst areas, China

    Institute of Scientific and Technical Information of China (English)

    韩贵琳; 刘丛强


    We have carried out a study on the variation of strontium isotope composition of river waters, Wujiang and Yuangjiang River, in karst areas of Guizhou Province, China. The results obtained permit us to characterize the geochemistry of the river draining karst terrain and obtain a better understanding of main controls of catchment geology, chemical weathering of different rocks, and evaluate impact of human activities on the environment. The isotopic ratios of dissolved Sr in all rivers are between 87Sr/86Sr =0.7077 and 0.7110, totally lower than the weighted average of 87Sr/86Sr =0.7119 for the world large rivers. The Wujiang River waters have Sr concentrations from 1.0 to 6.1 μmol/L, while the Yuanjiang River waters have much lower Sr concentrations ranging from 0.28 to 1.3 μmol/L. Most of the river waters from the Wujiang river are characterized by low Ca/Sr and Mg/Sr, and 87Sr/86Sr ratios, in which a majority of river waters are of 87Sr/86Sr ratios lower than the average Sr isotope ratio (87Sr/86Sr

  5. Changing compositions in the Iceland plume; Isotopic and elemental constraints from the Paleogene Faroe flood basalts

    DEFF Research Database (Denmark)

    Søager, Nina; Holm, Paul Martin


    -type component similar in geochemistry to the Icelandic Öræfajökull lavas. This component is believed to be recycled pelagic sediments in the plume but it can alternatively be a local crustal or lithospheric mantle component. The enriched Faroe high-Ti lavas erupted inland from the rift have isotopic......Elemental and Sr, Nd, Hf and high precision Pb isotopic data are presented from 59 low-Ti and high-Ti lavas from the syn-break up part of the Faroe Flood Basalt Province. The depleted MORB-like low-Ti lavas erupted in the rift zone between the Faroe Islands and central East Greenland around...... the time of break up of the North Atlantic have isotopic end-member compositions different from the depleted Iceland lavas. We suggest that the main low-Ti mantle component is NAEM (North Atlantic End-Member (Ellam and Stuart, 2000, J. Petrol. 41, 919) and that the 207Pb/204Pb value of the component should...

  6. The carbon isotopic compositions of Non-methane Hydrocarbons in atmosphere

    Institute of Scientific and Technical Information of China (English)

    PENG Lin; ZHANG HuiMin; REN ZhaoFang; MU Ling; SHI RuiLiang; CHANG LiPing; LI Fan


    Carbon isotopic compositions of atmospheric Non-methane Hydrocarbons (NMHCs) in the urban areas of Taiyuan and Lanzhou in summer were reported and the sources of NMHCs are discussed.Carbon isotopic ratios (δ13C) of vehicle exhaust,coal-combustion exhaust,fuel volatiles and cooking exhaust were also measured with thermal desorption-gas chromatography-isotope ratio-mass spectrometry (TD-GC-IR-MS).δ13C values of NMHCs in the urban areas of Lanzhou and Taiyuan range from -32.3‰ to -22.3‰ and from -32.8‰ to -18.1‰.δ13C values of vehicle exhaust,coal-combustion exhaust,fuel volatiles and cooking exhaust are -32.5‰--21.7‰,-24.5‰--22.3‰,-32.5%--27.4‰ and -31.6‰--24.5‰,respectively.The data indicate that vehicle exhaust and cooking exhaust make a significant contribution to the atmospheric NMHCs.Therefore,to reduce emissions of vehicle exhaust and cook-ing exhaust is critical for controlling atmospheric NMHCs pollution in summer.

  7. Continuous monitoring of summer surface water vapor isotopic composition above the Greenland Ice Sheet

    Directory of Open Access Journals (Sweden)

    H. C. Steen-Larsen


    Full Text Available We present here surface water vapor isotopic measurements conducted from June to August 2010 at the NEEM (North Greenland Eemian Drilling Project camp, NW Greenland (77.45° N, 51.05° W, 2484 m a.s.l.. Measurements were conducted at 9 different heights from 0.1 m to 13.5 m above the snow surface using two different types of cavity-enhanced near-infrared absorption spectroscopy analyzers. For each instrument specific protocols were developed for calibration and drift corrections. The inter-comparison of corrected results from different instruments reveals excellent reproducibility, stability, and precision with a standard deviations of ~ 0.23‰ for δ18O and ~ 1.4‰ for δD. Diurnal and intraseasonal variations show strong relationships between changes in local surface humidity and water vapor isotopic composition, and with local and synoptic weather conditions. This variability probably results from the interplay between local moisture fluxes, linked with firn–air exchanges, boundary layer dynamics, and large-scale moisture advection. Particularly remarkable are several episodes characterized by high (> 40‰ surface water vapor deuterium excess. Air mass back-trajectory calculations from atmospheric analyses and water tagging in the LMDZiso (Laboratory of Meteorology Dynamics Zoom-isotopic atmospheric model reveal that these events are associated with predominant Arctic air mass origin. The analysis suggests that high deuterium excess levels are a result of strong kinetic fractionation during evaporation at the sea-ice margin.

  8. Interactive Evolution of Multiple Water-Ice Reservoirs on Mars: Insights from Hydrogen Isotope Compositions

    CERN Document Server

    Kurokawa, Hiroyuki; Sato, Masahiko


    Remote sensing data from orbiter missions have proposed that ground ice may currently exist on Mars, although the volume is still uncertain. Recent analyses of Martian meteorites have suggested that the water reservoirs have at least three distinct hydrogen isotope compositions (D/H ratios): primordial and high D/H ratios, which are approximately the same and six times that of ocean water on Earth, respectively, and a newly identified intermediate D/H ratio, which is approximately two to three times higher than that in ocean water on Earth. We calculate the evolution of the D/H ratios and the volumes of the water reservoirs on Mars by modeling the exchange of hydrogen isotopes between multiple water reservoirs and the atmospheric escape. The D/H ratio is slightly higher in the topmost thin surface-ice layer than that in the atmosphere because of isotopic fractionation by sublimation, whereas the water-ice reservoir just below the exchangeable topmost surface layer retains the intermediate D/H signature found ...

  9. Interpreting bryophyte stable carbon isotope composition: Plants as temporal and spatial climate recorders (United States)

    Royles, Jessica; Horwath, Aline B.; Griffiths, Howard


    are unable to control tissue water content although physiological adaptations allow growth in a wide range of habitats. Carbon isotope signals in two mosses (Syntrichia ruralis and Chorisodontium aciphyllum) and two liverworts (Conocephalum conicum and Marchantia polymorpha), whether instantaneous (real time, Δ13C), or organic matter (as δ13COM), provide an assimilation-weighted summary of bryophyte environmental adaptations. In mosses, δ13COM is within the measured range of Δ13C values, which suggests that other proxies, such as compound-specific organic signals, will be representative of historical photosynthetic and growth conditions. The liverworts were photosynthetically active over a wider range of relative water contents (RWC) than the mosses. There was a consistent 5‰ offset between Δ13C values in C. conicum and M. polymorpha, suggestive of greater diffusion limitation in the latter. Analysis of a C. aciphyllum moss-peat core showed the isotopic composition over the past 200 years reflects recent anthropogenic CO2 emissions. Once corrected for source-CO2 inputs, the seasonally integrated Δ13COM between 1350 and 2000 A.D. varied by 1.5‰ compared with potential range of the 12‰ measured experimentally, demonstrating the relatively narrow range of conditions under which the majority of net assimilation takes place. Carbon isotope discrimination also varies spatially, with a 4‰ shift in epiphytic bryophyte organic matter found between lowland Amazonia and upper montane tropical cloud forest in the Peruvian Andes, associated with increased diffusion limitation.

  10. Characterizing the oxygen isotopic composition of phosphate sources to aquatic ecosystems. (United States)

    Young, Megan B; McLaughlin, Karen; Kendall, Carol; Stringfellow, William; Rollog, Mark; Elsbury, Katy; Donald, Elizabeth; Paytan, Adina


    The oxygen isotopic composition of dissolved inorganic phosphate (delta18Op) in many aquatic ecosystems is not in isotopic equilibrium with ambient water and, therefore, may reflect the source delta18Op. Identification of phosphate sources to water bodies is critical for designing best management practices for phosphate load reduction to control eutrophication. In order for delta18Op to be a useful tool for source tracking, the delta18Op of phosphate sources must be distinguishable from one another; however, the delta18Op of potential sources has not been well characterized. We measured the delta18Op of a variety of known phosphate sources, including fertilizers, semiprocessed phosphorite ore, particulate aerosols, detergents, leachates of vegetation, soil, animal feces, and wastewater treatment plant effluent. We found a considerable range of delta18Op, values (from +8.4 to +24.9 per thousand) for the various sources, and statistically significant differences were found between several of the source types. delta18Op measured in three different fresh water systems was generally not in equilibrium with ambient water. Although there is overlap in delta18Op values among the groups of samples, our results indicate that some sources are isotopically distinct and delta18Op can be used for identifying phosphate sources to aquatic systems.

  11. Nitrogen and oxygen isotopic composition of N sub(2)O from suboxic waters of the eastern tropical North Pacific and the Arabian Sea - measurement by continuous-flow isotope-ratio monitoring

    Digital Repository Service at National Institute of Oceanography (India)

    Yoshinari, T.; Altabet, M.A.; Naqvi, S.W.A.; Codispoti, L.; Jayakumar, D.A.; Kuhland, M.; Devol, A.

    and of the dual stable isotopic composition of N sub(2)O in the eastern tropical North Pacific (ETNP) and the Arabian Sea. The stable isotopic composition of N sub(2)O was determined by a new method that required only 80-100 nmol of N sub(2)O per sample analysis...

  12. Dielectric and impedance behavior of neodymium substituted strontium hexaferrite (United States)

    Bhat, Bilal Hamid; Samad, Rubiya; Want, Basharat


    In this study, dielectric behavior and complex impedance of neodymium (Nd) substituted strontium hexaferrite system: Sr1- x Nd x Fe12O19 ( x = 0.0, 0.05, 0.1, 0.15, 0. 20), synthesized by citrate precursor technique, have been evaluated as a function of applied frequency and temperature. Variation of dielectric constant and dielectric loss with frequency shows the identical behavior for all the compositions. The value of dielectric constant increases with Nd doping. Relaxation process is observed in the composition x = 0.20, and the peaks in this composition shift toward the higher-frequency region as the temperature increases. The dielectric constants show temperature-independent behavior at low temperature, whereas at higher temperatures it increases for all the frequencies. The AC conductivity follows Jonscher's power law, showing that conduction mechanism is due to polaron hopping. Complex impedance as a function of composition and temperature is used to examine the role of grain and grain boundary in the prepared material. Cole-cole plot shows only one semicircle up to x = 0.15, while as for x = 0.20 two semicircles are observed. The conduction mechanism is explained on the basis of both grain and grain boundary.

  13. Dielectric and impedance behavior of neodymium substituted strontium hexaferrite

    Energy Technology Data Exchange (ETDEWEB)

    Bhat, Bilal Hamid; Samad, Rubiya; Want, Basharat [University of Kashmir, Solid State Research Lab., Department of Physics, Srinagar (India)


    In this study, dielectric behavior and complex impedance of neodymium (Nd) substituted strontium hexaferrite system: Sr{sub 1-x}Nd{sub x}Fe{sub 12}O{sub 19} (x = 0.0, 0.05, 0.1, 0.15, 0.20), synthesized by citrate precursor technique, have been evaluated as a function of applied frequency and temperature. Variation of dielectric constant and dielectric loss with frequency shows the identical behavior for all the compositions. The value of dielectric constant increases with Nd doping. Relaxation process is observed in the composition x = 0.20, and the peaks in this composition shift toward the higher-frequency region as the temperature increases. The dielectric constants show temperature-independent behavior at low temperature, whereas at higher temperatures it increases for all the frequencies. The AC conductivity follows Jonscher's power law, showing that conduction mechanism is due to polaron hopping. Complex impedance as a function of composition and temperature is used to examine the role of grain and grain boundary in the prepared material. Cole-cole plot shows only one semicircle up to x = 0.15, while as for x = 0.20 two semicircles are observed. The conduction mechanism is explained on the basis of both grain and grain boundary. (orig.)

  14. Isotopic composition of low-latitude paleoprecipitation during the Early Cretaceous (United States)

    Suarez, M.B.; Gonzalez, Luis A.; Ludvigson, Greg A.; Vega, F.J.; Alvarado-Ortega, J.


    The response of the hydrologic cycle in global greenhouse conditions is important to our understanding of future climate change and to the calibration of global climate models. Past greenhouse conditions, such as those of the Cretaceous, can be used to provide empirical data with which to evaluate climate models. Recent empirical studies have utilized pedogenic carbonates to estimate the isotopic composition of meteoric waters and calculate precipitation rates for the AptianAlbian. These studies were limited to data from mid(35??N) to high (75??N) paleolatitudes, and thus future improvements in accuracy will require more estimates of meteoric water compositions from numerous localities around the globe. This study provides data for tropical latitudes (18.5??N paleolatitude) from the Tlayua Formation, Puebla, Mexico. In addition, the study confirms a shallow nearshore depositional environment for the Tlayua Formation. Petrographic observations of fenestral fabrics, gypsum crystal molds, stromatolitic structures, and pedogenic matrix birefringence fabric support the interpretation that the strata represent deposition in a tidal flat environment. Carbonate isotopic data from limestones of the Tlayua Formation provide evidence of early meteoric diagenesis in the form of meteoric calcite lines. These trends in ??18O versus ??13C were used to calculate the mean ??18O value of meteoric water, which is estimated at -5.46 ?? 0.56??? (Vienna Standard Mean Ocean Water [VSMOW]). Positive linear covariant trends in oxygen and carbon isotopic values from some horizons were used to estimate evaporative losses of vadose groundwater from tropical exposure surfaces during the Albian, and the resulting values range from 8% to 12%. However, the presence of evaporative mineral molds indicates more extensive evaporation. The added tropical data improve latitudinal coverage of paleoprecipitation ??18O estimates. The data presented here imply that earlier isotope mass balance models most

  15. Isotopic Composition of Boron Secondary Ions as a Function of Ion-Beam Fluence. (United States)

    Baumel, Laurie Michelle

    The experiment performed in this work isolates and examines the effects of mass on the composition of the sputtered flux from a multi-component target. Chemical complexities are minimized by measuring sputtered ions from a target consisting only of two isotopes of one element. In this case, chemical effects as well as inter-atomic potentials are assumed to be identical for all constituents moving within the target, thus simplifying the target kinematics. Since any non-stoichiometry in the sputtered material should be caused only by the effects of mass on the kinetics in the target, measuring the sputtered material and comparing various analytical predictions with the experimental results leads to a better understanding of mass effects in these targets. 100-keV argon and neon were used to sputter an elemental target comprising the two naturally occurring isotopes of boron. The resulting secondary ions were examined with an electrostatic quadrupole mass analyzer. At low beam fluences (~1 times 20^{15} ions/cm ^2) a light-isotope secondary ion enhancement is observed relative to the steady-state secondary ion yields collected at higher beam fluences ( ~5 times 10 ^{17} ions/cm^2 ). The steady-state ion yields are representative of the bulk composition of the target. The enhancement (46.1perthous for Ne^+ irradiation and 51.8perthous for Ar^+ irradiation) is large compared to the predictions of analytical theories and is determined to be independent of variations in surface potential, chemical effects, and surface impurities. This effect is consistent with an explanation based on an energy and momentum asymmetry in the collision cascade. The asymmetry was caused by an extra collision mechanism which allowed light particles to backscatter 180^circ (towards the target surface) from underlying heavier target particles whereas the reverse process can not occur. When irradiated with projectiles heavier than the target constituents, the heavier target particles had a higher

  16. Calcium isotopic composition of mantle xenoliths and minerals from Eastern China (United States)

    Kang, Jin-Ting; Zhu, Hong-Li; Liu, Yu-Fei; Liu, Fang; Wu, Fei; Hao, Yan-Tao; Zhi, Xia-Chen; Zhang, Zhao-Feng; Huang, Fang


    This study presents calcium isotope data for co-existing clinopyroxenes (cpx), orthopyroxenes (opx), and olivine (ol) in mantle xenoliths to investigate Ca isotopic fractionation in the upper mantle. δ44/40Ca (δ44/40Ca (‰) = (44Ca/40Ca)SAMPLE/(44Ca/40Ca)SRM915a - 1) in opx varies from 0.95 ± 0.05‰ to 1.82 ± 0.01‰ and cpx from 0.71 ± 0.06‰ to 1.03 ± 0.12‰ (2se). δ44/40Ca in ol (P-15) is 1.16 ± 0.08‰, identical to δ44/40Ca of the co-existing opx (1.12 ± 0.09‰, 2se). The Δ44/40Caopx-cpx (Δ44/40Caopx-cpx = δ44/40Caopx-δ44/40Cacpx) shows a large variation ranging from -0.01‰ to 1.11‰ and it dramatically increases with decreasing of Ca/Mg (atomic ratio) in opx. These observations may reflect the effect of opx composition on the inter-mineral equilibrium fractionation of Ca isotopes, consistent with the theoretical prediction by first-principles theory calculations (Feng et al., 2014). Furthermore, Δ44/40Caopx-cpx decreases when temperature slightly increases from 1196 to 1267 K. However, the magnitude of such inter-mineral isotopic fractionation (1.12‰) is not consistent with the value calculated by the well-known correlation between inter-mineral isotope fractionation factors and 1/T2 (Urey, 1947). Instead, it may reflect the temperature control on crystal chemistry of opx (i.e., Ca content), which further affects Δ44/40Caopx-cpx. The calculated δ44/40Ca of bulk peridotites and pyroxenites range from 0.76 ± 0.06‰ to 1.04 ± 0.12‰ (2se). Notably, δ44/40Ca of bulk peridotites are positively correlated with CaO and negatively with MgO content. Such correlations can be explained by mixing between a fertile mantle end-member and a depleted one with low δ44/40Ca, indicating that Ca isotopes could be a useful tool in studying mantle evolution.

  17. The Effect of Phytase on the Oxygen Isotope Composition of Phosphate (United States)

    von Sperber, C.; Tamburini, F.; Bernasconi, S. M.; Frossard, E.


    Plants and microorganisms under phosphorus (P) stress release extracellular phosphatases as a strategy to acquire inorganic phosphate (Pi) (1-2). These enzymes catalyze the hydrolysis of phosphoesters leading to a release of Pi. The enzymatic hydrolysis leads, via a nucleophilic attack, to the incorporation of one oxygen atom from the water into the newly formed Pi molecule. During the incorporation, an isotopic fractionation occurs, which might be used to identify the origin of Pi in the environment (3-6). While the effect of phosphomonoesterases and phosphodiesterases on the oxygen isotope composition of phosphate has been examined, there are, so far, no studies dealing with the effect of phytases (4-6). Phytases catalyze the hydrolysis of myo-inositol-hexakis-phosphate (IP6), which is an important component of organic P in many ecosystems (7). Enzymatic assays with phytase from wheat germ and Aspergillus niger were prepared under sterile and temperature controlled conditions in order to determine the effect of phytases on the oxygen isotope composition of phosphate, which has been liberated from IP6 via enzymatic hydrolysis. Assays with phytase from wheat germ lead to a turnover of the substrate close to 100%, while assays with phytase from Aspergillus niger lead to a turnover of the substrate close to 80%. In the case of the assays with phytase from wheat germ, our results indicate that one sixth of the total 24 oxygen which are associated to the phosphates in IP6 are exchanged with oxygen from water. From this we conclude that the incorporation of one oxygen atom from water occurs only at four phosphate molecules of IP6, while two phosphate molecules do not experience an incorporation of oxygen. This suggests that during the enzymatic hydrolysis, four P-O bonds and two C-O bonds are broken. Provided that, the isotopic fractionation can be calculated with an isotopic mass balance resulting in -8.4‰ (×3.6 SD). This is a value very similar to those reported

  18. The Boron Isotopic Composition of Elephant Dung: Inputs to the Global Boron Budget (United States)

    Williams, L. B.; Hervig, R. L.


    A survey of boron in kerogen showed isotopically light δ11B values (0 to -50%) that are distinctly different from most mineral and natural water B reservoirs. Diagenesis releases this isotopically light B into pore fluids when hydrocarbons are generated, thus enriching oilfield brines in 10B. This observation suggests that borated biomolecules (BM) are primarily tetrahedral favoring 10B, whereas 11B is preferred in trigonal coordination. Plants, with optimal concentrations up to 100ppm, contribute more B than animal remains to sediment. Elephants are one of the largest herbivores on earth, consuming 200 - 250 kg of plant material/day and producing 50 kg of manure/day. They are inefficient at digestion, thus the manure contains >50% undigested plant material. Dung samples are therefore ideal for studying the δ11B of both the food input and digested output of a significant B supply to sedimentary systems. Horse and rabbit manure were studied for comparison to evaluate B isotope variations in the food supply and potential vital effects on the output. B-content and isotopic composition of dung plant material and digested fractions were measured in the solid state by secondary ion mass spectrometry. The digests were rinsed in 1.8% mannitol, a B-complexing agent, to remove surface adsorbed-B, then air dried and Au-coated for charge compensation. Results showed that the elephant diet contains 3-13 ppm B, with an average δ11B of -20 ± 0.8% (1σ), while rabbit food had 88 ppm B with a δ11B of -50 ± 1.3 %. The digested fraction of the elephant dung contains 4-10ppm B with average δ11B values of -12 ± 1.2%. In comparison, horse manure with 11-21 ppm B has a δ11B of -10.7 ± 0.5% and rabbit manure contains 2-3 ppm B with a δ11B of -8.8 ± 1%. Boron isotope compositions of these manures are indistinguishable (within error). Clearly plant material is a major contributor of isotopically light B to sediments. The herbivores studied fractionate their total B intake in

  19. In situ oxygen isotope compositions in olivines of different types of cosmic spherules: An assessment of relationships to chondritic particles

    Digital Repository Service at National Institute of Oceanography (India)

    Rudraswami, N.G.; ShyamPrasad, M.; Jones, R.H.; Nagashima, K.

    et al., 2015a). The micrometeorites that have entered Earth’s atmosphere at high zenith angle and low velocity are interesting because their petrologic and isotopic characteristics are largely preserved thereby providing constraints on the parent... et al., 2012). Oxygen isotope studies complemented by mineralogical compositions are vital to unravel the complexity involved in distinguishing the known components of micrometeorites and their parent bodies. For carbonaceous chondrites...

  20. Stable chromium isotopic composition of meteorites and metal-silicate experiments:Implications for fractionation during core formation


    Bonnand, P; WILLIAMS, H. M.; Parkinson, I. J.; Wood, B.J.; Halliday, A. N.


    We present new mass independent and mass dependent Cr isotope compositions for meteorites measured by double spike thermal ionisation mass spectrometry. Small differences in both mass independent 53Cr and 54Cr relative to the Bulk Silicate Earth are reported and are very similar to previously published values. Carbonaceous chondrites are characterised by an excess in 54Cr compared to ordinary and enstatite chondrites which make mass independent Cr isotopes a useful tool for distinguishing bet...

  1. Stable isotope composition of bulk and secondary carbonates from the Quaternary loess-paleosol sequence in Sutto, Hungary

    DEFF Research Database (Denmark)

    Koeniger, Paul; Barta, Gabriella; Thiel, Christine


    , and microscale secondary (authigenic) carbonates (calcified root cells, carbonate coatings, hypocoatings, and earthworm biospheroids) and concretions at 10 cm resolution were analysed to interpret stable isotope variations. Isotope values of bulk samples were in the range of 2.6 parts per thousand to -13.9 parts......, secondary carbonates showed more depleted values than bulk samples. Calcified root cells have the most depleted isotope composition with mean values of -16.0 parts per thousand and -11.8 parts per thousand for delta C-13 and 8180, respectively. Results indicate that loess and paleosol secondary carbonates...

  2. The Nitrogen and Oxygen Isotope Composition of Porewater Nitrate from Bering Sea Sediments (United States)

    Lehmann, M. F.; Sigman, D. M.; McCorkle, D. C.; Berelson, W. M.; Brunelle, B. G.; Hoffmann, S. S.


    We have measured the δ15N and δ18O of nitrate from sediment pore waters and the water column of the Bering Sea basin. The first high-resolution sediment porewater profile (with pore waters extracted by whole-core squeezing) shows an increase in nitrate δ15N and δ18O with depth in the sediment column (by 26‰ and 20‰ , respectively) as the nitrate concentration decreases from 45 to 0.5 μM, due to denitrification at depth. However, the nitrate δ15N and δ18O values in the shallow zone of nitrification are equal to or slightly lower than those of bottom water, suggesting that the deep denitrification does not greatly alter the isotopic composition of the nitrate in the shallowest porewaters or, in turn, in the bottom water. These results appear to be consistent with results from ex situ incubation and in situ benthic chamber experiments by ourselves and other investigators (Brandes et al., 1997), which show that loss of nitrate due to sedimentary denitrification is not accompanied by an isotopic effect on the nitrate of the overlying water. Measurements conducted during the GEOSECS and WOCE programs revealed the existence of a sizable deficit of remineralized nitrate in the deep Bering Sea, but water-column denitrification is not a likely mechanism for nitrate loss, since oxygen concentrations found in Bering Sea waters are too high (> 15 μM) to allow for bacterial nitrate reduction. Our water column measurements indicate that the nitrate deficit in the deep Bering Sea is not associated with nitrate isotopic enrichment. Together, our sediment and water column nitrate isotope analyses provide strong support for the earlier hypothesis that the deep Bering Sea nitrate deficit is due to sedimentary denitrification. J. A. Brandes and A. H. Devol, Geochim. Cosmochim. Acta, 61(9), 1793-1801 (1997).

  3. Regional source identification of atmospheric aerosols in Beijing based on sulfur isotopic compositions (United States)

    Lianfang, Wei; Pingqing, Fu; Xiaokun, Han; Qingjun, Guo; Yele, Sun; Zifa, Wang


    65 daily PM2.5 (aerosol particle with aerodynamic diameter less than 2.5 μm) samples were collected from an urban site in Beijing in four months representing the four seasons between September 2013 and July 2014. Inorganic ions, organic/elemental carbon and stable sulfur isotopes of sulfate aerosols were analyzed systematically. The "fingerprint" characteristics of the stable sulfur isotopic composition, together with trajectory clustering modeled by HYSPLIT-4 and potential source contribution function (PSCF), were employed for identifying potential regional sources. Results obviously exhibited the distinctive seasonality for various aerosol speciation associated with PM2.5 in Beijing with sulfate, nitrate, ammonium, organic matter, and element carbon being the dominant species. Elevated chloride associated with higher concentration of organics were found in autumn and winter, due to enhanced coal combustion emissions. The δ34S values of Beijing aerosol samples ranged from 2.94‰ to 10.2‰ with an average value of 6.18±1.87‰ indicating that the major sulfur source is direct fossil fuel burning-related emissions. Owning to a temperature-dependent fractionation and elevated biogenic sources of isotopically light sulfur in summer, the δ34S values had significant seasonal variations with a winter maximum ( 8.6‰)and a summer minimum ( 5.0‰). The results of trajectory clustering and the PSCF method demonstrated that higher concentrations of sulfate with lower sulfur isotope ratios ( 4.83‰) were associated with air masses from the south, southeast or east, whereas lower sulfate concentrations with higher δ34S values ( 6.69‰) when the air masses were mainly from north or northwest. These results suggested two main different kinds of regional coal combustion sources contributed to the pollution in Beijing.

  4. Compositional impact of acidification and warming on Fucus vesiculosus: First biogeochemical and stable isotope results from coastal benthocosm experiments (United States)

    Winde, Vera; Al-Janabi, Balsam; Sokol, Steffani; Buchholz, Björn; Escher, Peter; Voss, Maren; Schneider, Bernd; Wahl, Martin; Böttcher, Michael E.


    In the frame of the German BIOACID II project, the separate and combined effects of warming and acidification on the elemental and stable isotope composition of Fucus vesiculosus are investigated by means of benthic mesocosm experiments in brackish waters of the Baltic Sea. We aim for a calibration of the composition of Fucus in response to single and combined temperature and pCO2 elevation. Benthocosm experiments are carried out in the Kiel Fjord with a fully crossed array of 2 globally importnant stressors: an increase in temperature and an increase in atmospheric CO2 partial pressure. The experiments run for almost 3 months per season (winter, spring, summer, autumn). There are analyses from the experiments of the aquatic chemistry (TA, pH, salinity, carbon isotope composition of DIC, main and trace elements and nutrients) as well as the composition of the Fucus vesiculosus organic tissues (C-N-S-P contents, and C and N stable isotope composition, as well as major and trace elements). The composition of the aqueous solution in the mesocosms was recovered two times a week and for the Fucus tissue at the start and the end of the experiments. In addition several 24h cycles were followed in high temporal resolution to characterize the community response to diurnal light cycles. It was found, that seasonal variations in the composition of the input solutions (brackish water from the Kiel Fjord) were reflected by changes in the experiments with short time delay. The changes in the aquatic chemistry of the mesocosms, however, were strongly superimposed for most parameters during daytime by biological activity. The response of the communities to light conditions was clearly observed during the 24h-campaigns, when alternating phases of net respiration and photosynthesis were creating strong variations in the dissolved carbonate system. These variations were accompanied by significant changes in the carbon isotope composition of DIC. The atmosphere of some experimental

  5. A kinetic chemistry tagging technique and its application to modelling the stable isotopic composition of atmospheric trace gases

    Directory of Open Access Journals (Sweden)

    S. Gromov


    Full Text Available Isotope composition, in many cases, holds unique information on sources, chemical modification and sinks of atmospheric trace gases. Vital to the interpretation and use of an increasing number of isotope analyses is appropriate modelling. However, the exact implementation of isotopic information is a challenge, and often studies use simplifications which limit their applicability. Here we confer a thorough isotopic extension to MECCA, a comprehensive kinetic chemistry sub-model. To this end, we devise a generic tagging technique for the kinetic chemistry mechanisms implemented as the sub-submodel MECCA-TAG. The technique constitutes a diagnostic tool that can benefit the investigation of various aspects of kinetic chemistry schemes; at the same time, the designed numerical optimisation reduces the computational effort while keeping important details unaffected. We further focus specifically on the modelling of stable isotopic composition, including the required extensions of the approach. The results of MECCA-TAG are evaluated against the reference sub-submodel MECCA-DBL, which is implicitly full-detailed, but necessarily is sub-optimal in practical applications due to its high computational demands. Furthermore, we evaluate the elaborate carbon and oxygen isotopic mechanism by simulating the multi-isotope composition of CO and other trace gases in the CAABA/MECCA box-model. The mechanism realistically simulates the oxygen isotope composition of key species resulting from the interchange with ozone and main atmospheric reservoirs, as well as the carbon isotope signature transfer. The model adequately reproduces the isotope chemistry features for CO under the limitation of the modelling domain. In particular, the mass-independently fractionated (MIF composition of CO due to reactions of ozone with unsaturated hydrocarbons (a source effect versus its intrinsic MIF enrichment induced in the removal reaction via oxidation by OH is assessed. As for

  6. A kinetic chemistry tagging technique and its application to modelling the stable isotopic composition of atmospheric trace gases

    Directory of Open Access Journals (Sweden)

    S. Gromov


    Full Text Available Isotope composition, in many cases, holds unique information on the sources, chemical modification and sinks of atmospheric trace gases. Vital to the interpretation and use of an increasing number of isotope analyses is appropriate modelling. However, the exact implementation of isotopic information in chemistry-climate models is a challenge, and often studies use simplifications which limit their applicability. Here we implement a thorough isotopic extension in MECCA, a comprehensive kinetic chemistry sub-model. To this end, we devise a generic tagging technique for the kinetic chemistry mechanisms implemented as the sub-submodel MECCA-TAG. The technique is diagnostic and numerically efficient and supports the investigation of various aspects of kinetic chemistry schemes. We focus specifically on the application to the modelling of stable isotopic composition. The results of MECCA-TAG are evaluated against the reference sub-submodel MECCA-DBL, which is implicitly full-detailed, but computationally expensive and thus sub-optimal in practical applications. Furthermore, we evaluate the elaborate carbon and oxygen isotopic mechanism by simulating the multi-isotope composition of CO and other trace gases in the CAABA/MECCA box-model. The mechanism realistically simulates the oxygen isotope composition of key species, as well as the carbon isotope signature transfer. The model adequately reproduces the isotope chemistry features for CO, taking into account the limits of the modelling domain. In particular, the mass-independently fractionated (MIF composition of CO due to reactions of ozone with unsaturated hydrocarbons (a source effect versus its intrinsic MIF enrichment induced in the removal reaction via oxidation by OH is assessed. The simulated ozone source effect was up to +1‰ in Δ17O(CO. The versatile modelling framework we employ (the Modular Earth Submodel System, MESSy opens the way for implementation of the novel detailed

  7. Chemical and isotopic composition of secondary organic aerosol generated by α-pinene ozonolysis (United States)

    Meusinger, Carl; Dusek, Ulrike; King, Stephanie M.; Holzinger, Rupert; Rosenørn, Thomas; Sperlich, Peter; Julien, Maxime; Remaud, Gerald S.; Bilde, Merete; Röckmann, Thomas; Johnson, Matthew S.


    Secondary organic aerosol (SOA) plays a central role in air pollution and climate. However, the description of the sources and mechanisms leading to SOA is elusive despite decades of research. While stable isotope analysis is increasingly used to constrain sources of ambient aerosol, in many cases it is difficult to apply because neither the isotopic composition of aerosol precursors nor the fractionation of aerosol forming processes is well characterised. In this paper, SOA formation from ozonolysis of α-pinene - an important precursor and perhaps the best-known model system used in laboratory studies - was investigated using position-dependent and average determinations of 13C in α-pinene and advanced analysis of reaction products using thermal-desorption proton-transfer-reaction mass spectrometry (PTR-MS). The total carbon (TC) isotopic composition δ13C of the initial α-pinene was measured, and the δ13C of the specific carbon atom sites was determined using position-specific isotope analysis (PSIA). The PSIA analysis showed variations at individual positions from -6.9 to +10. 5 ‰ relative to the bulk composition. SOA was formed from α-pinene and ozone in a constant-flow chamber under dark, dry, and low-NOx conditions, with OH scavengers and in the absence of seed particles. The excess of ozone and long residence time in the flow chamber ensured that virtually all α-pinene had reacted. Product SOA was collected on two sequential quartz filters. The filters were analysed offline by heating them stepwise from 100 to 400 °C to desorb organic compounds that were (i) detected using PTR-MS for chemical analysis and to determine the O : C ratio, and (ii) converted to CO2 for 13C analysis. More than 400 ions in the mass range 39-800 Da were detected from the desorbed material and quantified using a PTR-MS. The largest amount desorbed at 150 °C. The O : C ratio of material from the front filter increased from 0.18 to 0.25 as the desorption temperature was

  8. Determination of the isotopic composition of atmospheric methane and its application in the Antarctic (United States)

    Lowe, David C.; Brenninkmeijer, Carl A. M.; Tyler, Stanley C.; Dlugkencky, Edward J.


    A procedure for establishing the C-13/C-12 ratio and the C-14 abundance in the atmospheric methane is discussed. The method involves air sample collection, measurement of the methane mixing ratio by gas chromotography followed by quantitative conversion of the methane in the air samples to CO2 and H2O, and analysis of the resulting CO2 for the C-13/C-12 ratio by stable isotope ratio mass spectrometry and measurement of C-14 content by accelerator mass spectrometry. The carbon isotropic composition of methane in air collected at Baring Head, New Zealand, and in air collected on aircraft flights between New Zealand and Antarctica is determined by the method, and no gradient in the composition between Baring Head and the South Pole station is found. As the technique is refined, and more data is gathered, small seasonal and long-term variations in C-13 are expected to be resolved.

  9. [Humus composition and stable carbon isotope natural abundance in paddy soil under long-term fertilization]. (United States)

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


    Soil samples were collected from an experimental paddy field with long-term (26 years) fertilization in Taihu Lake region of Jiangsu Province to study the effects of different fertilization on the organic carbon distribution and stable carbon isotope natural abundance (delta 13C) in the soil profile, and on the humus composition. The results showed that long-term fertilization increased the organic carbon content in top soil significantly, and there was a significantly negative exponential correlation between soil organic carbon content and soil depth (P humus (humin) was the main humus composition in the soil, occupying 50% or more, and the rest were loosely and stably combined humus. Long-term fertilization increased the content of loosely combined humus and the ratio of humic acid (HA) to fulvic acid (FA).

  10. Sr and Nd isotopic and trace element compositions of Quaternary volcanic centers of the Southern Andes (United States)

    Futa, K.; Stern, C.R.


    Isotopic compositions of samples from six Quaternary volcanoes located in the northern and southern extremities of the Southern Volcanic Zone (SVZ, 33-46??S) of the Andes and from four centers in the Austral Volcanic Zone (AVZ, 49-54??S) range for 87Sr 86Sr from 0.70280 to 0.70591 and for 143Nd 144Nd from 0.51314 to 0.51255. The ranges are significantly greater than previously reported from the southern Andes but are different from the isotopic compositions of volcanoes in the central and northern Andes. Basalts and basaltic andesites from three centers just north of the Chile Rise-Trench triple junction have 87Sr 86Sr, 143Nd 144Nd, La Yb, Ba La, and Hf Lu that lie within the relatively restricted ranges of the basic magmas erupted from the volcanic centers as far north as 35??S in the SVZ of the Andes. The trace element and Sr and Nd isotopic characteristics of these magmas may be explained by source region contamination of subarc asthenosphere, with contaminants derived from subducted pelagic sediments and seawater-altered basalts by dehydration of subducted oceanic lithosphere. In the northern extremity of the SVZ between 33?? and 34??S, basaltic andesites and andesites have higher 87Sr 86Sr, Rb Cs, and Hf Lu, and lower 143Nd 144Nd than basalts and basaltic andesites erupted farther south in the SVZ, which suggests involvement of components derived from the continental crust. In the AVZ, the most primitive sample, high-Mg andesite from the southernmost volcanic center in the Andes (54??S) has Sr and Nd isotopic compositions and K Rb and Ba La similar to MORB. The high La Yb of this sample suggests formation by small degrees of partial melting of subducted MORB with garnet as a residue. Samples from centers farther north in the AVZ show a regionally regular northward increase in SiO2, K2O, Rb, Ba, Ba La, and 87Sr 86Sr and decrease in MgO, Sr, K Rb, Rb Cs, and 143Nd 144Nd, suggesting increasingly greater degrees of fractional crystallization and associated intra

  11. Processes controlling the Si-isotopic composition in the Southern Ocean and application for paleoceanography

    Directory of Open Access Journals (Sweden)

    F. Fripiat


    Full Text Available Southern Ocean biogeochemical processes have an impact on global marine primary production and global elemental cycling, e.g. by likely controlling glacial-interglacial pCO2 variation. In this context, the natural silicon isotopic composition30Si of sedimentary biogenic silica has been used to reconstruct past Si-consumption:supply ratios in the surface waters. We present a new dataset in the Southern Ocean from a IPY-GEOTRACES transect (Bonus-GoodHope which includes for the first time summer δ30Si signatures of suspended biogenic silica (i for the whole water column at three stations and (ii in the mixed layer at seven stations from the subtropical zone up to the Weddell Gyre. In general, the isotopic composition of biogenic opal exported to depth was comparable to the opal leaving the mixed layer and did not seem to be affected by any diagenetic processes during settling, even if an effect of biogenic silica dissolution cannot be ruled out in the northern part of the Weddell Gyre. We develop a mechanistic understanding of the processes involved in the modern Si-isotopic balance, by implementing a mixed layer model. We observe that the accumulated biogenic silica (sensu Rayleigh distillation should satisfactorily describe the δ30Si composition of biogenic silica exported out of the mixed layer, within the limit of the current analytical precision on the δ30Si. The failures of previous models (Rayleigh and steady state become apparent especially at the end of the productive period in the mixed layer, when biogenic silica production and export are low. This results from (1 a higher biogenic silica dissolution:production ratio imposing a lower net fractionation factor and (2 a higher Si-supply:Si-uptake ratio supplying light Si-isotopes into the mixed layer. The latter effect is especially expressed when the summer mixed layer becomes strongly Si-depleted, together with a large

  12. Processes controlling the Si-isotopic composition in the Southern Ocean and application for paleoceanography

    Directory of Open Access Journals (Sweden)

    F. Fripiat


    Full Text Available Southern Ocean biogeochemical processes have an impact on global marine primary production and global elemental cycling, e.g. by likely controlling glacial-interglacial pCO2 variation. The natural silicon isotopic composition30Si of sedimentary biogenic silica has been used to reconstruct past Si-consumption:supply ratio in the surface waters. We present a new dataset in the Southern Ocean which includes for the first time summer δ30Si signatures of suspended biogenic silica (i for the whole water column at three stations and (ii in the mixed layer at seven stations from the sub-tropical zone up to the Weddell Gyre.

    In general, the biogenic silica isotopic composition at depth reflected a mixed layer origin and seemed not affected by any diagenetic effect in the water column, even if in the northern part of the Weddell Gyre an effect of biogenic silica dissolution cannot be ruled out.

    We develop a mechanistic understanding of the processes involved in the modern Si-isotopic balance, by implementing a mixed layer model. We observe that the accumulated biogenic silica (sensu Rayleigh should satisfactorily describe the δ30Si composition of biogenic silica exported out of the mixed layer, within the limit of the current analytical precision on the δ30Si. The failures of previous models (Rayleigh and steady state become apparent especially at the end of the productive period in the mixed layer, when biogenic silica production is low. This results from: (1 a higher biogenic silica dissolution:production ratio imposing a lower net fractionation factor and (2 a higher Si-supply:Si-uptake ratio supplying light Si-isotopes into the mixed layer. The latter effect is especially expressed when the summer mixed layer becomes strongly Si-depleted together with a large vertical silicic acid gradient.

  13. An approach to noble-gas isotopic compositions in natural gases and gas-source tracing in the Ordos Basin, China

    Institute of Scientific and Technical Information of China (English)


    Isotopic compositions of noble gases, i.e. He Ar Kr and Xe, are measured in natural gases from the Zhongbu gasfield in the Ordos Basin. And heavy noble-gas isotopes (Kr, Xe) are here first used in geochemically studying natural gases and gas-source correlation. Isotopic compositions of heavy noble gases in natural gases, especially Xe, show two-source mixing in the Zhongbu gasfield. Gas sources are somewhat different in the northeast and the southwest of the gasfield. Generally, the gas source of the Lower Paleozoic makes a greater contribution in the southwest than in the northeast in the field. Two kinds of gases can be differentiated from isotopic compositions of heavy noble gases and from their relation with the Ar isotopic composition, Therefore, the comprehensive study on isotopic compositions of light and heavy noble gases can supply more useful information on gas-source correlation and tracing.

  14. Australian atmospheric lead deposition reconstructed using lead concentrations and isotopic compositions of archival lichen and fungi. (United States)

    Wu, Liqin; Taylor, Mark Patrick; Handley, Heather K; Wu, Michael


    Lead concentrations and their isotopic compositions were measured in lichen genera Cladonia and Usnea and fungi genus Trametes from the Greater Sydney region (New South Wales, Australia) that had been collected and archived over the past 120 years. The median lead contents were elevated in lichens and fungi prior to the introduction of leaded petrol (Cladonia 12.5 mg/kg; Usnea 15.6 mg/kg; Trametes 1.85 mg/kg) corresponding to early industrial development. During the use of leaded petrol for automobiles in Australia from 1932 to 2002, total median lead concentrations rose: Cladonia 18.8 mg/kg; Usnea 21.5 mg/kg; Trametes 4.3 mg/kg. Following the cessation of leaded petrol use, median total lead concentrations decreased sharply in the 2000s: Cladonia 4.8 mg/kg; Usnea 1.7 mg/kg. The lichen and fungi isotopic compositions reveal a significant decrease in (206)Pb/(207)Pb values from the end of 19th century to the 1970s. The following decades were characterised by lower allowable levels of lead additive in fuel and the introduction of unleaded petrol in 1985. The environmental response to these regulatory changes was that lichen and fungi (206)Pb/(207)Pb values increased, particularly from 1995 onwards. Although the lead isotope ratios of lichens continued to increase in the 2000s they do not return to pre-leaded petrol values. This demonstrates that historic leaded petrol emissions, inter alia other sources, remain a persistent source of anthropogenic contamination in the Greater Sydney region.

  15. Factors Controlling the Stable Nitrogen Isotopic Composition (δ15N of Lipids in Marine Animals.

    Directory of Open Access Journals (Sweden)

    Elisabeth Svensson

    Full Text Available Lipid extraction of biomass prior to stable isotope analysis is known to cause variable changes in the stable nitrogen isotopic composition (δ15N of residual biomass. However, the underlying factors causing these changes are not yet clear. Here we address this issue by comparing the δ15N of bulk and residual biomass of several marine animal tissues (fish, crab, cockle, oyster, and polychaete, as well as the δ15N of the extracted lipids. As observed previously, lipid extraction led to a variable offset in δ15N of biomass (differences ranging from -2.3 to +1.8 ‰. Importantly, the total lipid extract (TLE was highly depleted in 15N compared to bulk biomass, and also highly variable (differences ranging from -14 to +0.7 ‰. The TLE consisted mainly of phosphatidylcholines, a group of lipids with one nitrogen atom in the headgroup. To elucidate the cause for the 15N-depletion in the TLE, the δ15N of amino acids was determined, including serine because it is one of the main sources of nitrogen to N-containing lipids. Serine δ15N values differed by -7 to +2 ‰ from bulk biomass δ15N, and correlated well with the 15N depletion in TLEs. On average, serine was less depleted (-3‰ than the TLE (-7 ‰, possibly due to fractionation during biosynthesis of N-containing headgroups, or that other nitrogen-containing compounds, such as urea and choline, or recycled nitrogen contribute to the nitrogen isotopic composition of the TLE. The depletion in 15N of the TLE relative to biomass increased with the trophic level of the organisms.

  16. A revision in hydrogen isotopic composition of USGS42 and USGS43 human-hair stable isotopic reference materials for forensic science. (United States)

    Coplen, Tyler B; Qi, Haiping


    The hydrogen isotopic composition (δ(2)HVSMOW-SLAP) of USGS42 and USGS43 human hair stable isotopic reference materials, normalized to the VSMOW (Vienna-Standard Mean Ocean Water)-SLAP (Standard Light Antarctic Precipitation) scale, was originally determined with a high temperature conversion technique using an elemental analyzer (TC/EA) with a glassy carbon tube and glassy carbon filling and analysis by isotope-ratio mass spectrometer (IRMS). However, the TC/EA IRMS method can produce inaccurate δ(2)HVSMOW-SLAP results when analyzing nitrogen-bearing organic substances owing to the formation of hydrogen cyanide (HCN), leading to non-quantitative conversion of a sample into molecular hydrogen (H2) for IRMS analysis. A single-oven, chromium-filled, elemental analyzer (Cr-EA) coupled to an IRMS substantially improves the measurement quality and reliability of hydrogen isotopic analysis of hydrogen- and nitrogen-bearing organic material because hot chromium scavenges all reactive elements except hydrogen. USGS42 and USGS43 human hair isotopic reference materials have been analyzed with the Cr-EA IRMS method, and the δ(2)HVSMOW-SLAP values of their non-exchangeable hydrogen fractions have been revised: [Formula: see text] [Formula: see text] where mUr=0.001=‰. On average, these revised δ(2)HVSMOW-SLAP values are 5.7mUr more positive than those previously measured. It is critical that readers pay attention to the δ(2)HVSMOW-SLAP of isotopic reference materials in publications as they may need to adjust the δ(2)HVSMOW-SLAP measurement results of human hair in previous publications to ensure all results are on the same isotope-delta scale.

  17. Mechanisms controlling the carbon stable isotope composition of phytoplankton in karst reservoirs

    Directory of Open Access Journals (Sweden)

    Baoli Wang


    Full Text Available In order to systematically understand the mechanisms controlling the carbon stable isotope composition of phytoplankton (δ13CPHYin freshwater ecosystems, seasonal changes in δ13CPHY and related environmental factors were determined in karst reservoirs from the Wujiang river basin, China. Substantial and systematic differences within seasons and reservoirs were observed for δ13CPHY, which ranged from -39.2‰ to -15.1‰. An increase in water temperature triggered fast growth of phytoplankton which assimilated more dissolved inorganic carbon (DIC, resulting in the increase of δ13CPHY, δ13CDIC and pH. When the concentration of dissolved carbon dioxide (CO2 was less than 10 mmol L–1, phytoplankton shifted to using HCO3– as a carbon source. This resulted in the sharp increase of δ13CPHY. The carbon stable isotope composition of phytoplankton tended to decrease with the increase of Bacillariophyta, which dominated in January and April, but tended to increase with the increase of Chlorophyta and Dinophyta, which dominated in July. Multiple regression equations suggested that the influence of biological factors such as taxonomic difference on δ13CPHY could be equal or more important than that of physical and chemical factors. Thus, the effect of taxonomic differences on δ13CPHY must be considered when explaining the δ13C of organic matter in lacustrine ecosystem.

  18. Bulk carbon, oxygen, and hydrogen stable isotope composition of recent resins from amber-producing Hymenaea. (United States)

    Nissenbaum, Arie; Yakir, Dan; Langenheim, Jean H


    Resins of Hymenaea, an angiosperm tree genus known to be a copious resin producer and a major source of amber since the Oligo-Miocene, were collected from a wide range of tropical environments from Latin America and Africa, and analyzed for their carbon, hydrogen, and oxygen stable isotope composition. The average value for delta13C in the resins was found to be -27.0+/-1.3 per thousand, which is very similar to the values reported for resins in other studies. Delta18O values for the Hymenaea resins averaged +11.2+/-1.6 per thousand, or about 20 per thousand more depleted than normal plant cellulose. DeltaD values of the resins ranged from -196 to -319 per thousand, with an average of -243+/-30 per thousand. Rough estimates suggest a fractionation of -200 to -210 per thousand between the resins and the environmental water. This value is similar to the -200 per thousand value observed for the fractionation between other plant lipids and environmental water. The present study suggests that the stable isotope composition of fossil resins (amber) has the potential to provide information on ancient environmental waters.

  19. Impact of metabolism and growth phase on the hydrogen isotopic composition of microbial fatty acids (United States)

    Heinzelmann, Sandra M.; Villanueva, Laura; Sinke-Schoen, Danielle; Sinninghe Damsté, Jaap S.; Schouten, Stefan; van der Meer, Marcel T. J.


    Microorganisms are involved in all elemental cycles and therefore it is important to study their metabolism in the natural environment. A recent technique to investigate this is the hydrogen isotopic composition of microbial fatty acids, i.e., heterotrophic microorganisms produce fatty acids enriched in deuterium (D) while photoautotrophic and chemoautotrophic microorganisms produce fatty acids depleted in D compared to the water in the culture medium (growth water). However, the impact of factors other than metabolism have not been investigated. Here, we evaluate the impact of growth phase compared to metabolism on the hydrogen isotopic composition of fatty acids of different environmentally relevant microorganisms with heterotrophic, photoautotrophic and chemoautotrophic metabolisms. Fatty acids produced by heterotrophs are enriched in D compared to growth water with εlipid/water between 82 and 359‰ when grown on glucose or acetate, respectively. Photoautotrophs (εlipid/water between −149 and −264‰) and chemoautotrophs (εlipid/water between −217 and −275‰) produce fatty acids depleted in D. Fatty acids become, in general, enriched by between 4 and 46‰ with growth phase which is minor compared to the influence of metabolisms. Therefore, the D/H ratio of fatty acids is a promising tool to investigate community metabolisms in nature. PMID:26005437

  20. Using trace element content and lead isotopic composition to assess sources of PM in Tijuana, Mexico (United States)

    Salcedo, D.; Castro, T.; Bernal, J. P.; Almanza-Veloz, V.; Zavala, M.; González-Castillo, E.; Saavedra, M. I.; Perez-Arvízu, O.; Díaz-Trujillo, G. C.; Molina, L. T.


    PM2.5 samples were collected at two urban sites (Parque Morelos (PQM) and CECyTE (CEC)) in Tijuana during the Cal-Mex campaign from May 24 to June 5, 2010. Concentration of trace elements (Mg, Al, Ti, V, Mn, Fe, Co, Ni, Zn, Cu, Ga, As, Se, Rb, Sr, Mo, Cd, Sn, Sb, Ba, La, Ce, and Pb), and Pb isotopic composition were determined in order to study the sources of PM impacting each site. Other chemical analysis (gravimetric, elemental and organic carbon (EC/OC), and polycyclic aromatic hydrocarbons (PAHs)), were also performed. Finally, back-trajectories were calculated to facilitate the interpretation of the chemical data. Trace elements results show that CEC is a receptor site affected by mixed regional sources: sea salt, mineral, urban, and industrial. On the other hand, PQM seems to be impacted mainly by local sources. In particular, Pb at CEC is of anthropogenic, as well as crustal origin. This conclusion is supported by the lead isotopic composition, whose values are consistent with a combination of lead extracted from US mines, and lead from bedrocks in the Mexican Sierras. Some of the time variability observed can be explained using the back-trajectories.

  1. Nitrogen isotopic composition of plant-soil in the Loess Plateau and its responding to environmental chanse

    Institute of Scientific and Technical Information of China (English)

    LIU WeiGuo; WANG Zheng


    The nitrogen isotope of soil is of emerging significance as an indicator of climatic change and bio-geochemical cycle of nitrogen in nature systems. In this paper, the nitrogen content and isotopic composition of modern ecosystems from arid and semiarid Loess Plateau in northwestern China, in-cluding plant roots and surface soil, were determined to investigate trends in δ15N variation of plant roots and soil along a precipitation and temperature gradient in northwestern China under the East Asian Monsoon climate condition. The δ15N values of surface soil from the study area vary from -1.2‰to 5.8‰, but from -5.1‰ to 1.9‰ in the plant roots. Our results indicate that (1) although the isotopic compositions of both plant roots and surface soil change with a similar trend along the climate gradient,the apparent nitrogen difference between plant roots and soil existed, with △δ15N values ranging from 0.3‰ to 7.2‰ with average of 4.1‰; and (2) mean annual precipitation (MAP) is the dominant factor for isotopic composition of plant-soil nitrogen in the Loess Plateau, and the δ15.N values are less correlated with MAT; we suggest that nitrogen isotopic composition of soil is a potential tracer for environmental changes.

  2. Stable isotopic composition of cryptocrystalline magnesite from deposits in Turkey and Austria (United States)

    Horkel, K.; Ebner, F.; Spötl, Ch


    Cryptocrystalline magnesite (CM) occurs all over the world predominantly in ultramafic rocks and within those mainly in ophiolite zones. The mineralization forms either veins and networks, which are strictly controlled by regional fault tectonics (Kraubath-type), or nodules and layers, which occur in sediments above the ophiolite close to the paleosurface (Bela Stena type). These types are well established and named after their type deposits in Austria and Serbia, respectively (Pohl, 1990; Prochaska, 2000; Wilson & Ebner, 2006). Stable isotopic studies of CM showed that in comparison to sparry magnesite CM has lower δ13C values (-18‰ to -6‰) and more constant δ18O values (+22‰ to +29‰) (Kralik et al., 1989). Furthermore, it was observed that the Kraubath-type and Bela Stena-type CM differ in their isotopic composition in that the latter is characterised by higher δ13C (-1‰ to +4‰) and δ18O values (+26‰ to +36‰) (Jurković & Pamić, 2003). The formation of CM is still a subject of debate. The δ18O values suggests formation temperatures below 80°C (Kralik et al., 1989; Ece et al., 2005). The C isotope data indicate that the C was either derived from the atmosphere or by decarboxylation of organic-rich sediments (Zedef et al. 2000). Our research addresses the following major questions: (a) What are the reasons for the difference in stable isotopic composition between the Kraubath and the Bela Stena-type? (b) Is it possible to distinguish different types of mineralizations within a deposit using stable isotope data and can this information be applied as a tool for CM exploration? (c) Do the individual isotopic patterns of the individual deposits reflect different conditions for formation or later (post-mineralization) alteration events? Our investigations were concentrated on the type locality in Kraubath (Austria) as well as on some currently operating deposits in the magnesite districts of Eskişehir and Tavşanlı (western Anatolia/ Turkey

  3. The origin and evolution of chondrites recorded in the elemental and isotopic compositions of their macromolecular organic matter (United States)

    Alexander, C. M. O.'D.; Fogel, M.; Yabuta, H.; Cody, G. D.


    Extraterrestrial organic matter in meteorites potentially retains a unique record of synthesis and chemical/thermal modification by parent body, nebular and even presolar processes. In a survey of the elemental and isotopic compositions of insoluble organic matter (IOM) from 75 carbonaceous, ordinary and enstatite chondrites, we find dramatic variations within and between chondrite classes. There is no evidence that these variations correlate with the time and/or location of chondrite formation, or with any primary petrologic or bulk compositional features that are associated with nebular processes (e.g., chondrule and volatile trace element abundances). Nor is there evidence for the formation of the IOM by Fischer-Tropsch-Type synthesis in the nebula or in the parent bodies. The elemental variations are consistent with thermal maturation and/or oxidation of a common precursor. For reasons that are unclear, there are large variations in isotopic composition within and between chondrite classes that do not correlate in a simple way with elemental composition or petrologic type. Nevertheless, because of the pattern of elemental variations with petrologic type and the lack of any correlation with the primary features of the chondrite classes, at present the most likely explanation is that all IOM compositional variations are the result of parent body processing of a common precursor. If correct, the range of isotopic compositions within and between chondrite classes implies that the IOM is composed of several isotopically distinct components whose relative stability varied with parent body conditions. The most primitive IOM is found in the CR chondrites and Bells (CM2). Isotopically, the IOM from these meteorites resembles the IOM in interplanetary dust particles. Chemically, their IOM resembles the CHON particles of comet Halley. Despite the large isotopic anomalies in the IOM from these meteorites, it is uncertain whether the IOM formed in the interstellar medium or

  4. Simulation of the isotopic composition of stratospheric water vapour - Part 2: Investigation of HDO / H2O variations (United States)

    Eichinger, R.; Jöckel, P.; Lossow, S.


    Studying the isotopic composition of water vapour in the lower stratosphere can reveal the driving mechanisms of changes in the stratospheric water vapour budget and therefore help to explain the trends and variations of stratospheric water vapour during recent decades. We equipped a global chemistry climate model with a description of the water isotopologue HDO, comprising its physical and chemical fractionation effects throughout the hydrological cycle. We use this model to improve our understanding of the processes which determine the patterns in the stratospheric water isotope composition and in the water vapour budget itself. The link between the water vapour budget and its isotopic composition in the tropical stratosphere is presented through their correlation in a simulated 21-year time series. The two quantities depend on the same processes; however, they are influenced with different strengths. A sensitivity experiment shows that fractionation effects during the oxidation of methane have a damping effect on the stratospheric tape recorder signal in the water isotope ratio. Moreover, the chemically produced high water isotope ratios overshadow the tape recorder in the upper stratosphere. Investigating the origin of the boreal-summer signal of isotopically enriched water vapour reveals that in-mixing of old stratospheric air from the extratropics and the intrusion of tropospheric water vapour into the stratosphere complement each other in order to create the stratospheric isotope ratio tape recorder signal. For this, the effect of ice lofting in monsoon systems is shown to play a crucial role. Furthermore, we describe a possible pathway of isotopically enriched water vapour through the tropopause into the tropical stratosphere.

  5. Neon isotopic composition of the mantle constrained by single vesicle analyses (United States)

    Péron, Sandrine; Moreira, Manuel; Colin, Aurélia; Arbaret, Laurent; Putlitz, Benita; Kurz, Mark D.


    The origin of volatiles on Earth is still a matter of debate. Noble gases are an efficient geochemical tool to constrain Earth formation processes due to their inertness. Several studies have focused on the neon isotopic composition of the lower mantle because the 20Ne/22Ne ratio is thought to reflect that of Earth's primordial components. Two models to explain the origin of light noble gases on Earth have been proposed: either solar wind implantation onto the Earth's solid precursors or dissolution into the mantle of a primordial atmosphere captured from solar nebula gas. In order to test these two models, we analyzed the noble gas compositions (helium, neon and argon) of two submarine oceanic island basalt glasses from Fernandina volcano (Galápagos archipelago), which have among the most primitive/unradiogenic terrestrial helium and neon isotopic compositions. Several sample pieces are studied both by step-crushing and by laser ablation analyses of single vesicles. Results of step-crushing are consistent with those of laser ablation analyses, but the latter results provide new insights into the origin of atmospheric contamination. The single-vesicle laser-ablation measurements overlap with the step crushing results, but have systematically higher 40Ar/36Ar, and 3He/36Ar, suggesting less atmospheric contamination using this method. The single vesicle data therefore suggest that atmospheric contamination is introduced by exposure to the modern atmosphere, after sample collection. 3He/4He values are about 23 times the atmospheric ratio (R/Ra) for the two Fernandina (Galápagos) samples, in agreement with previous studies. We obtain 20Ne/22Ne and 40Ar/36Ar isotopic ratios as high as 12.91 and 9400, respectively, for the mantle source of the Galápagos hotspot. The new data show that step-crushing and laser ablation analyses are complementary methods that should be used together to derive the noble gas ratios in uncontaminated samples. The results of neon

  6. Variation of the isotopic composition of complexing reaction products as a result of isotopically selective excitation of the molecules of one of the reagents

    Energy Technology Data Exchange (ETDEWEB)

    Kapralova, G.A.; Makharinskii, L.E.; Trofimova, E.M.; Chaikin, A.M.


    The possibility of influencing the complexing reaction rate by laser radiation was examined. The variation of the isotopic composition of BCl/sub 3/ in the reaction BCl/sub 3/+N(CH/sub 3/)/sub 3/=BCl/sub 3/N(CH/sub 3/)/sub 3/ was shown experimentally as a result of selective excitation of /sup 11/BCl/sub 3/ by CO/sub 2/ laser radiation.

  7. Potassium Stable Isotopic Compositions Measured by High-Resolution MC-ICP-MS (United States)

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


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

  8. Nitrate dual isotopic composition in the northern South China Sea and neighboring West Philippine Sea (United States)

    Yang, J.; Xu, M.; Wu, Y.; Dai, M.; Kao, S.


    Nitrate nitrogen and oxygen isotopic compositions (δ15NNO3 and δ18ONO3) were used to diagnose nitrate dynamics and the origins of water masses in the northern South China Sea (SCS) and West Philippine Sea (WPS) where water exchanges via the Luzon Strait at different depths. In the SCS, 1-3‰ greater upward increase in δ18ONO3 relative to corresponding δ15NNO3 was just observed in the lower euphotic zone (EZ), indicating a rapid internal cycle of nitrate assimilation and remineralization. Much lower nitrate concentration in the EZ of WPS does not allow us to measure its dual isotopes. From 500 m deep to the base of EZ in the WPS, non-proportional decreases in δ15NNO3 (from 6.4‰ to 2.1-2.6‰) and δ18ONO3 (from 3.0‰ to 1.1‰) accompanying with elevated N:P ratio anomalies (N* from -1.2 μM up to 2 μM), suggest the accumulation of atmospheric-derived N (e.g. N2 fixation and/or N deposition). This allochthonous N signal cumulated in the subsurface of WPS may regulate the δ15NNO3 in the SCS subsurface due to seasonal Kuroshio intrusion, which could supply isotopically light nitrate as newly fixed N source to the SCS. The higher (~0.5‰) δ15NNO3 and δ18ONO3 values, associated with lower N* were detected in the WPS intermediate water (WPS-IW, σθ = 26.5~27.1 kg m-3) around depth of 600-800 m (especially at a southern site) when compared to those of the conventional water source coming from North Pacific Intermediate Water (NPIW). By combining nitrate concentration, N* and δ15NNO3 as constraints, we propose that an additional southerly source other than NPIW may feed into the WPS-IW. On the other hand, the SCS intermediate water (SCS-IW, ~400-700 m), which supposedly sourced from WPS-IW along similar isopycnal levels, showed ~1‰ lower δ15NNO3 and δ18ONO3 values. This reduction in nitrate duel isotopes indicates intense diapycnal mixing primarily due to basin-wide upwelling in the SCS interior. This is the first hand data in the SCS for deep profiles

  9. Extraction of seawater-derived neodymium from different phases of deep sea sediments by selective leaching (United States)

    Blaser, P.; Lippold, J. A.; Frank, N.; Gutjahr, M.; Böhm, E.


    In order to deduce reliable information about the interaction of the oceans with the climate system as a whole in the past, the reconstruction of water mass circulation is crucial. The analysis of seawater-derived neodymium isotopes (143Nd/144Nd, expressed as ɛNd) in marine sediments provides a unique proxy for deep water provenance in particular in the Atlantic [1]. The ɛNd signature and thus the mixing proportion of the local bottom water masses is archived in authigenic phases in the sediment. Obtaining seawater ɛNd from authigenic accretions bound to foraminiferal tests has lately become the preferred since most reliable method [2]. Attempts have also been made to extract the Nd-rich authigenic metal fraction by leaching it off the bulk sediment and thereby use this proxy with less effort, in the highest possible resolution and in sediments where foraminifera are not sufficiently present. However, often other sedimentary components are also leached in the process and contaminate the extracted Nd [3,4]. In this project several core-top and older sediments across the Atlantic have been leached in ten consecutive steps with either dilute buffered acetic acid or an acid-reductive solution. The leachates were analysed on their elemental and Nd isotope compositions, as well as rare earth element (REE) distributions. By graduating the total leaching procedure into smaller stages the results display which processes take place in the course of sediment leaching in the laboratory and which components of the sediment are most reactive. Thus, they help to better evaluate the quality of sediment leaches for ɛNd analysis. Clearly, organic calcite acts as a fast reacting buffer and at the point where its amount is sufficiently reduced the leaching of other components commences and the Nd concentration peaks. Corruption of the extracted ɛNd signal by non-authigenic sources in many cases occured early in the leaching sequence, indicating that only very cautious leaching

  10. Constant Molybdenum Isotope Composition of Ocean Water and Fe-Mn crusts for the Last 70 Myr (United States)

    Siebert, C.; Nagler, T. F.; von Blankenburg, F.; Kramers, J. D.


    In the relatively new field of heavy stable isotope geochemistry, molybdenum (Mo) is one of the very promising elements. Molybdenum is a redox-sensitive trace metal. Isotope fractionation during terrestrial processes such as low-temperature redox transitions, chemical weathering, changes in the composition of the atmosphere, hydrothermal activity and sedimentary cycling is likely. Molybdenum is also an essential element for biological nitrogen fixation. Therefore, biogeochemical Mo isotope fractionation is also probable. The oceans represent an important terrestrial Mo reservoir. Dissolved concentrations in seawater are relatively high (0.01 ppm). The global ocean residence time is corresponding high with 800 kyr. The aim of this study is to characterise the principle present day oceanic Mo reservoirs and their changes with time. Molybdenum isotopic compositions were determined precisely using a Nu instruments MC-ICP-MS. Instrumental and laboratory mass fractionation is separated from natural mass dependent fractionation by addition of a molybdenum double spike prior to chemical separation (Siebert et al., 2001). The external standard reproducibility is at or below 0.1 per mil for the 98Mo/95Mo ratio (2s.d.). We analysed ocean water samples from the Atlantic (n=3, 0m-2400m depth), the Pacific and the Indian Ocean (deep water). These yield a homogeneous Mo isotopic composition as would be expexted from the long residence time of Mo in the oceans. Ocean water has the heaviest Mo isotopic composition measured to date (+2.3 per mil on the 98Mo/95Mo ratio relative to a Johnson Mattey ICP standard solution, lot 602332B). In view of the homogeneous ocean water ratios, we propose the use of present day ocean water as an reference standard (Mean Ocean Molybdenum: MOMO). Significantly lighter compositions from -2.7 to -3.1 per mil on the 98Mo/95Mo ratio relative to MOMO were determined for six Fe-Mn crust surface layers. Pelagic clay (-2.7 per mil) and clastic sediments (-2

  11. Effect of Wood Aging on Wine Mineral Composition and (87)Sr/(86)Sr Isotopic Ratio. (United States)

    Kaya, Ayse D; Bruno de Sousa, Raúl; Curvelo-Garcia, António S; Ricardo-da-Silva, Jorge M; Catarino, Sofia


    The evolution of mineral composition and wine strontium isotopic ratio (87)Sr/(86)Sr (Sr IR) during wood aging were investigated. A red wine was aged in stainless steel tanks with French oak staves (Quercus sessiliflora Salisb.), with three industrial scale replicates. Sampling was carried out after 30, 60, and 90 days of aging, and the wines were evaluated in terms of general analysis, phenolic composition, total polysaccharides, multielement composition, and Sr IR. Li, Be, Mg, Al, Sc, Ti, V, Mn, Co, Ni, Cu, Zn, Ga, Ge, As, Rb, Sr, Y, Zr, Mo, Sb, Cs, Ba, Pr, Nd, Sm, Eu, Dy, Ho, Er, Yb, Lu, Tl, and Pb elements and (87)Sr/(86)Sr were determined by quadrupole inductively coupled plasma mass spectrometry (Q-ICP-MS) and Na, K, Ca, and Fe by flame atomic absorption spectrometry (FAAS). Two-way ANOVA was applied to assess wood aging and time effect on Sr IR and mineral composition. Wood aging resulted in significantly higher concentrations of Mg, V, Co, Ni, and Sr. At the end of the aging period, wine exhibited statistically identical Sr IR compared to control. Study suggests that wood aging does not affect (87)Sr/(86)Sr, not precluding the use of this parameter for wine traceability purposes.

  12. The effects of magmatic processes and crustal recycling on the molybdenum stable isotopic composition of Mid-Ocean Ridge Basalts (United States)

    Bezard, Rachel; Fischer-Gödde, Mario; Hamelin, Cédric; Brennecka, Gregory A.; Kleine, Thorsten


    Molybdenum (Mo) stable isotopes hold great potential to investigate the processes involved in planetary formation and differentiation. However their use is currently hampered by the lack of understanding of the dominant controls driving mass-dependent fractionations at high temperature. Here we investigate the role of magmatic processes and mantle source heterogeneities on the Mo isotope composition of Mid-Ocean Ridges Basalts (MORBs) using samples from two contrasting ridge segments: (1) the extremely fast spreading Pacific-Antarctic (66-41°S) section devoid of plume influence and; (2) the slow spreading Mohns-Knipovich segment (77-71°N) intercepted by the Jan Mayen Plume (71°N). We show that significant variations in Mo stable isotope composition exist in MORBs with δ98/95Mo ranging from - 0.24 ‰ to + 0.15 ‰ (relative to NIST SRM3134). The absence of correlation between δ98/95Mo and indices of magma differentiation or partial melting suggests a negligible impact of these processes on the isotopic variations observed. On the other hand, the δ98/95Mo variations seem to be associated with changes in radiogenic isotope signatures and rare earth element ratios (e.g., (La/Sm)N), suggesting mantle source heterogeneities as a dominant factor for the δ98/95Mo variations amongst MORBs. The heaviest Mo isotope compositions correspond to the most enriched signatures, suggesting that recycled crustal components are isotopically heavy compared to the uncontaminated depleted mantle. The uncontaminated depleted mantle shows slightly sub-chondritic δ98/95Mo, which cannot be produced by core formation and, therefore, more likely result from extensive anterior partial melting of the mantle. Consequently, the primitive δ98/95Mo composition of the depleted mantle appears overprinted by the effects of both partial melting and crustal recycling.

  13. Potential methane production rates and its carbon isotopic composition from ornithogenic tundra soils in coastal Antarctic

    Institute of Scientific and Technical Information of China (English)

    BAO Tao; ZHU Renbin; BAI Bo; XU Hua


    Methane (CH4) is one of important greenhouse gases with chemical activity. The determination of isotopic compositions for CH4 emitted from the soils helps us to understand its production mechanisms. CH4 isotope measurements have been conducted for different types of global terrestrial ecosystems. However, no isotopic data of CH4 have been reported from Antarctic tundra soils. In this paper, ornithogenic soil profiles were collected from four penguin colonies, and potential CH4 production rates and its13C ratio (δ13C) were investigated based upon laboratory incubation experiments. The mean CH4 production rates are highly variable in these soil proifles, ranging from 0.7 to 20.3 μg CH4−C kg−1∙h−1. These ornithogenic soils had high potential production rates of CH4 under ambient air incubation or under N2 incubation, indicating the importance of potential CH4 emissions from penguin colonies. Most of the soil samples had higher δ13C-CH4 under N2 incubation (−39.28%~−43.53%) than under the ambient air incubation (−42.81%~−57.19%). Highly anaerobic conditions were conducive to the production of CH4 enriched in13C, and acetic acid reduction under N2 incubation might be a predominant source for soil CH4production. Overall theδ13C-CH4 showed a signiifcant negative correlation with CH4 production rates in ornithogenic tundra soils under N2 incubation (R2=0.41,p<0.01) or under the ambient air incubation (R2=0.50,p<0.01). Potential CH4 production from ornithogenic soils showed a signiifcant positive correlation with total phosphorus (TP) and NH4+−N contents, pH and soil moisture (Mc), but the δ13C-CH4 showed a signiifcant negative correlation with TP and NH4+−N contents, pH and Mc, indicating that the deposition amount of penguin guano increased potential CH4 production rates from tundra soils, but decreased the δ13C-CH4. The CH4 emissions from the ornithogenic soils affect carbon isotopic compositions of atmospheric CH4in coastal Antarctica.

  14. Constraints on Earth degassing history from the argon isotope composition of Devonian atmosphere (United States)

    Stuart, F. M.; Mark, D.


    The primordial and radiogenic isotopes of the noble gases combine to make them a powerful tool for determining the time and tempo of the outgassing of the Earth's interior. The outgassing history of the Earth is largely constrained from measurements of the isotopic composition of He, Ne, Ar and Xe in samples of modern mantle, crust and atmosphere. There have been few unequivocal measurement of the isotopic composition of noble gases in ancient atmosphere. We have re-visited whether ancient Ar is trapped in the ~400 Ma Rhynie chert [1]. We have analysed samples of pristine Rhynie chert using the ARGUS multi-collector mass spectrometer calibrated against the new determination of atmospheric Ar isotope ratios [2]. 40Ar/36Ar ratios are low, with many lower than the modern air value (298.8). Importantly these are accompanied by atmospheric 38Ar/36Ar ratios indicating that the low 40Ar/36Ar are not due to mass fractionation. We conclude that the Rhynie chert has captured Devonian atmosphere-derived Ar. The data indicate that the Devonian atmosphere 40Ar/36Ar was at least 3 % lower than the modern air value. Thus the Earth's atmosphere has accumulated at least 5 ± 0.2 x 1016 moles of 40Ar in the last 400 million years, at an average rate of 1.24 ± 0.06 x 108 mol 40Ar/year. This overlaps the rate determined from ice cores for the last 800,000 years [3] and implies that there has been no resolvable temporal change in Earth outgassing rate since mid-Palaeozoic times. The new data require the Earth outgassed early, and suggests that pristine samples of Archaean and Proterozoic chert may prove useful as palaeo-atmosphere tracers. [1] G. Turner, J. Geol. Soc. London 146, 147-154 (1989) [2] D. Mark, F.M. Stuart, M. de Podesta, Geochim. Cosmochim. Acta 75, 7494-7501 [3] M. Bender et al., Proc. Nat. Acad. Sci. 105, 8232-8237 (2008)

  15. Nd isotopic compositions of the Tethyan Himalayan Sequence in southeastern Tibet

    Institute of Scientific and Technical Information of China (English)


    The Himalayan orogen consists of three major lithologic units that are separated by two major north-dipping faults: the Lesser Himalayan Sequence (LHS) below the Main Central Thrust (MCT), the Greater Himalayan Crystalline Complex (GHC) above the MCT, and the Tethyan Himalayan Sequence (THS) juxtaposed by the South Tibet Detachment fault (STD) over the GHC. Due to widespread meta-morphism and intense deformation, differentiating the above three lithologic units is often difficult. This problem has been overcome by the use of Sm-Nd isotopic analysis. The previous studies suggested that the LHS can be clearly distinguished from the GHC and THS by their Nd isotope compositions. However, the lack of detailed and systematic Sm-Nd isotopic studies of the THS across the Himalaya in general has made differentiation of this unit from the nearby GHC impossible, as the two appear to share overlapping Nd compositions and model ages. To address this problem, we systematically sam-pled and analyzed Nd isotopes of the THS in southeastern Tibet directly north of Bhutan. Our study identifies two distinctive fields in a εNd -TDM plot. The first is defined by the εNd(210 Ma) values of -3.45 to -7.34 and TDM values of 1.15 to 1.29 Ga from a Late Triassic turbidite sequence, which are broadly similar to those obtained from the Lhasa block. The second field is derived from the Early Cretaceous meta-sedimentary rocks with εNd(130 Ma) values from -15.24 to -16.61 and TDM values from 1.63 to 2.00 Ga; these values are similar to those obtained from the Greater Himalayan Crystalline Complex in Bhutan directly south of our sampling traverse, which has εNd(130 Ma) values of -10.89 to -16.32 and Nd model ages (TDM) of 1.73 to 2.20 Ga. From the above observations, we suggest that the Late Triassic strata of the southeast Tibetan THS were derived from the Lhasa block in the north, while the Early Cretaceous strata of the THS were derived from a source similar to the High Himalayan Crystalline

  16. Variogram analysis of stable oxygen isotope composition of daily precipitation over the British Isles (United States)

    Kohán, Balázs; Tyler, Jonathan; Jones, Matthew; Kern, Zoltán


    Water stable isotopes are important natural tracers in the hydrological cycle on global, regional and local scales. Daily precipitation water samples were collected from 70 sites over the British Isles on the 23rd, 24th, and 25th January, 2012 [1]. Samples were collected as part of a pilot study for the British Isotopes in Rainfall Project, a community engagement initiative, in collaboration with volunteer weather observers and the UK Met Office. Spatial correlation structure of daily precipitation stable oxygen isotope composition (δ18OP) has been explored by variogram analysis [2]. Since the variograms from the raw data suggested a pronounced trend, owing to the spatial trend discussed in the original study [1], a second order polynomial trend was removed from the raw δ18OP data and variograms were calculated on the residuals. Directional experimental semivariograms were calculated (steps: 10°, tolerance: 30°) and aggregated into variogram surface plots to explore the spatial dependence structure of daily δ18OP. Each daily data set produced distinct variogram plots. -A well expressed anisotropic structure can be seen for Jan 23. The lowest and highest variance was observed in the SW-NE and NNE-SSW direction, respectively. Meteorological observations showed that the majority of the atmospheric flow was SW on this day, so the direction of low variance seems to reflect this flow direction, while the maximum variance might reflect the moisture variance near the elongation of the frontal system. -A less characteristic but still expressed anisotropic structure was found for Jan 24 when a warm front passed the British Isles perpendicular to the east coast, leading to a characteristic east-west δ18OP gradient suggestive of progressive rainout. The low variance central zone has a 100 km radius which might correspond well to the width of the warm front zone. Although, the axis of minimum variance was similarly SW-NE, the zone of maximum variance was broader and

  17. Mercury Isotopic Composition of Young-of-Year Fish in San Francisco Bay (United States)

    Gehrke, G. E.; Blum, J. D.; Slotton, D. G.; Greenfield, B. K.


    Variations in the stable isotopic composition of mercury (Hg) can provide information about sources and biogeochemical transformations of Hg in the environment. Mass-dependent fractionation of Hg isotopes, reported as δ202Hg relative to NIST 3133, has been observed during multiple processes including volatilization, diffusion, reduction and de-methylation. Large mass-independent fractionation of Hg (>0.2‰) reported as Δ199Hg, has been observed only during photochemical reduction of Hg and MeHg. In this study we analyzed the Hg isotopic composition of sediments and young (South and Lower South Bay (+0.10 to +0.60‰), San Pablo Bay (-0.25 to -0.03‰), and Suisun Bay (+0.13 to +0.42‰). Fish δ202Hg values roughly correlate with sediment δ202Hg values from the same sites. We suggest that each of the Guadalupe, Petaluma, and Sacaramento-San Joaquin river systems supply a distinct source of Hg to San Francisco Bay, likely associated with contaminated sediment. Mississippi silverside have Δ199Hg values ranging +0.46 to +1.55‰. Unlike the δ202Hg values, fish Δ199Hg values do not vary in a regular pattern throughout the Bay. Rather, fish from approximately one-third of sites analyzed exhibit relatively elevated Δ199Hg (> 0.8‰), possibly associated with high water clarity. In all fish analyzed, the ratio of Δ199Hg to Δ201Hg values have a narrow range of 1.19 to 1.40 (avg = 1.26 ± 0.06). These ratios in fish are consistent with laboratory studies of photochemical MeHg degradation, which yielded Δ199Hg: Δ201Hg ratios of ~1.3 (Bergquist and Blum, 2007). We suggest that Δ199Hg in fish varies with the extent of photochemical MeHg degradation prior to food web uptake. Bergquist, B. A. and Blum, J. D., 2007. Mass-dependent and -independent fractionation of Hg isotopes by photoreduction in aquatic systems. Science 318, 417-420.

  18. Direct effects of CO{sub 2} concentration on growth and isotopic composition of marine plankton

    Energy Technology Data Exchange (ETDEWEB)

    Wolf-Gladrow, D.A.; Riebesell, Ulf; Burkhardt, Steffen; Bijma, Jelle [Alfred-Wegener-Institut fuer Polar- und Meeresforschung, Bremerhaven (Germany)


    The assessment of direct effects of anthropogenic CO{sub 2} increase on the marine biota has received relatively little attention compared to the intense research on CO{sub 2}-related responses of the terrestrial biosphere. Yet, due to the rapid air-sea gas exchange, the observed past and predicted future rise in atmospheric CO{sub 2} causes a corresponding increase in seawater CO{sub 2} concentrations, [CO{sub 2}], in upper ocean waters. Increasing [CO{sub 2}] leads to considerable changes in the surface ocean carbonate system, resulting in decreases in pH and the carbonate concentration, [CO{sub 3}{sup 2-}]. These changes can be shown to have strong impacts on the marine biota. Here we will distinguish between CO{sub 2}-related responses of the marine biota which (a) potentially affect the ocean`s biological carbon pumps and (b) are relevant to the interpretation of diagnostic tools (proxies) used to assess climate change on geological times scales. With regard to the former, three direct effects of increasing [CO{sub 2}] on marine plankton have been recognized: enhanced phytoplankton growth rate, changing elemental composition of primary produced organic matter, and reduced biogenic calcification. Although quantitative estimates of their impacts on the oceanic carbon cycle are not yet feasible, all three effects increase the ocean`s capacity to take up and store atmospheric CO{sub 2} and hence, can serve as negative feedbacks to anthropogenic CO{sub 2} increase. With respect to proxies used in paleo-reconstructions, CO{sub 2}-sensitivity is found in carbon isotope fractionation by phytoplankton and foraminifera. While CO{sub 2}-dependent isotope fractionation by phytoplankton may be of potential use in reconstructing surface ocean pCO{sub 2} at ancient times, CO{sub 2}-related effects on the isotopic composition of foraminiferal shells confounds the use of the difference in isotopic signals between planktonic and benthic shells as a measure for the strength of

  19. Determination of the isotopic composition of evapotranspiration in a mature oil palm plantation in Jambi province, Indonesia. (United States)

    Bonazza, Mattia; Meijide, Ana; Knohl, Alexander


    Evapotranspiration (ET) is defined as the sum of the water vapor fluxes from evaporation (E) and transpiration (T). The relative proportion between these two quantities depends on the species, on their age and on the structure of the stand and canopy. Evaporation represents the fraction of water that doesn't contribute to plants growth hence it often considered as "unused" water by the plants root system. For this reason, in a fast changing environment like Indonesia where, since almost 30 years, tropical rainforests are gradually converted into extensive oil palm plantation, it is important to quantify the amount of evaporated water to improve agricultural practices and water quality. As powerful tracers of the hydrological cycle, water stable isotopes represent an important tool to estimate the isotopic composition of the evapotranspiration flux and they can be used as a starting point for the determination of the T/ET ratio, which can be considered as a plant water uptake efficiency indicator. The isotopic composition (δDvand δ18Ov) and the mixing ratio (qv) of water vapor measured in a stand is the result of the isotopic mixing between two members; ecosystem evapotranspiration (δET) and background air (δa). With the implementation of laser-based isotopic analysers we are now able to improve the measurement frequency of δDvand δ18Ov that leads us to an improved estimation of δET. Here we present the results of a measurement campaign, performed with a Picarro L-2120i and conducted in a mature oil palm plantation in the province of Jambi, Indonesia. We measured the atmospheric water vapor mixing ratio and isotopic composition at 5 sampling heights (21 m, 16 m, 9 m, 3.5 and 0.3 m) along a flux tower throughout the oil palm canopy (average height 10 m). The range of the water vapor isotopic composition was between -19 and -11 and -134 and -82 ‰ for δ18Ov and δDvrespectively. A fairly open canopy structure resulted in small mixing ratio gradients along the

  20. Os-isotopic Compositions of Peridotite Xenoliths from the Oceanic Mantle: Implications for the Age of Isotopic Domains in the Oceanic Mantle. (United States)

    Jackson, M. G.; Shirey, S. B.; Hauri, E. H.; Kurz, M. D.


    Os-isotopic compositions of abyssal peridotites and peridotite xenoliths from oceanic hotpots that sample the convecting mantle extend to relatively unradiogenic compositions. However, they do not preserve a record of early-formed (Hadean and Archean) depleted mantle domains, either by earlier cycles of ridge-related depletion, continent extraction, or subcontinental lithospheric mantle erosion. The lack of preservation of early-formed (Hadean and Archean) depleted Os-isotopic compositions is consistent with the lack of preservation of Hadean 142Nd/144Nd variability in the modern convecting mantle, but is in stark contrast to the existence of early-formed (early-Hadean), heterogeneous 129Xe/130Xe isotopic anomalies in the modern mantle. Mukhopadhay (Nature, 2012) suggested that the erasure of 142Nd/144Nd, but not 129Xe/130Xe, anomalies from the convecting mantle may be due to the small magnitude of the 142Nd/144Nd anomalies (10% variability observed) because the smaller 142Nd/144Nd anomalies would have been more easily erased than the larger magnitude 129Xe/130Xe anomalies. This model does not work for the Re-Os system because the magnitude of Os-isotopic heterogeneities in the mantle are large, yet early-formed Os-isotopic signatures have been erased. For example, the 187Os/188Os of early-formed depleted mantle at 4.55 Ga was ~0.095, which is >25% lower than the modern mantle. Given that there were substantial amounts of mantle partial melting throughout the Hadean and Archean, it is hard to understand how some refractory residues retaining some vestige of these low, early-formed Os isotopic compositions have not have been preserved in the modern mantle. Therefore, the lack of preservation of early-formed, large magnitude 187Os/188Os excursions in the modern convecting mantle suggests that the preservation of early geochemical heterogeneities was not necessarily a function of the original geochemical anomaly. We explore alternative solutions to the paradox of

  1. Rubidium isotopic composition of the Earth, meteorites, and the Moon: Evidence for the origin of volatile loss during planetary accretion (United States)

    Pringle, Emily A.; Moynier, Frédéric


    Understanding the origin of volatile element variations in the inner Solar System has long been a goal of cosmochemistry, but many early studies searching for the fingerprint of volatile loss using stable isotope systems failed to find any resolvable variations. An improved method for the chemical purification of Rb for high-precision isotope ratio measurements by multi-collector inductively-coupled-plasma mass-spectrometry. This method has been used to measure the Rb isotopic composition for a suite of planetary materials, including carbonaceous, ordinary, and enstatite chondrites, as well as achondrites (eucrite, angrite), terrestrial igneous rocks (basalt, andesite, granite), and Apollo lunar samples (mare basalts, alkali suite). Volatile depleted bodies (e.g. HED parent body, thermally metamorphosed meteorites) are enriched in the heavy isotope of Rb by up to several per mil compared to chondrites, suggesting volatile loss by evaporation at the surface of planetesimals. In addition, the Moon is isotopically distinct from the Moon in Rb. The variations in Rb isotope compositions in the volatile-poor samples are attributed to volatile loss from planetesimals during accretion. This suggests that either the Rb (and other volatile elements) were lost during or following the giant impact or by evaporation earlier during the accretion history of Theia.

  2. Investigation of Hg uptake and transport between paddy soil and rice seeds combining Hg isotopic composition and speciation

    Directory of Open Access Journals (Sweden)

    C. Feng


    Full Text Available Abstract Human consumption of rice constitutes a potential toxicological risk in mercury (Hg polluted areas such as Hg mining regions in China. It is recognized to be an important source of Hg for the local human diet considering the efficient bioaccumulation of methylmercury (MeHg in rice seed. To assess Hg sources and uptake pathways to the rice plants, Hg speciation and isotopic composition were investigated in rice seeds and their corresponding paddy soils from different locations within the Wanshan Hg mining area (Guizhou Province, China. A large variation of Hg speciation is observed in rice seeds and paddy soils irrespective of the sampling location. Mass dependent fractionation (MDF of Hg in rice seeds differs by up to ∼4.0 ‰ in δ202Hg values, while mass independent fractionation (MIF of Hg isotopes remains constant (Δ199Hg ∼ 0‰. Hg isotopic composition in rice seeds covaries with that of paddy soils but exhibits lighter isotopic signature (δ202Hg. Such isotopic offset is mainly attributed to plant uptake and translocation processes. Also, seeds containing higher MeHg (MeHg/total Hg > 50% have significantly heavier Hg isotopes suggesting that MeHg uptake and transport to the seed in such rice plants is facilitated compared to inorganic Hg.

  3. Oxygen- and magnesium-isotope compositions of calcium-aluminum-rich inclusions from CR2 carbonaceous chondrites (United States)

    Makide, Kentaro; Nagashima, Kazuhide; Krot, Alexander N.; Huss, Gary R.; Hutcheon, Ian D.; Bischoff, Addi


    We report both oxygen- and magnesium-isotope compositions measured in situ using a Cameca ims-1280 ion microprobe in 20 of 166 CAIs identified in 47 polished sections of 15 CR2 (Renazzo-type) carbonaceous chondrites. Two additional CAIs were measured for oxygen isotopes only. Most CR2 CAIs are mineralogically pristine; only few contain secondary phyllosilicates, sodalite, and carbonates - most likely products of aqueous alteration on the CR2 chondrite parent asteroid. Spinel, hibonite, grossite, anorthite, and melilite in 18 CAIs have 16O-rich (Δ 17O = -23.3 ± 1.9‰, 2 σ error) compositions and show no evidence for postcrystallization isotopic exchange commonly observed in CAIs from metamorphosed CV carbonaceous chondrites. The inferred initial 26Al/ 27Al ratios, ( 26Al/ 27Al) 0, in 15 of 16 16O-rich CAIs measured are consistent with the canonical value of (4.5-5) × 10 -5 and a short duration (oxygen- and magnesium-isotope compositions (˜11 and 23‰/amu, respectively), a deficit of 26Mg, and a relatively low ( 26Al/ 27Al) 0 = (2.0 ± 1.7) × 10 -5. This could be the first FUN ( Fractionation and Unidentified Nuclear effects) CAI found in CR2 chondrites. Because this inclusion is slightly 16O-depleted compared to most CR2 CAIs and has lower than the canonical ( 26Al/ 27Al) 0, it may have experienced multistage formation from precursors with nonsolar magnesium-isotope composition and recorded evolution of oxygen-isotope composition in the early solar nebula over 0.9+2.2-0.7 My. Eight of the 166 CR2 CAIs identified are associated with chondrule materials, indicating that they experienced late-stage, incomplete melting during chondrule formation. Three of these CAIs show large variations in oxygen-isotope compositions (Δ 17O ranges from -23.5‰ to -1.7‰), suggesting dilution by 16O-depleted chondrule material and possibly exchange with an 16O-poor (Δ 17O > -5‰) nebular gas. The low inferred ( 26Al/ 27Al) 0 ratios of these CAIs (2 My after crystallization

  4. Spatial, seasonal, and source variability in the stable oxygen and hydrogen isotopic composition of tap waters throughout the USA (United States)

    Landwehr, Jurate M.; Coplen, Tyler B.; Stewart, David W.


    To assess spatial, seasonal, and source variability in stable isotopic composition of human drinking waters throughout the entire USA, we have constructed a database of δ18O and δ2H of US tap waters. An additional purpose was to create a publicly available dataset useful for evaluating the forensic applicability of these isotopes for human tissue source geolocation. Samples were obtained at 349 sites, from diverse population centres, grouped by surface hydrologic units for regional comparisons. Samples were taken concurrently during two contrasting seasons, summer and winter. Source supply (surface, groundwater, mixed, and cistern) and system (public and private) types were noted. The isotopic composition of tap waters exhibits large spatial and regional variation within each season as well as significant at-site differences between seasons at many locations, consistent with patterns found in environmental (river and precipitation) waters deriving from hydrologic processes influenced by geographic factors. However, anthropogenic factors, such as the population of a tap’s surrounding community and local availability from diverse sources, also influence the isotopic composition of tap waters. Even within a locale as small as a single metropolitan area, tap waters with greatly differing isotopic compositions can be found, so that tap water within a region may not exhibit the spatial or temporal coherence predicted for environmental water. Such heterogeneities can be confounding factors when attempting forensic inference of source water location, and they underscore the necessity of measurements, not just predictions, with which to characterize the isotopic composition of regional tap waters. Published 2013. This article is a U.S. Government work and is in the public domain in the USA.

  5. Petrology and oxygen isotope compositions of chondrules in E3 chondrites (United States)

    Weisberg, Michael K.; Ebel, Denton S.; Connolly, Harold C.; Kita, Noriko T.; Ushikubo, Takayuki


    Chondrules in E3 chondrites differ from those in other chondrite groups. Many contain near-pure endmember enstatite (Fs metal, Cr-bearing troilite, and, in some cases Mg, Mn- and Ca-sulfides. Olivine and more FeO-rich pyroxene grains are present but much less common than in ordinary or carbonaceous chondrite chondrules. In some cases, the FeO-rich grains contain dusty inclusions of metal. The oxygen three-isotope ratios (δ 18O, δ 17O) of olivine and pyroxene in chondrules from E3 chondrites, which are measured using a multi-collection SIMS, show a wide range of values. Most enstatite data plots on the terrestrial fractionation (TF) line near whole rock values and some plot near the ordinary chondrite region on the 3-isotope diagram. Pyroxene with higher FeO contents (˜2-10 wt.% FeO) generally plots on the TF line similar to enstatite, suggesting it formed locally in the EC (enstatite chondrite) region and that oxidation/reduction conditions varied within the E3 chondrite chondrule-forming region. Olivine shows a wide range of correlated δ 18O and δ 17O values and data from two olivine-bearing chondrules form a slope ˜1 mixing line, which is approximately parallel to but distinct from the CCAM (carbonaceous chondrite anhydrous mixing) line. We refer to this as the ECM (enstatite chondrite mixing) line but it also may coincide with a line defined by chondrules from Acfer 094 referred to as the PCM (Primitive Chondrite Mineral) line ( Ushikubo et al., 2011). The range of O isotope compositions and mixing behavior in E3 chondrules is similar to that in O and C chondrite groups, indicating similar chondrule-forming processes, solid-gas mixing and possibly similar 16O-rich precursors solids. However, E3 chondrules formed in a distinct oxygen reservoir. Internal oxygen isotope heterogeneity was found among minerals from some of the chondrules in E3 chondrites suggesting incomplete melting of the chondrules, survival of minerals from previous generations of

  6. Stable isotopic composition of pedogenic carbonate in soils of Minusinsk Hollow (United States)

    Vasil'chuk, Jessica; Krechetov, Pavel; Budantseva, Nadine; Chizhova, Julia; Vasil'chuk, Yurij


    The purpose of the research is to characterize the isotopic composition of carbonate neoformations in soils and estimate its correlation with isotopic composition of water and parent material. The study site is located in the Minusinsk Hollow that is situated among Kuznetsk Alatau and Sayan Mountains. Three key-sites with in different parts of hollow, under mainly steppe vegetation with calciphilic grasses and diverse parent material were studied including: 1) Kazanovka Khakass state national reserve in foothills of Kuznetsk Alatau 2) Hankul salt lake that is considered as natural monument 3) region of Sayanogorsk aluminum smelter on a left bank of the Yenisei river. The samples of pedogenic and lithogenic carbonates as well as water samples were analyzed using the Delta-V mass spectrometer with a standard option of a gas bench according to standard methods. Carbonate coatings (also called pendants or cutans) is one of the most common types of carbonate neoformations occurring in the region. Fine coatings' layers one over another usually can be found on the bottom sides of rubble and gravel inside the soil profile colour varies from white to brownish and yellowish (probably depending on the impurities of organic matter). In Petric Calcisols, Chernozems and Kastanozems δ18O values of coatings vary in a rather small range from - 8.9 to - 10.1 ‰ PDB. This probably shows that their forming took place approximately in the same climatic conditions. While δ18O values of carbonate parent rocks are close to them and are vary from - 11.1 to - 11.9 ‰ PDB. Also, δ13C values of coatings strongly decrease from inner (older) to outer (younger) layers, that can indicate differences connected with the diffusion of organic material. River waters' δ18O values also show a small range from - 16.62 to - 17.66‰ SMOW, while salt lakes' waters due to the fractionation evaporation effects demonstrate much heavier values from - 4.73 to - 9.22‰ SMOW. The groundwater shows δ18O

  7. Minor Sulfur Isotope Constraints on the composition of Earth's Archean atmosphere (United States)

    Claire, M.


    Minor sulfur isotope anomalies in the sedimentary record are direct recorders of ancient chemical reactions that occurred in the atmosphere, and therefore form the most direct proxy for Archean atmospheric composition. The mere presence of mass-independently fractionated sulfur isotopes (MIF-S) in the rock record has resolved nearly a century's worth of debate by constraining atmospheric oxygen to trace levels prior to 2.4 billion years ago, and indirectly indicates the presence of a dominant reducing gas, likely H2 or CH4. The MIF-S database has grown substantially in the past decade, and reveals complex time- and facies-dependent changes in MIF-S magnitudes. The structure within the sedimentary MIF-S record suggests that constraints beyond this simple "on-off" switch for atmospheric O2 are possible once we understand the mechanisms that generate and preserve the signal in the rock record. Recently, I proposed an initial quantitative framework for predictions of atmospheric MIF-S [1], but concluded that new measurements of MIF-S generation mechanisms were needed to provide robust constraints. Since then, identification of MIF-S arising from SO2 photoexcitation [2], and updated absorption cross-sections for SO2 and SO [3-4] provide critical new ground-truth on all 4 isotopes of sulfur. Furthermore, breakthroughs in coupled photochemical-climate modeling have enabled better predictions of UV transparency within hazy atmospheres [5] such as those that might have dominated in the Archean [6-8]. I will present 1-D photochemical modeling results based on these new fundamental constraints, in comparison with MIF-S data from the Archean, to interpret the steady-state composition of the Archean atmosphere and time-dependent perturbations to it. In particular, Δ36S/Δ33S resulting from perturbations to atmospheric species will be discussed as a key tool for constraining the composition of the reducing atmosphere. [1] Claire et al. (2014) GCA; [2] Whitehill et al., PNAS

  8. Temporal variations of Sr isotopic compositions for the rocks from Dogo, Oki islands Shimane Prefecture

    Energy Technology Data Exchange (ETDEWEB)

    Fujimaki, Hirokazu; Xu Hong; Aoki, Ken-ichiro (Tohoku Univ., Sendai (Japan). Faculty of Science)


    Fifty-three volcanic rocks from Dogo island, Oki, Shimane Prefecture, southwestern Japan were analyzed for Sr isotopic compositions with two basement rocks. The rock samples consist of calc-alkali rock suite, Nagaoda shoshonite-banakite suite, Oki trachyte-rhyolite suite, Dogo mugearite suite, Hei trachyte and Tsuzurao rhyolite series, and Daimanjiyama, Ohmine, Kuroshima, Shiroshimazaki, Saigo, and Misaki alkali basalt groups in the order of probable eruption sequence. The volcanic rocks of calc-alkali suite and shoshonite-banakite suite were produced before Japan Sea opening (ca. 15 Ma), and both have {sup 87}Sr/{sup 86}Sr ratios higher than 0.7068. Long after Japan Sea opening Oki-trachyte-rhyolite suite was erupted (ca. 6.6 Ma); they have rather low {sup 87}Sr/{sup 86}Sr ratios (0.7066-0.7081). Mugearites followed and have similar Sr isotopic composition, whereas 4.6 Ma old Daimanjiyama basalts have clearly low {sup 87}Sr/{sup 86}Sr ratios (0.7050-0.7051). The rocks erupted 3-4 Ma seem to have the lowest {sup 87}Sr/{sup 86}Sr ratios; they are Ohmine, Kuroshima, Shiroshimazaki alkali basalt suites (0.7044-0.7048). The {sup 87}Sr/{sup 86}Sr ratios of the Saigo basalts erupted 0.84 Ma are higher than those erupted 3-4 Ma. The latest volcanic products in Dogo island, Misaki basalt suite has even higher {sup 87}Sr/{sup 86}Sr ratios (0.7054-0.7057) than the Saigo basalt suite. Thus, temporal and systematic variation of Sr isotopic compositions of the volcanic rocks from Dogo can be recognized. The {sup 87}Sr/{sup 86}Sr ratios of the rocks were once as high as 0.7066 or even higher than 0.708, but they started decreasing down to ca. 0.7044-0.7048 4-3 Ma ago. Since then the ratios rebounded to 0.7049-0.7055. The Hei trachyte and Tsuzurao rhyolite series are not included in this temporal and systematic change. (Abstract Truncated)

  9. A 15N-poor isotopic composition for the solar system as shown by Genesis solar wind samples. (United States)

    Marty, B; Chaussidon, M; Wiens, R C; Jurewicz, A J G; Burnett, D S


    The Genesis mission sampled solar wind ions to document the elemental and isotopic compositions of the Sun and, by inference, of the protosolar nebula. Nitrogen was a key target element because the extent and origin of its isotopic variations in solar system materials remain unknown. Isotopic analysis of a Genesis Solar Wind Concentrator target material shows that implanted solar wind nitrogen has a (15)N/(14)N ratio of 2.18 ± 0.02 × 10(-3) (that is, ≈40% poorer in (15)N relative to terrestrial atmosphere). The (15)N/(14)N ratio of the protosolar nebula was 2.27 ± 0.03 × 10(-3), which is the lowest (15)N/(14)N ratio known for solar system objects. This result demonstrates the extreme nitrogen isotopic heterogeneity of the nascent solar system and accounts for the (15)N-depleted components observed in solar system reservoirs.

  10. Distribution and isotopic composition of uranium in lower Nueces River, Nueces Bay and Corpus Christi Bay, Texas (United States)

    Holmes, Charles W.; Slade, Elizabeth Ann


    The uranium concentration and isotopic composition of water and suspended sediment from the Nueces River, Nueces Bay and Corpus Christi Bay were determined by alpha-spectroscopy. The average dissolved uranium concentration and radioactivity ratio (U234/U238) of Nueces River water were determined to be 2.44 µg/1 and 1.15 respectively. Water from a tributary of the Nueces River, Cayamon Creek, was found to contain an average dissolved uranium concentration of 42.8 µg/1 with an isotopic radioactivity ratio of 1.56. Close inspection of the lateral concentration and isotopic activity ratio of uranium revealed an increase below the confluence of Cayamon Creek with the Nueces River. A model was derived based on equations used in isotopic dilution analysis, which predicts these increases within analytical error. This model may be useful in future studies to locate anomalous uranium within the hydrologic environment.

  11. Toward forward modeling for paleoclimatic proxy signal calibration: A case study with oxygen isotopic composition of tropical woods (United States)

    Evans, M. N.


    A forward model of the oxygen isotopic composition (δ18O) of wood cellulose is parameterized for time series prediction in tropical environments and driven with meteorological data observed at La Selva Biological Research Station, Costa Rica, for 1985-2001. Monthly-resolution model results correlate modestly (r = 0.34, p Selva suggests that isotopic variations are strongly controlled by rainfall amount. The model simulates an analogous but stronger than observed negative isotopic anomaly associated with positive July-September rainfall anomalies during El Niño-Southern Oscillation (ENSO) warm phase event years. Simulated tree isotope data for the global tropics suggest that a network of well-replicated data series from selected locations may resolve the large-scale precipitation anomaly pattern associated with ENSO.

  12. Variations in atmospheric concentrations and isotopic compositions of gaseous and particulate boron in Shizuoka City, Japan (United States)

    Sakata, Masahiro; Phan, Hang Giang; Mitsunobu, Satoshi


    To clarify the partitioning and isotopic fractionation of boron (B) into the gas and particle phases in the atmosphere, the concentrations and isotopic compositions of gaseous and particulate B were measured concurrently for more than one year at a site in Shizuoka City, Japan. This area has few anthropogenic sources of B, such as coal combustion facilities. Gaseous B concentration showed clearly a seasonal variation, increasing during summer and decreasing during winter. Conversely, particulate B concentration tended to decrease during the warm season and increase during winter. The increase in gaseous B concentration during summer is attributable to the enhanced emissions of B from sea-salt degassing owing to higher temperatures and the predominance of winds from the Pacific Ocean. Moreover, the decrease in gaseous B concentration and the increase in particulate B concentration during winter is probably due to the enhanced condensation of gaseous B on atmospheric particles. The δ11B values of gaseous and particulate B varied largely, and did not indicate a distinctive seasonal variation. A positive correlation was observed between the δ11B values of gaseous and particulate B (R2 = 0.518, P < 0.001). Moreover, the δ11B values of particulate B were approximately 0-20‰ lower than those of gaseous B. There is an isotopic fractionation (ΔB(OH)4- -B(OH)3) of about -20‰ between B(OH)3 and B(OH)4- species in solution (Kakihana et al., 1977). This tends to support the hypotheses that gaseous B is transformed to particulate B through the reaction of condensed B(OH)3 with chemical constituents on particles to precipitate borates, and that the condensed B(OH)3 remaining on particles is unstable and evaporates.

  13. Climatic and physiological controls on the stable isotope composition of modern and ancient Cupressaceae (United States)

    Zinniker, D.; Tipple, B.; Pagani, M.


    Unique and abundant secondary metabolites found in waxes and resins of the Callitroid, Cupressoid, and Taxodioid clades of the Cupressaceae family can be identified and quantified in complex mixtures of sedimentary organic compounds. This unusual feature makes it possible to study relatively simple (taxon-specific) isotope systems back in time across the broad array of environments in which these conifers are found. Work on these systems can potentially provide both robust paleoenvironmental proxies (i.e. for source water δD and growing season relative humidity) and quantitative probes into the ecophysiology of these plants in modern and ancient environments. Our research focuses on three genera representing environmental end-members of Cupressaceae - Juniperus, Thuja, and Chamaecyparis - (1) across geographic and environmental gradients in the field, and (2) in specific Holocene and late Pleistocene environmental records. The latter research focuses on peat cores from New England and Oregon and fossil packrat middens from the southwestern United States. Modern transects highlight the sensitivity of Cupressaceae to climatic variables. These include both variables during growth (relative humidity, soil moisture, etc.) and variables affecting seasonal and diurnal growth rates (temperature, winter precipitation, insolation, microhabitat, etc.). Work on ancient records has demonstrated the sensitivity of these unique taxon-specific archives to both subtle and dramatic climate shifts during the Pleistocene and Holocene. This work will result in an improved understanding of climatic and physiological controls on the stable isotopic composition of modern and ancient Cupressaceae - and by extension, other arborescent gymnosperms and C3 plants - providing a framework for understanding more complexly sourced organic inputs to sediments, coals, and petroleum prior to the advent of C4 plants. This research also has direct implications for stratigraphic stable isotope studies

  14. Effect of microtopography on isotopic composition of methane in porewater and efflux at a boreal peatland

    Energy Technology Data Exchange (ETDEWEB)

    Dorodnikov, M.; Wilmking, M. [Greifswald Univ. (Georgia). Inst. of Botany and Landscape Ecology; Marushchak, M.; Biasi, C. [Univ. of Eastern Finland, Kuopio (Finland). Dept. of Environmental Science, Bioteknia 2], E-mail:


    The application of stable isotopes is an approach to identify pathways of methanogenesis, methane (CH{sub 4}) oxidation and transport in peatlands. We measured the stable C isotopic characteristics ({delta}C-13) of CH{sub 4} in peat profiles below hummocks, lawns and hollows of a Finnish mire to study the patterns of CH{sub 4} turnover. Porewater CH{sub 4} concentrations ([CH{sub 4}]; at 0.5-2 m) increased with depth below all microforms. Emissions of CH{sub 4} from hummocks were the lowest, and increased with the increasing water-saturated zone, being {approx}10 times higher from hollows. Thus, the microtopography of the peatland did not affect the porewater [CH{sub 4}] in the water-saturated part of the peat profile, but the CH{sub 4} emissions were affected due to differences in the oxidative potential of the microforms. There was a decrease in {delta}C-13-CH{sub 4} with depth below all microforms indicating dominance of CO{sub 2}-reduction over acetate cleavage pathway of methanogenesis at deep peat layers. However, estimated potential portions of transported CH{sub 4} comprised 50%-70% of the {delta}C-13-CH{sub 4} enrichment on microforms at the 0.5-m depth, hereby masking the acetate cleavage pathway of methanogenesis. Stable C composition ({delta}C-13) of CH{sub 4} proved to be a suitable (but not sufficient) tool to differentiate between types of methanogenesis in continuously water-saturated layers below microforms of a peatland. Combined flux-based and multi-isotopic approaches are needed to better understand the CH{sub 4} turnover process. (orig.)

  15. A comparative study on isotopic composition of precipitation in wet tropic and semi-arid stations across southern India

    Indian Academy of Sciences (India)

    C Unnikrishnan Warrier; M Praveen Babu


    Isotopic composition of monthly composite precipitation samples from Kozhikode ( = 31), a wet tropic station and Hyderabad ( = 25), a semi-arid station across southern India were studied for a period of four years from 2005 to 2008. During the study period, the Kozhikode station recorded an average rainfall of 3500 mm while the Hyderabad station showed an average rainfall of 790 mm. The average stable isotope values in precipitation at the Kozhikode station were 18O= -3.52‰, d-excess = 13.72‰; 18O = -2.94‰, d-excess = 10.57‰; and 18O = -7.53‰, d-excess = 13.79‰, respectively during the pre-monsoon (March–May), monsoon (June–September) and post-monsoon (October–February) seasons. For the Hyderabad station, the average stable isotope values were 18O = −5.88‰, d-excess = 2.34‰; 18O = −4.39‰, d-excess = 9.21‰; and 18O = −8.69‰, d-excess = 14.29‰, respectively for the three seasons. The precipitation at the two stations showed distinctive isotopic signatures. The stable isotopic composition of precipitation at the Hyderabad station showed significant variations from the global trend while the Kozhikode station almost followed the global value. These differences are mainly attributed to the latitudinal differences of the two stations coupled with the differences in climatic conditions.

  16. Origin of magnetite in oxidized CV chondrites: in situ measurement of oxygen isotope compositions of Allende magnetite and olivine. (United States)

    Choi, B G; McKeegan, K D; Leshin, L A; Wasson, J T


    Magnetite in the oxidized CV chondrite Allende mainly occurs as spherical nodules in porphyritic-olivine (PO) chondrules, where it is associated with Ni-rich metal and/or sulfides. To help constrain the origin of the magnetite, we measured oxygen isotopic compositions of magnetite and coexisting olivine grains in PO chondrules of Allende by an in situ ion microprobe technique. Five magnetite nodules form a relatively tight cluster in oxygen isotopic composition with delta 18O values from -4.8 to -7.1% and delta 17O values from -2.9 to -6.3%. Seven coexisting olivine grains have oxygen isotopic compositions from -0.9 to -6.3% in delta 18O and from -4.6 to -7.9% in delta 17O. The delta 17O values of the magnetite and coexisting olivine do not overlap; they range from -0.4 to -2.6%, and from -4.0 to -5.7%, respectively. Thus, the magnetite is not in isotopic equilibrium with the olivine in PO chondrules, implying that it formed after the chondrule formation. The delta 17O of the magnetite is somewhat more negative than estimates for the ambient solar nebula gas. We infer that the magnetite formed on the parent asteroid by oxidation of metal by H2O which had previously experienced minor O isotope exchange with fine-grained silicates.

  17. Alteration of the carbon and nitrogen isotopic composition in the Martian surface rocks due to cosmic ray exposure (United States)

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


    13C/12C and 15N/14N isotopic ratios are pivotal for our understanding of the Martian carbon cycle, history of the Martian atmospheric escape, and origin of the organic compounds on Mars. Here we demonstrate that the carbon and nitrogen isotopic composition of the surface rocks on Mars can be significantly altered by the continuous exposure of Martian surface to cosmic rays. Cosmic rays can effectively produce 13C and 15N isotopes via spallation nuclear reactions on oxygen atoms in various Martian rocks. We calculate that in the top meter of the Martian rocks, the rates of production of both 13C and 15N due to galactic cosmic rays (GCRs) exposure can vary within 1.5-6 atoms/cm3/s depending on rocks' depth and chemical composition. We also find that the average solar cosmic rays can produce carbon and nitrogen isotopes at a rate comparable to GCRs in the top 5-10 cm of the Martian rocks. We demonstrate that if the total carbon content in a surface Martian rock is Mars can explain its high-temperature heavy nitrogen isotopic composition (15N/14N). Applications to Martian meteorites and the current Mars Science Laboratory mission are discussed.

  18. Alteration of the Carbon and Nitrogen Isotopic Composition in the Martian Surface Rocks Due to Cosmic Ray Exposure (United States)

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


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

  19. Isotopic composition of H2 from wood burning: Dependency on combustion efficiency, moisture content, and δD of local precipitation

    NARCIS (Netherlands)

    Röckmann, T.; Gómez Álvarez, C.X.; Walter, S.; van der Veen, C.; Wollny, A.G.; Gunthe, S.S.; Helas, G.; Pöschl, U.; Keppler, F.; Greule, M.; Brand, W.A.


    Differences in isotopic composition between the various sources of H2 are large, but only a few measurements have been carried out to constrain them. Two conflicting values have been published for H2 from biomass burning. Both rely on the assumption that the isotopic composition of H2 should scale w

  20. Isotopic composition of H2 from wood burning: Dependency on combustion efficiency, moisture content, and δD of local precipitation

    NARCIS (Netherlands)

    Röckmann, T.|info:eu-repo/dai/nl/304838233; Gómez Álvarez, C.X.; Walter, S.; van der Veen, C.; Wollny, A.G.; Gunthe, S.S.; Helas, G.; Pöschl, U.; Keppler, F.; Greule, M.; Brand, W.A.


    Differences in isotopic composition between the various sources of H2 are large, but only a few measurements have been carried out to constrain them. Two conflicting values have been published for H2 from biomass burning. Both rely on the assumption that the isotopic composition of H2 should scale

  1. A model composition for Mars derived from the oxygen isotopic ratios of martian/SNC meteorites. [Abstract only (United States)

    Delaney, J. S.


    Oxygen is the most abundant element in most meteorites, yet the ratios of its isotopes are seldom used to constrain the compositional history of achondrites. The two major achondrite groups have O isotope signatures that differ from any plausible chondritic precursors and lie between the ordinary and carbonaceous chondrite domains. If the assumption is made that the present global sampling of chondritic meteorites reflects the variability of O reservoirs at the time of planetessimal/planet aggregation in the early nebula, then the O in these groups must reflect mixing between known chondritic reservoirs. This approach, in combination with constraints based on Fe-Mn-Mg systematics, has been used previously to model the composition of the basaltic achondrite parent body (BAP) and provides a model precursor composition that is generally consistent with previous eucrite parent body (EPB) estimates. The same approach is applied to Mars exploiting the assumption that the SNC and related meteorites sample the martian lithosphere. Model planet and planetesimal compositions can be derived by mixing of known chondritic components using O isotope ratios as the fundamental compositional constraint. The major- and minor-element composition for Mars derived here and that derived previously for the basaltic achondrite parent body are, in many respects, compatible with model compositions generated using completely independent constraints. The role of volatile elements and alkalis in particular remains a major difficulty in applying such models.

  2. Chemical characterization and stable carbon isotopic composition of particulate polycyclic aromatic hydrocarbons issued from combustion of 10 Mediterranean woods

    Directory of Open Access Journals (Sweden)

    A. Guillon


    Full Text Available The objectives of this study were to characterize polycyclic aromatic hydrocarbons from particulate matter emitted during wood combustion and to determine, for the first time, the isotopic signature of PAHs from nine wood species and Moroccan coal from the Mediterranean Basin. In order to differentiate sources of particulate-PAHs, molecular and isotopic measurements of PAHs were performed on the set of wood samples for a large panel of compounds. Molecular profiles and diagnostic ratios were measured by gas chromatography coupled with a mass spectrometer (GC/MS and molecular isotopic compositions13C of particulate-PAHs were determined by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS. Wood species present similar molecular profiles with benz(aanthracene and chrysene as dominant PAHs, whereas levels of concentrations range from 1.8 to 11.4 mg g−1 OC (sum of PAHs. Diagnostic ratios are consistent with reference ratios from literature but are not sufficient to differentiate the different species of woods. Concerning isotopic methodology, PAH molecular isotopic compositions are specific for each species and contrary to molecular fingerprints, significant variations of δ13C are observed for the panel of PAHs. This work allows differentiating wood combustion from others origins of particulate matter (vehicular exhaust using isotopic measurements (with δ13CPAH = −28.7 to −26.6‰ but also confirms the necessity to investigate source characterisation at the emission in order to help and complete source assessment models. These first results on woodburnings will be useful for the isotopic approach of source tracking.

  3. Chemical characterization and stable carbon isotopic composition of particulate Polycyclic Aromatic Hydrocarbons issued from combustion of 10 Mediterranean woods

    Directory of Open Access Journals (Sweden)

    A. Guillon


    Full Text Available The objectives of this study were to characterize polycyclic aromatic hydrocarbons from particulate matter emitted during wood combustion and to determine, for the first time, the isotopic signature of PAHs from nine wood species and Moroccan coal from the Mediterranean Basin. In order to differentiate sources of particulate-PAHs, molecular and isotopic measurements of PAHs were performed on the set of wood samples for a large panel of compounds. Molecular profiles and diagnostic ratios were measured by gas chromatography/mass spectrometry (GC/MS and molecular isotopic compositions (δ13C of particulate-PAHs were determined by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS. Wood species present similar molecular profiles with benz(aanthracene and chrysene as dominant PAHs, whereas levels of concentrations range from 1.8 to 11.4 mg g−1 OC (sum of PAHs. Diagnostic ratios are consistent with reference ratios from literature but are not sufficient to differentiate the species of woods. Concerning isotopic methodology, PAH molecular isotopic compositions are specific for each species and contrary to molecular fingerprints, significant variations of δ13C are observed for the panel of PAHs. This work allows differentiating wood combustion (with δ13CPAH = −28.7 to −26.6‰ from others origins of particulate matter (like vehicular exhaust using isotopic measurements but also confirms the necessity to investigate source characterisation at the emission in order to help and complete source assessment models. These first results on woodburnings will be useful for the isotopic approach to source tracking.

  4. Deposition of nitrogen and phosphorus on the Baltic Sea: seasonal patterns and nitrogen isotope composition

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    C. Rolff


    Full Text Available Atmospheric deposition of nitrogen and phosphorus on the central Baltic Sea (Baltic Proper was estimated monthly at two coastal stations and two isolated islands in 2001 and 2002. Yearly nitrogen deposition ranged between 387 and 727 mg N m−2 yr−1 (average 617 and was composed of ~10% organic N and approximately equal amounts of ammonium and nitrate. Winter nitrate peaks at the isolated islands possibly indicated ship emissions. Load weighted δ15N of deposited N was 3.7‰ and 0.35‰ at the coastal stations and the isolated islands respectively. Winter δ15N was ~3‰ lighter than in summer, reflecting winter dominance of nitrate. The light isotopic composition of deposited nitrogen may cause overestimates of nitrogen fixation in basin-wide isotopic budgeting, whereas relatively heavy deposition of ammonium during summer instead may cause underestimates of fixation in budgets of the upper mixed layer. δ15N in atmospherically deposited nitrate and ammonium was estimated by regression to −7.9 and 13.5‰ respectively. Phosphorus deposition showed no clear seasonal pattern and was considerably lower at the isolated islands. Organic P constituted 20–40% of annual P deposition. P deposition is unlikely to be a major source for cyanobacterial blooms but may potentially prolong an ongoing bloom.

  5. Concentration and stable carbon isotopic composition of CO2 in cave air of Postojnska jama, Slovenia

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    Magda Mandic


    Full Text Available Partial pressure of CO2 (pCO2 and its isotopic composition (δ13CairCO2 were measured in Postojnska jama, Slovenia, at 10 locations inside the cave and outside the cave during a one-year period. At all interior locations the pCO2 was higher and δ13CairCO2 lower than in the outside atmosphere. Strong seasonal fluctuations in both parameters were observed at locations deeper in the cave, which are isolated from the cave air circulation. By using a binary mixing model of two sources of CO2, one of them being the atmospheric CO2, we show that the excess of CO2 in the cave air has a δ13C value of -23.3 ± 0.7 ‰, in reasonable agreement with the previously measured soil-CO2 δ13C values. The stable isotope data suggest that soil CO2 is brought to the cave by drip water.

  6. Determining the geographical origin of Chinese cabbages using multielement composition and strontium isotope ratio analyses. (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


    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.

  7. Nitrogen Isotope Composition of Thermally Produced NOx from Various Fossil-Fuel Combustion Sources. (United States)

    Walters, Wendell W; Tharp, Bruce D; Fang, Huan; Kozak, Brian J; Michalski, Greg


    The nitrogen stable isotope composition of NOx (δ(15)N-NOx) may be a useful indicator for NOx source partitioning, which would help constrain NOx source contributions in nitrogen deposition studies. However, there is large uncertainty in the δ(15)N-NOx values for anthropogenic sources other than on-road vehicles and coal-fired energy generating units. To this end, this study presents a broad analysis of δ(15)N-NOx from several fossil-fuel combustion sources that includes: airplanes, gasoline-powered vehicles not equipped with a three-way catalytic converter, lawn equipment, utility vehicles, urban buses, semitrucks, residential gas furnaces, and natural-gas-fired power plants. A relatively large range of δ(15)N-NOx values was measured from -28.1‰ to 8.5‰ for individual exhaust/flue samples that generally tended to be negative due to the kinetic isotope effect associated with thermal NOx production. A negative correlation between NOx concentrations and δ(15)N-NOx for fossil-fuel combustion sources equipped with selective catalytic reducers was observed, suggesting that the catalytic reduction of NOx increases δ(15)N-NOx values relative to the NOx produced through fossil-fuel combustion processes. Combining the δ(15)N-NOx measured in this study with previous published values, a δ(15)N-NOx regional and seasonal isoscape was constructed for the contiguous U.S., which demonstrates seasonal and regional importance of various NOx sources.

  8. Determining the geographical origin of Chinese cabbages using multielement composition and strontium isotope ratio analyses (United States)

    BONG, Y.; Shin, W.; Gautam, M. K.; Jeong, Y.; Lee, A.; Jang, C.; Lim, Y.; Chung, G.; Lee, K.


    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.

  9. Isotopic composition of strontium in three basalt-andesite centers along the Lesser Antilles arc (United States)

    Hedge, C.E.; Lewis, J.F.


    Si87/Sr86 ratios have been determined for lavas and py lastic rocks from three basalt-andesite centers along the Lesser Antilles arc-Mt. Misery on the island of St. Kitts, Soufriere on the island of St. Vincent, and Carriacou, an island of The Grenadines. The average Si87/Sr86 content of these rocks is 0.7038 for Mt. Misery, 0.7041 for Soufriere, and 0.7053 for Carriacou. All the Sr87/Sr86 values from each center are the same within analytical uncertainty (??0.0002). The constancy of strontium isotopic data within each center supports the hypothesis that basalts and andesites for each specific center investigated are generated from the same source - in agreement with petrographic and major- and minor-element data. Strontium isotopic compositions and elemental concentrations, particularly of strontium and nickel, indicate that this source was mantle peridotite and that the relationship between the respective basalts and andesites is probably fractional crystallization. ?? 1971 Springer-Verlag.

  10. Anthropogenic stressors and eutrophication processes as recorded by stable isotopes compositions in coral skeletons

    Directory of Open Access Journals (Sweden)

    O. Levy


    Full Text Available The northern Gulf of Aqaba, in the northeastern branch of the Red Sea, is a clear example of humans effecting on the health of fringing reefs. Our results demonstrate the effect of an anthropogenic stressor on the carbon and oxygen stable isotopes compositions, namely net pen fish farming with annual fish production of 2.4×106 kg yr−1. We sampled and studied long coral cores from stressed, remote and intermediate localities and short- term transplanted Porites sp. colonies from the west side of the Gulf of Aqaba to a remote and a polluted sites, respectively. The data shows that mariculture and other human related stressors did not influence the oxygen isotopic signature over a period of two decades. However, the carbon fractionation changed along a geographical gradient and depended on proximity to the source of contamination. We suggest that δ13C of coral skeleton is a promising proxy for identifying long term processes of coral growth under high nutrient loads and potential disturbances to the coral reef ecology.

  11. Skeletal and isotopic composition and paleoclimatic significance of late Pleistocene carbonates, Ross Sea, Antarctica

    Energy Technology Data Exchange (ETDEWEB)

    Taviani, M. (Ist. per la Geologia Marina, Bologna (Italy)); Reid, D.E.; Anderson, J.B. (Rice Univ., Houston, TX (United States))


    Carbonates cover an extensive area of the northwestern Ross Sea continental shelf. Radiocarbon dates yield late Pleistocene (stage 3) ages for these deposits, hence the carbonates appear to be correlative with widespread tills and glacial marine deposits in the region. Four carbonate facies are recognized on the basis of skeletal composition: a barnacle/foraminifer facies, a muddy bryozoan facies, a bryozoan/barnacle/pelecypod/foraminifer facies, and a planktonic foraminiferal facies. These deposits occur on the shelf and upper slope, while carbonate turbidities derived from them occur on the adjacent continental slope and rise. Compositional analyses of Ross Sea carbonates lend support to previously recognized criteria for identifying cold water carbonates. These include: (1) the presence of an associated ice-rafted component (including dropstones); (2) a dominance of calcite relative to other carbonate minerals (the remaining fraction consists solely of aragonite); (3) allochems that are entirely skeletal; and (4) heavy oxygen isotopic compositions (in the range of +3.0 to +5.1% PDB).

  12. Chemical and boron isotopic composition of tourmaline from the Mariinsky emerald deposit, Central Urals, Russia (United States)

    Baksheev, Ivan A.; Trumbull, Robert B.; Popov, Mikhail P.; Erokhin, Yuri V.; Kudryavtseva, Olesya E.; Yapaskurt, Vasily O.; Khiller, Vera V.; Vovna, Galina M.; Kiselev, Vladimir I.


    Tourmaline is abundant at the Mariinsky schist-hosted emerald deposit in the Central Urals, Russia, both in emerald-bearing phlogopite veins (type 1) and later, emerald-free pockets, lenses, and veinlets cutting the phlogopite veins (type 2). The Ca content in tourmaline is influenced by the host rocks (ultramafic and mafic rocks), associated minerals, and minerals crystallized before tourmaline (amphibole, fluorite, margarite). The Na concentration in tourmaline depends on the presence or absence of paragonite, and the association with micas also strongly influences the contents of Li, Zn, Ni, and Co in tourmaline. Type 1 tourmalines associated with phlogopite are relatively depleted in these elements, whereas type 2 tourmalines associated with margarite or paragonite are enriched. Some differences in isomorphic substitutions along with the trace element composition (Zn, V, Sr, Co, REE) may have value in exploration of emerald-bearing and emerald-free veins in schist-hosted emerald deposits. The δ11B values in tourmaline of all types fall in a narrow total range from -11.3 to -8.4‰. These values, combined with a mineralization temperature of 420-360 °C, yield an estimated δ11B fluid composition of -7.4 to -6.8‰ suggesting a mixed source of boron, likely dominated from the granitic rocks surrounding the emerald belt. The narrow range of B-isotope compositions in tourmaline from throughout the Mariinsky deposit suggests a well-mixed hydrothermal system.

  13. Lead contamination and transfer in urban environmental compartments analyzed by lead levels and isotopic compositions. (United States)

    Hu, Xin; Sun, Yuanyuan; Ding, Zhuhong; Zhang, Yun; Wu, Jichun; Lian, Hongzhen; Wang, Tijian


    Lead levels and isotopic compositions in atmospheric particles (TSP and PM2.5), street dust and surface soil collected from Nanjing, a mega city in China, were analyzed to investigate the contamination and the transfer of lead in urban environmental compartments. The lead contents in TSP and PM2.5 are significantly higher than them in the surface soil and street dust (p atmospheric particles. The plots of (206)Pb/(207)Pb vs.(208)Pb/(206)Pb and (206)Pb/(207)Pb vs. 1/Pb imply that the street dust and atmospheric particles (TSP and PM2.5) have very similar lead sources. Coal emissions and smelting activities may be the important lead sources for street dust and atmospheric particles (TSP and PM2.5), while the deposition of airborne lead is an important lead source for urban surface soil.

  14. Correlated Strontium and Barium Isotopic Compositions of Acid-Cleaned Single Silicon Carbides from Murchison

    CERN Document Server

    Liu, Nan; Gallino, Roberto; Davis, Andrew M; Bisterzo, Sara; Gyngard, Frank; Kaeppeler, Franz; Cristallo, Sergio; Dauphas, Nicolas; Pellin, Michael J; Dillmann, Iris


    We present strontium, barium, carbon, and silicon isotopic compositions of 61 acid-cleaned presolar SiC grains from Murchison. Comparison with previous data shows that acid washing is highly effective in removing both strontium and barium contamination. For the first time, by using correlated $^{88}Sr$/$^{86}Sr$ and $^{138}Ba$/$^{136}Ba$ ratios in mainstream SiC grains, we are able to resolve the effect of $^{13}C$ concentration from that of $^{13}C$-pocket mass on s-process nucleosynthesis, which points towards the existence of large $^{13}C$-pockets with low $^{13}C$ concentration in AGB stars. The presence of such large $^{13}$R-pockets with a variety of relatively low $^{13}C$ concentrations seems to require multiple mixing processes in parent AGB stars of mainstream SiC grains.

  15. Pyrogenic carbon from tropical savanna burning: production and stable isotope composition

    Directory of Open Access Journals (Sweden)

    G. Saiz


    C4 grasses ranging from 35 to 99% of total biomass. Residues from each fire were partitioned into PyC and further into recalcitrant (HyPyC components, with each of these also partitioned into proximal (> 125 μm and distal (13C compositions of PyC and HyPyC were generally lower by 1–3‰ relative to the original biomass, with marked depletion up to 7 ‰ for grasslands dominated by C4 biomass. δ13C values of CO2 produced by combustion was computed by mass balance and ranged from ~0.4 to 1.3‰. The depletion of 13C in PyC and HyPyC relative to the original biomass has significant implications for the interpretation of δ13C values of savanna soil organic carbon and of ancient PyC preserved in the geologic record, and for global 13C isotopic disequilibria calculations.

  16. Nitrogen Isotopic Composition of Organic Matter in a Pristine Collection IDP (United States)

    Messenger, S.; Nakamura-Messenger, K.; Keller, L. P.; Clemett, S. J.; Nguyen, A. N.; Walker, Robert M.


    Anhydrous chondritic porous interplanetary dust particles (CP IDPs) are probable cometary materials that show primitive characteristics, such as unequilibrated mineralogy, fragile structure, and abundant presolar grains and organic matter [1-3]. CP IDPs are richer in aliphatic species and N-bearing aromatic hydrocarbons than meteoritic organics and commonly exhibit highly anomalous H and N isotopic compositions [4,5]. Cometary organic matter is of interest in part because it has escaped the hydrothermal processing experienced by meteorites. However, IDPs are collected using silicon oil that must be removed with strong organic solvents such as hexane. This procedure is likely to have removed some fraction of soluble organic phases in IDPs. We recently reported the first stratospheric collection of IDPs without the use of silicone oil [6]. Here we present initial studies of the carbonaceous material in an IDP from this collection.

  17. Variations of stable isotopic compositions in precipitation on the Tibetan Plateau and its adjacent regions

    Institute of Scientific and Technical Information of China (English)


    There is no temperature effect in the southern Tibetan Plateau and South Asia to the south of the Tanggula Mountains. Amount effect has been observed at a few sampling stations accounting for about a half of the statistical stations. There is notable temperature effect in the middle and northern Tibetan Plateau and its adjacent Central Asia to the north of the Tanggula Mountains. Because vapor directly originates from low-latitude oceans, the relative heavy ( 18O with small variation characterizes the rainfall in South Asia. A sharp depletion of the stable isotopic compositions in precipitation takes place from Kyangjin on the southern slope of the Himalayas to the Tanggula Mountains in the middle plateau. From the Tanggula Mountains to the northern Tibetan Plateau, the ( 18O in precipitation increases with increasing latitude.


    Energy Technology Data Exchange (ETDEWEB)

    Liu, Nan; Savina, Michael R.; Gallino, Roberto; Davis, Andrew M.; Bisterzo, Sara; Gyngard, Frank; Käppeler, Franz; Cristallo, Sergio; Dauphas, Nicolas; Pellin, Michael J.; Dillmann, Iris


    We present strontium, barium, carbon, and silicon isotopic compositions of 61 acid-cleaned presolar SiC grains from Murchison. Comparison with previous data shows that acid washing is highly effective in removing both strontium and barium contamination. For the first time, by using correlated Sr-88/Sr-86 and Ba-138/Ba-136 ratios in mainstream SiC grains, we are able to resolve the effect of C-13 concentration from that of C-13-pocket mass on s-process nucleosynthesis, which points toward the existence of large C-13 pockets with low C-13 concentrations in asymptotic giant branch stars. The presence of such large C-13 pockets with a variety of relatively low C-13 concentrations seems to require multiple mixing processes in parent asymptotic giant branch stars of mainstream SiC grains.


    Energy Technology Data Exchange (ETDEWEB)

    Liu, Nan; Davis, Andrew M.; Dauphas, Nicolas; Pellin, Michael J. [Department of the Geophysical Sciences, The University of Chicago, Chicago, IL, 60637 (United States); Savina, Michael R. [Chicago Center for Cosmochemistry, Chicago, IL 60637 (United States); Gallino, Roberto; Bisterzo, Sara [Dipartimento di Fisica, Università di Torino, I-10125 Torino (Italy); Gyngard, Frank [Laboratory for Space Sciences, Washington University, St. Louis, MO 63130 (United States); Käppeler, Franz [Karlsruhe Institute of Technology, Institut für Kernphysik, Karlsruhe D-76021 (Germany); Cristallo, Sergio [INAF, Osservatorio Astronomico di Collurania, I-64100 Teramo (Italy); Dillmann, Iris, E-mail: [TRIUMF, 4004 Wesbrook Mall, Vancouver BC V6T 2A3 (Canada)


    We present strontium, barium, carbon, and silicon isotopic compositions of 61 acid-cleaned presolar SiC grains from Murchison. Comparison with previous data shows that acid washing is highly effective in removing both strontium and barium contamination. For the first time, by using correlated {sup 88}Sr/{sup 86}Sr and {sup 138}Ba/{sup 136}Ba ratios in mainstream SiC grains, we are able to resolve the effect of {sup 13}C concentration from that of {sup 13}C-pocket mass on s-process nucleosynthesis, which points toward the existence of large {sup 13}C pockets with low {sup 13}C concentrations in asymptotic giant branch stars. The presence of such large {sup 13}C pockets with a variety of relatively low {sup 13}C concentrations seems to require multiple mixing processes in parent asymptotic giant branch stars of mainstream SiC grains.

  20. Stable hydrogen isotope composition of n-alkanes in urban atmospheric aerosols in Taiyuan, China (United States)

    Bai, Huiling; Li, Yinghui; Peng, Lin; Liu, Xiangkai; Liu, Xiaofeng; Song, Chongfang; Mu, Ling


    The hydrogen isotope compositions (δD) of n-alkanes associated with particulate matter with a diameter of ≤10 μm from Taiyuan, China, during heating and non-heating periods were measured via gas chromatography-isotope ratio mass spectrometry to reveal the spatial and temporal characteristics of five functional zones and to provide another constraint on atmospheric pollutants. The δD values of n-C16 to n-C31 during the heating and non-heating periods ranged from -235.9‰ to -119.8‰ and from -231.3‰ to -129.2‰, respectively, but these similar spans had different distribution features. During the heating period, the δD distributions between non-central heating and commercial districts were consistent, as were those between residential and industrial districts; the n-alkanes came from two or more types of emission sources. Coal soot might be the primary local emission source, but not the only source. During the non-heating period, the n-alkanes of n-C16 to n-C20 were more depleted in D with the increasing carbon number in all functional zones, but there was no rule for n-C21 to n-C31. Specifically, coal soot and vehicle exhaust might be the primary sources of n-alkanes for non-central heating districts in the heating and non-heating periods, respectively, according to the δD distribution of n-C18 to n-C22; gasoline vehicle exhaust might be an n-alkane source, and the hydrogen isotope fractionation effect during the condensation process should be a pollution mechanism for the commercial district during the heating period; the δD distribution difference of n-C16 to n-C18 between the two periods in the residential and industrial districts was consistent, which indicates a similar source of fossil fuel combustion and a similar isotope fractionation effect during the non-heating period.

  1. Oxygen isotopic composition of ice of the glacier № 30, Suntar-Khayata Mountains

    Directory of Open Access Journals (Sweden)

    N. A. Budantseva


    Full Text Available The object of research is the mountain-valley glacier № 30, located in the central part of the Suntar-Khayatа Ridge – one of the largest centers of modern glaciation of the North-East of Russia. This glacier had been chosen due to lamination of ice on its surface, providing successive sampling of increasingly young ice upward the glacier slope. At the end of August 2013, surface ice of the glacier was sampled within the altitude range 2060–2510, an age of this ice here was estimated to be about 500 years old. Variations of δ18О values in the glacier ice amounted about 5.5‰: from −20.2 to −25.9‰ that is numerically consistent with isotopic values for the neighboring glaciers № 29 and 31. No essential relation between the ice isotopic composition and altitude, age or the change of the ice granularity was found. Absence of high-altitude isotope effect is explained by the fact that preciptation on the glacier № 30 falls at the same level of condensation as well as by intensive infiltration-congelation ice formation and fixation in the firn and snow cover of a part of the meltwater coming from higher and steeper areas on gently sloping sites of the glacier. The δ18О values of ice from glacier № 30 are rather «heavy» for glaciers being formed in severe climate conditions with average January temperature of −28 °C. According to Dansgaard's dependence δ18Оprecipitation – t °Cair the winter snow on the glacier № 30 should be hypothetically characterized by the δ18О values from −30 to −40‰ which are typical ones for the winter snow in Siberia. Oxygen isotope values of the ice show insignificant contribution of winter snow into formation of the glacier and prevalence of spring-autumn snowfalls. No definite trend of changes in the glacier alimentation and the ice-formation process was found for the last 500 years.

  2. Atmospheric pCO2 control on speleothem stable carbon isotope compositions (United States)

    Breecker, Daniel O.


    The stable carbon isotope compositions of C3 plants are controlled by the carbon isotope composition of atmospheric CO2 (δ13Ca) and by the stomatal response to water stress. These relationships permit the reconstruction of ancient environments and assessment of the water use efficiency of forests. It is currently debated whether the δ13C values of C3 plants are also controlled by atmospheric pCO2. Here I show that globally-averaged speleothem δ13C values closely track atmospheric pCO2 over the past 90 kyr. After accounting for other possible effects, this coupling is best explained by a C3 plant δ13C sensitivity of - 1.6 ± 0.3 ‰ / 100 ppmV CO2 during the Quaternary. This is consistent with 20th century European forest tree ring δ13C records, providing confidence in the result and suggesting that the modest pCO2-driven increase in water use efficiency determined for those ecosystems and simulated by land surface models accurately approximates the global average response. The δ13C signal from C3 plants is transferred to speleothems relatively rapidly. Thus, the effect of atmospheric pCO2 should be subtracted from new and existing speleothem δ13C records so that residual δ13C shifts can be interpreted in light of the other factors known to control spleleothem δ13C values. Furthermore, global average speleothem δ13C shifts may be used to develop a continuous radiometric chronology for Pleistocene atmospheric pCO2 fluctuations and, by correlation, ice core climate records.

  3. Understanding the source: The nitrogen isotope composition of Type II mantle diamonds (United States)

    Mikhail, Sami; Howell, Dan; Jones, Adrian; Milledge, Judith; Verchovsky, Sasha


    Diamonds can be broadly subdivided into 2 groups based on their nitrogen content; type I with > 10ppm nitrogen and type II with growth nitrogen can be incorporated into diamond as a compatible element in a closed system and therefore the N/C ratio in the source can be depleted by Rayleigh fractionation as the first diamonds to crystallise will partition nitrogen atoms into their lattice as a 1:1 substitution for carbon atoms (type I diamonds). However nitrogen may behave as an incompatible element in diamond (and be a compatible element in the metasomatic fluid), this coupled with an open system would lead to the removal of nitrogen by the metasomatic fluids, thus causing the source to progressively become depleted in nitrogen. Continued diamond crystallization in either system will produce diamonds with ever decreasing nitrogen concentrations with time, possibly to the point of them being almost nitrogen free. 2- It is conceivable that type I & II diamonds found in the same deposit and sharing a common paragenesis (eclogitic or peridotitic) may have formed from different metasomatic fluids in separate diamond forming events. The latter has been proposed for samples from the Cullinan mine (South Africa) based on their carbon isotope compositions (3). Both models can be tested using the stable isotope compositions of carbon and nitrogen with the N/C ratio of the diamonds in a given population with varying nitrogen content (from type I to type II). 1.D. G. Pearson, D. Canil, S. B. Shirey, D. H. Heinrich, K. T. Karl, in Treatise on Geochemistry. (Pergamon, Oxford, 2003), pp. 171-275. 2.C. McCammon, Science 293, 813 (August 3, 2001, 2001). 3.A. E. Moore, South African Journal of Geology 112, 23 (March 1, 2009, 2009).

  4. Investigation of magnesium isotope fractionation during basalt differentiation: Implications for a chondritic composition of the terrestrial mantle (United States)

    Teng, F.-Z.; Wadhwa, M.; Helz, R.T.


    To investigate whether magnesium isotopes are fractionated during basalt differentiation, we have performed high-precision Mg isotopic analyses by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) on a set of well-characterized samples from Kilauea Iki lava lake, Hawaii, USA. Samples from the Kilauea Iki lava lake, produced by closed-system crystal-melt fractionation, range from olivine-rich cumulates to highly differentiated basalts with MgO content ranging from 2.37 to 26.87??wt.%. Our results demonstrate that although these basalts have diverse chemical compositions, mineralogies, crystallization temperatures and degrees of differentiation, their Mg isotopic compositions display no measurable variation within the limits of our external precision (average ??26Mg = - 0.36 ?? 0.10 and ??25Mg = - 0.20 ?? 0.07; uncertainties are 2SD). This indicates that Mg isotopic fractionation during crystal-melt fractionation at temperatures of ??? 1055????C is undetectable at the level of precision of the current investigation. Calculations based on our data suggest that at near-magmatic temperatures the maximum fractionation in the 26Mg/24Mg ratio between olivine and melt is 0.07???. Two additional oceanic basalts, two continental basalts (BCR-1 and BCR-2), and two primitive carbonaceous chondrites (Allende and Murchison) analyzed in this study have Mg isotopic compositions similar to the Kilauea Iki lava lake samples. In contrast to a recent report [U. Wiechert, A.N. Halliday, Non-chondritic magnesium and the origins of the inner terrestrial planets, Earth and Planetary Science Letters 256 (2007) 360-371], the results presented here suggest that the Bulk Silicate Earth has a chondritic Mg isotopic composition. ?? 2007.

  5. Chondritic osmium isotopic composition of late Archean convecting upper mantle:Evidence from Zunhua podiform chromitites, Hebei, North China

    Institute of Scientific and Technical Information of China (English)

    XIA Qiongxia; ZHI Xiachen; LI Jianghai; HUANG Xiongnan


    Podiform chromite deposits are a characteristic feature of the mantle sequences of harzburgitic ophiolites. The chromites usually have very low Re and high Os contents, which makes it the most resistant phase remaining from the primary magmatic history of the ultramafic sections of ophiolites. The podiform chromite is one of the robust indicators of initial Os isotopic compositions of the ophiolites where podiform chromites were derived from, which provides strong evidence for the origin and evolution of oceanic lithosphere. The Re and Os contents and the Os isotopic compositions of seven podiform chromitites from Zunhua ophiolitic mélange belt, North China are reported in this study. The Re contents range from 0.019 to 0.128 ng/g, Os from 8.828 to 354.0 ng/g, and the 187Os/188Os ratio from 0.11003 to 0.11145. Three massive chromitites among the sample set have very high Os contents (>300 ng/g), and their 187Os/188Os ratios range from 0.11021 to 0.11030, averaging 0.11026 ± 0.00005 (σ), equivalent to a γOs = -0.12 ± 0.06 at 2.6 Ga, which means that the Os isotopic composition of convecting upper mantle is chondritic in late Archean. It is the Os isotopic composition of podiform chromitites that are derived from the oldest ophiolite in the world till now.

  6. The chromium isotopic composition of an Early to Middle Ordovician marine carbonate platform, eastern Precordillera, San Juan, Argentina

    DEFF Research Database (Denmark)

    D'Arcy, Joan Mary; Frei, Robert; Gilleaudeau, Geoffrey Jon;

    A broad suite of redox proxy data suggest that despite ocean and atmosphere oxygenation in the late Neoproterozoic, euxinic conditions persisted in the global deep oceans until the at least Ordovician [1,2,3]. Major changes in the sulphur isotopic composition of carbonate associated sulphate and ...

  7. Amphiboles as indicators of mantle source contamination: Combined evaluation of stable H and O isotope compositions and trace element ratios

    NARCIS (Netherlands)

    Demény, A.; Harangi, S.; Vennemann, T.W.; Casillas, R.; Horváth, P.; Milton, A.J.; Mason, P.R.D.; Ulianov, A.


    Stable isotope and trace element compositions of igneous amphiboles from different tectonic settings (ocean island basalts, intraplate alkaline basalts, subduction-related andesitic complexes) were compiled to help understand the role of fluids and melts in subduction-related mantle metasomatism

  8. Processes controlling the chromium isotopic composition of river water: Constraints from basaltic river catchments (United States)

    D'Arcy, Joan; Babechuk, Michael G.; Døssing, Lasse Nørbye; Gaucher, Claudio; Frei, Robert


    We report chromium (Cr) isotope compositions and concentrations (and additional geochemical and physicochemical data) of bedrock, soils and river waters from two geographically distinct basaltic river catchments, the Uruguay River catchment (Uruguay) and the Glenariff River catchment (Northern Ireland, United Kingdom), to investigate the processes that control Cr mobilisation and fractionation during weathering and riverine transport to the sea. Our results show that the Cr isotope compositions of soils are a function of the modal abundance and weathering rates of Cr-bearing minerals. The accumulation of weathering resistant Cr-spinels in the soils of Northern Ireland results in soils which are enriched in Cr and have δ53Cr values within the range of local bedrock (δ53Cr value of -0.21 ± 0.12‰, 2σ, n = 4). By contrast, the more easily weathered Cr-silicates in the bedrock of Uruguay results in greater Cr loss from the soil and a depletion in the heavy isotopes of Cr (with average δ53Cr value of -0.32 ± 0.04‰, 2σ, n = 4) relative to the local bedrock (δ53Cr value of -0.22 ± 0.08‰, 2σ, n = 4). The river waters in both catchments are predominantly